FI67737C - FOERFARANDE FOER ATT FRAMSTAELLA VATTENDISPERSIONER FOER FOERSTAERKTA HARTSER - Google Patents

Description

R35 ^ T1 ri mv * ANNOUNCEMENT, nn-, n ro ^ UTLACGNINCSSKRIFT 6/7 57 ^ '(51) KvMtflMLct D 21 H 3/32 FINLAND — FINLAND (21) 77,676 (22) Hakembptlv · —AnaBtcningidag 25.05.77' ' (23) AlkypM ^ GlMcMKtae 07.05.76 (41) Mk HUnU —IMt «KMillt no. , 77

Patent and Registration Administrators' _ ._ _. . (44) NUKMUfMM and moonshine date. -

Patent- och refisterstyrelsw v 'Anfikan uthgd oeh utUkrtton publtond 31.01.85 (32) (33) (31) Pyr1 · »/ etMoiksM» —Begird prtorttat (71) Hercules incorporated, Wilmington, Delaware 19899, USA (US) (72) Paul Harwood Aldrich, Greenville, Delaware, USA (74) Oy Hei nänen Ab (54) Process for the preparation of aqueous dispersions of reinforced resins - Förfarande för att framställa vattendispersioner förstärkta hartser (62) Separated by application 1586/74 (patent 63433) The present invention relates to a new process for the preparation of substantially stable aqueous dispersions from a finely divided rosin-based substance.

Aqueous dispersions prepared in accordance with the present invention are particularly useful in the manufacture of finished paper using papermaker's alum (aluminum sulfate) or similar precipitants commonly used in such cases to precipitate a resin-based material into paper fibers. The dispersions of this invention can be used in internal finishing methods and external finishing methods. In the internal finishing, the dispersion and alum are sonicated separately in the aqueous suspension of paper pulp fibers in the stages before the sheet is made, and in the external finishing, a paper web is first made **. · * Is then treated by known methods using an aqueous dispersion to obtain a finished paper. The water dissipation compositions made in accordance with the present invention can be used to make paper products such as paper webs having good resistance to the penetration of 67,737 μl of water and aqueous inks. The process of the present invention provides a substantially stable aqueous dispersion of a resin-based material suitable for use in finishing cellulosic pulp fibers. The essential features of the invention will become apparent from the claims.

Anionic dispersants are known in the art. In carrying out the process of this invention, a preferred anionic dispersant is a soap such as sodium soap or a resin-based agent such as a resin-based agent included in the dispersion. Other suitable anionic dispersants include synthetic extraction agents such as salts of alkylarylsulfonic acid, salts of condensed naphthalenesulfonic acids, salts of dialkyl esters of sulfomeric resin, salts of alkyl half-esters of sulfuric acid and alkylene of sulfuric acid (polyethylene).

In the case of an alkylarylsulfonate, the alkyl group may be straight-chain or branched having 10 to 18 carbon atoms. Various mixtures of these alkylarylsulfonates can be used. The preferred aryl group is phenyl. Sodium alkyl benzene sulfonates, which are particularly useful, are commercially available under various trade names, such as Ultrawet D.S. (Arco Chemical Co.). Condensed salts of naphthalenesulfonic acids are also available under various trade names, such as Tamol S.N. (Rohm & Haas Co.) and Stepantan A (Stepan Chemica1 Co.).

In the case of salts of dialkyl esters of ruleric succinic acids, the alkyl group may be cyclohexyl, hexyl, isobutyl, octyl, pentyl and tridesil. In the case of salts of olole alkyl esters of sulfuric acid, the alkyl group may have from 10 to 18 carbon atoms. In the case of salts of alkylphenoxy (polyethyleneoxy) ethanolic esters of sulfuric acid, the soniva alkyl group is a namyl group obtained by trimerization of propylene. The rolyoxyethylene content may be on average 1 to 20 moles per mole, but the average number is preferably 4 to 12. The amount of synthetic emulsifier used is 1 to 5, with 1 to 5 to 2.5% being preferred based on the amount of resin-based substance.

