JP6760749B2 - Chloroprene rubber latex adhesive composition - Google Patents
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Description
本発明は、親展ハガキの製造に好適な特性を有するクロロプレンゴムラテックス接着剤組成物に関するものである。 The present invention relates to a chloroprene rubber latex adhesive composition having properties suitable for the production of confidential postcards.
郵便法の改正に伴い、親展性の隠蔽はがきシステムが実用化され、普及している。この親展性の隠蔽はがきは、個人的用件、広告や案内等の各種情報が記載されたはがきを折り畳み、重ね合わせ部分を接着して情報内容を隠蔽して郵送し、受取人が重ね部分を剥がして情報内容を見ることができるものである。このような情報隠蔽手段は郵送用はがきに限らず利用されており、情報担持シートと総称されている。 With the revision of the Postal Law, a confidential concealment postcard system has been put into practical use and has become widespread. This confidential concealment postcard folds a postcard containing various information such as personal matters, advertisements, guidance, etc., glues the overlapped part to hide the information content and mails it, and the recipient puts the overlapped part The information content can be viewed by peeling it off. Such information hiding means are used not only for postcards for mailing, but are collectively called information-carrying sheets.
このような情報担持シートの製造方法としては、予め接着剤を塗布したシートを製造しておいて、秘匿面に情報を印刷した後、秘匿面を貼り合せる方法が一般的である。したがって、情報担持シート用接着剤には開封されるまで秘匿面を保持できる接着力、開封時にシートの破壊や糊残りによる汚染がない再剥離性だけではなく、印刷前の保管時に貼り付いてしまわない保存性などが要求される。 As a method for manufacturing such an information-carrying sheet, a method is generally used in which a sheet coated with an adhesive is manufactured in advance, information is printed on the concealed surface, and then the concealed surface is bonded. Therefore, the adhesive for information-carrying sheets has not only adhesive strength that can hold a concealed surface until it is opened, removability without sheet breakage or contamination due to adhesive residue at the time of opening, but also sticking during storage before printing. No storage stability is required.
従来、情報担持シートには天然ゴムラテックスを用いた接着剤が多く用いられてきたが、各要求性能をバランス良く満たすことは難しかった。そこで、特許文献1では変性した天然ゴムラテックスを用いる方法が開示されている。また、天然ゴムラテックスは天然物を由来とするため品質のバラツキが避けられず、物性の微調整が困難であった。
本発明の課題は、情報担持シートの製造に好適な特性、即ち開封されるまで秘匿面を保持できる接着力、開封時にシートの破壊や糊残りによる汚染がない再剥離性、印刷前の保管時に貼り付いてしまわない保存性を有するクロロプレンゴムラテックス接着剤組成物を提供することである。 The problems of the present invention are properties suitable for manufacturing an information-carrying sheet, that is, adhesive strength capable of holding a concealed surface until opened, removability without sheet breakage or contamination due to adhesive residue at the time of opening, and storage before printing. It is an object of the present invention to provide a chloroprene rubber latex adhesive composition having a storage stability that does not stick.
本発明は、ゲル分率が35重量%以上であり、結晶化時間が24時間以上であるクロロプレンゴムラテックス(a)、シリカ(b)を含有し、接着剤組成物全体の固形分に対して前記シリカ(b)を25〜75重量%含有することを特徴とするクロロプレンゴムラテックス接着剤組成物である。 The present invention contains chloroprene rubber latex (a) and silica (b) having a gel content of 35 % by weight or more and a crystallization time of 24 hours or more, based on the solid content of the entire adhesive composition. The chloroprene rubber latex adhesive composition is characterized by containing 25 to 75% by weight of the silica (b) .
本発明のクロロプレンゴムラテックス接着剤組成物は接着力、再剥離性および保存性に優れるため、情報担持シートに有用である。特に工業的に製造されるクロロプレンゴムラテックスを用いるため品質のバラツキが少なく、物性の微調整も容易である。 The chloroprene rubber latex adhesive composition of the present invention is useful as an information-carrying sheet because it has excellent adhesive strength, removability and storage stability. In particular, since industrially manufactured chloroprene rubber latex is used, there is little variation in quality and fine adjustment of physical properties is easy.
