* » ρ/υυ/(Χ)ΐ ίβ/5Λ>ι Section 29 AUSTRALIA Patents Act 1990 PATENT REQUEST: STANDARD PATENT/PATENT OF ADDITION
We, being the person(s) identified below as the Applicant, request the grant of a patent to the person Identified below as the Nominated Person, for an invention described in the accompanying standard complete specification.
Full application details follow. [71] Applicant: UPAT GmbH & CO. Address: F aiburger Str. 9, D-7830 Emmendingen, Bundesrepubllk Duetschland
[70] Nominated Person: UPAT GmbH & CO. Address: Frelburger Str. 9, D-7830 Emmendingen, Bundesrepubllk Duetschland COMPOSITION [54] Invention Title: REAGENT -K4T FOR THE PRODUCTION OF SYNTHETIC RESIN *· ANO AKCHOfclNGcF FIXING BODIES ELEMENTS FOR BON DIN FIXARON ELEMENTS IN PLAGE-4N-AN ATTACHMENT SURFACE A FIKIN6 BASS
?*·**· [72] Names of actual inventors: Christian Weber, JOrgen GrOn and Elke Wasmer W k * [74] Address for service In Australia: c/o WATERMARK PATENT & TRADEMARK ATTORNEYS, of 290 Burwood Road, • Hawthorn, Victoria 3122, Australia. '»***· Attorney Code: WM - ·c u .Λ BASIC CONVENTION APPLICATION(S) DETAILS [31] Application Number [33] Country Country [32] Date of Application Code
• * P4121832.9 Germany DE 2/7/91
• · 4» ·« 1
., ..UPATJSmfeH &-C.Q.. •1 ♦ By our Patent Attorneys ..-..WATERMARK PATENT & TRADEMARK ATTORNEYS
/ ...... 9 August 1995. Karen J. Sinclair PAXt/OOSb 12/11/91 Section 29 (Γ Regulation 3.1 (2, AUSTRALIA
Patents Act 1990
NOTICE OF ENTITLEMENT (To be filed before acceptance)
VMe, UPAT GmbH & CO., of Freiburger Str. 9, D-7830 Emmendingen, Bundesrepublik Deutschland, being the applicant in respect of Application No. 21737/92 state the following:-
• « »4 »· O * The person nominated for the or»n* of the patent has entitlement from the actual * * · inventors under German inventc > law by virtue of an employment contract. •ζ** e* * · · ♦ · ♦ M «·
The person nominated for the grant of the patent is the applicant of the application listed in the declaration under Article 8 of the PCT. « H A 4 · • e* * • · ft 4 * A „The basic application listed on the request form is the first application made in a • · * • •‘Convention country.
····
„,f.-UPAT GmbH & CO. By my Patent Attorneys, WATERMARK PATENT & TRADEMARK ATTORNEYS
9 August, 1995.
Registered.. Patent..Attorney AU9221737
(12) PATENT ABRIDGMENT (11) Document No. AU-B-21737/92 (19) AUSTRALIAN PATENT OFFICE (10) Acceptance No. 666866
(54) Title REAGENT COMPOSITION FOR THE PRODUCTION OF SYNTHETIC-RESIN BODIES FOR BONDING AND ANCHORING OF FIXING ELEMENTS IN A FIXING BASE International Patent Classlfication(s) (51)5 C09J 004/00 C09J 004/06 ' (21) Application No.: 21737/92 (22) Application Date : 27.06.92 (87) PCT Publication Number: W093/01246 (30) Priority Data (31) Number (32) date (33) Country 4121832 02.07.91 DE GERMANY (43) Publication Date : 11.02.93 (44) Publication Date of Accepted Application : 29.02.96 (71) Applicant(s) UPAT GMBH & CO. (72) Inventor(s) CHRISTIAN WEBER; JURGEN GRUN; ELKE WASMER (74) Attorney or Agent WATERMARK PATENT & TRADEMARK ATTORNEYS , Locked Bag 5, HAWTHORN VIC 3122 (57) Claim 1. Reagent composition for the production of synthetic resin bodies for bonding and anchoring of fixing elements in a fixing base, the reagent composition comprising: (a) a reaction mixture which comprises at least one ethylenically unsaturated monomer, (b) a curing agent component of an organic peroxide and (c) a filler component, the curing agent component (b) being separated from the reaction mixture (a) before use, characterised in that the reaction mixture (a) comprises: 51.0 to 100.00 parts by weight of monomeric 2,2- bis[4-(methacryloxyethoxyjphenyl]propane, and 49.0 to 0.0 parts by weight of unsaturated polyester resin, vinyl ester resin or acrylic resin or a mixture thereof, based on the total weight of (a). 9. Destructible multiple chamber cartridge for the in situ production of synthetic, resin bodies for bonding and anchoring of fixing elements in a fixing base containing a reagent composition comprising: (a) a reaction mixture which comprises at least one ethylenically unsaturated monomer, (b) a curing agent component of an organic peroxide and
.../2 (11) AU-B-21737/92 -2- (10) 666856 (c) a filler component, wherein the curing agent component (b) and the reaction mixture (a) are retained separately from each other in different chambers of the multiple chamber cartridge characterised in that the reaction mixture (a) comprises: 51.0 to 100.0 parts by weight of monomeric 2,2-bis[4-methacryloxyethoxy)phenyl]- propane, and 49,0 to 0.0 parts by weight of unsaturated polyester resin, vinyi ester resin or acrylic resin or a mixture thereof, based on the total weight of (a). OPI DATE 11/02/93 APPLN. ID 21737/92 AOJP DATE08/04/93 PCT NUMBER PCT/EP92/01451 AU9221737
(51) Internationale Patentklassifikation 5 ; (11) Internationale Veroffcntlichungsnummer: WO 93/01246 C09J4/00, 4/06 (43) Internationales Veroffentlichungsdatum: 21.Januar 1993 (21.01.93)
(21) Internationales Aktenzeichen: PCT/EP92/01451 (74)Anwa!t: STERNAGEL, Hans-GUnther; Sander Aue 30, I D-5060 Bergisch Gladbach 2 (DE). (22) Internationales Anmeldedatum: 27. Juni 1992(27.06.92) i (Sl)Bestimmungsstaaten: AU, CA, Fl, JP, NO, RU, US, euro- ϋ (30) Prioritatsdaten: pflisches Patent (AT, BE, CH, DE, DK, ES, FR, GB, P41 21 832,9 2. Juli 1991 (02.07.91) DE GR, IT, LU, MC, NL, SE).
