KR20220021109A - (Meth)acrylic reactive resin that cures with little or no odor - Google Patents

Abstract

The present invention relates to a novel (meth)acrylic reactive resin cured with little or no bad odor. Particularly, the present invention relates to a reactive resin including a reactive (meth)acrylic monomer selected from the group of polar cyclic substituted esters of (meth)acrylic acid monomer boiling at high temperature, and more particularly, glycerin acetal-, ketal- or carbonate-methacrylates. The novel ingredient is used as a substitute for MMA forming a main part of bad odor in the existing reactive resin systems according to the related art. The novel ingredient allows preparation of a resin formulation having a glass transition temperature similar to the glass transition temperature of MMA-based resins and properties comparable to the properties of MMA-based resins. The novel reactive resin according to the present invention can have a shorter curing time as compared to the MMA-based systems according to the related art. According to the present invention, the term 'reactive resin' means a reactive monomer mixture or mixture of a monomer with a polymer that can be cured with ease when being used as a 2K system.

Description

(Meth)acrylic reactive resin that cures with little or no odor

The present invention relates to an innovative (meth)acrylic reactive resin that cures with little or no odor. More particularly, the present invention relates to a reactive resin comprising a polar cyclic substituted ester of (meth)acrylic acid, more particularly a high boiling point reactive (meth)acrylic monomer selected from the group consisting of glycerol acetal, ketal or carbonate methacrylate. will be. This novel component is used as a replacement component for MMA, which represents a major part of odor hazardous substances in the reactive resin system of the prior art. Using this novel component, it is possible to obtain a resin formulation having a glass transition temperature similar to that of an MMA-based resin and properties comparable thereto. The innovative reactive resins of the present invention may also exhibit faster cure than prior art MMA-based systems. The reactive resins of the present invention are readily curable reactive monomer mixtures or mixtures of monomers and polymers when used as a two-component system.

Reducing the volatile components of reactive resins of the type used as coating materials, casting resins, road markings or floor coatings, and therefore the odor hazards caused by the application of these materials, has been a development goal for a relatively long time. . In present use, systems based on reactive monomer mixtures or mixtures of polymers and monomers, generally (meth)acrylate-based, are used as reactive resins. The monomers here generally comprise a mixture of a difunctional or trifunctional crosslinking agent with a standard component such as MMA. (Meth)acrylates, more particularly acrylates or methacrylates with small alkyl radicals, are monomers with high vapor pressure, and therefore their odor is easily recognized. When working with acrylates, you need to match the corresponding MAC level. Reactive resins of this type are disclosed, for example, in EP 0 973 835. DE 1 769 792 contains a reactive resin having an MMA fraction of 30% to 70% by weight. DE 19 826 412 discloses low-temperature-curing reactive (meth)acrylate resins having a reduced odor by means of a relatively high fraction of vinylaromatics or vinyl esters. However, even this type of reactive resin still emits an unpleasant odor, and the long-term adhesion is low compared to conventional systems. EP 2 054 453 discloses reactive resins containing from 30% to 50% by weight of MMA as well as up to 15% by weight of urethane (meth)acrylates. Systems of this type of course have associated residual odors during application. One alternative to pure (meth)acrylate systems is reactive resins comprising unsaturated polyesters, as for example disclosed in EP 0 871 678. EP 0 871 676 discloses the transfer of the same unsaturated bicyclic groups having protons that are readily removable from the polyester to other polymers such as polyolefins or other polymethacrylates. It goes without saying, however, that this system also contains predominantly a very volatile monomer component. WO98/40424 discloses two- and three-component formulations based on unsaturated polyesters in unsaturated ethylenic compounds or on methacrylic polymers in methacrylic monomers. Such a system, of course, also has disadvantageous properties in terms of odor emission.

The problem to be solved by the present invention is to provide a reactive resin in which the generation of odor is significantly reduced when applied compared to the prior art. A specific problem to be solved by the present invention is to provide a reactive resin system which also exhibits an improvement over the prior art in terms of toxicity and environment. Another challenge is to provide a two-component system based on the reactive resins of the present invention, which can be used, for example, as road markings or floor coatings, can be widely used, can be formulated flexibly and has a relatively long shelf life. One specific task is to achieve a road marking, or excellent surface properties, cohesion and adhesion to a substrate, which has at least a lifetime comparable to that of the prior art and has good retroreflectivity, good day and night visibility, high and stable whiteness and good gripping properties even when the road is wet. To provide a reactive resin that enables a long-life floor coating with It will be possible to clearly grasp other problems not specified through the overall specification, claims, and examples described below.

