TW495538B - Hydrophobically modified resin compositions and uses thereof - Google Patents

Abstract

Resin compositions that are the reaction product of epihalohydrin and hydrophobically modified aminoamide obtained by the reaction of: (a) aminoamide containing at least one primary amine group and at least one secondary and/or tertiary amine groups, the aminoamide being obtained by reaction of polyamine containing at least two primary amine groups and at least one secondary and/or tertiary amine group, with dicarboxylic acid or derivatives thereof, wherein the molar ratio of polyamine to dicarboxylic acid or derivative thereof, is greater than about 1.4:1, and, (b) hydrophobizing agent having from about 12 to about 40 carbon atoms, wherein the amount of hydrophobizing agent employed is sufficient to react with at least a portion of the primary amine groups, but insufficient to react with more than about 60% of the secondary and/or tertiary amine groups of the aminoamide. Also disclosed are uses of the compositions in the treatment of paper, particularly the sizing of paper.

Description

A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) The invention of the city This invention relates to hydrophobically modified epoxy propylene oxide-amine amine resin and its uses. BACKGROUND OF THE INVENTION The papermaking industry has used a variety of substances for surface sizing paper. It includes a styrenic ketene monopolymer, a styrene-maleic anhydride (SMa) polymer, and epichlorohydrin modified modified stearylamine. Individuals have serious disadvantages when used. For example, alkylketene dimers and stearylamines significantly reduce the coefficient of friction of paper when applied to a surface. This will adversely affect the paper during high-speed conversion operations. In addition, stearylamine has a negative effect on the tensile properties of paper. SMA solution polymers are foam-like, which can be supplied in low solids and can only be used for limited sizing in some grades 4. In addition, SMA polymers are not effective when applied to paper without internal sizing. The material of the present invention does not cause deterioration of the tensile properties of the applied paper, nor does it cause a significant decrease in the coefficient of friction. Does not blister excessively and is a highly effective sizing agent, even when applied to paper without internal sizing. U.S. Patent No. 3,922,243 to Aldrich et al. Discloses that water-insoluble water is a dispersive thermosetting cationic resin, which is derived by reacting a water-soluble aminopolyamine, a hydrophobic compound, and propylene oxide. The aminopolyamine contains a second amine group and is prepared using a polyalkylene polyamine to a dicarboxylic acid with a molar ratio from about 0.9 to about 1.2. The amount of hydrophobizing agent is not sufficient to react with more than 50 / L > diamine. Dumas U.S. Patent Nos. 3 923 745, 3,968 317, and 3,992 345 disclose water-insoluble, water-dispersible thermosetting cationic resins, which are passed through two paper-size papers. ^ ~ (—CNS—) A4 grid (210X 2971 ^ 7 (Please read the notes on the back before filling this page)

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I 丁 I I..:: -M _____ TVJ * V • Line -4- ^ 538 ^ 538 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 _________ β7 5. Description of the invention (2) Monoamine polymer, hydrophobic compound Derived from epoxy-propane reaction. SUMMARY OF THE INVENTION A resin composition comprising a reaction product of epoxy propane and a hydrophobically modified amidoamine, which is obtained by the following reaction: (a) Amineamine contains at least one first amino group and at least one The non-first amine group is selected from the group consisting of a second and a third amine group, and the amine group is obtained by reacting an amine composition with a dicarboxylic acid or a derivative thereof. The amine composition includes a polyamine containing at least one first amine group. The monoamine group and at least one amine group are selected from the group consisting of second and third amine groups, wherein the molar ratio of polyamine to dicarboxylic acid or its derivative is greater than about 1.4: 1, and (b) contains about 12 to about The 40 carbon atom hydrophobing agent, wherein the amount of the hydrophobing agent is sufficient to react with at least part of the first amine group, but not enough to react with more than about 60% of the non-first amine group. A method for preparing a resin composition, comprising: a) reacting an amine composition with dikimic acid or a derivative thereof, the amine composition comprising a polyamine containing at least two first amine groups and at least one selected from the group including a second And the third amine group, wherein the molar ratio of the polyamine to the dicarboxylic acid or its derivative is greater than about 14: i 'to form an amine group containing at least one first amine group and at least one optional Non-first amine groups from the second and third amine groups; b) the amine group is reacted with a hydrophobizing agent containing about 12 to about 40 carbon atoms to form a hydrophobic modified amine group, wherein the The amount of the agent is sufficient to react at least part of the first amine group, but not enough to react with more than about 60% of the non-first amine group of the amine group; and 0 hydrophobically modified amine group reaction with the epihalohydrin.

This paper button _ standard (CNS

495538

V. Description of the invention (A method for sizing paper, which includes adding a resin composition aqueous suspension to the surface of the paper. Another method for stenting paper includes the following steps: ⑷ providing an aqueous pulp suspension; (b) water-based pulp An aqueous suspension of a resin composition is added to the suspension; (0) forming the pulp into paper; and (d) drying the paper to obtain zen and sizing paper. Detailed description of the invention The aminoamine used to prepare the resin composition is prepared via two Derived from the reaction of a carboxylic acid or its derivative with a polyamine containing at least two first amine groups and one or more second or third amine groups. Dicarboxylic acid derivatives suitable for the preparation of amines include esters , Anhydrides, and halogens. Dicarboxylic acids used to make aminoamidoamines include aliphatic, cycloaliphatic, or aromatic dibasic acids or their derivatives containing 2 to about 44 carbon atoms. Preferred diene acids Is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, fumaric acid, maleic acid, phthalic acid, terephthalic acid Text, monoglycolic acid, CwC: 44 dimer acid, dilute succinic acid and succinic acid. Dicarboxylic acids Adipic acid and alkenyl succinic acid are preferred. Ck-C44 dimer acid is derived from the dimerization or polymerization of natural unsaturated fatty acids, and is available under the name EMPOL® dimer acid from Henkel-Emery, Ohio Cincinnati. Alkenyl succinic acid or anhydride can be obtained through the reaction of maleic anhydride with linear or branched olefins, with the following general formula 丨 and ^ (Please read the precautions on the back before filling this page) -I Ϊ--! I. • Install.

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-COOH, CO〇H ① (Π) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -6-A7 1 '~~~ _____ __B7 V. Description of the invention (4) —-/, Middle R is a linear branched unsaturated alkyl group containing about 8 to about 22 carbon atoms, preferably about 16 to about 22 carbon atoms. Alkenyl succinic acid or succinic acid can be prepared by chlorinating the corresponding alkenyl succinic acid or anhydride. Specific examples of anhydrides of the formula I are isosteenyl succinic anhydride, n-octadecenyl succinic anhydride, n-hexadecenyl succinic anhydride, n-hexadecenyl succinic anhydride, isoprenyl succinic anhydride , N-pinenyl succinic anhydride, n-octenyl succinic anhydride and isobutene first-polymer succinic anhydride. The corresponding acid is derived from anhydrides by hydrolysis. Preferably at least 50 mole% of the amine combination used for the dicarboxylic acid reaction is a polyamine containing at least two first amine groups and one or more second or third amine groups. A preferred polyamine is N-alkylfluorene (3-aminopropylamine), where N_alkyl is an alkyl group containing from 1 to about 12 carbon atoms; and containing two first amine groups and at least one second amine A polyalkylene polyamine in which the nitrogen atom is bonded via a phenyl group, where η is 2 to 6. Preferred polyalkylene polyamines include polyethylenamine, polypropylenamine, and polybutylenamine. Polyethylenamine is more preferred. More preferred polyethylenamines for use in the present invention are diethylene triamine, triethylene tetramine or tetraethylene pentaamine. The most preferred is diethylene triamine. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs as a preferred N-carbon (3-aminopropylamine) is succinylmethylamine (3-aminopropylamine). Except containing at least one first amine group and one or more In addition to the polyamine of the second or third amine group, the amine composition used for the reaction with a dicarboxylic acid contains other diamines, preferably diamines of the formulae III, IV and V. This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 495538 A7 B7 V. Description of the invention (CH ,, (Qing Xing, (m) H2N-CH-CH2 [0-CH2CH] y-iI I ch3 ch3 (IV) ch3 ch3 Printed by H2N-CH-CH2- [OCHCH2.] r [OCH2CH2-] b- [〇CH2CH-] c-NH2 (V) where X is 2 to An integer of about 10, y is an integer of 2 to about 100, b is an integer of 2 to about 100, and a and c are the same or different integers of 0 to about 5. Example of Formula III "A private is ethylidene Diamine, propylene diamine and hexamethylene diamine. Materials corresponding to formula IV can be obtained from Jeffamine (R) d_230, D-400, D-2000 and D-4000 from Huntsman, Houston, Texas The substances corresponding to formula V can be obtained from Huntsman Company by Jeffamine ed-600, ED-900 and ED-2001. When preparing aminoamine, the amount of amine composition is substantially more than that of dicarboxylic acid. Aminopyramine contains a real amine group and is an oligomer, that is, it contains about i to about 6 repeating units. To obtain these properties, the molar ratio of polyamine to dicarboxylic acid is about L4: 1 .The preferred molar ratio is about ... About 3: Bu Gen Jia She 55: 1 to about 2.5: Bu and the best about 16: 1 to about μ., The reaction temperature of the di-acid and amine can be about n (rc to about (please read first) (Notes on the back then fill out this page)

