JP2739132B2 - Modified paper - Google Patents
Modified paperInfo
- Publication number
- JP2739132B2 JP2739132B2 JP63269636A JP26963688A JP2739132B2 JP 2739132 B2 JP2739132 B2 JP 2739132B2 JP 63269636 A JP63269636 A JP 63269636A JP 26963688 A JP26963688 A JP 26963688A JP 2739132 B2 JP2739132 B2 JP 2739132B2
- Authority
- JP
- Japan
- Prior art keywords
- paper
- methylol
- compound
- cellulose
- polyethylene glycol
- 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 - Fee Related
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/20—Chemically or biochemically modified fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
Description
【発明の詳細な説明】 ［産業上の利用分野］ この発明はセルロースのヒドロキシル基に含まれる水
素基の一部をメチロール化合物で置換した紙に関する。
この紙は劣化（rot）に対し良好な抵抗性を要求される
分野に利用するのに特に適している。Description: TECHNICAL FIELD The present invention relates to paper in which some of the hydrogen groups contained in the hydroxyl groups of cellulose have been replaced with methylol compounds.
The paper is particularly suitable for applications where good resistance to rot is required.
［従来の技術］ Ｌnnen Tehtaat Oyの公開特許出願WO 84/4553によ
れば、セルロースをある種のメチロール化合物特にジメ
チロールジヒドロキシエチレンウレアまたはモノメチロ
ールジヒドロキシエチレンウレアで置換すると、特に針
葉樹セルロースの劣化抵抗性が向上すると言われる。こ
の方法で得られた紙は耐湿強度も良好であるが、脆いこ
とが欠点である。[0002] According to the published patent application WO 84/4553 of Lnnen Tehtaat Oy, the substitution of cellulose with certain methylol compounds, in particular dimethylol dihydroxyethylene urea or monomethylol dihydroxyethylene urea, leads to a deterioration resistance, especially of softwood cellulose. Is said to improve. Although the paper obtained by this method has good moisture resistance, it is disadvantageous in that it is brittle.
［発明が解決しようとする課題］ 本発明の目的は上記の欠点を解消した劣化抵抗性の大
きい改質紙を提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to provide a modified paper having a high resistance to deterioration which has solved the above-mentioned disadvantages.
［課題を解決するための手段］ ある種のＮ−メチロール化合物を使用し、且つ、適当
な例へばヒドロキシ官能性重合体を繊維の間に付着させ
れば脆さを減小させる。とくに好ましい重合体はポリエ
チレングリコール（PEG）でる。SUMMARY OF THE INVENTION Brittleness is reduced by using certain N-methylol compounds and, where appropriate, attaching a hydroxy-functional polymer between the fibers. A particularly preferred polymer is polyethylene glycol (PEG).
使用するポリエチレングリコール分子は単量体を２−
200個含み、10−40個含むものが好ましい。The polyethylene glycol molecule used is a monomer of 2-
Those containing 200, preferably 10-40 are preferred.
Ｎ−メチロール化合物はメチロールジヒドロキシエチ
レンウレア類及びメチロールアセチレンジウレア類から
なる群から選ばれる。これらの中でジメチロールジヒド
ロキシエチレンウレア（DMDHEU）が有効であるが、例へ
ばテトラメチロールアセチレンジウレア（TMADU）も好
適である。The N-methylol compound is selected from the group consisting of methylol dihydroxyethylene ureas and methylol acetylene ureas. Among them, dimethylol dihydroxyethylene urea (DMDHEU) is effective, but tetramethylol acetylene diurea (TMADU) is also suitable, for example.
紙は例へばマツの硫酸セルロールから製造したものが
好ましい。The paper is preferably made, for example, from pine sulfate cellulose.
本発明の紙を製造するには、Ｎ−メチロール化合物と
ポリエチレングリコールを含む溶液を用いて紙を含浸し
た後、昇温して紙を乾燥すれば、Ｎ−メチロール化合物
とセルロースとの間に反応が起き未発明の紙が生成す
る。反応を促進するため適当な触媒を用いる。To produce the paper of the present invention, the paper is impregnated with a solution containing an N-methylol compound and polyethylene glycol, and then heated and dried to form a reaction between the N-methylol compound and cellulose. Occurs and uninvented paper is produced. An appropriate catalyst is used to promote the reaction.
