JPS5874546A - Laminate safety glass and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing impact-resistant laminates and to improved laminates obtained by this method. More specifically, the present invention uses a photocurable epoxy prepolymer composition to
The present invention relates to a method for producing a safety glass laminate which exhibits excellent properties over a wide temperature range by forming an intermediate structural and adhesive layer between at least two layers of visually transparent sheet material.

It is well known that laminated structures are used for shatterproof glass such as automobile windshields. Generally, a plastic interlayer is sandwiched between two sheets of glass. The plastic interlayer acts to deflect foreign objects that hit the windshield, and when the outer glass layer breaks, the broken glass pieces remain in contact with the interlayer, creating a dangerous feeling associated with flying glass.

Early conventional glass laminates included an interlayer formed of Motoμ cellulose material. Tetrocell mouth - The thin layer inside the glass does not adhere well to the glass. Although these laminates had better performance than unlaminated glass sheets, they lacked sufficient impact strength for most applications. These sheets also tend to discolor over time and are not sufficient for use as automatic windshields.

Responding to development in the field of hinyl resin 1. Progress has also been made in the field of glass laminates. Specifically, RobertsO
U.S. Patent No. 2/A 2. l, '71, 7g2.
/1,2,1. '19 and No. 2] 1,2J, R0, and in particular partial polyvinyl acetals as described in Re1d US Al Patent No. 1,2009/20.62g. The development of resins has made it possible to use superior laminated safety glass as a windshield, and it has been used as a standard product in the automobile industry for many years. To make partially polyvinyl acetal resin, polyvinyl alcohol is reacted with a suitable amount of aldehyde to produce an incompletely acetalized polyvinyl resin. The resin is blended with an ester plasticizer to obtain a softened resin which is then formed into a sheet by any suitable method, such as extrusion, calendering or evaporation. Remove the water by drying the sheet at about 0.degree. C. and then carefully abut the dried resin sheet against a pre-cleaned glass plate. At this time, be careful not to create air bubbles between the plastic intermediate layer and the glass. 4) Next, place the second glass plate against the other side of the resin sheet.
7. The resulting "sand inch" structure is separated between two mouths to expel residual air. Next, the glass layer is bonded to the resin intermediate layer by one pressure of heating pressure. -Cru.

Typically, the sandwich is heated with steam A----)
・Put it in a crepe and finish with 1" ethylene chloride.
Cia is here. The temperature inside the autoclave is qO-/50
” (: Increase the pressure to 150-300 with compressed air.
= jζnd/'square inch (psi). These υ] conditions are maintained for a sufficient time to achieve adhesion t7
, After the progress (σ), cool the glycol slowly by circulating cold water 1. .

During this time, keep the pressure constant and press the plastic
to prevent air bubbles from forming between the glass and the glass. Once the glue has cooled to about 73°C, the pressure is released, the sandwich is removed, and the sandwich laminate is allowed to cool to room temperature. Thoroughly wash the laminate in the ash to remove any adhering glycol. Safe lath product 111 produced by this σ) method has good transparency 8AI! L2 adhesion and strength l1. At the same time exhibits elasticity and extensibility. These ram plates have the disadvantage that the polyvinyl butyral resin intermediate layer tends to stiffen and become brittle at low temperatures, resulting in reduced crush resistance under winter operating conditions. Furthermore, these conventional laminate manufacturing methods require many steps, including considerable temperature control, and use solvents, which only increases the manufacturing cost of laminates by as much as 5. .

Furthermore, various advances have been made in recent years in the field of polymers, and new liquid compositions that can be catalyzed by heat or light to form solid materials are now available. Examples of such compositions are provided in commonly assigned US Pat. / 73.5! ; No. / and No. DA, No. 02 b, No. 705. Particularly noteworthy is Cr1v, ello's US Patent No. 9.0! ;
g, 401 and Barton's U.S. patent rate da, 0
No. 90.936. The truly curable compositions described in these patents contain an evoquino-containing organic material, a phase bath '4boly--, and an aromatic complex salt photoinitiator in the form of a Vla group aromatic onium salt. Photocuring of these compositions is
It occurs upon exposure to radiation sources that emit actinic radiation at wavelengths in the ultraviolet and visible -\ spectral regions. Alternatively, the composition can be cured by exposure to electron beam radiation kc.

