JP2009185429A - Process release paper - Google Patents
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- JP2009185429A JP2009185429A JP2008029023A JP2008029023A JP2009185429A JP 2009185429 A JP2009185429 A JP 2009185429A JP 2008029023 A JP2008029023 A JP 2008029023A JP 2008029023 A JP2008029023 A JP 2008029023A JP 2009185429 A JP2009185429 A JP 2009185429A
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- release paper
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Landscapes
- Laminated Bodies (AREA)
- Paper (AREA)
Abstract
Description
本発明は、工程剥離紙に関するものであり、より詳しくは、炭素繊維強化樹脂材料（プリプレグ）製造時に使用する工程剥離紙に関するものである。 The present invention relates to a process release paper, and more particularly to a process release paper used when manufacturing a carbon fiber reinforced resin material (prepreg).
剥離紙は粘着シートの剥離紙（一般の粘着テープやラベルなど）、産業用基材（例えば、マーキングシート、金属箔等の剥離紙など）、包装用紙（例えば、紙袋、ブックカバーなど）、工程剥離紙（例えば、合成皮革、プリプレグ、プラスチックフィルム等の工程剥離紙）などとして多用されている。
プラスチックフィルム製造用の工程剥離紙の使用方法の一例を説明する。工程剥離紙上に溶剤と混合したモノマーを展開し、熱や電子線でモノマー同士を反応させ、もってプラスチックフィルムを得る。
Release paper is adhesive sheet release paper (general adhesive tape, label, etc.), industrial substrate (eg, marking sheet, release paper such as metal foil), packaging paper (eg, paper bag, book cover, etc.), process It is frequently used as release paper (for example, process release paper such as synthetic leather, prepreg, and plastic film).
An example of a method for using the process release paper for producing a plastic film will be described. The monomer mixed with the solvent is developed on the process release paper, and the monomers are reacted with each other by heat or electron beam to obtain a plastic film.
プリプレグ製造用の工程剥離紙の使用方法の一例を説明する。プリプレグは、ゴルフシャフト、釣竿、テニスラケット、スキーストック等のレジャー・スポーツ用品、宇宙及び航空機関連等の分野の材料として使用される。工程用剥離紙上に、固形のエポキシ樹脂を加熱して流動性を持たせた状態で一定の厚さで均一に塗布後に、冷却して半硬化状態でエポキシ樹脂を仮接着させる。その後、このエポキシ樹脂を仮接着させたものを上下に対向させ、これらの中間に炭素繊維を挟み込み、加熱により炭素繊維内にエポキシ樹脂を塗工又は含浸させ、炭素繊維とエポキシ樹脂を一体化したのち冷却して、工程剥離紙とともに巻き取り、プリプレグとする。これは用途に応じて巻き取りのまま、または、シート状に断裁した状態で冷所で保管され、成形する直前に工程剥離紙は剥がされてプリプレグが成形に使用される。
これらの工程剥離紙には、剥離性を付与するために剥離剤としてシリコーンを塗布または含浸させている。剥離剤に用いられるシリコーンは、有機溶剤に分散させた溶剤性シリコーン、水に分散・乳化させた水性シリコーン、無溶剤性シリコーンの３種類がある。
An example of how to use the process release paper for prepreg production will be described. The prepreg is used as a material in fields such as golf shafts, fishing rods, tennis rackets, skis and other leisure / sports goods, space and aircraft. A solid epoxy resin is heated on a release paper for process and applied uniformly with a constant thickness in a state where it has fluidity, and then cooled and temporarily adhered to the epoxy resin in a semi-cured state. Thereafter, the epoxy resin temporarily bonded is vertically opposed, the carbon fiber is sandwiched between them, and the epoxy resin is applied or impregnated in the carbon fiber by heating to integrate the carbon fiber and the epoxy resin. Then, it is cooled and wound with a process release paper to form a prepreg. This is stored in a cold place as it is wound up or cut into a sheet depending on the application, and the process release paper is peeled off immediately before molding, and the prepreg is used for molding.
These process release papers are coated or impregnated with silicone as a release agent in order to impart releasability. There are three types of silicone used for the release agent: solvent-based silicone dispersed in an organic solvent, aqueous silicone dispersed / emulsified in water, and solvent-free silicone.
特許文献１には、剥離剤として水性シリコーンを使用した剥離紙が開示されている。また、特許文献２には、プリプレグ製造用の工程剥離紙が開示されている。
工程剥離紙の剥離剤として水性シリコーンを用いた場合、剥離強度が経時的に変化するため、製造直後と一定期間放置後で剥離強度が大幅に変動する問題があった。 When aqueous silicone is used as the release agent for the process release paper, the peel strength changes with time, and there is a problem that the peel strength varies greatly immediately after production and after standing for a certain period of time.
プリプレグ製造用の工程剥離紙の剥離強度は約０．７〜３．０Ｎ／２５ｍｍであり、一般の粘着シート用に用いられる剥離紙の剥離強度、０．２Ｎ／２５ｍｍ前後と比較して重剥離タイプであるため、経時的に剥離強度が変化しやすい。工程剥離紙は、通常１ヶ月以上のエージング期間を設ける。経時変化により剥離強度が更に大きくなると、プリプレグ製造工程においてプリプレグにシリコーンが付着するトラブルが発生しやすくなる。一方、経時的に剥離強度が変化し、剥離強度が小さくなると、使用前にプリプレグが工程剥離紙から剥がれるというトラブルが発生しやすくなる。
以上のように、水性シリコーンを塗布した工程剥離紙において、経時で安定した剥離強度を有し、効率的にプリプレグを製造できる工程剥離紙は、いまだ得られていなかった。
本発明は、水性シリコーンを剥離剤として用いた工程剥離紙において、経時で安定した剥離強度を有する工程剥離紙を提供すること目的とする。
The peel strength of the process release paper for manufacturing the prepreg is about 0.7 to 3.0 N / 25 mm, and the peel strength of the release paper used for general pressure-sensitive adhesive sheets is heavy peel compared to around 0.2 N / 25 mm. Because of the type, the peel strength is likely to change over time. The process release paper is usually provided with an aging period of one month or longer. If the peel strength is further increased due to the change over time, troubles in which silicone adheres to the prepreg in the prepreg manufacturing process are likely to occur. On the other hand, when the peel strength changes with time and the peel strength becomes small, a trouble that the prepreg peels off from the process release paper before use tends to occur.
