Abstract:
The stiffness, wet strength and bursting strength of paper is improved by adding a latex such as milk to the paper and then subjecting the paper to steps of high temperature treatment and immediate rewetting.

Description:
This application is a continuation-in-part of United States patent application Ser. No. 768,783, filed Aug. 23, 1985 abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention: 
     This invention relates to the art of papermaking, particularly to treating paper products with milk and then high temperature to improve its properties, including wet stiffness, wet tensile strength and bursting strength. 
     2. Description of the Prior Art: 
     There is currently considerable interest in improving various properties of paper and boards. Quantifiable paper properties include: dry and wet tensile strength, folding endurance, stiffness, compressive strength, and bursting strength, among others. Which qualities should desirably be enhanced depends upon the intended application of the product. In the case of milk carton board, for example, stiffness is of particular importance, whereas for linerboard, wet strength, folding endurance, and high humidity compression strength may be more important. 
     All of these properties can be measured by well-known standard tests. As used herein, then, &#34;wet strength&#34; means wet tensile strength as measured by American Society for Testing and Materials (ASTM) Standard D829-48. &#34;Folding endurance&#34; is defined as the number of times a board can be folded in two directions without breaking, under conditions specified in Standard D2176-69. &#34;Stiffness&#34; is defined as flexural rigidity and is determined by the bending moment in g-cm. &#34;Linerboard&#34;, as used herein, is a medium-weight paper product used as the facing material in corrugated carton construction, and is usually made from pulp produced by the kraft process. Folding carton board is a medium to heavy weight paper product made of unbleached and/or bleached pulps having basis weights from 40-350 g/m 2 . 
     Prior workers in this field have recognized that high-temperature treatment of paperboard can improve its wet strength. See, for example E. Back, &#34;Wet stiffness by heat treatment of the running web&#34;, Pulp &amp; Paper Canada, vol. 77, No. 12, pp. 97-106 (Dec. 1976). This increase has been attributed to the development and cross-linking of naturally occurring lignins and other polymers, which phenomenon may be sufficient to preserve product wet strength even where conventional synthetic resins or other binders are entirely omitted. 
     It is noteworthy that wet strength improvement by heat curing has previously been thought attainable only at the price of increased brittleness (i.e., reduced folding endurance). Embrittled board is not acceptable for many applications involving subsequent deformation, and therefore heat treatment alone, to develop the wet strength of paperboard and carton board, has not gained widespread acceptance. Heat treatment has most successfully been used to produce hardboard. It has not been practiced on paper having latex or milk additives. 
     It is therefore an object of the invention to produce paperboard having both improved stiffness and wet strength, and adequate folding endurance. 
     With a view to the foregoing, a process has been developed which dramatically and unexpectedly increases not only the stiffness and wet tensile and bursting strengths of various paperboards, but also preserves their folding endurance. In its broadest sense, the invention comprises steps of (1) applying a natural latex, preferably milk, to paperboard, and then (2) heating the paperboard so treated to an internal temperature of at least 400° F. (205° C.) for a period of time sufficient to increase the wet strength of the board. We prefer to raise the internal temperature of the board to at least 450° F. (232° C.) during the heat treating step, as greater stiffness and wet strength are then achieved. This may be because at higher temperatures, shorter step duration is necessary to develop bonding, and there is consequently less time for fiber degradation to occur. Also, shorter required durations enable one to achieve higher production speeds for a treating apparatus of a given length. 
     While the heat treatment may cover a range of temperatures and durations, these factors are interrelated. Higher temperatures requires a heat treating step of shorter duration, and vice-versa. For example, at 550° F. (289° C.), a duration of 2 seconds has been found sufficient to obtain the desired improvements, while at 420° F., considerably longer is required. 
     Optionally, the paper may then be subjected to a third step of rewetting the board immediately after the heat treatment and while the paper temperature is above 100° C. to at least 1% mositure by weight. These steps are followed by conventional drying and/or conditioning of the treated board. It is to be understood that steps 2 and 3 can be repeated several times. 
     Of course, those skilled in the art will recognize the necessity of the product conditioning to a normal moisture content after this very hot treatment. See, for example, U.S. Pat. No. 3,395,219. A certain amount of remoisturizing is normally done, and in fact must be done prior to use or testing. Conventional rehumidification is done after the product has substantially cooled, at temperatures well below 100° C. 
     Our rewetting treatment differs from conventional conditioning in that we add water, by spraying or otherwise, to a very hot and dry paper or board at the very end of the heat treatment, without intermediate cooling. It is important that the water be applied to the product while it is still hot, certainly above 100° C. (212° F.), and preferably above 205° C. (400° F.). Another heat treatment or drying step may follow rewetting, on or off the machine, during a subsequent operation such as sizing, coating or calendering. 
     DESCRIPTION OF THE PREFERRED EMBODIMENT 
     The invention can be carried out either on a conventional papermaking machine or off the machine in an oven after a size-press, but for high speed production, a continuous papermaking machine would be used. 
     In either event, the paper fibers are first treated by adding a latex. Latex is a water-based suspension of protein, and milk is one naturally occurring latex. The additive may be mixed with the pulp prior to sheet forming, or it may be added to a formed sheet by spraying or other means. The wet web is conventionally pressed to unite the pulp fibers and remove excess water. Following wet pressing, the paper product is heat treated. 
     For the heat treatment step to be effective, the initial water content of the web must be in the range of 1-20% by weight and preferably within the 10-15% range. Sufficient heat is then applied to the board to achieve an internal paper temperature of at least 400° F. (205° C.). The heat can be applied in the form of hot air, superheated steam, heated drying cylinders, infrared heaters, or by other means. Alternatively, the paper may be heat-treated in an oven after a size-press. After heat treatment, if the paper is conventionally conditioned, improved wet strength will be observed. 
     Preferably, however, the paper is immediately rewetted following the heat treating step, and while it is still hot. To rewet the paper, water may be applied by spraying, immersion or other means. Even though one effect of the water application is to cool the paper, it is important that the paper not cool substantially before the water application. We have found that the best results are obtained when the paper is rewetted while the web is substantially still at heat treating temperature. In a continuous machine, this goal is achieved by placing the water applicator as close as possible to the exit of the heat treatment unit. 
     The heat treated and rewetted paper is dried, if necessary, and is then cooled, conditioned, and calendered according to conventional procedure. 
     The invention has been practiced as described in the following examples. An improvement in product quality will be apparent from an examination of the test results listed in the tables below. 
    
