IE903966A1 - Process for the stabilization of chlorinated paraffins - Google Patents
Process for the stabilization of chlorinated paraffinsInfo
- Publication number
- IE903966A1 IE903966A1 IE396690A IE396690A IE903966A1 IE 903966 A1 IE903966 A1 IE 903966A1 IE 396690 A IE396690 A IE 396690A IE 396690 A IE396690 A IE 396690A IE 903966 A1 IE903966 A1 IE 903966A1
- Authority
- IE
- Ireland
- Prior art keywords
- chlorinated
- weight
- paraffin
- chlorinated paraffin
- color
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
- B41M5/1655—Solvents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/42—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Color Printing (AREA)
Abstract
Chlorinated paraffins containing aliphatic or cycloaliphatic amines as stabiliser are highly suitable as solvents for colour formers in chemically reacting copy papers.
Description
HOECHST AKTIENGESELLSCHAFT, a Joint Stock Company organized and existing under the laws of the Federal Republic of Germany, of D-6230 Frankfurt am Main 80, Federal Republic of Germany.
-1IE 903966 f l-τ
HOECHST AKTIENGESELLSCHAFT HOE 89/F 355 Dr.DA/fe
Description
Process for stabilizing chlorinated paraffins
The invention relates to the stabilization of chloro5 paraffins which are used as solvents for the colorformers of chemically reactive copying papers.
The carbon-free copying papers which are mostly used nowadays operate by the principle of color formation by the reaction of an electron-donating organic compound, the so-called color former, which has no inherent color or only an extremely slight inherent color, with an electron-accepting substance, the so-called color developer.
The customary pressure-sensitive copying papers are composed of a combination of an upper sheet of paper, on the reverse side of which the micro-encapsulated emulsion of the color-former is applied (donor layer = CB layer = coated back). The electron-accepting substance for the color development is applied to the lower sheet of paper (acceptor layer = CF layer = coated front). In the case of a copying set containing 3 or more sheets, intermediate sheets carrying the CF layer on the upper side and the CB layer on the underside (CFB intermediate sheets) are used.
The microcapsules in which the dissolved color-former is enclosed are destroyed by pressure or impact, and the color-former solution is immediately adsorbed and fixed by the absorbent acceptor layer.
The following are known as electron-accepting substances or color developers for the CF layer:
acid-activated aluminum phyllosilicates based on montmorillonite, activated grades of clay, such as, for example, siltone, bentonites, attapulgites, or
- 2 synthetic products, such as, for example, treated anhydrides, aluminum silicates or magnesium silicates , specific zinc salicylate compounds,
- phenolic resins, such as, for example, condensation products of paraphenylphenol or para-alkylphenols with formaldehyde.
Examples of color-formers used for the CB layer are crystal violet lactone, malachite green lactone, benzoyl10 leucomethylene blue, rhodamine-B lactone and similar substances. In most cases a mixture of different colorformers is employed.
Many organic liquids can be used as solvents for the color-formers, the customary substances being modified terphenyls or alkylated naphthalenes or diphenyls in combination with various types of kerosene.
The use of linear, chlorinated paraffin hydrocarbons having 6 to 18 carbon atoms and chlorine contents of 20 to 60 % by weight as solvents for the color-formers is known (cf. British Patent 1,296,477). Chloroparaffins have the desired properties required of the solvent. They are good solvents for the color-formers and they are available in all grades of viscosity by suitable variation of the carbon chain lengths of the paraffins and the degree of chlorination. They have no troublesome odor.
Chlorinated paraffins do not reduce the sensitivity of the CF layer for color formation.
However, it has been found that stabilization with the epoxidized oils usually employed in chlorinated paraf30 fins, for example epoxidized soyabean oil, or resins containing epoxide groups, does not alone suffice to prevent color formation in the color-former solution, even at room temperature. This effect makes itself noticeable by the formation of a haze on the copying papers, which is increased further by elevated
- 3 temperature or by solar irradiation. The intensity of the print image also suffers through this undesired color formation.
