JPS6116767B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a novel, essentially non-thermosetting, ten retention aid resin for paper ten.
related to resin). Cationic, water-soluble thermosetting resins obtained by the reaction of amino polymers with epihalohydrins are well-known wet strength agents for paper. A typical example of such a wet strength agent is U.S. Patent No.
This is the resin No. 2926154. This patent describes a resin obtained by the reaction of an aminopolyamide derived from a polyalkylene polyamine and a dicarboxylic acid with epichlorohydrin. In the field of wet strength resins, aminopolymers obtained from polyalkylenepolyamines and dicarboxylic acids are known as polyaminopolyamides, which are also sometimes referred to as "aminopolyamides" and "polyamides." There is. Other patents describing cationic thermoset wet strength resins for paper include U.S. Pat.
There are No. 3224990, No. 3240664, No. 3332901, and No. 3700623. According to the teachings of U.S. Pat. No. 3,224,990, an aminopolyamide obtained from diethylenetriamine and adipic acid is combined with epichlorohydrin and ammonium hydroxide in a molar ratio of aminopolyamide:ammonium hydroxide:epichlorohydrin of 1.0:0.5. :
React with an amount of 2.5. The aminopolyamide and ammonium hydroxide may be premixed prior to the reaction with epichlorohydrin, or the epichlorohydrin and ammonia may be reacted before mixing with the aminopolyamide. can. Under the conditions disclosed in this patent, the aminopolyamide and ammonium hydroxide each react with and consume epichlorohydrin at similar rates. If the ammonium hydroxide and epichlorohydrin are pre-reacted before being added to the aminopolyamide, slightly more epichlorohydrin will react with the ammonium hydroxide than would otherwise be the case. However, at least some will still be present to react with the aminopolyamide. The resin of this patent is a cationic thermoset resin that has utility as a wet strength agent for paper. The cationic resins described above are thermosetting, which makes them particularly suitable for use as wet strength agents for paper when added to a slurry of pulp before papermaking. At the same time, this resin can also serve as a retention aid for the tenten material present in the pulp slurry. Wet strength is not necessarily a desirable property in tenner containing papers. The presence of thermosetting resins makes reprocessing of the scrap difficult. It would therefore be desirable to have a tenner retention aid resin available that does not impart wet strength properties to the paper. In accordance with the present invention, a novel resin which is essentially non-thermosetting and is an effective retention aid resin for paper tensile properties, yet provides little, if any, wet strength properties to the paper. An ionic resin is provided. The retention aid resins of the present invention are aminohydroxyalkylamino polymers and aminohydroxyalkyl quaternary ammonium polymers. These are (1)
General formula RRR′N (where each R is hydrogen and C ₁ -C ₄
freely selected from alkyl, R′ is hydrogen, C ₁ −C ₄
(2) polymers containing multiple secondary and/or tertiary amino groups and epoxides difunctional towards amines (e.g., epichloro); hydrin, 1,2:3,4-diepoxybutane,
1,2:5,6-diepoxyhexane, diglycidyl ether and 3,4-epoxy(epoxyethyl)cyclohexane). . The base resin used in the present invention will be explained in more detail later. The above nitrogen-containing compounds (hereinafter simply referred to as "nitrogen compounds") that can be used in the present invention include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropyl Amine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine,
Tributylamine, isobutylamine, diisobutylamine, triisobutylamine, t-butylamine, di-t-butylamine, N-ethyl-N
-Methyl-propylamine, N,N-dimethyl-
Ethylamine, N,N-diethyl-propylamine, N,N-dimethyl-isopropylamine, N
-ethyl-N-isopropyl-butylamine, N
-ethyl-N-propyl-t-butylamine, N
-Methyl-N-ethyl-isobutylamine, N-
Methyl-propylamine, N-ethyl-propylamine, N-propyl-t-butylamine, N-
Ethyl-dipropylamine, N-methyl-diethylamine, N-propyl-di-t-butylamine, N-methyl-ethylamine, N-ethyl-butylamine, N-hydroxy-methylamine, N
-hydroxy-dimethylamine, hydroxylamine, N-hydroxy-N-methyl-propylamine, N-hydroxy-N-methyl-t-butylamine, N-hydroxy-N-methylamine, N
-hydroxy-diisopropylamine, N-hydroxy-diethylamine and N-hydroxy-ethylamine. In producing the resin of the present invention, the reaction between the base resin and the nitrogen compound is carried out using a liquid that is a solvent for both the reactants and is inert to both the reactants and the reaction products. Carry out in a medium (liquid at the reaction temperature). Preferably, the reaction is carried out in an aqueous medium. The solids concentration of the base resin in the reaction medium before the reaction is about 1 to about 25% by weight,
Preferably it will be about 6 to about 15% by weight. The reaction can be carried out at temperatures from about 0°C to about 150°C, and can be carried out at higher temperatures if desired. Preferred temperatures are within the range of about 50°C to about 100°C.