    
     EXAMPLE 1 
     A commercial bleached kraft board was sized with different potato starch (PS)/milk mixtures. The starch and milk solution concentrations were 8% and 4% polymer by weight, respectively. The size press pressure was adjusted to yield a polymer add-on of 2.4% by weight. A part of the samples was conventionally dried (&#34;C&#34; in the Tables) on Emerson speed drier, model 10 at 230° F. (110° C.). Another portion of the samples was heat treated (&#34;HT&#34; in the Tables) at 400° F. (205° C.) for 30 seconds and rewetted immediately after heat treatment. After conditioning for 48 hours under standard conditions (70° F., 65% relative humidity), the samples were tested. The results of testing appear in Table 1. 
     
                       TABLE 1______________________________________            PS:MILK     PS:MILK   NO MILK  50:50       70:30PROPERTIES     (C)     (HT)   (C)   (HT)  (C)   (HT)______________________________________Basis weight     160.1   150.3  168.5 165.9 165.4 164.0(lb/3000 ft.sup.2)Caliper   18.9    19.0   19.2  18.6  19.2  18.6(mils)Corrected 158/75  164/   161/81                          182/91                                145/  166/81Stiffness         88                 69g-cm(MD/CD)% Stiffness     --      3.8/   1.9/8 15.2/21                                -8.2/ 45.1/8Improvement       -9                 -8(MD/CD)______________________________________ 
    
