JP4455853B2 - Low density agent for paper and method for producing low density paper - Google Patents
Low density agent for paper and method for producing low density paper Download PDFInfo
- Publication number
- JP4455853B2 JP4455853B2 JP2003318753A JP2003318753A JP4455853B2 JP 4455853 B2 JP4455853 B2 JP 4455853B2 JP 2003318753 A JP2003318753 A JP 2003318753A JP 2003318753 A JP2003318753 A JP 2003318753A JP 4455853 B2 JP4455853 B2 JP 4455853B2
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- JP
- Japan
- Prior art keywords
- paper
- density
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- group
- oxide
- 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.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 69
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 32
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 28
- 239000000194 fatty acid Substances 0.000 claims description 28
- 229930195729 fatty acid Natural products 0.000 claims description 28
- 150000004665 fatty acids Chemical class 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 229920000768 polyamine Polymers 0.000 claims description 25
- 125000003342 alkenyl group Chemical group 0.000 claims description 20
- 239000003638 chemical reducing agent Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 125000002252 acyl group Chemical group 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000007112 amidation reaction Methods 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 9
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- 239000002253 acid Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 6
- PCAXITAPTVOLGL-UHFFFAOYSA-N 2,3-diaminophenol Chemical compound NC1=CC=CC(O)=C1N PCAXITAPTVOLGL-UHFFFAOYSA-N 0.000 claims description 5
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 claims description 5
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 5
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004472 Lysine Substances 0.000 claims description 5
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 claims description 5
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 5
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 5
- 229920000333 poly(propyleneimine) Polymers 0.000 claims description 5
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 5
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 claims description 4
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 claims description 4
- IMENJLNZKOMSMC-UHFFFAOYSA-N n'-[2-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCNCCN IMENJLNZKOMSMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000009435 amidation Effects 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 229920000083 poly(allylamine) Polymers 0.000 claims description 3
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
- 239000000123 paper Substances 0.000 description 169
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- 229910001873 dinitrogen Inorganic materials 0.000 description 42
- 238000012360 testing method Methods 0.000 description 42
- -1 wallpaper Substances 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 238000007664 blowing Methods 0.000 description 30
- 238000006297 dehydration reaction Methods 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 21
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 15
- 235000021355 Stearic acid Nutrition 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 14
- 239000008117 stearic acid Substances 0.000 description 14
- 230000018044 dehydration Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 11
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 11
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 11
- 239000005642 Oleic acid Substances 0.000 description 11
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 11
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 11
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 11
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
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- 235000004443 Ricinus communis Nutrition 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 125000002636 imidazolinyl group Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 6
- 239000005639 Lauric acid Substances 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 5
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000013054 paper strength agent Substances 0.000 description 3
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- LUBJVSFIHRXLJG-UHFFFAOYSA-N C(CCCCCCCC=C/CCCCCCCC)(=O)O.N1=C(N)N=C(N)N=C1N Chemical compound C(CCCCCCCC=C/CCCCCCCC)(=O)O.N1=C(N)N=C(N)N=C1N LUBJVSFIHRXLJG-UHFFFAOYSA-N 0.000 description 2
- QAPMKLRPALGYET-UHFFFAOYSA-N C(CCCCCCCC=C/CCCCCCCC)(=O)O.NCCCCCCN Chemical compound C(CCCCCCCC=C/CCCCCCCC)(=O)O.NCCCCCCN QAPMKLRPALGYET-UHFFFAOYSA-N 0.000 description 2
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- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
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- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
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- XFRHMVNVCKLHSW-UHFFFAOYSA-N n-[2-[2-(octadecanoylamino)ethylamino]ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNCCNC(=O)CCCCCCCCCCCCCCCCC XFRHMVNVCKLHSW-UHFFFAOYSA-N 0.000 description 2
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- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- JTWBMEAENZGSOQ-UHFFFAOYSA-N 1,2-bis(phenoxymethyl)benzene Chemical compound C=1C=CC=C(COC=2C=CC=CC=2)C=1COC1=CC=CC=C1 JTWBMEAENZGSOQ-UHFFFAOYSA-N 0.000 description 1
- NAXUFNXWXFZVSI-UHFFFAOYSA-N 4-aminobutan-2-ol Chemical compound CC(O)CCN NAXUFNXWXFZVSI-UHFFFAOYSA-N 0.000 description 1
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- 241000270708 Testudinidae Species 0.000 description 1
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Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
- Paper (AREA)
Description
本発明は、紙用低密度化剤及び低密度紙の製造方法に関する。さらに詳しくは、本発明は、低密度性、不透明度、白色度に優れた低密度紙を容易に製造することができる紙用低密度化剤及び低密度紙の製造方法に関する。 The present invention relates to a paper density reducing agent and a method for producing low density paper. More specifically, the present invention relates to a paper density-reducing agent and a method for producing low-density paper, which can easily produce low-density paper excellent in low density, opacity and whiteness.
近年、パルプ資源の不足、パルプ価格の高騰、地球環境保護の必要性などによって、パルプの使用量をできるだけ抑えるために、紙製品の坪量を下げる努力がなされている。新聞用紙、微塗工紙、塗工紙、塗工原紙、インクジェット記録紙、感熱記録紙などの印刷用紙、記録用紙、包装用紙、壁紙、襖用原紙、裏打ち紙などの紙製品の坪量を低減することにより、コスト低減はもちろん、森林資源の確保など、地球環境問題の解決に大きな効果をもたらすと考えられる。
また、一方では、印刷適性やボリューム感のある高品質の紙が求められており、紙の嵩を高くした密度の低い紙が要望されている。従来より、紙の密度を低くする方法として、架橋パルプを用いる方法や、合成繊維との混抄による方法、パルプ繊維に無機物を充填する方法などが行われている。しかし、架橋パルプを用いる方法や合成繊維と混抄による方法では、紙のリサイクルが難しく、コスト的にも高くなり、また、無機物の充填による方法では、紙の強度を著しく低下させるという欠点がある。
これらの欠点を解消するために、抄紙時に有機化合物を添加して紙の密度を低くする紙用低密度化剤が検討されている。例えば、パルプ原料を抄紙して得られたシートの嵩高を、紙力を損なうことなく向上させることのできる紙用嵩高剤として、油脂系非イオン界面活性剤、糖アルコール系非イオン界面活性剤又は糖系非イオン界面活性剤を含有する紙用嵩高剤（特許文献１）、高級脂肪酸のアルキレンオキサイド付加物を含有する紙用嵩高剤（特許文献２）、高級アルコールのアルキレンオキサイド付加物を含有する紙用嵩高剤（特許文献３）が提案されている。また、添加量が少なくても十分な嵩高効果が得られ、製紙工程で添加されるサイズ剤の性能をも低下させない紙用嵩高剤として、ＨＬＢ１〜１４、融点１００℃以下のオキシアルキレン基を有する多価アルコール脂肪酸エステル化合物が提案されている（特許文献４）。
On the other hand, there is a demand for high-quality paper with printability and volume feeling, and there is a demand for low-density paper with high paper bulk. Conventionally, as a method for reducing the density of paper, a method using a cross-linked pulp, a method using a mixed paper with synthetic fibers, a method of filling pulp fibers with an inorganic substance, and the like have been performed. However, the method using cross-linked pulp and the method based on blending with synthetic fibers are difficult to recycle paper and are expensive, and the method based on filling with inorganic substances has a drawback that the strength of the paper is remarkably reduced.
In order to eliminate these drawbacks, paper density reducing agents for reducing the density of paper by adding an organic compound during papermaking have been studied. For example, as a bulking agent for paper that can improve the bulk of a sheet obtained by papermaking a pulp raw material without impairing paper strength, an oil-based nonionic surfactant, a sugar alcohol-based nonionic surfactant or Contains a bulking agent for paper containing a sugar-based nonionic surfactant (Patent Document 1), a bulking agent for paper containing an alkylene oxide adduct of a higher fatty acid (Patent Document 2), and an alkylene oxide adduct of a higher alcohol. A bulking agent for paper (Patent Document 3) has been proposed. Moreover, even if there is little addition amount, sufficient bulkiness effect is acquired, and it has HLB1-14 as a bulking agent for paper which does not reduce the performance of the sizing agent added in a papermaking process, and has an oxyalkylene group with a melting point of 100 ° C. or less. A polyhydric alcohol fatty acid ester compound has been proposed (Patent Document 4).
本発明は、低密度性、不透明度、白色度に優れた低密度紙を容易に製造することができる紙用低密度化剤及び低密度紙の製造方法を提供することを目的としてなされたものである。
さらに本発明者達は原紙に特定の化合物を付着して、紙層構造を変えることによって、紙の断熱性を向上させ、発色性、保存性の良い感熱記録材料が得られることを見いだし、この知見に基づいて本発明を完成するに至った。
The present invention was made for the purpose of providing a low-density agent for paper and a method for producing low-density paper that can easily produce low-density paper excellent in low density, opacity, and whiteness. It is.
Furthermore, the present inventors have found that by attaching a specific compound to the base paper and changing the paper layer structure, the thermal insulation of the paper is improved, and a heat-sensitive recording material with good color development and storage can be obtained. The present invention has been completed based on the findings.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、ポリアミンと脂肪酸から得られるアミド化合物の活性水素に、アルキレンオキシドを付加した化合物の製紙工程への添加が、低密度性、不透明度、白色度に優れた低密度紙の製造に有効であることを見いだし、この知見に基づいて本発明を完成するに至った。
さらに本発明の化合物を製紙工程に添加することにより、原紙の紙層構造を変え、紙の断熱性を向上させ、該原紙を使って発色性、保存性の良い、感熱記録向け用紙、感熱記録材料を完成するに至った。
すなわち本発明は、
（１）下記一般式［１］で表される化合物の少なくとも１種として、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、４,４'−ジアミノジフェニルメタン、メラミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサエチレンへプタミン、ヘプタエチレンオクタミン、ジプロピレントリアミン、トリプロピレンテトラミン、アミノエチルエタノールアミン、ジアミノフェノール、メチロールメラミン、リシン、トリアミノ安息香酸、ポリ(エチレンイミン)、ポリ(プロピレンイミン)、アリルアミン又はジアリルアミンの重合体であるポリアミンの活性水素の一部を脂肪酸によってアミド化したのち、残りの活性水素にエチレンオキシド、プロピレンオキシド、ブチレンオキシド及び／又はスチレンオキシドを付加して得られる化合物を紙用低密度化剤として含有して抄紙した紙の白色度が、該化合物を含有しないだけで他は同一抄紙条件で抄紙した紙よりも白色度に優れた紙となることを特徴とする白色度に優れた紙用低密度化剤、
（２）第１項記載のエチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、４,４'−ジアミノジフェニルメタン、メラミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサエチレンへプタミン、ヘプタエチレンオクタミン、ジプロピレントリアミン、トリプロピレンテトラミン、アミノエチルエタノールアミン、ジアミノフェノール、メチロールメラミン、リシン、トリアミノ安息香酸、ポリ(エチレンイミン)、ポリ(プロピレンイミン)、アリルアミン又はジアリルアミンの重合体であるポリアミンの活性水素の一部を脂肪酸によってアミド化したのち、残りの活性水素にエチレンオキシド、プロピレンオキシド、ブチレンオキシド及び／又はスチレンオキシドを付加して得られる化合物を、さらに脂肪酸によってエステル化して得られる化合物を含有する第１項記載の白色度に優れた紙用低密度化剤、
（３）一般式［１］のＢが、下記一般式［３］で表される構造を有する第１項又は第２項記載の白色度に優れた紙用低密度化剤、
−(Ｃ2Ｈ4Ｏ)a−(Ｃ3Ｈ6Ｏ)b−(Ｃ4Ｈ8Ｏ)c−(ＣＨ2ＣＨＰｈＯ)d− …［３］
（ただし、式中、Ｐｈは、フェニル基であり、ａ、ｂ、ｃ及びｄは、それぞれ０〜１００であり、ａ＋ｂ＋ｃ＋ｄ＝１〜１００であり、ａ、ｂ、ｃ及びｄは、(Ｃ2Ｈ4Ｏ)、(Ｃ3Ｈ6Ｏ)、(Ｃ4Ｈ8Ｏ)及び(ＣＨ2ＣＨＰｈＯ)のモル数のみを表し、(Ｃ2Ｈ4Ｏ)、(Ｃ3Ｈ6Ｏ)、(Ｃ4Ｈ8Ｏ)及び(ＣＨ2ＣＨＰｈＯ)の結合順序は任意である。）、
（４）Ｘ1が、炭素数１〜３６のアシル基である第１項ないし第３項のいずれかに記載の白色度に優れた紙用低密度化剤、
（５）Ｘ2が、炭素数１〜３６のアルキル基又は炭素数２〜３６のアルケニル基である第１項ないし第４項のいずれかに記載の白色度に優れた紙用低密度化剤、
（６）第１項ないし第５項のいずれかに記載の紙用低密度化剤を製紙工程に添加することを特徴とする白色度に優れた低密度紙の製造方法、及び、
（７）第６項記載の方法により製造された低密度紙の表面に、無色又は淡色で加熱により発色する感熱記録層を設けてなることを特徴とする感熱記録紙、
を提供するものである。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that addition of a compound obtained by adding an alkylene oxide to an active hydrogen of an amide compound obtained from a polyamine and a fatty acid to a papermaking process has a low density property. The present invention has been found to be effective in the production of low density paper having excellent opacity and whiteness, and the present invention has been completed based on this finding.
