JPS6123320B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a method for surface sizing paper comprising impregnating the paper with an aqueous sizing liquid and drying the paper, comprising: (a) 2,2-bis-(4'-hydroxyphenyl);
- polyglycidyl ether of propane 1.0 epoxide group equivalent; (b) monoaliphatic amine with at least one type of 12 to 24 carbon atoms 0.1 to 0.85 amino group equivalent; and (c) (c') 16 to 22 carbon atoms. A polyalkylene amino polyamide produced from a polymerized aliphatic unsaturated fatty acid derived from a fatty acid having 0.3 to 2 amino group equivalents and an aliphatic polyalkylene polyamine having (c″) 4 to 12 carbon atoms. and (d) if desired, 0.1 to 1.0 epihalogenohydrin.
moles or nitriles of ethylenically unsaturated monocarboxylic acids with 3 or 4 carbon atoms 0.1
~1.0 mol and (e) an acid in an amount of 10 to 40% by weight of at least one water-dispersible or water-soluble salt of the reaction product prepared in an inert organic solvent at a temperature up to 95°C. Including,
The present invention relates to a paper surface sizing method characterized by using an aqueous sizing liquid containing a compound having a pH value of 2 to 8. The epoxide used in the production of the reaction product salt used in the method of the invention has an epoxide content of 1.8 to
5.8, preferably 5 to 5.5 epoxide group equivalents/Kg. Particularly preferred epoxides have the formula (In this formula, z is the average value of 0 to 0.65.) Note that 0 is particularly interesting as z. Such epoxides are obtained, for example, by the reaction of epichlorohydrin with 2,2-bis-(4'-hydroxyphenyl)-propane. Particularly suitable as component (b) are carbon atoms.
12-24, preferably 16-22 and especially 16-18
It is a saturated or unsaturated monoaliphatic amine with These amines are therefore e.g. laurylamine,
Arachidylamine or behenylamine and especially palmitinamine, stearylamine or oleylamine. Mention may also be made, inter alia, of mixtures of these amines as obtained as industrial products. The polymerized unsaturated fatty acids used as the component (c') used in the production of the polyalkylene amino polyamide (c) are preferably dimerized or trimerized fatty acids, especially those having 16 to 22 carbon atoms. It is derived from monocarboxylic acids with 16 to 18 carboxylic acids. These monocarboxylic acids are fatty acids having at least one ethylenically unsaturated bond, preferably 2 to 5 bonds. Examples of acids of this type are oleic acid, hyragonic acid, eleostearic acid, licanic acid, arachidonic acid, clupanodonic acid and especially linoleic acid and linolenic acid. These fatty acids are obtained from natural oils that occur primarily as glycerides. The above dimerized or trimerized fatty acids (c') can be obtained by dimerization of the above-mentioned types of monocarboxylic acids by methods known per se. So-called dimerized fatty acids always contain trimerized acids and, to a lesser extent, monomeric acids. Particularly suitable as component (c') are 2 to 3.
It is merized linoleic or linolenic acid. Industrial products of these acids are generally acid dimers 75-95
% by weight and 4-25% by weight of acid trimer and traces to 3% of acid monomer. Thus, the molar ratio of acid dimer to trimer is about 5:1 to 36:1. As the component (c″), in particular, the formula H ₂ N—(CH ₂ —CH ₂ —NH)n—CH ₂ —CH ₂ —
Polyalkylenepolyamines of the formula NH ₂ (2) in which n is 1, 2 or 3 are suitable, ie diethylenetriamine, triethylenetetraamine or tetraethylenepentamine. Note that triethylenetetraamine is particularly important. In the case of amine mixtures, the average value of n is not necessarily an integer and can for example be between 1 and 2. Technical amine mixtures of this type are also preferred. Component (c) of particular interest is a polyalkylene amino polyamide made from dimerized or trimerized linoleic or linolenic acid and triethylenetetraamine. Monoaliphatic amine as component (b) and component (c)
Particularly preferred are polyalkylene amino polyamides having 3 to 4 amino group equivalents/Kg. The reaction product of the epoxide as component (a), the fatty amine as component (b) and the polyalkylene amino polyamide as component (c) can be optionally
It can also be obtained in combination with component (d). As component (d) it is advantageous to use nitrites of acrylic acid or methacrylic acid, such as acrylonitrile. Particularly preferred as component (d) is epichlorohydrin. When component (d) is used in combination, 0.1 to 0.5 mole of component (d) per 1 epoxide group equivalent of component (a), especially
Preferably, 0.1-0.2 mol is used. However, in the method of the present invention, from only components (a), (c) and (e),
That is, the salt of the reaction product produced in the absence of component (d) is primarily used. In this case, for one epoxide group equivalent of component (a), preferably
0.4 to 0.8 (especially 0.4 to 0.6) amino group equivalents and preferably 0.3 to 1.5 (especially 0.3 to 0.5) amino group equivalents of component (c) are used. In general, components (a) and (b) are first reacted to form an epoxide-fatty amine reaction product, followed by a polyalkylene amino polyamide as component (c) and, if desired, unsaturation as component (d). Further reaction with a nitrile or epihalohydrin of the monocarboxylic acid. Ingredients although less suitable
When using component (d) together, the reaction order is component (c)
Polyalkylene amino polyamide as an ingredient
Of next importance is the reaction with the nitrile or epihalohydrin as (d) and the epoxide-fatty amine reaction product from components (a) and (b).