     EXAMPLE 2 
     Board as in Example 1 was treated with a 50:50 mixture of starch and acrylic latex (Rohm-Maas Rhoplex HA-16). The starch and latex concentrations were 8% and 50% respectively. The size press pressure was adjusted to achieve a polymer add-on of 10.5%. A portion of the samples was conventionally dried on Emerson Speed drier, model 10 at 230° F. (110° C.). Another portion of the samples was heat treated at 400° F. (250° C.) for 30 seconds. All the samples were conditioned for 48 hours under standard conditions. The resultant sample properties are listed in Table 2. 
     
                       TABLE 2______________________________________      NO ADDITIVE PS:LATEXPROPERTIES   C        HT       C      HT______________________________________Basis weight 160.1    l50.3    179    177(lb/3000 ft.sup.2)Caliper       18.9     19.0    19.2   18.6(mils)Corrected    158/75   164/88   166/92 188/99Stiffness,g-cm(MD/CD)% Stiffness  --        3.8/-9   5.1/22.6                                 19.5/32Improvement(MD/CD)______________________________________ 
    
     EXAMPLE 3 
     A commercial kraft unbleached linerboard having a kappa number of 105 and Canadian Standard Freeness of 720 mls was sized and treated as in Example 1. All the samples were conditioned for 48 hours under standard conditions. The resultant board properties are listed in Table 3. 
     
                       TABLE 3______________________________________   NO  ADDITIVE  PS:MILK 50:50                        WHOLE MILKProperties    C       HT      C     HT    C     HT______________________________________Basis weight    135.2   128.0   137.1 138.6 136.6 138.2lb/3000 ft.sup.2Caliper   12.9    12.4    l2.9  12.6  13.0  12.4(mils)Dry Tensile     64.6/   62.4/   66.1/                           72.0/                                 65.9/                                       74.7/lb/in MD/CD     21.6    20.6    22.4  26.2  21.1  22.3Wet Tensile     8.1/    9.6/    6.9/  15.3/                                 6.2/  16.4/lb/in MD/CD     3.1     3.3     2.5   4.9   2.3   5.5Stiffness     14.8/   14.0/   16.5/                           16.0/                                 16.3/                                       15.8/g-cm      5.0     5.0     5.3   6.3   4.8   4.8STFI comp.     46.7/   21.7/   46.7/                           51.0/                                 44.2/                                       48.6/MD/CD     24.5    44.6    26.6  27.7  22.6  21.5MIT Fold --      703/    --    1027/ --    1101/MD/CD    --      424     --     618  --     724Mullen   147.3   121.3   164.0 156.7  15.7 148.7______________________________________ 
    
     EXAMPLE 4 
     The same board as in Example 3 was sized and treated as in Example 3, using a 50% potato starch, 50% latex mixture. All the samples were conditioned for 48 hours under standard conditions. The resultant product properties are listed in Table 4. 
     
                       TABLE 4______________________________________      NO ADDITIVE PS:LATEX 50:50Properties   C        HT       C      HT______________________________________Basis weight 135.2    128.0    143.7  145.0lb/3000 ft.sup.2Caliper       12.9     12.4     13.1   12.3(mils)Dry Tensile   64.6/    62.4/    83.5/  82.2/lb/in MD/CD   21.6     20.6     31.2   30.1Wet Tensile   8.1/     9.6/     13.7/  24.8/lb/in MD/CD   3.1      3.3      4.7    9.6Stiffness     14.8/    14.0/    15.3/  16.5/g-cm          5.0      5.0      6.8    6.0STFI comp.    46.7/    21.7/    53.6/  57.0/MD/CD         24.5     44.6     29.6   31.0MIT Fold     --       703/     --     939/MD/CD        --       424      --     559Mullen       147.3    121.3    191.0  178.0______________________________________ 
    
     EXAMPLE 5 
     Samples of bleached kraft board were sized with various additives and then processed as in Example 1. The results of testing appear in tables 5.1-5.7. 
     