Further, by adding the compound of the present invention to the papermaking process, the paper layer structure of the base paper is changed, the heat insulation of the paper is improved, and the base paper is used for thermal recording paper, thermal recording paper, good color development and storage stability. The material was completed.
That is, the present invention
(1) As at least one compound represented by the following general formula [1], ethylenediamine, propylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, melamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, dipropylenetriamine, tripropylenetetramine, aminoethylethanolamine, diaminophenol, methylolmelamine, lysine, triaminobenzoic acid, poly (ethyleneimine), poly (propyleneimine) A portion of the active hydrogen of polyamine, which is a polymer of allylamine or diallylamine, is amidated with a fatty acid, and then the remaining active hydrogen is converted to ethylene oxide or propylene oxide. The whiteness of the paper and paper a compound obtained by adding butylene oxide and / or styrene oxide contained as a low-density agent for paper, from paper others that paper in the same paper making conditions not only contain the compound A paper density reducing agent with excellent whiteness, characterized in that the paper also has excellent whiteness,
(2) Ethylenediamine, propylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, melamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneocta described in item 1 Activity of polyamines that are polymers of amines, dipropylenetriamine, tripropylenetetramine, aminoethylethanolamine, diaminophenol, methylolmelamine, lysine, triaminobenzoic acid, poly (ethyleneimine), poly (propyleneimine), allylamine or diallylamine After amidation with a fatty acid part of the hydrogen, ethylene oxide to the remaining active hydrogen, propylene oxide, butylene oxide and / or styrene oxide The compounds obtained by adding, further paper for low density agent having excellent whiteness as set forth in claim 1, wherein comprising a compound obtained by esterifying the fatty acids,
(3) B in the general formula [1] has a structure represented by the following general formula [3];
- (C 2 H 4 O) a - (C 3 H 6 O) b - (C 4 H 8 O) c - (CH 2 CHPhO) d - ... [3]
(In the formula, Ph is a phenyl group, a, b, c, and d are each 0-100, a + b + c + d = 1-100, and a, b, c, and d are (C 2 Only the number of moles of (H 4 O), (C 3 H 6 O), (C 4 H 8 O) and (CH 2 CHPhO) is represented, and (C 2 H 4 O), (C 3 H 6 O), ( C 4 H 8 O) and (CH 2 CHPhO) may be combined in any order.),
(4) The paper density-reducing agent excellent in whiteness according to any one of Items 1 to 3, wherein X 1 is an acyl group having 1 to 36 carbon atoms,
(5) The paper density reducing agent having excellent whiteness according to any one of Items 1 to 4, wherein X 2 is an alkyl group having 1 to 36 carbon atoms or an alkenyl group having 2 to 36 carbon atoms. ,
(6) A method for producing low-density paper excellent in whiteness, characterized by adding the paper density-reducing agent according to any one of items 1 to 5 to the paper-making process; and
(7) A heat-sensitive recording paper comprising a heat-sensitive recording layer that is colorless or light-colored by heating on the surface of the low-density paper produced by the method according to item 6,
Is to provide.
本発明の紙用低密度化剤及び低密度化紙の製造方法によれば、紙を低密度化するのみならず、紙の不透明性と白色度を向上させ、含水伸度を低下させることができる。その結果、パルプの使用量を節減し、生産性を向上し、原料コストを低減することが可能になる。また、印刷適性やボリューム感のある高品質の紙を製造することができる。さらに、不透明度の向上によっても、パルプ、無機填料などの使用量を節減し、白色度の高い品質の良好な紙を製造することができる。また、本発明の低密度化剤にて得られた低密度紙を感熱発色記録層の支持体に使った感熱記録紙向け用紙で、得られた感熱記録材料は発色性、保存性に優れることがわかった。
本発明者達は原紙に特定の化合物を付着して、紙層構造を変えることによって、紙の断熱性を向上させ、発色性、保存性の良い感熱記録材料が得られることを見いだし、この知見に基づいて本発明を完成するに至った。すなわち、表記薬剤を処理してなる紙の支持体と、前記支持体の表面上に形成された通常無色または淡色で熱時発色する感熱記録層からなる感熱記録紙において、前記支持体が特定の化合物を付着させないで得られた紙に対して２％以上密度が低下した紙であることを目的とする。本発明は裏面が加熱されることによって活性化する時に起こることが殆どである発色を防止する感熱記録紙を提供するものである。これらの発色は、本発明においては、支持体として、パルプと表記薬剤を処理して作成することによって得られた低密度の紙を用い、裏面からの熱に対する断熱効果を持たせることによって感熱発色層の発色を防止できた。さらに、前記支持体がサイズの機能を持つため、熱応答性の良好な感熱記録層をもつ感熱記録紙を得ることができる。
According to the paper density-reducing agent and the method for producing density-reduced paper of the present invention, not only can the density of the paper be reduced, but also the opacity and whiteness of the paper can be improved, and the water content elongation can be reduced. it can. As a result, the amount of pulp used can be reduced, productivity can be improved, and raw material costs can be reduced. In addition, high-quality paper with printability and volume can be produced. Furthermore, the improvement in opacity can also reduce the amount of pulp, inorganic fillers, etc. used to produce good white paper with good quality. In addition, the heat-sensitive recording material obtained by using the low-density paper obtained by the low-density agent of the present invention as a support for the heat-sensitive color-developing recording layer is excellent in color developability and storage stability. I understood.
The present inventors have found that by attaching a specific compound to the base paper and changing the paper layer structure, the heat insulation of the paper is improved, and a heat-sensitive recording material with good color development and storage stability can be obtained. Based on this, the present invention has been completed. That is, in a heat-sensitive recording paper comprising a paper support obtained by treating the notation agent and a heat-sensitive recording layer formed on the surface of the support that is usually colorless or light-colored when heated, the support is a specific substance. It is intended to be a paper having a density reduced by 2% or more with respect to the paper obtained without adhering the compound. The present invention provides a heat-sensitive recording paper that prevents color development that is most likely to occur when the back surface is activated by being heated. In the present invention, these colorings are heat-sensitive coloring by using a low-density paper obtained by processing pulp and a notation agent as a support, and having a heat insulating effect against heat from the back side. Color development of the layer could be prevented. Further, since the support has a function of size, it is possible to obtain a thermal recording paper having a thermal recording layer with good thermal response.
本発明の紙用低密度化剤は、一般式［１］で表される化合物を含有する。
本発明において、ポリアミンとは、アミノ基とイミノ基を合計して２個以上有し、活性水素を３個以上有する化合物である。ポリアミンとしては、例えば、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、４,４'−ジアミノジフェニルメタンなどのジアミン、メラミンなどのトリアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサエチレンへプタミン、ヘプタエチレンオクタミン、ジプロピレントリアミン、トリプロピレンテトラミンなどのポリアルキレンポリアミン、アミノエチルエタノールアミン、ジアミノフェノール、メチロールメラミンなどのヒドロキシル基を有するポリアミン、リシン、トリアミノ安息香酸などのカルボキシル基を有するポリアミン、ポリ(エチレンイミン)、ポリ(プロピレンイミン)などのポリ(アルキレンイミン)、アリルアミン、ジアリルアミンなどの単独重合体又は共重合体、メラミンの低分子量重合体などを挙げることができる。重合体のポリアミンの構造に制限はなく、直鎖状の重合体と分岐を有する重合体のいずれをも用いることができる。これらのポリアミンは、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。 In the present invention, the polyamine is a compound having a total of 2 or more amino groups and imino groups and 3 or more active hydrogens. The polyamines, e.g., ethylenediamine, propylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane such as diphenylmethane, triamines such as melamine, diethylenetriamine, triethylenetetramine, tetraethylene pen data, pentaethylene hexamine, to hexaethylene Polyalkylene polyamines such as ptamine, heptaethyleneoctamine, dipropylenetriamine and tripropylenetetramine, polyamines having hydroxyl groups such as aminoethylethanolamine, diaminophenol and methylolmelamine, polyamines having carboxyl groups such as lysine and triaminobenzoic acid , Poly (ethyleneimine), poly (alkyleneimine) such as poly (propyleneimine), allylamine, diallylamine Homopolymers or copolymers, such as, and the like low molecular weight polymer of melamine. There is no restriction | limiting in the structure of the polyamine of a polymer, Both a linear polymer and the polymer which has a branch can be used. These polyamines can be used individually by 1 type, or can also be used in combination of 2 or more type.
本発明に用いる一般式［１］で表される化合物の製造方法に特に制限はなく、例えば、ポリアミンとカルボン酸又はその誘導体との反応によりアミド化合物を合成し、該アミド化合物の活性水素にオキシラン又はその誘導体を付加反応させ、さらに、必要に応じて、ポリエーテル鎖の末端ヒドロキシル基をエーテル化又はエステル化することができ、あるいは、ボリアミンにその活性水素と当量より１モル以上少ないオキシラン又はその誘導体を反応させて、アミノ基又はイミノ基１個以上を有するポリアミンのオキシラン又はその誘導体付加物とし、該付加物とカルボン酸又はその誘導体との反応によりアミド化合物とし、必要に応じて、該アミド化合物にさらにオキシラン又はその誘導体を付加反応させ、さらに必要に応じて、ポリエーテル鎖の末端をエーテル化又はエステル化することができる。これらの中で、ポリアミンにカルボン酸又はその誘導体を反応させてアミド化したのち、オキシラン又はその誘導体を付加反応させる方法を好適に用いることができる。 There is no particular limitation on the method for producing the compound represented by the general formula [1] used in the present invention. For example, an amide compound is synthesized by reacting a polyamine with a carboxylic acid or a derivative thereof, and oxirane is added to the active hydrogen of the amide compound. Alternatively, the terminal hydroxyl group of the polyether chain can be etherified or esterified, if necessary, or, if necessary, the oxirane or the oxirane less than the equivalent of the active hydrogen to the active hydrogen. A derivative is reacted to form an oxirane of a polyamine having one or more amino groups or imino groups or an adduct thereof, and an amide compound is obtained by reacting the adduct with a carboxylic acid or a derivative thereof. The compound is further subjected to an addition reaction with oxirane or a derivative thereof, and if necessary, It can be etherified or esterified terminal Le chain. Among these, a method in which a polyamine is reacted with a carboxylic acid or a derivative thereof for amidation and then an oxirane or a derivative thereof is subjected to an addition reaction can be suitably used.