That is, component (d) can be reacted first with component (c) and then with the epoxide-fatty amine reaction product from components (a) and (b), or in the reverse order. can. In many cases, reactions can be carried out simultaneously if there is no significant difference in reactivity. To carry out the reaction to form the reaction product from components (a), (b), (c) and, if desired, (d), polyaddition products which are dispersible or especially soluble in water are used. The PH value of the reaction mixture diluted with an inert organic solvent or preferably water to 10-40% by weight, preferably 25-35% by weight, is adjusted to 2-8, preferably 2-8, preferably after the end of the reaction at the latest. Be careful to adjust the temperature between 3 and 5.5. To adjust to this PH value, use ingredient (e)
using inorganic or organic acids as Inorganic acids include, inter alia, hydrochloric acid, nitric acid, preferably phosphoric acid, especially phosphoric acid or sulfamic acid. As an organic acid, carbon atoms at most
Mention may be made of 20 aromatic or especially aliphatic mono- or di-carboxylic acids or their functional derivatives, such as especially the anhydrides. Preferred fatty acids include mono- or di-carboxylic acids having at most 18 carbon atoms, preferably lower saturated monocarboxylic acids having from 1 to 4 carbon atoms, such as formic acid, acetic acid or propionic acid, having from 12 to 18 carbon atoms. higher saturated or unsaturated, optionally hydroxylated fatty acids, such as lauric acid, myristic acid, oleic acid, stearic acid or ricinoleic acid, saturated or unsaturated dicarboxylic acids having 4 to 18 carbon atoms, especially 4 to 10 carbon atoms; Acids such as malonic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, corkic acid,
azelaic acid or sebacic acid, or a carbon atom
Cycloaliphatic acids such as the 20 resin acids, such as -pimaric acid, d-pimaric acid and abietic acid, may be mentioned. As anhydride, especially carbon atoms 4-
Anhydrides of aliphatic or aromatic, preferably unsaturated, dicarboxylic acids having 8 atoms, such as maleic anhydride or phthalic anhydride, may be mentioned. Mixtures of these acids can also be used, in particular technical fatty acid mixtures such as coconut oil fatty acids or resin acid mixtures such as rosin. Of particular interest are liquid saturated monocarboxylic acids having 1 to 4 carbon atoms, such as formic acid and especially acetic acid. For example, for example, acetic acid or especially acetic acid is mainly used when addition of other of the above-mentioned acids results in salts that are only dispersible in water. In this case, water-soluble salts are obtained by further addition of phosphoric acid or, in particular, acetic acid. That is, water-soluble salts are preferable to water-dispersible salts. Particular preference is given to using as component (e) orthophosphoric acid, sulfamic acid, azelaic acid or rosin, if desired in the presence of acetic acid, i.e. sulfamic acid used alone and orthophosphoric acid, azelaic acid. Alternatively, use rosin by adding acetic acid after adding this. Note that to add vinegar to the reaction mixture, component (a) and
Immediately or after some time after the start of the reaction of the epoxide-fatty amine reaction mixture from (b) with the polyalkylene amino polyamide of component (c), a portion of the acid is added continuously or in portions during the reaction. I recommend adding more acid. Furthermore, it is preferred to operate at temperatures up to 95[deg.]C, eg from 25 to 95[deg.]C, in particular from 60 to 95[deg.]C. The reaction product salt thus obtained is at least dispersible or preferably soluble in water. The reaction of components (a), (b), (c), (e) and, if desired, (d) is carried out in an inert organic solvent which does not react with these components. Suitable organic solvents are mainly water-soluble organic solvents that are optionally miscible with water. Examples include cycloaliphatic or aliphatic ethers with 2 or 3 oxygen atoms and 2 to 8 carbon atoms, such as dioxane, ethylene glycol mono-n-butyl ether (i.e. n-butyl glycol), diethylene glycol mono-n-butyl ether and Particular mention may be made of alkanols having 1 to 4 carbon atoms, such as isopropanol, ethanol and methanol. The above reaction can also be carried out in water-insoluble organic solvents such as benzene hydrocarbons such as benzene