EP0280115A1 - Oil proof composition for paper - Google Patents

Oil proof composition for paper Download PDF

Info

Publication number
EP0280115A1
EP0280115A1 EP88101967A EP88101967A EP0280115A1 EP 0280115 A1 EP0280115 A1 EP 0280115A1 EP 88101967 A EP88101967 A EP 88101967A EP 88101967 A EP88101967 A EP 88101967A EP 0280115 A1 EP0280115 A1 EP 0280115A1
Authority
EP
European Patent Office
Prior art keywords
salt
onh2
group
c2h4oh
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88101967A
Other languages
German (de)
French (fr)
Other versions
EP0280115B1 (en
Inventor
Hirokazu Aoyama
Yoshio Amimoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of EP0280115A1 publication Critical patent/EP0280115A1/en
Application granted granted Critical
Publication of EP0280115B1 publication Critical patent/EP0280115B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/11—Halides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/10—Phosphorus-containing compounds

Definitions

  • the present invention relates to an oil proof composition for paper. More particularly, it relates to a composition for imparting oil resistance to paper which comprises a salt of fluorophosphate or a salt of fluoro­phosphonate and at least one anionic surfactant.
  • oil proof agents for paper namely sizing agents added to the paper in order to render the sheet more resistant to penetration of oils
  • salts of fluoroalkyl phos­phate or salts of N-alkyl fluoroalkanesulfonamidoalkyl phos­phate are known.
  • Such conventional oil proof agents are applied to paper either by internal addition (internal sizing) which comprises dissolving or dispersing the agent in a pulp suspension or slurry for paper making, or by external addition (surface sizing) which comprises dipping a sheet of paper in an aqueous solution or dispersion of the agent or brushing over the sheet with the solution or dispersion to coat the surface of paper with the agent.
  • the oil proof agent when water has too high hardness, the oil proof agent can be dissolved in a small amount of hard water.
  • the agent when the agent is added to a large amount of hard water or the aqueous solution of the agent is diluted with a large amount of hard water, the salt of fluoroalkyl phosphate or the salt of N-alkyl fluoroalkane­sulfonamidoalkyl phosphate is precipitated, which results in decrease of sizing effect or deterioration of oil resistance of processed paper.
  • finishing agents such as aluminum sulfate is used, the same drawback arises as when hard water is used.
  • a salt of fluoroalkenyloxyaralkyl phosphonate may be used as an oil proof agent for paper. But, it has the same drawback as the salt of fluoroalkyl phosphat when it is used in hard water.
  • An object of the present invention is to provide an oil proof composition for paper which is not precipitated in hard water and can impart good oil resistance to paper.
  • an oil proof composition for paper which comprises at least one salt selected from the group consisting of fluoroalkyl phosphate salts, N-alkyl fluoro­alkanesulfonamidoalkyl phosphate salts and fluoroalkenyloxy­aralkyl phosphonate salts and at least one anionic surfac­tant.
  • the salt of fluoroalkyl phosphate may be a salt of the formula: (R f 1-A1-O) m PO(OX1) 3-m (I) wherein R f 1 is each a C5-C21 perfluoroalkyl or ⁇ -hydroper­fluoroalkyl group, A1 is each a C1-C10 alkylene group, X1 is an alkali metal or an ammonium group which may be substitu­ted by a C1-C10 alkyl or hydroxyalkyl group, and m is 1 or 2.
  • Preferred salts (I) are (C8F17CH2CH2O)2PO-ONH2(C2H4OH)2 C8F17CH2CH2OPO[ONH2(C2H4OH)2]2 (C6F13CH2CH2O)2PO-ONH2(C2H4OH)2 (C10F21CH2CH2O)2PO-ONH2(C2H4OH)2 (C12F25CH2CH2O)2PO-ONH2(C2H4OH)2 (C14F29CH2CH2O)2PO-ONH2(C2H40H)2 (C8F17CH2CH2O)2PO-ONH4 C8F17CH2CH2OPO(ONH4)2 (C8F17CH2CH2O)2PO-ONH(C2H4OH)3 (HC6F12CH2O)2PO-ONH2(C2H4OH)2 HC6F12CH2CH2OPO[ONH2(C2
  • the salt of N-alkyl fluoroalkanesulfonamidoalkyl phosphate may be a salt of the formula: wherein R f 2 is each a C5-C21 perfluoroalkyl group, A2 is each a C1-C10 alkyl group, A3 is each a C1-C10 alkylene group, X2 is an alkali metal or or an ammonium group which may be substituted by a C1-C10 alkyl or hydroxyalkyl group, and n is 1 or 2.
  • Preferred salts (II) are [C8F17SO2N(C2H5)CH2CH2O]2PO-ONH4 C8F17SO2N(C2H5)CH2CH2OPO(ONH4)2 [C6F13SO2N(C2H5)CH2CH2O]2PO-ONH4 [C10F21SO2N(C2H5)CH2CH2O]2PO-ONH4 [C12F25SO2N(C2H5)CH2CH2O]2PO-ONH4 [C14F29SO2N(C2H5)CH2CH2O]2PO-ONH4 [C8F17SO2N(C2H5)CH2CH2O]2PO-ONH2(CH2CH2OH)2 C8F17SO2N(C2H5)CH2CH2OPO[ONH2(CH2CH2OH)2]2 [C8F17SO2N(C2H5)CH2CH2OPO[ONH2(CH2CH2OH)2]
  • the salt of fluoroalkenyloxyaralkyl phosphonate may be a salt of the formula: (R f 3O) p Ar(CH2) q PO(OX3)2 (III) wherein R f 3 is each a C6-C12 perfluoroalkenyl group, p is 1, 2 or 3 and Ar is an aromatic group which may have a substi­tuent (e.g.