本発明の一つの態様によれば、グリオキザールをポリ
エチレングリコールと併用する。その量はPEG 1モルに
対して２モル以上が好ましい。グリオキザールはPEGの
末端基と反応する。しかしながらＮ−メチロール化合
物、グリオキザール及びPEGとセルロースとの反応形式
は未だ確立されていない。According to one embodiment of the present invention, glyoxal is used in combination with polyethylene glycol. The amount is preferably 2 mol or more per 1 mol of PEG. Glyoxal reacts with the end groups of PEG. However, the reaction mode between N-methylol compound, glyoxal and PEG and cellulose has not been established yet.
［実施例］ 以下、本発明を実施例によりさらに詳細に説明する。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
Ｎ−メチロール化合物、PEG及び触媒の含有する溶液
により紙を含浸し、次ぎにその紙を昇温させて乾燥し
た。得られた紙の特性はいわゆる菌埋没処理の前後に測
定した。The paper was impregnated with a solution containing the N-methylol compound, PEG and the catalyst, and then the paper was heated and dried. The properties of the obtained paper were measured before and after so-called fungal burying treatment.
菌埋没処理は次の通り行った。 Bacterial burial was performed as follows.
所要器具及び素材はオートクレーブ中で圧力１バー
ル、温度120℃で50分滅菌した。純培養菌体（アスペル
ギルス・ニガー＋クラドスポリウム・レジネ）を火炎滅
菌した白金線によりデカンターグラス内の蒸溜水へ接種
した。次にこれを攪拌し、菌体を水中へできるだけ分散
させた。試験片をこの菌水中に４時間浸漬した後、基礎
肥料を付与した培養用滅菌泥炭へ移し、箔容器へ入れ
た。容器をプラスチック箔で保護し、孵卵器へ入れ温度
28℃、相対湿度100％に所定時間保持した。The required equipment and materials were sterilized in an autoclave at a pressure of 1 bar and a temperature of 120 ° C. for 50 minutes. Pure culture cells (Aspergillus niger + Cladosporium resine) were inoculated into distilled water in a decanter glass with a flame-sterilized platinum wire. Next, the mixture was stirred to disperse the cells in water as much as possible. After the test piece was immersed in this bacterial water for 4 hours, it was transferred to a sterilized peat for culture provided with a basic fertilizer and placed in a foil container. Protect the container with plastic foil and place it in an incubator.
It was kept at 28 ° C. and 100% relative humidity for a predetermined time.
実施例１ 次の成分を含むDMDHEU基本溶液を調製した。Example 1 A DMDHEU basic solution containing the following components was prepared.
濃度45％のDMDHEU溶液 40g MgCl2・６H2O 4g 水 １ また次の成分を含むPEG基本溶液を調製した。45% DMDHEU solution 40 g MgCl 2 .6H 2 O 4 g water 1 A PEG basic solution containing the following components was prepared.
濃度45％のPEG（ｎ＝２−181）溶液 18−1350g 濃度50％のグリオキザール溶液 24g Al2（SO4）3・16H2O 2g 酒石酸 1g 水 １ MgCl2はDMDHEUの反応を促進し、Al2（SO4）3はグリオ
キザールの反応を促進する。PEGの量は平均単量体数ｎ
により変動する。酒石酸により含浸溶液は酸性になっ
た。前記基本溶液を容積比4:1で混合した。クラフト紙
（UG70g/m2）にこの混合溶液を含浸し（ピックアップ10
0％）、160℃で10分間乾燥した。45% PEG (n = 2-181) solution 18-1350 g Glyoxal solution 50% concentration 24 g Al 2 (SO 4 ) 3 .16H 2 O 2 g tartaric acid 1 g water 1 MgCl 2 promotes the reaction of DMDHEU, 2 (SO 4 ) 3 promotes the reaction of glyoxal. The amount of PEG is the average number of monomers n
It fluctuates by Tartaric acid made the impregnation solution acidic. The base solutions were mixed at a volume ratio of 4: 1. Impregnated with this mixed solution kraft paper (UG70g / m 2) (pickup 10
0%) and dried at 160 ° C. for 10 minutes.
