JP3508967B2 - Size processing method - Google Patents
Size processing methodInfo
- Publication number
- JP3508967B2 JP3508967B2 JP06897596A JP6897596A JP3508967B2 JP 3508967 B2 JP3508967 B2 JP 3508967B2 JP 06897596 A JP06897596 A JP 06897596A JP 6897596 A JP6897596 A JP 6897596A JP 3508967 B2 JP3508967 B2 JP 3508967B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- dimethyldi
- meth
- papermaking
- ketene dimer
- 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
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明はサイズ処理法に関するも
のであり、詳しくはケテン二量体系サイズ剤を含有する
製紙原料スラリーを抄紙するにあたり、ジメチルジ(メ
タ)アリルアンモニウム塩の(共)重合体を併用するこ
とによりドライヤーパートでの乾燥後、サイズの立ち上
がりが早まるサイズ処理法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sizing method, and more specifically, in producing a papermaking raw material slurry containing a ketene dimer sizing agent, a (co) polymer of dimethyldi (meth) allyl ammonium salt. The present invention relates to a size treatment method in which the rise of size is accelerated after drying in the dryer part by using together.
【0002】[0002]
【従来の技術】中性抄紙用サイズ剤として現在最も広く
使用されているものはケテン二量体系サイズ剤(以下A
KDと略記)である。AKDは乳化分散液として調製し
ても一定期間保存可能なのでアルケニル無水コハク酸系
サイズ剤と較べると取扱も良くサイズ効果も安定してい
る。しかしAKDの一番の問題点はドライヤーパートで
乾燥した後直ちにサイズ効果が十分発現せず、塗工原紙
としてその後加工する場合の障害となっている。この点
を改良する目的で二級ジアリルアミン系重合体を含有す
ることによりサイズ効果の立ち上がりを早めたとするA
KD分散液の製造法が出願されている(特開平6−29
9494)。しかしながらAKDは中性抄紙用サイズ剤
であり、炭酸カルシウムを填料として使用した抄紙系の
pHは7.5〜8.2と高く、二級アミンの解離は抑制
されてしまいその効果ははなはだ不十分である。またA
KDサイズ効果向上を目的としてポリジアリルアンモニ
ウム塩重合体およびジシアンジアミド−ホルマリン縮合
物を併用する処方はすでに存在する(特公平3−164
37)。しかしこれはジシアンジアミド−ホルマリン縮
合物かポリジアリルアンモニウム塩重合体のうち一方が
添加されないとサイズ効果の向上は認められないこと、
サイズ効果の立ち上がりについては言及されていない。
ジシアンジアミド−ホルマリン縮合物と併用しないと十
分効果が発現しない理由として考えられる最も重要な点
はジメチルジ(メタ)アリルアンモニウム塩重合体の固
有粘度が低く効果が不十分だったことが考えられる。The most widely used sizing agent for neutral papermaking is the ketene dimer sizing agent (hereinafter referred to as A).
(Abbreviated as KD). Since AKD can be stored for a certain period of time even when prepared as an emulsion dispersion, it is easier to handle and has a stable size effect compared to alkenyl succinic anhydride sizing agents. However, the biggest problem of AKD is that the size effect is not fully exhibited immediately after drying in the dryer part, which is an obstacle when it is further processed as a coated base paper. In order to improve this point, the secondary diallylamine-based polymer is contained to accelerate the onset of the size effect.
A method for producing a KD dispersion has been filed (Japanese Patent Laid-Open No. 6-29).
9494). However, AKD is a sizing agent for neutral papermaking, and the pH of a papermaking system using calcium carbonate as a filler is as high as 7.5 to 8.2, dissociation of secondary amine is suppressed, and its effect is far insufficient. Is. Also A
There is already a formulation in which a polydiallylammonium salt polymer and a dicyandiamide-formalin condensate are used together for the purpose of improving the KD size effect (Japanese Patent Publication No. 3-164).
37). However, this is because no improvement in the size effect is observed unless one of the dicyandiamide-formalin condensate and the polydiallylammonium salt polymer is added.
No mention is made of the onset of the size effect.
