JPH0257027B2 - - Google Patents
Info
- Publication number
- JPH0257027B2 JPH0257027B2 JP59093963A JP9396384A JPH0257027B2 JP H0257027 B2 JPH0257027 B2 JP H0257027B2 JP 59093963 A JP59093963 A JP 59093963A JP 9396384 A JP9396384 A JP 9396384A JP H0257027 B2 JPH0257027 B2 JP H0257027B2
- Authority
- JP
- Japan
- Prior art keywords
- color developer
- sheet
- color
- paper
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- Color Printing (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
本発明は新規な顕色剤シートの製造方法に関
し、更に詳しくは顕色剤配合樹脂を押出し成形し
た後熱処理を施して該顕色剤を表面に移行・偏在
化させることを特徴とする顕色剤シートの製造方
法に関するものである。
ノンカーボン紙は発色剤マイクロカプセルと顕
色剤とを別々の紙に塗布してなる所謂転移タイプ
と、両剤を紙の表面に２層に重ね、或いは混合し
て塗布してなるセルフコンテインドタイプとに大
別される。しかし、これらのノンカーボン紙はい
ずれも文字通り紙を基材とするため、耐水性に欠
けるという致命的欠点を有し、更には強度の面で
も十分とは云えない。かかる欠点が克服されるな
らばノンカーボン紙の用途は飛躍的に拡大される
可能性がある。例えば荷札等の配送用ラベル類に
あつては雨や水に濡れると強度が低下し、配送中
に破損し、配送作業に支障を来すという欠点があ
る。
かかる問題を解消せんとして、合成樹脂フイル
ムに発色剤マイクロカプセルと顕色剤とを塗布し
てなる感圧フイルムが開発され、既に出願されて
いる。しかし、上記感圧フイルムは筆記性、耐水
性及び強度については満足すべきものではある
が、例えば配送中等において他の荷物等との摩擦
により発色して汚れるという問題が残されてい
る。
一方、転移タイプとして、フイルムに顕色剤を
塗工する方法が考えられるが、この場合はフイル
ム製造プロセスと顕色剤塗工プロセスの２工程を
必要とする欠点があり、他方、単純に顕色剤をブ
レンドして押出しする方法は多量の顕色剤を用い
ないと十分な発色効果を得られず、従つてコスコ
アツプとなり、また多量の顕色剤の使用は押出し
の際に種々の不都合を生じ、更に顕色剤シートの
厚みを薄くできない等の問題を孕んでいる。
本発明はかかる実情に鑑み、上記問題を解消せ
んとして鋭意研究の末、フイルム形成と顕色剤フ
イルムとを一工程で一挙に製造し、且つ少量の顕
色剤で優れた発色効果を有し、且つ十分な強度、
耐水性を有する顕色剤シートの製造方法を提供す
るものである。
即ち、本発明はオレフイン系樹脂に顕色剤を混
合し、該混合物をシート状に押出し成形した後熱
処理を施して前記顕色剤を該シートの表面に移行
させることを特徴とする顕色剤シートの製造方法
を内容とするものである。
本発明に用いられる顕色剤としては特に制限は
なく公知のものが全て使用でき、感圧又感熱の方
式により、それぞれの目的によつて各種のものが
あり、例えばビスフエノールＡ、ビスフエノール
Ｂ、α−ナフトール、β−ナフトール、「三東レ
ジン」（三井東圧社製）等のノボラツク型フエノ
ール樹脂やサルチル酸誘導体系顕色剤等が好適で
ある。
本発明に用いられるオレフイン系樹脂としては
ポリエチレン、ポリプロピレン、これらの共重合
体等が好適である。顕色剤とオレフイン系樹脂と
の混合割合はポリオレフイン樹脂、及び顕色剤の
種類、発色度、等により一概には規定できない
が、ポリオレフイン系樹脂100重量部に対し、顕
色剤は1.0〜10.0重量部が好適である。10.0重量部
を越えると顕色剤シートの押出しに際し困難を生
じ、また1.0重量部未満では発色が十分でない。
本発明における熱処理はオレフイン系樹脂と顕
色剤との混合物からなるシート状押出成形体の表
面に顕色剤を移行させ、偏在化させるためのもの
で、温度は顕色剤の融点以上、オレフイン系樹脂
の融点以下が好ましく、処理時間は処理温度が高
温で、移行促進剤添加量が多い程短時間で十分な
発色が得られる。例えば、ポリエチレン100重量
部、「三東レジン」３重量部、２−エチルヘキサ
ン酸亜鉛２重量部の顕色剤シートでは60℃〜100
℃、１分〜30分間の熱処理が好適である。
オレフイン系樹脂と顕色剤とからなる混合物に
２−エチルヘキサン酸亜鉛の如き移行促進剤を添
加することにより、移行・偏在化を効果的に達成
することができる。移行促進剤の添加量はポリオ
レフイン系樹脂100重量部に対し、0.1〜3.0重量
部が適当である。0.1重量部未満では顕色剤の移
行促進効果は十分ではなく、3.0重量部を越える
と、顕色剤シートにベタツキが生じ取扱いに不便
である。
本発明の顕色剤シートは単独で、或いは紙、
布、不織布、セロフアン、合成樹脂フイルム、金
属箔、合成樹脂フイルムと金属箔とのラミネート
等の基材の上に塗工、共押出し等による積層物の
形で用いられるが、該シートを不透明にし、発色
に対してコントラストを大きくする不透明化剤を
添加することは感圧発色させた筆記内容を見易く
する点で好ましい態様である。かかる不透明化剤
としてはTiO2、SiO2、CaCO3、タルク、活性白
土、酸性白土等か好ましい。不透明化剤の添加量
は顕色剤シートの目的厚さにより調整され、厚い
程添加割合は少なくてよい。一例を示せば、ポリ
オレフイン系樹脂100重量部に対し、0.1〜10.0重
量部が好適で10.0重量部を越えると、顕色剤シー
トの薄膜化が困難になり、0.1重量部未満では十
分な不透明化が達成されない。
本発明において、感圧又は感熱のいずれの方式
に用いる場合も、熱処理を施した後、コロナ処理
を施すのが望ましい。コロナ処理を施すことによ
り、顕色剤シート表面の漏れが改善され、発色剤
塗工紙を重ね発色させた際に発色剤の顕色剤シー
トへの転移が効果的に行われ、発色濃度が向上す
る。コロナ処理は一般は行なわれている樹脂フイ
ルム、紙等の表面濡れ、接着性の改善の為のコロ
ナ処理と同様であり、50〜200w／m2の処理で十
分である。