(71) Anmelder (filr alle Bestimmungsstaaten ausser US): UPAT Veroffentlicht GMBH & CO. [DE/DEJ; Freiburger-StraSe 9, D-7830 Mil internationalem Recherchenbericht. Emmendingen (DE). Vor Ablatif der Jiir Anderungen der Anspriiche zugelasse- nen Frist. Veroffentlichung wird wiederholt falls Anderlin (72) Erfinder; und gen eintreffen. (75) Erfinder/Anmelder (nur fur US) : WEBER, Christian [DE/ DE]; Theodor-Storm-Weg 9, D-7830 Emmendingen (DE). GRtJN, Jilrgen [DE/DEJ; MarchstraBe 11, D-7805 BOtzingen (DE). WASMER, Elke [DE/DE]; Scheffelweg 11a, D-7830 Emmendingen (DE).
------composCOMpOSlTWH mow------—B'OPT'ES------XFrtF7fjTCteOI(3 (54) Title: REAGENT^KFF FOR THE PRODUCTION OF SYNTHETIC-RESIN EfcEMENTS FOR BONDING FPwVHGN· OpFlKlNS ELEMENTS IN-FcAGE-IN-AN-ATTAC-HM&NT-SURFAGE A F lllUG βΑ6£------Λ
(54) Bezeichnung: REAKTIONSSATZ ZUM ERZEUGEN VON KUNSTHARZKORPERN ZUR KLEBEVERANKERUNG VON BEFESTIGUNGSELEMENTEN IN BEFESTIGUNGSGRUND
(57) Abstract
The invention concerns a reagent kit designed to produce elements of synthetic resin for anchoring fixation elements in place by bonding them in multi-cavity plugs. The reagent kit comprises (a) a reagent mixture containing 2,2-b£s-[4-(methacrylox- yethoxy)phenyl]propane and an optionally unsaturated polyester resin, vinyl resin or acrylic resin or a mixture of these, (b) an ac celerator component comprising an organic peroxide and (c) a filler component, the accelerator component (b) being kept sepa rate from the reagent mixture (a) before use.
(57) Zusammenfassung
Reaktionssatz zum Erzeugen von Kunstharzkfirpern fUr die Klebbefestigung und Verankerung von Berestigungselementen in Befestigungsgrund in Mehrkammerpatronen Oder Kartuschen, wobei der Reaktionssatz eine 2,2-Bis-[4-(Methacryloxyet- hoxy)phenyl]propan und ggf. ungesllttigtes Polyesterharz, Vinylharz, Acrylharz oder eine Mischung derselben enthaltenden Re- akttonsmischung (a), einc Hllrterkomponente (b) aus einem organischen Peroxid und eine Filllstoffkomponente (c) enthlllt, wobei die Hllrterkomponente (b) Vor VerwendUng von der Reaktionsmischung (a) getrennt ist. WO 93/01246 - 1 - PCT/EP92/01451 “REAGENT COMPOSITION FOR THE PRODUCTION OF SYNTHETIC RESIN BODIES FOR BONDING AND ANCHORING OF FIXING ELEMENTS IN A FIXING BASE”. .. .
C.om.po s rfl o The invention relates to a reagent -k±t· for the (Skud bonei/ruc. production of synthetic resin bodies for anchoringz ofJ 5 fixing elements in a fixing base, which can be used, in particular, in cartouches or destructible multi-cavity cartridges. It has been known for a long time that curing synthetic resins can be employed for reliable fixing of 10 anchor rods and the like in mature rock, masonry, con crete and the like. In this procedure, the starting components of the synthetic resin and a suitable curing agent are intro duced at the fixing sites separately from one another and 15 are mixed there by driving in the fixing element. The formation of the synthetic resin body formed, which bonds the fixing element to the fixing base, is therefore started only when the fixing element is in its final position. .i, compos ·τι οκ-s 20 When reagent Atertes are used in so-called one- component cartouches, the curing agent for the synthetic resin is enclosed in capsules which can be destroyed by pressure and,Is mixed with the other constituents of the C,om.posi+ton, reagent^ tett·, i.e. a curable synthetic resin and fillers, 25 in the cartouche, without the capsules being destroyed. The reagentis introduced into the prepared bore hole from the cartouche and the fixing element is then driven into the bore hole. During this operation, the capsules are destroyed and distribute the curing agent in the 30 reaction mixture. In the case of destructible multi-cavity cart ridges, these are introduced into the bore hole and are destroyed by driving in the fixing elements, for example anchor rods. During this operation, the constituents are 35 mixed, with one another and the curing reaction of the synthetic resin is initiated.
