JP4339915B2 - Low density process paper - Google Patents

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JP4339915B2
JP4339915B2 JP2008028360A JP2008028360A JP4339915B2 JP 4339915 B2 JP4339915 B2 JP 4339915B2 JP 2008028360 A JP2008028360 A JP 2008028360A JP 2008028360 A JP2008028360 A JP 2008028360A JP 4339915 B2 JP4339915 B2 JP 4339915B2
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裕明 湯浅
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Daio Paper Corp
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本発明は、プリント配線板用途の基板として利用される積層板等を製造される工程において使用される工程合紙に関し、特にクッション性、低発塵性にすぐれ、また古紙原料にリサイクル可能な低密度工程紙に関するものである。   The present invention relates to a process paper used in a process for producing a laminated board or the like used as a substrate for printed wiring boards, and in particular, has excellent cushioning properties and low dust generation properties, and can be recycled to raw paper raw materials. It relates to density process paper.

従来より、特にプリント配線板用の積層板に用いられる積層板原紙として、例えば特許文献1に示されるように、エポキシ樹脂、フェノール樹脂などの熱硬化性樹脂を含浸させ、これを加熱乾燥して半硬化樹脂の状態にし、さらにこれを複数枚積層し、金属箔と共に熱圧成形することにより製造された無塵紙等が用いられている。   Conventionally, as a laminate base paper used for a laminate for a printed wiring board, for example, as shown in Patent Document 1, it is impregnated with a thermosetting resin such as an epoxy resin or a phenol resin, and this is heated and dried. Dust-free paper or the like produced by making a semi-cured resin, further laminating a plurality of these, and hot pressing with a metal foil is used.

熱圧成形とは、熱圧成形の対象物すなわちプレス対象物を熱板あるいは鏡板と呼ばれるステンレス鋼板のプレス板の間に挟みこみ、一定の圧力と熱をかけて成形する方法である。このとき、精度のよい成型品を得るために、プレス対象物とプレス板との間に平板状の成型熱プレス用クッション材を介在させてプレス対象物に加えられる高圧及び高熱がプレス対象物の全面に均一に亘るようにすることが通常行われている。   The hot pressing is a method in which an object to be hot pressed, that is, an object to be pressed, is sandwiched between press plates of stainless steel plates called hot plates or mirror plates, and is formed by applying a certain pressure and heat. At this time, in order to obtain an accurate molded product, a high-pressure and high heat applied to the press object by interposing a flat molding heat press cushion material between the press object and the press plate It is common practice to make it even over the entire surface.

この熱圧成形される際に使用される成型熱プレス用クッション材(工程合紙)として、従来より、ガラス繊維布、ガラス不織布などのガラス繊維系のもの、クラフト紙、リンター紙などのセルロース系繊維を主体とした紙、石綿布などの無機質繊維系のシート状または帯状物のものが使用されている。これらの中でも特に、コスト等の観点から、クラフト紙が用いられることが多い。   Conventionally, as a cushioning material for molding hot press (process slip paper) used in this hot-press molding, glass fiber fabrics such as glass fiber cloth and glass nonwoven fabric, and cellulose systems such as kraft paper and linter paper Inorganic fiber-based sheet-like or belt-like materials such as fiber-based paper and asbestos cloth are used. Among these, kraft paper is often used from the viewpoint of cost and the like.

しかしながら、このような従来の工程合紙は、主として熱圧成形における、金属箔の表面および熱圧成形機の金属表面の保護を目的としているため、金属表面からの剥離性が悪く、また剛性も悪く、合紙抜取り作業が円滑に行えないという問題があった。さらにクッション性が悪く、プリント配線板用の積層板を損傷させるといった問題があった。   However, such conventional process slips are mainly for the purpose of protecting the surface of the metal foil and the metal surface of the hot-press molding machine in hot-press molding, so that the peelability from the metal surface is poor and the rigidity is also low. Unfortunately, there was a problem that the slip sheet removal operation could not be performed smoothly. Furthermore, there was a problem that the cushioning property was poor and the laminated board for the printed wiring board was damaged.

そこで、クッション性を有する板紙として、例えば特許文献2に示される嵩高板紙や、特許文献3に示される低密度紙等が提案され、実用化されている。このような嵩高な板紙は、熱伝導率に関わる表裏均一な空気層を得るために原料パルプ中に嵩高剤を含有させる、嵩高な特性を持つ機械パルプ、針葉樹パルプを含有させる、原料パルプのフリーネスを高くする、抄紙工程におけるプレス線圧、カレンダー線圧を低くする等の手段が用いられている。しかしながら、いずれの手段もパルプ繊維同士の絡み合いを弱くする、又は少なくするものであり、その結果、クッション性には優れるものの、繊維間強度の低下を招くため、発塵が多く、積層板が損傷するという問題を解決することはできなかった。   Therefore, as a paperboard having cushioning properties, for example, a bulky paperboard shown in Patent Document 2, a low-density paper shown in Patent Document 3, and the like have been proposed and put into practical use. Such bulky paperboard contains a bulking agent in the raw pulp to obtain a uniform air layer on both sides of the thermal conductivity, mechanical pulp with soft properties, softwood pulp freeness Means such as increasing the press line pressure and the calender line pressure in the paper making process are used. However, either means weakens or reduces the entanglement between the pulp fibers, and as a result, although it has excellent cushioning properties, it causes a decrease in inter-fiber strength. The problem of doing was not able to be solved.

また、近年の電気製品の薄型化・小型化によりIC、コンデンサー、抵抗器などの電気部品の装着密度が高くなり、プリント配線の導体パターンの細線化が進んできている。従って、熱圧成形において、積層板に大きな寸法変化やそり・ねじれ・キズなどの変形が生じた場合、工程上でトラブルが発生すると共に、製品が実用に供し得なくなる可能性もある。このため、積層板にも電気的性能はもちろんのこと、積層板の加工工程における寸法変化や、そり・ねじれ・キズなどの変形防止に関する要求がますます強くなってきている。   In addition, with the recent thinning and miniaturization of electrical products, the mounting density of electrical components such as ICs, capacitors, resistors, etc. has increased, and the conductor patterns of printed wiring have been made thinner. Therefore, when a large dimensional change or deformation such as warping, twisting, or scratching occurs in the laminated plate during hot pressing, troubles may occur in the process and the product may not be put to practical use. For this reason, not only the electrical performance of laminates but also the demands for preventing deformation such as warpage, torsion, and scratches in the machining process of laminates is increasing.

しかしながら、上述した例えば引用文献2や3等に記載の嵩高板紙等は、積層板の加工工程において工程合紙として使用すると、寸法変化することがあり、部品の装着密度のより高い電気機器用のプリント配線板や高精度を必要とするコンピューターなどの電子機器用のプリント配線板用として熱圧成形機における工程合紙としては適していない。また、このような工程合紙は資源の有効利用や環境配慮面等の観点からも問題がある。   However, the above-described bulky paperboard described in, for example, the cited documents 2 and 3 may change in dimensions when used as a process slip sheet in a laminated board processing step, and is used for electrical equipment with a higher component mounting density. It is not suitable as a process slip sheet in a hot-pressure molding machine for printed wiring boards or printed wiring boards for electronic devices such as computers that require high precision. Such process slips also have problems from the viewpoint of effective use of resources and environmental considerations.

特開2003−211614号公報Japanese Patent Laid-Open No. 2003-21614 特開2001−73299号公報JP 2001-73299 A 特開平11−200282号公報JP-A-11-200222

本発明は、上述したような実情に鑑みてなされたもので、その目的とするところは、プリント配線用の積層板の加工工程における熱圧成形機にて、積層板が大きく寸法変化し、そり・ねじれ・キズなどの変形の発生を防止すると共に、クッション性を有し、発塵が少なく、かつ使用後においてもリサイクル可能な低密度工程紙を提供することにある。   The present invention has been made in view of the above-described circumstances, and the object of the present invention is to use a hot-press molding machine in a process for processing a laminated board for printed wiring, in which the laminated board undergoes a large dimensional change and warpage. The object is to provide low-density process paper that prevents deformation such as twisting and scratching, has cushioning properties, generates little dust, and can be recycled even after use.

