AMIDE COMPOUND

Abstract

An oil-resistant agent containing an amide compound including a bio-based material modified with a long-chain hydrocarbon group having 7 to 40 carbon atoms and an amide group. Also disclosed is a fiber product containing the amide compound, and a water dispersion containing the amide compound.

Claims

1. An oil-resistant agent comprising an amide compound comprising a bio-based material modified with a long-chain hydrocarbon group having 7 to 40 carbon atoms and an amide group.

2. The oil-resistant agent according to claim 1, wherein the amide compound comprises at least one long-chain hydrocarbon amide group selected from the group consisting of —NHC(═O)—R C(═O)NH—R —NHC(═O)O—R OC(═O)NH—R —NHC(═O)NH—R —NH—S(═O).sub.2—R, and —S(═O).sub.2—NH—R wherein each R is independently a long-chain hydrocarbon group having 7 to 40 carbon atoms.

3. The oil-resistant agent according to claim 1, wherein the bio-based material is a polymer.

4. The oil-resistant agent according to claim 1, wherein the bio-based material is sugar.

5. The oil-resistant agent according to claim 1, wherein the amide compound is a graft polymer obtained by graft modification of the bio-based material with a polymer having a long-chain hydrocarbon group having 7 to 40 carbon atoms.

6. The oil-resistant agent according to claim 5, wherein the polymer has a repeating unit derived from an amide monomer (al) having at least one amide group and represented by the following formula:
CH.sub.2═C(—X.sup.1)—C(═O)—Y.sup.1—Z(—Y.sup.2—R.sup.1).sub.n wherein R.sup.1 is each independently a long-chain hydrocarbon group having 7 to 40 carbon atoms, X.sup.1 is a hydrogen atom, a monovalent organic group or a halogen atom, Y.sup.1 is —O— or —NH—, Y.sup.2 is each independently a group composed of at least one selected from a direct bond, —O—, —C(═O)—, —S(═O).sub.2— or —NH—, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.

7. The oil-resistant agent according to claim 1, wherein the long-chain hydrocarbon group has 12 or more carbon atoms.

8. The oil-resistant agent according to claim 1, wherein the amide compound has a biobased content according to ASTM D6866 of 40% or more.

9. The oil-resistant agent according to claim 1, wherein the oil-resistant agent is an additive for paper.

10. A fiber product comprising an amide compound comprising a bio-based material modified with a long-chain hydrocarbon group having 7 to 40 carbon atoms and an amide group attached to the fiber product.

11. The fiber product according to claim 10, wherein the fiber product is a paper product.

12. The fiber product according to claim 11, wherein the paper is a food packaging material.

13. A water dispersion comprising an amide compound comprising a bio-based material modified with a long-chain hydrocarbon group having 7 to 40 carbon atoms and an amide group.

14. The water dispersion according to claim 13, wherein the amide compound comprises at least one long-chain hydrocarbon amide group selected from the group consisting of —NHC(═O)—R C(═O)NH—R —NHC(═O)O—R OC(═O)NH—R —NHC(═O)NH—R —NH—S(═O).sub.2—R, and —S(═O).sub.2—NH—R wherein each R is independently a long-chain hydrocarbon group having 7 to 40 carbon atoms.

15. The water dispersion according to claim 13, wherein the amide compound is a graft polymer obtained by graft modification of the bio-based material with a polymer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, wherein the polymer has a repeating unit derived from an amide monomer (al) having at least one amide group and represented by the following formula:
CH.sub.2═C(—X.sup.1)—C(═O)—Y.sup.1—Z(—Y.sup.2—R.sup.1).sup.n wherein R.sup.1 is each independently a long-chain hydrocarbon group having 7 to 40 carbon atoms, X.sup.1 is a hydrogen atom, a monovalent organic group or a halogen atom, Y.sup.1 is —O— or —NH—, Y.sup.2 is each independently a group composed of at least one selected from a direct bond, —O—, —C(═O)—, —S(═O).sub.2— or —NH—, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.

