CA1266740A - Process for the production of light resistant polyvinyl butyral foils - Google Patents
Process for the production of light resistant polyvinyl butyral foilsInfo
- Publication number
- CA1266740A CA1266740A CA000470549A CA470549A CA1266740A CA 1266740 A CA1266740 A CA 1266740A CA 000470549 A CA000470549 A CA 000470549A CA 470549 A CA470549 A CA 470549A CA 1266740 A CA1266740 A CA 1266740A
- Authority
- CA
- Canada
- Prior art keywords
- hydroxy
- absorber
- laminated glass
- tert
- benzotriazole
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
It is proposed to add to laminated safety glasses with intermediate layers of polyvinyl butyral foils with contents of phenolic stabilisers and contents of phosphorous acid triesters or phosphonous acid diesters, additional UV
absorbers for the removal of yellowing over a longer period of use.
It is proposed to add to laminated safety glasses with intermediate layers of polyvinyl butyral foils with contents of phenolic stabilisers and contents of phosphorous acid triesters or phosphonous acid diesters, additional UV
absorbers for the removal of yellowing over a longer period of use.
Description
;;79L~
The present invention relates to a process for the production of light resistant polyvinyl butyral foils.
More particularly,-the present invention relates to plasticiser-containing foils of partially acetalised polyvinyl alcohols which are used as bonding foils in laminated safety glasses. Most particularly, the invention relates to the production of new polyvinylbutyral foils and to the use of these foils for the production oE laminated safety glasses.
]0Laminated safe~y glasses consist in general of two silicate glass panes and an adhesive foil connecting the ; glass panes. Optionally, one of the silicate glass panes can be replaced by a plastics pane. Such laminated safety panes are employed chiefly as windscreens in vehicles; they can however also be employed in the building industry when, according to their use, even more than two silicate or plastics panes are connected by adhesive foils. Such multiple laminates serve Eor example as laminated armoured glasses. The laminated safety glasses are produced by compressing the Eoils and the glass panes at 5 to 20 ~p/cm and 125 to 155 C in a press or, particularly preferably, in an au-toclave.
Plasticised partially acetalised polyvinyl alcohol foils serve chiefly as adhesive foils in composite glasses.
The partially acetalised polyvinyl alcohols necessary for their production are produced by saponification of polyvinyl acetate and subsequent acetalisation with aliphatic aldehydes with 3 to 10 C-atoms such as, especially, formaldehyde, acetaldehyde, butyraldehyde. The saponification is, in general, not carried out completely so that the polyvinyl alcohols generally still contain 0.5 to 5 weight ~ acetyl groups, --,, 1 calculated as vinylacetate groups. ~ven theacetalisation is in gen~ral not completely carried out so thak the partially acetalised polyvinyl a7cohol e~ployed ~or the production of the foils generally still contain 5 free O~-groups, with the partially butyralised polyvinyl alcohol (in the following, denoted by PVB), this OH
content can amount to between 10 and 27 weight calculated as vinyl alcohol. Unless otherwise ind~cated the ter~
partialIy acetali ~ polyvinyl alcohol(s) in ~he following is 10 used both for partially acetalised as well as also for partially butyralised polyvinyl alcoh~1.
In the production of laminated safety glasses, these partially acetalised polyvinyl alcohols are employed as foils with a definite plasticiser content.
15 The type and amount of the plasticiser employed influence the properties of the laminated safety glass. In practice, it has therefore become clear that an especially splinter proof laminated safety glass should have as intermediate foil a PVB foil which possesses a 20 plasticiser content of 15 to 40 weight 4, preferably 25 to 31% and whose content of free O~ groups amounts to 10 to 25 weight ~, preferably 16 to 23 weight ~, related to plasticiser-free PVB resin. The moisture content of such a PVB f oil should lie between 0.2 and 0.9 weight ~.
The invention relates especially to foils of plasticised partially acetalised polyvinyl alcohols with good oxidation and temperature resistance and outstanding light resistance. Plasticiser-containing polyvinyl-butyral is exposed under the conditions for its working 30 to foils and the sub~e~uent working to laminated glass to high temperatures which lead to a certain extent to yellowing. The optical properties are in this way especially deteriorated.
It is known that, to use phenolic compounds, such 35 as 2,6-di-tert.-butyl-p-cresol, 2,4,6-trimethylphenol, octylphenol, bornyl-xylenol etc. to stabilise the material ~German Patent Specification 2 208 167).It is 4~
1 further known that phosphorous -acid triesters such as trilaurylphosphite, decylphenyl-phosphite etc. are used for avoidance of yellowing (German Patent Specification 2 ~0~ 167~.
In contrast to soft PVC formulations, in which the initial colour, transparence and light stability is improved by employment of phosphorous acid triesters as co-stabilisers, it has however been shown that phosphorous acid triester-containing PVB foils lose their 1~ original bright colour after longer periods in the light and become yellow to an extent which cannot be dealt with. In particular, with the water clear safety glass ; foils required, most recently by users, the task of the present invention has been to find a way to improve the 15 long ter~l light stability and to prevent, in the course of time, increasing yellowing.
Yellowing by exposure to light for a long time was observed with use of a series of phosphorous acid triesters or phosphonous acid diesters such as, for 20 example decyl-diphenyl-phosphite, trilauryl phosphite, didecyl-phenyl-phosphite, tris-nonylphenylphosphi~e, triphenylphosphite, trist2,4-di-tert.butylphenyl) phosphite, di-~isodecyl)-pentaerythrityl-diphosphite, di-stearylpentaerythrityl-diphosphite, tetrakis-(2r4-di-tert.-butylphenyl)-4~4l-biphenylylenedi-phosphonite.
There therefore existed the object of stabilising the polyvinylbutyral foils, that is PVB ~oils in laminated safety glass with contents of the indicated 30 phenollc compounds and sta~ilisers based on phosphorous acid triesters and/or phosphonous acid diesters by additional measures against the influence of daylight, specifically, or periods of use of laminated safety glass panes with PVB foils contained therein over years, 35 to achieve a protection against ageing with prominent long term effect against yellowing.
Surprisingly, it has now been found that a long 3L~6~4~3 term efEect against yellowing of phosphite-containing foil formulations is achieved by -the addition of selected UV-absorbers and the yellowing achieved by the necessaryaddition of phosphite or phosphonite, even with longer action of light, is prevented.