一般式［１］において、Ａで表されるアシル基に特に制限はなく、例えば、脂肪酸、脂環式カルボン酸、芳香族カルボン酸などに由来するアシル基を挙げることができる。Ａで表されるアシル基は、飽和又は不飽和のいずれであってもよく、無置換であっても、ヒドロキシル基、アミノ基、ハロゲンなどの置換基を有していてもよい。これらの中で、Ａが一般式［２］で表される構造を有するアシル基であることが好ましい。
ポリアミンをカルボン酸と反応させてアミド化したとき、脱水が進んでイミダゾリン環が形成される場合があるが、すべてのアミノ基又はイミノ基がイミダゾリン環を形成した化合物も、一部のアミノ基又はイミノ基がイミダゾリン環を形成した化合物も、一般式［１］で表される化合物の中間物質として用いることができ、また、これらの化合物とイミダゾリン環を有しないポリアミンとの混合物も一般式［１］で表される化合物の中間物質として用いることができる。さらに、２個の以上のイミダゾリン環が形成される場合、イミダゾリン環の位置や数については特に制限はなく、一般式［１］で表される化合物の中間物質として使用することができる。 When a polyamine is reacted with a carboxylic acid to be amidated, dehydration may proceed to form an imidazoline ring, but a compound in which all amino groups or imino groups form an imidazoline ring may also be used for some amino groups or A compound in which an imino group forms an imidazoline ring can also be used as an intermediate substance of the compound represented by the general formula [1], and a mixture of these compounds and a polyamine having no imidazoline ring can also be used as a general formula [1]. It can be used as an intermediate substance of the compound represented by Further, when two or more imidazoline rings are formed, the position and number of the imidazoline rings are not particularly limited, and can be used as an intermediate substance of the compound represented by the general formula [1].
本発明において、一般式［１］で表される化合物のポリエーテル基Ｂを導入する方法に特に制限はなく、例えば、水酸化ナトリウム、水酸化カリウムなどの触媒の存在下に、オキシラン又はその誘導体を活性水素に付加反応させることができ、あるいは、末端にヒドロキシル基を有するポリエーテルを、脱水反応により活性水素と置換することもできる。これらの中で、オキシラン又はその誘導体の付加反応を好適に用いることができる。Ｂで表されるポリエーテル基の構造に特に制限はないが、オキシラン又はその誘導体が、エチレンオキシド、プロピレンオキシド、ブチレンオキシド又はスチレンオキシドであって、Ｂが一般式［３］で表される構造を有することが好ましい。
−(Ｃ2Ｈ4Ｏ)a−(Ｃ3Ｈ6Ｏ)b−(Ｃ4Ｈ8Ｏ)c−(ＣＨ2ＣＨＰｈＯ)d− ・・・［３］
In the present invention, the method for introducing the polyether group B of the compound represented by the general formula [1] is not particularly limited. For example, oxirane or a derivative thereof in the presence of a catalyst such as sodium hydroxide or potassium hydroxide. Can be subjected to addition reaction with active hydrogen, or a polyether having a hydroxyl group at the end can be replaced with active hydrogen by dehydration reaction. Among these, an addition reaction of oxirane or a derivative thereof can be preferably used. The structure of the polyether group represented by B is not particularly limited, but the oxirane or derivative thereof is ethylene oxide, propylene oxide, butylene oxide or styrene oxide, and B is a structure represented by the general formula [3]. It is preferable to have.
- (C 2 H 4 O) a - (C 3 H 6 O) b - (C 4 H 8 O) c - (CH 2 CHPhO) d - ··· [3]
ただし、一般式［３］において、ａ、ｂ、ｃ及びｄは、それぞれ０〜１００であり、ａは、より好ましくは０〜５０、さらに好ましくは０〜２０であり、ｂは、より好ましくは０〜６０、さらに好ましくは０〜３０であり、ｃは、より好ましくは０〜３０、さらに好ましくは０〜１５であり、ｄは、より好ましくは０〜２０、さらに好ましくは０〜１０であり、ａ＋ｂ＋ｃ＋ｄ＝１〜１００、より好ましくはａ＋ｂ＋ｃ＋ｄ＝２〜６０である。一般式［３］において、ａ、ｂ、ｃ及びｄは、(Ｃ2Ｈ4Ｏ)、(Ｃ3Ｈ6Ｏ)、(Ｃ4Ｈ8Ｏ)及び(ＣＨ2ＣＨＰｈＯ)のモル数のみを表し、(Ｃ2Ｈ4Ｏ)、(Ｃ3Ｈ6Ｏ)、(Ｃ4Ｈ8Ｏ)及び(ＣＨ2ＣＨＰｈＯ)の結合順序は任意である。すなわち、エチレンオキシド、プロピレンオキシド、ブチレンオキシド及びスチレンオキシドは、ランダム状態、ブロック状態、ランダム単位とブロック単位とのブロック状態、異なるランダム単位のブロック状態などの任意の付加状態とすることができる。ポリエーテル基を、エチレンオキシドとともに、プロピレンオキシド、ブチレンオキシド又はスチレンオキシドとの共重合体構造とすることにより、紙用低密度化剤の低温安定性を向上することができる。 However, in the general formula [3], a, b, c and d are each 0 to 100, a is more preferably 0 to 50, still more preferably 0 to 20, and b is more preferably. 0 to 60, more preferably 0 to 30, c is more preferably 0 to 30, further preferably 0 to 15, and d is more preferably 0 to 20, further preferably 0 to 10. A + b + c + d = 1 to 100, more preferably a + b + c + d = 2 to 60. In the general formula [3], a, b, c and d represent only the number of moles of (C 2 H 4 O), (C 3 H 6 O), (C 4 H 8 O) and (CH 2 CHPhO). And the bonding order of (C 2 H 4 O), (C 3 H 6 O), (C 4 H 8 O) and (CH 2 CHPhO) is arbitrary. That is, ethylene oxide, propylene oxide, butylene oxide, and styrene oxide can be in any additional state such as a random state, a block state, a block state of random units and block units, or a block state of different random units. By making the polyether group into a copolymer structure with propylene oxide, butylene oxide or styrene oxide together with ethylene oxide, the low temperature stability of the paper density reducing agent can be improved.
本発明において、一般式［１］で表される化合物のＸ1が水素原子、すなわち、ポリエーテル鎖を付加したままの状態で紙用低密度化剤として用いることができ、あるいは、必要に応じて、ポリエーテル鎖の末端のヒドロキシル基をエーテル化又はエステル化することもできる。末端のヒドロキシル基をエーテル化する方法に特に制限はなく、例えば、ハロゲン化アルキル又はハロゲン化アルケニルとの脱ハロゲン化水素反応によりアルキルエーテル化又はアルケニルエーテル化することができる。末端のヒドロキシル基をエステル化する方法に特に制限はなく、例えば、ｐ−トルエンスルホン酸などの触媒を用いて、カルボン酸との脱水反応によりエステル化することができ、カルボン酸エステルとのエステル交換反応によりエステル化することもでき、あるいは、カルボン酸ハロゲン化物との脱ハロゲン化水素反応によりエステル化することもできる。Ｘ1で表されるアルキル基は、炭素数１〜３６であることが好ましく、炭素数２〜２２であることがより好ましい。Ｘ1で表されるアルケニル基は、炭素数２〜３６であることが好ましく、炭素数２〜２２であることがより好ましい。Ｘ1で表されるアシル基は、炭素数１〜３６であることが好ましく、炭素数８〜２２であることがより好ましい。Ｘ1で表されるアシル基は、飽和又は不飽和のいずれであってもよく、無置換であっても、ヒドロキシル基、アミノ基、ハロゲンなどの置換基を有していてもよい。ポリエーテル基の末端をエーテル化又はエステル化することにより、低密度紙の密度を下げ、不透明度と白色度を高めることができる。 In the present invention, X 1 of the compound represented by the general formula [1] can be used as a paper density reducing agent with a hydrogen atom, that is, with a polyether chain added, or as necessary. Thus, the hydroxyl group at the end of the polyether chain can be etherified or esterified. The method for etherifying the terminal hydroxyl group is not particularly limited, and for example, alkyl etherification or alkenyl etherification can be performed by dehydrohalogenation reaction with an alkyl halide or an alkenyl halide. The method for esterifying the terminal hydroxyl group is not particularly limited. For example, it can be esterified by a dehydration reaction with a carboxylic acid using a catalyst such as p-toluenesulfonic acid, and transesterified with a carboxylic acid ester. It can be esterified by reaction, or can be esterified by dehydrohalogenation reaction with a carboxylic acid halide. The alkyl group represented by X 1 preferably has 1 to 36 carbon atoms, and more preferably 2 to 22 carbon atoms. The alkenyl group represented by X 1 preferably has 2 to 36 carbon atoms, and more preferably 2 to 22 carbon atoms. The acyl group represented by X 1 preferably has 1 to 36 carbon atoms, and more preferably 8 to 22 carbon atoms. The acyl group represented by X 1 may be either saturated or unsaturated, may be unsubstituted, or may have a substituent such as a hydroxyl group, an amino group, or a halogen. By etherifying or esterifying the end of the polyether group, the density of the low density paper can be lowered, and the opacity and whiteness can be increased.
本発明において、一般式［１］で表される化合物のＸ2が水素原子、すなわち、ポリアミンの活性水素が残存したままの状態で紙用低密度化剤として用いることができ、あるいは、必要に応じて、残存する活性水素をアルキル基又はアルケニル基で置換することもできる。残存する活性水素をアルキル基又はアルケニル基で置換する方法に特に制限はなく、例えば、ハロゲン化アルキル又はハロゲン化アルケニルとの脱ハロゲン化水素反応によりアルキル基又はアルケニル基で置換することができる。Ｘ2で表されるアルキル基は、炭素数１〜３６であることが好ましく、炭素数２〜２２であることがより好ましい。Ｘ2で表されるアルケニル基は、炭素数２〜３６であることが好ましく、炭素数２〜２２であることがより好ましい。
本発明においては、上記のポリアミンとカルボン酸類の反応によりＡで表されるアシル基を導入した中間物質、Ｂで表されるポリエーテル基を導入した一般式［１］で表される化合物、Ｘ1で表される基を導入した一般式［１］で表される化合物又はさらにＸ2で表される基を導入した一般式［１］で表される化合物に、尿素、ジシアンジアミド、グアニジン、ホルマリン、エピハロヒドリン、イソシアネート、グリシジルエーテル、アルキレンイミン、ハロゲン化アルキルなどを用いて、付加反応又は架橋反応を行い、複量化又は分子内架橋した化合物も、一般式［１］で表される化合物として使用することができる。
In the present invention, X 2 of the compound represented by the general formula [1] can be used as a paper densifying agent in a state where X 2 is a hydrogen atom, that is, active hydrogen of polyamine remains, or as necessary. Accordingly, the remaining active hydrogen can be substituted with an alkyl group or an alkenyl group. There is no particular limitation on the method of substituting the remaining active hydrogen with an alkyl group or alkenyl group, and for example, it can be substituted with an alkyl group or alkenyl group by dehydrohalogenation reaction with an alkyl halide or halogenated alkenyl. The alkyl group represented by X 2 preferably has 1 to 36 carbon atoms, and more preferably has 2 to 22 carbon atoms. The alkenyl group represented by X 2 preferably has 2 to 36 carbon atoms, and more preferably 2 to 22 carbon atoms.
In the present invention, an intermediate substance into which an acyl group represented by A is introduced by the reaction of the above polyamine and carboxylic acids, a compound represented by the general formula [1] into which a polyether group represented by B is introduced, X 1. Urea, dicyandiamide, guanidine, formalin to the compound represented by the general formula [1] into which the group represented by 1 is introduced or the compound represented by the general formula [1] into which the group represented by X 2 is further introduced , Epihalohydrins, isocyanates, glycidyl ethers, alkyleneimines, alkyl halides, etc., which are subjected to addition reaction or cross-linking reaction to form multimerized or intramolecularly cross-linked compounds are also used as compounds represented by the general formula [1]. be able to.
