JPH07237944A - Intermediate film for laminated glass - Google Patents

Abstract

PURPOSE:To obtain an intermediate film for laminated glass improved in impact resistance, transparency and adhesiveness by alternately laminating a specific layer and a layer containing a silane coupling agent, etc., and forming one or more layers in the outermost layer from a layer containing the silane coupling agent, etc. CONSTITUTION:100 pts. wt. of an ethylene/vinyl acetate copolymer or an ethylene/(meth)acrylic acid ester copolymer is blended with 0.01-4.0 pts.wt. of a condensation reaction product of a pentavalent or more polyhydric alcohol (derivative) with a 1.8-2.8 equivalent benzaldehyde (derivative) or a 4-tert- butylcalix[4]arene of the formula [(n) is 4-16] and the blend is pressed under heating to obtain a sheet-like layer (A). Then, 0.01-4.0 pts.wt. of a silane coupling agent containing one or more amino groups is added to an ethylene/vinyl acetate copolymer or an ethylene/(meth)acrylic acid ester polymer to afford a layer (B). Then, the layers A and the layers B are alternately laminated in two or more layers and one or more layers of outermost layer are formed of the layer B to produce the objective intermediate film for glass.

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 using glass or a transparent synthetic resin plate.

[0002]

2. Description of the Related Art Laminated glass is a safety glass for automobiles,
It is used for glazing materials in public facilities and sports facilities, partitions, crime prevention doors, etc., and consists of multiple sheets of inorganic glass, or part of it as organic glass, that is, transparent synthetic resin plate, and intermediate glass for laminated glass. It is processed through the film.

As the interlayer film for laminated glass, a polyvinyl butyral resin plasticized with a plasticizer has excellent adhesiveness with glass, tough tensile strength, and high transparency, and is the most common one. Has been used as.

However, in the interlayer film for laminated glass using the above-mentioned plasticized polyvinyl butyral resin, when it is stored in a roll, if the interlayer film for laminated glass has a strong self-adhesive property at 10 ° C. or more, it is 5 ° C. It is necessary to store it below, or take a measure to prevent blocking by interposing a release paper between the interlayer films for laminated glass. In addition, the glass is conditioned before being processed with glass, and then autoclaved to produce high pressure,
It is necessary to process under high heat, making the alignment process complicated.

Further, in the method using the plasticized polyvinyl butyral resin, when the glass and the transparent synthetic resin plate are processed together, the plasticizer bleeds at the interface with the transparent synthetic resin plate, and the adhesiveness with the glass is improved. There is a problem that the transparent synthetic resin plate is whitened at the same time as it is lowered.

In order to make up for the above-mentioned drawbacks, a method of using an acid modification product of an ethylene / vinyl acetate copolymer (hereinafter referred to as "EVA") as an interlayer film for laminated glass is disclosed in JP-B-4.
In Japanese Patent Publication No. 7-2103, there is disclosed in Japanese Patent Publication No. 53381/1990, a laminated glass obtained by thermosetting an interlayer film for laminated glass composed of EVA and an organic peroxide during the laminating process.

However, in the method using the acid modified product of EVA, the hygroscopicity is high, and when it absorbs moisture, the adhesiveness with glass is lowered, and since EVA is a crystalline resin, transparency,
In particular, it has the drawback of low haze.

On the other hand, in the method of using the interlayer film for laminated glass consisting of EVA and organic peroxide, it has high transparency and can be subjected to the bonding process without being stored at room temperature and without humidity control, but it is formed by decomposition of the organic peroxide. Since radicals are used for thermosetting, a processing temperature of 130 ° C. or higher is required, and when used for decorative laminated glass, a heat resistant dye is required, which leads to deterioration in processing workability and high cost. Further, when a transparent synthetic resin plate is used, it has a drawback of being thermally deformed.

As described above, none of the above-mentioned prior art interlayer films for laminated glass are satisfactory in terms of storability, laminating processability, transparency, adhesiveness and the like.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above drawbacks, and is applied to a laminated glass having transparency, moisture resistance, weather resistance, impact resistance, adhesiveness with a transparent synthetic resin plate, and the like. It is an object of the present invention to provide an interlayer film for laminated glass which can be stored in a roll at 50 ° C. or lower and can be laminated without damaging the necessary basic characteristics and without requiring humidity control and autoclave.