The object was therefore to find a means of stabilization 5 which does not have the disadvantages mentioned above.
It has been found that the premature discoloration of the color-former solution can be prevented by the addition of certain amines to the chlorinated paraffin.
The invention therefore relates to a process for stabi10 lizing a chlorinated, essentially linear, paraffin having to 35 carbon atoms and a chlorine content of 10 to 72 % by weight, which comprises adding to the chlorinated paraffin 0.05 to 2 % by weight, relative to the chlorinated paraffin, of at least one amine of the formula XR3 in which R1, R2 and R3 are identical or different and denote a hydrogen atom, a C3-Cx8-alkyl group, a C6-C8cycloalkyl group or a C2-C8-aminoalkyl group, the total number of carbon atoms in the molecule being at least six and the boiling point at normal pressure being above
90°C.
The invention also relates to a chlorinated, essentially linear, paraffin having 7 to 35 carbon atoms and a chlorine content of 10 to 72 % by weight, containing 0.05 to 2 % by weight, relative to the chlorinated paraffin, of at least one amine of the formula
R2
R1XR3 .
in which R1, R2 and R3 have the meaning mentioned above, and to its use.
The chlorinated paraffins to be stabilized in accordance with the invention are chlorination products of essentially linear paraffins having 7 to 35 carbon atoms in the molecule, preferably of technical paraffin cuts having, for example, 10 to 13, 14 to 17, 18 to 24 etc. carbon atoms. The chlorine content of these chlorination products is 10 to approx. 72 % by weight.
The amines to be used in accordance with the invention are formally derivatives of ammonia in which one or more hydrogen atoms have been replaced by alkyl or cycloalkyl radicals. A distinction is drawn between primary, secondary and tertiary amines, depending on the degree of substitution”:
R1-N\ primary amine
R^N secondary amine
R1-N/ tertiary amine
R1, Rz and R3 are identical or different and denote a hydrogen atom, a C3-C18-alkyl group, preferably a CA-alkyl to C12-alkyl group, a C6-C8-cycloalkyl group or a C2-C8aminoalkyl group, the total number of carbon atoms in the molecule being at least 6 and the boiling point under normal pressure being above 90°C.
The alkyl radicals can be linear, branched-chain or cycloaliphatic.
- 5 The starting materials for the syntheses of the monoamines are principally the aldehydes or alcohols available from the 0X0 synthesis (hydroforming), which are converted into the corresponding amines by aminating hydrogenation or ammonolysis (replacement of the OH groups in the alcohol by ammonia).
The cyclic amines are formed by reacting aldehydes and ketones with ammonia or primary amines.
In addition to the monoamines, it is also possible to use diamines and triamines for the stabilization of the chloroparaffins described above. The preparation of the diamines and triamines takes place mainly via an addition reaction to acrylonitrile. The aminonitriles first formed are converted into the corresponding diamines and tri15 amines by subsequent catalytic hydrogenation.
Examples of suitable amines are di-n-propylamine, tri-npropylamine, n-hexylamine, octylamine, din-octylamine, tri-n-octylamine, di-isononylamine, di-(2ethylhexyl)amine, ethylenediamine or laurylamine.
The alkylamines or cycloalkylamines are present in the chlorinated hydrocarbon in an amount of 0.05 to 2 % by weight, preferably 0.05 to 1.8 % by weight, relative to the chlorinated paraffin.
The chlorinated paraffin used can, in addition, also contain the known stabilizers, for example epoxidized oils, such as epoxidized soya bean oil, or epoxidized resins, for example a cycloaliphatic diepoxide, in an amount of 1 to 4 % by weight. Stabilization by means of a combination of cycloaliphatic glycidyl esters with tertiary esters of phosphorous acid is also possible.
The stabilization of the chlorinated paraffin is appropriately carried out immediately after the completion of chlorination, by incorporating the stabilizer or
- 6 stabilizers into the chlorination product while it is still warm. Optimum degrees of stabilization are obtained in this way.