、 1T ►The standard of wood paper is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) A7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ^ __________ B7 V. Description of the invention (6) 1 ~ '' 250 C or The above temperature changes. Take about 160. (: To 21〇. (: The temperature is better. When using low pressure, as known in the industry, lower temperatures can be used. The reaction time is usually from about 1/2 hour to about 2 hours, but depending on the reaction conditions, it can be used Known: or longer reaction time. The reaction time is inversely proportional to the temperature. When preparing the novel resin composition of the present invention, amidoamine reacts with at least one compound hereinafter referred to as a "hydrophobing agent" to form a hydrophobic modified substance Water-insoluble amidoamine. Hydrophobing agent is a compound containing about 12 to about 40 carbon atoms, which will react with the first and second amino groups of aminoamidoamine to form a substantially water-insoluble compound. Suitable hydrophobing agent It includes, for example, acids, anhydrides, halogens, esters, and isocyanates. The amount of the hydrophobizing agent is sufficient to react with at least part of the first amine group, but not enough to react with more than about 60% of the non-first amine group The amount of the hydrophobing agent is preferably sufficient to react with at least about 200/00 of the first amine group, but not enough to react with more than about 30% of the non-first amine group. A more preferred amount of the hydrophobing agent is sufficient to At least about 20% first amine reaction But it is not enough to react with more than about 1000/0 non-first amine group. Examples of preferred hydrophobizing agents are: a) a carboxylic acid or derivative thereof of the formula RCOOH, where the R group is an alkyl group and an alkenyl group , Aryl, cycloalkyl or cycloalkenyl; substituted succinic anhydride of formula I

ω Here R 'is an alkyl group, alkenyl group, cycloalkenyl group containing about 8 to about 22 carbon atoms. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -9-(Please read first Note on the back then fill out this page}

1T ▼ Line 495538 Printed by the Consumer Cooperative of the Central Standards Bureau of Didi A7 B7 V. Description of the invention (7) Aralkyl or arkenyl; and C) Diene or polymer of formula VI enone

