TWI575005B - Iron-based accelerator for curing resins - Google Patents

Description

Iron-based accelerator for curing resins

The present invention relates to an accelerator solution suitable for forming a redox system with a peroxide, a pre-accelerated resin composition comprising an unsaturated polyester resin or a vinyl ester resin, and a resin composition comprising the pre-acceleration A two-component composition of matter.

The redox system can be applied to resin curing. Conventional redox systems contain an oxidizing agent (such as a peroxide) and a soluble transition metal ion as an accelerator. Accelerators are used to increase the activity of the oxidant at low temperatures and thereby accelerate curing.

The accelerator system can be added to the resin to be cured in different ways. One method involves adding individual accelerator components to the resin prior to the addition of the peroxide. This can be done just before the addition of the peroxide or a few days or weeks before the peroxide is added. In the latter case, we refer to a pre-accelerated resin composition comprising a resin and an accelerator component and which can be stored until further use and curing with a peroxide. Another method involves pre-preparing an accelerator solution containing an accelerator component which can be stored until further use and added to the resin. The pre-accelerated resin can be prepared by adding individual components of the accelerator system to the resin or by adding such a mixture in the form of an accelerator solution.

A typical accelerator system comprises a transition metal salt or a complex. The most common transition metal used for this purpose is cobalt. However, in view of the toxicity of cobalt, regulations require a reduction in the amount of cobalt.

Therefore, it is necessary to provide a Co-free accelerator. However, the Co-free accelerator system that has been developed to date does not have the good performance of a conventional Co-containing accelerator system.

Examples of documents which disclose such Co-free accelerator systems are WO 2008/003492, WO 2008/003497 and WO 2008/003500. The metals used in place of Co in the accelerator system according to these documents are Mn, Cu, Fe, and Ti. The disclosed accelerator system is present in the unsaturated polyester or vinyl ester resin in the form of a pre-accelerated resin. The pre-accelerated resin is said to contain less than 0.01 mmol Co per kg of resin.

It has now been found that the reactivity of iron-based accelerator systems can be enhanced by the addition of reactive promoters. This reactive promoter is a transition metal salt or a complex which is present in the accelerator system in a relatively small amount compared to the iron compound.

Accordingly, the present invention relates to an accelerator solution suitable for forming a redox system with a peroxide comprising (i) selected from the group consisting of iron carboxylate, 1,3-dioxa iron complex and dicyclopentadienyl The iron compound of the iron complex, and (ii) the compound of the second transition metal; the weight ratio of the first transition metal: the second transition metal is in the range of 3:1 to 200:1, and the restriction condition is that the accelerator solution is basically Contains no ascorbic acid.

The invention also relates to a pre-accelerated resin composition comprising (i) a curable resin, (ii) selected from the group consisting of iron carboxylate, 1,3-dioxa iron complex and dicyclopentadienyl The iron compound of the iron complex, and (iii) the compound of the second transition metal; the weight ratio of the first transition metal: the second transition metal is in the range of 3:1 to 200:1, and the restriction condition is pre-acceleration The resin is substantially free of ascorbic acid.

The invention further relates to a two-component composition comprising a first component and a second component, the first component comprising a pre-accelerated resin composition as defined above, the second component comprising a peroxide .

The iron compound is preferably present in the accelerator solution in an amount of at least 50 mmol/l, more preferably at least 100 mmol/l, as determined by metal. It is preferably present in the accelerator solution in an amount of less than 5000 mmol/l, more preferably less than 2500 mmol/l, and most preferably less than 1000 mmol/l.

The iron compound is preferably present in the pre-accelerated resin in an amount of at least 1 mmol/kg resin, more preferably at least 2 mmol/kg resin, as determined by metal. It is preferably present in an amount of no more than 75 mmol/kg resin, more preferably no more than 50 mmol/kg resin, even more preferably no more than 25 mmol/kg resin, and most preferably no more than 10 mmol/kg resin.

The iron compound is selected from the group consisting of iron carboxylate, 1,3-dioxa iron complex, and dicyclopentadienyl iron complex.

Examples of suitable iron carboxylates are iron lactate, iron naphthenate, iron 2-ethylhexanoate (i.e., iron octoate), iron formate, iron acetate, iron propionate, iron butyrate, iron valerate, caproic acid. Iron, iron heptanoate, iron octoate, iron citrate, iron citrate, iron neodecanoate and iron dodecanoate.