Chlorinated paraffins stabilized in this manner produce, 5 as solvents for the color formers, no haze formation on the copying papers prepared therewith. As a result of the good solubility of the alkylamines in chlorinated paraffins, additional solubilizing agents are not necessary.
The chlorinated paraffins stabilized in accordance with the invention can, as is generally customary in practice, be mixed with another solvent, for example with a hydrocarbon diluent, for example a kerosene grade.
The invention will be illustrated in greater detail in the examples below.
Example 1:
0.2 g of color-former (CVL = crystal violet lactone) was dissolved in each case in 100 g of chlorinated paraffin stabilized with an alkylamine. This solution was heated at 120°C for a period of 80 minutes. Samples were taken at intervals of 10, 15, 20, 30, 40, 50, 60 and 80 minutes and were cooled rapidly to room temperature, and the optical density (light absorption) of the sample at 605 nm was measured in a 1 cm cell by means of a spectral photometer. The blank sample used was the same chlori25 nated paraffin containing alkylamine, but no colorformer, and this was heated under the same conditions. At the end of the test time of 80 minutes, the iodine color number of the color-former solution was also measured in order to determine the aging of the chlori30 nated paraffin.
Example 2:
0.2 g of color-former (BLMB = benzoylleukomethylene blue)
- Ί was dissolved in each case in 100 g of chlorinated paraffin stabilized with an alkylamine. This solution was heated at 12O°C for a period of 80 minutes. Samples were taken at intervals of 10, 15, 20, 30, 40, 50, 60 and
80 minutes and were cooled rapidly to room temperature, and the optical density of the sample at 660 nm was measured in a 1 cm cell by means of a spectrophotometer. The blank sample used was the same chlorinated paraffin containing alkylamine, but no color-former, and this was heated under the same conditions. At the end of the test time of 80 minutes, the iodine color number of the colorformer solution was also measured in order to determine the aging of the chlorinated paraffin.
Example 3:
0.2 g of color-former (mixture of dyestuffs composed of % by weight of crystal violet lactone, 15 % by weight of benzoylleukomethylene blue, 15 % by weight of Olive 1G and 20 % by weight of Red 1-6B) was dissolved in each case in 100 g of chlorinated paraffin stabilized with an alkylamine. The dyestuffs are commercial products. This solution was heated at 120°C for a period of 80 minutes. Samples were taken at intervals of 10, 15, 20, 30, 40, 50, 60 and 80 minutes and were cooled rapidly to room temperature, and the optical density of the sample at
605 nm was measured in a 1 cm cell by means of a spectrophotometer. The blank sample used was the same chlorinated paraffin containing alkylamine, but no color-former, and this was heated under the same conditions. At the end of the test time of 80 minutes, the iodine color number of the color-former solution was also measured in order to determine the aging of the chlorinated paraffin.
The following chlorinated paraffins were employed:
A: a chlorinated, essentially linear, paraffin having
14-17 carbon atoms and a chlorine content of approx.
40 % by weight, a commercial product.
- 8 B: a chlorinated, essentially linear, paraffin having
-13 carbon atoms and a chlorine content of approx. 40 % by weight, a commercial product.
The chlorinated paraffins were stabilized with a cyclo5 aliphatic diepoxide (commercial product).
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Claims (7)
1. A process for stabilizing a chlorinated, essentially linear, paraffin having 7 to 35 carbon atoms and a chlorine content of 10 to 72 % by weight, which comprises adding to the chlorinated paraffin 0.05 to 2 % by weight, relative to the chlorinated paraffin, of at least one amine of the formula R 1 - N in which R 1 , R 2 and R 3 are identical or different and denote a hydrogen atom, a C 3 -C 18 -alkyl group, a C 6 Cg-cycloalkyl group or a C 2 -C 6 -aminoalkyl group, the total number of carbon atoms in the molecule being at least six and the boiling point at normal pressure being above 90 e C.
