JPH05106192A - Interlaminar adhesive for paperboard and the like and papermaking process - Google Patents
Interlaminar adhesive for paperboard and the like and papermaking processInfo
- Publication number
- JPH05106192A JPH05106192A JP27847491A JP27847491A JPH05106192A JP H05106192 A JPH05106192 A JP H05106192A JP 27847491 A JP27847491 A JP 27847491A JP 27847491 A JP27847491 A JP 27847491A JP H05106192 A JPH05106192 A JP H05106192A
- Authority
- JP
- Japan
- Prior art keywords
- starch
- adhesive
- paperboard
- dicarboxylic acid
- papermaking
- 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.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 24
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 24
- 239000011087 paperboard Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- 230000008569 process Effects 0.000 title abstract description 8
- 229920002472 Starch Polymers 0.000 claims abstract description 74
- 235000019698 starch Nutrition 0.000 claims abstract description 73
- 239000008107 starch Substances 0.000 claims abstract description 70
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006467 substitution reaction Methods 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000002619 bicyclic group Chemical group 0.000 claims abstract description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 14
- 239000011229 interlayer Substances 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000001384 succinic acid Substances 0.000 claims description 3
- 229920000881 Modified starch Polymers 0.000 abstract description 4
- 150000008064 anhydrides Chemical class 0.000 abstract description 3
- 239000004368 Modified starch Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 2
- FLISWPFVWWWNNP-BQYQJAHWSA-N dihydro-3-(1-octenyl)-2,5-furandione Chemical compound CCCCCC\C=C\C1CC(=O)OC1=O FLISWPFVWWWNNP-BQYQJAHWSA-N 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 239000000123 paper Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 235000013808 oxidized starch Nutrition 0.000 description 5
- 239000001254 oxidized starch Substances 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- -1 bicyclic aliphatic dicarboxylic acids Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920002261 Corn starch Polymers 0.000 description 3
- 239000008120 corn starch Substances 0.000 description 3
- 239000011121 hardwood Substances 0.000 description 3
- 235000019426 modified starch Nutrition 0.000 description 3
- 239000011122 softwood Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KCYQMQGPYWZZNJ-BQYQJAHWSA-N hydron;2-[(e)-oct-1-enyl]butanedioate Chemical compound CCCCCC\C=C\C(C(O)=O)CC(O)=O KCYQMQGPYWZZNJ-BQYQJAHWSA-N 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000011044 succinic acid Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- DJKGDNKYTKCJKD-BPOCMEKLSA-N (1s,4r,5s,6r)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid Chemical compound ClC1=C(Cl)[C@]2(Cl)[C@H](C(=O)O)[C@H](C(O)=O)[C@@]1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-BPOCMEKLSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 1
- DMNJWIGKABXQGQ-AATRIKPKSA-N 2-[(e)-hex-1-enyl]butanedioic acid Chemical compound CCCC\C=C\C(C(O)=O)CC(O)=O DMNJWIGKABXQGQ-AATRIKPKSA-N 0.000 description 1
- FDYJJKHDNNVUDR-UHFFFAOYSA-N 2-ethyl-2-methylbutanedioic acid Chemical compound CCC(C)(C(O)=O)CC(O)=O FDYJJKHDNNVUDR-UHFFFAOYSA-N 0.000 description 1
