JPH09188548A - Interlayer for laminated glass and laminated glass for vehicular side window - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both an interlayer for a laminated glass, storable at normal temperatures without deteriorating basic characteristics required for the laminated glass such as transparency, moisture, weather and impact resistances and adhesion and capable of carrying out the lamination processing at relatively low temperatures without requiring humidity conditioning and an autoclave in a production process and the laminated glass using the interlayer therefor. SOLUTION: This interlayer for a laminated glass is formed of a resin composition comprising 100 pts.wt. ethylene-vinyl acetate copolymer or ethylene-alkyl (meth)acrylate copolymer, 0.01-4 pts.wt. transparency improver, 0.01-4 pts.wt. silane coupling agent having an organic functional group and a hydrolyzable group and 1-40 pts.wt. rosin-based or hydrocarbon-based resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an interlayer film containing an ethylene-vinyl acetate copolymer or an ethylene-alkyl (meth) acrylate copolymer as a main component, and a laminated glass using the interlayer film. This invention also
The present invention relates to a laminated glass for a vehicle side window.

[0002]

2. Description of the Related Art Conventionally, laminated glass has been widely used for safety glass plates for automobiles, glazing materials for public facilities and sports facilities, partitions, crime prevention doors, etc. A sheet of inorganic glass plate (some of which may be replaced with an organic glass plate, that is, a transparent synthetic resin plate) is processed through an intermediate film.

As an interlayer film of laminated glass, polyvinyl butyral resin plasticized by a plasticizer is used.
It is most commonly used because it has excellent adhesion to glass plates, strong tensile properties, and high transparency. However, when actually producing a laminated glass with an interlayer film made of the polyvinyl butyral resin, humidity control processing of the interlayer film is required before the bonding process with the glass plate, and the bonding process is performed under high temperature and high pressure by an autoclave. Since it needs to be performed, the work of the alignment process is complicated.

Further, in the case of processing a synthetic resin transparent plate together, the plasticizer bleeds out at the interface between the intermediate film and the synthetic resin plate to lower the adhesiveness, and at the same time erodes and whitens the synthetic resin plate. There was a drawback.

As a solution to the above drawbacks, ethylene-
An intermediate film formed from a thermoplastic resin obtained by partially esterifying a partially saponified vinyl acetate copolymer with phthalic anhydride is disclosed in, for example, Japanese Patent Publication No. 47-2103. Further, a heat-crosslinkable interlayer film formed from a resin composition obtained by blending an ethylene-vinyl acetate copolymer with an organic peroxide and a silane coupling agent is disclosed, for example, in JP-B-2.
-53381 publication. Further, an interlayer film for laminated glass formed from a resin composition obtained by adding a transparency improving agent such as a condensation reaction product to an ethylene-vinyl acetate copolymer or an ethylene-alkyl (meth) acrylate copolymer. However, for example, Japanese Patent Laid-Open No. 7-2
It is disclosed in Japanese Patent No. 551.

However, the interlayer film made of a partially esterified product of an ethylene-vinyl acetate copolymer has the drawbacks of poor adhesion to a glass plate and poor transparency, weather resistance and moisture resistance.

The interlayer film composed of an ethylene-vinyl acetate copolymer and an organic peroxide has improved crystallinity at the time of thermal denaturation, and thus has improved transparency, and can be stored at room temperature, so that the humidity control before laminating can be performed. It is unnecessary and has the advantage that it can be processed without an autoclave. However, since radicals generated by the decomposition of the organic peroxide are used for the thermosetting reaction, a bonding processing temperature of 140 to 150 ° C. is required, and a heat resistant dye is required when manufacturing a colored decorative laminated glass, There are drawbacks such as deterioration of workability and increase in cost. Further, when this intermediate film is processed together with the synthetic resin plate, there is a problem that the synthetic resin plate is thermally deformed at a high temperature.

Further, in an interlayer film comprising an ethylene-vinyl acetate copolymer or an ethylene-alkyl (meth) acrylate copolymer and a transparency improving agent, the transparency,
Without damaging the basic properties required for laminated glass, such as moisture resistance, impact resistance, and adhesion to synthetic resin plates, there is no self-adhesion of the film, no humidity control is required, and low processing temperature without autoclave, processing Although it is possible to perform matching processing with pressure, there was a problem with durability as described below.

When a glass plate is incorporated in a window sash made of metal, a bead made of soft plastic (called a glazing channel) is used as a cushioning material. When laminated glass is applied by this method, the plasticizer in the beads migrates from the edge of the laminated glass into the interlayer film and diffuses,
There was a problem that peeling occurred at the interface between the interlayer film and the glass plate.

The durability that does not cause peeling is called plasticizer resistance (or grechanic resistance). All of the above-mentioned interlayer films had problems in terms of plasticizer resistance.

A first object of the present invention is that it can be stored at room temperature without impairing the basic properties required for laminated glass such as transparency, moisture resistance, weather resistance, impact resistance, and adhesiveness, and the manufacturing process Another object of the present invention is to provide an interlayer film for laminated glass, which can be laminated at a relatively low temperature without the need for humidity control and autoclave, and a laminated glass using the same.

A second object is to provide an interlayer film and a laminated glass in which the long-term plasticizer resistance of the laminated glass is improved.

As described above, a plasticized polyvinyl butyral interlayer film is mainly used for a front window of a vehicle such as an automobile. On the other hand, side windows of vehicles such as automobiles are not as demanding as safety as windshields, and therefore tempered glass, which is cheaper than laminated glass using a plasticized polyvinyl butyral interlayer, is widely used. There is.

However, recently, from the viewpoint of heightening safety awareness and preventing theft of articles inside the vehicle, there is a demand for a side window glass of a vehicle such as an automobile, which is hard to be broken and has a laminated glass that does not scatter glass fragments even when broken. Came to be.

It is known to use a laminated glass having a plasticized polyvinyl butyral interlayer film as a side window glass of an automobile (for example, Japanese Utility Model Publication 57-11651).
No. 0).

Generally, a rimless glass plate is attached to a side window of an automobile so as to be able to move up and down. When a laminated glass using a plasticized polyvinyl butyral intermediate film is used as such a glass plate having no edge, the intermediate film is exposed at the edge of the laminated glass.

Therefore, with long-term use, the edge portion of the laminated glass absorbs moisture from the exposed edge portion of the interlayer film and is whitened, or its interface is peeled off, resulting in poor appearance, which is a safety hazard. There is a problem that occurs. Further, even if the edge is treated, it is difficult to completely prevent moisture absorption since the treated portion may be fatigued due to long-term use.

A third object of the present invention is that the moisture absorption from the edge of the laminated glass is small even if it is used for a long period of time, and the appearance of the interlayer film at the edge is not deteriorated due to whitening or interfacial peeling. (EN) Provided is an excellent laminated glass for a vehicle side window.

[0019]

First, a first invention relating to an intermediate film will be described.

The first purpose is to add 100 parts by weight of ethylene-vinyl acetate copolymer or ethylene-alkyl (meth) acrylate copolymer and 0.01 to 4 of transparency improver.
Formed by a resin composition comprising 1 part by weight, 0.01 to 4 parts by weight of a silane coupling agent having an organic functional group and a hydrolyzable group, and 1 to 40 parts by weight of a rosin resin or a hydrocarbon resin. And an interlayer film for laminated glass, and a laminated glass using this interlayer film.

