Filler mixture for chemical fastening systems and use thereof

Abstract

A hardener composition can be used for a reactive resin system containing a reactive resin based on radically curable, ethylenically unsaturated compounds. The hardener composition contains a hardener for the reactive resin and a filler mixture. The filler mixture is composed of a first filler having a first average particle size d.sub.50,1 and a second filler having a second average particle size d.sub.50,2. The first average particle size d.sub.50,1 of the first filler is greater than the second average particle size d.sub.50,2 of the second filler (d.sub.50,1>d.sub.50,2). The ratio d.sub.50,1 to d.sub.50,2 (d.sub.50,1:d.sub.50,2) is in the range of 8:1 to 100:1. The filler mixture is useful, and a reaction resin system can contain the hardener composition.

Claims

1: A hardener composition for a reactive resin system comprising a reactive resin based on radically curable, ethylenically unsaturated compounds, wherein the hardener composition comprises: a hardener for the reactive resin, and a filler mixture, wherein the filler mixture consists of a first filler having a first average particle size d.sub.50,1 and a second filler having a second average particle size d.sub.50,2, wherein the first average particle size d.sub.50,1 of the first filler is greater than the second average particle size d.sub.50,2 of the second filler (d.sub.50,1>d.sub.50,2), and a ratio d.sub.50,1 to d.sub.50,2 (d.sub.50,1:d.sub.50,2) is in a range of approx. 8:1 to approx. 100:1.

2: The hardener composition according to claim 1, wherein the first average particle size d.sub.50,1 of the first filler is 16 to 130 μm.

3: The hardener composition according to claim 1, wherein the second average particle size d.sub.50,2 of the second filler is 0.16 to 16 μm.

4: The hardener composition according to claim 1, wherein the first filler and the second filler of the filler mixture are each selected from the group consisting of a metal oxide, a semi-metal oxide, a metal hydroxide, a metal salt, a mineral or mineral-like filler, a hydraulically curable filler, a metal, carbon black, and a polymeric filler.

5: The hardener composition according to claim 4, wherein the first filler is selected from the group consisting of a metal oxide, a metal hydroxide and a metal salt.

6: The hardener composition according to claim 1, wherein a proportion of the first filler is greater than a proportion of the second filler.

7: The hardener composition according to claim 1, wherein the hardener for the reactive resin is based on a radically curable compound.

8: The hardener composition according to claim 1, wherein the hardener composition also contains water.

9: A method, comprising: mixing a hardener composition into a reactive resin composition for chemical fastening comprising a reactive resin based on radically curable, ethylenically unsaturated compounds, wherein the hardener composition comprises a filler mixture consisting of a first filler having a first average particle size d.sub.50,1 and a second filler having a second average particle size d.sub.50,2, wherein the first average particle size d.sub.50,1 of the first filler is greater than the second average particle size d.sub.50,2 of the second filler (d.sub.50,1>d.sub.50,2), and a ratio d.sub.50,1 to d.sub.50,2 (d.sub.50,1:d.sub.50,2) is in a range of 8:1 to 100:1.

10: The method according to claim 9, wherein the first average particle size d.sub.50,1 of the first filler is 16 to 130 μm.

11: The method according to claim 9, wherein the second average particle size d.sub.50,2 of the second filler is 0.16 to 16 μm.

12: A multi-component reaction resin system, comprising: a resin component comprising a radically curable, ethylenically unsaturated compound, and a hardener component comprising the hardener composition according to claim 1.

13: The multi-component reaction resin system according to claim 12, wherein the radically curable, ethylenically unsaturated compound comprises at least one reaction resin, at least one reactive diluent, or a mixture of at least one reaction resin and a reactive diluent.

14: The multi-component reaction resin system according to claim 13, wherein the radically curable, ethylenically unsaturated compound is a compound based on urethane (meth)acrylate, a compound based on epoxy (meth)acrylate, a methacrylate of an alkoxylated bisphenol, or a compound based on other ethylenically unsaturated compounds.

15: The multi-component reaction resin system according to claim 12, wherein the resin component further comprises an inorganic aggregate.

16: The multi-component reaction resin system according to claim 12, wherein the resin component further comprises an inhibitor and/or an accelerator.

17: The multi-component reaction resin system according to claim 12, wherein the multi-component reaction resin system is a two-component system.

Description

PREFERRED EMBODIMENTS

[0132] In the embodiments described below, the quantities (wt. %) in each case relate to the individual components, i.e. the resin component and the hardener component, unless otherwise stated. The actual amounts are such that the wt. % of the particular component add up to 100.

[0133] In a first preferred embodiment of the hardener composition according to the invention, said composition contains: [0134] at least one peroxide as a hardener, [0135] water, and [0136] a filler mixture consisting of a first filler FS1 having a first average particle size d.sub.50,1 of between 16 and 130 μm and a second filler FS2 having a second average particle size d.sub.50,2 of between 0.16 and 16 μm, wherein the ratio d.sub.50,1 to d.sub.50,2 (d.sub.50,1:d.sub.50,2) is in the range of 8:1 to 100:1.

[0137] In a preferred aspect of this first embodiment, the peroxide is solid and suspended in the water.

[0138] In a second preferred embodiment of the hardener composition according to the invention, said composition contains: [0139] at least one peroxide as a hardener. [0140] water, and [0141] a filler mixture consisting of a first filler FS1 having a first average particle size d.sub.50,1 of between 16 and 130 μm and a second filler FS2 having a second average particle size d.sub.50,2 of between 0.16 and 16 μm, [0142] wherein the ratio d.sub.50,1 to d.sub.50,2 (d.sub.50,1:d.sub.50,2) is in the range of 8:1 to 100:1, and wherein the fillers are selected from the group consisting of metal oxides, semi-metal oxides, metal hydroxides, metal salts, mineral or mineral-like fillers, hydraulically curable fillers, metals, carbon black and polymeric fillers, preferably metal oxides, metal hydroxides and metal salts.

