JPH07118038A - Intermediate film for laminated glass - Google Patents

Abstract

PURPOSE:To obtain an intermediate film capable of laminating at a relatively low temp. without using an autoclave and excellent in adhesiveness to a glass plate and transparency by improving the autohesion property, hygroscopicity and heat resistance of the intermediate film and resistance to the bleed of a plasticizer. CONSTITUTION:The intermediate film for laminated glass is obtained by adding 0.01-4 pts.wt. silane coupling agent having amino group, glycidyl group or mercapto group into 100 pts.wt. thermoplastic resin, which is 50-300 thousands in weight average molecular weight, 0.5-10 in melt index and <=110 deg.C in incipient fluidization temp. and is obtained by allowing 100 pts.wt. ethylene-vinyl acetate copolymer containing 15-40wt.% vinyl acetate or ethylene-(meth)acrylic ester copolymer containing 15-40wt.% (meth)acrylic ester to react with 0.01-5 pts.wt. organic peroxide at 100-250 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an interlayer film for laminated glass using an ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylic acid ester 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 type of polyvinyl butyral interlayer film and laminated glass using this interlayer film still have problems in particular in terms of self-adhesiveness of the interlayer film, hygroscopicity, heat resistance, and bleeding of the plasticizer, and they are fully satisfactory. It's not good.

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

In the above technique, the thermally crosslinkable intermediate film is
By heating and pressurizing in the autoclave, a crosslinking reaction occurs due to the action of the organic peroxide, and transparency is improved.
The action of the silane coupling agent improves the adhesiveness with the glass plate.

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

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

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

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

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

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above drawbacks, and an object thereof is self-adhesiveness, hygroscopicity, less bleeding of a plasticizer, excellent heat resistance, and an autoclave. It is an object of the present invention to provide an interlayer film for a laminated glass, which can be laminated at a relatively low temperature without using a glass, and has good adhesiveness to a glass plate and good transparency.

[0011]

The ethylene-vinyl acetate copolymer used in the present invention contains 15 to 40 vinyl acetate.
The ethylene- (meth) acrylic acid ester copolymer contains 15 to 40% by weight of (meth) acrylic acid ester.
Contains by weight%.

When the vinyl acetate content or the (meth) acrylic acid ester content exceeds 40% by weight, the transparency of the obtained interlayer film is improved but the tensile strength is lowered, and conversely, the vinyl acetate content or ( When the content of the (meth) acrylic acid ester is less than 15% by weight, the tensile strength of the obtained interlayer film is sufficient, but the transparency is lowered, so the content is limited to this range.

Examples of the (meth) acrylic acid ester constituting the ethylene- (meth) acrylic acid ester copolymer include methyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Can be given.

The thermoplastic resin used in the present invention is the above-mentioned ethylene-vinyl acetate copolymer or ethylene- (meth)
It is obtained by reacting 100 parts by weight of an acrylate copolymer with 0.01 to 5 parts by weight of an organic peroxide at 100 to 250 ° C. This reaction is a radical reaction due to the decomposition of the organic peroxide, and the above-mentioned copolymer is crosslinked by this reaction. Any method may be adopted for the reaction, and examples thereof include a method in which the copolymer and the organic peroxide are supplied to a reactor such as a Labo Plastomill or a roll mill, and the mixture is melt-kneaded at the above temperature.

The organic peroxide is preferably an organic peroxide which decomposes to generate radicals at a temperature of 100 ° C. or higher, for example, 1,1-bis (t-butylperoxy)-
3,3,5-Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, t-butylperoxyisopropyl carbonate, t-butylperoxyisobutyrate, t-butylperoxy (2-ethylhexa) Noate), m-toluoyl peroxide and the like. These organic peroxides may be used alone or in combination of two or more.

When the amount of the organic peroxide added is less than 0.01 parts by weight or more than 5 parts by weight, the transparency of the obtained interlayer film or laminated glass is lowered. Also,
If the reaction temperature is less than 100 ° C, the reaction does not proceed and is 250 ° C.
When it exceeds, the copolymer is thermally deteriorated, and in any case, the transparency of the obtained interlayer film or laminated glass is lowered.

When the above copolymer is reacted with an organic peroxide, the thermoplastic resin obtained by this reaction has a weight average molecular weight of 50,000 to 300,000 and a melt index of 0.5 to.
10. It is necessary to select reaction conditions so that the flow starting temperature is 110 ° C. or lower.

Here, the weight average molecular weight is a value measured by gel permeation chromatography (GPC).
The melt index is a value measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kgf based on JIS K7210. In addition, the flow start temperature was measured by a Koka flow tester with a die diameter of 1 mm, a die length of 1 mm and a load of 10
Measured under the conditions of 0 kgf and a heating rate of 6 ° C./min, and means the temperature at which the softened resin starts to flow out from the die outlet.