The reaction can be carried out under pressure or atmospheric pressure. If the temperature is above the boiling point of the reaction mixture, it may be necessary to carry out the reaction under pressure. The reaction occurs when substantially all of the sites derived from the bifunctional epoxide of the base resin (hereinafter referred to as "epoxide sites" in the claims) have finished reacting with the nitrogen compound, and the resulting resin is heated. Even if it has curable properties, it can be continued until it has very little curability. Reaction time varies inversely with temperature. Thus, for example, at 50°C the reaction time will be about 0.5 to 3 hours, while at 100°C this will be about 1 to 10 minutes. The amount of nitrogen compound used is such that all of the epoxide sites react essentially completely with the nitrogen compound.
It should be at least stoichiometrically equivalent to the amount of epoxide moieties in the base resin, and preferably in considerable excess. When carrying out the reactions of the invention, undesired gelation of the reaction mixture may occur. Therefore, to substantially eliminate this possibility, a significant excess of the stoichiometric amount of nitrogen compound is used. About 2 times to about 40 times the stoichiometric amount is preferred. The amount of nitrogen compound required to avoid gelation will be approximately directly proportional to the solids content of the base resin in the reaction mixture. It is well within the skill of those skilled in the art, armed with the teachings of this invention, to prepare the retention aid resins of this invention while avoiding undesirable gelation without extensive experimentation. Unreacted nitrogen compounds can be left in the resulting resin solution, or, if desired, can be removed from the resin solution by known means (e.g., heating under atmospheric or reduced pressure). You can also do it. The unreacted nitrogen compounds thus removed can be recovered and reused if desired. The novel retention aid resins of the present invention can be used as retention aids for a wide variety of paper ten materials, such as calcium carbonate, various clays (eg, kaolin), and titanium dioxide. Retention aid resins are generally added to the pulp-tenage slurry immediately prior to paper making in an amount of about 0.002 to about 1.0 percent by weight, based on the weight of the dry pulp. However, it can also be added at an earlier point in the papermaking system. The novel retention aid resins of this invention can be used in both alum-containing and non-alum-containing systems. Retention aid resin obtained from aminopolyamide-epichlorohydrin base resin and nitrogen compound According to one aspect of the present invention, the retention aid resin is obtained from the reaction of a nitrogen compound and an aminopolyamide-epichlorohydrin thermosetting resin. obtained by. Water soluble aminopolyamide-epichlorohydrin thermosets are well known in the paper industry. Examples of certain aminopolyamide-epichlorohydrin thermosets are described in U.S. Pat. No. 2,926,154. An aminopolyamide is first prepared by reacting a dicarboxylic acid and a polyalkylene polyamine under conditions to form a long chain aminopolyamide. Suitable dicarboxylic acids that can be used to prepare the aminopolyamides include diglycolic acid and saturated aliphatic dicarboxylic acids having 4 to 12 carbon atoms (e.g. succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid). , azelaic acid, sebacic acid, methyladipic acid, and metalglutaric acid)
There is. Other suitable dicarboxylic acids include aromatic carboxylic acids (e.g., terephthalic acid, isophthalic acid, and phthalic acid) and α,β-unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid, itaconic acid, glutaconic acid, citraconic acid). acid and mesaconic acid). Available anhydrides of the above acids can also be used to prepare aminopolyamides. Amides of the above-mentioned acids can also be used to produce aminopolyamides. Esters of the above acids can also be used to prepare aminopolyamides if desired. Further esters that can be used are esters of malonic acid, such as dimethyl malonate, diethyl malonate and dipropyl malonate.