2. The process as claimed in claim 1, wherein the amine is a primary, secondary or tertiary alkylmonoamine or polyamine.
3. The process as claimed in claim 1, wherein 0.05 to 4 % by weight, relative to the chlorinated paraffin, of an epoxide stabilizer is added to the chlorinated paraffin in addition.
4. A chlorinated, essentially linear, paraffin having 7 to 35 carbon atoms and a chlorine content of 10 to 72 % by weight, containing 0.05 to 2 % by weight, relative to the chlorinated paraffin, of at least one amine of the formula R 1 - N in which R 1 , R 2 and R 3 are identical or different and denote a hydrogen atom, a C 3 -C 18 -alkyl group, a C 8 C a -cycloalkyl group or a C 2 -C 8 -aminoalkyl group, the total number of carbon atoms in the molecule being at least six and the boiling point at normal pressure being above 90°C.
5. The use of the chlorinated paraffin as claimed in claim 1 for the preparation of chemically reactive copying papers.
6. A process as claimed in claim 1, substantially as hereinbefore described and exemplified.
7. A chlorinated paraffin as claimed in claim 4, substantially as hereinbefore described and exemplified. Dated this the 2nd day of November, 1990
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19893936731 DE3936731A1 (en) | 1989-11-04 | 1989-11-04 | METHOD FOR STABILIZING CHLORINE PARAFFINS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| IE903966A1 true IE903966A1 (en) | 1991-05-08 |
Family
ID=6392854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE396690A IE903966A1 (en) | 1989-11-04 | 1990-11-02 | Process for the stabilization of chlorinated paraffins |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0427096A1 (en) |
| JP (1) | JPH03153640A (en) |
| DE (1) | DE3936731A1 (en) |
| FI (1) | FI905408A0 (en) |
| IE (1) | IE903966A1 (en) |
| PT (1) | PT95759A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4678625B1 (en) * | 2010-10-28 | 2011-04-27 | 株式会社リングストン | Double bag with chuck and manufacturing method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE685125C (en) * | 1935-08-07 | 1939-12-12 | Johann Karl Wirth Dipl Ing | Process for the production of stable, high molecular weight, liquid chlorinated paraffins |
| US2543575A (en) * | 1948-11-17 | 1951-02-27 | Ethyl Corp | Method of fractionating chlorinated hydrocarbons |
| DE1275531B (en) * | 1965-12-10 | 1968-08-22 | Wacker Chemie Gmbh | Stabilization of dichloroethylene, trichlorethylene or perchlorethylene |
| US4032584A (en) * | 1976-05-03 | 1977-06-28 | Stauffer Chemical Company | Stabilized methylene chloride |
| DE2922700A1 (en) * | 1979-06-02 | 1980-12-11 | Hoechst Ag | STABILIZED HALOGEN HYDROCARBONS |
| DE3534984C1 (en) * | 1985-10-01 | 1986-10-23 | Dynamit Nobel Ag, 5210 Troisdorf | Stabilized chlorinated paraffins and their use in carbonless papers |
-
1989
- 1989-11-04 DE DE19893936731 patent/DE3936731A1/en not_active Withdrawn
-
1990
- 1990-10-31 EP EP90120853A patent/EP0427096A1/en not_active Withdrawn
- 1990-10-31 PT PT9575990A patent/PT95759A/en not_active Application Discontinuation
- 1990-11-01 FI FI905408A patent/FI905408A0/en not_active Application Discontinuation
- 1990-11-01 JP JP29378990A patent/JPH03153640A/en active Pending
- 1990-11-02 IE IE396690A patent/IE903966A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0427096A1 (en) | 1991-05-15 |
| FI905408A0 (en) | 1990-11-01 |
| JPH03153640A (en) | 1991-07-01 |
| PT95759A (en) | 1991-09-13 |
| DE3936731A1 (en) | 1991-05-08 |
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