[0011]

EV used in the present invention
As for A, when the vinyl acetate content is high, the tensile strength is low, and the strength at break is low, and when the vinyl acetate content is low, the flow process starting temperature is high and the workability is low, and the transparency is also low. 18 to 35% by weight is preferred.

When the content of the (meth) acrylic acid ester in the ethylene / (meth) acrylic acid ester copolymer used in the present invention is high, the tensile strength is low, and the strength at break is low, and when it is low, the fluidity is low. Since the starting temperature rises, the workability for laminating is lowered, and the transparency is remarkably lowered, so that 18 to 35% by weight is preferable.

Examples of the (meth) acrylate ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The above EVA or ethylene / (meth) acrylic acid ester copolymer is produced by a known production method such as a high pressure method or an emulsification method, and a melt index (hereinafter referred to as "MI") measured according to ASTM. Unit "g /
"10 minutes" is omitted. ) Becomes larger, the resulting interlayer film for laminated glass becomes softer, and after the laminating process, the interlayer film for laminated glass sticks out from the edge of the glass or the thickness decreases. However, the processing time becomes long, so 0.1 to 100 is preferable.

The condensation reaction product used in the present invention is 5
It can be obtained by reacting a polyvalent alcohol (derivative) having a valence of 3 or more with benzaldehyde (derivative).

As the polyvalent alcohol (derivative),
For example, sorbitol, xylitol, mannitol,
Examples thereof include dulcitol, sorbose, arabinitol, ribitol, fructose and the like. These may be used alone or in combination of two or more kinds, and particularly, a condensation reaction product obtained from sorbitol, xylitol, mannitol and dulcitol is used. If so, the transparency of the obtained interlayer film for laminated glass is significantly improved.

Examples of the above-mentioned benzaldehyde (derivative) include benzaldehyde, substitution products such as chlorine atom of hydrogen atom of benzene ring of benzaldehyde, alkyl group, aryl group and alkoxy group, which may be used alone, You may use 2 or more types together.

The above-mentioned condensation reaction product is a Japanese Patent Publication No. 40-15.
It can be synthesized as described in Japanese Patent Publication No. 489 and Japanese Patent Publication No. 47-7460, and when the ratio of the aldehyde group of benzaldehyde or its derivative to the hydroxyl group of the polyvalent alcohol (derivative) is large, hemiaceta -A large amount of ruthenium is produced as a by-product, and when it becomes less, monoacetate-
Since a large amount of ruthenium is produced as a by-product, the amount is limited to 1.8 to 2.8 times the equivalent.

In the above condensation reaction, for example, a polyhydric alcohol (derivative) having a valence of 5 or more and a benzaldehyde (derivative) are charged in a reactor equipped with a cooling pipe and a stirrer in the presence of an inert gas to obtain a condensation acid catalyst. It is obtained by adding and 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.

As the compound represented by the general formula (1),
For example, 4-t-butylcalix [4] arene, 4
-T-butylcalix [6] arene, 4-t-butylcalix [8] arene, 4-t-butylcalix [10] arene, 4-t-butylcalix [1]
2] arene, 4-t-butylcalix [14] arene, and 4-t-butylcalix [16] arene, which may be used alone or in combination of two or more kinds.

The compound represented by the general formula (1) can be obtained, for example, by the condensation reaction of pt-butylphenol and formaldehyde in the presence of a basic catalyst.

The silane coupling agent having one amino group, glycidyl group or mercapto group used in the present invention includes 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane and 3-amino. Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N
A silane coupling agent having an amino group such as-(2-aminoethyl) -3-aminopropyltrimethoxysilane; 3-glycidoxypropyldimethylethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3 A silane coupling agent having a glycidyl group such as glycidoxypropyltrimethoxysilane; mercaptomethyldimethylethoxysilane, (mercaptomethyl) methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples thereof include silane coupling agents having a mercapto group such as 3-mercaptopropyltriethoxysilane, and these may be used alone or in combination of two or more kinds.

