KR20030004306A - Use of a cast resin and a duroplastic edge seal for producing a sandwich system that consists of a screen and a glass pane - Google Patents

Abstract

The present invention relates to the use of transparent casting resins composed of reactive acrylate and methacrylate monomers, acrylate and methacrylate oligomers, binders and initiators. The present invention also relates to the use of an edge sealant for producing a sandwich system consisting of a screen, a casting resin layer and an edge sealant, wherein the edge sealant surrounds the casting resin and the glass plate sideways.

Description

{USE OF A CAST RESIN AND A DUROPLASTIC EDGE SEAL FOR PRODUCING A SANDWICH SYSTEM THAT CONSISTS OF A SCREEN AND A GLASS PANE}

The present invention relates to a method of using a permanently flexible edge-sealing composition and casting resin to attach a glass sheet to the front of a display screen.

The diagonal of the front of the display screen of the cathode ray tube has been very extended during development. In particular, in the case of large display screens, the display screens will break when impact-loaded and eventually implosion will occur. In this case, the viewer may be hurt by the pieces scattering around. In order to protect these pieces, it is known to adhere the plastic film over the entire area of the front of the display screen. In this regard, the front of the display screen may be flat or spherically smooth.

It is an object of the present invention to reduce the breaking sensitivity of the front of the display screen and to avoid pieces of glass scattering around when the front (flat or spherical) of the display screen is broken.

This object is solved by using a transparent casting resin to form a sandwich arrangement consisting of a display screen, a casting resin layer and a glass sheet. The casting resin consists of reactive acrylate and methacrylate monomers, acrylate and methacrylate oligomers, binders and initiators. When cured, the reactive acrylate and methacrylate monomers form a copolymer that may have a crosslinked structure. In addition, the casting resin may contain non-reactive acrylate and methacrylate homopolymers and copolymers, plasticizers, tackifying additives and stabilizers. The casting resin contains the abovementioned components in an amount of the following weight percent:

a) reactive acrylate and methacrylate monomers 50-97

b) acrylate functional and

Methacrylate functional oligomers 1 to 40

c) non-reactive acrylates and methacrylates

Homopolymers and Copolymers 0-15

d) fillers 0-5

e) plasticizer 0 to 15

f) binder 0.3 to 3

g) photoinitiator 0.01 to 3

h) tackifying additives 0-5

i) stabilizers 0 to 2

Preferably, a casting resin containing the aforementioned components in an amount of the following weight percent is prepared:

a) reactive acrylate and methacrylate monomers 80-97

b) acrylate functional and

Methacrylate functional oligomers 1 to 20

c) non-reactive acrylates and methacrylates

Homopolymers and Copolymers 0-15

d) fillers 0-5

e) plasticizer 0 to 15

f) binder 0.3 to 3

g) photoinitiator 0.05 to 1

h) tackifying additives 0-5

i) stabilizers 0 to 2

Esters of monofunctional and polyfunctional, preferably monofunctional, acrylic acid or methacrylic acid were used as reactive acrylate and methacrylate monomers (crosslinkers). The alcohol components of the esters used are functional groups (e.g. methyl, ethyl, n-propyl, iso-propyl, n-butyl, tertiary butyl, pentyl, hexyl, isomers and higher homologs, e.g. 2- Alkylhexyl, phenoxyethyl, hydroxyethyl, 2-hydroxypropyl, caprolactone hydroxyethyl, polyethylene glycol, polypropylene glycol and dimethylaminoethyl). Also usable as reactive monomers are acrylic acid and methacrylic acid itself and amides of these acids (eg dimethyl acrylamide or diethyl acrylamide, methylethyl acrylamide and acrylonitrile). Mixtures of reactive acrylate and methacrylate monomers may also be used. Examples of reactive acrylate and methacrylate monomers having one double bond include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i- Propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, i-octyl acrylate, i-octyl methacrylate, n-octyl acrylate, n-octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-decyl acrylate, n-decyl methacrylate, i-decyl acrylate, lauryl acrylic Lauryl methacrylate, stearyl acrylate, stearyl methacrylate, tridecyl methacrylate, phenoxyethyl arc Latex, nonylphenol ethoxyacrylate, β-carboxyethyl acrylate, i-bornyl acrylate, i-bornyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, cyclohexyl acrylate , Cyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, propylene glycol monoacrylate, propylene glycol monomethacrylate, 2 (2-ethoxyethoxy) ethyl acrylate, N Vinylpyrrolidone, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate or 2-hydroxypropyl methacryl There is a rate. Examples of reactive acrylate and methacrylate monomers having two double bonds include butanediol diacrylate, butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate with an average molecular weight of 200, 400 or 600 g / mol, polyethylene glycol with an average molecular weight of 200, 400 or 600 g / mol Dimethacrylate, dipropylene glycol diacrylate or tri A ropil butylene glycol diacrylate. Examples of reactive acrylates and methacrylates having three double bonds include trimethylolpropane triacrylate, trimethylolpropane methacrylate, pentaerythritol triacrylate, ethoxylated or propoxylated trimethylolpropane triacrylic There is a methacrylate or tris (2-hydroxyethyl) isocyanurate triacrylate corresponding to the acrylate having a rate and an average molecular weight of 40 to 1000. Examples of reactive acrylate and methacrylate monomers having several double bonds are pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate or di (trimethylolpropane) tetraacrylate.

Examples of acrylate functional and methacrylate functional oligomers are epoxy acrylates, urethane acrylates, polyester acrylates and silicone acrylates.

The oligomers may be monofunctional or higher functional, which are preferably used in bifunctional form. Mixtures of oligomers may also be used.

Epoxy acrylates are based on bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, each of which terminates with acrylic acid or methacrylic acid in their oligomers or in novolak glycidyl ethers.

Urethane acrylates are synthesized from isocyanates (e.g. toluylene, tetramethylxylylene, hexamethylene, isophorone, cyclohexylmethane, trimethylhexamethylene, xylylene or diphenylmethane diisocyanate) and polyols Functionalized with hydroxy acrylate (eg 2-hydroxyethyl acrylate) or hydroxy methacrylate (eg hydroxyethyl methacrylate).