本発明における感圧方式における顕色剤シート
は、押出し成形と同時に、又は熱処理の前もしく
は後に表面の凹凸加工処理を施すのが望ましい。
該凹凸加工により感圧発色の際の摩擦を大きくし
発色剤マイクロカプセルの破壊を助け、顕色剤と
の反応を促進すると共に、発色後は摩擦による表
記事項の不明確化を阻止し、更には表面の凹凸が
光を乱反射させ発色とのコントラストを高める効
果がある。該凹凸加工は例えば(a)押出された顕色
剤シートが冷却固化される際に、表面がマツト加
工された冷却ロールを通す方法、(b)熱処理前に表
面をサンド加工する方法、(c)加熱処理前に予め粗
面化されたフイルムを顕色剤シートの表面に加圧
圧着させ、加熱処理後該フイルムを取り除き、該
フイルムの粗面を顕色剤シートの表面に転写する
方法、(d)顕色剤シートを押出しフイルム化し、延
伸する方法等が好適である。上記方法の中で、(a)
は顕色剤シートの製造と同時に行なうことができ
また簡易である点で特に好適であり、また(c)も採
用する温度によつては熱処理と同時に行なうこと
ができる利点がある。
以下、本発明を実施例及び比較例を挙げて更に
詳細に説明するが、これらにより本発明は何ら制
限を受けるものではない。
実施例１〜２、比較例１〜２
ポリオレフイン樹脂として低密度ポリエチレン
「ミラソンＭ−14（MI15.1ｇ／10分、密度：0.919
ｇ／cm3）」（三井ポリケミカル製）100重量部に対
し、顕色剤として、ノボラツク型フエノール樹脂
「三東レジン」（三井東圧製）３重量部を混合した
後、この混合物をベント式押出機（ダイス出口温
度210℃）により溶融混合し、ペレタイザーによ
りペレツト化した。
該ペレツトを50℃で十分乾燥させた後、Ｔダイ
押出機（径40mm、Ｔダイ温度250℃）によりシー
ト化させ紙（50ｇ／m2）上に塗工し、顕色剤シー
ト積層紙を作成した。
得られた顕色剤シート積層紙を乾燥機を用いて
90℃で30分間熱処理し、得られた積層紙をサンプ
ルＡとし、更に熱処理の後出力周波数5KHzのソ
リツドステート式コロナ装置で200w／m2の処理
を施したものをサンプルＢとした。
一方、比較のために、熱処理を施していないも
のをサンプルＣ、熱処理を施さずにコロナ放電処
理したものをサンプルＤとした。
上記サンプルＡ〜Ｄを神崎製紙製「KSコピ
ー・ブライト上用紙（発色剤マイクロカプセル塗
工紙）」を重ね合わせ、同一圧力で感圧発色させ、
発色濃度を肉眼で比較し５段階で評価した。結果
を第１表に示す。
The present invention relates to a novel method for manufacturing a color developer sheet, and more specifically, a color developer characterized by extrusion molding a color developer-containing resin and then subjecting it to heat treatment to cause the color developer to migrate and become unevenly distributed on the surface. The present invention relates to a method for manufacturing a drug sheet. Non-carbon paper is of the so-called transfer type, in which color former microcapsules and color developer are coated on separate sheets of paper, and self-contained type, in which both agents are coated on the surface of the paper in two layers or mixed. It is broadly divided into. However, since all of these non-carbon papers literally use paper as a base material, they have the fatal drawback of lacking water resistance, and furthermore cannot be said to be sufficient in terms of strength. If these drawbacks could be overcome, the uses of non-carbon paper could be dramatically expanded. For example, shipping labels such as shipping tags have the disadvantage that their strength decreases when they get wet with rain or water, causing them to be damaged during shipping and hindering shipping operations. In order to solve this problem, a pressure-sensitive film made by coating a synthetic resin film with color former microcapsules and a color developer has been developed, and an application has already been filed. However, although the above-mentioned pressure-sensitive film is satisfactory in terms of writability, water resistance, and strength, it still has the problem of coloring and staining due to friction with other packages during shipping, for example. On the other hand, as a transfer type method, a method of coating a color