  • Preferred salts (III) are C6F11O-C6H4-CH2PO(ONa)2 C9F17O-C6H4-CH2PO(ONH4)2 C9F17O-C6H4-CH2PO[ONH2(C2H4OH)2]2 C9F17O-C6H4-CH2CH2PO(ONa)2
  • the above salt of phosphate or phosphonate may be prepared by neutralizing at least one partial ester selected from the group consisting of fluoroalkyl partial esters of phosphoric acid, N-alkyl fluoroalkanasulfoneamidoalkyl par­ tial esters of phosphoric acid and fluoroalkenyloxyaralkyl partial esters of phosphonic acid with a base (e.g. hydro­xides of alkali metals, amines, etc.) according to a conven­tional method.
  • a base e.g. hydro­xides of alkali metals, amines, etc.
  • the anionic surfactant is preferably a hydrocarbon type anionic surfactant.
  • the anionic surfactant are C5-C15 alkylbenzenesulfonic acids, C5-C15 alkylbenzene­sulfonate salts, di-C5-C15 alkyl sulfosuccinate salts, C9-­C21 alkyl sulfate salts, C10-C20 alkylsulfonate salts, C3-­C15 alkylnaphthalenesulfonate salts, mono- or di-C9-C21 alkyl phosphate salts, salts of C9-C25 fatty acids and the like.
  • the salt may be a sodium, potassium, ammonium, mono-, di- or tri-C1-C5 alkyl or hydroxyalkylammonium salt.
  • the amount of anionic surfactant is from 1 to 15 % by weight based on the weight of phosphate or phosphonate which is converted to the weight of corresponding partial ester.
  • the oil proof composition of the present invention may be used together with other processing agents such as a bonding agent such as Sumilets resin FC-50L and Sumilets resin 675 (both available from Sumitomo Chemical Co., Ltd.).
  • a bonding agent such as Sumilets resin FC-50L and Sumilets resin 675 (both available from Sumitomo Chemical Co., Ltd.).
  • the amount of bonding agent is from 0.5 to 3 times by weight based on the weight of oil proof composition (the weight of the salt of fluorophosphate and/or fluorophosphonate being converted to a weight of corresponding partial ester).
  • the oil resistant imparting composition is easily prepared by mixing the salt of phosphate or phosphonate and the anionic surfactant.
  • Oil resistant imparting composition of the present invention is not precipitated when diluted with compara­tively hard water or water containing aluminum sulfate, or when stirred vigorously. Even when the oil proof composi­tion is added to paper by the internal addition, paper has good properties such as sizing degree in addition to oil resistance.
  • Example 6 To the emulsion of oil proof agent obtained in Example 6, hydrochloric acid was added to give an emulsion of oil proof agent having pH of 9 (Example 8) or pH of 7 (Example 9).
  • compositions and pH values of the oil proof compositions prepared in Examples and Comparative Examples are summarized in Table 1.
  • the emulsion was diluted with water having various hardness to adjust the concentration of the oil proof agent to 1 %. Then, one portion of the diluted emulsion was stir­ red at 3,000 ppm for 3 minutes while another portion was not stirred. Then, both were kept standing for one day and a precipitated amount per 10 ml was measured. The results are shown in Table 2.
  • the sizing degree was measured as follows:
  • Oil resistance of the paper as prepared in Experi­ment 4 was evaluated as follows:
  • Castor oil (chemically pure (c.p.) grade), toluene (c.p. grade) and heptane (c.p. grade) were mixed in a ratio shown in Table 5 to prepare mixed solvent Nos. 1 to 16. Then, each mixed solvent was dropped on a sheet of paper placed on a clean flat surface from a height of about 2.5 cm above the sheet of paper. After 15 seconds from the comple­tion of dropping of the mixed solvent, conditions of the paper sheet where the mixed solvent was dropped were obser­ved. When any black spot was formed, the oil resistance was evaluated as "unacceptable” irrespective of the area of the spot, while no spot was formed, the oil resistance was eva­luated as "acceptable”. The oil resistance was expressed in terms of the maximum number of mixed solvent for which the oil resistance was acceptable. The larger the number of mixed solvent, the better the oil resistance of paper. The results are also shown in Table 4 above.
  • the emulsion was diluted with water containing 50 ppm of Ca2+ to adjust the concentration of the oil proof agent to 1 % or with water containing 75 ppm of Ca2+ to adjust the concentration of the oil proof agent to 0.2 %. Then, each diluted emulsion was stirred at 3,000 ppm for 3 minutes. The conditon of the emulsion was observed and evaluated according to the same criteria as used in Experi­ment 3. The results are shown in Table 5.
  • Oil resistance of the paper prepared in Experiment 7 was evaluated in the same manner as in Experiment 5.