The polyols may be polyester polyols or polyether polyols. The polyester polyols are dicarboxylic acids or several dicarboxylic acids, preferably dicarboxylic acids (eg adipic acid, phthalic acid or anhydrides thereof) and one or more diols or polyols, preferably diols And mixtures of triols (for example 1,6-hexanediol, 1,2-propanediol, neopentyl glycol, 1,2,3-propanetriol, trimethylolpropane, pentaerythritol or ethylene glycol, for example , Diethylene glycol). Polyester polyols can also be obtained by reaction of hydroxycarboxylic acids (eg starting from caprolactone) with themselves. Polyether polyols can be produced by etherifying diols or polyols with ethylene oxide or propylene oxide.

Polyester acrylates are the polyester polyols described above, which are functionalized with acrylic acid or methacrylic acid.

Silicone acrylates used in the present invention are known to be based on poly (dimethylsiloxanes) with various molecular weights, which are functionalized with acrylates.

Non-reactive acrylate or methacrylate homopolymers and copolymers are homopolymers and copolymers of acrylic acid, methacrylic acid and esters of these acids. The casting resin may also contain a mixture of the above-mentioned homopolymers and copolymers. Casting resins can also be produced without non-reactive acrylate and methacrylate homopolymers and copolymers.

The filler may or may not be reinforced. Usable as fillers are preferably hydrophilic and / or surface treated pyrogenic or condensed silicic acid and cellulose derivatives such as cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate, methylcellulose and hydroxypropyl methylcellulose. The casting resin may also contain a mixture of such fillers. Casting resins can also be produced without fillers.

Examples of plasticizers include esters of phthalic acid, such as di-2-ethylhexyl, diisodecyl, diisobutyl, dicyclohexyl and dimethyl phthalate, esters of phosphoric acid such as 2-ethylhexyldiphenyl, tri (2-ethyl Hexyl) and tricresyl phosphate, esters of trimellitic acid such as tri (2-ethylhexyl) and triisononyl trimellitate, esters of citric acid such as acetyltributyl and acetyltriethyl citrate, and dicar Esters of acids, such as di-2-ethylhexyl adipate and dibutyl sebacate. The casting resin may also contain a mixture of the above mentioned plasticizers. Casting resins can also be produced without plasticizers.

The binder is an organofunctional silane group such as 3-glycidyloxypropyl trialkoxysilane, 3-aminopropyl trialkoxysilane, N-aminoethyl-3-aminopropyl trialkoxysilane, 3-methacryloxypropyl trialkoxysilane , Vinyl trialkoxysilanes, iso-butyl trialkoxysilanes, mercaptopropyl trialkoxysilanes, and silicic acid ester groups such as tetraalkyl orthosilicates. The casting resin may also contain a mixture of the abovementioned binders.

Usable as photoinitiators are benzoin ether group, benzyl ketal group, α-dialkoxyacetophenone group, α-hydroxyalkylphenone group, α-aminoalkylphenone group, acyl phosphine oxide group, benzophenone group or thioxane Compounds from tone groups, or mixtures thereof. Examples are 2-hydroxy-2-methyl-1-phenylpropanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2,2-dimethoxy-1,2-diphenyl Ethan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholonopropanone-1.

Tackifying additives can be selected from the group of natural or synthetic resins, which resins are later modified. Usable as resins include hydrocarbon resins, colophony and derivatives thereof, polyterpenes and derivatives thereof, coumarone / indene resins, phenolic acid resins, polybutenes, hydroxide polybutenes, polyisobutenes and hydroxide polyisobutenes There is this. The casting resin may also contain a mixture of the above mentioned tackifying additives. Casting resins can also be produced without tackifying additives.

Stabilizers can be antioxidants such as phenol (eg 4-methoxyphenol) or steric hindrance phenol (eg 2,6-di-tert-butyl-4-methylphenol), or It may be a mixture of antioxidants. Casting resins can also be produced without stabilizers.

Preferably, a casting resin adjusted to have a low viscosity is applied, since this casting resin is particularly suitable for the process, ie a reasonable casting process. The viscosity specified at 23 ° C. is 1 mPa · s to 1000 mPa · s, preferably 1 mPa · s to 500 mPa · s, and in a particularly preferred manner, 1 mPa · s to 100 mPa · s (MK20 / 157 cone (25 mm diameter, 1 Measured with a velocity gradient of D = 40 1 / s using a Rheonlab MC20 rotary viscometer from Physica. Curing of the casting resin is carried out with UV light. In this process, the casting resin is transformed into a transparent and colorless polymer film as possible.

Preferably, the transparency of the casting resin in the cured state is 0.01 haze to 2 haze, preferably 0.01 haze to 1 haze, in a particularly preferred manner, from 0.01 haze to 0.5 haze (4 mm float glass / 2 mm casting resin / A sample having a 4 mm float glass structure was measured by a measuring device of Hazegard XL-211 type manufactured by Byk.

Preferably, the color of the casting resin in the cured state is L ^* 50 to 99, a ^* -10 to 10, b ^* -10 to 10, preferably, L ^* 80 to 99, a ^* -5 to 5 , b ^* -5 to 5, in a particularly preferred manner, L ^* 90 to 99, a ^* -5 to 0, b ^* -1 to 2 (for samples with 4mm float glass / 2mm casting resin / 4mm float glass structure Measured with a spectrophotometer of Lambda 12 type manufactured by Perkin Elmer. These data were measured with standardized light D65 and a 2 ° standard observer.

The casting resin used is produced by mixing the components in a suitable apparatus. If high shear forces are required to break up the filler accumulation in the mixing process, the device may be a negative cracker equipped with a disintegrating disk that rotates at high speed. If high shear forces are not required in the mixing process, the device may be a stirred vessel equipped with a paddle mixer or alternating current mixer. Depending on the components used, high or low shear forces are required. For example, a disintegrating disk is clearly required to incorporate pyrogenic silicic acid into the liquid. For low viscosities, bead mills may be necessary.