本発明の低密度紙の製造方法においては、本発明の紙用低密度化剤を製紙工程に添加する。本発明方法において、紙用低密度化剤を添加する製紙工程に特に制限はなく、例えば、離解工程、叩解工程、薬品などを配合する調成工程、抄紙前などを挙げることができる。また、古紙などの場合は、再生処理工程などを挙げることができる。紙用低密度化剤の添加方法に特に制限はなく、例えば、そのままを添加することができ、あるいは、微量の界面活性剤、水、溶剤などを配合して水又は熱水に自己乳化するように製剤化したのち添加することもでき、さらに、水、溶剤などに溶解、分散又は乳化して添加することもできる。
本発明方法においては、紙料に他の薬品を添加することができる。他の薬品としては、例えば、湿潤紙力剤、乾燥紙力剤、澱粉、ポリビニルアルコールなどの紙力剤、ドライヤー剥離剤、ピッチコントロール剤、スライムコントロール剤、脱墨剤、サイズ剤、紙質改良剤、填料、顔料、染料、消泡剤などを挙げることができる。
In the method for producing low density paper of the present invention, the paper density reducing agent of the present invention is added to the paper making process. In the method of the present invention, there is no particular limitation on the papermaking process in which the paper densifying agent is added, and examples include a disaggregation process, a beating process, a preparation process in which chemicals are blended, and before papermaking. Further, in the case of used paper, a recycling treatment process can be exemplified. There is no particular limitation on the method of adding the paper density reducing agent, and for example, it can be added as it is, or it can be self-emulsified in water or hot water by adding a trace amount of surfactant, water, solvent, etc. It can also be added after it is formulated, and it can also be added after being dissolved, dispersed or emulsified in water, a solvent or the like.
In the method of the present invention, other chemicals can be added to the stock. Other chemicals include, for example, wet paper strength agents, dry paper strength agents, starch strength, polyvinyl alcohol and other paper strength agents, dryer release agents, pitch control agents, slime control agents, deinking agents, sizing agents, and paper quality improvers. , Fillers, pigments, dyes, antifoaming agents and the like.
本発明方法により低密度化させる紙は、植物繊維又はその他の繊維を絡み合わせて膠着することにより得られる薄層物である。使用するパルプなどの原料に特に制限はなく、例えば、広葉樹、針葉樹などから得られる木材パルプ、バガス、ケナフ、竹パルプ、藁パルプなどの植物繊維、レーヨンなどの再生繊維、ポリエステルなどの合成繊維、繊維状無機材料、古紙再生パルプなどを挙げることができる。本発明の紙用低密度化剤は、また、パルプモールドなど繊維材料にも適用することができる。
本発明方法により製造する低密度紙に特に制限はなく、例えば、新聞用紙、微塗工紙、塗工紙、塗工原紙、インクジェット記録紙、感熱記録紙などの印刷用紙、記録用紙、包装用紙、板紙、ライナー、中芯などの段ボール用紙、壁紙、襖紙原紙やその裏打ち紙などを挙げることができる。紙を低密度化することにより、めくりやすさ、印刷適性、ボリューム感、風合い、手触りなどの柔軟性、紙の割れ防止性、層間剥離のしやすさ、吸水性、吸油性、吸樹脂性、不透明性などを改良し、コストを低減することができる。
本発明の紙用低密度化剤及び低密度紙の製造方法によれば、紙を低密度化し得るのみならず、紙の不透明性と白色度を向上させ、紙の含水伸度を低下させることができる。
The paper to be reduced in density by the method of the present invention is a thin layer product obtained by intertwining vegetable fibers or other fibers and sticking them together. There are no particular restrictions on raw materials such as pulp to be used, for example, wood pulp obtained from hardwood, conifer, etc., plant fiber such as bagasse, kenaf, bamboo pulp, straw pulp, regenerated fiber such as rayon, synthetic fiber such as polyester, Examples thereof include fibrous inorganic materials and recycled paper recycled pulp. The paper density-reducing agent of the present invention can also be applied to fiber materials such as pulp molds.
There is no particular limitation on the low density paper produced by the method of the present invention. For example, printing paper such as newsprint paper, fine coated paper, coated paper, coated base paper, ink jet recording paper, thermal recording paper, recording paper, packaging paper And corrugated paper such as paperboard, liner and core, wallpaper, base paper and backing paper. By reducing the density of paper, it is easy to turn, printability, voluminous feel, texture, touch, etc., paper crack prevention, ease of delamination, water absorption, oil absorption, resin absorption, The opacity and the like can be improved and the cost can be reduced.
According to the low density agent for paper and the method for producing low density paper of the present invention, not only can the paper be reduced in density, but also improve the opacity and whiteness of the paper and reduce the water content elongation of the paper. Can do.
以下に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例によりなんら限定されるものではない。
なお、実施例及び比較例において、試験紙は下記の方法により評価した。
（１）密度
ＪＩＳ Ｐ ８１１８に従って測定する。
（２）不透明度
ＪＩＳ Ｐ ８１３８に従い、COLORIMETER［(株)村上色彩技術研究所、ＣＭ−５３Ｄ］を用いて測定する。
（３）白色度
ＪＩＳ Ｐ ８１２３に従い、測色機［(株)ミノルタ、ＣＭ−３７００ｄ］を用いて測定する。
（４）含水伸度
ＪＩＳ Ｐ ８１１１に従って前処理した試験紙に、鉛筆で長さ１５ｃｍの実線を５カ所に描き、２０℃の水に１５分浸漬した後の実線の長さを測定し、含水伸度の平均値を算出する。
（５）熱応答性
感熱印字装置［(株)大倉電機］を用い、パルス巾３ｍｓで、０.０７ｍＪ／ｄｏｔ毎に印字エネルギーを高めて発色を行う。その中で０.２８ｍＪ／ｄｏｔの印字エネルギーで得られた画像の色濃度を、マクベス濃度計を用いて測定した。
（６）断熱性
熱傾斜計［(株)東洋精機製作所］を用いて、９５℃に加熱した熱板を、感熱記録紙の感熱記録層面に０.２ＭＰａの圧力で５秒間接触させ、接触面の色濃度を測定する。感熱記録層面の色濃度、感熱記録層の裏面の色濃度を、マクベス濃度計を用いて測定し、感熱記録層面と裏面の色濃度差ΔＣを求めた。断熱性は色濃度差ΔＣの値が大きい程、断熱性が高いとした。
色濃度差ΔＣ ＝ 感熱記録層面の色濃度 − 感熱記録層の裏面の色濃度
（７）発色性
熱傾斜計［(株)東洋精機製作所］を用いて、９５℃に加熱した熱板を、感熱記録紙の感熱記録層面に０.２ＭＰａの圧力で５秒間接触させ、接触面の色濃度を測定する。感熱記録層の裏面の色濃度Ｃ２、試験前の感熱記録層裏面の色濃度をＢ０として、マクベス濃度計を用いて測定し、感熱記録層の裏面の発色濃度差ΔＢを求めた。発色性は発色色濃度ΔＢの値が小さい程、裏面の発色性が低いとした。
発色濃度差ΔＢ ＝ 感熱記録層の裏面の色濃度 − 試験前の感熱記録層裏面の色濃度
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the examples and comparative examples, the test paper was evaluated by the following method.
(1) Density Measured according to JIS P 8118.
(2) Opacity Measured according to JIS P 8138 using COLORIMETER [Murakami Color Research Laboratory, CM-53D].
(3) Whiteness Measured using a colorimeter [Minolta, Inc., CM-3700d] in accordance with JIS P 8123.
(4) Water content elongation On a test paper pretreated according to JIS P 8111, a 15 cm long solid line is drawn at five locations with a pencil, and the length of the solid line after being immersed in water at 20 ° C. for 15 minutes is measured. The average value of elongation is calculated.
(5) Thermal responsiveness Using a thermal printing device [Okura Electric Co., Ltd.], with a pulse width of 3 ms, the printing energy is increased every 0.07 mJ / dot for color development. Among them, the color density of an image obtained with a printing energy of 0.28 mJ / dot was measured using a Macbeth densitometer.
(6) Thermal insulation Using a thermal inclinometer [Toyo Seiki Seisakusho Co., Ltd.], a hot plate heated to 95 ° C. was brought into contact with the thermal recording layer surface of the thermal recording paper at a pressure of 0.2 MPa for 5 seconds. Measure the color density. The color density of the heat-sensitive recording layer surface and the color density of the back surface of the heat-sensitive recording layer were measured using a Macbeth densitometer, and the color density difference ΔC between the heat-sensitive recording layer surface and the back surface was determined. The heat insulating property is said to be higher as the value of the color density difference ΔC is larger.
Color density difference ΔC = color density on the surface of the heat-sensitive recording layer−color density on the back surface of the heat-sensitive recording layer (7) Color developability Using a thermal inclinometer [Toyo Seiki Seisakusho Co., Ltd.] The surface of the recording paper is brought into contact with the surface of the heat-sensitive recording layer at a pressure of 0.2 MPa for 5 seconds, and the color density of the contact surface is measured. The color density C2 on the back surface of the heat-sensitive recording layer and the color density on the back surface of the heat-sensitive recording layer before the test were set to B0 and measured using a Macbeth densitometer to determine the color density difference ΔB on the back surface of the heat-sensitive recording layer. Regarding the color developability, the smaller the value of the developed color density ΔB, the lower the color developability of the back surface.
Color density difference ΔB = color density on the back side of the thermal recording layer−color density on the back side of the thermal recording layer before the test
実施例１
温度計と窒素ガス吹き込み管を取り付けた四つ口フラスコに、ステアリン酸５６８ｇ（２モル）を仕込み、窒素ガスを吹き込みながら、マントルヒーターで徐々に加熱昇温し、１００〜１１０℃でジエチレントリアミン１０３ｇ（１モル）を、約１時間かけて滴下した。さらに、徐々に温度を上げて２００〜２５０℃にて５時間脱水アミド化反応を行い、アミド化合物を得た。
このアミド化合物を耐圧反応容器に仕込み、触媒として水酸化ナトリウム０.７ｇを加え、内部を窒素ガスで置換し、エチレンオキシド１３２ｇ（３モル）を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら約８時間で吹き込み、ジエチレントリアミンステアリン酸ジアミドのエチレンオキシド３モル付加物を得た。
広葉樹晒しクラフトパルプと針葉樹晒しクラフトパルプを質量比で７０／３０に配合し、カナダ標準型濾水度４４０ｍＬに叩解してパルプスラリーを調製した。ケミスターラーを用いて上記のエチレンオキシド付加物を水に分散した分散液を、このパルプスラリーにエチレンオキシド付加物の添加量がパルプに対して０.５質量％になるように添加し、その５分後に硫酸バンドを加えてｐＨを４.５に調整し、その５分後にエマルジョンサイズ剤［日本ＰＭＣ(株)、ＡＬ−１２０Ｆ］をパルプに対して１質量％添加し、さらに５分後に湿潤紙力剤［日華化学(株)、トータス６０４Ｔ］をパルプに対して０.７質量％添加し、その後１０分間撹拌を継続して紙料を調成した。
次に、試験用角形シートマシンにて坪量８０ｇ／ｍ2に抄紙し、プレス機を用いて７００ｋＰａで５分間プレスしたのち、試験用ヤンキードライヤーを用いて１０５℃で３分間乾燥し試験紙を得た。
得られた試験紙の密度は０.５５９ｇ／ｃｍ3、不透明度は８７.５％、白色度は７９.３、含水伸度は１.０５％であった。
Example 1
A four-necked flask equipped with a thermometer and a nitrogen gas blowing tube was charged with 568 g (2 mol) of stearic acid, gradually heated with a mantle heater while nitrogen gas was blown, and 103 g of diethylenetriamine at 100 to 110 ° C. 1 mol) was added dropwise over about 1 hour. Furthermore, the temperature was gradually raised and a dehydration amidation reaction was carried out at 200 to 250 ° C. for 5 hours to obtain an amide compound.
This amide compound was charged into a pressure resistant reactor, 0.7 g of sodium hydroxide was added as a catalyst, the inside was replaced with nitrogen gas, and 132 g (3 mol) of ethylene oxide was maintained at a reaction temperature of 140 to 150 ° C. and a pressure of 392 kPa or less. Blowing was performed in 8 hours to obtain an ethylene oxide 3 mol adduct of diethylenetriamine stearic acid diamide.