When the weight average molecular weight of the thermoplastic resin is less than 50,000, the impact resistance of the interlayer film is lowered, and conversely, when it exceeds 300,000, the processability of the interlayer film is lowered. Further, when the melt index is less than 0.5, the defoaming property and thermocompression bonding property during the laminating process of the interlayer film are deteriorated. On the contrary, when the melt index exceeds 10, the fluidity of the interlayer film is too high. It protrudes from the glass plate and the film thickness after the laminating process decreases.

Further, when the flow starting temperature exceeds 110 ° C., the laminating temperature rises, and when laminating is performed using an organic glass plate such as polycarbonate or polymethylmethacrylate, these organic glass plates are used. Can not be used because it will be deformed by heat.

The silane coupling agent used in the present invention is a silane coupling agent having an amino group, a glycidyl group or a mercapto group.

Examples of the silane coupling agent having an amino group include 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and N. -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N
Examples thereof include-(2-aminoethyl) -3-aminopropyltrimethoxysilane.

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

As the silane coupling agent having a mercapto group, for example, mercaptomethyldimethylethoxysilane, mercaptomethylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3
-Mercaptopropyltriethoxysilane and the like.

The above silane coupling agents may be used alone or in combination of two or more. If the addition amount of the silane coupling agent is less than 0.01 parts by weight, the adhesiveness between the glass plate and the intermediate film will not be improved, and if it exceeds 4 parts by weight, the transparency of the obtained intermediate film or laminated glass will be improved. Since it decreases, it is 0.0 per 100 parts by weight of the thermoplastic resin.
1 to 4 parts by weight is added.

The interlayer film for laminated glass of the present invention comprises the above-mentioned thermoplastic resin and a silane coupling agent, but if necessary, known additives such as a heat stabilizer, an antioxidant and an ultraviolet absorber are added. May be.

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

Examples of the UV absorber include benzotriazole-based and hindered amine-based UV absorbers. Examples of the benzotriazole-based UV absorber include "Tinuvin P", "Tinuvin 320" and "Tinuvin 326" manufactured by Ciba-Geigy. "Tinubin 328 and the like can be mentioned, and examples of the hindered amine-based compound include" LA-57 "manufactured by ADEKA ARGUS CORPORATION.

The interlayer film for laminated glass of the present invention has the above composition, and any conventionally known method may be adopted to obtain an interlayer film from this composition. For example, a method of extruding with an extruder, a roll And the like. At this time, it is preferable to mold at a temperature at which the silane coupling agent does not evaporate.

Using the interlayer film for laminated glass of the present invention,
To produce a laminated glass, generally, the interlayer film of the present invention is interposed between a transparent inorganic glass plate such as float glass or a transparent organic glass plate such as polycarbonate or polymethylmethacrylate, and this sandwich is put in a rubber bag, After degassing at a vacuum degree of 20 torr or less for a certain period of time, transfer it to an oven at about 80 ° C. or higher in the degassed state
A method of adhering the glass plate and the intermediate film by holding the temperature for a certain period of time is adopted.

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

Between the interlayer films for laminated glass,
It is also possible to produce a laminated glass by using a film or a sheet such as a polyester film, paper, a metal sheet or the like on which various patterns are printed to form a multilayered interlayer film or a decorative interlayer film, and using this.

[0033]

[Function] Ethylene-vinyl acetate copolymer or ethylene-
The (meth) acrylic acid ester copolymer has already been cross-linked by the action of the organic peroxide before the bonding process with the glass plate, and the cross-linking improves the transparency of the interlayer film. Further, the action of the silane coupling agent improves the adhesiveness of the intermediate film.

The thermoplastic resin obtained from the cross-linked copolymer has a weight average molecular weight of 50,000 to 300,000, a melt index of 0.5 to 10 and a flow starting temperature of 11
Since it is adjusted to 0 ° C or less, the processability of the obtained interlayer film is excellent, and after degassing with, for example, a rubber bag or a pressure rubber roll without using an autoclave, at a relatively low temperature with an oven or a press. Can be combined.

[0035]

EXAMPLES Examples and comparative examples of the present invention will be shown below. Preparation of thermoplastic resin A Vinyl acetate content 28% by weight, Melt Idex 10
Ethylene-vinyl acetate copolymer of 00 (Ultrasen 7
25: 100 parts by weight of Toso Co., Ltd., 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane (Perhexa 3M: manufactured by NOF CORPORATION) was mixed in an amount of 1 part by weight, and this was rotated by a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) at 140 ° C. for 10 minutes at 60 rpm. The thermoplastic resin A was obtained by melt-kneading and reacting at a rate of 1 / min.