- HLWLFKQBSHRRCB-UHFFFAOYSA-N 2-nonylbutanedioic acid Chemical compound CCCCCCCCCC(C(O)=O)CC(O)=O HLWLFKQBSHRRCB-UHFFFAOYSA-N 0.000 description 1
- FPOGSOBFOIGXPR-UHFFFAOYSA-N 2-octylbutanedioic acid Chemical compound CCCCCCCCC(C(O)=O)CC(O)=O FPOGSOBFOIGXPR-UHFFFAOYSA-N 0.000 description 1
- OMJWPOCAMRXQKG-UHFFFAOYSA-N 3,4,5,6-tetrahydroxyphthalic acid Chemical compound OC(=O)C1=C(O)C(O)=C(O)C(O)=C1C(O)=O OMJWPOCAMRXQKG-UHFFFAOYSA-N 0.000 description 1
- XCNITIAYTWFPIS-UHFFFAOYSA-N CC(C(C(=O)O)CC1=CC=CC=C1)(C(=O)O)C Chemical compound CC(C(C(=O)O)CC1=CC=CC=C1)(C(=O)O)C XCNITIAYTWFPIS-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- MYAXYRZTMGVKDX-UHFFFAOYSA-N bis(2-methylprop-1-enyl) 2,2,3,3-tetrakis(2-methylprop-1-enyl)butanedioate Chemical compound CC(C)=COC(=O)C(C=C(C)C)(C=C(C)C)C(C=C(C)C)(C=C(C)C)C(=O)OC=C(C)C MYAXYRZTMGVKDX-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、多層構造を有する板紙
等のシートを抄造するに際して、糊剤として使用する変
性澱粉に係わり、その目的とするところは効果的な接着
層の形成とそれに伴う接着強度の安定化、紙層内への澱
粉の歩留りの向上による排水系への流失の少ない優れた
糊剤を提供することにある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified starch which is used as a sizing agent when making a sheet of paperboard or the like having a multi-layer structure, and its purpose is to form an effective adhesive layer and to accompany it. It is an object of the present invention to provide an excellent sizing agent with less loss to the drainage system by stabilizing the adhesive strength and improving the yield of starch in the paper layer.
【０００２】[0002]
【従来の技術】従来、この分野に糊剤として使用されて
いる澱粉には、低価格の未化工澱粉が多いが、抄紙速度
の向上した高速抄紙機では尿素燐酸エステル化澱粉、エ
ーテル化澱粉、カチオン化澱粉、アセチル化澱粉などの
変性澱粉も広く使用されている。これらの変性澱粉は種
々の変性により糊化温度を低くしてあるので、抄造時の
抄き合わせ工程で噴霧、塗布された澱粉粒が乾燥工程中
で糊になり易く、未化工澱粉より安定した接着性能が得
やすいため使用される機会が多くなってきている。2. Description of the Related Art Conventionally, many starches used as sizing agents in this field are low-priced unmodified starches, but in a high-speed paper machine with an improved papermaking speed, urea phosphate esterified starch, etherified starch, Modified starches such as cationized starch and acetylated starch are also widely used. Since these modified starches have a low gelatinization temperature due to various modifications, the starch granules sprayed and applied in the combining step during papermaking tend to become paste during the drying step, and are more stable than unmodified starch. Since it is easy to obtain adhesive performance, it is increasingly used.
【０００３】[0003]
【発明が解決しようとする課題】抄造速度の速い高速抄
紙機では、乾燥工程を極めて短時間で通過するために板
紙等のシートを形成する際に用いられる層間接着剤とし
ての澱粉は、上記したように抄き合わせ層に一様に分
散、分布することが必要であり、更に乾燥工程で速やか
に糊化することが求められる。In a high-speed paper machine having a high paper-making speed, the starch as an interlayer adhesive used for forming a sheet such as paperboard in order to pass through the drying process in an extremely short time is as described above. As described above, it is necessary to uniformly disperse and distribute in the assembling layer, and further it is required to gelatinize quickly in the drying step.
【０００４】これらの澱粉は、価格が安価であることか
ら添加量に対する効果を特に重視しなくても糊剤として
充分使用に耐えるため広く使用され現在に至っている。
しかしながら、澱粉を多量に使用した場合、板紙のよう
なシート状物の抄造では、その工程で多量の水を使用す
ることから排出水の中に糊剤として使用した澱粉が充分
に歩留まらずに流出し、排水を汚濁させる恐れがある。
このような問題を避けるために、パルプ等に歩留まりや
すいカチオン澱粉を使用することが考えられるが、その
場合、澱粉の価格が一般澱粉よりも高価になるという問
題を有する。また、得られたシートを食品容器として使
用した場合、食用に適さないカチオン澱粉を使用してい
ることから内容物に溶出した場合の懸念も想定される。Since these starches are low in price, they have been widely used since they can be sufficiently used as a sizing agent even if the effect on the added amount is not particularly emphasized.
