Patent Application
20220098453
The present invention relates to a hot melt single-component sealant composition. The present invention further relates to the use of said sealant composition as a primary sealant in insulating glass (IG) structures, such as windows or doors. Finally, the invention relates to an insulated glass structure or unit, comprising, as a primary sealant, a sealant composition according to the invention.
Hot melt, single-component, sealant compositions are currently used in the Insulating Glass (IG) sealant market for the manufacture of IG units.
Insulating glass (IG) units are used in a wide variety of applications, such as skylights, high temperature environment viewing windows, architectural windows, fridge doors, just to name a few. IG units are typically utilized to reduce heat transfer, for instance between the inside and outside of a building.
A typical IG unit is formed by two glass sheets (or glass panes) separated near their edges by a spacer with a substantially rectangular cross-section, in order to provide a chamber between the two glass sheets. This chamber is typically filled with a selected insulating atmosphere, such as argon, to enhance the insulating characteristics of the IG unit.
A sealant system is used to bond the two glass sheets to the spacer. The sealant system is expected to provide sufficient structural strength to maintain the unity of the IG unit and also to provide sufficient protection against the insulating atmosphere leaking out of the chamber and/or moisture vapor in the ambient atmosphere outside the IG unit from being transmitted into the chamber. Prevention of outside ambient atmosphere from being transmitted into the chamber is important to avoid the risk of water condensation inside the unit, on the inner surface of the glass pane, which would be detrimental both to the transparency of the IG unit and to its insulation efficiency.
The strength and performance of the IG unit depend heavily upon the sealant system and type of sealant used to secure the glass sheets to the spacer. The majority of sealants currently in use may be divided generally into two major types:
Edge sealants form a bond between the glass sheet and the spacer and promote the structural integrity of the IG unit. Examples of edge sealants include butyl rubber and thermoset materials, such as polysulfides, polyurethanes, and silicone. These materials have appropriate mechanical properties, in particular a relatively high “modulus” with respect to their stress/strain relationship.
However, these edge sealants generally provide poor MVTR characteristics, and also provide relatively high gas transmission rates. As a result, IG units made only with conventional edge sealants do not generally provide commercially acceptable MVTR characteristics or gas retention properties.
On the other hand, low MVTR sealants, which do not adhere as efficiently to the glass sheets and/or the spacer, provide improved MVTR characteristics and improved gas barrier capabilities compared to edge sealants, but provide little or no structural integrity. Examples of low MVTR sealants include thermoplastic materials, such as hot-melt materials, in particular polyisobutylene (abbreviated hereafter as PIB) based compositions.
To compensate the relative advantages and drawbacks of edge sealants and low MVTR sealants, many sealant systems used in IG units are a “dual-seal” system having two separate or distinct sealant regions:
The use of hot melt single-component sealant compositions is appreciated by the IG units manufacturers with respect to other technologies based (for instance) on two-component chemically-cured sealant, because of their lack of curing mechanism and ease of application. Indeed, mixing of two-components is not required, staging areas are not required either as in slow cure two-component sealant compositions, and window units can be handled and moved immediately after manufacture.
During the manufacturing of the IG units, hot-melt sealants are generally applied by extrusion to the surface of the panes of glass and/or of the spacer, by means of hot melt pumps and linear extruders at a temperature from 140 to 250° C., preferably at a temperature of from 170 to 200° C., and more preferably at a temperature from 180 to 195° C., for instance by using any suitable applicator including a hand held glue gun, an extruder, a linear extruder or an automated application equipment.
Further, because hot-melt single-component sealant compositions are non-curing and of thermoplastic nature, the adhesive joint which results from their application to the relevant substrate, may have a problem of heat resistance, in particular to the high temperatures (for instance, up to 75° C.) which may apply during transport and storage of the final IG units. There is the risk, for instance, that under such a temperature, a primary sealant consisting of a hot-melt, for instance of a PIB based composition, may, when exposed to heat, flow and/or deform excessively within the cavity between the 2 transparent glass panes. This of course would be detrimental both with respect to the esthetics of the IG unit, and to the barrier effect of the primary sealant towards gas and moisture vapor.
