The adhesive composition for the manufacture of laminated glass

 

(57) Abstract:

The composition is mainly used as an intermediate layer in laminated safety glass. It contains alkylacrylate C1-C12and/or alkylmethacrylamide C1-C18the polyurethane (meth)acrylate (mol. m 400 - 10000, contents of the residues of (meth)acrylic acid is not less than 2 per molecule of the polyurethane (meth)acrylate, thermo stabilizer and a radical initiator, which allows to obtain glass with high optical characteristics and resistance to different kinds of aging. 3 C.p. f-crystals, 1 table.

The invention relates to adhesive compositions used for the manufacture of layered silicate, organic and polycarbonate glasses. The composition is mainly used as an intermediate layer in laminated safety glass.

Known adhesive composition for the silicate triplexes (RF patent 2007432, C 09 J 4/02 1994) on the basis of a mixture of (meth)acrylic monomers with three cross-linking agents: monomethacrylate, deletecriticalsection and triallylisocyanurate taken in the claimed amounts.

A disadvantage of the known adhesive compositions is the complexity of cross-linking and the fir to offer the technical essence is a composition for the silicate triplexes (ed.mon. The USSR 1659436, C 08 L 75/04 1991), based on the mixture of (meth)acrylic monomers with hydroxyl - and isocyanatobenzene components, of which later formed polyurethane reticulated polymer poly(meth)acrylate, which may also be filed dimethacrylate by suturing. Crosslinked polyurethane is formed by the interaction of hexamethylenediisocyanate with polyoxypropylene mol. m 500-1500 in the presence of an ORGANOTIN catalyst in the first stage of curing the intermediate layer for 4-20 h at room temperature.

In the second stage of the curing proceeds thermal - or UV-polymerization of (meth)acrylic monomers for 0.5-2 hours, the Adhesive composition is operable at concentrations in the intermediate polyurethane layer 30-70 wt.% and poly(meth)acrylate 70-30 wt.%

The disadvantages of this adhesive composition is used in priming mixtures of toxic isocyanates, a multi-stage curing of the adhesive, applying adhesive to improve the adhesion strength of the adhesive layer and use only silicate triplexes.

Known [3] the adhesive composition for application Japan N 59-86676 (class C 09 J 3/14) containing polyurethane(meth)acrylate (PUA) with 2 unsaturated functional groups, 10-250 is etilenglikola, of trimethylolpropane, trimethanolamine, glycerol, or (di)pentaerythritol/ and 10-250 including non-volatile mono (meth)acrylate monomers [(meth)acrylates methoxy-, di-, otoxicity-methoxypolyethyleneglycol, tetrahydrofurfuryl alcohol or glycidoxypropyl] is only used for bonding sheet materials to each other, but cannot be used as an intermediate layer in laminated safety glass. After curing, the formed adhesive layer thickness of the order of several microns (6 μm), which at such thickness should possess excessive rigidity to provide a high strength adhesive bonding of the layered products.

Therefore, in such adhesive formulations, in particular in Japanese application N 59-86676 used silkroadonline crosslinking monomers in high concentrations, as urethaneacrylate oligomer.

Excessive rigidity of the adhesive layer contributes through the crack propagation under impact loads, while the multilayer structure has no advantages over monolithic glazing.

We offer same adhesive composition comprising (meth)acrylic monomer and a radical initiator, and as a (meth)acrylic monomer - t mol. m 400-10000 and content of residues of (meth)acrylic acid is not less than 2 per molecule of the polyurethane(meth)acrylate and thermo stabilizer allows you to obtain strong elastic intermediate layer with a thickness of 1-1 .5 mm, providing a level of strength properties greater than the voltage arising from the operation of construction (works like a shock absorber), has good adhesion to the silica and organic glass, high optical characteristics, heat and gradostroitelstvu, resistance to heat, light and other types of aging.

Polyurethanemetacrylate mol. m 400-10000 is administered in an amount of 0.1-10 wt. hours at 100 wt.h. (meth)acrylic monomer.

Thermo stabilizer is administered in the amount of 0.001-1 wt.h. on 100 wt.h. adhesive compositions.

As the polyurethane(meth)acrylate used is 0.1-10 wt.h. the reaction product isocyanatomethyl components (polyisocyanates, isocyanato(meth)acrylates, but better diisocyanate with a hydrocarbon residue of from 2 to 30 carbon atoms) with simple and/or complex polyether polyols (preferably dialami and/or trioligy) and/or hydroxyl and/or aminecontaining (meth)acrylates, which has a molecular mass of 400-10000 and contains the remains of (meth)acrylic acid in a quantity which/P> As the polymerization initiator used thermal and UV initiators: dicyclohexylperoxydicarbonate (CTC), peroxide lauroyl, peroxide benzoylamino, diisopropanolamine (Dilf).