However, when a large amount of starch is used, a large amount of water is used in the papermaking process of a sheet-like material such as paperboard, so that the starch used as a sizing agent in the discharged water is not sufficiently retained. It may run out and pollute the wastewater.
In order to avoid such a problem, it is possible to use a cationic starch that is easy to retain in pulp or the like, but in that case, there is a problem in that the price of the starch becomes higher than that of general starch. In addition, when the obtained sheet is used as a food container, there is a possibility that it may be eluted into the contents because the edible cationic starch is used.
【０００５】[0005]
【課題を解決するための手段】本発明者らはこれらの状
況を考慮して種々研究を重ねた結果、ジカルボン酸無水
物で澱粉をエステル化したジカルボン酸エステル化澱粉
がこの目的を達するのに適していることを見出して本発
明を完成した。Means for Solving the Problems As a result of various studies conducted by the present inventors in consideration of these circumstances, it was found that a dicarboxylic acid esterified starch obtained by esterifying starch with a dicarboxylic acid anhydride achieves this object. The present invention has been completed by finding out that it is suitable.
【０００６】ジカルボン酸エステル化澱粉は、ジカルボ
ン酸の分子構造上、二価のカルボキシル基のうち一個の
みが澱粉の水酸基とのエステル結合に関与し、もう一方
のカルボキシル基は、結合に与からずに存在することが
一般に知られている。このような形で存在するカルボキ
シル基は水中では負に帯電しており、正に帯電している
紙料中の多価金属と結合しやすい状態になっている。In the dicarboxylic acid esterified starch, due to the molecular structure of the dicarboxylic acid, only one of the divalent carboxyl groups is involved in the ester bond with the hydroxyl group of the starch, and the other carboxyl group is not involved in the bond. It is generally known to exist in. The carboxyl group existing in such a form is negatively charged in water, and is in a state of easily binding to the positively charged polyvalent metal in the paper material.
【０００７】なお、ジカルボン酸エステル化澱粉は、通
常、生澱粉のスラリーにジカルボン酸無水物や類似の酸
無水物を添加し、常法に従ってエステル化反応によって
製造され、原料の澱粉としては特に限定されることな
く、トウモロコシ澱粉、馬鈴薯澱粉、タピオカ澱粉、小
麦澱粉、サゴ澱粉等いずれのものも使用できる。The dicarboxylic acid esterified starch is usually produced by adding a dicarboxylic acid anhydride or a similar acid anhydride to a slurry of raw starch and performing an esterification reaction according to a conventional method, and the starch as a raw material is not particularly limited. Without being used, any of corn starch, potato starch, tapioca starch, wheat starch, sago starch and the like can be used.