Here η is an integer of 0 to about 20, R and R " may be the same or different, and are saturated or unsaturated straight or branched alkyl groups containing 8 to 24 carbon atoms, and about 5 to about 40 carbons Atoms are saturated or unsaturated linear or branched alkyl groups. Suitable carboxylic acid RCOOH derivatives include esters, anhydrides, hydrazones, and isocyanate esters. For the ketene dimer and polymer family of formula VI, dilute dimers are preferred. The most preferred hydrophobizing agent is a substituted succinic anhydride of formula I. Specific examples of usable formulas RCOOH-carboxylic acids or derivatives thereof include rosin acid's myristic acid, palmitic acid, oleic acid and stearic acid. Specific examples of anhydrides of formula I are isooctadecyl succinic anhydride, n-octadecyl succinic anhydride, n-hexadecyl succinimide, n-hexadecadienyl succinic anhydride, # 廿二 dibutyl succinic anhydride , N-pinenyl succinic anhydride, and n-octenyl succinic anhydride. The ketene dimer used in the method of the present invention has a structural formula of ¥ 1, where R and R groups may be the same or different to each other as a hydrocarbon group. Preferably, the alkynyl group is a silk or alkenyl group containing at least 6 carbon atoms, a cyclic alkyl group containing at least 6 carbon atoms, an aryl group containing at least 6 carbon atoms, and an aromatic group containing at least 8 carbon atoms. Alkyl radicals of V 妷 妷 atoms and mixtures thereof. More preferred diketene dimers are selected from the group consisting of octyl'decyl, dodecyl, tetradecyl, hexadecyl, octyl, fluorenyl, fluorenyl, tetrabenzyl, benzyl, fluorenyl, β -Felt basic paper ruler ~ —— ~~ __— (Please read the notes on the back before filling in this page) • Installation · · Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperatives, India 495538 A7 B7 ___ 5. Description of the invention ( 8) and cyclohexenone dimer, and (b) an ketene dimer prepared from an organic acid selected from the group consisting of montanic acid, naphthenic acid, 9,10-decenoic acid, 9,10_Dodecenoic acid, palmitoyl oleic acid, oleic acid, ricinoleic acid, linoleic acid, paulownic acid; natural fatty acid mixtures appear in coconut oil, babassu oil, palm kernel oil, Palm oil, olive oil, peanut oil, rapeseed oil, tallow, lard, whale foaming agent; and a mixture of any of the foregoing fatty acids with each other. The most preferred ketene dimer is selected from the group consisting of octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, fluorenyl, fluorenyldiyl, fluorenyltetrayl, phenyl, fluorenyl , Β-felt and cyclohexenone dimer. Suitable ketene dimers are disclosed in U.S. Patent No. 4,279,794, British Patent Nos. 903,416; 1,373,788 and 1,533,434 and European Patent Application Publication No. 0666368 A3. The fluorenone dimer is commercially available as Aquapel® and Precis® sizing agents from Hercules Corporation, Wilmington, Delaware. Preferred are Aguabel® 364 and Pilisis 787® sizing agents. The ketene polymer used in the method of the present invention has Formula VI, where η is an integer of at least 1, R and R " may be the same or different, and contain 8 to 24 carbon atoms', preferably 14 or 16 Saturated or unsaturated straight or branched alkyl groups of carbon atoms; and ΪΤ is a saturated or unsaturated straight or branched alkyl group containing about 5 to about 40 carbon atoms, preferably 5 to about 20 carbon atoms. The ketene polymer belongs to European Patent Application Publication No. 0629741A1, European Patent Application Publication No. 0666368A3, and US Patent No. 5,685,815. The reaction of the amino amine with the hydrophobizing agent can be carried out neat or in a solvent. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -11-丨 ----- ^ ---- pack one (please read the precautions on the back before filling this page, 11 ^ 538 V. Description of the invention (9 A7 B7 The printing of the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is performed under relatively mild conditions, so the only reaction that is generally carried out is only the reaction of the hydrophobizing agent with the first and second (if present) amines, Therefore, depending on the specific hydrophobizing agent used and the reaction conditions, the amines are converted into amidoamines, castors, β-ketoamidoamines, imidazolones, or β-amidoamino acids. Such aminoamidoamines Reacts with a hydrophobing agent at atmospheric or higher pressure at a reaction temperature of about 0 ° C to about 250 ° C to produce a generally water-insoluble reaction product. When the hydrophobing agent is a formula I substituted succinic anhydride, it is particularly convenient for the absence of a solvent The reaction was carried out under relatively mild temperature conditions of 10 ° C (50 ° C) and was found to be very suitable. The reaction of the substituted succinic anhydrides with the first amine can result in the formation of a cyclic fluorene imine at a sufficiently high temperature. Epoxy propane is preferably epoxy Water of chloropropane, amidoamine and hydrophobizing agent / Valley reaction product reaction to obtain cationic hydrophobic modified resin. The reaction with epoxy halopropane appeared in the hydrophobic modified amino amine amine group. It is believed that the reaction of the third amines with epoxy halopropane is to open the epoxy first Ring, then remove the halide anion and close the epoxy ring again to form a glycidyl (2,3-epoxypropyl) ammonium salt; the second amine reacts with the epoxy propane to form a third amine group. To form a reactive 3-methylated salt; and the first group reacts to form an iS hydroxypropyl group to replace the second amine, and then reacts with the second Moore epoxy Burning reaction. The reaction with epoxy resin can be carried out in an aqueous medium or solvent. Solvents include: alcohols such as methanol, ethanol, propanol, Tianxian isopropanol and butanol; 'toluene, etc. can be used if necessary. A mixture of two kinds of polyphenols. The solvent and reactant or reaction product used in the solution are not reactive under the conditions of ", ...". The reaction with the epihalohydrin is about 0 ° c. To the best, this paper size is suitable for China National Standard (CNS) A4 specification (210 '乂297 公 1 " (Please read the note on the back 4 to complete this page first)-Binding-Order i ——_ Thread Benzene 20 -12-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economy ___ B7 V. Description of the invention ( 10) ~ ~ ^ ~ ~ C to about 40 C for about 1/2 hours to about 3 hours (time is inversely proportional to temperature). The amount of epoxy propane is sufficient to be present in the hydrophobic modified aminoamidoamine At least 40%, preferably at least 70% and most preferably at least 90% of the amine group. The epoxy halogenated reaction composition can be further crosslinked by heating at a temperature of about 40.0 to about 90.0. The solids content of the hydrophobized amidoamine is preferably from about 5% to about 50%. If the reaction with epoxypropane is carried out in an aqueous medium, the hydrophobized amidoamine can be provided to the reaction as an aqueous dispersion. When the reaction between the hydrophobizing agent and the amidoamine is carried out by melting, this dispersion is conveniently prepared by adding water to the molten reaction product under agitation. Further dispersion can be achieved by homogenization. If the reaction with epihalohydrin will be carried out in a solvent, the net hydrophobized amidoamine can be dissolved in a suitable solvent before the reaction with epihalohydrin. In addition, if the hydrophobized amidoamine is prepared in a solvent, the product solution can be directly used in the epoxyhalopropane reaction. Water can be added to the reaction mixture before, during, or after the addition of epihalohydrin. When water is used as the reaction medium for the epoxy-propane reaction, the anti-stag product (which is a thermosetting cationic resin) can be homogenized in its aqueous reaction medium if necessary to reduce the solid particle size. The pH of the dispersion can then be adjusted from about 2.5 to about 8 to provide the best stability of the dispersion. In this way, stable dispersions having a solids content of from about 5% to about 50% can be prepared. When the reaction with epoxy propane is performed in a non-aqueous solvent, an aqueous dispersion of the product can be prepared by the following procedure. The reaction product solution is homogeneously dispersed in water under vigorous agitation, for example, under a pressure of about 1000 to 5000 p.s.i. to provide a substantially stable aqueous emulsion. Subsequent steaming of this paper under atmospheric pressure or under vacuum applies the Chinese National Standard (CNS) A4 specification (210X 297 male f) (Please read the precautions on the back before filling out this page) • Install ------ Order I .------ line I --- ^ — -13-kl Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (11) ~ In addition to organic solvents, a stable aqueous dispersion of reaction products is obtained . The resin composition of the present invention is usually an aqueous dispersion and can be used for papermaking or other fiber-containing substrates. It can be used to manufacture surface-treated paper, especially after the paper is formed, it is usually applied to the surface of the paper by a sizing press. The resin composition can also be incorporated into the pulp at the wet end of a paper machine to provide sizing or other properties such as improved asphalt dispersion, sediment control, paper bulking, paper softness and size enhancement. The amount of resin used for paper sizing usually ranges from about 0.05% to about 2% by weight of the dry paper fibers. After the resin composition of the present invention is combined with paper by mixing with pulp or by adding to the surface, the resin is cured into a hot solid by moist heat. Usually, the heating is performed on the paper at a temperature of about 85 C to about 125 C for about 5 seconds to about 60 seconds. In practice, conventional drum drying of treated paper can provide sufficient curing of the resin. The present invention is illustrated by the following examples, which are provided for illustrative purposes only and are not limiting. All percentages and parts are weight ratios based on the weight of anhydrous pulp unless otherwise indicated. Example 1 This example illustrates the preparation of amine amidine from adipic acid and diethylene triamine and its reaction with the hydrophobing agent cetyl succinic anhydride. 131.5 g (0.9 mol) of succinic acid was added to 154.8 g (1.5 mol) of ethylenediamine in a stirred reaction vessel. The mixture was adjusted to 170 ° C and maintained for 3 hours while removing condensed water by distillation. The molten amidoamine was then cooled to 120 ° C. Assuming that all carboxyl groups react with the first amine group, it is calculated that 254 g of the product contains 1.5 equivalents of the second amine group and 1 · 2 equivalents of the first amine group. The paper size is suitable for financial compensation (standard TcNS) Α4 specification _ (210X297 male ϋ • I! I Β I-- 丨 丨 Γ --- 0-packing 丨 丨 (Please read the precautions on the back before filling this page) 、 = 口 --- · 线 -14- Printed by A7 of the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (12). Add 129.6 g (12 Mo) to the total amino amidamine at 12 () c. Ear) is mainly cetyl succinic anhydride (ASA 100, available from Dixie Chemicals, Houston, Texas) containing 95-98% C16 succinic anhydride, and the rest is higher than The temperature is 1241; it is maintained for 2 hours. After cooling, the product has an acid value of 耄 g of potassium hydroxide / g and an amine value of 4.05 meq / g (equal to the amine equivalent weight of 247). Epoxy propane was reacted with the hydrophobically modified amidoamine prepared in Example 1 to prepare a crosslinked hydrophobically modified cationic resin composition. The aminoamidoamine (98.5 g, 0.40 equivalent amine) of Example 1 was crushed and dispersed in 281 g of water. Epoxy propane (43 2 g, 0.47 mol) was then slowly added to the dispersion while the temperature was maintained below about 400 ° C. The resulting reaction was then mixed The mixture was stirred at 40C for 30 minutes, and then crosslinked by heating at 85 ° C for 2 hours. The parent resin was homogenized using a homogenizer in the laboratory while cooling to room temperature. The product contained 19.1% total solids and had a pH of 50. 2 and particle size 0.5 micron. It contains 0.70% 1,3-dichloropropanol, 0.19% 2,3 propanediol and less than 0.01% residual epichlorohydrin. Example 3 This example illustrates the use of epoxy gas. Propane was reacted with the hydrophobic modified aminoamidoamine prepared in Example 丨 in an organic solvent to prepare a crosslinked hydrophobic modified aminoamido resin composition. The hydrophobic modified aminoamidoamine of Example 1 (97 · 6 g, 0.39 equivalents of amine ) After crushing and dissolving in a mixture of toluene (440 g) and ethanol (496 g). Deionized water (468 g) is added to the amidoamine solution to form a dispersion. Then the epoxy paper size applies the Chinese national standard (CNS) Α4 specification (210 × 297 mm),!-Ί --- 0-¾ 衣 — 丨 (Please read the precautions on the back before filling this page), 1 '丨 • 线 -15- ^ 5538 Jing Di Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China A7 ______B7 V. Description of the Invention P) ~~~~ ^-Propane (43.4 g Square · 47 mole) was slowly added to the dispersion while maintaining the temperature below about 40 ° C. The resulting reaction mixture was stirred at 40 ° C for 2 hours and then crosslinked by heating at 75 t under reflux for 2 hours. The crosslinked resin was cooled to 20 ° C, diluted with water (1180 g), mixed and homogenized using a laboratory homogenizer. The solvent was removed by distillation. The product contained 10.8% total solids with ρΗ6.6 and particles with a particle Z of 0.047 microns. Contains 0.48% 13-dichloropropanol, 0.012% 23-chloropropanediol, and residual epoxy propane less than 0.01%. Example 4 This example illustrates the preparation of amidoamine from adipic acid and diethylene triamine. Modification was performed by reaction with the hydrophobing agent cetyl succinic anhydride. Adipic acid (65.77 g, 0.45 mol) was added to the ethylene glycol diamine (77.35 g, 0.75 mol) in the stirred reaction vessel. The mixture was adjusted to 170. 〇 and maintained at this temperature for 3 hours while removing condensed water by distillation. The molten product was cooled to 123 ° C, and then 97.8 grams (0.3 moles) of hexadecyl succinic anhydride (ACCOsize®) 18 was obtained from Cytek Industries, West Paterson, New Jersey ), The resulting mixture was maintained at 125t for 1 hour and at 146 ° C for 1 hour 'and then quenched by adding water. The product aminoamidoamine has an amine value of 451 meq / g (amine equivalent weight 222) and an acid value of 38. The molecular weight measured by SEC was 756 number average molecular weight and 468 weight average molecular weight. The product was diluted with a sufficient amount of water to produce a dispersion, which was measured in an oven at 150 ° C to contain 23.3% solids. The pH of the dispersion was 10.2. Example 5 A crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamidine of Example 4. Dispersed hydrophobic modified amidoamine (125.4 g, 29.2) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -16- (Please read the precautions on the back before filling in this page j • Packing ·-Ding, = mouth · Line 5 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 — ^ 一 ______ B7 Invention Description () ~ grams of solids, 0.13 amine equivalents, mixed with 651 grams of water. Slowly add the ring Oxychloropropane (11.1 g, 0.12 mol) while maintaining the temperature below 4 (rc. The resulting reaction mixture was stirred at 40 ° C for 30 minutes, then heated to cross-link at 65 ° C for 2 hours, and then diluted by adding a sufficient amount of water. The mixture was adjusted to about 15% solids. The product was divided into two parts. The first part was homogenized using a laboratory homogenizer at room temperature. The second part was not further processed. The product from the first part contained 15.1% solids, pH 5.4 And particle size of 0.13 micron. The second product contains 151% solids, pH 5.4 and particle size of 0.15 micron, and contains 16% 丨, 3 • dichloropropan-2-ol, 0.07% 2,3- Propylene glycol and less than 0.01% residual epichlorohydrin. Potassium sorbate (0.1%) was added to two servings. Biocide. Example 6 This example verifies the surface sizing effect of the products of Examples 2 and 3 of the present invention and compares it with conventional commercial sizing agents. It is composed of bleached kraft hardwood and softwood pulp at 50: 50% The base paper was prepared on a test papermaking machine with a basis weight of 64.9 kg / 1000 square meters. The paper was prepared on papermaking at pH 8.0 and contained 0.5% of water content (based on anhydrous pulp). The paper was unfilled and did not undergo surface treatment. Paper The laboratory sizing press used at room temperature is treated with an aqueous resin solution. The aqueous content of the paper to achieve the desired sizing agent content requires the resin content to pass through when the paper is only treated with water in the sizing press. The amount of water picked up is determined. Then the resin content in the dispersion is adjusted accordingly to obtain the desired concentration added to the paper. After processing, the paper is dried at 104.0 ° drum. After the paper is stored for one week, the size is measured and measured. Use Hercules sizing tester (Hercules Company, Wilmington, Delaware) at 80% reflectance. Use this paper. Standards applicable to Chinese National Standards (CNS) A4 (2 丨 〇297 & Install ------ Order) One * —line _ (Please read the precautions on the back before filling this page) -17- Μ __Β7 — V. Description of the invention (15) Ⅰ — Measurement of 1% formic acid and green dye ink. (Reference: Sizing of Paper, Second Edition Edited by WFReynold, TAIPI Press, 1989). The higher the value, the more the sizing is more south. The commercial sizing agent used is the Scripset (Scripset @) 74 from Monsanto, Montana, Montana. 〇 Styrene_maleic anhydride copolymer and Heixcm® 70 from Hercuies, Wilmington, Delaware, based on alkyl ketene dimer sizing agent. Alkyl ketene dimers are known to provide slip-related properties to paper when applied in sufficient quantities to the surface of the paper. (Please read the notes on the back before filling this page)

