JP2752093B2 - Base paper for impregnation - Google Patents
Base paper for impregnationInfo
- Publication number
- JP2752093B2 JP2752093B2 JP21843888A JP21843888A JP2752093B2 JP 2752093 B2 JP2752093 B2 JP 2752093B2 JP 21843888 A JP21843888 A JP 21843888A JP 21843888 A JP21843888 A JP 21843888A JP 2752093 B2 JP2752093 B2 JP 2752093B2
- Authority
- JP
- Japan
- Prior art keywords
- base paper
- impregnation
- paper
- resin
- pulp
- 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
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は樹脂などを含浸するための原紙に関するもの
である。このような含浸用原紙は、電子機器、および電
気機器に使用される紙基材積層板の原紙、或いは書籍の
表紙などに用いられる樹脂含浸紙の原紙として用いられ
るものである。The present invention relates to a base paper for impregnating a resin or the like. Such base paper for impregnation is used as base paper for a paper base laminate used for electronic equipment and electric equipment, or base paper for resin-impregnated paper used for book covers and the like.
〔従来の技術〕 通常の電子機器又は電気機器用紙基材積層板は、原紙
にフェノール樹脂、エポキシ樹脂等の熱硬化性樹脂を含
浸し、これを加熱乾燥して含浸樹脂を半硬化の状態（プ
リプレグ）にし、このプリプレグの複数枚を金属箔と共
に積層し、この積層物を加熱加圧して成形することによ
り製造されている。[Prior art] Ordinary electronic equipment or electric equipment paper base laminate is prepared by impregnating a base paper with a thermosetting resin such as a phenolic resin or an epoxy resin, and heating and drying this to obtain a semi-cured state of the impregnated resin ( Prepreg), a plurality of the prepregs are laminated together with a metal foil, and the laminate is molded by heating and pressing.
このような紙基材積層板に使用される含浸用原紙には
下記の特性が必要とされている。The following characteristics are required for the impregnating base paper used for such a paper base laminate.
１）含浸工程の作業効率を上げるため、原紙内空孔中へ
の樹脂溶液の浸透速度が速いこと。1) In order to increase the working efficiency of the impregnation step, the penetration rate of the resin solution into the pores in the base paper must be high.
２）定められた重量の樹脂を紙層内部に保持することが
可能で、かつ樹脂が紙層表面上に残留して粘着性を呈す
るという問題、（表面付きトラブル）を起こさないこ
と。2) A resin having a predetermined weight can be held inside the paper layer, and the resin does not remain on the surface of the paper layer and exhibit adhesiveness (trouble with surface).
３）樹脂の含浸むらが少ないこと。3) The resin impregnation unevenness is small.
近年、紙基材積層板にも高い耐熱性と寸法安定性とを
要求するようになり、このため含浸樹脂に、その耐熱性
を向上させるための変性処理が施されたり、従来からの
フェノール樹脂以外に、エポキシ樹脂やポリエステル樹
脂が使用されるようになっている。このような特殊含浸
用樹脂の溶液には粘性が高いという傾向がある。従っ
て、樹脂溶液の浸透速度が速く、かつ、表面付きトラブ
ルを起こさないような、含浸用原紙の必要性が益々高ま
って来ている。In recent years, paper base laminates have also been required to have high heat resistance and dimensional stability. For this reason, the impregnated resin has been subjected to a modification treatment to improve its heat resistance, or a conventional phenol resin has been used. In addition, epoxy resins and polyester resins are used. Such special impregnating resin solutions tend to have high viscosity. Therefore, there is an increasing need for a base paper for impregnation that has a high penetration rate of the resin solution and does not cause trouble with the surface.
また、書籍類の表紙、あるいは他の産業用基材に用い
られる含浸用原紙にも、上記と同様に種々の性能の向上
が要求されるようになってきている。Further, in the same manner as described above, the base paper for impregnation used for the cover of books or other industrial base materials is required to have various improvements in performance.