Preparation of Thermoplastic Resin B Vinyl acetate content 20% by weight, Melt Idex 35
0 ethylene-vinyl acetate copolymer (Ultracene 68
1: Tosoh Co., Ltd.) 100 parts by weight, 1,1-bis (t-
1 part by weight of butylperoxy) cyclohexane (Perhexa C: manufactured by NOF CORPORATION) was added, and a thermoplastic resin B was obtained in the same manner as above.

Preparation of Thermoplastic Resin C 100 parts by weight of a methyl methacrylate content of 25% by weight, 100 parts by weight of Melt Idex 20 ethylene-methyl methacrylate copolymer (Aklift KW402: manufactured by Sumitomo Chemical Co., Ltd.)
1 part by weight of t-butyl peroxyisopropyl carbonate (Perbutyl I: manufactured by NOF CORPORATION) was added, and a thermoplastic resin C was obtained in the same manner as above.

Preparation of Thermoplastic Resin D To 100 parts by weight of ethylene-methyl methacrylate copolymer (Acryft KW506: manufactured by Sumitomo Chemical Co., Ltd.) having a methyl methacrylate content of 38% by weight and Melt Idex 50.
1,1-bis (t-butylperoxy) -3,3,5-
1 part by weight of trimethylcyclohexane (Perhexa 3M, manufactured by NOF CORPORATION) was added, and a thermoplastic resin D was obtained in the same manner as above.

Preparation of Thermoplastic Resin E Vinyl acetate content 28% by weight, Melt Idex 10
Ethylene-vinyl acetate copolymer of 00 (Ultrasen 7
25: 100 parts by weight of Toso Co., Ltd., 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane (Perhexa 3M: manufactured by NOF CORPORATION) was mixed in an amount of 7 parts by weight to obtain a thermoplastic resin E in the same manner as above.

Preparation of Thermoplastic Resin F Vinyl acetate content 20% by weight, Melt Idex 35
0 ethylene-vinyl acetate copolymer (Ultracene 68
1: Tosoh Co., Ltd.) 100 parts by weight, 1,1-bis (t-
Butyl peroxy) cyclohexane (Perhexa C: manufactured by NOF CORPORATION) was added in an amount of 0.005 part by weight to obtain a thermoplastic resin F in the same manner as above.

Thermoplastic resins A to F obtained by the above method
Table 1 and Table 2 show the weight average molecular weight (Mw), melt index (MI), and flow starting temperature.

The weight average molecular weight (Mw) was measured by gel permeation chromatography (LS8000 series: manufactured by Tosoh Corporation) (column: inner diameter 8 mm, length 300 mm, polystyrene gel KF-802, KF-803 manufactured by Showa Denko KK, K
F-8 was used).

The melt index (MI) is measured by a melt flow index tester manufactured by Yasuda Seiki Seisakusho.
Based on JIS K7210, it was measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kgf.

The flow start temperature was measured by a high-performance flow tester manufactured by Shimadzu Corporation under conditions that the die diameter was 1 mm, the die length was 1 mm, the load was 100 kgf, and the heating rate was 6 ° C./min. The temperature at which it started to flow out was measured.

Examples 1 to 8 and Comparative Examples 1 to 4 Predetermined amounts of the thermoplastic resin (A to
F), N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane [abbreviated as I (amino group)], 3
-Mercaptopropyltriethoxysilane [abbreviated as II (mercapto group)], 3-glycidoxypropyltrimethoxysilane [abbreviated as III (glycidyl group)], and 3-
Aminopropyltriethoxysilane [abbreviated as IV (amino group)] was supplied to Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) and heated and melted at 140 ° C. for 2 minutes at 60 revolutions / minute, and sandwiched between polyester films, After forming into a sheet with a press machine, peel off the polyester film to obtain a thickness of 4
Various interlayers of 00 μm were produced.

The obtained interlayer films are shown in Tables 1 and 2 as a transparent float glass having a thickness of 3 mm and a transparent polycarbonate plate having a thickness of 3 mm (Iupilon sheet NF2000U:
Mitsubishi Gas Chemical Co., Ltd.) or 3 mm thick polymethylmethacrylate (Acrylite HR: Mitsubishi Rayon Co., Ltd.), and put this sandwich in a rubber bag for 10 t.
After degassing for 20 minutes at a vacuum degree of orr, it was transferred to an oven at the following temperature in the degassed state and kept at this temperature for 20 minutes to bond the glass plate and the interlayer film to each other, and various laminated glass Obtained.

In all of Examples 1 to 8 and Comparative Examples 2 and 4, the oven temperature was 100 ° C. In Comparative Examples 1 and 3, the temperature of the oven was set to 13 in order to obtain good adhesive strength.
The temperature was 0 ° C., and the temperature was maintained for 1 hour.

