JPS58140349A - Sandwich glass - Google Patents

Abstract

PURPOSE:To obtain superior sandwich glass by a simple method without requiring severe control of temp. and humidity, by interposing an interlayer consisting of an ethylene-vinyl acetate copolymer which is subjected to an adhering treatment between two sheets of glass plates. CONSTITUTION:An interlayer consisting essentially of an ethylene-vinyl acetate copolymer which is subjected to an adhering treatment is interposed between two sheets of glass plates. Methods such as compounding of adhesive polymers, electric discharge treatment by plasma at low temp. or irradiation of electron rays are adapted to the above-described adhering treatment. Ethylenic resins contg. hydroxyl groups or carboxyl groups in molecules are used as the adhesive polymers to be adapted for the adhering treatment. The ethylene-vinyl acetate copolymer to be used is preferably the copolymer contg. 19-40wt% vinyl acetate contents.

Description

[Detailed description of the invention] Concerning glass.

The most commonly manufactured laminated glass used for car windshields, building window glass, etc. has been the interlayer film (polyvinyl butyral resin). Resin is thermoplastic and has some problems when laminated with glass.In other words, the adhesive strength is adjusted by the water content, but if the water content is too high, foaming, clouding, etc. may occur. Optical properties V This problem occurs, and if there is a small gap, the adhesive strength increases, causing problems in penetration resistance, and the polyvinyl butyral film itself is sticky, causing blocking, etc., and the quality of the laminated glass is also poor even when the resin film and L7 are used. It was difficult to manage.

The inventors of the present invention have made extensive studies to solve this problem, and have found that the main component is ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as EVA), and organic peroxide or photosensitizer is added to this. Patent application No. 56-811915 for a laminated glass having an interlayer film made of a composition containing a sensitizing agent.

In Japanese Patent Application No. 56-158723, we discovered properties superior to Proposal 1-7, a polyvinyl butyral resin interlayer film.

However, subsequent studies revealed that this intermediate film also had some problems. These include restrictions on storage stability in high-temperature locations or in extreme conditions, and restrictions on manufacturing conditions resulting from the decomposition temperature of the organic peroxide blended.

Furthermore, the silane coupling agent used to adjust the adhesive strength of the +4 V A interlayer film has excellent effects such as controlling adhesive strength and preventing foaming, but because it is easily hydrolyzed by moisture, the silane coupling agent is There is a high possibility that a large number of substances will be produced, and there is a concern that this substance will not be miscible with the entire system in EVA, and that stiffness will cause the laminated glass to become slightly cloudy.

In this way, the previously proposed 14VA interlayer film not only requires extreme care during storage such as temperature control, but also has the disadvantages of being economical due to the high cost of the 7-rank compres- ing agent used to adjust the adhesive strength. VC was also hardly advantageous.

Therefore, the present inventors developed an excellent adhesive using a relatively simple method that provides sufficient adhesive strength even without the use of a silane coupling agent and does not require strict humidity and temperature control.
As a result of extensive research into the vA interlayer film,
The present invention was developed with the aim of achieving the objective by a method of vomiting. The first is the formulation of the adhesive polymer, and the second is the formulation of the adhesive polymer.
No. 3 is low-temperature plasma discharge treatment, and No. 3 is electric wire irradiation treatment.

The present invention will be explained in detail below. First, the I>VA resin, which is the main component of the interlayer film, will be explained. The vinyl acetate content is 15 to 50% by weight! It is preferably 4j%, more preferably 19 to 40%. If the vinyl acetate content exceeds 5% by weight, the transparency is good, but when an acrylic acid or methacrylic acid derivative is added to the resin to serve as a cross-linking agent, the penetration resistance is also good. ζ) I like it because it's hard to get caught''!
,＜No. If the reverse K l is less than 5 times &jt ratio, it becomes difficult to improve transparency. However, in laminated glass VC whose purpose is only to prevent glass breakage and scattering without placing emphasis on transparency, it may be used even if the thickness is less than 15 W4.