developer on a film is considered, but in this case, there is a drawback that it requires two steps: a film manufacturing process and a color developer coating process. In the method of blending and extruding colorants, a sufficient coloring effect cannot be obtained unless a large amount of color developer is used, resulting in an increase in cost, and the use of a large amount of color developer causes various inconveniences during extrusion. This also causes problems such as the inability to reduce the thickness of the color developer sheet. In view of the above circumstances, the present invention was developed as a result of intensive research in order to solve the above-mentioned problems, and it is possible to manufacture a film and a color developer film in one step, and to achieve an excellent coloring effect with a small amount of color developer. , and sufficient strength,
The present invention provides a method for producing a color developer sheet having water resistance. That is, the present invention provides a color developer characterized in that a color developer is mixed with an olefin resin, the mixture is extruded into a sheet, and then heat treated to transfer the color developer to the surface of the sheet. The content is the manufacturing method of the sheet. There are no particular restrictions on the color developer used in the present invention, and all known ones can be used, and there are various types depending on the purpose of the pressure-sensitive or heat-sensitive method, such as bisphenol A and bisphenol B. , α-naphthol, β-naphthol, novolac type phenolic resins such as “Santo Resin” (manufactured by Mitsui Toatsu Co., Ltd.), and salicylic acid derivative color developers are suitable. As the olefin resin used in the present invention, polyethylene, polypropylene, copolymers thereof, etc. are suitable. The mixing ratio of the color developer and the olefin resin cannot be absolutely defined depending on the type of polyolefin resin, the color developer, the degree of color development, etc., but the color developer should be 1.0 to 10.0 parts by weight per 100 parts by weight of the polyolefin resin. Parts by weight are preferred. If it exceeds 10.0 parts by weight, it will be difficult to extrude the color developer sheet, and if it is less than 1.0 parts by weight, color development will not be sufficient. The heat treatment in the present invention is to transfer the color developer to the surface of the sheet-like extrusion molded product made of a mixture of an olefin resin and a color developer, and to make it unevenly distributed. The temperature is preferably below the melting point of the system resin, and the higher the treatment temperature and the greater the amount of transfer accelerator added, the shorter the time and sufficient color development can be obtained. For example, a color developer sheet containing 100 parts by weight of polyethylene, 3 parts by weight of "Santo Resin", and 2 parts by weight of zinc 2-ethylhexanoate has a temperature of 60°C to 100°C.