Comparative Examples 5 and 6 Vinyl acetate content 32% by weight, Melt Idex 30
Ethylene-vinyl acetate copolymer (Ultracene 75
0: manufactured by Toso Co., Ltd.) was hydrolyzed to obtain a partially saponified product having a saponification degree of 90% by weight. 180 parts by weight of this partially saponified product, 104 parts by weight of phthalic anhydride and 40 parts by weight of pyridine were added to 1.5 parts by weight.
The resin composition was obtained by mixing in xylene by weight and reacting at 110 ° C. for 4 hours.

The resin composition thus obtained had a vinyl acetate content of 3.2% by weight and a vinyl alcohol content of 16.1
% By weight, vinyl phthalate content 12.7, ethylene content 68.0% by weight.

Using the resin composition thus obtained, a laminated glass was obtained in the same manner as in Example 1 (Comparative Example 5).
Further, a laminated glass laminated on two polycarbonate plates was obtained in the same manner as in Example 5 (Comparative Example 6).

Comparative Examples 7 and 8 Melt Idex 2 ethylene-vinyl acetate copolymer (EVAFLEX 36 with a vinyl acetate content of 25% by weight)
0: Mitsui DuPont Polychemical Co., Ltd.) 100 parts by weight,
Triallyl isocyanurate (Taike: Nippon Kasei Co., Ltd.)
3 parts by weight, 1,1-bis (t-butylperoxy)-
3,3,5-Trimethylcyclohexane (Perhexa 3
M: manufactured by Nippon Oil & Fats Co., Ltd.) (1.0 parts by weight) and γ-methacryloxypropyltrimethoxysilane (0.3 parts by weight) were mixed and kneaded by a roll mill at 100 ° C (perhexa3M does not decompose at this temperature). A resin composition was obtained.

Using the resin composition thus obtained, a laminated glass was obtained in the same manner as in Example 1 except that the oven temperature was changed to 130 ° C. (Comparative Example 7). Also, the oven temperature is 130 ℃
A laminated glass laminated on two polycarbonate plates was obtained in the same manner as in Example 5 except for the above (Comparative Example 8).

The laminated glass was subjected to a transparency test, an adhesive strength test, a cold heat test, a humidity resistance test and a boiling test by the following methods. The results are shown in Tables 3 and 4.

Regarding the laminated glass obtained in Examples 1 to 8, according to JIS R3205, a 45 kg weight hitting body filled with lead shot was allowed to freely fall from a height of 30 cm in a pendulum manner. The shot bag test (the number of samples: 4) was conducted, and all passed the regulations.

Transparency test Integral turbidimeter (manufactured by Tokyo Denshoku Co., Ltd.) for laminated glass
Was used to measure the total light transmittance and haze.

Adhesive strength test The transparent float glass or transparent polycarbonate plate shown in Table 1 and Table 2 was used on one side and a polyester film was used on the opposite side, and the above intermediate film was sandwiched between them to produce the laminated glass. Adhesion was performed under the same conditions as above, and this was cut into a sample having a width of 2 cm and a length of 10 cm to obtain a sample. With respect to these samples, a polyester film was peeled at 90 degrees at a pulling speed of 500 mm / min using Tensilon (manufactured by Orientec Co., Ltd.), and the peel strength was measured.

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

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

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

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

Further, when a laminated glass is manufactured using the interlayer film for laminated glass of the present invention, the laminated glass can be easily processed without the need for an expensive autoclave, so that the manufacturing cost of the laminated glass is low. Furthermore, since it is possible to carry out a bonding process at a relatively low temperature, for example, 100 ° C., not only an inorganic glass plate but also an organic glass plate such as polycarbonate or polymethylmethacrylate can be used as a glass plate without being thermally deformed. When producing a decorative laminated glass, it is not necessary to use a heat-resistant dye in the printing ink, and the cost is low.

Therefore, the laminated glass using the interlayer film for laminated glass of the present invention is suitably used for vehicle window glasses, building window glasses, glazing materials for exercise facilities and public facilities, partitions, and crime prevention doors. It

Claims (1)

[Claims] 1. An ethylene-vinyl acetate copolymer having a vinyl acetate content of 15 to 40% by weight or an ethylene- (meth) acrylic acid ester copolymer having a (meth) acrylic acid ester content of 15 to 40% by weight. Parts and organic peroxide 0.01 to 5 parts by weight at 100 to 250 ° C. to obtain a weight average molecular weight of 5 to 300,000, a melt index of 0.5 to 10 and a flow starting temperature of 110 ° C. or less. 100 parts by weight of the thermoplastic resin, and a silane coupling agent having an amino group, a glycidyl group or a mercapto group 0.01 to
An interlayer film for laminated glass consisting of 4 parts by weight.