JPS62138522A - Resin composition and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The industrial application field of the invention is that resin A is a reaction product of an epoxidized fatty acid ester of a polyhydric alcohol with a carboxylic acid, and resin B is a reaction product of a polyhydric alcohol modified with a carboxylic acid. The present invention relates to a resin composition consisting of a mixture of at least two resins A and B, which are esters, and also to a process for producing the resin composition.

Background of the Invention This resin composition was patented in the Netherlands Patent Application Publication No. 84.
02455 specification 13) and others.

This reference contemplates resin compositions suitable as linoleum cements.

There are a number of methods applied to the production of resinous compositions for the production of linoleum (resin compositions hereinafter referred to as linoleum cement; in the linoleum industry this is also referred to as Bedford cement, following the method by which it was formed). ), causing choking and dryness (hardening)
One or more perennial saturated oils are used. Drying oils represent esters of natural fatty acids with polyhydric alcohols, especially glycerol or pentaerythritol.

During or after drying, these drying oils are mixed with resins, especially rosins, which form Pedford cement.

After mixing this cement with fillers and pigments, the resulting linoleum mixture 21 is usually calendered and applied to a substrate, primarily jute. The product thus formed is then cured at 60-80° C. (for example Ullmann,
ncyklopladie der techn
ischenChemie) Volume 12 (1976),
p., 24 et seq., and Encycle, of Pol, Sci.

and techni, (encycle, of p
ol.

Sci, and Techn, ), VOl,
1 (1964), p. 403 et seq.).

The disadvantage of these methods for the production of linoleum is that, depending on the thickness of the linoleum layer, a long time is required for the curing of the product. Furthermore, extensive manual inspection is required to determine whether the desired hardness has been reached.

Dutch patent application no. Ru. This resin composition consists of a mixture of two resins A and B. Resin A is the reaction product of an epoxidized fatty acid ester of polyfluoric acid with a -valent carboxylic acid, -
10,000 resin B is a carboxylic acid-modified ester of polyhydric alcohol. In this context, the term "carboxylic a-modified 1" encompasses the presence of carboxylic anhydride groups in place of carboxylic acid groups or in addition to carboxylic acid groups. This resin composition, however,
Its viscosity is the resin composition present in the entire linoleum industry.
It has the disadvantage that it is difficult to manufacture using manufacturing equipment.

PROBLEM SOLVED AND OBJECTED BY THE INVENTION The problem of the present invention is to provide a method in which resin A is a reaction product of an epoxy fatty acid ester of a polyhydric alcohol with a carboxylic acid, which is advantageously produced using equipment existing in the linoleum industry. and resin B is a carboxylic acid ester of a polyhydric alcohol.

Means for Solving the Problems The resin composition according to the present invention is prepared by applying resins A and B at such a time and temperature that the resin composition undergoes partial pre-curing Jr5+.
It is characterized by the fact that it can be obtained by mixing.

This partially pre-reacted state is henceforth also referred to as the B-1 stage. The dynamic viscosity (nd) is between 10 and 105 Pas, preferably between 10'' and 10' Pas, giving the resin composition the consistency required to yield a product that is excellent for further Bloeing onto linoleum. Give.1
This dynamic viscosity as a function of the frequency of i Hz at 00”C was measured using a parallel plate viscometer (RheOmetrlC eye JS 6
05) i.

According to a suitable embodiment of the invention, resins A and B (
Partial pre-reaction is carried out at a temperature of 0 to 250 DEG C. for 5 minutes to 4 hours, more preferably at a temperature of 120 DEG to 180 DEG C. for a period of 0.5 to 2.5 hours.

In the formulation of both resin A and resin B, it is advantageous to start from a transformable and pourable oil. In the case of fat A, dry oils are applied in epoxidized form, in particular epoxides kW of soybean oil, linseed oil, sunflower oil and/or tall oil fatty acid esters. Polyhydric alcohols in esters are selected from the group formed by glycerol, pentaerythritol, trimethylolpropane and/or polyalkene glycols. Mixtures of these or other polyhydric alcohols are also applicable.