Description

EXAMPLES

[0159] Next, the present disclosure will be specifically described by way of Examples. However, the description does not limit the present disclosure. Hereinafter, “parts”, “%” or “ratios” indicate “parts by weight”, “% by weight” or “weight ratios” unless particularly otherwise described.

[0160] Testing methods used below are as follows.

(Oil Resistance (KIT))

[0161] Oil resistance (KIT method) was determined according to TAPPI T-559 cm-02. KIT test fluids are test fluids obtained by mixing castor oil, toluene and heptane in the ratios of Table 1. One droplet of the test fluid shown in Table 1 was placed on paper, and the state of permeation of the oil was observed after 15 seconds. KIT test fluids that did not permeate were found out, and the point of the highest degree of oil resistance among those given by the found fluids was regarded as the oil resistance. As the number of the KIT test fluid increases, the oil resistance is more favorable.

TABLE-US-00001 TABLE 1 Mixing ratio (vol %) Degree of oil resistance (KIT test fluid) Castor oil Toluene Heptane 1 100 0 0 2 90 5 5 3 80 10 10 4 70 15 15 5 60 20 20 6 50 25 25 7 40 30 30 8 30 35 35 9 20 40 40 10 10 45 45 11 0 45 55 12 0 50 50
(Oil Resistance (Test with Oil for Practical Use, 1))

[0162] Approximately 1 g of a commercially available olive oil was dropped on the obtained paper dish or treated paper (the weight of the treated paper was approximately 0.1 g) and left to stand at room temperature (20° C.) for 15 minutes, and the state of penetration on the rear side of the paper dish or treated paper was observed. Numerical grades were set according to the degree of penetration on the rear side, as described below.

[0163] 5: 0% to 5%

[0164] 4: 6% to 20%

[0165] 3: 21% to 50%

[0166] 2: 51% to 75%

[0167] 1: 76% to 100%

(Oil Resistance (Test with Oil for Practical Use, 2))

[0168] 100 ml of an evaluation fluid (corn oil) (80° C.) was poured into a molded pulp product in a container shape, left to stand still for 30 minutes and then disposed of, and the state of penetration of the evaluation fluid into the molded pulp product (container) was visually evaluated according to the following scale.

[0169] 4: Oil stain is rarely observed on the inside of the bottom of the molded pulp container.

[0170] 3: Oil stain is not observed on the outside of the bottom of the molded pulp container.

[0171] 2: Oil stain is observed in less than 5% of the area of the outside of the bottom of the molded pulp container.

[0172] 1: Oil stain is observed in 5% or more and less than 50% of the area of the outside of the bottom of the molded pulp container.

[0173] 0: Oil stain is observed in 50% or more of the area of the outside of the bottom of the molded pulp container.

(Water Resistance (Test with Water for Practical Use))

[0174] 100 ml of an evaluation fluid (tap water) (80° C.) was poured into a molded pulp product molded in a container shape, left to stand still for 30 minutes and then disposed of, and the state of penetration of the evaluation fluid into the molded pulp product (container) was visually evaluated according to the following scale.

[0175] 4: Water stain is rarely observed on the inside of the bottom of the molded pulp container.

[0176] 3: Water stain is not observed on the outside of the bottom of the molded pulp container.

[0177] 2: Water stain is observed in less than 5% of the area of the outside of the bottom of the molded pulp container.

[0178] 1: Water stain is observed in 5% or more and less than 50% of the area of the outside of the bottom of the molded pulp container.

[0179] 0: Water stain is observed in 50% or more of the area of the outside of the bottom of the molded pulp container.

Synthesis Example 1

[0180] 60 parts of processed tapioca starch (trade name: TSK-13, product of Nihon Shokuhin Kako Co., Ltd.) was suspended in 700 parts of water under stirring in a reactor equipped with a stirrer and a heater, and the resultant was heated up to 90° C. to cause gelatinization. 15.0 parts of stearic acid amide acrylate (C18AmEA, melting point: 70° C.) and 11.9 parts of stearyl trimethyl ammonium chloride were dissolved at 80° C., and emulsified with ultrasonic waves in the above-described gelatinized starch solution to be finely dispersed such that the average particle size of liquid droplets was 500 nm or less. Next, 1.32 parts of cerium diammonium nitrate as an initiator was added thereto, and the resulting mixture was mixed and stirred in a nitrogen atmosphere at 60° C. for 5 hours to thereby cause graft-polymerization. The solid content of the obtained starch graft polymer-containing solution was 10% by weight.