従来の含浸用原紙、特に、紙基材積層板用原紙には、
主として広葉樹パルプが未叩解で用いられることが多
い。一般に、広葉樹パルプは1.0未満のルンケル比を有
するものが多く、繊維壁が薄いため、抄造工程におい
て、パルプ繊維が潰れやすいことが知られている。この
ような繊維壁の潰れたパルプから形成された紙層内に
は、孔径の小さい空孔の含有率が高くなり、このような
紙層に粘着性の高い熱硬化性樹脂溶液を含浸してプリプ
レグを製造しようとすると、原紙への樹脂の含浸性が不
十分となるという問題を発生する。Conventional base paper for impregnation, especially base paper for paper base laminate,
Hardwood pulp is mainly used unbeaten. In general, hardwood pulp often has a Runkel ratio of less than 1.0, and it is known that pulp fibers are easily crushed in a papermaking process due to a thin fiber wall. In the paper layer formed from such a pulp having a crushed fiber wall, the content of pores having a small pore diameter becomes high, and such a paper layer is impregnated with a highly adhesive thermosetting resin solution. When attempting to manufacture a prepreg, there arises a problem that the impregnating property of the base paper with the resin becomes insufficient.
また、含浸性を改善する手段として、原紙の密度を下
げ、空孔率を上げることが考えられる。しかし、密度を
下げると、得られる原紙の強度が低下し、含浸工程で紙
切れなどのトラブルを発生する恐れがある。従って密度
の低下にも許容限界があり、密度は0.48〜0.52g/cm3の
範囲内にあることが好ましい。Further, as a means for improving the impregnation property, it is conceivable to lower the density of the base paper and increase the porosity. However, when the density is reduced, the strength of the obtained base paper is reduced, and there is a possibility that troubles such as paper breakage may occur in the impregnation step. Therefore, there is an allowable limit for the decrease in density, and the density is preferably in the range of 0.48 to 0.52 g / cm 3 .
本発明は、含浸工程において、樹脂溶液の浸透速度が
速く、樹脂含浸量の高い含浸用原紙を提供しようとする
ものである。An object of the present invention is to provide an impregnating base paper having a high resin impregnation rate and a high resin solution penetration rate in an impregnation step.
本発明の含浸用原紙は、1.0以上のルンケル比を有す
る少なくとも１種のパルプ繊維を、10〜100重量％の含
有率で含み、かつ多数の空孔を有する原紙であって、そ
の全空孔容積に対する、15μｍ以上の換算孔径を有する
空孔の合計容積の比が、40〜80％であることを特徴とす
るものである。The base paper for impregnation of the present invention is a base paper containing at least one pulp fiber having a Runkel ratio of 1.0 or more at a content of 10 to 100% by weight and having a large number of pores. The ratio of the total volume of pores having a converted pore size of 15 μm or more to the volume is 40 to 80%.
本発明者は、含浸工程における原紙の含浸不良に起因
するトラブルを可及的に防止するために、含浸性と原紙
物性の関係について種々検討し、さらに、種々のパルプ
材を蒸解・漂白し、そのパルプ繊維形態と原紙物性との
関係を検討した。その結果、1.0以上の、好ましくは1.2
〜4.0のルンケル比を有する少なくとも１種のパルプ繊
維を、10〜100重量％、好ましくは30〜100重量％の含有
率で含み、かつ、多数の空孔を有する原紙であって、そ
の全空孔容積に対する、15μｍ以上の換算孔径を有する
空孔の合計容積の比が40％〜80％である含浸用原紙が、
粘性の高い熱硬化性樹脂液に対しても、優れた含浸性を
有することを見出し、本発明を完成したものである。The present inventor, in order to prevent as much as possible troubles due to impregnation failure of the base paper in the impregnation process, variously examined the relationship between the impregnation and the physical properties of the base paper, further, digested and bleached various pulp materials, The relationship between the pulp fiber morphology and the physical properties of the base paper was examined. As a result, 1.0 or more, preferably 1.2
A base paper containing at least one pulp fiber having a Runkel ratio of .about.4.0 at a content of 10 to 100% by weight, preferably 30 to 100% by weight, and having a large number of pores, Base paper for impregnation in which the ratio of the total volume of pores having a converted pore size of 15 μm or more to the pore volume is 40% to 80%,
The present invention has been found to have excellent impregnating properties even for highly viscous thermosetting resin liquids, and has completed the present invention.