Mixtures of two or more of the abovementioned reagents can also be used for the preparation of aminopolyamides. Therefore,
For example, mixtures of two different dicarboxylic acids can also be used. Mixtures of two different anhydrides can also be used. Mixtures of two different esters can also be used. Mixtures of two different amides can also be used.
Mixtures of one or more acids and one or more esters can also be used. Mixtures of one or more anhydrides and one or more acids can also be used. Also, one or more acids, 1
Mixtures of more than one anhydride and one or more esters can also be used. Some polyalkylene polyamines that can be used in the production of aminopolyamides can be represented by the following general formula. (In the above formula, R″ is hydrogen, C ₁ -C ₁₂ alkyl or C ₁ -C ₁₂ hydroxyalkyl; n is an integer from 2 to 6, and x is an integer from 1 to 4.) C ₁ Examples of −C ₁₂ alkyl are methyl, ethyl,
Butyl, hexyl and dodecyl. _C1 − _C12
Examples of hydroxyalkyl are hydroxyethyl, 2
-hydroxypropyl, 2-hydroxybutyl and 2-hydroxydodecyl. Specific examples of polyalkylene polyamines of the above formula that can be used include diethylene triamine,
Triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, dihexamethylenetriamine, pentaethylenehexamine, iminobis(propylamine), and methylbis(3
-aminopropyl)amine. Other polyalkylene polyamines that may be used that are not included in the general formula above include 1,
These include 4-bis(3-aminopropyl)piperazine and 1-(2-aminoethyl)piperazine. 2
Mixtures of more than one polyalkylene polyamine can also be used if desired. The spacing between amine nitrogens in the aminopolyamide can be increased as desired. To do this, diamines (e.g. ethylenediamine, 1,3-
Diaminopropane, 1,2-diaminopropane,
hexamethylene diamine, aminoethyl ethanolamine, etc.) may be used in place of a portion of the polyalkylene polyamine. For this purpose,
Up to about 80% of the polyalkylene polyamine can be replaced with equimolar amounts of diamine. However, usually a substitution of about 50% or less will be sufficient. The temperature used when carrying out the reaction between dicarboxylic acids and polyalkylene polyamines is approximately
Ranges from 50°C to about 250°C or more. Approximately 80
Temperatures between 0C and 210C are preferred. By using reduced pressure, lower temperatures can be used. Reaction time will be about 0.5 to 4 hours and will vary inversely with temperature. When carrying out this reaction, the amount of dicarboxylic acid used is sufficient to react substantially completely with the primary amine groups of the polyalkylene polyamine, but not with the secondary amine groups and/or Preferably, the amount is insufficient to react to a substantial extent with the tertiary amine groups. To do this, the molar ratio of polyalkylene polyamine:dicarboxylic acid is approximately 0.9:
A ratio of 1 to about 1.2:1 will usually be necessary. However, molar ratios of about 0.8:1 to about 1.4:1 can be used. The aminopolyamide thus obtained is reacted with epichlorohydrin at a temperature of about 45°C to about 100°C, preferably about 45°C to about 70°C. The reaction is carried out until the viscosity of the 15% (solid content) aqueous solution at 25° C. reaches approximately A or higher on the Gardner-Holdt viscometer scale. This reaction is preferably carried out in an aqueous solution to control the reaction. Adjustment of PH is usually not necessary. However, as the polymerization stage of the reaction progresses,
Since the PH is lowered, it may be desirable in some cases to add alkali to combine with at least some of the acid produced. Once the desired viscosity is reached, water can be added to adjust the concentration (solids content) of the aqueous resin solution to the desired value, usually about 2 to 50%. When preparing an aqueous reaction medium for the epichlorohydrin-aminopolyamide reaction, it is desirable that essentially all of the aminopolyamide be dissolved in the medium. Water-miscible alcohols (e.g., methanol, ethanol, propanol, isopropanol, and t-butanol) are used to completely dissolve aminopolyamides that are not completely water-soluble.