As described above, the process release paper coated with aqueous silicone has not yet obtained a process release paper that has a stable peel strength with time and can efficiently produce a prepreg.
It is an object of the present invention to provide a process release paper having a release strength that is stable over time in a process release paper using aqueous silicone as a release agent.
上記課題を解決するために、本発明は、基紙と、前記基紙上に設けられた剥離層とからなり、前記剥離層は、水性シリコーンと、水溶性樹脂とを含み、前記剥離層にエポキシ含浸プリプレグテープを２ｋｇの荷重で貼合して７日間放置した後に１８０°の方向に速度１００ｍｍ／分で剥がした際の応力を剥離強度とすると、前記剥離層を設けて１ヶ月以上経過した後の前記剥離強度が０．７〜３．０Ｎ／２５ｍｍである工程剥離紙である。 In order to solve the above problems, the present invention comprises a base paper and a release layer provided on the base paper, and the release layer includes an aqueous silicone and a water-soluble resin, and the release layer is epoxy-coated. After the impregnated prepreg tape is bonded with a load of 2 kg and left for 7 days and then peeled off at a speed of 100 mm / min in the direction of 180 °, the peel strength is taken, and after one month or more has elapsed after providing the release layer Is a process release paper having a peel strength of 0.7 to 3.0 N / 25 mm.
前記水溶性樹脂は、好ましくはポリビニルアルコールであり、さらに好ましくはケン化度が７７〜８９ｍｏｌ％のポリビニルアルコールである。 The water-soluble resin is preferably polyvinyl alcohol, more preferably polyvinyl alcohol having a saponification degree of 77 to 89 mol%.
さらに、前記剥離層は、好ましくは、アセトアセチル化ポリビニルアルコールを含み、前記ポリビニルアルコールと前記アセトアセチル化ポリビニルアルコールの質量比率が、１０：９０〜９０：１０であることが好ましい。 Furthermore, the release layer preferably contains acetoacetylated polyvinyl alcohol, and the mass ratio of the polyvinyl alcohol to the acetoacetylated polyvinyl alcohol is preferably 10:90 to 90:10.
上記工程剥離紙は、例えば、炭素繊維強化樹脂材料製造用の工程剥離紙として用いられる。 The process release paper is used as, for example, a process release paper for producing a carbon fiber reinforced resin material.
本発明によると、経時で安定した剥離強度を有し、かつプリプレグ製造用に適した剥離強度を有する工程剥離紙が得られ、かかる工程剥離紙を用いた場合好適にプリプレグを製造することができる。 According to the present invention, a process release paper having a peel strength that is stable over time and having a peel strength suitable for prepreg production is obtained, and when such a process release paper is used, a prepreg can be preferably produced. .
以下、本発明について実施形態を示して詳細に説明するが、本発明はこれらの記載に限定して解釈されない。 Hereinafter, although an embodiment is shown and explained in detail about the present invention, the present invention is limited to these descriptions and is not interpreted.
本発明は、基紙と、前記基紙上に設けられた剥離層とからなり、前記剥離層は、水性シリコーンと、水溶性樹脂とを含む、工程剥離紙である。 This invention consists of a base paper and the peeling layer provided on the said base paper, and the said peeling layer is process release paper containing water-based silicone and water-soluble resin.
基紙の材料としては、通常の原料パルプを使用することができる。例えば、未晒針葉樹パルプ（ＮＵＫＰ）、未晒広葉樹パルプ（ＬＵＫＰ）、晒針葉樹パルプ（ＮＢＫＰ）、晒広葉樹パルプ（ＬＢＫＰ）等の化学パルプ；ストーングランドパルプ（ＳＧＰ）、加圧ストーングランドパルプ（ＰＧＷ）、リファイナーグランドパルプ（ＲＧＰ）、ケミグランドパルプ（ＣＧＰ）、サーモグランドパルプ（ＴＧＰ）、グランドパルプ（ＧＰ）、サーモメカニカルパルプ（ＴＭＰ）、ケミサーモメカニカルパルプ（ＣＴＭＰ）、リファイナーメカニカルパルプ（ＲＭＰ）等の機械パルプ等を使用することができる。また、古紙からなる古紙パルプを使用することも可能であり、例えば、雑誌古紙、チラシ古紙、オフィス古紙等から製造される離解・脱墨古紙パルプ、離解・脱墨・漂白古紙パルプ等があげられる。本発明では、これらの中から１種又は２種以上を適宜選択して使用することができる。 As a material for the base paper, ordinary raw pulp can be used. For example, chemical pulp such as unbleached softwood pulp (NUKP), unbleached hardwood pulp (LUKP), bleached softwood pulp (NBKP), bleached hardwood pulp (LBKP), etc .; Stone Grand Pulp (SGP), Pressurized Stone Grand Pulp (PGW) ), Refiner Grand Pulp (RGP), Chemi Grand Pulp (CGP), Thermo Grand Pulp (TGP), Grand Pulp (GP), Thermo Mechanical Pulp (TMP), Chemi Thermo Mechanical Pulp (CTMP), Refiner Mechanical Pulp (RMP) Mechanical pulp such as can be used. It is also possible to use waste paper pulp made of waste paper, such as disaggregated / deinked waste paper pulp, disaggregated / deinked / bleached waste paper pulp, etc. produced from magazine waste paper, flyer waste paper, office waste paper, etc. . In the present invention, one or more of these can be appropriately selected and used.