本発明の上記目的は、少なくとも表層、裏層、及び前記表層と前記裏層との間に配置される1層又は複数層から成る中間層を有する低密度工程紙であって、前記中間層の少なくとも1層に平均粒子径が5〜15μmで、75〜130℃の加熱により膨張を開始する熱発泡性粒子を、予め熱発泡性粒子とカチオン性高分子樹脂とを混合(凝集)して得た熱発泡性粒子の凝集体とし、前記中間層のパルプ固形分に対して、固形分換算で1〜8質量%配合し、かつ、前記熱発泡粒子の定着剤として、ポリアクリルアミド系又はポリエチレンイミン系の高分子をパルプ固形分換算で0.1〜0.8質量%含有させて発泡層とし、前記表層及び前記裏層を構成する原料はNBKP及び/又はLBKPからなるクラフトパルプであり、また、前記表層、前記裏層及び前記中間層に使用される原料パルプの濾水度が500〜600ccであり、密度が0.45〜0.55g/cm、圧縮紙厚残存率が55〜61%、前記表層及び前記裏層の熱伝導率差が0.001W/mk以下、SEMI G67−0996に準じた、引裂き試験による10μm以上の発塵量が500個/cm以下であることを特徴とする低密度工程紙を提供することによって達成される。
The above object of the present invention is a low-density process paper having at least a surface layer, a back layer, and an intermediate layer composed of one or more layers disposed between the surface layer and the back layer. Heat-expandable particles having an average particle diameter of 5 to 15 μm in at least one layer and starting to expand by heating at 75 to 130 ° C. are obtained by previously mixing (aggregating) the heat-expandable particles and the cationic polymer resin. and aggregates of the heat expandable particles, relative to the pulp solid content of the intermediate layer, blended 1-8 wt% in terms of solid content, and, as a fixing agent for the thermally expandable particles, polyacrylamide or polyethyleneimine 0.1 to 0.8% by mass of a polymer based on pulp solid content is used to form a foam layer, and the raw material constituting the surface layer and the back layer is NBKP and / or LBKP, and , The surface layer, before Freeness of pulp used for the backing layer and the intermediate layer is 500~600Cc, density 0.45~0.55g / cm 3, compressed paper thickness residual ratio was 55 to 61%, the surface layer and Low density process characterized in that thermal conductivity difference of said back layer is 0.001 W / mk or less, and dust generation amount of 10 μm or more by tear test according to SEMI G67-0996 is 500 pieces / cm 2 or less This is accomplished by providing paper.

本発明に係る低密度工程紙によれば、少なくとも表層、裏層、及び表層と裏層との間に配置される1層又は複数層から成る中間層を有し、中間層の少なくとも1層に熱発泡性粒子を配合して発泡層とし、表層及び裏層を構成する原料をNBKP及び/又はLBKPからなるクラフトパルプとしたので、クッション性に優れ、熱伝導性の表裏差が少なく、発塵量の少ない低密度工程紙とすることができるので、プリント配線用の基板として利用される積層板を製造する工程における熱圧成形時に使用される工程合紙(クッション材)として用いることができる。   The low-density process paper according to the present invention has at least a surface layer, a back layer, and an intermediate layer composed of one or more layers disposed between the front layer and the back layer, and at least one of the intermediate layers. The foamed layer is formed by blending thermally foamable particles, and the raw material constituting the surface layer and back layer is kraft pulp made of NBKP and / or LBKP. Since it can be used as a low-density process paper with a small amount, it can be used as a process slip sheet (cushion material) used at the time of hot-pressure molding in the process of manufacturing a laminated board used as a printed wiring board.

以下、本発明に係る低密度工程紙について、表層、1層の中間層、及び裏層の3層の紙層から成る場合を例に詳細に説明する。なお、本発明に係る低密度工程紙は、以下の実施形態に限定されるものではなく、特許請求の範囲を逸脱しない範囲内において、その構成を適宜変更できることはいうまでもない。   Hereinafter, the low-density process paper according to the present invention will be described in detail by taking, as an example, a case where the low-density process paper is composed of three paper layers of a surface layer, one intermediate layer, and a back layer. The low-density process paper according to the present invention is not limited to the following embodiments, and it is needless to say that the configuration can be changed as appropriate without departing from the scope of the claims.

本発明に係る低密度工程紙(以下、「本低密度工程紙」という。)は、表層、少なくとも1層の中間層、及び裏層の3層の紙層により構成され、中間層の原料パルプ中に熱発泡性粒子を配合する。   The low-density process paper according to the present invention (hereinafter referred to as “the present low-density process paper”) is composed of a three-layer paper layer of a surface layer, at least one intermediate layer, and a back layer, and is a raw material pulp of the intermediate layer A heat-expandable particle is mix | blended in it.

本低密度工程紙は、このように多層抄きとすることにより、中間層のみに熱発泡性粒子を含有させることができる。すなわち、表層及び裏層には熱発泡性粒子を含有することなく、低密度工程紙を構成することができる。これにより、抄紙工程で熱発泡性粒子を含有しない表層、裏層の湿紙の持つ熱量が中間層の熱発泡性粒子の膨張を加速させることでより安定した熱発泡粒子の発泡体を形成させることができる。また、熱発泡性粒子の発泡体形成後のドライヤー内やドライヤー出口以降の工程において、熱発泡性粒子が紙表面に剥き出しにならない(紙の表面に現れない)ため、発泡粒子や繊維との結合物がドライヤーや用具、ロールの表面等に付着することがなくなる。なお、単層紙の場合には、おのずと熱発泡性粒子が紙表面に剥き出しとなりドライヤーや用具、ロールに付着するため、操業性が低下してしまうほか、抄紙後の製品の発塵が増加してしまうため、プリント配線板用の積層板等の精密機器の加工工程におけるクッション材として用いることができなくなる。   The low-density process paper can be made into a multi-layer paper as described above, so that only the intermediate layer can contain heat-expandable particles. That is, a low density process paper can be comprised, without containing a thermally foamable particle in a surface layer and a back layer. This makes it possible to form a more stable foam of thermally foamable particles by accelerating the expansion of the thermally foamable particles of the intermediate layer by the amount of heat of the wet paper of the front and back layers not containing the thermally foamable particles in the papermaking process. be able to. In addition, in the dryer after forming the foam of thermally foamable particles and in the process after the dryer outlet, the thermally foamable particles are not exposed on the paper surface (does not appear on the paper surface), and thus bonded to the foamed particles and fibers. Objects do not adhere to the surface of the dryer, tools, rolls, etc. In the case of single-layer paper, the heat-expandable particles are naturally exposed on the paper surface and adhere to the dryer, tools, and rolls, resulting in reduced operability and increased dust generation in the product after papermaking. Therefore, it cannot be used as a cushion material in the processing process of precision equipment such as a laminated board for printed wiring boards.

また、本低密度工程紙の中間層の原料パルプ中に、熱発泡性粒子を含有させて中間層をクッション層とし、密度を0.45〜0.55g/cmとして、表裏の熱伝導率の差を少なくした。なお、本低密度工程紙は中間層を2層以上の複数層から構成しても良く、この場合は、中間層の全層に熱発泡性粒子を含有させてクッション層としても良い。すなわち、中間層の少なくとも1層に熱発泡性粒子を含有させてクッション層とすれば、本願発明の目的を達成することができ、クッション性に優れ、熱伝導性の表裏差が少なく、発塵量の少ない低密度工程紙とすることができるので、プリント配線用の基板として利用される積層板を製造する工程における熱圧成形時に使用される工程合紙(クッション材)として好適に用いることができ、かつ使用後においてもリサイクル可能とすることができる。 Moreover, in the raw material pulp of the intermediate layer of the present low-density process paper, thermally foamable particles are contained, the intermediate layer is a cushion layer, the density is 0.45 to 0.55 g / cm 3 , and the thermal conductivity of the front and back sides Reduced the difference. In the low-density process paper, the intermediate layer may be composed of two or more layers. In this case, the entire layer of the intermediate layer may contain thermally foamable particles to form a cushion layer. That is, if at least one intermediate layer contains thermally foamable particles to form a cushion layer, the object of the present invention can be achieved, and the cushioning property is excellent, the thermal conductivity has a small difference in front and back, and the dust generation Since it can be a low-density process paper with a small amount, it can be suitably used as a process slip sheet (cushion material) used at the time of hot-pressure molding in the process of manufacturing a laminated board used as a printed wiring board. And can be recycled after use.