紙について含浸による重量増加、前記の菌埋没劣化処
理前における乾燥引張強さ及び湿潤引張強さ、並びに劣
化処理後の湿潤引張強さを測定した。試験結果を次表に
示す。The paper was measured for the weight increase due to impregnation, the dry tensile strength and wet tensile strength before the above-mentioned bacteria burying and deterioration treatment, and the wet tensile strength after the deterioration treatment. The test results are shown in the following table.
高分子量のPEGを使用すると劣化に対する抵抗力が低
下することが表より明らかである。 It is clear from the table that the use of high molecular weight PEG reduces the resistance to degradation.
実施例２ 単量体数22のPEGを使用し、実施例１と同様の方法に
より溶液を調製した。含浸と試験を実施例１と同様の方
法により行った。試験結果は次表の通りになった。Example 2 Using PEG having 22 monomers, a solution was prepared in the same manner as in Example 1. The impregnation and the test were performed in the same manner as in Example 1. The test results are as shown in the following table.
溶液中のPEGの割合が増加すると劣化に対する抵抗性
が低下することが表より明らかである。PEGの割合は約1
0−30％が最適である。 It is evident from the table that the resistance to degradation decreases as the proportion of PEG in the solution increases. PEG ratio is about 1
0-30% is optimal.
実施例３ 実施例１においてDMDHEU溶液に触媒としてMgCl2・６H
2Oの代わりにZn（NO3）2・４H2Oを4g/l用いた以外は実
施例１と全く同様に行い、乾燥条件を変化させた。試験
結果を次表に示す。Example 3 In Example 1, MgCl 2 .6H was added to DMDHEU solution as a catalyst.
Except that 4 g / l of Zn (NO 3 ) 2 .4H 2 O was used instead of 2 O, the same procedure as in Example 1 was carried out, and the drying conditions were changed. The test results are shown in the following table.
Zn触媒を使用すると、Mg触媒を用いた場合に比べて高
い劣化抵抗性が得られる。 When a Zn catalyst is used, higher degradation resistance can be obtained than when a Mg catalyst is used.
実施例４ DMDHEUの代りにTMADUを用いた以外は実施例３と全く
同様にして溶液を調製し含浸を行った。試験結果を次表
に示す。Example 4 A solution was prepared and impregnated exactly in the same manner as in Example 3 except that TMADU was used instead of DMDHEU. The test results are shown in the following table.
TMADUの場合には、DMDHEUと同様の優れた劣化抵抗性
は得られなかった。 In the case of TMADU, the same excellent deterioration resistance as DMDHEU was not obtained.
実施例５ 単量体数45のPEGを使用し、溶液の割合を変えて実施
例２の方法により含浸を行った。紙の折りたゝみ耐折回
数を測定した。試験結果を次表に示す。Example 5 Impregnation was carried out by the method of Example 2 using PEG having 45 monomers and changing the ratio of the solution. The number of folding times of the paper was measured. The test results are shown in the following table.
PEGの量が増加するほど耐折回数が増加することは表
より明らかである。 It is clear from the table that the folding endurance increases as the amount of PEG increases.
実施例６ 単量体数22のPEGを使用し、溶液の割合を変えて実施
例２の方法により含浸を行った。紙の乾燥引裂き強さ及
び湿潤引裂き強さを測定した。試験結果を次表に示す。Example 6 Impregnation was performed by the method of Example 2 using PEG having 22 monomers and changing the ratio of the solution. The dry and wet tear strength of the paper was measured. The test results are shown in the following table.
改質により乾燥引裂き強さは低下するが、湿潤引裂き
強さは増大する。 Modification decreases dry tear strength but increases wet tear strength.
