DE1092189B - Process for the production of preformed rubber-like floor coverings or wall coverings - Google Patents

Description

GERMAN

The invention relates to a method for the production of preformed, rubber-like floor coverings or Wall coverings in which the filler material has free NCO groups, some of which are based on oxidizable vegetable oils having binders is bound.

According to the invention, the procedure is such that a mixture of oxidizable or blown as a binder vegetable oil, which has at least two groups per molecule, those with isocyanate groups can react, and an essentially linear, terminally free isocyanate or isothiocyanate groups containing reaction product of polyoxy compounds and polyisocyanates or polyisothiocyanates are used will.

The preformed, rubber-like coverings produced according to the invention are distinguished by an increased mechanical resistance, measured against the covering material belonging to the state of the art, the Manufacturing process by significantly shortening the curing time.

A covering material has already been proposed which has good drying properties, which consists of fillers, oxidizable, vegetable oil and low molecular weight isocyanate compounds.

In addition to the state of the art, a method for the production of elastic grinding wheels should be mentioned, which is characterized in that as a binder for the abrasive grain mixtures of castor oil or one Derivative of castor oil with isocyanates can be used.

It is also known that the drying oils used as binders for linoleum-like floor coverings Otter condensation products from aliphatic dicarboxylic acids and polyhydric alcohols or the organic ones Fillers can be treated with small amounts of diisocyanate in any production stage. These Treatment should lead to an increase in the water resistance of the coverings.

It has also been proposed to use a film-forming composition that has good drying properties on the Based on alkyd resins and an organic compound that has more than one isocyanate or isothiocyanate group has to produce. If necessary, the alkyd resin could be mixed with fatty oils or with drying oils be modified. Such a material works well for impregnation purposes.

The binder to be used according to the invention can additionally contain other substances, namely Vinyl resins (ζ. Β. Polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and polyvinyl acetals of formaldehyde, butyraldehyde and other vinyl acetals), resins made from pentaerythritol, phenol-aldehyde resins Method of manufacture

of preformed rubbery

Floor coverings or wall coverings

Applicant:
Dunlop Rubber Company Limited, London

Representative: Dipl.-Ing. E. Rathmann, patent attorney,
Frankfurt / M., Neue Mainzer Str. 40-42

Claimed priority:
UK 3 April 1957

Wilfrid Henry Hogg, Sutton Coldfield, Warwickshire, and Peter Ford, Great Barr, Birmingham \

(Great Britain),
have been named as inventors

(e.g. xylenol-formaldehyde novolak resins) and natural Resins (e.g. tree resins, dammar and other copal resins). Plasticizers, such as phosphoric acid and phthalic acid esters, especially if a material of the polyvinyl chloride type is used. Glycolates and sulfonamide plasticizers can be used along with polyvinyl acetals be used; Nitrile rubbers are to be used as plasticizers for phenolic resins and the like.

The oxidizable or blown vegetable oils that are used include non-oxidized Oils and also partially oxidized oils, for example blown or gelled linseed oil and blown castor oil. The oxidizable or blown vegetable oils can be obtained from a wide variety of plants be. It is therefore quite possible, for example, linseed oils, tung oils (wood oil), rapeseed oil, and castor oil use dehydrated castor oil together. Along with the vegetable oils you can too animal oils are used. Many of the oils listed are opposed to in their natural state Isocyanates not or only insufficiently reactive. To make these oils sufficient for the present purpose To make isocyanate-reactive, they are with glycerine, glycol or other polyvalent polyhydroxyl compounds heated. The same effect is also

009 630/429

3 4

incorporated by heating with an amine or hydroxylamine to or isothiocyanates according to the invention reach. The responsiveness to Isocya- may have been sufficiently resistant Ability can also be obtained through other treatment modalities, if they only last a few hours for example by blowing, gelling or similar, have been cured at ordinary temperature, partially oxidizing processes may be brought about. All- 5 When a vinyl chloride material (for example, poly said a treated or untreated oil is vinyl chloride or a copolymer of vinyl chloride Suitable for the present purposes if it is in and vinylidene chloride) or a similar material If at least two metal-replaceable molecules are working, then the new covering material still has Has hydrogen atoms. the further advantage of better tolerability