本発明のクロロプレンゴムラテックス接着剤組成物は、ゲル分率が30重量%以上であり、結晶化時間が24時間以上であるクロロプレンゴムラテックス(a)を含有する。クロロプレンゴムラテックスのゲル分率が30重量%以上であることによって剥離性が向上し、結晶化時間が24時間以上であることにより、接着力を確保できる。 The chloroprene rubber latex adhesive composition of the present invention contains the chloroprene rubber latex (a) having a gel fraction of 30% by weight or more and a crystallization time of 24 hours or more. When the gel fraction of the chloroprene rubber latex is 30% by weight or more, the peelability is improved, and when the crystallization time is 24 hours or more, the adhesive strength can be secured.
本発明におけるゲル含有率は、以下の方法により測定する。予め固形重量を測定したクロロプレンラテックスにTHFを添加して3時間密閉容器内で撹拌・分散させた後、遠心分離を行う。遠心分離後、容器底部のゲルを吸い上げないように上澄み液の固形分を測定することにより非ゲル量を測定し、残分をゲル量としてゲル含有率を算出する。 The gel content in the present invention is measured by the following method. THF is added to the chloroprene latex whose solid weight has been measured in advance, and the mixture is stirred and dispersed in a closed container for 3 hours, and then centrifuged. After centrifugation, the non-gel amount is measured by measuring the solid content of the supernatant so as not to suck up the gel at the bottom of the container, and the gel content is calculated using the remaining amount as the gel amount.
また、本発明における結晶化時間は、以下の方法により測定する。クロロプレンゴムラテックスをガラス製パッド上で23℃雰囲気下において乾燥することにより、厚み0.5〜1mm程度の乾燥フィルムを作成する。複数作成した乾燥フィルムを重ね合わせることにより1.5〜5mmの厚さとする。この際に空気層が残らないように十分に押し、約50×50mmの大きさに切り取って試験片とする。試験片を70℃雰囲気下で30分間加熱した後、タイプA硬度を測定し(経過時間0分とする)、その後直ぐに−5℃雰囲気下に静置し、測定開始から硬度が10上昇するまでの時間を結晶化時間とする。なお、硬度測定は5点で行って平均値にて評価する。また、測定は48時間までとし、48時間経過時点で硬度が10上昇していない場合であっても、本発明においては結晶化時間48時間として取り扱うものとする。 The crystallization time in the present invention is measured by the following method. Chloroprene rubber latex is dried on a glass pad in an atmosphere of 23 ° C. to prepare a dry film having a thickness of about 0.5 to 1 mm. A thickness of 1.5 to 5 mm is obtained by stacking a plurality of prepared dry films. At this time, push it sufficiently so that no air layer remains, and cut it into a size of about 50 × 50 mm to make a test piece. After heating the test piece in an atmosphere of 70 ° C. for 30 minutes, measure the type A hardness (elapsed time is 0 minutes), and immediately leave it in an atmosphere of -5 ° C. from the start of measurement until the hardness increases by 10. Let the crystallization time be. The hardness is measured at 5 points and evaluated by the average value. Further, the measurement is limited to 48 hours, and even if the hardness does not increase by 10 after 48 hours, the crystallization time is treated as 48 hours in the present invention.