` An object of -the invention is therefore to provide a process for the production of a foil of phenolically stabilised, plasticised, partially acetalised polyvinyl alcohols of superior oxidation-, temperature- and light-stability, by using, in addition to phosphorous acid triesters or phosphonous acid diester~s, further selected UV-absorbers.
A further object of the inven-tion is to use such a foil as a component of laminated glass.
In meeting these objects, -the invention provides laminated glass having as a component a foil, having superior resisance to oxidation, heat and light, comprising phenolically stabilized, plas-ticized, partly acetalated polyvinyl alcohols containing phosphorous-acid triesters and phosphonous-acid diesters and at least one UV-absorber having a long-term action, selected from the group consisting of:
a) derivative of benzo-triazole b) deriva-tives of acrylonitrile or cinnamonitrile c) hydroxybenzophenones and their mixtures.
The invention also provides certain foils used in the above laminates.
The UV-absorbers are added as protection against aging and have pronounced long-term action agains-t -the yellowing resulting from exposure to daylight.
Surprisingly, the UV-absorbers used in the method of this invention achieve the re~uired protection against aginy and the long term effect against yellowing in ~i6'~0 fulfilment of -the above objec-ts. Other groups of the usual UV absorbers, ln contrast fail to work.
For example, the phenyl salicylates and derivatives thereof known as UV-absorbers, such as phenyl salicylate, 4--tert.butylphenyl salicylate or 4-octylphenyl salicylate, and the sterically hindered amines likewise acting as liyht protective agents, such as for example sebacic acid-bis-2,2,6,6--tetramethyl-4-piperidyl ester, do not yield the indicated long-term effec-t and show too high E
1~ or YI values in the long term -test.
According to the inven-tion, suitable UV-absorbers in the previously noted classes of material are:
1. Derivatives of benzotriazole, especially hydroxyphenyl-benzotriazole, such as:
i - 4a -674~
1 2-(2'-hydroxy~5l-methylphenyl)-benzotria~ole~
The present invention relates to a process for the production of light resistant polyvinyl butyral foils.
More particularly,-the present invention relates to plasticiser-containing foils of partially acetalised polyvinyl alcohols which are used as bonding foils in laminated safety glasses. Most particularly, the invention relates to the production of new polyvinylbutyral foils and to the use of these foils for the production oE laminated safety glasses.
]0Laminated safe~y glasses consist in general of two silicate glass panes and an adhesive foil connecting the ; glass panes. Optionally, one of the silicate glass panes can be replaced by a plastics pane. Such laminated safety panes are employed chiefly as windscreens in vehicles; they can however also be employed in the building industry when, according to their use, even more than two silicate or plastics panes are connected by adhesive foils. Such multiple laminates serve Eor example as laminated armoured glasses. The laminated safety glasses are produced by compressing the Eoils and the glass panes at 5 to 20 ~p/cm and 125 to 155 C in a press or, particularly preferably, in an au-toclave.
Plasticised partially acetalised polyvinyl alcohol foils serve chiefly as adhesive foils in composite glasses.
The partially acetalised polyvinyl alcohols necessary for their production are produced by saponification of polyvinyl acetate and subsequent acetalisation with aliphatic aldehydes with 3 to 10 C-atoms such as, especially, formaldehyde, acetaldehyde, butyraldehyde. The saponification is, in general, not carried out completely so that the polyvinyl alcohols generally still contain 0.5 to 5 weight ~ acetyl groups, --,, 1 calculated as vinylacetate groups. ~ven theacetalisation is in gen~ral not completely carried out so thak the partially acetalised polyvinyl a7cohol e~ployed ~or the production of the foils generally still contain 5 free O~-groups, with the partially butyralised polyvinyl alcohol (in the following, denoted by PVB), this OH
content can amount to between 10 and 27 weight calculated as vinyl alcohol. Unless otherwise ind~cated the ter~
partialIy acetali ~ polyvinyl alcohol(s) in ~he following is 10 used both for partially acetalised as well as also for partially butyralised polyvinyl alcoh~1.
In the production of laminated safety glasses, these partially acetalised polyvinyl alcohols are employed as foils with a definite plasticiser content.
15 The type and amount of the plasticiser employed influence the properties of the laminated safety glass. In practice, it has therefore become clear that an especially splinter proof laminated safety glass should have as intermediate foil a PVB foil which possesses a 20 plasticiser content of 15 to 40 weight 4, preferably 25 to 31% and whose content of free O~ groups amounts to 10 to 25 weight ~, preferably 16 to 23 weight ~, related to plasticiser-free PVB resin. The moisture content of such a PVB f oil should lie between 0.2 and 0.9 weight ~.
The invention relates especially to foils of plasticised partially acetalised polyvinyl alcohols with good oxidation and temperature resistance and outstanding light resistance. Plasticiser-containing polyvinyl-butyral is exposed under the conditions for its working 30 to foils and the sub~e~uent working to laminated glass to high temperatures which lead to a certain extent to yellowing. The optical properties are in this way especially deteriorated.
It is known that, to use phenolic compounds, such 35 as 2,6-di-tert.-butyl-p-cresol, 2,4,6-trimethylphenol, octylphenol, bornyl-xylenol etc. to stabilise the material ~German Patent Specification 2 208 167).It is 4~
1 further known that phosphorous -acid triesters such as trilaurylphosphite, decylphenyl-phosphite etc. are used for avoidance of yellowing (German Patent Specification 2 ~0~ 167~.
In contrast to soft PVC formulations, in which the initial colour, transparence and light stability is improved by employment of phosphorous acid triesters as co-stabilisers, it has however been shown that phosphorous acid triester-containing PVB foils lose their 1~ original bright colour after longer periods in the light and become yellow to an extent which cannot be dealt with. In particular, with the water clear safety glass ; foils required, most recently by users, the task of the present invention has been to find a way to improve the 15 long ter~l light stability and to prevent, in the course of time, increasing yellowing.
Yellowing by exposure to light for a long time was observed with use of a series of phosphorous acid triesters or phosphonous acid diesters such as, for 20 example decyl-diphenyl-phosphite, trilauryl phosphite, didecyl-phenyl-phosphite, tris-nonylphenylphosphi~e, triphenylphosphite, trist2,4-di-tert.butylphenyl) phosphite, di-~isodecyl)-pentaerythrityl-diphosphite, di-stearylpentaerythrityl-diphosphite, tetrakis-(2r4-di-tert.-butylphenyl)-4~4l-biphenylylenedi-phosphonite.