Examples of 1,3-dioxa iron complexes are iron acetylacetonate, and acetamidine, benzamidine, benzotrimethane and acetamidine acetate (such as diethyl Ethylacetamide, dimethylacetamidine, dipropylacetamidine, dibutylacetamidine, ethyl acetate, ethyl acetate, ethyl acetate Iron complex of ester and butyl acetate.

An example of a dicyclopentadienyl iron complex is a complex comprising iron and two substituted or unsubstituted cyclopentadienyl ligands, wherein the cyclopentadienyl ring is optionally present The substituent is selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an aryl group and an aralkyl group, which may optionally be substituted with a hetero atom selected from the group consisting of O, N, S, Si and P. An example of a dicyclopentadienyl iron complex is ferrocene.

Both Fe(II) and Fe(III) complexes can be used.

Examples of the second transition metal (ie, a reactive promoter) are transition metals which may exist in two oxidation states, such as cobalt, titanium, vanadium, manganese, copper, tin, chromium, nickel, molybdenum, niobium, tantalum, palladium, Platinum, rhodium, ruthenium, osmium, iridium, osmium, platinum, gold, mercury, ruthenium, osmium and iridium.

Preferred second transition metals for use as reactive promoters in accordance with the present invention are copper, cobalt and manganese. Since it can be used in a small amount, the cobalt compound can be used as the second transition metal (reactivity promoter) without causing regulatory and toxicity problems.

Suitable compounds of the second transition metal are salts and complex compounds thereof such as halides, nitrates, sulfates, sulfonates, phosphates, phosphonates, oxides or carboxylates. Examples of suitable carboxylates are lactate, 2-ethylhexanoate, acetate, propionate, butyrate, oxalate, laurate, oleate, linoleate, palmitate , stearate, acetoacetate, octoate, decanoate, heptanoate, neodecanoate or naphthenate.

Preferably, the second transition metal is at least 10 mmol/l as measured by metal, more preferably An amount of at least 25 mmol/l is present in the accelerator solution. It is preferably present in the accelerator solution in an amount of less than 1000 mmol/l, more preferably less than 500 mmol/l, and most preferably less than 250 mmol/l.

The second transition metal is preferably present in the pre-accelerated resin in an amount of at least 0.005 mmol/kg resin, more preferably at least 0.02 mmol/kg resin, as determined by metal. It is preferably present in an amount of no more than 0.5 mmol/kg resin, more preferably no more than 0.25 mmol/kg resin.

The accelerator solution according to the present invention contains a solvent in addition to the metal compound. Examples of suitable solvents are phosphorus compounds and hydroxyl functional solvents.

Examples of suitable phosphorus compounds are those having the formula P(R) ₃ and P(R) ₃ =O wherein each R is independently selected from hydrogen, an alkyl group having from 1 to 10 carbon atoms and having from 1 to 10 Alkoxy group of a carbon atom. Preferably, at least two R groups are selected from alkyl or alkoxy groups. Specific examples of suitable phosphorus-containing compounds are diethyl phosphate, dibutyl phosphate, tributyl phosphate, triethyl phosphate (TEP), dibutyl phosphite, and triethyl phosphate.

The term "hydroxy-functional solvent" includes compounds of the formula HO-(-CH ₂ -C(R ¹ ) ₂ -(CH ₂ ) _m -O-) _n -R ² wherein each R ^{1 is} independently selected from hydrogen, having a group consisting of an alkyl group of 1 to 10 carbon atoms and a hydroxyalkyl group having 1 to 10 carbon atoms, n = 1 to 10, m = 0 or 1, and R ² is hydrogen or has 1 to 10 carbon atoms Alkyl group. Most preferably, each R ^{1 is} independently selected from the group consisting of H, CH ₃ and CH ₂ OH. Examples of suitable hydroxy-functional solvents are diols such as diethylene glycol monobutyl ether, ethylene glycol, diethylene glycol, dipropylene glycol and polyethylene glycol, glycerol and pentaerythritol.