本発明のクロロプレンゴムラテックス接着剤組成物は、シリカ(b)を含有する。シリカを含有することにより、通常接触では塗工面同士が接着しなくなり、また塗工紙の巻き取りも可能となるなど、意図しない接着を防ぐことができ、接着性能の調整も可能となる。なお、シリカを直接クロロプレンゴムラテックスへ分散させようとすると凝集しやすいため、いったん水溶性高分子溶液へ分散させた後にクロロプレンラテックスへ分散させる方法が好ましい。このような水溶性高分子としては、ポリビニルアルコール、ヒドロキシエチルセルロース、キサンタンガムなどが挙げられる。 The chloroprene rubber latex adhesive composition of the present invention contains silica (b). By containing silica, it is possible to prevent unintended adhesion such that the coated surfaces do not adhere to each other in normal contact and the coated paper can be wound up, and the adhesive performance can be adjusted. If silica is to be directly dispersed in chloroprene rubber latex, it tends to aggregate. Therefore, a method of once dispersing in a water-soluble polymer solution and then dispersing in chloroprene latex is preferable. Examples of such a water-soluble polymer include polyvinyl alcohol, hydroxyethyl cellulose, xanthan gum and the like.
シリカの配合量は、接着剤組成物全体の固形分に対して25〜75重量%とすることが好ましい。25重量%以上とすることで保管時の貼り付きを防ぐことができ、75重量%以下とすることで圧締時の接着性を確保できる。 The amount of silica blended is preferably 25 to 75% by weight based on the solid content of the entire adhesive composition. When the content is 25% by weight or more, sticking during storage can be prevented, and when the content is 75% by weight or less, the adhesiveness at the time of compression can be ensured.
本発明の接着剤組成物にさらに粘着付与樹脂(c)を配合することによりシリカ配合時の安定性が向上し、また、剥離強度の調整を行うことができる。
粘着付与樹脂の具体例として、ガムロジン、トールロジン、ウッドロジン、不均斉化ロジン、重合ロジン、これらロジンのグリセリンエステルやペンタエリスリトールエステル、これらの水素添加物などのロジン系樹脂、テルペン樹脂、炭化水素変性テルペン樹脂、これらの水素添加物などのテルペン系樹脂、テルペンフェノール樹脂、テルペンフェノール樹脂の水素添加物などのテルペンフェノール系樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、芳香族系石油樹脂、共重合系石油樹脂、ジシクロペンタジエン系石油樹脂、ピュアーモノマー系石油樹脂、これらの水素添加物などの石油系樹脂、スチレン系樹脂、クマロンインデン系樹脂、アルキルフェノール系樹脂、キシレン系樹脂、ダンマル、コーパル、シェラックなどが挙げられる。
中でもロジン系樹脂が好ましく、クロロプレンゴムラテックスへの分散性の点からエマルジョンであることがより好ましい。
By further blending the tackifier resin (c) with the adhesive composition of the present invention, the stability at the time of blending silica can be improved, and the peel strength can be adjusted.
Specific examples of the tackifier resin include gum rosin, tall rosin, wood rosin, asymmetric rosin, polymerized rosin, glycerin ester and pentaerythritol ester of these rosins, rosin-based resins such as these hydrogenated additives, terpene resins, and hydrocarbon-modified terpenes. Resins, terpene resins such as these hydrogen additives, terpene phenol resins, terpene phenol resins such as terpene phenol resin hydrogen additives, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, Copolymerized petroleum resin, dicyclopentadiene petroleum resin, pure monomer based petroleum resin, petroleum resin such as these hydrogen additives, styrene resin, Kumaron inden resin, alkylphenol resin, xylene resin, dammar, Examples include copal and shelac.
Of these, a rosin-based resin is preferable, and an emulsion is more preferable from the viewpoint of dispersibility in chloroprene rubber latex.
粘着付与樹脂の配合量は、固形分を基準として前記クロロプレンゴムラテックス100重量部に対して0〜100重量部程度が好ましい。 The blending amount of the tackifier resin is preferably about 0 to 100 parts by weight with respect to 100 parts by weight of the chloroprene rubber latex based on the solid content.
本発明のクロロプレンゴムラテックス接着剤組成物には前記各添加剤の他、炭酸カルシウムやシリカなどの無機充填材、老化防止剤、加硫促進剤、界面活性剤、防腐剤、消泡剤、分散剤、レベリング剤、凍結安定剤などを適宜配合できる。 In addition to the above-mentioned additives, the chloroprene rubber latex adhesive composition of the present invention includes inorganic fillers such as calcium carbonate and silica, antiaging agents, vulcanization accelerators, surfactants, preservatives, defoaming agents, and dispersions. Agents, leveling agents, freeze stabilizers and the like can be appropriately blended.