本低密度工程紙の密度が0.45g/cm未満であると繊維間の距離が大きくなるため、繊維間結合が弱くなり、発塵が多く、低初塵性に劣る。一方、密度が0.55g/cmを超えるとクッション性がなくなり、基板状の異物、凹凸を吸収できなくなり、プリント配線板用の積層板を損傷してしまう問題が発生する。 If the density of the low-density process paper is less than 0.45 g / cm 3 , the distance between the fibers becomes large, so that the bond between fibers becomes weak, the amount of dust generation is large, and the low initial dust property is poor. On the other hand, if the density exceeds 0.55 g / cm 3 , the cushioning property is lost, the substrate-like foreign matters and irregularities cannot be absorbed, and there is a problem that the printed wiring board laminate is damaged.

また、熱発泡性粒子は、添加される中間層のパルプ固形分に対して、固形分換算で1〜8質量%、好ましくは2〜5質量%添加される。これにより、圧縮紙厚残存率を55〜61%とすることができ、本低密度工程紙の熱伝導性及び低発塵性の効果のバランスがより優れたものとなる。なお、圧縮紙厚残存率とは、プレス圧縮前の本低密度工程紙の紙厚とプレス圧縮直後の紙厚を測定し、プレス圧縮直後の紙厚をプレス圧縮前の本低密度工程紙の紙厚で除したものであり、元の紙厚(圧縮前の紙厚)に対して残存している紙の割合を表した率を言う。   Moreover, 1-8 mass% in conversion of solid content is added with respect to the pulp solid content of the intermediate | middle layer added, Preferably heat-expandable particle is added 2-5 mass%. Thereby, the residual thickness ratio of the compressed paper can be 55 to 61%, and the balance between the thermal conductivity and the low dusting effect of the low-density process paper becomes more excellent. The compressed paper thickness remaining rate is a measurement of the paper thickness of the low-density process paper before press compression and the paper thickness immediately after press compression, and the paper thickness immediately after press compression is the thickness of the low-density process paper before press compression. It is the ratio of the remaining paper to the original paper thickness (paper thickness before compression) divided by the paper thickness.

中間層の1層当り(中間層が2層以上の複数層で構成されている場合は、熱発泡性粒子が添加される各層の1層当り)の熱発泡性粒子の含有量が1質量%未満であると、熱発泡性粒子が発泡した状態であっても、熱発泡性粒子間の距離が遠くなり、熱発泡性粒子の膨張効果が発揮されず十分な繊維間空隙が得られないため、所定の密度を紙に付与することが難しくなる。一方、1層当りの熱発泡性粒子の含有量が8質量%を超えると、熱発泡性粒子を均一に発泡させるための熱量の調整が困難で発泡不良が発生し、紙面の見栄えが悪化するとともに、製造コストが高くなってしまう。   The content of heat-expandable particles per layer of the intermediate layer (when the intermediate layer is composed of two or more layers, one layer of each layer to which the heat-expandable particles are added) is 1% by mass. If it is less than this, even if the thermally foamable particles are in a foamed state, the distance between the thermally foamable particles is increased, and the expansion effect of the thermally foamable particles is not exhibited, so that sufficient inter-fiber voids cannot be obtained. It becomes difficult to impart a predetermined density to the paper. On the other hand, if the content of heat-expandable particles per layer exceeds 8% by mass, it is difficult to adjust the amount of heat for uniformly foaming the heat-expandable particles, resulting in poor foaming, and the appearance of the paper is deteriorated. At the same time, the manufacturing cost is increased.

本低密度工程紙に使用することができる熱発泡性粒子としては、アクリル系コポリマーを主成分とする熱可塑性合成樹脂で構成された微細粒子外殻内に低沸点溶剤を封入したものである。なお、この熱発泡性粒子は、平均粒径が5〜15μmで、75〜130℃の加熱により膨張を開始するものが好ましい。これにより、本低密度工程紙のクッション性、熱伝導性、低発塵性の効果のバランスがより優れたものとなる。   The heat-expandable particles that can be used in the low-density process paper are those in which a low-boiling solvent is enclosed in a fine particle outer shell made of a thermoplastic synthetic resin mainly composed of an acrylic copolymer. The thermally foamable particles preferably have an average particle diameter of 5 to 15 μm and start to expand upon heating at 75 to 130 ° C. Thereby, the balance of the cushioning property of this low density process paper, thermal conductivity, and the effect of low dust generation becomes more excellent.

外殻を構成する熱可塑性合成樹脂としては、例えば塩化ビニリデン、アクリロニトリル、アクリル酸エステル、メタクリル酸エステル等の共重合体等を挙げることができる。   Examples of the thermoplastic synthetic resin constituting the outer shell include copolymers such as vinylidene chloride, acrylonitrile, acrylic acid ester, and methacrylic acid ester.

また、外殻内に封入される低沸点溶剤としては、例えば、イソブタン、ペンタン、石油エーテル、ヘキサン、低沸点ハロゲン化炭化水素、メチルシラン等を挙げることができる。   Examples of the low boiling point solvent enclosed in the outer shell include isobutane, pentane, petroleum ether, hexane, low boiling point halogenated hydrocarbon, and methylsilane.

このような熱発泡性粒子としては、例えば、松本油脂製薬株式会社製造の「マツモトマイクロスフェアF−20シリーズ」、「同F−30シリーズ」、「同F−36シリーズ」、「同F−46シリーズ」や、日本フィライト株式会社販売の「エクスパンセルWU」、「同DU」などを使用することができるが、本低密度工程紙に使用する熱発泡性粒子はこれらに限定されるものではない。   Examples of such thermally expandable particles include “Matsumoto Microsphere F-20 Series”, “F-30 Series”, “F-36 Series”, and “F-46” manufactured by Matsumoto Yushi Seiyaku Co., Ltd. Series "," Expancel WU "and" Same DU "sold by Nippon Philite Co., Ltd. can be used, but the heat-expandable particles used in this low-density paper are not limited to these. Absent.

しかしながら、本発明においては、一般的に紙乾燥工程の温度が100〜130℃程度であることから、熱発泡性粒子の発泡開始温度は75〜130℃で発泡する低温膨張タイプが好ましい。   However, in the present invention, since the temperature of the paper drying step is generally about 100 to 130 ° C., the low temperature expansion type in which the foaming start temperature of the thermally expandable particles is 75 to 130 ° C. is preferable.

熱発泡性粒子は、外殻を構成する熱可塑性合成樹脂の軟化点以上に加熱され、同時に封入されているイソブタン等の低沸点溶剤が気化し蒸気圧が上昇し、外殻が膨張して粒子が膨張し、膨張時は、内圧と殻の張力・外圧が釣り合って膨張状態が保持される。熱発泡性樹脂は、一般的にはこの状態まで膨張させ、軽量化剤、嵩高化剤、クッション剤、断熱剤などとして利用されている。この膨張状態の熱発泡性樹脂にさらに熱を加えて、過剰に熱を加えた場合には、膨張して薄くなった殻からガスが透過拡散し、内圧よりも殻の張力・外圧が大きくなってしまい、発泡した樹脂が収縮してしまう。   The thermally foamable particles are heated above the softening point of the thermoplastic synthetic resin constituting the outer shell, and at the same time, the low boiling point solvent such as isobutane encapsulated is vaporized to increase the vapor pressure, and the outer shell expands. During expansion, the internal pressure and the tension / external pressure of the shell are balanced to maintain the expanded state. Thermally foamable resins are generally expanded to this state and used as lightening agents, bulking agents, cushioning agents, heat insulating agents, and the like. If additional heat is applied to this expanded thermo-expandable resin, and gas is permeated and diffused from the expanded and thin shell, the tension and external pressure of the shell become larger than the internal pressure. As a result, the foamed resin shrinks.

本低密度工程紙に使用される熱発泡性粒子は、乾燥工程でドライヤーにより発泡させるが、上記理由により、発泡開始温度が75〜130℃の低温膨張タイプの熱発泡性粒子を用いることが好ましいのである。すなわち、発泡開始温度が75℃未満の熱発泡性粒子であると、乾燥工程のドライヤーにより発泡させた場合、上述したように一旦膨張した粒子が再び収縮してしまい、熱伝導率に関わる均一な空気層を中間層に付与することが難しくなる。   The heat-expandable particles used in the low-density process paper are foamed by a dryer in the drying process. For the above reasons, it is preferable to use low-temperature expansion type heat-expandable particles having a foaming start temperature of 75 to 130 ° C. It is. That is, when the foaming start temperature is less than 75 ° C., when the foaming is performed by the dryer in the drying process, the once expanded particles are contracted again as described above, and the thermal conductivity is uniform. It becomes difficult to apply an air layer to the intermediate layer.