Hardwood bleached kraft pulp and softwood bleached kraft pulp were blended at a mass ratio of 70/30 and beaten to a Canadian standard freeness of 440 mL to prepare a pulp slurry. A dispersion obtained by dispersing the above-mentioned ethylene oxide adduct in water using a chemistor was added to this pulp slurry so that the amount of ethylene oxide adduct added was 0.5% by mass with respect to the pulp. A sulfuric acid band was added to adjust the pH to 4.5. After 5 minutes, 1% by mass of an emulsion sizing agent [Japan PMC Co., Ltd., AL-120F] was added to the pulp. An agent [Nikka Chemical Co., Ltd., Tortoise 604T] was added in an amount of 0.7% by mass with respect to the pulp, and then stirring was continued for 10 minutes to prepare a paper stock.
Next, paper is made to a basis weight of 80 g / m 2 using a test square sheet machine, pressed at 700 kPa for 5 minutes using a press machine, and then dried at 105 ° C. for 3 minutes using a test Yankee dryer. Obtained.
The density of the obtained test paper was 0.559 g / cm 3 , the opacity was 87.5%, the whiteness was 79.3, and the water content elongation was 1.05%.
実施例２
温度計と窒素ガス吹き込み管を取り付けた四つ口フラスコに、オレイン酸５６４ｇ（２モル）を仕込み、窒素ガスを吹き込みながら、マントルヒーターで徐々に加熱昇温し、１００〜１１０℃でジエチレントリアミン１０３ｇ（１モル）を、約１時間かけて滴下した。さらに徐々に温度を上げて２００〜２５０℃にて５時間脱水アミド化反応を行い、アミド化合物を得た。
このアミド化合物を耐圧反応容器に仕込み、触媒として水酸化ナトリウム０.７ｇを加え、内部を窒素ガスで置換し、エチレンオキシド１３２ｇ（３モル）を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら約５時間で耐圧反応容器に吹き込み、さらにプロピレンオキシド１７４ｇ（３モル）を同様に吹き込み、ジエチレントリアミンオレイン酸ジアミドのエチレンオキシド３モル・プロピレンオキシド３モルブロック付加物を得た。
このエチレンオキシド・プロピレンオキシドブロック付加物を用いて、実施例１と同様に試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５６５ｇ／ｃｍ3、不透明度は８７.３％、白色度は７９.２、含水伸度は１.０５％であった。
実施例３
温度計と窒素ガス吹き込み管を取り付けた四つ口フラスコに、ステアリン酸２８４ｇ（１モル）とオレイン酸２８２ｇ（１モル）を仕込み、窒素ガスを吹き込みながら、マントルヒーターで徐々に加熱昇温し、１００〜１１０℃でジエチレントリアミン１０３ｇ（１モル）を、約１時間かけて滴下した。さらに、徐々に温度を上げて、２００〜２５０℃にて５時間脱水アミド化反応を行い、アミド化合物を得た。
このアミド化合物を耐圧反応容器に仕込み、触媒として水酸化ナトリウム０.７ｇを加え、内部を窒素ガスで置換し、エチレンオキシド２２０ｇ（５モル）を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら約５時間で吹き込み、さらにエチレンオキシド１３２ｇ（３モル）とプロピレンオキシド１７４ｇ（３モル）の混合物を同様に吹き込み、ジエチレントリアミン(ステアリン酸／オレイン酸)ジアミドのエチレンオキシド５モルブロック・エチレンオキシド３モル／プロピレンオキシド３モルランダム付加物を得た。
さらにこのエチレンオキシド・プロピレンオキシド付加物を四つ口フラスコに仕込み、オレイン酸２８２ｇ（１モル）を加え、窒素ガスを吹き込みながら、１８０〜２４０℃で５時間脱水反応を行い、ジエチレントリアミン(ステアリン酸／オレイン酸)ジアミドのエチレンオキシド５モルブロック・エチレンオキシド３モル／プロピレンオキシド３モルランダム付加物のオレイン酸エステル化物を得た。
このオレイン酸エステル化物を用い、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５５８ｇ／ｃｍ3、不透明度は８７.９％、白色度は７９.４、含水伸度は１.０４％であった。
Example 2
A four-necked flask equipped with a thermometer and a nitrogen gas blowing tube was charged with 564 g (2 mol) of oleic acid, gradually heated with a mantle heater while nitrogen gas was blown, and 103 g of diethylenetriamine at 100 to 110 ° C. 1 mol) was added dropwise over about 1 hour. Furthermore, the temperature was gradually raised and a dehydration amidation reaction was carried out at 200 to 250 ° C. for 5 hours to obtain an amide compound.
This amide compound was charged into a pressure resistant reactor, 0.7 g of sodium hydroxide was added as a catalyst, the inside was replaced with nitrogen gas, and 132 g (3 mol) of ethylene oxide was maintained at a reaction temperature of 140 to 150 ° C. and a pressure of 392 kPa or less. In 5 hours, 174 g (3 mol) of propylene oxide was blown in the same manner to obtain an adduct of 3 mol of ethylene oxide and 3 mol of propylene oxide of diethylenetriamineoleic acid diamide.
Using this ethylene oxide / propylene oxide block adduct, a test paper was made in the same manner as in Example 1 and evaluated. The density of the obtained test paper was 0.565 g / cm 3 , the opacity was 87.3%, the whiteness was 79.2, and the water content elongation was 1.05%.
Example 3
A four-necked flask equipped with a thermometer and a nitrogen gas blowing tube was charged with 284 g (1 mol) of stearic acid and 282 g (1 mol) of oleic acid, gradually heated with a mantle heater while blowing nitrogen gas, At 100 to 110 ° C., 103 g (1 mol) of diethylenetriamine was added dropwise over about 1 hour. Furthermore, the temperature was gradually raised, and a dehydration amidation reaction was performed at 200 to 250 ° C. for 5 hours to obtain an amide compound.
This amide compound was charged into a pressure-resistant reaction vessel, 0.7 g of sodium hydroxide was added as a catalyst, the inside was replaced with nitrogen gas, and 220 g (5 mol) of ethylene oxide was maintained at a reaction temperature of 140 to 150 ° C. and a pressure of 392 kPa or less. Blow in 5 hours, and in the same manner, blow in a mixture of 132 g (3 mol) of ethylene oxide and 174 g (3 mol) of propylene oxide, diethylenetriamine (stearic acid / oleic acid) diamide, 5 mol of ethylene oxide, 3 mol of ethylene oxide, 3 mol of propylene oxide. A random adduct was obtained.
Further, this ethylene oxide / propylene oxide adduct was charged into a four-necked flask, 282 g (1 mol) of oleic acid was added, and dehydration reaction was carried out at 180 to 240 ° C. for 5 hours while blowing nitrogen gas, to obtain diethylenetriamine (stearic acid / olein). An oleic acid ester of an acid) diamide 5 mol block ethylene oxide 3 mol / ethylene oxide 3 mol / propylene oxide 3 mol random adduct was obtained.
Using this oleate, a test paper was made in the same manner as in Example 1 and evaluated. The density of the obtained test paper was 0.558 g / cm 3 , the opacity was 87.9%, the whiteness was 79.4, and the water content elongation was 1.04%.
実施例４
温度計と窒素ガス吹き込み管を取り付けた四つロフラスコに、ラウリン酸２００ｇ（１モル）とステアリン酸２８４ｇ（１モル）を仕込み、窒素ガスを吹き込みながら、マントルヒーターで徐々に加熱昇温し、１００〜１１０℃でトリエチレンテトラミン１４６ｇ（１モル）を、約１時間かけて滴下した。さらに徐々に温度を上げて、２００〜２５０℃にて５時間脱水アミド化反応を行い、アミド化合物を得た。
このアミド化合物を耐圧反応容器に仕込み、触媒として水酸化ナトリウム０.７ｇを加え、内部を窒素ガスで置換し、エチレンオキシド４４０ｇ（１０モル）を、反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら約５時間で吹き込み、トリエチレンテトラミン(ステアリン酸／ラウリン酸)ジアミドのエチレンオキシド１０モル付加物を得た。
さらにこのエチレンオキシド付加物を四つ口フラスコに仕込み、ステアリン酸２８４ｇ（１モル）を加え、窒素ガスを吹き込みながら、１８０〜２４０℃で５時間脱水反応を行い、トリエチレンテトラミン(ステアリン酸／ラウリン酸)ジアミドのエチレンオキシド１０モル付加物のステアリン酸エステル化物を得た。
このステアリン酸エステル化物を用い、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５５７ｇ／ｃｍ3、不透明度は８７.９％、白色度は７９.５、含水伸度は１.０４％であった。
実施例５
温度計と窒素ガス吹き込み管を取り付けた四つ口フラスコに、ベヘニン酸３４０ｇ（１モル）を仕込み、窒素ガスを吹き込みながら、マントルヒーターで徐々に加熱昇温し、１００〜１１０℃でトリエチレンテトラミン１４６ｇ（１モル）を、約１時間かけて滴下した。さらに徐々に温度を上げて２００〜２５０℃にて５時間脱水アミド化反応を行い、アミド化合物を得た。
このアミド化合物を耐圧反応容器に仕込み、触媒として水酸化ナトリウム０.７ｇを加え、内部を窒素ガスで置換し、エチレンオキシド４４０ｇ（１０モル）を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら約５時間で吹き込み、さらにプロピレンオキシド１,１６０ｇ（２０モル）を同様に吹き込み、その後さらにブチレンオキシド２１６ｇ（３モル）を同様に吹き込み、トリエチレンテトラミンベヘニン酸アミドのエチレンオキシド１０モル・プロピレンオキシド２０モル・ブチレンオキシド３モルブロック付加物を得た。
さらにこのエチレンオキシド・プロピレンオキシド・ブチレンオキシド付加物を四つ口フラスコに仕込み、ヒマシ脂肪酸３００ｇ（１モル）を加え、窒素ガスを吹き込みながら、１８０〜２４０℃で５時間脱水反応を行い、トリエチレンテトラミンベへニン酸アミドのエチレンオキシド１０モル・プロピレンオキシド２０モル・ブチレンオキシド３モルブロック付加物のヒマシ脂肪酸エステル化物を得た。
このヒマシ脂肪酸エステル合物を用いて、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５５７ｇ／ｃｍ3、不透明度は８７.８％、白色度は７９.４、含水伸度は１.０４％であった。
Example 4
Lauric acid 200 g (1 mol) and stearic acid 284 g (1 mol) were charged in a four-flask equipped with a thermometer and a nitrogen gas blowing tube, and gradually heated with a mantle heater while nitrogen gas was being blown. At ˜110 ° C., 146 g (1 mol) of triethylenetetramine was added dropwise over about 1 hour. Further, the temperature was gradually raised and a dehydration amidation reaction was carried out at 200 to 250 ° C. for 5 hours to obtain an amide compound.
This amide compound was charged into a pressure-resistant reaction vessel, 0.7 g of sodium hydroxide was added as a catalyst, the inside was replaced with nitrogen gas, and 440 g (10 mol) of ethylene oxide was maintained at a reaction temperature of 140 to 150 ° C. and a pressure of 392 kPa or less. Blowing was performed in about 5 hours to obtain a 10-mol ethylene oxide adduct of triethylenetetramine (stearic acid / lauric acid) diamide.
Further, this ethylene oxide adduct was charged into a four-necked flask, 284 g (1 mol) of stearic acid was added, and dehydration reaction was performed at 180 to 240 ° C. for 5 hours while blowing nitrogen gas, to obtain triethylenetetramine (stearic acid / lauric acid). ) A stearic acid esterified product of diamide ethylene oxide 10 mol adduct was obtained.
Using this stearic acid ester product, a test paper was made in the same manner as in Example 1 and evaluated. The density of the obtained test paper was 0.557 g / cm 3 , the opacity was 87.9%, the whiteness was 79.5, and the water content elongation was 1.04%.
Example 5
A four-necked flask equipped with a thermometer and a nitrogen gas blowing tube was charged with 340 g (1 mol) of behenic acid, gradually heated with a mantle heater while blowing nitrogen gas, and triethylenetetramine at 100 to 110 ° C. 146 g (1 mol) was added dropwise over about 1 hour. Furthermore, the temperature was gradually raised and a dehydration amidation reaction was carried out at 200 to 250 ° C. for 5 hours to obtain an amide compound.