The second object can be achieved by using, among the above-mentioned rosin resin or petroleum resin, especially petroleum resin.

It is known that the ethylene-vinyl acetate copolymer used in the present invention has a difference in transparency and mechanical properties depending on its vinyl acetate content. The vinyl acetate content of this copolymer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, particularly preferably 18 to 35%.
% By weight. Further, it is known that the ethylene-alkyl (meth) acrylate copolymer used in the present invention has different transparency and mechanical properties depending on the content of the alkyl (meth) acrylate component (structural unit).
The content of the alkyl (meth) acrylate component in this copolymer is preferably 5 to 50% by weight, more preferably 10 to 4%.
It is 0% by weight, particularly preferably 18 to 35% by weight. Here, the alkyl (meth) acrylate constituting the ethylene-alkyl (meth) acrylate copolymer is, for example, methyl (meth) acrylate methyl, butyl (meth) acrylate, 2-ethimehexyl (meth) acrylate, or the like.

In the ethylene-vinyl acetate copolymer or the ethylene-alkyl (meth) acrylate copolymer, if the content of the vinyl acetate component or the alkyl (meth) acrylate component is too high, the transparency of the resulting interlayer film is improved. However, mechanical strength such as tensile strength decreases. On the other hand, when the content of vinyl acetate component or alkyl (meth) acrylate component is too low, the tensile strength of the obtained interlayer film is sufficient, but the transparency is lowered, and the flow initiation temperature is high, resulting in degassing and processing. Matching workability such as period becomes poor.

Melt index of ethylene-vinyl acetate copolymer or ethylene- (meth) acrylate copolymer (value measured according to ASTM D1238,
Hereinafter referred to as "MI") is preferably 0.1 to 500 g.
/ 10 minutes, more preferably 1 to 200 g / 10 minutes. If the MI is too small, the fluidity of the obtained interlayer film is lowered, and the workability of combining (deaeration and processing time) is lowered.
On the other hand, if the MI is too large, the viscosity of the obtained intermediate film decreases, the intermediate film protrudes from the end portion after the laminating process, the thickness decreases, and the impact resistance of the obtained laminated glass decreases.

The above ethylene-vinyl acetate copolymer and ethylene- (meth) acrylate copolymer are prepared by the high pressure method,
It can be produced by a known production method such as an emulsification method, and its average weight molecular weight is preferably 3,000 to 500,0.
00, more preferably 5,000 to 300,000, and most preferably 10,000 to 250,000.

If desired, the ethylene-vinyl acetate copolymer or ethylene- (meth) acrylate copolymer may be modified by plasticization, partial saponification, acid modification, crosslinking or the like to obtain a modified product. In addition, if necessary, a compounding agent such as an adhesiveness adjusting agent, an ultraviolet absorber, a heat stabilizer, and an antioxidant may be added.

These copolymers, modified products thereof, and various compounding agents are already known and described in, for example, JP-B-47-2103, JP-B-2-53381, and JP-A-7-2551. In the present invention, an appropriate one can be selected from such known copolymers, modified products thereof, and various compounding agents.

Next, the transparency modifier used in the present invention will be described.

The transparency improver compounded in the ethylene-vinyl acetate copolymer or ethylene- (meth) acrylate copolymer improves the transparency of the resulting interlayer film, and is, for example, pentavalent or higher. The polycondensation product obtained by reacting the polyhydric alcohol or its derivative of 1. with 1.8 to 2.8 times equivalent of benzaldehyde or its derivative or the compound represented by the general formula (I) is preferably used. To be done.

[0030]

Embedded image (In the formula, n represents an integer of 4 to 16)

Examples of the polyhydric alcohol or its derivative used in the condensation reaction include sorbitol, xylitol, mannitol, dulcitol, sorbose, arabinitol, ribitol, fructose and the like, and these are used alone or in combination of two or more. it can. Among the above, especially sorbitol, xylitol,
Condensation reaction products obtained from mannitol and dulcitol are preferable because they provide an interlayer film with good transparency.

Examples of the above-mentioned benzaldehyde or a derivative thereof include benzaldehyde, a hydrogen atom of a benzene ring of benzaldehyde, a chlorine atom, an alkyl group, an aryl group,
Examples thereof include those substituted with an alkoxy group and the like, and these can be used alone or in combination of two or more.

In the condensation reaction, for example, a polyhydric alcohol having a valence of 5 or more or a derivative thereof and benzaldehyde or a derivative thereof are charged into a reactor equipped with a cooling pipe and a stirrer in the presence of an inert gas, Add a condensation acid catalyst,
It is obtained by reacting with heating.

Examples of the condensed acid catalyst include sulfuric acid,
Examples thereof include p-toluenesulfonic acid, phosphoric acid, hydrochloric acid, zinc chloride and the like.

The compound represented by the general formula (I) can be produced by a known technique. For example, the production method is described in Accounts of Chemical Research, 16, 161 (198).
It is described in 3).

As an example of the condensation reaction product or compound (I), a dibenzylidene sorbitol compound, a dibenzylidene xylitol compound, a dibenzylidene dulcitol compound, a dibenzylidene compound as described in JP-A-7-2551. Examples thereof include mannitol compounds and calixarene compounds. These transparency improvers may be used alone or in combination of two or more. Of these, dibenzylidene sorbitol compounds and calixarene compounds 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 calixarene compounds include 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] ] Arene, 4-
t-Butylcalix [10] arene, 4-t-butylcalix [11] arene, 4-t-butylcalix [12] arene, 4-t-butylcalix [1]
3] arenes, 4-t-butylcalix [14] arenes, 4-t-butylcalix [15] arenes, 4
Examples thereof include -t-butylcalix [16] arene. In particular, calixarene in which n in the general formula (I) is 4 to 8 is preferable because it has good dispersibility in a resin. still,
The number in the above [] indicates the value of n in the above general formula (I).

As other transparency improving agents, tribenzylidene sorbitol, sodium bis (4-t-butylphenyl) phosphate, sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate, Aluminum hydroxy-di (t-butylbenzoate) can also be used. The other transparency improver is at least one transparency improver selected from the group consisting of the dibenzylidene sorbitol compound, dibenzylidene xylitol compound, dibenzylidene dulcitol compound, dibenzylidene mannitol compound and calixarene compound. When used in combination, the transparency of the obtained interlayer film or laminated glass is further improved.

The transparency improver used in the present invention is an ethylene-vinyl acetate copolymer or ethylene- (meth)
0.01 to 100 parts by weight of acrylate copolymer
-4 parts by weight, preferably 0.02-1 part by weight. If the blending amount of the transparency improver is too low, the effect of improving the transparency of the interlayer film becomes insufficient, and if it is too high, the compatibility with the ethylene-vinyl acetate copolymer or the ethylene- (meth) acrylate copolymer becomes insufficient. And the transparency decreases.

Next, the silane coupling agent used in the present invention will be described.