The isocyanate or isothiocyanate that is found in the preparation of the prepolymers to anio between the binders derived from vegetable oils can be medium constituents and the remaining binder constituents can be a relatively simple compound, such as toluene diisoparts. This fact is thought to be the result of the cyanate. From polyester, polyester amide, polyglycol, conversion of the former into crosslinked products by the or similar compounds and simple recyanates or diisothiocyanates containing diiso- isocyanate or isothiocyanate groups will first be considered in action products. This improvement in the known manner of an essentially uncrosslinked compatibility is very considerable because this action product is produced. This type of reaction phenomenon with the growth of mechanical products is widely known and is associated with the resilience of the product.
Called prepolymers. Thus particularly suitable a prepolymer is not less 20 found in the described mixtures than 20 ° / ₀ for the purpose In general, the weight of the binder of the invention as obtained from tolylene diisocyanate and a poly of the total weight of the mixture. The amount of mers made from propylene glycol of a molecular weight oxidizable or blown vegetable oils is preferably 700 to 3000. wise between 2 and 50% of the total weight of the

Blends with improved elastic modulus have been blended and are 10 to 65% of the weight of the

obtained from prepolymers made from a simple binder. The proportion of isocyanates and / or

Diisocyanate or diisothiocyanate and a polyglycol isothiocyanate, which is used, is preferred

or trimethylolpropane and / or other aliphatic 1 to 30% of the weight of the oxidizable or

tables consist of polyhydroxyl compounds. blown oil, according to the molecular weight of the

The prepolymers should consist of such large proportions of the isocyanates and / or isothiocyanates and the reaction reactants be made that the molecule 30 ability between the isocyanate groups of the prepolyte Prepolymer contains free NCO (or N C S) residues with the oxidizable or blown plant. As mentioned above, it is possible to borrow oil in place. The numbers 1 to 30% correspond to the one (or in addition to) a compound that contains at least times the isocyanates or isothiocyanates that make up the contains two XCO and / or NCS residues, such prepolymer was also formed. So that means that To use compounds that have such radicals at 35 numbers do not refer to the prepolymer itself. Warming form. Examples of compounds of the latter. If a vinyl resin is used, then this is done in advance of Art are dissociable dimers of isocyanates (and) preferably in weight limits of up to 50% of the total isothiocyanates, z. B. Dimers of toluene diisocyanates weight of the binder.

and dissociable addition products of isocyanates, the new covering material can be produced (and Isothiocyanates) with different hydroxyl 40 are represented by (1) the constituents other than iso compounds. An example of this is an addition containing cyanate and / or isothiocyanate groups Product called, whose molecule is made up of 3 molecules of reaction products at elevated temperatures, for example toluene diisocyanate and 1 molecule of trimethylolpropane are mixed in a Banbury mixer, was formed. (2) the temperature, if necessary, slightly

The particular advantages that are reduced by the invention and (3) then the “use of the isocyanate or isothiocyanate products in accordance with the reaction” are mixed in. After mixing, the group-containing reaction products according to) are rolled out and / or injected into sheets, according to the invention, consist, as already indicated when material of the type of polyvinyl chloride and a, in a shortening of the hardening time of the plasticizer for the latter , for example tricresyl-produced covering material, which is still present in the 50 phosphate, in the mixture in a sufficient amount before compared to known covering material significantly increased, the mixing can have normal tempera strength. These mechanical resistance doors are made to form a paste. In this case the ability is due to the reaction of the isocyanate or iso- these resins in a finely powdered state with all thiocyanate groups with the oxidizable or borrowed other components of the mixture in a blown vegetable oil. This reaction is processed so long at room temperature that the molecules of the oxidizable or blown until they form a stiff, putty-like mixture. The vegetable oil is homogeneously mixed by urea or urethane bridges between the resin and the plasticizer (or by analogous sulfur compounds), which itself can also originate at the same time as the reaction between the isocyanate (or isothiocyanate) groups containing again from the isocyanate or isothiocyanate molecules both during the storage of the reaction product and the oxidizable or blown products to be produced according to the invention with ordinary vegetable oil during the final pouring temperature or during the heating of the drive in the heat.
Products instead. This can be the case, for example, in the case of the pre-The invention will be shaped in more detail in the following examples, that is to say pressing or casting, which is explained. All data relate to parts by weight, of course the reaction proceeds faster. 65