The layer (A) used in the present invention comprises 100 parts by weight of an ethylene / vinyl acetate copolymer or an ethylene / (meth) acrylic acid ester copolymer, a polyhydric alcohol (derivative) having a valence of 5 or more, and 1. A condensation reaction product obtained by reacting 8 to 2.8 times equivalent amount of benzaldehyde (derivative) or a compound represented by the general formula (1).

When the condensation reaction product or the compound represented by the general formula (1) is added in a large amount, the condensation reaction product or the compound represented by the general formula (1) becomes difficult to disperse, and thus it is obtained. The transparency of the interlayer film for laminated glass is lowered, and when it is reduced, no improvement in transparency is observed. Therefore, with respect to 100 parts by weight of an ethylene / vinyl acetate copolymer or an ethylene / (meth) acrylic acid ester copolymer, 0.
It is from 01 to 4.0 parts by weight.

The layer (B) used in the present invention comprises EVA or an ethylene / (meth) acrylic acid ester copolymer containing 1 or more amino groups, glycidyl groups or mercapto groups.
It consists of a silane coupling agent having at least one.

When the amount of the above-mentioned silane coupling agent added is large, the transparency of the interlayer film for laminated glass obtained is low, and when it is small, the adhesiveness of the interlayer film for laminated glass obtained with glass or transparent resin plate is low. Therefore, EVA or ethylene / (meth) acrylic acid ester copolymer 10
It is 0.01 to 4.0 parts by weight with respect to 0 parts by weight.

EV used in the layers (A) and (B)
A or ethylene / (meth) acrylic acid ester copolymer may be the same or different, and one may be EVA and the other may be ethylene / (meth) acrylic acid ester copolymer. .

In addition to the above, the layer (A) and the layer (B) include a stabilizer, an antioxidant, and an ultraviolet ray for the purpose of preventing the deterioration of EVA or ethylene / (meth) acrylic acid ester copolymer. An absorber or the like can be added as needed.

Examples of the stabilizer include calcium stearate soap, dialkanol aliphatic tertiary amine and the like. Examples of the antioxidant include t-butylhydroxytoluene (BHT), "Irganox 1010" manufactured by Ciba-Geigy. Etc.

Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, and hindered amine-based ones. Examples of the benzotriazole-based ultraviolet absorber include:
"Chinubin P" made by Ciba Geigy, "Chinubin 32"
0 "," Tinuvin 326 "," Tinuvin 327 "and the like are preferably used. In the benzophenone series, for example," Seesorb 101 "," Seesorb 102 "manufactured by Cypro Kasei,
"Seesaw 103", "Seesaw 104" and the like are preferably used, and examples of the hindered amine type include "LA-57" manufactured by ADEKA ARGUS.

The above-mentioned condensation reaction product or the compound represented by the general formula (1) may be added to the layer (B) for the purpose of improving transparency.

The interlayer film for laminated glass of the present invention can be obtained by alternately laminating the layers (A) and (B).

Examples of the layer structure obtained by the above-mentioned lamination include the following. (1) Layer (A) / layer (B) two-layer structure, (2) layer (B) / layer (A) / layer (B) three-layer structure, (3) layer (B) / layer (A) ) / Layer (B) / Layer (A).

Further, in the interlayer film for laminated glass of the present invention, a layer (C) which does not impair the properties of the interlayer film for laminated glass, for example, a polyethylene terephthalate (PET) film which is undecorated or decoratively printed. It may be a laminate of a paper sheet and a metal thin film.

Examples of the layer structure of the interlayer film for laminated glass include the following. (1) Layer (B)
/ Layer (A) / layer (C) / layer (A) / layer (B), 5 layer structure, (2) layer (B) / layer (A) / layer (B) / layer (C) /
7-layer constitution of layer (B) / layer (A) / layer (B).

In the above layer structure, the layer (B) is preferably the outermost layer structure in order to enhance the adhesiveness to the glass or the transparent synthetic resin plate.

The thickness of the interlayer film for laminated glass is preferably 100 to 2000 μm, and more preferably 200 to 800 μm, since the impact resistance strength decreases as the thickness decreases and the transparency decreases as the thickness increases.

The thickness of the layer (B) is preferably 0.1 μm or more, more preferably 1 μm or more, because the adhesiveness decreases as the layer (B) becomes thinner.

