JP6104104B2 - Liquid bulking agent for paper - Google Patents
Liquid bulking agent for paper Download PDFInfo
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- JP6104104B2 JP6104104B2 JP2013176769A JP2013176769A JP6104104B2 JP 6104104 B2 JP6104104 B2 JP 6104104B2 JP 2013176769 A JP2013176769 A JP 2013176769A JP 2013176769 A JP2013176769 A JP 2013176769A JP 6104104 B2 JP6104104 B2 JP 6104104B2
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- 239000004067 bulking agent Substances 0.000 title claims description 38
- 239000007788 liquid Substances 0.000 title claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 11
- -1 ethyleneoxy group Chemical group 0.000 description 11
- 238000005187 foaming Methods 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000010893 paper waste Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 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 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000002761 deinking Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Paper (AREA)
Description
本発明は、紙用液体嵩高剤に関する。 The present invention relates to a liquid bulking agent for paper.
近年、白色度、不透明度、印刷適性、そしてボリューム感等の面に優れた品質の高い紙が求められている一方で、環境への配慮からパルプ使用量の少ない軽量な紙が望まれている。これらを紙の嵩高さによって解決すべく、これまでに種々の嵩向上の方法が試みられており、その一つとして嵩高剤等の紙質向上剤の利用が挙げられる。 In recent years, high quality paper with excellent whiteness, opacity, printability, volume, etc. has been demanded, while lightweight paper with low pulp usage is desired for environmental considerations. . In order to solve these problems by the bulkiness of paper, various methods for improving the bulk have been attempted so far, and one of them is the use of a paper quality improver such as a bulking agent.
特許文献１には、紙用嵩高剤として特定のアルコールのアルキレンオキサイドを付加した化合物及び該化合物を多価アルコール型非イオン界面活性剤により乳化状態の嵩高剤として、パルプスラリーに均一に混合することを容易にする技術が開示されている。また、特許文献２には、カチオン性化合物、アミン、アミンの酸塩及び両性化合物から選ばれた少なくとも１種の化合物を含有する紙用嵩高剤が開示されている。特許文献２には、前記化合物に、非イオン界面活性剤を併用できることが記載されている。 Patent Document 1 discloses that a compound obtained by adding an alkylene oxide of a specific alcohol as a bulking agent for paper and that the compound is uniformly mixed with a pulp slurry as a bulking agent in an emulsified state by a polyhydric alcohol type nonionic surfactant. A technique for facilitating the above is disclosed. Patent Document 2 discloses a paper bulking agent containing at least one compound selected from a cationic compound, an amine, an acid salt of an amine, and an amphoteric compound. Patent Document 2 describes that a nonionic surfactant can be used in combination with the compound.
一方、嵩高剤は、取り扱い性や設計の自由度拡張などの点から、液状であることが望ましい場合がある。この観点から、有効分濃度が高く、保存安定性に優れた液状製品についての検討も種々されている。特許文献３には、エチレンオキシ基とプロピレンオキシ基とを有する所定の化合物Ａと、炭素数６〜２２の１価脂肪酸とを含有する液状紙用嵩高剤が開示されている。また、特許文献４には、エチレンオキシ基とプロピレンオキシ基とを有する所定の化合物Ａと、スルホコハク酸と炭素数１〜６の直鎖アルコールとのエステル化合物と、炭素数１４〜２２の不飽和脂肪酸とを含有する液状紙用嵩高剤が開示されている。 On the other hand, it may be desirable that the bulking agent is liquid in terms of handling properties and expansion of design flexibility. From this point of view, various studies have been conducted on liquid products having a high effective component concentration and excellent storage stability. Patent Document 3 discloses a bulking agent for liquid paper containing a predetermined compound A having an ethyleneoxy group and a propyleneoxy group and a monovalent fatty acid having 6 to 22 carbon atoms. Patent Document 4 discloses a predetermined compound A having an ethyleneoxy group and a propyleneoxy group, an ester compound of sulfosuccinic acid and a linear alcohol having 1 to 6 carbon atoms, and unsaturated having 14 to 22 carbon atoms. Liquid bulking agents containing fatty acids are disclosed.
また、紙に柔軟性を付与する薬剤として紙用柔軟剤が知られており、特許文献５には、特定の非イオン性界面活性剤とカチオン性界面活性剤とを含有する紙用柔軟剤が開示されている。 In addition, a paper softener is known as an agent that imparts flexibility to paper. Patent Document 5 discloses a paper softener containing a specific nonionic surfactant and a cationic surfactant. It is disclosed.
紙の嵩を高くするには、嵩高剤を多く添加することが１つの方策となるが、添加量を多くすると、製紙設備に粘着汚れが発生する場合があることが判明した。 In order to increase the bulk of the paper, it is one measure to add a large amount of a bulking agent. However, it has been found that if the addition amount is increased, adhesive stains may occur in the papermaking equipment.