The first method of the present invention is to add an adhesive polymer and a peroxide or a photosensitizer as a catalyst to the iI4 V A resin, and in this case, the adhesive polymer It is an ethylene resin having a hydroxyl group or a carboxyl group in the molecule. Partially saponified products of ethylene resins having hydroxyl groups and ethylene-vinyl acetate copolymer resins, Nisdel-exchanged products of ethylene-vinyl acetate copolymers, polyvinyl butyral resins, etc. These include acid copolymers, ethylene-methacrylic acid copolymers, carboxylated ethylene-vinyl acetate copolymers, metal salt crosslinked products of ethylene-acrylic acid or ethylene-methacrylic acid copolymers, and the like.

The addition needle of the ethylene resin having a hydroxyl group or a carboxyl group in the part is 1 to 20 parts by weight, preferably 2 to 10 parts by weight, to the EvA resin.

If more than 20wt fb is added, the performance of EVA as a laminated glass may deteriorate. Also 1
If the weight is less than I-H, no improvement in adhesion is observed.

2) To add the above-mentioned ethylene resin to the VA resin, it may be mixed with a peroxide or a photosensitizer catalyst by conventional mechanical kneading, such as an open roll or an extruder. The kneading temperature at this time must be at a temperature higher than the softening temperature of each resin.If the kneading temperature is extremely high and is higher than the decomposition temperature of peroxides, etc., first After kneading and forming a sheet, peroxide or the like dissolved in a solvent may be added by a dipping method or the like as disclosed in Japanese Patent Application No. 176551/1983.

Peroxides used in the VC of the present invention include ketone peroxides, hydroperoxides, dialkyl peroxides, diacyl peroxides, dialkyl peroxides, peroxy esters, and the like. These peroxides may be used alone or in combination.

Also, as photosensitizers, hachenzoin, benzophenone, dibenzyl, 5-nitroacenaphdene, hexachlorocyclopentadiene, valanitrodiphenyl s 112-
Examples include benzanthraquinone. These catalysts are EV
A100 east [11 parts to 5 parts or less, used alone or in combination of 2 or more parts (heavily used). , alicyclic solvents, paraffinic oils, naphthenic oils, phthalate ester plastics, adipate Nisdale plastics,
Plasticizers such as sepatic acid ester plasticizers, phosphoric acid plasticizers, and ether plasticizers can be used singly or in combination of two or more.

The second low-temperature plasma discharge treatment is a method in which an intermediate film sheet containing thermosetting or photocurable EV resin as a main component is subjected to low-temperature plasma discharge treatment. Thermosetting or photocuring 1; VA is EvA and peroxide or photosensitizer in 5 parts by weight (b VA l (for 10 parts by weight) or less) as in the case of the first method. It has one addition of .

The low-temperature plasma discharge performed in the present invention includes corona discharge, glow discharge, high frequency discharge, microwave discharge, etc., all of which are applicable to the present invention. In particular, corona discharge treatment is an industrially highly efficient treatment method that allows continuous treatment of sheets. In the case of corona discharge treatment, the preferred treatment power for adhesion treatment of the resin interlayer sheet is 3 to 20 W/r, which is theoretically sufficient.

By carrying out this low-temperature plasma treatment, a suitable adhesive force is developed between the glass and the glass, which prevents the glass from scattering and provides a laminated glass with good blood and spot permeability.

The third 'electron beam irradiation treatment' is a method of irradiating an interlayer film sheet containing EV, A resin as a main component with an electron beam.

In this case, the intermediate film kt EV A resin or Iru~'
This is a resin in which a compound containing an acryloxy group or a methacryloxy group is added to resin A, and does not require the addition of a peroxide or a photosensitizer.

Acrylic acid, methacrylic acid, and their derivatives, namely esters and amides, are generally used as compounds containing an acryloxy group or methacryloxy group, and these compounds are added in a proportion of 20 wttt% or less to the EVA resin VC. be done.

The electron beam irradiation carried out in the present invention is usually carried out at an accelerating voltage of 300 to 750 Ke~', although this varies depending on the thickness of the intermediate film. The irradiation dose required to reach a practical degree of crosslinking is 0.
．． 5-20 megarads (81 rad), preferably &:i2
, 5 to 15 megarads.

The composition described above is made into a sheet using an extruder, calendar roll, inflation, hot press, etc. [1.
The desired interlayer film can be obtained by irradiating one side of the material with a suitable electron beam using an electron beam irradiation device. Further, electron beam irradiation may be performed on both sides of the sheet.