Synthesis Example 2

[0181] 32.7 Parts of gluconic acid was added to 300 parts of an aqueous solution of 24.6 parts of stearic acid monoethanolamide and 2.5 parts of dodecyl benzene sulfonic acid (DBSA), and the resultant was stirred at 75° C. for 10 hours. The reaction solution became a white turbid emulsion. After 10 hours elapsed, NaHCO.sub.3 was added to stop the reaction. A crude product was extracted with ethyl acetate, washed with saline water and dried on Na.sub.2SO.sub.4, and the solvent was removed, thereby obtaining a reaction product. The reaction product was dispersed in 100 parts of water to adjust the solid content to 10% by weight.

Synthesis Example 3

[0182] 60 parts of sucrose was suspended in 700 parts of water under stirring in a reactor equipped with a stirrer and a heater, and the resultant was heated up to 90° C. to cause gelatinization. 15.0 parts of stearic acid amide acrylate (C18AmEA, melting point: 70° C.) and 11.9 parts of stearyl trimethyl ammonium chloride were dissolved at 80° C., and emulsified with ultrasonic waves in the above-described gelatinized starch solution to be finely dispersed such that the average particle size of liquid droplets was 500 nm or less. Next, 1.32 parts of cerium diammonium nitrate as an initiator was added thereto, and the resulting mixture was mixed and stirred in a nitrogen atmosphere at 60° C. for 5 hours to thereby cause graft-polymerization. The solid content of the obtained starch graft polymer-containing solution was 10% by weight.

Comparative Synthesis Example 1

[0183] 32.7 Parts of gluconic acid was added to 300 parts of an aqueous solution of 24.6 parts of stearyl alcohol and dodecyl benzene sulfonic acid (DBSA, 2.5 parts), and the resultant was stirred at 75° C. for 10 hours. The reaction solution became a white turbid emulsion. After 10 hours elapsed, NaHCO3 was added to stop the reaction. A crude product was extracted with ethyl acetate, washed with saline water and dried on Na2SO4, and the solvent was removed, thereby obtaining a reaction product. 100 parts of water was added to the reaction product to adjust the solid content to 10% by weight.

Comparative Synthesis Example 2

[0184] 100 parts of methyl ethyl ketone (MEK) as a solvent was added to a reactor equipped with a stirrer and a heater and stirred, and 100 parts of stearyl acrylate (StA, melting point: 30° C.) as a monomer and 1.2 parts of PERBUTYL PV as an initiator were added in this order. The resulting mixture was mixed and stirred in a nitrogen atmosphere at 65° C. to 75° C. for 12 hours to thereby cause copolymerization. The solid content of the obtained copolymer-containing solution was 50% by weight.

[0185] As a post treatment, 142 g of a 0.4% acetic acid aqueous solution was added to 50 g of the obtained copolymer solution, dispersed, and the resultant was then heated under reduced pressure using an evaporator to distilled away MEK, thereby obtaining a light brown copolymer water dispersion (the content of a volatile organic solvent was 1% by weight or less). Ion exchange water was further added to this water dispersion to obtain a water dispersion having a solid content of 15% by weight.

Example 1

[Evaluation by External Sizing Method]

[0186] Plant pulp prepared was a pulp slurry in which the weight proportions of leaf bleached kraft pulp (LBKP) and northern bleached kraft pulp (NBKP) was 60% by weight and 40% by weight, respectively, and which has a freeness of the pulp of 400 ml (Canadian Standard Freeness). A wet paper strengthening agent and a sizing agent were added thereto, and paper having a paper density of 0.58 g/cm.sup.3 and a basis weight of 45 g/m.sup.2 was produced and used as base paper of an external sizing treatment (size pressing treatment) with a fourdrinier paper machine. The oil resistance (KIT value) of this base paper was 0.