The hot-melt single component PIB based sealant compositions which are likely to be used as primary sealant and which are available commercially comprise an inorganic filler which is generally selected from a plurality of materials such as chalks, natural or ground or precipitated calcium carbonate, calcium magnesium carbonates, silicates, talc, and carbon black. The content in said inorganic filler may go from 10 to 60 weight %, and preferably from 15 to 40 weight %, based on the total weight of the sealant.
Owing, in particular, to this inorganic filler, such a hot melt single component PM based sealant composition is opaque.
Now, as a means of enriching the solutions which may be offered to the IG unit manufacturers, it is an aim of the present invention to propose a hot-melt single component PIB based sealant composition, and its use as a primary sealant, which is transparent while ensuring a proper application performance and resulting in a final IG unit with acceptable heat resistance.
The need for such a transparent sealant derives from the need for obtaining a fully transparent IG unit, in which the spacer bar also consists of a transparent material like glass or a polymer such as PolyMethylMethAcrylate (PMMA) or polycarbonate.
Another aim of the present invention is to propose a transparent hot melt single component sealant composition which provides good application performance by an equipment operating at a temperature from 140 to 250° C., preferably from 170 to 200° C., and more preferably from 180 to 195° C., in particular through an extrusion equipment.
Another aim of the present invention is to propose a transparent hot-melt single component sealant composition which provides, once implemented in an IG unit, an adhesive joint with an improved heat resistance.
Another aim of the present invention is to propose a transparent hot-melt single component sealant composition with good gas and moisture properties, including good MVTR properties.
It has now been found that the above aims can be achieved in all or in part by means of the hot-melt single component sealant composition which is the subject matter of the present invention.
According to a first object of the invention, the present application relates to a hot-melt single component sealant composition, characterized in that it comprises from 70% to 99 weight % of polyisobutylene, preferably from 73% to 99%, based on the total weight of the composition.
Surprisingly, it has been found that said sealant composition is well suited as a primary sealant in IG units, and as the same time may result in a transparent sealant likely to be implemented in a transparent IG unit.
Indeed, it possesses a low MVTR, and more precisely a MVTR less than 0.1 g/m2. MVTR was determined according to ASTM E96-90, the test being conducted at 23° C. and 92% relative humidity on a sealant film having a thickness of 2 mm.
Further, the sealant composition according to the invention is, due to its flow properties, also well adapted to its application by extrusion to the surface of the panes of glass and/or of the spacer, by means of a conventional application equipment. Such adaptability is assessed by a value of the Melt Flow Index (MFI) greater than 10 g/10 minute, preferably laying in the range from 10 to 70 g/10 minute. MFI is determined according to ASTM D1238 AT 190° C. and for a weight of 2.16 kg.
At last, the sealant composition according to the invention advantageously also has a heat resistance which is at least as satisfying and even improved, with respect to known PIB based sealant compositions comprising an inorganic filler. Heat resistance is assessed by measurement of the softening point, also called Ring & Ball method according to ASTM D-36, using silicone oil as medium. The softening point of the present sealant composition is greater than 90° C., and preferably between 100° C. and 150° C.
The content of PIB, as well as of any possible other ingredient, in the sealant composition according to the invention is given in percentage by weight and is expressed relatively to the total weight of the hot melt sealant composition according to the invention.
PM is widely commercially available, in particular from BASF under such various grades as OPPANOL® B15N, OPPANOL® B12, OPPANOL® B12N, OPPANOL® N50 or GLISSOPAL® V1500 or GLISSOPAL® V640.
Preferably, the composition according to the invention comprises several grades of PIB with different molecular weights.