This amide compound was charged into a pressure-resistant reaction vessel, 0.7 g of sodium hydroxide was added as a catalyst, the inside was replaced with nitrogen gas, and 440 g (10 mol) of ethylene oxide was maintained while maintaining a reaction temperature of 140 to 150 ° C. and a pressure of 392 kPa or less. Blow in 5 hours, and further inject 1,160 g (20 mol) of propylene oxide in the same manner, then inject 216 g (3 mol) of butylene oxide in the same manner, and then add 10 mol of ethylene oxide of triethylenetetramine behenic acid amide · 20 in propylene oxide. A mole butylene oxide 3 mole block adduct was obtained.
Further, this ethylene oxide / propylene oxide / butylene oxide adduct was charged into a four-necked flask, 300 g (1 mol) of castor fatty acid was added, and a dehydration reaction was performed at 180 to 240 ° C. for 5 hours while blowing nitrogen gas. A castor fatty acid esterified product of ethylene oxide 10 mol / propylene oxide 20 mol / butylene oxide 3 mol block adduct of behenic acid amide was obtained.
Using this castor fatty acid ester compound, a test paper was made in the same manner as in Example 1 and evaluated. The density of the obtained test paper was 0.557 g / cm 3 , the opacity was 87.8%, the whiteness was 79.4, and the water content elongation was 1.04%.
実施例６
温度計と窒素ガス吹き込み管を取り付けた四つ口フラスコに、トール油脂肪酸２８９ｇ（１モル）を仕込み、窒素ガスを吹き込みながら、マントルヒーターで徐々に加熱昇温し、１００〜１１０℃でテトラエチレンペンタミン１８９ｇ（１モル）を、約１時間かけて滴下した。さらに徐々に温度を上げて２００〜２５０℃にて５時間脱水アミド化反応を行い、アミド化合物を得た。
このアミド化合物を耐圧反応容器に仕込み、触媒として水酸化ナトリウム０.７ｇを加え、内部を窒素ガスで置換し、エチレンオキシド１３２ｇ（３モル）を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら約５時間で吹き込み、さらにプロピレンオキシド２９０ｇ（５モル）を同様に吹き込み、その後さらにスチレンオキシド２４０ｇ（２モル）を添加し、テトラエチレンペンタミントール油脂肪酸アミドのエチレンオキシド３モル・プロピレンオキシド５モル・スチレンオキシド２モルブロック付加物を得た。
さらにこのエチレンオキシド・プロピレンオキシド・スチレンオキシドブロック付加物を四つ口フラスコに仕込み、ヒマシ脂肪酸３００ｇ（１モル）を加え、窒素ガスを吹き込みながら、１８０〜２４０℃で５時間脱水反応を行い、テトラエチレンペンタミントール油脂肪酸アミドのエチレンオキシド３モル・プロピレンオキシド５モル・スチレンオキシド２モルブロック付加物のヒマシ脂肪酸エステル化物を得た。
このヒマシ脂肪酸エステル化物を用い、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５５９ｇ／ｃｍ3、不透明度は８７.６％、白色度は７９.３、含水伸度は１.０５％であった。
実施例７
温度計と窒素ガス吹き込み管を取り付けた四つ口フラスコに、オレイン酸５６４ｇ（２モル）を仕込み、窒素ガスを吹き込みながら、マントルヒーターで徐々に加熱昇温し、１００〜１１０℃でポリエチレンイミン［(株)日本触媒、エポミンＳＰ−００６、平均分子量６００］１,０００ｇ（１モル）を、約１時間かけて滴下した。さらに徐々に温度を上げて２００〜２５０℃にて５時間脱水アミド化反応を行い、アミド化合物を得た。
このアミド化合物を耐圧反応容器に仕込み、触媒として水酸化ナトリウム０.７ｇを加え、内部を窒素ガスで置換し、エチレンオキシド２２０ｇ（５モル）とプロピレンオキシド２９０ｇ（５モル）の混合物を、反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら約５時間で吹き込み、さらにエチレンオキシド４４０ｇ（１０モル）とプロピレンオキシド１７４ｇ（３モル）の混合物を同様に吹き込み、ポリエチレンイミンオレイン酸ジアミドのエチレンオキシド５モル／プロピレンオキシド５モルランダム・エチレンオキシド１０モル／プロピレンオキシド３モルランダム付加物を得た。
さらにこのエチレンオキシド・プロビレンオキシド付加物を四つ口フラスコに仕込み、ステアリン酸２８４ｇ（１モル）を加え、窒素ガスを吹き込みながら、１８０〜２４０℃で５時間脱水反応を行い、ポリエチレンイミンオレイン酸ジアミドのエチレンオキシド５モル／プロピレンオキシド５モルランダム・エチレンオキシド１０モル／プロピレンオキシド３モルランダム付加物のステアリン酸エステル化物を得た。
このステアリン酸エステル化物を用い、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた紙の密度は０.５５８ｇ／ｃｍ3、不透明度は８７.７％、白色度は７９.３、含水伸度は１.０５％であった。
Example 6
A four-necked flask equipped with a thermometer and a nitrogen gas blowing tube was charged with 289 g (1 mol) of tall oil fatty acid, gradually heated with a mantle heater while nitrogen gas was blown, and tetraethylene at 100 to 110 ° C. 189 g (1 mol) of pentamine was added dropwise over about 1 hour. Furthermore, the temperature was gradually raised and a dehydration amidation reaction was carried out at 200 to 250 ° C. for 5 hours to obtain an amide compound.
This amide compound was charged into a pressure resistant reactor, 0.7 g of sodium hydroxide was added as a catalyst, the inside was replaced with nitrogen gas, and 132 g (3 mol) of ethylene oxide was maintained at a reaction temperature of 140 to 150 ° C. and a pressure of 392 kPa or less. Blow in 5 hours, and inject 290 g (5 mol) of propylene oxide in the same manner, and then add 240 g (2 mol) of styrene oxide, and add 3 mol of ethylene oxide, 5 mol of propylene oxide and 5 mol of styrene of tetraethylenepentamine oil fatty acid amide. An oxide 2 mole block adduct was obtained.
Further, this ethylene oxide / propylene oxide / styrene oxide block adduct was charged into a four-necked flask, 300 g (1 mol) of castor fatty acid was added, and dehydration was performed at 180 to 240 ° C. for 5 hours while blowing nitrogen gas. A castor fatty acid esterified product of pentamitol oil fatty acid amide adduct of 3 mol of ethylene oxide, 5 mol of propylene oxide and 2 mol of styrene oxide was obtained.
Using this castor fatty acid ester product, a test paper was made in the same manner as in Example 1 and evaluated. The density of the obtained test paper was 0.559 g / cm 3 , the opacity was 87.6%, the whiteness was 79.3, and the water content elongation was 1.05%.
Example 7
A four-necked flask equipped with a thermometer and a nitrogen gas blowing tube was charged with 564 g (2 mol) of oleic acid, gradually heated with a mantle heater while nitrogen gas was blown, and a polyethyleneimine [100 to 110 ° C. 1,000 g (1 mol) of Nippon Shokubai Co., Ltd., Epomin SP-006, average molecular weight 600] was added dropwise over about 1 hour. Furthermore, the temperature was gradually raised and a dehydration amidation reaction was carried out at 200 to 250 ° C. for 5 hours to obtain an amide compound.
This amide compound is charged into a pressure-resistant reaction vessel, 0.7 g of sodium hydroxide is added as a catalyst, the inside is replaced with nitrogen gas, and a mixture of 220 g (5 mol) of ethylene oxide and 290 g (5 mol) of propylene oxide is added at a reaction temperature of 140 Blowing in about 5 hours while maintaining a pressure of ˜150 ° C. and a pressure of 392 kPa or less, further blowing a mixture of 440 g (10 mol) of ethylene oxide and 174 g (3 mol) of propylene oxide, 5 mol of ethylene oxide of polyethyleneimine oleic acid diamide / propylene oxide A 5 mol random ethylene oxide 10 mol / propylene oxide 3 mol random adduct was obtained.
Furthermore, this ethylene oxide / propylene oxide adduct was charged into a four-necked flask, 284 g (1 mol) of stearic acid was added, and dehydration reaction was carried out at 180 to 240 ° C. for 5 hours while blowing nitrogen gas, and polyethyleneimine oleic acid diamide was added. Of stearic acid ester of 5 mol random ethylene oxide / 5 mol random propylene oxide / 10 mol ethylene oxide / 3 mol random propylene oxide.
Using this stearic acid ester product, a test paper was made in the same manner as in Example 1 and evaluated. The density of the obtained paper was 0.558 g / cm 3 , the opacity was 87.7%, the whiteness was 79.3, and the water content elongation was 1.05%.
実施例８
温度計と窒素ガス吹き込み管を取り付けた四つ口フラスコに、ヤシ脂肪酸４２３ｇ（２モル）を仕込み、窒素ガスを吹き込みながら、マントルヒーターで徐々に加熱昇温し、１００〜１１０℃でアミノエチルエタノールアミン１０４ｇ（１モル）を、約１時間かけて滴下した。さらに徐々に温度を上げて２００〜２５０℃にて５時間脱水アミド化反応を行い、アミド化合物を得た。
このアミド化合物を耐圧反応容器に仕込み、触媒として水酸化ナトリウム０.７ｇを加え、内部を窒素ガスで置換し、エチレンオキシド２２０ｇ（５モル）とプロピレンオキシド２９０ｇ（５モル）の混合物を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら約５時間で吹き込み、さらにスチレンオキシド２４０ｇ（２モル）を添加し、アミノエチルエタノールアミンヤシ脂肪酸ジアミドのエチレンオキシド５モル／プロピレンオキシド５モルランダム・スチレンオキシド２モルブロック付加物を得た。
さらにこのエチレンオキシド・プロピレンオキシド・スチレンオキシド付加物を四つ口フラスコに仕込み、ラウリン酸２００ｇ（１モル）を加え、窒素ガスを吹き込みながら、１８０〜２４０℃で５時間脱水反応を行い、アミノエチルエタノールアミンヤシ脂肪酸ジアミドのエチレンオキシド５モル／プロピレンオキシド５モルランダム・スチレンオキシド２モルブロック付加物のラウリン酸エステル化物を得た。
このラウリン酸エステル化物を用い、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５５７ｇ／ｃｍ3、不透明度は８７.８％、白色度は７９.４、含水伸度は１.０４％であった。
実施例９
温度計と窒素ガス吹き込み管を取り付けた四つ口フラスコに、オレイン酸５６４ｇ（２モル）を仕込み、窒素ガスを吹き込みながら、マントルヒーターで徐々に加熱昇温し、１００〜１１０℃でエチレンジアミン６０ｇ（１モル）を、約１時間かけて滴下した。さらに徐々に温度を上げて２００〜２５０℃にて５時間脱水アミド化反応を行い、アミド化合物を得た。
このアミド化合物を耐圧反応容器に仕込み、触媒として水酸化ナトリウム０.７ｇを加え、内部を窒素ガスで置換し、エチレンオキシド３０８ｇ（７モル）を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら約５時間で吹き込み、エチレンジアミンオレイン酸ジアミドのエチレンオキシド７モル付加物を得た。
さらにこのエチレンオキシド付加物を四つ口フラスコに仕込み、トール油脂肪酸２８９ｇ（１モル）を仕込み、窒素ガスを吹き込みながら、１８０〜２４０℃で５時間脱水反応を行い、エチレンジアミンオレイン酸ジアミドのエチレンオキシド７モル付加物のトール油脂肪酸エステル化物を得た。
このトール油脂肪酸エステル化物を用い、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５６２ｇ／ｃｍ3、不透明度は８７.６％、白色度は７９.３、含水伸度は１.０６％であった。
Example 8
A four-necked flask equipped with a thermometer and a nitrogen gas blowing tube is charged with 423 g (2 moles) of coconut fatty acid, heated gradually with a mantle heater while blowing nitrogen gas, and aminoethylethanol at 100 to 110 ° C. 104 g (1 mol) of amine was added dropwise over about 1 hour. Furthermore, the temperature was gradually raised and a dehydration amidation reaction was carried out at 200 to 250 ° C. for 5 hours to obtain an amide compound.