                       TABLE 5.1______________________________________BLEACHED BOARD + NO ADDITIVES                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/3000 ft.sup.2)            209.1      208.4    209.4Caliper (0.001 in)            21.9       21.4     21.5Tensile    Dry    MD     88       108    101(lb/in)           CD     52       60     58% Stretch         MD     2.3      2.6    2.4             CD     3.5      4.1    3.9Tensile    Wet    MD     19       37     31(lb/in)           CD     17       25     22% Stretch         MD     2.0      2.4    2.2             CD     2.5      3.7    3.5Mullen Burst      Dry    89       99     92(psi)             Wet    20       37     39Corrected Taber   MD     270      292    288Stiffness gm-cm   CD     145      161    165______________________________________ 
    
     
                       TABLE 5.2______________________________________BLEACHED BOARD + STARCH(8% Aqueous) (4.8% Add-on)                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/3000 ft.sup.2)            212.0      213.7    210.2Caliper (0.001 in)            21.3       20.8     20.2Tensile    Dry    MD     124      121    128(lb/in)           CD     69       60     69% Stretch         MD     3.9      3.6    3.4             CD     5.1      4.8    4.8Tensile    Wet    MD     30       35     28(lb/in)           CD     15       17     18% Stretch         MD     2.9      2.9    2.8             CD     5.4      5.2    5.5Mullen Burst      Dry    150      148    149(psi)             Wet    29       39     41Corrected Taber   MD     294      308    315Stiffness gm-cm   CD     168      172    181______________________________________ 
    
     
                       TABLE 5.3______________________________________BLEACHED BOARD + SKIM MILK(3.5% Proteins) (5% Add-on)                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/3000 ft.sup.2)            208.2      210.4    208.1Caliper (0.001 in)            21.9       21.0     20.5Tensile    Dry    MD     95       107    108(lb/in)           CD     57       61     65% Stretch         MD     2.5      2.5    2.4             CD     4.0      4.2    4.1Tensile    Wet    MD     29       42     47(lb/in)           CD     16       23     31% Stretch         MD     3.0      2.9    3.0             CD     5.4      5.6    6.0Mullen Burst      Dry    117      113    109(psi)             Wet    35       54     62Corrected Taber   MD     297      312    321Stiffness gm-cm   CD     138      150    158______________________________________ 
    
     
                       TABLE 5.4______________________________________BLEACHED BOARD &amp; CONDENSED MILK(7.0% Proteins) (4.8% Add-on)                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/3000 ft.sup.2)            215.6      214.7    212.7Caliper (0.001 in)            21.5       21.1     20.8Tensile    Dry    MD     112      110    118(lb/in)           CD     54       58     59% Stretch         MD     2.5      2.5    2.5             CD     3.4      4.0    3.4Tensile    Wet    MD     27       52     51(lb/in)           CD     14       25     25% Stretch         MD     2.4      2.8    2.8             CD     5.1      5.6    6.1Mullen Burst      Dry    111      110    115(psi)             Wet    28       57     48Corrected Taber   MD     301      312    333Stiffness gm-cm   CD     160      159    167______________________________________ 
    
     
                       TABLE 5.5______________________________________BLEACHED BOARD &amp; RECONSTITUTED DRY MILK(14% Proteins) (4.8% Add-on)                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/3000 ft.sup.2)            231.0      225.7    222.5Caliper (0.001 in)            22.0       21.4     20.9Tensile    Dry    MD     123      127    128(lb/in)           CD     66       69     71% Stretch         MD     2.6      2.7    2.4             CD     4.0      4.1    3.1Tensile    Wet    MD     26       39     42(lb/in)           CD     14       23     22% Stretch         MD     2.8      3.4    3.5             CD     5.4      6.4    6.3Mullen Burst      Dry    143      139    121(psi)             Wet    33       46     51Corrected Taber   MD     335      396    398Stiffness gm-cm   CD     214      221    241______________________________________ 
    
