DE2502084A1 - PROCESS AND COMPOSITION FOR INTERNAL GLUING OF CELLULOSE MATERIALS - Google Patents

Description

63? Giessen / Lahn . -

Ludwigstrasse 67 H / He (756)

The Dow Chemical Company, Midland, Michigan. UNITED STATES.

Method and composition for internal sizing of cellulosic materials.

Priorities: February 1, 1974, USA Serial No. 438 913 August 15, 1974 USA Serial No. 497 581 October 21, 1974 USA Serial No. 516 337

This invention relates to a method for internal Sizing cellulosic materials such as paper and the like. by treating with an internal glue and a retention aid, which is used as the internal glue a water-dispersible and water and alkali-insoluble milk polymer of an alpha, beta-ethylenic unsaturated hydrophobic monomers and an alpha, beta-ethylenically unsaturated carboxylic acid reacted with ammonia and as a retention aid, a water-dispersible reaction product of an epihalohydrin and Ammonia, an alkylamine or aliphatic polyamine with at least 2 amino hydrogens per molecule or a mixture of ammonia and such an amine and / or polyamine used.

The invention also includes an internal composition Gluing of cellulosic materials, the above-mentioned copolymer as internal glue and the above-mentioned Contains reaction product of an epihalohydrin and ammonia and / or an amine.

In a preferred embodiment, the composition used for sizing cellulosic materials contains sizing agent to increase the sizing efficiency of the interior

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ORIGINAL INSPECTED

and the retention aid additionally rosin and aluminum sulfate.

The internal sizing of the cellulose materials takes place according to the invention preferably in a pH range of moderately acidic to strongly alkaline. The internally sized cellulosic materials obtained show a very high degree of water resistance and a satisfactory resistance to acidic and alkaline solutions. Very big What is important is the fact that the above-mentioned copolymers are used as glue in combination with the above-mentioned Cationic retention aids are not limited to use in the acidic pH range, but for the treatment of neutral, alkaline and also acidic paper pulp are suitable. It is also beneficial that only mild drying and hardening conditions are required to achieve the full sizing effect of these internal sizing agents to develop.

The term "cellulosic materials" as used herein includes paper, paperboard and other fibrous, sheet-like materials or molded masses made from wood, wood pulp or cotton or other raw materials for cellulose fibers derive. The term also includes sheet-like or shaped masses made from combinations of cellulosic materials and non-cellulosic materials, e.g. combinations of cellulosic materials with fibers made of polyamides, polyesters, Polyacrylonitrile and mineral fibers such as asbestos and glass fibers.

The term "internal sizing" is to be understood as meaning a glue process in which the cellulose material as raw material, for example as a fibrous raw material such as paper pulp , is brought into contact with the glue under conditions in which the cellulose material is glued, that is to say that the glue is deposited on the fiber and cured to its full glue effect. The expression

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"Internal sizing" is comprehensive and as a result closes such terms as e.g. "Mass sizing in the Dutch", "Mass sizing in the paper machine" and "Mass sizing am End of the wet end of the paper machine ".

The internal glue used in the invention are copolymers of an alpha, beta-ethylenically unsaturated hydrophobic monomer and an alpha, beta-ethylenically unsaturated carboxylic acid reacted with ammonia, ie the alpha, beta-ethylenically unsaturated carboxylic acid in the form of its ammonium salt. Such copolymers are generally water-dispersible, semi-solid or solid substances. These copolymers have molecular weights which give melt flow viscosities in the range from about 0.2 decig / min according to ASTM D-1238-65T (E) to about 50 decig / min according to ASTM D-1238-65T (B), with the exception that with this method the opening of the extrusion plastometer is 0.5 mm. The copolymer preferably has an average number molecular weight in the range from 1,000 to 10,000, determined by ebulliometry and a melt flow viscosity in the range from 0.5 to 50 decig / min, determined according to ASTM D-1238-65T (B) using the plastometer with one opening of 0.5 mm. The preferred copolymers are film-forming at the temperatures in question for sizing. "Dispersible in water" is understood here to mean a material which can exist in the form of a permanent aqueous colloidal dispersion in the absence of a surface-active agent An "alpha, beta-ethylenically unsaturated hydrophobic monomer" is to be understood as meaning any monomer which is immiscible with water and has a terminal

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Has double bond that allows it to polymerize under the normal conditions of addition polymerization to form a water-insoluble homopolymer with a Polyethylene backbone enabled. Under an "alpha, beta-ethylenically unsaturated carboxylic acid" is one To understand alpha, beta-ethylenically unsaturated carboxylic acid due to its ethylenic double bond is capable of addition copolymerization with the alpha, beta-ethylenically unsaturated hydrophobic monomers. "With ammonia reacted alpha, beta-ethylenically unsaturated carboxylic acid" is to be understood that in the Copolymer the carboxyl groups are neutralized with ammonia.

The internal sizing agent is preferably a normally solid thermoplastic insoluble in water and alkali Addition polymer which is in the form of a liquid aqueous colloidal dispersion. The one with ammonia converted acidic groups should preferably be distributed generally over the macromolecule, so that each macromolecule should contain a minimum of active salt groups, which are sufficient to give the polymer in the specified Way to make it dispersible in water. The maximum number of acidic groups reacted with ammonia, which may be present in the macromolecules is determined by the requirement that the molecule essentially should be soluble in water. Such a copolymer generally contains 6 to 40% by weight of that with ammonia reacted acidic comonomers, preferred copolymers 10 to 20 wt.% Of the reacted with ammonia acidic comonomers and particularly preferred copolymers contain 15 to 18% by weight of this comonomer.