以下に、パルプ繊維のルンケル比、含浸用原紙の全空
孔容積、換算孔径15μｍ以上の空孔の合計容積および換
算孔径測定法、並びに含浸性の評価法（ひまし油浸透度
測定法、プリプレグ製造装置による含浸作業性評価）に
ついて詳細に述べる。The Runkel ratio of the pulp fiber, the total pore volume of the base paper for impregnation, the total volume of pores with a converted pore size of 15 μm or more and the converted pore size measurement method, and the evaluation method of impregnation (castor oil permeability measurement method, prepreg manufacturing device) Evaluation of impregnation workability) will be described in detail.
ルンケル比 ルンケル比Ｒはパルプ繊維の形態を特徴ずけるための
指標であり、第１図に示すように、繊維のルーメン（内
腔）の幅Ｌと細胞壁の厚さｔとから、下記式によって求
められる値である。Runkel Ratio The Runkel ratio R is an index for characterizing the morphology of pulp fiber. As shown in FIG. 1, the following formula is used based on the width L of the lumen (lumen) of the fiber and the thickness t of the cell wall. This is the required value.
Ｒ＝２・t/L ルンケル比Ｒの大きなパルプ繊維は、叩解、抄紙工程
において、潰れたり変形することが少ない。R = 2 · t / L Pulp fibers having a large Runkel ratio R are less likely to be crushed or deformed in the beating and papermaking processes.
孔空容積および換算孔径測定法 含浸用原紙の孔空容積、および孔径分布は、水銀ポロ
シメーター（例えば、Carlo Erba Pressure Porosimete
r 2000,Macropore Unit 120）を用いて測定することが
できる。Pore volume and reduced pore size measurement method The pore volume and pore size distribution of the impregnated base paper are measured using a mercury porosimeter (eg, Carlo Erba Pressure Porosimete).
r 2000, Macropore Unit 120).
この測定法は、水銀が紙などの固体を濡らさない性質
を利用したものであり、水銀の表面張力を480dyn/cm、
接触角を141゜とし、水銀の圧入圧力をＰ（kg/cm2）と
すると、紙中の空孔の換算孔径ｄ（μｍ）は次式によっ
て求めることができる。This measurement method utilizes the property that mercury does not wet solids such as paper.The surface tension of mercury is 480 dyn / cm,
Assuming that the contact angle is 141 ° and the pressure of mercury injection is P (kg / cm 2 ), the converted pore diameter d (μm) of the pores in the paper can be obtained by the following equation.
ｄ＝15.3/P また、圧入圧力（Ｐ）500kg/cm2における水銀圧入量
をもって、その原紙の全空孔容積とした。孔径分布は各
圧力での水銀圧入量に基づき上記式から計算で求めるこ
とができる。また換算孔径15μｍ以上の空孔の合計容積
は、圧入圧力1.02kg/cm2における水銀圧入量をもって表
わされる。d = 15.3 / P Further, the mercury injection amount at an injection pressure (P) of 500 kg / cm 2 was defined as the total pore volume of the base paper. The pore size distribution can be calculated from the above equation based on the mercury intrusion at each pressure. The total volume of pores having a converted pore size of 15 μm or more is expressed as the amount of mercury injected at an injection pressure of 1.02 kg / cm 2 .
ひまし油浸透度測定法 含浸用原紙のひまし油浸透度は、下記の方法で測定す
ることができる。Castor oil permeability measurement method The castor oil permeability of the base paper for impregnation can be measured by the following method.
供試含浸用原紙から20mm角の試験片10枚を切り取る。
室温30℃に保った恒温槽中にひまし油の入った容器を入
れ、ひまし油の温度を30℃一定にコントロールし、試験
片を水平にひまし油液面に落とし、試験片がひまし油に
接した瞬間から、ひまし油が試験片の上側表面に均一に
浸透するまでの時間を、ストップウォッチで測定する。
紙の表裏について試験片５枚づつ測定し、平均値を算出
する。この数値の低いものほど含浸性が良好であること
を示す。Cut out 10 test pieces of 20 mm square from the test impregnating base paper.