REPLACEMENT SHEET I WO 93/01246 2 PCT/EP92/01451 The widespread use of this technique is due to its convenient application and easier storage, transportation and metering of the reactive starting materials of the synthetic resin body. 5 Cartridges which contain reaction mixtures for the preparation of cured synthetic resin bodies have already been described in DE-A-1,205,038 in connection with a method for fixing anchor rods without a strutting head in anchor support systems of pit rooms. These are 10 glass or Bakelite cartridges into whose filling, which comprises curable polyester resin or epoxy resin [lacuna] a relatively large amount by weight of quartz sand or fine-ground quartz, a capsule containing the curing agent is introduced. Organic peroxides are used as curing 15 agents. If pre-accelerated epoxy resins are employed, an amine curing agent is used. The pre-accelerated epoxy resins cure slowly with amines, so that if a rapid load carrying capacity of the fixing element is required, the glass cartouche and anchor rod have to be preheated to 20 temperatures above 150°C. Peroxide-cured polyester resins are not sufficiently resistant to chemicals, and in par ticular are not resistant to alkalis. In the case of a basic fixing base in particular, this leads to a reduc tion in the mechanical properties of the plastic body in 25 the long term. Moreover, polyester resins cured in this way also exhibit a relatively high absorbtion of water, which can also give rise to corrosion problems in connec tion with metallic fixing elements. In order to eliminate the disadvantages of such 30 known materials, EP-A-150,555 has proposed two-cavity cartridges in which the inner or outer cavity of a two- cavity cartridge built up from two glass cylinders in serted one into the other contains a fine-grained naturally occuring or synthetic mineral filler together 35 with a vinyl ester epoxy resin based on acrylate or methacrylate, while the curing agent, an organic peroxide, is in the other respective cavity. The peculiarity of the cartridges according to EP-A-150,555
REPLACEMENT SHEET » WO 93/01246 3 PCT/EP92/01451 is that the resxn components additionally comprise an ester of an epoxy resin with acrylic or methacrylic acid dissolved in a reactive monomer. However, the storage stability of the pre-accelerated vinyl ester epoxy resin 5 has proved to be unsatisfactory. The pre-accelerated resin components for such a Co/xp o s'i+l reagent^kife known from WO-88/03599 have a considerable [sic] longer storage stability. The storage stability is increased considerably by mixing 3 to 60 parts by weight 10 of a vinyl ester epoxy resin, 63 to 3 parts by weight of an unsaturated polyester resin and 10 to 0.1 parts by weight of a conventional epoxy resin together with 28 to 45 parts by weight of one or more ethylenically unsat urated reactive monomers. 15 EP-A-199,671 describes the use of a curable acrylate for multi-cavity cartridges, which is obtained by reaction of acrylic acid derivatives with bisphenol compounds and/or novolak compounds containing epoxide groups dissolved in a reactive diluent, preferably 20 styrene. The acrylate is, in particular, bisphenol A methyl methacrylate of the formula
2
3 3
wherein n has values from 1 to 2. DE-A-3,940,138 (Al) describes the use of cyclo- 25 aliphatic compounds which are curable by polymerisation and are mono- or polysubstituted by ethylenically un- saturated radicals in or as plug compositions, which are distinguished by a low viscosity, extremely low volatili ty, extremely high boiling point, high flashpoint, low 30 toxicity, and hydrophobicity and by a high compatibility with many polymers and resins. A lower intrinsic shrink age and high hydrolytic stability of the cured composi tion, including under alkaline and acid conditions, is
REPLACEMENT SHEET
/•V X T '3
VA'T Ov , WO 93/01246 4 PCT/EP92/01451
thereby achieved. In spite of the improvement in properties in respect of the chemical resistance and low absorption of water, the known resins have a relatively large shrinkage 5 in volume after curing. The object of tlie present invention is to improve c.or*.p o j ι T<'ans the known reagent^kiW further, in particular to provide synthetic resin bodies which have a low shrinkage in volume during curing and low absorption of water and at 10 the the same have a good chemical resistance. ,, C.ot'h-POS'l Tt'OrX- This object is achieved by a reagent. .for the Λ and- banalH-Oj production of synthetic resin bodies for anchoring fixing elements in a fixing base, the reagent^ktt comprising: (a) a reaction mixture which comprises at least one 15 ethylenically unsaturated monomer, (b) a curing agent component of an organic peroxide and (c) a filler component, the curing agent component (b) being separated from the reaction mixture (a) before use, characterised in that the reaction mixture in 20 (a) comprises 51.0 to 100.00 parts by weight of monomeric ( 2,2-bis[4-(methacryloxyethoxy)phenyl]- propane, and 49.0 to 0.0 parts by weight of unsatur ated polyester resin, vinyl ester resin or acrylic resin or a mixture thereof. 25 The subclaims relate to preferred embodiments of the invention. The reaction mixture (a) preferably comprises 75 to 99 parts by weight of the specific monomeric propane derivative, 25 to 1 parts by weight of the abovementioned 30 polymer resins and 0.1 to 5.0 parts by weight of ac celerating agent. The total parts by weight of the reaction mixture preferably in each case give 100 parts by weight. A particular advantage of an embodiment of the 35 reaction mixture according to the invention is that, in addition to the specific monomeric propane derivative, it comprises no other reactive monomers, in particular, this reaction mixture according to the invention comprises no
REPLACEMENT SHEET 4a monomeric styrene, in contrast to many of the known reaction mixtures. Furthermore, use of the reaction mixture results in the fixing elements being physically anchored in place by forces such as friction, but also 5 chemically bonded in place. I WO 93/01246 5 PCT/EP92/01451
In another embodiment of the invention, the reaction mixture can also additionally comprise other 5 reactive ethylenically unsaturated monomers. In a further embodiment, the reaction mixture is pre-accelerated in order to obtain a rapid curing reac tion on contact with the curing agent component. Accelerators which can be used are diethylaniline, di 10 methylaniline, Ν,Ν-dimethyltoluidines, 4,4-bis(dimethyl amino) diphenylmethane, cobalt naphthenate, cobalt octoate or mixtures thereof. The reaction mixture (a) comprises 51. 0 to 98.0 parts by weight of monomeric, 2,2-bis- [4-(methacryloxyethoxy)phenyl]propane, 0.0 to 48.9 parts 15 by weight of unsaturated polyester resin, vinyl ester resin or acrylic resin or a mixture thereof and 0.1 to 5.0 parts by weight of accelerating agent. The reaction mixture according to the invention can additionally also comprise one or more liquid, non- 20 reactive organic diluents, in order to bring the vis cosity of the reaction mixture into the desired range and if appropriate also to modify the flexibility of the synthetic resin body formed on curing. Suitable non-reactive organic diluents are 25 acetone, dimethylformamide, toluene, methyl ethyl ketone (MEK), dibutyl phthalate, dimethyl phthalate, dihexyl phthalate or a mixture thereof. In such a case, the pre-accelerated reaction mixture (a) comprises 51 to 99.9 parts by weight of 30 specific monomeric propane derivative, 39 to 0.0 [lacuna] unsaturated polyester resin, vinyl ester resin or acrylic resin or a mixture thereof, 0.1 to 5.0 parts by weight of accelerating agent and 0 to 10 parts by weight of one or more liquid non-reactive organic diluent(s), based on the 35 total weight of (a). The reaction mixture preferably comprises up to 5 parts by weight of non-reactive diluent and correspond ingly more monomer and/or unsaturated polyester resin,
