(19)

*EP003095601B1*
(11) EP 3 095 601 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) International Patent Classification (IPC):
of the grant of the patent: B32B 17/10 (2006.01) B32B 27/08 (2006.01)
05.07.2023 Bulletin 2023/27 B32B 27/30 (2006.01)

(21) Application number: 15168791.0 (52) Cooperative Patent Classification (CPC):

B32B 17/10761; B32B 17/10036; B32B 17/10596;
(22) Date of filing: 22.05.2015 B32B 17/10605; B32B 17/10633; B32B 17/10688;
B32B 27/08; B32B 27/306; B32B 2307/56

(54) PENETRATION RESISTANT LAMINATED GLASS MANUFACTURED WITH INTERLAYER FILM

LAYERS HAVING REDUCED ADHESION AND LOW PLASTICIZER CONTENT
PENETRATIONSRESISTENTES, MIT ZWISCHENSCHICHTFILMSCHICHTEN MIT REDUZIERTER
HAFTUNG UND NIEDRIGEM WEICHMACHERGEHALT HERGESTELLTES VERBUNDGLAS
VERRE FEUILLETÉ RÉSISTANT À LA PÉNÉTRATION, FABRIQUÉ AVEC DES COUCHES DE FILM
INTERCOUCHES PRÉSENTANT UNE ADHÉRENCE RÉDUITE ET UNE FAIBLE TENEUR EN
PLASTIFIANT

(84) Designated Contracting States: (72) Inventor: Keller, Uwe

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB 53177 Bonn (DE)
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO
PL PT RO RS SE SI SK SM TR (74) Representative: Janßen, Christian Oliver
Kuraray Europe GmbH
(43) Date of publication of application: Phillip-Reis-Straße 4
23.11.2016 Bulletin 2016/47 65795 Hattersheim (DE)

(73) Proprietor: Kuraray Europe GmbH (56) References cited:

65795 Hattersheim (DE) US-A1- 2005 118 445 US-A1- 2014 110 039
US-A1- 2014 224 423 US-B2- 7 462 664
EP 3 095 601 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Processed by Luminess, 75001 PARIS (FR)

 EP 3 095 601 B1

Description

Technical Field

5 [0001] The present invention relates to laminated glass comprising two glass sheets combined by an adhesive interlayer
film which is manufactured with at least one layer based on polyvinyl acetal having low plasticizer content and an adhesion
control agent to provide good penetration resistance.
[0002] For manufacturing laminated glazing with good penetration resistance, for example for automotive application
like windscreens according to ECE R43 or in buildings according to EN 356 it is known to laminate two glass sheets
10 with plasticized polyvinyl butyral having reduced adhesion to glass. The reduced adhesion shall ensure energy uptake
by the interlayer in case of a mechanical impact by stretching rather than breaking. On the other hand, adhesion should
be high enough to prevent delamination of glass splinters from the interlayer. Both effects can be summarized by the
property "penetration resistance".
[0003] The adhesion of such plasticized polyvinyl butyral films (PVB films) is usually adjusted by adding small amounts
15 of adhesion control agents like metal salts, especially alkali or alkaline earth metal salts to the bulk of the film. During
lamination to the glass, such metal ions interact with the glass surface, resulting in a reduced adhesion of the PVB-film
to the glass surface. The amount of adhesion control agent depends on the composition of the PVB film and the surface
chemistry of the glass sheets. Of course, adhesion control is necessary for all interfaces between glass and film surfaces,
since the penetration resistance is limited by the interface with highest adhesion. Thus, a laminated glass with one
20 interface of low adhesion and a second interface of high adhesion will rather exhibit the poor impact performance of a
laminated glass with too high adhesion on both interfaces.
[0004] Recently, thin PVB-films having a low or no plasticizer content have been proposed as "functionality carrier" in
addition with thick PVB-films having the usual content of plasticizer and adhesion control agent for the production of
functionalized laminated glazing.
25 [0005] In such laminates, the thin PVB-films ca be in contact with the glass surface. It was found that although metal
salts are thought to migrate from the plasticized, thick PVB-films to the thin PVB-films, the resulting adhesion of the
interlayer film to the glass was too high to achieve good penetration resistance.
[0006] Furthermore, it was found that simply adding the same amount and type of adhesion control agent commonly
used in thick, plasticized PVB film in contact with glass does not reduce adhesion of low plasticized PVB films as
30 necessary by for example the impact requirements as stipulated by ECE R43.
[0007] Usually, plasticized PVB film in contact with glass are additionally supplied with magnesium salts as adhesion
control agent in order to reduce differences in surface chemistry of the glass sheets. Surprisingly, it was found that
magnesium salts have a very limited impact on adhesion of low plasticized PVB-films to glass as compared to plasticized
PVB-film.
35 [0008] US2014/224423 A1 discloses a laminated glass obtained by laminating at least one film containing a polyvinyl
acetal and a low or no plasticiser content and at least one film containing a polyvinyl acetal and a standard content of
plasticiser in between two glass sheets.

Object of the invention

40
[0009] Object of the present invention was therefore to provide layers for laminated glazing with a reduced plasticizer
content which give the final laminated glass good penetration properties.
[0010] It has been found that a certain amount of alkali metal ions in the thin, low plasticizer film provides sufficient
reduction of adhesion to the glass surface.
45 [0011] The invention therefore relates to laminated glass obtained by laminating at least one film A containing a
polyvinyl acetal PA and optionally at least one plasticiser WA and at least one film B containing a polyvinyl acetal PB
and at least one plasticiser WB between two glass sheets, wherein prior to lamination

- the amount of plasticiser WA in film A is less than 16 % by weight

50 - the amount of plasticiser WB in film B is at least 16 % by weight and
- film A comprises 39 to 1170 ppm potassium ions and has an alkaline titer higher than 10.