Put the container containing castor oil in a thermostat kept at room temperature 30 ° C, control the temperature of castor oil at 30 ° C constant, drop the test piece horizontally on the castor oil liquid, and from the moment the test piece comes in contact with castor oil, The time required for the castor oil to uniformly penetrate the upper surface of the test specimen is measured with a stopwatch.
The measurement is performed on each of the five test pieces on the front and back sides of the paper, and the average value is calculated. The lower the value, the better the impregnation.
プリプレグ製造装置による含浸作業性評価 プリプレグ製造装置（例えば、井上金属（株）製、複
合材用プリプレグ製造装置）により、下記のようにして
含浸作業性を評価することができる。Evaluation of Impregnation Workability by Prepreg Manufacturing Apparatus A prepreg manufacturing apparatus (for example, a composite material prepreg manufacturing apparatus manufactured by Inoue Metal Co., Ltd.) can evaluate impregnation workability as follows.
含浸は樹脂を変えて２回行う。１回目は水溶性レゾー
ル樹脂（例えば、昭和高分子製BRL−2854）を用い、２
回目は油変性レゾール樹脂（例えば、昭和高分子製BLS
−3122）を用いて行い、樹脂の表面付きおよび断紙の発
生の有無について評価する。The impregnation is performed twice by changing the resin. The first time was performed using a water-soluble resole resin (for example, BRL-2854 manufactured by Showa Polymer).
The second time is an oil-modified resole resin (for example, Showa High Polymer BLS
-3122) to evaluate the surface of the resin and the presence or absence of paper breakage.
本発明の含浸用原紙は、1.0以上のルンケル比を有す
る少なくとも１種のパルプ繊維を10〜100重量％、好ま
しくは30〜100重量％含むものである。このような比較
的大きなルンケル比を有するパルプ繊維の含有率が10重
量％未満になると、得られる含浸用原紙において、粘性
の高い熱硬化性樹脂液に対し、その含浸性が不十分にな
る。The base paper for impregnation of the present invention contains 10 to 100% by weight, preferably 30 to 100% by weight, of at least one pulp fiber having a Runkel ratio of 1.0 or more. When the content of the pulp fiber having such a relatively large Runkel ratio is less than 10% by weight, the impregnating property of the obtained impregnating base paper with respect to the highly viscous thermosetting resin liquid becomes insufficient.
1.0以上のルンケル比を有するパルプ繊維としては、
国内材として、シラカシ、アカガシ、イスノキなどのパ
ルプ繊維があり、輸入材として、マングローブ、ユーカ
リ、アピトン、カメレレ、リグナムバイタなどのパルプ
繊維があげられる。As a pulp fiber having a Runkel ratio of 1.0 or more,
Domestic materials include pulp fibers such as shirakashi, red oak, and horse mackerel. Imported materials include pulp fibers such as mangrove, eucalyptus, apiton, chamelere, and lignum vita.
また、一般的に、パルプ繊維を叩解すると、含浸用原
紙の強度は強くなるが、含浸用原紙への熱硬化性樹脂液
の含浸性は低下する。しかし、1.0以上のルンケル比を
有するパルプ繊維を用いると、叩解しても、繊維の潰れ
が少ないため、得られる原紙の含浸性の低下は少ない。
この傾向はルンケル比が大きいほど顕著である。In general, when pulp fibers are beaten, the strength of the base paper for impregnation is increased, but the impregnation property of the base paper for impregnation with the thermosetting resin liquid is reduced. However, when pulp fibers having a Runkel ratio of 1.0 or more are used, the fibers are less crushed even when beaten, so that the impregnating property of the obtained base paper is small.
This tendency becomes more remarkable as the Runkel ratio increases.