     
                       TABLE 5.6______________________________________BLEACHED BOARD + STARCH: RECONSTITUTED DRYMILK (7% Proteins) (5.0% Add-on)                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/3000 ft.sup.2)            223.6      223.2    220.2Caliper (0.001 in)            22.4       21.9     21.3Tensile    Dry    MD     123      127    132(lb/in)           CD     67       70     70% Stretch         MD     2.9      2.9    2.5             CD     4.3      4.6    3.4Tensile    Wet    MD     27       38     43(lb/in)           CD     16       22     24% Stretch         MD     2.8      3.1    3.2             CD     5.6      6.0    5.9Mullen Burst      Dry    129      136    132(psi)             Wet    29       42     45Corrected Taber   MD     333      381    379Stiffness gm-cm   CD     188      215    219______________________________________ 
    
     
                       TABLE 5.7______________________________________BLEACHED BOARD + IMPREGNATED WITH1% CaCl.sub.2 AND CONDENSED MILK(7% Proteins) (5% Add-on)                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/3000 ft.sup.2)            219.9      261.6    211.2Caliper (0.001 in)            22.0       21.5     20.5Tensile    Dry    MD     106      96     105(lb/in)           CD     58       59     58% Stretch         MD     2.5      2.4    2.1             CD     4.3      4.2    3.0Tensile    Wet    MD     24       45     41(lb/in)           CD     15       22     24% Stretch         MD     2.7      3.0    2.8             CD     5.3      5.2    4.2Mullen Burst      Dry    114      88     92(psi)             Wet    29       38     35Corrected Taber   MD     330      349    340Stiffness gm-cm   CD     164      172    174______________________________________ 
    
     EXAMPLE 6 
     Samples of unbleached kraft linerboard were subjected to the treatment of Example 5; the resulting products were tested as in Example 5. The results appear in the following tables. 
     
                       TABLE 6.1______________________________________UNBLEACHED BOARD (LINERBOARD) + NOADDITIVES                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/1000 ft.sup.2)            49.5       49.8     49.6Caliper (0.001 in)            13.4       13.3     13.4Tensile    Dry    MD     99       115    105(lb/in)           CD     42       49     47% Stretch         MD     3.5      3.6    3.5             CD     4.2      4.4    4.4Tensile    Wet    MD     9        27     24(lb/in)           CD     4        13     11% Stretch         MD     1.4      2.2    2.1             CD     3.8      4.4    4.3Mullen Burst      Dry    105      158    152(psi)             Wet    10       49     41STFI (lb/in)      MD     40       46     44             CD     28       31     32______________________________________ 
    
     
                       TABLE 6.2______________________________________UNBLEACHED BOARD + STARCH(8% Aqueous) (5.0% Add-on)                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/1000 ft.sup.2)            50.4       49.7     49.0Caliper (0.001 in)            13.7       13.7     13.2Tensile    Dry    MD     126      128    147(lb/in)           CD     67       54     64% Stretch         MD     5.5      4.7    5.5             CD     6.6      5.7    5.6Tensile    Wet    MD     16       25     25(lb/in)           CD     7        12     12% Stretch         MD     2.1      2.4    2.4             CD     4.8      5.6    5.8Mullen Burst      Dry    222      196    190(psi)             Wet    18       34     38STFI (lb/in)      MD     47       48     53             CD     32       30     35______________________________________ 
    
     
                       TABLE 6.3______________________________________UNBLEACHED BOARD + SKIM MILK(3.5% Protein) (4.9% Add-on)                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/1000 ft.sup.2)            49.7       48.7     48.0Caliper (0.001 in)            13.5       13.6     12.6Tensile    Dry    MD     109      119    1l8(lb/in)           CD     43       45     54% Stretch         MD     3.9      4.4    4.0             CD     4.l      5.5    5.1Tensile    Wet    MD     15       32     30(lb/in)           CD     6        15     15% Stretch         MD     1.7      2.6    2.8             CD     4.0      6.2    6.3Mullen Burst      Dry    133      183    164(psi)             Wet    16       53     58STFI (lb/in)      MD     47       58     54             CD     27       32     31______________________________________ 
    