or petroleum ether, benzene, halogenated or lower alkylated benzenes such as toluene, xylene or chlorobenzene, alicyclics such as tetralin and cyclohexane. It can also be carried out in compounds of the formula, halogenated hydrocarbons such as methylene chloride, methylene bromide, chloroform, carbon tetrachloride, ethylene chloride, ethylene bromide, symmetrical tetrachloroethane or especially trichlorethylene or perchloroethylene. Generally, all reactions are performed in the same solvent. In this case, the solvent is particularly preferably isopropanol. The reaction mixture, which has been adjusted to the above pH value by means of an acid, is treated with 10 to 40% by weight of the salt of the reaction product, preferably 25% by weight, in a water-soluble inert organic solvent of the above type or preferably with water after the end of the reaction. Suitable dilutions are made to produce formulations that can be used in the process of the invention containing amounts of ~35% by weight. Such formulations are solutions or dispersions (usually thin milky to cloudy solutions) and are characterized by high storage stability. It should also be noted that if the formulation is kept at room temperature or elevated temperature after addition of acid and water, e.g. 70° C. for 4 hours or longer at lower temperatures,
A formulation with advantageous properties for use is obtained. The invention also concerns the salts of the reaction products present as aqueous formulations for use in the process of the invention and the use of the salts of the reaction products for surface sizing of paper. Before using the formulation in the process of the invention, it is diluted with water to give an aqueous size liquor with a product salt content of 0.02 to 0.2% by weight, preferably 0.06 to 0.14% by weight. In the process of the invention, this size liquid is applied to the paper, for example by spraying or preferably by padding, generally at room temperature. next,
The paper thus impregnated is heated at 60-140°C (preferably 90°C).
~110°C) for 0.1 to 10 minutes (preferably 2 to 6 minutes). After drying, the amount of reaction product salt supported on the surface is 50-150mg/ ^m2 (preferably 60-120mg/m2).
m ² ) is obtained. The paper to be sized by the method of the invention is any type of paper of any planar weight, such as paper and cartons made of bleached or unbleached sulfite cellulose or sulfate cellulose. The invention also relates to paper having a surface sized by the method of the invention. The process of the invention offers the essential advantage of achieving high size effects on paper with low surface loadings of reaction product salts. This high size efficiency is evaluated based on positive results of tests such as alkaline drop test, ink float time and Cobb water absorption measurements. In particular, because of their low surface loading, the operation is fast, e.g. high surface sizing can be achieved in about 20 to 40 seconds at drying temperatures of 90 to 110 DEG C. Furthermore, the reaction product salts according to the invention can be used in combination with the usual auxiliaries used in the paper industry, such as dyes, powders,
High compatibility with binders, especially fluorescent brighteners and other additives. Furthermore, the reaction product salts do not produce undesirable foam. Next, the present invention will be explained in more detail with reference to Examples. In these examples, all parts and percentages are by weight. Production Example A 56.2 parts (0.2 parts) of a fatty amine mixture of palmitylamine, stearylamine, and oleylamine
(amino group equivalent) was dissolved in 15 parts of isopropanol, and 75 parts of epoxide (0.4 epoxide group equivalent) produced from 2,2-bis-(4'-hydroxyphenyl)-propane and epichlorohydrin was dissolved in 15 parts of isopropanol. Dissolve in 80~
Add for 1 hour at 90°C. After the epoxide addition is complete, the reaction mixture is held at 85-90°C for 15 minutes. Next, 42.75 parts (0.17
(amino equivalent) dissolved in 15 parts of isopropanol and added. Once the polyamide has been added, the reaction mixture is held at 85-90°C for an additional 2 hours. A mixture of 12.5 parts of 85% orthophosphoric acid and 13 parts of acetic acid (as glacial acetic acid) is then added to the reaction mixture over 30 minutes and then 412 parts of deionized water are added. A very fluid solution is thus obtained.