According to an embodiment, the PM based sealant composition of the present invention further comprises a thermoplastic polymer selected among polyalkylenes (e.g. polyethylene, polypropylene and polybutylene), poly-alpha-olefin polymer including, e.g. homo-, co- and terpolymers of aliphatic mono-1-olefins (alpha olefins) (e.g. C2 to C10 poly(alpha)olefins), homogeneous linear or substantially linear interpolymers of ethylene having at least one C3 to C20 alphaolefin, poly(alkylene oxides), poly(phenylenediamine terephthalamide), polyesters (e.g. polyethylene terephthalate), polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitriles, copolymers of acrylonitrile and monomers including, e.g. butadiene, styrene, polymethyl pentene, and polyphenylene sulfide (e.g. styrene-acrylonitrile, acrylonitrile-butadiene-styrene, acrylonitrile-styrene-butadiene rubbers), polyimides, polyamides, copolymers of vinyl alcohol and ethylenically unsaturated monomers, polyvinyl acetate (e.g. ethylene vinyl acetate), polyvinyl alcohol, vinyl chloride homopolymers and copolymers (e.g. polyvinyl chloride), terpolymers of ethylene, carbon monoxide and acrylic acid ester or vinyl monomer, polysiloxanes, polyurethanes, polystyrene, and combinations thereof, and homopolymers, copolymers and terpolymers thereof, and mixtures thereof. Other useful classes of thermoplastic polymers include asphalts, bitumens, crude rubbers, fluorinated rubbers, and cellulosic resins.
According to a preferred embodiment, the thermoplastic polymer is selected among amorphous poly-alpha-olefin polymer, and preferably a propylene-based polymer selected from homopolymers of propylene or copolymers of propylene with one or more C2 to C10 alpha-olefins comonomers, copolymer of ethylene and vinyl acetate, copolymer of ethylene and ethyl acrylate, copolymer of ethylene and acrylic acid, polyethylene, polypropylene, polyamide, styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers, and mixtures thereof.
According to a more preferred embodiment, the thermoplastic polymer is a copolymer of ethylene and vinyl acetate. Use can be made, as an example, of commercial grades EVATANE® 28-420 and EVATANE® 28-25 which can be obtained from Arkema.
The sealant composition according to the invention may advantageously comprise from 0.5 to 10 weight %, and preferably from 1 to 5%, of the thermoplastic polymer, based on the total weight of the sealant composition.
According to another embodiment, the PM based sealant composition of the present invention further comprises a transparent tackifying resin selected among the following classes:
(a) natural and modified rosins such as, for example, gum rosins, wood rosins, tall-oil rosins, distilled rosins, hydrogenated rosins, dimerized rosins and polymerized rosins;
(b) glycerol and pentaerythritol esters of natural and modified rosins, such as, for example, the glycerol esters of pale wood rosin, the glycerol esters of hydrogenated rosin, the glycerol esters of polymerized rosin, the pentaerythritol esters of pale wood rosin, the pentaerythritol esters of hydrogenated rosin, the pentaerythritol esters of tall oil rosin and the phenolic modified pentaerythritol esters of rosin;
(c) polyterpene resins including hydrogenated polyterpene resins having a Ring and Ball softening point of from about 20° C. to 140° C., the latter polyterpene resins generally resulting from the polymerization of terpene hydrocarbons, such as the monoterpene known as pinene, in the presence of Friedel-Crafts catalysts at moderately low temperatures;
(d) phenolic-modified terpene resins such as, for example, those resulting from the condensation, in an acidic medium, of a terpene and a phenol;
(e) aliphatic (including cycloaliphatic) petroleum hydrocarbon resins (C5) having a Ring and Ball softening point of from about 60° C. to 140° C., said resins resulting from the polymerization of C5-hydrocarbon monomers; and the corresponding hydrogenated derivatives resulting from a subsequent total or partial hydrogenation thereof;
(f) aromatic petroleum hydrocarbons resins (C9) having Ring and Ball softening point of from about 60° C. to 140° C., said resins resulting from the polymerization of C9-hydrocarbon monomers; and the corresponding hydrogenated derivatives resulting from a subsequent total or partial hydrogenation thereof;
(g) aliphatic (including cycloaliphatic) and/or aromatic petroleum resins (C5/C9) having a Ring and Ball softening point of from about 60° C. to 140° C., said resins resulting from the polymerization of C5/C9-hydrocarbon monomers; and the corresponding hydrogenated derivatives resulting from a subsequent total or partial hydrogenation thereof.