This amide compound was charged into a pressure-resistant reaction vessel, 0.7 g of sodium hydroxide was added as a catalyst, the inside was replaced with nitrogen gas, and a mixture of 220 g (5 mol) of ethylene oxide and 290 g (5 mol) of propylene oxide was reacted at a reaction temperature of 140 to Blow in about 5 hours while maintaining a pressure of 392 kPa or less at 150 ° C., and then add 240 g (2 mol) of styrene oxide, 5 mol of ethylene oxide of aminoethylethanolamine coconut fatty acid diamide / 5 mol of propylene oxide, 2 mol of styrene oxide An adduct was obtained.
Further, this ethylene oxide / propylene oxide / styrene oxide adduct was charged into a four-necked flask, 200 g (1 mol) of lauric acid was added, and dehydration reaction was carried out at 180 to 240 ° C. for 5 hours while blowing nitrogen gas. A lauric esterified product of 5 mol of ethylene oxide 5 mol of ethylene palm fatty acid diamide / 5 mol of propylene oxide and 2 mol of random styrene oxide block was obtained.
Using this lauric ester, a test paper was made in the same manner as in Example 1 and evaluated. The density of the obtained test paper was 0.557 g / cm 3 , the opacity was 87.8%, the whiteness was 79.4, and the water content elongation was 1.04%.
Example 9
A four-necked flask equipped with a thermometer and a nitrogen gas blowing tube was charged with 564 g (2 mol) of oleic acid, gradually heated with a mantle heater while nitrogen gas was blown, and 60 g of ethylenediamine (100 to 110 ° C.) 1 mol) was added dropwise over about 1 hour. Furthermore, the temperature was gradually raised and a dehydration amidation reaction was carried out at 200 to 250 ° C. for 5 hours to obtain an amide compound.
This amide compound was charged into a pressure-resistant reaction vessel, 0.7 g of sodium hydroxide was added as a catalyst, the inside was replaced with nitrogen gas, and 308 g (7 mol) of ethylene oxide was maintained at a reaction temperature of 140 to 150 ° C. and a pressure of 392 kPa or less. Blowing was performed in 5 hours to obtain an ethylene oxide 7 mol adduct of ethylenediamineoleic acid diamide.
Further, this ethylene oxide adduct was charged into a four-necked flask, charged with 289 g (1 mol) of tall oil fatty acid, and subjected to a dehydration reaction at 180 to 240 ° C. for 5 hours while blowing nitrogen gas, to 7 mol of ethylene oxide of ethylenediamineoleic diamide An adduct tall oil fatty acid esterified product was obtained.
Using this tall oil fatty acid esterified product, a test paper was made in the same manner as in Example 1 and evaluated. The density of the obtained test paper was 0.562 g / cm 3 , the opacity was 87.6%, the whiteness was 79.3, and the water content elongation was 1.06%.
実施例１０
温度計と窒素ガス吹き込み管を取り付けた四つロフラスコに、オレイン酸５６４ｇ（２モル）を仕込み、窒素ガスを吹き込みながら、マントルヒーターで徐々に加熱昇温し、１００〜１１０℃でヘキサメチレンジアミン１１６ｇ（１モル）を、約１時間かけて滴下した。さらに徐々に温度を上げて２００〜２５０℃にて５時間脱水アミド化反応を行い、アミド化合物を得た。
このアミド化合物を耐圧反応容器に仕込み、触媒として水酸化ナトリウム０.７ｇを加え、内部を窒素ガスで置換し、エチレンオキシド１３２ｇ（３モル）を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら約５時間で吹き込み、さらにプロピレンオキシド２９０ｇ（５モル）を同様に吹き込み、ヘキサメチレンジアミンオレイン酸ジアミドのエチレンオキシド３モル・プロピレンオキシド５モルブロック付加物を得た。
さらにこのエチレンオキシド・プロピレンオキシド付加物を四つ口フラスコに仕込み、トール油脂肪酸２８９ｇ（１モル）を加え、窒素ガスを吹き込みながら、１８０〜２４０℃で５時間脱水反応を行い、ヘキサメチレンジアミンオレイン酸ジアミドのエチレンオキシド３モル・プロピレンオキシド５モルブロック付加物のトール油脂肪酸エステル化物を得た。
このトール油脂肪酸エステル化物を用い、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５５８ｇ／ｃｍ3、不透明度は８７.７％、白色度は７９.４、含水伸度は１.０５％であった。
実施例１１
温度計と窒素ガス吹き込み管を取り付けた四つ口フラスコに、オレイン酸５６４ｇ（２モル）とメラミン１２６ｇ（１モル）を仕込み、窒素ガスを吹き込みながら、マントルヒーターで徐々に加熱昇温し、２００〜２５０℃にて５時間脱水アミド化反応を行い、アミド化合物を得た。
このアミド化合物を耐圧反応容器に仕込み、触媒として水酸化ナトリウム０.７ｇを加え、内部を窒素ガスで置換し、プロピレンオキシド２９０ｇ（５モル）を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら約５時間で吹き込み、メラミンオレイン酸ジアミドのプロピレンオキシド５モル付加物を得た。
さらにこのプロピレンオキシド付加物を四つ口フラスコに仕込み、ラウリン酸２００ｇ（１モル）を加え、窒素ガスを吹き込みながら、１８０〜２４０℃で５時間脱水反応を行い、メラミンオレイン酸ジアミドのプロピレンオキシド５モル付加物のラウリン酸エステル化物を得た。
このラウリン酸エステル化物を用い、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５５７ｇ／ｃｍ3、不透明度は８７.９％、白色度は７９.５、含水伸度は１.０４％であった。
Example 10
Into a four-flask equipped with a thermometer and a nitrogen gas blowing tube, 564 g (2 mol) of oleic acid was charged, and gradually heated with a mantle heater while nitrogen gas was blown, and 116 g of hexamethylene diamine at 100 to 110 ° C. (1 mol) was added dropwise over about 1 hour. Furthermore, the temperature was gradually raised and a dehydration amidation reaction was carried out at 200 to 250 ° C. for 5 hours to obtain an amide compound.
This amide compound was charged into a pressure resistant reactor, 0.7 g of sodium hydroxide was added as a catalyst, the inside was replaced with nitrogen gas, and 132 g (3 mol) of ethylene oxide was maintained at a reaction temperature of 140 to 150 ° C. and a pressure of 392 kPa or less. It blown in 5 hours, and also 290 g (5 mol) of propylene oxide was blown in the same manner to obtain an ethylene oxide 3 mol / propylene oxide 5 mol block adduct of hexamethylenediamine oleic acid diamide.
Further, this ethylene oxide / propylene oxide adduct was charged into a four-necked flask, 289 g (1 mol) of tall oil fatty acid was added, and a dehydration reaction was carried out at 180 to 240 ° C. for 5 hours while blowing nitrogen gas. Hexamethylenediamine oleic acid A tall oil fatty acid esterified product of diamide of 3 mol of ethylene oxide and 5 mol of propylene oxide was obtained.
Using this tall oil fatty acid esterified product, a test paper was made in the same manner as in Example 1 and evaluated. The density of the obtained test paper was 0.558 g / cm 3 , the opacity was 87.7%, the whiteness was 79.4, and the water content elongation was 1.05%.
Example 11
A four-necked flask equipped with a thermometer and a nitrogen gas blowing tube was charged with 564 g (2 mol) of oleic acid and 126 g (1 mol) of melamine, and gradually heated with a mantle heater while blowing nitrogen gas. A dehydration amidation reaction was carried out at ˜250 ° C. for 5 hours to obtain an amide compound.
This amide compound was charged into a pressure-resistant reaction vessel, 0.7 g of sodium hydroxide was added as a catalyst, the inside was replaced with nitrogen gas, and 290 g (5 mol) of propylene oxide was maintained at a reaction temperature of 140 to 150 ° C. and a pressure of 392 kPa or less. Blowing was performed in about 5 hours to obtain a 5 mol propylene oxide adduct of melamine oleic acid diamide.
Further, this propylene oxide adduct was charged into a four-necked flask, 200 g (1 mol) of lauric acid was added, a dehydration reaction was performed at 180 to 240 ° C. for 5 hours while blowing nitrogen gas, and propylene oxide 5 of melamine oleic acid diamide was added. A laurate esterified product of a molar adduct was obtained.
Using this lauric ester, a test paper was made in the same manner as in Example 1 and evaluated. The density of the obtained test paper was 0.557 g / cm 3 , the opacity was 87.9%, the whiteness was 79.5, and the water content elongation was 1.04%.
比較例１
ジエチレントリアミンステアリン酸ジアミドのエチレンオキシド３モル付加物を添加しない以外は、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.６０５ｇ／ｃｍ3、不透明度は８４.４％、白色度は７７.６、含水伸度は１.２０％であった。
比較例２
ステアリン酸ナトリウムを熱水に乳化分散した分散液を低密度化剤として用い、ステアリン酸ナトリウムの添加量がパルプに対して０.５質量％になるように添加した以外は、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.６０２ｇ／ｃｍ3、不透明度は８４.４％、白色度は７７.５、含水伸度は１.１２％であった。
比較例３
ステアリルアルコールのエチレンオキシド５モル付加物を水に乳化分散した分散液を低密度化剤として用い、ステアリルアルコールのエチレンオキシド５モル付加物の添加量がパルプに対して０.５質量％になるように添加した以外は、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５８６ｇ／ｃｍ3、不透明度は８６.６％、白色度は７８.１、含水伸度は１.１０％であった。
比較例４
ステアリン酸のエチレンオキシド５モル・プロピレンオキシド３モルブロック付加物を水に乳化分散した分散液を低密度化剤として用い、ステアリン酸のエチレンオキシド５モル・プロピレンオキシド３モルブロック付加物の添加量がパルプに対して０.５質量％になるように添加した以外は、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５８７ｇ／ｃｍ3、不透明度は８６.５％、白色度は７８.０、含水伸度は１.１１％であった。
比較例５
ペンタエリスリトールのジステアロイルエステル化物に、ラウリルアルコールのエチレンオキシド１０モル・プロピレンオキシド５モルランダム付加物の１０質量％を配合し、熱水に乳化分散した分散液を低密度化剤として用い、ペンタエリスリトールのジステアロイルエステル化物の添加量がパルプに対して０.５質量％になるように添加した以外は、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５７７ｇ／ｃｍ3、不透明度は８６.９％、白色度は７８.６、含水伸度は１.１１％であった。
比較例６
高級アルコール［三菱化学(株)、ドバノール、主成分炭素数１２〜１３のアルコール］のプロピレンオキシド３モル・エチレンオキシド２モルブロック付加物を熱水に乳化分散した分散液を低密度化剤として用い、高級アルコールのプロピレンオキシド３モル・エチレンオキシド２モルブロック付加物の添加量がパルプに対して０.５質量％になるように添加した以外は、実施例１と同様にして試験紙を抄紙し、評価を行った。得られた試験紙の密度は０.５７０ｇ／ｃｍ3、不透明度は８７.１％、白色度は７８.９、含水伸度は１.０４％であった。
以下の方法にて、実施例、比較例で得られた紙を使って感熱記録紙を製造した。
３−ジブチルアミノ−６−メチル−７−アニリノフルオラン４０質量部、１０質量％ポリビニルアルコール水溶液８０質量部及び水４０質量部を、サンドミルを用いて４時間微粉砕して分散させることにより、発色物質分散液（Ａ液）を調製した。
４−イソプロポキシ−４'−ヒドロキシジフェニルスルホン２８質量部、１０質量％ポリビニルアルコール水溶液１２０質量部及び水５２質量部を、サンドミルを用いて４時間微粉砕して分散させることにより、顕色物質分散液（Ｂ液）を調製した。
１,２−ビス(フェニルオキシメチル)ベンゼン２８質量部、１０質量％ポリビニルアルコール水溶液１２０質量部及び水５２質量部を、サンドミルを用いて４時間微粉砕して分散させることにより、増感物質分散液（Ｃ液）を調製した。
さらに、Ｂ液６０質量部、Ｃ液６０質量部、１０質量％ポリビニルアルコール水溶液１６質量部及びカオリン１２.２質量部を、ディスパーを用いて撹拌混合し、Ｄ液を調製した。
次いで、Ａ液１１.３質量部及びＤ液１００質量部を混合して、感熱発色層の塗布液を調製した。
実施例（比較例）の紙に、乾燥塗布量が約６ｇ／ｍ2となるように塗布し、風乾し、カレンダー処理により感熱記録紙を得た。
作成した感熱記録紙は、印字エネルギー０.２８ｍＪ／ｄｏｔのとき色濃度により発色性試験を、９５℃での色濃度差ΔＣで断熱性試験を、裏面白紙部の発色色濃度差ΔＢを発色性試験を行った。
中間物質の合成に用いたポリアミンと脂肪酸を第１表に、実施例１〜１１で用いた一般式［１］で表される化合物を第２表に、比較例１〜６で用いた化合物を第３表に、実施例１〜１１及び比較例１〜６の低密度紙の性能評価結果を第４表に示す。
Comparative Example 1
A test paper was made and evaluated in the same manner as in Example 1 except that 3 moles of ethylene oxide adduct of diethylenetriamine stearic acid diamide was not added. The density of the obtained test paper was 0.605 g / cm 3 , the opacity was 84.4%, the whiteness was 77.6, and the water content elongation was 1.20%.