さらに中間層の原料パルプ中に添加される熱発泡性粒子は、予め熱発泡性粒子をカチオン性高分子樹脂で混合(凝集)させた凝集体が用いられる。以下、本発明における熱発泡性粒子とカチオン性高分子樹脂の混合(凝集)について記述する。   Further, as the thermally foamable particles added to the raw material pulp of the intermediate layer, an aggregate obtained by mixing (aggregating) the thermally foamable particles with a cationic polymer resin in advance is used. Hereinafter, mixing (aggregation) of the thermally foamable particles and the cationic polymer resin in the present invention will be described.

熱発泡性粒子とカチオン性高分子樹脂とを混合(凝集)して熱発泡性粒子の凝集体を得るには、熱発泡性粒子、カチオン性高分子樹脂、及び水で形成されるスラリーの濃度を5〜30%、好ましくは10〜20%とする。すなわち、熱発泡性粒子とカチオン性高分子樹脂とが混合(凝集)されたスラリーの濃度が5%未満であるとスラリーの粘性が低く、熱発泡性粒子の凝集体ができず、歩留りが低下する。一方、熱発泡性粒子とカチオン性高分子樹脂の混合(凝集)されたスラリー濃度が30%を超えると、スラリーの粘性が高くなりすぎて分散状態が悪くなり、粒状で配合されるため、低密度工程紙を製造した際に異物として検出されてしまう。   In order to obtain an aggregate of thermally foamable particles by mixing (aggregating) the thermally foamable particles and the cationic polymer resin, the concentration of the slurry formed by the thermally foamable particles, the cationic polymer resin, and water Is 5 to 30%, preferably 10 to 20%. That is, if the concentration of the slurry in which the heat-expandable particles and the cationic polymer resin are mixed (aggregated) is less than 5%, the viscosity of the slurry is low, the aggregate of the heat-expandable particles cannot be formed, and the yield decreases. To do. On the other hand, if the concentration of the slurry in which the heat-expandable particles and the cationic polymer resin are mixed (aggregated) exceeds 30%, the viscosity of the slurry becomes too high and the dispersion state is deteriorated, and it is blended in a granular form. When the density process paper is manufactured, it is detected as a foreign object.

なお、熱発泡性粒子は自己定着しないため定着剤を用いることが好ましい。この定着剤としては、ポリアクリルアミド系紙力剤、ポリアミドエピクロロヒドリン系紙力剤、ポリエチレンイミン系紙力剤、澱粉,酸化澱粉,カルボキシメチル化澱粉等の澱粉類、植物ガム、ポリビニルアルコール、カルボキシメチルセルロース等、公知の種々のものを用いることができる。これらの中でも特に、ポリアクリルアミド系又はポリエチレンイミン系の高分子薬品が好ましい。具体的には、例えばハクトロンKC−100(伯東株式会社製)などのカチオン性の定着剤、またはアニオン性のセラフィックスST(明成化学工業社製)とカチオン性のファイレックスM(明成化学工業社製)とを併用したものが好ましく用いられる。   Note that it is preferable to use a fixing agent because the thermally foamable particles do not self-fix. As this fixing agent, polyacrylamide type paper strength agent, polyamide epichlorohydrin type paper strength agent, polyethyleneimine type paper strength agent, starches such as starch, oxidized starch, carboxymethylated starch, plant gum, polyvinyl alcohol, Various known materials such as carboxymethyl cellulose can be used. Of these, polyacrylamide-based or polyethyleneimine-based polymer chemicals are particularly preferable. Specifically, for example, a cationic fixing agent such as Haktron KC-100 (manufactured by Hakuto Co., Ltd.) or an anionic ceramic fix ST (manufactured by Meisei Chemical Co., Ltd.) and a cationic Phyrex M (Meisei Chemical Industry Co., Ltd.) And a combination thereof are preferably used.

また、定着剤の含有量は、パルプ固形分に対して固形分換算で0.1〜0.8質量%、好ましくは0.2〜0.5質量%含有させる。なお、アニオン性の定着剤とカチオン性の定着剤とを併用する場合には、その合計量が前記含有量となるようにする。なお、定着剤の含有量が0.1質量%未満であると十分な定着効果がなく、0.8質量%を超えると、凝集効果が高くなり、パルプがフロックとなってしまい、地合が悪く、熱発泡性粒子の定着効果が頭打ちとなり、コストに対する効果を発揮できなくなる。   Further, the content of the fixing agent is 0.1 to 0.8% by mass, preferably 0.2 to 0.5% by mass in terms of solid content with respect to the pulp solid content. When an anionic fixing agent and a cationic fixing agent are used in combination, the total amount is set to the above content. When the content of the fixing agent is less than 0.1% by mass, there is no sufficient fixing effect. When the content exceeds 0.8% by mass, the aggregating effect is increased, and the pulp becomes flock, and the formation is Unfortunately, the fixing effect of the heat-expandable particles reaches a peak, and the cost effect cannot be exhibited.

本低密度工程紙は、中間層の原料パルプに熱発泡性粒子を予めカチオン性高分子樹脂で混合(凝集)させた凝集体を含有することにより、クッション性、熱伝導性、低発塵性に優れるようになるが、表面強度、層間強度が低下してしまう。このため、表層及び裏層を構成する原料パルプとしてNBKP及び/又はLBKPからなるクラフトパルプを用い、またカチオン性PAMを内添する。   This low-density process paper contains cushions, thermal conductivity, low dust generation by containing aggregates in which heat-expandable particles are mixed (aggregated) with a cationic polymer resin in the raw pulp of the intermediate layer in advance. However, the surface strength and interlayer strength are reduced. For this reason, kraft pulp made of NBKP and / or LBKP is used as a raw material pulp constituting the surface layer and the back layer, and cationic PAM is internally added.

本低密度工程紙の表層及び裏層を構成する原料パルプとしては、広葉樹晒クラフトパルプ(LBKP)、針葉樹晒クラフトパルプ(NBKP)、広葉樹未晒クラフトパルプ(LUKP)、針葉樹未晒クラフトパルプ(NUKP)、広葉樹亜硫酸パルプ、針葉樹亜硫酸パルプ、等の木材繊維を含む主原料として、化学的に処理されたパルプ、木材以外の繊維原料であるケナフ、麻、葦等の非木材繊維を主原料として化学的に処理されたパルプやチップを機械的にパルプ化したグランドパルプ、木材またはチップに化学薬品を添加しながら機械的にパルプ化したケミグランドパルプ、及びチップを柔らかくなるまで蒸解した後、レファイナー等でパルプ化したセミケミカルパルプ等がある。しかしながら、本低密度工程紙は、主にプリント配線用の積層板の加工工程におけるクッション材として用いられるため、紙からの発塵・異物がないことが求められている。従って、非木材パルプはパルプ強度が弱く、発塵性が高いこと、未晒パルプは晒パルプに比べて異物、ノットが多いこと、そして機械パルプは微細繊維の割合が多く、この微細繊維に起因する発塵が多いことなどから、LBKP、NBKPのクラフトパルプを用いる。さらに、本技術分野における使用方法においては、LBKPとNBKPとでは、NBKPよりもLBKPの方が発塵量は少ないが、繊維間強度や断裁適性や剛性など他の品質とのバランスの点から、特に表層及び裏層の各層に使用される原料パルプの20〜40質量%をNBKPとすることが好ましい。   The raw pulp constituting the surface layer and the back layer of the low-density processed paper includes hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), hardwood unbleached kraft pulp (LUKP), and softwood unbleached kraft pulp (NUKP) ), Main raw materials containing wood fibers such as hardwood sulfite pulp, coniferous sulfite pulp, etc., chemically treated pulp, non-wood fibers such as kenaf, hemp, straw, etc. which are fiber raw materials other than wood Pulp, which has been mechanically pulped from treated pulp and chips, chemi-ground pulp, which has been mechanically pulped with chemicals added to wood or chips, and digesters until chips are softened, then refiner, etc. Semi-chemical pulps pulped with However, since the low-density process paper is mainly used as a cushioning material in a process for processing a laminated board for printed wiring, it is required that there is no dust generation / foreign matter from the paper. Therefore, non-wood pulp has weak pulp strength and high dusting properties, unbleached pulp has more foreign matter and knots than bleached pulp, and mechanical pulp has a higher proportion of fine fibers, which is attributed to these fine fibers. LBKP or NBKP kraft pulp is used because it generates a lot of dust. Furthermore, in the method of use in this technical field, in LBKP and NBKP, LBKP generates less dust than NBKP, but in terms of balance with other qualities such as inter-fiber strength, cutting suitability and rigidity, In particular, it is preferable to use NBKP at 20 to 40% by mass of the raw material pulp used for the front and back layers.