The viscosity is significantly increased by the mixing of the fillers. Vacuum or protective gas may be required for the mixing process.

The mixing temperature is about room temperature at the beginning of mixing and can be raised to 70 ° C. depending on the energy input of the mixing apparatus used and the concentration of the mixture. If a low boiling point monomer such as methyl methacrylate is used, for example a coolant may be required.

In the present invention, in the use of the casting resin, a sandwich arrangement composed of a display screen, a casting resin layer and a glass plate can be formed. The formation of the sandwich arrangement can be divided into each of the following process steps:

1. Clean and dry the display screen and glass sheet.

2. Apply edge sealant (on display screen front or glass sheet, preferably on display screen front).

3. Place the glass sheet on the front of the display screen.

4. Pressurize the obtained composite consisting of the display screen and the glass sheet so that the gap between the display screen and the glass sheet is the desired distance.

5. Fill with casting resin.

6. Remove the air in the interspace and seal the filling opening.

7. Check the space filled with casting resin so that there are no air bubbles.

8. Curing the casting resin by emitting UV light.

9. Final check the finished sandwich arrangement.

Each work step can be performed as follows:

The display screen front and the glass sheet are cleaned and dried in a known manner such as using conventional glass cleaners. Preferably, this operation can be carried out automatically in the washing machine. After washing, the glass sheet should be completely dry and oil and detergent residues removed. It is beneficial to check for cleanness. This can be achieved visually by light rays transmitted in the case of glass sheets and by reflection by fluorescent tubes in the front of the display screen. The process of cutting the previous glass sheet to size is advantageously carried out with a water soluble coolant or a coolant which is dried without residue.

Edge sealing can be carried out with a double-sided adhesive tape or, preferably, a permanently flexible material (a compound for edge sealing), which has thermoplastic properties and, after being fused, the front of the glass sheet or display screen It is applied in the form of beads or strands.

The edge sealant used must be compatible with the casting resin used, ie no chemical reaction should occur between the edge sealant and the casting resin, and must be physically compatible. For this purpose, the adhesion per unit area of the casting resin in the curing step should be higher than the yield point of the edge sealant at room temperature. This ensures that no unwanted separation occurs.

Usable as adhesive tapes are, for example, acrylate foam tapes coated with contact adhesive on both sides, such as acrylic foam tape type 4951, 4611 or 4945/4664, made by 3M, or Polyurethane foam tape coated with contact adhesive, for example, made by Nordson, or a clear, original tacky acrylate tape, such as acrylic tape type 4910 or 4915 made by 3M. to be. The width of the adhesive tape is 3 mm to 9 mm, preferably 6 mm, and the thickness is 1 mm to 2 mm, preferably 1.2 mm to 1.5 mm. Due to their flexibility, transparent acrylate tapes offer an advantage over foam tapes in their compressibility. This is because the cast resin provided exhibits a shrinkage of 5 to 17% by volume in the curing process. As a result of this shrinkage, pressure is formed in the casty resin layer during curing. As the volume of the casting resin shrinks, the thickness of the glass across the surface becomes more rugged, the glass sheet becomes thicker, and above all, the edge sealant becomes harder and more elastic, and this pressurization becomes greater.

It is common practice to coalesce the glass sheet onto the front of the display screen, pressurize the composite consisting of the display screen and the glass sheet at the desired spacing, fill and deplete the interspace with a casting resin, and seal the filling opening. Is achieved.

Filling is preferably accomplished by a flat nozzle consisting of a stainless-steel sheet having a thickness of less than 0.2 mm, a 50 mm maximum width, preferably a 20 mm maximum width. This filling is achieved from above with a slightly inclined position of the sandwich arrangement, or from below by a small aluminum nozzle (consisting of aluminum sheets having a thickness of up to 0.2 mm) fixed in position by the adhesive. These nozzles are about 5 mm wide, 1 mm thick, and have a rectangular to elliptical position where they are attached and bonded into the sandwich arrangement. However, filling is preferably performed from above.

After filling, the sandwich arrangement is preferably freed of air in such a way that the sandwich arrangement is slowly guided horizontally at the inclined position. After air removal, the filling opening is sealed. This can be done with a thermoplastic edge seal composition or with a hot melt adhesive based on, for example, an ethylene / vinyl-acetate copolymer.

Sandwich arrangements that have not yet cured are inspected for air bubbles that may still be present. These can be removed, for example, by cannula.

Curing of the casting resin is achieved by UV light. Low pressure tubes in invisible light blue with photoinitiators used herein have proven to be very useful for this purpose. These tubes consume less current. Several tubes are arranged in such a way that uniformly irradiated radiation occurs. Radiation force from 15 W / m ² to 25 W / m ² (200 nm to 400 nm complete value) measured by a Radialex type measuring device manufactured by Heraeus, required until curing is completed. The time is 3 to 20 minutes. The exact value depends on the casting resin mixture used.

Due to the poor planarity of the different display screens with respect to the float glass, undesirable pressure may occur in the course of the induction of the display-screen sandwich arrangement into the adhesive tape as an edge sealant.

Edge seals considered as models may be springs and / or dampers. In the case of a spring, it is compressed by the polymerization shrinkage of the casting resin during curing. The spring is permanently under pressure and the interlayer adjacent polymer casting resin is permanently under pressure. This means that during the entire operating life of the sandwich arrangement, the interlayer of the polymer casting resin must adapt to static loads due to spring and polymerization shrinkage. The adhesive tape to which both sides are bonded represents a composite of a spring and a damper. This is the tensile force on the glass sheet and display screen permanently applied by the polymerization shrinkage, and some of this tensile force deforms the edge seal. In the model, the damping characteristic of the edge seal is due to this.

Nevertheless, due to the flexibility of the adhesive tape, the remaining pressure is preserved. The viscous portion of the edge sealant induces damping properties and the elastic portion induces flexibility. This means that the elastomer synthesized from the adhesive tape is viscous and elastic.

Edge seals that act as little as a spring and act as much as a damper are desirable to reduce as much polymerization-shrinkage as possible.