In addition, the accelerator solution according to the present invention may further comprise other organic Compounds such as aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and solvents which carry aldehydes, ketones, ethers, esters, alcohols, phosphates or carboxylic acid groups. Examples of suitable solvents are aliphatic hydrocarbon solvents such as petroleum solvents and odorless mineral spirits (OMS); aromatic hydrocarbon solvents such as naphthenes and mixtures of naphthenes and paraffins; isobutanol; pentanol; 1,2- Diterpene; N-methylpyrrolidone; N-ethylpyrrolidone; dimethylformamide (DMF); dimethyl hydrazine (DMSO); 2,2,4-trimethylpentanediol Isobutyrate (TxIB); esters, such as dibutyl maleate, dibutyl succinate, ethyl acetate, butyl acetate, monoesters and diesters of ketoglutaric acid, pyruvate and Ascorbate (such as ascorbyl palmitate); aldehyde; monoester and diester, more specifically diethyl malonate and diethyl succinate; 1,2-dione, specifically diacetyl and Glyoxal; benzyl alcohol and fatty alcohol.

The total amount of the solvent preferably present in the accelerator solution is from 1 wt% to 50 wt%, preferably from 5 wt% to 30 wt%. In the pre-accelerator resin, it is preferably from 0.1 to 100 g/kg of the resin, preferably from 0.5 to 60 g/kg of the resin.

Since ascorbic acid tends to counteract the action of the reactive promoter, the accelerator solution and the pre-accelerated resin according to the present invention are substantially free of ascorbic acid, meaning that the solution contains less than 1 wt% of ascorbic acid and pre-accelerated resin. Contains less than 0.01 wt% of ascorbic acid. The second metal acts as an inhibitor rather than a reactive promoter in the presence of ascorbic acid.

In the present specification, the term ascorbic acid includes L-ascorbic acid and D-isoascorbic acid. Most preferably, both the accelerator solution and the pre-accelerated resin according to the present invention do not contain ascorbic acid.

The accelerator solution and the pre-accelerated resin according to the present invention may optionally contain one or more promoters, bases, water, inhibitors, additives and/or fillers. Agent.

There are two important classes of promoters: ammonium, alkali metal or alkaline earth metal carboxylates, and 1,3-diketones.

Examples of the 1,3-diketone are acetamidineacetone, benzamidineacetone, and benzamidine methane, and acetamidine acetate such as diethyl acetamidine, dimethylacetamidine, Dipropyl acetamidine, dibutyl acetamidine, methyl acetate, ethyl acetate, acetonitrile propyl acetate and butyl acetate.

Examples of suitable metal carboxylates of ammonium, alkali metal and alkaline earth metals are 2-ethylhexanoate (i.e., octoate), decanoate, heptanoate, neoheptanoate and naphthenate. A preferred alkali metal is potassium. The salt may be added to the accelerator solution or resin itself, or it may be formed on the spot. For example, an alkali metal 2-ethylhexanoate can be prepared in situ in the solution after the addition of the alkali metal hydroxide and 2-ethylhexanoic acid to the accelerator solution.

Acetyl acetate is a particularly preferred accelerator. Especially preferred is diethyl acetamidine. Even more preferably, it is a combination of diethyl acetamidine and potassium 2-ethylhexanoate.

If one or more promoters are present in the accelerator solution, the amount is preferably at least 0.01 wt%, more preferably at least 0.1 wt%, even more preferably at least 1 wt%, more preferably at least the total weight of the accelerator solution. 10 wt%, and most preferably at least 20 wt%; preferably not more than 90 wt%, more preferably not more than 80 wt%, and most preferably not more than 70 wt%.

Suitable nitrogenous bases to be present in the accelerator solution and the pre-accelerated resin are primary, secondary and tertiary amines such as triethylamine, dimethylaniline, diethylaniline or N,N-dimethyl Base-p-toluidine (DMPT); polyamines, such as 1,2-(dimethylamine)ethane; a secondary amine such as diethylamine; an ethoxylated amine such as triethanolamine, dimethylaminoethanol, diethanolamine or monoethanolamine; and an aromatic amine such as Pyridine or bipyridine. The nitrogen-containing base is preferably present in the accelerator solution in an amount of from 5 wt% to 50 wt%. In the pre-accelerator resin, it is preferably present in an amount of from 0.5 to 10 g/kg of the resin.

