JP2941158B2 - Interlayer for laminated glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interlayer for laminated glass using an ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylate copolymer.

[0002]

2. Description of the Related Art As an interlayer film for laminated glass, a polyvinyl butyral interlayer film containing a plasticizer is widely used. However, this kind of polyvinyl butyral interlayer and laminated glass using this interlayer still have problems, particularly in terms of self-adhesion of the film, hygroscopicity, heat resistance, and bleeding of the plasticizer, and are sufficiently satisfactory. It doesn't work.

[0003] As an interlayer film and a laminated glass in which the above-mentioned disadvantages have been improved, Japanese Patent Publication No. 2-53381 discloses an ethylene-vinyl acetate copolymer mixed with an organic peroxide and a silane coupling agent. Forming a crosslinkable interlayer,
There is disclosed a technique in which this intermediate film is interposed between glass plates and heated and pressurized in an autoclave to thermally crosslink the intermediate film and integrate it into a laminated glass.

[0004] In this case, unless heating and pressurizing at a relatively high temperature (about 130 ° C. or more) in an autoclave, good crosslinking reaction does not take place and transparency is not improved. Actually, heating and pressing are performed at about 160 ° C. for 20 minutes in an autoclave.

However, autoclaves are expensive,
The operation also has the drawback that the number of steps increases and the operation becomes complicated, and the manufacturing cost increases. Further, when an organic glass plate such as polycarbonate or polymethyl methacrylate is used as the glass plate, there is a disadvantage that the organic glass plate is thermally deformed and is limited to an inorganic glass plate.

Further, when a decorative laminated glass is produced using the above-mentioned intermediate film, a polyester film or the like on which a decorative pattern is printed is interposed between the intermediate films, and a heat-resistant dye is required as a printing ink for this film. And this also increases the cost.

In Japanese Patent Publication No. 47-2103,
An intermediate film is formed using a resin of a specific component obtained by partially esterifying a partially saponified product of an ethylene-vinyl acetate copolymer with phthalic anhydride, and the intermediate film is interposed between glass plates and heated by a press or the like. There is disclosed a technique of integrating into a laminated glass by applying pressure.

[0008] In this case, a press machine or the like can be used in addition to the autoclave, which is advantageous in this respect. However, in practice, the temperature is 30 ° C. at 130 ° C. or 140 ° C.
For example, the glass plate is limited to an inorganic glass plate as described above. It is to be noted that, although it is possible to integrate by heating and pressing at a relatively low temperature, for example, about 100 ° C., at such a temperature, adhesiveness and transparency are reduced.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and has as its object the purpose of the present invention is to provide an autoclave having excellent self-adhesiveness, low hygroscopicity, little bleeding of a plasticizer, excellent heat resistance, and excellent heat resistance. An object of the present invention is to provide an interlayer film for laminated glass that can be laminated at a relatively low temperature without using it and has good adhesiveness to a glass plate and excellent transparency.

[0010]

The ethylene-vinyl acetate copolymer or ethylene- (meth) acrylate copolymer (A) used in the present invention is prepared by a known production method such as a high pressure method or an emulsification method. Although produced, the transparency and the mechanical properties differ depending on the content of the vinyl acetate or (meth) acrylate. The content of vinyl acetate or (meth) acrylate is suitably from 5 to 50% by weight.
A particularly preferred range is 15 to 35% by weight. If the content is 50% by weight or more, the transparency is good, but the tensile properties are poor, that is, the strength at break is low, and it is not suitable for forming an interlayer film for laminated glass. At a content of 5% by weight or less, tensile properties can be expected,
Since the flow start temperature rises, the workability for alignment deteriorates, and the transparency sometimes drops significantly.

The weight average molecular weight of the ethylene-vinyl acetate copolymer or ethylene- (meth) acrylate copolymer is suitably in the range of 1 × 10 ⁴ to 30 × 10 ⁴ . A particularly preferred range is 5 × 10 ^{4 to} 25 × 10 ^4.
And a more preferable range is 10 × 10 ^{4 to} 20 × 10 ^4
4 When the weight average molecular weight is 1 × 10 ⁴ or less, the fluidity becomes excessively large, and when the weight average molecular weight is 30 × 10 ⁴ or more, the fluidity is reduced, so that there is a problem in the processability of alignment.