なお、本低密度工程紙の中間層に使用される原料パルプとしては、古紙を100%配合した原料パルプであっても、熱発泡性粒子の膨張に影響を与えることなく使用できる。しかしながら、本低密度工程紙は、主に上述したようにプリント配線用の積層板等の加工工程におけるクッション材として用いられるため、古紙を100%配合したパルプであると、微細繊維の多さから発塵量が多くなるとともに、濾水性が悪くなり、生産スピードが落ち、また熱発泡粒子の発泡体形成不良が発生し、紙面の見栄えが悪化してしまう。従って、古紙パルプの配合率を40%未満とした原料パルプを用いることが好ましい。さらに、本技術分野における使用方法においては、LBKPとNBKPとでは、NBKPよりもLBKPの方が発塵量は少ないが繊維間強度や断裁適性や剛性など他の品質とのバランスの点から、特に中間層に使用する原料パルプの20〜40質量%をNBKPとすることが好ましい。   In addition, as a raw material pulp used for the intermediate | middle layer of this low-density process paper, even if it is a raw material pulp which mix | blended 100% of used paper, it can be used, without affecting the expansion | swelling of a heat-expandable particle. However, since the low-density process paper is mainly used as a cushioning material in the processing process of a laminated board for printed wiring as described above, the pulp containing 100% used paper has a lot of fine fibers. As the amount of dust generation increases, the drainage rate deteriorates, the production speed decreases, the foam formation defect of the thermally foamed particles occurs, and the appearance of the paper surface deteriorates. Therefore, it is preferable to use raw material pulp having a waste paper pulp content of less than 40%. Furthermore, in the method of use in the present technical field, LBKP and NBKP have a smaller amount of dust generation than LBKP, but in terms of balance with other qualities such as inter-fiber strength, cutting suitability and rigidity. It is preferable that 20-40 mass% of the raw material pulp used for the intermediate layer is NBKP.

表層及び裏層に使用される原料パルプの濾水度は、500〜600ccとするのが好ましい。濾水度が600ccを超えると、繊維間の空隙が増加し、繊維間結合力が低下するため、表面強度が低下してしまう。このため、摩擦により容易に紙粉が発生したり、表層剥離の問題が発生し、また、低密度工程紙の発塵量の増加が著しくなるため、本低密度塗工紙を、プリント配線用の基板等の加工工程に使用することが難しくなる。さらに、低密度塗工紙の表面が凸凹で紙厚が均一となるため、プレス成型時の圧と熱が紙表面に均一にかからなくなるという問題も生じる。一方、濾水度が500cc未満であると繊維間の結合力は増すものの、繊維間の空隙が減少しすぎてしまい、繊維が緻密になるため、一定の紙厚を出そうとすると坪量を増やさなければならず、紙の密度が増加してしまう。この結果、クッション性に劣る工程紙となり、プレス成型時の熱伝導性に問題が生じる。   The freeness of the raw pulp used for the surface layer and the back layer is preferably 500 to 600 cc. When the freeness exceeds 600 cc, voids between the fibers increase and the bonding strength between the fibers decreases, so that the surface strength decreases. For this reason, paper dust is easily generated due to friction, surface peeling problems occur, and the amount of dust generation in low-density process paper increases significantly, so this low-density coated paper is used for printed wiring. It becomes difficult to use it for the processing steps of the substrate. Furthermore, since the surface of the low density coated paper is uneven and the paper thickness is uniform, there is a problem that pressure and heat during press molding are not uniformly applied to the paper surface. On the other hand, if the freeness is less than 500 cc, the bonding strength between the fibers increases, but the gaps between the fibers decrease too much, and the fibers become dense. It must be increased and the paper density will increase. As a result, the process paper is inferior in cushioning properties, and there is a problem in thermal conductivity during press molding.

また、中間層に使用される原料パルプの濾水度は500〜600ccとするのが好ましい。濾水度が600ccを超えると繊維間の空隙が増し、繊維間結合力が低下するため、低密度工程紙の発塵量の増加が著しくなるとともに、熱発泡性粒子による均一な空気層が形成されず、熱伝導性にも問題が生じる。一方、濾水度が500cc未満であると、繊維間の結合力は増すものの、繊維間の空隙が減少しすぎてしまい、繊維が緻密になるため、一定の紙厚を出そうとすると坪量を増やさなければならず、紙の密度が増加してしまう。この結果、クッション性に劣る低密度工程紙となり、プレス成型時の熱伝導性に問題が生じる。   Moreover, it is preferable that the drainage degree of the raw material pulp used for an intermediate | middle layer shall be 500-600cc. When the freeness exceeds 600 cc, the gap between fibers increases and the bonding force between fibers decreases, so the amount of dust generated from low-density process paper increases significantly and a uniform air layer is formed by thermally foamable particles. This also causes a problem in thermal conductivity. On the other hand, if the freeness is less than 500 cc, the bonding strength between the fibers increases, but the gap between the fibers decreases too much and the fibers become dense. Must be increased, which increases the density of the paper. As a result, it becomes a low-density process paper having inferior cushioning properties, which causes a problem in thermal conductivity during press molding.

また、本低密度工程紙においては表層及び裏層に特定のカチオン性ポリアクリルアマイド(カチオン性PAM)を含有させる。なお、本低密度工程紙は、上述したように多層抄きであるので、表層及び裏層のみにカチオン性PAMを含有させることができる。   Further, in the present low density process paper, a specific cationic polyacrylamide (cationic PAM) is contained in the surface layer and the back layer. In addition, since this low density process paper is a multilayer papermaking as mentioned above, cationic PAM can be contained only in a surface layer and a back layer.

このように、本低密度工程紙は、中間層の原料パルプ中に熱発泡性粒子を含有し、表層及び裏層を構成する原料パルプとしてNBKP及び/又はLBKPから成るクラフトパルプを用い、またカチオン変性PAMを含有することによって、表層剥離によるトラブルが生じず、しかもクッション性、熱伝導性、低発塵性に優れるという相反する品質を満足させることができたものである。   Thus, this low-density process paper contains thermally foamable particles in the raw material pulp of the intermediate layer, uses kraft pulp made of NBKP and / or LBKP as the raw material pulp constituting the surface layer and the back layer, and is also cationic. By containing the modified PAM, troubles due to peeling of the surface layer do not occur, and it is possible to satisfy the conflicting quality of being excellent in cushioning properties, thermal conductivity, and low dust generation.

上述した表層、中間層、及び裏層の各層の原料パルプが、公知の抄紙工程、例えばワイヤーパート、プレスパート、ドライヤーパート、サイズプレス、カレンダーパートなどを経て本低密度工程紙が形成される。   The raw pulp of each of the surface layer, the intermediate layer, and the back layer described above is subjected to a known paper making process, for example, a wire part, a press part, a dryer part, a size press, a calendar part, and the like to form the present low density process paper.