本実施形態においては、以上の原料パルプを混合して抄紙原料（紙料スラリー）を調製するが、当該原料パルプには、例えば、内添サイズ剤、紙力増強剤、紙厚向上剤、歩留向上剤等の通常の製紙工程で配合される種々の添加剤を、その種類及び配合量を適宜調整して内添することができる。 In the present embodiment, the above raw material pulp is mixed to prepare a papermaking raw material (stock slurry). For the raw material pulp, for example, an internal sizing agent, a paper strength enhancer, a paper thickness improver, a step Various additives blended in a normal papermaking process such as a retention improver can be internally added by appropriately adjusting the kind and blending amount thereof.
また、基紙を抄造する抄紙機も特に限定されず、例えば、長網方式、ツインワイヤー方式、ギャップフォーマー方式、丸網方式など各方式を適宜用いることができる。但し、工程剥離紙においては、環境（温度、湿度）の変化により、水分の吸湿・放湿によるシワが発生し、工程剥離紙からプリプレグや合成皮革が剥離する、いわゆる浮き剥がれトラブルが発生することがある。このため、本発明の工程剥離紙には寸法安定性の良い丸網抄紙機を用いて抄造した紙が好適に用いられる。また、平滑度を高め、より剥離性の調整を容易にするために、ヤンキードライヤーやソフトカレンダーなどの平滑化処理を行うことが好ましい。 Also, the paper machine for making the base paper is not particularly limited, and various systems such as a long net system, a twin wire system, a gap former system, and a round net system can be used as appropriate. However, in the process release paper, wrinkles due to moisture absorption and desorption will occur due to changes in the environment (temperature, humidity), and so-called floating problems will occur, where the prepreg and synthetic leather peel from the process release paper. There is. For this reason, paper made with a round net paper machine having good dimensional stability is preferably used as the process release paper of the present invention. Further, in order to increase the smoothness and make it easier to adjust the peelability, it is preferable to perform a smoothing treatment such as a Yankee dryer or a soft calender.
本発明においては、基紙上に剥離層を設ける前に、基紙に水溶性樹脂を主成分とする目止め層を設けても良い。一般に、目止め層を設けずにシリコーン溶液を塗布すると、シリコーン溶液が原紙に沈み込み、経時で剥離強度が向上し、剥離し難くなるトラブルがある。本発明は、剥離層における剥離強度の変化を少なくする効果があるため、特に目止め層を設ける必要は無いが、剥離層の平坦性を向上させるために、剥離層を塗工する前に、下塗り塗工を行い、基紙の表面粗さを改善させても良い。 In the present invention, before the release layer is provided on the base paper, a sealing layer containing a water-soluble resin as a main component may be provided on the base paper. In general, when a silicone solution is applied without providing a sealing layer, the silicone solution sinks into the base paper, and there is a problem that the peel strength improves with time and the peel becomes difficult. Since the present invention has an effect of reducing the change in peel strength in the release layer, it is not particularly necessary to provide a sealing layer, but in order to improve the flatness of the release layer, before applying the release layer, An undercoat may be applied to improve the surface roughness of the base paper.
この基紙、または下塗り塗工を行った基紙原紙の上に、水性シリコーンを主成分とする剥離層を設けるが、本発明者らは、剥離強度の経時変化を改善する目的で鋭意研究を重ねた結果、この剥離層に水溶性樹脂（Ａ）を含有させることでシリコーンが基紙に吸収されることを防止することができ、有効であることを知見した。 A release layer mainly composed of aqueous silicone is provided on this base paper or base paper that has undergone undercoating. The present inventors have conducted intensive research for the purpose of improving the change in peel strength over time. As a result of overlapping, it was found that the release layer contains the water-soluble resin (A) to prevent the silicone from being absorbed by the base paper, which is effective.
本発明で用いる水性シリコーンは、シリコーン化合物を乳化剤等の界面活性剤を用いて水中に乳化したシリコーンエマルジョンであっても良く、親水基による変性等によりシリコーン化合物を水中に分散させて得られたシリコーン分散体でも良い。 The aqueous silicone used in the present invention may be a silicone emulsion obtained by emulsifying a silicone compound in water using a surfactant such as an emulsifier, or a silicone obtained by dispersing a silicone compound in water by modification with a hydrophilic group or the like. A dispersion may be used.
水溶性樹脂（Ａ）としては、ポリビニルアルコール（ＰＶＡ）；カルボキシメチルセルロース（ＣＭＣ）、メチルセルロース、ヒドロキシプロピルセルロース（ＨＰＣ）、ヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、ヒドロキシエチルセルロース（ＨＥＣ）等のセルロース誘導体から選択される一種または二種以上の混合物等が挙げられる。中でも、より安定性が良好なポリビニルアルコールが好ましい。 The water-soluble resin (A) is selected from cellulose derivatives such as polyvinyl alcohol (PVA); carboxymethylcellulose (CMC), methylcellulose, hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC), and hydroxyethylcellulose (HEC). One kind or a mixture of two or more kinds may be mentioned. Among these, polyvinyl alcohol having better stability is preferable.