、 1T Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs-18- This paper is applicable to Guanjia County (CNS) (21Gx 297 mm) 5 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 _____ Β7 Description of Invention (16 ) Table 1 HST sizing (seconds to 80% reflectance) Sizing content (dry) Sizing agent 0.05% 〇10Λ Example 2 product 6 1 /. 1/0 91 0.2% 218 ^ Example 3 product 2.5 83. 298 Scricket 740 1 9 62 Hurgon 70 308 494 590 The data in Table 1 show that the sizing available for the resin of the present invention is between two commercial sizing agents Scrix 74 and 70 . tMl This example illustrates that the amine amine prepared from adipic acid and diethylene triamine is used to react the paper with a cetyl succinic anhydride hydrophobizing agent. Add adipic acid (0.66 g, 0.45 mol) to the stirred reaction vessel and add diethylenetriamine (7 44 g, 0.75 mol). The mixture was adjusted to 170 ° C and maintained at this temperature for 3 hours while the condensed water was removed by the steaming hall. The molten product was cooled to 122 and then 97.8 g (0.3 mol) of hexadecyl succinic anhydride (ASA 100) was added. The resulting mixture was maintained at 123 C for 2 hours and then quenched with water. The product amine amide has an amine value of 4.44 milliequivalents / gram (amine equivalent weight of 225) and an acid value of 44. The product was diluted with a sufficient amount of water to obtain a dispersion having a solid measurement value of 20.6%. The dispersion has a pH of 10.6. Example 8 A crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamidine of Example 7. Dispersed hydrophobically modified amidoamine (142.0 g, 29.4 g solid ' 0.13 amino equivalent) was mixed with 48.6 g of water. Slowly add epoxy-propane (11.1 g, 0.12 mol) while maintaining the temperature below 40 ° C. The resulting reaction mixture was stirred at 40 ° C for 30 minutes, and then heated to 65 ° C for 2 hours. This paper was delivered to the paper in accordance with Chinese National Standards (CNS) A4 specifications (210, 乂 297) — ~ " ----- -衣 丨 丨 (Please read the precautions on the back before filling this page)

, 1T _line -19-

5. Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (I?). Hot products were homogenized using a laboratory homogenizer. The product contains 20.2% solids, pH 6.2 and a particle size of 0.074 microns. The product contained 0.17% 1,3-dipropane-2-ol, 0.06% 2,3-chloropropanediol, and less than 0.02% residual epichlorohydrin. Example 9 This example illustrates that the crosslinked hydrophobically modified cationic resin composition of Example 8 has a lower foaming tendency than common commercial surface sizing agents. A modified laboratory foaming unit consisting of a pump and an air introduction device allows air to percolate through a powder solution containing a crosslinked hydrophobically modified cationic resin composition. Record the time required for the foam to reach the specified height in the graduated cylinder. The test solution (700 g) contains 0.25% resin (based on anhydrous starch), and 0.6% sodium gasification (based on anhydrous starch) is added to 6% Stayco M (Aestaley Manufacturing, Decatur, IL) ) Solution, Steco solution is prepared by cooking at 95 ° C for 30 minutes. Commercial sizing agents used for comparison were Scrixel 720 and Scrixel 740 styrene-maleic anhydride copolymers available from Monsanto, St. Louis, Montana. The results shown in Table 2 are the time required for the foam to reach a volume of 800 milliliters. The lower the value, the lower the tendency to not foam. Table 2 Time to 1800 ml foaming time (seconds) Sizing time, seconds Scricket 720-75 Scricket 740 60 Product of Example 8 255 Example 10 This example illustrates the use of adipic acid and diethylene glycol Triamine-based amine-based makeup is modified by reaction with hexadecyl succinic anhydride hydrophobizing agent. Adipic acid This paper is sized for China National Standard (CNS) Α4 (210X297 mm) (Please read the precautions on the back before filling this page. • Packing ·

、 1T -line-20-printed by A7 ~ S, * s ----- -— of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (18) — " '— ~' 一 (54.80 g, G .375 moles) was added to diethylenetriamine (77.35 g, 0.75 moles) in a stirred reaction vessel. The mixture was adjusted to and maintained at this temperature for 3 hours, while condensed water was removed by a steaming hall. The molten product was cooled to 125 ° C and then 9.12.8 g (28 mol) of hexadecyl succinic anhydride (ASA 100) was added. The resulting mixture was at 125. 〇 When maintaining π, maintain it for 1 day, and then quench it by adding water. The product amine amine has an amine value of 5. 亳 equivalents / gram (amine equivalent weight 178) and acid value 42 (acid equivalent weight U36). The product was diluted with sufficient water to obtain a dispersion with a solid measurement of 23 4%. The dispersion had a pH of 10.4. Example 11 ------------ A crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamidine of Example 10. Dispersed hydrophobically modified amidoamine (123.3 grams, 289 grams of solids, 0.16 amine equivalents) was mixed with 65.4 grams of water. Epoxy letter propylene (11.1 g '0-12 mol) was slowly added while maintaining the temperature below 40. 〇. The resulting reaction mixture was stirred at 4 ° C for 30 minutes, and then heated at 651 for 2 hours to crosslink ^