When the melt index (MI) of the ethylene-vinyl acetate copolymer or the ethylene- (meth) acrylate copolymer decreases, the fluidity of the resin composition decreases and the processability (degassing, processing) decreases. Time) is remarkably reduced, and when it is increased, the viscosity of the resin composition is reduced and the impact resistance of the laminated glass obtained is reduced. Also, after the laminating process, the interlayer film protrudes from the edge or the thickness is reduced. Preferably 0.1 to 500 g / 10 min (AST
M 1238-65T), more preferably 1-2.
00 g / 10 min.

Examples of the (meth) acrylate constituting the ethylene- (meth) acrylate copolymer include methyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. And the like.

The condensation reaction product (B) used in the present invention comprises:
It is a condensation reaction product of a 5- to 12-valent polyhydric alcohol or a derivative thereof and twice as much benzaldehyde or a derivative thereof. If benzaldehyde is less than twice equivalent, a large amount of monoacetalized compound is generated, and if it is more than twice equivalent, a large amount of hemiacetalized compound is generated, and these by-products hinder improvement of transparency.

This condensation reaction product is disclosed in JP-B-40-1548.
No. 9, JP-B-47-7460, 5 to 12-valent polyhydric alcohols and derivatives thereof are placed in a reaction vessel equipped with a cooling pipe and a stirrer in the presence of an inert gas. It can be synthesized by charging, adding sulfuric acid or the like which is a condensed acid catalyst, and causing a heating reaction.

Representative examples of the polyhydric alcohols and derivatives thereof include sorbitol (glucitol), xylitol, mannitol, dulcitol, sorbose, arabinitol, ribitol, fructose and the like. In particular, sorbitol, xylitol,
When a condensation reaction product obtained from mannitol and dulcitol is used, the transparency is significantly improved. These may be used alone or in combination of two or more.

Examples of the above-mentioned benzaldehyde and its aldehyde derivative include those substituted with a chlorine atom, an alkyl group and an alkoxy group of benzaldehyde. Specifically, chlorobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, pentylbenzaldehyde, hexylbenzaldehyde, methoxybenzaldehyde, methoxybenzaldehyde, methoxybenzaldehyde, propoxybenzaldehyde are substituted at ortho, meta and para positions in the benzene nucleus. Pentoxybenzaldehyde, butoxybenzaldehyde, hexylbenzaldehyde and the like. Furthermore, 2,4,5-trimethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,6-dichlorobenzaldehyde, 2,3,6-trichlorobenzaldehyde, 3-methyl, 5-chlorobenzaldehyde and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the condensation catalyst used in synthesizing the above condensation reaction product include sulfuric acid, p-toluenesulfonic acid, phosphoric acid, hydrochloric acid, zinc chloride and the like.

Examples of the condensation reaction product include a dibenzylidene sorbitol compound represented by the general formula (III).

[0020]

Embedded image In the formula, R ¹ and R ² represent a hydrogen atom, a chlorine atom or a carbon atom
Represents an alkyl group of 1 to 6. R ¹ and R ² may be the same or different. If the number of carbon atoms in the alkyl group is too large, the transparency of the obtained transparent laminate will be reduced.

As the dibenzylidene sorbitol compound, for example, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (ethylbenzylidene) sorbitol, bis (propylbenzylidene)
Sorbitol, bis (butylbenzylidene) sorbitol, bis (pentylbenzylidene) sorbitol, bis (hexylbenzylidene) sorbitol, bis (chlorobenzylidene) sorbitol, and the like. These may be used alone or in combination. Good.

Examples of other condensation reactants include bis (ethylbenzylidene) xylitol, dibenzylidene dulcitol, dibenzylidene mannitol and the like.

The amount of the condensation reaction product to be added is suitably in the range of 0.01 to 4 parts by weight based on 100 parts by weight of the ethylene-vinyl acetate copolymer or the ethylene- (meth) acrylate copolymer. . A preferred range is 0.02
To 2 parts by weight, more preferably 0.05 to 1 part by weight. If the amount is less than 0.01 part by weight, the transparency is not sufficiently improved. If the amount exceeds 4 parts by weight, the fluidity and tensile strength decrease.

The calixarene compound (B) used in the present invention is represented by the formula (I).

[0025]

Embedded image

The above calixarene compound can be prepared by a known technique (Accounts of Chemical®).
essearch, 16, 161 (1983)).