There therefore existed the object of stabilising the polyvinylbutyral foils, that is PVB ~oils in laminated safety glass with contents of the indicated 30 phenollc compounds and sta~ilisers based on phosphorous acid triesters and/or phosphonous acid diesters by additional measures against the influence of daylight, specifically, or periods of use of laminated safety glass panes with PVB foils contained therein over years, 35 to achieve a protection against ageing with prominent long term effect against yellowing.
Surprisingly, it has now been found that a long 3L~6~4~3 term efEect against yellowing of phosphite-containing foil formulations is achieved by -the addition of selected UV-absorbers and the yellowing achieved by the necessaryaddition of phosphite or phosphonite, even with longer action of light, is prevented.
` An object of -the invention is therefore to provide a process for the production of a foil of phenolically stabilised, plasticised, partially acetalised polyvinyl alcohols of superior oxidation-, temperature- and light-stability, by using, in addition to phosphorous acid triesters or phosphonous acid diester~s, further selected UV-absorbers.
A further object of the inven-tion is to use such a foil as a component of laminated glass.
In meeting these objects, -the invention provides laminated glass having as a component a foil, having superior resisance to oxidation, heat and light, comprising phenolically stabilized, plas-ticized, partly acetalated polyvinyl alcohols containing phosphorous-acid triesters and phosphonous-acid diesters and at least one UV-absorber having a long-term action, selected from the group consisting of:
a) derivative of benzo-triazole b) deriva-tives of acrylonitrile or cinnamonitrile c) hydroxybenzophenones and their mixtures.
The invention also provides certain foils used in the above laminates.
The UV-absorbers are added as protection against aging and have pronounced long-term action agains-t -the yellowing resulting from exposure to daylight.
Surprisingly, the UV-absorbers used in the method of this invention achieve the re~uired protection against aginy and the long term effect against yellowing in ~i6'~0 fulfilment of -the above objec-ts. Other groups of the usual UV absorbers, ln contrast fail to work.
For example, the phenyl salicylates and derivatives thereof known as UV-absorbers, such as phenyl salicylate, 4--tert.butylphenyl salicylate or 4-octylphenyl salicylate, and the sterically hindered amines likewise acting as liyht protective agents, such as for example sebacic acid-bis-2,2,6,6--tetramethyl-4-piperidyl ester, do not yield the indicated long-term effec-t and show too high E
1~ or YI values in the long term -test.
According to the inven-tion, suitable UV-absorbers in the previously noted classes of material are:
1. Derivatives of benzotriazole, especially hydroxyphenyl-benzotriazole, such as:
i - 4a -674~
1 2-(2'-hydroxy~5l-methylphenyl)-benzotria~ole~
2-(2'-hydroxy-3', 5'-di-tert.butylphenyl) 5-chlorbenzotriazole, 2-(2'-hydroxy-3',5'~di-tert.
butylphenyl)-benzotriazole, 2-~2'-hydroxy-3'-tert.
butyl-5-methylphenyl-5-chlorbenzotriazole, 2~(2'-hydroxy-3',5l-di-tert.amylphenyl)-benzotriazole, 2-t2'-hydroxy-5'-tert.octylphenyl)-benzotriazole.
2. Derivatives of acrylonitrile or of cinnamonitrile fox example ~-cyano-B,~ diphenylacrylic acid ethyl ester, ~-cyano- ~ -me~hyl-4-methoxycinnamnic acid methyl ester.
butylphenyl)-benzotriazole, 2-~2'-hydroxy-3'-tert.
butyl-5-methylphenyl-5-chlorbenzotriazole, 2~(2'-hydroxy-3',5l-di-tert.amylphenyl)-benzotriazole, 2-t2'-hydroxy-5'-tert.octylphenyl)-benzotriazole.
2. Derivatives of acrylonitrile or of cinnamonitrile fox example ~-cyano-B,~ diphenylacrylic acid ethyl ester, ~-cyano- ~ -me~hyl-4-methoxycinnamnic acid methyl ester.
3. Hydroxybenzophenones such as:
2,~'-dihydroxy-4-methoxy-benzophenone, 2-hydroxy-
2,~'-dihydroxy-4-methoxy-benzophenone, 2-hydroxy-
4-n-octyl-oxy-benzophenone, 2-hydroxy-5-chloro-benzophenone, 2,2',4,4'-tetrahydroxybenzophenone.
Mixtures of such UV-absorbers from the same or different classes of materials are possible.
The use of those W-absorbers which possess no colour of their own or whose own colour is less or which 20 do not achieve any colouration of the foil material, e.g.
2-t2'-hydroxy-5'-methylphenyl)-benzotriazole or ~-cyano-diphenylacrylic acid ethyl ester is advanta~eous.
It often suffices to limit to addition amounts of UV absorber of 0~1 to 0.2 weight %. In general the use 25 of 0.01 to 0.40 weight ~, preferably of 0.03 to 0.30 ; weight %, succeeds.
The long term effect of the added UV-absorber was measured in exposure experiments on composite glasses of 0.8 mm PVB foils between two 2.8 mm glass panes in the 30 rotation solarium according to German Utility Model 78 19 931 at intervals of 1 week to a total of 20 weeks. For the purposes of appraisal, the total colour difference E
according to DIN 6174 or the Yellowness Index (YI) according to ASTM-D-1925 is determined.
In the following Examples, for the purpose of comparability, the same basic composition of PVB foil and the above indicated thickness of a composite glass are o l chosen, with like reductions o~ measured values being, however, achieved by the addi~ion of the W absorber according to the invention in further PVB compositions.
Exam~
S A PVs foil of 0.8 mm thickness suitable for the production of vehicle panes, based on a basic composition of 70 weight 4 of partially butyralised polyvinyl alcohol with 20 weight ~ polyvinyl alcohol content, 30 weight %
triethyleneglycol ester with 2-ethylbutyric acid as lO plasticiser and 0.3 weight ~ bornyl-xylenol as phenolic stabiliser, as well as, in the Comparative Examples 2 to 6 with a phosphite or phosphonite as additive was compounded and thereupon worked up to foils.