3,67737 When using synthetic emulsifiers other than alkyl aryl sulfonates, it is important that the aqueous solution, unstable dispersion, or final emulsion is not kept at temperatures above 100 ° C for more than a few minutes, otherwise the emulsifier may decompose by hydrolysis. As a result, it is advantageous to use a continuous process for heating and emulsification as well as rapid cooling.

The plastic-based materials used may contain 0-95% by weight of resin and 100 -n. 5% by weight of a resin adduct reaction support and an acidic compound having an -E = = - E = O group, wherein the amount of the acidic compound added is about 1 to 20% of the total weight of the solids.

As mentioned above, the preferred anionic dispersant is a soap or a salt of a resin-based agent. In addition, according to a preferred embodiment of the present invention, a relatively small amount of the resin-based substance may be present as a soap or a salt thereof which acts as an anionic dispersant. Unless otherwise required, other anionic dispersants may be added if desired.

Thus, either a small amount of saponified resin or a small amount of saponified resin adduct, or a small amount of both, may be present. The amount of saponified resin-based substance present as said percentage of available saponified carboxyl groups is from about 0-5 to about 20%, and preferably from about 4% to about 10%. The preferred amount of solids in the dispersion is from 0 to about 85% by weight of the resin adduct and from 100 to about 15% by weight of the resin adduct, wherein the amount of the acidic compound as an adduct is about 4 to about 8 1% and the saponified resin-based resin adduct. the amount of the substance present, calculated as a percentage of the saloonized knoxoxy groups used, is about 4 to 10

A suitable way to prepare an unstable aqueous dispersion is to mix together the desired amount of water, the desired amount of resin-based agent and an alkaline agent such as sodium hydroxide in amounts sufficient to provide the desired amount of saponified resin-based agent.

4,67737

It is not necessary that the sonicated resin-based substance be prepared in a mixture, i.e. in situ. If desired, it can be prepared before preparing an unstable aqueous dispersion. Thus, for example, an unstable aqueous dispersion may be prepared by mixing together a water, a resin-based agent and a saponylated resin-based agent such as the sodium salt of an adductive resin in amounts sufficient to provide various amounts of the above-mentioned unstable aqueous dispersion. This method can be used if other anionic dispersants are also used. Thus, for example, before homogenization, an unstable aqueous dispersion is prepared by mixing water, a resin-based agent and an anionic dispersant.

After preparation of the unstable aqueous dispersion: it is heated to temperatures of about 150 ° C to 195 ° C. In this case, the mixture is stirred until the desired temperature is reached. The heated dispersion is then subjected to a very strong rubbing effect, whereby a substantially stable aqueous dispersion is obtained. A very strong friction effect is preferably obtained by using the homoyenizer Oria. In this case, the heated mixture is passed at least once through a homogenizer using a pressure of the order of about 140 to about 560 bar, whereby a substantially stable dispersion is obtained.

The aqueous emulsion is then cooled to provide the novel dispersions of this invention. Cooling can be performed using conventional means, but it is preferred that the emulsion be passed to a cooling coil where it cools rapidly.

This coil contains a cooled emulsified product which is pumped through a heat exchanger. The pressure in the coil is kept so high that evaporation of the product is prevented.

Certain particles may form heavy agglomerates which may possibly separate from the dispersion after a certain period of time. These can be readily removed from the substantially stable dispersion, if desired, by filtration, decantation, or other means known in the art.

The particles contained in the di-operated phase are relatively small in size and have a particle size of about 0.01 microns, - about 1 micron. ;

At least 90 of the weighted bent particles have a particle size of less than about 0.5 microns. '

When the resin is used as part of a resin-based substance, it may be a commercial type of resin such as wood resin, rubber resin, tall oil resin, or rosin, or a mixture thereof in either crude or purified state. Partially or substantially completely hydrogenated resins and polymerized resins as well as resins which have been treated to prevent crystallization, for example by heat treatment, i.e. by reaction with formaldehyde, can be used as well as mixtures thereof.