The most important reason considered to be that the effect is not sufficiently expressed unless it is used together with the dicyandiamide-formalin condensate is that the dimethyldi (meth) allylammonium salt polymer has a low intrinsic viscosity and the effect is insufficient.
【0003】[0003]
【発明の課題】ケテン二量体系サイズ剤は、中性、アル
カリ性抄紙において安定したサイズ効果を発現し十分実
用に耐えるものであるが、ドライヤーパートでの乾燥直
後、サイズの立ち上がりが遅く、その後の加工に大きな
障害になっている。従ってこの点が改善されるならば製
紙工業において大きな生産性向上につながることは言う
までもない。The ketene dimer sizing agent exhibits a stable sizing effect in neutral and alkaline papermaking and is sufficiently practical, but the size rise is slow immediately after drying in the dryer part and It is a major obstacle to processing. Therefore, it goes without saying that if this point is improved, it will lead to a great improvement in productivity in the paper manufacturing industry.
【0004】[0004]
【課題を解決する為の手段】本発明者等は上記課題を解
決するため鋭意研究をおこなった結果、AKDを含有す
る製紙原料を抄紙するにあたり、ケテン二量体系サイズ
剤の添加に先立ってカチオン変性デンプンとジメチルジ
(メタ)アリルアンモニウム塩の(共)重合体の各々を
この順に添加することにより、サイズ効果の立ち上がり
が早い紙が製造可能なことを発見し本発明に到達した。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that when making a papermaking raw material containing AKD , ketene dimer size
Each of the (co) polymers of cation-modified starch and dimethyldi (meth) allyl ammonium salt is added prior to the addition of the agent.
The present invention was found by discovering that papers having a rapid onset of the size effect can be produced by adding them in this order .
【0005】この理由はいまだ明らかではないが、本発
明で使用するジメチルジ(メタ)アリルアンモニウム塩
(共)重合体の添加によってAKDのサイジング反応が
促進されることが推測される。AKDはアルキルケテン
二量体であるが、この組成のままではパルプに吸着して
もサイズ効果は発現しない。これが別の物質に分解する
ことによって初めてサイジングが完了するとする説が有
力である。すなわちこの分解反応を促進するよう(共)
重合体が働くと考えることができる。またもう一つ考え
られるのはAKDの定着率が向上することである。即ち
抄紙系に存在する種々のアニオン性物質を電気的に中和
し、AKD粒子表面の電荷を適切な値に調節する。Although the reason for this is not yet clear, it is speculated that the addition of the dimethyldi (meth) allylammonium salt (co) polymer used in the present invention accelerates the sizing reaction of AKD. AKD is an alkylketene dimer, but with this composition as it is, the size effect is not exhibited even when adsorbed to pulp. The theory that sizing is completed only when this is decomposed into another substance is influential. That is, to promote this decomposition reaction (co)
It can be considered that the polymer works. Another possibility is that the AKD fixing rate is improved. That is, various anionic substances present in the papermaking system are electrically neutralized to adjust the charge on the surface of AKD particles to an appropriate value.