Its dry content is 30% and PH value is 4.0. B-Z, AA and BB. In Example A, the reaction mixture was substituted with the following first
The same procedure is followed except that the acid or acid mixture listed in the table is added in the indicated amount. The dry content of the solutions thus obtained is in each case 30%, as in Example A. The amount of water required to obtain this dry content and the PH value of the resulting solution are also listed in Table 1.

【table】

【table】

[Table] CC Fatty amine mixture of palmitylamine and stearylamine 18.9 parts (0.07 amino group equivalent)
Dissolve in 20 parts of isopropanol and add 2,
19 parts of epoxide (0.1 epoxide group equivalent) produced from 2-bis-(4'-hydroxyphenyl)-propane and epichlorohydrin are dissolved in 15 parts of isopropanol and added at 80-85°C over 1 hour. After the epoxide addition is complete, the reaction mixture is held at 85-90°C for 15 minutes. Next, 37.8 parts (0.15 amino equivalents) of polyethylene amino polyamide produced from linoleic acid polymer and triethylenetetraamine are added to the reaction mixture dissolved in 15 parts of isopropanol. Once the epoxide has been added, the reaction mixture is held at 85-90°C for an additional 2 hours. Next, 9.6 parts of rosin dissolved in 7.2 parts of glacial acetic acid is added to this reaction mixture. After adding the rosin, keep the reaction mixture at 85°C for 20 minutes. next,
Dilute the reaction mixture with 166 parts of deionized water.
A solution with a dry content of 30% and a pH of 7.0 is thus obtained. DD 32.4 parts (0.12 amino group equivalent) of a fatty amine mixture of palmitylamine, stearylamine, and oleylamine was added to ethylene glycol.
Dissolve in 25 parts of n-butyl ether and add 2,
38 parts of epoxide produced from 2-bis-(4'-hydroxyphenyl)-propane and epichlorohydrin (0.2 epoxide group equivalent) was dissolved in 25 parts of ethylene glycol mono-n-butyl ether at 80 to 85°C. Add in 1 hour. After adding the epoxide, heat the reaction mixture at 85-90 °C for 15 min.
Hold for a minute. Next, 37.8% of polyethylene aminopolyamide produced from linoleic acid polymer and triethylenetetraamine was added to the reaction mixture.
(0.15 amino equivalents) dissolved in 15 parts of isopropanol. Once the polyamide has been added, the reaction mixture is held at 85-90°C for an additional 2 hours. Next, add 7.76 parts of sulfamic acid to the reaction mixture in water.
Dissolve and add to 159 parts. Thus dry content 30
% and a solution with pH 5.9 is obtained. Example 1 A pure cellulose filter paper with a planar weight of 140 g/m ² was heated at a speed of 4 m/min and under a pressing pressure of 10 Kg/cm ² to collect an aqueous solution (the solution obtained according to Preparation Examples A to Z, AA or BB). Pad with a solution containing 0.1% of the salt of the reaction product by diluting with water. Dry the padded paper at 120-130°C for 30 minutes. The surface sizing of the paper thus treated is evaluated by the following test. Water absorption according to Cobb according to DIN 53132 with an action time of 30 seconds (WA Cobb ₃₀ ): The lower the water absorption, the better the surface rising of the treated paper. Ink floating time (TSD) with test inks according to DIN 53126: in a porcelain chalet with dimensions 10 x 12 cm
Pour Paper Test Ink Blue according to DIN 53126 to a depth of 0.5 cm. Fold the test paper into a small boat shape with the ends together (size 4
×4cm). Place this small boat on the ink surface with tweezers. Press the stopwatch at the same time,
Measure the time until the test ink is visible to the naked eye. The results are shown in seconds at 10 second intervals. In untreated paper, the test ink penetrates immediately.
The more time the test ink has to penetrate the sized paper, the better the sizing. Alkaline drop test (ATP): from a height of 5 cm on a test paper held horizontally.
One drop of 1.0N aqueous sodium hydroxide solution is added dropwise from a 1 ml pipette. Press the stopwatch at the same time. Measure the time it takes for the paper to absorb the droplet.
The end point is the point at which the gloss disappears. The result
Shown in seconds at 10 second intervals. Untreated paper absorbs alkaline droplets immediately, but
The higher the sizing effect of sized paper, the slower it absorbs alkali droplets. The test results for paper treated by the method of the invention and for untreated paper are summarized in Table 2 below. WA Cobb ₃₀ values are the average of four measurements.

[Table] Production examples Y, Z, AA, BB, CC or DD
A similar result is obtained when adding a solution containing a salt of the reaction product by. Example 2 In Example 1, a filter paper is padded with an aqueous solution prepared by diluting the solution obtained in Preparation Example CC or DD with water to contain 0.1% of the reaction product salt. The padded paper is dried at a speed of 4 m/min on a cylinder with a surface temperature of 100°C. The surface sizing of the paper thus treated is evaluated by the test described in Example 1. The results of this test are summarized in Table 3 below.

[Table] Note that similar results are obtained when solutions containing salts of the reaction products according to Production Examples A to Z, AA and BB are used.

Claims (1)

[Claims] 1. A method for surface sizing paper comprising impregnating the paper with an aqueous sizing liquid and drying the paper, the aqueous sizing liquid comprising: (a) 2,2-bis-(4'-hydroxyphenyl);
- polyglycidyl ether of propane 1.0 epoxide group equivalent; (b) monoaliphatic amine of at least one type with 12 to 24 carbon atoms 0.1 to 0.85 amino group equivalent; and (c) (c') 16 to 22 carbon atoms. A polyalkylene amino polyamide produced from a polymerized aliphatic unsaturated fatty acid derived from a fatty acid having 0.3 to 2 amino group equivalents and an aliphatic polyalkylene polyamine having (c″) 4 to 12 carbon atoms. and (d) if desired, from 0.1 to 1.0 mol of an epihalogenohydrin or from 0.1 to 1.0 mol of a nitrile of an ethylenically unsaturated monocarboxylic acid having 3 or 4 carbon atoms.
1.0 mol and (e) an acid in an amount of 10 to 40% by weight of at least one water-dispersible or water-soluble salt of the reaction product prepared in an inert organic solvent at a temperature up to 95°C; A method for surface sizing paper, characterized in that an aqueous sizing liquid containing a formulation with a pH value of 2 to 8 is used. 2. A reaction product produced from a polyglycidyl ether having an epoxide group equivalent of 5 to 5.5 equivalents/Kg of 2,2-bis-(4'-hydroxyphenyl)-propane as component (a), as a compound. The method according to claim 1, wherein the method uses a salt containing a salt of 3 As a blend, carbon atoms 16 to 16 as component (b)
Claim 1 using a product containing a salt of a reaction product produced from a monoaliphatic amine having 18 aliphatic amines.
The method described in Section 1 or Section 2. 4 As a compound, carbon atoms as component (c′)
4. A method according to any one of claims 1 to 3, characterized in that it comprises a salt of a reaction product prepared from ethylenically unsaturated fatty acids having 16 to 18 fatty acids. 5. Claim 1 in which the formulation contains a salt of a reaction product produced from diethylenetriamine, triethylenetetraamine or tetraethylenepentamine as component (c'')
4. The method according to any one of items 4 to 4. 6. The formulation contains a salt of a reaction product produced from a monoaliphatic amine and a polyalkylene amino polyamide, each having an amino group equivalent of 3 to 4 equivalents/Kg as components (b) and (c). The method according to any one of claims 3 to 5 for use. 7. Any of claims 1 to 6 in which the formulation contains a salt of a reaction product produced only from components (a), (b), (c), and (e). Method described in Crab. 8 As a blend, 1.0 epoxide equivalent of component (a), 0.4 to 0.8 amino group equivalent of component (b), and 0.3 to 0.3 of component (c)
8. The method according to claim 7, wherein a salt of a reaction product prepared from 1.5 amino group equivalents is used. 9 As a blend, 1.0 epoxide equivalent of component (a), 0.4 to 0.6 amino group equivalent of component (b), and 0.3 to 0.3 of component (c)
9. The method according to claim 8, wherein a salt of a reaction product prepared from 0.5 amino group equivalents is used. 10. Reaction products prepared from at least one inorganic acid, aromatic or aliphatic mono- or dicarboxylic acid having at most 20 carbon atoms or anhydride thereof as component (e), as a blend. 10. The method according to any one of claims 1 to 9, wherein a product containing a salt is used. 11 As a blend, hydrochloric acid, nitric acid as component (e),
Phosphoric acid, sulfamic acid, cycloaliphatic resin acid with 20 carbon atoms, aliphatic mono- or dicarboxylic acid with at most 18 carbon atoms, or 4 carbon atoms
11. The process according to claim 10, which comprises a salt of a reaction product prepared from an anhydride of an aliphatic or aromatic dicarboxylic acid having .about.8. 12 As a formulation, as component (e) phosphoric acid, sulfamic acid, rosin, aliphatic saturated monocarboxylic acids with 1 to 4 carbon atoms, dicarboxylic acids with 4 to 18 carbon atoms, 12 to 18 carbon atoms 12. The method according to claim 11, wherein the method comprises a salt of a reaction product prepared from a fatty acid, phthalic anhydride or maleic anhydride, having the following properties. 13 Orthophosphoric acid as component (e) as a formulation,
13. A process as claimed in claim 12, comprising salts of reaction products prepared from sulfamic acid, azelaic acid or rosin, optionally in the presence of acetic acid. 14. A method according to any of claims 10 to 13, using a formulation containing a water-soluble salt of the reaction product. 15. The method according to any one of claims 10 to 14, using a formulation having a PH value of 3 to 5.5. 16 Claim 14 or 15 using a formulation containing the salt of the reaction product in an amount of 25 to 35% by weight
The method described in section. 17. A method according to any one of claims 1 to 16, using a formulation comprising a salt of the reaction product prepared at 60-95°C in the presence of an inert organic solvent. 18 2 or 3 oxygen atoms as inert organic solvent
18. A process as claimed in claim 17, in which cycloaliphatic or aliphatic ethers having 1 and 2 to 8 carbon atoms are used. 19. The process according to claim 17, wherein alkanols having 1 to 4 carbon atoms are used as inert organic solvents. 20. The method according to any one of claims 1 to 19, wherein an aqueous size solution containing the salt of the reaction product in an amount of 0.02 to 0.2% by weight is used. 21. The method according to any one of claims 1 to 20, wherein the paper is dried at 60 to 140°C. 22. The method according to claim 21, wherein the paper is dried at 90 to 110°C. 23 (a) Polyglycidyl ether of 2,2-bis-(4'-hydroxyphenyl)-propane
1.0 epoxide group equivalent; (b) at least one monoaliphatic amine having 12 to 24 carbon atoms; 0.1 to 0.85 amino group equivalent; and (c') a fatty acid having 16 to 22 carbon atoms. (d) 0.3 to 2 amino group equivalents of a polyalkylene amino polyamide prepared from a polymerized aliphatic unsaturated fatty acid and (c″) an aliphatic polyalkylene polyamine having 4 to 12 carbon atoms; and (d) if desired. For example, epihalogenohydrin 0.1-1.0
moles or nitriles of ethylenically unsaturated monocarboxylic acids with 3 or 4 carbon atoms 0.1
and (e) an acid in an amount of 10 to 40% by weight of at least one water-dispersible or water-soluble salt of the reaction product prepared from ~1.0 mol and (e) an acid in an inert organic solvent at temperatures up to 95°C. , a paper surface sizing formulation with a pH value of 2 to 8. 24. A formulation according to claim 23 for use as a 0.02-0.2% by weight aqueous size liquid.