Electron beam irradiation increases or decreases the adhesive strength with glass.
This crosslinking contributes to improved transparency and further improves physical properties. At this time, the effect is even more remarkable if the sheet is previously heated to an extent that it will not be thermally deformed prior to electron beam irradiation.

Furthermore, addition of a compound containing an acryloxy group or a methacryloxy group has the effect of increasing the degree of crosslinking.

In addition to the additives described in the first to third methods of the present invention, if necessary, colorant-1 ultraviolet absorber, aging μB +
) - agent, discoloration inhibitor, etc. can be added in appropriate amounts.Thus, in the first method; 1. In the second method, the interlayer film and the t3
A composition prepared by blending 1 degree of peroxide or photosensitizer with VA resin is passed through a sheet v and subjected to low temperature plasma discharge treatment [7] to form an interlayer film.
(VA resin and a compound containing an acryloxy group or a methacryloxy group are blended 17 to form a sheet, and this is subjected to electron beam irradiation 1 to 1 to form an interlayer film. After that, air is evacuated and pressure bonded according to a conventional method. In the first and second methods, a heat curing treatment is then performed to produce a laminated glass with good adhesion and high transparency.

According to the adhesive treatment of the present invention, when an adhesive polymer is blended, the adhesion between the glass and the interlayer film can be improved without impairing the original performance of 14 V A. It exhibits stable and sufficient adhesion to the surface, does not substantially impair the workability during pressure bonding and processing, the transparency of the laminated glass, and the impact resistance. Furthermore, in the case of electron beam irradiation, the interlayer film The adhesion between glass and glass is improved, and since no peroxides or photosensitizers are used, manufacturing process 1. Productivity increases in the direction of Ls without being subject to temperature constraints in the process.
.

1. Moreover, since there is no need for heat curing or light curing, the manufacturing process can be simplified.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (Hereinafter blank) 1 Table 1,) Toyo Soda M1 Ha/A Vinyl acetate-containing hJ2.
512) Ethylene-acrylic acid copolymer resin manufactured by Dow Chemical Company 3) Ionomer (separate type) manufactured by Mikata Polychemical Company 4) Partially saponified EVA manufactured by Kurade Pharmaceutical Co., Ltd. 5) Carboxylated EVA manufactured by Mitsubishi Yuka Company 6) γ- Glycidoxy7'
Lobiltrimethoxysilane - Knead each component with an open roll heated to 115°C according to the recipe in Table 1. 1. Ta. After that, each composition was wrapped in a polyester film (thickness: 50/I), and then a stainless steel wire mesh of L/T/C 60 mesh was placed on it and pressed at 120°C to a thickness of 0.41I.
A sheet of paper II with embossed patterns on both sides was obtained. A sheet with polynisdel film removed is 300 m square and 3 m thick.
Place it between two pieces of float glass in a rubber bag under reduced pressure with a vacuum pump, place it on a hot plate at 120°C, and press it to release the air [
A double laminated glass was obtained.

This laminated glass was further left on a hot plate heated to 160°C for 20 minutes to cross-cure the interlayer film, and the sample was subjected to penetration resistance tests according to JIS) t3211 and 212. Passed all heights of 1.5m and passed through all heights of 1-12m.

Further, the peeling glass resistance at this time was as shown in Table VC, and was comparable to that of the sample to which γ-glycidoxypropyltrimethoxysilane was added as an adhesion additive. However, without blending adhesive ethylene resin (V A
It can be seen that the adhesion of the interlayer film to the laminated glass is poor.

Example 2 The composition shown in Table 2 (1) was kneaded in a roll mill and then pressed to form a uniform embossed sheet with a thickness of 0.1 m and a size of 30 x 1 inch. This is corona discharge treatment equipment fi (VI4TAPIIONl; manufactured by Generator maximum output (1.9kW, effective treatment width 9
)G) The surface treatment was performed continuously under the following conditions.

Electric fij: Rotating insulated electrode required electricity crab 1, 3. lkW/m''/Hyundai In the actual processing operation, the sheet was attached to the banking roll of the device, and the front and back sides were treated once each at room temperature.The appearance of the sheet after treatment was different from that of the sheet before treatment. , no shape synchronized VC change was observed.

