CA1133372A - Polyvinyl butyral laminates with tetraethyleneglycol di-n-heptanoate plasticizer - Google Patents
Polyvinyl butyral laminates with tetraethyleneglycol di-n-heptanoate plasticizerInfo
- Publication number
- CA1133372A CA1133372A CA359,206A CA359206A CA1133372A CA 1133372 A CA1133372 A CA 1133372A CA 359206 A CA359206 A CA 359206A CA 1133372 A CA1133372 A CA 1133372A
- Authority
- CA
- Canada
- Prior art keywords
- polyvinyl butyral
- tetraethyleneglycol
- plasticizer
- heptanoate
- laminar structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
- B32B17/10816—Making laminated safety glass or glazing; Apparatus therefor by pressing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31627—Next to aldehyde or ketone condensation product
- Y10T428/3163—Next to acetal of polymerized unsaturated alcohol [e.g., formal butyral, etc.]
Abstract
ABSTRACT OF THE DISCLOSURE
Laminates of glass and polyvinyl butryral plasticized with tetraethyleneglycol di-n-heptanoate.
Laminates of glass and polyvinyl butryral plasticized with tetraethyleneglycol di-n-heptanoate.
Description
3L~33372 -TITLE
POLYVINYL BUTYRAL LAMINATES ~IT~
TETRAETHYLENEGLYCOL DI-N-~EPTANOATE PLASTICIZER
BACKGROUND OF THE INVEN?ION
Polyvinyl butyral is widely used in combination with one or more layers of glass to provide a composi~e which is r~sistant to shat~ering. The polyvinyl butyral typically contains a ~lasticizer to provide a balance of mec~anical 10 properties sati~factory for s~bsequent handling and performance requirements. It has been ~ound that while certain plasticizers perform satisfactorily in combination with polyvinyl butyral, high concentrations of the plasticizer are qenerally 15 necessary for satisfactory handling characteristics.
In addition, many known plasticizers are incompatible with polyvinyl butyral outside of limited ranges of hydroxy' cor.'ent.
SUMMARY OF THE INVENTION
The instant invention provides laminates of at least one layer of glass and a plastic layer adhering to the glass, wherein the plastic layer is polyvinyl ~utyral plasticized with tetraethyleneglycol di-n-heptanoate of the formula:
O O
C~3(C~2)5C-O(C~2 CH2o)4c(cH2)sc~3 BRIEF_DESCRIPTION OF THE FIGURE
- The ~iqure is a graphical representation o~
the compatability of the compositions used in the 30 present invention with polyvinyl butyral as compared with known plasticizers.
DETAILED DESGRIPTION OF T~E INVENTION
The present invention is based on the AD-5025~ discovery of a new composition, tetraethyleneglycol . ~
~;
~ :~133372 di-n-heptanoate, and its particular suitability as a piasticizer in polyvinyl butyral laminates. The composition has the following formula:
O O
.. " .
C~3~c~2)sc-o(cH2 C~2O)4C~CH2)5CH3 This composition can be prepared by bringing into contact tetraethyleneglxcol and heptanoic acid.
These compou~ds are believed to react according to the equation:
POLYVINYL BUTYRAL LAMINATES ~IT~
TETRAETHYLENEGLYCOL DI-N-~EPTANOATE PLASTICIZER
BACKGROUND OF THE INVEN?ION
Polyvinyl butyral is widely used in combination with one or more layers of glass to provide a composi~e which is r~sistant to shat~ering. The polyvinyl butyral typically contains a ~lasticizer to provide a balance of mec~anical 10 properties sati~factory for s~bsequent handling and performance requirements. It has been ~ound that while certain plasticizers perform satisfactorily in combination with polyvinyl butyral, high concentrations of the plasticizer are qenerally 15 necessary for satisfactory handling characteristics.
In addition, many known plasticizers are incompatible with polyvinyl butyral outside of limited ranges of hydroxy' cor.'ent.
SUMMARY OF THE INVENTION
The instant invention provides laminates of at least one layer of glass and a plastic layer adhering to the glass, wherein the plastic layer is polyvinyl ~utyral plasticized with tetraethyleneglycol di-n-heptanoate of the formula:
O O
C~3(C~2)5C-O(C~2 CH2o)4c(cH2)sc~3 BRIEF_DESCRIPTION OF THE FIGURE
- The ~iqure is a graphical representation o~
the compatability of the compositions used in the 30 present invention with polyvinyl butyral as compared with known plasticizers.