【０００８】本発明においてエステル化に使用するジカ
ルボン酸としては、脂肪族、芳香族、脂環族もしくは二
環式脂肪族のジカルボン酸からなる群から選ばれる炭素
原子数４〜22のジカルボン酸が用いられる。これらの例
としては、例えばマレイン酸、フタル酸、トリメリット
酸、ピロメリット酸、エンドメチレンテトラヒドロフタ
ル酸、クロレンド酸、メチルエンドメチレンテトラヒド
ロフタル酸、テトラヒドロキシフタル酸、ジフェン酸、
シトラコン酸、グルタコン酸、グルタル酸、コハク酸、
ヘキサイソブテニルコハク酸、ノニルコハク酸、ｎ−オ
クチルコハク酸、２−エチル２−メチルコハク酸、ジメ
チルベンジルコハク酸、オクテニルコハク酸、ヘキセニ
ルコハク酸、デシニルグルタル酸、ドデセニルコハク
酸、イタコン酸などを挙げることができ、特にオクテニ
ルコハク酸等のコハク酸類が好ましい。これらのジカル
ボン酸は澱粉とのエステル化反応に際しては、それぞれ
の酸無水物として用いられる。ジカルボン酸の炭素原子
数が３以下ではエステル化度を大にしないと糊化温度が
低下せず、エステル化度を大にすると可溶化分が多くな
るため好ましくなく、また炭素原子数が２３以上ではエ
ステル化が充分に行われず目的とする性質のエステル化
澱粉が得にくいことから、炭素原子数を上記の範囲に定
めた。The dicarboxylic acid used for esterification in the present invention is a dicarboxylic acid having 4 to 22 carbon atoms selected from the group consisting of aliphatic, aromatic, alicyclic or bicyclic aliphatic dicarboxylic acids. Used. Examples of these include maleic acid, phthalic acid, trimellitic acid, pyromellitic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methylendomethylenetetrahydrophthalic acid, tetrahydroxyphthalic acid, diphenic acid,
Citraconic acid, glutaconic acid, glutaric acid, succinic acid,
Hexaisobutenyl succinic acid, nonyl succinic acid, n-octyl succinic acid, 2-ethyl 2-methyl succinic acid, dimethylbenzyl succinic acid, octenyl succinic acid, hexenyl succinic acid, decynyl glutaric acid, dodecenyl succinic acid, itaconic acid and the like can be mentioned. Particularly preferred are succinic acids such as octenyl succinic acid. These dicarboxylic acids are used as their respective acid anhydrides in the esterification reaction with starch. When the number of carbon atoms of the dicarboxylic acid is 3 or less, the gelatinization temperature does not decrease unless the degree of esterification is increased, and when the degree of esterification is increased, the solubilized content increases, which is not preferable, and the number of carbon atoms is 23 or more. However, since the esterification is not sufficiently carried out and it is difficult to obtain the esterified starch having the desired properties, the number of carbon atoms is set within the above range.
【０００９】ジカルボン酸の置換度としては、本発明の
場合、0.005 〜0.9 の範囲が好ましい。置換度が、0.00
5 以下では、置換したカルボキシル基量が少ないため、
充分な層間接着強さが得られない。また置換度が、0.9
以上ではカルボキシル基同士の自己架橋が進行し、抄紙
工程での乾燥余熱だけでは糊化しなくなり、その結果、
層間接着強さが発揮されなくなってくる。In the present invention, the substitution degree of the dicarboxylic acid is preferably in the range of 0.005 to 0.9. The degree of substitution is 0.00
Below 5, the amount of substituted carboxyl groups is small,
Sufficient interlayer adhesive strength cannot be obtained. The degree of substitution is 0.9
In the above, self-crosslinking of the carboxyl groups progresses, gelatinization will not be achieved only by the residual heat of drying in the papermaking process, and as a result,
The interlayer adhesive strength will not be exhibited.
【００１０】上記のことから、本発明の板紙等の層間接
着剤は、脂肪族、芳香族、脂環族もしくは二環式脂肪族
のジカルボン酸無水物よりなる群から選ばれる炭素原子
数４〜22の無水ジカルボン酸と澱粉を反応させて得られ
る置換度0.005 〜0.9 のジカルボン酸エステル化澱粉よ
りなることを特徴とする。また、本発明は上記ジカルボ
ン酸エステル化澱粉からなる層間接着剤を、抄紙時に抄
き合わされる板紙等のシートの層間に噴霧、塗布する接
着剤としての澱粉スラリーにおいて、澱粉として上記ジ
カルボン酸エステル化澱粉を使用することを特徴とする
板紙等の抄紙方法に関するものである。From the above, the interlayer adhesive for paperboard or the like of the present invention has 4 to 4 carbon atoms selected from the group consisting of aliphatic, aromatic, alicyclic or bicyclic aliphatic dicarboxylic acid anhydrides. It is characterized in that it comprises a dicarboxylic acid esterified starch having a substitution degree of 0.005 to 0.9 obtained by reacting 22 of dicarboxylic anhydride with starch. The present invention also provides an inter-layer adhesive consisting of the above-mentioned dicarboxylic acid esterified starch, which is sprayed and applied between the layers of sheets such as paperboard to be laminated at the time of papermaking, in the starch slurry as an adhesive, and the above-mentioned dicarboxylic acid esterified as starch. The present invention relates to a papermaking method for paperboard and the like characterized by using starch.
