JPH0681798B2 - Casting resins based on liquid, curable, liquid acrylic and methacrylic acid polymers and finely divided inorganic fillers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The object of the present invention relates to a casting resin based on a polymer of curable acrylic and methacrylic acid esters and a finely divided inorganic filler and containing an organosilicon compound as an adhesion promoter.

It is known to mix curable acrylic and methacrylic acid ester-based casting resins (hereinafter also referred to as unsaturated casting resins) with inorganic fillers. Furthermore, casting resins containing inorganic fillers in amounts of more than 50% are also known, the fillers here being particularly finely granular. The use of organosilanes as adhesion promoters in the last-mentioned cast resins has also been described (see West German Patent Application Publication No. 2449656). This known casting resin containing fine-grained filler has a higher density, a higher density and a good rigidity than the unsaturated casting resin without filler.

Moreover, the inorganic filler reduces the heating properties of the resin and its shrinkability during curing.

If there is a large amount of fine filler that is evenly distributed in this casting resin while sharing the use of organosilane as an adhesion aid, the bending strength and impact strength of the molded product made from this resin will increase. . Moldings produced from this known unsaturated casting resin include in particular hygiene products such as sinks or washbasins.

In the production of these moldings, the unsaturated casting resin should have the lowest possible viscosity, so that when filling the mold, it will be filled as accurately as possible in the mold and retain the required filling degree. can do. Since there are many fillers,
This requirement is not met by many unsaturated casting resins. The addition of organosilicon compounds does not solve this problem, and some organosilicon compounds rather act to additionally increase the viscosity.

Therefore, a known unsaturated casting resin based on acrylic esters and finely divided inorganic fillers, containing an organosilicon compound as an adhesion aid, which is as small as possible than the viscosity of the unmodified casting resin, is processed. There was the problem of improving to have the required viscosity. However, in this case, the novel casting resin should have good physical properties as well as the known unsaturated casting resin.

To meet this task, based on polymers of acrylic and methacrylic acid esters and finely divided inorganic fillers,
A casting resin containing an organosilicon compound as an adhesion aid was discovered, which is characterized in that the organosilicon compound has one or more ethylenically unsaturated groups, and the casting resin additionally has a periodic table. It contains a metal acid ester or organic complex salt of a Group IVb or Group Vb metal.

Unsaturated casting resins according to the invention surprisingly have a viscosity in the uncured state which is significantly lower than the viscosity of similar casting resins without the addition of the constituents required according to the invention. On the contrary, if only one of the components is contained in the casting resin in the same quantity ratio as the mixture satisfying the requirements of the invention, the same low viscosity number as obtained when using the mixture of the invention is obtained. It is impossible to obtain a cast resin having There is also a synergistic effect here between these two given groups of compounds.

The amount of organosilicon compound and metal acid ester used is very small. In practice, their content can vary within wide limits with respect to the fillers contained in the casting resin. The organosilicon compound is generally 0.2-4% by weight, preferably 0.4-1.
The amount of 2% by weight and the metal acid ester used in an amount of 0.05 to 1% by weight, preferably 0.1 to 0.6% by weight. The quantity of individual compounds or groups of compounds in the casting resin can be high, but it no longer serves to significantly improve the desired effect.

The ratio of metal acid ester to organosilicon compound can vary within wide limits. It can be between 1:10 and 10: 2. The advantageous range lies between 4:10 and 10: 4.

A functional organosilicon compound having an ethylenically unsaturated group, which is also referred to herein as an unsaturated organosol, is
Di- and trialkoxysilanes which have one cc-double bond in their organic functional groups. This group is always attached to the silicon atom via one carbon atom,
In this case, this carbon atom is adjacent to the c- which has one double bond, as in vinyltrialkoxysilane.
May be bound to an atom. However, the cc-double bond is separated from the si-atom by one or more c-atoms as in, for example, allyltrioxysilane or γ-methacryloxypropyltrialkoxysilane.
It is also possible to use the corresponding dialkoxysilanes, the second organofunctional group having one cc-double bond at this si-atom, which is generally the first organofunctional group. 1 or an alkyl group preferably having 1 to 4 carbon atoms. The alkoxy groups of unsaturated organosilanes preferably have 4 c-atoms, which carbon atoms may optionally be interrupted by 1 ether oxygen.