DETAILED DESGRIPTION OF T~E INVENTION
The present invention is based on the AD-5025~ discovery of a new composition, tetraethyleneglycol . ~
~;
~ :~133372 di-n-heptanoate, and its particular suitability as a piasticizer in polyvinyl butyral laminates. The composition has the following formula:
O O
.. " .
C~3~c~2)sc-o(cH2 C~2O)4C~CH2)5CH3 This composition can be prepared by bringing into contact tetraethyleneglxcol and heptanoic acid.
These compou~ds are believed to react according to the equation:
2(C~3tCH2]5CO2~) + HO(C~2CH2O)4H-O . O
C~3(c~2)5c-O(cH2cH2O)4ctcH2)5c~3 + 2~2O
While the desired product will generally be obtained in 15 all proportions of the reactants, for maximum purity of the desired tetraethyleneglycol di-n-heptanoate at least two moles of heptanoic acid should be present for each mole of tetraethyleneglycoi. ~igher concen-trations of the heptanoic acid, for example, up to 20 about 2.5 moles of heptanoic acid for each mole of tetraethyleneglycol, are preferred when no additional catalyst or solvent is used in the reaction.
The reaction of heptanoic acid and tetraethyleneglycol can be carried out without a 25 catalyst. ~owever, the rate and ease of reaction are facilitated by the presence of a catalyst. The catalyst can, and the most basic situation, be a minor excess of the heptanoic acid itself. Other catalysts which can be used include a variety of acids, includin~
30 sulfuric, formic, polyphosphor~c, or p-toluenesulfonic acid and combinations of such acids. The catalyst, when used, is generally present in an amount to equal to about from 0.01 to 5.0 weight per cent of the to~al reactants.
A solvent in addition to the reactants can be used in the preparation of the tetraethyleneglycol di-n-heptanoate if desired. The solvent should be inert to the reactants and should preferably form an azeotrope with tbe water that is formed in the course of the reaction. Particularly satisfactory and 5 convenient are organic solvents such as toluene, xylene, and benzene.
The preparation of the compound used in the present invention can be carried out at ambient temperatures and pressures. However, to facilitate 10 the reaction and for ease of removal of the water formed in the reaction, the synthesis is preferably carried out at elevated temperatures o~ about from 50 to 300 & . Particularly satisfactory is a temperature equivalent to the boiling point of an 15 azeotrope of water with either the heptanoic acid or solvent used in the reaction.
The water formed by the reaction of the two components is preferably removed during the course of the reaction to both increase the rate of reaction~
20 drive the reaction to completion and to monitor its progress ~y measurement of the quantity of water generated. The water is conveniently removed by distillation of the azeotrope of water and acid or ~olvent.
After completion of the reaction, the tetraethyleneglycol di-n-hep~anoate can be recovered as a viscous colorless oil. If desired, residual solvent, water, catalyst or other impurities can be removed by conventional purification techniques, 30 including filtration through anhydrous magnesium sulfate or charcoal or by vacuum distillation. The product as prepared frequently contains minor quantities, for example, up to 10 weight percent of various unreacted glycols such as ethylene, 35 diethylene, triethylene and tetraethylene glycols,
C~3(c~2)5c-O(cH2cH2O)4ctcH2)5c~3 + 2~2O
While the desired product will generally be obtained in 15 all proportions of the reactants, for maximum purity of the desired tetraethyleneglycol di-n-heptanoate at least two moles of heptanoic acid should be present for each mole of tetraethyleneglycoi. ~igher concen-trations of the heptanoic acid, for example, up to 20 about 2.5 moles of heptanoic acid for each mole of tetraethyleneglycol, are preferred when no additional catalyst or solvent is used in the reaction.
The reaction of heptanoic acid and tetraethyleneglycol can be carried out without a 25 catalyst. ~owever, the rate and ease of reaction are facilitated by the presence of a catalyst. The catalyst can, and the most basic situation, be a minor excess of the heptanoic acid itself. Other catalysts which can be used include a variety of acids, includin~
30 sulfuric, formic, polyphosphor~c, or p-toluenesulfonic acid and combinations of such acids. The catalyst, when used, is generally present in an amount to equal to about from 0.01 to 5.0 weight per cent of the to~al reactants.