can be added to the aqueous medium. The amount of alcohol used is that amount necessary to produce substantially complete dissolution of the aminopolyamide and can be readily determined by one skilled in the art. In the aminopolyamide-epichlorohydrin reaction, the amount of epichlorohydrin used is about 0.1 to about 2 moles, preferably about 1 to about 2 moles, for each secondary or tertiary amine group in the aminopolyamide. The amount is 1.5 moles. Thus, the aminopolyamide-epichlorohydrin reaction product comprises an aminopolyamide in an amount such that the molar ratio of epichlorohydrin to amine groups (secondary or tertiary) of the aminopolyamide is from about 0.1 to about 2. and epichlorohydrin, thereby forming a water-soluble aminopolyamide-epichlorohydrin base resin. The reaction of the nitrogen compound with the aminopolyamide-epichlorohydrin-based resin is preferably carried out in an aqueous medium, which is the same reaction medium used for the reaction of the epichlorohydrin with the aminopolyamide. Good too. The reaction with nitrogen compounds is
This can be carried out immediately after the reaction between the epichlorohydrin and the aminopolyamide is substantially complete. If the base resin solution is stored for a certain period of time before reacting with the nitrogen compound, gelation can be prevented by adding water-soluble acids such as hydrochloric acid and sulfuric acid to adjust the pH to about 6 or less. It can be stabilized against The reactions with nitrogen compounds to produce the retention aid resins of the present invention are conducted at a PH of greater than 7, preferably at a PH of about 8 or higher. If desired, an excess portion of the nitrogen compound can be used to effect the necessary PH adjustment. The resin obtained in this manner has the following structure, for example. (Here, R is alkylene, x is 1 to 4, R ₁
and _R2 are hydrogen or _C1 - _C4 alkyl, and R is a divalent residue derived from a dicarboxylic acid, and n is 7
or greater) The following examples are illustrative of this aspect of the invention. In these examples, all parts and percentages are by weight unless otherwise specified. Example 1 A mixture of 200 parts of diethylenetriamine and 290 parts of adipic acid is heated with stirring to 170-175°C for 1.5 hours, during which water is evolved, cooled to 140°C, and then solidified with about 400 parts of water. Dilute to 50% for min. The reduced specific viscosity (RSV) of aminopolyamide is
0.16 (1 mol when C = 2g/100ml)
Specific viscosity when measured at 25℃ in NH ₄ Cl aqueous solution /
C). 100 parts of this 50% aqueous solution of diethylenetriamine-adipate polyamide was diluted with 300 parts of water, heated to 40°C, and diluted with epichlorohydrin.
27.5 parts until the Gardner-Holdt viscosity rises to the value of E (measured on samples cooled to 25°C).
Heat and stir at 75°C for about 1 hour. The resulting resin is then diluted with 302.5 parts of water and the pH is adjusted to 4.6 with concentrated sulfuric acid. A stabilized aqueous resin solution containing about 10% solids is obtained. Example 2 100% solids resin solution described in Example 1
Add enough NaOH to adjust the pH to 7. This solution is then mixed with 18.7 parts of concentrated aqueous ammonia (28%) and heated to reflux at 80-85°C for 2 hours. The resulting solution contains approximately 10.1% non-volatile solids. The resin produced here has the following structure. Example 2a 10% resin solution prepared according to Example 1
Add enough NaOH to adjust the pH to 7 to 100 parts. This solution is then mixed with 14.7 parts of concentrated aqueous ammonia (28%) and left to react at room temperature (approximately 25°C) for one month. A solution containing about 10.1% non-volatile solids is obtained. Example 3 10% solids resin solution prepared according to Example 1
1000 parts were adjusted to pH 7 with NaOH, then treated with 196.9 parts of 28% aqueous ammonia, and heated under reflux at 80°C for 2 hours. This mixture is then distilled. Distillation is carried out until 320.4 parts of resin solution remain in the distillation flask. The resulting resin solution has a concentration of non-volatile matter.