These compositions are 100% solids, solvent-free, and tack-free wAvc photocurable at room temperature or below.
It's a dragon. The cured material adheres well to metal or other surfaces and has good resistance to etching and plating chemicals. These compositions have been used as photoresist films for producing printed circuits, printing plates, etc. It has been found that the composition is particularly suitable for VC production of impact resistant laminates. □The present invention provides a new/improved method for producing visible light transmitting MI laminates for use in automotive windshields and VC*. &! ', ft, H
The visible light-transmitting liquid composition is sandwiched between at least two layers of the visible light-transmitting sheet material σ) to form an intermediate layer between the two layers. The photocurable composition is then exposed to i-rays to initiate the photocuring reaction. Continue photo-curing until the child is fully grown. Forming a solid structure-cum-adhesive intermediary l- bonded to two adjacent layers of material [7, thus obtaining a safety glass laminate.

The photocurable composition used in the present invention comprises an epoxy prepolymer and an effective amount of an aromatic sulfonium complex.3. q-
It consists of epoxycyclohexane lupoxylate triphenylsulfonium hexafluoroantimonate.

The visually transparent sheet material can be glass or plastic, such as poly(bisphenol A carbonate), poly(methyl methacrylate), or other apparently equivalent materials. The oligoradiation source that initiates the photohardening reaction can be any source of actinic radiation, such as mercury, xenon, carbon arc and tungsten filament lamps, sunlight, etc. By comparison, safety glass laminates are significantly simpler to manufacture.

f) Other objects and advantages of the present invention will become apparent from the following detailed description.

The improved method of the present invention for producing oJ visible light transmissive impact resistant laminates comprises sandwiching a photocurable liquid composition between at least two layers of visible light transmissive sheet material and forming an intermediate layer of a single curable composition. It consists of a method in which σ) is exposed to a chemical and the resulting photocuring reaction is allowed to proceed until the desired completion. In this manner, the photocurable liquid composition is cured to form an adhesively bonded solid structure intermediate layer 11 to adjacent layers of notebook material, thereby providing an ON impact resistant laminate.

The photocurable composition used in the present invention is Mu KC, 4-K.

SLJ with epoxy prepolymers, ohium salts of Va group elements, onium salts of Via group elements, and aromatics.
Aromatic complex salt photoinitiator selected from nium salts]-11
It has the effect of F. In addition, the epoxy-based prepolymer employed includes a mixture of an epoxy-containing organic material and optionally (but preferably) an organic polymer. Epoxy-containing materials useful in photocurable compositions include organic compounds having a polymerization ring (J) upon ring opening. These materials are generally referred to as epoxy resins; Including monomer-type epoxy compounds and polymer-type Evoquine resins. Polymer-type epoxy resins include linear polymers with terminal epoxy groups (e.g., diglycidyl ethers of polyoxyalkylene glycols), polymers with backbone oxirane units. (e.g., polybutadiene polyethylene), and polymers with side chain epoxy groups (e.g.,
glycidylmethac, rylate polymers or copolymers).・・■・Boyatsuki, engineering pure compound 1.
Good, but usually mixtures containing 2° or more epoxy groups per molecule. Conveniently, the epoxy resin used can be a mixture of different types of materials. However, the average monofunctional poxy functionality of the mixture must be in the range of about /-3.

do not have. What is the average number of epoxy groups per molecule?

It is determined by dividing the total number of epoxy groups in the epoxy-containing material by the total number of epoxy molecules present.

In order to cause the proper amount of curing of the composition upon exposure to light so that the photocured composition is solid, i.e., %it+ and extensible in the cured state, it is necessary to It was determined that the functionality must be in the range of about /-5.

These useful epoxy-containing materials change from low-molecular-heptanomeric materials to high-molecular weight polymers11, greatly changing the nature of their backbones and substituents. For example, the backbone can be of any tight type, and the t substituent on the 7 can be any group that does not have an active hydrogen atom that is reactive with the oxyphne ring at room temperature. Specific examples of substituents that can exist include halogen, ester group, ether group, sulfonic acid group,
70 gisan groups.

There are nitro groups, phosphoric acid groups, etc. The molecular weight of the epoxy-containing material can vary from about 5' g-ioo, ooo, or more.