A solvent in addition to the reactants can be used in the preparation of the tetraethyleneglycol di-n-heptanoate if desired. The solvent should be inert to the reactants and should preferably form an azeotrope with tbe water that is formed in the course of the reaction. Particularly satisfactory and 5 convenient are organic solvents such as toluene, xylene, and benzene.
The preparation of the compound used in the present invention can be carried out at ambient temperatures and pressures. However, to facilitate 10 the reaction and for ease of removal of the water formed in the reaction, the synthesis is preferably carried out at elevated temperatures o~ about from 50 to 300 & . Particularly satisfactory is a temperature equivalent to the boiling point of an 15 azeotrope of water with either the heptanoic acid or solvent used in the reaction.
The water formed by the reaction of the two components is preferably removed during the course of the reaction to both increase the rate of reaction~
20 drive the reaction to completion and to monitor its progress ~y measurement of the quantity of water generated. The water is conveniently removed by distillation of the azeotrope of water and acid or ~olvent.
After completion of the reaction, the tetraethyleneglycol di-n-hep~anoate can be recovered as a viscous colorless oil. If desired, residual solvent, water, catalyst or other impurities can be removed by conventional purification techniques, 30 including filtration through anhydrous magnesium sulfate or charcoal or by vacuum distillation. The product as prepared frequently contains minor quantities, for example, up to 10 weight percent of various unreacted glycols such as ethylene, 35 diethylene, triethylene and tetraethylene glycols,
- 3 -~33372 _ 4 _ unreacted Xeptanoic and alpha-methylhexanoic acids as well as the mono- and di- esters thereof.
The tetraethyleneglycol di-n-heptanoate (4G7) can be incorporated into polyvinyl butyral as a 5 plasticizer using technigues that are usually used for other plasticizers. The polyvinyl but~ral and diesters of this acid as well as plasticizer are present in quantities which result in a compatible admixture. The quantities of plasticizer which can 10 be added to any polyvinyl butyral vary according to the residual hydoxyl content of the polyvinyl butyral as illustrated in the Figure. Thus, in polyvinyl butyral having a residual hydroxyl content of 20 percent, as much as 49 parts by weight of 4G7 15 plasticizer can be added per each hundred parts of polyvinyl butyral. However, for polyvinyl butyral resins having 25 weight percent residual hydrox~l content, a maximum of only about 32 parts of 4G7 plasticizer can be added per hundred parts of 20 polyvinyl butyral resin. At or below these maximum quantlties or at intermediate points along the line ~ndicating maximum compatible plasticizer level, the quantity of plasticizer can be adjusted to achieve the desired level of polymer sheet characteristics.
The plasticized polyvinyl butyral sheeting can be laminated to one or more layers of glass according to the procedures generally used in the art and illustrated, for example, in U.S. Patents 2,293,656, 3,838~091 and 4,107,366.
The composition used in the instant invention provides outstanding plasticization of polyvinyl butyral and excellent performance in the glass laminates. It has been found that the composition is compatible with polyvinyl butyral over 3s a wide range of hydroxyl contents, and provides 1~3337Z
_ 5 _ sheeting with excellent dimensional stability, tensile strength and stiffness at plasticizer concentrations which are lower then those re~uired, fo~ example, using triethyleneglycol di-2-ethyl-5 butyrate (3GH). In addition, if desired, thesecompositions can ~e used in conjunction with triethyleneglycol di-2-ethylbutyrate. Although any proportion of the two plasticizers can be used, the beneficial effe~ts of the lnstant compositions are 10 most apparent in such mixtures when the tetraethyleneglycol di-n-heptanoate represents at least 10 weight percent of the blend of the two plasticizers.
The present invention is further illustrated 15 in the following specific examples, in which parts and percentages are by weight unless otherwise indicated. In these examples, the following-procedures and tes~s were used.
PVB Residual ~ydroxyl (Weight Percent as 20 PVA): ASTM D1396.
Pummel Adhesion: SAE J1208 Penetration Resistance: ANSI Z26.1 using a staircase method to determine mean break height instead of the one level test of Z26.1 as described 25 in U. S. Patent 3,718;516.
Edge Stability: ANSI Z26.1 with samples tested for four weeks instead of two.