REPLACEMENT SHEET WO 93/01246 6 PCT/EP92/01451
vinyl ester resin, acrylic resin or a mixture thereof. The reaction mixture (a) can additionally com prise, although this is not preferred, further other reactive monomers, such as styrene, methyl methacrylate, 5 ethyl methacrylate, α-methylstyrene, chlorostyrene, butyl acrylate, diallyl phthalate, trimethylolpropane trimethacrylate, dicyclopentenyloxylethyl [sic] methacrylate, 3,3,5-trimethylcyclohexyl methacrylate or benzyl methacrylate. 10 In such a case, the pre-accelerated reaction mixture (a) comprises 51 to 99.9 parts by weight of specific monomeric propane derivative, 24 to 0.0 parts by weight of unsaturated polyester resin, vinyl ester resin or acrylic resin or a mixture thereof, 0.1 to 5.0 parts 15 by weight of accelerating agent and 25 to 0 parts by weight of one or more other reactive ethylenically unsaturated monomer(s), based on the total weight of (a). It is in principle also possible for the reaction mixture to comprise both non-reactive diluent(s) and 20 further other reactive monomer(s). In such an embodiment of the invention, the pre-accelerated reaction mixture (a) comprises 51 to 99.9 parts by weight of specific monomeric propane derivative, 24 to 0.0 parts by weight of unsaturated polyester resin, vinyl ester resin or 25 acrylic resin or a mixture thereof, 0.1 to 5.0 parts by weight of accelerator, 10 to 0 parts by weight of non reactive liquid organic diluent(s) and 15 to 0 parts by weight of one or more other ethylenically unsaturated monomers, based on the total weight of (a). 30 Suitable unsaturated polyester resins are un saturated polyesters which are prepared on the basis of dibasic acids, such as maleic acid, o-phthalic acid and/or m-phthalic acid or isophthalic acid with a dihydric alcohol, such as ethylene glycol and/or 35 propylene glycol. The unsaturated polyester resins cure or continue their polymerisation to give higher molecular weight solid polymers when they are brought into contact with a curing agent. The polyester resins usually
REPLACEMENT SHEET WO 93/01246 - 7 - PCT/EP92/01451 comprise a diluent, which can be an ethylenically unsaturated monomer, such as styrene. To prepare a particularly environment-friendly reaction mixture, unsaturated polyester resins which 5 comprise no styrene are preferred. The ester number of the polyesters should preferably be in the range from 250 to 460 mg of KOH/g of polyester resin. The ester number is determined in accordance with DIN 53401. Suitable vinyl ester resins are those which are 10 obtained by reaction of polyepoxides with ethylenically unsaturated monocarboxylic acids. The known polyepoxides, such as glycidyl ethers of polyhydric alcohols and polyhydric phenols, epoxy-novolak and epoxidized un saturated polyesters, can be used for the preparation of 15 the vinyl ester resins as long as they contain more than one epoxide group per molecule. The polyepoxides can be monomers or polymers. Suitable unsaturated carboxylic acids for the reaction with polyepoxides are α,β-unsatur- ated monocarboxylic acids, such as acrylic acid, 20 methacrylic acid and crotonic acid. Particularly preferred polyepoxides for the reaction with ethylenically unsaturated monocarboxylic acids are bisphenol A epoxy resins, bisphenol F epoxy resins, novolak epoxy resins, epoxy resins of the halo- 25 genated bisphenol type, epoxy resins of the polyglycidyl ester type, such as diglycidyl phthalate, and epoxy resins of the polyglycidyl ether type, such as a glycidyl ether of an aliphatic alcohol. If appropriate, the secondary hydroxyl groups of the vinyl ester resins can 30 be reacted with a dicarboxylic acid anhydride in order to form attached half-ester groups. The preferred styrene-free vinyl ester resins or vinyl ester epoxy resins have an average molecular maes of 450 to 1200 daltons. The vinyl ester resins preferably 35 have an ester number of 90 to 240 g of KOH/g of resin. The ester number is determined in accordance with DIN 53401, as already’described. An acrylic resin which can be used is, for example, polymethyl methacrylate
REPLACEMENT SHEET WO 93/01246 8 PCT/EP92/01451 (PMMA), particle size 0.1 mm, if appropriate partly dissolved in methyl methacrylate. The main component of the reaction mixture according to the invention is a bifunctional self-cross 5 linking monomer of the formula
H C = C-C-O-CH—-CH·—0 “ 2 2 2 2
CH CH 3
which imparts a surprisingly low shrinkage in volume of 1 to 2 percent to the resin body formed. However, the resin body also has an outstanding chemical resistance 10 against the action of acids and bases and a low water absorption capacity. It also has a high heat resistance. To achieve the low viscosity required for intro- duction of the curing agent component when used with multi-cavity cartridges or cartouches, the reaction 15 mixture (a) preferably has a viscosity at 25°C of 300 mPa.s to 10000 mPa.s. Suitable peroxide curing agentsi are benzoyl peroxide, lauroyl peroxide, p-butyl :hydroperoxide , p-butyl perbenzoate and methyl ethyl ketone peroxide. 20 Filler(s) is (are) added to the reaction mixture according to the invention as filler component(s). Preferred fillers are quartz sand, magnesium oxide, clinker, marble dust, calcium carbonate,and glass beads. pre-tepeUiiy The particle size of the fillers, is in the range from A 25 0.001 to 5 mm. In the case of multi-cavity cartridges which can be destroyed,.by pressure, the weight ratio of the total reagentAk£t is preferably 20 to 50 parts by weight of cartridge glass, 30 18 to 25 parts by weight of pre-accelerated reaction
REPLACEMENT SHEET WO 93/01246 9 FCT/SP92/01451 mixture 0.4 to 1.5 parts by weight of peroxide curing agent and 30 to 55 parts by weight of filler component. In the case or cartouches with an encapsulated 5 peroxide curing agents the weight ratio of the total reagent^ kit is preferably (a) 35 to 50 parts by weight of pre-accelerated reaction mixture 1 to 8.0 parts by weight of thixotropic agent 10 50 to 65 parts by weight of filler component 1 to 8.0 parts by weight of encapsulated per oxide curing agent 0.5 to 4.0 parts by weight of thixotropic auxili ary 15 (b) 35 to 50 parts by weight of reaction mixture 1 to 8.0 parts by weight of thixotropic agent 50 to 65 parts by weight of filler component 0.2 to 1.6 parts by weight of encapsulated amine accelerator 20 1 to 8.0 parts by weight of encapsulated per oxide curing agent 0.5 to 4.0 pasts by weight of thixotropic auxili ary. A suitable thixotropic agent is, for example, 25 silicic acid (Aerosil 200). Suitable thixotropic auxiliaries are, for ex ample, polyhydroxycarboxamide solutions (Byk-R 605 from Byk-Chemie) and glycerol. The low shrinkage in volume of the resin body 30 produced with the reaction mixture according to the Invention for adhesive anchoring of fixing elements becomes clt-ar from the following comparisons. Shrinkage in volume of the test specimens of the known reaction mixtures and from the reaction mixture 35 according to the invention.