Suitable epoxy-containing materials include those containing cyclohexene oxide groups, such as epoxy cyclohexene carboxylate, specifically 3. Darevoxycyclohexylmethyl-3, Darevoxycyclo'\xanecarboxylate, 3. 7 chlorohexylmethyl-3, +-evo*cy 2-methylcyclohexanecarboxylate, yohibis<3.4c-epoxy-6-methylcyclohexylmethyl)adipate to der epoxy-comethyl. A more detailed list of useful epoxy resins of this nature is found in U.S. Patent No. 3. / / '7. It is described in θ99. Many other suitable epoxy-containing materials useful in the present invention are described in the aforementioned US patents.

The organic polymer that is optionally included in the photocurable composition used in the present invention must be compatible or compatible with the epoxy-containing material. The amount of this first copolymer used can range from about S to 90% based on the weight of the epoxy-containing material, and λ-pc is the epoxy-containing material that provides the photocurable liquid composition with a suitable viscosity for processing. Based on the weight of (・
The amount is preferably in the range of about 'tO-Aθ%.

The desired component, the trivalent polymer, can be derived from acrylate, methacrylate) or adipate monomers (i.e., the 9-mer As7J=Mo11ζ1).
Either marmer or copolymer is fine.) b”-, 71
ζIJ vinyl butyral polymers and copolymers of styrene and allyl alcohol have been found to be effective. The organic polymer is about -qO<0>C to 103<0>C - preferably 1.
It was established that <1 must have a glass transition temperature in the range 3Q-bO°C, where the hanging chain [polymer]
is a high blood combination, i.e. about i, ooo, ooo-! It includes not only polymers having a number average molecular weight of about i, but also oligomers, such as materials having a low number average molecular weight, such as &f about 1 oooυ.

The number average molecular weight of the organic polymer is about 15ρOθ~bo,
It is preferable that it is in the range of oθ0.

Although it has been established that the desired component organic polymer can have l@ or multiple droxyl groups or other groups, such as merkaft groups, in other respects the organic polymer may have ``active hydrogen 1''. Must not be used - "Active hydrogen" is well known and frequently used in the industry, and is also used here.
nn, Chem, Soc,', Vol, 119
(/9 pieces).

3/g/active hydrogen as determined by Zerewitinoff's method. Of course, the organic polymer is also substantially free of thermally or photolabile groups. That is,
The polymeric material does not decompose or liberate volatile components under the desired radiation exposure of the photocurable composition.

The organic polymer may therefore be hydroxy-functional or mercapto-functional, or substantially non-functional (i.e. 1. substantially free of groups reactive with the epoxy resin), or mixtures of these types. It can be done. If the organic polymer contains a hydroxyl or methylated, capto functional group, even if the group(s) is located terminally.

It may also be a side group from a polymer or copolymer.

The equivalent weight (i.e., number average equivalent JIIL) of useful hydroxy- and mercapto-functional organic polymers ranges from about 200 or more, preferably from about 600 to /5(')O.

Suitable organic polymers, which are the desired components, can be derived from a variety of sigma polymers. The resulting polymer has a glass transition temperature in the range of -00C to 103"C. Representative useful acrylate and methacrylate monomers include the following:

Methyl methacrylate n-butyl acrylate hydroxyethyl acrylate hydroxyethyl methacrylate n-butyl methacrylate hydroxypropyl acrylate hydroxypropyl methacrylate ethyl acrylate Preferred acrylate, methacrylate and adipate monomers include acrylic acid, methacrylic #Lttake adipic acid and an aliphatic alcohol having 7 carbon atoms or an aliphatic diol having 7 to 7 carbon atoms.

Useful condensation polymers are derived from dicarboxylic acids such as adipic acid and terephthalic acid and diols such as butanediol, neopentyl glycol, and the like. Among this group, BoIJ (/, A-hexylene 0-phthalate 1) is preferred.

Other suitable optional polymers may be polyvinyl pteral polymers, such as those available from Monaanto under the trade name "B".
Type of Bo IJ available in the “utvar” series
Vinyl butyral polymers may be mentioned. For example, 'B
utvarB-'76'' has a hydroxyl content (expressed as % of polyvinyl alcohol) from 9 to 13%, acetate content (expressed as % of polyvinyl acetate') 0 to 25% and a butyral content (expressed as % of polyvinyl butyral and 12%).
33%). The glass transition temperature of these polymers is
It is in the range of 55'C.