The accelerator solution may optionally contain water. If present, the water content of the solution is preferably at least 0.01 wt%, and more preferably at least 0.1 wt%. The water content is preferably not more than 50% by weight, more preferably not more than 40% by weight, more preferably not more than 20% by weight, even more preferably not more than 10% by weight, and most preferably not more than 5, based on the total weight of the accelerator solution. Wt%.

The accelerator solution can be prepared by simply mixing the ingredients, optionally with an intermediate heating and/or mixing step. The iron complex can be added to the solution in the form of a complex or can be formed in situ by adding a ligand and another iron salt to the solution. The pre-accelerated resin can be prepared in a different manner by mixing the individual ingredients with the resin or by mixing the resin, including optionally monomers, with the accelerator solution according to the invention. The latter method is preferred.

Suitable resins to be cured using the accelerator solution according to the present invention and intended to be present in the pre-accelerated resin composition include alkyd resins, unsaturated polyester (UP) resins, vinyl ester resins, (meth) acrylate resins , polyurethanes, epoxies and mixtures thereof. Preferred resins are (meth) acrylate resins, UP resins, and vinyl ester resins. In the context of this application, the terms "unsaturated polyester resin" and "UP resin" refer to a combination of an unsaturated polyester resin and an ethylenically unsaturated monomer compound. The term "(meth)acrylate resin" means an acrylate or methacrylate resin and an ethylenically unsaturated single. a combination of body compounds. UP resins and acrylate resins as defined above are customary and commercially available. Curing is usually initiated by adding an accelerator solution and an initiator (peroxide) according to the invention to the resin, or by adding a peroxide to the pre-accelerated resin.

Suitable UP resins to be cured by the method of the present invention are so-called ortho-resin, iso-resin, isophthalic acid-neopentyl glycol type resins ( Iso-npg resin) and dicyclopentadiene (DCPD) resin. Examples of such resins are maleic acid type, fumaric acid type, allyl type, vinyl type and epoxy type resin, bisphenol A resin, terephthalic acid resin and composite resin.

The vinyl ester resin includes an acrylate resin based on, for example, methacrylate, diacrylate, dimethacrylate, and oligomers thereof.

Acrylate resins include acrylates, methacrylates, diacrylates, and dimethacrylates and oligomers thereof.

Examples of the ethylenically unsaturated monomer compound include styrene and a styrene derivative such as α-methylstyrene, vinyltoluene, anthracene, divinylbenzene, vinylpyrrolidone, vinyl azide, ethylene. Benzoamine, hydrazine and diallyl phthalate, dibenzylideneacetone, allylbenzene, methyl methacrylate, methyl acrylate, (meth)acrylic acid, diacrylate, dimethyl Acrylate, acrylamide; vinyl acetate, triallyl cyanurate, triallyl isocyanurate, allyl compound for optical applications (such as (di) ethylene glycol diallyl Carbonate), chlorostyrene, t-butyl styrene, tert-butyl acrylate, butanediol dimethacrylate, and mixtures thereof. A suitable example of a (meth) acrylate reactive diluent is PEG 200 Di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 2,3-butanediol di(methyl) Acrylate, 1,6-hexanediol di(meth)acrylate and isomers thereof, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, glycerin II Methyl) acrylate, trimethylolpropane di(meth) acrylate, neopentyl glycol di(meth) acrylate, dipropylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate , PPG250 di(meth) acrylate, tricyclodecane dimethylol di(meth) acrylate, 1,10-nonanediol di(meth) acrylate, tetraethylene glycol di(methyl) Acrylate, trimethylolpropane tri(meth)acrylate, glycidyl (meth)acrylate, (bis) maleimide, (bis)methylsuccinimide, (double ) ketimine and mixtures thereof.

The amount of the ethylenically unsaturated monomer in the preaccelerated resin is preferably at least 0.1 wt%, more preferably at least 1 wt%, and most preferably at least 5 wt%, based on the weight of the resin. The amount of the ethylenically unsaturated monomer is preferably not more than 50% by weight, more preferably not more than 40% by weight, and most preferably not more than 35% by weight.

If the accelerator solution is used to cure the resin or to prepare a pre-accelerated resin, the accelerator solution is usually at least 0.01 wt%, preferably at least 0.1 wt%, and preferably not more than 5 wt%, more preferably by weight of the resin. No more than 3 wt% of accelerator solution is used.