REPLACEMENT SHEET WO 93/01246 - 10 - PCT/EP92/01451
Shrinkage in volume in %
1. Unsaturated polyester resin, pre accelerated by amine, with 30% by 5 weight of styrene, viscosity at 23°C 2300 mPa.s 6.3 2. Vinyl ester resin, pre-accelerated by amine, with 38% by weight of styrene, viscosity at 23°C 500 mPa.s 7.8
10 3. Reaction mixture according to the invention, as in Example 1, viscosity at 23°C 1500 mPa.s 1.02
The invention will now be described in more detail with the aid of the following examples.
15 Example 1 Cartridge of size M12/anchor rod Reaction mixture (a) 3.6 g of 2,2-bis[4-(meth acryloxyethoxy) phenyl] propane are pre-accelerated with 0.03 part by weight of dimethyl-paratoluidines and mixed 20 with 9.2 g of quartz sand (particle size 0.04 to 0.07 mm). 0.4 g of dibenzoyl peroxide (20 percent, inhibited in gypsum) is used as the curing agent com ponent in the second cavity. The multi-cavity cartridge comprises a total of 25 5.4 g of cartridge glass. Anchor rod M 12 x 160> threaded rod quality 12.9 After a curing time of 0.5 hour at room tem perature, the following strength values are determined in concrete: 30 Concretes B25, actual strength 27 N/mm2 Average extraction value 80 kN Bond stress: 16.2 N/mm2 Failures bond fracture
REPLACEMENT SHEET WO 93/01246 11 PCT/EP92/01451
Example 2 Cartridge of size M12/anchor rod 3.6 g of specific propane derivative as in Example 1 are formulated to a pre-accelerated reaction 5 mixture with 8 parts by weight of vinyl ester, styrene- free, ester number = 133 mg of KOH/g [lacuna] unsaturated polyester resin, styrene-free, ester number = 360 mg of KOH/g and 0.04 g of dimethyl-paratoluidines. 9.2 g of quartz sand (average particle size 1.2 10 to 1.8 mm) are used as the filler component. The other cavity of the two-cavity cartridge contains 0.25 g of dibenzoyl peroxide (50 percent, in hibited in N-phthalate [sic]). The total amount of cartridge glass is 5.4 g. 15 Anchor rod: M 12 x 160, threaded rod quality 9.8 After a curing time of 1 hour at room tempera ture, the following strength values are obtained: Concrete: B25, actual strength 27 N/ram2 Average extraction value 84 kN 20 Bond stress: 17 N/mm2 (quality of the anchor rod) Failure: anchor rod fracture
Example 3 Cartridge of size M12/anchor rod 3.6 g of specific monomeric propane derivative 25 pre-accelerated as in Example 1 are formulated to a reaction mixture with 0.36 g of available unsaturated polyester, styrene-free, ester number = 440 mg of KOH/g and 0.18 g of acetone, and the mixture is mixed with 9.0 g of quartz sand (particle size 1.2 to 1.8 mm) and 30 introduced into the outer cavity of the cartridge. The second cavity contains 0.35 g of dibenzoyl peroxide (30 percent, inhibited in inert filler and phthalate). The content of cartridge gla&s in the reagent kit is 5.4 g. 35 Anchor rod: M 1.2 x 160, threaded rod quality 9.8 After a curing * iine of 1 hour at room tempera ture, the following strength values are determined:
REPLACEMENT SHEET 'wo 93/01246 12 PCT/EP92/01451
Concrete: B25, actual strength 27.4 N/mm2 Average starting value 84 kN Bond stress: 17 N/mm2 Failure: bond fracture
5 Example 4 2.6 g of specific propane derivative are formu lated to a pre-accelerated reaction mixture with 0.72 g of vinyl ester, styrene-free, ester number = 140 mg of KOH/g, 0.72 got msthyl methacrylate and 0.1 of N,N-di-> 10 methyl-p-toluidine . 9.0 g of quartz sand (particle size 1.2 to 1.8 mm) are used as the filler component. The other cavity of the two-cavity cartridge contains 0.26 g of curing agent (50 percent by weight of 15 benzoyl peroxide, inhibited in phthalate). The content of cartridge glass in the reagent kit is 5.4 g. Anchor rod? M 12 x 160, threaded rod quality 9.8 After a curing time of 0.5 hour at room tempera- 20 ture, the following strength values are determined: Concrete: B 50 Average extraction value >81 kN Bond stress: 16.4 N/mm2 Failure: steel fracture
25 Example 5 3.4 g of specific propane derivative are formu lated to a pre-accelerated reaction mixture with 0.21 g of plasticiser (phthalic acid polyester), 0.63 g of vinyl ester, styrene-free, ester number = 109 mg of KOH/g and 30 0.02 g of N,N-dimethyl-p-toluidine. 9.0 g of quartz sand (particle size 1.2 to 1.8 mm) are used as the filler component. The other cavity of the two-cavity cartridge contains 0.35 g of dibenzoyl peroxide (30 percent by 35 weight, inhibited in inert filler and phthalate). The content of cartridge glass in the reaction
REPLACEMENT SHEET WO 93/01246 13 PCT/EP92/01451 kit is 5.4 g. Anchor rod: M 12 x 160, threaded rod quality 9.8 After a curing time of 0.5 hour at room tempera ture, the following strength values are determined: 5 Concrete: B 50 Average extraction value >85 kN Bond stress: 17.2 N/mm2 Failure: steel fracture
Example 6 10 2.59 g of specific propane derivative are formu lated to a pre-accelerated reaction mixture with 0.63 g of styrene, 0.95 g of vinyl ester, ester number = 109 mg of KOH/g, and 0.034 g of N,N-dimethyl-p-toluidine. 8.8 g of glass beads (particle size 0.6 to 2 nun) 15 are used as the filler component. The other cavity of the two-cavity cartridge contains 0.25 g of curing agent (50 percent by weight of benzoyl peroxide, inhibited in phthalate). The content of cartridge glass in the reaction 20 kit is 5.5 g. Anchor rod: M 12 x 160, threaded rod quality 9.8 After a curing time of 20 minutes at room tem perature, the following strength values are determined: Concrete: B 50, actual strength 27.4 N/mm2 25 Average extraction value 84 kN Bond stress: 17 N/mm2 Failure: bond fracture