The carboxylic acids that are reacted with the epoxidized drying oil are monovalent carboxylic acids such as benzoic acid, para-butyl-benzoic acid, tall oil fatty acids, etc.
2 filli-like G1 multi-f
1i1i carboxylic acids and/or mixtures thereof. For the production of linoleum (in order to maintain the unique Tlk of linoleum produced by Rossonka et al., rosins are particularly advantageous as acids. Suitable polyvalent carboxylic acids are carboxylic acids having 4 to 54 C atoms in the molecule. Acids, in particular ni- or tri-claw fatty acids or mixtures thereof, are used as polycarboxylic acids.

The modified carboxylic ester in resin B is an ethylene-containing unsaturated 1- or polyhydric carboxylic acid or its anhydride if! of an unsaturated fatty acid ester of a polyhydric alcohol. It consists of reaction products with 1N or several species.

Starting from unsaturated fatty acid esters, vegetable oils or tall oil fatty acid esters, esterification is carried out with glycecol, pentaerythritol, trimethylolpropane and/or polyalkene glycols (polyhydric alcohols from the group formed by C-nitrogen), - Mixtures of these or polyhydric alcohols are also applicable.

Suitable vegetable oils in the sense of the invention are, in particular, soybean oil, linseed oil, sunflower oil, olive oil, safflower oil and/or rapeseed oil.

The ethylenically unsaturated carboxylic acid or its anhydride used for the production of resin B may contain one or more ethylenically unsaturated groups in the molecule. Acrylic acid, methacrylic acid, rubic acid and/or crotonic acid are preferably used as monovalent carboxylic acids. Maleic acid and/or fumaric acid and/or its anhydride are preferably used as polyvalent carboxylic acids.

Maleic anhydride is particularly suitable for this purpose, since so-called maleic oils are easy to prepare and are commercially available.

The carboxylic acid modified ester in resin B also consists of the reaction product of a hydroxy-functional fatty acid ester of a polyhydric alcohol with a polyhydric carboxylic acid. For this purpose, in particular all esters derived from castor oil, hydroxystearic acid and/or siehydroquine palmitic acid are used.

The polyhydric alcohol used for the esterification is then preferably selected from the group formed into glycerol, pentaerythritol, trimethylolpropane and/or polyalkene glycols. Mixtures of these or other polyhydric alcohols are also applicable. The polyhydric carboxylic acid reacted with the hydroxy-functional fatty acid ester is preferably selected from the group formed by phthalic acid, tetra- or hexahydrophthalic acid and trimellitic acid.

Resin B also comprises an acid-functional alkyd resin and/or an acid-functional hydrocarbon resin and/or a mixture thereof.

In the production process, first of all, the epoxidized ester A is produced by the reaction with the carboxylic acid. The preparation is carried out at a temperature of 100 DEG to 250 DEG C., preferably 150 DEG to 20 DEG C., in the presence of an EL catalyst. The catalyst is preferably an acid-epoxy reactant, such as triethylamine.
One page touch for the heart! 5 Use all.

When combining resin A with resin B, the same type of catalyst used in the production of resin A is added.

The resin composition according to the invention may also be applied in combination with a resin composition based on one or more perennially saturated oils which have been dried with air.

Although the application of the resin composition according to the present invention in the production of surface coating layers, especially in the production of linoleum, has been mainly discussed above, the application of the resin composition according to the present invention (in the production of linoleum) is not limited to this. It's nothing special.

Other systems using resin compositions, usually in the form of so-called two-component resins, for obtaining surface wave polishing are suitable for the application of this resin composition. Among the possible applications are the roof corrugators and the so-called 1-floor protection material (1) in the automatic Y1L industry.
"Unterbodenschutz".

The invention will now be described in detail with reference to the following examples.

It is not limited to.