The silane coupling agent used in the present invention improves the adhesiveness of the resulting intermediate film and has at least one organic functional group and at least one hydrolyzable group.
Organic functional groups are amino groups, glycidyl groups, mercapto groups,
Examples thereof include vinyl group and methacryl group. The hydrolyzable group is an alkoxy group or the like. For example, JP-A-7-255 described above.
A silane coupling agent as described in Japanese Patent No. 1 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) -3-Aminopropyltrimethoxysilane and the like can be mentioned.

As the silane coupling agent having a glycidyl group, 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

As the silane coupling agent having a mercapto group, mercaptomethyldimethylethoxysilane, mercaptomethylmethyldiethoxysilane, 3
-Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethylethoxysilane, 3-mercaptopropylmethyldiethoxysilane and the like.

Examples of the silane coupling agent having a vinyl group include vinyltriethoxysilane.

Examples of the silane coupling agent having a methacryl group include γ-methacryloxypropyltrimethoxysilane.

The silane coupling agent may be used alone or in combination of two or more.

Such a silane coupling agent is used in an amount of 0.01 to 100 parts by weight based on 100 parts by weight of an ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylate copolymer.
The amount is 4 parts by weight, preferably 0.02 to 2 parts by weight. In the resin composition, if the content of the silane coupling agent is too low, the effect of improving the adhesiveness of the obtained intermediate film is not recognized, and if it is too high, the obtained intermediate film may yellow. Further, the transparency of the obtained interlayer film or laminated glass is lowered.

Further, in the present invention, the ethylene-vinyl acetate copolymer or the ethylene- (meth) acrylate copolymer is mixed with a rosin resin or a hydrocarbon resin. This rosin-based resin or hydrocarbon-based resin ensures long-term storability by preventing a decrease in the adhesiveness between the glass plate and the interlayer film during long-term storage of the obtained laminated glass. In particular, hydrocarbon-based resins such as petroleum-based resins suppress the deterioration of the adhesiveness between the glass plate and the interlayer film at the end face portion due to the plasticizer in the bead (rim) during long-term use, in addition to the above-mentioned long-term storability. It improves the long-term plasticizer resistance, and this point is significantly different from the interlayer film and laminated glass proposed in the above-mentioned JP-A-7-2551.

Among the above hydrocarbon resins, petroleum resins are preferable from the viewpoint of improving long-term plasticizer resistance. Further, in order to improve the long-term weather resistance, it is preferably 88.
A hydrogenated petroleum resin having a hydrogenation rate of not less than 95% by weight, more preferably not less than 95% by weight is used.

As the rosin-based resin, rosin (wood rosin, gum rosin, tall oil rosin, etc.), polymerized rosin, hydrogenated rosin, rosin ester, hydrogenated rosin ester and the like are used.

As the petroleum resin, aliphatic petroleum resin,
Examples thereof include aromatic petroleum resin, alicyclic petroleum resin, copolymer petroleum resin, hydrogenated petroleum resin, and pure monomer petroleum resin. Specifically, aliphatic (C ₅ ) based petroleum resin, aromatic (C ₉ ) based petroleum resin, alicyclic (hydrogenated (C ₉ ) based petroleum resin, C ₅ -C ₉ copolymerized petroleum resin and styrene based Pure monomer-based petroleum resins such as oligomers are used.
Coumarone indene resin, coumarone resin, terpene resin,
α-methylstyrene polymer, vinyltoluene polymer, α
-Methylstyrene / vinyltoluene copolymer and the like can also be used.

The rosin resin or the hydrocarbon resin may be used alone or in combination of two or more.

The above rosin resin is blended in an amount 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) acrylate copolymer. To be done. If the amount of the rosin resin blended is too low, the long-term storage stability of the resulting laminated glass will be insufficient, and if it is too high, the resulting interlayer film will have poor mechanical strength such as tensile strength.

The above hydrocarbon-based resin is ethylene-
1 to 40 parts by weight per 100 parts by weight of vinyl acetate copolymer or ethylene- (meth) acrylate copolymer,
It is preferably compounded in the range of 2 to 30 parts by weight. If the amount of the petroleum-based resin is too low, the effect of improving the long-term storage stability and long-term plasticizer resistance of the resulting laminated glass becomes insufficient,
If it is too high, the dispersibility in the copolymer becomes poor, and the transparency of the obtained interlayer film or laminated glass decreases.

The interlayer film for laminated glass of the present invention may contain a heat stabilizer, if necessary, for the purpose of preventing deterioration of the resin.
Antioxidants, ultraviolet absorbers and the like may be added.

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

As the ultraviolet absorber, 2- (2'-
Hydroxy-5'-methylphenyl) benzotriazole ("Tinupine P" manufactured by Ciba-Geigy), 2- (2'-
Hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole (“Tinuvin 32” manufactured by Ciba Geigy)
0 "), 2- (2'-hydroxy-3'-t-butyl-
Benzotriazoles such as 5'-methylphenyl) -5-chlorobenzotriazole ("Tinupine 326" manufactured by Ciba-Geigy): "LA-57" manufactured by ADEKA ARGUS
Hindered amines such as; "Seesorb 101", "Seesorb 102", "Seesorb 10" manufactured by Cypro Kasei
Examples thereof include benzophenone type compounds such as "3" and "Seesaw 104".

When preparing the above resin composition, it is necessary to uniformly mix the ethylene-vinyl acetate copolymer or the ethylene- (meth) acrylate copolymer with various additives. As the mixing method, a method of melt-kneading an ethylene-vinyl acetate copolymer or an ethylene-alkyl (meth) acrylate copolymer and other components using a mixer such as a roll mill; an ethylene-vinyl acetate copolymer or Dry blending method in which an ethylene- (meth) acrylate copolymer and other components are directly kneaded; a master batch pellet containing a component other than the ethylene-vinyl acetate copolymer or the ethylene- (meth) acrylate copolymer in a high concentration A high-concentration masterbatch method in which is diluted with an ethylene-vinyl acetate copolymer or an ethylene-alkyl (meth) acrylate copolymer to a predetermined concentration is used.

Examples of the method for forming an intermediate film for laminated glass from the above resin composition include a method of molding the resin composition into a sheet by an extrusion method, a pressing method, a calender method or the like.

The thickness of the intermediate film is appropriately determined depending on the use, but generally a thickness of 0.05 to 1.2 mm is preferable. When the thickness of the interlayer film is too thin, the impact resistance of the obtained laminated glass is lowered, and when the thickness of the interlayer film is too thick, the transparency of the obtained laminated glass is lowered.

To produce the laminated glass of the present invention using the thus obtained intermediate film, for example, a sheet-like intermediate film is sandwiched from both sides thereof between transparent rigid plates such as glass plates or synthetic resin plates, The sandwich structure in an uncompressed state is put into a rubber bag, deaerated at a vacuum degree of 0 to 20 Torr for a certain period of time, and then placed in an oven at a temperature of 80 ° C. or higher in the deaerated state and kept at this temperature for a certain period of time, or the above Examples include a method in which the sandwich structure is passed through a pressure rubber roll heated to a temperature of 100 ° C. or higher for a certain period of time, and then heated and held in an oven.

The layer structure of the laminated glass obtained by using the above-mentioned intermediate film is basically glass / intermediate film / glass, but the following layer structures are also included.