Example 7 3.35 g of specific propane derivative are formu 30 lated to a pre-accelerated reaction mixture with 0.2 g of polymethyl methacrylate (particle size 0.1 mm), 0.4 g of methyl methacrylate and 0.03g of N,N-dimethyl-p-tolui- dine. 9.9 g of quartz sand (particle size 1.2 to 35 1.8 nun) are used as the filler component. The other cavity of the two-cavity cartridge
REPLACEMENT SHEET I
WO 93/01246 - 14 - PCT/EP92/01451
contains 0.35 g of dibenzoyl peroxide (30 percent by weight, inhibited in inert filler and phthalate). The content of cartridge glass in the reaction kit is 5.5 g. 5 Anchor rods M 12 x 160, threaded rod quality 12.9. After a curing time of 0.5 hour at room tempera ture, the following strength values are determined: Concretes B 50, actual strength 54.2 N/mmz Average extraction value 99.9 kN 10 Bond stress: 20.4 N/mm2 Failure: bond fracture
Example 8 73.4 g of specific propane derivative are mixed with 9.63 g of vinyl ester, ester number = 133 mg of KOH/g, 15 4.62 g of plasticiser (phthalic acid polyester), 0.32 g of accelerator (N,N-dimethyl-p-toluidine), 4.4 g of thixotropic agent, 2.0 g of thixotropic auxiliary, 9.0 g of encapsulated curing agent (32 percent by 20 weight of benzyl [sic] peroxide, inhibited in phthalate) and 96.0 g of quartz sand (particle size 0.1 to 0.5 mm) to give a uniform reactive resin mortar, and the mortar is introduced into a one-cavity cartouche. 25 The mixed composition is introduced into a bore hole of 14.3 mm diameter. An anchor rod M 12 with several tapers and a wire mesh sheath is inserted. After a curing time of 0.5 hour at room tempera ture, the following strength values are determined: 30 Concrete: B 25, actual strength 25.8 N/mm2 Failure: anchor rod fracture
Example 9 73.4 g of specific propane derivative are mixed with 9.63 g of vinyl ester, ester number = 133 mg of KOH/g, 35 6.0 g of methyl acrylate, 0.38 g of encapsulated accelerator (70 percent by
<>V REPLACEMENT SHEET
?1 £ ‘ ‘ WO 93/01246 15 PCT/EP92/01451 weight of diathylaniline [sic] and 30 percent by weight of dimethyl-p-toluidine), 6.0 g of thixotropic agent, 6.0 g of encapsulated curing agent (50 percent by 5 weight of benzoyl peroxide, inhibited in phthalate) and 100.0 g of quartz sand (particle size 0.1 to 1.2 nun) to give a uniform reaction kit, and the kit is introduced into a polyamide hose (width 26 mm). 10 Cartridge weight: about 28 g The cartridge is introduced into a bore hole of 17.0 mm diameter. A threaded anchor rod, size M 16, rotating on impact, is inserted. After a curing time of 0.5 hour at room tempera- 15 ture, the following strength values are determined: Concrete: B 50, actual strength 54.2 N/mm2 Average extraction value: 84 kN Failure: anchor rod fracture
REPLACEMENT SHEET 16 THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:
1. Reagent composition for the production of synthetic resin bodies for bonding and anchoring of fixing elements in a fixing base, the reagent composition comprising: (a) a reaction mixture which comprises at least one ethylenically unsaturated monomer, (b) a curing agent component of an organic peroxide and (c) a filler component, the curing agent component (b) being separated from the reaction mixture (a) before use, characterised in that the reaction
• · • o • · · mixture (a) comprises: 51.0 to 100.00 parts by weight of monomeric 2,2- a ·· • · 1 bis[4-(methacryloxyethoxy)phenyl]propane, and 49.0 to 0.0 parts by • a • · · weight of unsaturated polyester resin, vinyl ester resin or acrylic resin or a a a mixture thereof, based on the total weight of (a). a a • • a 2. Reagent composition according to Claim 1, characterised in that the
• · • · • H 0 reaction mixture (a) comprises 51 to 98.0 parts by weight of monomeric 2,2- ···· • · a · • · bis[4-methacryloxyethoxy)phenyl]propane, 0.0 to 48.9 parts by weight of • ·· · ·' a ···· unsaturated polyester resin, vinyl ester resin or acrylic resin or a mixture thereof a and 0.1 to 5.0 parts by weight of accelerating agent, based on the total weight of • a • · • · ···· (a). a 3. Reagent composition according to Claim 1, characterised in that the reaction mixture (a) comprises 51 to 99.9 parts by weight of monomeric 2,2- bls[4-(methacryloxyethoxy)phenyl]propane, 39 to 0.0 parts by weigh* of unsaturated polyester resin, vinyl ester resin or acrylic resin or a mixture thereof, 0.1 to 5.0 parts by weight of accelerating agent and 10 to 0 parts by weight of one or more liquid non-reactive organic diluent(s), based on the total weight of (a). 17 4. Reagent composition according to Claim 3, characterised in that the non reactive organic diluent is acetone, dimethylformamide, toluene, MEK, dibutyl phthalate, dimethyl phthalate, dihexyl phthalate or a mixture thereof.
5. Reagent composition according to Claim 1, characterised in that the reaction mixture (a) comprises 51 to 99.9 parts by weight of monomeric 2,2- bis[4-(methacryloxyethoxy)phenyl]propane, 24 to 0.0 parts by weight of unsaturated polyester resin, vinyl ester resin or acrylic resin of a mixture thereof, 0.1 to 5.0 parts by weight of accelerating agent and 25 to 0 parts by weight of one or more other reactive ethylenically unsaturated monomer(s), based on the total weight of (a). • · · · · · •β · · 6. Reagent composition according to Claim 5, characterised in that the other ·:···:* reactive monomers are styrene, methyl methacrylate, ethyl methacrylate, benzyl :**·.: methacrylate or a mixture thereof.