The calixarene compounds include:
Formula (I) wherein n is 4 to 16 is used. That is, 4-t-butylcalix [4] arene,
-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] arene, 4-t-butyl calix [14] arene, 4-t-butyl calix [15] arene,
-T-butylcalix [16] arene. In particular, those of the formula (I) wherein n is 4 to 8 are preferable because of good dispersibility in the copolymer.

The amount of the calixarene compound to be added is suitably in the range of 0.01 to 4 parts by weight based on 100 parts by weight of the ethylene-vinyl acetate copolymer or the ethylene- (meth) acrylate copolymer. . The preferred range is 0.02 to 2 parts by weight, more preferably 0.05 to 2 parts by weight.
１1 part by weight. If the amount is less than 0.01 part by weight, the transparency cannot be sufficiently improved. If added in an amount exceeding 4 parts by weight, the transparency will be reduced.

The addition reactant (C) used in the present invention comprises:
An addition reaction product of a (meth) acrylate ester, which is a reaction product of an alcohol having 25 or less carbon atoms with (meth) acrylic acid, and a silane coupling agent having an amino group and an alkoxy group, wherein It is represented by

[0030]

Embedded image In the formula, m is an integer of 1 to 4, R is hydrogen or a methyl group, R ¹
Is a hydrocarbon group or an amino group-containing hydrocarbon group, R ² is hydrogen or the following formula,

Embedded image R ³ represents an alcohol residue, and X ^{1 to} X ³ represent an alkoxy group.

The addition reaction product (C) is obtained by adding an amino group of a silane coupling agent to a carbon-carbon double bond of a (meth) acrylic acid ester. It can be easily obtained by mixing and reacting a silane coupling agent having an alkoxy group and a (meth) acrylic acid ester at room temperature or under heating.

In this case, it is preferable to use a (meth) acrylate having two or more (meth) acryloyl groups in order to add a large amount of the silane coupling agent. Further, in order to prevent the reaction system from being significantly thickened or gelled, it is preferable to react the (meth) acrylic acid ester with the silane coupling agent such that the active hydrogen derived from the amino group is 1 mol or more.

The alcohol has a carbon number of 25 or less and includes, for example, propanol, butanol, hexanol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decane. Diol, 1,3,5-pentanetriol, 2-
And hydroxyethyl-2-ethyl-1,3-propanediol.

The (meth) acrylic acid ester which is a reaction product of an alcohol and (meth) acrylic acid includes, for example, 1,3-propylene glycol di (meth) acrylate.
Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,3,5-pentanetriol di (meth) Acrylate, 2-hydroxyethyl-2-ethyl-1,3
-Propanediol tri (meth) acrylate and the like. When an alcohol having a carbon number of 25 or more (meth) acrylate is used, the compatibility with the copolymer (A) decreases, and the transparency of the obtained interlayer film deteriorates.

Examples of the silane coupling agent having an amino group and an alkoxy group include 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane. Silane, N- (2
-Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N, N-bis- [3- (trimethoxysilyl) propyl] amine, 3- [N-allyl-N- (2-aminoethyl)] aminopropyltrimethoxysilane and the like.

The addition amount of the addition reactant (C) is in the range of 0.01 to 4 parts by weight based on 100 parts by weight of the copolymer (A). When the amount is less than 0.01 part by weight, the adhesiveness is not improved, and when it exceeds 4 parts by weight, the transparency is lowered.

The interlayer film for laminated glass of the present invention comprises the above-mentioned copolymer (A), condensation product or calixarene compound (B) and addition reaction product (C). Known additives such as an antioxidant and an ultraviolet absorber may be added.

Examples of the heat stabilizer include calcium stearate and dialkanol aliphatic tertiary amine. Examples of the antioxidant include t-butylhydroxytoluene (BHT) and “Irganox 1010” manufactured by Ciba-Geigy.

Examples of the ultraviolet absorber include benzotriazole-based and hindered amine-based ultraviolet absorbers. As benzotriazoles, for example,
"Tinuvin P" and "Tinuvin 32" manufactured by Ciba Geigy
0, "Tinuvin 326", "Tinuvin 328" and the like, and as the hindered amine-based compound, for example, "LA-57" manufactured by Adeka Argus Co., Ltd. is mentioned.

In order to obtain the interlayer film for laminated glass of the present invention, any conventionally known method may be employed.
Mixture of the above composition (including masterbatch)
Is extruded into a sheet by melt-kneading with an extruder, or a sheet is formed by melt-kneading with a roll.