The above-mentioned problems are solved by providing an innovative reactive resin, and more particularly by providing a (meth)acrylate-based reactive resin comprising a monomer having a cyclic radical containing two or more oxygen atoms. The reactive resin of the present invention comprises the following components: a) a crosslinking agent(s), preferably from 0.5% to 30% by weight of dimethacrylate, b) (meth)acrylic acid and a cyclic radical containing at least two oxygen atoms from 5% to 99.5% by weight, preferably 96% by weight, of an ester with an alcohol having % to 90% by weight, d) 0% to 5% by weight of an accelerator or initiator, and optionally other adjuvants.

The crosslinking agent, component a), comprises more particularly polyfunctional (meth)acrylates, such as allyl (meth)acrylates. di- or tri-(meth)acrylates such as 1,4-butanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate or trimethylolpropane tri(meth)acrylate ) acrylates are particularly preferred. The fraction of the crosslinking agent is more particularly preferably from 2% to 20% by weight and very particularly preferably from 3% to 15% by weight. Component b) specifically comprises esters of (meth)acrylic acid with acetals, ketals or carbonates of glycerol, substituted glycerol or unsubstituted or substituted trimethylolpropane. More particularly, component b) comprises a monomer of formula (1) or (2). Formula 1 R=H, Me R2=H, Et Z=H, (=O), alkyl, benzyl, aryl, O-alkyl Formula 2 component b) is more preferably glycerol formal (meth)acrylate, trimethyl allpropane formal(meth)acrylate or isopropylideneglycerol (meth)acrylate (Solketal methacrylate). In a composition particularly suitable for road marking, the reactive resin may further comprise 1% to 60% by weight of component e), said component e) comprising at least one prepolymer, preferably poly(meth)acrylate or including polyester. Further monomers of component c) present in the reactive resin are (meth)acrylates such as methyl(meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth) ) acrylate, hydroxyethyl (meth)acrylate, stearyl (methacrylate, benzyl (methyl) acrylate or lauryl (meth) acrylate. In component c), Said further monomers may also be (meth)acrylate-miscible monomers such as itaconic acid, methacrylamide, 1-alkene or styrene. The reactive resin contains preferably not more than 10% by weight, more preferably not more than 5% by weight and very preferably not more than 2% by weight of (meth)acrylates having radicals of 1 to 6 carbon atoms. It is also possible to use mono(meth)acrylates of macromolecular monomers, such as polyethers, for example polyethylene glycol or polypropylene glycol. Another macromolecular monomer used as component c) is urethane (meth)acrylate. In the present invention, urethane (meth)acrylate is understood as a compound having (meth)acrylate functionalities bonded to each other via a urethane group. For example, the compound can be obtained through the reaction of a hydroxyalkyl (meth)acrylate with a polyisocyanate having a hydroxyl functionality of 2 and polyoxyalkylene. An example of a commercial product prepared from a polyol, an isocyanate and a hydroxyl-functional methacrylate is Ebecryl 210-5129 available from UCB Chemicals. The reactive resin of the present invention may include the aforementioned urethane (meth)acrylate in an amount of 5 wt% to 30 wt%. Component c) is advantageously selected in its fraction and composition according to the technical function desired in particular. The monomer fraction of the reactive resin is more particularly between 10% and 85% by weight for systems composed exclusively of monomers and between 10% and 60% by weight for systems known as MO-PO systems, which will be described below. In another embodiment particularly suitable as road markings or floor coatings, the reactive resin further comprises component e). Therefore, in these systems known as MO-PO systems, there are also polymers, preferably polyesters or poly(meth)acrylates, which are hereby designated as prepolymers for distinction. The prepolymer is used to improve polymerization properties, mechanical properties, adhesion to substrates and optical requirements imposed on the resin. The prepolymer fraction of the reactive resin in this embodiment is between 10% and 60% by weight, preferably between 15% and 40% by weight. Both polyesters and poly(meth)acrylates may contain further functional groups, for example in the form of double bonds, for imparting adhesion or for copolymerization in crosslinking reactions. However, for improved color stability in the road marking portion, it is preferred that the prepolymer contains no double bonds. The poly(meth)acrylate generally consists of the same monomers listed above for the monomers in the resin system. They can be obtained by solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization or precipitation polymerization, and are added to the system as pure substances. The polyester is prepared in bulk through polycondensation or ring-opening addition polymerization, and consists of a building block known in the art. The reactive resins of the present invention are used as substrates for preparing formulations