This object is achieved by using an edge sealant composed of a composition which is permanently flexible at room temperature, is thermoplastic, and after fusion is applied in the form of beads or strands on the front of the display screen or on the glass sheet.

The edge seal composition used consists of a base polymer and optionally additional components.

The base polymer may be composed of homopolymers, copolymers, trimers, or mixtures thereof, or homopolymers and / or copolymers of acrylates and / or methacrylates or mixtures thereof.

Additional components may be thermoplastic polymers, natural and synthetic rubbers, tackifying additives, plasticizers, binders, reinforcing and unreinforcing fillers, stabilizers and other additives.

Preferably the edge seal composition used contains the following weight percent base polymer and additional components:

a) base polymer 30-100

b) thermoplastic polymer 0-50

c) natural and synthetic rubbers 0-50

d) tackifying additives 0 to 30

e) plasticizer 0-50

f) binders 0-5

g) stabilizers 0 to 5

h) reinforcing and non-reinforcing fillers 0 to 70

The edge seal composition used particularly preferably contains the following weight percent of the base polymer and additional components:

a) base polymer 40-100

b) thermoplastic polymer 0-30

c) natural and synthetic rubbers

d) tackifying additives 0-25

e) plasticizer 0-30

f) binders 0 to 3

g) stabilizers 0 to 3

h) reinforcing and non-reinforcing fillers 0 to 60

Homopolymers of isobutylene are commercially available polyisobutylenes in a range of molecular weights. The trade names for the polyisobutylene examples are Oppanol (BASF AG), Vistanex (Exxon) or Efrolen (Efremov). to be. The state of polyisobutylene is soft resin type or rubber type in liquid. The molecular weight is as mentioned below: the average of the molar mass is 2000 to 1,000,000 g / mol, preferably 24,000 to 600,000 g / mol, and the average viscosity of the molar mass is 5000 to 6,000,000 g / mol, preferably 40,000 to 4,000,000 g / mol.

Copolymers and trimers of isobutylene are comonomers and termonomers, which include 1,3-dienes such as isoprene, butadiene, chloroprene or β-pinene, functional vinyl compounds such as styrene, α-methyl Styrene, p-methylstyrene or divinylbenzene or further monomers. Examples of copolymers formed from isobutylene and isoprene are butyl rubbers with a low ratio of isoprene; Commercially available are various butyl forms made from Bayer AG, Exxon Chemical or Kautschuk-Gesellschaft, for example. The trimers of isobutylene with isoprene and divinylbenzene monomers are in particular crosslinked butyl-rubbers, which are also obtainable by the subsequent crosslinking of butyl rubber and are commercially available, for example exons LC butyl manufactured by Chemical, Kalar manufactured by Hardmand, or Polysar Butyl XL manufactured by Bayer Actiengegel Shaft. Homopolymers, copolymers and trimers of isobutylene can also be subjected to subsequent chemical modifications, which are known to convert butyl rubber to halogen (chlorine, boron), which is chlorobutyl rubber or bromobutyl Induce rubber. The conversion of isobutylene, p-methylstyrene and p-bromomethylstrin to trimers formed from bromine of copolymers formed from isobutylene and p-methylstyrene is carried out in a similar manner, which is produced in exon chemical Available under the trade name EXXPRO.

Homopolymers or copolymers of acrylates or methacrylates (poly (meth) acrylates) are polymers of esters of acrylic acid or methacrylic acid, for example as functional groups (e.g. methyl, ethyl, propyl, isopropyl) as alcohol components , n-butyl, iso-butyl, tert-butyl, pentyl and hexyl and their isomers and higher homologs, 2-ethylhexyl, phenoxyethyl, hydroxyethyl, 2-hydroxypropyl, caprolactone hydroxyethyl, Dimethylaminoethyl) or an alkyl group unsubstituted. Also included are polymers of acrylic acid, methacrylic acid, amides of the aforementioned acids and acrylonitrile. It may also consist of partially crosslinked poly (meth) acrylates and mixtures of polyacrylates and polymethacrylates, wherein the crosslinking is, for example, with diethylene glycol or trimethylenepropane as the alcohol component. Achieved by polyfunctional monomers.

Examples of thermoplastic polymers include polyolefins as homopolymers and copolymers, which are synthesized from monomers ethylene, propylene, n-butene and higher homologs and isomers thereof, and are functional vinyl compounds such as vinyl acetate, vinyl chloride, styrene and α. Synthesized from methylstyrene. Further examples are polyamides, polyimides, polyacetals, polycarbonates, polyesters and polyurethanes and mixtures of the aforementioned polymers. However, edge sealing compositions used according to the invention can also be produced without thermoplastic polymers.

Natural and synthetic rubbers can be selected from homopolymer groups of dienes, copolymers and trimer groups of dienes and olefins, and copolymer groups of olefins. Examples are block copolymers with blocks composed of polybutadiene, polyisoprene, polychloroprene, styrene / butadiene rubber, styrene and butadiene or isoprene, ethylene / vinyl-acetate rubber, ethylene / propylene rubber, and dicyclopentadiene as diene components Or ethylene / propylene / diene rubber with ethyldiene norbornene. Rubbers can also be used in hydrogenated and mixed forms. However, the edge seal composition used according to the invention can also be used without rubber.

Tackifying additives include, in particular, natural and synthetic resins including hydrocarbon resins, colophony and derivatives thereof, polyterpenes and derivatives thereof, coumarone / indene resins and phenolic resins, such groups of resins modified afterwards, And polybutene, polyisobutene and decomposed liquid rubbers (eg butyl rubber or EPDM), which can be hydrogenated. Mixtures of the tackifying additives mentioned may also be used. However, the edge seal compositions used according to the invention can also be used without tackifying additives.

Examples of plasticizers include phthalic acid (eg, di-2-ethylhexyl, diisodecyl, diisobutyl or dicyclohexyl phthalate), phosphorous acid (eg, 2-ethylhexyldiphenyl, tri (2-ethylhexyl) ) Or tricresyl phosphate), trimellitic acid (e.g. tri (2-ethylhexyl) or triisononyl trimellitate), citric acid (e.g. acetyltributyl or acetyltriethyl citrate) or dica Esters of leric acid (eg, di-2-ethylhexyl adipate or butyl sebacate). Mixtures of plasticizers can also be used. However, edge sealing compositions used according to the invention can also be used without plasticizers.