Abstract

An oil proof composition for paper which comprises at least one salt selected from the group consisting of fluoroalkyl phosphate salts, N-alkyl fluoroalkanesulfon­amidoalkyl phosphate salts and fluoroalkenyloxyaralkyl phos­phonate salts and at least one anionic surfactant, which can impart not only oil resistance but also a sizing effect and does not precipitate when diluted with hard water or stirred at a high revolution rate.

Description

    BACKGROUND OF THE INVENTION Field of the Invention
  • The present invention relates to an oil proof composition for paper. More particularly, it relates to a composition for imparting oil resistance to paper which comprises a salt of fluorophosphate or a salt of fluoro­phosphonate and at least one anionic surfactant.
    • Description of the Prior Arts
  • As oil proof agents for paper, namely sizing agents added to the paper in order to render the sheet more resistant to penetration of oils, salts of fluoroalkyl phos­phate or salts of N-alkyl fluoroalkanesulfonamidoalkyl phos­phate are known. Such conventional oil proof agents are applied to paper either by internal addition (internal sizing) which comprises dissolving or dispersing the agent in a pulp suspension or slurry for paper making, or by external addition (surface sizing) which comprises dipping a sheet of paper in an aqueous solution or dispersion of the agent or brushing over the sheet with the solution or dispersion to coat the surface of paper with the agent. In either of these additions, when water has too high hardness, the oil proof agent can be dissolved in a small amount of hard water. However, when the agent is added to a large amount of hard water or the aqueous solution of the agent is diluted with a large amount of hard water, the salt of fluoroalkyl phosphate or the salt of N-alkyl fluoroalkane­sulfonamidoalkyl phosphate is precipitated, which results in decrease of sizing effect or deterioration of oil resistance of processed paper. When other finishing agents such as aluminum sulfate is used, the same drawback arises as when hard water is used.
  • A salt of fluoroalkenyloxyaralkyl phosphonate may be used as an oil proof agent for paper. But, it has the same drawback as the salt of fluoroalkyl phosphat when it is used in hard water.
    • SUMMARY OF THE INVENTION
  • An object of the present invention is to provide an oil proof composition for paper which is not precipitated in hard water and can impart good oil resistance to paper.
  • According to the present invention, this and other objects are achieved by an oil proof composition for paper which comprises at least one salt selected from the group consisting of fluoroalkyl phosphate salts, N-alkyl fluoro­alkanesulfonamidoalkyl phosphate salts and fluoroalkenyloxy­aralkyl phosphonate salts and at least one anionic surfac­tant.
    • DETAILED DESCRIPTION OF THE INVENTION
  • The salt of fluoroalkyl phosphate may be a salt of the formula:
        (Rf¹-A¹-O)mPO(OX¹)3-m      (I)
    wherein Rf¹ is each a C₅-C₂₁ perfluoroalkyl or ω-hydroper­fluoroalkyl group, A¹ is each a C₁-C₁₀ alkylene group, X¹ is an alkali metal or an ammonium group which may be substitu­ted by a C₁-C₁₀ alkyl or hydroxyalkyl group, and m is 1 or 2. Preferred salts (I) are

    (C₈F₁₇CH₂CH₂O)₂PO-ONH₂(C₂H₄OH)₂
    C₈F₁₇CH₂CH₂OPO[ONH₂(C₂H₄OH)₂]₂
    (C₆F₁₃CH₂CH₂O)₂PO-ONH₂(C₂H₄OH)₂
    (C₁₀F₂₁CH₂CH₂O)₂PO-ONH₂(C₂H₄OH)₂
    (C₁₂F₂₅CH₂CH₂O)₂PO-ONH₂(C₂H₄OH)₂
    (C₁₄F₂₉CH₂CH₂O)₂PO-ONH₂(C₂H₄0H)₂
    (C₈F₁₇CH₂CH₂O)₂PO-ONH₄
    C₈F₁₇CH₂CH₂OPO(ONH₄)₂
    (C₈F₁₇CH₂CH₂O)₂PO-ONH(C₂H₄OH)₃
    (HC₆F₁₂CH₂O)₂PO-ONH₂(C₂H₄OH)₂
    HC₆F₁₂CH₂CH₂OPO[ONH₂(C₂H₄OH)₂]₂
  • The salt of N-alkyl fluoroalkanesulfonamidoalkyl phosphate may be a salt of the formula:
    Figure imgb0001
     wherein Rf² is each a C₅-C₂₁ perfluoroalkyl group, A² is each a C₁-C₁₀ alkyl group, A³ is each a C₁-C₁₀ alkylene group, X² is an alkali metal or or an ammonium group which may be substituted by a C₁-C₁₀ alkyl or hydroxyalkyl group, and n is 1 or 2. Preferred salts (II) are