7. Reagent composition according to Claim 1, characterised in that the reaction mixture (a) comprises 51 to 99.9 parts by weight of monomeric 2,2- b!s[4-(methacryloxyethoxy)phenyl]propane, 24 to 0.0 parts by weight of unsaturated polyester resin, vinyl ester resin or acrylic resin or a mixture thereof, 0.1 to 5.0 parts by weight of accelerating agent, 10 to 0 parts by weight of non reactive organic diluent and 15 to 0 parts by weight of one or more other reactive ethylenically unsaturated monomer(s), based on the total weight of (a).
8. Reagent composition according to Claim 1, characterised in that the reaction mixture (a) comprises 75 to 99.9 parts by weight of monomeric 2,2- bis[4-(methacryloxyethoxy)phenyl]pro^ane, 25 to 0.1 parts by weight of unsaturated polyester resin, vinyl estei resin or acrylic resin or a mixture thereof and 0.1 to 5.0 parts by weight of accelerating agent, based on the total weight of (a). 18 9. Destructible multiple chamber cartridge for the in situ production of synthetic, resin bodies for bonding and anchoring of fixing elements in a fixing base containing a reagent composition comprising: (a) a reaction mixture which comprises at least one ethylenically unsaturated monomer, (b) a curing agent component of an organic peroxide and (c) a filler component, wherein the curing agent component (b) and the reaction mixture (a) are retained separately from each other in different chambers of the multipie chamber cartridge characterised in that the reaction mixture (a) comprises: 51.0 to 100.0 parts by weight of monomeric 2,2-bis[4-methacryloxyethoxy)phenyl]- propane, and 49,0 to 0.0 parts by weight of unsaturated polyester resin, vinyl ester resin or acrylic resin or a mixture thereof, based on the total weight of (a).
10. Cartridge according to claim 9, characterised in that the reaction mixture (a) comprises 51 to 98.0 parts by weight of monomeric 2,2-bis[4- methacryloxyethoxy)phenyl]propane, 0.0 to 48.9 parts by weight of unsaturated polyester resin, vinyl ester resin or acrylic resin or a mixture thereof and 0.1 to 5.0 parts by weight of accelerating agent.
11. Cartridge according to claim 9, characterised in that the reaction mixture (a) comprises 51 to 99.9 parts by weight of monomeric 2,2-bis[4- (methacryloxyethoxy)phenyl]propane, 39 to 0.0 parts by weight of unsaturated polyester resin, vinyl ester resih or acrylic resin or a mixture thereof, 0.1 to 5.0 parts by weight of accelerating agent and 10 to 0 parts by weight of one or more liquid non-reactive organic diluent(s).
12. Cartridge according to claim 11, characterised in that the non-reactive organic diluent is acetone, dimethylformamide, toluene, MEK, dlbutyl phthalate, dimethyl phthalate, dihexyl phthalate or a mixture thereof. 19 13. Cartridge according to claim 9, characterised in that the reaction mixture (a) comprises 51 to 99.9 parts by weight of monomeric 2,2-bis[4- (methacryloxyethoxy)phenyl]propane, 24 to 0.0 parts by weight of unsaturated polyester resin, vinyl ester resin or acrylic resin of a mixture thereof, 0.1 to 5.0 parts by weight of accelerating agent and 25 to 0 parts by weight of one or more other reactive ethylenically unsaturated monomer(s).
14. Cartridge according to claim 13, characterised in that the other reactive monomers are styrene, methyl methacrylate, ethyl methacrylate, benzyl methacrylate or a mixture thereof.
15. Cartridge according to claim 9, characterised in that the reaction mixture (a) comprises 51 to 99.9 parts by weight of monomeric 2,2-bis[4- (methacryloxyethoxy)phenyl]propane, 24 to 0.0 parts by weight of unsaturated polyester resin, vinyl ester resin or acrylic resin or a mixture thereof, 0.1 to 5.0 parts by weight of accelerating agent, 10 to 0 parts by weight of non-reactive organic diluent and 15 to 0 parts by weight of one or more other reactive ethylenically unsaturated monomer(s).
16. Cartridge according to claim 9, characterised in that the reaction mixture (a) comprises 75 to 99.9 parts by weight of monomeric 2,2-bis[4- (methacryloxyethoxy)phenyl]propane, 25 to 0.1 parts by weight of unsaturated polyester resin, vinyl ester resin or acrylic resin or a mixture thereof and 0.1 to 5.0 parts by weight of accelerating agent. DATED this 10th day of October, 1995. UPAT GmbH & CO.
WATERMARK PATENT & TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA INTERNATIONAL SEARCH REPORT International application No. PCT/EP 92/01451
A. CLASSIFICATION OF SUBJECT MATTER Int: CL. 5; C09J 4/00; C09J 4/06
According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documcntauoo searched (classification system Col lowed by classification symbols)
Int. Cl. 5: C09J; C08F; E21D
Dccumeoutioo searched other than minimum documentation to the extent that such documents are included io the fields searened
Electronic data oase consultea auring the international search < name of data ease ana. wnere practicable, searen terms usedI
C. DOCUMENTS CONSIDERED TO BE RELEVANT
Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.
A FR, A, 2 381 072 (DENKI KAGAKU KOGYO) 1-8 15 September 1978 see page 4. line 16 - line 28 s
A FR, A, 2 505 347 (LOCTITE) 1-8 12 November 1982 see page 6, line 27 - line 30 see page 12, line 3 - line 36
A EP, A, 0 199 671 (HILTI) 1-3 29 October 1986 cited in the application r
| ] Further documents are listed in (he continuation of Box C. f~“] See patent family annex.