The binder is, for example, 3-glycidyloxypropyl trialkoxysilane, 3-aminopropyl trialkoxysilane, N-aminoethyl-3-aminopropyl trialkoxysilane, 3-methacryloxypropyl trialkoxysilane, vinyl tri Alkoxysilane, isobutyl trialkoxysilane, silane group which may include 3-mercaptopropyl trialkoxysilane, silicic acid ester group, for example tetraalkyl orthosilicate, metalate group, for example tetraylalkyl titanate Or tetraylalkyl zirconates, and mixtures of the binders mentioned. However, the edge seal composition used according to the invention can also be used without a binder.

Stabilizers are types represented by steric hindrance phenols (eg, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane) or mercaptans , A type represented by a sulfur based antioxidant such as sulfide, polysulfide, thiourea, mercaptal, thioaldehyde, thioketone, etc., a type represented by benzotriazole, benzophenone or HALS type (a hindered amine UC-blockers, or anti-ozonating agents of Hindered Amine Light Stabiliser. These may be used by themselves or in combination. However, the edge seal compositions used according to the invention can also be used without stabilizers.

Examples of reinforced and unreinforced fillers include pyrogenic or condensed silicic acid, silica gel, condensed or ground chalk (also surface treated), calcium oxide, clay, kaolin, talc, quartz, zeolite, titanium oxide, glass fiber or aluminum And zinc powders, and mixtures thereof. Carbon black, carbon fiber or graphite may also be used, provided the color of the edge sealant according to the invention is dark. However, edge sealing compositions used according to the invention can also be used without fillers.

The preferred edge encapsulant has a yield point of up to 4000 Pa, preferably 2000 Pa at 120 ℃ (measured at a vibration frequency of 1Hz, the 0.1mNm to 100mNm torque range and to about 10 ^-4 s ^-1 shear rate of 1s ^-1 Measured with a flow meter having a plate / plate geometry with a plate diameter of 25 cm).

The edge seal composition used according to the invention is produced by mixing the base polymer in a suitable device. The additional ingredients described above may also be mixed. If high shear forces are required, the mixing device may be, for example, a kneader, a twin screw mixer or a single screw mixer. If high shear forces are not required, mixing can be performed in an oily dissolver, a paddle mixer with a dissolver disc, an alternating current mixer or a similar device. High or low shear forces are used depending on the hardness of the initial material and the particular product, and high shear forces are required to mix the rubber or reinforcing fillers.

Mixing temperature is 40-200 degreeC, Preferably it is 70-180 degreeC. Mixing can optionally be carried out under protective gas or under vacuum.

After being fused, the thermoplastic edge sealing composition is known in the form of beads or strands at a temperature of 40 to 200 ° C., preferably at 70 to 180 ° C., as known processing devices (eg, conventional hot melt adhesive application devices or extruders) It is applied to the front of the sheet or display screen. The cross-sectional shape of the beads or strands may be rectangular, triangular, circular or oval with short sides rounded.

Circles to ellipses are particularly advantageous because the thermoplastic edge sealing composition is cooled more slowly by smaller surface contact with the glass surface, as a result of which pressurization of the sandwich arrangement is possible even at lower pressures. This is particularly necessary if the glass sheet is thinner than 2 mm, since otherwise the glass may be broken in the process of pressing the thin glass by excessive pressurization.

According to the filling method provided, for example, a filling opening of 10 mm to 70 mm for the casting resin is located at the corner of one longitudinal surface. After applying the edge seal composition, the glass sheets are laminated to coalesce on the front of the display screen. The thickness of the edge sealant is controlled by pressing so that the thickness of the casting resin layer does not become thin at any point of the sandwich arrangement to less than 0.2 mm, preferably less than 0.5 mm.

Edge sealing compositions used according to the invention have the advantage of exhibiting the required chemical and mechanical compatibility with the casting resin.

Since the yield point of the edge seal composition used according to the invention depends on the temperature of the sandwich arrangement after curing, this has the advantage of softening the arrangement.

In the present invention, the advantage of using the described casting resin is to lower the breaking sensitivity of the display screen produced in this way. In the present invention, the simultaneous use of the edge sealant described can still further reduce the breaking sensitivity of the display screen. The present invention is particularly important with regard to the production of flat panel display screens with reduced breaking sensitivity.

The content of the present invention will be explained in more detail based on the following examples.

Example 1 Synthesis by UV Polymerization of Poly (meth) acrylate Based Base Polymers for Use in Subsequent Production of Edge Sealing Compositions.

0.8 g (0.4% monomer ratio) of benzyl dimethyl ketal was added to a mixture of 200 g of 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and acrylic acid (weight ratio 65: 33: 2). The mixture was passed through a composite consisting of a polyester film (Hostaphan made from Hoechst) and a Teflon plate provided with a non-stick coating and polymerized by UV radiation treatment for 20 minutes ( Tube type: Philips TL 36 W / 08), the polyester film is coated on both sides with a contact adhesive, and the edge is sealed with an adhesive tape having a thickness of 2 mm.

Example 2: Preparation of Edge Sealing Compositions Based on Poly (meth) acrylates

60 g (69.0%) of the base polymer of Example 1 was mixed with 6 g (6.9%) of highly dispersed silicic acid (filler), 20 g (23.0%) of acrylate resin (Jaegotex AP made from Jaeger). 273, tackifier additive) and 1 g (1.1%) of tetrakis [methylene-3- (3,5-tert-butyl-4-hydroxyphenyl) propionate] methane (Raschig) Ralox 630, stabilizer) was kneaded in a kneader at 130 ° C. for 60 minutes. Thereafter, after vacuuming at 130 ° C. for 30 minutes, the composition was placed in a cartridge.