【0006】本発明で使用するジメチルジ(メタ)アリ
ルアンモニウム塩の(共)重合体はラジカル重合により
容易に製造できる。すなわち重量パーセントで10〜5
0%に調製した後、ラジカル重合開始剤により水溶液重
合、分散重合、逆相乳化重合パール重合等が可能であ
り、また増感剤を添加した光重合等も可能であり重合法
は特に制限されない。またジメチルジ(メタ)アリルア
ンモニウム塩と共重合するノニオン性単量体としてアク
リルアミド、アクリロニトリル、N−ビニルピロリド
ン、酢酸ビニル、アクリル酸アルキル、N−ビニルカル
ボン酸アミド等があげられる。これらノニオン性単量体
の全単量体中にしめる共重合比率は0〜50モル%の範
囲が好ましく、0〜20モル%の範囲がさらに好まし
い。ジメチルジ(メタ)アリルアンモニウム塩の共重合
比率が50モル%以下になるとカチオン電荷密度が低く
なる等機能が低下しサイズ効果の立ち上がり促進が見ら
れなくなる。また本発明の重合体は、25℃の1N食塩
水中における固有粘度〔η〕が、0.6dl/g以上で
あることを必須とする。これ以下であると効果が低下す
る。The (co) polymer of dimethyldi (meth) allyl ammonium salt used in the present invention can be easily produced by radical polymerization. That is 10 to 5 by weight percent
After being adjusted to 0%, aqueous solution polymerization, dispersion polymerization, reverse phase emulsion polymerization pearl polymerization, etc. are possible with a radical polymerization initiator, and photopolymerization with addition of a sensitizer is also possible, and the polymerization method is not particularly limited. . Further, examples of the nonionic monomer copolymerized with the dimethyldi (meth) allyl ammonium salt include acrylamide, acrylonitrile, N-vinylpyrrolidone, vinyl acetate, alkyl acrylate, N-vinylcarboxylic acid amide and the like. The copolymerization ratio of these nonionic monomers in all monomers is preferably in the range of 0 to 50 mol%, more preferably 0 to 20 mol%. When the copolymerization ratio of the dimethyldi (meth) allyl ammonium salt is 50 mol% or less, the cationic charge density is lowered and the functions are deteriorated, and the rise of the size effect is not promoted. Further, it is essential that the polymer of the present invention has an intrinsic viscosity [η] of 0.6 dl / g or more in 1N saline solution at 25 ° C. If it is less than this, the effect decreases.
【0007】次に重合体の添加場所についてのべる。重
合体の添加場所はマシンチェストが第一候補である。マ
シンチェストでは一般の抄紙用添加薬品、たとえば紙力
増強剤、カチオン変性デンプン、硫酸バンド、炭酸カル
シウム、カオリン、タルク、二酸化チタン、ホワイトカ
ーボン、微粉末シリカ、染料、顔料、消泡剤、スライム
コントロール剤等が添加される。またAKDもこのマシ
ンチェストで添加される場合が多いが、ジメチルジ(メ
タ)アリルアンモニウム塩の(共)重合体よりも先にA
KDが添加されると抄紙系のアニオン物質等がAKDと
反応してしまい(共)重合体の添加効果が発揮されな
い。したがって理想的にはジメチルジ(メタ)アリルア
ンモニウム塩の(共)重合体を先に添加し、その後AK
Dを添加するのが効果的である。この場合AKDはマシ
ンチェストとファンポンプの間で添加する。Next, the place where the polymer is added will be described. Machine chests are the primary candidates for polymer additions. In machine chest, general additives for papermaking such as paper strengthening agent, cation modified starch, sulfuric acid band, calcium carbonate, kaolin, talc, titanium dioxide, white carbon, fine powder silica, dye, pigment, defoaming agent, slime control. Agents and the like are added. In addition, AKD is often added in this machine chest, but AKD is added before the (co) polymer of dimethyldi (meth) allyl ammonium salt.
When KD is added, the paper-making anionic substance and the like react with AKD, and the effect of adding the (co) polymer is not exhibited. Therefore, ideally, the (co) polymer of dimethyldi (meth) allyl ammonium salt is added first, and then AK
It is effective to add D. In this case AKD is added between the machine chest and the fan pump.
【0008】次に本発明で使用する重合体の添加方法お
よび添加率について述べる。ジメチルジ(メタ)アリル
アンモニウム塩の(共)重合体はアクリル系の歩留剤、
濾水性向上剤などに較べ粘度が低いので、製品の数倍か
ら10倍程度に希釈して添加することができる。この際
希釈は容易に行うことができるのでラインミキサー等を
用い、直接抄紙ラインに添加できる省力化メリットがあ
る。重合体の添加率は一般に対製紙原料固形分あたり
0.002〜0.4重量%であり、好ましくは0.01
〜0.2%である。添加率が0.002%より少なけれ
ばサイズ立ち上がり促進効果は無く、0.4%より多け
れば抄紙系のパルプや填料の表面電荷が正に傾きすぎた
り、未吸着の重合体が抄紙系に遊離しワイヤー上でのワ
ンパスリテンションが低下する等、悪影響をおよぼす。Next, the addition method and addition rate of the polymer used in the present invention will be described. The (co) polymer of dimethyldi (meth) allyl ammonium salt is an acrylic retention agent,
Since it has a lower viscosity than drainage improving agents, it can be added after being diluted several times to 10 times the product. At this time, since dilution can be easily performed, there is a labor-saving merit that it can be directly added to a papermaking line by using a line mixer or the like. The addition rate of the polymer is generally 0.002 to 0.4% by weight based on the solid content of the papermaking raw material, preferably 0.01.