[0143] In a preferred aspect of this second embodiment, the peroxide is solid and suspended in the water.

[0144] In a third preferred embodiment of the hardener composition according to the invention, said composition contains: [0145] at least one solid peroxide as a hardener, [0146] water, [0147] a filler mixture consisting of a first filler FS1 having a first average particle size d.sub.50,1 of between 16 and 130 μm and a second filler FS2 having a second average particle size d.sub.50,2 of between 0.16 and 16 μm, [0148] wherein the ratio d.sub.50,1 to d.sub.50,2 (d.sub.50,1:d.sub.50,2) is in the range of 8:1 to 100:1, and the fillers are selected from the group consisting of metal oxides, metal hydroxides and metal salts, and [0149] inorganic and/or organic additives.

[0150] In a preferred aspect of this third embodiment, the peroxide is suspended in the water.

[0151] In a fourth preferred embodiment of the hardener composition according to the invention, said composition contains: [0152] a solid peroxide as a hardener, [0153] water, [0154] a filler mixture consisting of a first filler FS1 having a first average particle size d.sub.50,1, of between 16 and 130 μm and a second filler FS2 having a second average particle size d.sub.50,2 of between 0.16 and 16 μm, [0155] wherein the ratio d.sub.50,1 to d.sub.50,2 (d.sub.50,1:d.sub.50,2) is in the range of 8:1 to 100:1, and the fillers are selected from the group consisting of metal oxides, metal hydroxides and metal salts, and the volume ratio of first filler to second filler (V.sub.FS1:V.sub.FS2) is in the range of 1.5:1 to 15:1, preferably 2:1 to 10:1, and more preferably 2.5:1 to 5:1, and [0156] inorganic and/or organic additives.

[0157] In a preferred aspect of this fourth embodiment, the peroxide is suspended in the water.

[0158] In a fifth preferred embodiment of the hardener composition according to the invention, said composition contains: [0159] a solid peroxide, [0160] water, [0161] a filler mixture consisting of a first filler FS1 having a first average particle size d.sub.50,1 of between 16 and 130 μm and a second filler FS2 having a second average particle size d.sub.50,2 of between 0.16 and 16 μm, [0162] wherein [0163] the ratio d.sub.50,1 to d.sub.50,2 (d.sub.50,1:d.sub.50,2) is in the range of 8:1 to 100:1, [0164] the fillers are selected from the group consisting of metal oxides, metal hydroxides and metal salts, [0165] the volume ratio of first filler to second filler (V.sub.FS1:V.sub.FS2) is in the range of 2.5:1 to 5:1, [0166] the limit filling level is between 55 and 75 vol. %, and [0167] inorganic and/or organic additives.

[0168] In a preferred aspect of this fifth embodiment, the peroxide is suspended in the water.

[0169] The hardener composition according to the invention is particularly suitable as a hardener component for a two-component reaction resin system for chemical fastening comprising a resin component and a hardener component. Preferred embodiments of such a two-component reaction resin system are described below.

[0170] In a preferred first embodiment of a reaction resin system, the resin component contains: [0171] at least one radically curable, ethylenically unsaturated compound and [0172] at least one inorganic filler,

[0173] and the hardener component contains: [0174] at least one peroxide as a hardener, [0175] water, and [0176] a filler mixture consisting of a first filler FS1 having a first average particle size d.sub.50,1 of between 16 and 130 μm and a second filler FS2 having a second average particle size d.sub.50,2 of between 0.16 and 16 μm, wherein the ratio d.sub.50,1 to d.sub.50,2 (d.sub.50,1:d.sub.50,2) is in the range of 8:1 to 100:1.

[0177] In a preferred aspect of this first embodiment of a reaction resin system, the peroxide is suspended in the water. In a further preferred aspect of this first embodiment of a reaction resin system, the resin component contains: [0178] 10 to 99.99 wt. %, preferably 15 to 97 wt. %, particularly preferably 30 to 95 wt. %, of the at least one radically curable compound, and [0179] 0.01 to 90 wt. %, preferably 3 to 85 wt. %, particularly preferably 5 to 70 wt. %, of the at least one inorganic filler,

[0180] and the hardener component contains: [0181] the first filler FS1 first filler FS1 having a first average particle size d.sub.50,1, and the second filler FS2 having a second average particle size d.sub.50,2 in a volume ratio of first filler to second filler (V.sub.FS1:V.sub.FS2) in the range of 1.5:1 to 15:1, [0182] 0.25 to 5 wt. %, preferably 1 to 30 wt. %, particularly preferably 5 to 25 wt. %, of the at least one peroxide, and [0183] 10 to 30 wt. %, preferably 10 to 25 wt. %, particularly preferably 15 to 25 wt. %, of water.

[0184] In a further, second preferred embodiment of the reaction resin system, the resin component contains: [0185] as a radically curable compound, a reaction resin mixture consisting of at least one reaction resin and a reactive diluent, [0186] at least one inorganic filler, [0187] at least one accelerator, and [0188] at least one inhibitor,

[0189] and the hardener component contains: [0190] at least one peroxide as a hardener. [0191] water, and [0192] a filler mixture consisting of a first filler FS1 having a first average particle size d.sub.50,1 of between 16 and 130 μm and a second filler FS2 having a second average particle size d.sub.50,2 of between 0.16 and 16 μm, wherein the ratio d.sub.50,1 to d.sub.50,2 (d.sub.50,1:d.sub.50,2) is in the range of 8:1 to 100:1.