Example 3 Preparation of Edge Sealing Compositions Based on Isobutylene Polymer

997.5 g (47.5%) of polyisobutylene (Vistanex LM-H, base polymer from Exxon) and 52.5 g (2.5%) of butyl rubber (butyl 065 from Exxon, rubber) 382.2 g (18.2%) of carbon black (Corax N 330 from Degussa, filler), 226.8 g (10.8%) of chalk (Oma 95T from Omya, filler), 336.0 g (16.0%) zeolite (Baylith L, filler from Bayer), 100.8 g (4.8%) talc (Fintalc M10, filler from Omar) and 4.2 g (0.2%) of tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (Ralox 630 manufactured by Rasching) And stabilizer) in a kneader for 60 minutes at 150 ℃. Thereafter, after vacuuming at 150 ° C. for 2 hours, the composition was removed from the kneader. The composition was extruded at 130 ° C. through a round nozzle to produce strands 3.3 mm in diameter.

Example 4: Preparation of Casting Resin

200.0 g (12.5%) acrylic acid and 1184.0 g (74.0%) 2-ethylhexyl acrylate as reactive acrylate monomer, 120.0 g (7.5%) benzyl-2-ethylhexyl adipate as plasticizer (manufactured by Bayer 2000 ml glass of Adimoll BO and 11.2 g (0.7%) of 3-glycidyloxypropyl trimethoxysilane (Dynasilan GLYMO from Sivento) as binder It was fed to a beaker and mixed over a 10 minute period with a propeller stirrer, after which 80.0 g (5.0%) of aliphatic urethane acrylate (Craynor Cien (Cray Valley) manufactured as an acrylate functional oligomer) Craynor CN) 965) within 15 minutes Finally, 4.8 g (0.3%) of oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone as photoinitiator ] (Esacure KIP 150 from Lamberti) was added and the mixture was added to 10 Homogenized for minutes.

Example 5: Preparation of Casting Resin

224.0 g (14.0%) acrylic acid as reactive acrylate monomer, 224.0 g (14.0%) n-butyl acrylate and 944.8 g (56.55%) 2-ethylhexyl acrylate, 200.0 g (12.5%) as plasticizer Diphenylcresyl phosphate (Disflamoll DPK from Bayer), 4.8 g (0.3%) of vinyl trimethoxysilane (Dynasilan VTMO from Sibento) as binder ), 40.0 g (2.5%) of aliphatic urethane acrylate (Craynorcyene 985 from Cray Valley) as acrylate functional oligomer, 2.4 g (0.15%) of 1-hydroxycyclohexyl phenyl ketone (Ciba) as photoinitiator Irgacure 184, manufactured by Ciba Spezialitaetenchemie, was fed into a 2000 ml wide neck bottle, which was homogenized over 30 minutes with a magnetic stir bar and a magnetic stir motor. .

Example 6 Preparation of Casting Resin

240.0 g (15.0%) acrylic acid as reactive acrylate monomer and 874.4 g (54.65%) 2-ethylhexyl acrylate, 160.0 g (10%) tricresyl phosphate (plastic made from Bayer) as plasticizer Disflamoll TKP), 4.8 g (0.3%) of γ-methacryloxypropyl trimethoxysilane (Dinasilane Memo (MEMO) manufactured by Sibento) and 0.8 g (0.05%) of benzyl as photoinitiator Dimethyl ketal (Lucirin BDK manufactured by BASF) was fed into a 3000 ml glass beaker, which was mixed for 15 minutes with a propeller stirrer. Thereafter, 320.0 g (20.0%) of aliphatic urethane acrylate (Genomer 4215 manufactured by Rahn) as an acrylate functional oligomer heated to 40 ° C. was slowly added to the strongly stirring mixture. And the mixture was homogenized over 20 minutes.

Example 7 Measurement of Cure Time of Casting Resin from Examples 4 to 6 for UV Radiation Through Float Glass

2 mm thick and 6 mm wide acrylate foam tape (Acrylic Foam Tape 4912 made from 3M) bonded to both sides is filled with casting resin on washed float glass 300 mm x 300 mm wide and 4 mm thick. The opening was positioned at the edge of the glass plate so that a gap of about 50 mm was maintained between the ends of the tape. Thereafter, a second, 3 mm thick, washed glass plate was positioned in situ and the arrangement was pressed by hand.

Each composite produced in this manner was filled with one of the casting resins from Examples 4 to 6 with a polyethylene hose from the edge to the fill opening, and the edge opening was filled in ethylene / vinyl-acetate hot melt adhesive (Chemetall). It was sealed with the produced Heisßschmelzkleber 22).

The sandwich arrangement was subjected to UV on the glass surface by radiation to a TL-D 36W / 08 type invisible light tube manufactured by Philips under UV-Himmel, manufactured by Torgauer Makinenbauer Machinenbau GmbH. The radiation was cured at 20 W / m ² . For the purpose of observing the curing time measurement, the temperature during UV radiation was measured with a temperature sensor PT 100 on a float glass plate 4 mm thick facing away from the UV tube and recorded on an x / y plotter. The initial temperature at the start of UV radiation was 23 ° C.

The results are shown in Table 1.

Example 8: Determination of curing time for UV radiation through gray colored cover glass with 60% conductivity

Example 7 was repeated with the cured resins from Examples 4 to 6 except that in each case a glass plate colored in gray and 60% conductivity was used instead of the second float glass plate. During the curing process of each composite, the colored glass plate was faced towards the UV tube.

The results are shown in Table 1.

Table 1: Curing Times of Cured Resins from Examples 4 to 6 Measured According to Examples 7 and 8

Curing time according to example 7 (spinning through float glass with a thickness of 3 mm) Curing time according to example 8 (spinning through gray colored glass with a thickness of 3 mm) Time to maximum temperature (minutes) Temperature (℃) Spinning time (minutes) Time to maximum temperature (minutes) Temperature (℃) Spinning time (minutes) Curing Resin of Example 4 10.5 72 20 16.0 70 25 Curing Resin of Example 5 10.5 80 20 17.5 19 30 Cured Resin of Example 6 7.5 77 15 13.5 78 25

Example 9 Haze Value Measurement of the Cast Resins of Examples 4 to 6

The haze value represents the percentage of transmitted light that deviates from the direction of the projection light during the process of transradiation of the sample as a result of forward scattering. Only luminous fluxes having a refraction higher than 2.5 ° are considered haze.