C. for 1 minute to 30 minutes is suitable. By adding a migration accelerator such as zinc 2-ethylhexanoate to a mixture consisting of an olefin resin and a color developer, migration and uneven distribution can be effectively achieved. The appropriate amount of the migration accelerator to be added is 0.1 to 3.0 parts by weight per 100 parts by weight of the polyolefin resin. If it is less than 0.1 part by weight, the effect of promoting transfer of the color developer is not sufficient, and if it exceeds 3.0 parts by weight, the developer sheet becomes sticky and is inconvenient to handle. The color developer sheet of the present invention can be used alone, or as paper,
It is used in the form of a laminate by coating, coextrusion, etc. on a base material such as cloth, nonwoven fabric, cellophane, synthetic resin film, metal foil, or laminate of synthetic resin film and metal foil, but it is possible to make the sheet opaque. It is a preferable embodiment to add an opacifying agent that increases the contrast with respect to color development in order to make it easier to see the handwritten content that has been pressure-sensitively colored. Preferred examples of such opacifying agents include TiO 2 , SiO 2 , CaCO 3 , talc, activated clay, and acid clay. The amount of the opacifying agent added is adjusted depending on the desired thickness of the color developer sheet, and the thicker the sheet, the smaller the addition ratio may be. For example, 0.1 to 10.0 parts by weight is suitable for 100 parts by weight of polyolefin resin; if it exceeds 10.0 parts by weight, it becomes difficult to make the color developer sheet thin, and if it is less than 0.1 parts by weight, it will not be sufficiently opaque. is not achieved. In the present invention, regardless of whether pressure-sensitive or heat-sensitive methods are used, it is desirable to perform corona treatment after heat treatment. By applying corona treatment, leakage on the surface of the color developer sheet is improved, and when the color former coated paper is layered to develop color, the color former is effectively transferred to the color developer sheet, and the color density is improved. improves. The corona treatment is similar to the corona treatment generally performed for improving the surface wettability and adhesion of resin films, paper, etc., and a treatment of 50 to 200 w/m 2 is sufficient. It is desirable that the surface of the color developer sheet used in the pressure-sensitive method of the present invention be subjected to surface roughening treatment at the same time as extrusion molding, or before or after heat treatment.