[0193] In a preferred aspect of this second embodiment of the reaction resin system, the peroxide is suspended in the water. In a further preferred aspect of this second embodiment of the reaction resin system, the resin component contains: [0194] as a radically curable compound, 10 to 99.99 wt. %, preferably 15 to 97 wt. %, particularly preferably 30 to 95 wt. %, of a mixture, namely the reaction resin mixture, consisting of 0 to 100 wt. %, preferably 30 to 70 wt. %, based on the total weight of the mixture, of the at least one reactive resin, and 100 to 0 wt. %, preferably 70 to 30 wt. %, based on the total weight of the mixture, of the at least one reactive diluent, and [0195] 0.01 to 15 wt. %, preferably 0.1 to 10 wt. %, particularly preferably 1 to 7 wt. %, of the at least one inorganic filler, [0196] 0.01 to 10 wt. %, preferably 0.5 to 5 wt. %, more preferably 1 to 3 wt. %, of the at least one accelerator, and [0197] 0.001 to 5 wt. %, preferably 0.01 to 3 wt. %, more preferably 0.1 to 1 wt. %, of the at least one inhibitor,

[0198] and the hardener component contains: [0199] the first filler FS1 first filler FS1 having a first average particle size d.sub.50,1, and the second filler FS2 having a first average particle size d.sub.50,2 in a volume ratio of first filler to second filler (V.sub.FS1:V.sub.FS2) in the range of 1.5:1 to 15:1, [0200] 0.25 to 5 wt. %, preferably 1 to 30 wt. %, particularly preferably 5 to 25 wt. %, of the at least one peroxide, and [0201] 10 to 30 wt. %, preferably 10 to 25 wt. %, particularly preferably 15 to 25 wt. %, of water.

[0202] In a particularly preferred third embodiment of the reaction resin system, the resin component contains: [0203] as a radically curable compound, a reaction resin mixture consisting of at least one reaction resin based on urethane (meth)acrylate and at least one reactive diluent based on (meth)acrylate, [0204] at least one inorganic filler, in particular a silica, [0205] at least one accelerator, and [0206] at least one inhibitor,

[0207] and the hardener component contains: [0208] at least one peroxide, in particular a diacyl peroxide, [0209] water, [0210] a filler mixture consisting of a first filler FS1 having a first average particle size d.sub.50,1, of between 16 and 130 μm and a second filler FS2 having a second average particle size d.sub.50,2 of between 0.16 and 16 μm, wherein the ratio d.sub.50,1 to d.sub.50,2 (d.sub.50,1:d.sub.50,2) is in the range of 8:1 to 100:1, and [0211] further inorganic and/or organic additives.

[0212] In a preferred aspect of this third embodiment of the reaction resin system, the peroxide is suspended in the water. In a further preferred aspect of this third embodiment of the reaction resin system, the reaction resin system contains the constituents in the amounts specified in the second aspect.

[0213] In a very particularly preferred fourth embodiment, the resin component contains: [0214] as a radically curable compound, a reaction resin mixture consisting of at least one reaction resin based on urethane (meth)acrylate and at least one reactive diluent based on (meth)acrylate, [0215] at least one inorganic filler, in particular pyrogenic silica, [0216] at least one hydraulically setting or polycondensable compound, in particular cement, [0217] at least one accelerator, and [0218] at least one inhibitor,

[0219] and the hardener component contains: [0220] at least one peroxide, in particular dibenzoyl peroxide, [0221] water, [0222] a filler mixture consisting of a first filler FS1 having a first average particle size d.sub.50,1 of between 16 and 130 μm and a second filler FS2 having a second average particle size d.sub.50,2 of between 0.16 and 16 μm, wherein the ratio d.sub.50,1 to d.sub.50,2 (d.sub.50,1:d.sub.50,2) is in the range of 8:1 to 100:1, and [0223] further inorganic and/or organic additives.

[0224] In a preferred aspect of this fourth embodiment of the reaction resin system, the peroxide is suspended in the water. In a further, preferred aspect of this fourth embodiment of the reaction resin system, the resin component contains: [0225] as a radically curable compound, 10 to 99.99 wt. %, preferably 15 to 97 wt. %, particularly preferably 30 to 95 wt. %, of a mixture, namely the reaction resin mixture, consisting of 0 to 100 wt. %, preferably 30 to 70 wt. %, based on the total weight of the mixture, of the at least one reactive resin, and 100 to 0 wt. %, preferably 70 to 30 wt. %, based on the total weight of the mixture, of the at least one reactive diluent, and [0226] 0.01 to 15 wt. %, preferably 0.1 to 10 wt. %, particularly preferably 1 to 7 wt. %, of the at least one inorganic filler, [0227] 0 to 40 wt. %, preferably 5 to 30 wt. %, of the hydraulically setting or polycondensable compound, wherein the total amount of fillers, including the hydraulically setting or polycondensable compound, is 20 to 90 wt. %, preferably 40 to 80 wt. %, particularly preferably 50 to 80 wt. %, based on the resin components, [0228] 0.01 to 10 wt. %, preferably 0.5 to 5 wt. %, more preferably 1 to 3 wt. %, of the at least one accelerator, and [0229] 0.001 to 5 wt. %, preferably 0.01 to 3 wt. %, more preferably 0.1 to 1 wt. %, of the at least one inhibitor,

[0230] and the hardener component contains: [0231] the first filler FS1 first filler FS1 having a first average particle size d.sub.50,1 and the second filler FS2 having a first average particle size d.sub.50,2 in a volume ratio of first filler to second filler (V.sub.FS1:V.sub.FS2) in the range of 1.5:1 to 15:1, [0232] 0.25 to 5 wt. %, preferably 1 to 30 wt. %, particularly preferably 5 to 25 wt. %, of the at least one peroxide, and [0233] 10 to 30 wt. %, preferably 10 to 25 wt. %, particularly preferably 15 to 25 wt. %, of water.