It was found that the flooring material of Example 1
normal composition based on linseed oil

The substances listed below are generally used in

becomes quite weak and brittle for a few weeks. an internal mixer (preferably in a Banbury

However, similarly structured material in which the isocyanates 70 mixer) are processed at 120 ° C:

5 6

Blown linseed oil 50 parts ratio 65: 35) with 100 parts polypropylene glycol

Copolymer of vinyl chloride with a molecular weight of 750 and a water content

and vinylidene chloride 70 parts below 0.05 percent by weight and 3 parts trimethylol

Dioctyl phthalate 10 parts propane in the presence of 0.1 part benzoyl chloride

Trixylyl phosphate 15 parts 5 and 3 hours of heating at 90 ° C was a prepolymer

Lead carbonate 8 parts of merisate produced in a conventional manner.

Asbestos fibers 100 parts The following substances were mixed together:

Chalk 250 parts Powdered pentaerythritol ester

Ρ ¹ *? ™ ^{111 10} parts of a resin acid 6.6 parts

,,. ,,. , ¹⁰ Powdered tree resin 10.3 parts

When the mixing process is almost complete, cork powder (0.75 mm) becomes 21.9 parts

the temperature lowered to 110 C. It is then wood flour (0.15 mm) 51.7 Teüe

a prepolymer was added, which was obtained as follows: titanium dioxide 6 6 parts

In 25 parts of a dehydrated polymeric propylene lead chromate 29 parts

glycol of molecular weight 2000 and 0.1 part phthalyl-15

chloride as a retarder, 5 parts of toluene diiso- 20.6 parts of gelled linseed oil cyanate were stirred into this mixture. Subsequently, 20.6 parts of blown castor oil with a viscosity of 120 ° C. were heated for 6 hours at and 20.6 parts. of 50 P added. The total mixture was heated in a After the addition of the prepolymer, the mixture was internal mixer 2 ¹ Z ₂ hours by well-rolled at 120 ° C, at 140 ° C in the desired form of cast 20 worked. The temperature was then cooled in the course of ^{1 and} _{2 minutes.} The result was a solid, temperature of the mass reduced to 90 ° C. Then were tough slab. . . 10.3 parts of the preparation prepared according to the above

isp polymer is added and mixing is continued for a further 2 minutes

The following components were carried out, after which the plastic mass was rolled out and

mixed and left to stand for one night at 110 ° C: 25 heated for 10 minutes under slight pressure at 140 ° C

Blown linseed oil was 50 parts. The result was a strong, leather-like product.

Tree resin 12.5 parts Example 5

Xylenol Formaldehyde Novolak Resin 7.5 parts

^, "_" ... ".,",,. Manufacture of the raw material used

Then 75 parts of a mixture of wood flour 30 Vnmnivmpriciatq

and pigment (in proportions 100: 6) added at 140 ° C oipuiymeitoiu,

and the mixture on a roller mill for as long as 150 parts of the trifunctional, trimeric oleic acid

works until it made a stiff paste. This paste's (equivalent weight of 282) was made with 150 parts

to be compared with binders that are used in the production of a polypro-

used by linoleum. 35 pylene glycol ethers (molecular weight 2000) and 20 parts were added to this paste

then combined 14.5 parts of a prepolymer and tolylene diisocyanate. This mass

a further 14.5 parts of the wood flour pigment mixture was added at 80 ° C. for 1 hour in a nitrogen atmosphere

given to stir the increase in the proportion of binder. Upon cooling, a syrup of

to compensate for the fact that the addition of the prepolymer has a viscosity of 20 P at 20 ° C.

took place. 40 In an internal mixer kept at 130 ° C

The prepolymer added was composed of 25 parts of a 90 parts according to the invention of the prepolymer thus produced

dehydrated polypropylene glycol from the molecular merizate with 290 parts of the mixture from below

Weight of about 750 and 12.5 parts of toluylene diiso components with 60 parts of gelled linseed oil (viscosity

obtained cyanate with 0.1 part of phthalyl chloride. 100 P) mixed.