After Ik, the mixture was adjusted to about 5% solids after being quenched and diluted by adding sufficient water. The product contained 15.7% solids, pH 60 and a particle size of 0.700 microns. The product a had 0.23 / 〇 1,3-dipropane alcohol, ΐ 6% 6% 2,3-propanediol and less than 0.01% residual epoxy propane. Example 12 This example illustrates another preparation example for the preparation of aminoamidamine from adipic acid and diethylene triamine, followed by reaction with cetyl succinic anhydride. Adipic acid (54.80 grams, 0.375 moles) in a stirred reaction container. The paper size applies the Chinese National Standard (CNS) A4 specification (2ι〇 × 297 male feet 1 --r ------ -Install ------- Order ------- ^ line (Please read the notes on the back before filling this page) -21-8 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs kl ^ ________ B7 Description of the invention (19) ~ _ added to diethylene triamine (77.38 g, G.75 mole). The mixture is adjusted to 17 (TC and maintained at this temperature for 3 hours, while condensate is removed by steaming crane. Melt products Cool to 125 ° C and then add 146.7 g (0.45 mol) of hexadecyl succinic anhydride (ASA 100). The resulting mixture was maintained at 125t for 1 hour, maintained at 1 ° C for 4 hours at 14 ° C, and then quenched by adding water The product aminoamine has an amine value of 3.69 milliequivalents / gram (amine equivalent weight 271) and an acid value of 57 5 (acid equivalent weight 975). The product is diluted with a sufficient amount of water to obtain a solid measurement value of 23 3%. Dispersion. The dispersion has a pH of 10.1. Example 13 A cross-linked hydrophobically modified cation tree composition was prepared from the hydrophobically modified aminoamidate of Example 12. The dispersed hydrophobic Amineamine (152.0 grams, 354 grams of solid '0.13 amine equivalent) was mixed with 69.3 grams of water. Epichlorohydrin (11.1 grams, 0.12 moles) was added slowly while maintaining the temperature below the temperature The resulting reaction mixture was stirred at 4 ° C for 30 minutes, and then heated at 65 ° C for 2 hours to crosslink,

After Ik, the mixture was adjusted to about 5% solids by quenching and diluting by adding sufficient water. The product contained 15.3% solids, 1) 1158, and a particle size of 218 microns. The product contained 0.084% 1,3-dichloropropan-2-ol, 0075% 2,3-chloropropanediol and less than 0.01% residual epichlorohydrin. Example 14 This example does not illustrate another example of the preparation of aminoamidine from adipic acid and diethylene triamine, followed by reaction with cetyl succinic anhydride. Adipic acid (54.80 g, 0.375 mol) was added to diethylenetriamine (68.78 g, 0.66 mol) in a stirred reaction vessel. The mixture is adjusted to the size of this paper to apply the Chinese National Standard (CNS) Α4 specification (21〇χ 297 & | · 7 · ^^ installed ------ order 丨, ---- line (please read the precautions on the back first) (Fill in this page again)--22- ΑΊ ΑΊ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ^ ------_ V. Description of the invention (20) One by one ~~ '170 ° C and at this temperature for 3 hours, At the same time, the condensed water was removed by the steaming hall. The smelted product was cooled to 125 ° C, and then 173.7 g (0.53 mol) of hexadecyl succinic anhydride (ASA 100) was added. The resulting mixture was at 125. (: maintenance For 1 hour, hold at 140 C for 1 hour, and then add leeches. The amine producing amine has an amine value of 2.35 milliequivalents per gram (amine equivalent weight 425) and an acid value of 54 (acid The equivalent weight is 1042). The product is diluted with a sufficient amount of water to obtain a dispersion with a solid measurement value of% · ι%. The dispersion has a pH of 9.0. Example 15 Preparation of a crosslinked hydrophobic modification from the hydrophobic modified aminoamidine of Example 14 Cationic resin composition. Dispersed hydrophobically modified amidoamine (178.65 g, 43.0 g solids, 0.10 amino equivalent) was mixed with 80.75 g of water. Epichlorohydrin (7.4 g, 0.08 mol) was added while maintaining the temperature below 400 c. The resulting reaction mixture was stirred at 40 ° C for 30 minutes, and then heated to cross-link it for 2 hours, followed by quenching. Turn off and dilute by adding enough water to adjust the mixture to about 15% solids. The product contains 14.8% solids, ρΗ 5 · 8 and a particle size of 114 microns.

The product contained 0.12% 1,3-dichloropropane-2-ol, 018 / (2,3-chloropropanediol) and less than 0.01% residual epichlorohydrin. B. Fortunately, cross column A. This example is a comparative example, illustrating the use of the polyamine to dicarboxylic acid ratio described in US Patent No. 3,922,243, but using water as the dispersion medium to prepare amine groups from adipic acid and diethylene triamine. Amidoamine, and hydrophobic modification with cetyl succinic anhydride. Adipic acid (109 g, 0.75 mol) is added to the second paper in the stirred reaction container. The size of the paper is applicable to the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm). ^ Yi Yi-(Please read the back first (Notes for filling in this page)

1T -line -23- Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Α7 __B7 V. Description of the Invention (21) ~-Ethyltriamine (77.38 g, 0.75 mol). The mixture was adjusted to ㈣ and maintained at this temperature for 5 hours, while condensed water was removed by a steaming hall. The fused product was cooled to 128 ° C and then 97.8 g (0.30 mol) of hexadecyl succinic anhydride (ASA 100) was added. The resulting mixture was maintained for 16 hours (rc) and then quenched by adding water to obtain the name product into two layers. 'Cannot be used to prepare resin. Comparative Example B Repeated Comparative Example A, but this example is applied to milder reaction conditions, that is, a hydrophobicizing agent Reaction at temperatures below 150 ° C. Adipic acid (109.6! G, 0.75 moles) was added to diethylenetriamine (77.38 g, 0.75 moles) in a stirred reaction vessel. Mixture adjustment To 160 ° C and maintained at this temperature until 1/3 of the theoretical condensate is distilled off. The molten product is cooled to 128 ° c and then 97 · 8 g (0.30 mol) hexadecyl succinic anhydride is added. (ASA 100). The resulting mixture was maintained at 125.0 for 1 hour, and was maintained at 14 ° C. for 1 hour, and then quenched by adding water to obtain a nominal 25% solid. The product amine amide has an amine value of 3.26 meq / g ( Amine equivalent weight 307) and acid value 33 (acid equivalent weight 1696). The product was diluted with a sufficient amount of water to obtain a dispersion having a measured solid value of 22.1%. The dispersion had a pH of 8.11. Comparative Example C From Comparative Example B Hydrophobic modified amidoamine to prepare cross-linked hydrophobic modified cationic resin composition. Aminopyramine (155.52 g, 34.37 g solid, 0.11 amine equivalent) was mixed with 60.73 g of water. Epichlorohydrin (11.10 g '0.12 mole) was slowly added while maintaining the temperature below 40 ° C. The resulting reaction mixture was 40 C 槚: Mix for 30 minutes, then heat at 65 ° C for 2 hours for cross-linking. Chinese National Standard (CNS) Α4 size (210X 297 mm) is applied according to the paper size. (Please read the precautions on the back before filling this page. ) Loading ·

、 1T-line -24- 495538 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of Didi A7 B7 Invention Description (22) After quenching and diluting by adding sufficient water, the mixture is adjusted to about 15% solids. The product contains 12.5% solids, pH 6.8 and particle size 0.32 microns. The product contained 0.42% 1,3-dipropane-2-ol, 0.45% 2,3-chloropropanediol and less than 0.02% residual epichlorohydrin.