本発明の原紙において、15μｍ以上の換算孔径を有す
る空孔の合計容積の、全空孔容積に対する比は40％〜80
％である。上記比が40％未満の場合は、得られる原紙の
含浸性が不満足なものになる。また上記比が80％を超え
ると得られる原紙の機械的強度が不十分になる。In the base paper of the present invention, the ratio of the total volume of pores having a converted pore size of 15 μm or more to the total pore volume is 40% to 80%.
%. When the above ratio is less than 40%, the impregnating property of the obtained base paper becomes unsatisfactory. On the other hand, when the above ratio exceeds 80%, the mechanical strength of the base paper obtained becomes insufficient.
以下実施例により、本発明を更に説明する。 Hereinafter, the present invention will be further described with reference to examples.
実施例１〜５ 実施例１〜５の各々において、ボルネオ産マングロー
ブ材チップ（容積重:710kg/cm3）を原料として得られ
た、LBKP（広葉樹晒しクラフトパルプ、ルンケル比:3.9
7）と北海道産広葉樹混合材チップ（容積重:500kg/m3）
を原料とした、LBKP（ルンケル比:0.4）を第１表に示す
割合で配合し、この配合パルプから坪量135g/m2、厚さ2
70μｍ（原紙密度:0.5g/cm3）の積層板用原紙を抄造
し、その全空孔容積、孔径分布および含浸性を測定し
た。さらに、この原紙について、プリプレグ製造装置
（井上金属（株）製、複合材用プリプレグ製造装置）に
より、その含浸作業性の評価を行った。結果を第１表に
示す。Examples 1 to 5 In each of Examples 1 to 5, LBKP (hardwood bleached kraft pulp, Runkel ratio: 3.9) obtained using mangrove wood chips (volume weight: 710 kg / cm 3 ) from Borneo as a raw material.
7) and Hokkaido hardwood admixture chip (volume weight: 500 kg / m 3)
LBKP (Runkel ratio: 0.4) was blended in the ratio shown in Table 1 and the basis weight was 135 g / m 2 and the thickness was 2
A base paper for laminate having a thickness of 70 μm (base paper density: 0.5 g / cm 3 ) was prepared, and its total pore volume, pore size distribution and impregnation were measured. Furthermore, the impregnating workability of this base paper was evaluated by a prepreg manufacturing apparatus (preparation apparatus for composite material, manufactured by Inoue Metal Co., Ltd.). The results are shown in Table 1.
実施例６ オーストラリア（ニューキャッスル）産ユーカリ材チ
ップ（容積重:670kg/m3）を原料として、LBKP（ルンケ
ル比:1.53）を製造し、このパルプから坪量135g/m2、厚
さ270μｍ（原紙密度:0.5g/cm3）の積層板用原紙を抄造
し、その全空孔容積、孔径分布および含浸性を測定し
た。さらに、プリプレグ製造装置により、この原紙の含
浸作業性の評価を行った。結果を第１表に示す。Example 6 LBKP (runkel ratio: 1.53) was produced from eucalyptus wood chips (volume weight: 670 kg / m 3 ) from Australia (Newcastle), and the basis weight was 135 g / m 2 and the thickness was 270 μm ( A base paper for a laminate having a base paper density of 0.5 g / cm 3 ) was prepared, and its total pore volume, pore size distribution and impregnation were measured. Furthermore, the impregnating workability of the base paper was evaluated using a prepreg manufacturing apparatus. The results are shown in Table 1.
比較例１ 北海道産広葉樹混合材チップ（容積重:500kg/m3）を
原料として、LBKP（広葉樹晒しクラフトパルプ、ルンケ
ル比:0.4）を製造し、このパルプから坪量135g/m2、厚
さ270μｍ（原紙密度:0.5g/m3）の積層板用原紙を抄造
し、その全空孔容積、孔径分布および含浸性を測定し
た。さらに、この原紙について、プリプレグ製造装置に
より、その含浸作業性の評価を行った。結果を第１表に
示す。Comparative Example 1 LBKP (hardwood bleached kraft pulp, Runkel ratio: 0.4) was produced from Hokkaido hardwood mixed wood chips (volume weight: 500 kg / m 3 ), and the basis weight was 135 g / m 2 and thickness from this pulp. A 270 μm (base paper density: 0.5 g / m 3 ) base paper for laminate was prepared, and its total pore volume, pore size distribution and impregnation were measured. Furthermore, the impregnating workability of this base paper was evaluated by a prepreg manufacturing apparatus. The results are shown in Table 1.