     
                       TABLE 6.4______________________________________UNBLEACHED BOARD + CONDENSED MILK(7.0% Proteins) (4.9% Add-on)                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/1000 ft.sup.2)            52.3       50.8     48.6Caliper (0.001 in)            13.6       13.6     12.5Tensile    Dry    MD     103      98     115(lb/in)           CD     48       52     50% Stretch         MD     3.5      2.6    3.6             CD     5.1      5.3    4.5Tensile    Wet    MD     12       38     36(lb/in)           CD     5        15     14% Stretch         MD     l.5      2.8    2.7             CD     4.3      6.0    6.6Mullen Burst      Dry    144      149    143(psi)             Wet    12       68     63STFI (lb/in)      MD     44       42     53             CD     26       34     32______________________________________ 
    
     
                       TABLE 6.5______________________________________UNBLEACHED BOARD + RECONSTITUTED DRY MILK(14% Proteins) (4.8% Add-on)                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/1000 ft.sup.2)            53.6       53.3     51.0Caliper (0.001 in)            14.1       13.6     12.5Tensile    Dry    MD     125      139    139(lb/in)           CD     53       61     66% Stretch         MD     3.4      4.5    4.6             CD     5.3      5.6    4.8Tensile    Wet    MD     11       40     41(lb/in)           CD     5        18     17% Stretch         MD     1.6      3.8    3.5             CD     4.3      6.8    7.1Mullen Burst      Dry    166      199    178(psi)             Wet    14       95     81STFI (lb/in)      MD     48       66     62             CD     31       40     34______________________________________ 
    
     
                       TABLE 6.6______________________________________UNBLEACHED BOARD + STARCH: RECONSTITUTEDDRY MILK (7.0% Proteins) (4.8% Add-on)                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/1000 ft.sup.2)            51.4       51.9     50.9Caliper (0.001 in)            13.7       13.5     12.7Tensile    Dry    MD     126      147    142(lb/in)           CD     45       56     51% Stretch         MD     4.1      4.5    4.1             CD     4.6      5.2    4.2Tensile    Wet    MD     13       34     39(lb/in)           CD     5        15     14% Stretch         MD     1.6      3.2    3.3             CD     3.8      6.3    6.0Mullen Burst      Dry    168      193    171(psi)             Wet    16       69     70STFI (lb/in)      MD     49       66     64             CD     31       40     41______________________________________ 
    
     
                       TABLE 6.7______________________________________UNBLEACHED BOARD + IMPREGNATED WITH 1%CaCl.sub.2 AND CONDENSED MILK(7% Proteins) (5.1% Add-on)                       HT +     HTPROPERTIES       CONTROL    REWET    ONLY______________________________________Basis Wt. (lb/1000 ft.sup.2)                       50.7     50.8Caliper (0.001 in)          13.8     13.0Tensile    Dry    MD              110    125(lb/in)           CD              54     54% Stretch         MD              3.5    3.5             CD              6.0    4.4Tensile    Wet    MD              34     40(lb/in)           CD              16     16% Stretch         MD              3.9    2.9             CD              6.1    6.8Mullen Burst      Dry             164    149(psi)             Wet             65     54STFI (lb/in)      MD              45     54             CD              30     33______________________________________ 
    
     The tables above show clearly that notable increases in wet strength, without substantial degradation of other qualities, are produced by heat treating paper having latex additives as described above. Use of the rewetting procedure is seen to improve folding endurance. 
     Inasmuch as the invention is subject to many variations and changes in detail, the foregoing description and examples should be regarded as illustrative of the invention defined by the following claims.