The uneven processing increases the friction during pressure-sensitive coloring, helps destroy the color former microcapsules, promotes reaction with the color developer, and prevents the description from becoming unclear due to friction after coloring. The unevenness of the surface has the effect of diffusing light and increasing the contrast with the color. The uneven processing includes, for example, (a) a method in which the extruded color developer sheet is passed through a cooling roll with a matte surface when it is cooled and solidified; (b) a method in which the surface is sanded before heat treatment; (c) a method in which the surface is sanded before heat treatment; ) A method in which a film whose surface has been roughened in advance is bonded under pressure to the surface of a color developer sheet, the film is removed after the heat treatment, and the rough surface of the film is transferred to the surface of the color developer sheet; (d) A method of extruding a color developer sheet into a film and stretching the film is suitable. Among the above methods, (a)
(c) is particularly suitable because it can be carried out simultaneously with the production of the color developer sheet and is simple, and (c) also has the advantage that it can be carried out simultaneously with the heat treatment depending on the temperature employed. Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited in any way by these. Examples 1-2, Comparative Examples 1-2 Low density polyethylene "Mirason M-14 (MI 15.1 g/10 min, density: 0.919) was used as the polyolefin resin.
g/cm 3 )" (manufactured by Mitsui Polychemicals) and 3 parts by weight of the novolac type phenolic resin "Santo Resin" (manufactured by Mitsui Toatsu) as a color developer, and then vented the mixture. The mixture was melt-mixed using a type extruder (die exit temperature: 210°C) and pelletized using a pelletizer. After sufficiently drying the pellets at 50°C, they were made into sheets using a T-die extruder (diameter 40 mm, T-die temperature 250°C) and coated on paper (50 g/m 2 ), and a developer sheet laminated paper was formed. Created. The obtained developer sheet laminated paper is dried using a dryer.
The laminated paper obtained by heat treatment at 90° C. for 30 minutes was designated as Sample A. After the heat treatment, the paper was further treated at 200 W/m 2 using a solid-state corona device with an output frequency of 5 KHz and was designated as Sample B. On the other hand, for comparison, sample C was not heat-treated, and sample D was corona discharge treated without heat treatment. The above samples A to D were stacked on Kanzaki Paper's "KS Copy Bright Top Paper (color former microcapsule coated paper)" and pressure sensitively developed using the same pressure.
The color density was compared with the naked eye and evaluated on a five-point scale. The results are shown in Table 1.
【表】
(注) ５：非常に鮮明、４：より鮮明、３：鮮
明 ２：やや不鮮明、１：不鮮明
実施例３〜４、比較例３〜４
前記実施例及び比較例において、移行促進剤と
して２−エチルヘキサン酸亜鉛1.5重量部を添加
した他は全く同様にしてテストを実施した。得ら
れた結果を第２表に示す。[Table] (Note) 5: Very clear, 4: Clearer, 3: Clear 2: Slightly blurred, 1: Blurred Examples 3 to 4, Comparative Examples 3 to 4 In the above Examples and Comparative Examples, transition promotion The test was conducted in exactly the same manner except that 1.5 parts by weight of zinc 2-ethylhexanoate was added as an agent. The results obtained are shown in Table 2.
【表】
第１表、第２表から本発明の熱処理、更には熱
処理とコロナ処理を施すことにより発色の状態が
良好であり、更に移行促進剤を加えることにより
発色の状態が更に良好となることが理解される。
実施例 ５
実施例１〜２において、Ｔダイ押出機により押
出されたシートをマツトロール（表面粗さ；120
メツシユ）を通過させ冷却固化させた他は同様に
してサンプルＡ（熱処理）、サンプルＢ（熱処理＋
コロナ処理）を得た。
得られたサンプルＡ、Ｂはいずれも凹凸加工を
施してないものに比し、より鮮明に発色すること
が確認された。
叙上の通り、発明によれば顕色剤シートが押出
し成形により一工程で一挙に製造でき従前の原紙
表面に顕色剤を塗工する方法に比し簡単であり、
しかも熱処理による表面移行効果により、少量の
顕色剤で十分な発色を発揮するから材料コストの
低減及び省資源に奉仕するものである。また基材
がポリオレフイン樹脂であるから耐水性、強度が
飛躍的に高められる。従つて、例えば本発明の顕
色剤シートを配送ラベルとして用いても発色紙の
方は控用とし、一方発色された顕色剤シートは配
送中の摩擦によつても汚染されることがなく、ま
た改ざん等のトラブルが生じる虞れがない。本発
明の顕色剤シートは紙、フイルム等の基材との積
層物としても広汎な用途に利用でき、その有用性
は極めて大である。[Table] Tables 1 and 2 show that the heat treatment of the present invention, as well as heat treatment and corona treatment, results in good color development, and the addition of a migration accelerator further improves the color development. That is understood. Example 5 In Examples 1 and 2, the sheet extruded by the T-die extruder was molded into a pine roll (surface roughness: 120
Sample A (heat treated), Sample B (heat treated +
Corona treatment) was obtained. It was confirmed that both of the obtained samples A and B developed colors more vividly than those that were not textured. As mentioned above, according to the invention, a color developer sheet can be manufactured in one step by extrusion molding, which is simpler than the conventional method of coating a color developer on the surface of base paper.