For samples produced according to Example 7 with the casting resins of Examples 4 to 6, measurements were carried out at 23 ° C. using a Hazegard-System XL211 made by Gardner. . The results are shown in Table 2.

Table 2: Haze Values for 3mm Float Glass / 2mm Casting Resin / 4mm Float Glass Structures

Casting Resin of Example 4 Casting Resin of Example 5 Casting Resin of Example 6 Haze value 0.13 0.17 0.10

Example 10 Preparation of Cast Resin Film for Investigating Mechanical Properties

A thin polyester film was first placed on a float glass plate 4 mm thick, wetted with water, 300 mm x 300 mm wide, softened, 2 mm thick, 6 mm wide, and bonded on both sides ( The acrylic foam tape 4912 made at 3M was attached to the edge region of the polyester film in such a way that a gap of about 50 mm from the ends of the tape was maintained. Then, similarly to the polyester film attached to the glass, a second glass plate having a thickness of 4 mm was collectively positioned in position and the arrangement was pressed by hand. Each composite produced in this manner is clamped at all four corners, filled with the casting resin of Examples 4-6 at an angle of about 80 ° by means of a PE tube via a filling opening at the edge, respectively, and the edge opening. Was sealed with an ethylene / vinyl-acetate hot melt adhesive (Hiskmeltsclever 21 manufactured by Kemetal). Curing was performed with invisible light in a manner similar to Example 7.

After cooling to room temperature, the polyester film was stripped from the cured casting resin film to investigate some mechanical properties of the cured casting resin.

Example 11 Measurement of Shore-A Hardness of the Cured Casting Resin According to Examples 4-6

The cast resin film produced according to Example 10 was cut into three pieces 40 mm × 40 mm in size and placed in combination with each other to produce a sample about 6 mm thick and sprinkled with talc. Shore-A hardness was measured according to DIN 53505 24 hours after film formation. The results are shown in Table 3.

Example 12 Measurement of Intrinsic Strength of the Cured Casting Resin According to Examples 4-6

After storage at room temperature for 24 hours, the tensile strength, extension on tear and tensile stress according to DIN 53504 for the cast resin film produced according to Example 10 were obtained at a drawing speed of 100 mm / min on an S2 standard bar under 23 ° C. It was confirmed with a Zwick universal test instrument. The results are shown in Table 3.

Table 3: Mechanical Properties of Casting Resins from Examples 4-6

Casting Resin of Example 4 Casting Resin of Example 5 Casting Resin of Example 6 Shore-A Hardness 16 13 47 Tensile Stress 25% (MPa) 0.11 0.09 0.42 50% tensile stress (MPa) 0.17 0.13 0.66 100% tensile stress (MPa) 0.26 0.18 1.22 % Extension 259 419 130 Tensile Strength (MPa) 0.95 1.28 1.81

Example 13: Determination of the shrinkage of the casting resin of Examples 4 to 6 during polymerization

'Shrinkage rate of the casting resin during polymerization' is understood as the average value of the volume percentage difference before and after curing.

For the purpose of measuring the shrinkage rate during the polymerization, the density of the liquid mixture in each case, and the density for the film pieces of the casting resins of Examples 4 to 6 at 20 ° C. after curing, were determined on the buoyancy principle by gravity in air and ethanol. The spindle was then identified using a Sartorius RC 250 S balance with a specific structure.

The shrinkage rate during polymerization was calculated according to the formula [1 / ρliquid-1 / ρfilm] * 100 / [1 / ρliquid], where ρ liquid is the density of the liquid casting resin and ρ film is the hardened casting The density of the resin is shown. The results are shown in Table 4.

Table 4: Density and Shrinkage of Catching Resin during Polymerization

Casting Resin of Example 4 Casting Resin of Example 5 Casting Resin of Example 6 Density of Liquid Casting Resin (g / ml) 0.923 0.944 0.977 Density of Cured Casting Resin (g / cm ³ ) 1.031 1.066 1.084 Shrinkage rate during polymerization (%) 10.5 11.5 9.9

Example 14 Viscosity Measurement of the Cast Resins of Examples 4 to 6

The viscosity of the casting resins of Examples 4 to 6 is a rotary viscometer (Riolab manufactured by Physica) equipped with a MK20 / 157 cone (25 mm diameter, 1 °) at a speed gradient D of 40 1 / s at 20 ° C. It was confirmed using MC 20 (Rheolab MC20). The results are shown in Table 5.

Table 5: Viscosity of Casting Resin

Casting Resin of Example 4 Casting Resin of Example 5 Casting Resin of Example 6 Viscosity (mPas) 3.4 2.3 17.6

Example 15: Production of a Sandwich Assembly Composed of Display Screen, Edge Sealant of Example 2, Casting Resin of Example 4, and Glass Sheet

The edge sealing composition of Example 2 was washed and at the beginning and end of the application under 150 ° C. using a heatable carriage gun in the form of a strand having a diameter of about 4 mm at the edge of the gray colored glass sheet (60% conductivity). The coating was applied in such a way that an opening of 50 mm width for filling with the casting resin was maintained in between. Immediately after application of the edge seal composition, the front of the glass sheet is placed on a cleaned flat display screen (32 inch, 16: 9 format), with a gap of about 1 mm at the center of the arrangement between the front glass and the flat display screen surface. Pressurized to 80kg load to occur.

In this composite, the casting resin of Example 4 was filled by a PE tube through the edge opening to the filling opening at an angle of about 30 °, and the opening was filled with ethylene / vinyl-acetate hot melt adhesive (Hiskmeltz manufactured by Kemetal). Sealed with Clever 21).

The sandwich arrangement was subjected to UV radiation of 20 W / m ² on the surface of the glass by radiation to a TL-D 36W / 08 invisible light tube manufactured by Philips under UV-Himmel, manufactured by Torugaer Makinenbau GmbH. Curing for 25 minutes.