which optionally constitute one of two to three components of a cold plastic similar to the present invention. In this case, there are two preferred embodiments. A first embodiment is a pure monomer system. Such formulations, according to the invention, contain from 5% to 99% by weight of a reactive resin of the invention comprising at least 0.1% by weight of at least one accelerator or initiator d), and at least one accelerator or initiator f) 0.1% to 5% by weight of a mixture comprising: wherein component d) comprises an initiator and at the same time component f) comprises an accelerator, or component d) comprises an accelerator and component f) comprises an initiator include In a second embodiment, which is a MO-PO system, the low-temperature plastic comprises from 9% to 45% by weight of a reactive resin of the invention, comprising at least 0.1% by weight, preferably at least one accelerator or initiator d) 1 0.1% to 5% by weight of a mixture comprising at least one initiator or accelerator f), 0% to 15% by weight of an inorganic pigment, preferably titanium dioxide, and 10% to 90% by weight of glass beads, organic or further inorganic fillers % by weight, wherein component d) comprises an initiator and at the same time component f) comprises an accelerator, or component d) comprises an accelerator and component f) comprises an initiator). In both embodiments, the initiator and accelerator are separated, prior to mixing, among the different components of the low temperature plastic. In a variant of the two embodiments, two reactive resins of the invention are mixed with each other in a weight ratio of 1:1 to 4:1, wherein one reactive resin comprises component d) and the other reactive resin comprises component f). include It is peroxides that act as initiators d) and f) - more particularly polymerization initiators -. In some situations, it may be advantageous to use mixtures of different initiators. Peroxides such as dilauroyl peroxide, dibenzoyl peroxide, tert-butyl peroctoate, di-tert-butyl peroxide (DTBP), di-tert-amyl peroxide (DTAP), tert-butyl peroxy It may be advantageous to use (2-ethylhexyl)carbonate (TBPEHC) and other peroxides that decompose at high temperatures as radical initiators. For reactive resins for application, for example for road marking, dilauroyl peroxide or dibenzoyl peroxide is particularly preferred. Generally, the peroxide in the second component is mixed with a diluent, for example a phthalate such as dibutyl phthalate, and an oil or other plasticizer. The low-temperature plastic of the present invention comprises, as the sum of the first component and the second component, and optionally the third component, 0.1% to 7% by weight, preferably 0.5% to 6% by weight of an initiator or a mixture of initiator and diluent; Very preferably 1% to 5% by weight is included. One specific embodiment of a redox initiator system for reactive resins is a mixture of a peroxide and an accelerator g), more particularly an amine. Examples of such amines include tertiary, aromatic substituted amines, such as more particularly N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine or N,N-bis(2- hydroxypropyl)-p-toluidine. The reactive resins of the invention may comprise up to 7% by weight, preferably up to 5% by weight and very preferably up to 3% by weight of accelerators. In another embodiment of the three-component system, more particularly suitable for road marking applications, the accelerator is present in the second component, such as in a diluent, and the initiator, such as a peroxide, is part of the reactive resin of the present invention. The third component includes, for example, glass beads and any necessary adhesion promoter. Alternatively, the accelerator is part of the reactive resin and the initiator or initiators are part of the second or third component of the reactive resin. The components of the low temperature plastic described above may be mixed prior to or during application. In addition, other auxiliaries may be present, such as stabilizers, for example UV stabilizers, inhibitors, chain transfer agents or waxes. In addition, each of the components may contain other adjuvants such as anti-foaming agents, rheological additives, flow control aids, wetting and/or dispersing agents, controlling (slip resistant) fillers, and anti-settling agents. Also, especially in the case of road markings, added glass beads for the purpose of improving reflection may be present in one of the components of the low-temperature plastic or further dispersed during application. In addition, depending on the application, colorants and fine and/or coarse particles may be added to the formulation. In the field of using the formulation as road marking or surface marking, it is preferable that the auxiliary agent and additive added are colorants. White, red, green and yellow inorganic pigments are particularly preferred, and white pigments such as titanium dioxide are particularly preferred. The particulate filler used is selected from the group consisting of calcium carbonate, barium sulfate, quartz, finely divided quartz, precipitated and fumed silica and cristobalite. The coarse fillers used are quartz, cristobalite, corundum