The mixture obtained was a soft, plastic _{mixture of the} additional ingredients:

Material was further processed on a roller mill. , __ ".,

and rolled out cold. Parts of this rolled-out mass of pentaerythritol ester of a resin acid are 178 parts

were heated to 130 ° C for 20 minutes. At the end ™ - ^ 80 parts

by this time the material was cured giving a £ ° F ^km fr

solid, rubber-like plate. Other parts of the ex- ₅ o; 5 ^olz ™; J ^ _ £

The rolled mixture was made up of potassium dioxide at room temperature

preserve. They were also cured after 2 days. Pigment 78 was light

and made a solid, rubber-like plate. The resulting rubber-like mass was on

. . rolled out on a two-roller mill. After heating the

Example 3 ₅₅ B _a b h _{NEN above it} for 30 minutes at 150 ° C was under slight

The working method was the same as after printing a flexible linoleum-like material,

game 2, with the exception that instead of 14.5 parts of the “. . ,,

Example 3 mentioned prepolymer thereof 72.5 parts - Example O

were used. In addition, 72.5 parts of the A prepolymer was prepared by that

Wood flour pigment mixture used instead of the 60 100 parts of a polypropylene glycol with a medium

Example 2 used 14.5 parts. Patterns of this out- molecular weight of 2000 and a water content of

rolled mixture gave a hard, linoleum-like 0.01 ⁰ Z ₀ , 3 parts of trimethylolpropane and 34 parts of toluene

Product after which the samples diisocyanate for 20 minutes at 130 ° C, which is 80 ° / ₀ from the 2,4-isomer and to

had been heated or consisted of the 2,6-isomer for 2 days at room 20 ⁰ Z _{0, for 2 hours}

temperature hardened. The end product was substantially heated to a temperature of 90 ° C together

tougher than the product of Example 2. The following ingredients were mixed in an internal mixer mixed together at 130 ° C:

^Bei P ^{iel 4} sawdust 350 TeUe

By mixing together 34 parts of toluene diiso-blown linseed oil 30 parts

cyanate (mixture of 2.4 and 2.6 parts isomers in 70 blown castor oil 30 parts

After this mass had been stirred for 1 hour, parts of the prepolymer were added and the Mixing process continued for another 5 minutes. After this time, the pasty mass was quickly from the Mixer discharged and through a two-ring calender, the two rollers of which were at 60 ° C, slightly in sheet form convicted. The sheet-like material was then cured at 140 ° C for 15 minutes under slight pressure, whereby a solid product was finally obtained.

IO

Claims (5)

Patent claims: 1. A process for the production of preformed, rubber-like floor coverings or wall coverings by binding filler material with binders containing free N ¹ CO groups, some of which are based on oxidizable vegetable oils, characterized in that a mixture of oxidizable or blown vegetable binders Oil which has at least two groups per molecule which can react with isocyanate groups and an essentially linear reaction product of polyoxy compounds and polyisocyanates or polyisothiocyanates containing terminal free isocyanate or isothiocyanate groups. S. 2. The method according to claim 1, characterized in that a polyester, Polyesteramide or polyether urethane is used. 3. The method according to claim 1 and 2, characterized in that a blown or gelled oil is used as the oil Linseed oil or blown or gelled castor oil is used. 4. Modification of the method according to claim 1 to 3, characterized in that an additional Vinyl polymer, a resin derived from pentaerythritol, a phenol-aldehyde resin and / or a natural resin, furthermore, a mixture optionally containing plasticizer is used. 5. Embodiment according to claim 1 to 4, characterized in that the vegetable oil in an amount from 2 to 50% of the total weight of the filler-containing mass and 10 to 65% of the binder mixture is applied. Considered publications:
German Patent No. 964,987;
U.S. Patent Nos. 2,358,475, 2,282,827;
"Angewandte Chemie", A, 59 (1947), pp. 264 to 266; "Excerpts from German patent applications", 1948, Vol. 8, 277. 009 630/429 10.60