JPS63120639A - Laminate of glass - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] (Conventional technology) There are several known methods for laminating large pieces of glass.

For example, there are methods such as thermo-compression bonding of butyral film, methods of pasting the periphery of glass together using double-sided adhesive tape and injecting adhesive, and methods of adhering the periphery of glass using a sealant and injecting adhesive. Alternatively, there is a method in which two pieces of glass are set, their surroundings are fixed with adhesive tape, and adhesive is injected. Also, the adhesive to be injected is xf
Oxy resin, unsaturated polyester resin, silicone resin, photocurable resin, etc. are known. As an example of injecting a photocurable resin, a case where the periphery is sealed with a polyester tape is shown in JP-A-59-164654.

Furthermore, the present applicant has filed Japanese Patent Application No. 61-87108 and Japanese Patent Application No. 1987-87108.
In No. 87109, an application was filed regarding a method of creating a frame using a photocurable adhesive and injecting the photocurable adhesive into the frame.

(Problems to be solved by the invention) Making a frame using photocurable adhesive Ai, photocurable adhesive B
1fr: Problems with methods other than injection are detailed in Japanese Patent Applications No. 61-87108 and No. 61-87109.

In addition, when a frame is made using the light-curing adhesive Ai and the glass is laminated by injecting the light-curing adhesive B, the light around the frame is
The necessary properties when making a frame using hardening adhesive A and when creating a fully adhesive laminated glass are specified in Japanese Patent Application No. 1987-871.
It is detailed in 09.

On the other hand, when laminating, for example, 600 x 800,111 wooden glass, the frame is made by curing the light-curing adhesive A, and the frame is made by injecting the light-curing adhesive B to a thickness of, for example, 10 mm. If the glass is placed vertically and injected from above, the glass will swell due to the weight of the adhesive B being injected, breaking the bond between the frame and the glass, and the injected adhesive B may leak out before it hardens. This phenomenon can be prevented by placing the glass on which the frame is made and injecting it onto the frame at an angle, but since the workability is poor, we use light-curing adhesive A around the frame, which has excellent adhesion strength to the glass. If used, it can be injected while standing vertically. As this photocurable adhesive A, Japanese Patent Application No. 61-87109 shows examples of a polyene/polythiol type and an acrylic type containing methacrylic acid and methacrylic ethyl acid phosphate. en/
The raw materials for the thiol type are quite expensive. On the other hand, the acrylic type can be made into a flexible and tough cured product with good adhesion to glass by using methacrylic acid and acidic phosphate ester containing vinyl groups, but methacrylic acid has a unique odor and is irritating. Furthermore, acidic phosphoric acid esters containing vinyl foundations have the disadvantage of being noticeably discolored when exposed to high temperatures.

(Means for Solving the Problem) In order to solve the above-mentioned problem, the present inventor made a frame by gluing the periphery of a plurality of pieces of glass using a light-curing adhesive A, and fixed the frame. In a glass lamination method in which the entire surface is bonded by pouring the photocuring adhesive B into the glass and curing it, the poured photocuring adhesive B is prevented from being washed away and the entire surface is bonded. A viscosity index of 5 or more, a hardness of the cured product of Shore A of 40 or less, and a radically polymerizable vinyl monomer, an acidic (meth)acrylate represented by the following formula (1), a photopolymerization initiator, and a titanium tropy imparter. This problem was solved by using a product that contains the agent as an essential ingredient.

In the formula, R is hydrogen or a methyl group, R2 is ethylene, propylene or other glycol residue, and R8 is an alkylene group having 1 or more carbon atoms.

That is, by using the photocurable adhesive A, when laminating a plurality of glasses, the photocurable adhesive A'l
jI: Fully adhesive type with a frame that does not leak even when the glass laminate with a frame made using the same is injected vertically and injected with photocurable adhesive B, has no irritating odor, and has a frame that does not discolor at high temperatures. It is now possible to make laminated glass.