使用するポリビニルアルコールは、ケン化度が９０ｍｏｌ％を超える完全ケン化タイプや、ケン化度が９０ｍｏｌ％以下の部分ケン化タイプの、いずれをも使用することができるが、ケン化度が７２〜８９ｍｏｌ％であることが好ましく、７７〜８９ｍｏｌ％であることが更に好ましく、８０〜８９ｍｏｌ％であることが特に好ましく、８７〜８９ｍｏｌ％であることが最も好ましい。ケン化度が７２ｍｏｌ％を下回ると、シリコーンの基紙への吸収を防止することができず、経時で剥離強度が強くなる。ケン化度が８９ｍｏｌ％を超過すると、シリコーンが基紙に浸み込みにくくなる一方、剥離層中でシリコーンの架橋が進み、経時で剥離強度が弱くなる。 As the polyvinyl alcohol to be used, either a complete saponification type with a saponification degree exceeding 90 mol% or a partially saponification type with a saponification degree of 90 mol% or less can be used. It is preferably 89 mol%, more preferably 77 to 89 mol%, particularly preferably 80 to 89 mol%, and most preferably 87 to 89 mol%. When the saponification degree is less than 72 mol%, the absorption of silicone into the base paper cannot be prevented, and the peel strength increases with time. If the degree of saponification exceeds 89 mol%, the silicone will hardly penetrate into the base paper, while the crosslinking of the silicone will proceed in the release layer, and the peel strength will decrease over time.
ポリビニルアルコールの重合度は、５００〜２，４００が好ましく、１，０００〜２，０００がより好ましい。重合度が５００を下回ると、ポリビニルアルコールが基紙に浸み込みやすく、シリコーンが基紙に吸収されやすくなり、経時で剥離強度が強くなる。重合度が２，４００を超過すると、ポリビニルアルコールが原紙に浸み込みにくく、剥離層中でシリコーンの架橋が進み、経時で剥離強度が弱くなる。 The polymerization degree of polyvinyl alcohol is preferably 500 to 2,400, and more preferably 1,000 to 2,000. When the degree of polymerization is less than 500, polyvinyl alcohol is likely to soak into the base paper, silicone is easily absorbed into the base paper, and the peel strength increases with time. When the degree of polymerization exceeds 2,400, polyvinyl alcohol hardly penetrates into the base paper, and the crosslinking of the silicone proceeds in the release layer, and the peel strength becomes weak over time.
剥離層を形成する塗工液におけるポリビニルアルコールの含有量としては、シリコーン１００質量部に対して、１０〜３０質量部が好ましく、１５〜２５質量部がより好ましい。含有量が１０質量部を下回ると、シリコーンの浸み込みを防止する効果が充分に得られず、剥離強度が強くなる。３０質量部を上回ると、ポリビニルアルコール自体がプリプレグと親和性が高いため、特にプリプレグ製造に用いられる場合には、剥離強度が強くなるので好ましくない。 As content of polyvinyl alcohol in the coating liquid which forms a peeling layer, 10-30 mass parts is preferable with respect to 100 mass parts of silicone, and 15-25 mass parts is more preferable. When the content is less than 10 parts by mass, the effect of preventing the penetration of silicone cannot be sufficiently obtained, and the peel strength becomes strong. If it exceeds 30 parts by mass, the polyvinyl alcohol itself has a high affinity with the prepreg, and therefore, particularly when used for prepreg production, the peel strength is increased, which is not preferable.
すなわち、ポリビニルアルコールがシリコーンの基紙への吸収を調整する作用を奏するため、シリコーンとポリビニルアルコールを併用することで、剥離強度の経時変化を抑制することができる。特に、特定の範囲のケン化度とすることで、水性シリコーンとの親和性を調整し、かつ、特定の重合度とすることで、ポリビニルアルコールそのものの基紙への浸み込みを調整するため、これらを組み合わせることで、得られる工程剥離紙の剥離強度の経時変化を抑制することができる。 That is, since polyvinyl alcohol has the effect of adjusting the absorption of silicone into the base paper, the change in peel strength with time can be suppressed by using silicone and polyvinyl alcohol together. In particular, to adjust the affinity with aqueous silicone by adjusting the degree of saponification within a specific range, and to adjust the penetration of polyvinyl alcohol itself into the base paper by setting the degree of polymerization to a specific degree. By combining these, it is possible to suppress the change over time in the peel strength of the resulting process release paper.
しかしながら、本発明者等は、さらに経時変化を抑制する方法を検討した結果、前記水溶性樹脂（Ａ）とともにアセトアセチル化ポリビニルアルコール（Ｂ）を上記剥離層に含有させることで、更に剥離強度の経時変化の少ない、優れた工程剥離紙を得ることを見出した。 However, as a result of studying a method for further suppressing the change with time, the present inventors have further improved the peel strength by containing the water-soluble resin (A) and the acetoacetylated polyvinyl alcohol (B) in the release layer. It was found that an excellent process release paper with little change with time was obtained.
すなわち、ポリビニルアルコールは水酸基が多いため、プリプレグとの親和性が高く、添加することで剥離強度が大きくなる問題があった。そのため、ポリビニルアルコールとプリプレグとの親和性を阻害しつつ、かつ、シリコーンとの親和性を阻害しない助剤が有効であると考え、さらにより水酸基の少ないアセトアセチル化ポリビニルアルコール（Ｂ）を添加したところ、上記効果が得られることを見出した。 That is, since polyvinyl alcohol has many hydroxyl groups, it has a high affinity with the prepreg, and there is a problem that the peel strength increases when added. Therefore, it is considered that an auxiliary agent that inhibits the affinity between polyvinyl alcohol and prepreg and does not inhibit the affinity with silicone is effective, and acetoacetylated polyvinyl alcohol (B) having fewer hydroxyl groups is added. However, it has been found that the above effects can be obtained.