本発明は、紙力の低下が少なく、嵩高性能、水への分散性に優れ、紙の厚みを向上させる事ができ、粘着物質の発生抑制効果と白水の泡立ち抑制効果にも優れた紙用液体嵩高剤を提供する。 The present invention is for paper with little reduction in paper strength, high bulk performance, excellent dispersibility in water, can improve the thickness of paper, and is excellent in the effect of suppressing the generation of adhesive substances and the suppression of foaming of white water. A liquid bulking agent is provided.
本発明は、下記一般式（１）で表される化合物〔以下、化合物（１）という〕、下記一般式（２）で表される化合物〔以下、化合物（２）という〕、及び下記一般式（３）で表される化合物〔以下、化合物（３）という〕を含有する、紙用液体嵩高剤に関する。
Ｒ1−Ｏ−（ＰＯ）m（ＥＯ）nＨ （１）
〔式中、Ｒ1は炭素数６以上、２２以下のアルキル基、炭素数６以上、２２以下のアルケニル基、又は炭素数４以上、２０以下のアルキル基を有するアルキルアリール基を示し、Ｐはプロピレン基、Ｅはエチレン基を示し、ｍ、ｎは平均付加モル数であり、ｍは１以上、２０以下の範囲の数であり、ｎは１以上、１０以下の範囲の数であり、（ＰＯ）m（ＥＯ）nはブロック付加である。〕
Ｒ2−Ｏ−（ＥＯ）o（ＰＯ）p（ＥＯ）qＨ （２）
〔式中、Ｒ2は炭素数６以上、２２以下のアルキル基、炭素数６以上、２２以下のアルケニル基、又は炭素数４以上、２０以下のアルキル基を有するアルキルアリール基を示し、Ｐはプロピレン基、Ｅはエチレン基を示し、ｏ、ｐ、ｑは平均付加モル数であり、それぞれ、１以上、１０以下の範囲の数である。ｏ、ｐ、ｑは同一でも異なってもよい。（ＥＯ）o（ＰＯ）p（ＥＯ）qは、ブロック付加である。〕
The present invention includes a compound represented by the following general formula (1) [hereinafter referred to as compound (1)], a compound represented by the following general formula (2) [hereinafter referred to as compound (2)], and the following general formula: The present invention relates to a liquid bulking agent for paper containing a compound represented by (3) [hereinafter referred to as compound (3)].
R 1 —O— (PO) m (EO) n H (1)
[Wherein, R 1 represents an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, or an alkylaryl group having 4 to 20 carbon atoms, and P is A propylene group, E represents an ethylene group, m and n are average addition mole numbers, m is a number in the range of 1 to 20, and n is a number in the range of 1 to 10; PO) m (EO) n is a block addition. ]
R 2 —O— (EO) o (PO) p (EO) q H (2)
[In the formula, R 2 represents an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, or an alkylaryl group having 4 to 20 carbon atoms, and P represents Propylene group, E represents an ethylene group, o, p, q are average addition mole numbers, and are numbers in the range of 1 or more and 10 or less, respectively. o, p, and q may be the same or different. (EO) o (PO) p (EO) q is a block addition. ]
〔式中、Ｒ3は炭素数６以上、２２以下のアルキル基、炭素数６以上、２２以下のアルケニル基、又は炭素数４以上、２０以下のアルキル基を有するアルキルアリール基を示し、Ｒ4、Ｒ5、Ｒ6は同一でも異なってもよく、炭素数１以上、３以下のアルキル基又はベンジル基を示し、Ｘ-は対イオンを示す。〕 [Wherein R 3 represents an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, or an alkylaryl group having 4 to 20 carbon atoms, and R 4 , R 5 and R 6 may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms or a benzyl group, and X − represents a counter ion. ]
本発明によれば、紙力の低下が少なく、嵩高性能、水への分散性に優れ、紙の厚みを向上させる事ができ、粘着物質の発生抑制効果と白水の泡立ち抑制効果にも優れた紙用液体嵩高剤が提供される。 According to the present invention, there is little reduction in paper strength, high bulk performance, excellent dispersibility in water, it is possible to improve the thickness of paper, and it is also excellent in the effect of suppressing the generation of adhesive substances and the effect of suppressing white water foaming A liquid bulking agent for paper is provided.