The photocurable composition used in the present invention also contains an aromatic @-photoopening agent. Although aromatic sulfonium fine salt photoinitiators are preferred, many complex complex photoinitiators that can be used in the present invention are well known in the art. Generally, the photoinitiator is selected from onium salts of the elements Vla & C, menium salts of Vla & 7C, and aromatic halonium salts. These complex salts can generate components that initiate epoxy reactions when exposed to ultraviolet light or electron beams.

More specifically, a photosensitive aromatic onium salt of a Via group element represented by the following formula: When exposed to radiant energy, norotonic acid 1, e.g. boron trifluoride, phosphorus pentafluoride, round fluoride It can be a source of arsenic, etc. By introducing a photosensitive aromatic onium salt into various cation-heavy organic materials as described above, a direct polymerizable composition can be obtained.

The aromatic onium salts of Vla and principal used in the polymerizable composition of the present invention are specifically determined by the following formula.

[(ru>a(f4 (R”)cX], →[M,, -(
e-fゝwhere R is a monovalent organic aromatic group, a monovalent organic aliphatic group selected from Wb alkyl-octacycloalkyl and fl11-substituted alkyl, t is an aliphatic group and an aliphatic group; Selected (one ring or multiple rings forming a fused ring structure)
an organic group; 411@, bkZ with 1 degree equal to θ~3
ml equal to O~2, C+z o cabinet? ,: an integer equal to hsl, the phase of □a + b + C is 3 or X
.

equal to the valence of [5, de-e-heavy, f is M O) an integer equal to the valence from 2 to 71, e 21-,, e is g
There are integers having the following values. The group represented by R is, for example, a C(6-13) aromatic hydrocarbon group, such as phenyl, tri-butonal, anthryl and rjc, -. Monovalent groups l-9 such as alkoxy, C(1-11)aryl, nido10, clay, hydroxy, etc.
These groups are substituted with 1, γ-aryl acyl group, etc.
h4゜R' with formula groups, such as pyridyl, furfuryl, etc.
b',, J<-j group is C alkyl and substituted γJv
^-L.

(1-11) ・For example -C,H,OCH, -C)l, C00C,H,,
-et-t, coctl, nato. The group represented by W has the following structure.

-(e-f) The complex anions contained in (MQ] in the above formula are BF4''-*PF',, , As, F6-,,5
bF6-, FeCl4-, 5nC1,-.

5b(-Na*BIC4-eAtk'@-",
GaC14*1nF49'l'lF,6-.

Zr)'lI-, etc., and M is a transition metal, such as sb, ・)'e, Sa*t3+*A
t* Cxa * lit * 1” * Zr *
bc+V, Cr, Mn, Cs, clay m7c books, such as lanthanides, specifically Ce,, Pr
, Nd, acti, nido, specifically 'mu'b, Pa
wU+NI), etc., and cattle metal, specifically “s
Pg A5, etc.

In the above formula, examples of group VIa element Oniudai salt include the following.

Group 8 sulfonium salts are well known in the art and are described in the aforementioned Cr+vello and BartOn patents. Aromatic sulfonium complex photoinitiators suitable for the present invention include triphenylsulfonium hekidium salts. .

This is a full 10 anti-seven net.

The photocurable composition used for this Yumei may or may not contain a surfactant, a surfactant, or a surfactant to improve the coating of the visible light-transmitting sheet material. Curing enhances the adhesion between the intermediate layer and the outer layer during curing.

Photocuring of the composition occurs upon exposure to any radiation source that emits actinic radiation at wavelengths within the ultraviolet region of the spectrum. Suitable radiation sources include water, gas, carbon arc and tungsten filament radiators, E1 light, and the like. Irradiation time should be approximately 1 second or longer, but depends on the specific epoxy material, organic polymer and aromatic complex dosage, and on the radiation source, distance from the radiation source, and curing. It depends on the thickness of the intermediate layer. The composition can also be cured by electron beam irradiation. Electron beam irradiation I/J main cost advantage 7 - Flies, marination due to actinic radiation (・The composition can be cured effectively at a high speed)
- This curing is a triggered reaction. That is, once the decomposition of the aromatic complex is initiated by exposure to a radiation source, the curing reaction proceeds and continues even after the radiation source is removed. The curing reaction can generally be accelerated by using a thermoplastic during or after exposure to a radiation source;
Even just increasing the temperature significantly accelerates the curing speed.