アセトアセチル化ポリビニルアルコールの重合度は、５００〜２，４００が好ましく、１，０００〜２，０００がより好ましい。その理由は、水溶性樹脂（Ａ）と同様に、重合度が５００を下回ると基紙への浸み込みが発生し易くなって剥離強度が大きくなり、また、重合度が２，０００を超過すると沈み込み浸み込みが発生し難くなって剥離強度が小さくなり、いずれも、経時での剥離強度の変動が大きくなる。 The polymerization degree of acetoacetylated polyvinyl alcohol is preferably 500 to 2,400, and more preferably 1,000 to 2,000. The reason for this is that, as with the water-soluble resin (A), when the degree of polymerization is less than 500, penetration into the base paper tends to occur and the peel strength increases, and the degree of polymerization exceeds 2,000. Then, subsidence and penetration hardly occur and the peel strength decreases, and in both cases, the fluctuation of the peel strength with time increases.
剥離層を形成する塗工液におけるアセトアセチル化ポリビニルアルコール（Ｂ）の含有量としては、シリコーン１００質量部に対して、１０〜３０質量部が好ましく、１５〜２５質量部がより好ましい。含有量が１０質量部を下回ると、ポリビニルアルコールとプリプレグとの親和性を充分に阻害できず、剥離強度が大きくなり、３０質量部を上回ると、ポリビニルアルコールとプリプレグとの親和性を必要以上に阻害し、また、シリコーンの浸み込み防止作用とあいまって剥離強度が小さくなりすぎるため、好ましくない。 As content of the acetoacetylated polyvinyl alcohol (B) in the coating liquid which forms a peeling layer, 10-30 mass parts is preferable with respect to 100 mass parts of silicone, and 15-25 mass parts is more preferable. When the content is less than 10 parts by mass, the affinity between the polyvinyl alcohol and the prepreg cannot be sufficiently inhibited, and the peel strength increases. When the content exceeds 30 parts by mass, the affinity between the polyvinyl alcohol and the prepreg is more than necessary. In addition, the peel strength is excessively reduced in combination with the silicone penetration preventing action, which is not preferable.
剥離層を形成する塗工液における水溶性樹脂（Ａ）と、アセトアセチル化ポリビニルアルコール（Ｂ）との割合は、目的とする剥離強度により異なるが、例えば後述する剥離強度測定方法で測定した剥離強度が０．７〜３．０Ｎ／２５ｍｍの重剥離タイプの場合は、上記理由から、１０：９０〜９０：１０が好ましく、２０：８０〜８０：２０がより好ましく、３０：７０〜７０：３０が特に好ましく、４０：６０〜６０：４０が最も好ましい。このようにして、剥離層に水性シリコーン、水溶性樹脂（Ａ）およびアセトアセチル化ポリビニルアルコール（Ｂ）を含有させることで、より剥離強度の経時変化が小さい工程剥離紙が得られる。 Although the ratio of the water-soluble resin (A) and the acetoacetylated polyvinyl alcohol (B) in the coating liquid for forming the release layer varies depending on the target peel strength, for example, the peel measured by the peel strength measuring method described later. In the case of a heavy peel type having a strength of 0.7 to 3.0 N / 25 mm, 10:90 to 90:10 is preferable, 20:80 to 80:20 is more preferable, and 30:70 to 70: 30 is particularly preferable, and 40:60 to 60:40 is most preferable. In this way, a process release paper having a smaller change in peel strength with time can be obtained by containing the aqueous silicone, the water-soluble resin (A) and the acetoacetylated polyvinyl alcohol (B) in the release layer.
本発明の工程剥離紙の剥離層においては、上記樹脂以外に、一般に製紙用途で用いられる接着剤を使用しても良い。接着剤としては具体的には、例えば、カゼイン、大豆蛋白等の蛋白質類；スチレン−ブタジエン共重合体ラテックス、メチルメタクリレート−ブタジエン共重合体ラテックス、スチレン−メチルメタクリレート−ブタジエン共重合体ラテックス等の共役ジエン系ラテックス；アクリル酸エステル及び／又はメタクリル酸エステルの重合体ラテックス若しくは共重合体ラテックス等のアクリル系ラテックス；エチレン−酢酸ビニル重合体ラテックス等のビニル系ラテックス；これらの各種共重合体ラテックスをカルボキシル基等の官能基含有単量体で変性したアルカリ質量部分溶解性又は非溶解性のラテックス等のラテックス類；オレフィン−無水マレイン酸樹脂、メラミン樹脂、尿素樹脂、ウレタン樹脂等の合成樹脂系接着剤；酸化澱粉、陽性化澱粉、エステル化澱粉、デキストリン等の澱粉類等を挙げることができ、これらの中から１種又は２種以上を適宜選択して使用することができる。 In the release layer of the process release paper of the present invention, an adhesive generally used for papermaking may be used in addition to the resin. Specific examples of the adhesive include proteins such as casein and soybean protein; conjugates such as styrene-butadiene copolymer latex, methyl methacrylate-butadiene copolymer latex, and styrene-methyl methacrylate-butadiene copolymer latex. Diene latex; acrylic latex such as acrylic acid ester and / or methacrylic acid ester polymer latex or copolymer latex; vinyl latex such as ethylene-vinyl acetate polymer latex; carboxyl of these various copolymer latexes Latexes such as alkali mass partially soluble or insoluble latex modified with functional group-containing monomers such as groups; synthetic resin adhesives such as olefin-maleic anhydride resin, melamine resin, urea resin, urethane resin ; Oxidized starch, positive Starches, esterified starches, can be mentioned dextrin starches such as such, it can be used by selecting one or more from among these as appropriate.
本発明の工程剥離紙の剥離層には、上記以外にも、一般に製紙用途で使用できる顔料、蛍光増白剤、蛍光増白剤の被染着物質、消泡剤、離型剤、着色剤、保水剤等の通常使用される各種薬品を適宜配合することもできる。 For the release layer of the process release paper of the present invention, in addition to the above, pigments that can generally be used for papermaking, fluorescent whitening agents, dyed substances of fluorescent whitening agents, antifoaming agents, release agents, colorants In addition, various commonly used chemicals such as water retention agents can be appropriately blended.