【００１１】本発明においてジカルボン酸エステル化澱
粉が抄紙時の層間接着剤として好ましい理由については
次のごとき理由が考えられる。抄紙工程では通常、ろ水
性の向上や添加薬品類の定着促進のために硫酸アルミニ
ウムを添加しているが、正に帯電したアルミニウムイオ
ンは速やかに、負に帯電したパルプ繊維に吸着される。
結合に与かっていないカルボキシル基を持つジカルボン
酸エステル化澱粉は、このようにパルプ繊維に定着した
アルミニウムイオンと容易に結合しやすいため、紙の抄
造工程でパルプ繊維との親和性が良好となり、これらの
接着剤として澱粉が極めて望ましい状態で機能するもの
と考えられる。また、パルプ繊維と澱粉との結合状態が
向上することから、抄紙工程の系外に澱粉が流失しにく
くなり、澱粉の定着率も向上するものと判断される。In the present invention, the reason why the dicarboxylic acid esterified starch is preferable as an interlayer adhesive at the time of papermaking is considered as follows. In the papermaking process, aluminum sulfate is usually added to improve drainage and promote the fixing of additives, but positively charged aluminum ions are quickly adsorbed by negatively charged pulp fibers.
The dicarboxylic acid esterified starch having a carboxyl group that is not involved in the binding easily binds to the aluminum ions fixed to the pulp fiber in this way, and thus has a good affinity with the pulp fiber in the paper making process. It is believed that starch functions as a highly desirable adhesive in an extremely desirable state. Further, since the binding state between the pulp fiber and the starch is improved, it is considered that the starch is less likely to be washed out of the system in the papermaking process and the starch fixing rate is also improved.
【００１２】カルボキシル基の澱粉への導入は、上記の
ような効果を期待できるが、通常カルボキシル基をもっ
た澱粉として一般的には、酸化澱粉がある。酸化澱粉
は、原料澱粉に次亜塩素酸ナトリウムを作用させ、澱粉
の分子鎖を切断して低分子化したものである。この処理
によって酸化澱粉分子内にカルボキシル基が導入される
ことが知られているが、この場合導入されるカルボキシ
ル基の数は少なく、パルプ繊維との親和性を充分に示す
量には至らない。また酸化澱粉はエステル化澱粉とは異
なり糊化温度があまり下がらず、本発明で述べている板
紙の抄造用には不適であった。また、更に低分子化して
いるために、接着力も充分でない。このように酸化澱粉
では本発明の目的は達成できない。The introduction of a carboxyl group into starch can be expected to have the above-mentioned effects, but as a starch having a carboxyl group, oxidized starch is generally used. Oxidized starch is made by lowering the molecular weight of starch by causing sodium hypochlorite to act on the raw starch and breaking the molecular chain of the starch. It is known that this treatment introduces a carboxyl group into the molecule of the oxidized starch, but in this case, the number of carboxyl groups introduced is small, and the amount does not sufficiently show the affinity with pulp fiber. Unlike esterified starch, oxidized starch did not lower the gelatinization temperature so much, and was not suitable for papermaking of the paperboard described in the present invention. Moreover, since the molecular weight is further reduced, the adhesive force is not sufficient. Thus, the object of the present invention cannot be achieved with oxidized starch.
【００１３】本発明におけるジカルボン酸エステル化澱
粉は、通常この種の分野で使用される接着剤と同様にし
て使用される。即ち、例えば澱粉を水中に懸濁させてス
ラリー化し、スプレーノズル等により噴霧塗布し、その
後乾燥工程で加熱するなどの方法によって使用できる。
乾燥工程での加熱も従来抄紙に使用されていた加熱条件
が使用でき、良好な糊化と接着強度が得られる。The dicarboxylic acid esterified starch in the present invention is generally used in the same manner as the adhesive used in this kind of field. That is, for example, it can be used by a method in which starch is suspended in water to form a slurry, spray-coated with a spray nozzle or the like, and then heated in a drying step.