    [C₈F₁₇SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₄
    C₈F₁₇SO₂N(C₂H₅)CH₂CH₂OPO(ONH₄)₂
    [C₆F₁₃SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₄
    [C₁₀F₂₁SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₄
    [C₁₂F₂₅SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₄
    [C₁₄F₂₉SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₄
    [C₈F₁₇SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₂(CH₂CH₂OH)₂
    C₈F₁₇SO₂N(C₂H₅)CH₂CH₂OPO[ONH₂(CH₂CH₂OH)₂]₂
    [C₈F₁₇SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₂(CH₂CH₂OH)₃
  • The salt of fluoroalkenyloxyaralkyl phosphonate may be a salt of the formula:
        (Rf³O)pAr(CH₂)qPO(OX³)₂      (III)
    wherein Rf³ is each a C₆-C₁₂ perfluoroalkenyl group, p is 1, 2 or 3 and Ar is an aromatic group which may have a substi­tuent (e.g. phenyl, naphthyl, or alkyl-, acyl-, alkoxy- or halogen-substituted phenyl or naphthyl), q is 1 or 2 and X³ is an alkali metal or an ammonium group which may be substi­tuted by a C₁-C₁₀ alkyl or hydroxyalkyl group. Preferred salts (III) are

    C₆F₁₁O-C₆H₄-CH₂PO(ONa)₂
    C₉F₁₇O-C₆H₄-CH₂PO(ONH₄)₂
    C₉F₁₇O-C₆H₄-CH₂PO[ONH₂(C₂H₄OH)₂]₂
    C₉F₁₇O-C₆H₄-CH₂CH₂PO(ONa)₂
  • The above salt of phosphate or phosphonate may be prepared by neutralizing at least one partial ester selected from the group consisting of fluoroalkyl partial esters of phosphoric acid, N-alkyl fluoroalkanasulfoneamidoalkyl par­ tial esters of phosphoric acid and fluoroalkenyloxyaralkyl partial esters of phosphonic acid with a base (e.g. hydro­xides of alkali metals, amines, etc.) according to a conven­tional method.
  • The anionic surfactant is preferably a hydrocarbon type anionic surfactant. Examples of the anionic surfactant are C₅-C₁₅ alkylbenzenesulfonic acids, C₅-C₁₅ alkylbenzene­sulfonate salts, di-C₅-C₁₅ alkyl sulfosuccinate salts, C₉-­C₂₁ alkyl sulfate salts, C₁₀-C₂₀ alkylsulfonate salts, C₃-­C₁₅ alkylnaphthalenesulfonate salts, mono- or di-C₉-C₂₁ alkyl phosphate salts, salts of C₉-C₂₅ fatty acids and the like. The salt may be a sodium, potassium, ammonium, mono-, di- or tri-C₁-C₅ alkyl or hydroxyalkylammonium salt.
  • The amount of anionic surfactant is from 1 to 15 % by weight based on the weight of phosphate or phosphonate which is converted to the weight of corresponding partial ester.
  • The oil proof composition of the present invention may be used together with other processing agents such as a bonding agent such as Sumilets resin FC-50L and Sumilets resin 675 (both available from Sumitomo Chemical Co., Ltd.). The amount of bonding agent is from 0.5 to 3 times by weight based on the weight of oil proof composition (the weight of the salt of fluorophosphate and/or fluorophosphonate being converted to a weight of corresponding partial ester).
  • The oil resistant imparting composition is easily prepared by mixing the salt of phosphate or phosphonate and the anionic surfactant.
  • Oil resistant imparting composition of the present invention is not precipitated when diluted with compara­tively hard water or water containing aluminum sulfate, or when stirred vigorously. Even when the oil proof composi­tion is added to paper by the internal addition, paper has good properties such as sizing degree in addition to oil resistance.
  • The present invention will be illustrated by following examples, in which "%" is by weight unless other­wise indicated.
    • Example 1 Preparation Example
  • In a 4 liter round flask equipped with a stirrer, CF₃CF₂(CF₂CF₂)nCH₂CH₂OH (n=2, 1 % by mole; n=3, 55 % by mole; n=4, 26 % by mole; n=5, 12 % by mole; n=6, 5 % by mole; n=7, 1 % by mole) (300 g) and 85 % phosphoric acid (6.4 g) were charged, and phosphorus oxychloride (33.8 g) was added at a temperature of 80 to 85°C with stirring over 30 minutes. After purging hydrogen chloride gas under redu­ced pressure, water (28 g) was added and stirred at a tem­perature of 95 to 100°C for 1 hour. Thereafter, the mixture was cooled to 85°C and isopropanol (66 g) was added to pre­pare a phosphate ester stock solution having the following composition:
    CF₃CF₂(CF₂CF₂)nCH₂CH₂OH      0.75 %
    CF₃CF₂(CF₂CF₂)nCH₂CH₂OPO(OH)₂      8.45 %
    [CF₃CF₂(CF₂CF₂)nCH₂CH₂O]₂POOH      53.24 %
