JPS6086057A - Interlayer of sandwich glass - Google Patents

Abstract

PURPOSE:To obtain the titled interlayer having excellent bonding workability, penetration resistance and transparency, by crosslinking a film composed of a specific resin composition with ionizing radiation. CONSTITUTION:(A) A resin obtained by the intermolecular crosslinking of an ethylene-(meth)acrylic acid copolymer and/or an ethylene-(meth)acrylic acid- (meth)acrylic acid ester terpolymer with 1-10wt% metallic ion, or (B) a resin composition obtained by blending 100pts.wt. of the above resin with 0.5-20pts. wt. of an ethylene copolymer having one or more groups selected from carboxyl group, acetoxy group and OH group in the molecule, is formed to a film. The film is irradiated with ionizing radiation at a dose of 2-20Mrad to effect the crosslinking of the polyethylene segments.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an interlayer film for laminated glass, and more specifically,
Resin and/or terpolymer consisting of ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/acrylic acid or methacrylic acid/acrylic ester or Nisdel methacrylate crosslinked with metal ions.
Alternatively, a resin composition obtained by adding a specific ethylene copolymer to the resin as a main component can be coated with electrically cutting radiation to create a C-crosslinked ring. In addition to improving penetration resistance and transparency, it is used for interlayer films for laminated glass.

Laminated glass, which is obtained by sandwiching an interlayer film for laminated glass between two glass bases and applying heat and pressure, is now widely used in window glass for automobiles, aircraft, high-rise buildings, etc.

Conventionally, a polyvinyl butyral film has been generally used as an interlayer film for laminated μ glass.In actual use, C is a high-quality film such as dibutyl sebaque-1 to (D138). Approximately 30 parts of υ11 steel III plasticizer is added to form an interlayer film and CO is formed. However, this plasticized polyvinyl butyral film has a strong adhesive surface at room temperature, so when winding up the produced interlayer film, a powdered anti-sticking agent such as soda bicarbonate is sprinkled on the film surface to prevent this. Prevents stickiness. The process of manufacturing this I-mixed glass involves complicated steps such as removing this powder by washing with water and then drying it, which adds a large amount of IlI members to the work process. Also, if the glass is sticky, it will be difficult to position the glass when fitting it together.
If l <-, air would remain between the glass and the glass, which would likely cause quality problems.

Therefore, when membranes were formed to reproduce these Dell fish, the membranes showed complete self-juvenility, and therefore, C1 conventionally plasticized bolivinyl butyral embryos were used. I need this anti-stick agent 1+! In addition, when producing laminated glass, it does not require washing or drying of the film.It has excellent surface resistance and is easy to scrape. C was desired.

As a result of extensive research, the present inventors have developed an interlayer film composition that meets the four desires described in -1-, and have published patent application No. 1lrJ 57-1.
1, Shikashi J., who filed the application No. 77510, said that the niburene acrylic acid copolymer 1p and 1 bottle s1;
・, optionally]-Dyrene/(meth)acrylic acid copolymer) (collectively referred to as ``direne/(meth)acrylic acid copolymer)'') A mixed composition with a specific dylene co-neutral polymer such as a resin in which ♀ group ions are bridged between the molecules 1'),' 4e
j Kosho 41-13267 '-? Metal ions (cross-linked?fiJ resin, and even tinder+1
1Cr iiQ No. 4504845 i, +41 ethylene (meth)acrylic acid, (meth)u'
A resin etc. in which the molecules of a neutral polymer consisting of Krylic 4-Sufur are cross-linked with metal ions has a poly 1112 portion, which essentially contains a crystalline portion.

These resins (ionomers) prevent ionic crosslinking and crystal growth, but depending on the method of manufacturing the glass, there remains a problem with transparency. , Laminated glass manufacturing 114, interlayer film sandwiched between glasses and heated Ij: After shielding, extremely slow cooling η
The crystals in the 192 portion of Rudopoly-I grow densely, causing a whitening phenomenon and impairing transparency. Therefore, it is preferable to avoid miniaturization of crystals in order to obtain good transparency. for example.

130° (heated at C) - After heating, the temperature was raised to 20°C.
Ii: The manufacturing operation is complicated, as it is necessary to either buy it directly in the tank, or to slowly cool it to a certain temperature (for example, 90°C) and then pour it into water.