The amount of aromatic complex salt photoinitiator used in the compositions of the present invention is about -θ/-20tL weight percent, preferably <, about aS-co, 0% by weight, based on the total weight of the composition. . In general, the curing rate increases with the use of complex salts at a given amount of light or irradiation, and the curing rate increases with increasing intensity of light or electron beam exposure. The composition can be prepared by mixing the aromatic complex salt with an organic material, i.e., an epoxy material plus an organic polymer, under safe light conditions, i.e., non-actinic light conditions. A hot solvent composition is produced by bathing an organic material with an aromatic complex salt without performing fA phase heating. 1 In this specification, Kawasaki [safety glass laminate] is used for convenience, but
Visible light transparent sheet material layer
, e.g. glass, poly(bisphenol carbonate)
), and poly(methyl methacrylate) r'- can be formed.Without photocuring, the photocurable composition used in the present invention has #1 excellent adhesion to almost all surfaces. present.

The new and improved aging organic polymers from which the impact resistant laminates of this invention are made are completely coated to form a bath-resistant material. Polymer coexists with solvent1. The solvent is removed by heating about 6 g of a solution of RAE, epoxy resin, and Bo-11mer to υ1° and evaporating the solvent under vacuum.

Cooling the epoxy resin-polymer solution1. While stirring, add the aromatic sulfonium complex photoinitiator, then slowly heat and stir until the photoinitiator in solution becomes solvated. Optionally, a surfactant, such as a fluorocarbon surfactant, is incorporated into the solution 1, thus completing the production of the photocurable composition.

Choose at least two layers of light-transparent sheet material 1
A sufficient amount of photocurable composition is sandwiched between both layers adjacent to the main surfaces of both layers to form a flexible laminated material. Solid content 700%
Since the photocurable composition has an appropriate viscosity, for example, a frame is provided at the outer edge of the visible light-transmitting layer to inject the composition. Form 15.
If a photocurable composition is injected here, b''- can be obtained.Alternatively, an appropriate amount of the photocurable composition is applied to one of the two layers, and the other layer is placed on top of it. The photocurable composition can be distributed between both layers by fusing them together. In any case, the photocurable composition is also coated to prevent air bubbles from forming between the composition and each sheet material layer. Care must be taken. The flexible laminate thus formed is then exposed to an actinic radiation source or electron beam radiation for a time sufficient to initiate the photocuring reaction. Once the photocuring has begun, 1
Once done, this reaction continues until complete Tr occurs.

The resulting rigid visible light-transparent laminate exhibits excellent shatter resistance over a wide temperature range. A plastic interlayer formed from a photocurable composition is strongly adhesively bonded to each adjacent light-transmitting layer, so that the laminate is suitable for automotive safety glass windshields or where impact and shatter resistance is desired. Other structures such as 1-<'t':z are also very suitable for use in glazing applications.

Examples of the present invention will be shown below to explain the present invention more specifically.

Example 1 Shielding actinic radiation 1. Meanwhile, a photocurable composition is manufactured from the following components.

Ingredients Weight part ERL t22
/ GSθ0・2 ucoflex / 02g -2/ O8Sθ0 cost 3 LJV)! , tonoda
21 bones 4 FCtri/
10/0,? , / normal / 3. II-Epoxy/Chlohexylme J-i
Leh 3. it-Evogyshicyclohexane 7-rate (manufactured by LJnioo Carbide, trade name) Hydroxyl-terminated polyester from neopentyl glycol and adipic acid ()lookerCbemic
(manufactured by General Electric Co., trade name) Fluorocarbon surfactant (? MCom)
made by pany, trade name) ERL Qco2/ and Rucoflex 102g-2i
Mix with θ.