    [CF₃CF₂(CF₂CF₂)nCH₂CH₂O]₃PO      15.89 %
    Water      3.82 %
    Isopropanol      17.85 %
    • Example 1
  • In a 4 liter round flask equipped with a stirrer, the phosphate ester stock solution prepared in Preparation Example (400 g) was charged followed by addition of dietha­nolamine (110 g) at a temperature of 70 to 75°C. Then, sodium salt of dodecyl benzenesulfonate (16 g, 6.5 % per weight of the phosphate salt) and warm water (50 g) were added followed by addition of warm water (1,500 g) to give an emulsion of oil proof agent (pH 10) having the following composition:
    Figure imgb0002
    • Example 2
  • In the same manner as in Example 1 but using 5.4 g (2.2 % per weight of the phosphate) of sodium salt of dode­cyl benzenesulfonate, an emulsion of oil proof agent (pH 10) was prepared.
    • Example 3
  • To the emulsion of oil proof agent prepared in Example 1, hydrochloric acid was added to give an emulsion of oil proof agent having pH of 7.
    • Example 4
  • In the same manner as in Example 1 but using 16 g of sodium salt of dioctyl sulfosuccinate in place of sodium salt of dodecyl benzenesulfonate, an emulsion of oil proof agent (pH 10) was prepared.
    • Example 5
  • In the same manner as in Example 1 but using 28 % ammonia water (110 g) in place of diethanolamine, an emul­sion of oil proof agent (pH 10) was prepared.
    • Example 6
  • In the same manner as in Example 5 but using 16 g of sodium dioctylsulfosuccinate in place of sodium salt of dodecyl benzenesulfonate, an emulsion of oil proof agent (pH 10) was prepared.
    • Example 7
  • In the same manner as in Example 6 but using 11.2 g of sodium dioctylsulfosuccinate (4.5 % per weight of the phosphate), an emulsion of oil proof agent (pH 10) was pre­pared.
    • Examples 8 and 9
  • To the emulsion of oil proof agent obtained in Example 6, hydrochloric acid was added to give an emulsion of oil proof agent having pH of 9 (Example 8) or pH of 7 (Example 9).
    • Comparative Example 1
  • In the same manner as in Example 1 but using no surfactant, an emulsion of oil proof agent was prepared.
    • Comparative Example 2
  • In the same manner as in Example 5 but using no surfactant, an emulsion of oil proof agent was prepared.
  • The compositions and pH values of the oil proof compositions prepared in Examples and Comparative Examples are summarized in Table 1.
    Figure imgb0003
    • Experiment 1
  • Dilution stability of the emulsion of oil proof agent prepared in Example 2 or Comparative Example 1 was examined.
  • The emulsion was diluted with water having various hardness to adjust the concentration of the oil proof agent to 1 %. Then, one portion of the diluted emulsion was stir­ red at 3,000 ppm for 3 minutes while another portion was not stirred. Then, both were kept standing for one day and a precipitated amount per 10 ml was measured. The results are shown in Table 2.
    Figure imgb0004
    • Experiment 2
  • Stability against aluminum sulfate of the same emulsions of oil proof agents as used in Experiment 1 was examined.
  • To 100 ml of the emulsion containing 0.5 % of the oil proof agent, 0.2 ml or 0.5 ml of a 1 % aqueous solution of aluminum sulfate was dropwise added and kept standing at room temperature for 1 hour. Just after the addition of aluminum sulfate and after kept standing for 1 hour, a pre­cipitation state was observed and evaluated according to the following criteria:
        O: No precipitate
        Δ: Few precipitates
        X: A few precipitates
        XX: Many precipitates
    The results are shown in Table 3.
    Figure imgb0005
    • Experiment 3
  • Mechanical stability of the emulsion of oil proof agent was evaluated.
  • Each of the emulsions of oil proof agents prepared in Examples 1-9 and Comparative Examples 1 and 2 was stirred at 3,000 rpm for 3 minutes and condition of the emulsion was observed and evaluated according to the following criteria:
        OO: No precipitate
        O: Few precipitates
        Δ: A few precipitates
        X: Many precipitates
    The results are shown in Table 4.
    Figure imgb0006
    • Experiment 4