化合物（１）は、主に嵩高性能の発現に寄与すると考えられる。また、化合物（１）に化合物（２）、化合物（３）を組み合わせることで、白水の泡立ち抑制効果にも優れたものとなる。
一般式（１）中、Ｒ1は炭素数６以上、２２以下のアルキル基、炭素数６以上、２２以下のアルケニル基、又は炭素数４以上、２０以下のアルキル基を有するアルキルアリール基であり、好ましくは炭素数８以上、より好ましくは１０以上、また、好ましくは１８以下、より好ましくは１６以下のアルキル基、もしくはアルケニル基である。
一般式（１）中、ｍは、プロピレンオキシ基ＰＯの平均付加モル数であり、１以上、２０以下の範囲の数である。嵩高性能の観点から、ｍは、好ましくは２以上、より好ましくは３以上、そして、好ましくは１５以下、より好ましくは１０以下である。
一般式（１）中、ｎは、エチレンオキシ基ＥＯの平均付加モル数であり、１以上、１０以下の範囲の数である。水への分散性及び白水の泡立ち抑制の観点から、ｎは、好ましくは１．５以上、より好ましくは２以上、そして、好ましくは７以下、より好ましくは５以下である。
一般式（１）では、（ＰＯ）m（ＥＯ）nは、この順にブロック付加している。
Compound (1) is considered to contribute mainly to the development of bulky high performance. Moreover, it becomes what was excellent also in the foaming suppression effect of white water by combining a compound (2) and a compound (3) with a compound (1).
In general formula (1), R 1 is an alkylaryl group having an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, or an alkyl group having 4 to 20 carbon atoms. The alkyl group is preferably an alkyl group or an alkenyl group having 8 or more carbon atoms, more preferably 10 or more carbon atoms, and preferably 18 or less, more preferably 16 or less carbon atoms.
In general formula (1), m is the average added mole number of propyleneoxy group PO, and is a number in the range of 1 or more and 20 or less. From the viewpoint of bulky high performance, m is preferably 2 or more, more preferably 3 or more, and preferably 15 or less, more preferably 10 or less.
In general formula (1), n is the average addition mole number of ethyleneoxy group EO, and is a number in the range of 1 or more and 10 or less. From the viewpoint of water dispersibility and suppression of white water foaming, n is preferably 1.5 or more, more preferably 2 or more, and preferably 7 or less, more preferably 5 or less.
In the general formula (1), (PO) m (EO) n is added as a block in this order.
化合物（２）は、化合物（１）や化合物（３）の水への分散性を更に高めると考えられる。水への分散性が更に高まる結果、嵩高性能がより効果的に発現し、添加量を低減しても優れた嵩高効果を得ることができる。 Compound (2) is considered to further enhance the dispersibility of compound (1) and compound (3) in water. As a result of further increasing the dispersibility in water, the bulky high performance is more effectively exhibited, and an excellent bulky effect can be obtained even if the amount added is reduced.
一般式（２）中、Ｒ2は炭素数６以上、２２以下のアルキル基、炭素数６以上、２２以下のアルケニル基、又は炭素数４以上、２０以下のアルキル基を有するアルキルアリール基であり、好ましくは炭素数８以上、より好ましくは１０以上、また、好ましくは１８以下、より好ましくは１６以下のアルキル基、もしくはアルケニル基である。
一般式（２）中、ｏ、ｑはエチレンオキシ基ＥＯの平均付加モル数であり、ｐはプロピレンオキシ基ＰＯの平均付加モル数であり、それぞれ、１以上、１０以下の範囲の数である。化合物（１）や化合物（３）の水中への分散性の観点から、ｏ、ｐ、ｑは、それぞれ、好ましくは３以上、より好ましくは５以上、そして、好ましくは９以下、より好ましくは８以下である。
また、ｐは、嵩高性能発現の観点から、好ましくは１．５以上、より好ましくは２以上、そして、好ましくは７以下、より好ましくは５以下である。
ｏ、ｐ、ｑは、同一でも異なってもよい。
一般式（２）では、（ＥＯ）o（ＰＯ）p（ＥＯ）qは、この順にブロック付加している。
In general formula (2), R 2 is an alkylaryl group having an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, or an alkyl group having 4 to 20 carbon atoms. The alkyl group is preferably an alkyl group or an alkenyl group having 8 or more carbon atoms, more preferably 10 or more carbon atoms, and preferably 18 or less, more preferably 16 or less carbon atoms.
In general formula (2), o and q are the average number of moles added of ethyleneoxy group EO, and p is the average number of moles added of propyleneoxy group PO, each in the range of 1 or more and 10 or less. . From the viewpoint of dispersibility of compound (1) and compound (3) in water, o, p and q are each preferably 3 or more, more preferably 5 or more, and preferably 9 or less, more preferably 8 It is as follows.
In addition, p is preferably 1.5 or more, more preferably 2 or more, and preferably 7 or less, more preferably 5 or less, from the viewpoint of high bulk performance.
o, p, and q may be the same or different.
In the general formula (2), (EO) o (PO) p (EO) q is added in blocks in this order.