Peroxides suitable for curing the resin and suitable for being present in the second component of the two-component composition include inorganic peroxides and organic peroxides, such as conventionally used ketone peroxides, peroxyesters, diaryls Base peroxides, dialkyl peroxides and peroxydicarbonates, as well as peroxycarbonates Oxidized ketals, hydroperoxides, dinonyl peroxides, and hydrogen peroxide. Preferred peroxides are organic hydroperoxides, ketone peroxides, peroxyesters and peroxycarbonates. Even more preferred are hydroperoxides and ketone peroxides. Preferred hydroperoxides include cumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butyl hydroperoxide, isopropyl cumene. Hydroperoxide, third amyl hydroperoxide, 2,5-dimethylhexyl-2,5-dihydroperoxide, decane hydroperoxide, p-menthane hydroperoxide, hydrazine Hydroperoxide and terpene hydroperoxide. Preferred ketone peroxides include methyl ethyl ketone peroxide, methyl isopropyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, and acetamidine peroxide.

It is of course also possible to use mixtures of two or more peroxides; for example hydroperoxides or combinations of ketone peroxides and peroxyesters.

A particularly preferred peroxide is methyl ethyl ketone peroxide. Those skilled in the art will appreciate that such peroxides can be combined with conventional additives such as fillers, pigments, and phlegmatizers. Examples of the desensitizing agent are hydrophilic esters and hydrocarbon solvents. The amount of peroxide to be used for curing the resin is preferably at least 0.1 (phr), more preferably at least 0.5 phr, and most preferably at least 1 phr per 100 parts of resin. The amount of peroxide is preferably not more than 8 phr, more preferably not more than 5 phr, and most preferably not more than 2 phr.

When the peroxide is mixed with the pre-accelerated resin, the peroxide is added to the premix of the resin and accelerator solution, or the peroxide is premixed with the resin before the accelerator solution is added. The resulting mixture was mixed and dispersed. Depending on the initiator system, the accelerator system, the compound that adjusts the cure rate, and the resin composition to be cured, the curing process can be any temperature between -15 ° C and 250 ° C. Under the degree. Preferably, it is in, for example, hand coating, spray coating, filament winding, resin transfer molding, coating (such as gel coating and standard coating), button manufacturing, centrifugal casting, corrugated sheet or flat panel, relining It is carried out at ambient temperatures commonly used in applications such as systems, kitchen sinks for pouring compounds. However, it can also be used in SMC, BMC, pultrusion techniques and the like, using temperatures up to 180 ° C, more preferably up to 150 ° C, optimally up to 100 ° C for the above techniques.

Other additives such as fillers, fibers, pigments, inhibitors, auxiliaries, and accelerators may be employed as appropriate in the curing process.

Examples of fibers are glass fibers, carbon fibers, aromatic polyamide fibers (e.g., Twaron®), natural fibers (e.g., jute, kenaf, industrial hemp, linen (linen), ramie, etc.).

Examples of fillers are quartz, sand, aluminum hydroxide, magnesium hydroxide, chalk, calcium hydroxide, clay and lime.

The cured resin may be subjected to post-cure treatment to further optimize the hardness. The post-curing treatment is usually carried out at a temperature ranging from 40 ° C to 180 ° C for 30 minutes to 15 hours.

Cured resins can be used in a variety of applications, including marine applications, chemical anchoring, roofing, construction, relining, piping and sump, flooring, windmill blades, laminates, and the like.

Instance Reference example

Prepared by dissolving 1 wt% of iron compound in triethyl phosphate (TEP) Four Fe-containing accelerator solutions; the iron compounds used are listed in Table 1. For further reference, a commercially available accelerator NL-53 (available from AkzoNobel) containing cobalt (II) 2-ethylhexanoate in an amount of 10 wt% Co (as metal) was used.

These accelerator solutions (2 phr (per 100 parts resin)) were used together with 1.5 phr of methyl ethyl ketone peroxide (Butanox® M50, available from AkzoNobel) for curing at 20 ° C based on phthalic acid Unsaturated polyester resin (Palatal® P6, available from DSM resin). Curing performance was analyzed by the method of the Society of Plastic Institute (SPI Method F/77.1; available from Akzo Nobel Polymer Chemicals). This method involves measuring the peak exotherm, the time to peak, and the gel time. According to this method, 25 g of a mixture comprising 100 parts of resin, 1.5 parts of peroxide and 2 parts of accelerator solution was poured into a test tube and a thermocouple was placed through the outer casing at the center of the tube. The glass tube was then placed in a climate controlled room maintained at 20 °C and the time-temperature curve was measured. The following parameters are calculated from this curve: Gel time (Gt) = time elapsed between the start of the experiment and the bath temperature above 5.6 ° C (minutes).