The interlayer film for laminated glass of the present invention can be manufactured, for example, as follows.

(Production of Mixture of Components Constituting Layer (A)) The above EVA or ethylene / (meth) acrylic acid ester copolymer, condensation reaction product or the compound represented by the general formula (1) is used in a roll mill. Melt kneading using such a kneading machine, dry blending method using a mixing machine such as a Henschel mixer, EVA or ethylene containing a condensation reaction product or the compound represented by the general formula (1) at a high concentration. Master pellets of / (meth) acrylic acid ester copolymer are made into EVA or ethylene /
A mixture of components constituting the layer (A) is obtained by, for example, a masterbatch method in which a pellet of the (meth) acrylic acid ester copolymer is diluted to a predetermined concentration.

The mixture of the components constituting the layer (B) can be produced in the same manner as above using EVA or a (meth) acrylic acid ester copolymer and a silane coupling agent.

(Production of Intermediate Film for Laminated Glass) An extruder or a calender equipped with a sheet mold is used for the mixture of the components constituting the layer (A) and the mixture of the components constituting the layer (B). Method for separately forming sheets from rolls and laminating with a laminer roll to produce an interlayer film for laminated glass A single die is attached to an extruder having two or more cylinders A method of supplying a mixture of components constituting the layer (A) and a mixture of components constituting the layer (B) to different cylinders and extruding an interlayer film for laminated glass as a multilayer sheet can be mentioned.

(Manufacture of Laminated Glass) A laminated glass can be manufactured by a known method using the interlayer film for laminated glass obtained above. For example, the interlayer film for laminated glass is washed in advance. After sandwiching it between two glass plates having a thickness of 3 mm, putting the sandwich body in a rubber bag, and degassing at a vacuum degree of 0 to 20 torr for a certain time,
A method for producing a laminated glass by transferring to an oven at 80 ° C. or higher in the degassed state and holding at this temperature for a fixed time, after passing the sandwiched body through a pressure rubber roll heated to 100 ° C. or higher for a fixed time, Examples thereof include a method of producing a laminated glass by heating and holding it in an oven.

The interlayer film for laminated glass of the present invention may be laminated with a rigid body other than glass, for example, a metal or an inorganic material, or may be laminated with a transparent synthetic resin plate such as a polycarbonate plate or an organic glass plate. You may. Furthermore, it is possible to form a multilayer laminated glass by using these and forming an interlayer film for laminated glass to form a multilayer.

In the case of the above-mentioned multi-layer, if there are at least two rigid bodies, a non-rigid film or the like can be inserted in the intermediate layer and the outer layer.

Examples of the above multi-layering include the following. (1) Glass / interlayer film for laminated glass / polyester film / interlayer film for laminated glass / glass (2) Glass / interlayer film for laminated glass / metal plate / interlayer film for laminated glass / glass / polyurethane film (3) glass / Examples of the interlayer film for laminated glass / paper / interlayer film for laminated glass / glass.

[0048]

EXAMPLES Next, examples of the present invention will be described. In the following, "parts" means "parts by weight". (Synthesis of Condensation Reaction Product) (Synthesis Example 1) 182 g (1.0 mol) of sorbitol and benzaldehyde 2 were placed in a reactor equipped with a reflux condenser and a stirrer.
12 g (2.00 mol), 800 g of toluene and 2.0 parts of concentrated sulfuric acid were added and reacted at 80 ° C. for 3 hours, toluene was distilled off, neutralized with potassium hydroxide, washed with hot water, filtered and dried. Then, 347 g of dibenzylidene sorbitol (hereinafter referred to as “B-1”) was obtained. (Yield 97.0%).

(Synthesis Example 2) 152 g of xylitol was used instead of sorbitol and benzaldehyde in Synthesis Example 1 above.
(1.00 mol), P-ethylbenzaldehyde 281
Using g (2.10 mol), the same reaction was performed to obtain 365 g of bis (diethylbenzylidene) xylitol (hereinafter referred to as "B-2") (yield 95.0%).

(Synthesis Example 3) 182 g (1.00 mol) of dulcitol was used in place of the sorbitol of Synthesis Example 1 and a similar reaction was conducted to obtain dibenzylidene dilucitol (hereinafter referred to as "B-
3 ") was obtained. (Yield 80.2%).