以下、実施例、比較例により本発明を更に説明する。また、当然のことながら本発明は実施例に制約されるものではない。 Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples. Further, as a matter of course, the present invention is not limited to the examples.
実施例1
クロロプレンゴムラテックス(a)としてショウプレン750(昭和電工社製、商品名、ゲル含有率60%、結晶化時間48時間)100重量部、シリカ(b)としてNipsil E−150J(東ソー・シリカ社製、商品名)75重量部、粘着付与樹脂(c)としてスーパーエステルE−865NT(荒川化学工業社製、商品名)50重量部、界面活性剤としてアミラヂン1820D(第一工業製薬社製、商品名)1.3重量部及びラテムルAD−25(花王社製、商品名)0.4重量部、熱劣化防止剤としてアデカスタブLX−61(ADEKA社製、商品名)1.5重量部、ポリビニルアルコールとしてPVA−224(クラレ社製、商品名)2.3重量部、シリカの事前分散水溶液用に水372.8重量部を添加し、実施例1の接着剤組成物を得た。
Example 1
Chloroprene rubber latex (a) as showprene 750 (manufactured by Showa Denko, trade name, gel content 60%, crystallization time 48 hours) 100 parts by weight, silica (b) as Nipsil E-150J (manufactured by Toso Silica), 75 parts by weight (trade name), 50 parts by weight of Superester E-865NT (manufactured by Arakawa Chemical Co., Ltd., trade name) as the tackifying resin (c), Amiradin 1820D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name) 1.3 parts by weight and Latemuru AD-25 (manufactured by Kao, trade name) 0.4 parts by weight, as a heat deterioration inhibitor Adecastab LX-61 (manufactured by ADEKA, trade name) 1.5 parts by weight, as polyvinyl alcohol 2.3 parts by weight of PVA-224 (manufactured by Kuraray Co., Ltd., trade name) and 372.8 parts by weight of water for the pre-dispersed aqueous solution of silica were added to obtain the adhesive composition of Example 1.
実施例2〜3、比較例1〜2
実施例1で用いた配合材料の他、クロロプレンゴムラテックスとしてショウプレン752(昭和電工株式会社製、商品名、ゲル含有率25%、結晶化時間48時間)、ショウプレン753(昭和電工株式会社製、商品名、ゲル含有率70%、結晶化時間48時間)、ショウプレン654(昭和電工株式会社製、商品名、ゲル含有率35%、結晶化時間24時間)、ショウプレンSD100(昭和電工株式会社製、商品名、ゲル含有率0%、結晶化時間30分)を用い、表1記載の配合(重量部)にて各配合材料を混合し、各接着剤組成物を得た。
Examples 2-3, Comparative Examples 1-2
In addition to the compounding materials used in Example 1, as chloroprene rubber latex, Shoprene 752 (manufactured by Showa Denko Co., Ltd., trade name, gel content 25%, crystallization time 48 hours), Shouprene 753 (manufactured by Showa Denko Co., Ltd., product Name, gel content 70%, crystallization time 48 hours), Choprene 654 (manufactured by Showa Denko Co., Ltd., product name, gel content 35%, crystallization time 24 hours), Choprene SD100 (manufactured by Showa Denko Co., Ltd., product) Name, gel content 0%, crystallization time 30 minutes) were used, and each compounding material was mixed according to the compounding (part by weight) shown in Table 1 to obtain each adhesive composition.