Example 16: Production of a Sandwich Assembly Composed of Display Screen, Edge Sealant of Example 3, Casting Resin of Example 5 and Glass Sheet

About 50 mm for filling the edge sealing composition of Example 3 with a casting resin between the beginning and the end of the strand in the form of a strand having a diameter of about 3.3 mm at the edge of the gray colored glass sheet (60% conductivity) The application was applied in such a way that the opening of the width was maintained. The front of the glass sheet is then placed on a washed flat display screen (32-inch, 16: 9 format) and weighed 50 kg to create a gap of about 0.5 mm in the center of the arrangement between the front glass and the flat display screen surface. It was loaded and pressurized.

In this composite, the casting resin of Example 5 was filled by means of a PE tube through the edge openings just below the filling openings at an angle of about 30 °, and the edge openings were made of ethylene / vinyl-acetate hot melt adhesive (made from kemetal). Sealed with Hiskmeltzclever 21).

The sandwich arrangement was subjected to UV radiation of 25 W / m ² on the surface of the glass by radiation to a TL-D 36W / 08 type invisible light tube manufactured by Philips under UV-Himmel, manufactured by Torugaer Makinenbau GmbH. Cured for 30 minutes.

Example 17: Production of a Sandwich Assembly Composed of Display Screen, Edge Sealant, Casting Resin of Example 6 and Glass Sheet

16: 9 format 32-inch planar display clay washed with permanently flexible edge sealing compound based on isobutylene polymer (Naftotherm BU-TPS manufactured by Kemetal) The edges were applied in such a way that about 50 mm gap was maintained as a filling opening for the casting resin between the two ends of the filament in the form of a round filament extruded to a screen of 4.6 mm diameter. The washed and gray colored glass sheet front (60% conductivity) was then placed in position and pressed to 60 kg so that a gap of about 1 mm occurred in the center between the front glass and the flat display screen surface.

This composite was filled with the casting resin of Example 6 by means of a PE tube through the edge openings just below the filling openings, and the edge openings were filled with ethylene / vinyl-acetate hot melt adhesives Sealed with Schmeltcleber 21).

20 W / m UV radiation on the glass surface by UV-radiation into a TL-D 36W / 08 invisible light tube manufactured by Philips under UV-Himmel, manufactured by Torgauer Makinenbau GmbH Cured with ² for 25 minutes.

Claims (9)

Transparent casting resins consisting of reactive acrylate and methacrylate monomers, acrylate and methacrylate oligomers, binders, and initiators, and edge sealants flanked by display screens, casting resin layers, casting resin layers, and Use of an edge sealant to produce a sandwich arrangement composed of glass sheets. Use according to claim 1, characterized in that the casting resin contains the components of a) to i): (Total weight% of the following components = 100%) a) reactive acrylate and methacrylate monomers 50-97 b) acrylate functional and Methacrylate functional oligomers 1 to 40 c) non-reactive acrylates and methacrylates Homopolymers and Copolymers 0-15 d) fillers 0-5 e) plasticizer 0 to 15 f) binder 0.3 to 3 g) photoinitiator 0.01 to 3 h) tackifying additives 0-5 i) stabilizers 0 to 2 Use according to claim 2, characterized in that the casting resin contains the components of a) to i): (Total weight% of the following components = 100%) a) reactive acrylate and methacrylate monomers 80-97 b) acrylate functional and Methacrylate functional oligomers 1 to 20 c) non-reactive acrylates and methacrylates Homopolymers and Copolymers 0-15 d) fillers 0-5 e) plasticizer 0 to 15 f) binder 0.3 to 3 g) photoinitiator 0.05 to 2 h) tackifying additives 0-5 i) stabilizers 0 to 2 The edge sealant of claim 1, wherein the edge sealant is thermoplastic and permanently flexible, after fusion, which is applied in the form of beads or strands on the front or glass sheet of the disc clay screen. Use, characterized in that the composition consists of. 5. The edge sealing composition according to claim 4, wherein the edge sealing composition contains the components of a) to h) wherein the base polymer is a homopolymer, copolymer or trimer of isobutylene, or a mixture thereof, or an acrylate and Use characterized in that it consists of homopolymers and / or copolymers of methacrylates, or mixtures thereof: (Total weight% of the following components = 100%) a) base polymer 30-100 b) thermoplastic polymer 0-50 c) natural and synthetic rubbers 0-50 d) tackifying additives 0 to 30 e) plasticizer 0-50 f) binders 0-5 g) stabilizers 0 to 5 h) reinforcing and non-reinforcing fillers 0 to 70 Use according to claim 4, characterized in that the edge seal composition contains the components of a) to h): (Total weight% of the following components = 100%) a) base polymer 40-100 b) thermoplastic polymer 0-30 c) natural and synthetic rubbers d) tackifying resin 0-25 e) plasticizer 0-30 f) binders 0 to 3 g) stabilizers 0 to 3 h) reinforcing and non-reinforcing fillers 0 to 60 The yield point of the edge sealant according to claim 4, wherein the yield point of the edge sealant is at 120 ° C. up to 4000 Pa (vibration frequency of 1 Hz, torque range of 0.1 mNm to 100 mNm and 10 ⁻⁴ s ⁻¹ to 1 s ^−1). Measured with a flow meter having a plate / plate geometry of 25 cm in diameter at the shear rate of Use according to claim 7, characterized in that the yield point of the edge sealant is at most 2000 Pa at 120 ° C. The method of claim 1, wherein the creation of the sandwich arrangement is 1. washing and drying the display screen and glass sheet; 2. Applying edge sealant onto the display screen front or glass sheet; 3. Placing the glass sheet on the front of the display screen; 4. Pressing the obtained composite consisting of the display screen and the glass sheet so that the gap between the display screen and the glass sheet is the desired gap; 5. filling with casting resin; 6. removing the air in the interspace and sealing the filling opening; 7. checking the space filled with the casting resin so that there is no air bubble; 8. curing the casting resin by emitting UV rays and 9. Use, characterized in that the final inspection of the finished sandwich arrangement.