(Synthesis Example 4) 182 g (1.00 mol) of mannitol was used in place of the sorbitol of Synthesis Example 1, and a similar reaction was conducted to obtain dibenzylidene mannitol (hereinafter referred to as "B-
4 ") was obtained. (Yield 75.0%).

In the following, an ethylene / methyl methacrylate copolymer having a methyl methacrylate content of 20% by weight, a weight average molecular weight of 180,000 and an MI of 4 is referred to as "EA-".
1 ", an ethylene / methyl methacrylate copolymer having a methyl methacrylate content of 25% by weight, a weight average molecular weight of 130,000, and an MI of 7 is" EA-2 ", 4-t-butyl. The calix [4] arene is "C-1", 3-glycidoxypropyltrimethoxysilane "S-2", 3-mercaptopropyltrimethoxysilane is "S-3", vinyltrimethoxysilane is "S". -4 "and γ-methacryloxypropyltrimethoxysilane are referred to as" S-5 ".

(Example 1) EVA of vinyl acetate content 28% by weight, weight average molecular weight 120,000, MI (hereinafter "EV
A-1 ". ) 100 parts and B-10.3 parts obtained in Synthesis Example 1 above were mixed in a mixer and then kneaded with a roll mill at 200 ° C., and then hot-pressed to form a layer (A) having a thickness of 380 μm. -Created

100 parts of the above EVA and 0.05 part of N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (hereinafter referred to as "S-1") were mixed in a mixer, and then mixed at 200 ° C. Kneading with a rumill, then
A sheet of 10 μm layer (B) was prepared by hot pressing.

The sheet of the layer (A) and the sheet of the layer (B) described above.
The sheets are superposed like a sheet of layer (B) / a sheet of layer (A) / a sheet of layer (B), and a polyethylene terephthalate sheet of 400 μm is used. -A layered product having a layer structure of layer (B) / layer (A) / layer (B) having a thickness of 400 μm is sandwiched between the two films by hot pressing, left to stand at room temperature, and the polyethylene terephthalate film is peeled off. , An interlayer film for laminated glass was prepared.

Next, two pieces of 3 which were previously washed and dried were used.
The interlayer film for laminated glass is sandwiched between mm-thick float glasses, placed in a rubber bag, deaerated for 20 minutes at a vacuum degree of 10 torr, and then transferred to an oven at 100 ° C. in a deaerated state at this temperature for 30 minutes. Hold for minutes to make a laminated glass.

One of the above float glasses was replaced with a polyethylene terephthalate film, and a laminated glass for measuring adhesive strength was prepared in the same manner as above.

Example 2 In place of EVA-1 of Example 1, the content of vinyl acetate was 25% by weight and the weight average molecular weight was 1
A laminated glass for measuring the adhesive strength and a laminated glass were prepared in the same manner as in Example 1 except that EVA having an MI of 2 was used (hereinafter, referred to as "EVA-2").

Example 3 A laminated glass for measuring adhesive strength and a laminated glass were prepared in the same manner as in Example 1 except that 0.3 part of B-1 was changed to 0.5 part of B-2. .

Example 4 A laminated glass for measuring adhesive strength and a laminated glass were prepared in the same manner as in Example 1 except that 0.3 part of B-1 was changed to 0.5 part of B-3. .

Example 5 A laminated glass for measuring adhesive strength and a laminated glass were prepared in the same manner as in Example 1 except that 0.3 part of B-1 was changed to 0.5 part of B-4. .

(Embodiment 6) 0.05 of S-1 of Embodiment 1
A laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner except that the part was changed to S-2 of 0.10 and the thicknesses of the layer (A) and the layer (B) were changed to 20 μm and 360 μm, respectively.

(Embodiment 7) 0.05 of S-1 of Embodiment 1
A laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner except that the parts were changed to 0.10 parts of S-3 and the thicknesses of the layer (A) and the layer (B) were changed to 20 μm and 360 μm, respectively.