EXAMPLES

[0234] List of the Constituents Used in the Examples and References (Explanation of Abbreviations) as Well as their Trade Names and Sources of Supply:

TABLE-US-00001 Raw material Comment Company Perkadox ® L-W40 dibenzoyl peroxide 40%, suspension in water Akzo Nobel Chemicals B.V. (CAS number 94-36-0) BP-40-SAQ dibenzoyl peroxide 40%, suspension in water, United initiators unbuffered (CAS number 94-36-0) Luperox® EZ-FLO dibenzoyi peroxide approx. 40%; suspension Arkema in water (CAS number 94-36-0) Benox ® B-50 dibenzoyl peroxide 50% in benzoate United Initiators (CAS number 94-36-0) Peroxan BP-40 WS dibenzoyl peroxide approx. 40%; suspension Pergan in water (CAS number 94-36-0) Trigonox ® C tert-butyl peroxy benzoate (99%, liquid), Akzo Nobel Functional (CAS number 614-45-9) Chemicals LLC LP-40-SAQ dilauroyl peroxide 40%, suspension in water United Initiators (CAS number 105-74-8) Water deionized Diethyl adipate Sigma-Aldrich Potassium dihydrogen water-free Sigma-Aldrich phosphate Disodium hydrogen citrate water-free Sigma-Aldrich Glycerol Sigma-Aldrich Aerosil ® 200 hydrophilic fumed silica; (CAS number: Evonik 112945-52-5; spec, surface area 200 m.sup.2/g; average particle size 0.2-0.3 μm (aggregates)) CAB-O-SIL ® TS720 hydrophobic PDMS-coated fumed silica Cabot OPTIGEL-CK activated phyllosilicate (bentonite): (spec, BYK-Chemie GmbH density 2.6 g/cm.sup.3, bulk density 550- 750 kg/m.sup.3, moisture content 10% ± 2%) Axiiat RH23 xanthan gum; viscosity (1% sol. in 1% KCL Synthomer (Brookfield LVT HI/60 rpm) 1200-1800 mPas; pH 6-8; fine powder (CAS number) Sodium hydroxide Sigma-Aldrich Sodium benzenesulfonate TCI Europe spec, d50 weight Filler [μm] [g/cm.sup.3] .sup.1) Main constituent Company OMYACARB ® 130AL 130 2.6 calcium carbonate Omya GmbH MILLISIL ® W3 90 2.65 quartz sand Quarzwerke GmbH Apyral ® 1E 50 2.4 aluminum hydroxide Nabaltec AG MILLISIL ® W6 40 2.65 quartz sand Quarzwerke GmbH OMYACARB ® 40AL 31 2.6 calcium carbonate Omya GmbH MILLISIL ® W12 16 2.65 quartz sand Quarzwerke GmbH Corundum 800 6.5 3.9 aluminum oxide Cerablast GmbH & Co KG Durcal 5 6 3.6 calcium carbonate Omya GmbH Albawhite 40 5 4.4 white spar Sachtleben Minerals GmbH & Co. KG OMYACARB ® 2AL 3.2 2.6 calcium carbonate Omya GmbH Albawhite 70 3 4.4 white spar Sachtleben Minerals GmbH & Co. KG KaMin 80 2.3 2.6 kaolin KaMin Performance Minerals Albawhite 80 2 4.4 white spar Sachtleben Minerals GmbH & Co. KG SF800 2 2.65 quartz, Quarzwerke GmbH fine powder Albawhite 90 1.2 4.4 white spar Sachtleben Minerals GmbH & Co. KG Apyral ® 60CD 1 2.4 aluminum hydroxide Nabaltec. AG BLANC FIXE ® F 1 4.4 synthetic barium Solvay & CPC GmbH & sulfate Co KG RG4000 0.6 3.9 monomodal alpha Almatis B.V. aluminum oxide SILMIKRON ® 795-10/1 0.5 2.65 quartz, ultra-fine Quarzwerke GmbH powder VP1171-850 0.3 2 fused silica Quarzwerke GmbH SACHTOPERSE ® HU-N 0.04 4.4 synthetic barium Sachtleben Minerals sulfate GmbH & Co. KG .sup.1) DIN EN ISO 787-10

[0235] To demonstrate the influence of the filler mixture according to the invention on the ejection forces of a hardener composition containing said mixture, the hardener compositions described below were prepared and their ejection forces were measured.

[0236] The example formulations using different fillers demonstrate that the effect is dependent on the particle size of the raw materials used.

[0237] It is within the knowledge and ability of a person skilled in the art formulating compositions according to the invention to eliminate chemical interactions between the individual constituents, such as with the use of acid-labile carbonates at pH values below 7.

[0238] Measurement of Ejection Forces

[0239] To determine the ejection forces of the hardener compositions, the compositions were placed, without bubbles, in plastic beakers at a height of 90 mm, the beakers having an inner diameter of 40 mm and a height of 100 mm, and were brought to the measuring temperature of 23° C. overnight.

[0240] Using a universal testing machine from Zwick-Roell (measuring range 5 kN), a perforated disc comprising conical holes (diameter 35 mm; Art. no. 130654) from Anton Paar was pressed 50 mm deep into the compound at a speed of 3 mm/sec, and the force was determined at a measuring depth of 35 mm.

[0241] The ejection forces of the hardener compositions according to the invention and of the comparative hardener compositions were measured at 23° C.

[0242] Determination of Influence of Total Filling Level

[0243] To demonstrate the influence of the total filling level of a hardener composition for resin components based on radically curable compounds on the ejection forces, hardener compositions were prepared in which the total filling level was increased by adding a further filler. The basic filling level, which indicates the content of solid peroxide and other solids before the addition of fillers FS1 and FS2, must also be taken into account when determining this influence.