[0012] The invention further relates to methods for producing the laminated glass as defined in the appended claims.
[0013] Hereinafter, the term "prior to lamination" is understood to mean the state of the films A and B prior to having
55 any contact to each other. For example, the term refers to the composition of each film separately formed and separately
wound to individual rolls. The term "prior to lamination" refers to the state for the layers or films before combining them
either in the lamination process of the laminated glass or prior to building a stack from the layers used for lamination.
[0014] Preferred ranges of concentration of the potassium ions are 78 - 780 ppm and preferably 117 - 780 ppm. It is

2
 EP 3 095 601 B1

furthermore preferred to add the potassium ions in form of salts of carboxylic acids having 1 to 10 carbon atoms.
[0015] Film A used in the laminates of the invention may additionally comprise alkaline earth ions, but since their effect
on adhesion is limited, only small amounts as compared to the alkali ion should be used. In a first embodiment of the
invention film A comprises 0 to 20 ppm alkaline earth ions, preferably 0 to 5 ppm. However, it is known that alkaline
5 earth ions have a balancing effect of adhesion when a plasticized PVB film faces two glass sheets with different surface
chemistry. Accordingly, in a second embodiment of the invention, film A comprises 5 - 20 ppm alkaline earth ions. The
alkaline earth ions can be added in form salts of carboxylic acids having 1 to 10 carbon atoms. Especially preferred is
magnesium acetate as secondary adhesion control agent. In this embodiment, the ratio of alkali ions to alkaline earth
ions in ppm in film A is preferable at least than 1, especially higher than 5 and more preferred higher than 10.
10 [0016] In addition, the alkaline titer of film A may be higher than 20, higher than 40, higher than 50, higher than 80,
higher than 90 and preferred higher than 100, in each case with a maximum value of 500. In contrast to film A, the
alkaline titer of film B is preferred to be lower, and more particularly the difference between alkaline titer (film A)-alkaline
titer (film B) is more than 2, 6 and preferably more than 10 AT units.
[0017] In order to avoid haze, the amount of chloride ions and/or nitrate ions and/or sulphate ions in film A may be
15 reduced.
[0018] The chloride content of the film A can thus be less than 150 ppm, preferably less than 100 ppm, and in particular
less than 50 ppm. In the ideal case, the chloride content of the film A is less than 10 ppm or even 0 ppm.
[0019] The nitrate content of film A optionally may be less than 150 ppm, preferably less than 100 ppm, and in particular
less than 50 ppm. In the ideal case, the nitrate content of film A is less than 10 ppm or even 0 ppm.
20 [0020] Again optionally, the sulphate content of film A may be less than 150 ppm, preferably less than 100 ppm, and
in particular less than 50 ppm. In the ideal case, the sulphate content of the film A is less than 10 ppm or even 0 ppm.
[0021] The adhesion of the interlayer film to the glass sheet can be assessed by measuring the compressive shear
strength of a test laminate according to DE 197 56 274 A1. In this test, the compressive shear strength is determined
for a laminate build from 2 mm float glass / film A with alkali metal ion / 0.76 mm film B of Mowital B75H (product of
25 Kuraray Europe GmbH) comprising 27.5 % 3G8/DBEA (10:1 mix by wght) as plasticizer, free of adhesion reducing
additives / film A with alkali metal ion /2 mm float glass, after one week conditioning the test laminate at 23 °C.
[0022] In another variant of the invention, the laminated glass may have a compressive shear strength according to
DE 197 56 274 A1 between 22 N/mm 2 and 4 N/mm 2, preferable between 20 N/mm2 and 4 N/mm2, preferable between
18 N/mm2 and 5 N/mm2, preferable between 16 N/mm 2 and 6 N/mm2, preferable between 15 N/mm2 and 7 N/mm2,
30 preferable between 14 N/mm2 and 7 N/mm2, preferable between 13 N/mm2 and 7 N/mm2, and most preferred between
12 N/mm2 and 8 N/mm 2.
[0023] The films A and B may contain, in the starting state prior to lamination and/or in a stack prepared for lamination
between glass sheets, a single plasticiser as well as mixtures of plasticisers both of different and identical composition.
The term "different composition" refers to both the type of plasticiser and proportion thereof in the mixture. Film A and
35 film B after lamination, i.e. in the finished laminated glass, preferably have the same plasticisers WA and WB. In a
preferred variant, film A in its starting state, however, does not contain any plasticiser and after lamination contains
plasticiser WB in equilibrium amount.
[0024] Plasticiser-containing films B used in accordance with the invention contain, in the starting state prior to lami-
nation, at least 16 % by weight, such as 16.1 - 36.0 % by weight, preferably 22.0 - 32.0 % by weight and in particular
40 26.0 - 30.0 % by weight plasticiser.
[0025] Films A used in accordance with the invention may contain, in the starting state prior to lamination, less than
16 % by weight (such as 15.9 % by weight), less than 12 % by weight, less than 8 % by weight, less than 6 % by weight,
less than 4 % by weight, less than 2 % by weight, less than 1 % by weight or even no plasticiser (0.0 % by weight). In
a preferred embodiment of the invention, films A with a low plasticiser content preferably contain 0.0 - 8 % by weight
45 plasticiser.
[0026] In the method according to the invention, the film A in the starting state prior to lamination has a thickness of
no more than 20 %, preferably 15 %, and preferably no more than 10 % of the thickness of the film or films B.
[0027] The thickness of a film A in the starting state prior to lamination is 10 - 250 pm, preferably 20 - 160 pm, preferably
30 - 120 pm, preferably 40 - 100 mm and at most preferably 50 - 80 mm. This range of thickness does not include
50 additional coating on the films. In the laminated glass, the thickness of the film can increase by transfer of plasticiser
from film B.
[0028] Film A is produced separately from film B (for example extruded or solvent cast) and has either no plasticiser
at all or sufficiently small proportion of plasticiser so that subsequent functionalization and processing is not adversely
influenced.
55 [0029] The thickness of a film B in the starting state is 450 - 2500 pm, preferably 600 - 1000 pm, preferably 700 - 900
mm. A plurality of films B may be used in the invention, either being stacked on each other or separated by films A.
[0030] If films B are stretched prior to production of the sandwich and/or additionally are adapted to the shape of a
screen (for example a windscreen) in a curved manner, the specified thicknesses at the moment of lamination may

3
 EP 3 095 601 B1

reduce once more by up to 20 %.