化合物（３）は、主に化合物（１）のパルプへの定着を促進すると考えられる。
一般式（３）中、Ｒ3は炭素数６以上、２２以下のアルキル基、炭素数６以上、２２以下のアルケニル基、又は炭素数４以上、２０以下のアルキル基を有するアルキルアリール基であり、好ましくは炭素数８以上、１８以下のアルキル基、もしくはアルケニル基である。
一般式（３）中、Ｒ4、Ｒ5、Ｒ6は同一でも異なってもよく、炭素数１以上、３以下のアルキル基又はベンジル基であり、好ましくは炭素数１もしくは２のアルキル基、又はベンジル基である。
一般式（３）中、Ｘ-は対イオンであり、塩化物イオン（Ｃｌ-）、臭化物イオン（Ｂｒ-）などのハロゲン化物イオン、エチルサルフェートイオン等が挙げられ、好ましくはハロゲン化物イオンであり、より好ましくは塩化物イオンである。
It is considered that the compound (3) mainly promotes the fixing of the compound (1) to the pulp.
In General Formula (3), R 3 is an alkylaryl group having an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, or an alkyl group having 4 to 20 carbon atoms. An alkyl group having 8 to 18 carbon atoms or an alkenyl group is preferable.
In the general formula (3), R 4 , R 5 and R 6 may be the same or different, and are an alkyl group having 1 to 3 carbon atoms or a benzyl group, preferably an alkyl group having 1 or 2 carbon atoms, Or it is a benzyl group.
In the general formula (3), X − is a counter ion, and halide ions such as chloride ion (Cl − ) and bromide ion (Br − ), ethyl sulfate ion and the like are preferable, and halide ion is preferable. More preferably, it is a chloride ion.
本発明の紙用液体嵩高剤は、嵩高性能の観点から、化合物（１）を、好ましくは７５質量％以上、より好ましくは７８質量％以上、さらに好ましくは８０質量％以上、そして、紙力維持の観点から、好ましくは９０質量％以下、より好ましくは８８質量％以下、さらに好ましくは８５質量％以下、含有する。 The liquid bulking agent for paper of the present invention is preferably 75% by mass or more, more preferably 78% by mass or more, still more preferably 80% by mass or more, and maintains paper strength from the viewpoint of bulk high performance. From this viewpoint, the content is preferably 90% by mass or less, more preferably 88% by mass or less, and still more preferably 85% by mass or less.
本発明の紙用液体嵩高剤は、水中への分散性の観点から、化合物（２）を、好ましくは１質量％以上、より好ましくは２質量％以上、そして、好ましくは７質量％以下、より好ましくは５質量％以下、含有する。 The liquid bulking agent for paper of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 7% by mass or less, from the viewpoint of dispersibility in water. Preferably it contains 5 mass% or less.
本発明の紙用液体嵩高剤は、化合物（１）のパルプヘの定着性を高め嵩高性能を向上する観点から、化合物（３）を、好ましくは２質量％以上、より好ましくは３質量％以上、さらに好ましくは４．５質量％以上、よりさらに好ましくは５質量％以上、そして、水中への分散性の観点から、好ましくは２０質量％以下、より好ましくは１５質量％以下、さらに好ましくは１０質量％以下、含有する。 The liquid bulking agent for paper of the present invention is preferably the compound (3), preferably 2% by mass or more, more preferably 3% by mass or more, from the viewpoint of improving the fixability of the compound (1) to the pulp and improving the bulk performance. More preferably 4.5% by mass or more, still more preferably 5% by mass or more, and from the viewpoint of dispersibility in water, it is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass. % Or less.
本発明の紙用液体嵩高剤の形態は、化合物（１）、化合物（２）、及び化合物（３）を含有する液体組成物であり、通常は、残部の水を含有する。水としては前記化合物等を有効分とする原料に含まれる水を用いることもできる。本発明の紙用液体嵩高剤が引火性を有さないようにする点から、水を、紙用液体嵩高剤中に５質量％以上含有することが好ましい。この観点から、本発明の紙用液体嵩高剤は、水を、好ましくは５質量％以上、より好ましくは６質量％以上、そして、好ましくは１２質量％以下、より好ましくは１１質量％以下、含有する。 The form of the liquid bulking agent for paper of the present invention is a liquid composition containing compound (1), compound (2), and compound (3), and usually contains the remaining water. As water, the water contained in the raw material which uses the said compound etc. as an effective component can also be used. From the viewpoint of preventing the liquid bulking agent for paper of the present invention from having flammability, it is preferable to contain 5% by mass or more of water in the liquid bulking agent for paper. From this viewpoint, the liquid bulking agent for paper of the present invention contains water, preferably 5% by mass or more, more preferably 6% by mass or more, and preferably 12% by mass or less, more preferably 11% by mass or less. To do.