(Example 8) 0.3 parts of B-1 of Example 1 was changed to 0.1 parts of C-1, and the thickness of the layer (A) and the layer (B) were changed by 5 μm and 390 μm, respectively. Other than the same,
A laminated glass for measuring adhesive strength and a laminated glass were prepared.

(Embodiment 9) The EVA-1 of the embodiment 1 is replaced with EV.
A laminated glass for measuring adhesive strength and a laminated glass were prepared in the same manner as in Example 1 except that 0.3 part of B-1 was changed to 0.1 part of C-1 in A-2.

(Example 10) 0.3 of B-1 of Example 1
Parts to 0.1 parts of C-1, 0.05 parts of S-1 to S-2
In the same manner as above, except that the thickness of the layer (A) and the thickness of the layer (B) were changed to 20 μm and 360 μm in 0.10 part, respectively, a laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner.

(Example 11) 0.3 of B-1 of Example 1
Parts to 0.1 part of C-1, 0.05 of S-1 to 0.10 parts of S-3, and the thickness of the layer (A) and the layer (B) are 2 respectively.
A laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner except that the thickness was changed to 0 μm and 360 μm.

Example 12 A laminated glass for measuring adhesive strength and a laminated glass were prepared in the same manner except that the glass of Example 1 was changed to a polycarbonate plate.

Example 13 A laminated glass for measuring the adhesive strength and a laminated glass were prepared in the same manner except that the glass of Example 1 was replaced with a polymethylmethacrylate plate.

(Embodiment 14) EVA-1 of Embodiment 1 is replaced with E.
A laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner as in Example 1 except that the laminated glass was changed to -A-1.

(Example 15) EVA-1 of Example 1
A laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner as in Example 1 except that the -A-2 was changed.

(Example 16) EVA-1 of Example 1 was replaced with E
A laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner as in Example 1 except that 0.3 part of B-1 was changed to 0.5 part of B-2 in A-1.

(Embodiment 17) The EVA-1 of Embodiment 1 is replaced with E.
A laminated glass for measuring adhesive strength and a laminated glass were prepared in the same manner as in Example 1 except that 0.3 part of B-1 was changed to 0.5 part of B-3 in A-1.

(Embodiment 18) The EVA-1 of Embodiment 1 is replaced with E.
A laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner as in Example 1 except that 0.3 part of B-1 was changed to 0.5 part of B-4 in A-1.

(Embodiment 19) EVA-1 of Embodiment 1 is replaced with E.
-A-1, 0.05 part of S-1 to 0.1 part of S-2, the thickness of the layer (A) and the layer (B) is 20 μm, 3 respectively.
A laminated glass for measuring adhesive strength and a laminated glass were prepared in the same manner except that the thickness was changed to 60 μm.

(Embodiment 20) EVA-1 of Embodiment 1 is replaced with E.
A laminated glass for measurement of adhesive strength and a laminated glass were prepared in the same manner except that 0.05 part of S-1 was replaced with 0.1 part of S-3 in A-1.

(Embodiment 21) EVA-1 of Embodiment 1 is replaced with E.
A laminated glass for measuring the adhesive strength and a laminated glass were prepared in the same manner except that 0.3 part of B-1 was changed to 0.1 part of C-1 in A-1.

(Embodiment 22) EVA-1 of Embodiment 1 is replaced with E.
A laminated glass for measurement of adhesive strength and a laminated glass were prepared in the same manner as in -A-2 except that 0.3 part of B-1 was changed to 0.1 part of C-1.

(Embodiment 23) EVA-1 of Embodiment 1 is replaced with E.
-A-1 to 0.3 parts of B-1 to 0.1 parts of C-1,
0.05 parts of S-1 to 0.1 parts of S-2, layer (A),
A laminated glass for measuring adhesive strength and a laminated glass were prepared in the same manner except that the thickness of the layer (B) was changed to 20 μm and 360 μm, respectively.

(Embodiment 24) EVA-1 of Embodiment 1 is replaced with E.
-A-1 to 0.3 parts of B-1 to 0.1 parts of C-1,
0.05 parts of S-1 to 0.1 parts of S-3, layer (A),
A laminated glass for measuring adhesive strength and a laminated glass were prepared in the same manner except that the thickness of the layer (B) was changed to 20 μm and 360 μm, respectively.