Glass / interlayer film / polyethylene terephthalate film / intermediate film / glass Glass / intermediate film / metal plate / intermediate film / glass / intermediate film /
Polyurethane film ・ Glass / intermediate film / paper / intermediate film / glass ・ Polycarbonate plate / intermediate film / polyethylene terephthalate film / intermediate film / polycarbonate plate ・ Acrylic resin plate / intermediate film / metal plate / intermediate film / acrylic resin plate ・ Acrylic resin Plate / Interlayer film / Paper / Interlayer film / Acrylic resin plate

Next, a second invention relating to a laminated glass for a vehicle side window will be described.

The laminated glass for a vehicle side window according to the present invention is made of laminated glass which is provided on the vehicle side window so as to be able to move up and down, and is formed by laminating a plurality of glass plates through an intermediate film. -A vinyl acetate copolymer, an ethylene-alkyl (meth) acrylate copolymer, or a resin composition containing as a main component a modified product of these copolymers.

Particularly, in the resin film, 100 parts by weight of an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylate copolymer, or a modified product of these copolymers was used as a silane coupling agent. 0.01 to 15 kg / c of the peel strength between the intermediate film and the inorganic glass plate or organic glass plate or plastic film or sheet in contact with the intermediate film.
It is preferably m, particularly 0.1 to 5 kg / cm.

If the peel strength is too low, the interlayer film and the inorganic glass plate or the organic glass plate or the plastic film or sheet are easily peeled off, and if it is too high, the laminated glass has poor penetration resistance (shock absorption), Safety is impaired.

The ethylene-vinyl acetate copolymer or ethylene- (meth) acrylate copolymer or the modified product of these copolymers, which constitutes the main component of the resin film, is the same as that described in the first invention. is there.

Melt flow rate of ethylene-vinyl acetate copolymer or ethylene- (meth) acrylate copolymer (JIS K7210 (temperature 190 ° C., load 2.1)
The value measured based on 6 kg), hereinafter referred to as "MFR") is preferably 0.1 to 500 g / 10 minutes, more preferably 1 to 200 g / 10 minutes. If the MFR is too small, the fluidity of the resulting interlayer film is lowered, and the workability for combination (deaeration and processing time) is lowered. On the other hand, if the MFR is too large, the viscosity of the obtained intermediate film decreases, the intermediate film protrudes from the edges or the thickness decreases after the laminating process, and the impact resistance of the obtained laminated glass decreases.

If necessary, the ethylene-vinyl acetate copolymer or ethylene- (meth) acrylate copolymer may be modified by plasticization, partial saponification, acid modification, crosslinking or the like to obtain a modified product. Further, if necessary, compounding agents such as an adhesive strength adjusting agent, a transparency improving agent, an ultraviolet absorber, a heat stabilizer and an antioxidant may be added. These are the same as those described in the first invention.

In particular, a silane coupling agent is added to the above-mentioned ethylene-vinyl acetate copolymer, ethylene- (meth) acrylate copolymer or a modified product of these copolymers as an adhesion improver for the interlayer film. Preferably,
Furthermore, in order to prevent deterioration of the adhesiveness between the glass plate and the interlayer film during long-term storage of the obtained laminated glass, and to ensure long-term storage stability, a rosin-based resin or a hydrocarbon-based resin may be added. preferable.

The silane coupling agent, rosin resin and hydrocarbon resin are the same as those described in the first invention.

Preparation of the resin composition, production of an intermediate film from the composition, and production of laminated glass from the intermediate film can be carried out by known methods. The details are as described for the first invention.

If necessary, the laminated glass may be reprocessed by placing it in a high temperature oven or an autoclave in order to sufficiently adhere the glass plate and the intermediate film. Note that the matching process is not limited to the vacuum bag method described above, and for example, a simple matching processing device manufactured by Hitech Engineer Co., Ltd. can be used.

Further, from the viewpoint of surely preventing the scattering of glass fragments, in the sandwich body comprising the interlayer film and the glass plates sandwiching the interlayer film, the transparent inorganic glass plate or the transparent organic glass on the inner side of the vehicle side window is used. , Or replace it with a plastic film or sheet such as polyethylene terephthalate, or by laminating a plastic film or sheet such as polyethylene terephthalate on the surface of the transparent inorganic glass plate or the transparent organic glass plate that is the inner side of the vehicle side window. It is also possible to manufacture laminated glass.

The laminated glass thus obtained is used in the same manner as conventional tempered glass by being mounted in a side window of a vehicle such as an automobile so as to be able to move up and down without a rim.

The interlayer film of this laminated glass was made of ethylene-
Vinyl acetate copolymer or ethylene-alkyl (meth)
A resin film containing an acrylate copolymer or a modified product of these copolymers as a main component, and such a resin film has a water absorption rate (temperature of 23 ° C. × 24 according to JIS K7209).
The water absorption rate per hour is about 1.5% by weight or less, and the water absorption rate is significantly lower than that of the plasticized polyvinyl butyral interlayer film (about 3.6% by weight), and it is less susceptible to water and humidity.

In particular, when the resin film contains an appropriate amount of a silane coupling agent, the adhesiveness between the intermediate film and the glass plate is improved, and the glass when the laminated glass of the side window is hard to break due to impact is broken. The anti-scattering property is further improved.

[0081]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention and comparative examples will be described. The basic physical properties of the obtained laminated glass are also shown. All "parts" below mean parts by weight.

Example 1 (1) Preparation of intermediate film 100 parts of ethylene-vinyl acetate copolymer X505 (manufactured by Mitsubishi Chemical Corporation) having a vinyl acetate content of 25% by weight and MI = 2, and dibenzylidene sorbitol (EC-1) -55: manufactured by EC Chemical Co., Ltd.), 0.1 part of 3-aminopropyltrimethoxysilane, and rosin ester (KE-3).
11: Arakawa Chemical Co., Ltd.) 10 parts, and the resulting mixture is fed to a Labo Plastomill (Toyo Seiki Co., Ltd.) at a temperature of 2
Melt kneading was carried out at 00 ° C. to obtain a resin composition.

This was sandwiched between polyethylene terephthalate films having a thickness of 0.1 mm, and the obtained sandwich was press-formed into a sheet at a temperature of 150 ° C. and a pressure of 120 kg / cm ² for 30 minutes to form an interlayer film. A resin sheet including a polyethylene terephthalate film laminated on both sides of the resin sheet was obtained. After the resin sheet was allowed to cool to 20 ° C., the polyethylene terephthalate films on both sides were peeled off to obtain an interlayer film having a thickness of 0.4 mm.

(2) Manufacture of laminated glass This interlayer film is 30 cm in length, 30 cm in width and 3 mm in thickness.
It was sandwiched between transparent float glass plates to obtain a sandwich body. This sandwich is then placed in a rubber bag and degassed for 20 minutes at a vacuum of 10 torr, then transferred to an open at a temperature of 90 ° C. and kept at this temperature for 1 minute.
The glass plate and the intermediate film were adhered to each other by holding for 0 minute to manufacture a laminated glass having a laminated structure of glass plate / intermediate film / glass plate.

Examples 2-4, Comparative Examples 1-2 As ethylene-vinyl acetate copolymer or ethylene-alkyl (meth) acrylate, transparency improver, silane coupling agent and rosin resin or hydrocarbon resin, An interlayer film was produced in the same manner as in Example 1 except that a specific amount shown in Table 1 was used, and then, using this, a laminated glass was produced in the same manner as in Example 1.