The adduct reaction product of a resin acidic compound having a group -Q = E - E = O is prepared by reacting the resin and an acidic compound at elevated temperatures of about 150 ° C to 210 ° C. Methods for preparing these adduct reaction products are described in U.S. Patent Nos. 2,628,918 and 2,684,300. These adduct reaction products are often referred to as Diels-Alder reaction products. The addition products are used in the following ?. sometimes also referred to as "resin adduct", "adduct" and "reinforced resin".

Examples of embarrassing compounds containing the group -p = CQ = C which can be used for the preparation of adducts are * = <, β-unsaturated polybasic organic acids and their known anhydrides, typical examples of which are fumaric acid, maleic acid, acrylic acid, maleic acid, maleic acid, itaconic acid, itaconic anhydride, hydraconic acid and citraconic anhydride.

The resin used in the preparation of the adduct products may be of any commercially available type of resin such as wood resin, rubber resin, tall oil resin or a mixture thereof in either their crude or purified state. Hydrogenated resins can also be used, as well as resins that have been treated to prevent their crystallization. It is also possible to use an adduct which is substantially completely hydrogenated after preparation of the adduct.

Suitable time substances which form a salt with the resin and resin adducts are the usual inorganic and organic basic substances used in the preparation of the saponified resin or saponified resin adduct. Examples of these are 6,67737, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, ammonia, and water-soluble amines such as morpholine, ethylamine, n-propylamine and n-butylamine. Preferred alkaline agents are potassium hydroxide and sodium hydroxide.

As mentioned above, salts or soaps obtained by the reaction of a resin or resin adduct with an alkaline agent can be used to prepare an unstable aqueous dispersion as well as other anionic dispersants if desired. Sodium soap of the adduct resin is one example of such a salt, i.e. soap, and can be prepared by adding hot aqueous sodium hydroxide solution to the molten adducted resin and maintaining the temperature of the reaction mixture at about 110 ° C until the reaction is substantially complete.

The resin-based materials present in the dispersion may all be derived from the same source of resin or from different sources of resin. Thus, for example, the resin component may be a mixture of substantially fully hydrogenated wood resin and unrefined wood resin, wherein the adduct component may be an adduct of unrefined wood resin and fumaric acid, and the sonicated substance acting as a dispersing agent may be a rubber resin. As another example, the resin component may be a pine oil resin, the adduct component may be an adduct of a wood resin and maleic anhydride, and the saponified agent may be a potassium salt or soap of a maleic acid adduct of a tall oil resin. In another example, the resin component may be a mixture of a partially hydrogenated wood resin and tall oil resin, the adduct component may be a mixture of a partially hydrogenated wood resin and fumaric acid, and the saponified agent may be a potassium salt of an adduced hydrogenated wood resin. The use of other and different combinations of components will be apparent to those skilled in the art.

The amount of saponified substance, i.e. the amount of salt of the resin adduct present in the aqueous suspension which acts as a deepener is such as to provide the desired stable dispersion. The amount of saponified substance present is expressed as a percentage of the total amount of available carboxyl groups (-COOH) present and reacted to form a salt (hereinafter referred to as "soap"), such as the sodium salt of 7,67737 (-COONa). ). For simplicity, this value is used in practical examples as "saponifoitumiBaste". For example, the phrase "degree of saponification 4" in the examples means that 4% of the carboxyl groups initially available have reacted, i.e. saponified with alkali. The degree of saponification may vary from 0.5 i ° to 20 i °, but is most preferably in the range of about 4 i ° to about 10. It should be noted that the acids from which the resin is formed contain one available carboxyl group. has reacted with an acid ynd: steer, as described above, to give a reinforcing resin, i.e. an added resin, other products may be used in the reaction product. carboxyl groups other than those contained in the reacted acidic compound.

Thus, according to a preferred embodiment of the invention, the process of the present invention is carried out by substantially homogenizing, at a pressure of about 140 to 560 bar, an aqueous dispersion heated to a temperature of about 125 ° C to about 180 ° C and most preferably about 130 to 10 ° C, said aqueous dispersion comprising substantially from about 50% to about 70% by weight of water and from about 25% to about 50% by weight of solids, wherein the solids contain substantially 0-95% by weight of resin and 100-5% by weight of> 6 resin adduct reaction product, and the acidic compound contains a group -0 = 0-0 = 0, wherein the amount of adducted acid amide compound is from about 1 to about 20% of the total solids, and wherein a relatively small amount of the resin-based material is saponified, expressed as a percentage of available carboxyl groups of the resin-based material. 0.5 to about 20%.