Add uvg loi to this, and stir and lightly heat the solution until UVh /θl is in a solvent phase state. Next K
FC171 surfactant is added and the composition is stirred until complete incorporation is achieved. The obtained photocurable composition is placed between two glass plates that have been cleaned in advance. That is, one composition is applied to a first glass plate, the first glass plate is pressed against the first glass plate, and the assembled acid is uniformly distributed between both plates, thus forming an uncured glass with a thickness of about 0.00 ft. Forming the Sanderutsch.

**Expose the uncured laminate to ultraviolet light from a 300 watt 7' inner medium pressure mercury vapor lamp for 20 seconds approximately 3 inches from the rung. The photocuring tube 6 is passed through for about 60 minutes, which is started by UV irradiation. A pleasant impact resistant visible light transparent laminate is obtained.

According to the present invention, it is clear that a high-quality spinning '-'EX method is provided for producing impact-resistant, visible light-transmitting slats in a small number of steps and at a low cost.

All patents mentioned above are cited as prior art to the present invention. Although the invention has been described in terms of preferred embodiments, it will be obvious that many changes and modifications will occur to those skilled in the art. For example, a portion of the epoxy S portion of the composition can be replaced with poly(vinyl bunafur). Such modifications are within the scope of the invention.

Claims (1)

[Scope of Claims] / (al) A visible light transmitting sheet material having at least 4λ layers is prepared, (b) an epoxy prepolymer and an onium salt of a group Va element, VIa between adjacent main surfaces of each pair of layers; sandwiching a photocurable adhesive layer consisting of an effective amount of an aromatic complex salt photoinitiator selected from the group consisting of onium salts of group elements and aromatic hascinium salts, (c) radiation +1!! (d) continuing photocuring until the adhesive layer is completely cured. The method according to claim 7, wherein the layer of visible light transparent sheet material is made of glass.Y) The method of claim 7, wherein the layer of visible light transparent sheet material is made of poly(bisphenol A carbonate). 1. The method according to claim 7. D. The method according to claim 7, wherein the layer of the visible light transparent sheet material is made of poly(methyl methacrylate). F. The method according to claim 7, wherein at least one of the layers of the visible light transparent sheet material 1
2. The method of claim 1, wherein one layer is glass and at least seven other layers are poly(bisphenol A carbonate). & at least one of the layers of the visible light transparent sheet material.
one layer is glass and at least one other layer is poly(
methyl methacrylate). 2. The method of claim 111, wherein the adhesive layer also contains an organic polymer other than an epoxy prepolymer.菰 The epoxy prepolymer is 3. 2. The method according to claim 1, which is der eboxycyclohexylmethyl-3, der eboxycyclohexane carboxylate. 9. Claim 7, wherein said copolymer is hydroxy-terminated poly(neopentyl glycol adipate).
The method described in section. lθ The aromatic complex salt photoinitiator is a photodegradable aromatic onium salt of a Via group element capable of curing an epoxy resin when exposed to radiant energy, and this aromatic onium salt has the following formula: % formula % ( In the formula, tn)t is a monovalent organic aromatic group; R1 is a monovalent organic aliphatic group selected from alkyl, cycloalkyl and substituted alkyl; R is a heterocycle selected from electroaliphatic groups and aromatic groups; vIa, a polyvalent organic group forming a fused ring structure, where X is selected from sulfur, selenium and tellurium;
group element, M is a metal or metalloid, Q represents a halogen group, a is an integer equal to θ ~ 3, b is an integer equal to θ ~ co,
C is an integer equal to Ol or l, the sum of a+L+c is a value equal to the valence of 3 rays X, d=e-f, f is the valence of M and an integer equal to 2 to 7, 2. The method according to claim 1, wherein f and e are integers with the following values. /l the aromatic Via group Oniwam complex salt photoinitiator)
+77: 1-Nylsulfonium to the method according to claim 1, which is fluoroantimone-1.
Q (a) Prepare a uJ phototransmissive sheet material of at least the U layer, (bl) Each pair of layers of the lI4I4 free interplane poxy-based prepolymer -,!: Onium salt of group Va element, group VIa element. and an effective amount of an aromatic complex salt photoinitiator selected from the group consisting of onium salts and aromatic halonium salts; (di) An impact-resistant, visible light-transmitting laminate manufactured by exposing the adhesive layer to m to initiate photo-curing of the adhesive layer and continuing photo-curing until the adhesive layer is completely cured.