[0244] For this purpose, a premixture V1 consisting of 48 wt. % of a 40% aqueous dibenzoyl peroxide dispersion (LUPEROX® EZ-FLO; Arkema Inc.), 42.7 wt. % of water, 5.8 wt. % of sodium hydrogen citrate (Na.sub.2H citrate, Sigma Aldrich) and 3.5 wt. % of a rheological additive based on an activated phyllosilicate (OPTIGEL-CK; BYK-Chemie GmbH) was first prepared. To this end, the sodium hydrogen citrate was dissolved in the water and added to the peroxide dispersion. After the phyllosilicate was added, the mixture was stirred briefly by hand using a spatula, and the premixture was sheared in a dissolver (1L, PC Laborsystem; dissolver disc 3.5 cm) for 10 minutes at a speed of 3,500 rpm.

[0245] Premixture V2 was prepared in a similar way, by mixing 87 wt. % of BP 40SAQ with 10.14 wt. % of water, 0.75 wt. % of potassium dihydrogen phosphate, 0.11 wt. % of sodium hydroxide and 2 wt. % of OPTIGEL-CK.

[0246] These premixtures were then each mixed by hand using a wooden spatula in a total amount of approx. 400 g with the fillers and quantity ratios specified in Table 1 and incorporated again in the dissolver as described above.

[0247] The ejection forces of the hardener compositions obtained in each case were measured after heating to 23° C. overnight. The results of the measurements are shown in Table 2.

[0248] Determination of the Limit Filling Level

[0249] To determine the limit filling level, the maximum filling level was first determined by gradually increasing the maximum amount of first filler FS1, starting from a filling level of 52 vol. %, the proportion of first filler FS1 such that the filling level of the hardener composition is increased by 2 vol. % each time. The ejection force was measured after each addition. Filler FS1 was added until the ejection force tripled for the first time. The increase in the ejection force was calculated from the ratio of the ejection force of a mixture having a given vol. % of filler FS 1 (x vol. % FS 1) to the ejection force of the mixture having 2 vol. % less filler FS 1 (x−2 vol. % FS 1). The results are shown in Table 3.

[0250] The comparative hardener compositions were filled with the particular filler FS1 until the maximum filling level was reached and beyond.

[0251] Tables 2 and 3 show that, for example, when Millisil® W12 is added as filler FS1, its maximum filling level is approx. 58 vol. %. By comparison, the maximum filling level for Millisil® W3 as filler FS1 is approx. 64 vol. %.

[0252] As stated above, the limit filling level is approx. 5 vol. % below the determined maximum filling level of FS1 at 58 vol. %-5 vol. %=53 vol. % for Millisil® W12 and at 59 vol. % for Millisil® W3.

[0253] FIG. 1 shows the dependency relationship between the ejection force and the proportion by volume of filler FS1, as can be seen from Table 2. It is clear from the curves that the proportion by volume is dependent on the filler used and must be determined individually for each filler.

[0254] The following list shows the example calculation of the filling level in vol. %.

TABLE-US-00002 Mass Mass Volume = Vol. Solid proportion proportion Density mass/density % (vol. %) Benzoyl peroxide 40% 25 Benzoyl peroxide 10 1.3 7.7 15.1 15.1 Water 5 20 1 20.0 39.1 Filler FS1 50 50 2.65 18.9 36.9 36.9 e.g. quartz Filler FS2 20 20 4.4 4.5 8.9 8.9 e.g. barite 100 100 51.1 100 60.9

[0255] Substances that are liquid and already contained in the peroxide dispersions are included in the aqueous proportion and may not be explicitly listed here or in the following examples. Thickeners and dissolved salts are not taken into account.

TABLE-US-00003 TABLE 1 Weights of filler FS1 in g per 100 g premixture Filling level in vol. %*) 52 54 56 58 60 62 64 66 68 70 FS1 Premixture Weight of filler FS1 [g] Millisil ® W12 V1 83 91.5 101 111 122.5 Millisil ® W6 V1 101 111 122.5 135 149 Apyral 1E V1 82.9 91.5 100.5 110.9 122.3 134.9 Millisil ® W3 V1 101 111 122.5 135 149 Omyacarb ® 130AL V2 98 102.2 106.5 110.5 *)contains solid peroxide and filler FS1

TABLE-US-00004 TABLE 2 Results of the measurement of the ejection forces of the mixtures from Table 1 Filling level in vol. % 52 54 56 58 60 62 64 66 68 70 Premixture Ejection force [N] Millisil ® W12 V1 5.4 10.3 27.3 161.8 1481.2 Millisil ® W6 V1 4.2 8.1 20.8 98.7 458 Apyral 1E V1 1.5 2.2 3.6 6.2 24 120 Millisil ® W3 V1 1.7 4 8.3 14 112.2 Omyacarb 130AL V2 4.2 8.1 20.8 79 *)contains solid peroxide and filler FS1

TABLE-US-00005 TABLE 3 Ratios of the ejection forces from Table 2 Filling level in vol. % Pre- 52 54 56 58 60 62 64 66 68 70 mixture Ejection force ratio (from Table 2) Millisil ® W12 V1 1.9 2.7 5.9 9.2 Millisil ® W6 V1 1.9 2.6 4.8 4.6 Apyral 1E V1 1.4 1.7 1.7 3.9 5.0 Millisil ® W3 V1 2.4 2.1 1.7 8.0 Omyacarb V2 1.9 2.6 3.8 130AL *)contains solid peroxide and filler FS1

[0256] Determination of Influence of Particle Size

[0257] To demonstrate the influence of the particle size of the filler of a hardener composition for resin components based on radically curable compounds on the ejection forces, hardener compositions were prepared from premixture 1, in which filler mixtures consisting of a first filler and a second filler were used, with the particle size of the second filler being varied. Furthermore, the amount of filler was increased by adding other further fillers. The fillers used in each case and the corresponding amounts are specified in Table 4. The ejection forces of the hardener compositions obtained in each case were measured after heating to 23° C. overnight. The results of the measurements are shown in Table 4.