The heating in the drying step can be performed under the heating conditions conventionally used for papermaking, and good gelatinization and adhesive strength can be obtained.
【００１４】本発明において、ジカルボン酸エステル化
澱粉の定着に利用される正に帯電している多価金属は必
ずしも必要でなく、必要に応じ適量使用すればよい。使
用量としてはジカルボン酸エステル化澱粉を定着するに
充分な量であればよく、通常板紙等の抄紙に使用される
量であれば充分である。正の多価金属としては通常硫酸
アルミニウムが使用されるが、他の多価金属塩でもよ
い。本発明において抄紙される板紙等は、従来の紙料か
らなるもので広葉樹パルプ、針葉樹パルプ、その他のケ
ミカルパルプ等何れのものでもよく、抄造時に二枚以上
積層されるものであれば使用できるが、紙料に混入して
使用することもできる。以下、本発明を実施例により説
明するが、本発明はこれに限定されるものではない。In the present invention, the positively charged polyvalent metal used for fixing the dicarboxylic acid esterified starch is not always necessary and may be used in an appropriate amount as needed. The amount used may be an amount sufficient to fix the dicarboxylic acid esterified starch, and may be an amount usually used for papermaking such as paperboard. Aluminum sulfate is usually used as the positive polyvalent metal, but other polyvalent metal salts may be used. The paperboard or the like to be paper-made in the present invention may be any of hardwood pulp, softwood pulp, other chemical pulp and the like made of conventional paper stock, and it can be used as long as two or more sheets are laminated at the time of papermaking. It can also be mixed with paper stock and used. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
【００１５】[0015]
【実施例】スプレーノズルより噴霧させるため、表１に
示す各澱粉をそれぞれ水中に懸濁させてスラリーを調製
した。針葉樹の晒クラフトパルプをろ水度 400mlに叩解
した紙料と広葉樹の晒クラフトパルプをろ水度 400mlに
叩解した紙料とを、それぞれ坪量 100ｇ／m2づつとなる
ように常法によりシートマシンで手抄きし、抄いた直後
の針葉樹パルプの未脱水シート上に予め懸濁させた上記
澱粉スラリーをスプレーノズルにより澱粉が１ｇ／m2付
着するように噴霧した。その後直ちに、同様に抄いた広
葉樹パルプの未脱水シートを重ね合わせ、プレス脱水し
た後、７５℃で乾燥した。このようにして、澱粉にて接
着させたシートを空調室（20℃、湿度65％）で数日間放
置した後、幅15mmに切り出して試片とし、この試片の端
部を長さ方向に少し剥離してショッパー型剥離試験機に
かけ、２層の層間の接着剥離強さを測定した。EXAMPLES In order to spray from a spray nozzle, each starch shown in Table 1 was suspended in water to prepare a slurry. Sheets of softwood bleached kraft pulp beaten to a freeness of 400 ml and hardwood bleached kraft pulp beaten to a freeness of 400 ml are formed by a conventional method so that the basis weight is 100 g / m 2 each. The starch slurry was hand-made by a machine, and immediately after the making, the above-mentioned starch slurry suspended in advance on a non-dehydrated sheet of softwood pulp was sprayed by a spray nozzle so that the starch adhered at 1 g / m 2 . Immediately thereafter, an undehydrated sheet of hardwood pulp obtained in the same manner was overlaid, press-dehydrated, and dried at 75 ° C. After leaving the sheet adhered with starch in this way for several days in an air-conditioned room (20 ° C, humidity 65%), it was cut into a piece with a width of 15 mm to make a test piece. After peeling a little, it was subjected to a Shopper type peel tester to measure the adhesive peel strength between the two layers.
【表１】 [Table 1]
【００１６】剥離試験の結果は表２に示すとおりで、ジ
カルボン酸エステル化とうもろこし澱粉が最も高い剥離
強さを示している。The results of the peel test are shown in Table 2, and the dicarboxylic acid esterified corn starch shows the highest peel strength.