* Seeds! caiaeoriea elated documents: ‘V laterdocum«ntpublUh«daiterth*iewmaUoaalfillasdat«orpriontv “Λ" Date of the actual completion of the international search Date of mailing cf the international search report * 02 NOVEMBER 1992 (02.11.92) 11 NOVEMBER 1992 (11.11.92) Name and mailing address of the ISA/ AUthonzed officer EUROPEAN PATENT OFFICE Ftmitnile No, Telephone No. Form PCT/1SA/210 (second sheet) (July 1992) > 1 I ' ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 9201451 SA 61457 Thi* annex loot the parent family members relntin* to the patent documents dtzd in the abovornentiooed tnternauonal search repsrt. The manner» are «» contained in the European Patent Office EOP file on The European Patent Office ii in no way liable for these particular* which are merely jrven for the purpose of information. 02/11/92 Parent document Publication Patent family Publication deed in search report dace tDcmherft) data FR-A-2381072 15-09-78 JP-C- 1011246 29-08-80 JP-A- =3102989 07-09-78 JP—9— =5002205 18-01-80 CA-A- 1087349 07-10-80 CH-A- 636114 13-05-83 DE-A.C 2806701 24-08-78 GB-A- 1566993 08-05-80 NL-A- 7801862 24-08-78 US-A- 4259462 31-03-81 US-A- 4174311 13-11-79 FR-A-2505347 12-11-82 US-A- 4417028 22-11-83 AU-B- 554145 07-08-86 BE-A- 893130 10-11-82 CA-A- 1180843 08-01-85 DE-A- 3217658 25-11-82 GB-A,B 2101622 19-01-83 JP-A- 57192476 26-11-82 ΕΡ-Ά-Ο199671 29-10-86 DE-A- 3514031 23-10-86 AU-B- 589172 05-10-89 AU-A- 5640186 23-10-86 DE-A- 3617702 03-12-87 JP-A- 61243876 30-10-86 t r e m r o u t Fee mere Mtatk abm thi* mm t >»· Official mtm of th* Esrepeaa Parent Office. No, tl/SX » o * J J ANHANG ZUM INTERNATION ALEN RECHERCHENBERICHT Ober die Internationale patentanmeldung nr. cP 9201451 SA 61457 la dicWtn Anhaag ciad ώ« Mitgbeder der Paceatfanalica der iai obengenaaatza taternaoonaten Rezherebenbenctit angeiiUnten PataKdokuioeutc aageseteo. Die Aagabea Uber die Faadtienantgiieder enotpredica dem Stand der Datei de* Earapaiscben Pateeaamca am Dime Angabsa dicsea nur zur Untzrrictang und erfoigea obne Gcwahr. 02/11/92 Im Reehcrcbenberidit Datum der .Mitglxd(er) der Datum der angefiihrtzs Panotdokmneac Verbifentlidamg Patentfamilie | V cto ffemli chung rR-A-2381072 15-09-78 JP-C- 1011246 29-08-80 JP-A- 53102989 07-09-78 JP-3- 55002205 18-01-80 CA-A- 1087349 07-10-80 CH-A- 636114 13-05-83 DE-A,C 2806701 24-08-78 GB-A- 1566993 08-05-80 NL-A- 7801862 24-08-78 US-A- 4259462 31-03-81 US-A- 4174311 • 13-11-79 FR-A-2505347 12-11-82 US-A- 4417028 22-11-83 AU-8- 554145 07-08-86 BE-A- 893130 10-11-82 CA-A- 1180843 08-01-35 DE-A- 3217658 25-11-82 GB-A.B 2101622 19-01-83 JP-A- 57192476 26-11-82 EP-A-0199671 29-10’86 DE-A- 3514031 23-10-86 AU-B- 589172 05-10-89 AU-A- 5640186 23-10-86 DE-A- 3617702 03-12-87 JP-A- 61243876 30-10-86 FO473 ZFOfORM Fir aaW» gnaibaiti a damn* Aafaag: ad· AmoddM dee Emrwf amdaea Patatamo. Nr.12/82 INTERNAT10NALER RECHLRCHENBERICHT laaaraaaaaaUa AtnaraarX· PCT/EP 92/01451 i. KLASSIFlkATlON OES AWMELDUNGSGEGENSTANDS (ba laanraraa Klamflkannaepaaotaa oad all· aatzugnM·)· Nat· it intwienooalan PuetulaetfUuuaoa (IPC) Mar naca dar tiwoua Klasrtflkanoa tnd it IPC Int.Kl. 5 C09J4/00; C0SJ4/06 U. RECHEROOERTE SACHGEBtETE " ' . .... Recaarcnitnar MlManpntfmff1 KlaB^Ueutomxyttn | KlastfUunoosynM· Int.Kl. 5 C09J ; C08F ; E21D Recaercn^KS mail tun Mlndentnrfrwff gtnonkndn Veroff«otlichung«a, sowen die* inter die rtcnecniwtea Sachgtolaa fallen1 ΠΙ. EINSCHLAGIGE VEROFFENTUCHUNGEN ’ Art.* | Kanaxachnung der Vtroffentlichung11 , sowtit trfontnlds unter Angahe der taaflgtollchM T«ltu | R«r. Aaapruca Nr.u A FR,A,2 381 072 (DENKI KAGAKU KOGYO) 1-3 15. September 1978 siehe Seite 4, Zeile 16 - Zeile 28 siehe Seite 13 siehe Anspriiche 1-11 A FR,A,2 505 347 (LOCTITE) 1-8 '_Z. November 1982 siehe Seite 6, Zeile 27 - Zeile 30 siehe Seite 12, Zeile 3 - Zeile 36 A ΕΡ,Α,Ο 199 671 (HILTI) ’ 1-8 29. Oktober 1986 in der Anmeldung erwahnt m ·····»■■ * 1 Beuodere ICatrgortn von xngrgrotnaa Veroffectllchun^M 10 : Ά* VtrtHtndidinn», die den allgwatintn Stand 4«r Techaik T Saatart Vereffentllchuae, die uiS den InteraaDonaJan An- deftniert, alter tucai al* btioMdr* oageuuui atuuMatn 1st meidedatM· oear den PiionUtMaran ytroffntllcat worden •r· <1,—. ■>->-__ -. a.. to 084 "" <« AnneidUBg tucnt IsollUltrt. Modern nut tun mttraa. Vwtiadnu 4M 4« Erftnauag zitgrundeiletndes Pnnxtps Qoaalae AantMadantn veroneaUIcbt women in 3« | rv. BESaonNIGUNG Duan den Abdcalunei dor taternaaonalen Raoeroe AbuodatMila d«* lataraanonalaa RacaaxnanawKau 02.NOVEMBER 1992 ' 11. 11.92 inttrnanoanlt QaawrciMnataticd* Unwntntot 4« btwHntatUgW· Btdltanttraz/ ' EUROPA1SCHES PATENTAMT ANDRIOLLO G.R. r«wMt rCT/cunuiMi» umt mn