In the present invention, when laminating a plurality of glasses, the periphery of the plurality of glasses is bonded in advance using a light-curing adhesive Ai to create a frame, and the light-curing adhesive Bi is poured into the frame and cured. Accordingly, in a glass laminate whose entire surface is bonded, the photocurable adhesive A has a structural viscosity index of 5 or more, a hardness of the cured product of 40 or less at Shore A, and a radically polymerizable vinyl This glass laminate is characterized by containing a monomer, an acidic (meth)acrylate represented by the following formula (1), a photopolymerization initiator, and a thixotropy imparting agent as essential components.

It is an alkylene group of number 1 or more.

First, the photocurable adhesive A used in the present invention will be explained. As the radically polymerizable vinyl monomer used in the photocurable adhesive A, it is best to use commonly used (meth)acrylate monomers, and other unsaturated polyesters, aromatic vinyl monomers, etc. can also be used.

(Meth)acrylate monomers include alkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, phenoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentadienyloxyethyl (meth)acrylate, polyether mono(
Mono(meth)acrylates such as meth)acrylate, polyurethane mono(meth)acrylate, polyesterno(meth)acrylate, polyester (meth)acrylate, epoxy poly(meth)acrylate, ? Examples include poly(meth)acrylates such as urethane poly(meth)acrylate, butadiene-modified poly(meth)acrylate, and trimethylolpropane tri(meth)acrylate.

The polymerizable vinyl monomer is about 50 to about 90% by weight in the adhesive.
Preferably included.

Various photopolymerization initiators are known. For example, benzophenone, p-methoxybenzophenone, acetophenone, propiophenone, xanthone, benzoin, benzoin alkyl ether, benzyl penzaldehyde, benzyl dimethyl ketal, naphthoquinone, anthraquinone, azobisisobutyronitrile, 2,4.7 trinitrofluorenone, etc. can be given.

Preferably, the photopolymerization initiator is included in an amount of about 0.01 to about 5% by weight of the adhesive.

Acidic (meth)acrylate has a hydroxyl group (meth)
Obtained as 7-7 ester of acrylate and dibasic acid. As a (meth)acrylate having a hydroxyl group,
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, diglobylene glycol mono(meth)acrylate, etc. are used, and the dibasic acids include malonic acid, succinic acid, and glutaric acid. Acid, adipic acid, etc. are used. The acidic (meth)acrylate is preferably used in an amount of about 5% by weight or more, preferably about 10 to about 40% by weight or more, based on the total amount of the adhesive.

The photocurable adhesive AK further requires a thixotropy imparting agent. As the thixotropy imparting agent, finely powdered silica is most commonly used, and finely powdered alumina and finely powdered titania are also used. Finely powdered silica is preferably used in an amount of 5 to about 5% by weight or more.

Furthermore, various plasticizers can be added to the photocurable adhesive A as non-reactive fillers in order to adjust the hardness of the cured product. For this purpose, commonly used plasticizers, polypropylene glycol, ethers thereof, etc. are used. Coupling agents such as a 7-run coupling agent and a titanate coupling agent, dye pigments, inorganic fillers, etc. can be added as additives to the composition within a range that does not significantly impair photocurability.

The photocurable adhesive A needs to have a structural viscosity index of 5 or more and a hardness of the cured product of Shore A of 40 or less. If the structural viscosity index is less than 5, the adhesive will flow by the time it is applied, the glasses are laminated, and hardened, especially when the gap between the glasses is to be thickened, and the necessary sealing performance cannot be achieved.

The hardness of the cured product is Shore A40'! If the temperature exceeds 100, it will not be possible to absorb the stress due to curing shrinkage strain of the photocurable adhesive B applied to the entire surface, and defects such as peeling will occur when a durability test such as a heat cycle test is conducted after the entire surface is bonded.

It is further desirable that the photocurable adhesive A has creep resistance to a certain degree of load in a state before curing. In other words, the thickness between multiple pieces of glass can be adjusted using spacers, etc., but if the thickness is adjusted to a predetermined value with creep resistance,
It is preferable that the thickness can be maintained constant even if left as is until UV irradiation. For this purpose, although it depends on the thickness of the glass plate and the area of the frame, it is preferable that the thickness does not change for about 10 minutes under a load of 20 to 30 P/d.