Comparative Examples l to 6 The following stabilisers were employed as additives for the indicated basic composition;
!. a = Decyldiphenyl phosphite b = Tris(2,4-di-tert.butylphenyl)phosphite c = Trisnonylphenyl phosphite 20 d = Di-stearyl-pentaerythrityl diphosphite = Tetrakis~2,4-di-tert.butylphenyl)-4,4'-bisphenylylene diphosphonite .
weight % Total colour difference Yell~ess-Index of additive ~ E with reference after 25to Standard after _ _ l week lO weeks 20 wee~ l week lO weeks 20 weeks 1 None D.73 D.31 1.79 1.17 1.76 2 79 2 0.1 a D.61 1.BL 4.5Z D.72 2.76 4-73 3 0.1 b 0.91 1.D6 3.53 0.99 2.57 4-2D
30 4 D.1 ~ D.77 1.72 4.4 4 D 9D 2 .77 ~ . 62 D.1 d 1.D7 1.5B 4.22 D.77 Z.4D 4.37 6 0.1 e D-67 1.0~ 3.24 D.9D 2.1L 3.69 The addition of phosphites or phosphonites achieves in the long term test increased colour values 35 which are perceived by the human eye as yellow .. . . .~
~Z~67~0 l colouration.
Exam~es 7 to ll 2-(2' hydroxy-5'-methylphenyl)-benzotriazole (m) was additionally added, as W-ab~orber according to the
Mixtures of such UV-absorbers from the same or different classes of materials are possible.
The use of those W-absorbers which possess no colour of their own or whose own colour is less or which 20 do not achieve any colouration of the foil material, e.g.
2-t2'-hydroxy-5'-methylphenyl)-benzotriazole or ~-cyano-diphenylacrylic acid ethyl ester is advanta~eous.
It often suffices to limit to addition amounts of UV absorber of 0~1 to 0.2 weight %. In general the use 25 of 0.01 to 0.40 weight ~, preferably of 0.03 to 0.30 ; weight %, succeeds.
The long term effect of the added UV-absorber was measured in exposure experiments on composite glasses of 0.8 mm PVB foils between two 2.8 mm glass panes in the 30 rotation solarium according to German Utility Model 78 19 931 at intervals of 1 week to a total of 20 weeks. For the purposes of appraisal, the total colour difference E
according to DIN 6174 or the Yellowness Index (YI) according to ASTM-D-1925 is determined.
In the following Examples, for the purpose of comparability, the same basic composition of PVB foil and the above indicated thickness of a composite glass are o l chosen, with like reductions o~ measured values being, however, achieved by the addi~ion of the W absorber according to the invention in further PVB compositions.
Exam~
S A PVs foil of 0.8 mm thickness suitable for the production of vehicle panes, based on a basic composition of 70 weight 4 of partially butyralised polyvinyl alcohol with 20 weight ~ polyvinyl alcohol content, 30 weight %
triethyleneglycol ester with 2-ethylbutyric acid as lO plasticiser and 0.3 weight ~ bornyl-xylenol as phenolic stabiliser, as well as, in the Comparative Examples 2 to 6 with a phosphite or phosphonite as additive was compounded and thereupon worked up to foils.
Comparative Examples l to 6 The following stabilisers were employed as additives for the indicated basic composition;
!. a = Decyldiphenyl phosphite b = Tris(2,4-di-tert.butylphenyl)phosphite c = Trisnonylphenyl phosphite 20 d = Di-stearyl-pentaerythrityl diphosphite = Tetrakis~2,4-di-tert.butylphenyl)-4,4'-bisphenylylene diphosphonite .
weight % Total colour difference Yell~ess-Index of additive ~ E with reference after 25to Standard after _ _ l week lO weeks 20 wee~ l week lO weeks 20 weeks 1 None D.73 D.31 1.79 1.17 1.76 2 79 2 0.1 a D.61 1.BL 4.5Z D.72 2.76 4-73 3 0.1 b 0.91 1.D6 3.53 0.99 2.57 4-2D
30 4 D.1 ~ D.77 1.72 4.4 4 D 9D 2 .77 ~ . 62 D.1 d 1.D7 1.5B 4.22 D.77 Z.4D 4.37 6 0.1 e D-67 1.0~ 3.24 D.9D 2.1L 3.69 The addition of phosphites or phosphonites achieves in the long term test increased colour values 35 which are perceived by the human eye as yellow .. . . .~
~Z~67~0 l colouration.
Exam~es 7 to ll 2-(2' hydroxy-5'-methylphenyl)-benzotriazole (m) was additionally added, as W-ab~orber according to the
5 invention to the basic PVB foil composition, provided with the additives according to Comparative Examples 2 to .
~ight ~ weight ~ ¦Total colour difference Yellowness-Index of addi- W- ~ E with reference after tive Absorber to Standard after _ _ m _ _ 1 week lO week 20 week ,1 week 10 wee~
0,10 ~.1 D.65 0.~5 0.~ 0.~9 1.D9 1-7~
D.lb 0.1 D.63 D,91 D.~6 1.~9 1.3Z l,D9 9 0.1c D.1 1.DL D ~2 0.95 1.35 1.5? 1.65 1D D-1d 0-1 D.63 D 53 D.56 D.9~ 1.2Z 1-35 15~1 D.le D.1 0 6D . D 72 D.9a 1.16 1.D9 1.1 The measured values of the long term test show essentially lower colour values with respect to the 2Q associated Comparative Examples 2 to 6. Practically no yellow colouration is perceivable with the eye.
Examples 12 to 14 To the basic PVB foil composition, provided with the additive of Comparative Example 2, were additionally 25 added the below indicated UV-absorbers according to the invention:
n = 2-(2'-hydroxy-3l,5'-di-tert.butylphenyl)-5-chlor-benzotriazole o = 2-hydroxy-4-n-octyloxy benzophenone 30 p = ~yano-~,~-diphehylacrylic acid ethyl ester weight ~ weight ~ Total colour difference Yell~ess-Index additive W-Absorb- ~ E with reference ~ter er to Standard after _ _ 1 week lO weeks 20 wee~ 1 week 10 weekc ~ S
1Z 0.1~ D.1 n 0.59 1.0~ 2.59 1.06 1.87 3.29 35 13 0.1a n.l O 1.01 D.59 0.63 0.7B 1.1~ 1.56 14 D.1a D.1 p 0.90 0.~6 Z.36 0-9~ 1.B2 2.B0 The measured values in the long term test also ~2667~
, 1 show for the UV-absorber n from the group of ben~otriazoles~ o rom the group of benzophenones and p from the group of cyano acrylates reduced values with respect to Comparative Example 2 and very low yellow 5 colouration on visual observation.