[0031] At least one thin film A is oriented towards a glass surface of the laminated glass according to the invention. It
is also possible to apply a film A to both glass surfaces, such that a laminated glass laminate with a layer sequence
glass/film A/film B/film A/glass is provided.
5 [0032] In the case of automotive glazing, it is not preferable for aesthetic and stability reasons to seal the edges of
the laminated glass laminates with sealants. This promotes the susceptibility of such glazing to the formation of edge
defects, such as detachments of the layers from one another or delamination of the layers from the glass surface.
[0033] In the method according to the invention, the film A having a low plasticiser content can be tailor cut and
positioned such that it does not reach everywhere in the laminated glass laminate as far as the edge of the laminate. In
10 particular, the film A can be smaller in the edge region by at least 1 mm compared with at least one glass sheet, such
that the film B in this edge region is in direct contact with the glass sheet elsewhere adjacent to and contacting film A.
[0034] Furthermore, the thin film A, which has a low plasticiser content or even no plasticiser content in the starting
state, can be perforated prior to the insertion into the glass/film sandwich, such that it can have openings, like passages,
holes or slits, in any geometric pattern.
15 [0035] The film A can thus have at least one opening, such that by means of this opening the film B is in direct contact
with at least one glass surface. Following adhesive bonding to form the finished laminated glass, the film B with higher
plasticiser content in the starting state is adhesively bonded at these points to the glass sheets without interruption. In
particular, openings can thus be obtained at points of the laminated glass behind which the function of sensor elements,
optics elements and/or antenna elements would otherwise be hindered by a heat-shielding or pigmented layer applied
20 carried by film A.
[0036] The thickness of film A may be utilized to compensate the thickness of another film which is not provided on
the complete surface of film B. In this case, optical distortion may result from the difference in thickness of the interlayer
film. Films A of the invention can equalize the thickness of the additional film, for example by using a frame or an opening
of film A to surround the additional film layer, i.e. the additional film layer is provided to the opening of film A. In this case,
25 the thickness of film A may differ less than 50 % of the thickness of the additional film layer, preferred less than 30%
and even more preferred less than 15%. At best, film A has substantially the same thickness as the additional film. It is
possible to combine several films A to achieve the required total thickness. The additional film may be equipped for
example with a IR reflective coating, light-reflective or guiding structures like a semitransparent mirror or holographic
layer or electrically conductive structures and/or provide additional penetration resistance like PET films.
30
Functionalized Films

[0037] Films A may be provided with a functionality like heat-shielding particles, heat-shielding coating, a reduced
transmission of light, colour and/or electrically conductive structures, such as heating wires, antennas as disclosed in
35 PCT/EP2014/075860.
[0038] When using more than one film A, they may each be provided with the same or different functionality.
[0039] In a preferred embodiment of the invention, films A are provided as heat-shielding film as disclosed in
PCT/EP2014/075853. Heat-shielding films are considered to be films which, with comparative measurement and eval-
uation according to ISO 13837:2008 (v = 14 m/s; value in %) in a test laminate consisting of 2 x 2.1 mm clear glass (for
40 example Planilux™) and, intermediately arranged as film B, a standard automotive film (for example TROSIFOL VG R10
0.76) as well as a film A without heat-shielding function and an accordingly structured laminate, in which film A has the
heat-shielding function, have a reduced total solar transmittance (TTS) as follows:

45

50 [0040] In addition, the furnishing according to the invention of film A with heat-shielding function upon comparison and
contrasting of the described test laminates can have the advantage that the light transmission (TL measured in accordance
with EN 410; 2011, value in %) is reduced to a smaller extent by introduction of the heat-shielding function, similarly to
the total solar transmittance TTS (according to ISO 13837:2008, v = 14 m/s; value in %).
[0041] Heat-shielding films A used in accordance with the invention preferably have quotients of TL/TTS of more than
55 1.2 or of more than 1.25 or of more than 1.30 or of more than 1.35 or of more than 1.40 or of more than 1.45.
[0042] The heat-shielding films A can contain, as heat-shielding particles or as heat- shielding coating, for example
ITO, ATO, AZO, IZO, zinc antimonates, tin-doped zinc oxide, silicon-doped zinc oxide, gallium-doped zinc oxide, tung-
stanates such as LiWO3, NaWO3, CsWO3, lanthanum hexaboride or cerium hexaboride.

4
 EP 3 095 601 B1

[0043] The heat-shielding particles preferably have a mean diameter from 5 to 500 nm. The proportion of heat-shielding
particles in the films A may be 1-20 % by weight, preferably 2-10 % by weight. Alternative or in addition to heat-shielding
particles, heat-shielding coatings based on metal layers or stacks of dielectric layers may be used on a surface of film A.
[0044] In order to avoid corrosion at the heat-shielding particles or heat-shielding coating, the amount of chloride ions
5 and/or nitrate ions and/or sulphate ions can be reduced as already disclosed.