[0258] In place of premixture 1, other hardener compositions comprising the constituents specified in Table 5 were also used in the amounts also specified in Table 5. Here too, the ejection forces of the hardener compositions obtained in each case were measured after heating to 23° C. overnight. The results of the measurements are shown in Table 5. The mixture of the hardener compositions in the examples shown in Table 5 were prepared in a similar way to premixture 1. When using Axilat RH23 as a rheological additive, the premixture was left to stand overnight in the dissolver before the compound was completed in order to swell the thickener.

TABLE-US-00006 TABLE 4 Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions as a function of the filling level and particle size Mass proportions [wt. %] Comparison 1 Comparison 2 Comparison 3 Comparison 4 Example 1 Example 2 Example 3 Premixture 1 50 50 50 50 50 50 50 Benzoyl peroxide 9.6 9.6 9.6 9.6 9.6 9.6 9.6 Water 35.75 35.75 35.75 35.75 35.75 35.75 35.75 Filler FS1 d.sub.50,1 [μm] MILLISIL ® W6 40 110 110 110 110 110 110 110 Filler FS2 d.sub.50,2 [μm] MILLISIL ® W6 40 10 20 30 Blanc Fixe F 1 16.7 33 50 d.sub.50,1:d.sub.50,2 1 1 1 1 40 40 40 Filling level *.sup.) vol. % 57.8 59.6 61.2 62.7 59.6 61.2 62.7 Ejection force [N] 4 8.6 23.1 122 2.35 2 2 *.sup.) sum of fillers FS1 and FS2 as well as the peroxide, if this is a solid. Thickeners and salts are not taken into account. Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions as a function of the filling level and particle size Mass proportions [wt. %] Example 4 Example 5 Example 6 Premixture 1 50 50 50 Benzoyl peroxide 9.6 9.6 9.6 Water 35.75 35.75 35.75 Filler FS1 d.sub.50,1 [μm] MILLISIL ® W6 40 110 110 110 Filler FS2 d.sub.50,2 [μm] Albawhite 80 2 16.7 33 50 d.sub.50,1:d.sub.50,2 20 20 20 Filling level [vol. %]* 59.6 61.2 62.7 Ejection force [N] 3.15 2.75 2.8 *sum of fillers FS1 and FS2 as well as the peroxide, if this is a solid. Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions of the ejection force as a function of the filling level and particle size Mass proportions Comparison 5 Comparison 6 Comparison 7 Comparison 8 Example 7 Example 8 Example 9 Premixture 1 50 50 50 50 50 50 50 Filler FS1 d.sub.50,1 [μm] MILLISIL ® W6 40 140 110 110 110 110 110 110 Filler FS2 d.sub.50,2 [μm] Apyral 1E 50 27.2 MILLISIL ® W12 16 30 Corundum 800 6.5 44.1 Albawhite 40 5 50 SF800 2 30 Albawhite 80 2 50 d.sub.50,1:d.sub.50,2 1 0.8 2.5 6.2 8 20 20 Filling level *.sup.) [vol. %] 62.7 62.8 62.7 62.7 62.8 62.7 62.8 Ejection force [N] 122 43.4 367 35.8 11.2 10.9 2.8 *.sup.) sum of filters FS1 and FS2 as well as the peroxide, if this is a solid. Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions as a function of the filling level and particle size Mass proportions Example 10 Example 11 Example 12 Example 13 Comparison 9 Comparison 10 Premixture 1 50 50 50 50 50 50 Filler FSI d.sub.50,1 [μm] MILLISIL ® W6 40 110 110 110 110 110 110 Filler FS2 d.sub.50,2 [μm] BlancFixe-F 1 50 Apyral 60CD 1 27.2 RG4000 0.6 44.1 795-10-1 0.5 30 VP1171 0.3 22.6 Sacht HU-N 0.04 50 d.sub.50,1:d.sub.50,2 40 40 66.7 80 133.3 1000 Filling level *.sup.) [vol. %] 62.8 62.8 62.7 62.7 62.7 62.8 Ejection force [N] 2 3.4 2.25 9.9 56.2 28.1 *.sup.) sum of fillers FS1 and FS2 as well as the peroxide, if this is a solid.