In the following examples, all parts and percentages are by weight and by weight. unless otherwise stated.

Example 1 illustrates the preparation of a shoulder adduct product. Example 1 160 parts of fumaric acid were added at elevated temperature with melted tall oil resin (840 parts). Fumaric acid dissolved in the molten tall oil resin and reacted with it to form a reaction mixture. After reacting the fumaric acid almost completely with the tall oil resin, the reaction mixture or product was allowed to cool to room temperature 8,67737 (about 23 ° C). The reaction mass is a mixture of an unreacted resin and a resin-fumaric acid reaction product, i.e. an adduct. The reaction product contains 16 tfo of fumaric acid, of which substantially all has reacted. The acid number of the reaction product was 240.

The following examples illustrate the invention when using resin-based soap as the anionic dispersant.

Example 2 1940 parts of wood resin, about 11 parts of CO adduct prepared according to Example 1, 4290 parts of water and 370 parts of 10% aqueous sodium hydroxide solution were mixed together and heated to about 175 ° C. The resulting hot mixture was passed through a homorenizer at a pressure of about 200 bar to give a dispersion which was immediately cooled to room temperature by passing it through a cooling coil. The stability of said dispersion was good and its solids content was about $ 40>. About 6% by weight of the solids was added fumaric acid. The degree of saponification was 7.1 °

Example 3

About 3,000 parts of an adduct containing 6% fumaric acid from formaldehyde-treated tall oil resin, 4,730 parts of water and 740 parts of 10% aqueous sodium hydroxide solution were mixed together and heated to about 170 ° C. The resulting heated mixture was passed through a homorenizer at a pressure of about 200 bar to give a dispersion which was immediately cooled to room temperature by passing it through a cooling coil. The resulting dispersion had good stability and a solids content of about 35 1 °. About 6 i <> by weight of solids contained adduced fumaric acid. The degree of saponification was 15

The finishing effect of the suspensions of Examples 2 and 3 was tested by making handmade sheets using varying amounts of solid finishes. To make the handmade sheets, the bleached Rayonier pulp suspended in standardized hard water was suspended and ground to 750 milliliters at an S-R degree of grinding in a Noble and Wood batch mill. Finishing additives were made in 2-liter portions of a ground slurry diluted 9,67737 to a solids of 2.5.

So much alum was added to each finisher-containing slurry that the pH became 4.5, after which the slurry was diluted to a consistency of 0.27 in a proportional mixer using acid already containing alum-containing dilution water.

The dilution water was prepared by lowering the pH of the water to a value of 5.0 of medium hardness with sulfuric acid, followed by the addition of so much alum that the amount of soluble Aluminum was 5 ppm. One liter portions of the pulp slurry obtained in a proportional mixer were further diluted with acid-alum dilution water in a deckle box to a consistency of 0.025 in order to obtain an 18.2 kg so-called basic weight (61 cmx91 cm- 500 sheets of rice). A closed white water system was used. The prepared sheets were wet pressed to 33 ° C containing solids and then dried at about 110 ° C (240 ° F) using a steam tumble dryer. All handmade sheets were conditioned for about two days at a temperature of about 23 ° C and 50% relative humidity and then tested under these conditions. The resistance to penetration of the test ink Test Ink 42 was tested using a Hercules Sizing Tester. The time required for the ink to penetrate to reduce the light reflectance to 80 i <> of the original value of the sheet was a measure of the degree of finishing.

The following Table I shows the finishing results obtained with a photometer using the finishing agents according to the examples when the finishing agent concentrations were 0.5. The finishing agent concentration is calculated by weight and is based on the weight of the dry pulp. Thus, for example, a finishing alum content of 0.5 means that 0.5% by weight of solids is added to the aqueous suspension referred to in each example, based on the amount of dry paper pulp therein.