36.7%, PH about 7, Gardner-Holt viscosity W
It is. This resin solution does not gel even when stored at 32°C for 90 days. Example 4 To 100 parts of a 10% solution of the resin described in Example 1 are added 14.75 parts of ethylamine. The generated solution
The mixture is heated under reflux at 70° C. for 2 hours, and then concentrated by evaporation under reduced pressure to remove unreacted ethylamine. Diluting the resulting solution with 75 parts of water yields a solution containing approximately 10.2% total solids. Example 5 200 parts of a 50% aqueous solution of diethylenetriamine-adipate polyamide (prepared as in Example 1) was diluted with 541 parts of water and diluted with epichlorohydrin.
Process in 57.5 parts. The mixture is then heated to 70-75°C until the Gardner-Holdt viscosity reaches approximately F. The mixture was then diluted with 378 parts of water,
Cool and adjust the pH to 4.7 to obtain a resin solution with a solids content of 12.5%. Adjust 160 parts of this resin solution to pH 7 with 50% NaOH aqueous solution, and then add 20% dimethylamine aqueous solution.
14.7 parts and heated under reflux at 72°C for 2 hours.
The solution is then concentrated by evaporation to a non-volatile solids content of 14.8%. Example 6 100 parts of a 10% resin solution prepared according to the method of Example 1 was mixed with 6.6 parts of hydroxylamine hydrochloride and
Treated with 13 parts of 10N aqueous sodium hydroxide solution at 85°C.
Heat for 2 hours. Total solids content is approximately 13.9%
A resin solution is obtained. Example 6a Example 6 is repeated, but using 9.12 parts of hydroxylamine hydrochloride and 17.4 parts of 10N aqueous sodium hydroxide solution. Total solids content is 14.4
% of the solution is obtained. Example 6b Example 6 is repeated, but using 4.56 parts of hydroxylamine hydrochloride and 8.9 parts of 10N aqueous sodium hydroxide solution. The resulting mixture is at 80℃
It gels when heated. Example 7 151.4 parts of tetraethylenepentamine are diluted with 35 parts of water and treated with 134.8 parts of sebacic acid. This mixture is distilled at 170-175°C for about 1.6 hours and 57.1 parts of distillate are collected. The polymer thus prepared is decanted and cooled to room temperature. The reduced specific viscosity (RSV) of this aminopolyamide is 0.244 (measured as in Example 1). 18 parts of this aminopolyamide are dissolved in 40 parts of isopropyl alcohol. The resulting solution was then diluted with 51 parts of water and treated with 21.9 parts of epichlorohydrin to give 58-
Heat to 60° C. for 0.2 hours to bring the mixture to a pregel state. This mixture is then diluted with 100 parts of water. Add 180 parts of this solution to 150 parts of water and
Diluted with 117 parts of concentrated ammonia water (28%) and heated to 70°C.
