CA1076285A - Process for the production of modified, partially acetalised polyvinyl alcohol films - Google Patents
Process for the production of modified, partially acetalised polyvinyl alcohol filmsInfo
- Publication number
- CA1076285A CA1076285A CA221,033A CA221033A CA1076285A CA 1076285 A CA1076285 A CA 1076285A CA 221033 A CA221033 A CA 221033A CA 1076285 A CA1076285 A CA 1076285A
- Authority
- CA
- Canada
- Prior art keywords
- silicon
- carbon atoms
- silane
- polyvinyl alcohol
- bond strength
- 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
- B32B17/1055—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
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
-
- 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
- B32B17/10688—Adjustment of the adherence to the glass layers
-
- 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
- C08K5/54—Silicon-containing compounds
-
- 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
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/04—Treatment by energy or chemical effects using liquids, gas or steam
- B32B2310/0409—Treatment by energy or chemical effects using liquids, gas or steam using liquids
-
- 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
- B32B2605/00—Vehicles
- B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Joining Of Glass To Other Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
This invention relates to a process for adjusting the bond strength of a plasticizer-containing partially acetalized polyvinyl alcohol film used for bonding inorganic glasses, to the pummel values required for vehicle windscreens or safety window panes. This process comprises the step of adding a predetermined quantity of: a) a silicon-functional silane to reduce the bond strength, preferably of the general formula:
or a mixture of different silicon-functional silanes, or b) a silicon-organo functional silane to increase the bond strength, preferably of the general formula:
This invention relates to a process for adjusting the bond strength of a plasticizer-containing partially acetalized polyvinyl alcohol film used for bonding inorganic glasses, to the pummel values required for vehicle windscreens or safety window panes. This process comprises the step of adding a predetermined quantity of: a) a silicon-functional silane to reduce the bond strength, preferably of the general formula:
or a mixture of different silicon-functional silanes, or b) a silicon-organo functional silane to increase the bond strength, preferably of the general formula:
Description
~L~7~ 35 The present invention relates to a process for adjusting -the bond streng-th of a plasticizer-containing, partially acetali-zed polyvlnylalcohol film used for bonding inorganic glasses to form a composite screen.
Composite screens consisting of two or more sheets of glass bonded by an adhesive film, such as, for example, a partial-ly acetalized polyvinyl alcohol, are already known.
I-t is also known -that plasticized polyvinyl bu-tyral (PVB) can be used as adhesive film, in -the manufacture of glass/plastics compos.ite screens.
It is further known that amorphous polyamides is recommended for the manufacture of suitable plastics screens (see Canadian paten-t no. 867,3~6, issued on March 30, 1971 in the name oE the Applicant).
Plasticized, partially butyralised polyvi.nyl alcohol .
films with a moisture content ranging from 0.2 to 0.9~ by weight, a free OH-group content ~expressed as vinyl alcohol) ranging from about 10 to about 25% by weight, preferably from ahout 16 to about 23% by weight, and a plasticizer content oE
about 18 to about 65 parts by weight, preferably from 33 to 44 parts by weight per 100 parts by weigh-t of PVB, have also proved to be particularly suitab].e for the produc-tion of compo-site safety screens which, for safety reasons, are required to have a particular, shatter-proof bond.
Composite safety screens, consisting of two sheets of glass bonded by an adhesive film, preferably of PVB, are ~ used in particular as windscreens in motor vehicles. In such ~ case, one of the sheets oE glass may optionally be replaced by a sheet of plastics material consisting predominantly of .
an amorphous pol.yamide.
Silicate glass/silica-tc glass and silicate glass/
plastics composite screens are also used in the building industry, for example as window panes or as partitions. In this case, multiple composite screen, i.e. composite screens consist-ing in more than two supporting layers, may optionally be used according to their par-ticular applications, such as, for example as relnforced composite glass.
The partially acetalized polyvinyl alcohols used as adhesive film are obtained by hydrolyzing polyvinyl acetate and acetalizing the resulting product with aldehydes, such as, for example formaldehyde, acetaldehyde, propionaldehyde, bu-tyralde-hyde and the like. They generally contain about 0.5 to 5~ by weight or in most cases, about 0.5 to 1.2~ by weigh-t, of acetyl groups, expressed as vinyl acetate radicals. They can also be obtained from other polyvinyl esters of aliphatic alcohols hav-ing up to 9 carbon atoms, by hydrolysis and subse~uent ace-taliza-tion.
The partially acetalized polyvinyl alcohol resins, hereinafter referred to as PVA resins, are processed in-to films in combination with plasticizers, optionally stabilizers and, optionally, other additives, in conventional machines of the kind normally used for producing plastics ~ilm, such as, for example extruders. They are optlonally subsequently treated in a conditioning chamber in order to adjust the moisture con-tent re-quired Eor the composite safety glass.
In practice, screens of composite saEety glass are generally produced by first establishin~ a preliminary bond between the supporting individual layers and the adhesive film, the laminate preferably being vented. This preliminary bond is then finished under the effect of temperature and pressure, t for example in an autoclave t under a pressure ran~ing Erom 10 to 15 ~p/cm and at temperatures in the range from about 130 to 150C.
The thickness of each ]ayer ~orming ~he composite safety screen may be varied at will, according to the particular application envisaged. The followin~ layer thicknesses have B
~L~76Z~3~
proved to be effective for motor vehicle windscreen~:
glass = from 1 to 3 mm, preferably 2 mm, PVB= ~rom about 0.30 to 0.80, preferably 0.76 mm; glass--from 2 -to 4 mm, preferably 3 mm.
Suitable plasticizers are esters of polyvalent acids or polyhydric alcohols, ~or example dibutyl sebacate, di~ butoxy ethyl)-adipate, dioctyl phthalate, trie-thylene glycol bis-diethyl acetate, triethylene glycol di-(2-ethyl butyrate) and the like.
In the case of composite safety glass intended for use as motor-vehicle windscreens, the strength with which the glass is bonded to the film must be optimal, because if the screen is broken under impact, a strong adhesion allows for pénetration at the centre of impact wi-thout shattering. In the case of a poor adhesion, although an impact-type testing tool, such as, for example a hammer or an object dropped on-to the screen, is elastically arrested by the ~ilm, the shattering effect is considerable. In the event of a head-on collision, in which the windscreen is broken by impact of the head, the film should on one hand slowly dissipate the kinetic energy of the impact by stretching, and the broken glass should on the other hand still adhere to the film wi-th sufEicient strength to avoi~ injuries in the form of cu-ts. For this re~son, the bond strength must be optimal.
By contrast, in cases where composite safety glass i5 used in the building industry, such as, for example, as window panes, high bond strength of the glass to the film is required because, in this case, it is primarily intended to eliminate the risk of injury through cutting.