Comparative Example D This example is a comparative example, which illustrates the use of a polyamine to dicarboxylic acid ratio as described in US Patent No. 3,922,243 to prepare aminoamidoamine from adipic acid and diethylene triamine, and cetyl Hydrophobic modification of succinic anhydride. The milder reaction conditions under which this patent is applied. Adipic acid (73.07 g, 0.50 mol) was added to the stirred reaction vessel to diethylenetriamine (5 1.59 g, 0.50 mol). The mixture was adjusted to 160 ° C and maintained at this temperature until 1/3 of the theoretical condensate was distilled off. The product was cooled to 128 ° C and 130.40 g (0.4 mole) of hexadecyl succinic anhydride (ASA 100) was added. The resulting mixture was maintained at 125 ° C for 1 hour and at 140 C for 1 hour, and then quenched by adding water to obtain a nominal 25% solid. The product amine amine has an amine value of 1.53 亳 equivalent / g (amine equivalent weight 652) and an acid value of 76 (acid equivalent weight 740). The product was diluted with a sufficient amount of water to obtain a dispersion having a solid measurement value of 24.0%. The dispersion had a pH of 5.7.

Comparative Example E A crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamidine of Comparative Example D. The dispersed hydrophobically modified amidoamine (197.71 g '47 .41 g solid, 0.07 amino equivalent) was mixed with 84.34 g of water. Epichlorohydrin (11.10 g, 0.12 mol) was added slowly while maintaining the temperature below 40 r. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling out this page)-binding-binding -25- 495538 A7 B7 printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Preparation 5. Description of the invention (23) The obtained reaction mixture was stirred at 40 ° C for 30 minutes, and then heated to crosslink for 2 hours, and then quenched and diluted by adding a sufficient amount of water to adjust the mixture to about 15% solids. The product contained 14.4% solids, pH 6.0 and a particle size of 0.28 microns. The product contained 0.21 / l > 1,3-monopropane-2-ol '0.64% 2,3-chloropropanediol and less than 0.19% residual epoxy propane. Comparative Example F This example is a comparative example, illustrating the use of U.S. Pat. No. 3,922,243 to describe the ratio of ceramide to monoacid acid. However, compared with the user of the previous comparative example, amines were prepared from adipic acid and diethylene triamine. Amine and hydrophobic modification with cetyl succinic anhydride. The milder reaction conditions of this patent application. Adipic acid (81.84 g, 0.56 mol) was added to diethylenetriamine (77.38 g, 0.75 mol) in a stirred reaction vessel. The mixture was adjusted to 170 C and maintained at this temperature for 3 hours, while the condensed water was removed by means of a steaming crane. The product was cooled to 129 ° C and 122.25 g (0.375 mol) of hexadecyl succinic anhydride (ASA 100) was added. The resulting mixture was maintained at 125 ° C for 1 hour and at 140 ° C for 1 hour, and then quenched by adding water to obtain a nominal 25% solid. The product Aminopyramine has an amine value of 2.78 milliequivalents per gram (aminous equivalent weight of 360) and an acid value of 49 (acid equivalent weight of 1156). The product was diluted with a sufficient amount of water to obtain a dispersion having a solid measurement of 25.2%. The dispersion had a pH of 9.0. Comparative Example G A crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamidine of Comparative Example F. Dispersed hydrophobically modified amidoamine (138.46 g, 34.88 g solid, 0.10 amino equivalent) was mixed with 80.34 g of water. Slowly add the paper size to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling in this tribute) -Installation · \\ 0 · Line-26- V. Description of the invention (24 ) A7 B7 Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China (t) (克 0.12 Mor) while maintaining the temperature below the thief. The resulting reaction mixture was stirred at 4 Gt for 3 G minutes and then cross-linked at the stage of addition, followed by quenching and dilution by adding a sufficient amount of water to adjust the mixture to about 15% solids. The product contained 14.2% solids, pH 5.4 and particle size of 0.30 microns. The product contained 0.04% U-dichloropropan-2-ol ', 15% 2,3-propanediol and less than 0.01% residual epichlorohydrin. Example 16 This example verifies the sizing effect of the resin of the present invention compared to the material described in US # 3,922,243. A base paper was prepared on a test paper machine. The paper is prepared from bleached kraft broadleaf and softwood pulp 5G: 5G blends with a basis weight of 64 9 kg η_ square meters. The paper was prepared at papermaking pH 8.0 and contained 05% Minglin and 12% Albacar 5970 'redundant carbonic acid per (Beijing Hengte Mining Company, Pennsylvania). The paper is unsurfaced. All additives are on a dry basis based on pulp dry weight. Paper used in a 65 C laboratory sizing press with 8% ()? (: D_15〇 oxidized starch solution (obtained from Muscatine, Iowa (5 ^ 4 treatment company) also contains a 7-knife powder form and The resin of the present invention. The resin content required for the starch solution is determined by measuring the absorption of the starch solution when the paper is treated with the starch solution in a sizing press. Then the resin content of the starch solution is adjusted to obtain the desired concentration (0.25 %). Sizing solution is prepared with (concentration 0.2% based on paper) and without optical brightener (Phorwite P, Mobay, Pittsburgh, PA). Optical brighteners are commonly used To increase the paper size of the paper with a sizing press @Associate (CNS) Α4 size (210X 297 mm) (Please read the precautions on the back before filling out this page)-Packing ·

, 1T -27- 495538 A7 B7 Λ 5 Description of the invention (25) Brightness. The paper was dried on a drum at 96 ° C just after treatment. Sizing results are shown in Table 3. Sizing was measured on paper using a Hercules sizing tester (Hercules, Wilmington, Delaware) with an ink containing 10/0 formic acid and green dye at 80% reflectance after two weeks of storage. The repeat of Example 2 was used as a control. The molar ratio of polyamines to dicarboxylic acids and the molar ratio of hydrophobizing agents to polyamines used to prepare hydrophobically modified amidoamines are shown for comparison. Table 3 Surface sizing comparison-HST sizing (grandchildren to 80% reflectance, sizing agent amine / mole diacid hydrophobing agent mole number / second amine equivalent HST does not contain optical brightener HST contains Optical Enhancer 1 丨 Product of Example 2 1.66 0.4 64 'Five DZL Tablets' J 56 Example 15 Product of 1.66 0.8 36 60 — Comparative Example E Product 1.0 0.8 2 24 Table 3 The results verify that the When the carboxylic acid ratio is greater than about ι.4, the surface sizing is generally improved. (Please read the precautions on the back before filling this page)

1. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Example 17 This example verifies the sizing effect of the resin of the present invention compared to the material described in US Patent No. 3,922 243 5. A base paper was prepared on a test paper machine. The paper is prepared from 50:50 blends of bleached kraft broadleaf and needle tea wood paper at a basis weight of 64.9 kg / 1000 square meters. The paper was prepared at papermaking pH 8.0 and contained 0.5% alum. The paper is unfilled and surface treated. All additives are on a dry basis based on pulp dry weight. The paper was treated with an aqueous resin dispersion using a laboratory sizing press at room temperature. The paper was tumble dried at just 104 ° C. The required sizing agent concentration in the aqueous dispersion is measured when the paper is only treated with water in the sizing press. The paper size is applicable to the Chinese National Standard (CNS) A4 size (2K) x 297 mm. -28- 495538 A7 B7 V. Description of the invention (26) The amount of water picked up is determined. The resin concentration of the dispersion was then adjusted accordingly to obtain the desired concentration (0.2%) added to the paper. Sizing results are shown in Table 3. Sizing was measured on paper using a Hercules sizing tester at 80% reflectance with an ink containing 1% formic acid and green dye after two weeks of storage. As a control, the repetition of Example 2 was used. The molar ratio of polyamine to dicarboxylic acid and the molar ratio of hydrophobizing agent to polyamine used to prepare hydrophobically modified amidoamine are shown for comparison. Table 4 Surface sizing comparison-HST sizing (seconds to 80% reflectance) Sizing agent amine / mole diacid ratio Hydrophobic agent Mole number HST, seconds / second amine equivalent Example 2 product 1.66 0.4 > 1200 Example 11 Product 2.00 0.4 1107 Example 13 Product 2.00 0.8 652 Comparative Example C Product 1.0 0.4 12 Comparative Example G Product 1.33 0.5 513 The data in Table 4 indicates that this resin is used when compared with resins prepared by the method of U.S. Patent No. 3,922,243. The resin obtained by the invention has a higher sizing degree. Comparative ExampleΗ This example describes the preparation of stearylamine. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Stearic acid (Emersol® 152, available from Henkel, Cincinnati, Ohio) 512.1 g (1.8 mol ) Melt and heat to 106 ° C in the stirred reaction container. Diethylenetriamine (103.2 g, 1.0 mole) was slowly added. The mixture was adjusted to 170 ° C and maintained at this temperature for 3 hours, while condensate was removed by distillation. The molten product is cooled. The product has a melting point of 105 ° C and an amine value of 2.02 meq / g (amine equivalent weight 495).