Comparative Examples_15 and 16 Corresponding to the proceeding Examples, there were employed substance q from the group of salicylates and r from the group of piperidyl esters of dicarboxylic 10 acids, which however fail.
q - phenyl salicylate r = sebacic acid-bis-2,2,6,6-tetramethyl-4-piperidyl ester ~:ight % weight % Tbtal colour difference Yellowness-Index 15 additive W-Absor~- ~ E with reference after er to Standard after 1 weekllO weeks O weeks 1 week 10 wee~ 20 w~ ks _ . ~ ................ _ _._ 15 0.1z 0.1 q ~.69 4.05 6~9~ 1 08 b.96 7.03 16 D-1n 0.1 r 0.42 1.38 3.56 1.33 3.D~ 5.~2 The results of the long term test show the unusability of substances q and r, whereas with shorter experimental periods disadvantages are not perceivable.
Yellow colouring is perceivable with the eye after the long term test.
25 Examples 17 to 34 To the basic composition, provided with the additive of Comparative Example 2, are added the UV-absorbers m, o and p in the below indicated amounts:
I
74~
weight weight ~ llbtal colo~r difference Y~llD~ness-lndex addi- W-Absor- ,~ E w.ith reference after ive ber ~o Sta ,dard aft r _ . _ ~ O wee~s ~0 weeks 1 week lO ~eek 20 wee~
17 0-1 a D.D1 ~~.77 2.Z7 5.34D,B9 3.16 5.63 50-1 ~ D.D3 ~0.73 1.~', 4.50 D.6~ 2.65 ~.91 D.1 s D.05 m0.96 0.56 2-35D.B5 1.69 3.25 .1 a D 07 mD .66 0. 5D 2D2 ~.B~ 1.41 2 .7L
0.1 e D.10 m~.6~ D.45 D.8~D.g9 1.09 1.2~
22 0.1 ~ D.2D m1-25 D.97 G.B61!1~ 1.~ D.67 lO23 D 1 ~ 0. al DD.5~ 1.36 .. 0.6a 2.D6 4-96 D-1 ~ 0.03 DO 66 D.74 3-42D.~f 1.42 3-32 O 1 ~ D. D5 oO .9D O .56 2-f~6 D .90 1-39 3.05 D.1 ~ D. D7 o1 .1~ D.53 1 55D . BE 1 .Z8 Z .35 D .1 ~ D .1D D1 .0 1 D .59 0 63 0 7~ 1; 1~ 1. 56 15ZB D.1 ~ D-Z0 D1.09 D.6D 0-60D-96 1.22 1.36 _ _ .
Z9 0.1 ~ D.D1 p0.75 D.~ 4.511-4D 1-90 4.47 D.1 ~ O-D3 p .91 1.65 6 .70 D-61 ~ sn 6 .74 0.1 ~ 0.05 p.61 1.03 4-921.03 2-32 5.06 0.1 a 0 D7 p.65 1.1~ 3-66D-~7 2-lB 3.~3 D. 1 e 0 . lD p 0 .9D0 .a6 2 .36 0 9~ 1 .a2 2.8D
3~ D. 1 a ~ .2D p D .530 .55 1.6~ 1.16 2 15 2 .53 _. . . . _ In the long term test, with additive a~,ounts of O.Ol to 0.03 weight ~, improvements in the colour values 25 are perceivable. Additive amounts between O.l and 0.2 weight % give very low colour values for special requirements or especially long periods of employment.
I
_ g _
~ight ~ weight ~ ¦Total colour difference Yellowness-Index of addi- W- ~ E with reference after tive Absorber to Standard after _ _ m _ _ 1 week lO week 20 week ,1 week 10 wee~
0,10 ~.1 D.65 0.~5 0.~ 0.~9 1.D9 1-7~
D.lb 0.1 D.63 D,91 D.~6 1.~9 1.3Z l,D9 9 0.1c D.1 1.DL D ~2 0.95 1.35 1.5? 1.65 1D D-1d 0-1 D.63 D 53 D.56 D.9~ 1.2Z 1-35 15~1 D.le D.1 0 6D . D 72 D.9a 1.16 1.D9 1.1 The measured values of the long term test show essentially lower colour values with respect to the 2Q associated Comparative Examples 2 to 6. Practically no yellow colouration is perceivable with the eye.
Examples 12 to 14 To the basic PVB foil composition, provided with the additive of Comparative Example 2, were additionally 25 added the below indicated UV-absorbers according to the invention:
n = 2-(2'-hydroxy-3l,5'-di-tert.butylphenyl)-5-chlor-benzotriazole o = 2-hydroxy-4-n-octyloxy benzophenone 30 p = ~yano-~,~-diphehylacrylic acid ethyl ester weight ~ weight ~ Total colour difference Yell~ess-Index additive W-Absorb- ~ E with reference ~ter er to Standard after _ _ 1 week lO weeks 20 wee~ 1 week 10 weekc ~ S
1Z 0.1~ D.1 n 0.59 1.0~ 2.59 1.06 1.87 3.29 35 13 0.1a n.l O 1.01 D.59 0.63 0.7B 1.1~ 1.56 14 D.1a D.1 p 0.90 0.~6 Z.36 0-9~ 1.B2 2.B0 The measured values in the long term test also ~2667~
, 1 show for the UV-absorber n from the group of ben~otriazoles~ o rom the group of benzophenones and p from the group of cyano acrylates reduced values with respect to Comparative Example 2 and very low yellow 5 colouration on visual observation.
Comparative Examples_15 and 16 Corresponding to the proceeding Examples, there were employed substance q from the group of salicylates and r from the group of piperidyl esters of dicarboxylic 10 acids, which however fail.
q - phenyl salicylate r = sebacic acid-bis-2,2,6,6-tetramethyl-4-piperidyl ester ~:ight % weight % Tbtal colour difference Yellowness-Index 15 additive W-Absor~- ~ E with reference after er to Standard after 1 weekllO weeks O weeks 1 week 10 wee~ 20 w~ ks _ . ~ ................ _ _._ 15 0.1z 0.1 q ~.69 4.05 6~9~ 1 08 b.96 7.03 16 D-1n 0.1 r 0.42 1.38 3.56 1.33 3.D~ 5.~2 The results of the long term test show the unusability of substances q and r, whereas with shorter experimental periods disadvantages are not perceivable.
Yellow colouring is perceivable with the eye after the long term test.