Examples of preferred copolymers are the random copolymers from the interpolymerization of mixtures of one or more polymerizable ethylenically unsaturated carboxylic acids with 3 to 8 carbons.

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substance atoms, including their anhydrides and alkyl half esters, such as acrylic acid, methacrylic acid, maleic acid and its anhydride, itaconic acid, fumaric acid, crotonic acid and Citraconic acid and its anhydride, acid methyl maleate, acid ethyl maleate and one or more alpha, beta-ethylenic unsaturated hydrocarbon monomers such as the aliphatic alpha olefin monomers, conjugated dienes, and aromatic carbocyclic monovinylidene monomers. In addition, other ethylenically unsaturated hydrophobic monomers, which are not pure hydrocarbons, are copolymerized with the acidic comonamers mentioned above. Examples of such suitable monomers are esters of alpha, beta-ethylenically unsaturated carboxylic acids, such as ethyl acrylate, methyl methacrylate, ethyl methacrylate, Methyl acrylate, isobutyl acrylate and methyl fumarate; unsaturated esters of non-polymerizable carboxylic acids, such as vinyl acetate, vinyl propionate and vinyl benzoate; Vinyl halides such as vinyl and vinylidene chloride; Vinyl ether; alpha, beta-ethylenically unsaturated amides and nitriles, such as acrylamide, acrylonitrile, methacrylonitrile and fumaronitrile. The hydrophobic monomers can with the preferred Hydrocarbon monomers and the acidic comonomer are copolymerized in such amounts that a polymer insoluble in water and alkali is obtained. Preferred copolymers include copolymers one from 70 to 90 wt.% ethylene, 10 to 20 wt.% of one or more ethylenically unsaturated acids reacted with ammonia, such as acrylic acid and methacrylic acid, and from 0 to 20% by weight of a suitable ethylenic unsaturated hydrophobic monomers, such as acrylonitrile, ■ "." ·. Ethyl acrylate and vinyl acetate.

Other copolymers suitable for the invention can be obtained from preformed, non-acidic polymers by subsequent chemical reactions. For example, the carboxyl group can be introduced by a

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acidic monomer such as acrylic acid or maleic acid grafted onto a polymer substrate such as polyethylene. Also can to hydrolyze copolymers containing groups such as carboxylic acid anhydride, ester, amide, acyl halide and Contain nitrile groups, whereby carboxyl groups are formed, which can then be neutralized to form the carboxyl groups reacted with ammonia.

It is also possible to use the alpha, beta-ethylenically unsaturated To copolymerize carboxylic acid in the form of its ammonium salt with the hydrophobic monomers to obtain a suitable Produce mixed polymer.

The methods and equipment for making the copolymers used in the invention are known. The preferred low molecular weight copolymers are obtained by the known procedures with which Exception that a telogenizing agent such as propylene is added to the reaction mixture. When the acidic copolymer is formed in bulk, it can be converted into an aqueous colloidal dispersion and then concentrated and react with ammonia. In general, processes for preparing the aqueous colloidal Dispersion of the copolymer preferably in which little or no emulsifier or other surface-active Funds is needed. The aqueous colloidal dispersion of the copolymer can preferably be a polymer solid content of 5 to 60 wt.% and so-

a lot of stabilizing ammonia to give the dispersion a pH of at least 7.5 · dispersions of higher Solids content can be derived from those with lower Produce solids content in a simple manner by known methods.

To obtain a satisfactory level of sizing for the manufacture of sized paper, including heavily sized

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Paper, it is necessary in the present invention to use the copolymer sizing agent in conjunction with a reaction product of an epihalohydrin and ammonia or an alkylamine or an aliphatic polyamine having at least 2 amino hydrogens per molecule or to use a mixture of ammonia and such an amine, said reaction products of the Epihalohydrins for short as epihalohydrin / amine reaction product are designated. These epihalohydrin / amine reaction products are useful additives to improve retention or Increase retention of the interpolymer sizing agent, probably by having the interpolymer sizing agent brought into greater proximity to the fibers of the cellulosic material during the sizing process will. Suitable epihalohydrin / amine reaction products are dispersible in water, preferably water-soluble. In general such water-dispersible reaction products have molecular weights in the range from 200 to 80,000. Preferred reaction products contain 0.9 to 2.1, especially 1.3 to 1.7 moles of epihalohydrin per mole of amine, e.g. Ammonia, alky ^ amine, polyamine or a mixture thereof. The preferred ammonia and / or polyamine reaction products have one or more molecular weight peaks in determining molecular weight by gel permeation chromatography and such peaks usually occur in the range of 2,000 to 70,000. Particularly preferred reaction products are those that at least have a peak in the molecular weight range of 40,000 to 70,000. The preferred alkylamines are from 10 to 22 carbon atoms in the alkyl chain and the preferred epihalohydrin / alkylamine reaction products have molecular weights in the range of 400 to 3,000.

When internal sizing of paper and other cellulose materials with these copolymers as internal sizing agents, a multitude of variations and working

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ways to be used. It is essential, however, that in all of the processes under consideration there should be one uniform Distribution of the sizing agent through the whole cellulose fiber is achieved during the internal sizing. The uniform Distribution can be effected in that the mixed polymer sizing agent reacted with ammonia in fully dispersed form, such as an aqueous colloidal dispersion, is used.