[0187] The water dispersion of the amide compound obtained in Synthesis Example 1 was used as an oil-resistant agent, and oil-resistant paper (processed paper) was obtained by the following treatment method. A treatment liquid was prepared such that the solid content of the water dispersion of the amide compound obtained in Synthesis Example 1 was 2.4% by weight and that the solid content of hydroxyethylated starch (trade name: Penford 290, product of Penford Corporation) was 7%. Treatment was performed with a size pressing machine and followed by drying with a drum dryer, thereby obtaining oil-resistant paper (processed paper). The amount, in terms of the solid content, of the starch and the amide compound applied to the obtained oil-resistant paper was 1.3 g/m.sup.2 (the amount of the copolymer applied was 0.33 g/m.sup.2). The obtained base paper was used as test paper, and a test was carried out. The results are shown in Table 1 (KIT value, Test with oil for practical use 1).

[Evaluation by Internal Sizing Method]

[0188] 2,400 g of a water dispersion containing 0.5% by weight of a mixture of 70 parts of leaf bleached kraft pulp and 30 parts of northern bleached kraft pulp beaded to a freeness of 550 cc (Canadian Freeness) was added under stirring. Next, 0.18 g of an aqueous solution containing 5%, in terms of solid content, of an alkyl ketene dimer (AKD) (Hercon (registered trademark) 79, manufactured by Solenis) was added, followed by continuously stirring for 1 minute, and then 36 g of the water dispersion of the amide compound of Synthesis Example 1 diluted to a solid content of 10% with water was added, followed by continuously stirring for 1 minute.

[0189] The above-described pulp slurry was put into a metal vessel. A metal mold for pulp molding with a number of suction holes was placed in the lower part of the vessel with a netlike body disposed thereon. The pulp-containing aqueous composition was suctioned and dehydrated through the mold for pulp molding and the netlike body with a vacuum pump from a side opposite to the netlike body side with respect to the mold for pulp molding, so that the solids (the pulp and the like) contained in the pulp-containing aqueous composition was deposited on the netlike body, thereby obtaining a molded pulp intermediate. Next, the obtained molded pulp intermediate was vertically pressed and dried in metal male-female molds heated to 60° C. to 200° C. Thus, a molded pulp product having a container shape was produced. Table 1 shows the ratio of the content of each component to that of the pulp in the obtained molded pulp product, and the results of evaluating the high-temperature oil-resistance (test with oil for practical use, 2) and the high-temperature water-resistance (test with water for practical use).

Example 2

[0190] A test was carried out in the same manner as in Example 1 except that the water dispersion of the amide compound of Synthesis Example 2 was used instead of the water dispersion of the amide compound of Synthesis Example 1 in Example 1.

[0191] The amount, in terms of the solid content, of the starch and the amide compound applied to the obtained oil-resistant paper was 0.9 g/m.sup.2 (the amount of the copolymer applied was 0.23 g/m.sup.2). The test results are shown in Table 1.

[0192] Furthermore, the evaluation results of the obtained molded pulp product are shown in Table 1.

Example 3

[0193] A test was carried out in the same manner as in Example 1 except that the water dispersion of the amide compound of Synthesis Example 3 was used instead of the water dispersion of the amide compound of Synthesis Example 1 in Example 1.

[0194] The amount, in terms of the solid content, of the starch and the amide compound applied to the obtained oil-resistant paper was 1.0 g/m.sup.2 (the amount of the copolymer applied was 0.26 g/m.sup.2). The test results are shown in Table 1.

[0195] Furthermore, the evaluation results of the obtained molded pulp product are shown in Table 1.

Comparative Example 1

[0196] A test was carried out in the same manner as in Example 1 except that the water dispersion of the ester compound of Comparative Synthesis Example 2 was used instead of the water dispersion of the amide compound of Synthesis Example 1 in Example 1.

[0197] The amount, in terms of the solid content, of the starch and the ester compound applied to the obtained oil-resistant paper was 0.8 g/m.sup.2 (the amount of the copolymer applied was 0.20 g/m.sup.2). The test results are shown in Table 1.

[0198] Furthermore, the evaluation results of the obtained molded pulp product are shown in Table 1.