本発明の紙用液体嵩高剤は、紙の製造時にパルプ原料に添加して用いられる。紙は、印刷用紙、新聞巻取紙、包装用紙、記録用紙などが挙げられ、印刷用紙が好ましい。よって、本発明の嵩高剤は、印刷用紙用液体嵩高剤として好適である。 The liquid bulking agent for paper of the present invention is used by adding to a pulp raw material at the time of paper production. Examples of the paper include printing paper, newspaper winding paper, packaging paper, recording paper, and the like, and printing paper is preferable. Therefore, the bulking agent of the present invention is suitable as a liquid bulking agent for printing paper.
本発明の紙用液体嵩高剤を適用できる紙用のパルプ原料としては、機械パルプ、化学パルプなどのヴァージンパルプから、再生パルプ、脱墨パルプなどの各種古紙パルプに至るものまで広くパルプ一般に適用できるものである。また、本発明の紙用液体嵩高剤の添加場所としては抄紙工程であれば特に限定するものではないが、例えば工場ではリファイナー、マシンチェスト、ヘッドボックスで添加するなど均一にパルプ原料にブレンドできる場所が望ましい。なお、本発明の紙用液体嵩高剤はパルプ原料に添加後、そのまま抄紙され効率よく紙中に残存する。本発明の紙用液体嵩高剤の添加量は、パルプに対して好ましくは０．０１質量％以上、より好ましくは０．１質量％以上、そして、好ましくは１０質量％以下、より好ましくは５質量％以下である。 The pulp raw material for paper to which the liquid bulking agent for paper of the present invention can be applied is widely applicable to pulp in general, from virgin pulp such as mechanical pulp and chemical pulp to various waste paper pulp such as recycled pulp and deinked pulp. Is. Further, the place for adding the liquid bulking agent for paper of the present invention is not particularly limited as long as it is a papermaking process. Is desirable. The liquid bulking agent for paper of the present invention is added to the pulp raw material and then made as it is and efficiently remains in the paper. The amount of the liquid bulking agent for paper of the present invention added is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass with respect to the pulp. % Or less.
本発明の紙用液体を用いて得られたパルプシートは、無添加品に比べて緊度（測定方法は、後述の実施例記載の方法による）が５％以上、好ましくは７％以上低く、且つＪＩＳ Ｐ ８１１２により測定された破裂強度が無添加品の７５％以上、好ましくは８０％以上であることがより好ましい。 The pulp sheet obtained by using the paper liquid of the present invention has a tenacity (measurement method according to the method described in Examples below) of 5% or more, preferably 7% or more lower than that of the additive-free product. The burst strength measured according to JIS P 8112 is 75% or more, more preferably 80% or more of the additive-free product.
表１の成分を用いて、表２の印刷用紙用液体嵩高剤を調製し、以下の評価を行った。結果を表２に示す。なお、表２では、化合物（１）に該当しない比較化合物も便宜的に化合物（１）の欄に示した。 Using the components shown in Table 1, the liquid bulking agent for printing paper shown in Table 2 was prepared and evaluated as follows. The results are shown in Table 2. In Table 2, comparative compounds not corresponding to the compound (1) are also shown in the column of the compound (1) for convenience.
（Ｉ）抄紙条件
＜パルプ原料＞
市中回収された原料古紙（新聞紙／チラシ＝６０／４０、質量比）を４ｃｍ×４ｃｍに裁断後、一定量を卓上離解機に入れ、その中に温水及び水酸化ナトリウム（対原料）０．３５％（質量基準、以下同様）、脱墨剤として、ステアリルアルコールのエチレンオキサイド５０モルプロピレンオキサイド４０モル付加物（平均付加モル数）０．３％（対原料）を加え、パルプ濃度１３％、４５℃で１０分間離解した。得られたパルプスラリーに温水を加えてパルプ濃度を１％に希釈し、５５℃にて５分間フロテーション処理を行った。フロテーション処理後、水洗、濃度調整を行い１％の脱墨パルプ（以下、ＤＩＰという）スラリーとして古紙パルプを用意した。このときのＤＩＰのフリーネスは２５０ｍｌであった。
(I) Papermaking conditions <pulp raw material>
Waste paper collected in the city (newspaper / flyers = 60/40, mass ratio) is cut into 4 cm × 4 cm, and a certain amount is put into a desktop disintegrator, and warm water and sodium hydroxide (vs. raw material) 35% (mass basis, the same applies hereinafter), as a deinking agent, stearyl alcohol 50 mol propylene oxide 40 mol adduct (average number of added moles) 0.3% (based on raw material) was added, pulp concentration 13%, It disaggregated for 10 minutes at 45 degreeC. Warm water was added to the obtained pulp slurry to dilute the pulp concentration to 1%, and a flotation treatment was performed at 55 ° C. for 5 minutes. After the flotation treatment, washing with water and adjusting the concentration were performed to prepare waste paper pulp as 1% deinked pulp (hereinafter referred to as DIP) slurry. The freeness of DIP at this time was 250 ml.