Heat under reflux for 2 hours. Isopropyl alcohol and unreacted ammonia are removed by stripping under reduced pressure. A solution containing 27.4% non-volatile solids is obtained. Example 8 116.3 parts of isophthalic acid are added to a mixture of 152.4 parts of etraethylenepentamine and 40 parts of water. The resulting mixture was heated at 170-177°C for 2.75 hours and 195-
Heating at 225° C. for 1.1 hours, during which time 67.5 parts of distillate are evolved. The mixture is then decanted and cooled. The reduced specific viscosity of the obtained aminopolyamide is approximately 0.11 when measured as described in Example 1. This amino polyamide 15.95
A solution of 1 part in 33 parts of isopropyl alcohol is diluted with 42 parts of water and then treated with 18.5 parts of epichlorohydrin. Heat this mixture at 60 °C until a pregel state is reached (approximately 0.5 h). The mixture is then mixed with 80 parts of water and isopropyl alcohol
Dilute with 63 parts then concentrated ammonia water (28%)
Processed in 120 copies. The resulting mixture is heated under reflux at 70° C. for 2 hours, diluted with 200 parts of water and then evaporated under reduced pressure to remove isopropyl alcohol and unreacted ammonia. A solution containing 9% solids is obtained. Example 9 260.2 parts of itaconic acid are added to a mixture of 200 parts of diethylenetriamine and 200 parts of water. The resulting mixture is then heated to 168-175°C for about 1.8 hours, producing about 257 parts of distillate. The mixture is then decanted and cooled. The reduced specific viscosity (measured as described in Example 1) of the aminopolyamide produced is approximately 0.106. A solution of 25 parts of this aminopolyamide in 131 parts of water is treated with 11.75 parts of epichlorohydrin. The resulting mixture was heated for 65 minutes until a pregel state was reached.
Heat at ℃ for 4.4 hours. The resin is diluted with 200 parts of water, then treated with 76.5 parts of concentrated aqueous ammonia (28%) and heated to reflux at 80° C. for 2 hours. Excess ammonia and water are removed under reduced pressure to produce a resin solution containing 16.1% non-volatile solids. Example 10 175.2 parts of adipic acid are added to a mixture consisting of 61.9 parts of diethylenetriamine, 19.77 parts of 1,3-diaminopropane and 16.2 parts of ethylenediamine. The resulting mixture is heated to 175° C. for 4 hours, during which time 39.7 parts of distillate are collected. The polymer thus obtained is then diluted with about 220 parts of warm water and stirred to yield a 52.1% solution. Reduced specific viscosity of this polymer (measured as in Example 1)
is approximately 0.144. This aminopolyamide solution
95.8 parts are diluted with 114.7 parts of water and treated with 15.08 parts of epichlorohydrin. The resulting mixture is heated at 70-75° C. for 2.75 hours until pregenic conditions are reached, then diluted with 500 parts of water and adjusted to PH 4 with sulfuric acid. A resin solution containing 8.8% non-volatile solids is obtained. Example 10a 56.8 parts of the resin solution of Example 10 are diluted with 5.7 parts of water and treated with 6.3 parts of concentrated aqueous ammonia (28%). The mixture is heated to reflux at 80° C. for 2 hours.
A solution is obtained with a total solids content of approximately 7.8%. Example 11 Adipic acid was added to a mixture of 51.6 parts of diethylenetriamine and 52.1 parts of aminoethylethanolamine.