Is about 0.2%. If the addition rate is less than 0.002%, there is no size rising promotion effect, and if it is more than 0.4%, the surface charge of the pulp and filler in the papermaking system is too positively inclined, and unadsorbed polymer is released into the papermaking system. However, the one-pass retention on the wire will be adversely affected.
【0009】また本発明で使用する重合体の添加は一般
のウェットエンド添加薬品、たとえば紙力増強剤、カチ
オン変性デンプン、硫酸バンド、炭酸カルシウム、カオ
リン、タルク、二酸化チタン、ホワイトカーボン、微粉
末シリカ、染料、顔料、消泡剤、スライムコントロール
剤等と併用できることは言うまでもない。The polymer used in the present invention may be added by a general wet end additive such as paper strengthening agent, cation-modified starch, sulfate band, calcium carbonate, kaolin, talc, titanium dioxide, white carbon, fine powder silica. Needless to say, it can be used in combination with dyes, pigments, defoaming agents, slime control agents and the like.
【0010】[0010]
【実施例】以下実施例および比較例によって本発明の内
容をさらに具体的に説明するが、本発明はその要旨を越
えない限り、以下の実施例に限定されるものではない。EXAMPLES The contents of the present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
【0011】〔本発明で使用する重合体の製造例〕表1
に記載する組成の単量体を、表1に記載する濃度となる
用にイオン交換水に溶解し、溶液のpHを3.5とす
る。単量体水溶液を40℃に保持し30分間窒素ガスを
流し溶液中の酸素を除く。単量体当たり2、2’アゾビ
スアミジノプロパン2塩酸塩(V50)をそれぞれ表記
のモル分率で添加し窒素ガスを流しながら40℃で20
時間保持し重合する。その後各溶液をアセトン中に投入
し重合体を析出させ、その後減圧乾燥して対応する重合
体を得た。これらを4%食塩水中に0.1、0.05、
0.01、0.005%の各濃度の溶液を調製し25℃
においてオストワルド粘度計を用いて還元粘度を測定し
たのち、濃度0に外挿することにより固有粘度〔η〕を
推定した。各共重合体のモル分率、V50の添加率、固
有粘度の測定結果を表1に示す。[Production Example of Polymer Used in the Present Invention] Table 1
The monomer having the composition described in 1 is dissolved in ion-exchanged water so as to have the concentration described in Table 1, and the pH of the solution is set to 3.5. The monomer aqueous solution is kept at 40 ° C. and nitrogen gas is flowed for 30 minutes to remove oxygen in the solution. Add 2,2 ′ azobisamidinopropane dihydrochloride (V50) per monomer in the indicated mole fractions and add nitrogen gas at 20 ° C. for 20 at 40 ° C.
Hold for time and polymerize. Thereafter, each solution was put into acetone to precipitate a polymer, and then dried under reduced pressure to obtain a corresponding polymer. These were added to 4% saline 0.1, 0.05,
Prepare 0.01 and 0.005% of each concentration solution at 25 ℃
In Example 1, the intrinsic viscosity [η] was estimated by measuring the reduced viscosity using an Ostwald viscometer and then extrapolating to zero concentration. Table 1 shows the measurement results of the molar fraction of each copolymer, the V50 addition rate, and the intrinsic viscosity.
【表−1】 [Table-1]
【0012】〔実施例1〜20〕広葉樹クラフトパルプ
(LBKP)をCSF−400mlに叩解し、濃度0.