基紙の表面への剥離層用塗工液の塗工は、一般の塗工紙用途設備で行えば足り、例えば、ブレードコーター、エアーナイフコーター、トランスファーロールコーター、ロッドメタリングサイズプレスコーター、カーテンコーター等の塗工装置を設けたオンマシンコーター又はオフマシンコーターによって、原紙上に一層又は多層に分けて塗工液を塗工できる。中でも、塗工層表面の高い平坦性が確保されるという点から、エアーナイフコーターを用いることが好ましい。また、ドライヤーパートでの乾燥方法としては、例えば、熱風加熱、ガスヒーター加熱、赤外線ヒーター加熱等の各種加熱乾燥方式を適宜採用することができる。 It is sufficient to apply the coating solution for the release layer to the surface of the base paper using general coating paper application equipment, for example, blade coater, air knife coater, transfer roll coater, rod metering size press coater, curtain. An on-machine coater or an off-machine coater provided with a coating device such as a coater can be used to coat the coating liquid in one layer or multiple layers on the base paper. Especially, it is preferable to use an air knife coater from the point that the high flatness of the coating layer surface is ensured. Moreover, as a drying method in the dryer part, for example, various heating drying methods such as hot air heating, gas heater heating, infrared heater heating and the like can be appropriately employed.
塗工量は０．３〜１．８ｇ／ｍ2が好ましく、０．５〜１．５ｇ／ｍ2がより好ましい。０．３ｇ／ｍ2未満では原紙の被覆性が低下し、良好な剥離強度が得られない。１．８ｇ／ｍ2を超過すると、乾燥ムラが発生しやすく、剥離層の表面強度が低下し、プリプレグや合成皮革に剥離層の一部が取られ易くなるため好ましくない。 Coating amount is preferably 0.3~1.8g / m 2, 0.5~1.5g / m 2 is more preferable. If it is less than 0.3 g / m 2 , the coverage of the base paper is lowered, and good peel strength cannot be obtained. If it exceeds 1.8 g / m 2 , drying unevenness is likely to occur, the surface strength of the release layer is lowered, and a part of the release layer is easily removed by the prepreg or synthetic leather, which is not preferable.
このようにして得られる本発明の工程剥離紙は、剥離強度が経時で変化し難い、優れた工程剥離紙となる。重剥離タイプのプリプレグ工程剥離紙としては、後述する剥離強度測定方法による剥離強度が０．７〜３．０Ｎ／２５ｍｍであることが好ましく、０．７〜２．５Ｎ／２５ｍｍであることがより好ましく、０．７〜２．０Ｎ／２５ｍｍであることが更に好ましく、０．８〜１．５Ｎ／２５ｍｍであることが特に好ましく、０．９〜１．５Ｎ／２５ｍｍであることが最も好ましい。なお、製造直後と、エージング後いずれの時点で測定しても剥離強度がともに上記範囲に入ることが好ましい。このような工程剥離紙であることにより、経時で安定した工程剥離紙となる。エージングの期間は通常１ヶ月以上であり、１ヶ月以上の期間を置いた場合には、剥離強度の変化が緩やかになり、約１ヶ月後の剥離強度が所望の範囲内の値であれば、通常その後もこれらの範囲の剥離強度が得られる。剥離強度が０．７Ｎ／２５ｍｍを下回ると、プリプレグを製造した後、プリプレグが工程剥離紙から浮く、いわゆる浮き剥がれトラブルが発生するため好ましくない。また、剥離強度が３．０Ｎ／２５ｍｍを超過すると、プリプレグに剥離層の一部が取られ、プリプレグを使用した加工品にシリコーンが混入し、強度が低下するため好ましくない。 The process release paper of the present invention thus obtained is an excellent process release paper whose peel strength hardly changes over time. As for the heavy release type prepreg process release paper, the peel strength according to the peel strength measuring method described later is preferably 0.7 to 3.0 N / 25 mm, more preferably 0.7 to 2.5 N / 25 mm. Preferably, it is 0.7 to 2.0 N / 25 mm, more preferably 0.8 to 1.5 N / 25 mm, and most preferably 0.9 to 1.5 N / 25 mm. It should be noted that the peel strength is preferably within the above range regardless of whether it is measured immediately after production or after aging. By using such a process release paper, the process release paper is stable over time. The aging period is usually 1 month or longer, and when a period of 1 month or longer is set, the change in peel strength becomes moderate, and if the peel strength after about 1 month is within a desired range, Usually, peel strengths in these ranges can be obtained thereafter. If the peel strength is less than 0.7 N / 25 mm, after the prepreg is produced, the prepreg is lifted off from the process release paper, and so-called floating trouble occurs, which is not preferable. On the other hand, when the peel strength exceeds 3.0 N / 25 mm, a part of the peel layer is taken on the prepreg, and silicone is mixed into a processed product using the prepreg, which is not preferable.
（剥離強度測定方法）
剥離紙を５０ｍｍ×１５０ｍｍの試験片として切り取り、この試験片の剥離層に２５ｍｍ×１５０ｍｍエポキシ含浸プリプレグテープ（品番：５１５０、寺岡製作所製）を貼付し、２ｋｇローラーを一往復させて貼合する。試験片を７日間放置後、エポキシ含浸プリプレグテープの、試験片に貼合していない面を、両面テープでＳＵＳ鋼板に固定し、試験片をエポキシ含浸プリプレグテープに対し、１８０°の方向に１００ｍｍ／分の速度で剥がした際の応力を、万能引張試験機（ＳＴＰＯＧＲＡＰＨ Ｖ１−Ｃ、東洋精機製）で測定する。応力の極大部を高い順に１０点、極小部を小さい順に１０点取り、合計２０点の平均値を剥離強度とする。
(Peel strength measurement method)
The release paper is cut out as a 50 mm × 150 mm test piece, a 25 mm × 150 mm epoxy-impregnated prepreg tape (product number: 5150, manufactured by Teraoka Seisakusho) is attached to the release layer of the test piece, and the 2 kg roller is reciprocated once for bonding. After leaving the test piece for 7 days, the surface of the epoxy-impregnated prepreg tape that is not bonded to the test piece is fixed to the SUS steel plate with double-sided tape, and the test piece is 100 mm in the direction of 180 ° with respect to the epoxy-impregnated prepreg tape. The stress at the time of peeling at a rate of / min is measured with a universal tensile testing machine (STPOGRAPH V1-C, manufactured by Toyo Seiki Co., Ltd.). Ten points are assigned to the maximum part of the stress in descending order and 10 points are taken in order from the smallest part, and the average value of 20 points in total is taken as the peel strength.