Examples 5 to 9 and Comparative Examples 3 to 6 As ethylene-vinyl acetate copolymer or ethylene-alkyl (meth) acrylate, transparency improver, silane coupling agent and rosin resin or hydrocarbon resin, An interlayer film was produced in the same manner as in Example 1, except that the specific amount shown in Table 2 was used. Then, using this, a laminated glass was produced in the same manner as in Example 1 except that the condition for holding the sandwich in the oven was 100 ° C. for 30 minutes.

Examples 10 to 21, Comparative Examples 7 to 15 As ethylene-vinyl acetate copolymer or ethylene-alkyl (meth) acrylate, transparency improver, silane coupling agent and rosin resin or hydrocarbon resin, Except for using a specific amount of those shown in Tables 3-4,
An intermediate film was produced in the same manner as in Example 1. Then, using this, Example 1 was repeated except that the condition for holding the sandwich in the oven was 100 ° C. for 10 minutes.
A laminated glass was manufactured in the same manner as in.

Examples 22 to 26, Comparative Examples 18 to 21 As ethylene-vinyl acetate copolymer or ethylene-alkyl (meth) acrylate, transparency improver, silane coupling agent and rosin resin or hydrocarbon resin, An interlayer film was produced in the same manner as in Example 1 except that the specific amount shown in Table 5 was used. Then, using this, a laminated glass was produced in the same manner as in Example 1 except that the condition for holding the sandwich in the oven was 100 ° C. for 30 minutes.

Comparative Example 16 Ethylene-Vinyl Acetate Copolymer (Mitsui DuPont Polychemical "Ethylene-Vinyl Acetate FLAX360", MI
= 2, vinyl acetate content 25% by weight) to 100 parts,
3 parts of triallyl isocyanurate (“Taike” manufactured by Nippon Kasei), 1,1-bis (t-butylperoxy)-
1,3 parts of 3,3,5-trimethylcyclohexane (“Perhexa 3M” manufactured by NOF CORPORATION) and 0.3 parts of γ-methacryloxypropyltrimethoxysilane were blended, and the resulting blend was heated by a roll mill at a temperature of 100 ° C. The resin composition was prepared by kneading.

Using this resin composition, a laminated glass and an adhesive strength test sample were prepared in the same manner as in Example 22. However, the holding temperature of the sandwich in the oven was 130 ° C.

Comparative Example 17 In a three-necked flask equipped with a stirrer and a reflux condenser,
Ethylene-vinyl acetate copolymer (vinyl acetate content 32
% By weight, MFR18) (Ultrasen 750: manufactured by Toso Corporation) 200 parts, 10% by weight aqueous sodium hydroxide solution 3
00 parts and 1500 parts of xylene were added, the reaction solution was stirred under reflux to carry out a hydrolysis reaction, and the solid content was collected by filtration to obtain a partially saponified product having a saponification degree of 90%.

Further, 180 parts of the partially saponified product, 104 parts of phthalic anhydride, 40 parts of pyridine, and 1500 parts of xylene were placed in a three-necked flask equipped with a stirrer and a reflux condenser, and the mixture was refluxed at a temperature of 110 ° C. for 4 hours. While stirring, the mixture was allowed to react, and the solid content was collected by filtration to obtain a modified product (a partially saponified product partially esterified with phthalic anhydride).

When the composition of this partially esterified product was examined by infrared analysis and chemical analysis, it was found that the vinyl acetate component was 3.2% by weight, the vinyl alcohol component was 16.1% by weight,
It was confirmed that the vinyl phthalate component was 12.7% by weight, and the rest consisted of the ethylene component.

Using this resin composition, a laminated glass and a sample for adhesive strength test were prepared in the same manner as in Example 22.

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

[0099]

[Table 5]

The symbols representing the composition in the above tables mean the following.

[0101]

[Table 6]

[0102]

[Table 7]

Transparency-improving agent-Dibenzylidene sorbitol (EC-1-55: manufactured by EC Chemical Co., Ltd.)-Bis (methylbenzylidene) sorbitol (Gelol MD: manufactured by Shin Nippon Rika Co., Ltd.)-Dibenzylidene sorbitol coated with higher fatty acid (EC-1-70: manufactured by EC Chemicals) 4-t-butylcalix [4] arene (manufactured by Kanto Chemicals) -dibenzylidene xylitol (combined product) -dibenzylidene mannitol (combined product) -dibenzylidene mannitol (commercial product) Combined product)

Silane Coupling Agent 3-Aminopropyltrimethoxysilane (manufactured by Chisso Corporation) 3-Aminopropyltriethoxysilane (manufactured by Chisso Corporation) N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (Manufactured by Chisso Corporation) -N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation) -3-mercaptopropyltriethoxysilane (manufactured by Chisso Corporation) -3-mercaptopropyltrimethoxysilane (Chisso Corporation) 3-glycidoxypropyltrimethoxysilane (Chisso)

Rosin-based resin Rosin KE-311: Rosin ester (KE-31
1. Arakawa Chemical Co., Ltd.)-Rosin KR-611: Rosin ester (KR-61)
1. Arakawa Chemical Co., Ltd.)-Rosin T-100X: Rosin ester (T-100
X, manufactured by Mitsui Petrochemical Co., Ltd.)

Petroleum Resin-Alcon M-90: Alicyclic Petroleum Resin, Hydrogenation Weight% (Alcon M-90, Arakawa Chemical Co., Ltd.)-Alcon M-100: Alicyclic Petroleum Resin, Hydrogenation 80
Weight% (Arcon M-100, Arakawa Chemical Co., Ltd.)-Arcon P-70: Alicyclic petroleum resin, hydrogenation 95 wt% (Arcon P-70, Arakawa Chemical Co., Ltd.)-Arcon P-90: Alicyclic Group petroleum resin, hydrogenation 95% by weight (Alcon P-90, manufactured by Arakawa Chemical Co., Ltd.)-Alcon P-100: Alicyclic petroleum resin, hydrogenation 95
Weight% (Alcon P-100, manufactured by Arakawa Chemical Co., Ltd.)-Alcon P-115: Alicyclic petroleum resin, hydrogenation 95
% By weight (Arcon P-115, manufactured by Arakawa Chemical Co., Ltd.) FTR-6100: Pure monomer petroleum resin, styrene oligomer, unhydrogenated (FTR6100, manufactured by Mitsui Petrochemical Co., Ltd.) FTR-8100: Pure monomer petroleum resin , Styrene-based oligomer, unhydrogenated (FTR8100, manufactured by Mitsui Petrochemical Co., Ltd.)

(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. The reaction was carried out at a temperature of 80 ° C. for 3 hours. Then, toluene was distilled off, the mixture was neutralized with potassium hydroxide, washed with hot water, filtered and dried to obtain 347 g of dibenzylidene sorbitol (yield 97% by weight).