In order to obtain a maximum distribution of the copolymer sizing agent on the fiber starting material and to achieve a To avoid flocculation of the sizing agent, it is especially useful when the epihalohydrin / amine reaction product is strong It is desirable for the copolymer sizing agent to be cationic to the fiber starting material before the addition of the reaction product or at the same time or shortly afterwards, usually within 30 minutes. Preferred becomes the copolymer-sizing agent-the slurry of the fiber raw material before the addition of the reaction product added. Regardless of the special procedure for adding the mixed polymer reacted with ammonia and the epihalohydrin / amine reaction product to the fiber starting material, care must be taken that a Contact of the mixed polymer reacted with ammonia and the reaction product before contact with the starting fiber material takes place.

The actual addition to the fibrous cellulosic material of either the reaction product or the sizing agent can take place at any point in the process for treating the cellulosic material prior to the final conversion of the moist fibrous material into a web, sheet or shaped article. For example, in the production of. Paper, the glue to be added to the paper mass while it is in the headbox, Dutchman, wet grinder or material container.

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In order to obtain good internal sizing, it is desirable that the sizing agents used with ammonia reacted copolymers uniformly contained in the interior of the Paser in the smallest possible particle size are. One method of achieving such uniform dispersions is to use the sizing agent in one aqueous medium is dispersed prior to its addition to the cellulosic material. In general it is advantageous to to use the copolymers reacted with ammonia as sizing agents in an aqueous colloidal dispersion, which is free of emulsifiers and other surfactants. Dispersions with such agents can but can also be used provided that these agents are volatile during sizing or effectiveness of the mixed polymer sizing agent.

The sizing agents according to the invention are very successful for the sizing of a wide variety of papers are used, which are obtained both from cellulosic fibers and from combinations of such fibers with non-cellulosic fibers. As cellulose fibers can be used with special Advantage of bleached and unbleached sulfate (Kraft) pulp, bleached and unbleached sulphite pulp, bleached and unbleached soda pulp, neutral sulphite pulp, semi-chemical pulp, chemically crushed wood, wood pulp and any combination of these fibers can be used. These names refer to wood pulp fibers that go through a variety of processes known in the pulp and paper industries are available.

In combination with the copolymer sizing agent according to the present invention, various additives, such as pigments, fillers, stabilizers, retention aids, and improvement aids can be used

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the wet strength and the dry strength and also other gluing agents can be used. Examples of such additives are kaolin clay, talc, titanium dioxide, calcium carbonate, diatomaceous earth, plastic pigments, aluminum trihydrate and precipitated silica. It has been found that the addition of rosin and aluminum sulfate is not effective when CaCO, is used as a filler. Aluminum sulfate is not as effective in the presence of ammonia treated ones Epihalohydrin and in the presence of amine treated epihalohydrin. The most preferred embodiment of the invention uses 0.05 to 2, preferably 0.5 up to 1 part by weight of aluminum sulfate and 0.05 to 2, preferably 0.5 to 1 part by weight of rosin per 2000 parts by weight of the dry cellulose material, the weight ratio of aluminum sulfate to rosin at 1: 3 to 5: 1, preferred about 1: 1. The ratio of the additives aluminum sulfate / rosin to the micropolymer glue reacted with ammonia is generally in the range from 0.01 to 4.0, preferably 0.12 to 2.5.

The copolymers treated with ammonia and used as glue are generally used in amounts such that the purpose of glueing, such as resistance to water, is achieved. In general, amounts in the range of 0.005 to 20% by weight based on the weight of the dry cellulosic material in the finished sheet or article are suitable, with the preferred amounts in the range of 0.05 to 2% by weight being particularly preferred Amounts range from 0.2 to 1% by weight. Within this range, the exact amount to be used in an individual case depends largely on the type of cellulosic material, the particular operating conditions and also the particular use for which the cellulosic material is intended. For example, a paper that is supposed to have good water resistance and good writability with ink requires the use of a higher one

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Concentration of the glue as a paper with features, which only require a small amount of glue. As a result, any suitable amount of glue can be used can be used as long as they have the desired effect results. The same factors apply to the amount of the epihalohydrin / amine reaction product, as a retention aid in connection with the mixed polymer glue reacted with ammonia is used. Those skilled in the art will readily determine the appropriate amounts of this reaction product and sizing agent for the specific operating conditions and identify areas of application. In general, however, this will be the epihalohydrin / amine reaction product used in an amount in the range from 0.5 to 5 parts by weight per 1 part by weight of the copolymer sizing agent, quantities of 1.5 to 3 parts by weight of the reaction product to 1 part by weight of the copolymer glue are preferred.

The invention will be further elucidated in the following examples explained. The embodiments marked with two asterisks are least preferred. All information about Parts and percentages are given by weight, unless expressly stated otherwise.

example 1

A 500 g portion of an ethylene acrylic acid copolymer (87.3 / 12.7) is added to 240 ml of aqueous ammonia (28% NH ₅ ) in a 4 liter kettle containing 2.94 liters of water. The copolymer has a molecular weight peak at 6,950, determined by gel permeation chromatography and a melt flow viscosity of 2 decig / min, determined according to ASTM D-1238-65T (B) using a plastometer with an opening of 0.5 mm. These starting materials are stirred at 100 ° C. for 8 hours; then the dispersion obtained is allowed to cool to room temperature. The dispersion is used to remove flocculated material

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a gauze fabric filtered. The filtrate obtained is a aqueous dispersion with a pH of about 8 and contains 13-6% of an ethylene ammonium acrylate copolymer (Solid).