The purpose of the present invention is to improve the complicated gluing process during the production of laminated glass, as well as to provide an intermediate layer for laminated glass that is oil-resistant and transparent, and is particularly suitable for automobiles. CFC 1 - Used for glass.

In line with the above-mentioned objective, the present inventors have investigated -C and found that -C contains an ethylene/(meth)acrylic acid copolymer and is obtained by cross-linking the molecules with metal ions, or has specific -C properties for these resins. [J on irradiating a film made of a resin composition containing a dylene copolymer with an electromagnetic radiation beam,
The present inventors have discovered that an interlayer film for laminated glass obtained by this method achieves the above object, and has arrived at the present invention.

That is, the present invention provides -[dylene/acrylic acid copolymer,
Cross-linking between molecules of at least one copolymer of ethylene/methacrylic acid copolymer, ethylene doacrylic acid or I is a terpolymer consisting of methacrylic acid and acrylic acid ester or Nisdel methacrylate with metal ions. Te1q
If the resin is the main component,
This has a /J-4-yl group in the molecule, ace1-1-J
1 (7 times 1) irradiating the filn made of a resin composition containing at least one type of hydroxyl group and a combination of soil and tyrene, and 7?i times 1] 1. NiJ,
It is cross-linked and located at the middle 111j for the lath. One example of the resin used in the present invention is ethylene/noacrylic acid, ethylene/methacrylic, and metal ion υ' crosslinked molecules.
Some of the carboxyl groups of methacryl 01j are intermolecularly cross-linked by metal cations, such as sodium ions, potassium ions, lithium ions, zinc ions, magnesium ions, etc. In warm, we played a strong 1-1 against non-7ij (Is there a J?
When heated, the cross-linking strength of the metal ions becomes weaker, making it possible to be molded like ordinary plastic resin.

Furthermore, in the present invention, in addition to these tyrene/(meth)acrylic acid copolymers, the J3
1, which is possible by using a resin in which the molecules of a terpolymer of teroprene, (meth)acrylic acid, and methacrylic acid ester are cross-linked with metal ions, as described in No. 45, etc. It is also known that this resin has good permeability when bonded with a laminated glass interlayer film.
I agree.

The present invention is roughly J3 (is, the previously filed application 1j35
For each of the above IBJ resins (ionomers) disclosed in 7-177!
4. Adding an ethylene copolymer containing at least one of a carbo-4 group, an aletoxy group, and a hydroxyl group to the straw molecule (a fat composition can also be used). The resin composition also contributes to the improvement of the intermembrane penetration resistance for JJ NOS. Ethylene acrylic M Jt polymer,
It is ethylene/methacrylic acid copolymerized foam, etc., and the amount added is appropriately selected, but it is 0.5 to 20 parts by weight per 100 parts of the θr mesh resin.

These resins or resin compositions containing the ethylene/(meth)acrylic acid copolymer described above may be used alone or in a blend.

Resins a3J and 151 cross-linked with these fully bent stitches,
or a resin composition (well, in general, the higher the amount of metal ions, the better the transparency, but the strength of the blade (EC)
Also, if the amount of metal ions is small, the tightness with glass (.
Since the clarity is not excellent, it is necessary to appropriately select the metal ion content, and in the present invention, the total ion content of d3L + 9F, J, and the total ion content is 1 to 10%.

The present invention [311, above J, sea urchin, these ethylene/(meth)acrylic acid copolymers, terpolymer of ethylene/(meth)acrylic acid/(meth)acrylic acid"-7 Cross-linked with metal ions, Iζ resin or these resins are the main components, and an ethylene copolymer containing carboxyl groups, alethoxy groups, and hydroxyl L (including 61 or more types) is added to the molecule. -C By irradiating the film made of the obtained resin composition with ionizing radiation, the adhesion properties are improved, and the penetration resistance and transparency of the intermediate layer for laminated glass are improved. This will further improve the results.

Of course, these metal ion crosslinked resins and/or resin compositions are crosslinked in their polyethylene portions by being irradiated with DA radiation.

Therefore, when manufacturing C1 glass, the crosslinking of the polyethylene portion not only improves the transparency but also improves the strength due to the growth of polyethylene crystals being aged during cold heating after hot press bonding. Ethylene/(meth)acrylic acid copolymer C with a low amount of metal ions failed the penetration resistance test when exposed to ionizing radiation for 4T.
It was also confirmed that the penetration resistance 11 was improved and the film passed the penetration resistance test.