The results are shown in Table 1, which shows that these iron solutions do not accelerate curing in this system.

Example 1

The above reference examples were repeated with 1 wt% iron octoate/TEP except that a small amount of the second metal compound was added to the resin. Table 2 presents the results and shows that small amounts of other metal compounds result in a significant increase in curing activity. The facts below confirm that this increase is not simply due to the other metal: in the absence of iron octoate, the curing takes 18 minutes when the experiment is repeated with the same amount of accelerator NL-53. In other words: this good result is provided by the synergistic effect of the iron compound and a small amount of the second metal.

Example 2

Example 1 was repeated with different iron compounds (all 1 wt% iron compound / TEP).

Table 3 presents the results and demonstrates that the results obtained in Example 1 also apply to other iron compounds.

Claims (13)

An accelerator solution suitable for forming a redox system with a peroxide comprising (i) selected from the group consisting of iron carboxylate, 1,3-dioxa iron complex and dicyclopentadienyl iron complex Iron compound, (ii) compound of second transition metal; weight ratio of iron: second transition metal in the range of 3:1 to 200:1, (iii) solvent selected from phosphorus compound and hydroxyl functional solvent, limitation The condition is that the accelerator solution contains less than 1% by weight of ascorbic acid. The accelerator solution of claim 1, wherein the second transition metal is selected from the group consisting of Co, Ti, Mn, Cu, Sn, Cr, Ni, Mo, Ge, Sr, Pd, Pt, Nb, Sb , Re, Os, Ir, Pt, Au, Hg, Te, Rb and Bi. The accelerator solution of claim 2, wherein the second transition metal is selected from the group consisting of Co, Mn, and Cu. The accelerator solution according to any one of claims 1 to 3, wherein the iron compound is present in the solution in an amount of 50 to 5000 mmol/l (measured as a metal). The accelerator solution according to any one of claims 1 to 3, wherein the second transition metal is present in the solution in an amount of 10 to 1000 mmol/l. The accelerator solution according to any one of claims 1 to 3, which further comprises an alkali metal or alkaline earth metal compound, a phosphorus-containing compound, and/or a 1,3-diketone. A two-component composition comprising a first component and a second component, the first One component comprises a pre-accelerated resin composition comprising (i) a curable resin, (ii) selected from the group consisting of iron carboxylate, 1,3-dioxa iron complex and bicyclic ring. An iron compound of a pentadienyl iron complex, (iii) a compound of a second transition metal; a weight ratio of iron: a second transition metal in the range of 3:1 to 200:1, subject to the pre-acceleration The resin contains less than 1% by weight of ascorbic acid, and the second component comprises a peroxide selected from the group consisting of organic hydroperoxides, ketone peroxides, peroxycarbonates, and peroxyesters. The two-component composition of claim 7, wherein the second transition metal is selected from the group consisting of Co, V, Ti, Mn, Cu, Sn, Cr, Ni, Mo, Ge, Sr, Pd, Pt , Nb, Sb, Re, Os, Ir, Pt, Au, Hg, Te, Rb and Bi. The two-component composition of claim 8, wherein the second transition metal is selected from the group consisting of Co, V, Mn, and Cu. The two-component composition according to any one of claims 7 to 9, wherein the iron compound is present in the pre-accelerated resin in an amount of from 1 to 75 mmol/kg of the resin (as determined by metal). The two-component composition of any one of claims 7 to 9, wherein the second transition metal is present in the pre-accelerated resin in an amount of 0.005 to 0.5 mmol/kg of resin (measured as metal). The two-component composition of any one of claims 7 to 9, wherein the pre-addition The instant resin further comprises an alkali metal or alkaline earth metal compound, a phosphorus-containing compound, and/or a 1,3-diketone. The two-component composition according to any one of claims 7 to 9, wherein the curable resin is an unsaturated polyester resin, a vinyl ester resin or a (meth) acrylate resin.