A 5 liter reaction flask equipped with a reflux condenser, stirrer, thermometer and feed funnel is charged with 431 g (7 gram mol) of 28-30% aqueous ammonia and partially immersed in a cooling bath. While maintaining a temperature of 16 to 20 ° C of the reaction mixture, 925 g (10 gram mol) of epichlorohydrin are added over a period of 4 hours. After the addition is complete, the reaction mixture is stirred for a further 16 hours at the same temperature, then 330 g of water are added and the mixture is heated to 100 ° C. and then cooled to room temperature over the course of 2 hours. A mixture of 200 parts by weight of this prepolymer resin is stirred with 100 parts of epichlorohydrin and 200 parts of water for 2 hours at 95 to 98 ° C. and then cooled to room temperature. The aqueous dispersion of the copolymer and the solution of the reaction product are separated into 236 parts of an aqueous slurry of bleached kraft pulp with a solids content of 0.33% and a pH of 7.8, which by adding H ₂ SO ^ to pH 4.5 is set, admitted. Hand-scooped test sheets according to TAPPI T-205m-53 are formed from this mass and dried. The surface wettability of these sheets is determined by water (contact angle) and the penetration of ink. The measured values are summarized in Table I.

To further illustrate this embodiment of the invention, a size composition is prepared for the internal sizing of this paper pulp which contains different amounts of the aqueous dispersion of the copolymer and the reaction product. The treated pulp will

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processed in the specified manner to hand samples, on which the surface wettability and the penetration of Ink is checked. These results are also given in Table I.

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Table I.

Sample mixed polymer. Reaction product penetration contact angle

No. sat conc. Type concentration of ink (3)

Parts / 2000 parts parts / 2000 parts % reflection pre-hardened

(1) . at 120 sec.

■. (2) ■

1 6 NH ^ / EPCH * 15 93 103 °

2 4 NH ^ / EPCH * 15 70 105 °

° * Reaction product of epichlorohydrin / ammonia in a molar ratio of 1.7: 1 with Molecular Co

cd weight peaks at 5,000 and 50,000 as measured by gel permeation chromatography.

to,

^1x3 (l) Measured as dry weight in parts of specified additive per 200 parts of _H.

ο paper pulp. . ⁴ ^ "

to. £

° (2) Photometric determination of the penetration of black ink through white or light colored paper by measuring the reflection of light on the side of the paper opposite to that on which a supply of black ink is applied. The paper tested before the ink was applied has a reflectance of 100% against a black background with a reflectance of 0%.

(3) The contact angle (surface wettability by water) before curing was

determined according to TAPPI-458m-48. ¹ ^

25Q2084

Example 2

A 3.3 kg portion of an ethylene acrylic acid copolymer is placed in a 37.85 liter kettle with stirring, of 28.4 liters of water and 2.3 liters of aqueous ammonia (2890

contains. The kettle is heated to 100 ° C. for 3 hours while stirring heated at a pressure of 3.2 kg / cm. The product will filtered through a 100 mesh stainless steel sieve with sieve openings of 0.149 mm. It will be a good amber color Obtained dispersion containing 10% copolymer solids.

line serving of 4 parts of the epichlorohydrin / ammonia reaction product of Example 1 is diluted with 27 parts of water. A serving of 2.9 parts of the above The copolymer dispersion explained is diluted with 4.8 parts of water. The two diluted compositions are separated into a slurry of bleached Kraft pulp added. The mixture is adjusted to a pH of 3.5 with sulfuric acid. From this paper pulp sample sheets are scooped by hand and dried. Then the ink strikethrough and the Contact angle measured when wetted with water. Similarly, test sheets are measured using Pulp slurries adjusted to pH values of 4.8, 6.1, 7.1, 7.9, 9.1 and 10.2 are set. The results of these tests are summarized in Table II, summed up. From these results it can be seen that the copolymer sizing agent according to the invention has a wide pH range is effective.

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Tabel II

Sample Concentration of the additive (l) Ink penetration contact angle pH (4) No. parts / 2000 parts , % reflection pre-hardened

Mixed polymer ammonia / epichlor- ^{at 120 sec} * ^^ &)

hydrin reaction product

15 15 15 15 15 15 15

(1) As in Table I.

(2) As in Table I.

(3) As in Table I.

(4) pH of pulp before processing into hand-scooped sample sheets.

1 10 2 10 cn 3 10 ο CD 4th 10 ex" co 5 10 Ni O 6th 10 co O 7th 10

98 115 ° 3.5 98 120 ° 4.8 99 117 ° 6.1 99 118 ° 7.1 100 122 ° 7.9 95 120 ° 9.1 98 118 ° 10.2

Example 3

A 40 g portion of an ethylene / acrylic acid copolymer (89/11) is added to 27 g of aqueous ammonia (28% NH,) and Put 200 g of water in a 0.5 liter stainless steel autoclave. The copolymer has a melt flow viscosity of 43 decig / min according to ASTM D-1238-65T (B) with an opening of 0.5 mm (number average molecular weight 4,075). The autoclave is closed and the reaction mixture is shaken at 95 ° C. for 3 hours. The dispersion obtained contains 15% mixed polymer solids.