According to a preferred embodiment, the tackifying resin belongs to classes (e) or (g).
According to another preferred embodiment, the tackifying resin does not comprise carbon-carbon double bond. In this latter case, the saturated tackifying resin(s) may be prepared by full hydrogenation of the insaturated tackifying resin(s).
According to another preferred embodiment, the tackifying resin possesses a softening point greater that 90° C., preferably between 100° C. and 140° C.
Tackifying resins are easily available commercially. As an example one may cite SUKOREZ® SU-525 from KOLON, which is a hydrogenated cycloaliphatic resin with a R&B of about 125° C. which results from the polymerization of C5-hydrocarbon monomers.
The tackifying resin is preferably present in the sealant composition according to the present invention in an amount of from 5 to 50 weight %, and preferably from 10 to 35 weight %, based on the total weight of the sealant composition.
According to an embodiment, the PM based sealant composition of the present invention further comprises an antioxidant stabilizer to protect the sealant composition according to the present invention from degradation induced by heat, light, UV radiations, during processing and storage. Several types of antioxidants can be used, either primary antioxidants like hindered phenols or secondary antioxidants like phosphite derivatives or blends thereof. Among commercial products, use can be made of Irganox® 1010 from BASF and Topanol® 0 from VERTELLUS.
The antioxidant stabilizer is preferably present in an amount of from 0.05 to 3 weight %, preferably from 0.1 to 1%, based on the total weight of the sealant composition.
The sealant composition according to the invention may also include an adhesion promoter selected among an epoxy-based silane and an amino-based silane, in an amount of from 0.1 to 2 weight %, preferably from 0.1 to 1%, based on the total weight of the sealant composition. Among the possible commercial adhesion promoters, one can cite Silquest® A187 from Momentive.
The sealant composition according to the invention may at last include minor amounts of other additives such as UV absorbers, waxes, lubricants, catalysts, rheology modifiers, biocides, corrosion inhibitors, dehydrators, surfactants, nucleating agents, flame retardants, and combinations thereof. A typical range of such minor amounts is between 0.1 and 2 weight %.
According to a particularly preferred embodiment, the sealant composition according to the invention comprises, and preferably consists essentially of:
According to another particularly preferred embodiment, the sealant composition according to the invention comprises, and preferably consists essentially of:
The method for preparing a sealant composition according to the invention comprises:
The mixture is maintained under vacuum during 1 to 2 hours, at the same temperature, until the ingredients are melted and uniformly blended.
According to a second object of the invention, the present application relates to the use of the hot-melt single component sealant composition according to the invention as a primary sealant (or gasket) in a manufacturing process of IG units, such as windows or doors.
IG units are formed by two glass sheets (or glass panes) separated near their edges by a spacer with a substantially rectangular cross-section, in order to provide a chamber between the two glass sheets. This chamber is typically filled with a selected insulating atmosphere, such as argon, to enhance the insulating characteristics of the IG unit. The primary sealant is located essentially between each side region of the spacer and the corresponding inner surface of both glass sheets.
According to a third object of the invention, the present application relates to an Insulating Glass unit (1) comprising:
characterized in that the primary sealant (51) is composed of the hot-melt single component sealant composition according to the invention.
In reference to
The inner surface (21) of the first pane (11) faces the inner surface (22) of the second pane (12), and the inner surfaces (21) and (22) are spaced apart by a spacer (3) which is attached, ie adhesively bonded, to the two panes (11) and (12) by a sealant system (5).
The spacer (3) may be any of the type used in the IG unit art, such as a conventional rigid spacer, with an essentially rectangular cross-section. In the illustrative embodiment shown in
The two panes (11) and (12) and the spacer (3) define a chamber (4) or “dead space” between the two panes (11) and (12). The chamber (4) can be filled with an insulating atmosphere, such as air or argon or krypton gas.
Preferably, the spacer (3) comprised in the IG unit according to the invention has a substantially rectangular cross-section.