When the resin or resin composition mentioned above is used as an intermediate film as it is, the strength and brightness of C as an interlayer film, However, as a result, the film becomes hard before being pressure-bonded to the glass, and the work process 111
In addition, as the carboxyl group in the resin or resin composition decreases due to the increase in metal ions, a problem arises in that the adhesion to glass decreases.
come.

According to the present invention, the polyethylene portion is cross-linked by irradiating the electrically unidirectional IJS1.IJ rays without increasing the total bending ion bridge.
It was found that the strength was improved without changing the content of carboxyl groups in the glass adhesion I11.More importantly, it became transparent when cooled. Since the growth of crystals which is responsible for the decrease in properties occurs in the polyethylene parts, cross-linking the polyethylene parts1,1 is of great help in preventing the formation of crystals.

The ionizing radiation used in the present invention includes electron beams, gamma rays, X-rays, etc., and electron beams that can be widely used in the T industry are preferably used.

The electron beam irradiation iii used in the present invention is 2 to 20
The range of Mratl is preferably used. The irradiation radiation is about 2M rad, and if it is smaller, the electron beam heat ((effect depends on the size!
If! t:L relatively small, irradiation radiation is 20 Mrad
, the degree of crosslinking of the poly]-dylene moiety is high <
4t, put the film after irradiation between the crows'/v ”
C--The fluidity becomes poor during heat-pressing, and on the contrary, it becomes difficult to adhere closely to the glass. In principle, the electron beam can be emitted from one side of the film, or if the accelerating voltage is low and the penetration ability is small, it is also possible to emit the electron beam from both sides.

Moreover, various additives can be added to the present invention in addition to the resin, 13, and/or the resin composition described above. Examples include plasticizers, ultraviolet absorbers, antioxidants, heat-resistant anti-aging agents, etc. In addition, at least two vinyl groups, (
It is also possible to add a compound having a meth)acryloyl group as a crosslinking agent to the raw form. Examples of these crosslinking agents include divinylbenzene, triallylisocyanurate,
■ Dilene glycol diacrylate 1, 1 to rimedylol propane triacrylate, etc., and 0.5 to 5 per 100 m1 of resin J3J and/or resin composition
．． 0 parts by weight are preferably used.

Hereinafter, the present invention will be specifically explained based on Examples, Comparative Examples, and Conventional Examples. Note that the formulation values in Tables 1 and 3 are parts by weight C.

Examples 1 to 12 and Comparative Examples 1 to 4 -C blended to the J formulation shown in Table 1, and four types of compositions A
, B, C, 'D and extrude them! IM'
c Press into a sheet of thickness 0.78m + n and press out - (
I sat down to watch the film.

This film was transferred to a conveyor 1-U, type Midron electron beam accelerator (<1.0 Me V, 10 mA).
(2.5.10 Mrad each, line: i/i'
c The electron beam was placed on the front side. Note that Comparative Examples 1 to /I were not irradiated.

Table 2 shows each electron beam as a general rule. ((700%, 200%, 300% of the film for
Tensile strength a5 and elongation at break are shown.

Next, in order to investigate the self-adhesion of these films, the adhesion between the films was measured using the following measuring method, and the results are shown in Table 2. , :,.

<Film IiJ's adhesion measurement method> Put two films together! c Place it horizontally and apply several layers of 0.5J10+f for 10.1 minutes in an atmosphere of 40℃, then perform a mold peeling test at 20℃.

Furthermore, this film was sandwiched between two pieces of glass with a thickness of 2.8 mm each measuring 30.5 ax and 30.5 C, and heated to 130°C.
15kg/c
Pressed for 100 m for 100 m, then exposed to air at 0°C until the thickness was 6.36111111 (medium 1 m 1 B).
A transparent impregnated glass with a thickness of 0.76 mm was obtained.

JIS-R-321 to check the performance of laminated glass
The resistance test and the a+Il determination of visible light transmittance were carried out in accordance with the following method in accordance with the 2R Test Method for Automotive Safety Glass. The results are shown in Table 2.

<Eyebrow resistance (1 test) Laminated glass kept at 20℃ was placed horizontally,
8 A steel ball with a smooth tag surface is dropped from a height of 4 m to the center of the glass surface, and the one that does not penetrate is A1.B is 1-3.

<Visible light transmittance> Spectral luminosity IT <manufactured by Hitachi, Ltd.) from 400 mμ to 7
Transmittance (%) up to 50111μ was measured.