Polyvinyl Acetal

[0045] The films A and B used in accordance with the invention contain polyvinyl acetals, which are produced by
10 acetalisation of polyvinyl alcohol or ethylene vinyl alcohol copolymer.
[0046] The films can contain polyvinyl acetals, each having a different polyvinyl alcohol content, degree of acetalisation,
residual acetate content, ethylene proportion, molecular weight and/or different chain lengths of the aldehyde of the
acetal groups.
[0047] In particular, the aldehydes or keto compounds used for the production of the polyvinyl acetals can be linear
15 or branched (that is to say of the "n" or "iso" type) containing 2 to 10 carbon atoms, which leads to corresponding linear
or branched acetal groups. The polyvinyl acetals are referred to accordingly as "polyvinyl (iso)acetals" or "polyvinyl
(n)acetals".
[0048] The polyvinylacetal used in accordance with the invention results in particular from the reaction of at least one
polyvinyl alcohol with one or more aliphatic unbranched keto-compounds containing 2 to 10 carbon atoms. To this end,
20 n-butyraldehyde is preferably used.
[0049] The polyvinyl alcohols or ethylene vinyl alcohol copolymers used to produce the polyvinyl acetals in the films
A or B may be identical or different, pure or a mixture of polyvinyl alcohols or ethylene vinyl alcohol copolymers with
different degree of polymerisation or degree of hydrolysis.
[0050] The polyvinyl acetate content of the polyvinyl acetals in the films A or B can be set by use of a polyvinyl alcohol
25 or ethylene vinyl alcohol copolymer saponified to an appropriate degree. The polarity of the polyvinyl acetal is influenced
by the polyvinyl acetate content, whereby the plasticiser compatibility and the mechanical strength of the respective
layer also change. It is also possible to carry out the acetalisation of the polyvinyl alcohols or ethylene vinyl alcohol
copolymers with a mixture of a number of aldehydes or keto compounds.
[0051] The films A or B preferably contain polyvinyl acetals having a proportion of polyvinyl acetate groups based on
30 the layers, either identically or differently, of 0.1 to 20 mol %, preferably 0.5 to 3 mol %, or 5 to 8 mol %.
[0052] The polyvinyl alcohol content of the polyvinyl acetal PA used in film A may be between 6 - 26 % by weight, 8
- 24 % by weight, 10 - 22 % by weight, 12 - 21 % by weight, 14 - 20 % by weight, 16 - 19 % by weight and preferably
between 16 and 21 % by weight or 10 - 16 % by weight.
[0053] Independent of film A, the polyvinyl alcohol content of the polyvinyl acetals PB used in film B may be between
35 14 - 26 % by weight, 16 - 24 % by weight, 17 - 23 % by weight and preferably between 18 and 21 % by weight.
[0054] In a preferred embodiment of the invention, film A comprises a polyvinyl acetal PA with a proportion of vinyl
alcohol groups from 6 to 26 % by weight and the film B comprises a polyvinyl acetal B with a proportion of vinyl alcohol
groups from 14 to 26 % by weight.
[0055] The films A or B preferably contain uncross-linked polyvinyl acetal. The use of cross-linked polyvinyl acetals
40 is also possible. Methods for cross-linking polyvinyl acetals are described, for example, in EP 1527107 B1 and WO
2004/063231 A1 (thermal self-cross-linking of polyvinyl acetals containing carboxyl groups), EP 1606325 A1 (polyvinyl
acetals cross-linked with polyaldehydes) and WO 03/020776 A1 (polyvinyl acetal cross-linked with glyoxylic acid).

Plasticizer
45
[0056] Films A and/or B used in accordance with the invention may contain, as plasticiser, one or more compounds
selected from the following groups:

- esters of polyvalent aliphatic or aromatic acids, for example dialkyl adipates, such as dihexyl adipate, dioctyl adipate,
50 hexyl cyclohexyl adipate, mixtures of heptyl adipates and nonyl adipates, diisononyl adipate, heptyl nonyl adipate,
and esters of adipic acid with cycloaliphatic ester alcohols or ester alcohols containing ether compounds, dialkyl
sebacates, such as dibutyl sebacate, and also esters of sebacic acid with cycloaliphatic ester alcohols or ester
alcohols containing ether compounds, esters of phthalic acid, such as butyl benzyl phthalate or bis-2-butoxyethyl
phthalate.
55 - esters or ethers of polyvalent aliphatic or aromatic alcohols or oligo ether glycols with one or more unbranched or
branched aliphatic or aromatic substituents, for example esters of glycerol, diglycols, triglycols or tetraglycols with
linear or branched aliphatic or cycloaliphatic carboxylic acids; Examples of the latter group include diethylene glycol-
bis-(2-ethyl hexanoate), triethylene glycol-bis-(2-ethyl hexanoate), triethylene glycol-bis-(2-ethyl butanoate), tetra-

5
 EP 3 095 601 B1

ethylene glycol-bis-n-heptanoate, triethylene glycol-bis-n-heptanoate, triethylene glycol-bis-n-hexanoate, tetraeth-

ylene glycol dimethyl ether and/or dipropylene glycol benzoate
- phosphates with aliphatic or aromatic ester alcohols, such as tris(2-ethylhexyl)phosphate (TOF), triethyl phosphate,
diphenyl-2-ethylhexyl phosphate, and/or tricresyl phosphate
5 - esters of citric acid, succinic acid and/or fumaric acid.

[0057] By definition, plasticisers are organic liquids having a high boiling point. For this reason, further types of organic
liquids having a boiling point above 120 °C can also be used as plasticiser.
[0058] Films A in the variants in which a plasticiser WA is present in film A in the starting state, and also films B
10 particularly preferably contain 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH) or triethylene glycol-bis-2-
ethyl hexanoate (3GO or 3G8) as plasticiser.
[0059] Film B may consist of at least two sub-films B’ and B", which have a different plasticiser content.
[0060] In addition, films A and B may contain further additives, such as residual quantities of water, UV absorber,
antioxidants, adhesion regulators, optical brighteners or fluorescent additives, stabilisers, colorants, processing aids,
15 inorganic or organic nanoparticles, pyrogenic silicic acid and/or surface active substances.
[0061] In particular, film B may comprise 0.001 to 0.1 % by weight of alkaline metal salts and/or alkaline earth salts
of carboxylic acids as adhesion control agent. It is preferred that film B contains magnesium ions in an amount of at
least 10 ppm, preferably 20 ppm and most preferably 30 ppm.

20 Lamination Process

[0062] The present invention also relates to a method for producing the described penetration resistant glass laminates,
in which the film A is positioned on a glass sheet, then covered by at least one film B, and a second glass sheet is then
applied.
25 [0063] Alternatively, it is possible for film B to be positioned on a glass sheet, then to be covered by at least one film
A, and for a second glass sheet to be applied.
[0064] The present invention relates furthermore to a method for producing a laminated glass wherein a stack com-
prising at least one film A and at least one film B is provided, the stack is positioned on a first glass sheet and a second
glass sheet is then applied.
30 [0065] It is possible in accordance with the invention to first melt the film A onto a glass sheet over the entire area or
locally by increased temperature and to then cover this with the film B. Alternatively, films A and B can be positioned
jointly between two glass sheets and melted at increased temperature.
[0066] The lamination step for producing a laminated glass is preferably carried out such that films A and B are
positioned between two glass sheets and the layered body thus prepared is pressed under increased or reduced pressure
35 and increased temperature to form a laminate.
[0067] To laminate the layered body, the methods with which a person skilled in the art is familiar can be used with
and without prior production of a pre-laminate.
[0068] What are known as autoclave processes are carried out at an increased pressure from approximately 10 to 15
bar and temperatures from 100 to 150 °C during approximately 2 hours. Vacuum bag or vacuum ring methods, for
40 example according to EP 1 235 683 B1, function at approximately 200 mbar and 130 to 145 °C.
[0069] What are known as vacuum laminators can also be used. These consist of a chamber that can be heated and
evacuated, in which laminated glazings can be laminated within 30 - 60 minutes. Reduced pressures from 0.01 to 300
mbar and temperatures from 100 to 200 °C, in particular 130 - 160 °C, have proven their worth in practice.
[0070] In the simplest case, in order to produce the laminated glass laminates, film A or B is positioned on a glass
45 sheet, and the further film B or A is positioned synchronously or subsequently. The second glass sheet is then applied
and a glass film laminate is produced. Excessive air can then be removed with the aid of any pre-lamination method
known to a person skilled in the art. Here, the layers are also already firstly lightly adhesively bonded to one another
and to the glass.
[0071] The glass film laminate may then be subjected to an autoclave process. Film A is preferably positioned on the
50 first glass sheet and covered by the thicker film B before the second glass sheet is applied. The method can be carried
out in many conceivable and, in principle, practicable variants. For example, film A is easily removed from a roll of an
appropriate width, whereas film B has been tailor-cut beforehand to the size of the laminated glass to be produced. This
is advantageous in particular in the case of windscreens and other automotive glazing parts. In this case, it is particularly
advantageous to additionally still stretch the thicker film B before it is tailor cut. This enables a more economical use of
55 film, or, for the case in which film B has a colour tint, allows the adaptation of the curvature thereof to the upper sheet edge.
[0072] In the automotive field, in particular for the production of windscreens, films A and/or B may be provided with
a coloured region like an ink ribbon in the upper region of the films. To this end, either the upper part of films A and B
can be coextruded with a suitably coloured polymer melt, or there may be a different colouration in some areas in a

6
 EP 3 095 601 B1

multi-layer system of one of the films A and B. In the present invention, this can be achieved by complete or partial
colouring of at least one of the films A and B.
[0073] In accordance with the invention, films B may therefore have a colour tint, which in particular has already been
adapted in a prior process step to the geometry of a windscreen.
5 [0074] It is also possible for the films B to have a wedge-shaped thickness profile. The laminated glass laminate
according to the invention obtains a wedge-shaped thickness profile even with plane-parallel thickness profile of the film
A and can be used in motor vehicle windscreens for HUD displays.
[0075] In the simplest case, film B is a commercially available PVB film with or without ink ribbon and with or without
a wedge-like thickness profile. Films B with nanoparticles dispersed therein for IR protection can also be used as coloured
10 films. Of course, a film B may also be a film having an acoustic function, such that soundproofing properties that are
further improved are obtained by combination with a film A. Of course, a film B may already also combine a number of
the mentioned functions.
[0076] The thin films A are generally produced by extrusion with use of a cast-film line or in the form of a blown film.
Here, a surface roughness may also be produced by controlled melt fracture or with the cast-film method additionally
15 by use of a structured chill roll and/or structure back roll. Alternatively solvent-cast method can be used for producing
film A prior to functionalization and use in the described penetration resistant glass laminates. Films used in accordance
with the invention preferably have a one-sided surface structure with a roughness Rz from 0 to 25 pm, preferably Rz
from 1 to 20 pm, particularly preferably Rz from 3 to 15 mm and in particular Rz from 4 to 12 mm. It is particularly preferable
if the side of film A coming into contact with the glass sheet has a surface roughness Rz of no more than 20 % of its
20 thickness.
[0077] If the surface of film A is provided with a heat-shielding coating, a particularly low surface roughness prior to
application of the coating is preferred. In particular, the roughness parameter Ra here is less than 3 mm and Rz is less
than 5 mm.

25 Examples

[0078] PVB resin powder (commercial grade Mowital B60H of Kuraray Europe GmbH) was fed to the inlet funnel of
a lab-extruder of the co-rotating twin screw type. Either no adhesion controller or aqueous solutions of the given alkali
metal and or alkaline earth metal salts were simultaneously dosed into the extruder inlet zone. The melt was extruded
30 from a 34 cm wide slit die onto a cooled chill roll to form and subsequently wind thin plasticizer free films in a width of
30 cm with a thickness between 120 and 130 mm (employed and evaluated as film A).
[0079] Prior to analytical determination of moisture content (Karl-Fischer-Method) and metal content (Ion-Chromatog-
raphy) the rolls were stored in an conditioned area having a constant climate of 23°C / 28% RH.
[0080] Commercial automotive grade PVB film with reduced adhesion (TROSIFOL® VG R10 0.76 from Kuraray Europe
35 GmbH = example of film B) and commercial high adhesion architectural grade PVB film (TROSIFOL® BG R20 0.76 from
Kuraray Europe GmbH) were conditioned at the same climate prior to producing the test laminates.
[0081] Test laminates in the dimension 30 x 30 cm were obtained by combining clear glass (Planilux® 2.1 mm, cleaned
with deionized water < 5 mS on a flat glass washing machine) with the film A and B in the following lay-up orders:

40 For adhesion test and penetration resistance in combination with automotive grade PVB: bottom glass (air side) -
film A - VG R10 - (tin side) top glass

For compressive shear characterization in combination with high adhesion grade PVB: bottom glass (air side) - film
A - BG R20 - film A - (air side) top glass
45
[0082] The different sandwiches were passed through a commercial flat glass laminating nipper-line to produce pre-
laminates. Lamination was accomplished by using an autoclave with standard conditions (90 min. comprising 30 min.
hold time at 140 °C and 12 bar).
[0083] Prior to further mechanical evaluation, laminates were allowed to sit for 1 week at 23 °C ambient conditions.
50 [0084] Penetrations resistance of the laminate structures was tested according ECE 43R.
[0085] The alkaline titer is measured as follows: 3 - 4 g of the polyvinyl acetal film are dissolved in 100 ml mixture of
ethyl alcohol/THF (80:20) on a magnetic stirrer overnight. 10 ml of diluted hydrochloric acid (c = 0,01 mol/l) are added.
Excess hydrochloric acid is potentiometrically titrated with a solution of tetrabutylammonium hydroxide in 2-propanol
(TBAH, c = 0,01 mol/l) using a titroprocessor (e.g. by Metrohm) against a blank sample. Alkaline titer is calculated as:
55

7
 EP 3 095 601 B1

[0086] The adhesiveness of the film to glass is given by ’pummel values’, in each case based on the air or tin side of
the glass. The pummel test is carried out in a manner known to the person skilled in the art.
[0087] As can be seen from table 1, laminates according to the invention have a high penetration resistance and pass
the impact test according ECE 43, as compared to the comparison examples in table 2 which all fail this test.
5
Table 1
Film A example example example example example example
1 2 3 4 5 6

10 adhesion control agent KAc KAc KAc/ KAc/ KC8 KC8

MgAc2 MgAc2
parts PVB resin (Mowital B60H) 100 100 100 100 100 100
% deionized water for dosage of 0,25 0,5 0,55 0,525 - -
15 adhesion controller salt. Weight-%
relative to PVB
MAGNESIUM-2-ETHYLHEXANOATE - - - - - -
(25%) solution in water
POTASSION-2-ETHYLHEXANOATE - - - - 0,223 0,446
20
(25%) in water
potassium acetate 0,025 0,05 0,02 0,035 - -
MAGNESIUM-ACETATE - - 0,035 0,0175 - -
TETRAHYDRATE
25

film analysis (after 48h conditioning at 23°C / 28% RH)

moisture content of film A by Karl- 0,9 0,92 0,9 0,92 0,9 0,92
30 Fischer-Method [%] prior to lamination
thickness of film A in mm prior lamination 0,12 0,12 0,12 0,12 0,12 0,12
ppm potassium by IC 94 193 78 136 118 226
ppm Mg by IC 0, 6 1 40 18 0, 6 0,5
35
ppm ratio K/Mg > 100 > 100 1,95 7,55 > 100 > 100
alkaline titer of film A 59 97 109 105 74 115

40 co-lamination with VG R10 (film B) laminates of 1 x film A with VG R10 0.76 between 2 x 2.1 mm clear glass
in air / tin orientation. Air side facing film A
laminate moisture 0,43 0,42 0,44 0,46 0,45 0,44
Pummel value film 5 2,5 4 2 5 1
45 A on air side
Pummel value film B (VG R10) on tin side 3 2,5 2 2,5 3 2,5
compressive shear strength in N/mm2 13,0 12,7 13,4 11,0 13,7 9,6
pass / fail in ball drop test ECE 43 2.26 pass pass pass pass pass pass
50 kg from 4m drop height

co-lamination with BG R20 0.76 (film B) laminates of 2 x film A with BG R20 0.76 between 2 x 2.1 mm clear glass
55
in air / air orientation. Air sides facing film A
compressive shear strength in N/mm2 16,7 11,0 15,2 9,8 10,5 9,2

8
 EP 3 095 601 B1

Table 2
Film A comp. comp. comp. comp. comp.
example 1 example 2 example 3 example 4 example 5
5
adhesion control agent no AC MgAc2 MgAc2 MgC8 MgC8
parts PVB resin (Mowital B60H) 100 100 100 100 100
% deionized water for dosage of adhesion
10 controller salt. Weight-% relative to PVB - 0,5 0,25 - -
MAGNESIUM-2-ETHYLHEXANOATE
(25%) solution in water - - - 0,24 0,12
POTASSION-2-ETHYLHEXANOATE
(25%) in water - - - - -
15
potassium acetate - - - - -
MAGNESIUM-ACETATE
TETRAHYDRATE - 0,035 0,0175 - -

20

film analysis (after 48h conditioning at 23°C / 28% RH)

moisture content of film A by Karl-Fischer-
Method [%] prior to lamination 1,02 1,03 0,98 0,97 0,99
25 thickness of film A in mm prior lamination 0,12 0,12 0,13 0,13 0,13
ppm potassium by IC <1 <1 <1 <1 <1
ppm Mg by IC 0,5 42 20 47 22
ppm ratio K/Mg - < 0,1 < 0,1 < 0,1 < 0,1
30
alkaline titer of film A 21 82 50 56 39

co-lamination with VG R10 (film B) laminates of 1 x film A with VG R10 0.76 between 2 x 2.1 mm clear
35 glass in air / tin orientation. Air side facing film A
laminate moisture 0,45 0,45 0,43 0,45 0,43
Pummel value film A
on air side 8 8 7 7 8
40 Pummel value film B (VG R10) on tin side 1,5 2 1,5 2 2
compressive shear strength in N/mm2 11,0 12,0 13,5 12,4 14,0
pass / fail in ball drop test ECE 43 2.26 kg
from 4m drop height fail fail fail fail fail
45

co-lamination with BG R20 0.76 (film B) laminates of 2 x film A with BG R20 0.76 between 2 x 2.1 mm clear
glass in air / air orientation. Air sides facing film A
50
compressive shear strength in N/mm2 26, 1 22, 8 25,6 24,2 23,9