'rhe problem of controlling the adhesion of a sheet of glass to a partially acetalized PVA film is a crucial factor in the manufacture of windscreens.
It is known that plasticized, partially butyralized ' '' ~0'76Z85 PVA film generally shows very strong adhesion to glass, which is undesirable in the manufacture o~ windscreens. Optimum bond-strength values for motor vehicle windscreens are in the range from 2 to 4.
~ 'here are in the literature numerous publications which are concerned with -the problem of manufacturing motor vehicle windscreens and in which it is proposed to obtain a reduction in bond strength by adding salts of organic acids.
Unortunately, these known processes have the disad-vantage that some salts cause the film to discolour. In addition,the use of such additives may be dangerous since the film may detach from the surface of the glass because the sal-ts are sen-sitive to moisture and, hence adversely affec-t the moisture content of the adhesive film. In addition, these additives mere-ly reduce bond strength.
It is also known that the adhesion of a synthetic resin to an inorganic substrate can be influenced by certain organo silicon compounds, such as silanes. Silanes are substi-tution products of silicon hydride. The substituents may differ in character. ~ccording to Nollj Chemie und Technik der Silikone, 2nd Edition, 1968, page 10, the silanes are divided in-to three groups the "only silicon-functional silanes", the "only organo functional silanes" and the "silicon-unct.ional and organo functional silanes". The Eunctional groups of the silicon-functio-nal silanes such as, for example halogens or alkoxy groups, are di.rectly attached -to the Si atom. Groups of this kind may easily be hydrolyzed. The functional groups oE the organo functional silanes are attached to silicon through one or more carbon atoms, and are reactive, such as, for example, through amino or epoxy groups or throu~h double bonds. This nomenclature introduced by Noll is also used hereinafter.
- It is known from -US-PS 3,341,399 that sheets of glass can be bonded to one ano-ther by using a silane treated PVB
_ ~ _
Composite screens consisting of two or more sheets of glass bonded by an adhesive film, such as, for example, a partial-ly acetalized polyvinyl alcohol, are already known.
I-t is also known -that plasticized polyvinyl bu-tyral (PVB) can be used as adhesive film, in -the manufacture of glass/plastics compos.ite screens.
It is further known that amorphous polyamides is recommended for the manufacture of suitable plastics screens (see Canadian paten-t no. 867,3~6, issued on March 30, 1971 in the name oE the Applicant).
Plasticized, partially butyralised polyvi.nyl alcohol .
films with a moisture content ranging from 0.2 to 0.9~ by weight, a free OH-group content ~expressed as vinyl alcohol) ranging from about 10 to about 25% by weight, preferably from ahout 16 to about 23% by weight, and a plasticizer content oE
about 18 to about 65 parts by weight, preferably from 33 to 44 parts by weight per 100 parts by weigh-t of PVB, have also proved to be particularly suitab].e for the produc-tion of compo-site safety screens which, for safety reasons, are required to have a particular, shatter-proof bond.
Composite safety screens, consisting of two sheets of glass bonded by an adhesive film, preferably of PVB, are ~ used in particular as windscreens in motor vehicles. In such ~ case, one of the sheets oE glass may optionally be replaced by a sheet of plastics material consisting predominantly of .
an amorphous pol.yamide.
Silicate glass/silica-tc glass and silicate glass/
plastics composite screens are also used in the building industry, for example as window panes or as partitions. In this case, multiple composite screen, i.e. composite screens consist-ing in more than two supporting layers, may optionally be used according to their par-ticular applications, such as, for example as relnforced composite glass.
The partially acetalized polyvinyl alcohols used as adhesive film are obtained by hydrolyzing polyvinyl acetate and acetalizing the resulting product with aldehydes, such as, for example formaldehyde, acetaldehyde, propionaldehyde, bu-tyralde-hyde and the like. They generally contain about 0.5 to 5~ by weight or in most cases, about 0.5 to 1.2~ by weigh-t, of acetyl groups, expressed as vinyl acetate radicals. They can also be obtained from other polyvinyl esters of aliphatic alcohols hav-ing up to 9 carbon atoms, by hydrolysis and subse~uent ace-taliza-tion.
The partially acetalized polyvinyl alcohol resins, hereinafter referred to as PVA resins, are processed in-to films in combination with plasticizers, optionally stabilizers and, optionally, other additives, in conventional machines of the kind normally used for producing plastics ~ilm, such as, for example extruders. They are optlonally subsequently treated in a conditioning chamber in order to adjust the moisture con-tent re-quired Eor the composite safety glass.
In practice, screens of composite saEety glass are generally produced by first establishin~ a preliminary bond between the supporting individual layers and the adhesive film, the laminate preferably being vented. This preliminary bond is then finished under the effect of temperature and pressure, t for example in an autoclave t under a pressure ran~ing Erom 10 to 15 ~p/cm and at temperatures in the range from about 130 to 150C.
The thickness of each ]ayer ~orming ~he composite safety screen may be varied at will, according to the particular application envisaged. The followin~ layer thicknesses have B
~L~76Z~3~
proved to be effective for motor vehicle windscreen~:
glass = from 1 to 3 mm, preferably 2 mm, PVB= ~rom about 0.30 to 0.80, preferably 0.76 mm; glass--from 2 -to 4 mm, preferably 3 mm.
Suitable plasticizers are esters of polyvalent acids or polyhydric alcohols, ~or example dibutyl sebacate, di~ butoxy ethyl)-adipate, dioctyl phthalate, trie-thylene glycol bis-diethyl acetate, triethylene glycol di-(2-ethyl butyrate) and the like.
In the case of composite safety glass intended for use as motor-vehicle windscreens, the strength with which the glass is bonded to the film must be optimal, because if the screen is broken under impact, a strong adhesion allows for pénetration at the centre of impact wi-thout shattering. In the case of a poor adhesion, although an impact-type testing tool, such as, for example a hammer or an object dropped on-to the screen, is elastically arrested by the ~ilm, the shattering effect is considerable. In the event of a head-on collision, in which the windscreen is broken by impact of the head, the film should on one hand slowly dissipate the kinetic energy of the impact by stretching, and the broken glass should on the other hand still adhere to the film wi-th sufEicient strength to avoi~ injuries in the form of cu-ts. For this re~son, the bond strength must be optimal.
By contrast, in cases where composite safety glass i5 used in the building industry, such as, for example, as window panes, high bond strength of the glass to the film is required because, in this case, it is primarily intended to eliminate the risk of injury through cutting.
'rhe problem of controlling the adhesion of a sheet of glass to a partially acetalized PVA film is a crucial factor in the manufacture of windscreens.
It is known that plasticized, partially butyralized ' '' ~0'76Z85 PVA film generally shows very strong adhesion to glass, which is undesirable in the manufacture o~ windscreens. Optimum bond-strength values for motor vehicle windscreens are in the range from 2 to 4.
~ 'here are in the literature numerous publications which are concerned with -the problem of manufacturing motor vehicle windscreens and in which it is proposed to obtain a reduction in bond strength by adding salts of organic acids.
Unortunately, these known processes have the disad-vantage that some salts cause the film to discolour. In addition,the use of such additives may be dangerous since the film may detach from the surface of the glass because the sal-ts are sen-sitive to moisture and, hence adversely affec-t the moisture content of the adhesive film. In addition, these additives mere-ly reduce bond strength.
It is also known that the adhesion of a synthetic resin to an inorganic substrate can be influenced by certain organo silicon compounds, such as silanes. Silanes are substi-tution products of silicon hydride. The substituents may differ in character. ~ccording to Nollj Chemie und Technik der Silikone, 2nd Edition, 1968, page 10, the silanes are divided in-to three groups the "only silicon-functional silanes", the "only organo functional silanes" and the "silicon-unct.ional and organo functional silanes". The Eunctional groups of the silicon-functio-nal silanes such as, for example halogens or alkoxy groups, are di.rectly attached -to the Si atom. Groups of this kind may easily be hydrolyzed. The functional groups oE the organo functional silanes are attached to silicon through one or more carbon atoms, and are reactive, such as, for example, through amino or epoxy groups or throu~h double bonds. This nomenclature introduced by Noll is also used hereinafter.
- It is known from -US-PS 3,341,399 that sheets of glass can be bonded to one ano-ther by using a silane treated PVB
_ ~ _
2~35 film. The silanes th~t are usedl include bo-th silicon-functional and silicon- and organo-functional silanes, such as amino alkyl -trlethoxy silane, alkyl triethoxy silane, aryl trie-thoxy silane and vinyl triethoxy silane. They are added to the Pvs in quanti-ties of ~rom 1 to 10% by weight in order to increase both the shear strength and the resistance to steam of the condensate.
However, the process disclosed in the above-mentioned US-PS is not concerned wi-th ajdusting the bond strength of a plasticizer containing, partially acetalized PVA film used for bonding inor-ganic glasses to the pummel values regarded as optimum for the particular application to which the bonded glasses are intended.
There is nothing in that US patent specification which could assist in solving the problem with which the present invention is concerned.
The present invention proposes a process for adjust-ing the bond strength of a plasticizer~con-taining, par-tially acetalized polyvinyl alcohol film usable for bonding inorganic glasses, to the pummel value required for its particular appli-cation which process comprises the step of adding a predetermined ~ 20 quantity of ~ a) a silicon-fwlctional silane to reduce the bond strength, or a mixture of different silicon-functional silanes, or b) a sili.con-organo :Eunctional silane to increase the bond strength, or a mixture o silicon-organo functional sil.anes, or ~ c) a mixtur.e of a-t least one silicon~Eunctional silane with at least one silicon-organo functional silane, to the partially acetalized polyvinyl alcohol resin before or during its processing to form the film, by any method known per se. .
The invention also proposes:a composite safety screen - which has been produced by using partially acetalized polyvinyl B
.. . . ~ . . .. . .. .. . . . .
- :~1[37~Z~S
alcohol films modified in th.is way.
In accordance with a preferred embodiment of the invention, the sillcon-Euncti.onal silanes us~d ~or reducin~ the bond strength, correspond to the general formula Rn Si ~ R4 n in which R represents identical or different, satur~ted, linear or branched alkyl radicals with 1 to 18 carbon atoms, R' repre-sents identical or different radicals selected from the group consisting of Cl and the saturated alkoxy groups with l to 8 carbon atoms, which may optionally be interrupted by hereto atoms such as -O- or -S-, and n is a number ranging from O to 3.
The following silicon~functional silanes are mentioned by way of example: propyl triethoxy silane, propyl trimethoxy silane, isopropyl dimethoxy ethoxy silane, n-butyl or isobutyl triethoxy and trimethoxy silane, and the like.
According to another preferred embodiment of the invention, silicon-organo functional silanes used for increasing bond strength correspond to the general formula R ~ Si A Z
I
: 3 - n in which R represents identical or different hydrolysable radicals selected from the group consisting of Cl and the saturated alkoxy groups having from l to 8 carbon atoms, optionally interrupted by hereto atoms such as -O- or -S-, R' represents an alkyl radi!cal with 1 to 18 carbon atoms, A represents a divalent alkylene radical with l to lO carbon atoms, and Z represents a functional radlcal, such as -CH-CH2 or : -CH_CH2 or N R VR''' where R v represents H~or an amino alkyl with 2 to 8 carbon atoms in the alkyl radical, and R''' repre-sents H or an alkyl group having Erom 1 to 8 carbon atoms and ' _ ~ _ .
~L~7~8~
n is a nun~er from 1 to 3 and p is the number 1 or, where Z- -CH-CH2, stands for 0.
Accordingly, the preferred silicon-organo functional silanes are bifunctional. In addition to at least one hydrolysa-ble group, which reacts with the surface of the glass in the com-posite material, there must also be one reactive group which is able to react with the partially acetalized PVA film.
The following are mentioned as examples of silicon-organo functional silanes of this kind: vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl-tris-(~-methoxy e-thoxy)-silane, ~ methacryloxy propyl trimetho-xy silane, ~- glycidoxy propyl trimethoxy silane, ~-amino propyl triethoxy silane and the like.
;According to the invention, isotubyl trimethoxy silane is preferably used as the silicon-functional silane, whilst ~- glycidoxy propyl trimethoxy silane is preferably used as the silicon-organo functional silane.
The starting material used in the process according to the invention, consists in partially acetalized, polyvinyl alcohol. resins which still contain OH-groups. Preferably, use can be made of partially acetalized, polyvinyl alcohol resins which contain from 10 to 25% by weigth and preferably from 17 to 23~ by weight of vinyl alcohol radicals. It is preferred to use partially butyralized polyvinyl alcohol.
In composite safety screens of the kind used in the build.ing industry, for example as window panes or as partitions, the bond strength of the i.norganic glass to the film is of cr~cial importance~ In the event of accident or breakage, the glass must adhere firmly to the film to avoid injuries in the : form of cuts. Accordingly, composite screens, in which high pummel values are required, are preferably produced with partial-ly acetalyzed polyvinyl alcohol films (hereinafter referred to .:
as partially acetalized PVA-films~, whose bond strength has been : - 7 - :
l~C `
. ~ .
~6;Z 8~i adjusted to the highes-t possible pummel values by the addition of silicon-organo functional silanes or mixtures thereof to the corresponding partially acetalized PVA-resins.
The advantage of the process according to the invention is tha-t the bond strength of a partially acetalized PVA film to inorganic glasses can be adjusted to an optimum pummel value depending on its particular application. For example, a partially acetali~ed PVA resin batch, in which a preliminary -test has shown that it will lead to a glass/
partially acetalized PVA film/glass composite which cann~t be used for motor vehicle windscreens, but only as a composite safety screen in the building industry by virtue of its high bond strength, can be converted to "windscreen grade" by the addition of a silicon-func-tional silane which reduces bond strength, in a quan-tity determined by the preliminary test.
In contrast, a partially acetalized PVA resin of a "windscreen grade" can be converted to a resin of a "building grade", by the a~dition of a silicon-organo functional silane ; in a quantity determined by a preliminary test. Accordingly, the particular quality of the partially acetalized PVA resins is not a crucial factor. There is no more need for bo-th grades to be stored. .
Film waste in the composite screen indus-try is normally taken back by the film manufacturer and ex-truded back into film after having been worked up with fresh film.
Unfortunately, this has an uncon-trollable effect ~.
upon the quality of the new films. In most cases, therefore, the waste is not strictly sorted into windscreen grade and building grade. Accordingly, an indefinable mixture of waste 30 leads to films with unknown adhesion to glass. According to the invention, it is possible to process even unsorted waste into films of predetermined bond strength by employing a suita-~: :
~6;~5 ble combination of -the silanes used in accord~nce with the invention.
Tests conducted with various, partially acetal~
zed PVA-fil~s of dif~erent, unknov~ quali~y in regard to pum-mel value~, have shown that the required objective can be achieved by adding to the composi l;ion from which the film is extruded a miYture consisting of a silicon-organo functional silane which increases bond strength and a silicon-functional silane which reduces bond strength.
The quan~it~ and type o~ silane added are governed both by the purpose for which the composi-te screen is to be used and also by the properties of the partially acetalized PVA resin to be modified. It is dependent upon the pummel value of the unmodified partially acetalized PVA-~ilm.
~ he bond strength o~ a sheet of g].ass to a pla~:ti-cizer~containing7 partially acetalized polyvinyl alcohol film is determined by the so-called ~IpwLmel testtl. A sheet of composite glass (glass/partially acetalized PVA-fil~/glass) measuring approximately 150 ~ 300 mm, is cooled a-t -lsoa -t Oo5C for about 2 to 8 hours~ It is then placed on a me-tal block inclined at an angle o~ about 45~ and ham~exed ~ th a ~lat-headed hammer until the glass has been pulverized. '~he -~e~t sur*ace measures approxima-tely 100 x 150 ~un. Adhesion L~
assessed on a scale of 0 to 10. These values have the fo~lov~ng meaning:
, '.
~3 .
76'~S
% free ~ilm surface Pummel ~alue 100 , o 1 ~ 0 Visual assessment is made easier by the fact that~
in addition to the pummel ~aluesg symbols are also applied to the scale alo~gside the respective pummel value~ It has been ~ound that this (no~-quantitati~e) pummel test is entirely adequate for practical purposes~ and that -the re~uired bond strength can be adjusted with suf~ioient accuracy on the basi~
o~ the visual assessment. -In case ~he pummel value of the resin to be -modifiea cannot be determQned in adva~ce as a result of the `, ~ 20 addition of film waste, it is best to add a minimum quantity a~a silicon~organo functio~al silane ~hi¢h leads to the highest pummel valueO ~t the same time, the silicon-functional silane i9 added in the ~uantit~ necessary (o~ the basi~ of calibrated tables) for adjusting the required pummel value. HoweYer~ it i~ al~o possible, before proeessing a ~ew batch of partially acetallsed PVA resin to ~orm a fi~m, to produce a sample ¢omposite sareen an~ to determine its pummel ~alue~ On the.
basis of this predeter~ined pummel ~alue9 it is possible to : add the silane ~uitable ~or the required purpose in the quantity . .
determined empirioally be~orehand in series testsO ..
In practice~ the silane is used in quantities o~ -from a~out 0~005 to 002% by weight~ based on 100 par-t~ by ~', , . . ~.:
10 ~-. ~ ~
weight of film composition.
The silanes added in accordance with the in~ention may be added to the partially acetali~ed polyvinyl alcohol resins before they are processed into film form. ~or example, the partially acetalised PVA resin particles still containing plasticiser, which are kept in constant motion~ are sprayed wlth the silanes or silane solutions or dispersions~ Preferred solvents or dispers~nts are ~olvents or dispersants which are inert or substantially inert with respect to the partially acetalised PVA resin. Suitable ~olven-ts are, ~or example, water an~ water/alcohol mixtures. The ~olvent or dispersant may optionally be removed in a subse~uent drying operation, leaving a free~flowing partially acetalised PVA resin which, following the addition of plastlciser in the re~uisite ~uanti-ty, is subsequently processed by the film manufacturer by methods known ~ se, preferably by extrusion.
It i~ preferred to mix the ~ilanes and the plasti-~iser in a melt with the partiallg acetalised polyvinyl alcohol resins during processing into film form, for example in an ~x-truder. Where thîs procedure is adopted, it is be~t initial-~ ly to dissolve or disperse the silanes ~n the plasticiser to be : added before adding the ~ilane/plasticiser mixture to the partially acetalised PVA resin~ to be extruded~ I-t is pre~erred to use plasticisers in which the silanes are soluble. The proces~ according to the invention may be carried out with the pla~ticisers mentioned earlier on in re~erence to the prior art~ txiethylene glycol di-(2-ethyl butyrate) being preferred~
~h0 ~uan-tities of plastici~er to be added ~orrespond to the quantities normal~y used in the production of partially aceta-~0 lised PYA ~ilms.
The partiall~ acetalised PVA films modified in accordance with the invention are preferably used as adhesive , .
7 ~
~ilms in the manner normally adopted in the composite safety ~creen industry.
It is preferred to use as the adhesive film a silane-modified partially butyralised poly~inyl alcohol ~ilm ~hioh (a) has a plasticiser content of about 18 to about 65 parts by weightg preferably 33 to ~ parts by weight, per 100 parts by weight of PVB, (b) has a water content ranging from 0.2 to 0.9% by weight and ~c) has an OH-group co~tent9 expressed as vinyl alcohol~ ranging from 10 to 25% by weight, preferably from 16 to 2~ % by weightO
~ he composite~safety screens~ in which the partial~
ly acetalised PVA films modified i~ accordance with the inven-tion are used~ consist of two or more sheets o~ glass and, be-tween two sheets of glass9 a partlall~ acetalised plasticiser-¢ontaining PVA Eilm modified with silanes in accordance with the invention. In a glass/glass composite7 one o~ the ~heets oE glass may optionally be replaced b~ a sheet OI plastics material, ~or ex~mple of an amorphous polyamide ~cf. for example German Patent 1~596~781)o ~n this connection, it is o~ advantage to arrange two adhesive films between the two sheets, the adhesi~e film adjoining the sheet o~ glass being modiEied with silanes in accordance with the invention~ whilst the adhesi.ve Eilm adjoinlng the sheet of plastics material is unmodified. ~he same procedure can be adopted in the case of composite materials consisting o~ more than two supporting ~h~ets, for example glass/plastics/glass composites~ In the case of glass/plastics/plastics/glass composi-tes, it is best to use only a~ unmodified partiall~ acetalised P~A film as the adhesive fi~m between the plastics/plastics sheets~
~- 30 EX~PJES
~ he breakage resistance ~uoted in the ~amples is determd~d in accordance with DIN 52 306 (Februa~r 197~) or . ' ';'.
~ 12 -1~7~85 U~A S~ Z 26.1 Test Number 26 (1966), using the dropped ball~
The change in the pummel values indicated in the ~ollowing ~ables, brought about by addition of the silane, was carried out on composite ~a~ety screen~ which had been produced as follows:
The silane was added to the PVB resin (OH-group oontent~ expres~ed as vinyl alcohol~ ~8~5% by weight) during production o~ thePVB film in an extruder. ~he PVB resin to which l`able 1 relates came from a dif~erent batch ~rom the PYB resin uæed in Table 20 Composite screens which contained two 3 mm thick sheets of glass with a 0~76 mm thick PVB film in between, were tested in the ~xamples~
~ hc composite screçns were produced over a period of 10 to 30 minutes under a pxe~sure of 10 to 15 kp/om2 and at a t0mperature of from 130 to 135Co Txiethylene glycol di-(2-ethyl butyrate) was u~ed : as the plastici~er in a quantity of 35 parts by weight per 100 parts by weight of PVB re~in.
~ .
, ~
: ~ 13 ~ . .
, ,, 7 ~Z ~ S
~able l _ Example ~ by Pummel BaJ.l % by ~ilm weight value dropping weight thickness of height of water mm silane*) m in the fil~
_, 1 0 101.50 0.5 0.76 2 0.~ 72.50 0.5 0.76
However, the process disclosed in the above-mentioned US-PS is not concerned wi-th ajdusting the bond strength of a plasticizer containing, partially acetalized PVA film used for bonding inor-ganic glasses to the pummel values regarded as optimum for the particular application to which the bonded glasses are intended.
There is nothing in that US patent specification which could assist in solving the problem with which the present invention is concerned.
The present invention proposes a process for adjust-ing the bond strength of a plasticizer~con-taining, par-tially acetalized polyvinyl alcohol film usable for bonding inorganic glasses, to the pummel value required for its particular appli-cation which process comprises the step of adding a predetermined ~ 20 quantity of ~ a) a silicon-fwlctional silane to reduce the bond strength, or a mixture of different silicon-functional silanes, or b) a sili.con-organo :Eunctional silane to increase the bond strength, or a mixture o silicon-organo functional sil.anes, or ~ c) a mixtur.e of a-t least one silicon~Eunctional silane with at least one silicon-organo functional silane, to the partially acetalized polyvinyl alcohol resin before or during its processing to form the film, by any method known per se. .
The invention also proposes:a composite safety screen - which has been produced by using partially acetalized polyvinyl B
.. . . ~ . . .. . .. .. . . . .
- :~1[37~Z~S
alcohol films modified in th.is way.
In accordance with a preferred embodiment of the invention, the sillcon-Euncti.onal silanes us~d ~or reducin~ the bond strength, correspond to the general formula Rn Si ~ R4 n in which R represents identical or different, satur~ted, linear or branched alkyl radicals with 1 to 18 carbon atoms, R' repre-sents identical or different radicals selected from the group consisting of Cl and the saturated alkoxy groups with l to 8 carbon atoms, which may optionally be interrupted by hereto atoms such as -O- or -S-, and n is a number ranging from O to 3.
The following silicon~functional silanes are mentioned by way of example: propyl triethoxy silane, propyl trimethoxy silane, isopropyl dimethoxy ethoxy silane, n-butyl or isobutyl triethoxy and trimethoxy silane, and the like.
According to another preferred embodiment of the invention, silicon-organo functional silanes used for increasing bond strength correspond to the general formula R ~ Si A Z
I
: 3 - n in which R represents identical or different hydrolysable radicals selected from the group consisting of Cl and the saturated alkoxy groups having from l to 8 carbon atoms, optionally interrupted by hereto atoms such as -O- or -S-, R' represents an alkyl radi!cal with 1 to 18 carbon atoms, A represents a divalent alkylene radical with l to lO carbon atoms, and Z represents a functional radlcal, such as -CH-CH2 or : -CH_CH2 or N R VR''' where R v represents H~or an amino alkyl with 2 to 8 carbon atoms in the alkyl radical, and R''' repre-sents H or an alkyl group having Erom 1 to 8 carbon atoms and ' _ ~ _ .
~L~7~8~
n is a nun~er from 1 to 3 and p is the number 1 or, where Z- -CH-CH2, stands for 0.
Accordingly, the preferred silicon-organo functional silanes are bifunctional. In addition to at least one hydrolysa-ble group, which reacts with the surface of the glass in the com-posite material, there must also be one reactive group which is able to react with the partially acetalized PVA film.
The following are mentioned as examples of silicon-organo functional silanes of this kind: vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl-tris-(~-methoxy e-thoxy)-silane, ~ methacryloxy propyl trimetho-xy silane, ~- glycidoxy propyl trimethoxy silane, ~-amino propyl triethoxy silane and the like.
;According to the invention, isotubyl trimethoxy silane is preferably used as the silicon-functional silane, whilst ~- glycidoxy propyl trimethoxy silane is preferably used as the silicon-organo functional silane.
The starting material used in the process according to the invention, consists in partially acetalized, polyvinyl alcohol. resins which still contain OH-groups. Preferably, use can be made of partially acetalized, polyvinyl alcohol resins which contain from 10 to 25% by weigth and preferably from 17 to 23~ by weight of vinyl alcohol radicals. It is preferred to use partially butyralized polyvinyl alcohol.
In composite safety screens of the kind used in the build.ing industry, for example as window panes or as partitions, the bond strength of the i.norganic glass to the film is of cr~cial importance~ In the event of accident or breakage, the glass must adhere firmly to the film to avoid injuries in the : form of cuts. Accordingly, composite screens, in which high pummel values are required, are preferably produced with partial-ly acetalyzed polyvinyl alcohol films (hereinafter referred to .:
as partially acetalized PVA-films~, whose bond strength has been : - 7 - :
l~C `
. ~ .
~6;Z 8~i adjusted to the highes-t possible pummel values by the addition of silicon-organo functional silanes or mixtures thereof to the corresponding partially acetalized PVA-resins.
The advantage of the process according to the invention is tha-t the bond strength of a partially acetalized PVA film to inorganic glasses can be adjusted to an optimum pummel value depending on its particular application. For example, a partially acetali~ed PVA resin batch, in which a preliminary -test has shown that it will lead to a glass/
partially acetalized PVA film/glass composite which cann~t be used for motor vehicle windscreens, but only as a composite safety screen in the building industry by virtue of its high bond strength, can be converted to "windscreen grade" by the addition of a silicon-func-tional silane which reduces bond strength, in a quan-tity determined by the preliminary test.
In contrast, a partially acetalized PVA resin of a "windscreen grade" can be converted to a resin of a "building grade", by the a~dition of a silicon-organo functional silane ; in a quantity determined by a preliminary test. Accordingly, the particular quality of the partially acetalized PVA resins is not a crucial factor. There is no more need for bo-th grades to be stored. .
Film waste in the composite screen indus-try is normally taken back by the film manufacturer and ex-truded back into film after having been worked up with fresh film.
Unfortunately, this has an uncon-trollable effect ~.
upon the quality of the new films. In most cases, therefore, the waste is not strictly sorted into windscreen grade and building grade. Accordingly, an indefinable mixture of waste 30 leads to films with unknown adhesion to glass. According to the invention, it is possible to process even unsorted waste into films of predetermined bond strength by employing a suita-~: :
~6;~5 ble combination of -the silanes used in accord~nce with the invention.
Tests conducted with various, partially acetal~
zed PVA-fil~s of dif~erent, unknov~ quali~y in regard to pum-mel value~, have shown that the required objective can be achieved by adding to the composi l;ion from which the film is extruded a miYture consisting of a silicon-organo functional silane which increases bond strength and a silicon-functional silane which reduces bond strength.
The quan~it~ and type o~ silane added are governed both by the purpose for which the composi-te screen is to be used and also by the properties of the partially acetalized PVA resin to be modified. It is dependent upon the pummel value of the unmodified partially acetalized PVA-~ilm.
~ he bond strength o~ a sheet of g].ass to a pla~:ti-cizer~containing7 partially acetalized polyvinyl alcohol film is determined by the so-called ~IpwLmel testtl. A sheet of composite glass (glass/partially acetalized PVA-fil~/glass) measuring approximately 150 ~ 300 mm, is cooled a-t -lsoa -t Oo5C for about 2 to 8 hours~ It is then placed on a me-tal block inclined at an angle o~ about 45~ and ham~exed ~ th a ~lat-headed hammer until the glass has been pulverized. '~he -~e~t sur*ace measures approxima-tely 100 x 150 ~un. Adhesion L~
assessed on a scale of 0 to 10. These values have the fo~lov~ng meaning:
, '.
~3 .
76'~S
% free ~ilm surface Pummel ~alue 100 , o 1 ~ 0 Visual assessment is made easier by the fact that~
in addition to the pummel ~aluesg symbols are also applied to the scale alo~gside the respective pummel value~ It has been ~ound that this (no~-quantitati~e) pummel test is entirely adequate for practical purposes~ and that -the re~uired bond strength can be adjusted with suf~ioient accuracy on the basi~
o~ the visual assessment. -In case ~he pummel value of the resin to be -modifiea cannot be determQned in adva~ce as a result of the `, ~ 20 addition of film waste, it is best to add a minimum quantity a~a silicon~organo functio~al silane ~hi¢h leads to the highest pummel valueO ~t the same time, the silicon-functional silane i9 added in the ~uantit~ necessary (o~ the basi~ of calibrated tables) for adjusting the required pummel value. HoweYer~ it i~ al~o possible, before proeessing a ~ew batch of partially acetallsed PVA resin to ~orm a fi~m, to produce a sample ¢omposite sareen an~ to determine its pummel ~alue~ On the.
basis of this predeter~ined pummel ~alue9 it is possible to : add the silane ~uitable ~or the required purpose in the quantity . .
determined empirioally be~orehand in series testsO ..
In practice~ the silane is used in quantities o~ -from a~out 0~005 to 002% by weight~ based on 100 par-t~ by ~', , . . ~.:
10 ~-. ~ ~
weight of film composition.
The silanes added in accordance with the in~ention may be added to the partially acetali~ed polyvinyl alcohol resins before they are processed into film form. ~or example, the partially acetalised PVA resin particles still containing plasticiser, which are kept in constant motion~ are sprayed wlth the silanes or silane solutions or dispersions~ Preferred solvents or dispers~nts are ~olvents or dispersants which are inert or substantially inert with respect to the partially acetalised PVA resin. Suitable ~olven-ts are, ~or example, water an~ water/alcohol mixtures. The ~olvent or dispersant may optionally be removed in a subse~uent drying operation, leaving a free~flowing partially acetalised PVA resin which, following the addition of plastlciser in the re~uisite ~uanti-ty, is subsequently processed by the film manufacturer by methods known ~ se, preferably by extrusion.
It i~ preferred to mix the ~ilanes and the plasti-~iser in a melt with the partiallg acetalised polyvinyl alcohol resins during processing into film form, for example in an ~x-truder. Where thîs procedure is adopted, it is be~t initial-~ ly to dissolve or disperse the silanes ~n the plasticiser to be : added before adding the ~ilane/plasticiser mixture to the partially acetalised PVA resin~ to be extruded~ I-t is pre~erred to use plasticisers in which the silanes are soluble. The proces~ according to the invention may be carried out with the pla~ticisers mentioned earlier on in re~erence to the prior art~ txiethylene glycol di-(2-ethyl butyrate) being preferred~
~h0 ~uan-tities of plastici~er to be added ~orrespond to the quantities normal~y used in the production of partially aceta-~0 lised PYA ~ilms.
The partiall~ acetalised PVA films modified in accordance with the invention are preferably used as adhesive , .
7 ~
~ilms in the manner normally adopted in the composite safety ~creen industry.
It is preferred to use as the adhesive film a silane-modified partially butyralised poly~inyl alcohol ~ilm ~hioh (a) has a plasticiser content of about 18 to about 65 parts by weightg preferably 33 to ~ parts by weight, per 100 parts by weight of PVB, (b) has a water content ranging from 0.2 to 0.9% by weight and ~c) has an OH-group co~tent9 expressed as vinyl alcohol~ ranging from 10 to 25% by weight, preferably from 16 to 2~ % by weightO
~ he composite~safety screens~ in which the partial~
ly acetalised PVA films modified i~ accordance with the inven-tion are used~ consist of two or more sheets o~ glass and, be-tween two sheets of glass9 a partlall~ acetalised plasticiser-¢ontaining PVA Eilm modified with silanes in accordance with the invention. In a glass/glass composite7 one o~ the ~heets oE glass may optionally be replaced b~ a sheet OI plastics material, ~or ex~mple of an amorphous polyamide ~cf. for example German Patent 1~596~781)o ~n this connection, it is o~ advantage to arrange two adhesive films between the two sheets, the adhesi~e film adjoining the sheet o~ glass being modiEied with silanes in accordance with the invention~ whilst the adhesi.ve Eilm adjoinlng the sheet of plastics material is unmodified. ~he same procedure can be adopted in the case of composite materials consisting o~ more than two supporting ~h~ets, for example glass/plastics/glass composites~ In the case of glass/plastics/plastics/glass composi-tes, it is best to use only a~ unmodified partiall~ acetalised P~A film as the adhesive fi~m between the plastics/plastics sheets~
~- 30 EX~PJES
~ he breakage resistance ~uoted in the ~amples is determd~d in accordance with DIN 52 306 (Februa~r 197~) or . ' ';'.
~ 12 -1~7~85 U~A S~ Z 26.1 Test Number 26 (1966), using the dropped ball~
The change in the pummel values indicated in the ~ollowing ~ables, brought about by addition of the silane, was carried out on composite ~a~ety screen~ which had been produced as follows:
The silane was added to the PVB resin (OH-group oontent~ expres~ed as vinyl alcohol~ ~8~5% by weight) during production o~ thePVB film in an extruder. ~he PVB resin to which l`able 1 relates came from a dif~erent batch ~rom the PYB resin uæed in Table 20 Composite screens which contained two 3 mm thick sheets of glass with a 0~76 mm thick PVB film in between, were tested in the ~xamples~
~ hc composite screçns were produced over a period of 10 to 30 minutes under a pxe~sure of 10 to 15 kp/om2 and at a t0mperature of from 130 to 135Co Txiethylene glycol di-(2-ethyl butyrate) was u~ed : as the plastici~er in a quantity of 35 parts by weight per 100 parts by weight of PVB re~in.
~ .
, ~
: ~ 13 ~ . .
, ,, 7 ~Z ~ S
~able l _ Example ~ by Pummel BaJ.l % by ~ilm weight value dropping weight thickness of height of water mm silane*) m in the fil~
_, 1 0 101.50 0.5 0.76 2 0.~ 72.50 0.5 0.76
3 ~4 54.00 0.5 0.76
4 0~5 35.50 0~5 0.76 ~) isobutyl trimethoxy silane ~ -10 Table 2 Bond strength is signi~icantly in¢reased~ as shown by the following Examples.
E~ample ~ by weight P~mmel % by weight of of silane ~) value water in the ~ilm 0 ~ 0~5 6 0.005 3 0~5 :
7 0.01 5 0-5 B 0~1 10 0O5 *) ~-glycidyl hydroxy propyl t~imethoxy silane .
' ' a~
E~amples 9 and 10 relate to the use o~ ~ilm waste ~ogether with ~resh, partially butyralised polyvinyl alcohol resin. ~hs pummel value cannot be de~ined on account of the ~luatuating aomposi~ion o~ the film material:
: Example 9: ~ilane l-001% by weight ~ silane 2-0.45% by weight, pummel ~alue e 5 Example 10: ~ilane 1=0.1% by weight ~ silane 2=Oo6% b~ weight~
: pummel ~alue - 2 ~: silane 1 - ~-glycidyl hydroxy propyl trimethoxy silane ~ilane 2 = isobutyl trimethoxy silane The ~uantities indicated in the ~able are based ~n ~00 parts by weight o~ film oompositionO
:
E~ample ~ by weight P~mmel % by weight of of silane ~) value water in the ~ilm 0 ~ 0~5 6 0.005 3 0~5 :
7 0.01 5 0-5 B 0~1 10 0O5 *) ~-glycidyl hydroxy propyl t~imethoxy silane .
' ' a~
E~amples 9 and 10 relate to the use o~ ~ilm waste ~ogether with ~resh, partially butyralised polyvinyl alcohol resin. ~hs pummel value cannot be de~ined on account of the ~luatuating aomposi~ion o~ the film material:
: Example 9: ~ilane l-001% by weight ~ silane 2-0.45% by weight, pummel ~alue e 5 Example 10: ~ilane 1=0.1% by weight ~ silane 2=Oo6% b~ weight~
: pummel ~alue - 2 ~: silane 1 - ~-glycidyl hydroxy propyl trimethoxy silane ~ilane 2 = isobutyl trimethoxy silane The ~uantities indicated in the ~able are based ~n ~00 parts by weight o~ film oompositionO
:
Claims (7)
1. A process for adjusting the bond strength of a plasticizer-containing, partially acetalized polyvinyl alcohol film used for bonding inorganic glasses, to the pummel value required for the particular application to which the bonded glasses are intended, said process comprising the step of adding a predetermined quantity of a) a silicon-functional silane to reduce the bond strength, or a mixture of different silicon-functional silanes, or b) a silicon-organo functional silane to increase the bond strength, or a mixture of silicon-organo functional silanes, or c) a mixture of at least one silicon-functional silane with at least one silicon-organo functional silane, to said plasticizer-containing, partially acetalized polyvinyl alcohol resin before or during its processing to form the film.
2. A process as claimed in claim 1, wherein the silicon-functional silanes used are of the general formula in which R represents identical or different saturated , linear or branched alkyl radicals with 1 to 18 carbon atoms, R' represents identical or different radicals selected from the group consisting of Cl, the saturated alkoxy groups having from 1 to 8 carbon atoms and the saturated alkoxy groups having from 1 to 8 carbon atoms interrupted by hereto atoms selected from the group consisting of -O- and -S-, and n is a number ranging from 0 to 3.
3. A process as claimed in claim 1, wherein the silicon-organo functional silanes used are of the general formula in which R represents identical or different hydrolysable radicals selected from the group consisting of Cl, the saturated alkoxy groups having from 1 to 8 carbon atoms, and the saturated alkoxy groups having from 1 to 8 carbon atoms interrupted by heteroatoms selected from the group consisting of - O - and - S -;
R' represents an alkyl radical with 1 to 18 carbon atoms, A represents a divalent alkylene radical with 1 to 10 carbon atoms;
Z represents a functional radical, selected from the group consisting of ;
-CH=CH2 and N R'vR''', where R'v represents H or an amino alkyl group with 2 to 8 carbon atoms in the alkyl radical, and R''' represents H or an alkyl group having from 1 to 8 carbon atoms n is a number from 1 to 3, and p stands for 1 or, where Z represents -CH=CH2, for 0.
R' represents an alkyl radical with 1 to 18 carbon atoms, A represents a divalent alkylene radical with 1 to 10 carbon atoms;
Z represents a functional radical, selected from the group consisting of ;
-CH=CH2 and N R'vR''', where R'v represents H or an amino alkyl group with 2 to 8 carbon atoms in the alkyl radical, and R''' represents H or an alkyl group having from 1 to 8 carbon atoms n is a number from 1 to 3, and p stands for 1 or, where Z represents -CH=CH2, for 0.
4. A process as claimed in claim 1 or 2, wherein the silicon-functional silane used is isobutyl trimethoxy silane.
5. A process as claimed in claim 1 or 3, wherein the silicon-organo functional silane used is ?-glycidoxy propyl trimethoxy silane.
6. A process as claimed in claim 1, 2 or 3, wherein the partially acetalized polyvinyl alcohol resin used is a partially butyralized polyvinyl resin containing from about 10 to 25% by weight of vinyl alcohol radicals.
7. A process as claimed in claim 1, 2 or 3, wherein the partially acetalized polyvinyl alcohol resin used is a polyvinyl butyral resin containing from 17 to 23% by weight of vinyl alcohol radicals.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742410153 DE2410153C3 (en) | 1974-03-02 | Process for adjusting the adhesive force of partially acetalized polyvinyl alcohol films containing plasticizers on inorganic glasses and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1076285A true CA1076285A (en) | 1980-04-22 |
Family
ID=5908979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA221,033A Expired CA1076285A (en) | 1974-03-02 | 1975-02-28 | Process for the production of modified, partially acetalised polyvinyl alcohol films |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS5839178B2 (en) |
| AT (1) | AT342809B (en) |
| BE (1) | BE826132A (en) |
| BR (1) | BR7501175A (en) |
| CA (1) | CA1076285A (en) |
| CH (1) | CH613217A5 (en) |
| CS (1) | CS203086B2 (en) |
| DD (1) | DD115103A5 (en) |
| FI (1) | FI750596A (en) |
| FR (1) | FR2262649B1 (en) |
| GB (1) | GB1503018A (en) |
| IN (1) | IN143364B (en) |
| IT (1) | IT1029904B (en) |
| NL (1) | NL7502410A (en) |
| RO (1) | RO70200A (en) |
| SE (1) | SE414168B (en) |
| YU (1) | YU39314B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2549474A1 (en) * | 1975-11-05 | 1977-05-12 | Dynamit Nobel Ag | METHOD FOR MANUFACTURING LAMINATED SAFETY GLASS |
| LU74681A1 (en) * | 1976-04-02 | 1977-10-26 | ||
| AR218642A1 (en) * | 1976-10-30 | 1980-06-30 | Dynamit Nobel Ag | PROCEDURE FOR THE MANUFACTURE OF SAFETY LAMINATED GLASSES |
| DE3128530A1 (en) * | 1981-07-18 | 1983-02-03 | Dynamit Nobel Ag, 5210 Troisdorf | SOFTENING FILMS FROM PARTLY ACETALIZED POLYVINYL ALCOHOLS |
| JPH0344042Y2 (en) * | 1985-03-19 | 1991-09-17 | ||
| JPS61207285U (en) * | 1985-06-14 | 1986-12-27 | ||
| EP1193185A1 (en) * | 2000-10-02 | 2002-04-03 | Heineken Technical Services B.V. | Glass container with improved coating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3341399A (en) * | 1966-11-16 | 1967-09-12 | Brockway Glass Co Inc | Glass to glass adhesives |
-
1974
- 1974-12-14 DD DD183048A patent/DD115103A5/xx unknown
-
1975
- 1975-01-23 FR FR7502156A patent/FR2262649B1/fr not_active Expired
- 1975-02-03 JP JP50014201A patent/JPS5839178B2/en not_active Expired
- 1975-02-24 IN IN348/CAL/1975A patent/IN143364B/en unknown
- 1975-02-24 CH CH227075A patent/CH613217A5/en not_active IP Right Cessation
- 1975-02-24 YU YU430/75A patent/YU39314B/en unknown
- 1975-02-27 SE SE7502242A patent/SE414168B/en unknown
- 1975-02-27 BR BR1175/75A patent/BR7501175A/en unknown
- 1975-02-28 IT IT48398/75A patent/IT1029904B/en active
- 1975-02-28 RO RO7581528A patent/RO70200A/en unknown
- 1975-02-28 FI FI750596A patent/FI750596A/fi not_active Application Discontinuation
- 1975-02-28 CA CA221,033A patent/CA1076285A/en not_active Expired
- 1975-02-28 AT AT154975A patent/AT342809B/en not_active IP Right Cessation
- 1975-02-28 BE BE153869A patent/BE826132A/en not_active IP Right Cessation
- 1975-02-28 CS CS751376A patent/CS203086B2/en unknown
- 1975-02-28 NL NL7502410A patent/NL7502410A/en not_active Application Discontinuation
- 1975-02-28 GB GB8590/75A patent/GB1503018A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1503018A (en) | 1978-03-08 |
| DD115103A5 (en) | 1975-09-12 |
| YU43075A (en) | 1982-05-31 |
| CS203086B2 (en) | 1981-02-27 |
| JPS5839178B2 (en) | 1983-08-27 |
| FR2262649B1 (en) | 1982-04-23 |
| ATA154975A (en) | 1977-08-15 |
| FI750596A (en) | 1975-09-03 |
| AT342809B (en) | 1978-04-25 |
| RO70200A (en) | 1982-04-12 |
| IN143364B (en) | 1977-11-12 |
| DE2410153A1 (en) | 1975-09-04 |
| FR2262649A1 (en) | 1975-09-26 |
| IT1029904B (en) | 1979-03-20 |
| JPS50119850A (en) | 1975-09-19 |
| CH613217A5 (en) | 1979-09-14 |
| BR7501175A (en) | 1975-12-02 |
| BE826132A (en) | 1975-06-16 |
| NL7502410A (en) | 1975-09-04 |
| YU39314B (en) | 1984-10-31 |
| SE7502242L (en) | 1975-09-03 |
| DE2410153B2 (en) | 1976-06-16 |
| SE414168B (en) | 1980-07-14 |
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