Examples of such unsaturated organosilanes are vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (methoxyethoxy) -silane, divinyldimethoxysilane, vinylmethyldimethoxysilane, γ-methacryloxypropylmethoxysilane or γ-methacryloxy. Propyltris (methoxyethoxy) -silane.

Organosilicon compounds having several unsaturated groups (referred to herein as unsaturated organosilane polymers) are copolymers according to the invention from numerous ethylenically unsaturated compounds. It has at least two different basic structures each having two linked c-atoms, one of which is
Is bonded to one alkoxysilyl group, which may be either directly or , And the other basic structures are
It has one α-halogencarboxylic acid group whose halogen atom may be substituted by one acrylic or methacrylic acid residue. Additionally, the copolymer may contain ethylenically unsaturated groups without functional groups. This compound was prepared according to West German Patent Application No. P3227552.
It is described in the specification (Japanese Patent Publication No. 5-1285).

This organosilicon compound is a copolymer obtained by polymerizing vinyl chloroacetate and vinyltrimethoxysilane or methacryloxypropyltrimethoxysilane by the method described in, for example, Japanese Examined Patent Publication No. 1285/1993, 1285. Obtained by reacting with sodium acrylate,
It is a radical copolymer having a viscosity of 02 to 2.0.

Metallic acid esters that can be used include esters of metallic acids of compounds of group IVb or Vb of the Periodic Table of the Elements, primarily titanium-, zirconium- and vanadates. In this case, the ester component may have 1 to 18 c-atoms and may be an aliphatic alcohol or an alkyl-substituted phenol.
It is also possible to use mixed esters. The compounds which can be used according to the invention include, in particular, methyl titanate, ethyl titanate, butyl titanate, butyl polytitanate, nonyl titanate, cetyl titanate, tributyl oleyl titanate, cresyl titanate, cresyl polytitanate, propyl zirconate, butyl. Examples include zirconate, ethyl vanadate and butyl vanadate.

From this list it is also clear that corresponding ester polymers can be used, as long as they are stable. As a mixed ester, one or more alkoxy groups in one complexing pair, for example in diisopropoxy-bis (2,4-pentadionato) -titanium (IV) (also called titanium acetylacetonate) Thus, for example, those substituted with acetylacetone or acetoacetate can also be used. It is also possible to use other metal acid-complexes without ester groups such as tris- (2,4-pentanedionato) -vanadium (III) or oxybis- (2,4-pentadionato) -vanadium (IV). .

It is advantageous to use metal acid esters which have a slight intrinsic color.

The resin component of the unsaturated casting resin according to the present invention is a curable acrylic resin, where the acrylic resin is understood to be a liquid polymer of acrylic acid ester optionally methyl- or ethyl-substituted in the α-position. Should be. The ester component here is derived from aliphatic or aromatic alcohols having 1 to 18 carbon atoms and may optionally be interrupted by ether oxygen atoms. These liquid polymers may optionally contain the same group of solid, non-curing polymers dissolved or dispersed therein. Methyl methacrylate is an advantageous ester in order to obtain a moderately reactive resin that does not tuft on cure. The highly reactive resin which becomes rugged when cured contains a tunable component such as ethylene glycol dimethacrylate, and butene diol or methacrylate of allyl alcohol.

Resins or resin mixtures which can be used as components for casting resins are known (see West German Patent Application Publication No. 2449656).

Curing of this resin or resin mixture is likewise known,
Depending on whether the curing is carried out, for example, at elevated temperature or at room temperature, it is carried out by adding an inorganic peroxide and optionally an activator or accelerator.

The casting resin further contains fillers in the form of fine particles with a maximum particle size of 100μ. The preferred particle size range is 0 to 10.0 μm, 0
-40 μm and 0-60 μm, the mixture of the present invention exhibits particularly good action and effect in the case of filling in the particle size range of 0-10 μm. The filler may be of natural or synthetic origin,
It should have a hardness depending on the purpose of use. Fillers of natural origin include, for example, minerals such as aluminum oxide, complex oxides of aluminum with alkali metals and / or alkaline earth metals, variously modified silicon dioxide, silicates, aluminosilicates, calcite and other carbonates, Carbides, oxides and sulfides. These materials can also be modified by subsequent processing steps. Examples of this filler are quartz powder, kaolin, talc, mica, clay, zinc white, chiyoke, coal stone, dolomite, gypsum and blank fix (Blan).
cfix). Examples of synthetic fillers are glass powder, residual fuel ash, and fine-grained synthetic sio ₂ .