【表２】 [Table 2]
【００１７】また、噴霧塗布した澱粉が脱水プレス過程
で過剰水と共に系外へ流失している程度を調べるため
に、酵素分解法にて供試紙の澱粉含有量を定量した。残
存澱粉量を塗布澱粉量で除した結果を澱粉歩留とした。
結果は表３に示すとおり、マレイン酸、フタル酸および
コハク酸でそれぞれエステル化されたジカルボン酸エス
テル化とうもろこし澱粉が紙中に留まっている比率が最
も高く、澱粉粒界面の変性の効果が現れていることが判
る。The starch content of the test paper was quantified by an enzymatic decomposition method in order to examine the extent to which the spray-coated starch was washed out of the system together with excess water during the dehydration pressing process. The starch yield was determined by dividing the amount of residual starch by the amount of applied starch.
As shown in Table 3, the proportion of dicarboxylic acid esterified corn starch esterified with maleic acid, phthalic acid and succinic acid was highest in the paper, and the effect of modifying the starch grain interface was revealed. It is understood that there is.
【表３】 [Table 3]
【００１８】[0018]
【発明の効果】以上説明したように、板紙等のシートの
抄造時に層間接着剤として本発明のジカルボン酸エステ
ル化澱粉を使用すると、抄紙原料であるパルプスラリー
に効率よく結合するため、澱粉の系外流失が少なく接着
剤として充分機能し、抄き合わせ層の剥離強度を飛躍的
に向上させることができる。そのため、澱粉の添加量を
減らすことが可能になり、経済的効果の向上を期待でき
るとともに、排水系への澱粉の流失が抑制されるため排
水中の有機物負荷が減少し環境保全上も極めて好まし
く、排水処理費用が低減できるなど多くの利点を有す
る。As described above, when the dicarboxylic acid esterified starch of the present invention is used as an interlayer adhesive during papermaking of a sheet such as paperboard, it efficiently binds to the pulp slurry which is a raw material for papermaking. Outflow loss is small and it functions sufficiently as an adhesive, and the peel strength of the papermaking layer can be dramatically improved. Therefore, it becomes possible to reduce the amount of starch added, which can be expected to improve the economic effect, and because the runoff of starch to the drainage system is suppressed, the load of organic substances in the wastewater is reduced, which is also extremely favorable for environmental conservation. It has many advantages such as reduction of wastewater treatment cost.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田中 進 神奈川県横浜市戸塚区東俣野町971番地１ 号 グリーンアベニユー Ｋ・Ｙ101号 (72)発明者 西田 義貴 神奈川県藤沢市亀井野１丁目21番23号 ロ イヤルハイツＩＩＩ 104号 (72)発明者 青木 隆明 神奈川県横浜市戸塚区原宿町1151−２ 戸 塚芙蓉ハイツＣ５号棟 403号 (72)発明者 江間 崇夫 神奈川県横浜市戸塚区影取町９番地 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Susumu Tanaka No. 971 Higashimatano-cho, Totsuka-ku, Yokohama-shi, Kanagawa No. 1, Green Avenyu KY101 (72) Inventor Yoshitaka Nishida 1-21, Kamenino, Fujisawa-shi, Kanagawa No. 23 Royal Heights III 104 (72) Inventor Takaaki Aoki 1151-2 Harajuku-cho, Totsuka-ku, Yokohama, Kanagawa Prefecture No. 403 Fuyo Heights C5 Building No. 403 (72) Inventor Takao Ema 9 Kagetori-cho, Totsuka-ku, Yokohama, Kanagawa Prefecture address
Claims (4)
の層間に使用するための接着剤であって、脂肪族、芳香
族、脂環族もしくは二環式脂肪族のジカルボン酸無水物
よりなる群から選ばれる炭素原子数４〜22の無水ジカル
ボン酸と澱粉を反応させて得られる置換度0.005 〜0.9
のジカルボン酸エステル化澱粉よりなることを特徴とす
る板紙等の層間接着剤。1. An adhesive for use between layers of a sheet such as a paperboard to be laminated at the time of papermaking, which comprises an aliphatic, aromatic, alicyclic or bicyclic aliphatic dicarboxylic acid anhydride. Degree of substitution 0.005 to 0.9 obtained by reacting starch with a dicarboxylic acid anhydride having 4 to 22 carbon atoms selected from the group
An interlayer adhesive for paperboard or the like, which is characterized by comprising the dicarboxylic acid esterified starch of.