＜抄紙方法＞
次に上記のＤＩＰスラリーを、抄紙後のシートの秤量が８０ｇ／ｍ2になるように量り取ってから、ｐＨを硫酸バンドで４．５に調整した。表２の嵩高剤を対パルプ１％添加し、丸型タッピ−抄紙機にて１５０メッシュワイヤーで抄紙しシートを得た。使用する水の温度は４０±５℃に調整した。抄紙後のシートは、０．３４ＭＰａで５分間プレス機にてプレスし、鏡面ドライヤーを用い０．１ＭＰａの線圧下、１０５℃で１分間乾燥した。乾燥されたシートは２３℃、湿度５０％の条件で１日間調湿してから、紙の嵩高性として紙の緊度、紙力性能として破裂強度を測定した。緊度と破裂強度は、それぞれ、１０回の平均値である。
<Paper making method>
Next, the above DIP slurry was weighed so that the weight of the sheet after papermaking was 80 g / m 2 , and then the pH was adjusted to 4.5 with a sulfuric acid band. A bulking agent of Table 2 was added to 1% of pulp, and a sheet was obtained by making paper with a 150-mesh wire using a round tappy paper machine. The temperature of the water used was adjusted to 40 ± 5 ° C. The sheet after paper making was pressed with a press at 0.34 MPa for 5 minutes, and dried at 105 ° C. for 1 minute under a linear pressure of 0.1 MPa using a mirror dryer. The dried sheet was conditioned at 23 ° C. and a humidity of 50% for 1 day, and then the paper tension was measured as the bulkiness of the paper and the burst strength was measured as the paper strength performance. Each of the tenacity and burst strength is an average of 10 times.
（II）評価
＜嵩高性（緊度）＞
調湿されたシートの秤量（ｇ／ｍ2）と厚み（ｍｍ）を測定し、下記式の計算値より緊度（ｇ／ｃｍ3）を求め、嵩高性の指標とした。
緊度＝（秤量）／（厚み）×０．００１
なお、緊度は値が小さいほど嵩高性能は高く、緊度の値の０．０１の差は有意な差である。
(II) Evaluation <bulkyness (tightness)>
The weighed sheet was weighed (g / m 2 ) and thickness (mm), and the tenacity (g / cm 3 ) was determined from the calculated value of the following formula, which was used as an index of bulkiness.
Tension = (Weighing) / (Thickness) × 0.001
Note that the smaller the value of the tension, the higher the bulk performance, and a difference of 0.01 in the value of the tension is a significant difference.
＜紙力（破裂強度）＞
調湿されたシートの破裂強度をＪＩＳ Ｐ ８１１２（紙−破裂強さ試験方法）に基づいて測定した。なお、破裂強度は値が大きいほど紙力は高く良好である。
<Paper strength (burst strength)>
The burst strength of the conditioned sheet was measured based on JIS P 8112 (paper-burst strength test method). The larger the burst strength, the higher the paper strength and the better.
＜白水の泡立ち＞
前記「（Ｉ）抄紙条件」の「＜抄紙方法＞」で表２の嵩高剤を対パルプ１％添加したＤＩＰスラリーについて、実機設備における泡立ちを想定した泡立ち評価を行った。
前記ＤＩＰを、８０メッシュワイヤーにてろ過し、採取したろ液（白水）の泡立ち性を確認した。泡立ち試験は、白水温度４０℃での循環滝落とし試験にて行った。循環流量は、１４００ｍＬ／分（白水量：５００ｇ）にて行い、循環３分後の泡高を評価した。泡立ち性の評価は下記の様にして求めた。なお、泡量は少ない方が好ましく、泡立ち試験の評価点が２以上であれば、実機において操業可能な範囲である。
３：循環開始３分後の泡量が５０ｍＬ以下である。
２：循環開始３分後の泡量が５０ｍＬ超、１００ｍＬ以下である。
１：循環開始３分後の泡量が１００ｍＬ超である。
<Bubbling of white water>
With respect to the DIP slurry to which 1% of the bulking agent shown in Table 2 was added in “<Paper making method>” in “(I) Papermaking conditions”, foaming evaluation was performed assuming foaming in actual equipment.
The DIP was filtered with an 80 mesh wire, and the foamability of the collected filtrate (white water) was confirmed. The foaming test was conducted by a circulating water drop test at a white water temperature of 40 ° C. The circulation flow rate was 1400 mL / min (white water amount: 500 g), and the foam height after 3 minutes of circulation was evaluated. Evaluation of foaming property was calculated | required as follows. In addition, it is preferable that the amount of foam is small, and if the evaluation score of the foaming test is 2 or more, it is within the range that can be operated in an actual machine.