The casting resin modified according to the invention contains at least 20% by weight of this filler. This amount may be up to 80% by weight. Advantageously, the filler content of the final medium resin injection is 50-70% by weight.

Due to the presence of the mixture according to the invention consisting of unsaturated organosilicon compounds and metal acid esters, West German Patent Application No.
It is unnecessary to use a dispersant as specified in the specification of 2449656 for the production of the casting resins generally described therein. The filler is evenly distributed in the unsaturated liquid casting resin and does not agglomerate when the resin is in any case produced by known methods.

Like the known filler-containing liquid casting resins, the casting resins according to the invention additionally contain, in addition to this filler, a fibrous reinforcing substance, which does not have to meet the requirements of fine particle size. You may Examples of this fibrous material include glass fibers, ore fibers or asbestos. The amount of this reinforcing material should be maximum, but not more than the amount of finely divided filler.

If desired, the casting resins of the invention may be pigmented and / or dyed. For this reason, it is advantageous to use products which are stable against yellowing, coking and decomposition. Examples thereof include iron oxide, titanium dioxide, blank fix, zinc white, ultramarin blue, and carbon black.

The production of liquid curable casting resins according to the invention is described in West German Patent Application Publication No. 2449656,
It is carried out by a known method.

In general, the additive according to the invention is first mixed with the unsaturated liquid resin and subsequently the filler and optionally the reinforcing substance are introduced and dispersed in the resulting mixture. In this case, the pre-existing resin may contain mixed curing catalysts, especially if the casting resin is to be cured by the action of heat. However, this curing catalyst and optionally an accelerator,
It is advantageous to mix just before the curing of the compound, after which the desired cast pieces are produced.

From the compounds according to the invention it is possible to produce, for example, hygiene products such as washbasins, shower boards, sinks or WC-tanks or moldings for the construction industry such as machine bases, machine floors or containers.

Examples 1 to 4 Cast compounds with the properties described in Tables 1 to 4 were all prepared in a similar manner: Highly reactive methacrylic resin (Firma Rhm G
mbH commercial product Plexit) 32g and methyl methacrylate 16g
The mixture from and was placed in a graduated vessel and the mixture was mixed with the amounts of unsaturated organosilane and metal acid ester listed in the table. Continued basket type agitator (Krbch
enrhrer) at 700 to 800 u / min for 8 to 10 minutes, or once, 72 g in total of fine quartz powder (particle size range 0 to 40 μm) is dispersed and introduced.

Tables 1 to 4 show the viscosities of the obtained compounds.
This is less for the compounds of the present invention than for those compounds containing only unsaturated organosilanes or metal acid esters. Furthermore, the table also shows that upon the slight addition of each of the two components of the mixture, a synergistic effect already appears, the optimum effect occurring at different mixing ratios depending on the metal acid ester used. There is.

Viscosity measurements were made here and in the following examples using a Brookfield RV-viscosimeter. For this purpose, each individual resin sample was heat treated to 20 ° C. and tested after a certain storage time. The measurement was performed at 10 and 50 U / min using the spindle 5.

Example 5 Plexite (Pl
exit) The procedure described in Examples 1 to 4 was repeated with the difference that a moderately reactive methacrylic resin obtained under the name M60 (a product of Rhm GmbH, Dar-mstadt) was used.

Experiments with varying amounts of γ-methacryloxypropyltrimethoxysilane (MEMO) and zirconbutyrate [Zr (Obu
t) ₄ ]. The measurement results are shown in Table 5, and even with a slight reactivity of the acrylic resin, the above-mentioned synergistic effect appears, and the optimum of the additive of the present invention depends on the resin type used.

