JPH0375499B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing laminated glass. In particular, the present invention relates to a method for manufacturing laminated glass with excellent cold resistance and transparency.

In the production of glass laminates, methods for bonding glass to glass using organic polymer films such as polyvinyl butyral are well known, but when such adhesives are used, lamination is complicated and time-consuming. is being carried out.

In order to improve these methods, liquid resins for glass lamination have been widely developed and are currently in use in some cases.

Examples of these resins include epoxy resins, unsaturated polyester resins, polyurethane resins, and silicone resins.

However, these resins generally require heat curing, and curing takes a very long time at room temperature.
Furthermore, since unsaturated polyesters, epoxies, and polyurethanes generally contain aromatic rings in their molecules, they have the disadvantage of turning brown and reducing transparency when exposed to ultraviolet rays for a long period of time. Furthermore, since silicone resin has a refractive index of around 1.40, which is significantly different from glass's 1.52, it has the drawback of large reflections at the interface between glass and adhesive.

The present invention provides a method for producing laminated glass having excellent transparency, cold resistance, durability, and moisture resistance, which improves these drawbacks.

That is, the present invention provides (A) represented by the following general formula and with a molecular weight of 116 to about
5000 (meth)acrylates, and the average molecular weight of the (meth)acrylates or mixtures thereof is about 300 or more (meth)
100 parts by weight of acrylate monomer However, R ₁ is hydrogen or a CH ₃ - group, R ₂ , R ₃ and R ₄ are long chain or branched alkylene groups, n ₁ and n ₄ are integers of 1 or more, and n ₂ and n ₃ are 0.
or an integer greater than or equal to 1.

(B) 0.001 to 10 parts by weight of a radical curing catalyst (C) 0.5 to 5 parts by weight of a silane coupling agent (D) Plasticity 0 to 100 parts by weight. This is a unique method for manufacturing laminated glass.

The (meth)acrylate monomer (A) used in the present invention is, for example, mono- or poly-ethylene glycol mono(meth)acrylate, mono-
or poly-propylene glycol mono(meth)
Mention may be made of acrylates, mono(meth)acrylates of polyether diols, such as mono(meth)acrylates of mono- or poly-butylene glycol, or mono(meth)acrylates of polyester diols.

For example, in the case of glycol mono(meth)acrylate which is a block or random copolymer of ethylene oxide and propylene oxide, each of R ₂ , R ₃ and R ₄ in the above formula is one molecule within the scope of the present invention. may contain different R ₂ , R ₃ or R ₄ , and (meth)acrylate may contain 1
Although it is possible to use either a species or a mixture of two or more kinds, it is necessary to use at least one (meth)acrylate having a molecular weight of about 300 or more. That is, the average molecular weight of the (meth)acrylate monomer is about 300 or more;
One of the above (meth)acrylates may be used, but in the case of a (meth)acrylate with an average molecular weight of less than about 300, for example, a (meth)acrylate with a molecular weight of 116, one (meth)acrylate with a molecular weight greater than 300 may be used. It is necessary that the average molecular weight of the mixture of (meth)acrylates is about 300 or more when used in combination. The average molecular weight of the (meth)acrylate mixture is about 300 or more, preferably about 300 to
By setting it to about 1000, the adhesive composition can be made into a cured product that has a low shrinkage rate, is flexible at low temperatures, and has a certain level of strength even at high temperatures.

When using an adhesive composition that has a low shrinkage rate, is flexible at low temperatures, and provides a cured product with a certain level of strength even at high temperatures, the adhesive composition may peel off even when laminated glass is exposed to low or high temperatures. Also, cracking of the glass or cured resin layer will not occur. In other words, if the curing shrinkage rate of the adhesive composition is high, a large stress will remain in the laminate, and since the expansion coefficients of glass and resin are significantly different, a hard resin layer that is not flexible at low temperatures will be unable to absorb stress at low temperatures. On the other hand, if the strength decreases significantly at high temperatures, peeling occurs at high temperatures.