A 0.18-part portion of the epichlorohydrin / ammonia reaction product according to Example 1 is diluted with 6 parts of water. The resulting solution is added to a slurry of bleached Kraft pulp in the amounts shown in Table III and stirred for 1 minute. A portion of 0.19 part of the copolymer dispersion described above is diluted with 7-7 parts of water and then added to the cellulose slurry as an internal glue in the amounts given in Table III. The pH of the paper pulp obtained is adjusted to 4.5 with sulfuric acid. Sample sheets are scooped out of the paper pulp by hand and dried. The ink strike through and the contact angle with water are measured. The results are given in Table III.

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Table III

Sample Concentration of the additive (1) No. parts / 2000 parts

. Mixed polymer ammonia / epichlorohydrin

reaction product ink strike through, % reflection at 120 sec. (2)

Pre-hardened contact angle (3)

10

15th

112

(1) - (3) As for Table I.

ro he; O

Example 4

Following the procedure of Example 1, an aqueous one Dispersion with a polymer solids content of 11% of a Ethylene / acrylic acid copolymer (86/14) reacted with ammonia and having an average number molecular weight manufactured by 4,500.

An aqueous solution of that further characterized in Table IV Retention aid is made into a slurry of bleached in the amounts shown in Table IV Kraft pulp (0, ^ 6 solids in water) with stirring given. Then the 'dispersion of the mixed polymer reacted with ammonia becomes the pulp slurry with stirring given in the amounts given in Table IV. From this mass, test sheets are made by hand scooped and dried according to TAPPI T-205m-53. The wettability with water (contact angle) is and determines the strike through of ink. The results are given in Table IV.

For comparison purposes, the same procedure is used Test sheets produced, but they contain a cationic starch as a retention aid. Even with these Test sheets are used to test surface wettability and ink strike through. The results are in compiled in Table IV.

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Table IV

sample • 1 Glue Type Conc Retention aid Dutch Contact Sleep through I.
ro No. 2 ** tration Concentrate type the pH angle gen of O
I. A * Parts / tration previous Ink (2) 2000 parts Parts / tet (3) Sec. (D 2000 parts Ät / AS (NH ₃ ) (a) 5 (D 6.4 117 ° 3614 Ät / AS (NH ₃ ) (b) 5 NH ₃ / EPCH (d) 9 6.65 60 ° 0.9 cn
σ Et / AS (NH ₃ ) (C) 10 η 9 "6.2 <20 ° 0.1 CO
OO
co * Not an example of Invention. Sta-lok 400 (e) 20 (a) With Ammonia-converted ethylene / acrylic acid copolymer (86/14) with a medium O
CD ren Number molecular weight of O . 4,500.

(b) Ethylene / acrylic acid copolymer reacted with ammonia (80.5 / 19.5) with an average Number molecular weight of 30,000.

(c) Ethylene / acrylic acid copolymer (80/20) reacted with ammonia and having a melt flow viscosity (ASTM-d-1238-65T (E)) of 250 decig / min corresponding to an average number molecular weight of about 18,300.

(d) Reaction product of epichlorohydrin and ammonia in a molar ratio of 1.61: 1 with peaks

in molecular weight at 2,500 and 65,000, measured by gel permeation chromatography,

(e) Potato starch with the following quaternary ammonium groups: (manufactured by A. E. Staley Manufacturing).

OH

CR

-CH ₂ -C-CH ₂ N ⁺ (CH ₃ :
H

OO r- »

(1) As in Table I.

(2) Time in seconds for a paper that has 80% reflectance using the test method outlined in Table I under (2).

(3) As in Table I. Example 5

A 22.7 kg portion of an ethylene / acrylic acid copolymer (85/15) with a melt flow viscosity of 15 decig / min (ASTM D-1238-65T (E)) becomes 34 kg of aqueous Ammonia (28% NEW) and 34 kg of water are placed in a 94.6 l kettle. The contents of the kettle will be on for 5 hours Heated at 140 ° C. The excess ammonia is at 85 ° C driven off and then the product is withdrawn from the kettle. The dispersion obtained contains 24% copolymer solids.

A 4.0 part portion of the epichlorohydrin / ammonia reaction product according to Example 1 (25% solids) is diluted with 27 parts of water. A 0.12 part portion of the ethylene copolymer dispersion mentioned above is diluted with 7.7 parts of water. The two diluted compositions are added to a bleached Kraft pulp slurry in the amounts shown in Table V. The pH of the resulting slurry is adjusted to 4.5 with sulfuric acid. Sample sheets are drawn from this slurry by hand. After drying, the ink strike through and the contact angle with water are measured. The values obtained are summarized in Table V.

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Table V

Sample Concentration of the additive (1) Ink penetration contact angle No. parts / 2000 parts ._gen, % reflection pre-hardened

Mixed polymer ammonia / epichlorohydrin- ^{at 120 sec #} ^ &)

reaction product

1 10 15 89 92 °

cn

° (D - (3) As in Table I.