Claims
55
1. Laminated glass obtained by laminating at least one film A containing a polyvinyl acetal PA and optionally at least
one plasticiser WA and at least one film B containing a polyvinyl acetal PB and at least one plasticiser WB between
two glass sheets, characterised in that prior to lamination

9
 EP 3 095 601 B1

- the amount of plasticiser WA in film A is less than 16 % by weight

- the amount of plasticiser WB in film B is at least 16 % by weight and
- film A comprises 39 to 1170 ppm potassium ions and has an alkaline titer higher than 10.

5 2. Laminated glass according to claim 1, characterised in that film A comprises 0 - 20 ppm alkaline earth ions.

3. Laminated glass according to claim 1 or 2, characterised in that the ratio of alkali ions to alkaline earth ions in ppm
in film A is at least 1.

10 4. Laminated glass according to one or more of claims 1 to 3, characterised in that the film A comprises a polyvinyl
acetal PA with a proportion of vinyl alcohol groups from 6 to 26 % by weight and the film B comprises a polyvinyl
acetal B with a proportion of vinyl alcohol groups from 14 to 26 % by weight.

5. Laminated glass according to one or more of claims 1 to 4, characterised in that the film B comprises 0.001 to 0.1
15 % by weight alkali metal and/or earth alkaline salts of carboxylic acids.

6. Laminated glass according to one or more of claims 1 to 5, characterised in that the film A has a smaller surface
area than film B.

20 7. Laminated glass according to one or more of claims 1 to 6, characterised in that the film A has at least one opening,
such that by means of this opening the film B is in direct contact with the glass sheet bearing against film A.

8. Laminated glass according to one or more of claims 1 to 7, characterised in that the film A has at least one opening,
to which an additional film layer is provided wherein the thickness of film A differs less than 50 % of the thickness
25 of the additional film layer.

9. Laminated glass according to one or more of claims 1 to 8, characterised in that the film B consists of at least two
sub-films B’ and B", which have a different plasticiser content.

30 10. Laminated glass according to one or more of claims 1 to 9, characterised in that the film B has a wedge-shaped
thickness profile.

11. Laminated glass according to one or more of claims 1 to 10, characterised in that the film B has a coloured region.

35 12. Laminated glass according to one or more of claims 1 to 11, characterised in that film A has a coloured region.

13. Laminated glass according to one or more of claims 1 to 12, characterised in that the film A has a thickness of 1
- 150 mm.

40 14. Laminated glass according to one or more of claims 1 to 13, characterised in that film A has less than 150 ppm
chloride ions and/or nitrate ions and/or sulphate ions.

15. Laminated glass according to one or more of claims 1 to 14, characterised in that film A is provided with heat-
shielding particles, heat-shielding coating and/or with electrically conductive structures.
45
16. A method for producing a laminated glass according to one of Claims 1 to 15, characterised in that the film A is
positioned on a first glass sheet, is then covered by at least one film B, and a second glass sheet is then applied.

17. A method for producing a laminated glass according to one of Claims 1 to 15, characterised in that a stack
50 comprising at least one film A and at least one film B is provided, the stack is positioned on a first glass sheet and
a second glass sheet is then applied.

Patentansprüche
55
1. Verbundglas, erhalten durch Laminieren mindestens einer Folie A enthaltend ein Polyvinylacetal PA und wahlweise
mindestens einen Weichmacher WA und mindestens einer Folie B enthaltend ein Polyvinylacetal PB und mindestens
einen Weichmacher WB zwischen zwei Glasscheiben, dadurch gekennzeichnet, dass vor dem Laminieren

10
 EP 3 095 601 B1

- die Menge an Weichmacher WA in Folie A weniger als 16 Gew.- % beträgt

- die Menge an Weichmacher WB in Folie B mindestens 16 Gew.- % beträgt und
- Folie A 39 bis 1170 ppm Kaliumionen umfasst und einen alkalischen Titer von höher als 10 aufweist.

5 2. Verbundglas nach Anspruch 1, dadurch gekennzeichnet, dass Folie A 0 - 20 ppm Erdalkaliionen umfasst.

3. Verbundglas nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Verhältnis von Alkali- zu Erdalkaliionen
in ppm in Folie A mindestens 1 beträgt.

10 4. Verbundglas nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass Folie A ein Po-
lyvinylacetal PA mit einem Vinylalkoholgruppen-Anteil von 6 bis 26 Gew.-% umfasst und Folie B ein Polyvinylacetal
B mit einem Vinylalkoholgruppen-Anteil von 14 bis 26 Gew.-% umfasst.

5. Verbundglas nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass Folie B 0,001 bis
15 0,1 Gew.-% Alkali- und/oder Erdalkalisalze von Carbonsäuren umfasst.

6. Verbundglas nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass Folie A eine
kleinere Oberfläche als Folie B aufweist.

20 7. Verbundglas nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass Folie A mindestens
eine Öffnung aufweist, derart, dass Folie B durch diese Öffnung in direktem Kontakt mit der an Folie A anliegenden
Glasscheibe steht.

8. Verbundglas nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass Folie A mindestens
25 eine Öffnung aufweist, an der eine zusätzliche Folienschicht bereitgestellt ist, wobei die Dicke der Folie A um weniger
als 50 % von der Dicke der zusätzlichen Folienschicht abweicht.

9. Verbundglas nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass Folie B aus
mindestens zwei Teilfolien B’ und B’ ’ besteht, die einen unterschiedlichen Weichmachergehalt aufweisen.
30
10. Verbundglas nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass Folie B ein keil-
förmiges Dickenprofil aufweist.