It is preferable that the photocurable adhesive B has a hardness of the cured product of 35 or less in Shore A, a hardness of 35% or less, and a curing shrinkage rate of 2% or less.

If the hardness of the cured product is high, for example, when laminated over a large area of 600 x 800 (W), the glass may crack or the adhesive portion may peel off when a durability test such as a heat cycle is performed. If the curing shrinkage rate is high, the resin may shrink at the injection port during curing, and the cured layer of the photocurable adhesive A may not be able to absorb stress due to curing shrinkage strain alone, resulting in peeling later.

Further, it is preferable that the photocurable adhesive B has a low viscosity. The viscosity can be lowered by heating during injection, but in order to increase the injection speed and defoam the trapped air, the viscosity must be 1 at room temperature.
It is preferably 00OCpS or less, and most preferably 300CI)S or less.

As the photocurable adhesive B, any one of polyene/polythiol type, nixy resin type, (meth)acrylic type, unsaturated polyester type, etc. can be used.

When manufacturing the glass laminate of the present invention, the photocurable adhesives A and B are generally cured using a known ultraviolet lamp, and in particular, the photocurable adhesive B is cured as uniformly as possible over the entire surface at 10 mW/W. Curing with ultraviolet light with a weak illuminance of cIiL or less leaves less distortion during curing.

The glass laminate according to the present invention can be used for laminating various types of large-sized laminated glass, such as safety glass, soundproof glass, or the front glass of cathode ray tubes.

The glass laminate of the present invention can be used as laminated glass such as soundproof glass and safety glass, or as an explosion-proof front glass-bonded cathode ray tube.

(Example) The present invention will be explained below with reference to Examples.

Example A photocurable adhesive A having the formulation of I1 was prepared.

The physical properties of each adhesive are shown in Table 2.

Next, 600+o+X 800x 3mm glass and 5
Q Q+o+X 30 Qmm At this time, the adhesive was bonded around the entire circumference with a width of about 15111 mm from the edge of the glass, leaving an injection hole of about 50 mm at the negative edge.

The UV irradiation during curing was 4 rIaR/7X for 30 minutes.

Monomethacrylate of copolymerized glycol of tetrahydrofuran and propylene oxide (Mn=1500)
98 parts by weight, 2 parts by weight of methacrylic acid, 0.5 parts by weight of silane coupling agent A-172 (manufactured by Nippon Unicar),
0.2 parts by weight of penzyl dimethyl ketal and methacrylate
A photocurable adhesive B consisting of 2 parts by weight of ylethyl acid phosphate was prepared.

The frame was glued using A-1 to A-6, and then the glass was stood vertically, and photocurable adhesive B was injected at a rate of about 1 kg/min, and after the injection, it was left for 30 minutes to test for leakage. . The results are shown in Table 3.

For those that did not leak, they were cured by irradiating them with 4 mW/crl ultraviolet rays for 30 minutes, and then heated at -40°C and +80°C.
A heat cycle of 2 hours each was performed 10 times, but no abnormalities were found. Further, when a heat resistance test was conducted at 150° C. for 10 hours, the adhesive layer of A-6 turned brown, but the other photocurable adhesives A only had a slight yellowish tinge.

Note that the photocurable adhesive B turned brown in the injection hole exposed to the air, but only slightly yellowed in other parts.

Table 2 Properties of photocurable adhesive A

Claims (1)

[Claims] When laminating a plurality of glasses, a frame is created by gluing the periphery of the plurality of glasses in advance using a light-curing adhesive A, and a light-curing adhesive B is poured into the frame. In a glass laminate whose entire surface is bonded by curing with 1. A glass laminate comprising, as essential components, a vinyl monomer, an acidic (meth)acrylate represented by the following formula (1), a photopolymerization initiator, and a thixotropy imparting agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) In the formula, R_1 is hydrogen or a methyl group, R_2 is ethylene,
Propylene or other glycol residue, R_3 has 1 carbon number
These are the above alkylene groups.