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

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

Test of Properties of Laminated Glass The laminated glasses obtained in Examples 1 to 26 and Comparative Examples 1 to 21 were cut into slips having a width of 2 cm and a length of 10 cm to obtain samples for physical property tests. With respect to this sample, a transparency test, an adhesive strength test, a long-term storage test, a cold heat test, a moisture resistance test, a boiling test and an impact test were conducted by the following methods. The results are shown in Tables 8-12.

From these results, it is possible to add the rosin-based resin or the hydrocarbon-based resin to the above-mentioned JP-A-7-255.
It can be seen that the long-term storability is improved as compared with the laminated glass described in JP-A-1.

(I) Transparency Test The total light transmittance (%) and the haze value at a temperature of 23 ° C. and a humidity of 50% were measured using “Integral turbidity meter” (trade name) manufactured by Tokyo Denshoku Co., Ltd. The test was conducted at n = 10.

(Ii) Adhesive Strength (Peeling Strength) Test A transparent float glass was used on one side and a polyethylene terephthalate film was used on the opposite side, and an intermediate film (immediately after production) was sandwiched between them, and the production conditions of the above laminated glass were Adhesion was performed under the same conditions, and this was cut into a sample having a width of 2 mm and a length of 10 cm to obtain a sample. The intermediate film at the edge of this sample was peeled off, and the edge of the peeled intermediate film was peeled off by pulling at 90 degrees at a pulling speed of 50 cm / min using a tensile tester (Tensilon UCE500: manufactured by Orientec Co., Ltd.). The strength was measured. The test was conducted at n = 10.

(Iii) Long-term storage test The interlayer film was left at a temperature of 40 ° C. for 40 days, and the peel strength of this interlayer film was measured in the same manner as in the above adhesive strength test.

(IV) Cold Heat Test After the laminated glass was left at a temperature of 70 ° C. for 2 hours, the temperature was kept at 7
After cooling from 0 ° C to -20 ° C over 2 hours and then leaving it at a temperature of -20 ° C for 2 hours, the temperature was from -20 ° C to 70 ° C.
Heated 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.

(V) Humidity resistance test [0116] The 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 delamination was observed. However, Example 1
The laminated glass of 0 to 21 and Comparative Examples 7 to 15 had a temperature of 6
After standing for 8 weeks at 0 ° C. and 95% relative humidity, the presence or absence of layer delamination was observed.

(Vi) Boiling Test After the laminated glass was left in boiling water for 2 hours, the presence or absence of layer delamination was observed.

(Vii) Impact resistance test A test was carried out in accordance with JIS R3205. That is, the laminated glass kept at a temperature of 23 ° C. and a humidity of 50% for 4 hours was vertically held by a supporting frame, and the weight was 45 kg and the maximum diameter was 7
A 5 mm hitting body was dropped freely from the height of 30 cm to the center of the laminated glass in a pendulum manner. 75m in diameter at the destroyed part
The case where an opening through which the sphere of m can freely pass is given as x, and the case where it does not occur is given as o.

(Viii) Weather resistance test Yellowness YI (based on JIS K7103) was measured at a black panel temperature of 63 ° C. using a sunshine weatherometer (based on JIS A1415).
In addition, YI measurement is performed with a reflection type, C light source, and a 2 degree visual field.
Evaluation was made by the difference between the initial value and YI after 1000 hours (ΔYI).

(Ix) Long-term plasticizer test A stainless steel vat was used as a plasticizer with di-2-phthalate.
Ethylhexyl (DOP) was put in, the laminated glass was immersed therein, and this was left in an oven at a temperature of 50 ° C. for 300 hours. Then, the layer peeling area at the peripheral edge of the laminated glass was measured, and the layer peeling area relative to the total area was measured. Shown as a percentage.

[0121]

[Table 8]

[0122]

[Table 9]

[0123]

[Table 10]

[0124]

[Table 11]

[0125]

[Table 12]

From these results, the laminated glass according to the present invention has improved long-term storability as compared with the laminated glass described in the above-mentioned JP-A-7-2551, by blending a rosin resin or a petroleum resin. I understand that it will be done. Further, it is understood that especially when a petroleum resin is blended, long-term storage stability and long-term plasticizer resistance are improved.

Example 27 (Window glass for vehicle side window) (1) Manufacture of intermediate film Ultrasene 751 (manufactured by Tosoh Corporation) having an ethylene-vinyl acetate copolymer of 28% by weight in vinyl acetate content and MFR = 6. 100 parts and N as a silane coupling agent
0.1 parts of-(2-aminoethyl) -3-aminopropylmethyldimethoxysilane was fed to the roll mill and the temperature was adjusted to 1
Melt kneading was carried out at 50 ° C. to obtain a resin composition.

This was sandwiched between polyethylene terephthalate films having a thickness of 0.1 mm, and the obtained sandwich was press-formed into a sheet at a temperature of 150 ° C. and a pressure of 120 kg / cm ² for 30 minutes to form an interlayer film. A resin sheet including a polyethylene terephthalate film laminated on both sides of the resin sheet was obtained. After the resin sheet was allowed to cool to 20 ° C., the polyethylene terephthalate films on both sides were peeled off to obtain an interlayer film having a thickness of 0.4 mm.

(2) Manufacture of laminated glass This interlayer film is 30 cm in length, 30 cm in width and 3 mm in thickness.
It was sandwiched between transparent float glass plates to obtain a sandwich body. The sandwiched body was then placed in a rubber bag, deaerated for 20 minutes at a vacuum of 10 torr, then transferred to an open room at 100 ° C. in the deaerated state, and kept at this temperature for 30 minutes to retain the glass plate and the interlayer film. And were adhered to each other to produce a laminated glass having a laminated structure of glass plate / intermediate film / glass plate.

Example 28 A 0.1 mm-thick polyethylene terephthalate film was laminated on a 0.4 mm-thick transparent interlayer film manufactured in the same manner as in Example 27, and the obtained laminate was 30 cm in length and 30 cm in width. And sandwiched between transparent float glass plates having a thickness of 3 mm to obtain a sandwich body. Then put this sandwich body in a rubber bag and apply a vacuum of 10 torr to 2
After deaeration for 0 minutes, the degassed state was transferred to an open at a temperature of 100 ° C., and this temperature was maintained for 30 minutes to bond the glass plate and the intermediate film. Then, this was cooled to room temperature, the vacuum state was released, the glass plate on the polyethylene terephthalate film side was removed, and laminated glass having a laminated structure of glass plate / intermediate film / polyethylene terephthalate film was produced.

Example 29 A transparent interlayer film of 0.4 mm obtained in the same manner as in Example 27 was used as a transparent float glass plate having a length of 30 cm, a width of 30 cm and a thickness of 3 mm, and a length of 30 cm, a width of 30 cm and a thickness. It is sandwiched between 3 mm transparent polycarbonate plates (Iupilon sheet NF2000U: manufactured by Mitsubishi Gas Chemical Co., Inc.), the sandwich body is put into a rubber bag, and after deaeration at a vacuum degree of 10 torr for 20 minutes, the temperature is kept deaerated at 10
It was transferred to an oven at 0 ° C. and kept at this temperature for 30 minutes.
Then, it was cooled to room temperature, the vacuum state was released, and laminated glass having a laminated structure of glass / interlayer film / polycarbonate plate was produced.