GD

OO ■

CO N)

σ co

ro

ro cn ο ro

00

Example 6

A portion of 3 »31 kg of the ethylene / acrylic acid copolymer (86/14) with an average number molecular weight of 4,500 and a melt flow viscosity according to ASTM D-1238-65T (B) using a plastometer with a 0.05 mm aperture at 2 decig / min becomes 2.33 liters aqueous ammonia (28% NH,) and 28.4 1 water in one 37.8 liter boiler given. These raw materials are Stirred for 3 hours at 100 ° C. and a pressure of 3.2 kg / cm. The dispersion obtained is allowed to cool to room temperature. The dispersion is then used to remove flocculated material. given through a gauze fabric. That The filtrate obtained is an aqueous dispersion containing 10% Contains solids of the ethylene / ammonium acrylate copolymer.

A 1 liter reaction flask equipped with a reflux condenser, stirrer, Thermometer and inlet funnel is equipped with 100 g of octadecylamine, which is dissolved in 100 g of 95% ethanol is charged and heated to 30 ° C. A portion of 44.3 g of epichlorohydrin is poured into the flask over the course of 15 minutes and the contents of the flask are heated to 100 ° C for 4 hours. The solvent will separated from the end product in a vacuum at a slightly elevated temperature. The reaction product has an average molecular weight of 510 (determined by ebulliometry) and contains the starting materials in the form of a condensation product with 1.4 "mol of epichlorohydrin per mol of octadecylamine. An emulsion of the reaction product is produced, by boiling the product in distilled water for a few minutes.

Unbleached soft wood pulp is made to a freeness of 425 SCF (Standard Canadian Freeness) in a laboratory dutch (valley beater) at a consistency of

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1.5% comminuted according to TAPPI Standard T200 os 70 ,. A partial sample of 100 ml is taken from the mixture obtained and diluted to 800 ml by adding 700 ml of water. While stirring this mixture, a 1 ml amount of 1% papermaker's alum (13.2 parts by weight / 2000 parts by weight, based on dry pulp) is added and the mixture is stirred for 5 minutes. A 3 ml amount of the 0.075% solution of the aforementioned epichlorohydrin / octadecylamine reaction product (3 parts by weight / 2000 parts by weight based on dry pulp) is added to the pulp mixture and then stirred for 3 minutes. A 6 ml amount of the latex of the ethylene / ammonium acrylate copolymer (6 parts by weight / 200 parts by weight, based on dry pulp) is added to the pulp mixture containing the reaction product, and the mixture obtained is stirred for 3 minutes. Using 0.1 N sulfuric acid, the pH of the pulp is adjusted to 5 and the pulp is then added to the pouring lid of a TAPPI sheet-forming machine containing 1 ml of 1% papermaker's alum. A few test sheets are produced in accordance with TAPPI Standard T205 os 71. The sheets are dried, hardened and conditioned overnight according to TAPPI Standard T400 os 70 at 72 ° C. and 50% relative humidity. These sheets are then tested for water resistance and ink permeability. The results are shown in Table VI. .

For comparison purposes, some samples are prepared using the same procedure with the exception that different amounts of the copolymer sizing agent (AAS) and epichlorohydrin / amine reaction product (EPI / ODA) are used. A control sample (sample no. C) is also prepared for which no AAS or EPI / ODA is used. Hand-scooped leaves are made from the various mixtures using the methods already mentioned and dried. The test sheets are examined and the test results are shown in Table VI.

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Table VI

Sample no.

1 2 3 4 5 ** 6 7 C *

Additive (1) parts by weight / 2000 parts by weight ÄAS (a) EPI / ODA (b)

2 2 3

3.5

1.5

1.5

0.

pH the

Dimensions

5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.1

Ink pass through
gen (2) sec. Cobb (3) Contact angle
(4) 309 35.2 94.5 ° > 1500 31.2 105.5 ° > 1500 11Y2 111.5 ° XL500 16.0 111.5 ° 3.1 * 48.4 99.5 ° > 1500 18.8 115.0 ° > 1500 14.0 107.5 ° 0.1 90.4 20 °

* Not an example of the invention.

(a) Ethylene / acrylic acid copolymer reacted with ammonia (86/14).

(b) epichlorohydrin / octadecylamine reaction product.

(1) Parts by weight of additive per 2000 parts by weight of the paper pulp, calculated on the dry weight,

(2) Time in seconds for the ink to strike through to achieve 80% reflection, determined using TAPPI Standard T4 31 ts- 65 ink and Hercules Sizing Tester.

(3) Cobb test (TAPPI Standard T441 os 69) using exposure times of ■ ■ ^,! 120 seconds., '' ■ ■ ■ '/ V. ',' ,.: ', - ■' ■ '■', "', .. ■' ■■■ ■■■ '.'■"'','■' ■■

(4) TAPPI Standard T458 os 70 using distilled water.

cn ο το

Example 7

The procedure of Example 6 is followed, but other copolymers are used as glue. Some samples are prepared in which 5 parts by weight of the copolymer and 5 parts by weight of the epichlorohydrin / octadecylamine reaction product are used as additive to 2000 parts of pulp. Test sheets are scooped from these paper pulps, dried and tested in the manner already indicated. The results are shown in Table VII.