Table I

Finishing agent from the example Finishing measured with a photometer as a function of the concentration of finishing agent_ 0.3 already 2 130 3 120 10 67737

As mentioned above, anionic disinfectants other than those based on resin can also be used in the preparation. dispersions of this invention. The upper limit on the amount of such anionic dispersants is critical, as the excess may have a detrimental effect on the final composition and may vary depending on the effectiveness of the dispersant used. As much as 5% (based on the amount of resin-based substance) of dispersant can be used, although preferably 25 ° is the upper limit. The lower limit is that which provides a stable dispersion when using particles of 0.1 to 1 micron in the finishing agent. The minimum amount for these requirements is about 1 i although in many cases 1.5 i'-lls gives better results. The shy finishing agent is used in combination with a resin-based disoergent, an amount as small as 0.1% can be used.

The following examples illustrate the use of other anionic dispersants.

Example 4

About 1000 parts of a 7.5 1 ° fumaric acid adduct of formaldehyde-treated tall oil resin, 1425 parts of water and 75 parts of Ultrawet 30DS (30 l of solid sodium alkyl alkyl benzene sulfonate) were mixed together and heated to about 170 ° C. The resulting hot mixture was passed through a homogenizer at about 300 bar to form a dispersion, which was then rapidly cooled to room temperature. The resulting dispersion had good stability and a solids content of about 40.

Example 5

About 1000 parts of a 1.5% fumaric acid adduct from formaldehyde-treated tall oil resin, 1800 parts of water and 57 parts of Ultrawet 30DS were mixed together and heated to about 180 ° C. The resulting heated mixture was passed through a homorenizer using a pressure of about 150 bar to prepare a dispersion, which was then rapidly cooled to room temperature. The resulting dispersion had good stability and a solids content of about 35 fo.

11 67737

Example 6 1000 parts of 6 f> fumaric acid adduct from formaldehyde-treated tall oil resin were mixed with 925 parts of water and 85 parts of Ultrawet 30DS were mixed together and heated to about 170 ° C. The resulting heated mixture was passed to a homoyenizer using a pressure of about 200 bar to prepare a dispersion, which was then rapidly cooled to room temperature. The resulting dispersion had good stability and a solids content of about 50.

Example 7

A 1 f solution of Tamol SU (sodium salt of condensed naphthylenesulfonic acid) in deionized water was pumped at 2100 parts per minute through a heat exchanger to heat it under pressure to 170 ° C, after which it was passed to a so-called in-line separator which was also pumped at 1400 parts per minute. adduced wood resin containing 6 ° Fumaric acid) preheated to 170 ° C. This mixture was passed through a Manton-Gaulin homogenizer operating at a temperature of 170 ° C and a pressure of 280 bar. The emulsion thus formed was rapidly cooled to below 80 ° C by passing it into a circulating, pre-cooled emulsion. The time that the Tamol SN solution and resin emulsion were kept at a temperature above 80 ° C was less than 3 minutes. The solids content of the stable emulsion thus made was about 40.

Example 8

A 1.25% solution of Duponel ME (duPont Co, sodium lauryl sulfate) in deionized water was pumped at a rate of 80 parts per minute through a heat exchanger to heat it under pressure to a temperature of about 150 ° C, after which it was passed to a so-called in-line mixer, which was also pumped with 40 parts per minute of molten adducted resin heated to about 165 ° C. The adducted resin used was an adduct of 6 fumaric acid from formaldehyde-treated tall oil resin. This mixture was passed through a Manton-Gaul bomo-reformer at a temperature of about 160 ° C and a pressure of about 200 bar. The emulsion was rapidly cooled to below 80 ° C by passing it through a heat exchanger. Touch tusai ka with aqueous solution 12 67737! and the emulsion were at a temperature above 80 ° C, was about 2 minutes.

The stable emulsion thus prepared had a solids content of about 35 7 °.

|

Example 9

A 1.1% solution of Aerosol CT (American Cyanamid, sodium sulfosuccinic acid dioctyl ester) in deionized water was used as an emulsifier, otherwise using the materials and method of Example 7. This gave a stable emulsion with a solids content of about 40 .mu.l.