Example 30 As a material resin for the interlayer film, a modified ethylene-vinyl acetate copolymer prepared in the same manner as in Comparative Example 17 was produced (a partially saponified ethylene-vinyl acetate copolymer was converted to phthalic anhydride). Partially esterified by the method of Example 2
An intermediate film was produced in the same manner as in Example 7, and a laminated glass having a laminated structure of glass / intermediate film / glass was produced in the same manner as in Example 27 using this intermediate film.

Example 31 (1) Production of intermediate film Ethylene-vinyl acetate copolymer (vinyl acetate content 19
% By weight, MFR = 2.5, Evaflex 460: Mitsui Dipon Polychemical Co., Ltd.) 100 parts, triallyl isocyanurate (TAIC: Nippon Kasei Co., Ltd.) 3 parts, 1,1
-Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (Perhexa 3M: NOF Corporation)
1 part and 0.3 part of γ-methacryloxypropyltrimethoxysilane (manufactured by Chisso Corporation) were supplied to a roll mill and melt-kneaded at a temperature of 100 ° C. to prepare a resin composition.

This resin composition was sandwiched between polyethylene terephthalate films having a thickness of 0.1 mm, and the resulting sandwich was pressed by a pressing machine at a temperature of 100 ° C. for 120 kg.
The sheet was press-molded at a pressure of / cm ² for 30 minutes to obtain a resin sheet including an intermediate film and a polyethylene terephthalate film laminated on both sides thereof. After the resin sheet was allowed to cool to 20 ° C., the polyethylene terephthalate films on both sides were peeled off to obtain an interlayer film having a thickness of 0.4 mm.

(2) Manufacture of laminated glass This interlayer film is 30 cm in length, 30 cm in width and 3 mm in thickness.
It was sandwiched between transparent float glass plates to obtain a sandwich body. The sandwiched body was then placed in a rubber bag, deaerated for 20 minutes at a vacuum of 10 torr, then transferred to an open room at 100 ° C. in the deaerated state, and kept at this temperature for 30 minutes to retain the glass plate and the interlayer film. A laminated glass was manufactured by bonding and.

This laminated glass was then thermocompression-bonded in an autoclave under the conditions of a temperature of 135 ° C. and a pressure of 12 kg / cm ² , and then cooled to room temperature to obtain a laminated glass having a laminated structure of glass / intermediate film / glass. I made it.

Example 32 Instead of the ethylene-vinyl acetate copolymer, ethylene-
Methyl methacrylate copolymer (methyl methacrylate content 20% by weight, MFR = 4, Acryft WH202,
Example 2 except that 100 parts of Sumitomo Chemical Co., Ltd.) was used.
An intermediate film was manufactured in the same manner as in No. 7, and then laminated glass was manufactured using this.

Example 33 Instead of the ethylene-vinyl acetate copolymer, ethylene-
Methyl methacrylate copolymer (methyl methacrylate content 20% by weight, MFR = 4, Acryft WH202,
Example 2 except that 100 parts of Sumitomo Chemical Co., Ltd.) was used.
An intermediate film was manufactured in the same manner as in 8, and then a laminated glass was manufactured using this.

Example 34 Instead of the ethylene-vinyl acetate copolymer, ethylene-
Methyl methacrylate copolymer (methyl methacrylate content 20% by weight, MFR = 4, Acryft WH202,
Example 2 except that 100 parts of Sumitomo Chemical Co., Ltd.) was used.
An intermediate film was manufactured in the same manner as in No. 9, and then laminated glass was manufactured using this.

Example 35 Instead of the ethylene-vinyl acetate copolymer, ethylene-
Example 27 except that 100 parts of ethyl acrylate copolymer (ethyl acrylate content 25% by weight, MFR = 20, UNC-6570, manufactured by Nippon Unicar Co., Ltd.) was used.
An intermediate film was manufactured in the same manner as in 1. and then a laminated glass was manufactured using this.

Example 36 Instead of the ethylene-vinyl acetate copolymer, ethylene-
Methyl methacrylate copolymer (methyl methacrylate content 20% by weight, MFR = 4, Acryft WH202,
Example 3 except that 100 parts of Sumitomo Chemical Co., Ltd.) was used.
An intermediate film was produced in the same manner as in 1, and then a laminated glass was produced using this.

Example 37 An intermediate film was prepared in the same manner as in Example 27 except that N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane was not used at all, and this was used. I made laminated glass.

Example 38 An intermediate film was prepared in the same manner as in Example 35 except that N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane was not used at all, and this was used. I made laminated glass.

Comparative Example 22 (1) Preparation of Intermediate Film 100 parts of polyvinyl butyral (polymerization degree 1700, butyralization degree 65 mol%, acetylation degree 1 mol%, residual vinyl alcohol 34 mol%), triethylene glycol di- 40 parts of 2-ethylbutyrate and 0.03 part of magnesium acetate are melt-kneaded with a two-roll roll at a temperature of 150 ° C., the obtained kneaded product is sandwiched between polyethylene terephthalate films, and the temperature is 150 ° C. at a pressure of 12 by a pressing machine.
A resin sheet composed of an intermediate film and a polyethylene terephthalate film laminated on both sides of the intermediate film was obtained by press molding into a sheet shape at 0 kg / cm ² . After cooling this resin sheet to a temperature of 20 ° C., the polyethylene terephthalate film on both sides was peeled off to a thickness of 0.4.
mm was obtained. This was placed in a constant temperature and humidity chamber to adjust the water content to 0.4 to 0.5% by weight.

(2) Preparation of Laminated Glass The above interlayer film was 30 cm in length, 30 cm in width and 3 mm in thickness.
It was sandwiched between transparent float glass plates to obtain a sandwich body. The sandwiched body was then placed in a rubber bag, deaerated for 20 minutes at a vacuum of 10 torr, then transferred to an open room at 100 ° C. in the deaerated state, and kept at this temperature for 30 minutes to retain the glass plate and the interlayer film. A laminated glass was manufactured by bonding and.

This laminated glass was then thermocompression-bonded in an autoclave under conditions of a temperature of 145 ° C. and a pressure of 13 kg / cm ² , and then cooled to room temperature to obtain a laminated glass of glass / interlayer film / glass. I made it.

Comparative Example 23 An interlayer film having a water content of 0.4 to 0.5% by weight obtained in the same manner as in Comparative Example 22 was used as a polyethylene terephthalate terephthalate film having a thickness of 0.1 mm (Lumirror: manufactured by Toray Industries, Inc.).
And the laminated body was sandwiched between transparent float glass plates having a length of 30 cm, a width of 30 cm and a thickness of 0.1 mm to obtain a sandwich body. The sandwiched body was then placed in a rubber bag, deaerated for 20 minutes at a vacuum of 10 torr, then transferred to an open room at 100 ° C. in the deaerated state, and kept at this temperature for 30 minutes to retain the glass plate and the interlayer film. A laminated glass was manufactured by bonding and.

This laminated glass was then thermocompression-bonded in an autoclave under the conditions of a temperature of 135 ° C. and a pressure of 12 kg / cm ² , and then cooled to room temperature to remove the glass plate on the side of the polyethylene terephthalate film. A laminated glass having a laminated structure of an interlayer film / polyethylene terephthalate film was manufactured.