エステル化澱粉であることを特徴する請求項１記載の接
着剤。2. The adhesive according to claim 1, wherein the dicarboxylic acid esterified starch is succinic acid esterified starch.
の層間に噴霧、塗布する接着剤としての澱粉スラリーに
おいて、澱粉として置換度0.005 〜0.9 の請求項１記載
のジカルボン酸エステル化澱粉を使用することを特徴と
する板紙等の抄紙方法。3. A starch slurry as an adhesive, which is sprayed and applied between layers of a sheet of paperboard or the like to be laminated at the time of papermaking, wherein the dicarboxylic esterified starch according to claim 1 having a degree of substitution of 0.005 to 0.9 is used as the starch. A papermaking method for paperboard and the like characterized by:
エステル化澱粉であることを特徴する請求項３記載の抄
紙方法。4. The papermaking method according to claim 3, wherein the dicarboxylic acid esterified starch is succinic acid esterified starch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27847491A JPH05106192A (en) | 1991-06-29 | 1991-09-30 | Interlaminar adhesive for paperboard and the like and papermaking process |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18574491 | 1991-06-29 | ||
| JP3-185744 | 1991-06-29 | ||
| JP27847491A JPH05106192A (en) | 1991-06-29 | 1991-09-30 | Interlaminar adhesive for paperboard and the like and papermaking process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05106192A true JPH05106192A (en) | 1993-04-27 |
Family
ID=26503294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27847491A Pending JPH05106192A (en) | 1991-06-29 | 1991-09-30 | Interlaminar adhesive for paperboard and the like and papermaking process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05106192A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001336089A (en) * | 2000-05-26 | 2001-12-07 | Oji Cornstarch Co Ltd | Method for making sheet-shaped material using interlayer adhesive for sheet-shaped material of fiber |
| JP2001336090A (en) * | 2000-05-26 | 2001-12-07 | Oji Cornstarch Co Ltd | Interlayer adhesive for sheet-shaped material of fiber and method for making sheet-shaped material |
| WO2002000803A3 (en) * | 2000-06-23 | 2002-05-02 | Nat Starch Chem Invest | Modified polysaccharides for aqueous foamable adhesives |
| JP4854161B2 (en) * | 2000-04-05 | 2012-01-18 | ヘンケル コーポレイション | Aqueous adhesive with releasability |
| JP2022048755A (en) * | 2020-09-15 | 2022-03-28 | 王子ホールディングス株式会社 | Multilayer non-woven fabric sheet containing polycarboxylic acid derivative |
-
1991
- 1991-09-30 JP JP27847491A patent/JPH05106192A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4854161B2 (en) * | 2000-04-05 | 2012-01-18 | ヘンケル コーポレイション | Aqueous adhesive with releasability |
| JP2001336089A (en) * | 2000-05-26 | 2001-12-07 | Oji Cornstarch Co Ltd | Method for making sheet-shaped material using interlayer adhesive for sheet-shaped material of fiber |
| JP2001336090A (en) * | 2000-05-26 | 2001-12-07 | Oji Cornstarch Co Ltd | Interlayer adhesive for sheet-shaped material of fiber and method for making sheet-shaped material |
| WO2002000803A3 (en) * | 2000-06-23 | 2002-05-02 | Nat Starch Chem Invest | Modified polysaccharides for aqueous foamable adhesives |
| JP2022048755A (en) * | 2020-09-15 | 2022-03-28 | 王子ホールディングス株式会社 | Multilayer non-woven fabric sheet containing polycarboxylic acid derivative |
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