(Embodiment 25) The EVA-1 of Embodiment 1 is replaced with E.
-The thickness of each of the layer (A) and the layer (B) is 40 in A-1.
A laminated glass for measuring adhesive strength and a laminated glass were prepared in the same manner except that the glass was changed to a polycarbonate plate to have a thickness of μm and 320 μm.

(Example 26) EVA-1 of Example 1 was replaced with E.
-The thickness of each of the layer (A) and the layer (B) is 40 in A-1.
Glass to a thickness of μm and 320 μm.
A laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner except that the laminated glass was used instead.

Comparative Example 1 EVA having a MI of 30, a weight average molecular weight of 100,000 and a vinyl acetate content of 32% by weight (manufactured by Tosoh: Ultracene 750) was hydrolyzed to obtain a partially saponified product having a saponification degree of 90% by weight. It was 180 g of this partially saponified product, 104 g of phthalic anhydride and 40 cc of pyridine were mixed with 1.5
The mixture was mixed in 1 liter of xylene and reacted at 110 ° C. for 4 hours. The composition of the obtained partial esterified product was examined by infrared spectrum and elemental analysis. As a result, the vinyl acetate content was 3.2% by weight, the vinyl alcohol content was 16.1% by weight, and the vinyl phthalate content was 12.7% by weight. It was confirmed that it consisted of ethylene component. Using this resin, a single-layer interlayer film for laminated glass was prepared in the same manner as in Example 1, and using this, a laminated glass for measuring adhesive strength and a laminated glass were prepared.

(Comparative Example 2) MI = 6, vinyl acetate content = 2
8 wt% EVA (Tosoh: Ultrasen 751) 1
00 parts, triallyl isocyanurate (manufactured by Nippon Kasei: Tayk) 3 parts, 1,1-bis (t-butylperoxy)
3,3,5-Trimethylcyclohexane (made by NOF CORPORATION:
Perhexa 3M) (1.0 part) and γ-trimethoxysilane (0.3) were mixed and kneaded with a roll mill heated to 100 ° C. to prepare a resin composition. Using this resin composition, an interlayer film for laminated glass was prepared in the same manner as in Example 1, and the adhesive strength was measured in the same manner as in Example 1 except that the oven temperature was set to 130 ° C. A laminated glass and a laminated glass were prepared.

Comparative Example 3 An interlayer film for laminated glass having a thickness of 400 μm was prepared in the same manner as in Example 1 except that B-1 and S-1 of Example 1 were not added and only EVA-1 was used. A laminated glass for measurement and a laminated glass were prepared.

(Comparative Example 4) A layer (A) having a thickness of 10 µm without adding B-1 of Example 1 and a layer having a thickness of 380 µm with only EVA-1 without adding S-1 of Example 1 Using (B), an interlayer film for laminated glass was prepared in the same manner as in Example 1 to prepare laminated glass for measuring adhesive strength and laminated glass.

COMPARATIVE EXAMPLE 5 0.3 part of B-1 in Example 1 was replaced with 0.1 part of C-1 and 0.05 part of S-1 was replaced with 0.003 part of S-1. A laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner except for the above.

Comparative Example 6 Adhesive strength was measured in the same manner except that B-1 of Example 1 was not added and 0.05 part of S-1 was replaced with 6.0 part of S-1. Laminated glass and laminated glass were prepared.

(Comparative Example 7) S-1 of Example 1 0.05
In the same manner, except that the parts were changed to 0.05 parts of S-4,
A laminated glass for measuring adhesive strength and a laminated glass were prepared.

Comparative Example 8 EVA-1 of Example 1 was replaced with E-
For A-1, a single-layer interlayer film for laminated glass having a thickness of 400 μm and containing only E-A-1 was prepared for A-1 without using B-1 and S-1, and the adhesive strength was measured in the same manner as in Example 1. A laminated glass and a laminated glass were prepared.

Comparative Example 9 EVA-1 of Example 1 was replaced with E-
To A-1, 0.3 part of B-1 to 6.0 part of B-1, S
A laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner as in Example 1 except that 0.05 of -1 was replaced with 0.003 part of S-1.