875%に調製する。 この分散液500mlをブリッ
ト式ダイナミクジャーに投入した後、軽質炭酸カルシウ
ム、カチオン変性デンプン、本発明の(共)重合体(試
作NO1〜10)各々表2およびその下に示した添加量
で、800rpmの攪拌により各々10秒間隔で添加
し、(共)重合体添加後30秒攪拌した後ケテン二量体
系サイズ剤(AS−261,日本PMC製)添加20秒
攪拌市、歩留向上剤添加30秒攪拌した後、ダイナミッ
クジャーに投入し、60メッシュのワイヤーで濾過しワ
イヤー上に残った紙料を採取し、坪量60g/m2 の紙
をタッピスタンダード手抄き抄紙機により抄紙した。各
成紙は2枚の濾紙にはさみ、5Kg/cm2 の条件で1
回プレスした。その後回転式ドラムドライヤーにより1
00℃、2分で乾燥し、65RH,20℃の恒温恒湿室
で直ちにステキヒト法(JIS8122)によりサイズ
度を測定した。同様に一時間後および24時間後のサイ
ズ度も測定した。 以上の結果を表2に示す。[Examples 1 to 20] Hardwood kraft pulp (LBKP) was beaten to CSF-400 ml to a concentration of 0.
Adjust to 875%. After adding 500 ml of this dispersion to a brit type Dynamixer, light calcium carbonate, cation-modified starch, and (co) polymer of the present invention (trial NO1-10) were added at 800 rpm at the addition amounts shown in Table 2 and below. Each at 10-second intervals by stirring, followed by stirring for 30 seconds after addition of the (co) polymer, addition of ketene dimer sizing agent (AS-261, made by Japan PMC) 20 seconds, stirring market, addition of yield improver 30 After stirring for 2 seconds, the mixture was put into a dynamic jar, filtered through a wire of 60 mesh to collect the paper material remaining on the wire, and a paper having a basis weight of 60 g / m 2 was paper-made by a tapi standard handmade paper machine. Each paper is sandwiched between two pieces of filter paper, and 1 is made under the condition of 5 Kg / cm 2.
Pressed twice. Then 1 by rotary drum dryer
It was dried at 00 ° C. for 2 minutes, and the size degree was immediately measured by the Steckigt method (JIS8122) in a thermo-hygrostat at 65 RH and 20 ° C. Similarly, the sizing degree after 1 hour and 24 hours was also measured. The above results are shown in Table 2.
【0013】〔比較例1〜5〕実施例と同様にして下記
比較品を用いた場合および無添加時の抄紙試験を行っ
た。
(比較品1)ジメチルアミン−エピクロロヒドリン−ペ
ンタエチレンヘキサミン縮合物(カチオン当量値8.0
meq/g,固有粘度0.1dl/g)
(比較品2)アクリロイルオキシエチルトリメチルアン
モニウムクロライド30モル%、アクリルアミド70モ
ル%共重合体(カチオン当量値2.5meq/g,固有
粘度1.0dl/g)
以上の結果をまとめて表2に示す。Comparative Examples 1 to 5 Paper-making tests were carried out in the same manner as in the examples using the following comparative products and no addition. (Comparative product 1) Dimethylamine-epichlorohydrin-pentaethylenehexamine condensate (cation equivalent value 8.0
meq / g, intrinsic viscosity 0.1 dl / g) (Comparative product 2) Acryloyloxyethyl trimethyl ammonium chloride 30 mol%, acrylamide 70 mol% copolymer (cation equivalent value 2.5 meq / g, intrinsic viscosity 1.0 dl / g) The above results are summarized in Table 2.
【表−2】 [Table-2]
【0014】〔実施例21〜40〕実施例1〜20と同
様にして、填料をカオリンとタルクの混合比を1:1と
したものに変え試験した。結果をまとめて表3に示す。[Examples 21 to 40] In the same manner as in Examples 1 to 20, tests were carried out by changing the filler to one having a mixing ratio of kaolin and talc of 1: 1. The results are summarized in Table 3.
【0015】〔比較例6〜10〕実施例21〜40と同
様の試験条件にて比較例1〜5と同様の添加物にて抄紙
試験を行った。 結果をまとめて表3に示す。[Comparative Examples 6 to 10] A papermaking test was conducted using the same additives as in Comparative Examples 1 to 5 under the same test conditions as in Examples 21 to 40. The results are summarized in Table 3.