Table 1 *1: Resin obtained by crosslinking ethylene/methacrylic acid copolymer with Zl+ ions (/11 content 0.9%).

*2: Resin obtained by crosslinking ethylene, methacrylic acid, and methacrylic acid 1-thyl Nisdel covalently combined with Na2I (
(Na containing J2.0 weight φ%).

:l:3: Resin in which ethylene/methacrylic acid copolymer is crosslinked with Na2(Na-containing 4.9jlJ)
k%).

:l: 4: Ethylene/vinyl acetate copolymer (vinyl acetate content 28% by weight).

*5: Ethylene/vinyl acetate/methacrylic acid copolymer (vinyl content 28%).

:l? 6: A polymer obtained by partially converting a clay tyrene/acid-resistant vinyl copolymer, and then converting maleic acid into graph 1- to give an agitated, hydroxyl, and carboxyl group.

Full = 7: 2-(2'-human[1x-3'-3-
1 Blue J'-Methylphenyl)-5-ricJr:+
・Benzotriazole.

:I: 8: l ~ Remeji 1 Colb U Panj ~ Reacrylate.

It is clear from the results in Table 2 that Examples 1 to 12 in which electron beams were irradiated are different from Comparative Examples 1 to 4 in which terahino rays were not irradiated.
The modulus and tensile strength are improved compared to the above. In addition, regarding the adhesion between the films, both the Examples and Comparative Examples show good peelability with good adhesion. Roughly,
Regarding the penetration resistance and visible light transmittance when used as an intermediate crotch for laminated glass, Examples 1 to 12 in which electron beam irradiation was applied showed better results compared to Comparative Examples 1 to 4 in which no irradiation was performed, and the results were sufficient for practical use. It was something I could offer.

Conventional Example 1 In order to evaluate plasticized polyvinyl butyral, which is generally used in automotive glass, commercially available polyvinyl butyral, dichloromethane, and an ultraviolet absorber were used to evaluate plasticized polyvinyl butyral. They were mixed according to the proportions shown in the table, and an interlayer film was obtained using an extruder. Similar to Example 1,
Adhesion between films J3, penetration resistance test after laminated glass, visible light I5i! The transmittance was measured and the results are shown in Table 3.

Table 3 In this conventional example 1, the adhesion force between the films is 5.2 kg/25
In order to exhibit the peeling force of IllIII and to prevent the films from getting too close to each other, it is necessary to apply an anti-adhesive agent to the film.
・Atsuko.

As explained above, the resin is a resin in which the molecules of an ethylene/(meth)acrylic acid copolymer are cross-linked with metal ions, and a ternary copolymer consisting of ethylene/(meth)acrylic acid/(meth)acrylic acid ester. Ionizing radiation is applied to a film made of a resin whose molecules are cross-linked with metal ions, or a resin composition obtained by using these resins as a component and adding a specific tyrenic copolymer. The intermediate crotch for the laminated crow of the present invention, which is made by irradiating the frame (6), is manufactured by II9.
Since the films do not exhibit self-adhesion 11 when kept at room temperature, there is no need to spray the anti-blocking agent conventionally used for plasticized polyvinyl butyral films, and therefore the films can be washed with water and dried. Since no treatment is required, the adhesive processability of the glass that is bonded to the interlayer film is improved.1.Also, when the interlayer film of the present invention is used to bond glass, it does not require the use of X151 copper wire beforehand. In comparison, it is not only highly resistant to U1, but also has excellent transparency, so it is suitable for automobiles)
It is suitably used as an interlayer film for window glass of 11n I to JJ laths, high-rise buildings, etc.

441 W'l Applicant Yokohama Rubber Co., Ltd. Agent Patent Attorney Tatsuo Ito Agent Patent Attorney Tetsuya Ito

Claims (1)

[Claims] 1. At least one copolymer of ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, or terpolymer consisting of ethylene, acrylic acid or methacrylic acid, and acrylic ester or Nisdel methacrylate. Cross-link between the molecules with metal ions and 1! ? resin, 1)
' and/or the resin as a main component, and at least one or more of carboxyl group, ace1-oxy group, and hydroxyl group in the molecule. Add ethylene copolymer to 1!1
A film made of a resin composition containing ionizing radiation 1. )
An interlayer film for laminated glass that is crosslinked by irradiation with J-rays.