25 Examples 17 to 34 To the basic composition, provided with the additive of Comparative Example 2, are added the UV-absorbers m, o and p in the below indicated amounts:
I
74~
weight weight ~ llbtal colo~r difference Y~llD~ness-lndex addi- W-Absor- ,~ E w.ith reference after ive ber ~o Sta ,dard aft r _ . _ ~ O wee~s ~0 weeks 1 week lO ~eek 20 wee~
17 0-1 a D.D1 ~~.77 2.Z7 5.34D,B9 3.16 5.63 50-1 ~ D.D3 ~0.73 1.~', 4.50 D.6~ 2.65 ~.91 D.1 s D.05 m0.96 0.56 2-35D.B5 1.69 3.25 .1 a D 07 mD .66 0. 5D 2D2 ~.B~ 1.41 2 .7L
0.1 e D.10 m~.6~ D.45 D.8~D.g9 1.09 1.2~
22 0.1 ~ D.2D m1-25 D.97 G.B61!1~ 1.~ D.67 lO23 D 1 ~ 0. al DD.5~ 1.36 .. 0.6a 2.D6 4-96 D-1 ~ 0.03 DO 66 D.74 3-42D.~f 1.42 3-32 O 1 ~ D. D5 oO .9D O .56 2-f~6 D .90 1-39 3.05 D.1 ~ D. D7 o1 .1~ D.53 1 55D . BE 1 .Z8 Z .35 D .1 ~ D .1D D1 .0 1 D .59 0 63 0 7~ 1; 1~ 1. 56 15ZB D.1 ~ D-Z0 D1.09 D.6D 0-60D-96 1.22 1.36 _ _ .
Z9 0.1 ~ D.D1 p0.75 D.~ 4.511-4D 1-90 4.47 D.1 ~ O-D3 p .91 1.65 6 .70 D-61 ~ sn 6 .74 0.1 ~ 0.05 p.61 1.03 4-921.03 2-32 5.06 0.1 a 0 D7 p.65 1.1~ 3-66D-~7 2-lB 3.~3 D. 1 e 0 . lD p 0 .9D0 .a6 2 .36 0 9~ 1 .a2 2.8D
3~ D. 1 a ~ .2D p D .530 .55 1.6~ 1.16 2 15 2 .53 _. . . . _ In the long term test, with additive a~,ounts of O.Ol to 0.03 weight ~, improvements in the colour values 25 are perceivable. Additive amounts between O.l and 0.2 weight % give very low colour values for special requirements or especially long periods of employment.
I
_ g _
Claims (26)
1. Laminated glass having as component a foil having superior resistance to oxidation, heat and light, comprising a phenolically stabilized, plasticized, partly acetalized polyvinyl alcohols containing phosphorous-acid triesters and phosphonous-acid diesters and at least one UV-absorber having a long-term action, selected from -the group consisting of:
a) derivatives of benzotriazole, b) derivatives of acrylonitrile or cinnamonitrile, c) hydroxybenzophenones, and their mixtures.
a) derivatives of benzotriazole, b) derivatives of acrylonitrile or cinnamonitrile, c) hydroxybenzophenones, and their mixtures.
2. Laminated glass according to claim 1, wherein 0.01 to 0.40% by weigh-t of -the UV-absorber is present.
3. Laminated glass according to claim 1, wherein 0.03 to 0.30% by weight of the UV-absorber is present.
4. Laminated glass according -to claim 1, 2 or 3, wherein (a) said derivatives of benzotrazole are selected from 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(2'-hydroxy-3', 5'-di-tert.butylphenyl)-5-chlorbenzotriazole, 2-(2'-hydroxy-3',5'-di-tert.butylphenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert.butyl-5-methylphenyl-5-chlorbenzotriazole, 2-(2'-hydroxy-3',5'-di-tert.amylphenyl)-benzotriazole and 2-(2'-hydroxy-5'-tert.oxtylphenyl)-benzotriazole;
(b) said derivatives of acrylonitrile or of cinnamonitrile are selected from .alpha.-cyano- .beta., .beta.-diphenylacrylic acid ethylester and .alpha.-cyano-.beta.-methyl-4-methoxYcinnamnic acid methyl ester; and (c) said hydroxybenzophenones are selected from 2,2'-dihydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octyl-oxy-benzophenone, 2-hydroxy-5-chlorobenzophenone and 2,2',4,4'-tetrahydroxybenzophenone.
(b) said derivatives of acrylonitrile or of cinnamonitrile are selected from .alpha.-cyano- .beta., .beta.-diphenylacrylic acid ethylester and .alpha.-cyano-.beta.-methyl-4-methoxYcinnamnic acid methyl ester; and (c) said hydroxybenzophenones are selected from 2,2'-dihydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octyl-oxy-benzophenone, 2-hydroxy-5-chlorobenzophenone and 2,2',4,4'-tetrahydroxybenzophenone.
5. Laminated glass havlng as a component a foil having superior resistance to oxidation, heat and light, comprising phenolically stabilized, plasticized, partly acetalized polyvinyl alcohols containing phosphorous-acid triesters and phosphonous-acid diesters and at least one derivative of benzotriazole as UV-absorber having a long-term action.
6. Laminated glass according to claim 5, wherein 0.01 to 0.40% by weight of the UV-absorber is present.
7. Laminated glass according to claim 5, wherein 0.03 to 0.30% by weight of the UV-absorber is present.
8. Laminated glass according to claim 5, 6, or 7, wherein said derivative of benzotriazole is selected from the group consisting of:
2-(2'-hydroxy-5'-methylphenyl-benzotriazole, 2-(2'-hydroxy-3', 5'-di-tert.butylphenyl)-5-chlorbenzo-triazole, 2-(2'-hydroxy-3',5'-di-tert.butylphenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert.butyl-5-methyl-phenyl-5-chlorbenzotriazole, 2-(2'-hydroxy-3',5'-di-tert.amylphenyl)-benzotriazole and 2-(2'-hydroxy-5'-tert.octylphenyl)-benzotriazole.
2-(2'-hydroxy-5'-methylphenyl-benzotriazole, 2-(2'-hydroxy-3', 5'-di-tert.butylphenyl)-5-chlorbenzo-triazole, 2-(2'-hydroxy-3',5'-di-tert.butylphenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert.butyl-5-methyl-phenyl-5-chlorbenzotriazole, 2-(2'-hydroxy-3',5'-di-tert.amylphenyl)-benzotriazole and 2-(2'-hydroxy-5'-tert.octylphenyl)-benzotriazole.