  • A sizing effect of each of the emulsions of oil proof agents prepared in Examples 1-9 and Comparative Exam­ples 1 and 2 was evaluated. By using, as a bonding agent, Sumilets resin FC-50L (0.2 % per weight of pulp) or Sumilets 675 (0.3 % per weight of pulp), the oil proof composition (0.35 % of solid materials per weight of pulp) was added to paper by the internal addition method.
  • The sizing degree was measured as follows:
  • From a sheet of paper containing the oil proof composition, a square piece of paper (50 mm × 50 mm) was cut out and its peripheral parts were folded upwardly along lines about 1 cm inside from and in parallel with the four edge lines to make a small box. As soon as the box was placed on a surface of a 2 % aqueous solution of ammonium rhodanate in a petri dish kept at 20±1°C, a drop of a 1 % aqueous solution of ferric chloride kept at the same tempe­rature was added in the box. Then, a period of time till three red spots appeared on the bottom of the paper box was measured.
    The sizing effect was expressed in terms of such period of time. The results are shown in Table 4.
    • Experiment 5
  • Oil resistance of the paper as prepared in Experi­ment 4 was evaluated as follows:
  • Castor oil (chemically pure (c.p.) grade), toluene (c.p. grade) and heptane (c.p. grade) were mixed in a ratio shown in Table 5 to prepare mixed solvent Nos. 1 to 16. Then, each mixed solvent was dropped on a sheet of paper placed on a clean flat surface from a height of about 2.5 cm above the sheet of paper. After 15 seconds from the comple­tion of dropping of the mixed solvent, conditions of the paper sheet where the mixed solvent was dropped were obser­ved. When any black spot was formed, the oil resistance was evaluated as "unacceptable" irrespective of the area of the spot, while no spot was formed, the oil resistance was eva­luated as "acceptable". The oil resistance was expressed in terms of the maximum number of mixed solvent for which the oil resistance was acceptable. The larger the number of mixed solvent, the better the oil resistance of paper. The results are also shown in Table 4 above.
    Figure imgb0007
    • Example 10
  • In a 4 liter round flask equipped with a stirrer, the phosphate ester stock solution prepared in Preparation Example (400 g) was charged followed by addition of dietha­nolamine (110 g) at a temperature of 70 to 75°C. Then, sodium salt of dodecyl benzenesulfonate (7.4 g, 3.0 % per weight of the phosphate salt) and warm water (50 g) were added followed by addition of warm water (1,500 g) to give an emulsion of oil proof agent (pH 10) having the following composition:
    Figure imgb0008
    • Comparative Example 3
  • In the same manner as in Example 10 but using Nonion HS-220 (a nonionic surfactant,
    Figure imgb0009
     in which an average of n is 20 manufactured by Nippon Oil and Fat Co., Ltd.) (7.4 g) in plase of the sodium salt of dodecyl benzenesulfonate, an emulsion of oil proof agent was prepared.
    • Experiment 6
  • Stability against dilution with hard water of the emulsion of oil proof agent prepared in Example 10 or Comparative Example 3 was examined.
  • The emulsion was diluted with water containing 50 ppm of Ca²⁺ to adjust the concentration of the oil proof agent to 1 % or with water containing 75 ppm of Ca²⁺ to adjust the concentration of the oil proof agent to 0.2 %. Then, each diluted emulsion was stirred at 3,000 ppm for 3 minutes. The conditon of the emulsion was observed and evaluated according to the same criteria as used in Experi­ment 3. The results are shown in Table 5.
    • Experiment 7
  • A sizing effect of each of the emulsions of oil proof agents prepared in Experiment 6 was evaluated.
  • To a 60 g/l pulp suspension, as a bonding agent, Sumilets resin FR-2P (0.3 % per weight of pulp) and the oil proof composition (0.25, 0.30 or 0.35 % of solid materials per weight of pulp) was added to paper by the internal addi­tion method. The average weight of paper was 60 g/m².
  • The sizing degree was measured in the same manner as in Experiment 4. The results are shown in Table 5.
    • Experiment 8
  • Oil resistance of the paper prepared in Experiment 7 was evaluated in the same manner as in Experiment 5.
  • The results are shown in Table 5.
    Figure imgb0010