なお、本低密度工程紙の抄紙方法については、特に限定されるものではないので、酸性抄紙法、中性抄紙法、アルカリ性抄紙法のいずれであっても良い。しかしながら、一般的な抄紙法は、酸性の抄紙工程で硫酸バンドを使用し、薬品の歩留まりを向上させる方法であるが、この抄紙法での紙のpHを測定すると約4付近となり、硫酸イオンの影響で、低密度工程紙の劣化が加速される。またこのため、クッション層である中間層に熱発泡性粒子を定着剤で定着させ、クッション機能を効率的に発揮させるため、熱水抽出pHが5〜9となるように中性抄紙で製造することが好ましい。   The paper making method of the present low density process paper is not particularly limited, and any of acidic paper making method, neutral paper making method and alkaline paper making method may be used. However, the general papermaking method uses a sulfuric acid band in an acidic papermaking process to improve the yield of chemicals. However, when the pH of the paper in this papermaking method is measured, it becomes about 4 and the sulfate ion Under the influence, deterioration of the low density process paper is accelerated. For this reason, in order to fix the heat-foamable particles to the intermediate layer, which is the cushion layer, with a fixing agent and to effectively exhibit the cushion function, the paper is manufactured by neutral papermaking so that the hot water extraction pH is 5-9. It is preferable.

また、抄紙機も特に限定されるものではないので、例えば長網抄紙機、ツインワイヤ抄紙機、円網抄紙機、円網短網コンビネーション抄紙機等の公知の種々の抄紙機を使用することができる。   Also, since the paper machine is not particularly limited, for example, various known paper machines such as a long net paper machine, a twin wire paper machine, a circular net paper machine, and a short net combination machine can be used. it can.

また、低密度工程紙の坪量に占めるクッション層の付け量の割合を60〜80質量%としたので、クッション性、熱伝導性、低発塵性の効果のバランスがより優れるものとすることができる。   Moreover, since the ratio of the applied amount of the cushion layer to the basis weight of the low-density process paper is 60 to 80% by mass, the balance of the effects of cushioning properties, thermal conductivity, and low dust generation properties should be more excellent. Can do.

以上のように構成された本低密度工程紙は、表裏の熱伝導率の差を少なくすることができる。すなわち、表裏の熱伝導率差を0.001W/mk以下とすることができる。また、本低密度工程紙はSEMI G67−0996に準じた、引裂き試験による10μm以上の発塵量が500個/cm以下、さらには200個/cm以下とすることができる。従って、本低密度工程紙を、プリント配線用の基板として利用される積層板を製造する工程における熱圧成形時に使用される工程合紙(クッション材)として好適に用いることができる。 The present low-density process paper configured as described above can reduce the difference in thermal conductivity between the front and back surfaces. That is, the difference in thermal conductivity between the front and back surfaces can be 0.001 W / mk or less. Further, according to SEMI G67-0996, the low density process paper can have a dust generation amount of 10 μm or more by a tear test of 500 pieces / cm 2 or less, and further 200 pieces / cm 2 or less. Therefore, this low-density process paper can be suitably used as a process slip sheet (cushion material) used at the time of hot-pressure molding in the process of manufacturing a laminated board used as a printed wiring board.

以上、本低密度工程紙について、紙層が表層、中間層及び裏層の3層から成る場合について説明したが、本発明はこのような低密度工程紙に限らず、例えば中間層を2層とし、4層の紙層から成る低密度工程紙や、中間層を3層とし、5層の紙層から成る低密度工程紙であっても良い。なお、複数層の中間層を有する低密度工程紙においては、中間層の全てをクッション層し、使用目的等に応じて、中間層がクッション層として形成されていれば良い。   As described above, the case where the paper layer is composed of the three layers of the surface layer, the intermediate layer, and the back layer has been described for the low density process paper. Also, a low-density process paper composed of four paper layers or a low-density process paper composed of three intermediate layers and five paper layers may be used. In the low-density process paper having a plurality of intermediate layers, all the intermediate layers may be cushion layers, and the intermediate layers may be formed as cushion layers according to the purpose of use or the like.

本発明に係る低密度工程紙の効果を確認するため、以下のような各種の試料を作製し、これらの各試料に対する品質を評価する試験を行った。なお、本実施例において、配合、濃度等を示す数値は、固形分又は有効成分の質量基準の数値である。また、本実施例で示すパルプ・薬品等は一例にすぎないので、本発明はこれらの実施例によって制限を受けるものではなく、適宜選択可能であることはいうまでもない。   In order to confirm the effect of the low-density process paper according to the present invention, the following various samples were prepared, and a test for evaluating the quality of each sample was performed. In addition, in a present Example, the numerical value which shows a mixing | blending, a density | concentration, etc. is a numerical value of the solid content or the mass reference | standard of an active ingredient. Moreover, since the pulp, chemical | medical agent, etc. which are shown in a present Example are only examples, it cannot be overemphasized that this invention is not restrict | limited by these Examples, and can be selected suitably.

本発明に係る15種類の低密度工程紙(これを「実施例1」ないし「実施例15」とする)と、これらの実施例1ないし実施例15と比較検討するために、6種類の低密度工程紙(これを「比較例1」ないし「比較例6」とする)を、表1に示すような構成で作製した。また、参考例として2種類の市販のクラフト紙及び無塵紙(これを「比較例7」及び「比較例8」とする)を評価した。   For comparison with 15 types of low-density process papers (referred to as “Example 1” to “Example 15”) according to the present invention and these Examples 1 to 15, Density-processed paper (referred to as “Comparative Example 1” to “Comparative Example 6”) was prepared with the configuration shown in Table 1. Moreover, two types of commercially available kraft paper and dust-free paper (referred to as “Comparative Example 7” and “Comparative Example 8”) were evaluated as reference examples.

Figure 0004339915
Figure 0004339915

(実施例1)
以下の原料を用いて、下記の製造法に従い、表層、裏層及び両層間に位置する中間層(4層)からなる6層構造の低密度工程紙を得た。
<原料>
・表層及び裏層
針葉樹晒クラフトパルプ(NBKP)を25質量%、広葉樹晒クラフトパルプ(LBKP)を75質量%混合し、カナディアンスタンダードフリーネス(CSF)を570ccに調整した原料に、カチオン性ポリアクリルアマイド(商品名「ハリフィックスUM570」ハリマ化成株式会社製)を固形分換算で0.25質量%配合して表層及び裏層の原料パルプスラリーを得た。
・中間層
NBKPを25質量%、LBKPを75質量%混合し、CSFを540ccに調整した原料に、平均粒子径が8〜14μmで、発泡開始温度が75〜100℃の熱発泡性粒子(商品名「マツモトマイクロスフェアF−46」松本油脂製薬株式会社製)を対パルプで4.0質量%、熱発泡性粒子の定着剤(「ハクトロンKC100」伯東株式会社製)を0.4質量%配合しパルプスラリーを得た。
これらの原料パルプスラリーを用い、円網6層抄紙機にて表層、4層の中間層、及び裏層の紙層を抄き合わせて、表層の付け量を75g/m、中間層の合計付け量を350g/m、裏層の付け量を75g/m、低密度工程紙全体の坪量が500g/mである6層抄きの低密度工程紙(実施例1)を得た。
(Example 1)
Using the following raw materials, a low-density process paper having a 6-layer structure consisting of a surface layer, a back layer, and an intermediate layer (4 layers) located between both layers was obtained according to the following production method.
<Raw material>
・ Surface and back layers Cationic polyacrylamide to 25% by weight of softwood bleached kraft pulp (NBKP), 75% by weight of hardwood bleached kraft pulp (LBKP), and adjusted to 570cc Canadian Standard Freeness (CSF) (Trade name “Harifix UM570” manufactured by Harima Kasei Co., Ltd.) was blended in an amount of 0.25 mass% in terms of solid content to obtain a raw material pulp slurry for the surface layer and the back layer.
・ Intermediate layer Thermally expandable particles with a mean particle size of 8-14 μm and a foaming start temperature of 75-100 ° C. (commodity) mixed with 25% by mass of NBKP and 75% by mass of LBKP and adjusted to 540 cc CSF The name “Matsumoto Microsphere F-46” manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) is 4.0% by mass with pulp and 0.4% by mass of heat-expandable particle fixing agent (“Haktron KC100” manufactured by Hakuto Co., Ltd.). A pulp slurry was obtained.
Using these raw material pulp slurries, the surface layer, the 4 layers of the intermediate layer, and the back layer of the paper layer were made with a circular 6-layer paper machine, and the surface layer weight was 75 g / m 2 . A 6-layer low density process paper (Example 1) having a weight of 350 g / m 2 , a back layer of 75 g / m 2 , and a basis weight of the entire low density process paper of 500 g / m 2 is obtained. It was.