Property Test of Laminated Glass With respect to the laminated glass obtained in Examples 27 to 38 and Comparative Examples 22 to 23, a moisture resistance test (whitening distance and peel strength) was measured by the following method. Table 1 shows the results.
3 and Table 14.

(I) Measurement of whitening distance The laminated glass immediately after preparation was heated at a temperature of 50 ° C. and a relative humidity of 95.
%, The whitening distance (mm) from the edge of the laminated glass to the inside was measured.

(Ii) Measurement of Peel Strength Using the interlayer films obtained in the above-mentioned Examples and Comparative Examples, transparent interlayer glass having a width of 2 mm and a length of 10 cm (Examples 27, 30, 31, 32, 35, 36, 37, 38 and Comparative Example 22), a transparent polycarbonate plate (Example 29,
34), a transparent polyethylene terephthalate film (Examples 28 and 33 and Comparative Example 23) was adhered to one surface under the same conditions as the manufacturing conditions of the laminated glass of each Example or Comparative Example, and a test of width 2 mm x length 10 cm was performed. Pieces were made.

This test piece was tested at a temperature of 50 ° C. and a relative humidity of 95.
% For 4 weeks, then peel off the intermediate film at the end,
The peeling strength was measured by pulling the end portion of the peeled interlayer film at 90 ° at a normal temperature and a pulling speed of 50 cm / min using a tensile tester (Tensilon UCE500: manufactured by Orientec Co., Ltd.). Further, the peel strength of the test piece (immediately after the production) before the humidity resistance test (the temperature is 50 ° C. and the relative humidity is 95% and is not left for 4 weeks) was also measured.

[0153]

[Table 13]

[0154]

[Table 14]

From these results, it is understood that the laminated glass for vehicle side windows according to the present invention exhibits good moisture resistance. Therefore, even if it is used for a long period of time with the edge of the laminated glass exposed, moisture absorption from the edge of the laminated glass is small, and appearance defects such as whitening of the intermediate film at the edge and interfacial peeling may occur. Since it does not exist, it can be seen that it can be optimally used as a vehicle side window glass.

[0156]

The intermediate film according to the first aspect of the present invention and the laminated glass produced using the same have the above-described structure, and therefore the intermediate film does not have self-adhesiveness or hygroscopicity, heat resistance, transparency and adhesion. The laminated glass has excellent properties and the long-term storage stability of the laminated glass is improved, and the decrease in adhesion between the glass plate and the interlayer film during long-term storage is improved.

Further, the long-term storage stability of the laminated glass and the long-term plasticizer resistance are improved, and the decrease in the adhesiveness between the glass plate and the interlayer film during long-term storage and long-term use 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.

Particularly, when a hydrogenated product having a hydrogenation rate of 88% by weight or more is used as the rosin resin or the hydrocarbon resin, the long-term weather resistance can be further improved.

Further, the interlayer film of the present invention has excellent workability in alignment, and after degassing with, for example, a rubber bag or a pressure rubber roll, without using an expensive autoclave, a relatively low temperature by an oven or a press, For example, since the laminating process can be easily performed at a temperature of 100 ° C., the manufacturing cost of the laminated glass is reduced.

Further, since the laminating process can be performed at a relatively low temperature, for example, a temperature of 100 ° C., not only the inorganic glass plate as a glass plate but also an organic glass plate such as polycarbonate or polymethylmethacrylate is not thermally deformed. It can be used, and when producing a decorative laminated glass, it is not necessary to use a heat-resistant dye in the printing ink, and the cost is reduced.

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

In the laminated glass for vehicle side windows according to the second aspect of the present invention, the intermediate film has an ethylene-vinyl acetate copolymer or an ethylene-alkyl (meth) acrylate copolymer or a modified product of these copolymers. Since it is formed from a resin composition containing as a main component, the hygroscopicity is lower than that of a laminated glass using a conventional plasticized polyvinyl butyral interlayer film, so that the edge of the laminated glass is exposed. Even if the laminated glass is used for a long period of time, moisture absorption from the edge of the laminated glass is small, and there is no risk of appearance defects such as whitening of the intermediate film at the edge and peeling of the interface.

Particularly, 0.01 to 4 parts by weight of a silane coupling agent is added to 100 parts by weight of an ethylene-vinyl acetate copolymer, an ethylene-alkyl (meth) acrylate copolymer or a modified product of these copolymers. Laminated glass formed from an interlayer film containing, or a laminated glass having a peel strength between the interlayer film and a glass plate or a plastic film or sheet in contact with the interlayer film is 0.01 to 15 kg / cm. Exert to

Further, the laminated glass for vehicle side windows according to the present invention is cheaper than the laminated glass using the conventional plasticized polyvinyl butyral interlayer film, and is harder to break than the conventional tempered glass, and even when broken, The glass shards are less likely to scatter, and it excels in safeguarding the human body in the event of a vehicle collision, and in the same way as laminated glass used for vehicle front windows, it prevents theft of articles inside the vehicle and provides a high degree of safety. You can secure the sex.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08L 23/08 LDF C08L 23/08 LDG LDG B60J 1/17 Z (72) Inventor Satoshi Hayashi Shiga Prefecture 1259 Izumi, Mizuguchi-cho, Koka-gun Sekisui Chemical Co., Ltd.

Claims (7)

[Claims] 1. An ethylene-vinyl acetate copolymer or an ethylene-alkyl (meth) acrylate copolymer 100.
Parts by weight, 0.01 to 4 parts by weight of a transparency improver, a silane coupling agent having an organic functional group and a hydrolyzable group.
An interlayer film for laminated glass, which is formed from a resin composition comprising 01 to 4 parts by weight and 1 to 40 parts by weight of a rosin resin or a hydrocarbon resin. 2. The interlayer film according to claim 1, wherein the rosin resin or hydrocarbon resin is a hydrogenated product having a hydrogenation rate of 88% by weight or more. 3. The transparency improving agent is a condensation reaction product obtained by reacting a polyhydric alcohol having a valence of 5 or more or a derivative thereof with benzaldehyde or a derivative thereof, or a compound represented by the general formula (I). The intermediate film according to claim 1 or 2, wherein Embedded image (In the formula, n represents an integer of 4 to 16) 4. A laminated glass, which is obtained by processing a plurality of glass plates together through the interlayer film according to any one of claims 1 to 3. 5. A vehicle side window is provided so as to be able to move up and down,
A laminated glass obtained by laminating a plurality of glass plates through an intermediate film, wherein the intermediate film is an ethylene-vinyl acetate copolymer or an ethylene-alkyl (meth) acrylate copolymer or a copolymer of these. A laminated glass for a vehicle side window, which is formed from a resin composition containing a modified product of the coalescence as a main component. 6. The silane coupling agent is added to the resin composition in an amount of 100 parts by weight of an ethylene-vinyl acetate copolymer, an ethylene-alkyl (meth) acrylate copolymer, or a modified product of these copolymers. 6. The laminated glass for a vehicle side window according to claim 5, wherein the laminated glass contains 0.01 to 4 parts by weight. 7. The peel strength between the intermediate film and the glass plate or plastic film or sheet in contact with the intermediate film is
It is 0.01-15 kg / cm, The laminated glass for vehicle side windows of Claim 5 or 6 characterized by the above-mentioned.