In addition, the adhesive compositions may contain other excipients, such as adhesive additives, thermal and UV stabilizers, dyes.

As adhesive additives adhesive compositions contain up to 10 wt.h. compound that is selected from the group comprising acrylic acid, methacrylic acid, phosphates, silanes, disilane.

To prevent premature polymerization of the adhesive composition during storage type stabilizers in amounts of 0.001-1 wt.h. to the total weight of the mixture, selected from the group comprising phenols, derivatives of phenols, quinones or hydrochinone.

As UV stabilizers adhesive compositions contain no more than 1 wt. including compounds selected from the group of esters of salicylic acid, substituted benzophenone or benzotriazole, benzoquinone, oksihinolina, phenol, aniline, cyclohexane.

As dye adhesive compositions contain no more than 0.1 wt.h. compounds selected from the class antrahinonovye and azo-dyes.

The change in the optimal quantities of functional groups in the polyurethane(meth)acrylate and/or the ratio of (meth)acrylic monomers and polyurethane(meth)acrylate leads to marriage laminated glass due to turbidity, waves, bubbles, Alipov intermediate layer (table).

Example 1. Sample triplex receive, collecting glass size 300x300 mm of the two silicate or other nature of glass as follows: the surface of the glass, going to gluing, washed with water until complete wetting, then wipe with a dry cloth. The gap in silicate form (1,0-1,5) mm create by using cushioning tube, and tightness provide a preload spacer tube with clamps.

The mixture is poured into a mold and utverjdayut its heat or by means of UV radiation (mode of curing is shown in the table). After curing, the form is released from the clamps, gasket tube remains in laminated glass as the sealing element.

The synthesis of the polyurethane(meth)acrylate is carried out in two stages.

In the second stage to the reaction mixture poured monomethacrylates at equimolar ratio of isocyanate and hydroxyl groups. The synthesis is carried out at a temperature of not more than 50oC in the presence of 0.05 wt.h. catalyst dibutylthiourea until complete consumption of the isocyanate groups.

The resulting polyurethane(meth)acrylate is a clear colourless viscous liquid not dissolved in water and soluble in most organic solvents.

To reduce the viscosity of the polyurethane(meth)acrylate may be diluted (meth)acrylic monomers used in the adhesive composition.

The adhesive composition is prepared as follows: 20 wt.h. of methyl methacrylate (MMA), 80 wt. hours of butyl acrylate (BA), 3 wt.h. polyurethane (methacrylate (PUA), 1 wt.h. Deaf and 1.01 wt.h. p-methoxyphenol (n-Fab) are thoroughly mixed and poured into the glass of the silicate glass.

After curing the adhesive compositions have a laminated appearance clear, colorless to light transmission of 87%, which withstands climatecheck the components and preparation of the glass is similar to example 1, but use a polyurethane (meth)acrylate (mol. m 400, the content of the methacrylic group 2 on one molecule and the ratio of polyurethane to methacrylic 1:1.

After curing the adhesive compositions have a laminated appearance clear, colourless, with a light transmission of 87% of withstanding climatic tests and hit the ball according to GOST 5727-88, properties listed in the table.

Example 3. Glass collected from two sheets of plexiglass analogously to example 1. For the preparation of adhesive compositions take 37 wt.h. MMA, 63 wt.h. BA, 3 wt. including polyurethane(meth)acrylate (mol. m 4000, 1 wt.h. Deaf, 0.01 wt.h. n-Fab and 0.4 wt.h. salol as a UV stabilizer. After curing of the adhesive composition are organic colorless transparent laminated glass with a transmittance of 89%, withstand climatic tests, the properties shown in the table.

Example 4. Glass collected from one lime and one organic glasses analogously to example 1, but using 41 wt.h. MMA, 59 wt.h. laurelcrest, 5 wt.h. the polyurethane(meth)acrylate, 1 wt.h. Deaf and 0.01 wt. h n-Fab.

After curing the adhesive compositions have a transparent, colorless glass with a transmittance of 89%, vyderzhannogo organic and one polycarbonate glasses analogously to example 1. For the preparation of adhesive compositions take 80 wt.h. octylacrylate (OMA), 20 wt. hours of butyl methacrylate (BMA), 5 wt.h. the polyurethane(meth)acrylate, mol. m 4000, 1 wt.h. Deaf and 0.01 wt.h. p-methoxyphenol.

The obtained laminated transparent and withstands climatic tests, the properties shown in the table.