Example 6 Several casting compounds were prepared in a similar manner using unsaturated organosilane polymers as follows: Highly reactive methacrylate-resin (Rhm GmbH, Darmsta
A mixture of 105 g of the dt product Plexit) and 35 g of methyl methacrylate is placed in a graduated container and, in this solution, the amount of unsaturated organosilane polymer described in Table 6 is added, optionally titanium. 1 mol of butyrate and 4 mol of acetoacetic acid ester (shown as MEMIG in the table) were mixed and introduced. Continue to use 2000U /
It took about 10 minutes at min, and first, fine quartz powder (particle size range 0
~ 40μm) 210g and then Ultramarine Blue pigment (Firma Reckitt's Colors SAComines / Frankre
ich product) 1.4 g was dispersed and introduced. Table 6 shows the viscosities of the contained compounds. This is lower for the compounds according to the invention than for those containing only unsaturated organosilane polymers or metal acid esters. This also applies to the use of unsaturated organosilane polymers which have a viscosity-reducing action without the addition of metal acid esters.

Viscosity is measured using a Brutsk Field-RV viscometer. For this purpose, the individual samples were each heat-treated at 20 ° C. and tested after a given storage time. The measurement was performed at 10 and 50 U / min using the spindle 5.

Explanation of Table 6: UPO1 = unsaturated organosilane polymer = sodium acrylate and 90 parts by weight of vinyl acetate, 5 parts by weight of vinyl chloroacetate and 5 parts by weight of vinyltrimethoxysilane to about 43 in triol.
% UPO2 = Unsaturated organosilane polymer = 85 parts by weight of sodium acrylate and vinyl acetate, 5 parts by weight of vinyl chloroacetate and 10 parts by weight of vinyltrimethoxysilane in triol About 43
% Of the reaction product from the polymer prepared by using it as a 10% solution. Example 7 140 g of the highly active methacrylate resin described in Example 1 (3:
(Diluted with methyl methacrylate at a ratio of 1) was placed in a reaction vessel, and further 1.68 g of γ-methacryloxypropyltrimethoxysilane and 0.42 g of zircon isobutyrate were mixed, and fine granular quartz powder was added to this mixture. 210 g (particle size range 0-40 μm) is dispersed and introduced. The mixture is subsequently stirred at 2000 U / min for 10 minutes.

After a deaeration time of about 16 hours, 0.7 g of a peroxide catalyst and an activator, which are specific for each acrylic resin, are introduced with stirring and from this mixture plates with dimensions 200 × 200 × 4 mm are cast. The plate cures within 20 minutes. It was subsequently post-cured at 80 ° C. for a further 14 hours.

For the impact- and flexural-strength measurements given in Table 6, standard plates of dimensions 50 x 6 x 4 mm were cut from the plates obtained.

The physical values obtained are given in table 7.

As a comparative example, a plate prepared by the same method but containing the same amount of γ-methacryloxypropyltrimethoxysilane was used instead of the mixture of methacrylsilane and zircon isobutyrate.

Example 8 After a degassing time of about 16 hours, 0.7 g of a peroxide catalyst and an activator, which are specific for each acrylic resin, were introduced into the sample of Example 6 by stirring and the mixture was measured to give a size of 200 × 200.
A × 4 mm plate was cast. The plate cured within 20 minutes. Subsequently, it was post-cured at 80 ° C. for 14 hours.

A standard body of dimensions 50 × 6 × 4 mm was cut from the obtained plate for the measurement of bending strength and impact strength. The physical property values of this test body are shown in Table 8.

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Claims (2)

[Claims] 1. A liquid curable liquid acrylic polymer and methacrylic acid polymer and 20 to 80% by weight (based on the casting resin) of a finely divided inorganic filler as an adhesion promoter. In a casting resin containing an organosilicon compound, the organosilicon compound has one or more ethylenically unsaturated groups and contains sodium acrylate and a) vinyl chloroacetate and b) vinyl- or methacryloxypropyl groups. It is a reaction product of a copolymer with an alkoxysilyl compound having (which optionally further contains a non-functional basic structure having an ethylenically unsaturated group). In addition, it contains one metal acid ester of a metal of Group IVb or Vb of the periodic table, in which case,
The organic silicon compound is contained in an amount of 0.2 to 4% by weight with respect to the filler, and the metal acid ester is contained in an amount of 0.05 to 1 with respect to the filler.
A castable resin based on a flowable, curable, liquid, acrylic and methacrylic acid polymer and a finely divided inorganic filler, characterized in that it is contained in an amount of% by weight. 2. A casting resin according to claim 1, which comprises, as metal acid ester, an ester of a compound from the group of titanic acid, vanadic acid and zirconic acid.