比較例２ 比較例１と同じパルプから坪量135g/m2、厚さ300μｍ
（原紙密度:0.45g/cm3）の積層板用原紙を抄造し、その
全空孔容積、孔径分布および含浸性を測定した。さら
に、プリプレグ製造装置により、含浸作業性の評価を行
った。結果を第１表に示す。Comparative Example 2 From the same pulp as Comparative Example 1, a basis weight of 135 g / m 2 and a thickness of 300 μm
(Base paper density: 0.45 g / cm 3 ) A base paper for a laminate was prepared, and its total pore volume, pore size distribution and impregnation were measured. Further, the impregnating workability was evaluated using a prepreg manufacturing apparatus. The results are shown in Table 1.
第１表から明らかなように、比較例1,2において得ら
れた比較原紙に対し、実施例１〜６で得られた本発明の
含浸用原紙は、含浸性が高く、含浸作業性も良好であっ
た。 As is clear from Table 1, the base paper for impregnation of the present invention obtained in Examples 1 to 6 has a high impregnation property and a good impregnation workability with respect to the comparative base paper obtained in Comparative Examples 1 and 2. Met.
本発明の含浸原紙は、粘性の高い樹脂液の迅速な含浸
を可能とするものであり、また、樹脂が紙層表面に残存
して粘着性を呈するなどのトラブルを発生することがな
い。従って本発明の含浸用原紙は種々の積層体用原紙、
および樹脂含浸紙用原紙として有効なものである。The impregnated base paper of the present invention enables rapid impregnation of a highly viscous resin solution, and does not cause troubles such as the resin remaining on the surface of the paper layer and exhibiting tackiness. Therefore, the base paper for impregnation of the present invention is various base papers for laminates,
And it is effective as a base paper for resin-impregnated paper.
第１図は、本発明に用いられるパルプ繊維の断面形状を
示す説明図である。 Ｌ……繊維のルーメン（内腔）の径、 ｔ……細胞壁の厚さ。FIG. 1 is an explanatory diagram showing a cross-sectional shape of a pulp fiber used in the present invention. L: diameter of fiber lumen (lumen), t: thickness of cell wall.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 奥島 俊介 東京都江東区東雲１丁目10番６号 王子 製紙株式会社中央研究所内 (56)参考文献 特開 昭57−82597（ＪＰ，Ａ) ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shunsuke Okushima 1-10-6 Shinonome, Koto-ku, Tokyo Oji Paper Co., Ltd. Central Research Laboratory (56) References JP-A-57-82597 (JP, A)
Claims (1)
１種のパルプ繊維を、10〜100重量％の含有率で含み、
かつ多数の空孔を有する原紙であって、その全空孔容積
に対する、15μｍ以上の換算孔径を有する空孔の合計容
積の比が、40％〜80％であることを特徴とする含浸用原
紙1. A pulp fiber comprising at least one pulp fiber having a Runkel ratio of 1.0 or more in a content of 10 to 100% by weight,
And a base paper having a large number of pores, wherein the ratio of the total volume of the pores having a converted pore size of 15 μm or more to the total pore volume is 40% to 80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21843888A JP2752093B2 (en) | 1988-09-02 | 1988-09-02 | Base paper for impregnation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21843888A JP2752093B2 (en) | 1988-09-02 | 1988-09-02 | Base paper for impregnation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0268394A JPH0268394A (en) | 1990-03-07 |
| JP2752093B2 true JP2752093B2 (en) | 1998-05-18 |
Family
ID=16719915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21843888A Expired - Lifetime JP2752093B2 (en) | 1988-09-02 | 1988-09-02 | Base paper for impregnation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2752093B2 (en) |
-
1988
- 1988-09-02 JP JP21843888A patent/JP2752093B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0268394A (en) | 1990-03-07 |
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