Comparative example J This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -29- 495538 Five I_I__ Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 Description of the invention (27) This example describes the comparative example Stearylamine is used to prepare a crosslinked cationic resin composition. Comparative Example Η Stearyl amine (97.0 g, 0.20 amine equivalent) was slowly mixed into hot water (1200 ml) to form a dispersion. The dispersion temperature was set at 85 ° C and epichlorohydrin (18.5 g, 0.20 mole) was quickly added. The mixture was stirred for 2 hours, then homogenized and then cooled to room temperature. The product contained 8.2% solids, pH 4.0 and a particle size of 0.40 microns. Example 18 This example verifies that the product of the present invention compares the sizing effect of stearylamine based sizing agents with the conventional commercial sizing agents and the effect on paper properties. The paper was paper on a test papermaking machine, and the sizing agent was added to the inside and surface of the paper in a sizing press. The paper is made from bleached kraft hardwood and softwood pulp refined to 75:25 搀 of 425 CSF with a basis weight of 64.9 kg / 1000 square meters. The paper was prepared at papermaking pH 8.0, containing 0.25% alum (based on pulp), filled with 10% Albaka 5970 precipitated calcium carbonate, and applied with 4% Starco M oxidized starch and 0.05% sodium chloride. The glue press solution is treated at 55 surface. For surface application, the solid concentration of the resin and vaporized sodium required to apply the required amount of material is determined by first determining the amount of absorbing powder solution that is picked up when the paper is treated with starch solution only in the sizing press. The concentration of resin and sodium vapor in the powder solution was adjusted accordingly to obtain the desired concentration to be added to the paper. The paper is dehydrated to obtain 4-6% moisture in the paper roll. The sizing agent is applied internally or in a sizing press solution. The base paper contains at least 0.05% Hurgon 70 alkylketene dimer sizing agent on all papers. 俾 Auxiliary sizing press operation. The results of sizing and friction coefficient (coF) are shown in the paper standard applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page).

, 1T -30-495538

7 7 A B V. Description of the invention (28) Table 5. All results were measured after one week of paper storage. The size was measured using a Hercules size tester (Hercules, Wilmington, Delaware) using an ink containing 1% acetic acid and a green dye at 80% reflectance. The COF system uses Thwing-Albert (Thing-Albert Instrument Co., Philadelphia, PA) in the machine direction, and a 200-gram skid is used to measure the felt-to-line. Display static COF. As a control, the sizing agent equivalent to Example 3 was used. Alkyl ketene dimer and ammonium stearylamine are known to cause problems related to slippage of paper when applied to the surface or inside of the paper in a sufficient amount. Table 5 Effects on sizing effect and paper properties Sizing agent sizing concentration (%) Sizing point HST, COF in seconds, static Hurbet 70 0.05 internal 2 0.482 Hurgon 70 0.075 internal 166 0.510 Hurgon 70 0.10 Internal 272 0.500 Example 3 0.025 Surface 41 0.575 Example 3 0.10 Surface 152 0.502 Example 3 0.10 Internal 43 0.525 Example 3 0.20 Internal 83 0.532 Comparative Example J 0.025 Surface 9 0.542 Comparative Example J 0.10 Surface 229 0.315 Comparative Example J 0.10 Internal 172 0.478 Comparative Example J 0.20 Internal 236 0.395 1. Unless otherwise specified, Hurgon 70 of all papers is 0.05%. Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Table 5 shows that the resin described here can provide significant application to paper when used in combination with a low concentration internal sizing agent. Glue concentration without negatively affecting the friction coefficient of the paper. The stearylamine sizing agent of Comparative Example J can provide sizing but also has a large negative effect on the coefficient of friction of paper. Commercial experience shows that high concentrations of alkyl ketene dimers based on sizing agents also negatively affect the friction coefficient of paper and the high-speed conversion performance of paper, such as CL Brungardt and JC Gast, TAPPI 1996 Papermaker Conference Proceedings, page 297 Discuss the paper size to the Chinese National Standard (CNS) A4 specification (210X297 mm) -31-^ 538 ^ 538 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs f A7 s_____B7_ V. Description of the invention (29) ο Example 19 This example does not illustrate the preparation of amidoamine from adipic acid and diethylene triamine via hydrophobic modification with stearic acid. 65.7 g (0.45 mole) of adipic acid was added to the stirred reaction vessel (77.4 g (0.75 mole)) of ethylene diamine. The mixture was adjusted to 170 ° C and maintained for 3 hours while removing condensed water by distillation. The molten amine was then cooled to 125 ° C. At 125 C, 85.3 g (0.3 mol) of 95% stearic acid (Aldrich Chemical Company, Milwaukee, Wisconsin) was added to the entire amount of aminoamidamine. The temperature rose to 170 C for 2 hours. The product was diluted with hot water to obtain 230% total solids. The measured total solids of the product were 21.9%, pH 10.4, acid value 13 mg potassium hydroxide / g and amino group value 5.39 meq / g (equal to total amino group equivalent 185). The number average molecular weight measured by SEC was 790. Example 20 This example illustrates the preparation of a crosslinked hydrophobically modified cationic resin composition by reacting epichlorohydrin with the hydrophobically modified amine sulfonamide prepared in Example 19. Example 19 was dispersed to a hydrophobically modified amine-based amine (6 7 4.4 g, 14 7 g solids, 0.8 equivalents of amine) and 308.7 g of water was mixed. Epoxy propane (611 g, 0.66 mol) was slowly added to the dispersion while the temperature was maintained below 400 ° C. The resulting reaction mixture was stirred at 40 ° C for 30 minutes, and then heated to cross-link at 65 ° C for 2 hours, and then quenched and diluted by adding a sufficient amount of water to adjust the mixture to about 10.5% solids. The product contains 10 · 7% of total solids' pH 5 · 91 and particle size 1 · 〇00 microns This paper size is applicable to China National Standard (CNS) A4 specifications (210 × 297 mm) (Please read the precautions on the back before filling this page )-Installed

、 1T -32- A7 —________ B7 ___ 5. Description of the invention (30). Contains 0.076% 1,3-dipropane-2-ol, 0.04% 2,3-chloropropanediol and less than 0.01% residual propane epoxy propane. Surface sizing with the product resin was performed using the procedure described in Example 18, but the paper was prepared at 75.0 kg / 1000 square meters, and the internal addition of Hurgon 70 was 0-075% based on dry pulp. In these cases, the sizing agent (0.2% based on paper) of this example can obtain 217 seconds HST sizing when added to the sizing press starch 'compared to the internal sizing and sizing press starch alone to obtain 1 s HST Sizing. The examples given here are not to be considered as limiting the present invention, but are provided to illustrate some specific specific examples of the present invention. Various modifications and changes may be made to the present invention without departing from the scope of the attached patent application. (Please read the notes on the back before filling out this page)-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

This paper size applies to China National Standard (CNS) A4 (210X 297mm) -33-

Claims (1)