フロントページの続き (56)参考文献 特開 昭62−45797（ＪＰ，Ａ) 特開 昭51−121041（ＪＰ，Ａ) 特表 昭60−501317（ＪＰ，Ａ)Continuation of the front page (56) References JP-A-62-45797 (JP, A) JP-A-51-121041 (JP, A) Tokushou 60-501317 (JP, A)
Claims (10)
ル化合物で置換したセルロースを含む改質紙において、
Ｎ−メチロール化合物としてメチロールジヒドロキシエ
チレンウレア類及びメチロールアセチレンジウレア類か
らなる群から選ばれた化合物とポリエチレングリコール
を含む溶液で処理したことを特徴とする改質紙。1. A modified paper containing cellulose in which a part of hydrogen groups of cellulose is substituted by an N-methylol compound,
A modified paper treated with a solution containing polyethylene glycol and a compound selected from the group consisting of methylol dihydroxyethylene ureas and methylol acetylene ureas as N-methylol compounds.
5〜10重量％である請求項１に記載の紙。(2) The amount of the N-methylol compound is 0.5 to paper.
The paper according to claim 1, which is 5 to 10% by weight.
0.5〜10重量％である請求項１に記載の紙。3. The amount of polyethylene glycol is based on paper.
The paper according to claim 1, which is 0.5 to 10% by weight.
200、好ましくは10〜40からなるものである請求項３に
記載の紙。4. The method according to claim 1, wherein the polyethylene glycol has 2 to 2 monomers.
4. The paper according to claim 3, which comprises 200, preferably 10 to 40.
ことを特徴とする請求項１ないし４のいずれか１項に記
載の紙。5. The paper according to claim 1, wherein the paper treating solution further comprises glyoxal.
ドロキシエチレンウレアまたはテトラメチロールアセチ
レンジウレアである請求項１ないし５に記載の紙。6. The paper according to claim 1, wherein the N-methylol compound is dimethylol dihydroxyethylene urea or tetramethylol acetylene urea.
に記載の紙。7. The method according to claim 1, which comprises coniferous cellulose.
Paper described in.
ル化合物で置換したセルロースを含む改質紙の製造法に
おいて、Ｎ−メチロール化合物としてメチロールジヒド
ロキシエチレンウレア類及びメチロールアセチレンジウ
レア類からなる群から選ばれた化合物を含み、且つ、ポ
リエチレングリコールを含む溶液を紙に適用し、加熱乾
燥処理することを特徴とする改質紙の製造法。8. A method for producing a modified paper containing cellulose in which a part of hydrogen groups of cellulose is substituted with an N-methylol compound, wherein the N-methylol compound is selected from the group consisting of methylol dihydroxyethylene ureas and methylol acetylene diureas. A method for producing a modified paper, comprising applying a solution containing a selected compound and containing polyethylene glycol to paper, and subjecting the paper to heat drying treatment.
を含むことを特徴とする請求項８に記載の製造法。9. The method according to claim 8, wherein the solution applied to the paper further contains glyoxal.