and aluminum silicate. As auxiliaries and additives, it is also possible to use chain transfer agents, plasticizers, paraffins, stabilizers, inhibitors, waxes and/or oils. Paraffin is added to inhibit polymerization by atmospheric oxygen. For this purpose, two or more paraffins with different melting points can be used in different concentrations. As chain transfer agents, all compounds known in the field of radical polymerization can be used. Preference is given to using mercaptans such as n-dodecyl mercaptan as well as polyfunctional mercapto compounds such as pentaerythritol tetrathioglycolate. As plasticizers, it is preferable to use esters, polyols, oils, low molecular weight polyethers or phthalates. In addition, conventional UV stabilizers may be used. The UV stabilizer is preferably selected from the group consisting of benzophenone derivatives, benzotriazole derivatives, thioxanthonate derivatives, piperidinocarboxylic acid ester derivatives or cinnamic acid ester derivatives. From the group of stabilizers and/or inhibitors, preference is given to using substituted phenols, hydroquinone derivatives, phosphines and phosphites. In addition, the following ingredients may be present in road marking formulations: It is preferable to use wetting, dispersing and flow controlling aids, these being alcohols, hydrocarbons, glycol derivatives, glycolic acid esters, acetic acid esters and derivatives of polysiloxanes, poly ethers, polysiloxanes, polycarboxylic acids and saturated and unsaturated polycarboxylic acid amine amides. As rheological additives, polyhydroxycarboxamides, urea derivatives, salts of unsaturated carboxylic acid esters, alkylammonium salts of acidic phosphoric acid derivatives, ketoxime, amine salts of p-toluenesulfonic acid, amine salts of sulfonic acid derivatives, and aqueous solutions of these compounds; Preference is given to using organic solutions or mixtures. Fumed or precipitated silicas, for example optionally silanized silica having a BET specific surface area of 10-700 nm 2 /g, are particularly suitable. The antifoaming agent used is preferably selected from the group consisting of alcohols, hydrocarbons, paraffinic mineral oil, glycol derivatives, glycolic acid esters, acetic acid esters and derivatives of polysiloxanes. This degree of formulation freedom demonstrates that the reactive resins of the present invention or low-temperature plastics comprising the reactive resins of the present invention can be formulated and added with additives for each specific application. The possible uses of the low temperature plastics of the present invention are numerous. For example, the low temperature plastics of the present invention are particularly suitable for road markings, road repair compositions, intumescent coatings or floor coatings. It can also be used to make gravel. Solid formulation ingredients, such as low-temperature plastics without fillers, may also be used to prepare, for example, floor coatings, casting resins, architectural preservatives, coatings or laminates - for example for orthopedic resins - and prepregs. Use as a reactive additive is also possible. Unexpectedly, the reactive resins of the present invention and the low-temperature plastics prepared therefrom are distinguished by very good properties, such as long life, mechanical properties, abrasion resistance, optionally whiteness or pigmentation, and gripping properties, all of which are at least in the prior art. It is excellent to the extent that it is comparable to the system of However, the system of the present invention contrasts particularly with the prior art in that it produces less odor and emits less volatile components. By formulating component b) together, it is possible to completely exclude particularly odorous monomers, such as ethyl acrylate, without impairing other properties of the low-temperature plastic, if additional monomers are selected. In addition, the system can also be optimized with regard to application by selecting suitable monomers, prepolymers, additives and/or adhesion promoters. Accordingly, the system of the present invention can be variously optimized and used for a wide range of applications. For example, in road marking applications, marking of surfaces of asphalt, concrete or natural stone is entirely possible. It goes without saying that the system of the present invention can be used flexibly in terms of application technology. The reactive resin and low temperature plastic of the present invention can be applied by spraying, casting or extrusion processes. Hereinafter, the present invention will be further described based on examples, but the following examples are not intended to limit the present invention.

Claims (1)

the following components: a) from 0.5% to 30% by weight of the crosslinking agent(s), b) from 5% to 99.5% by weight of an ester of (meth)acrylic acid with an alcohol having a cyclic radical containing at least two oxygen atoms, c ) 0% to 90% by weight of components copolymerizable with other (meth)acrylates and/or (meth)acrylates, d) 0% to 5% by weight of accelerators or initiators, and optionally other auxiliaries. (meth)acrylate-based reactive resin.