3: The amount of foam 3 minutes after the start of circulation is 50 mL or less.
2: The amount of foam 3 minutes after the start of circulation is more than 50 mL and 100 mL or less.
1: The amount of foam 3 minutes after the start of circulation is more than 100 mL.
＜インキ成分の溶解性＞
粘着異物発生の尺度として、インキ成分の溶解性を確認した。スクリュー管Ｎｏ．７（株式会社マルエム製）のふたの内側に新聞インキ（ＤＩＣ株式会社製 Ｎ／ＺナチュラリスＮＫ墨）を０．１ｇ塗布し、５０℃にて３日間乾燥した。スクリュー管に、表２の嵩高剤を１０００ｐｐｍの濃度で含有する水分散液を５０ｇ調製し、先の、インキを塗布したふたをはめ、４０℃条件下でレシプロシェーカー（大洋科学工業製 Ｒ−１）にてレベル１０の強さで２４時間振盪した。
２４時間振盪後の混合液をメンブランフィルター（セルロースアセテート、孔径０．８μｍ）にてろ過し、１晩放置、乾燥後のメンブランフィルターの白色度を測定し、インキ成分の溶解性とした。インキ成分の溶解性が高い程、混合液中にインキが溶出し、ろ過した後のメンブランフィルター上に多くのカーボンブラックが残り、白色度の値が低くなる。逆にインキ成分の溶解性が低いと、溶液中へのインキの溶出が無く、ろ過後のフィルター上に残る物はなく、白色度の値は高くなる。
なお、白色度の測定は、Ｔｅｃｈｎｉｄｙｎｅ社製のＣｏｌｏｒ ＴｏｕｃｈＰＣにて行った。
実機操業において、粘着異物の発生原因は多様であると考えられるが、近年、ほとんどの抄造物に古紙パルプが用いられることから、古紙パルプ中のインキ成分由来の粘着異物の発生が確認されている。古紙パルプ中のインキ成分由来の粘着異物は、古紙パルプ中のインキ成分が紙表面の物性を制御する抄紙薬剤等により白水中に溶け出し、製紙設備や紙表面上で再凝集することにより発生するものと考えられる。したがって、粘着異物を低減するためには、インキの溶解性を低減することが重要であると考えられる。
この評価では、白色度が、８０％以上であれば、例えば、古紙パルプ中のインキ成分の溶解性は低く、実機操業において粘着物トラブルが起きにくいものと判断できる。
<Solubility of ink components>
The solubility of the ink component was confirmed as a measure of the occurrence of adhesive foreign matter. Screw tube No. 0.1 g of newspaper ink (N / Z Naturalis NK ink, manufactured by DIC Corporation) was applied to the inside of the lid of 7 (manufactured by Maruemu Co., Ltd.) and dried at 50 ° C. for 3 days. 50 g of an aqueous dispersion containing the bulking agent of Table 2 at a concentration of 1000 ppm was prepared in a screw tube, and the above-mentioned ink-coated lid was put on, and a reciprocating shaker (R-1 manufactured by Taiyo Kagaku Kogyo Co., Ltd.) was used. ) At a strength of level 10 for 24 hours.
The mixed solution after shaking for 24 hours was filtered through a membrane filter (cellulose acetate, pore size 0.8 μm), allowed to stand overnight, the whiteness of the dried membrane filter was measured, and the solubility of the ink component was determined. As the solubility of the ink component is higher, the ink is eluted in the mixed solution, and more carbon black remains on the membrane filter after filtration, resulting in a lower whiteness value. Conversely, if the solubility of the ink component is low, there is no elution of the ink into the solution, no matter remains on the filter after filtration, and the whiteness value is high.
The whiteness was measured with a Color Touch PC manufactured by Technodyne.
In actual machine operation, it is thought that the cause of the occurrence of adhesive foreign matter is diverse, but in recent years, waste paper pulp is used in most paper products, and the occurrence of adhesive foreign matter derived from ink components in waste paper pulp has been confirmed. . Adhesive foreign matter derived from ink components in waste paper pulp is generated when the ink components in waste paper pulp are dissolved in white water by papermaking chemicals that control the physical properties of the paper surface and re-aggregate on the papermaking equipment and paper surface. It is considered a thing. Therefore, it is considered important to reduce the solubility of ink in order to reduce adhesive foreign matter.
In this evaluation, when the whiteness is 80% or more, for example, the solubility of the ink component in the waste paper pulp is low, and it can be determined that the trouble of the sticky material does not easily occur in the operation of the actual machine.