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cn ο co οο co ro

ο co σ

Tabel VII Cobb (3)
gZm ² Contact angle Mixed polymer glue (l) Ink-through 32.0 (4) beat (2) 16.0 102.5 ° AZASNH ₄ (85Z15) DO.OOO) XL5OO 19.6 110.0 ° AZAAZASNH ₄ (67.6Zi4.7Zl7.8) Oo.OOOO It 22.4 101.5 ° ÄZASK (56Z44) C54OO ^ Il 34.4 111.0 ° AZASNH ₄ (8OZ20) CL8.3OO3 It 58.8 93.5 ° AZASNH ₄ (9OZIO) C3O.OOO0 It 18.8 109.5 ° Ä / ASNa (60Z40) OOOQD N 115.0 ° AZIBaZASNH ₄ (67.5Z16.7Z15.8) O.15CQ Il

2 3 **

5 6 **

(1) Ä = ethylene, ÄA = ethyl acrylate, IBA = isobutyl acrylate, ASNH ₄ = ammonium acrylate, ASK = potassium acrylate and ASNa = sodium acrylate. In parentheses, the weight fraction of the individual monomers is given in% and the average numbers in square brackets * molecular weight of the copolymers. .

(2) - (3) As in Table VI.

(4) As (4) in Table VI, except that TAPPI Standard T4 31 ts 65 ink is used instead of distilled water «

I l \ J

Cr; O ro

OD r—.

Example 8

Following the procedure of Example 7, using bleached Kraft pulp made from 50% hard wood and 50% soft wood, some samples are prepared using the additives in various amounts as indicated in Table VIII. Test sheets are produced and tested in the usual way. The results
are summarized in Table VIII.

509832/0 901

Table VIII

CD OO OJ K)

sample
No.

.1
2
3

5 6th

A ₂ *

Additive (1) parts by weight / 2000 parts by weight ÄAS (a) EPI / ODA (b)

1.5
2.0
4.0
4.0
6.0
4.0
0.0
0.0

3.0 4.0 4.0 8.0 12.0 8.0 4.5 3.0.

ΑΙ sulfate

26.3 26.3 26.3 26.3

14.0 26.3 26.3

pH of the ink strikethrough mass (2) sec.

Cobb

i ³⁾

555

XL500

1042

> 1500

> 1500

> 1500

0.5

26.8 18.8 16.0 16.8 24.0 16.0 66.8 130.8

Contact angle (4)

105 ^C 123 ^C 118 ^C

121 *

88 '38 ⁽

* Not an example of the invention. (a) - (b) As in Table VI. (1) - (4) As in Table VII.

CJT CD

Example 9

500 g of an ethylene / acrylic acid copolymer (87.3 / 12.7) with an average number molecular weight of 6950 (determined by Ebulliometry) are added to 240 ml of aqueous ammonia (28% NH,) in a 4 liter kettle containing 2.94 liters of water contains, given. These starting materials are stirred for 8 hours at 100 ° C. and atmospheric pressure. The received The dispersion is allowed to cool to room temperature. The dispersion is used to remove flocculated material filtered through a gauze fabric. The resulting film is an aqueous dispersion that is 13.6% solids of the ethylene / ammonium acrylate copolymer.

A 5 liter reaction flask equipped with a reflux condenser, stirrer, thermometer and inlet funnel is provided with 291 g (17.1 moles) of aqueous ammonia (28%) were charged and partially immersed in a cooling bath. During this reaction mixture is kept at 30 to 35 ° C, 555 g (6 mol) of epichlorohydrin in the course of 1.5 hours admitted. At the end of the addition, the reaction mixture is stirred for a further 0.33 hours at the same temperature. 1000 g of water are then added and the mixture is heated to 60 to 65.degree. The reaction mixture is kept at this temperature and stirred for 2 hours. Then this prepolymer resin becomes a serving of 1000 ml of water was added. The mixture is then stirred for 10 minutes, then 250 g of 50% NaOH are added and the mixture is stirred for 30 minutes. 151 g of epichlorohydrin are then added to the mixture over the course of 10 Given minutes and the. The mixture is heated to 60 to 65 ° C. for 2 hours. The pH of the mixture is adjusted to 4.0-4.5 adjusted and then the mixture is cooled to room temperature.

A portion of 0.375% fortified rosin in water is mixed with 0.375% aluminum sulfate in water to form a cloudy persistent complex.

50983 2/0901

Bleached kraft pulp made from soft wood and bleached Hardwood Kraft pulps become 425 SCF (Standard Canadian Freeness) freeness all in one Laboratory Dutch chopped to a 1.5% consistency using TAPPI Standard T200 os 70. Equal amounts of the two pulps are mixed to form a pulp cut with an SCF freeness of 409. A portion of 400 ml is taken from this mixture and made 1892 ml by adding 1492 ml of water diluted. The rosin / aluminum sulfate complex is added to the diluted mixture while stirring in the method used for sample no. added amount indicated in Table IX. The mixture is stirred for 1 minute. -4.9 ml of the 0.375% solution of the aforementioned epichlorohydrin / ammonia reaction product (3.1 kg / ton of dry pulp) are added to the pulp mixture with stirring for 30 seconds. then 2.96 ml of the latex of the ethylene / ammonium acrylate copolymer (1.8 kg / ton of dry pulp) to the pulp mixture that contains the reaction product and the rosin / Contains aluminum sulfate complex, added and the mixture is stirred again for 30 seconds. The received Paper pulp, which has a pH of 8, is then placed in the casting part of a Noble and Wood sheet paper former and test sheets are produced. The test sheets are dried and cured at 80 ° C. for 30 minutes and conditioned according to TAPPI Standard T400 os 70 (at 23 ° C and 50% relative humidity). The leaves are was checked for ink permeation and the results are summarized in Table IX.