Accelerated Edge Cloud/Edge Stability: Test laminates were prepared by placing 30-mil film 30 between two pieces of 12 x 12 x Q.l-inch ~30.5 x 30.5 x 0.25 cm) glass, and treating with the followin~
heat and pressure cycle: (1) 1 minute at 200C
then press between nip rolls, ~2) 3 minutes at 200C then press again between nip rolls, and ~3) 9 35 minutes at 135C and 225 psig (1.55MPa, gage) in an ~3337 oil autoclave. The laminate is immersed in commercial, ammoniacal alcohol glass cleaning solution at 60~C for 30 days. The laminate is then removed from the solution and the resulting edge 5 cloud is measured îmmediately. After standing at ambient conditions for an additional 30 days, the laminate is reexamined for edge delaminations.
Plasticizer Content by Vacuum ~istillation:
Molded or extruded sheeting samples are dried in an 10 oven at 60C for 30-60 minutes and weighed into a test tube. An accurately tared receiver is then attached. The tube is placed in a 285 +2C heating block and vacuum (13 Pa minimum) is applied. After 45 minutes, the receiver containing evolved 15 plasticizer is disconnected and weighed. The parts of plasticizer per hundred parts resin is calculated by multiplying the weight of collected plasticizer ~y 100 and dividing by the difference between the original sample weight minus the weight plasticizer.
EXA~PLE 1 & COMPARATIVE EXA~iPLES A & B
Tetraethyleneglycol di-n-heptanoate (4G7) ~as blended with polyvinyl butyral and the resulting blend formed into sheeting. The plasticized polyvinyl butyral sheeting was laminated between two 25 layers of glass as described above in the accelerated Edge Cloud/Edge Stability test~ The resulting samples were tested and the results summarized in the following Table.
In Comparative Examples A & B, the above 30 laminating and testing procedures were repeated, using commercially available polyvinyl butyral sheeting plasticized with triethyleneglycol di-2-ethylbutyrate ~3G~) and triethyleneglycol di-n-heptanoate (3G7).
l'hBI.E
__ Examples Y 1 ~ B
PVB Residual Hydroxyl, ~ 23.0 23.2 20.8 Plasticizer, phr 35.2 44.0 38.0 Alkalinity Titer, cc 167.1 130~0 192.0 1 Interlayer Thickness, 31.4 30.4 2~.8 -mils (mm) (0.80) (0.77) (0.76) Moisture, ~ 0.55 0.42 0.43 Penetration Resistance 20.0 1.7.3 ~8.3 (Mean Break Height), (6.10) (5.27) (5.58) - Ft (m) Pu~mel Adhesion 3 2 umidit~Test (4-week ?
Edge Cloud, 64th in (mm) 11 - 24 20 Edge Sta~iiity, let-goes ~4.4j (3.5) (7.~j Accelerated WINDEX* Test - 4 week Edge Cioud, 64th in ~mm) 30.5 46 --(12.1) 118.3) The laminates of tne present invention, using 25 polyvinyl ~utyral plasticized with 4G7, exhibit superior mechanical properties as well as edge cloud resistance.
* denotes trade mark ;
The tetraethyleneglycol di-n-heptanoate (4G7) can be incorporated into polyvinyl butyral as a 5 plasticizer using technigues that are usually used for other plasticizers. The polyvinyl but~ral and diesters of this acid as well as plasticizer are present in quantities which result in a compatible admixture. The quantities of plasticizer which can 10 be added to any polyvinyl butyral vary according to the residual hydoxyl content of the polyvinyl butyral as illustrated in the Figure. Thus, in polyvinyl butyral having a residual hydroxyl content of 20 percent, as much as 49 parts by weight of 4G7 15 plasticizer can be added per each hundred parts of polyvinyl butyral. However, for polyvinyl butyral resins having 25 weight percent residual hydrox~l content, a maximum of only about 32 parts of 4G7 plasticizer can be added per hundred parts of 20 polyvinyl butyral resin. At or below these maximum quantlties or at intermediate points along the line ~ndicating maximum compatible plasticizer level, the quantity of plasticizer can be adjusted to achieve the desired level of polymer sheet characteristics.
The plasticized polyvinyl butyral sheeting can be laminated to one or more layers of glass according to the procedures generally used in the art and illustrated, for example, in U.S. Patents 2,293,656, 3,838~091 and 4,107,366.