TABLE-US-00007 TABLE 5 Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions as a function of the filling level and particle size (mass proportions) Mass Comparison Comparison Example Example Comparison Comparison Example Example proportions 11 12 14 15 13 14 16 17 Peroxide .sup.1) 19 19 19 19 18.8 18.8 18.8 18.8 Water 34 34 34 34 33.6 33.6 33.6 33.6 Phosphate 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 NaOH 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Optigel CK 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Filler FS1 d.sub.50,1 [μm] MILLISIL ® 16   65.5 65.5 65.5 65.5 W12 MILLISIL ® 40   67.5 67.5 67.5 67.5 W6 Filler FS2 d.sub.50,2 [μm] RG4000  0.6 39.6 Apyral ® 60CD 1  27.2 24.5 Albawhite ® 90  1.2 49.8 Omyacarb ®  3.2 30 2AL Durcal ® 5 6  27 MILLISIL ® 16   30 27 W12 d.sub.50,1:d.sub.50,2 1 5 16 13.3 6.7 2.5 66.7 40 Filling level *.sup.) 59.8 59.8 59.8 59.8 59.9 59.9 59.9 59.9 [vol. %] Ejection force 1990 1579 26 24.8 1006 855 27.8 14.7 [N] *.sup.) sum of fillers FS1 and FS2 as well as the peroxide, if this is a solid; .sup.1) BP-40-SAQ Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions as a function of the filling level and particle size (mass proportions) Mass Comparison Comparison Comparison Example Example Comparison Comparison Example Example proportions 15 16 17 18 19 18 19 20 21 Peroxide .sup.1) 17.2 17.2 17.2 17.2 17.2 17.4 17.4 17.4 17.4 Water 30.8 30.8 30.8 30.8 30.8 31 2 31.2 31.2 31.2 Sodium 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 dihydrogen phosphate NaOH 0.05 0.05 0.05 0.05 0.05 0.06 0.06 0.06 0.06 Optigel CK 1 1 1 1 1 1 1 1 1 Filler FS1 d.sub.50,1 [μm] MILLISIL ® 90   71.5 71.5 71.5 71.5 71.5 90 90 90 90 W3 Filler FS2 d.sub.50,2 [μm] Sachtoperse  0.04 54.8 HU-N Apyral 60CD 1   30.3 27.7 Omyacarb 2AL 3.2 30 Albawhite 70 3   54.8 MILLISIL ® 16   33 30 W12 Omyacarb 40AL 31   33 Apyral 1E 50   27.7 d.sub.50,1:d.sub.50,2 5.6 2.5 2250 90 30 5.6 1.3 90 28.1 Filling level *.sup.) 63.1 63.2 63.1 63.2 63.1 63.5 63.5 63.5 63.5 [vol. %] Ejection force 118 108 419 14.6 15.3 550 370 13 30 [N] *.sup.) sum of fillers FS1 and FS2 as well as the peroxide, if this is a solid; .sup.1) BP-40-SAQ Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions as a function of the filling level and particle size (mass proportions) Mass Comparison Comparison Example Example Example Example Example Example Example proportions 20 21 22 23 24 25 26 27 28 Peroxide .sup.2) 20.7 20.7 20.7 20.7 20.7 20.7 20.7 20.7 20.7 Water 36.9 36.9 36.9 36.9 36.9 36.9 36.9 36.9 36.9 Disodium 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 hydrogen citrate Optigel CK 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 Filler FS1 d.sub.50,1 [μm] MILLISIL ® 40   75 75 75 75 75 75 75 75 75 W6 Filler FS2 d.sub.50,2 [μm] VP1171-850  0.5 22.6 RG4000  0.6 44 Apyral 60CD 1  27.2 Albawhite 90  1.2 49.8 SF800 2  30 KaMin 80  2.3 30 Albawhite 40 5  49.8 MILLISIL ® 16   30 W12 MILLISIL ® 40   30 W6 d.sub.50,1:d.sub.50,2 2.5 1 80 66.7 40 33.3 20 17.4 8 Filling level 60.1 60.1 60.1 60.1 60.1 60.1 60.1 60.1 60.1 [vol. %] Election force 1092 912 10.9 3.8 4.3 3.2 4.9 2.85 6.7 [N] *.sup.) sum of fillers FS1 and FS2 as well as the peroxide, if this is a solid; .sup.2) Peroxan BP40W Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions as a function of the filling level and particle size (mass proportions) Mass Comparison Comparison Example Example Example Example Example proportions 22 23 29 30 31 32 33 Peroxide .sup.1) 17.6 17.6 17.6 17.6 17.6 17.6 17.6 Water 31.4 31.4 31.4 31.4 31.4 31.4 31.4 Citrate 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Axilat RH23 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Aerosil 200 Filler FS1 d.sub.50,1 [μm] MILLISIL ® 40   70 70 70 70 70 70 70 W6 Filler FS2 d.sub.50,2 [μm] RG4000  0.6 48.4 Apyral 60CD 1  30.3 KaMin 80  2.3 33 Albawhite 70 3  54.8 Albawhite 40 5  54.8 MILLISIL ® 16   33 W12 MILLISIL ® 40   33 W6 d.sub.50,1:d.sub.50,2 2.5 1 66.7 40 17.4 13.3 8 Filling level *.sup.) 62.5 62.5 62.5 62.6 62.5 62.5 62.5 [vol. %] Ejection force 1000 1793 4.9 4.15 25.1 10.2 16.4 [N] *.sup.) sum of fillers FS1 and FS2 as well as the peroxide, if this is a solid; .sup.1) BP-40-SAQ Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions as a function of the filling level and particle size (mass proportions) Mass Comparison Comparison Example Example Example Example Example proportions 24 25 34 35 36 37 38 Peroxide .sup.3) 18 18 18 18 18 18 18 Water 31.1 31.1 31.1 31.1 31.1 31.1 31.1 Citrate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Aerosil 200 2 2 2 2 2 2 2 Filler FS1 d.sub.50,1 [μm] MILLISIL ® 40   69.9 69.9 69.9 69.9 69.9 69.9 69.9 W6 Filler FS2 d.sub.50,2 [μm] RG4000  0.6 44 Apyral 60CD 1  27.2 SF800 2  30 Albawhite 70 3  49.8 BlancFixe N 3  49.8 MILLISIL ® 16   30 W12 MILLISIL ® 40   30 W6 d.sub.50,1:d.sub.50,2 2.5 1 66.7 40 20 13.3 13.3 Filling level *.sup.) 62.4 62.4 62.4 62.4 62.4 62.4 62.4 [vol. %] Ejection force 1988 134 6.5 7.1 48.4 14.4 23.6 [N] *.sup.) sum of fillers