FI103353B - Process for making paper and cationic chemical - Google Patents

Description

103353

Paper making process and cationic chemical - Förfarande för framställning av papper och en katjonisk chemikalie

The present invention relates to a process for the production of paper or a similar fibrous product which comprises hydrophobising the paper or a corresponding fibrous product. The invention also relates to a cationic chemical which can be used as a hydrophobizing chemical, such as a bulk adhesive or a surface adhesive or as a fixative or dispersant.

In hydrophobic gluing of paper, the paper is made water repellent or hydrophobic and thereby prevents or slows down the penetration of aqueous liquids into the paper. Hydrophobation can be accomplished by hydrophobic bulk sizing, whereby a hydrophobic chemical is added to the aqueous fiber mass suspension prior to forming the web, or hydrophobic surface sizing, whereby a hydrophobic chemical is added to the pre-formed web.

Various types of synthetic paper-making chemicals are known, of which: - alkenyl succinic anhydride (ASA) described in U.S. Patent 3,821,069; alkyl isocyanate and resin anhydride, - quaternary organic ammonium salt, described in DE-A-36 34 277 A1.

The two largest market-dominated cellulose hydrophobic chemicals in the neutral region are currently ASA and AKD.

In the manufacture of paper, it is also possible to add auxiliary chemicals to a fibrous mass suspension, such as a wet strength chemical, i.e., a wet strength adhesive such as formaldehyde-urea adduct and dimethylol melamine, and a fixative such as polyaluminum chloride (PAC).

Known hydrophobic chemicals usually have one or more of the following disadvantages: - they are not water-soluble and require stabilizers when dispersed in water, - they are not adsorbed to the fiber surface efficiently by dilute aqueous solutions, - AKD and ASA are rapidly worked efficiently in the presence of a filler, and 5 - difficult to manufacture.

An essential ingredient of the composition described in DE-A-36 34 277 A1 is a polymer containing anionic groups, whereby the quaternary ammonium salt alone without the aforementioned polymer softens the paper fibers, resulting in a shorter paper break length.

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It is a general object of the invention to provide a cationic chemical which, when used as a hydrophobising chemical, avoids the above disadvantages and can also be used, for example, as a surface sizing agent, a fixative or a dispersing agent. It is also an object of the invention to provide a process for hydrophobizing a fibrous product using such a cationic chemical.

These objects have been achieved by the process of the invention and by the cationic chemical of the invention, the principal features of which are apparent from the appended claims.

Accordingly, the invention relates to a process for the production of paper or a similar fibrous product, characterized in that a cationic chemical is added to the paper or similar fibrous product to hydrophobize the paper or similar fibrous product having the formula

R 1 UX 'R 4 -n-R 3 1 R 2 wherein R 1, R 2 and R 3 are the same or different and each is a saturated or unsaturated acyclic, cyclic or aromatic hydrocarbon containing from 1 to 41 carbon atoms, R 4 is a saturated or an unsaturated acyclic, cyclic or aromatic hydrocarbon containing at least one oxygen atom, and X "is an anion.

The invention further relates to a cationic chemical for the hydrophobization of paper or a similar fibrous product, characterized in that it contains a moiety of a compound having 30 OH groups and a quaternary ammonium salt and has the above formula I and has the ability to adhere anionic surfaces.

When unsaturated, the hydrocarbon radicals R 1 to R 4 may contain one or more double bonds. The hydrocarbon groups R1-R4 may be derived from a fatty acid deprotection. Examples of such suitable fatty acids include stearic acid, palmitic acid, linoleic acid, oleic acid, montanic acid, pinolenic acid and tallow fatty acid. The hydrocarbon groups R1-R4 may also be derived from resin acid or dispro-resin containing fused ring structures.

For example, the oxygen atom in R 4 may be part of a chain (e.g. ether or ester) or part of a cyclic structure (e.g. cyclic ether) or may be a hydroxyl substituent.

A preferred group of compounds are those compounds of formula I wherein R 4 is a glycidyl group.