The composition used in the instant invention provides outstanding plasticization of polyvinyl butyral and excellent performance in the glass laminates. It has been found that the composition is compatible with polyvinyl butyral over 3s a wide range of hydroxyl contents, and provides 1~3337Z
_ 5 _ sheeting with excellent dimensional stability, tensile strength and stiffness at plasticizer concentrations which are lower then those re~uired, fo~ example, using triethyleneglycol di-2-ethyl-5 butyrate (3GH). In addition, if desired, thesecompositions can ~e used in conjunction with triethyleneglycol di-2-ethylbutyrate. Although any proportion of the two plasticizers can be used, the beneficial effe~ts of the lnstant compositions are 10 most apparent in such mixtures when the tetraethyleneglycol di-n-heptanoate represents at least 10 weight percent of the blend of the two plasticizers.
The present invention is further illustrated 15 in the following specific examples, in which parts and percentages are by weight unless otherwise indicated. In these examples, the following-procedures and tes~s were used.
PVB Residual ~ydroxyl (Weight Percent as 20 PVA): ASTM D1396.
Pummel Adhesion: SAE J1208 Penetration Resistance: ANSI Z26.1 using a staircase method to determine mean break height instead of the one level test of Z26.1 as described 25 in U. S. Patent 3,718;516.
Edge Stability: ANSI Z26.1 with samples tested for four weeks instead of two.
Accelerated Edge Cloud/Edge Stability: Test laminates were prepared by placing 30-mil film 30 between two pieces of 12 x 12 x Q.l-inch ~30.5 x 30.5 x 0.25 cm) glass, and treating with the followin~
heat and pressure cycle: (1) 1 minute at 200C
then press between nip rolls, ~2) 3 minutes at 200C then press again between nip rolls, and ~3) 9 35 minutes at 135C and 225 psig (1.55MPa, gage) in an ~3337 oil autoclave. The laminate is immersed in commercial, ammoniacal alcohol glass cleaning solution at 60~C for 30 days. The laminate is then removed from the solution and the resulting edge 5 cloud is measured îmmediately. After standing at ambient conditions for an additional 30 days, the laminate is reexamined for edge delaminations.
Plasticizer Content by Vacuum ~istillation:
Molded or extruded sheeting samples are dried in an 10 oven at 60C for 30-60 minutes and weighed into a test tube. An accurately tared receiver is then attached. The tube is placed in a 285 +2C heating block and vacuum (13 Pa minimum) is applied. After 45 minutes, the receiver containing evolved 15 plasticizer is disconnected and weighed. The parts of plasticizer per hundred parts resin is calculated by multiplying the weight of collected plasticizer ~y 100 and dividing by the difference between the original sample weight minus the weight plasticizer.
EXA~PLE 1 & COMPARATIVE EXA~iPLES A & B
Tetraethyleneglycol di-n-heptanoate (4G7) ~as blended with polyvinyl butyral and the resulting blend formed into sheeting. The plasticized polyvinyl butyral sheeting was laminated between two 25 layers of glass as described above in the accelerated Edge Cloud/Edge Stability test~ The resulting samples were tested and the results summarized in the following Table.
In Comparative Examples A & B, the above 30 laminating and testing procedures were repeated, using commercially available polyvinyl butyral sheeting plasticized with triethyleneglycol di-2-ethylbutyrate ~3G~) and triethyleneglycol di-n-heptanoate (3G7).
l'hBI.E
__ Examples Y 1 ~ B
PVB Residual Hydroxyl, ~ 23.0 23.2 20.8 Plasticizer, phr 35.2 44.0 38.0 Alkalinity Titer, cc 167.1 130~0 192.0 1 Interlayer Thickness, 31.4 30.4 2~.8 -mils (mm) (0.80) (0.77) (0.76) Moisture, ~ 0.55 0.42 0.43 Penetration Resistance 20.0 1.7.3 ~8.3 (Mean Break Height), (6.10) (5.27) (5.58) - Ft (m) Pu~mel Adhesion 3 2 umidit~Test (4-week ?
Edge Cloud, 64th in (mm) 11 - 24 20 Edge Sta~iiity, let-goes ~4.4j (3.5) (7.~j Accelerated WINDEX* Test - 4 week Edge Cioud, 64th in ~mm) 30.5 46 --(12.1) 118.3) The laminates of tne present invention, using 25 polyvinyl ~utyral plasticized with 4G7, exhibit superior mechanical properties as well as edge cloud resistance.