Using the interlayer film for laminated glass of the present invention,
In order to manufacture a laminated glass, generally, the interlayer of the present invention is interposed between a transparent inorganic glass plate such as a float glass or a transparent organic glass plate such as a polycarbonate or polymethyl methacrylate, and the sandwich body is placed in a rubber bag. After degassing for a certain period of time at a degree of vacuum of 20 torr or less, it is transferred to an oven at about 80 ° C. or more while being degassed,
A method is employed in which the glass plate and the intermediate film are adhered to each other by maintaining the temperature at this temperature for a certain period of time.

Further, the above sandwich body was heated at 100 ° C.
After passing through a pressurized rubber roll of about
It is also possible to adopt a method in which the glass plate and the intermediate film are bonded by transferring the film to an oven at a temperature of not less than ° C. and maintaining the temperature at this temperature for a certain period of time.

Incidentally, between the interlayer films for laminated glass,
A laminated interlayer or decorative interlayer can be formed by interposing a film or sheet such as a polyester film, paper, or a metal sheet on which various patterns are printed, and a laminated glass can be manufactured using the interlayer or decorative interlayer.

[0044]

Embodiments of the present invention will be described below. Examples 1 to 14, Comparative Examples 1 to 8 Ethylene-vinyl acetate copolymer, ethylene- (meth) acrylate copolymer, condensation product, calixarene compound and addition product shown in Tables 1 to 4 Table 5
A predetermined amount shown in 7 was supplied to Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) and melted by heating at 180 ° C. for 5 minutes at 60 rpm.
This was sandwiched between polyester films, formed into a sheet by a press machine, and then the polyester film was peeled off to obtain an intermediate film having a thickness of 400 μm.

The obtained intermediate film was used as a transparent float glass plate having a thickness of 3 mm, a transparent polycarbonate plate having a thickness of 3 mm (Iupilon sheet NF200U: manufactured by Mitsubishi Gas Chemical Co., Ltd.) or a resin having a thickness of 3 mm as shown in Tables 5 to 7. A sandwich is placed between transparent polymethyl methacrylate plates (Acrylite HR: manufactured by Mitsubishi Rayon Co., Ltd.), and the sandwich body is placed in a rubber bag and 10 tons.
After degassing for 20 minutes at a vacuum degree of orr, the substrate was transferred to an oven at 100 ° C. in a degassed state, and kept at this temperature for 30 minutes to bond the glass plate and the intermediate film to obtain a laminated glass.

COMPARATIVE EXAMPLES 9 and 10 A partially saponified product having a saponification degree of 90% by weight was obtained by hydrolyzing an ethylene-vinyl acetate copolymer of MI30 (Ultracene 750, manufactured by Tohso Corporation) having a vinyl acetate content of 32% by weight. I got
180 parts by weight of this partially saponified product, 104 parts by weight of phthalic anhydride and 40 parts by weight of pyridine were mixed in 1.5 parts by weight of xylene and reacted at 110 ° C. for 4 hours to obtain a resin composition.

The composition of the obtained resin composition was such that the vinyl acetate content was 3.2% by weight and the vinyl alcohol content was 16.1%.
% By weight, the content of vinyl phthalate was 12.7, and the content of ethylene was 68.0% by weight.

Using the obtained resin composition, an intermediate film was obtained in the same manner as in Example 1, and the obtained intermediate film was adhered to a float glass plate or a polycarbonate plate, and the following combinations were obtained. Was obtained. That is, Comparative Example 9 (resin composition x float glass plate) and Comparative Example 10 (resin composition x polycarbonate plate) were obtained.

Comparative Examples 11 and 12 100 parts by weight of an ethylene-vinyl acetate copolymer of MI2 (EVAFLEX 360: manufactured by Mitsui Dupont Polychemicals) having a vinyl acetate content of 25% by weight and triallyl isocyanurate (Taike: manufactured by Nippon Kasei Co., Ltd.) ) 3 parts by weight, 1,1-
Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (Perhexa 3M: manufactured by NOF Corporation)
1.0 part by weight and 0.3 part by weight of γ-methacryloxypropyltrimethoxysilane were blended, kneaded with a roll mill at 100 ° C. (Perhexa 3M does not decompose at this temperature), and sandwiched between polyester films. After being formed into a sheet by a pressing machine, the polyester film was peeled off to obtain an uncrosslinked interlayer having a thickness of 400 μm.