Example (1) Production of resin A Mechanical 61 equipped with stirring rock, thermometer and vertical cooling device 3
Add epoxidized linseed oil (nibuno#) onto the reaction vessel.
(Edenol) B 313, Henkel, 8.5
% total oxirane), 77740 parts by weight and 1 part by weight of triinbutylamine.

The reaction mixture is heated rapidly to k 180 'O while passing through nitrogen. TNiKOH/
Keep at this temperature until reduced to 9. The product is completely cooled down. Epoxy equivalent weight is 600.

(2 Preparation of Resin B In an apparatus similar to that used for Resin A, 878 parts by weight of linseed oil are heated to 200° C. under nitrogen. Then 294 parts by weight of maleic anhydride are carefully added in small portions over a period of 2 hours. .

The temperature should not exceed 200'C. After all additions, the temperature is gradually increased to 225°C and held for 4 hours.

(3) Production of step B Resin A and resin B obtained as described above were mixed at 100°C in a weight ratio of 1:1 and heated to 125°C. The resin is subsequently kept at this temperature for 2 hours, after which the composition is cooled.

Immediately after this, the resin composition can be processed into linoleum in a conventional manner.

(4) Measurement of viscosity Parallel plate viscometer (rheometrics (Rheo-meir)
The dynamic viscosity (nd) of the resin composition is measured as a function of vibration at 100° C. using an RMS 605 spectrometer). This viscosity (IHzf) &X 6 X 10
” It is Pas.

(5) Determination of the cure rate of the linoleum final product Test sheets are manufactured using a Schwabenthan two-roller mill (diameter 30 mm, speed 27/35 rpm). From this test sheet,
The plates (250x250x4) are then molded at 100° C. for 4 minutes. Test bars are punched out from this and, after curing, their elastic modulus, tensile strength and elongation at break are measured.

Curing at 80° C. is carried out for 1, 5, 11 or 50 days.

Tensile strength Elongation (N/mm (N/mm) (%) 2 days in the refrigerator 23±1 1.6±0.1 6.7±0.41
Days 105±47.8￥0.8 4.9±0.75 days 150±5 12.6±0.7 5.8±0.11
1 day 307 ± 3 11.7 ± 0.1
4.7±0.650 days 450±0.115.4±0.
34.1±0.1 This indicates that the resin composition yields a product with rapid curing and outstanding % pour.

Claims (1)

[Scope of Claims] 1. At least 2 resins, wherein 1. resin A is a reaction product of an epoxidized fatty acid ester of a polyhydric alcohol with a carboxylic acid, and resin B is a carboxylic acid-modified ester of a polyhydric alcohol. A resin composition consisting of a mixture of two resins A and B, characterized in that it is obtained by mixing the resins A and B at a time and temperature such that the resin composition undergoes a partial pre-reaction. Composition. 2. Resin A and B were heated to 60-250 for 5 minutes to 4 hours.
Claim 1 partially prereacted at a temperature of °C.
The resin composition described in . 3. Resins A and B were heated at 120-1 for 0.5-2 hours.
3. A resin composition according to claim 1 or 2, which is partially prereacted at a temperature of 80<0>C. 4. Claim 1 adapted for processing into linoleum using manufacturing equipment existing in the linoleum industry
The resin composition according to any one of Items 1 to 3. 5. A mixture of at least two resins A and B, wherein resin A is the reaction product of an epoxidized fatty acid ester of a polyhydric alcohol with a carboxylic acid and resin B is a carboxylic acid modified ester of a polyhydric alcohol. A process for preparing a resin composition comprising: a resin A;
A method for producing a resin composition, characterized in that it is obtained by mixing and B. 6. Resin A and B were heated to 60-250 for 5 minutes to 4 hours.
Claim 5 partially prereacted at a temperature of °C.
The method described in section. 7 Resins A and B were heated at 120° C. for 0.5 to 2.5 hours.
7. Process according to claim 5 or 6, partially pre-reacted at a temperature of -180<0>C.