9. Laminated glass having as a component a foil having superior resistance to oxidation, heat and light, comprising phenolically stabilized, plasticized, partly acetalized polyvinyl alcohols containing phosphorous-acid triesters and phosphonous-acid diesters and at least one derivative of actylonitrile or cinnamonitrile as UV-absorber having a long-term action.
10. Laminated glass according to claim 9, wherein 0.01 to 0.40% by weight of the UV-absorber is present.
11. Laminated glass according to claim 9, wherein 0.03 to 0.30% by weight of the UV-absorber is present.
12. Laminated glass according to claim 9, 10 or 11, wherein said derivative of acrylonitrile or cinnamonitrile is .alpha.-cyano-.beta., .beta.-diphenylacrylic acid ethyl ester or .alpha.-cyano-.beta.-methyl-4-methoxycinnamnic acid methyl ester respectively.
13. Laminated glass having as a component a foil having superior resistance to oxidation, heat and light, comprising phenolically stabilized, plasticized, partly acetalized, polyvinyl alcohols containing phosphorous-acid triesters and phosphonous-acid diesters and at least one hydroxybenzophenone as UV-absorber having a long-term action.
14. Laminated glass according to claim 13, wherein 0.01 to 0.40% by weight of the UV-absorber is present.
15. Laminated glass according to claim 13, wherein 0.03 to 0.30% by weight of the UV-absorber is present.
16. Laminated glass according to claim 13, 14 or 15, wherein said hydroxybenzophenone is selected from 2,2'-dihydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octyl-oxy-benzophenone, 2-hydroxy-5-chlorobenzophenone and 2,2',4'4'-tetrahydroxybenzophenone.
17. A foil comprising phenolically stabilized, plasticized, partly acetalized, polyvinyl alcohols containing phosphorous-acid triesters and phosphonous-acid diesters and at least one UV-absorber having a long-term action, selected from -the group consisting of:
2-(2'-hydroxy-3',5'-di-tert.amylphenyl)-benzotriazole, 2-(2'-hydroxy-5'-tert.octylphenyl)-benzotriazole, 2,2'-dihy-droxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octyl-oxy-benzo-phenone, 2-hydroxy-5-chlorobenzophenone and 2,2',4,4'-tetra-hydroxybenzophenone.
2-(2'-hydroxy-3',5'-di-tert.amylphenyl)-benzotriazole, 2-(2'-hydroxy-5'-tert.octylphenyl)-benzotriazole, 2,2'-dihy-droxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octyl-oxy-benzo-phenone, 2-hydroxy-5-chlorobenzophenone and 2,2',4,4'-tetra-hydroxybenzophenone.
18. A foil according to claim 17, wherein said U.V. absorber is 2-(2'-hydroxy-3',5'-di-tert.amylphenyl)-benzotriazole.
19. A foil according to claim 17, wherein said U.V. absorber is 2-(2'-hydroxy-5'-tert.octylphenyl)-benzo-triazole.
20. A foil according to claim 17, wherein said U.V. absorber is 2,2'-dihydroxy-4-methoxy-benzophenone.
21. A foil according to claim 17, wherein said U.V. absorber is 2-hydroxy-4-n-octyl-oxy-benzophenone.
22. A foil. according to claim 17, wherein said U.V. absorber is 2-hydroxy-5-chlorobenzophenone.
23. A foil according to claim 17, wherein said U.S. absorber is 2,2',4,4'-tetrahydroxybenzophenone.
24. Laminated glass having as component a foil according to claim 17.
25. Laminated glass having as component a foil according to claim 18, 19 or 20.
26. Laminated glass having as component a foil according to claim 21, 22 or 23.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3347040A DE3347040C2 (en) | 1983-12-24 | 1983-12-24 | Process for the production of light-resistant polyvinyl butyral films and the use of the films |
| DEP3347040.5 | 1983-12-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1266740A true CA1266740A (en) | 1990-03-13 |
Family
ID=6218116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000470549A Expired - Fee Related CA1266740A (en) | 1983-12-24 | 1984-12-19 | Process for the production of light resistant polyvinyl butyral foils |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0148397B1 (en) |
| JP (1) | JPS60156742A (en) |
| KR (1) | KR920000029B1 (en) |
| AR (1) | AR241121A1 (en) |
| AT (1) | ATE37722T1 (en) |
| AU (1) | AU585491B2 (en) |
| BR (1) | BR8406660A (en) |
| CA (1) | CA1266740A (en) |
| CS (1) | CS254335B2 (en) |
| DE (2) | DE3347040C2 (en) |
| ES (1) | ES8700285A1 (en) |
| IN (1) | IN162565B (en) |
| SU (1) | SU1438613A3 (en) |
| ZA (1) | ZA849953B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5322875A (en) * | 1988-06-07 | 1994-06-21 | Saint-Gobain Vitrage | Polyvinylbutyral-based thermoplastic composition, useful for fixing bases on a glazing |
| US5384346A (en) * | 1992-05-08 | 1995-01-24 | Hoechst Ag | Polyvinyl butyrals having improved thermal stability and light resistance |
| US5573842A (en) * | 1993-07-19 | 1996-11-12 | Hoechst Aktiengesellschaft | Polyvinylbutyral films having improved optical properties |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2760494B2 (en) * | 1987-02-23 | 1998-05-28 | ハウス食品株式会社 | Spices for kneading spices |
| FR2632315B1 (en) * | 1988-06-07 | 1992-02-21 | Saint Gobain Vitrage | THERMOPLASTIC COMPOSITION BASED ON POLYVINYLBUTYRAL, USEFUL FOR FIXING BASES ON GLAZING |
| DE3909876A1 (en) * | 1989-03-25 | 1990-09-27 | Huels Troisdorf | MOLDING FOR THE PRODUCTION OF FILMS FOR COMPOSITE SAFETY WINDOWS |
| DE4024330A1 (en) * | 1990-07-31 | 1992-02-06 | Huels Troisdorf | Photochromic film prodn. for laminated safety glass - by extruding plasticised, acetalised polyvinyl-alcohol contg. photochromic cpds. which are pre-mixed with polymer and-or plasticiser |
| EP0672718B1 (en) * | 1994-03-14 | 2001-06-06 | Mitsubishi Gas Chemical Company, Inc. | Polyvinyl alcohol film, process for the production thereof and laminate |