Another preferred group of compounds are compounds of the formula

Rl 1+ X '

B-O-A-N-R3 II

R 2 wherein R 1, R 2, R 3 and X "have the same meaning as in formula I, A is a hydrocarbon containing from 1 to 6 carbon atoms which may contain one or more oxygen atoms, and B is a saturated or unsaturated acyclic, cyclic or aromatic hydrocarbon B may be derived from an alcohol such as a polyol (such as Penta 20 E or starch).

A third preferred group of compounds are those compounds of formula O R j Y-

Il 1 + x

R-C-O-A-N-R3 III

r 2 wherein R 1, R 2, R 3, X "and A have the same meaning as in formulas I and II and R is a saturated or unsaturated acyclic, cyclic or aromatic hydrocarbon containing from 1 to 41 carbon atoms. R may be derived from a carboxylic acid.

4 103353 X "is preferably halogen, but it may also be another anion moiety.

In one embodiment of the invention, in Formula I, two of R 1 -R 3 are a hydrocarbon group containing 7 to 20 carbon atoms and the third is an alkyl group of 1 to 6 carbon atoms, such as methyl, R 4 is propylene oxide and X "is halogen.

In another embodiment of the invention, in Formula I, one of R 1 -R 3 is a hydrocarbon group containing 7 to 20 carbon atoms and the other two groups are alkyl groups of 1 to 6 carbon atoms, such as methyl, R 4 is propylene oxide and X "is halogen.

In a third embodiment of the invention, in Formula II, R 10 and B are hydrocarbon groups having 7 to 41 carbon atoms, R 1 and R 2 are alkyl groups of 1 to 6 carbon atoms, such as methyl, A is hydroxypropyl and X "is halogen.

In a fourth embodiment of the invention, in Formula III, R3 and R3 are hydrocarbon groups containing 7 to 41 carbon atoms, R 1 and R 2 are alkyl groups of 1 to 6 carbon atoms, such as methyl, A is hydroxypropyl and X 'is halogen.

According to a preferred embodiment, said cationic chemicals are added as a bulk adhesive to an aqueous fibrous pulp suspension, optionally containing a filler, optionally adding a retention agent to the fibrous pulp suspension. The filler may, for example, be calcium carbonate. Said cationic chemicals can also be used as a surface sizing agent, whereby they are applied to the web by an adhesive press. In this case, a known mass adhesive such as ASA or AKD may be used as the mass adhesive.

The process of the invention may further comprise a maturation treatment at elevated temperature, wherein the maturation temperature is preferably about 110-140 ° C and the maturation time is preferably about 1-120 min.

Said cationic chemicals are typically added in an amount of about 0.01 to 2% by weight, preferably about 0.3 to 0.6% by weight, based on the dry weight of the fiber.

The cationic chemical of formula I can be used in combination with known auxiliary chemicals which chemically bond the chemical to the fiber. Such auxiliary chemicals include, for example, wet bone adhesives such as formaldehyde urea adduct and 5 103353 dimethylol molelamine, and other chemicals known to those skilled in the art.

The process of the invention is suitable for hydrophobising not only paper but also other fibrous products such as cardboard.

Compounds of formula I wherein R 4 is a glycidyl group can be prepared, for example, by reaction of a glycidyl halide with an amine R 2 R 3 NR 2 to give the desired product in high yield. This reaction can be carried out under NTP conditions. The compound of formula I may also be prepared by any other method well known to those skilled in the art.

Compounds of formula II may be prepared by reacting an alcohol of formula

B-OH IV

wherein B is as defined above, reacting with 2,3-epoxypropylammonium halide of the formula O 1 R 1/1 + x * ch 2 -ch-CH 2 -N-R 3 v r 2 wherein R 1, R 2, R 3 and X " have the same meaning as above.

Compounds of formula III may be prepared by reacting a carboxylic acid of formula

O

II

R-C-OH VI

wherein R is as defined above, with a 2,3-epoxy-20 propylammonium halide of formula V.

The compound of formula V used as starting material can be prepared by reacting the glycidyl halide with the amine R 2 R 3 NR 1 to give the desired product in high yield. This reaction can be carried out under NTP conditions. The compound of formula V may also be prepared by any other method well known to those skilled in the art.

Ä 103353

O

Advantageous and surprising features of the invention are the compounds of the invention being water-soluble or readily dispersible in water, the compounds of the invention adhering to the fiber surface from dilute aqueous solutions (cf. Table 5 below), maturing the fibrous material to which the compounds of the invention täysliimaus; Cobb 60 <20 (cf. Table 1 below), works under both neutral and acidic conditions, 10 - various types of cellulose and their mixtures can be used (e.g. pine, spruce, groundwood; cf. Table 1 below), also works in the presence of a filler (CaCC> 3 2-20%) (see Table 1 below), adjusting the lengths of the hydrocarbon chains B / R and R1-R3 can reduce the maturation time of the chemical used in dosing / temperature (cf.

Table 1 below), also serves e.g. as a fixative where it is 2-3 times more potent than PAC (cf. Tables 3 and 4 below), can be chemically bonded by means of an epoxy group or the remaining OH group 20 (cf. below) Table 7), chemical anchoring enhances hydrophobization (see Table 6 below) ·

The Cobb value, or water absorption of paper, refers to the amount of water that the surface of the paper absorbs from a 1 cm water column over a given time. The lower the Cobb value, the better the gluing result. The Cobb method is further described in SCAN-P 12:64.

The invention will now be described in more detail by way of examples and experiments. Example 1 (Formula I; R 1 = dodecyl, R 2 and R 3 = methyl, R 4 = 2,3-epoxypropyl) A cationization reagent is prepared which contains one long hydrocarbon chain. The starting materials used are epibromohydrin and dodecyldimethylamine. The reaction is carried out, for example, according to the method mentioned in BE Patent 671 687. The product has an epoxide content of about 90%.

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Example 2 (Formula I; R 1 = tallow hydrocarbon, R 2 and R 3 = methyl, R 4 = 2,3-epoxypropyl)

The reaction is carried out according to Example 1 using dimethylitalamine as the amine.

The product has an epoxide content of about 80%.

Example 3 (Formula I; R 1 = tallow hydrocarbon, R 2 and R 3 = methyl, R 4 = 2,3-epoxypropyl)

The reaction is carried out according to Example 2 using epichlorohydrin as the epoxide source. The product has an epoxide content of about 80%.

Example 4 (Formula I; R 1 = methyl, R 2 and R 3 = tallow fat, R 4 = 2,3-epoxypropyl)

Prepare a cationization reagent containing two long hydrocarbon chains. Epibromohydrin and dital fat methylamine are used as starting materials. The reaction is carried out according to the method mentioned, for example, in U.S. Patent No. 671,687. The product has an epoxide content of about 80%.

Example 5 (Formula I; R1 = methyl, R2 and R3 = tallow fat, R4 = 2,3-epoxypropyl)

The reaction is carried out according to Example 4 using epichlorohydrin as the epoxide source. The product has an epoxide content of about 80%.

Example 6 (Formula III; R = saturated acyclic hydrocarbon, A = hydroxypropyl, R 1 = R 2 = R 3 = methyl)

Weigh 50 g of a mixture of stearic acid and palmitic acid, a commercial product 25 (about 60% palmitic acid and about 40% stearic acid).

This is dissolved in 2-propanol and poured into the reaction vessel. The solution is heated at 100 ° C in an oil bath with stirring.

8 103353

100 g of 2,3-epoxypropyltrimethylammonium chloride are added. Stirring is continued at the same temperature, after which the mixture is poured into a separatory funnel and allowed to cool to room temperature. Two phases are obtained. The lower phase contains excess cationic reagent. The upper phase contains the product and 2-propanol. The upper phase 5 is washed with water and the 2-propanol is evaporated off. Analysis of the reaction product was performed, e.g., by FT-IR, which gave a peak value of 1708.9 / 1737.3 for acid / ester signals.

Example 7 (Formula III; R = unsaturated acyclic / saturated acyclic hydrocarbon having one or more double bonds, A = hydroxypropyl, R 1 = R 2 = R 3 = methyl)

The reaction is carried out according to Example 6 using as the acid a fatty acid, typically consisting of oleic acid, linoleic acid, pinolenic acid, palmitic acid and stearic acid. Analysis of the reaction product was performed, e.g., by FT-IR, which gave a peak value of acid / ester signals of 1695.0 / 1720.6.

Example 8 (Formula III; R = unsaturated cyclic / saturated or aromatic hydrocarbon having one or more double bonds, A = hydroxypropyl, R 1 = R 2 = R 3 = methyl)

The reaction is carried out according to Example 6 using as the acid a resin acid or a dispro-resin, typically consisting of abietic acid, levopimal acid, palutric acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, pimalaric acid. Analysis of the reaction product was carried out, e.g., by FT-IR which gave a peak value of 1707.3 / 1738.3 for acid / ester signals.

Example 9 (Formula III; R = saturated acyclic hydrocarbon, A = hydroxypropyl, R 1 = dodecyl, R 2 = R 3 = methyl)

In the first step, a cationization reagent is prepared which contains one long hydrocarbon chain. The starting materials used are epibromohydrin and dodecyldimethylamine. The reaction is carried out, for example, according to the process disclosed in BE 671 687. The product has an epoxide content of about 90%.

9 103353

In the second step, a water-soluble chemical containing two long carbon-hydrogen chains is prepared according to Example 6. Analysis of the reaction product was performed, e.g., by FT-IR, which gave a peak value of 1708.9 / 1736.6 for acid / ester signals.

Example 10 5 (Formula III; R = saturated acyclic hydrocarbon, A = hydroxypropyl, R 1 = R 2 = R 3 = methyl)

The reaction is carried out according to Example 6 using Montan wax as an acid. Analysis of the reaction product was carried out, e.g., by FT-IR, which gave a peak value of 1708.9 / 1737.3 for the acid / ester signals.

Example 11 (Formula III; R = saturated acyclic hydrocarbon, A = hydroxypropyl, R 1 = tallow derived hydrocarbon, R 2 = R 3 = methyl)

The first step of the reaction is carried out according to Example 9 using dimethylitalamine as the amine. The product has an epoxide content of ~ 80%. The second step of the reaction is carried out as in Example 6. Analysis of the reaction product was carried out, e.g., by FT-IR which gave a peak value of 1708.9 / 1736.6 for acid / ester signals.

Example 12 (Formula II; B = starch, A = hydroxypropyl, R1 = methyl, R2 and R3 = tallow hydrocarbons)

The first step of the reaction is carried out according to Example 7 using dital fat methylamine as the amine. The product has an epoxide content of ~ 80%.

The second step is carried out, for example, according to the method mentioned in U.S. Patent 2,516,633, using barley starch as starch. Analysis of the reaction product was performed, for example, by a total nitrogen assay which gave a DS (degree of substitution) of 0.1.

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Test 1 103353

Use of the Compound of the Invention as Bulk Adhesive The test results are shown in Table 1 below.

table 1

Chemical Mass Maturation Maturation Dosage Retentio Cobb 60 example temperature working time no ___ == ^ ========= (Type) (° C) (min) {% mas- (% portion- / After food.

_____of_the) maturation 4 100% brown 125 5 0.15 42 / 28.9 pulp, _4% CaC03______ 6 100% pine 130 60 1.75__20 111/25 7 ____ ”____ 15__125 / 105 8 __” ____ l__119 / 100 8 __ "__-__-__ 20__ 120 / 93.5 9 __u ___" __ "__ 04__50 110/20 70% Pulp 9 30% Pine __" ____ 03__142 / 20 2% CaC03 10 100% Pine __ ^ __ 2.5 0.2__104 / 48 100% Pine 11 10% CaC03 HI 5 1 0.4 I - 112/18 PILOT Test Run ______ 100% Pine 11 20% PCC 110-115 2.5 0.4 __- / 21_ 70% Grind 11 30% Wreck 110-115 15 0, 5 - - / 20 - 2% CaCO 3 _____ 5 PCC stands for doped calcium carbonate.

Experiment 2

Use of a compound of the invention as a surface adhesive

A 2.5% aqueous solution of the product of Example 4 in 10 paper containing 30% pine pulp and 70% birch pulp supplemented with 103353 π 20% PCC (precipitated calcium carbonate) was tested as the surface sizing agent. Both AS Aita and AKD were used as glue.

When using ASA as a mass adhesive, the Cobb 60 instant value was obtained at 71.7 and the Cobb 60 oven (125 ° C / 5min) was 15.6.

Using AKD as a stock adhesive, the Cobb 60 was set to 20.7 and the Cobb 60 (125 ° C / 5min) to 17.5.

Experiment 3

Use of another compound of the invention as a surface adhesive

As the top sizing, 2.5% aqueous dispersion of the product of Example 12 in paper made from 100% pine pulp was tested. For comparison, a commercial SMA (styrene maleic anhydride) adhesive was used. The results are shown in Table 2.

Table 2 Chemical used Maturation time Maturation temperature Cobb 60 value (min) (° C) SMA = 2 ^ 5 Π5: 22

2.5 115 22 Chemical according to Example 12 15 Test 4

Use of a compound of the invention as a fixative

As a fixative, a 1% aqueous solution of the product of Example 2 in a coated wreck with a consistency of 2.53% was tested. The filtrate turbidity: change as a function of chemical dose was measured and compared with corresponding values obtained with PAC (polyamine chloride). The results are shown in Table 3.

12 103353

Table 3

Chemical - Turbidity, PAC - Turbidity,

dosage of NTU dosage of NTU

(%) * 103 (%) * 103 0.1 0.204 0.4 0.274 0.3 0.147 0.8 0.260 1.0 0.075 1.0 0.240

Experiment 5

Use of a Second Compound of the Invention as a Fixative A 1.5% aqueous solution of the product of Example 10 in peroxide bleached TMP having a consistency of 3.8% was tested. Measurements were made according to Experiment 3. The results are shown in Table 4.

Table 4

Chemical - Turbidity, PAC - Turbidity,

dosage of NTU dosage of NTU

(%) * 103 (%) * 103 0.05 0.196 0.3 0200 0.1 0.177 0.6 0.141 0.3 0.172 1.0 0.073 1.0 0.036 1.5 0.048 10

Experiment 6

Adsorption of a chemical according to the invention

The chemicals of the invention shown in Table 5 below were prepared in a manner similar to Example 6 using stearic acid, abietic acid, oleic acid and resin acid.

The results of adsorption measurements are shown in Table 5.

13 103353

Table 5

Chemical Dosage amount Adsorbed fiber dry amount of fiber matter (%) dry matter (%)

Stearic Acid Derivative__1.75__0.55_ __2J5__0.90

Abietic Acid Derivative__1.75__0.16_ Oleic Acid Derivative__1.00__0.15_ __K75__0.37

Hartsihappojohdannainen_1,75__0,14_

Experiment 7

Cobb average values of 60 s, g / m 2 before and after maturation (1 h, 125-128 ° C) using the chemical of the invention alone or in combination with a known wet-glue or using a wet-glue known as a reference chemical alone

The chemical of the invention shown in Table 6 below was prepared in a manner similar to Example 6 using stearic acid.

The experimental results are shown in Table 6 below.

Table 6

Chemical Cobb 60 s, g / m ^ -ka. Cobb 60 s, g / m ^ -ka.