Claims (7)

1. An oil proof composition for paper which comp­rises at least one salt selected from the group consisting of fluoroalkyl phosphate salts, N-alkyl fluoroalkanesulfon­amidoalkyl phosphate salts and fluoroalkenyloxyaralkyl phos­phonate salts and at least one anionic surfactant.
2. The oil proof composition according to claim 1, wherein the salt is a salt of fluoroalkyl phosphate of the formula:
      (Rf¹-A¹-O)mPO(OX¹)3-m
wherein Rf¹ is each a C₅-C₂₁ perfluoroalkyl or ω-hydroper­fluoroalkyl group, A¹ is each a C₁-C₁₀ alkylene group, X¹ is an alkali metal or an ammonium group which may be substi­tuted by a C₁-C₁₀ alkyl or hydroxyalkyl group, and m is 1 or 2.
3. The oil proof composition according to claim 2, wherein the salt of fluoroalkylphosphate is a salt of the formula:

(C₈F₁₇CH₂CH₂O)₂PO-ONH₂(C₂H₄OH)₂
C₈F₁₇CH₂CH₂OPO[ONH₂(C₂H₄OH)₂]₂
(C₆F₁₃CH₂CH₂O)₂PO-ONH₂(C₂H₄OH)₂
(C₁₀F₂₁CH₂CH₂O)₂PO-ONH₂(C₂H₄OH)₂
(C₁₂F₂₅CH₂CH₂O)₂PO-ONH₂(C₂H₄OH)₂
(C₁₄F₂₉CH₂CH₂O)₂PO-ONH₂(C₂H₄OH)₂
(C₈F₁₇CH₂CH₂O)₂PO-ONH₄
C₈F₁₇CH₂CH₂OPO(ONH₄)₂
(C₈F₁₇CH₂CH₂O)₂PO-ONH(C₂H₄OH)₃
(HC₆F₁₂CH₂O)₂PO-ONH₂(C₂H₄OH)₂ or
HC₆F₁₂CH₂CH₂OPO[ONH₂(C₂H₄OH)₂]₂.
4. The oil proof composition according to claim 1, wherein the salt is a salt of N-alkyl fluoroalkanesulfon­amidoalkyl phosphate of the formula:
Figure imgb0011
 wherein Rf² is each a C₅-C₂₁ perfluoroalkyl group, A² is each a C₁-C₁₀ alkyl group, A³ is each a C₁-C₁₀ alkylene group, X² is an alkali metal or or an ammonium group which may be substituted by a C₁-C₁₀ alkyl or hydroxyalkyl group, and n is 1 or 2.
5. The oil proof composition according to claim 4, wherein the salt of N-alkyl fluoroalkanesulfonamidoalkyl phosphate is a salt of the formula:

[C₈F₁₇SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₄
C₈F₁₇SO₂N(C₂H₅)CH₂CH₂OPO(ONH₄)₂
[C₆F₁₃SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₄
[C₁₀F₂₁SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₄
[C₁₂F₂₅SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₄
[C₁₄F₂₉SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₄
[C₈F₁₇SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₂(CH₂CH₂OH)₂
C₈F₁₇SO₂N(C₂H₅)CH₂CH₂OPO[ONH₂(CH₂CH₂OH)₂]₂ or
[C₈F₁₇SO₂N(C₂H₅)CH₂CH₂O]₂PO-ONH₂(CH₂CH₂OH)₃.
6. The oil proof composition according to claim 1, wherein the salt is a salt of fluoroalkenyloxyaralkyl phos­phonate of the formula:
      (Rf³O)pAr(CH₂)qPO(OX³)₂
wherein Rf³ is each a C₆-C₁₂ perfluoroalkenyl group, p is 1, 2 or 3 and Ar is an aromatic group which may have a substi­tuent (e.g. phenyl, naphthyl, or alkyl-, acyl-, alkoxy- or halogen-substituted phenyl or naphthyl), q is 1 or 2 and X³ is an alkali metal or an ammonium group which may be substi­tuted by a C₁-C₁₀ alkyl or hydroxyalkyl group.
7. The oil proof composition according to claim 1, wherein the salt of fluoroalkeneyloxyaralkyl phosphate is a salt of the formula:

C₆F₁₁O-C₆H₄-CH₂PO(ONa)₂
C₉F₁₇O-C₆H₄-CH₂PO(ONH₄)₂
C₉F₁₇O-C₆H₄-CH₂PO[ONH₂(C₂H₄OH)₂]₂ or
C₉F₁₇O-C₆H₄-CH₂CH₂PO(ONa)₂.
EP19880101967 1987-02-12 1988-02-10 Oil proof composition for paper Expired - Lifetime EP0280115B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP30003/87 1987-02-12
JP3000387 1987-02-12

Publications (2)

Publication Number Publication Date
EP0280115A1 true EP0280115A1 (en) 1988-08-31
EP0280115B1 EP0280115B1 (en) 1993-01-13

Family

ID=12291724

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880101967 Expired - Lifetime EP0280115B1 (en) 1987-02-12 1988-02-10 Oil proof composition for paper

Country Status (2)

Country Link
EP (1) EP0280115B1 (en)
DE (1) DE3877377T2 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0462063A1 (en) * 1990-06-13 1991-12-18 Ciba-Geigy Ag Fluorinated paper sizes
WO1992018694A1 (en) * 1991-04-17 1992-10-29 Minnesota Mining And Manufacturing Company Method for sizing paper
US5271806A (en) * 1991-04-17 1993-12-21 Minnesota Mining And Manufacturing Company Method for sizing paper
EP1000996A1 (en) * 1998-11-10 2000-05-17 Asahi Glass Company Ltd. Phosphate type water and oil repellent composition
EP1094099A1 (en) * 1999-04-28 2001-04-25 Asahi Glass Company Ltd. Water-and-oil repellant composition of aqueous dispersion type
WO2005014931A1 (en) * 2003-07-25 2005-02-17 Basf Aktiengesellschaft A method for the production of paper
EP2492395A1 (en) 2011-02-22 2012-08-29 Lamberti SPA Oil and grease resistant treatment compositions