Comparative Example 2

[0199] A test was carried out in the same manner as in Example 1 except that the water dispersion of the ester compound of Comparative Synthesis Example 2 was used instead of the water dispersion of the amide compound of Synthesis Example 1 in Example 1.

[0200] The amount, in terms of the solid content, of the starch and the ester compound applied to the obtained oil-resistant paper was 1.1 g/m.sup.2 (the amount of the copolymer applied was 0.28 g/m.sup.2). The test results are shown in Table 1.

[0201] Furthermore, the evaluation results of the obtained molded pulp product are shown in Table 1.

TABLE-US-00002 TABLE 1 Comparative Comparative Example 1 Example 2 Example 3 Example 1 Example 2 Compound Synthesis Synthesis Synthesis Synthesis Comparative Comparative Example Example 1 Example 2 Example 3 Synthesis Synthesis Example 1 Example 2 Main chain Polysaccharide Monosaccharide Disaccharide Monosaccharide Polyacrylate Side chain Alkylamide Alkylamide Alkylamide Alkylester Alkylester Oil KIT value 4 3 4 3 4 resistance Test with oil 5 3 4 2 5 for practical use, 1 Test with oil 4 3 3 1 2 for practical use, 2 Water Test with 4 3 4 2 2 resistance water for practical use

[0202] Examples of the embodiments of the present disclosure are as described below.

[Item 1]

[0203] An amide compound comprising a bio-based material modified with a long-chain hydrocarbon group having 7 to 40 carbon atoms and an amide group.

[Item 2]

[0204] The amide compound according to Item 1, comprising at least one long-chain hydrocarbon amide group selected from the group consisting of

[0205] —NHC(═O)—R

[0206] —C(═O)NH—R

[0207] —NHC(═O)O—R

[0208] —OC(═O)NH—R

[0209] —NHC(═O)NH—R

[0210] —NH—S(═O).sub.2—R, and

[0211] —S(═O).sub.2—NH—R

[0212] wherein each R is independently a long-chain hydrocarbon group having 7 to 40 carbon atoms.

[Item 3]

[0213] The amide compound according to any one of Item 1 or 2, wherein the bio-based material is a polymer.

[Item 4]

[0214] The amide compound according to any one of Items 1 to 3, wherein the bio-based material is sugar.

[Item 5]

[0215] The amide compound according to any one of Items 1 to 4, wherein the amide compound is a graft polymer obtained by graft modification of the bio-based material with a polymer having a long-chain hydrocarbon group having 7 to 40 carbon atoms.

[Item 6]

[0216] The amide compound according to Item 5, wherein the polymer has a repeating unit derived from an amide monomer (al) having at least one amide group and represented by the following formula:

CH.sub.2═C(—X.sup.1)—C(═O)—Y.sup.1—Z(—Y.sup.2—R.sup.1).sub.n

[0217] wherein R.sup.1 is each independently a long-chain hydrocarbon group having 7 to 40 carbon atoms,

[0218] X.sup.1 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0219] Y.sup.1 is —O— or —NH—,

[0220] Y.sup.2 is each independently a group composed of at least one selected from a direct bond, —O—, —C(═O)—, —S(═O).sub.2— or —NH—,

[0221] Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and [0222] n is 1 or 2.

[Item 7]

[0223] The amide compound according to any one of Items 1 to 6, wherein the long-chain hydrocarbon group has 12 or more carbon atoms.

[Item 8]

[0224] The amide compound according to any one of Items 1 to 7, wherein the amide compound has a biobased content according to ASTM D6866 of 40% or more.

[Item 9]

[0225] An oil-resistant agent comprising the amide compound according to any one of Items 1 to 8.

[Item 10]

[0226] The oil-resistant agent according to Item 9, wherein the oil-resistant agent is an additive for paper.

[Item 11]

[0227] A fiber product comprising the amide compound according to any one of Items 1 to 8 attached thereto.

[Item 12]

[0228] The fiber product according to Item 11, wherein the fiber product is a paper product.

[Item 13]

[0229] The fiber product according to Item 12, wherein the paper is a food packaging material.