1.75% pre-ripening after maturation

Formaldehydiurea Adduct (Comparison) __ 1_12__94,8_

Dimethylol melamine (comparison) __ 1_10__94,5_: Stearic acid derivative__111,5__26_

Stearic Acid + Formaldehydiurea Adduct__97,3__20,6_

Stearic Acid + Dimethylolimelamine__93,6__21,6_

Test 8 14 103353

To determine the amount of adhesive chemically adhered to the fiber of the invention, a certain percentage of adhesive was applied to a suitable number of sheets. The sheets were weighed dry and then extracted with boiling methanol overnight. After these 5 treatments, the amount of glue chemically adhered to the sheets was calculated according to the following equation: weight of sheets prior to extraction - mass of substance removed during extraction = amount of chemically adhered. Calculations include material removed from non-adhesive sheets. The experimental results are shown in Table 7 below.

The chemical of the invention shown in Table 7 was prepared in a manner similar to Example 6 using stearic acid.

Table 7

Chemical Cobb 60 s, Chemically bonded 1.75% adhesion in g / m 2. before nut chemical (%) _curing

Stear.happojohdannainen__106__0_

Stearic Acid + Formaldehydiurea Adduct__85,6__627_

Stearic Acid + Dimethylolimelamine__80__8 ^ 2_

Claims (11)

103353 A process for the production of paper or similar fibrous product, characterized in that a cationic chemical is added to the paper or similar fibrous product to hydrophobize the paper or similar fibrous product, wherein the cationic chemical has the formula R 1+ X 1 r 4 -n-r 3 the same or different and each is a saturated or unsaturated acyclic, cyclic or aromatic hydrocarbon containing from 1 to 41 carbon atoms, R 4 is a saturated or unsaturated acyclic, cyclic or 10 aromatic hydrocarbon containing from 1 to 41 carbon atoms containing at least one oxygen atom, and X "is an anion . A process according to claim 1, characterized in that the cationic chemical added to the paper or the like fiber product has the formula 1 wherein R 4 is a glycidyl group. A process according to claim 1, characterized in that the cationic chemical added to the paper or the like fiber product has the formula I wherein R 4 is a group BOA or O II RCOA - wherein A is a hydrocarbon containing 1 to 6 carbon atoms which may contain one or more 20 oxygen atoms, and B and R are the same or different and each is a saturated or unsaturated acyclic, cyclic or aromatic hydrocarbon containing from 1 to 41 carbon atoms. A process according to any one of the preceding claims, characterized in that said cationic chemical is water-soluble or readily dispersible in water. A method according to any one of the preceding claims, characterized in that said cationic chemical is added to an aqueous pulp suspension which may optionally contain a filler, and optionally a retention agent is added to the pulp suspension. Process according to any one of the preceding claims, characterized in that it further comprises a maturation treatment at elevated temperature, wherein the maturation temperature is preferably about 110-140 ° C and the maturation time is preferably about 1-120 minutes. A process according to any one of the preceding claims, characterized in that said cationic chemical is added in an amount of about 0.01 to 2% by weight, preferably about 0.3 to 0.6% by weight, based on the dry matter of the fiber. 8. A cationic chemical for the hydrophobization of paper or a similar fibrous product, characterized in that it contains a moiety of a compound having an OH group and a quaternary ammonium salt moiety and has the formula R 1+ X 1 R 4 -N-R 3 R 2 wherein R 1, R 2 and R 3 are the same or different and each is a saturated or unsaturated acyclic, cyclic or aromatic hydrocarbon containing from 1 to 41 carbon atoms, R4 is a saturated or unsaturated acyclic, cyclic or aromatic hydrocarbon containing from 1 to 41 carbon atoms and containing at least one oxygen atom, and X "is an anion, and has the ability to adhere to anionic surfaces. A chemical according to claim 8, characterized in that in formula I R 4 is a glycidyl group or a group BOA or O: RCOA- wherein A is a hydrocarbon containing from 1 to 6 carbon atoms which may contain one or more oxygen atoms and B and R are the same or different and each is a saturated or unsaturated acyclic, cyclic or aromatic hydrocarbon containing from 1 to 41 carbon atoms. 103353 A chemical according to claim 8 or 9, characterized in that it is in the form of an aqueous solution or dispersion. A chemical according to any one of claims 8 to 10, characterized in that it is used in the manufacture of paper or similar fibrous product as a pulp or surface adhesive or as a fixative or dispersant.