(Comparative Example 10) EVA-1 of Example 1 was replaced with E.
-A-1 to 0.3 parts of B-1 to 0.1 parts of C-1,
A laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner as in Example 1 except that S-1 was not added.

(Comparative Example 11) EVA-1 of Example 1 was replaced with E.
A laminated glass for adhesive strength measurement and a laminated glass were prepared in the same manner as in Example 1 except that 0.3 part of B-1 was replaced with 0.004 part of B-1 in A-1.

COMPARATIVE EXAMPLE 12 EVA-1 of Example 1 was replaced with E.
A laminated glass for measuring adhesive strength and a laminated glass were prepared in the same manner as in Example 1 except that 0.05 part of S-1 was changed to 0.05 part of S-4 in A-1.

With respect to the laminated glass obtained in Examples 1 to 26 and Comparative Examples 1 to 12, impact test, transparency test,
A cold heat test, a moisture resistance test and a boiling test were carried out, and an adhesive strength test was carried out using a laminated glass for measuring adhesive strength, and the results are shown in Tables 1 and 2.

The above test method is as follows.

(Impact Test) According to JIS R3205, a ball having a diameter of 75 mm and an impacting body having a weight of 45 kg are 120 cm.
Pendulum type free fall from the height of 4 and hold it in a temperature-controlled room at 23 ± 2 ° C for 4 hours with 4 laminated glass, and each of them is hit once near the center point, and a ball with a diameter of 75 mm is free. The case where an opening passing through was formed was x, and the case where it was not formed was o.

(Transparency test) The total light transmittance and haze of the laminated glass were measured using "Integral turbidity meter" manufactured by Tokyo Denshoku.

(Adhesive strength test) A test piece having a width of 2 cm and a length of 10 cm was cut out from a laminated glass for an adhesive strength test, and 90-degree peel strength was measured at a pulling speed of 500 mm / min using a product name "Tensilon UCE500" manufactured by Orientec. did.

(Cooling test) The laminated glass was left at 70 ° C. for 2 hours, then from 70 ° C. to −20 ° C. for 2 hours, and further left at −20 ° C. for 2 hours, then from −20 ° C. to 70 ° C. for 2 hours. The presence or absence of delamination of the glass and the interlayer film for laminated glass was observed after 10 cycles as one cycle.

(Humidity resistance test) The laminated glass was allowed to stand at 55 ° C. and 98% relative humidity for 2 weeks, and then the presence or absence of delamination between the glass and the interlayer film for laminated glass was observed.

(Boiling test) Laminated glass is put in boiling water for 2 minutes.
After standing for a period of time, the presence or absence of layer peeling between the glass and the interlayer film for laminated glass was observed.

[0103]

[Table 1]

[0104]

[Table 2]

[0105]

INDUSTRIAL APPLICABILITY As described above, the interlayer film for laminated glass of the present invention is EVA or ethylene / (meth) acrylic acid ester copolymer, a condensation reaction product of polyvalent alcohol and benzaldehyde (derivative) or calix. Since the layer (A) composed of an arene and the layer (B) composed of EVA or / (meth) acrylic acid ester copolymer and a silane coupling agent are laminated, the impact resistance which is a basic property as an intermediate film is obtained. It has excellent transparency and adhesion to glass without sacrificing properties, and has excellent performance in that it can be machined without an autoclave and has excellent process characteristics, so it is suitable for construction and vehicles. It can be used as an intermediate film for glass.

Claims (1)

[Claims] 1. An ethylene / vinyl acetate copolymer or an ethylene / (meth) acrylic acid ester copolymer 100 parts by weight, and a polyhydric alcohol (derivative) having a valence of 5 or more and 1.8-.
2.8 times equivalent of a condensation reaction product of benzaldehyde (derivative) or a compound represented by the general formula (1) 0.01 to
A layer (A) consisting of 4.0 parts by weight and a silane having at least one of an amino group, a glycidyl group and a mercapto group in an ethylene / vinyl acetate copolymer or an ethylene / (meth) acrylic acid ester copolymer. Coupling agent 0.0
An interlayer film for laminated glass, wherein two or more layers (1) to (4) are alternately laminated, and at least one of the outermost layers is the layer (B). [Chemical 1] [In the formula, n is a natural number of 4 to 16. ]