The sealant composition according to the invention is used in a dual seal system (5) having two separate or distinct regions: an outer or secondary sealant (52) and an inner or primary sealant (51), wherein the sealant composition according to the invention is used to form the primary sealant (51).
The primary sealant (51) is located mainly in the side regions of the spacer (3), namely the majority of the sealant is located between the outer surfaces (42), (43) of each side (32), (33) and the inner surfaces (21), (22) of the respective adjacent panes (11), (12).
The secondary sealant (52) preferably extends across the width of the outside of the spacer (3) (outer region), e.g. extends across the perimeter groove formed by the outer surface of the base (31) of the spacer (3) and the outer marginal edges of the inner surfaces (21) and (22) of the panes (11) and (12).
The sealants (51), (52) may be of any suitable dimensions to adhere the panes (11), (12) to the spacer (3).
According to a preferred embodiment, the secondary sealant (52) is a conventional edge sealant, such as a conventional thermoset sealant material. For example, the secondary sealant (52) can comprise one or more conventional silicone, polyurethane, polysulfide or butyl rubber based edge sealant materials as are known in the art.
The sealant composition according to the invention may be applied, as a primary sealant, to the surface of the panes of glass by hot melt pumps and linear extruders at a temperature from 140 to 250° C., preferably at a temperature of from 170 to 200° C., and more preferably at a temperature from 180 to 195° C., for instance by using any suitable applicator including a hand held glue gun, extruder, linear extruder, other forms of extruder beads, automated application equipment, and combinations thereof.
The following examples are given purely by way of illustration of the invention and should not, under any circumstances, be interpreted as limiting the scope thereof.
The test procedures used in the examples are the following:
Moisture Vapor Transmission Rate (MVTR):
The MVTR was determined according to ASTM E96-90. The test was conducted at 23° C. and 92% relative humidity on a sealant film having a thickness of 2 mm. Said film was sealed to the open mouth of a test dish containing a desiccant. The assembly was placed in the controlled atmosphere. Periodic weighings determined the rate of moisture vapour movement through the sealant film into the desiccant.
Melt Flow Index (MFI):
The MFI was determined according to ASTM D1238. The MFI is the weight of composition (placed beforehand in a vertical cylinder) which flows in 10 minutes through a die having a fixed diameter, under the effect of a pressure exerted by a loaded piston having a total weight of 2.16 kg.
Softening Point:
The softening point is determined by the Ring & Ball method according to ASTM D-36, using silicone oil as a medium, the principle of which is as follows. A brass ring about 2 cm in diameter is filled with the resin to be tested in the melt state. After cooling to room temperature, the ring and the solid resin are placed horizontally in a thermostatted glycerol bath, the temperature of which may vary by 5° C. per minute. A steel ball about 9.5 mm in diameter is centered on the solid resin disk. The softening temperature is, during the rise in temperature of the bath at a rate of 5° C. per minute, the temperature at which the resin disk flows by an amount of 25.4 mm under the weight of the ball.
The raw materials used in the examples are listed in Table 1:
The composition of example A in Table 1 is prepared as follows.
A part of PIB and antioxidant stabilizer are added in a mixing device, and are heated to a temperature comprised between 100° C. and 160° C. Then carbon black is added to the mixing device, the content of which is mixed under vacuum until the mixture is uniform before adding the remaining PIB, ground calcium carbonate and wax.
The mixture is maintained under vacuum during a period of time from about 30 min to 1 h, at the same temperature, until the ingredients are melted and uniformly blended.
This composition is opaque.
It is tested according to the Melt Flow Index, softening point and MVTR tests, as described above.
The results are given in Table 1.
The composition of examples 1-3 in Table 1 are prepared as pointed out above.
They are found to be transparent.
They are tested according to the Melt Flow Index, softening point and MVTR tests, as described above.
The results are given in Table 1.
The values obtained for the softening point correspond to a significantly improved heat resistance with respect to example A.
| Number | Date | Country | Kind |
|---|---|---|---|
| 19154826.2 | Jan 2019 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/052055 | 1/28/2020 | WO | 00 |