【表−3】 [Table-3]
【0016】[0016]
【発明の効果】本発明のサイズ処理法を適用すれば、ド
ライヤーパートにおける乾燥後のサイズの立ち上がりが
早まり、塗工などその後の加工がオンマシン的に操業可
能であり、生産性が向上するため製紙工業における貢献
は多大なものがある。EFFECTS OF THE INVENTION When the size treatment method of the present invention is applied, the size start-up after drying in the dryer part is accelerated, the subsequent processing such as coating can be operated on-machine, and the productivity is improved. The contribution to the paper industry is enormous.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) D21H 11/00 - 27/42 C08F 6/00 - 246/00 ─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. 7 , DB name) D21H 11/00-27/42 C08F 6/00-246/00
Claims (4)
原料スラリーを抄紙するにあたり、ケテン二量体系サイ
ズ剤の添加に先立ってカチオン変性デンプンとジメチル
ジ(メタ)アリルアンモニウム塩の(共)重合体の各々
をこの順に添加することを特徴とするサイズ処理法。1. A Upon papermaking papermaking raw material slurry containing ketene dimer system sizing agent, ketene dimer system Sai
Each of the (co) polymers of cation-modified starch and dimethyldi (meth) allylammonium salt prior to the addition of the cooling agent.
Is added in this order .
塩の(共)重合体のジメチルジ(メタ)アリルアンモニ
ウム塩構造単位が50〜100モル%であることを特徴
とする請求項1に記載のサイズ処理法。2. The sizing method according to claim 1, wherein the dimethyldi (meth) allylammonium salt (co) polymer has 50 to 100 mol% of dimethyldi (meth) allylammonium salt structural units. .
塩の(共)重合体の25℃の1N食塩水中における固有
粘度〔η〕が0.6dl/g以上であることを特徴とす
る請求項1あるいは請求項2に記載のサイズ処理法。 3. dimethyldi (meth) allyl ammonium salt (co) according to claim 1 or claim intrinsic viscosity in 1N saline 25 ° C. of the polymer [η] is characterized in that it is 0.6 dl / g or more Item 3. The sizing method according to Item 2.
原料スラリーを抄紙するにあたり、カチオン変性デンプWhen making a raw slurry, a cation-modified demp
ン、ジメチルジ(メタ)アリルアンモニウム塩の(共)(Co) of dimethyldi (meth) allylammonium salt
重合体、ケテン二量体系サイズ剤の各々をこの順に添加Add polymer and ketene dimer sizing agent in this order
することを特徴とする請求項1に記載のサイズ処理法。The sizing method according to claim 1, wherein:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP06897596A JP3508967B2 (en) | 1996-03-01 | 1996-03-01 | Size processing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP06897596A JP3508967B2 (en) | 1996-03-01 | 1996-03-01 | Size processing method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH09241997A JPH09241997A (en) | 1997-09-16 |
JP3508967B2 true JP3508967B2 (en) | 2004-03-22 |
Family
ID=13389193
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP06897596A Expired - Fee Related JP3508967B2 (en) | 1996-03-01 | 1996-03-01 | Size processing method |
Country Status (1)
Country | Link |
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JP (1) | JP3508967B2 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4222699B2 (en) * | 1999-11-08 | 2009-02-12 | ハイモ株式会社 | Size fixing method |
US20030127204A1 (en) * | 2001-09-06 | 2003-07-10 | Varnell Daniel F. | Amphoteric polymer resins that increase the rate of sizing development |
US7659354B2 (en) * | 2002-12-23 | 2010-02-09 | Ciba Specialty Chemiclas Corporation | Hydrophobically modified polymers as laundry additives |
JP5691425B2 (en) * | 2010-11-17 | 2015-04-01 | 星光Pmc株式会社 | Paper manufacturing method |
-
1996
- 1996-03-01 JP JP06897596A patent/JP3508967B2/en not_active Expired - Fee Related
Also Published As
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JPH09241997A (en) | 1997-09-16 |
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