（用途）
本発明の工程剥離紙は、合成皮革、プリプレグ、プラスチックフィルム等の各種シート製造用の工程剥離紙として用いることができ、特に本発明の工程剥離紙の剥離強度が適しているプリプレグ製造用に好ましく用いられる。
(Use)
The process release paper of the present invention can be used as a process release paper for manufacturing various sheets of synthetic leather, prepreg, plastic film, etc., and is particularly preferable for manufacturing a prepreg suitable for the peel strength of the process release paper of the present invention. Used.
次に、実施例、比較例を挙げて本発明による作用効果を明らかにするが、本発明はこれら実施例に限定されるものではない。 Next, although an example and a comparative example are given and the operation effect by the present invention is clarified, the present invention is not limited to these examples.
１．実施例１〜４７、比較例１，２の工程剥離紙の製造
〔基紙〕
表１中のヤンキー紙、上質紙、コート紙ともに、原料として広葉樹晒クラフトパルプ１００％のパルプを使用し、フリーネスを３７０ｍｌとした。そして、絶乾パルプ１ｔに対して、カチオン化澱粉を５ｋｇ、サイズ剤０．２ｋｇをそれぞれ有効成分基準で内添し、填料として軽質炭酸カルシウムを灰分１０％となるよう内添した。その後、長網抄紙機で抄造・乾燥後、米坪１５７ｇ／ｍ2の基紙を得た。以上の製造工程において、上質紙の場合は、ツインワイヤー（ハイブリッドフォーマー）からなるワイヤーパート、オープンドローのないストレートスルー型のプレスパート、ダブルデッキ方式のドライヤーパートを用いて抄紙した。ヤンキー紙は上記工程の後、８０℃のヤンキードラムに湿紙を押し付けて製造した。コート紙は上記工程の後、ロッドメタリングサイズプレスコーターで、微粒カオリンクレー（品番：ＡＭＡＺＯＮ、カダム社製）３０質量部、湿式重質炭酸カルシウム（品番：エスカロン＃９０、三共製粉（株）製）７０質量部、接着剤としてスチレン−ブタジエンラテックス（品番：ＰＡ５０３６、日本エイアンドエル（株）製）１０質量部を含む塗工液を、片面あたり８．０ｇ／ｍ2の塗工量となるよう、原紙の両面に塗工して製造した。
1. Production of process release papers of Examples 1 to 47 and Comparative Examples 1 and 2 [Base paper]
For all the Yankee paper, fine paper, and coated paper in Table 1, 100% hardwood bleached kraft pulp was used as a raw material, and the freeness was 370 ml. Then, 5 kg of cationized starch and 0.2 kg of sizing agent were internally added to the absolutely dry pulp 1 t on the basis of active ingredients, respectively, and light calcium carbonate as a filler was internally added so as to have an ash content of 10%. Thereafter, paper making and drying were carried out using a long paper machine to obtain a base paper having a rice floor of 157 g / m 2 . In the above manufacturing process, in the case of fine paper, paper was made using a wire part made of twin wire (hybrid former), a straight-through press part without open draw, and a double deck type dryer part. Yankee paper was manufactured by pressing wet paper against a Yankee drum at 80 ° C. after the above process. After the above process, the coated paper is a rod metering size press coater, 30 parts by weight of fine kaolin clay (product number: AMAZON, manufactured by Kadam), wet heavy calcium carbonate (product number: ESCALON # 90, manufactured by Sankyo Flour Milling Co., Ltd.) ) A coating liquid containing 70 parts by mass and 10 parts by mass of styrene-butadiene latex (product number: PA5036, manufactured by Nippon A & L Co., Ltd.) as an adhesive so that the coating amount is 8.0 g / m 2 per side. It was manufactured by coating on both sides of the base paper.
〔剥離層の形成〕
まず、表１に示す種類及び割合で、水性シリコーン、水溶性樹脂（Ａ）、アセトアセチル化ポリビニルアルコール（Ｂ）を常温にて混合撹拌して剥離層用の塗工液を得た。なお、用いたシリコーン、水溶性樹脂（Ａ）、アセトアセチル化ポリビニルアルコール（Ｂ）は以下のとおりである。また、表１の水溶性樹脂（Ａ）、アセトアセチル化ポリビニルアルコール（Ｂ）の配合量は、シリコーン１００質量部に対する値である。
(Formation of release layer)
First, aqueous silicone, water-soluble resin (A), and acetoacetylated polyvinyl alcohol (B) were mixed and stirred at room temperature in the types and proportions shown in Table 1 to obtain a release layer coating solution. In addition, the used silicone, water-soluble resin (A), and acetoacetylated polyvinyl alcohol (B) are as follows. Moreover, the compounding quantity of water-soluble resin (A) of Table 1 and acetoacetylated polyvinyl alcohol (B) is a value with respect to 100 mass parts of silicone.