Example 6. Glass collected from one lime and one polycarbonate glasses analogously to example 1. For the preparation of adhesive compositions take 90 wt. am C12-C18-methacrylate, 10 wt.h. BMA, 1 - wt.h. the polyurethane(meth)acrylate (mol. m 10000, 1 wt.h. Deaf and 0.01 wt.h. n-Fab.

The obtained laminated transparent and withstands climatic tests, the properties shown in the table.

Example 7. The composition, the ratio of the components and preparation of the glass is similar to example 1, but additionally used as a dye antrahinonovye blue in an amount of 0.01 wt.h.

The obtained laminated transparent, bright blue color and can withstand climatic tests, the properties shown in the table.

Example 8. The composition, the ratio of the components and preparation of the glass is similar to example 1, but additionally is used as the transparent plexi, colorless with a light transmission of 87%, good resistance to climatic tests and hit the ball according to GOST 5727-88, properties listed in the table.

Example 9. Glass collected from two silicate glasses analogously to example 1. For the preparation of adhesive compositions take 100 wt.h. of methyl acrylate (MA), 5 wt.h. the polyurethane(meth)acrylate (mol. m 4000, 2 wt.h. Deaf and 0.01 wt.h. p-methoxyphenol.

The obtained laminated transparent and withstands climatic tests, the properties shown in the table.

Example 10. Glass collected from two silicate glasses analogously to example 1. For the preparation of adhesive compositions take 100 wt.h. exilicauda (GMA), 5 wt.h. the polyurethane(meth)acrylate (mol. m 4000, 0.1 wt.h. dicyclohexylperoxydicarbonate (CTC), 0.01 wt.h. p-methoxyphenol.

The obtained laminated transparent and withstands climatic tests, the properties shown in the table.

For comparison here is the experimental data in the approximation to the author.the certificate of the USSR N 1659436 (example 11) and the application of Japan N 59-86676 (example 12).

Example 11. Glass collected from two silicate glasses, pre-pureed alcohol solution of polyvinyl butyral, with a gap of 3 mm between them is ocyanate (GMDC) (NCO/CH=1). After that, 40 wt.h. MMA dissolve 0.01 wt.h. dibutyltindilaurate tin and 0.05 wt. including benzoin and add to the mixture. The liquid composition is stirred for 5 minutes and serve in a glass. After 6 hours, the liquid is transformed into a gel-like state. After 18 h after mixing triplex placed under a source of ultraviolet radiation for 0.5 hours

The obtained laminated transparent, colorless, withstands climatic tests, with the transmittance of 87%, the properties shown in the table.

Example 12. In approaching the application of Japan N 59-86676. Glass collected from two silicate glasses analogously to example 1. For the preparation of adhesive compositions take 40 wt.h. the polyurethane(meth)acrylate (mol. M. 2000, 28 wt.h. tetraacrylate pentaerythritol, 4 wt.h. hexa - and pentakill of dipentaerythritol, 28 wt.h. tetrahydrofurfurylamine and 1 wt.h. Deaf.

The obtained laminated transparent, but with Otopeni, climatic tests does not stand up.

From the table it is seen that the invention solved tasked with securing the adhesive composition to create a transparent, durable, with high adhesion of the intermediate layer in multilayer products from heterogeneous glasses. Laminated glass is any combination. The intermediate layer according to the proposed technical solution get in one stage at a constant temperature.

In the reaction mixture is injected modified rubber, simultaneously performing the functions of adhesion and cross-linking agent, all of the source materials are non-toxic.

The adhesive composition according to the proposed solution provides the intermediate layer, resistant to solar radiation, temperature changes, for temperatures from -60 to 80oC, i.e. under all climatic conditions.

1. The adhesive composition for the manufacture of laminated glass comprising (meth)acrylic monomer and a radical initiator, characterized in that it contains as (meth)acrylic monomer alkylacrylate C1-C12and/or alkylmethacrylamide C1-C18and optionally 0.1 to 10 wt.h. on 100 wt.h. (meth)acrylic monomer polyurethane(meta)acrylate (mol.m. 400 - 10000 and content of residues of (meth)acrylic acid is not less than 2 per molecule of the polyurethane(meth)acrylate and thermo stabilizer in the amount of 0.001 - 1 wt.h. on 100 wt.h. adhesive compositions.

2. The composition according to p. 1, characterized in that it further comprises a UV stabilizer in an amount not more than 1 wt.h. at 100 m the dye in an amount of not more than 0.1 wt.h. on 100 wt.h. adhesive compositions.

4. The composition according to PP.1 to 3, characterized in that it further comprises adhesive additive selected from the group comprising acrylic and methacrylic acid, phosphates, silanes, disilane.

 

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