Comparative Example 2
Example 1 was used except that a dispersion obtained by emulsifying and dispersing sodium stearate in hot water was used as a densifying agent, and sodium stearate was added in an amount of 0.5% by mass based on the pulp. Then, a test paper was made and evaluated. The density of the obtained test paper was 0.602 g / cm 3 , the opacity was 84.4%, the whiteness was 77.5, and the water content elongation was 1.12%.
Comparative Example 3
Using a dispersion obtained by emulsifying and dispersing ethylene oxide 5 mol adduct of stearyl alcohol in water as a densification agent, add so that the addition amount of stearyl alcohol 5 mol adduct of stearyl alcohol is 0.5% by mass with respect to the pulp. Except that, the test paper was made in the same manner as in Example 1 and evaluated. The density of the obtained test paper was 0.586 g / cm 3 , the opacity was 86.6%, the whiteness was 78.1, and the water content elongation was 1.10%.
Comparative Example 4
A dispersion obtained by emulsifying and dispersing 5 mol of stearic acid in ethylene oxide and 3 mol of propylene oxide in water was used as a densification agent. On the other hand, a test paper was made in the same manner as in Example 1 except that 0.5% by mass was added, and evaluation was performed. The density of the obtained test paper was 0.587 g / cm 3 , the opacity was 86.5%, the whiteness was 78.0, and the water content elongation was 1.11%.
Comparative Example 5
Pentaerythritol esterified product is blended with 10% by mass of a random adduct of 10 moles of ethylene oxide and 5 moles of propylene oxide of lauryl alcohol, and a dispersion obtained by emulsifying and dispersing in hot water is used as a density reducing agent. A test paper was made and evaluated in the same manner as in Example 1 except that the amount of distearoyl esterified product added was 0.5% by mass with respect to the pulp. The density of the obtained test paper was 0.577 g / cm 3 , the opacity was 86.9%, the whiteness was 78.6, and the water content elongation was 1.11%.
Comparative Example 6
A dispersion obtained by emulsifying and dispersing a propylene oxide 3 mol / ethylene oxide 2 mol block adduct of higher alcohol [Mitsubishi Chemical Corporation, Dobanol, alcohol having 12 to 13 carbon atoms as a main component] in hot water is used as a low-density agent. Test paper was made and evaluated in the same manner as in Example 1 except that the addition amount of propylene oxide 3 mol / ethylene oxide 2 mol block adduct of higher alcohol was 0.5% by mass with respect to the pulp. Went. The density of the obtained test paper was 0.570 g / cm 3 , the opacity was 87.1%, the whiteness was 78.9, and the water content elongation was 1.04%.
A thermal recording paper was produced by the following method using the paper obtained in the examples and comparative examples.
By dispersing 40 parts by weight of 3-dibutylamino-6-methyl-7-anilinofluorane, 80 parts by weight of a 10% by weight aqueous polyvinyl alcohol solution and 40 parts by weight of water using a sand mill for 4 hours, A coloring substance dispersion (liquid A) was prepared.
The developer was dispersed by finely pulverizing and dispersing 28 parts by mass of 4-isopropoxy-4′-hydroxydiphenylsulfone, 120 parts by mass of a 10% by weight aqueous polyvinyl alcohol solution and 52 parts by mass of water using a sand mill for 4 hours. A liquid (liquid B) was prepared.
Dispersion of sensitizer by pulverizing and dispersing 28 parts by weight of 1,2-bis (phenyloxymethyl) benzene, 120 parts by weight of a 10% by weight aqueous polyvinyl alcohol solution and 52 parts by weight of water using a sand mill for 4 hours. A liquid (liquid C) was prepared.
Furthermore, 60 mass parts of B liquid, 60 mass parts of C liquid, 16 mass parts of 10 mass% polyvinyl alcohol aqueous solution, and 12.2 mass parts of kaolin were stirred and mixed using the disper, and D liquid was prepared.
Next, 11.3 parts by mass of Liquid A and 100 parts by mass of Liquid D were mixed to prepare a coating solution for the thermosensitive coloring layer.
The paper of Example (Comparative Example) was applied so that the dry coating amount was about 6 g / m 2 , air-dried, and a thermal recording paper was obtained by calendaring.
The produced thermal recording paper has a color development test based on the color density at a printing energy of 0.28 mJ / dot, a heat insulation test based on the color density difference ΔC at 95 ° C., and a color development color density difference ΔB on the back blank paper portion. A test was conducted.
The polyamines and fatty acids used for the synthesis of the intermediate substances are shown in Table 1, the compounds represented by the general formula [1] used in Examples 1 to 11 are shown in Table 2, and the compounds used in Comparative Examples 1 to 6 are shown. Table 3 shows the performance evaluation results of the low density papers of Examples 1 to 11 and Comparative Examples 1 to 6 in Table 4.
第４表に見られるように、一般式［１］で表される化合物を添加して抄紙した実施例１〜１１の試験紙は、密度０.５５７〜０.５６５ｇ／ｃｍ3、不透明度８７.３〜８７.９％、白色度７９.２〜７９.５、含水伸度１.０４〜１.０６％であり、密度が低く、不透明度が高く、白色度が高く、含水伸度が低い。
これに対して、従来の低密度化剤を添加して抄紙した比較例２〜６の試験紙は、密度０.５７０〜０.６０２ｇ／ｃｍ3、不透明度８４.４〜８７.１％、白色度７７.５〜７８.９、含水伸度１.０４〜１.１２％であり、実施例において得られた低密度紙に比べて、全般的に性能が劣っている。
また、第４表に見られるように、実施例の結果が示すように本発明の化合物を使用した場合、熱応答性（色濃度）は０.６１〜０.９９であり、断熱性（感熱記録層面と裏面の色濃度差）は０.９３〜１.０７発色性（発色濃度差）は０.０８〜０.１９であった。一方比較例の結果は熱応答性は０.３４〜０.４７であり、断熱性は０.４３〜０.５８発色性は０.３１〜０.４７であった。
実施例の結果は比較例に比べて色濃度が高く、発色性に優れていた。また、感熱記録層面と裏面の色濃度差が高く断熱性に優れていた。また、発色濃度差が低く発色性に優れていた。
As can be seen in Table 4, the test papers of Examples 1 to 11 made by adding the compound represented by the general formula [1] had a density of 0.557 to 0.565 g / cm 3 and an opacity of 87. 0.3 to 87.9%, whiteness 79.2 to 79.5, water content elongation 1.04 to 1.06%, low density, high opacity, high whiteness, water content elongation Low.
On the other hand, the test papers of Comparative Examples 2 to 6 made by adding a conventional densifying agent have a density of 0.570 to 0.602 g / cm 3 , an opacity of 84.4 to 87.1%, The whiteness is 77.5 to 78.9, the water content elongation is 1.04 to 1.12%, and the performance is generally inferior to the low density paper obtained in the examples.
Further, as shown in Table 4, when the compound of the present invention is used as shown in the results of Examples, the thermal response (color density) is 0.61 to 0.99, and the heat insulating property (heat sensitive) The color density difference between the recording layer surface and the back surface was 0.93 to 1.07, and the color developability (color density difference) was 0.08 to 0.19. On the other hand, as a result of the comparative example, the thermal responsiveness was 0.34 to 0.47, and the heat insulating property was 0.43 to 0.58, and the coloring property was 0.31 to 0.47.
The results of the examples were higher in color density than in the comparative examples and excellent in color development. Further, the color density difference between the heat-sensitive recording layer surface and the back surface was high, and the heat insulation was excellent. Further, the color density difference was low and the color development was excellent.
本発明の紙の低密度化剤及び低密度紙の製造方法は、紙製品のパルプ原料の使用量を低減でき、製品の製造スピードの向上や原料コストの低減ができる。また、一方では、印刷適正やボリューム感のある高品質の紙が製造できる。
さらに不透明度の向上によっても、紙製品のパルプ原料の使用量を低減でき、製品の製造スピードの向上や原料コストの低減ができ、無機填料など使用量が低減できる。
さらに白色度の向上によって、良品質の紙の製造が可能となる。
さらに、本発明の高感度感熱記録材料及びその製造法紙によれば、断熱性の向上に伴う、熱応答性及び、発色性を向上させることができ、高品質の感熱記録材料が製造できる。
本発明は、紙パルプ業界に大きく貢献でき、強いては地球環境問題に寄与できるものである。
The paper density-reducing agent and the method for producing low-density paper of the present invention can reduce the amount of pulp raw material used in paper products, improve the production speed of the product, and reduce raw material costs. On the other hand, it is possible to produce high-quality paper with printability and volume.
Further, by improving the opacity, the amount of pulp raw material used in paper products can be reduced, the production speed of the product can be improved, the raw material cost can be reduced, and the amount of inorganic filler used can be reduced.
Further, by improving the whiteness, it is possible to produce a good quality paper.
Furthermore, according to the high-sensitivity heat-sensitive recording material and paper for producing the same of the present invention, it is possible to improve the thermal response and color developability associated with the improvement of heat insulation, and it is possible to produce a high-quality heat-sensitive recording material.
The present invention can greatly contribute to the pulp and paper industry, and can contribute to global environmental problems.
Claims (7)
−(Ｃ2Ｈ4Ｏ)a−(Ｃ3Ｈ6Ｏ)b−(Ｃ4Ｈ8Ｏ)c−(ＣＨ2ＣＨＰｈＯ)d− …［３］
（ただし、式中、Ｐｈは、フェニル基であり、ａ、ｂ、ｃ及びｄは、それぞれ０〜１００であり、ａ＋ｂ＋ｃ＋ｄ＝１〜１００であり、ａ、ｂ、ｃ及びｄは、(Ｃ2Ｈ4Ｏ)、(Ｃ3Ｈ6Ｏ)、(Ｃ4Ｈ8Ｏ)及び(ＣＨ2ＣＨＰｈＯ)のモル数のみを表し、(Ｃ2Ｈ4Ｏ)、(Ｃ3Ｈ6Ｏ)、(Ｃ4Ｈ8Ｏ)及び(ＣＨ2ＣＨＰｈＯ)の結合順序は任意である。） The paper density-reducing agent excellent in whiteness according to claim 1 or 2, wherein B in the general formula [1] has a structure represented by the following general formula [3].
- (C 2 H 4 O) a - (C 3 H 6 O) b - (C 4 H 8 O) c - (CH 2 CHPhO) d - ... [3]
(In the formula, Ph is a phenyl group, a, b, c, and d are each 0-100, a + b + c + d = 1-100, and a, b, c, and d are (C 2 Only the number of moles of (H 4 O), (C 3 H 6 O), (C 4 H 8 O) and (CH 2 CHPhO) is represented, and (C 2 H 4 O), (C 3 H 6 O), ( The order of bonding of (C 4 H 8 O) and (CH 2 CHPhO) is arbitrary.)
A heat-sensitive recording paper comprising a heat-sensitive recording layer that is colorless or light-colored by heating and is formed on the surface of the low-density paper produced by the method according to claim 6.
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