FS1 and FS2 as well as the peroxide, if this is a solid; .sup.3) Perkadox L-W-40 Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions as a function of the filling level and particle size Mass Comparison Comparison Example Example Comparison Example Example Example proportions 26 27 39 40 28 41 42 43 Peroxide .sup.1) 2.4 2.4 2.4 2.4 2.9 2.9 2.9 2.9 Water 33.7 33.7 33.7 33.7 35.9 35.9 35.9 35.9 Sodium 2.2 2.2 2.2 2.2 2.4 2.4 2.4 2.4 dihydrogen phosphate Optigel CK 1.5 1.5 1.5 1.5 1.4 1.4 1.4 1.4 Glycerol 2 2 2 2 Sodium 0.05 0.05 0.05 0.05 benzene- sulfonate Filler FS1 d.sub.50,1 [μm] MILLISIL ® 40   80.2 80.2 80.2 80.2 85 85 85 85 W6 Filler FS2 d.sub.50,2 [μm] RG4000  0.6 73.6 58.9 Apyral 60CD 1  36.2 SF800 2  50 Albawhite 70 3  66.4 MILLISIL ® 16   50 W12 MILLISIL ® 40   50 40 W6 d.sub.50,1:d.sub.50,2 2.5 1 66.7 20 1 68.7 40 13.3 Filling level *.sup.) 60.2 60.2 60.2 60.2 56.6 56.6 56.6 56.6 [vol. %] Ejection force 980 1603 68.5 13.7 1170 31 8.6 19.4 [N] *.sup.) sum of fillers FS1 and FS2 as well as the peroxide, if this is a solid; .sup.1) BP-40-SAQ Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions as a function of the filling level and particle size Mass Comparison Comparison Example Example Example Example Comparison Example Example proportions 29 30 44 45 46 47 31 48 49 Peroxide .sup.1) 6.8 6.8 6.8 6.8 6.8 6.8 7.2 7.2 7.2 Water 32.9 32.9 32.9 32.9 32.9 32.9 34.6 34.6 34.6 Phosphate 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 Optigei CK 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 Filler FS1 d.sub.50,1 [μm] MILLISIL ® 40   77.2 77.2 77.2 77.2 77.2 77.2 85 85 85 W6 Filler FS2 d.sub.50,2 [μm] RG4000  0.6 59.4 Apyral 60CD 1  36.7 36.2 Albawhite 90  1.2 67.2 SF800 2  40.5 40 MILLISIL ® 16   40.5 W12 MILLISIL ® 40   40.5 40 W6 d.sub.50,1:d.sub.50,2 2.5 1 66.7 40 33.3 20 1 40 20 Filling level *.sup.) 60.1 60.1 60.1 60.1 60.1 60.1 60.4 60.4 60.4 [vol. %] Ejection force 1270 1542 49 62.6 42.4 3.8 1030 9.4 5.4 [N] *.sup.) sum of fillers FS1 and FS2 as well as the peroxide, if this is a solid; .sup.1) BP-40-SAQ Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions as a function of the filling level and particle size Comparison Comparison Example Comparison Example 32 33 50 34 51 Peroxide .sup.  17.4 .sup.1) .sup.  19.4 .sup.4) .sup.  19.4 .sup.4) .sup.  25 .sup.5) .sup.  25 .sup.5) Water 36.2 29.1 29.1 Benzoate 25 25 plasticizers Potassium  0.77 dihydrogen phosphate Sodium  0.1 hydroxide Optigel CK 1  Aerosil ® 200  1.5  1.5 Filler FS1 d.sub.50,1 [μm] Millisil® WB 40   30 30 Omyacarb 16   90   130AL Apyral 1E 50   85  85  Filler FS2 d.sub.50,2 [μm] Apyral 60CD  0.6 25  Blanc Fixe F  1.2   16.6 Millisil ® W6 40   10 Omyacarb 16   30   130AL Apyral IE 40   25  d.sub.50,1:d.sub.50,2 1  1  50   1 40 Filling level *.sup.) 62.2 67.6 67.6   57.9   57.9 [vol. %] Ejection force 1570.8   30.4 18.2   54.5   28.5 [N] *) sum of fillers FS1 and FS2 as well as the peroxide, if this is a solid; .sup.1) BP-40-SAQ; .sup.4) Luperox ® EZ-FLO; .sup.5) Benox ® B-50 Results of the measurements of the ejection force of the hardener composition according to the invention and of the comparative hardener compositions as a function of the filling level and particle size Comparison Example Comparison Example 35 52 36 53 Peroxide .sup.  4 .sup.6) .sup.  4 .sup.6) .sup.  20 .sup.7) .sup.  20 .sup.7) Water 30 30 Diethyl adipate 46  46  CAB-O-SIL ® 3 3 TS720 Filler FS1 d.sub.50,1 [μm] Millisil ® W6 40   135  135  Omyacarb 16   50 50 130AL Filler FS2 d.sub.50,2 [μm] Albawhite 80 2  795-10-1  0.5 40   33.2 Millisil ® W6 40   40  20 d.sub.50,1:d.sub.50,2 1 80   1 93 Filling level *.sup.)  56.9  56.9   56.4   56.4 [vol. %] Ejection force 1812.8   48.4  157.4   10.4 [N] *.sup.) sum of fillers FS1 and FS2 as well as the peroxide, if this is a solid (total filling level); .sup.6) Trigonox ® C; .sup.7) LP-40-SAQ

[0259] It is clear from the results of the measurement of the ejection forces shown in Tables 4 and 5 that by increasing the total filling level from 47.3% (vol/vol) to 53.4% (vol/vol), by adding a second filler selected such that the ratio d.sub.50,1:d.sub.50,2 was 40 or 20, the ejection force was not increased. If the same filling level was set by further addition of the first filler such that the ratio d.sub.50,1:d.sub.50,2 was 1, an increase in the ejection force from 4 N to 122 N was observed.

[0260] Furthermore, the results of the measurement of the ejection forces shown in Tables 4 and 5 clearly show that, when using a filler mixture consisting of a first and a second filler, the particle size of the second filler has a significant influence on the ejection forces. If the second filler is selected such that the ratio d.sub.50,1:d.sub.50,2 is between 8 and 100, the ejection forces the measured values barely increase and are approximately 100 N or less. If the second filler is selected such that the ratio d.sub.50,1:d.sub.50,2 is outside the range of 8 to 100, the ejection forces increase significantly and, in some cases, increase tenfold.