Example 10

A 2.5% aqueous solution of Alipol CO 430 (GAF Corp., alkylphenol-poly (ethyleneoxy) ethanol sulfate ester) was used as the emulsifier, otherwise using the materials and method of Example 7. This gave a stable emulsion with a solids content of about $ 40.

Example 11

A solution of 0.5 sodium hydroxide and 0.2% fresh Duponol ME in deionized water was used as the aqueous phase of the method of Example 7. This gave a stable emulsion with a solids content of about 40 fo.

Example 12

Example 2 was followed except that 31 parts of Ultrawet 30 DS sodium hydroxide solution was added. A stable emulsion with a solids content of 48% was obtained.

Example 13

A $ 1.5 solution of Duponol WAQE (du Pont Co., sodium lauryl sulfate) in deionized water was pumped at 100 p.p.m. through a heat exchanger to heat it under pressure to a temperature of about 140 ° C, after which it was passed to a so-called in-line mixer granule, which was also pumped at 50 p.p.m. at about 165 ° C melted adduced tall oil resin (containing 2.75 rf of reacted ίο rf / (7 n, JO / f O / formaldehyde and 8 fo of reacted fumaric acid) This mixture was passed to a homogenization nitrite maintained at about 155 ° C. C, and an immediately circulating flow of a pre-cooled emulsion to immediately cool the emulsion to a temperature below 60 C. The resulting stable emulsion had a solids content of 35

Example 14

A 3% solution of Duponol WAQE in deionized water was used to emulsify the adducted resin used in Example 13 using the same technique except that equal amounts of solution and molten plastic were used. A stable emulsion was obtained with a solids content of about 51%.

To determine the finishing performance of the water suspensions of Examples 4-11, surface finishing experiments were performed using bleached kraft paper (18.2 kg per 500 sheets 61 cm x 91 Cm) prepared at pH 6.5 with the addition of 0.5% alum. The sheets were processed using a small laboratory scale horizontal press by adding samples of the aqueous suspension diluted to about 0.29 i ° through the press point of the finishing press and passing the sheets of paper through the solution before pressing between the rolls of the finishing press. Under these conditions, the sheets received about 70 pounds by weight of finishing press solution, from which about $ 0.2 finishing agent was transferred to the sheet. The finished sheets were dried for about 20 seconds in a laboratory tumble dryer with a surface temperature of about 90 ° C (200 ° P). The sheets were allowed to expire for 4 days, after which they were tested using the number 2 test solution in the "Hercules Sizing Test" for $ 80 reflectance. The following results were obtained.

Finishing agent from the example Test results "Hercules Sizin'-Test" in seconds_ 4 130 5 136 6 115 7 131 8 141 9 118 10 112 11 138 12 133 13 125 1! \ 110

Claims (9)

A method for obtaining a substantially stable water dispersion of a substance based on rosin, ie. take 11 o'clock resin suitable for bonding ripple pulp springs, in which process an unstable water dispersion is homogenized under a pressure of about 140-560 bar and at a temperature of about 125-180 ° C, which water dispersion contains approx. 25-50% by weight of solid, of which about 0-95¾ is rosin and about 100-5% is an adduct reaction product of rosin and of an acidic compound containing the group -C = CC = 0 in which the amount of 1. in the said acidic compound is added about 1-20% of the total amount of the solids, characterized in that the process is carried out in the presence of an anionic dispersant. 2. A process according to claim 1, characterized in that as an anionic dispersant, a pre-diluted rosin-based substance is used in which the saponification rate of the reacting carboxy groups in said rosin-based substance is about 0.5-20%. 3. A process according to claim 1, characterized in that as an anionic dispersant is a synthetic emulsifier and that the amount of anionic dispersant is about 1-5% of the amount of solids present in the emulsion. 4. A process according to claim 3, characterized in that the amount of the anionic dispersant is c. 1.5-2.5%. Process according to claim 2, characterized in that the amount of solids is c. 30-50% and the amount of water is c. 70-50%.