11. Verbundglas nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass Folie B einen
35 farbigen Bereich aufweist.

12. Verbundglas nach einem oder mehreren der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass Folie A einen
farbigen Bereich aufweist.

40 13. Verbundglas nach einem oder mehreren der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass Folie A eine
Dicke von 1 - 150 mm aufweist.

14. Verbundglas nach einem oder mehreren der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass Folie A weniger
als 150 ppm Chloridionen und/oder Nitrationen und/oder Sulfationen aufweist.
45
15. Verbundglas nach einem oder mehreren der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass Folie A mit
Hitzeschutzpartikeln, einer Hitzeschutzbeschichtung und/oder mit elektrisch leitfähigen Strukturen versehen ist.

16. Verfahren zum Herstellen eines Verbundglases nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet,
50 dass Folie A auf einer ersten Glasscheibe angeordnet und anschließend mit mindestens einer Folie B bedeckt wird
und anschließend eine zweite Glasscheibe aufgebracht wird.

17. Verfahren zum Herstellen eines Verbundglases nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet,
dass ein Stapel umfassend mindestens eine Folie A und mindestens eine Folie B bereitgestellt wird, der Stapel auf
55 einer ersten Glasscheibe angeordnet wird und anschließend eine zweite Glasscheibe aufgebracht wird.

11
 EP 3 095 601 B1

Revendications

1. Verre laminé obtenu en laminant au moins un film A contenant un acétal de polyvinyle PA et éventuellement au
moins un plastifiant WA et au moins un film B contenant un acétal de polyvinyle PB et au moins un plastifiant WB
5 entre deux feuilles de verre, caractérisé en ce qu’avant la lamination

- la quantité de plastifiant WA dans le film A est de moins de 16 % en poids

- la quantité de plastifiant WB dans le film B est d’au moins 16 % en poids et
- le film A comprend 39 à 1170 ppm d’ions potassium et a un titre alcalin supérieur à 10.
10
2. Film laminé selon la revendication 1, caractérisé en ce que le film A comprend 0 à 20 ions alcalino-terreux.

3. Verre laminé selon la revendication 1 ou 2, caractérisé en ce que le rapport d’ions alcalin à ions alcalino-terreux
en ppm dans le film A est d’au moins 1.
15
4. Verre laminé selon l’une ou plusieurs des revendications 1 à 3, caractérisé en ce que le film A comprend un acétal
de polyvinyle PA avec une proportion de groupes d’alcool vinylique de 6 à 26 % en poids e le film B comprend un
acétal de polyvinyle B avec une proportion de groupes d’alcool vinylique de 14 à 26 % en poids.

20 5. Verre laminé selon l’une ou plusieurs des revendications 1 à 4, caractérisé en ce que le film B comprend 0,001 à
0,1 % en poids de sels de métal alcalin et/ou alcalino-terreux d’acides carboxyliques.

6. Verre laminé selon l’une ou plusieurs ds revendications 1 à 5, caractérisé en ce que le film A a une surface plus
petite que le film B.
25
7. Verre laminé selon l’une ou plusieurs des revendications 1 à 6, caractérisé en ce que le film A a au moins une
ouverture, de telle manière qu’au moyen de cette ouverture le film B est en contact direct avec la feuille de verre
portée contre le film A.

30 8. Verre laminé selon l’une ou plusieurs des revendications 1 à 7, caractérisé en ce que le film A a au moins une
ouverture, à laquelle une couche de film supplémentaire est fournie l’épaisseur du film A différant de moins de 50
% de l’épaisseur de la couche de film supplémentaire.

9. Verre laminé selon l’une quelconque des revendications 1 à 8, caractérisé en ce que le film B est constitué d’au
35 moins deux sous-films B’ e B’’, qui ont une teneur en plastifiant différente.

10. Verre laminé selon l’une ou plusieurs ds revendications 1 à 9, caractérisé en ce que le film B a un profil d’épaisseur
en forme de cale.

40 11. Verre laminé selon l’une ou plusieurs des revendications 1 à 10, caractérisé en ce que le film B a une région colorée.

12. Verre laminé selon l’une ou plusieurs des revendications 1 à 11, caractérisé en ce que le film A a une région colorée.

13. Verre laminé selon l’une ou plusieurs des revendications 1 à 12, caractérisé en ce que le film A a une épaisseur
45 de 1 à 150 mm.

14. Verre laminé selon l’une ou plusieurs des revendications 1 à 13, caractérisé en ce que le film A a moins de 150
ppm d’ions chlorure et/ou d’ions nitrate et/ou d’ions sulfate.

50 15. Verre laminé selon l’une ou plusieurs des revendications 1 à 14, caractérisé en ce que le film A est fourni avec
des particules de protection contre la chaleur, un revêtement de protection contre la chaleur et/ou avec des structures
électriquement conductrices.

16. Procédé de production d’un verre laminé selon l’une des revendications 1 à 15, caractérisé en ce que le film A est
55 positionné sur une première feuille de verre, est ensuite recouvert par au moins un film B et une seconde feuille de
verre est ensuite appliquée.

17. Procédé de production d’un verre laminé selon l’une des revendications 1 à 15, caractérisé en ce qu’une pile

12
 EP 3 095 601 B1

comprenant au moins un film A et au moins un film B est fournie, la pile est positionnée sur une première feuille de
verre et une seconde feuille de verre est ensuite appliquée.

10

15

20

25

30

35

40

45

50

55

13
 EP 3 095 601 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 2014224423 A1 [0008] • WO 2004063231 A1 [0055]

• DE 19756274 A1 [0021] [0022] • EP 1606325 A1 [0055]
• EP 2014075860 W [0037] • WO 03020776 A1 [0055]
• EP 2014075853 W [0039] • EP 1235683 B1 [0068]
• EP 1527107 B1 [0055]

14