For comparison purposes, some samples are prepared in the same way, with the exception that different amounts of the copolymer glue (Ä / AS), epichlorohydrin / ammonia reaction product (EPI / NH ^) and / or rosin / aluminum sulfate complex are used. In addition, comparative samples (sample no. C ₁ - C ^) are produced in which no rosin / aluminum sulfate is used. Even from such mi-

509832/0901

260208 4

test sheets are produced and checked. For these sample sheets, too, the results are in Table IX specified.

Table IX

Sample additive (l) rosin pH of ink no. Parts by weight / 2000 parts by weight aluminum mass through

ÄAS (a) EPI / NH3 (b) ^{sulfate (c)} If) ¹ S ^

1 3.7 6.17 1.23 8.1 241.5

2 3.3 5.49 1.10 8.0 231.6

3 3.5. 5.8 1.16 8.0 211.4

4 3.1 5.15 1.05 8.0 176.8

C ₁ * 3.7 6.17 8.1 120.8

C ₂ * 4.0 6.57 8.1 154.6

C ₃ * 3.5 5.8 8.0 3.5

* Not an example of the invention.

(a) Ethylene / acrylic acid copolymer reacted with ammonia. (86/14).

(b) epichlorohydrin / ammonia reaction product.

(1) Parts by weight of additive per 2000 parts by weight of pulp on a dry weight basis. ·

(2) Time in seconds for ink to strike through to to achieve 80% reflection, determined using TAPPI Standard T4 31 ts 65 ink and Hercules Sizing Tester.

509832/0901

Claims (19)

Claims; 1. A process for the internal sizing of cellulose materials by treating with an internal sizing agent and a retention aid, characterized in that the internal sizing agent is a water-dispersible and water and alkali-insoluble copolymer of an alpha, beta-ethylenically unsaturated hydrophobic monomer and one with ammonia converted alpha, beta-ethylenically unsaturated carboxylic acid and a water-dispersible reaction product of an epihalohydrin and ammonia, an alkylamine or aliphatic polyamine with at least 2 amino hydrogens per molecule or a mixture of ammonia and such an amine and / or polyamine is used as a retention aid. 2. The method according to claim 1, characterized in that the reaction product has at least one molecular weight peak in the range from 2,000 to 70,000, determined by Gel Permeation Chromatography, - possesses. 3. The method according to claim 1 or 2, characterized in that the reaction product is water-soluble and the molar ratio of epihalohydrin to amine is 0.9 to 2.1 moles of epihalohydrin per 1 mole of amine. 4. The method according to any one of claims 1 to 3, characterized in that that pulp is used as cellulose material. 5. The method according to any one of claims 1 to 4, characterized in that the hydrophobic monomer is an alpha, is beta-ethylenically unsaturated hydrocarbon. 6. The method according to claim 5 »characterized in that the unsaturated hydrocarbon is an aliphatic alpha-monoolefin having 2 to 14 carbon atoms. . 50 983 2/090 1 7. The method according to claim 6, characterized in that the aliphatic alpha-monoolefin is ethylene. 8. The method according to any one of claims 1 to 7, characterized in that that the unsaturated carboxylic acid is acrylic acid. 9. The method according to any one of claims 1 to 7, characterized in that that the unsaturated carboxylic acid is methacrylic acid. 10. The method according to any one of claims 1 to 9, characterized in, that the copolymer is film-forming under the conditions of internal sizing. 11. The method according to claim 10, characterized in that the copolymer has an average number molecular weight peak in the range from 1000 to 10,000 and 10 to 20% by weight of the alpha, beta-ethylenically unsaturated Contains carboxylic acid. 12. The method according to any one of claims 1 to 11, characterized in that that the cellulosic material is internally sized under pH conditions of at least 7. 13. The method according to any one of claims 1 to 12, characterized in that that additionally rosin and aluminum sulfate are used to increase the effectiveness of the interior To increase the glue and the retention aid. 14. Composition for the internal sizing of cellulose materials, characterized in that it is a water-dispersible and insoluble in water and alkali copolymer of an alpha, beta-ethylenically unsaturated hydrophobic monomer and as the internal sizing agent
an alpha, beta-ethylenic reacted with ammonia 509832/0901 2b02084 unsaturated carboxylic acid and, as a retention aid, a water-dispersible reaction product of a Epihalohydrin and ammonia, an alkylamine or an aliphatic polyamine with at least 2 amino hydrogens contains per molecule or a mixture of ammonia and such an amine and / or polyamine. 15. Composition according to claim 14, characterized in that the reaction product has at least one molecular weight peak in the range of 2000 to 70,000 as determined by gel permeation chromatography. 16. Composition according to claim 14 or 15 »characterized in that that the reaction product is water-soluble and the molar ratio of epihalohydrin is 0.9 to 2.1 moles of epihalohydrin to 1 mole of amine. 17. Composition according to any one of claims 14 to 16, characterized in that the hydrophobic monomer is ethylene and the carboxylic acid is acrylic acid. 18. Composition according to any one of claims 14 to 16, characterized in that the hydrophobic monomer is ethylene and the unsaturated carboxylic acid is methacrylic acid, 19. Composition according to any one of claims 14 to 18, characterized in that it also contains rosin and contains aluminum sulfate. 509832/0901 ^