(Leaving space above) Table 2 1) Vinyl acetate content 28 Melt flow index 152) 2,5-dimethyl-2,5-di(t-butylperoxy)hexane: () Silane coupling agent 4) Toshi; Integral type turbidity meter '1'C-8P made by Te'Kameirosha
After measurement with a mold, the /-t is 0.4wn thick 3 (1
Place the laminated glass between two pieces of float glass of 0x 31111 body size, degas it in a rubber bag, heat it to 11 (1°C), and then take it out and place it on a hot plate at 16 (1°C). After heat treatment at 1 m for 20 minutes, a completely transparent crushed laminated glass without air was obtained.

Next, as a comparative example, laminated glasses I and I were prepared according to the above method according to the composition shown in Table 2, and J Is
R: (Weight 225 f based on 205K (30 D steel balls)
0 x 30 Om size laminated glass with a height of 5 m in the center
Table 2 shows the bundles whose penetration resistance was measured after being dropped.

From Table 2, it can be seen that the examples of the present invention sufficiently have the performance required as an interlayer film for laminated glass, that is, transparency, impact resistance, and ease of contact with glass.

Comparative Example I In order to investigate the influence of moisture on the silane coupling agent in EvA resin laminated glass, a press sheet with the formulation shown in Table 2 (thickness 0.1 Dark 311 (1X: (01
) m size) in pure water for 10 minutes.
After soaking and thoroughly air-drying, a laminated glass was created using the method of Example 2 (without corona discharge treatment).
A clear decline in transparency was observed. (-Is measured value (), 6, transmittance 83cm) Example 3 After kneading the products listed in Table 3 using an open roll at 100°C for M and N and 130°C for P, Sandwiched between 50μ thick hollyester sheets and placed in an iron mold, N1,
N was molded using a real press at 100°C and P & -11311°C to obtain a 1 m thick sheet.

One side of this sheet was irradiated with a beam 111 of 5 N1 rad and 10 Mrad at an accelerating voltage of 500 KeV using an electron beam irradiation device, and was subjected to DI together with the unirradiated sample.
Punching was performed using a No. 3 dumbbell with a chuck distance of 20 m+ and a pulling speed of 200 m1=. The results of the tensile test are shown in Table 4.

(Left below) From the results shown below, it can be seen that crosslinking occurs in each sample due to electron beam irradiation.

Example 4 Each sample kneaded at 1.7 in Example 3 was sandwiched between polyester films, and then sandwiched between 60 mesh wire mesh from above and below. 0.4 t thick using a spacer in a hot press heated to
It was pressed to a thickness of a.

The resulting sheet has an embossed pattern made of wire mesh on both sides. This sheet was prepared at a dose of 5 Mra in the same manner as in Example 3.
d. Irradiation with an electron beam of 10 Mrad. Each thickness is 3aon, 300X300 including unirradiated ones.
A laminated glass was obtained by press-bonding +W-size float glass to remove air using a vacuum degassing method using a rubber bag.

Separately, a laminated glass having the composition Q-8 shown in Table 5 was prepared.

(Left below) Part 5 Knead the table with electricity +l111! These are unirradiated films that were air-released and pressure-bonded, and then cured by heating on a hot plate at a temperature of 160° C. for ÷2θ minutes. JI81L using these laminated glasses
Based on 3211 and 3212, a penetration resistance test was conducted,
The penetration resistance height and peelable glass b() were measured.

In addition, using exactly the same sample, Nippon Shairo Kogyo Co., Ltd.
The haze value of each sample was measured using a haze meter.

The results are shown in Table 6.

(Margin below)

Claims (2)

[Claims] (1) Ethylene bonded between two glass plates
Laminated glass with an interlayer film mainly composed of vinyl acetate copolymer (2) The laminated glass according to claim 11 (3) The adhesive polymer is an ethylene resin having a hydroxyl group or a carboxyl group in the molecule. The laminated glass (5) according to claim (1), wherein the bonding treatment is a low-temperature plasma discharge treatment.
) The adhesion treatment is an electron beam irradiation treatment.
]) Laminated glass described in section