＜水分散液の濁度＞
水中への分散性の指標として水分散液の濁度を測定した。濁度の値が小さいほど、嵩高剤の水中への分散性が高く、単位質量当たりの嵩高性能が高い事になる。嵩高剤の固形分（水以外の成分）について、１質量％水分散液を調製し、ニッコーハンセン（株）製のポータブル濁度計ＴＮ１００ＩＲにて水分散液の濁度を測定した。なお、濁度の数値が小さいほど、水への嵩高剤成分の分散性は良好であるといえる。
<Turbidity of aqueous dispersion>
The turbidity of the aqueous dispersion was measured as an index of dispersibility in water. The smaller the turbidity value, the higher the dispersibility of the bulking agent in water, and the higher the bulk performance per unit mass. A 1% by mass aqueous dispersion was prepared for the solid content of the bulking agent (components other than water), and the turbidity of the aqueous dispersion was measured with a portable turbidimeter TN100IR manufactured by Nikko Hansen Co., Ltd. In addition, it can be said that the dispersibility of the bulking agent component in water is so favorable that the numerical value of turbidity is small.
化合物Ａ、Ｂ、Ｃ、Ｄ、Ｅ、Ｆ、Ｇ、Ｉ、Ｎ−１、Ｎ−２は、特許第３１８７８４６号公報の合成例１〜１０の何れかの方法に準じて合成した。 Compounds A, B, C, D, E, F, G, I, N-1, and N-2 were synthesized according to any method of Synthesis Examples 1 to 10 in Japanese Patent No. 318784.
比較例８、９は、嵩高剤の調製後に分離が生じたが、強制的に混合して各評価に用いた。 In Comparative Examples 8 and 9, separation occurred after preparation of the bulking agent, but they were forcibly mixed and used for each evaluation.
Claims (3)
Ｒ1−Ｏ−（ＰＯ）m（ＥＯ）nＨ （１）
〔式中、Ｒ1は炭素数６以上、２２以下のアルキル基、炭素数６以上、２２以下のアルケニル基、又は炭素数４以上、２０以下のアルキル基を有するアルキルアリール基を示し、Ｐはプロピレン基、Ｅはエチレン基を示し、ｍ、ｎは平均付加モル数であり、ｍは１以上、２０以下の範囲の数であり、ｎは１以上、１０以下の範囲の数であり、（ＰＯ）m（ＥＯ）nはブロック付加である。〕
Ｒ2−Ｏ−（ＥＯ）o（ＰＯ）p（ＥＯ）qＨ （２）
〔式中、Ｒ2は炭素数６以上、２２以下のアルキル基、炭素数６以上、２２以下のアルケニル基、又は炭素数４以上、２０以下のアルキル基を有するアルキルアリール基を示し、Ｐはプロピレン基、Ｅはエチレン基を示し、ｏ、ｐ、ｑは平均付加モル数であり、それぞれ、１以上、１０以下の範囲の数である。ｏ、ｐ、ｑは同一でも異なってもよい。（ＥＯ）o（ＰＯ）p（ＥＯ）qは、ブロック付加である。〕
〔式中、Ｒ3は炭素数６以上、２２以下のアルキル基、炭素数６以上、２２以下のアルケニル基、又は炭素数４以上、２０以下のアルキル基を有するアルキルアリール基を示し、Ｒ4、Ｒ5、Ｒ6は同一でも異なってもよく、炭素数１以上、３以下のアルキル基又はベンジル基を示し、Ｘ-は対イオンを示す。〕 A liquid bulking agent for paper containing a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3).
R 1 —O— (PO) m (EO) n H (1)
[Wherein, R 1 represents an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, or an alkylaryl group having 4 to 20 carbon atoms, and P is A propylene group, E represents an ethylene group, m and n are average addition mole numbers, m is a number in the range of 1 to 20, and n is a number in the range of 1 to 10; PO) m (EO) n is a block addition. ]
R 2 —O— (EO) o (PO) p (EO) q H (2)
[In the formula, R 2 represents an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, or an alkylaryl group having 4 to 20 carbon atoms, and P represents Propylene group, E represents an ethylene group, o, p, q are average addition mole numbers, and are numbers in the range of 1 or more and 10 or less, respectively. o, p, and q may be the same or different. (EO) o (PO) p (EO) q is a block addition. ]
[Wherein R 3 represents an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, or an alkylaryl group having 4 to 20 carbon atoms, and R 4 , R 5 and R 6 may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms or a benzyl group, and X − represents a counter ion. ]
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| JP2013176769A JP6104104B2 (en) | 2013-08-28 | 2013-08-28 | Liquid bulking agent for paper |
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| JP2013176769A JP6104104B2 (en) | 2013-08-28 | 2013-08-28 | Liquid bulking agent for paper |
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