各接着剤組成物を上質紙にバーコーターで固形分換算5g/m2となるように塗工し、110℃で300秒間乾燥した。乾燥後、23℃、50%RHで24時間養生し塗工紙を得た。各塗工紙について、以下の方法で評価を行った。なお表1における左側の数値は剥離強度(N/25mm)、右側は剥離時の外観をb:基材破壊あり、c:基材破壊なし、にて示した。 Each adhesive composition was applied to woodfree paper with a bar coater so as to have a solid content equivalent of 5 g / m 2, and dried at 110 ° C. for 300 seconds. After drying, it was cured at 23 ° C. and 50% RH for 24 hours to obtain a coated paper. Each coated paper was evaluated by the following method. The numerical values on the left side in Table 1 are shown by peeling strength (N / 25 mm), and on the right side, the appearance at the time of peeling is shown by b: with substrate destruction and c: without substrate destruction.
初期強度
塗工紙を作成後、25mm幅に切断して塗工面同士を合わせて50kgf/25mmの荷重で圧着し、引張り試験機を使用して変位速度100mm/分でT字剥離試験を行い、剥離強度及び剥離時の外観を確認する。
After making the initial strength coated paper, it is cut to a width of 25 mm, the coated surfaces are put together and crimped with a load of 50 kgf / 25 mm, and a T-shaped peeling test is performed at a displacement speed of 100 mm / min using a tensile tester. Check the peel strength and appearance at the time of peeling.
経時安定性(常温)
圧着していない塗工紙及び50kgf/25mmの荷重で圧着した塗工紙を23℃、50%RH雰囲気下で4週間静置する。静置後、圧着していない塗工紙については50kgf/25mmの荷重で圧着し、予め圧着した塗工紙についてはそのままの状態で引張り試験機を使用して変位速度100mm/分でT字剥離試験を行い、剥離強度及び剥離時の外観を確認する。
Stability over time (normal temperature)
The uncrimped coated paper and the coated paper crimped with a load of 50 kgf / 25 mm are allowed to stand for 4 weeks in an atmosphere of 23 ° C. and 50% RH. After standing, the uncrimped coated paper is crimped with a load of 50 kgf / 25 mm, and the pre-crimped coated paper is peeled T-shaped at a displacement speed of 100 mm / min using a tensile tester as it is. Perform a test to check the peel strength and appearance at the time of peeling.
経時安定性(高温高湿)
圧着していない塗工紙及び50kgf/25mmの荷重で圧着した塗工紙を40℃、90%RH雰囲気下で4週間静置する。静置後に23℃、50%RH雰囲気に移して更に24時間静置し、予め圧着していない塗工紙については50kgf/25mmの荷重で圧着し、圧着した塗工紙についてはそのままの状態で引張り試験機を使用して変位速度100mm/分でT字剥離試験を行い、剥離強度及び剥離時の外観を確認する。
Stability over time (high temperature and high humidity)
The uncrimped coated paper and the coated paper crimped with a load of 50 kgf / 25 mm are allowed to stand at 40 ° C. in a 90% RH atmosphere for 4 weeks. After standing, move to a 50% RH atmosphere at 23 ° C and let stand for another 24 hours, crimp the coated paper that has not been crimped in advance with a load of 50 kgf / 25 mm, and leave the crimped coated paper as it is. A T-shaped peeling test is performed at a displacement speed of 100 mm / min using a tensile tester to confirm the peeling strength and the appearance at the time of peeling.
各実施例の接着剤組成物は初期強度、経時安定性(常温及び高温高湿)のいずれも良好であった。一方、ゲル含有率が低い接着剤組成物は高温高湿下で保存した場合に紙破が見られ、また結晶化時間が速いクロロプレンゴムラテックスを使用した接着剤組成物は剥離強度が小さく、接着力が不足していた。 The adhesive composition of each example had good initial strength and stability over time (normal temperature and high temperature and high humidity). On the other hand, the adhesive composition having a low gel content shows paper breakage when stored under high temperature and high humidity, and the adhesive composition using chloroprene rubber latex having a fast crystallization time has low peeling strength and adheres. I was lacking in power.
Claims (3)
An information-carrying sheet produced by using the chloroprene rubber latex adhesive composition according to claim 1 or 2 .
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