The radical curing catalyst contained in the adhesive composition used in the method of the present invention includes actinic ray initiators represented by benzophenone, benzoin alkyl ether, benzyl dimethyl ketal, benzoyl peroxide, and azobisisobutyronitrile. or redox initiators consisting of peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, and cumyl peroxide, and reducing agents such as toluidine derivatives, salts of metals such as cobalt, vanadium, and iron, and thioamide derivatives. However, thermal initiators require heating, and redox initiators require conversion into two liquids, so actinic ray initiators that can be made into one liquid and cured in a short time at room temperature are particularly preferred.

As the silane coupling agent contained in the adhesive composition used in the method of the present invention, a known silane coupling agent can be used, but a silane coupling agent having a vinyl group, a methacryloyl group, or a mercapto group is particularly preferable. Moisture resistance and durability are particularly improved by using a coupling agent.

Examples of silane coupling agents include vinyl-
Examples include tris(2-methoxyethoxy)silane (A-172 manufactured by Nippon Unicar Co., Ltd.), gamma-methacryloxypropyltrimethoxysilane (A-174 manufactured by Nippon Unicar Co., Ltd.), and gamma-mercaptopropyltrimethoxysilane.

Plasticizers that can be added to the adhesive composition used in the method of the present invention are those that do not reduce the transparency of the cured product of the adhesive composition (including at low temperatures). However, aromatic plasticizers may cause long-term coloring.
Furthermore, from the viewpoint of the above-mentioned transparency and bleedability at high temperatures, it is preferable to use glycol or polyester polyol or a derivative thereof, which is used in the mono(meth)acrylate ester (A) in the present invention.

Specific examples of plasticizers include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol, polyethylene adipate diol, polybutylene adipate diol, poly-1,6-hexane adipate diol, polycaprolactone polyol,
Polyester polyols such as polyether polycaprolactone polyols and polycarbonate diols, and esters of these compounds with organic acids such as acetic acid, propionic acid, butyric acid, caproic acid, palmitic acid, and stearic acid, or methyl, ethyl, and propyl of the above polyols. Examples include derivatives of alkyl ethers such as

If necessary, a radical polymerization stabilizer, a dye, and a filler that does not impair transparency can be added to the adhesive composition used in the method of the present invention.

Furthermore, the adhesive composition used in the method of the present invention includes:
(Meth)acrylate monomers other than (A) can also be added in small amounts as long as they do not impair the purpose of the present invention.

The laminated glass made by the method of the present invention is
It is characterized by transparency, heat insulation, sound insulation, no scattering of glass when broken, and cold resistance, and by using the adhesive composition of the present invention, laminated glass for use in doors, windows, or aquariums, for example, Anti-reflection glass can be laminated onto safety glass for vehicles or aircraft, or cathode ray tube display screens.

Test method 1 in Examples Heat cycle test Heat cycle of 1 hour at low temperature and 1 hour at high temperature
Repeat this 20 times and visually inspect for cracks in the glass, cracks in the cured adhesive layer, peeling and discoloration between the glass and adhesive layer.

2 Cold Resistance Test Leave the adhesive at the specified temperature for 96 hours, observe the transparency (presence or absence of cloudiness) of the cured adhesive at the low temperature, and after returning to room temperature, inspect the heat cycle items mentioned above.

3 Heat Resistance Test Leave at the specified temperature for 96 hours, inspect the above heat cycle items, and further inspect for the presence or absence of bleed.

4 Tensile strength According to ASTMD-1002-64, 3 mm thick glass was 5 cm at a distance of 5 cm using a 40W Bratz clamp.
Measurements were made after irradiating for a minute to cure and bond.

5 Transmittance A white board with a thickness of 3 mm was cured and bonded in the same manner as in the case of tensile strength in Section 4, and the spectral transmittance was measured using a Shimadzu W-beam spectrophotometer UV-200.
Measured using

6 Humidity Test The product was left at a predetermined temperature and humidity for 10 days, and the state of peeling between the glass and adhesive layer was observed.