(実施例2〜3)
中間層の原料パルプスラリーに含有される熱発泡性粒子の添加率と、定着剤の添加率を表1に示すように変更した他は実施例1と同様にして得た低密度工程紙。
(Examples 2-3)
A low-density process paper obtained in the same manner as in Example 1 except that the addition ratio of the heat-expandable particles contained in the raw material pulp slurry of the intermediate layer and the addition ratio of the fixing agent are changed as shown in Table 1.

(実施例4)
中間層の原料パルプスラリーに含有される熱発泡性粒子の種類、すなわち品番を表1に示すように変更した他は実施例1と同様にして得た低密度工程紙。
(Example 4)
Low density process paper obtained in the same manner as in Example 1 except that the type of thermally expandable particles contained in the raw material pulp slurry of the intermediate layer, that is, the product number, was changed as shown in Table 1.

(実施例5)
表層及び裏層の原料パルプスラリー中の原料パルプの配合と濾水度(CSF)とを表1に示すように変更した他は実施例1と同様にして得た低密度工程紙。
(Example 5)
Low density process paper obtained in the same manner as in Example 1 except that the composition of raw material pulp and the freeness (CSF) in the raw pulp slurry of the surface layer and the back layer were changed as shown in Table 1.

(実施例6〜8)
中間層の原料パルプスラリー中の原料パルプの配合と濾水度(CSF)とを表1に示すように変更した他は実施例1と同様にして得た低密度工程紙。
(Examples 6 to 8)
A low-density process paper obtained in the same manner as in Example 1 except that the composition of the raw pulp in the intermediate pulp slurry and the freeness (CSF) were changed as shown in Table 1.

(実施例9〜10)
表層及び裏層の原料パルプスラリー中のカチオン性PAMの添加率を表1に示すように変更した他は実施例1と同様にして得た低密度工程紙。
(Examples 9 to 10)
Low density process paper obtained in the same manner as in Example 1 except that the addition rate of the cationic PAM in the raw pulp slurry of the surface layer and the back layer was changed as shown in Table 1.

(比較例1)
中間層の原料パルプスラリー中の熱発泡性粒子の添加率を表1に示すように変更した他は実施例1と同様にして得た低密度工程紙。
(Comparative Example 1)
Low-density process paper obtained in the same manner as in Example 1 except that the addition ratio of the heat-expandable particles in the raw material raw material slurry is changed as shown in Table 1.

(比較例2)
表層及び裏層の原料パルプスラリーを使用せず、中間層の原料パルプスラリーのみを用い、付け量(坪量)を430g/mの単層の低密度工程紙とした他は表1に示すように実施例1と同様にして得た低密度工程紙。
(Comparative Example 2)
Table 1 shows that except that the raw pulp slurry of the surface layer and the back layer is not used, only the raw pulp slurry of the intermediate layer is used, and the weight (basis weight) is a single layer low density process paper of 430 g / m 2. Thus, a low-density process paper obtained in the same manner as in Example 1.

(比較例4)
中間層の原料パルプスラリー中の熱発泡性粒子の種類、すなわち品番と平均粒子径と発泡開始温度とを表1に示すように変更した他は実施例1と同様にして得た低密度工程紙。
(Comparative Example 4)
Low density process paper obtained in the same manner as in Example 1 except that the type of thermally foamable particles in the raw material pulp slurry of the intermediate layer, that is, the product number, average particle diameter, and foaming start temperature were changed as shown in Table 1. .

(比較例5)
中間層の原料パルプスラリー中の熱発泡性粒子の種類、すなわち品番と平均粒子径と発泡開始温度、及び定着剤の添加率を表1に示すように変更した他は実施例1と同様にして得た低密度工程紙。
(Comparative Example 5)
In the same manner as in Example 1 except that the type of thermally expandable particles in the raw material pulp slurry of the intermediate layer, that is, the product number, average particle diameter, foaming start temperature, and addition rate of the fixing agent were changed as shown in Table 1. The obtained low density process paper.

(比較例6)
中間層の原料パルプスラリー中の原料パルプの配合と、濾水度(CSF)とを表1に示すように変更した他は実施例1と同様にして得た低密度工程紙。
(Comparative Example 6)
Low density process paper obtained in the same manner as in Example 1 except that the composition of the raw pulp in the raw pulp slurry of the intermediate layer and the freeness (CSF) were changed as shown in Table 1.

(比較例7)
表層及び裏層の原料パルプスラリー中の原料パルプの配合と、濾水度(CSF)と、付け量とを表1に示すようにしたクラフト紙である(「市販されているクラフト紙」)。
(Comparative Example 7)
It is a kraft paper in which the composition of the raw pulp in the raw pulp slurry of the surface layer and the back layer, the freeness (CSF), and the weight are as shown in Table 1 (“commercially available kraft paper”).

(比較例8)
表層及び裏層の原料パルプスラリー中の原料パルプの配合と、濾水度(CSF)と、付け量とを表1に示すようにした無塵紙である(「市販されている無塵紙」)。
(Comparative Example 8)
It is a dust-free paper in which the blending of the raw pulp in the raw-layer pulp slurry of the surface layer and the back layer, the freeness (CSF), and the application amount are as shown in Table 1 (“commercially available dust-free paper”).

表1中の「付け量(g/m)」とは、各試料の層剥離を行い、各層の坪量をJIS−P8142に記載の「紙及び板紙―坪量測定方法」に準拠して測定した値である。なお、層剥離は以下の手順で行った。まず、各試料から得た各サンプルを室温の水に約1時間浸漬する。水に浸漬した各サンプルを、角を起点として10mmΦ程度の丸棒に巻き付けた後、丸棒を転がして各サンプルをしごく。この操作を各サンプルの四隅の全ての角を起点に繰り返し、各方向からサンプルにしごきの力を加える。これにより、各サンプルの層間の一部が剥離してくるので、これを利用して、表層、中間層、及び裏層に分離して層剥離を行う。層剥離を行った後、各サンプルの各層を熱風乾燥機などで十分に乾燥し、試験に使用した。 “Amount (g / m 2 )” in Table 1 refers to the delamination of each sample and the basis weight of each layer in accordance with “Paper and paperboard—basis weight measurement method” described in JIS-P8142. It is a measured value. The delamination was performed according to the following procedure. First, each sample obtained from each sample is immersed in water at room temperature for about 1 hour. Each sample immersed in water is wound around a round bar of about 10 mmΦ starting from a corner, and then the round bar is rolled to squeeze each sample. This operation is repeated starting from all four corners of each sample, and the ironing force is applied to the sample from each direction. As a result, a part of the layers of each sample is peeled off, and this is used to separate the layers into a surface layer, an intermediate layer, and a back layer. After delamination, each layer of each sample was sufficiently dried with a hot air dryer or the like and used for the test.

これらの全実施例及び比較例についての品質評価を行った結果は、表2に示すとおりであった。   The results of quality evaluation for all of these Examples and Comparative Examples are as shown in Table 2.

なお、表2中の「坪量(g/m)」とは、各試料全層、すなわち低密度工程紙全体の坪量で、JIS−P8142に記載の「紙及び板紙―坪量測定方法」に準拠して測定した値である。 In addition, “basis weight (g / m 2 )” in Table 2 is the basis weight of all layers of each sample, that is, the entire low density process paper, and is described in “Paper and paperboard—basis weight measuring method” described in JIS-P8142. It is a value measured according to.

また、「紙厚(μm)」とは、JIS−P8118に記載の「紙及び板紙―厚さ及び密度の試験方法」に準拠して測定した値である。   The “paper thickness (μm)” is a value measured in accordance with “Paper and paperboard—Test method for thickness and density” described in JIS-P8118.

「密度(g/cm)」とは、JIS−P8142に記載の「紙及び板紙―坪量測定方法」に準拠して測定した坪量と、JIS−P8118に記載の「紙及び板紙―厚さ及び密度の試験方法」に準拠して測定した厚さから算出した値である。 “Density (g / cm 3 )” refers to the basis weight measured in accordance with “paper and paperboard—basis weight measurement method” described in JIS-P8142, and “paper and paperboard—thickness” described in JIS-P8118. It is a value calculated from the thickness measured according to the “Test method for thickness and density”.

「透気度(秒)」とは、JIS−P8117に記載の紙及び板紙−透気度試験方法(ガーレ試験方法)に準拠して測定した値である。   “Air permeability (second)” is a value measured according to the paper and paperboard-air permeability test method (Gurley test method) described in JIS-P8117.