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953283A (en) * 1972-10-05 1976-04-27 Continental Can Company, Inc. Paperboard having improved oil resistance
GB2117021A (en) * 1982-03-16 1983-10-05 Sandoz Products Ltd Flameproofing compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953283A (en) * 1972-10-05 1976-04-27 Continental Can Company, Inc. Paperboard having improved oil resistance
GB2117021A (en) * 1982-03-16 1983-10-05 Sandoz Products Ltd Flameproofing compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ABSTRACTS BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY, vol. 52, no. 11, May 1982, page 1347, abstract no. 12816, Appleton, Wisconsin, US; & JP-A-56 138 197 (DAIKIN TRADE & INDUSTRY CO.) 28-10-1981 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0462063A1 (en) * 1990-06-13 1991-12-18 Ciba-Geigy Ag Fluorinated paper sizes
AU639790B2 (en) * 1990-06-13 1993-08-05 Ciba-Geigy Ag Fluorinated paper sizes
WO1992018694A1 (en) * 1991-04-17 1992-10-29 Minnesota Mining And Manufacturing Company Method for sizing paper
US5271806A (en) * 1991-04-17 1993-12-21 Minnesota Mining And Manufacturing Company Method for sizing paper
AU653607B2 (en) * 1991-04-17 1994-10-06 Minnesota Mining And Manufacturing Company Method for sizing paper
EP1000996A1 (en) * 1998-11-10 2000-05-17 Asahi Glass Company Ltd. Phosphate type water and oil repellent composition
US6315822B1 (en) 1998-11-10 2001-11-13 Asahi Glass Company Ltd. Phosphate type water and oil repellent composition
EP1094099A1 (en) * 1999-04-28 2001-04-25 Asahi Glass Company Ltd. Water-and-oil repellant composition of aqueous dispersion type
EP1094099A4 (en) * 1999-04-28 2002-09-18 Asahi Glass Co Ltd Water-and-oil repellant composition of aqueous dispersion type
WO2005014931A1 (en) * 2003-07-25 2005-02-17 Basf Aktiengesellschaft A method for the production of paper
EP2492395A1 (en) 2011-02-22 2012-08-29 Lamberti SPA Oil and grease resistant treatment compositions

Also Published As

Publication number Publication date
DE3877377D1 (en) 1993-02-25
DE3877377T2 (en) 1993-05-27
EP0280115B1 (en) 1993-01-13

Similar Documents

Publication Publication Date Title
US4956110A (en) Aqueous fluid
JP4243483B2 (en) Optical brightener compositions, their manufacture and their use
US4617414A (en) Process for the preparation of phosphate surfactants
CA1105442A (en) Metal lubricants
JP2873092B2 (en) In situ formation of copper pyrithione in paint.
US3945931A (en) Utilization of amido-acids for the production of aqueous fluids for the working of metals
EP0107199A2 (en) Anionic surface active agents and the preparation thereof
EP0127132B1 (en) Use of alkenylsuccinic monoamides as corrosion inhibitors
US4594177A (en) Surface demoisturizing composition and use thereof
EP0280115A1 (en) Oil proof composition for paper
JPH0159395B2 (en)
JPS584001B2 (en) Jyoso Sosabutsu
US3320164A (en) Non-corrosive, lubricating, cutting and cooling additives
CA1232279A (en) Salt free phosphobetaines
US4144182A (en) Salts of alkylenediamine carboxylic acids and aqueous solutions thereof
EP0846690B1 (en) Melamin polycarboxylic amides and their use as corrosion inhibitor
US4857205A (en) Method for inhibition of scale formation
US5103048A (en) Surface-active compounds having a perfluoroalkyl group and a nitrogen-containing aliphatic radical, a process for their preparation and their use
EP0549006A2 (en) Ammonium and phosphonium salts and their use as biocides
US4360474A (en) Derivatives of polyphosphoric acid partial esters
JP2582108B2 (en) Oilproofing agent for paper
US2265944A (en) Amidine salts of sulphosuccinic esters
GB1358478A (en) Liquid mixtures of basic zinc salts of dialkyl dithiophosphates
US2815324A (en) Cutting oil emulsion containing estersalts of phosphoric acid
EP0041039A1 (en) Use of salts or partial esters of aminotriazine-carboxylic acids as corrosion inhibitors for metals in aqueous systems

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19881219

17Q First examination report despatched

Effective date: 19910102

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 3877377

Country of ref document: DE

Date of ref document: 19930225

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070207

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20070208

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070208

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20080209