Add 146.14 parts. The resulting mixture is heated and stirred at 175° C. for 2 hours, and the distillate generated during this time is discarded. The resulting aminopolyamide is diluted with about 220 parts of warm water to obtain a solution with a solids content of 44.3%. The RSV (measured as in Example 1) of the aminopolyamide produced is approximately 0.166. 101.5 parts of this 44.3% aminopolyamide solution are diluted with 98.4 parts of water, then treated with 12.37 parts of epichlorohydrin and heated to 70°C. When the resin reaches the pregel state, dilute with 400 parts of water. Adjust the pH with 7.9 parts of concentrated sulfuric acid and 11.4 parts of 50% aqueous sodium hydroxide solution. A solution containing 10.2% non-volatile solids is obtained. Example 11a 49 parts of the solution of Example 11 was diluted with 13.5 parts of water,
Treated with 6.3 parts of concentrated ammonia water (28%) and heated to 75℃
Heat to reflux for 2 hours and cool. The resulting solution contains approximately 8.0% solids. Example 12 200 parts of a 50% aqueous solution of diethylenetriamine-adipate aminopolyamide (prepared as in Example 1) are treated with 55.4 parts of 90% formic acid and 42 parts of 37% formaldehyde, gradually heated to the boiling point and refluxed. Boil for 1 hour. The solution is then cooled, diluted with 180 parts of water, adjusted to a pH of 8.5, and then treated with 47.9 parts of epichlorohydrin. The resulting mixture is heated to 60-65°C for about 1 hour to bring the Gardner-Holdt viscosity (for the sample cooled to 25°C) to approximately LM. The resulting solution is cooled and acidified to pH 4.5, resulting in a resin solution containing 35% non-volatile solids. This solution does not gel when stored at 32°C for 90 days. Example 12a A resin solution is prepared according to Example 12, but
However, the resin solution is not stabilized by adjusting the pH to 4.5 before storage. This unstabilized resin solution gels within two days when stored at 32°C. Example 13 Evaluation of Retention Aid The resins of each of the above examples were evaluated as retention aids by the method described below. A Alum-free system 180 parts of Rayonier softwood pulp and kraft pulp and Weyerhaeuser hardwood pulp and kraft pulp
The mixture with 180 parts is dissolved to a consistency of 2.5% and Canadian standard water content of 300 c.c. 3000 parts of this 2.5% pulp slurry (containing 75 parts of pulp) is adjusted to pH 8 with 10% NaOH solution, treated with 7.5 parts of kaolin and stirred for 5 minutes. The resulting slurry is diluted with hard water in a thickener to a total weight of 12,000 parts and mixed for 5 minutes. Add 500 parts of this diluted slurry to the resin.
Treat with 5, 15 and 50 parts of a 0.005% solution (corresponding to 0.01, 0.03 and 0.1% by weight of the pulp, respectively). This resin-treated slurry was stirred for 30 seconds and diluted with water to a total of 5000 parts.
Paper is made in the box of a Noble-Wood hand-made machine to make hand-made paper. B Alum-containing system: 180 parts of Rayonier softwood pulp and kraft pulp and Weyerhaeuser hardwood pulp and kraft pulp
The mixture with 180 parts is dissolved to a consistency of 2.5% and Canadian standard water content of 300 c.c. 3000 parts of this 2.5% pulp slurry (containing 75 parts of pulp) is adjusted to PH 6.5 with 10% H ₂ SO ₄ and then treated with 8.2 parts of 9.1% alum solution. Adjust this slurry to _PH4.5 with 10% _H2SO4 or NaOH as needed. The slurry is then treated with 7.5 parts of kaolin and stirred for 5 minutes.
The total weight of the obtained slurry is adjusted in a concentration controller.
Dilute with hard water to 12,000 parts and mix for 5 minutes. Add 500 parts of this diluted slurry to 0.005 parts of resin.
% solution 5, 15 and 50 parts (respectively of pulp)
0.01, 0.03 and 0.1% by weight).
This resin-treated slurry was stirred for 30 seconds and the total
Dilute with water to make 5000 parts, Noble−
Handmade paper is made by making paper using the standard box of a Wooden handmade machine. The ash content is measured on these handmade papers.
The tenage retention rate (%) is calculated from the ash content using the following formula.

[Table] 〓Ten fee%〓

Claims (1)

[Scope of Claims] 1. Epihalohydrin and amino polymer with the formula
RRR′N, where each R is independently selected from the group consisting of hydrogen and C ₁ -C ₄ alkyl; R′ is hydrogen;
_a water-soluble or water-dispersible substrate containing an _epoxide moiety; resin [this can be polyaminopolyamide-epihalohydrin resin, polyaminopolyurein-epihalohydrin resin or poly(diallylamine)-
any epihalohydrin resin, which is the reaction product between an epihalohydrin and an amino polymer] at a temperature of about 0-150°C in an amount at least stoichiometrically equivalent to the epoxide moieties of the base resin. The above-mentioned nitrogen-containing compound is reacted with the nitrogen-containing compound until substantially all of the epoxide moieties of the base resin have reacted with the nitrogen compound to form a non-thermosetting resin.