「表面強度(A)」とは、JIS−P8129のワックスピック試験法に記載の紙及び板紙−表面強さの試験方法に準拠して測定した値であり、紙表面の剥がれが発生しない最も高いワックス番号(A)を測定し5以上を合格とした。   “Surface strength (A)” is a value measured according to the paper and paperboard-surface strength test method described in the wax pick test method of JIS-P8129, and is the highest value that does not cause peeling of the paper surface. The wax number (A) was measured and 5 or more was determined to be acceptable.

「圧縮紙厚残存率(%)」とは、熱プレス機において120℃、60kg/cmの条件下で30分間プレスした直後の紙厚と、初期紙厚(プレス前の紙厚)の比率を、下記の式により算出した値である。なお、熱プレスは熱圧縮試験機(TP500G型、江藤製作所製)を使用した。
(式)圧縮紙厚残存率(%)=プレス直後の紙厚/初期紙厚×100(%)
「熱伝導率差(W/mk)」とは、JIS−A1412−2の熱伝導率試験法に記載の「熱絶縁材の熱抵抗及び熱伝導率の測定方法−第2部:熱流計法の試験方法」に準拠して、英宏精機製熱伝導率測定装置(HC−072)を用い、紙面の表と裏(各試料の表面及び裏面)の熱伝導率を測定し、その測定値の差を算出した値である。
“Compressed paper thickness remaining rate (%)” is the ratio of the paper thickness immediately after pressing for 30 minutes under the conditions of 120 ° C. and 60 kg / cm 2 in a hot press to the initial paper thickness (paper thickness before pressing). Is a value calculated by the following equation. The hot press used was a thermal compression tester (TP500G type, manufactured by Eto Seisakusho).
(Formula) Compressed paper thickness remaining rate (%) = paper thickness immediately after pressing / initial paper thickness × 100 (%)
“Thermal conductivity difference (W / mk)” means “Measurement method of thermal resistance and thermal conductivity of thermal insulation material-Part 2: Heat flow meter method” described in the thermal conductivity test method of JIS-A1412-2. Measure the thermal conductivity of the front and back of the paper (the front and back of each sample) using the Eihiro Seiki thermal conductivity measuring device (HC-072) in accordance with It is the value which calculated the difference of.

「発塵量(個/cm)」とは引き裂き発塵紙粉量のことで、SEMI G67−0996の「シート材料から発生する粒子の測定」に準じて以下のように測定した。
(引裂き試験による発塵量測定)
(1)各試料を押切りカッターにて流れ方向50mm×巾方向200mmに断裁してサンプルを作製する。
(2)サンプルを1枚用意し、グローブボックス内で縦方向に5等分に引き裂く。
(3)グローブボックス内の空気0.1mをパーティクルカウンターで測定し、引き裂きによって発生した10μm以上の紙粉の数(個数/m)を測定し、測定値をサンプルの断面積cm当りで除した数値を算出し、その個数を発塵量とした。
“Dust generation amount (pieces / cm 2 )” refers to the amount of tear dusting paper powder, and was measured as follows according to “Measurement of particles generated from sheet material” of SEMI G67-0996.
(Dust generation measurement by tear test)
(1) Each sample is cut into a flow direction of 50 mm and a width direction of 200 mm with a press cutter to produce a sample.
(2) Prepare one sample and tear it into 5 equal parts in the vertical direction in the glove box.
(3) Measure 0.1 m 2 of air in the glove box with a particle counter, measure the number of paper dust of 10 μm or more (number / m 3 ) generated by tearing, and measure the value per cm 2 of the cross-sectional area of the sample The numerical value divided by was calculated, and the number thereof was defined as the amount of dust generation.

「焼付き評価」とは、ステンレス鋼板への各試料(低密度工程紙)の焼付きを目視評価したものである。なお、この評価は5段階の点数で評価し、点数が大きい程、「焼付きがない、ステンレス鋼板から低密度工程紙を剥離しやすい」ということを表しており、3点以上を合格点とした。   “Evaluation of seizure” is a visual evaluation of seizure of each sample (low density process paper) on a stainless steel plate. In addition, this evaluation is evaluated by a score of 5 stages, and the larger the score, the more “represents that there is no seizure and the low-density process paper is easily peeled from the stainless steel plate”, and 3 points or more are regarded as passing points. did.

「地合い」とは、紙面の地合いを評価したものである。すなわち、210×297mmサイズの原紙中に見られる繊維の結束によるフロック、発泡ムラの個数を測定し、5個以下を○、6〜10個を△、11個以上を×とし、△以上を合格とした。
The “texture” is an evaluation of the paper texture. That is, the number of flocs and foaming unevenness due to the bundling of fibers found in a 210 × 297 mm size base paper is measured, 5 is 5 or less, 6 to 10 is Δ, 11 or more is X, and Δ is passed. It was.

Figure 0004339915
Figure 0004339915

表2から、本願発明に係る低密度工程紙、すなわち実施例1〜15に係る低密度工程紙は、積層板が大きく寸法変化することがないと共に、クッション性を有し、さらに発塵が少ないことが分かる。
From Table 2, the low-density process paper according to the present invention, that is, the low-density process paper according to Examples 1 to 15, has a cushioning property and a small amount of dust generation while the laminated board does not undergo a large dimensional change. I understand that.

Claims (1)

少なくとも表層、裏層、及び前記表層と前記裏層との間に配置される1層又は複数層から成る中間層を有する低密度工程紙であって、
前記中間層の少なくとも1層に平均粒子径が5〜15μmで、75〜130℃の加熱により膨張を開始する熱発泡性粒子を、予め熱発泡性粒子とカチオン性高分子樹脂とを混合(凝集)して得た熱発泡性粒子の凝集体とし、前記中間層のパルプ固形分に対して、固形分換算で1〜8質量%配合し、かつ、前記熱発泡粒子の定着剤として、ポリアクリルアミド系又はポリエチレンイミン系の高分子をパルプ固形分換算で0.1〜0.8質量%含有させて発泡層とし、
前記表層及び前記裏層を構成する原料はNBKP及び/又はLBKPからなるクラフトパルプであり、
また、前記表層、前記裏層及び前記中間層に使用される原料パルプの濾水度が500〜600ccであり、
密度が0.45〜0.55g/cm、圧縮紙厚残存率が55〜61%、前記表層及び前記裏層の熱伝導率差が0.001W/mk以下、SEMI G67−0996に準じた、引裂き試験による10μm以上の発塵量が500個/cm以下であることを特徴とする低密度工程紙。

A low-density process paper having at least a surface layer, a back layer, and an intermediate layer composed of one or more layers disposed between the surface layer and the back layer,
At least one of the intermediate layers has an average particle diameter of 5 to 15 μm, and heat-expandable particles that start to expand by heating at 75 to 130 ° C. are previously mixed (aggregated) with heat-expandable particles and a cationic polymer resin. ) To obtain an agglomerate of heat-expandable particles, blended in an amount of 1 to 8% by mass in terms of solid content with respect to the pulp solid content of the intermediate layer, and polyacrylamide as a fixing agent for the heat-expandable particles Or 0.1 to 0.8% by mass of a polymer or polyethyleneimine polymer in terms of pulp solid content to form a foam layer,
The raw material constituting the surface layer and the back layer is kraft pulp made of NBKP and / or LBKP,
Moreover, the freeness of the raw material pulp used for the said surface layer, the said back layer, and the said intermediate | middle layer is 500-600cc,
Density is 0.45-0.55 g / cm 3 , compressed paper thickness remaining rate is 55-61%, thermal conductivity difference between the surface layer and the back layer is 0.001 W / mk or less, according to SEMI G67-0996 A low-density process paper characterized by having a dust generation amount of 10 μm or more by a tear test of 500 pieces / cm 2 or less.

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JP5937380B2 (en) * 2012-02-29 2016-06-22 大王製紙株式会社 Manufacturing method of cushion material for hot press molding
JP6251942B2 (en) * 2014-09-11 2017-12-27 特種東海製紙株式会社 Interleaving paper for glass plate
CN110700009B (en) * 2019-10-10 2020-08-18 建滔(佛冈)绝缘材料有限公司 Production process and application of hot-pressed paperboard for pressing copper-clad plate as cushion layer

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