* denotes trade mark ;
Claims (7)
1. A laminar structure comprising at least one layer of glass and a layer of a plastic composition comprising polyvinyl butyral and, in compatible admixture therewith, a plasticizer comprising at least about 10 weight percent tetraethyleneglycol di-n=heptanoate of the formula:
.
.
2. A laminar structure of Claim 1 wherein the polyvinyl butyral has a hydroxyl content of about from 15 to 30 percent calculated as polyvinyl alcohol.
3. A laminar structure of Claim 2 wherein the polyvinyl butyral has a hydroxyl content of about from 20 to 25 weight percent, calculated as polyvinyl alcohol.
4. A laminar structure of Claim 1 wherein the plasticizer consists essentially of tetraethyleneglycol di-n-heptanoate in a quantity of about from 20 to 55 parts parts per hundred of polyvinyl butyral.
5. A laminar structure of Claim 4 wherein the tetraethyleneglycol di-n-heptanoate is present in a quantity of about 30 to 45 parts per hundred of polyvinyl butyral,
6. A laminar structure of Claim 1 wherein the plasticizer comprises a mixture of tetraethyleneglycol di-n-heptanoate and triethyleneglycol di-2-ethylbutyrate.
7. A laminar structure of Claim 1 comprising two layers of glass and one layer of the plastic composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/071,535 US4230771A (en) | 1979-08-31 | 1979-08-31 | Polyvinyl butyral laminates with tetraethyleneglycol di-n-heptanoate plasticizer |
| US071,535 | 1979-08-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1133372A true CA1133372A (en) | 1982-10-12 |
Family
ID=22101950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA359,206A Expired CA1133372A (en) | 1979-08-31 | 1980-08-28 | Polyvinyl butyral laminates with tetraethyleneglycol di-n-heptanoate plasticizer |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4230771A (en) |
| EP (1) | EP0024730B1 (en) |
| JP (1) | JPS5942629B2 (en) |
| BR (1) | BR8005352A (en) |
| CA (1) | CA1133372A (en) |
| DE (1) | DE3060809D1 (en) |
| MX (1) | MX156298A (en) |
| ZA (1) | ZA803841B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4293615A (en) * | 1980-05-30 | 1981-10-06 | E. I. Du Pont De Nemours And Company | Polyvinyl butyral laminates |
| US4292372A (en) * | 1980-06-02 | 1981-09-29 | E. I. Du Pont De Nemours And Company | Polyvinylbutyral sheeting |
| US4276351A (en) * | 1980-06-30 | 1981-06-30 | E. I. Du Pont De Nemours And Company | Polyvinyl butyral plasticized with tetraethyleneglycol di-2-ethylhexanoate |
| FR2495169B1 (en) * | 1980-12-02 | 1986-07-04 | Saint Gobain Vitrage | PLASTICIZER FOR POLYVINYLBUTYRAL, APPLICATION TO THE PRODUCTION OF INSERTS FOR SAFETY SHEET GLAZING AND PRODUCTS THUS OBTAINED |
| FR2522003A1 (en) * | 1982-02-23 | 1983-08-26 | Saint Gobain Vitrage | PROCESS FOR THE PREPARATION OF POLYVINYLBUTYRAL |
| DE3303111A1 (en) * | 1983-01-31 | 1984-08-02 | Hoechst Ag, 6230 Frankfurt | THERMOPLASTIC MOLDS FROM SOFTENER-CONTAINING POLYVINYLBUTYRAL |
| US4705736A (en) * | 1985-12-05 | 1987-11-10 | Minnesota Mining And Manufacturing Company | Thermal diazo composition |
| EP0815166B1 (en) * | 1995-03-14 | 2000-07-12 | E.I. Du Pont De Nemours And Company | Process for preparing polyvinylbutyral sheet |
| US6451435B1 (en) * | 1997-12-19 | 2002-09-17 | E. I. Du Pont De Nemours & Co. | Interlayer structure for laminated glass |
| EP1759832A1 (en) | 1998-05-14 | 2007-03-07 | E.I.Du pont de nemours and company | Glass laminates for threat resistant window systems |