Moreover, due to the surface migration effect caused by heat treatment, sufficient color development can be achieved with a small amount of color developer, which contributes to material cost reduction and resource conservation. Furthermore, since the base material is polyolefin resin, water resistance and strength are dramatically improved. Therefore, for example, even if the color developer sheet of the present invention is used as a shipping label, the colored paper can be saved, and the colored developer sheet will not be contaminated by friction during shipping. , and there is no risk of problems such as tampering. The color developer sheet of the present invention can be used in a wide range of applications as a laminate with a base material such as paper or film, and its usefulness is extremely large.
Claims (1)
物をシート状に押出し成形した後熱処理を施して
前記顕色剤を該シートの表面に移行させることを
特徴とする顕色剤シートの製造方法。 ２ 混合物に移行促進剤を添加する特許請求の範
囲第１項記載の方法。 ３ 混合物に不透明化剤を添加する特許請求の範
囲第１項又は第２項記載の方法。 ４ 熱処理を施した後コロナ処理を行なう特許請
求の範囲第１項記載の方法。[Scope of Claims] 1. A developer characterized in that a color developer is mixed with an olefin resin, the mixture is extruded into a sheet shape, and then heat treated to transfer the color developer to the surface of the sheet. A method for manufacturing a colorant sheet. 2. The method according to claim 1, wherein a migration accelerator is added to the mixture. 3. The method according to claim 1 or 2, wherein an opacifying agent is added to the mixture. 4. The method according to claim 1, wherein corona treatment is performed after heat treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59093963A JPS60236717A (en) | 1984-05-10 | 1984-05-10 | Manufacture of developer sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59093963A JPS60236717A (en) | 1984-05-10 | 1984-05-10 | Manufacture of developer sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60236717A JPS60236717A (en) | 1985-11-25 |
| JPH0257027B2 true JPH0257027B2 (en) | 1990-12-03 |
Family
ID=14097059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59093963A Granted JPS60236717A (en) | 1984-05-10 | 1984-05-10 | Manufacture of developer sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60236717A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04158263A (en) * | 1990-10-23 | 1992-06-01 | Yamatake Honeywell Co Ltd | Flow speed sensor |
| JPH04295768A (en) * | 1991-03-25 | 1992-10-20 | Yamatake Honeywell Co Ltd | Fluid detector |
| JPH04295767A (en) * | 1991-03-25 | 1992-10-20 | Yamatake Honeywell Co Ltd | Fluid detector |
-
1984
- 1984-05-10 JP JP59093963A patent/JPS60236717A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04158263A (en) * | 1990-10-23 | 1992-06-01 | Yamatake Honeywell Co Ltd | Flow speed sensor |
| JPH04295768A (en) * | 1991-03-25 | 1992-10-20 | Yamatake Honeywell Co Ltd | Fluid detector |
| JPH04295767A (en) * | 1991-03-25 | 1992-10-20 | Yamatake Honeywell Co Ltd | Fluid detector |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60236717A (en) | 1985-11-25 |
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