Example 1 100 g of polypropylene glycol mono(meth)acrylate (average molecular weight 400), 1 g of benzoin methyl ether, 1 g of pinyl-tris(2-methoxyethoxy)silane (A-172 manufactured by Nippon Unicar Co., Ltd.) as a silane coupling agent, and hydroquinone monomethyl 0.05 g of ether was placed in a brown polyethylene bottle, and the mixture was heated and stirred at 60°C for 2 hours. Thickness 3 with the obtained adhesive sandwiched between 5 mm thick spacers
The adhesive was injected between 100 mm square glass plates (sealed with tape on three sides to prevent adhesive from leaking) and irradiated for 5 minutes at a distance of 5 cm using a 40 W black light to cure.

The obtained laminated glass was subjected to a heat cycle at -55°C and +120°C, a cold resistance test at -55°C, and a heat resistance test at +200°C, and was found to be good.

The tensile strength was 7.5Kg/ ^cm2 .

Transmittance is 87.5% (400nm), 94.3% (500nm),
They were 95.8% (600nm) and 95.7% (700nm).

Further, this adhesive was cured using a 40W black light in the same manner as above, and the cure shrinkage rate and hardness at -55°C (Shor D) of the cured product were measured. The curing shrinkage rate was 4.8%, and the shore D hardness was 31.

Example 2 100 g of polypropylene glycol monomethacrylate (average molecular weight 600), 10 g of 2-hydroxyethyl methacrylate, 1 g of benzoin ethyl ether, 1 g of silane coupling agent vinyl-tris(2-methoxyethoxy)silane (A-172)
g, and 0.5 g of hydroquinone monomethyl ether was produced in the same manner as in Example 1, and a laminated glass was produced in the same manner as in Example 1.

The obtained laminated glass performed well when subjected to heat cycles at -55°C and +120°C, cold resistance test at -55°C, and cold resistance test at +120°C.

The tensile strength was 6.9Kg/cm ² .

Transmittance is 87.9% (400nm), 94.8% (500nm),
They were 96.5% (600nm) and 96.6% (700nm).

In addition, this adhesive was cured using 40W black light, and the curing shrinkage rate and -55℃ of the cured product were measured.
The hardness (Shore D) was measured. The curing shrinkage rate was 4.6% and the shore hardness was 35. The average molecular weight per methacrylate group of the monomer in this adhesive was approximately 440.

Comparative Example 1 100 g of polypropylene glycol monomethacrylate (average molecular weight 600), 63 g of 2-hydroxyethyl methacrylate, 1 g of benzoin ethyl ether, 1 g of the above-mentioned silane coupling agent A-172, and 0.5 g of hydroquinone monomethyl ether.
An adhesive consisting of g was produced in the same manner as in Example 1. This adhesive was cured by 40 W blacklight irradiation in the same manner as in Example 1, and the cure shrinkage rate of the cured product was 7.9%, and the hardness (Shore D) at -55°C was 60.

A laminated glass was manufactured using this adhesive in the same manner as in Example 1. When this laminated glass was subjected to a cold resistance test at -55°C and a heat cycle at -55°C and +120°C in the same manner as in Example 1, peeling occurred from the periphery.

The average molecular weight per methacrylate group of the monomer in this adhesive was approximately 250.

Example 3 Using a laminated glass manufactured in the same manner as in Example 2, a humidity resistance test was conducted at a temperature of 60° C. and a humidity of 90%, and no peeling or the like was observed. In addition, it remained good even after a further 30-day humidity test.

Comparative Example 2 A laminated glass was produced in the same manner as in Example 2, but without using a silane coupling agent, and a moisture resistance test was conducted under the same conditions as in Example 3. Spontaneous peeling occurred at the interface.

Claims (1)

[Scope of Claims] 1 (A) It is represented by the following general formula and has a molecular weight of 116 to
100 parts by weight of a (meth)acrylate monomer consisting of one or more types of (meth)acrylates having an average molecular weight of approximately 300 or more; However, R ₁ is hydrogen or a CH ₃ - group, R ₂ , R ₃ and R ₄ are linear or branched alkylene groups, n ₁ and n ₄ are integers of 1 or more, and n ₂ and n ₃
is an integer of 0 or 1 or more. (B) 0.001 to 10 parts by weight of a radical curing catalyst (C) 0.5 to 5 parts by weight of a silane coupling agent (D) Plasticity 0 to 100 parts by weight. Features: A manufacturing method for laminated glass.