| FR2721252B1 (en) * | 1994-06-17 | 1996-08-09 | Saint Gobain Vitrage | Laminated glazing with low energy transmission for transport vehicle. |
| WO2005019278A1 (en) * | 2003-08-19 | 2005-03-03 | Kuraray Specialities Europe Gmbh | Color-stable polyvinyl acetal, method for the production and the utilization thereof |
| DE102004000058A1 (en) * | 2004-12-01 | 2006-06-08 | Kuraray Specialities Europe Gmbh | Organophosphine-stabilized polymer blends |
| DE102005003756A1 (en) * | 2005-01-27 | 2006-08-03 | Iistone Gmbh | Stone-glass element, useful as building facade element, comprises at least one thin stone plate and a supporting plate |
| US20100233453A1 (en) * | 2006-03-23 | 2010-09-16 | Bridgestone Corporation | Intermediate film for laminated glass, laminated glass using the intermediate film, and process for the preparation of the laminated glass |
| US20210095081A1 (en) * | 2019-09-26 | 2021-04-01 | Chang Chun Petrochemical Co., Ltd. | Polymeric film and laminated glass containing the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL124226C (en) * | 1962-06-15 | |||
| BE795793A (en) * | 1972-02-22 | 1973-08-22 | Hoechst Ag | POLYBUTYRAL VINYL STABILIZED AND STABILIZER FOR POLYBUTYRAL VINYL |
| US3823113A (en) * | 1972-10-27 | 1974-07-09 | Monsanto Co | Stabilized polyvinyl acetal interlayers |
| CH626385A5 (en) * | 1976-02-05 | 1981-11-13 | Ciba Geigy Ag | |
| DE3228076A1 (en) * | 1982-07-28 | 1984-02-02 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING A POLYVINYLBUTYRAL MOLDED BODY |
-
1983
- 1983-12-24 DE DE3347040A patent/DE3347040C2/en not_active Expired
-
1984
- 1984-11-24 IN IN917/MAS/84A patent/IN162565B/en unknown
- 1984-11-29 EP EP84114493A patent/EP0148397B1/en not_active Expired
- 1984-11-29 AT AT84114493T patent/ATE37722T1/en not_active IP Right Cessation
- 1984-11-29 DE DE8484114493T patent/DE3474456D1/en not_active Expired
- 1984-12-04 SU SU843818857A patent/SU1438613A3/en active
- 1984-12-17 AR AR298979A patent/AR241121A1/en active
- 1984-12-19 CA CA000470549A patent/CA1266740A/en not_active Expired - Fee Related
- 1984-12-20 ZA ZA849953A patent/ZA849953B/en unknown
- 1984-12-21 CS CS8410205A patent/CS254335B2/en unknown
- 1984-12-21 BR BR8406660A patent/BR8406660A/en not_active IP Right Cessation
- 1984-12-21 ES ES538927A patent/ES8700285A1/en not_active Expired
- 1984-12-21 AU AU37077/84A patent/AU585491B2/en not_active Ceased
- 1984-12-22 KR KR1019840008279A patent/KR920000029B1/en not_active IP Right Cessation
- 1984-12-24 JP JP59271095A patent/JPS60156742A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5322875A (en) * | 1988-06-07 | 1994-06-21 | Saint-Gobain Vitrage | Polyvinylbutyral-based thermoplastic composition, useful for fixing bases on a glazing |
| US5384346A (en) * | 1992-05-08 | 1995-01-24 | Hoechst Ag | Polyvinyl butyrals having improved thermal stability and light resistance |
| US5573842A (en) * | 1993-07-19 | 1996-11-12 | Hoechst Aktiengesellschaft | Polyvinylbutyral films having improved optical properties |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE37722T1 (en) | 1988-10-15 |
| KR920000029B1 (en) | 1992-01-06 |
| ES538927A0 (en) | 1986-10-01 |
| ES8700285A1 (en) | 1986-10-01 |
| DE3474456D1 (en) | 1988-11-10 |
| DE3347040C2 (en) | 1987-01-29 |
| AU585491B2 (en) | 1989-06-22 |
| AR241121A1 (en) | 1991-11-15 |
| EP0148397B1 (en) | 1988-10-05 |
| BR8406660A (en) | 1985-10-22 |
| SU1438613A3 (en) | 1988-11-15 |
| CS254335B2 (en) | 1988-01-15 |
| AU3707784A (en) | 1985-07-04 |
| EP0148397A3 (en) | 1985-08-21 |
| AR241121A2 (en) | 1991-11-15 |
| ZA849953B (en) | 1985-08-28 |
| JPS60156742A (en) | 1985-08-16 |
| DE3347040A1 (en) | 1985-06-27 |
| CS1020584A2 (en) | 1987-06-11 |
| EP0148397A2 (en) | 1985-07-17 |
| IN162565B (en) | 1988-06-11 |
| KR850004787A (en) | 1985-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1266740A (en) | Process for the production of light resistant polyvinyl butyral foils | |
| US5573842A (en) | Polyvinylbutyral films having improved optical properties | |
| US4361625A (en) | Plasticizer-containing films of partially acetalized polyvinyl alcohols | |
| CA1145500A (en) | Transparent polyvinyl butyral sheet and process for the manufacture thereof | |
| US20050256258A1 (en) | PVB Film for Composite Safety Glass and Composite Safety Glass | |
| US5618863A (en) | UV stable polyvinyl butyral sheet | |
| EP0003440B1 (en) | Polyvinyl butyral compositions containing a blend of plasticizers | |
| US6982296B2 (en) | PVB film containing a plastifying agent | |
| EP1809474B1 (en) | Fire resistant polymer sheets | |
| CA1285673C (en) | Fire-resistant interlayer | |
| AU2006344717A1 (en) | Thermoplastic resin compositions suitable for use in transparent laminates | |
| US6001462A (en) | Laminated glazing unit with polyvinyl chloride interlayer | |
| CZ299771B6 (en) | Film of partially acetylated polyvinyl alcohols containing plasticizer | |
| US3841955A (en) | Plasticized polyvinyl butyral interlayers | |
| US4335036A (en) | Plasticized polyvinyl butyral employing propylene oxide oligomers | |
| US4293615A (en) | Polyvinyl butyral laminates | |
| JPS6060149A (en) | Plastic polyvinylbutyrate intermediate film, manufacture and mixed plasticizer therefor | |
| DE3128530A1 (en) | SOFTENING FILMS FROM PARTLY ACETALIZED POLYVINYL ALCOHOLS | |
| GB2320503A (en) | Safety glass interlayer | |
| JPH0429697B2 (en) | ||
| EP1817365A1 (en) | Organophosphine-stabilized intermediate layer films for laminated glazings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |