WO2000040634A2

WO2000040634A2 - Modified epoxies for paper sizing

Info

Publication number: WO2000040634A2
Application number: PCT/US1999/030347
Authority: WO
Inventors: Angie H. Ma; Tuyen T. Nguyen
Original assignee: Hercules Incorporated
Priority date: 1998-12-30
Filing date: 1999-12-17
Publication date: 2000-07-13
Also published as: AU2372200A; WO2000040634A3

Abstract

Hydrophobically modified epoxy resin comprising (a) a polyfunctional epoxy resin backbone optionally chain extended with at least one difunctional group and (b) at least one hydrophobic moiety, such resin being particularly well suited as sizing agent for paper.

Description

Modified Epoxies For Paper Sizing

Backgound of the Invention Field of Invention

The present invention relates to hydrophobically modified epoxy resins and more particularly it relates to such resins made by the reaction of a polyepoxide with an epoxide reactable hydrophobic reactant such as fatty acid, rosin acid, alkyl phenol; and optionally a chain extender such as a polyacid, polyphenol; and optionally a modifier such as an organic acid, or amine, or a phenol compound.

Description of the Prior Art

Epoxy resins that contain a hydrophobic group have been described in USP 3,459,715 and 5,677,397. In USP 3,459,715, an unsaturated fatty acid was reacted with an olefin-reactive anhydride such as maleic anhydride to give a polycarboxylic acid mixture. This mixture is then treated with epichlorohydrin to form the epoxy. USP 5,677,397 describes the making of epoxy resin with hydrophobic group from alkylated phenol. In this type of epoxy resin the alkylated phenol is part of the main chain of the epoxy resin.

Summary of the Invention According to the present invention, there is provided a hydrophobically modified epoxy resin comprising (a) a polyfunctional epoxy resin backbone optionally chain extended with at least one difunctional group, and at least one hydrophobic moiety.

Further provided according to the present invention is a process for preparing a hydrophobically modified epoxy resin comprising (a) providing polyepoxide reactant, (b) providing epoxide reactablde hydrophobic reactant, (c) optionally poviding chain extender reactant, (d) optionally providing modifier reactant, and (e) reacting said reactants. Still further provided according to the present invention are sizing agents for paper and paper sized with such sizing agents.

Detailed Description of the Invention A hydrophobically modified epoxy resin comprising (a) a polyfunctional epoxy resin backbone optionally chain extended with at least one difunctional group, and (b) at least one hydrophobic moiety has been found to be an effective sizing agent for paper.

Polyfunctional epoxy resin is the main backbone of the sizing component. Epoxies made from the reaction of epichlorohydrin with a polyhydroxy compound, a polyamino compound, a hydroxy amino compound are useful for this application. Some of such epoxies are: diglycidyl ether of bisphenol A (Epon 828, Epon 1001 , Epon 1009 from Shell Chemical Co., DER 331 , DER 31 , DER 334 from Dow Chemical Co., EPN 1138 from Ciba Geigy Corp.), diglycidyl ethers of 4,4'- dihydroxydiphenyl methane 4,4'-dihydroxydiphenyl sulfone, resorcinol, biphenol, dihydroxydiphenyl sulfide, 4,2'-biphenol, tris(4-hydroxyphenyl)methane, 1 ,1,2,2 tetrakis(hydroxy-phenyl)methane, pentaerythritol tetraglycidylether, glycerol triglycidyl ether, butanediol diglycidyl ether and trimethylolpropane glycidyl ether. Polyglycidyl derivatives of phenolformaldehyde novolaks of the following chemical structure are also usable:

where: R=H, CH₃; R'=CH₂, n=1-10. Some of the commercially available epoxy novolaks are: D.E.N. 431 , D.E.N. 438, D.E.N. 485 (Dow Chemical Co.), ECN 1138, ECN 1235, ECN 1273, ECN 1299 (Ciba-Geigy Corporation).

Epoxy adducts of epichlorohydrin and amines are also useful such as N,N- 5 diglycidyl aniline, N,N-diglycidyl toluidine, N,N,N ,N -tetraglycidylbis(methylamino)- cyclohexane, N,N,N ,N ,-tetraglycidyl-4,4'-di-aminodiphenyl methane, N,N,N ,N - tetraglycidyl-3,3'diaminodiphenyl sulfone, N,N -dimethyl-N,N -diglycidyl- 4,4'diaminodiphenyl methane. Commercially available epoxies of this type include Araldite MY-720 (Ciba-Geigy Corp.), PGA-C and PGA-X (Sherwin-Williams Co., 0 Chicago, Illinois), Glyamine 125 and Glyamine 135 (F. I. C. Corp., San Francisco, CA)

The hydrophobic moiety of the hydrophobically modifed epoxy resin can be an alkyl phenol, and/or an alkylated monocarboxylic acid. The alkyl group can be any alkyl group with a number of carbon atoms from 1 to 40. The alkyl phenol may 5 also be substituted with a halide (I, Br, Cl, F), -NO₂, -SO₃H, -SO₂H, -PO₃H, - COOH, an aryl group, -OR or another alkyl group. The carboxylic acid may be of alkyl carboxylic (C1-C40), or an alkaryl carboxylic acid. Rosin acids and fluorinated carboxylic acid with a number of carbon atoms from 1 to 40 are also expected to provide both water and oil repellency. o The preferred alkyl phenol component is dinonyl phenol and the preferred alkylated monocarboxylic acid is stearic acid.

The epoxy backbone may be chain extended with a difunctional group such as a bisphenol, or dicarboxylic acid. Any known bisphenol or dihydroxyaryl compound can be used. Some of these compounds are: bisphenol A, bisphenol F, 5 rescorcinol, hydroquinone, dihydroxy napthalene, 4,4'-dihydroxydiphenyl sulfone, 4,4' dihydroxydiphenyl cyclohexane, 4,4'-dihydroxy-diphenyl ethane, 4,4'dihydroxy benzophenone, 4,4'-dihydroxydiphenyl ether etc. All of the dihydroxy compounds described in USP 4,925,910 are suitable, and the disclosure of USP 4,925,910 is hereby incorporated by reference. These dihydroxy compounds have the general o formula

O R³ where X is a chemical bond or -S-, -O-, -C II-, -C I -

R⁴ (R³ and R⁴ are different when n and p are simultaneously O) or

(only when n or p is 0), R and R² are each alkyl or alkoxy, each of 1 to 6 carbon atoms, R³ and R⁴ are each hydrogen, alkyl of 1 to 6 carbon atoms, aryl or halogen-substituted alkyl of 1 to 4 carbon atoms, m is 0 or 1 and n and p are 0, 1 , 2, 3 or 4.

The dicarboxylic acid may come from the following structure:

HOOC-R-COOH

where R= benzenoid, napthalenoid, anthracenoid, alkyl (linear, cyclic, cycloaromatic, branched) having from 1 to 40 carbon atoms. A mixed difunctional carboxylic acid and a phenolic can also be used such as hydroxy benzoic acid, hydroxy napthoic acid, hydroxy anthracenoic acid etc. The hydrophobically modified epoxy resin of the present invention can optionally be further modified with an organic acid, or amine or phenolic compound, such as diacids, diamines and polyphenols. The mixture of epoxy and chain extender can also be modified with a primary amine of the formula R-NH₂ where R is an organic moiety having from 1 to 30 carbon atoms and secondary amines of the formula R^NH where R, and R₂ can be the same or different organic moiety having from 1-30 carbon atoms.

The mole ratio of polyfunctional epoxy resin to hydrophobic moiety generally is at least about 0.1 :1. preferably about 1 :0.8. The mole ratio can be up to about

10:1 , preferably up to about 1 :0.4. Other additives that contain epoxy group or epoxy reactive group can also be added to the formulation to impart other functionalities such as cationic charge and aldehyde. An example of this is the addition of Dow quat, glycidyltrimethylammonium chloride available from Dow Chemical Co. and 4-hydroxy benzaldehyde. This modification utilities the same chemistry that is involved in the reaction between an epoxide and a nucleophile. The purpose of this modification is not hydrophobic modification but to provide other properties that are useful for a paper making application such as cationic charge, and cellulose reactive group.

The modified epoxy can be made from a polyepoxide, one or more than one hydrophobe modifier, and a chain extender by heating. Sometimes a catalyst can be added to speed up the reaction. Catalysts such as ethyltriphenyl phosphonium iodide, imidazole, trialkyl amine etc are suitable.

The synthesis of the resin of the present invention involves heating of a mixture of all ingredients and catalysts together at a temperature of at least about

50°C. The temperature can be up to about 200°C. The reaction can be carried out with or without solvent. It is preferable to do the reaction without a solvent to minimize cost. When solvent is used it can be toluene, acetone, methylethyl, ketone, heptane, etc. Ingredients may be added at once or in stages to provide a needed molecular structure. The general synthesis scheme of modified epoxy is illustrated in Scheme I.

Scheme I Synthesis of Epoxy Sizing Agents

15

Stearic acid

130°C, 4 hrs Nonyl Phenol, Bisphenol A / Diaci

20

Sizing Procedure:

A solution of the modified epoxy is dissolved in 1 ,2-dichloropropane (DCP) at the desired concentration. For example: 0.1 g in 100 g DCP for 0.1 % loading or 0.25 g in 100 g DCP for 25% loading. This solution is poured into an aluminum pan (6" x9"). A 5"X8" sheet of paper is dipped into this solution for 3 seconds and it is laid flat to dry. After 24 hrs, the sizing efficiency is determined using a Hercules Sizing Tester.

Sizing efficiency of modified epoxy is tested by solvent impregnation method since this test is independent of retention of the emulsion particles on paper. The sizing efficiency is measured by the Hercules Size Test.

The Hercules Size Test (HST) is a standard test in the industry for measuring the degree of sizing. This method employs an aqueous dye solution as the penetrant to permit optical detection of the liquid front as it moves through the sheet. The apparatus determines the time required for the reflectance of the sheet surface not in contact with the penetrant to drop to a predetermined percentage of its original reflectance. All HST testing data reported measured the seconds to 80% reflection with 1% formic acid ink mixed with naphthol green B dye (Hercules Test Ink #2) unless otherwise noted. The use of this formic acid ink is a more severe test than neutral ink and tends to give faster test times. High HST values are better than low values. The amount of sizing desired depends upon the kind of paper being made and the system used to make it.

Example 1

A mixture of EPN 1138 a glycidyl ether of a low molecular weight novolak phenolic resin available from Ciba Geigy (10 g), nonyl phenol (11 g) and 0.2 g of ethyl triphenyl phosphonium iodide [ETPP1] was heated at 100° C for 3 hrs. The sizing was done using DCP as solvent and the sizing value is measured within 24 hrs of application to the paper. At 1 % loading of this material, unfilled paper gave

206 sec, filled paper (12% precipitated calcium carbonate) gave 76 sec measured by Hercules Sizing Test (HST) using ink of pH=2. The control gave less than 1 second of HST. Control is the paper (50% hardwood/50% softwood Kraft pulp, premade by a standard paper making process. If it is unfilled it has no calcium carbonate, if it is filled, it has 12% of calcium carbonate by weight) without the sizing treatment.

Example 2

A mixture of EPN 1138 (5 g), stearic acid (7.9 g) and ETPPI (0.1 g) was heated at 130° C for 3 hrs. The result was a solid with a melting point start at 40° C.

The sample was dissolved in propylene dichloride (PDC) and sized on filled and unfilled paper. Sizing test was performed within 24 hrs of application. At 1 % loading of this material, unfilled paper gave 3 sec. , filled paper gave 9 sec.

Example 3 A mixture of EPN 1138 (5 g), stearic acid (5.9 g) and ETPPI (0.1) was heated at 130° C for 4 hrs. A solid was formed with a softening point at 45° C. At 1% loading of this material, unfilled paper gave 12 sec, and filled paper gave 17 sec. HST.

Example 4

A mixture of EPN 1138 (10 g), stearic acid (7.9 g) and ETPPI (0.2 g) was heated at 130° C for 4 hrs. A solid with softening point of 40° C was obtained. At 0.5 % loading of this material, unfilled paper gave 115 sec and filled paper gave 34 sec. of HST within 24 hrs of application. Natural aged samples (2 weeks)

Example 5

A mixture of EPN 1138 (10 g), stearic acid (4 g) and 0.2 g of ETPPI was heated together at 140° C for 4 hrs. A solid with softening point of 40° C was obtained. At 0.5 % loading of this material, unfilled paper gave 16 sec and filled paper gave 3 sec. of HST within 24 hrs of application. Natural aged samples (2 weeks) gave 626 sec and 122 sec. of HST, respectively.

Example 6

A mixture of EPN 1138 (10 g), Pamite 90 rosin acid available from Hercules Incorporated (16.8 g) and ETPPI (0.2 g) was heated together at 140° C for 4 hours. A solid with softening point of 100° C was obtained. At 0.1% loading of this material, unfilled paper gave 272 sec and filled paper gave 8 sec of HST within 24 hrs of application.

Example 7 A mixture of EPN 1138 (10 g), abietic acid (18 g) and ETPPI (0.2 g) was heated together at 140° C for 4 hrs. A solid with softening point of 108° C was obtained. At 0.1 % loading of this material, unfilled paper gave 580 sec and filled paper gave 140 sec of HST within 24 hrs of application. Natural aged samples (2 weeks) gave 736 sec and 140 sec of HST, respectively.

Example 8

A mixture of EPN 1138 (100 g) and Pamite 90 (94.5 g) was heated together at 140° C for 4 hrs. A solid with softening point of 66°C was obtained. At 0.1% loading of this material, unfilled paper gave 188 sec and filled paper gave 2 sec of HST within 24 hrs of application. After 2 weeks, the samples gave 383 sec and 6 sec of HST, respectively.

Example 9

A mixture of EPN 1138 (10 g), Pamite 90 (8.4 g) and ETPPI (0.2 g) was heated at 140° C for 4 hrs. A solid with softening point of 79° C was obtained. At 0.1% loading of this material, unfilled paper gave 124 sec and filled paper gave 2 sec of HST.

Example 10

A mixture of EPN 1138 (10 g), Pamite 90 (4.2 g) and ETPPI (0.2 g) was heated at 140° C for 4 hrs. A solid with softening point of 48°C was obtained. At 0.1% loading of this material, unfilled paper gave 66 sec and filled paper gave 2 sec of HST. After two weeks the samples gave 59 sec and 2 sec of HST, respectively.

Example 11

A mixture of EPN 1138 (5 g), nonyl phenol (4.9 g), bisphenol A (0.6 g) and ETPPI was heated at 130°C for 4 hrs. A solid with softening point of 45°C was obtained. At 0.25% loading of this material, unfilled paper gave 101 sec and filled paper gave 95 sec of HST.

Example 12 A mixture of EPN 1138 (5 g), nonyl phenol (4.9 g), t-phthalic acid (0.46 g) and

ETPPI (0.1g) was heated at 130°C for 5 hrs. A solid with softening point of 47°C was obtained. At 0.25% loading of this material, unfilled paper gave 64 sec and filled paper gave 100 sec of HST.

Example 13

A mixture of EPN 1138 (5 g), nonyl phenol (4.3 g), bisphenol A (1 g) and ETPPI (0.1 g) was heated at 130°C for 3 hrs. A solid with softening point of 55°C was obtained. At 0.25% loading of this material, unfilled paper gave 330 sec and filled paper gave 295 sec of HST. After 2 weeks of aging, the samples gave 342 sec and 243 sec of HST, respectively.

Example 14

A mixture of EPN 1138 (5 g), nonyl phenol (4.3 g), adipic acid (0.6 g) and ETPPI (0.1 g) was heated at 130°C for 3 hrs. A solid with softening point of 55°C was obtained. At 0.25% loading of this material, unfilled paper gave 43 sec and filled paper gave 29 sec of HST.

Example 15

A mixture of EPN 1138 (5 g), nonyl phenol (4.2 g), bisphenol A (1.0 g) and ETPPI (0.1 g) was heated at 130°C for 3 hrs. A solid with softening point of 58°C was obtained. At 0.25% loading of this material, unfilled paper gave 282 sec and filled paper gave 306 sec of HST.

Example 16

A mixture of EPN 1138 (5 g), stearic acid (5.4 g), bisphenol A (1 g) and ETPPI (0.1 g) was heated at 130°C for 3.5 hrs. A solid with a softening point of 43°C was obtained. At 0.25% loading of this material, unfilled paper gave 242 sec and filled paper gave 209 sec of HST.

Example 17

A mixture of EPN 1138 (5 g), di-nonyl phenol (6.5 g), bisphenol A (1 g) and ETPPI (0.1 g) was heated at 130°C for 3 hrs. A solid with a softening point of 45°C was obtained. At 0.25% of this material, unfilled paper gave 153 sec, and filled paper gave 168 sec of HST. Example 18

A mixture of EPN 1138 (5 g), nonyl phenol (4.3 g), sebacic acid (0.8 g) and ETPPI (0.1 g) was heated at 130°C for 3 hrs. A solid with a softening point of 40°C was obtained. At 0.25% loading of this material, unfilled paper gave 39 sec and filled paper gave 33 sec of HST.

Example 19

A mixture of EPN 1138 (5 g), abietic acid (8.4 g),biphenol (0.8 g) and ETPPI (0.1g) was heated at 140°C for 3 hrs. A solid with a softening point of 105°C was obtained. At 0.25% loading of this material, unfilled paper gave 230 sec and filled paper gave 257 sec of HST.

Example 20 A mixture of EPN 1138 (5 g), nonyl phenol (4.3 g), bi-naphthol (1.2 g) and

ETPPI (0.1 g) was heated at 130°C for 3.5 hrs. A solid with a softening point of 55°C was obtained. At 0.25% loading of this solid, unfilled paper gave 245 sec and filled paper gave 272 sec of HST. After two weeks, the paper gave 240 sec and 280 sec of HST, respectively.

Example 21

A mixture of EPN 1138 (5 g), nonyl phenol (2.1 g), abietic acid (2.9 g), bisphenol A (1 g) and ETPPI (0.1 g) was heated at 130°C for 3.5 hrs. A solid with a softening point of 85°C was obtained. At 0.25% loading of this material, unfilled paper gave 315 sec and filled paper gave 409 sec of HST.

Example 22

A mixture of EPN 1138 (5 g), stearic acid (2.8 g), abietic acid (4.2 g), bisphenol A (1 g) and ETPPI (0.1 g) was heated at 130°C for 3 hrs. A silid with softening point of 65°C was obtained. At 0.25% loading of this solid, unfilled paper gave 228 sec and filled paper gave 243 sec of HST. Example 23

A mixture of EPN 1138 (5 g), nonyl phenol (2.8 g), Pamite 90 (2.1 g), bisphenol A (1 g) and ETPPI (0.1 g) was heated at 130°C for 3 hrs. A solid with a softening point of 68°C was obtained. At 0.25 % loading of this material, unfilled paper gave 262 sec and filled paper gave 269 sec of HST. After 2 weeks, the papers gave 250 sec and 290 sec of HST, respectively.

Example 24

A mixture of EPN 1138 (5 g), nonyl phenol (2.1 g), Pamite 90 (2.9 g), bisphenol A (1.0 g) and ETPPI (0.1 g) was heated to 130°c for 3 hrs. A solid with a softening point of 80°C was obtained. At 0.25% loading of this material, unfilled paper gave 233 sec and filled paper gave 354 sec of HST. After 2 weeks the paper samples gave 282 sec and 350 sec of HST, respectively.

Example 25

A mixture of EPN 1138 (5 g), nonyl phenol (4.3 g), 2-hydroxy napthoic acid (0.7 g) and ETPPI (0.1 g) was heated at 140°C for 4 hrs. A solid with a softening point of 43° C was obtained. At 0.25% loading of this material, unfilled paper gave 31 sec, and filled paper gave 6 sec of HST.

Example 26

A mixture of EPN 1138 (5 g), nonyl phenol (4.3 g), 2-naphthol (0.6 g) and ETPPI. (0.1g) was heated at 140°C for 3.5 hr. A solid with a softening point of 39°C was obtained. At 0.25% loading of this material, unfilled paper gave 87 sec, and filled apepr gave 11 sec.of HST.

The reactants used in these Examples, their mole ratio and the loading of the sizing composition are summarized in Table I. TABLE I

Mole

Example Reactants Ratio Loadin

Example 1 EPN 1138/Nonyl phenol 1/0.9 1%

Example 2 EPN 1138/Stearic Acid 1/1 1%

Example 3 EPN 1138/Stearic Acid 1/0.75 1 %

Example 4 EPN 1138/Stearic Acid 1/0.5 0.5%

Example 5 EPN 1138/Stearic Acid 1/0.25 0.5%

Example 6 EPN 1138/Pamite 90 1/1 0.1%

Example 7 EPN 1138/Abietic Acid 1/0.75 0.1%

Example 8 EPN 1138/Pamite 90 1/0.6 0.1%

Example 9 EPN 1138/Pamite 90 1/0.5 0.1%

Example 10 PN 1138/Pamite 90 1/025 0.1% Chain Extension with a Difunctional Group

Example 11 PN 1138/NP/BPA 1/0.8/0.1 0.25% Example 12 PN 1138/NP/PthA 1/0.8/0.1 0.25% Example 13 PN 1138/NP/BPA 1/0.7/0.15 0.25% Example 14 PN 1138/NP/ADP 1/0.7/0.15 0.25% Example 15 PN 1138/NP/BPA 1/0.7/0.16 0.25% Example 16 PN 1138/SA/BPA 1/0.7/0.16 0.25% Example 17 PN 1138/DNP/BPA 1/0.7/0.16 0.25% Example 18 PN 1138/NP/SBA 1/0.7/0.15 0.25% Example 19 PN 1138/AA/BP 1/0.7/0.15 0.25% Example 20 PN 1138/NP/BNP 1/0.7/0.15 0.25% Example 21 PN 1138/NP// BPA 1/0.35/0.35/0.15 0.25% Example 22 PN 1138/SA/AA/BPA 1/0.35/0.35/0.15 0.25% Example 23 PN1138/NP/Pamite 90/BPA 1/0.45/0.25/0.15 0.25% Example 24 PN1138/NP/Pamite 90/BPA 1/0.35/0.35/0.15 0.25%

Modification with a naphthalenic group Example 25 PN 1138/NP/2-NAA 1/0.7/0.15 0.25%

Example 26 PN 1138/NP/2-NAP 1/0.7/0.15 0.25% Example 27 EPN 1138/Stearis Acid/Bisphenol A/Decyl amine (1/0.62/0.08/0.09)

A mixture of EPN 1138 (20 g), stearic acid (19.6 g), bisphenol A (2.54 g),

ETPPI (0.15 g) was heated at 145°C for 10 hrs. The temperature of the reaction mixture was lowered to 80°C, and adipic acid (0.97 g) was added. The mixture was kept at 80°C for 2 hrs. At 0.25% loading of this material, filled paper gave 54 sec and unfilled paper gave 207 sees of HST. After 2 weeks, the HST values became 213 sec and 388 sec, respectively.

Example 28

EPN 1138/Stearic Acid/Bisphenol A/Decyl Amine (1/0.62/0.08/0.09)

A mixture of EPN 1138 (20 g), stearic acid (19.6 g), bisphenol A (2.03 g) and ETPPI (0.15 g) was heated at 145°C for 10 hrs. The temperature of the reaction mixture was lowered to 80°C, and decyl amine (1.57 g) was added. The mixture was kept at 80°C for 2 hrs. At 0.25% loading of this material, filled paper gave 136 sec and unfilled paper gave 449 sees of HST. After 2 weeks, the HST values became 141 sec and 387 sec, respectively.

Example 29 EPN 1138/Stearic Acid/Bisphenol A/Octyl amine (1/0.62/0.08/0.09)

A mixture of EPN 1138 (20 g), stearic acid (19.6 g), bisphenol A (2.03 g) and ETPPI (0.15 g) was heated at 145°C for 10 hrs. The temperature of the reaction mixture was lowered to 80°C. Octyl amine (1.29 g) was added. The mixture was kept at 80°C for 2 hrs. At 0.25% loading of this material, filled paper gave 164 sec and unfilled paper gave 492 sees of HST. After 2 weeks, the HST values became 137 sec and 455 sec, respectively.

Example 30 EPN 1138/Stearic Acid/Bisphenol A/hexyl amine (1/0.62/0.08/0.12) A mixture of EPN 1138 (8.89 g), stearic acid (8.7 g), bisphenol A (0.90 g),

ETPPI (0.07 g) and hexyl amine (0.06 g) was heated at 145°C for 10 hrs. At 0.25% loading of this material, filled paper gave 241 sec and unfilled paper gave 545 sees of HST. After 2 weeks, the HST values became 215 sec and 743 sec, respectively. Example 31 EPN 1138/Stearic Acid/Bisphenol A/dibutyl amine(1/0.62/0.08/0.08)

A mixture of EPN 1138 (20 g), stearic acid (19.6 g), bisphenol A (2.03 g) and ETPPI (0.15 g) was heated at 145°C for 10 hrs. The temperature of the reaction mixture was lowered to 80°C. Dibutyl amine (1.15 g) was added. The mixture was kept at 80°C for 2 hrs. At 0.25% loading of this material, filled paper gave 15 sec and unfilled paper gave 390 sees, of HST . After 2 weeks, the HST values became 62 sec and 824 sec, respectively.

Example 32

EPN 1138/Stearic Acid/Bisphenol A/Dow quat (1/0.68/0.18/0.05)

A mixture of EPN 1138(8.89 g), stearic acid (21.5 g), bisphenol A (4.57 g), ETPPI (0.07 g) and Dow quat glycidyltrimethylammonium chloride available from Dow Chemical Co. (0.84 g) was heated at 145°C for 10 hrs. At 0.25% loading of this material, filled paper gave 202 sec and unfilled paper gave 537 sees of HST. After 2 weeks, the HST values became 202 sec and 653 sec, respectively.

Example 33

EPN 1138/Stearic Acid/Bisphenol A/4-Hydroxybenzaldehyde (1/0.5/0.2/0.15) A mixture of EPN 1138(20 g), stearic acid (15.8 g), bisphenol A (3.8 g),

ETPPI (0.15 g) and 4-hydroxybenzaldehyde (2.7 g) was heated at 145°C for 10 hrs. At 0.25% loading of this material, filled paper gave 231 sec and unfilled paper gave 477 sees of HST. After 2 weeks, the HST values became 246 sec and 592 sec, respectively.

Claims

What is claimed:

5 1. A hydrophobically modified epoxy resin comprising (a) a polyfunctional epoxy resin backbone optionally chain extended with at least one difunctional group, and (b) at least one hydrophobic moiety.

2. The resin of claim 1 wherein the polyfunctional epoxy resin is selected 0 from the group consisting of (i) polyepoxides comprising the reaction product of epichlorohydrin with polyhydroxy compound, polyamino compound or hydroxyamino compound; (ii) polyglycidyl derivatives of phenolformaldehyde novolaks; and (iii) epoxy adducts of epichlorohydrin and amines.

5 3. The resin of claim 1 wherein the hydrophobic moiety is selected from the group consisting of alkyl phenols and alkylated monocarboxylic acids, wherein the alkyl group has from 1 to 40 carbon atoms.

4. The resin of claim 1 wherein the difunctional group, if present, is o selected from the group consisting of bisphenols, dicarboxylie acids and mixed difunctional carboxylic acid and phenolic.

5. The resin of claim 1 wherein the mole ratio of polyfunctional epoxy resin to hydrophobic moiety is at least about 0.1 :1. 5

6. The resin of claim 1 wherein the mole ratio of polyfunctional epoxy resin to hydrophobic moiety is up to about 10:1.

7. The resin of claim 2 wherein the hydrophobic moiety is selected from the group consisting of alkyl phenols and alkylated monocarboxylic acids, wherein the alkyl group has from 1 to 40 carbon atoms, the difunctional group if present is selected from the group consisting of bisphenols and dicarboxylie acids, and the mole ratio of polyfunctional epoxy resin to hydrophobic moiety is from about 0.1 :1 to about 10:1.

8. The resin of claim 7 wherein the polyepoxide is selected from the group consisting of diglycidyl ether of bisphenol A, diglycidyl ethers of 4,4'dihyroxydiphenyl methane, 4,4'-dihydroxydiphenyl sulfone, resorcinol, biphenol, dihydroxydiphenyl sulfide, 4,2'-biphenol, tris(4-hydroxyphenyl)methane, 1 ,1 ,2,2tetrakis(hydroxyphenyl)methane, pentaerythritol tetraglycidyl ether, glycerol triglycidyl ether, butanediol diglycidyl ether and trimethylolpropane glycidyl ether; the 0 polyglycidyl derivatives of phenol-formaldehyde novolaks has the structure

5 where R=H, CH₃; R'=CH₂ and n=1 to 10; and the epoxy adduct is selected from the group consisting of N,N-diglycidyl aniline, N,N-diglycidyl toluidine, N,N,N',N^,-tetraglycidylbis(methylamino)-cyclohexane, N.N.N'.N'.-tetraglycidyM^'-di-aminodiphenyl methane, N.N'.N'.-tetraglycidyl- 3,3'diaminodiphenyl sulfone, N.N'-dimethyl-N.N'-diglycidyM^'-diaminodiphenyl o methane.

9. The resin of claim 7 wherein the alkyl phenol is selected from the group consisting of alkyl phenol, alkaryl phenol and their substituted derivatives substituted with halide, -NO₂, -SO₃H, -S0₂H, -P0₃H, -COOH, -OR, aryl group or another alkyl group, and the alkylated monocarboxylic acid is selected from the group consisting of alkyl carboxylic acids, alkaryl carboxylic acids, rosin acids and fluorinated carboxylic acids.

10. The resin of claim 7 wherein the bisphenol, if present, is selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, resorcinol, hydroquinone, dihydroxy naphthalene, 4,4'-dihydroxydiphenyl sulfone, 4,4'- dihydroxydiphenyl cyclohexane, 4,4'-dihydroxydiphenyl ethane, 4,4'dihydroxy benzophenone, 4,4'-dihydroxydiphenyl ether and hydroxy compounds of the general formula

where X is a chemical bond or

(R³ and R⁴ are different when n and p are simultaneously 0) or

(only when n or p is 0), R¹ and R² are each alkyl or alkoxy, each of 1 to 6 carbon atoms, R³ and R⁴ are each hydrogen, alkyl of 1 to 6 carbon atoms, aryl or halogen- substituted alkyl of 1 to 4 carbon atoms, m is 0 or 1 and n and p are 0, 1 , 2, 3 or 4, the dicarboxylie acid, if present, has the general formula HOOC-R-COOH where R= benzenoid, naphthalenoid, anthracenoid and linear, branched, cyclic, cycloaromatic alkyl having from 1 to 40 carbon atoms, and the mixed difunctional carboxylic acid and phenolic, if present, is selected from the group consisting of hydroxy benzoic acid, hydroxy naphthoic acid and hydroxy anthracenoic acid.

11. The resin of claim 7 wherein the mole ratio of polyfunctional epoxy resin to hydrophobic moiety is at least about 1 :0.8.

12. The resin of claim 7 wherein the mole ratio of polyfunctional epoxy resin to hydrophobic moiety is up to about 1 :0.4.

13. The resin of claim 8 wherein the alkyl phenol is selected from the group consisting of alkyl phenol, alkaryl phenol and their substituted derivatives substituted with halide, -N0₂, -SO₃H, -SO₂H, -PO₃H, -COOH, -OR, aryl group or another alkyl group, and the alkylated monocarboxylic acid is selected from the group consisting of alkyl carboxylic acids, alkaryl carboxylic acids, rosin acids and fluorinated carboxylic acids, the bisphenol, if present, is selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, resorcinol, hydroquinone, dihydroxy naphthalene, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl cyclohexane, 4,4'-dihydroxydiphenyl ethane, 4,4'dihydroxy benzophenone, 4,4'- dihydroxydiphenyl ether and hydroxy compounds of the general formula

where X is a chemical bond or

(R³ and R⁴ are different when n and p are simultaneously 0) or

(only when n or p is 0), R¹ and R²are each alkyl or alkoxy, each of 1 to 6 carbon atoms, R³and R⁴ are each hydrogen, alkyl of 1 to 6 carbon atoms, aryl or halogen- substituted alkyl of 1 to 4 carbon atoms, m is 0 or 1 and n and p are 0, 1 , 2, 3 or 4, the dicarboxylie acid, if present, has the general formula HOOC-R-COOH where R= benzenoid, naphthalenoid, anthracenoid and linear, branched, cyclic, cycloaromatic alkyl having from 1 to 40 carbon atoms, and the mixed difunctional carboxylic acid and phenolic if present, is selected from the group consisting of hydroxy benzoic acid, hydroxy naphthoic acid and hydroxy anthracenoic acid and the mole ratio of polyfunctional epoxy resin to hydrophobic moiety is from about 1 :0.8.to about 1 :0.4.

14. The resin of claim 13 wherein the polyepoxide is 4,4' dihydroxy diphenyl methane and the polyglycidyl derivatives of phenol formaldehyde novolaks are those wherein n = 3-4.

15. The resin of claim 13 wherein the alkyl phenol is dinonyl phenol and the alkylated monocarboxylic acid is stearic acid.

16. The resin of claim 13 wherein the bisphenol, if present, is bisphenol A the dicarboxylie acid, if present, is adipic acid.

17. The resin of claim 1 modified with a modifier selected from the group consisting of organic acids, amines and phenolic compounds.

18 The resin of claim 7 modified with a modifier selected from the group consisting of diacids, diamines and polyphenols.

19. The resin of claim 13 modified with a modifier selected from the group consisting of diacids, diamines and polyphenols.

20. A process for preparing a hydrophobically modified epoxy resin comprising (a) providing polyepoxide reactant, (b) providing epoxide reactablde hydrophobic reactant, (c) optionally providing chain extender reactant, (d) optionally providing modifier reactant, and (e) reacting said reactants.

21. The process of claim 20 wherein the temperature is at least about 50°C.

22. The process of claim 20 wherein the temperature is up to about 200°C.

23. The process of claim 20 wherein the polyepoxide reactant is selected from the group consisting of (i) polyepoxides comprising the reaction product of epichlorohydrin with polyhydroxy compound, polyamino compound or hydroxyamino compound; (ii) polyglycidyl derivatives of phenolformadehyde novolaks, and (iii) epoxy adducts of epichlorohydrin and amines.

24. The process of claim 20 wherein the hydrophobic reactant is selected from the group consisting of alkyl phenols and alkylated monocarboxylic acids, wherein the alkyl group has from 1 to 40 carbon atoms.

25. The process of claim 20 wherein the chain extender reactant, if present, is selected from the group consisting of bisphenols, dicarboxylie acids and mixed difunctional carboxylic acid and phenolic.

26. The process of claim 20 wherein the modifier reactant, if present is selected from the group consisting of diacids, diamines and polyphenols.

27. The process of claim 20 wherein the ratio of polyepoxide reactant to hydrophobic reactant is at least about 0.1 :1.

28. The process of claim 20 wherein the mole ratio of polyepoxide reactant to hydrophobic reactant is up to about 10:1.

29. The process of claim 23 wherein the hydrophobic reactant is selected from the group consisting of alkyl phenols and alkylated monocarboxylic acids, wherein the alkyl group has from 1 to 40 carbon atoms, the chain extender reactant, if present, is selected from the group consisting of bisphenols, dicarboxylie acids and mixed difunctional carboxylic acid and phenolic, the modifier, if present, is selected from the group consisting of diacids, diamines and polyphenols, the temperature is from about 50 to about 200°C and the mole ratio of polyepoxide reactant to hydrophobic reactant is from about 0.1 :1 to about 10:1.

30. The process of claim 29 wherein the polyepoxide is selected from the group consisting of diglycidyl ether of bisphenol A, diglycidyl ethers of 4,4'dihyroxydiphenyl methane, 4,4'-dihydroxydiphenyl sulfone, resorcinol, biphenol, dihydroxydiphenyl sulfide, 4,2'-biphenol, tris(4- hydroxyphenyl)methane,1 ,1 ,2,2tetrakis(hydroxyphenyl)methane, pentaerythritol tetraglycidyl ether, glycerol triglycidyl ether, butanediol diglycidyl ether and trimethylolpropane glycidyl ether; the polyglycidyl derivatives of phenol formaldehyde novolaks has the structure

where R=H, CH₃, R'=CH₂and n=1 to 10; and the epoxy adduct is selected from the group consisting of N,N-diglycidyl aniline, N,N-diglycidyl toluidine, N,N,N',N'- tetraglycidylbis(methylamino) -cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-di- aminodiphenyl methane, N.N.N'.N'-tetraglycidyl-S.S'diaminodiphenyl sulfone, N,N' dimethyl-N,N'-diglycidyl-4,4'diaminodiphenyl methane.

31. The process of claim 29 wherein the alkyl phenol is selected from the group consisting of alkyl phenol, alkaryl phenol and their substituted derivatives substituted with halide, -N0₂, -SO₃H, -SO₂H, -PO₃H, -COOH, -OR, aryl group or another alkyl group, and the alkylated monocarboxylic acid is selected from the group consisting of alkyl carboxylic acids, alkaryl carboxylic acids, rosin acids and fluorinated carboxylic acids.

32. The process of claim 29 wherein the bisphenol, if present, is selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, resorcinol, hydroquinone, dihydroxy naphthalene, 4,4'-dihydroxydiphenyl sulfone, 4,4'- dihydroxydiphenyl cyclohexane, 4,4'-dihydroxydiphenyl ethane, 4,4'dihydroxy benzophenone, 4,4'-dihydroxydiphenyl ether and hydroxy compounds of the general formula

where X is a chemical bond or

(R³ and R⁴ are different when n and p are simultaneously 0) or

O

II

-s-

II O

(only when n or p is 0), R¹ and R² are each alkyl or alkoxy, each of 1 to 6 carbon atoms, R³and R⁴ are each hydrogen, alkyl of 1 to 6 carbon atoms, aryl or halogen- substituted alkyl of 1 to 4 carbon atoms, m is 0 or 1 and n and p are 0, 1 , 2, 3 or 4, the dicarboxylie acid, if present, has the general formula HOOC-R-COOH where R= benzenoid, naphthalenoid, anthracenoid and linear, branched, cyclic, cycloaromatic alkyl having from 1 to 40 carbon atoms, and the mixed difunctional carboxylic acid and phenolic, if present, is selected from the group consisting of hydroxy benzoic acid, hydroxy naphthoic acid and hydroxy anthracenoic acid.

33. The process of claim 29 wherein the mole ratio of polyepoxide reactant to hydrophobic reactant is at least about 1:0.8.

34. The process of claim 29 wherein the mole ratio of polyepoxide reactant to hydrophobic reactant is up to about 1 :0.4.

35. The process of claim 29 wherein the temperature is at least about 100°C.

36. The process of claim 29 wherein the temperature is up to about 140°C.

37. The process of claim 30 wherein the alkyl phenol is selected from the group consisting of alkyl phenol, alkaryl phenol and their substituted derivatives substituted with halide, -NO₂, -SO₃H, -SO₂H, -PO₃H, -COOH, -OR, aryl group or another alkyl group, and the alkylated monocarboxylic acid is selected from the group consisting of alkyl carboxylic acids, alkaryl carboxylic acids, rosin acids and fluorinated carboxylic acids, the bisphenol, if present, is selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, resorcinol, hydroquinone, dihydroxy naphthalene, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl cyclohexane, 4,4'-dihydroxy-diphenyl ethane, 4,4'dihydroxy benzophenone, 4,4'- dihydroxydiphenyl ether and hydroxy compounds of the general formula

where X is a chemical bond or

(R³ and R⁴ are different when n and p are simultaneously 0) or

O

II

-s-

B (only when n or p is 0), R¹ and R² are each alkyl or alkoxy, each of 1 to 6 carbon atoms, R^{3 and R}4 are each hydrogen, alkyl of 1 to 6 carbon atoms, aryl or halogen- substituted alkyl of 1 to 4 carbon atoms, m is 0 or 1 and n and p are 0, 1 , 2, 3 or 4, the dicarboxylie acid, if present, has the general formula HOOC-R-COOH where R= benzenoid, naphthalenoid, anthracenoid and linear, branched, cyclic, cycloaromatic alkyl having from 1 to 40 carbon atoms, and the mixed difunctional carboxylic acid and phenolic, if present, is selected from the group consisting of hydroxy benzoic acid, hydroxy naphthoic acid and hydroxy anthracenoic acid, the mole ratio of polyepoxide reactant to hydrophobic reactant is from about 1 :0.8 to about 1 :0.4 and the temperature is from about 100 to about 140°C.

38. A sizing agent for paper comprising the resin of claim 1.

39. A sizing agent for paper comprising the resin of claim 2.

40. A sizing agent for paper comprising the resin of claim 3.

41. A sizing agent for paper comprising the resin of claim 7.

42. A sizing agent for paper comprising the resin of claim 13.

43. A sizing agent for paper comprising the resin of claim 17.

44. Paper sized with the sizing agent of claim 39.

45. Paper sized with the sizing agent of claim 40.

46. Paper sized with the sizing agent of claim 41

47. Paper sized with the sizing agent of claim 42.

48. Paper sized with the sizing agent of claim 43.