ール化合物で置換したセルロースを含む改質紙として、
Ｎ−メチロール化合物がメチロールジヒドロキシエチレ
ンウレア類及びメチロールアセチレンジウレア類からな
る群から選ばれた化合物で、且つ、ポリエチレングリコ
ールを含む溶液で処理した改質紙を用いたことを特徴と
する植物生育セルシステム。10. A modified paper containing cellulose in which a part of hydrogen groups of cellulose is substituted by an N-methylol compound,
A plant growth cell system, wherein the N-methylol compound is a compound selected from the group consisting of methylol dihydroxyethylene ureas and methylol acetylene diureas, and a modified paper treated with a solution containing polyethylene glycol is used. .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI874769A FI80741C (en) | 1987-10-29 | 1987-10-29 | PAPER MODIFICATION. |
| FI874769 | 1987-10-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH026692A JPH026692A (en) | 1990-01-10 |
| JP2739132B2 true JP2739132B2 (en) | 1998-04-08 |
Family
ID=8525314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63269636A Expired - Fee Related JP2739132B2 (en) | 1987-10-29 | 1988-10-27 | Modified paper |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JP2739132B2 (en) |
| CA (1) | CA1339948C (en) |
| DE (1) | DE3836658C2 (en) |
| ES (1) | ES2009085A6 (en) |
| FI (1) | FI80741C (en) |
| FR (1) | FR2622608A1 (en) |
| GB (1) | GB2211519A (en) |
| SE (1) | SE8803758L (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ232813A (en) * | 1989-03-10 | 1992-08-26 | Snow Brand Milk Products Co Ltd | Human fibroblast glycoprotein, cell differentiation, blood vessel endothelial cell growth factor, cellular immunology inforcing factor of 78 or 74 thousand daltons plus or minus two thousand daltons |
| JP2769656B2 (en) * | 1992-03-27 | 1998-06-25 | 日本甜菜製糖株式会社 | Agricultural paper and its manufacturing method |
| US7780816B2 (en) | 2004-10-12 | 2010-08-24 | Certainteed Corporation | Fibrous insulation with fungicide |
| KR100792929B1 (en) * | 2006-10-10 | 2008-01-08 | 현대자동차주식회사 | Piller trim structure |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH367385A (en) * | 1957-11-02 | 1963-02-15 | Schickedanz Ver Papierwerk | Process for the production of non-textile structures |
| BE595844A (en) * | 1959-10-08 | |||
| FR1482617A (en) * | 1965-06-08 | 1967-05-26 | Stockholms Superfosfat Fab Ab | Improvements in the processing of wood products |
| US3629052A (en) * | 1970-06-26 | 1971-12-21 | Us Agriculture | Process for imparting flame-retardancy to resin-treated cotton batting |
| US3858273A (en) * | 1971-05-11 | 1975-01-07 | Sun Chemical Corp | Corrugated paperboard compositions |
| DE2332294C3 (en) * | 1973-06-25 | 1980-01-31 | Feldmuehle Ag, 4000 Duesseldorf | Lightweight, high-stiffness, high-volume paper |
| JPS51121041A (en) * | 1975-04-16 | 1976-10-22 | Sumitomo Chem Co Ltd | Paper coating compositions |
| FI831767L (en) * | 1983-05-19 | 1984-11-20 | Laennen Tehtaat Oy | CHEMISTRY OF PAPPER INNEHAOLLANDE SUBSTITUTES CELLULOSA. |
| JPH0635695B2 (en) * | 1985-08-23 | 1994-05-11 | 株式会社豊田自動織機製作所 | Weft processing method for shuttleless loom |
-
1987
- 1987-10-29 FI FI874769A patent/FI80741C/en not_active IP Right Cessation
-
1988
- 1988-10-20 SE SE8803758A patent/SE8803758L/en not_active Application Discontinuation
- 1988-10-26 ES ES8803258A patent/ES2009085A6/en not_active Expired
- 1988-10-27 DE DE3836658A patent/DE3836658C2/en not_active Expired - Fee Related
- 1988-10-27 JP JP63269636A patent/JP2739132B2/en not_active Expired - Fee Related
- 1988-10-28 CA CA000581630A patent/CA1339948C/en not_active Expired - Fee Related
- 1988-10-28 GB GB8825307A patent/GB2211519A/en not_active Withdrawn
- 1988-10-28 FR FR8814159A patent/FR2622608A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH026692A (en) | 1990-01-10 |
| FI874769A0 (en) | 1987-10-29 |
| SE8803758D0 (en) | 1988-10-20 |
| DE3836658C2 (en) | 2002-12-12 |
| FR2622608A1 (en) | 1989-05-05 |
| GB8825307D0 (en) | 1988-11-30 |
| GB2211519A (en) | 1989-07-05 |
| CA1339948C (en) | 1998-07-14 |
| SE8803758L (en) | 1989-04-30 |
| DE3836658A1 (en) | 1989-05-11 |
| FI80741C (en) | 1990-07-10 |
| ES2009085A6 (en) | 1989-08-16 |
| FI874769A (en) | 1989-04-30 |
| FI80741B (en) | 1990-03-30 |
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