・水性シリコーン（品番：ＫＭ−３９５１、信越シリコーン（株）製）
・溶剤シリコーン（品番：ＫＳ−３６０１、信越シリコーン（株）製）
・ポリビニルアルコール（クラレ（株）社製）
品番：Ｌ−１０、ケン化度：７２〜７４ｍｏｌ％。
品番：Ｌ−９−７８、ケン化度：７７〜７９ｍｏｌ％。
品番：ＰＶＡ−４０５、ケン化度：８０〜８３ｍｏｌ％。
品番：ＰＶＡ−２１７、ケン化度：８７〜８９ｍｏｌ％。
品番：ＰＶＡ−１１７、ケン化度：９８〜９９ｍｏｌ％。
・アセトアセチル化ポリビニルアルコール（日本合成化学社製、品番：ゴーセファイマーＺ４１０、ケン化度９９％、重合度２１００）
・カルボキシメチルセルロース（品番：ＦＩＮＮＦＩＸ ＣＭＣ、三晶（株）製）
・カゼイン（日成共益株式会社製）
水性シリコーンの質量は、剥離剤そのものの質量であり、水を含む質量とする。またポリビニルアルコールは、表１に記載のケン化度のものを用いた。
・ Aqueous silicone (Product number: KM-3951, manufactured by Shin-Etsu Silicone Co., Ltd.)
・ Solvent silicone (Product number: KS-3601, manufactured by Shin-Etsu Silicone Co., Ltd.)
・ Polyvinyl alcohol (Kuraray Co., Ltd.)
Product number: L-10, saponification degree: 72-74 mol%.
Product number: L-9-78, saponification degree: 77-79 mol%.
Product number: PVA-405, saponification degree: 80-83 mol%.
Product number: PVA-217, degree of saponification: 87-89 mol%.
Product number: PVA-117, saponification degree: 98-99 mol%.
Acetoacetylated polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd., product number: Gohsephimer Z410, saponification degree 99%, polymerization degree 2100)
・ Carboxymethylcellulose (Product No .: FINNFIX CMC, manufactured by Sanki Co., Ltd.)
・ Casein (manufactured by Nissei Kyobun Co., Ltd.)
The mass of the aqueous silicone is the mass of the release agent itself and includes water. Polyvinyl alcohol having a saponification degree shown in Table 1 was used.
上記塗工液を、前述した基紙にエアーナイフコーターで、片面あたり乾燥質量が表１に記載の値となるように塗工し、熱風乾燥機で乾燥させた。 The coating liquid was applied to the above-described base paper with an air knife coater so that the dry mass per side was the value shown in Table 1, and dried with a hot air dryer.
２．評価方法
以上のようにして製造した工程剥離紙について、以下のとおり測定・評価を行った。結果は、表１に示した。
１）剥離強度測定
上述の剥離強度測定方法により、各実施例および各比較例の工程剥離紙の剥離強度を測定した。剥離強度は、剥離層を設けた直後の工程剥離紙の剥離強度と、剥離層を設けた後に１ヶ月間エージングした後の工程剥離紙の剥離強度とを測定した。結果を表１に示す。
2. Evaluation Method The process release paper produced as described above was measured and evaluated as follows. The results are shown in Table 1.
1) Peel strength measurement The peel strength of the process release paper of each Example and each Comparative Example was measured by the above-described peel strength measurement method. For the peel strength, the peel strength of the process release paper immediately after providing the release layer and the peel strength of the process release paper after aging for one month after providing the release layer were measured. The results are shown in Table 1.
本発明の工程剥離紙は、種々のシート製造用の工程剥離紙として使用することができ、特にプリプレグ製造用として有用である。 The process release paper of the present invention can be used as a process release paper for manufacturing various sheets, and is particularly useful for manufacturing a prepreg.
Claims (6)
前記剥離層は、水性シリコーンと、水溶性樹脂とを含む、工程剥離紙であって、
前記剥離層にエポキシ含浸プリプレグテープを２ｋｇの荷重で貼合して７日間放置した後に１８０°の方向に速度１００ｍｍ／分で剥がした際の応力を剥離強度とすると、前記剥離層を設けて１ヶ月以上経過した後の前記剥離強度が０．７〜３．０Ｎ／２５ｍｍであることを特徴とする、工程剥離紙。 Consisting of a base paper and a release layer provided on the base paper,
The release layer is a process release paper containing an aqueous silicone and a water-soluble resin,
When the release strength is defined as the stress when the epoxy impregnated prepreg tape is bonded to the release layer with a load of 2 kg and left for 7 days and then peeled in the direction of 180 ° at a speed of 100 mm / min, the release layer is provided. The process release paper, wherein the peel strength after elapse of a month or more is 0.7 to 3.0 N / 25 mm.
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| JP2001072711A (en) * | 1999-09-08 | 2001-03-21 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition |
| JP2003147693A (en) * | 2001-11-09 | 2003-05-21 | Asahi Kasei Corp | Releasable material and releasing agent |
| JP2005220482A (en) * | 2004-02-06 | 2005-08-18 | Lintec Corp | Processing paper for prepreg |
| JP2006052356A (en) * | 2004-08-16 | 2006-02-23 | Shin Etsu Chem Co Ltd | Ultraviolet-curable coating composition |
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| JP2001072711A (en) * | 1999-09-08 | 2001-03-21 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition |
| JP2003147693A (en) * | 2001-11-09 | 2003-05-21 | Asahi Kasei Corp | Releasable material and releasing agent |
| JP2005220482A (en) * | 2004-02-06 | 2005-08-18 | Lintec Corp | Processing paper for prepreg |
| JP2006052356A (en) * | 2004-08-16 | 2006-02-23 | Shin Etsu Chem Co Ltd | Ultraviolet-curable coating composition |
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| JP2010180502A (en) * | 2009-02-05 | 2010-08-19 | Daio Paper Corp | Process release paper |
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