| US6383647B1 (en) | 1998-09-30 | 2002-05-07 | Sekisui Chemical Co., Ltd. | Intermediate film for laminated glass and laminated glass |
| CA2484231A1 (en) * | 2002-05-16 | 2003-11-27 | E.I. Du Pont De Nemours And Company | Laminated structures with superior impact resistance and process for making same |
| CN1708398A (en) * | 2002-10-29 | 2005-12-14 | 纳幕尔杜邦公司 | Polyvinylbutyral interlayers having superior acoustical properties and method of preparing same |
| JP5317696B2 (en) * | 2006-05-31 | 2013-10-16 | 積水化学工業株式会社 | Laminated glass interlayer film and laminated glass |
| US8197928B2 (en) | 2006-12-29 | 2012-06-12 | E. I. Du Pont De Nemours And Company | Intrusion resistant safety glazings and solar cell modules |
| US20080268270A1 (en) | 2007-04-30 | 2008-10-30 | Wenjie Chen | High impact polymer interlayers |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2045130A (en) * | 1936-02-25 | 1936-06-23 | Pittsburgh Plate Glass Co | Safety glass |
| US2120927A (en) * | 1936-07-01 | 1938-06-14 | Carbide & Carbon Chem Corp | Plastic composition |
| US2274672A (en) * | 1938-04-30 | 1942-03-03 | Pittsburgh Plate Glass Co | Safety glass |
| US2202160A (en) * | 1939-07-13 | 1940-05-28 | Du Pont | Plastic composition for use in interlayer sheets |
| US2412469A (en) * | 1943-11-16 | 1946-12-10 | Kay Fries Chemicals Inc | Triethylene glycol diheptoate |
| US3178334A (en) * | 1961-09-14 | 1965-04-13 | Du Pont | Safety-glass laminate |
| US3296211A (en) * | 1961-11-01 | 1967-01-03 | Aerojet General Co | Hydroxy-terminated polyesters |
| US3361565A (en) * | 1964-01-21 | 1968-01-02 | Du Pont | Silver halide photographic element containing a polyanionic color former and a gelatin antiabrasion layer |
| US3384532A (en) * | 1965-04-21 | 1968-05-21 | Monsanto Co | Plasticized polyvinyl acetals containing admixtures of three different esters |
| US3525703A (en) * | 1966-08-22 | 1970-08-25 | Bridgestone Tire Co Ltd | Method of adhering a synthetic fibre to a rubber,an adhesive solution and a laminate obtained by improving a method of adhering a synthetic fibre to a rubber |
| US3578621A (en) * | 1968-08-27 | 1971-05-11 | Carlisle Chemical Works | Diesters exhibiting internal-external lubricating properties in structural resins |
| US3841955A (en) * | 1972-12-07 | 1974-10-15 | Monsanto Co | Plasticized polyvinyl butyral interlayers |
| JPS51134123A (en) * | 1975-05-15 | 1976-11-20 | Fuji Photo Film Co Ltd | Photosensitive compositions for image formation |
-
1979
- 1979-08-31 US US06/071,535 patent/US4230771A/en not_active Expired - Lifetime
-
1980
- 1980-06-26 ZA ZA00803841A patent/ZA803841B/en unknown
- 1980-08-25 BR BR8005352A patent/BR8005352A/en not_active IP Right Cessation
- 1980-08-28 DE DE8080105119T patent/DE3060809D1/en not_active Expired
- 1980-08-28 CA CA359,206A patent/CA1133372A/en not_active Expired
- 1980-08-28 EP EP19800105119 patent/EP0024730B1/en not_active Expired
- 1980-08-29 JP JP55118567A patent/JPS5942629B2/en not_active Expired
- 1980-08-29 MX MX183745A patent/MX156298A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5942629B2 (en) | 1984-10-16 |
| US4230771A (en) | 1980-10-28 |
| MX156298A (en) | 1988-08-09 |
| BR8005352A (en) | 1981-03-10 |
| EP0024730A3 (en) | 1981-03-18 |
| ZA803841B (en) | 1982-01-27 |
| JPS5637154A (en) | 1981-04-10 |
| EP0024730A2 (en) | 1981-03-11 |
| DE3060809D1 (en) | 1982-10-28 |
| EP0024730B1 (en) | 1982-09-01 |
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