The obtained uncrosslinked interlayer film and a float glass plate or a polycarbonate plate were heated at an oven temperature of 13
Bonding was performed in the same manner as in Example 1 except that the temperature was set to 0 ° C., to obtain a laminated glass having the following combination. That is, Comparative Example 11 (crosslinked interlayer film × float glass plate), Comparative Example 1
2 (crosslinked interlayer x polycarbonate plate) was obtained. In addition,
In Example 12, since the oven temperature was as high as 130 ° C., the polycarbonate plate was deformed.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

About the laminated glass thus obtained,
By the following methods, transparency test, adhesive strength test, cooling test,
A moisture resistance test and a boiling test were performed. Tables 8 and 9 show the results.
It was shown to.

The laminated glass obtained in Examples 1 to 14 was allowed to fall freely in a pendulum-type pendulum from a height of 30 cm from a height of 30 cm, in accordance with JIS R3205. A shot bag test (4 samples) was performed, and all passed the regulations.

Transparency test: For the laminated glass, an integral turbidity meter (manufactured by Tokyo Denshoku Co., Ltd.)
Was used to measure the total light transmittance and haze.

Adhesion strength test A transparent float glass or a transparent polycarbonate plate was used on one side, and a polyester film was used on the other side, and the above-mentioned intermediate film was interposed therebetween, and bonded under the same conditions as those for the laminated glass. Was cut into 2 cm in width and 10 cm in length to obtain a sample. For these samples, a tensile speed of 500 using Tensilon (manufactured by Orientec) was used.
The polyester film was peeled at 90 ° at a rate of mm / min, and the peel strength was measured.

Cooling test After leaving the laminated glass at 70 ° C. for 2 hours, it was cooled from 70 ° C. to −70 ° C. over 2 hours, and further cooled at −70 ° C. for 2 hours.
After leaving for a time, heat from -70 ° C to 70 ° C over 2 hours. This was regarded as one cycle, and after a total of 10 cycle tests, the presence or absence of delamination was observed.

Moisture Resistance Test After the laminated glass was left at a temperature of 55 ° C. and a relative humidity of 98% for 2 weeks, the presence or absence of delamination was observed.

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

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

[0066]

[Table 9]

[0067]

The structure of the interlayer film for laminated glass of the present invention is as described above, and the interlayer film has excellent self-adhesiveness, hygroscopicity, small bleeding of the plasticizer, and excellent heat resistance, transparency and adhesiveness. ing. In addition, the processability of the interlayer is excellent, and it is possible to perform the process at a relatively low temperature, for example, 100 ° C, by using an oven or a press after deaeration with a rubber bag or a pressurized rubber roll without using an autoclave. It is.

When a laminated glass is produced using the interlayer film for a laminated glass of the present invention, the laminated glass can be easily laminated without requiring an expensive autoclave, and the production cost of the laminated glass is reduced. Furthermore, since the lamination can be performed at a relatively low temperature, for example, 100 ° C., not only an inorganic glass plate as a glass plate, but also an organic glass plate such as polycarbonate or polymethyl methacrylate can be used without being thermally deformed. When producing 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 using the interlayer film for laminated glass of the present invention is suitably used for window glass of vehicles, window glass of buildings, glazing materials for sports facilities and public facilities, partitions, and security doors. You.

Claims (1)

(57) [Claims] (A) an ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylate copolymer 10
0 parts by weight, (B) 5- to 12-valent polyhydric alcohol or its derivative 1
Condensation product of an equivalent and 2 equivalents of benzaldehyde or a derivative thereof, or 0.01 to 4 parts by weight of a calixarene compound represented by the formula (I), and (C) a carbon number of 25 or less represented by the formula (II) Is the reaction product of (meth) acrylic acid with the alcohol of (meth)
An interlayer film for laminated glass, comprising 0.01 to 4 parts by weight of an addition reaction product of an acrylate ester and a silane coupling agent having an amino group and an alkoxy group. Embedded image Embedded image (Where n is an integer of 4 to 16, m is an integer of 1 to 4, R is hydrogen or a methyl group, R ¹ is a hydrocarbon group or an amino group-containing hydrocarbon group, R ² is hydrogen or the following formula, Embedded image R ³ represents an alcohol residue, and X ^{1 to} X ³ represent an alkoxy group. )