495538 A8 B8 C8 D8 Six 1-1 Patent scope No. 087103237 Patent application scope amendment date of this amendment: December 89 A resin composition containing epihalohydrin and hydrophobically modified amino group 醯The reaction product of amine, which is obtained by the following reaction: (a) Amine amine, which contains one or more first amine groups and one or more second and third amine groups, the amine amine system Obtained through the following reaction: (i) A monoamine composition is obtained by reacting a dicarboxylic acid or a derivative thereof. The amine composition comprises a polyamine, and the polyamine contains two or more second or third amine groups, wherein The polyamine comprises one or more selected from the group consisting of alkyl hydrazine (3-aminopropylamine, and polyalkylene polyamines, wherein the alkyl group contains 1 to 12 carbon atoms, and the The polyalkylene polyamine is selected from the group consisting of diethylene triamine, triethylene tetramine and tetra ethylene pentamine, and (ii) a dicarboxylic acid or an ester or anhydride thereof. Or hydrazone derivatives, such derivatives are selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid The group consisting of fumaric acid, maleic acid, palate acid, Teng acid, diglycolic acid, Gw dimer acid and the dicarboxylic acids having the formula in # Packing -------- Order --- ΓΙ —, ---, Ι ^ Γ (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Π) COOH COOH where R is a straight or branched saturated or unsaturated alkyl group of 8 to 22 carbon atoms, the alkyl group is selected from the group consisting of isostetenyl, n-octadecyl, n-hexadecenyl, n Dodecyl, isododecenyl, n-decenyl, and original paper sizes are applicable to the Chinese National Standard (CNS) A4 (210 X 297 cm). Group of patent applications. Octene oligomers. Wherein; the molar number ratio of the polyamine to the dicarboxylic acid or its derivative is from 1. 5 ·· 1 to 3: 1, and (b) a hydrophobizing agent having from 12 to 40 carbon atoms, comprising At least one member selected from the group consisting of a carboxylic acid or a derivative thereof of formula RCOOH, where the R group is selected from the group consisting of alkyl, alkenyl, aromatic In the group consisting of alkyl, cycloalkyl, or cyclodiluent; ii) a dicarboxylic anhydride having the formula Wherein Rf is a linear or branched saturated or unsaturated alkyl group having 8 to 22 carbon atoms, and iii) a dimer or dimer having the formula: Where η is an integer from 0 to 20, and may be the same or different scales and R " is a straight or branched saturated or unsaturated alkyl group having 8 to 24 carbon atoms, and R is a group having $ to 40 carbon atoms The amount of the linear or branched saturated or unsaturated alkyl group, and the amount of the hydrophobizing agent can react with the non-first amine group between 1000/60 and 60%. For example, the resin composition in claim 1 of the patent scope, in which the polyamine p-diacidic acid or 4 ^ 538 ch3 A8 B8 C8 D8 6. Application scope of the patent The mole ratio of the derivative is from 1.55] to 2.5: 1. 3. The resin composition as described in claim 1 of the patent scope, wherein the molar ratio of polyamine to diferulic acid or its derivative is from 1.6: 1 to 2: 1. 4. The resin composition according to item 1 of the patent application scope, wherein at least 50 mole% of the amine composition comprises a polyamine, the polyamine contains at least two first amine groups and at least one selected from the group consisting of the second and third Amine group. 5. The resin composition according to item 1 of the scope of application, wherein the N-alkylfluorene (3-aminopropyl fee) is methyl carbamide (3-aminopropylamine). 6. The resin composition as claimed in claim 4, wherein the amine composition further comprises a diamine selected from the group consisting of: HWCHU H2N-CH-CH2 [0-CH2CH], NH2, and I i ch3 〒h3 ch3 ch3 H2N-CH-CH2_ [OCHCHrH0CH2C · ^^ where X is an integer from 2 to 10, y is an integer from 2 to 100, b is an integer from 2 to 100, and a and C may be the same or different from each other. Integer to 5. 7. The resin composition according to item 1 of the patent application scope, wherein the dicarboxylic acid includes an aliphatic, cycloaliphatic or aromatic dicarboxylic acid containing 2 to 44 carbon atoms or one of these derivatives. For example, the resin composition according to item 7 of the application, wherein the dicarboxylic acid is adipic acid, or an ester, anhydride, or a fluorenyl derivative thereof. 9 · As stated in the scope of the patent, the resin composition of item 1, wherein the polyamine contains diethylene triamine and the dicarboxylic acid contains adipic acid and its derivatives. The size of the paper is applicable to China National Fresh (CNS) A4 specifications. (210 X 297 mm) I ϋ n I if nn ϋ I · ϋ n ϋ ϋ · ϋ I n _ ϋ I n «I ϋ I · (Please read the note on the back first? Matters before filling out this page) Ministry of Economy Printed by the Intellectual Property Bureau Employee Cooperatives A8 B8 C8 D8 2. The scope of patent application 1 〇 · The resin composition according to the item of the scope of patent application, wherein the amount of the hydrophobizing agent is less than 30% of the amount of the amino group when the amino group contains a second amino group Non-first amine reaction. 11. The resin composition according to item 10 of the application, wherein the amount of the hydrophobizing agent is not sufficient to react with more than 100/0 of the non-first amine group of aminoamidoamine. 12. The resin composition as claimed in claim 1, wherein the amount of the hydrophobizing agent is sufficient to react with at least 20% of the first amine group. 13. The resin composition according to item 1 of the patent application scope, wherein the epoxy halopropane comprises epoxy propane. 14. Resin composition as claimed in the scope of patent application 1. At least 40% of the amine groups in the resin composition as claimed in the scope of patent application have been reacted with epihalohydrin. 16. The resin composition according to item 1 of the patent application, wherein the polyamine includes diethylene triamine; the dicarboxylic acid includes adipic acid or a derivative thereof; epihalohydrin is an epoxy propylene oxide compound. ; Hydrophobizing agent contains substituted butadiene needle of the following formula: 0 O R1- 〇 where R is a linear or branched dilute group containing 8 to 22 broken atoms, and the amount of hydrophobizing agent is sufficient with at least 20% of the first amine group Reaction; of which at least 70% of the second amine group has been reacted with propane. 17. A method for preparing a resin composition, comprising: a) reacting an amine composition with a dicarboxylic acid or a derivative thereof, the amine composition comprising a polyamine, the polyamine containing at least two first amine groups And at least one selected from amine groups including second and third amine groups, wherein the polyamine is a mol of dicarboxylic acid or a derivative thereof, and the paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) ) Please read; read the f, i, and r items. Note the I items and I items. Among them, hydrophobic modified aminoamines are printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs to print 495538 A8 B8 C8 D8. 6. The scope of application for patents ranges from 1.5: 1 to 3: 1, and aminoamines are formed. At least one first amine group and at least one non-first amine group selected from the second and third amine groups; b) the amine group reacts with a hydrophobic agent having 12 to 40 carbon atoms to form a hydrophobic modified amine Amidoamine, wherein the amount of the hydrophobic agent is sufficient to react at least part of the first amino group, but not enough to react with more than 60% of the non-first amino groups of the amidoamine; and c) hydrophobically modified amidoamine and the ring Oxypropane reaction. 18. A method as claimed in claim π, wherein the epihalohydrin comprises epichlorohydrin. 19. The method according to item 17 of the application for a patent, wherein the hydrophobing agent comprises at least one member selected from the group consisting of: i) an acid or a derivative thereof of the formula RCOOH, where the R group is selected from the group consisting of alkenyl and alkenyl , Aryl, cycloalkyl, or cycloalkenyl; ii) Dicarboxylic anhydrides with chemical formulas (please read the note on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs where R is a saturated or unsaturated straight bond or branched radical containing 8 to 22 carbon atoms; iii) a dimer or polymer; iv) a dilute ketone polymer; And v) such mixtures. 20. The method according to item 19 of the application, wherein the hydrophobizing agent has the structure of Formula I and the reaction temperature of the aminoamine and the hydrophobizing agent is 100 ° C to 150 ° C. 21. The method according to item 17 of the patent application scope, further comprising (d) crosslinking the resin composition by heating the resin composition at 40 ° C to 90 ° C. 22. A resin composition prepared by a method as described in any one of the scope of patent application H21. This paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm) 495538 8888 ABCD =, patent application scope 23.- A method of sizing paper, including application on the paper surface An aqueous suspension of the resin composition according to any one of 16 items. 24. A sizing paper prepared by a method such as the 23rd item in the patent application. 25. A method for preparing sizing paper, comprising the steps of: (i) providing water ^ pulp suspension ocean liquid; (ii) adding the water of the tree moon-day composition as described in the scope of the patent application to the water-based paper poly suspension. Suspension; 客 g will form pulp into sheet paper in the shoe; and (d) drying the sheet paper to obtain sized paper. 26 · —Seed 'sizing paper, which was prepared by the method of item 25 of the profit-seeking rail track (please read the precautions on the back before filling this page) -------- ---- & JT, Ding ___ ml ^ r L, ---- t Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of IT and Economy