JP6269128B2 - Laser printing laminate - Google Patents
Laser printing laminate Download PDFInfo
- Publication number
- JP6269128B2 JP6269128B2 JP2014022554A JP2014022554A JP6269128B2 JP 6269128 B2 JP6269128 B2 JP 6269128B2 JP 2014022554 A JP2014022554 A JP 2014022554A JP 2014022554 A JP2014022554 A JP 2014022554A JP 6269128 B2 JP6269128 B2 JP 6269128B2
- Authority
- JP
- Japan
- Prior art keywords
- laser
- layer
- printing
- film
- base material
- 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.)
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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- 239000002537 cosmetic Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
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- BUJJNPWRTNNUCG-UHFFFAOYSA-L iron(2+);dibenzoate Chemical compound [Fe+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 BUJJNPWRTNNUCG-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
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- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
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- 239000000347 magnesium hydroxide Substances 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 235000006748 manganese carbonate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
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- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
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- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
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Images
Description
本発明は、レーザ照射により印字したレーザ印字積層体に関する。 The present invention relates to a laser-printed laminate printed by laser irradiation.
ＰＬ法（製造物責任法）が施工され、包装体、ラベル等には多種の印字が必要になっている。偽造、欠陥等の事故を防ぐセキュリティーの為、あるいはトレーサビリティの観点から、表示の重要性が高まっている。
その分野は、医薬品のみならず、電子機器や電子部品の他、食品類や日用品、包装品に至るまでの多種多様な製品の包装、ラベル、キャップの他、ガラス瓶、金属缶、プラスチック容器にもおよび、その製品、用途に見合った印字が求められている。
The PL Act (Product Liability Act) has been implemented, and various types of printing are required for packaging, labels, and the like. The importance of display is increasing for security to prevent accidents such as forgery and defects, or from the viewpoint of traceability.
Its fields include not only pharmaceutical products but also electronic devices and electronic parts, as well as packaging of various products ranging from foods, daily necessities, and packages, labels, caps, glass bottles, metal cans, and plastic containers. In addition, there is a demand for printing suitable for the product and application.
かかる表示は、具体的にはその型式や規格、製造年月日、賞味期限、会社ロゴマーク、産地表示、肥培管理表示、遺伝子組み替え表示、添加物表示、アレルギーに関する表示、栄養表示、成分表示、包装に関する表示であり、法で定められた情報の他、消費者が望む情報付加、生産者、販売者の商品戦略を反映した内容であり、それぞれの製品、使用状況に応じた印字が必要になっている。 Such indications are specifically the model and standard, date of manufacture, expiration date, company logo, production area indication, fertilizer management indication, genetic recombination indication, additive indication, allergy indication, nutrition indication, ingredient indication, This is a label on the packaging that reflects the information added by the consumer, the information that the consumer wants, and the product strategy of the producer and seller, and it is necessary to print according to each product and usage. It has become.
従来、包装資材、ラベル、キャップ、フイルム、容器等への印刷は、グラビア印刷法、フレキソ印刷法、オフセット印刷法、シルクスクリーン印刷法などの有版方式で行われてきた。また、賞味期限、製造年月日、ロット番号の日時や機械で変化する可変印字は、スタンプ印刷法、インクジェット印刷法、感熱転写リボン法、刻印印刷法等で行われている。 Conventionally, printing on packaging materials, labels, caps, films, containers, and the like has been performed by plate systems such as gravure printing, flexographic printing, offset printing, and silk screen printing. Further, the best-before date, the date of manufacture, the date and time of the lot number, and variable printing that changes with the machine are performed by a stamp printing method, an ink jet printing method, a thermal transfer ribbon method, a stamp printing method, and the like.
可変文字の他、産地表示、肥培管理表示、栄養表示、成分表示などを行う場合、可変印字ではないにしても、小さなロットになるのは避けられない。市場ニーズ、商品戦略を反映するためには少量多品種になるが、それを有版方式で行うことは、高価な版を多数用意することになり、版コストの他、版の管理など極めて高コストで煩雑な作業となる。 In addition to variable characters, when performing production area display, fertilizer management display, nutrition display, component display, etc., it is inevitable that the lot will be small even if it is not variable printing. In order to reflect market needs and product strategies, it becomes a small quantity and a wide variety, but if you do it with a plate method, you will have to prepare a lot of expensive plates, and in addition to the plate cost, the management of the plate is extremely high Costly and cumbersome work.
それらの課題解決のため、レーザマーキングによる積層体への可変情報の印字が提案されている。 In order to solve these problems, printing of variable information on a laminate by laser marking has been proposed.
レーザ照射によるレーザ印字はレーザ発色層の発色剤の変色、周辺樹脂の炭化、分解、気化により起こる。よって、特定の厚みのレーザ発色層に所定のエネルギーを与えれば、一定の発色が得られる
事が想定されるが、積層体の構成によっては、視認性が異なる現象が生じ、レーザ印字による視認性が安定しない現象が発生する問題があった。またレーザによる印字では、文字を印字するにあたって、本数により印字の視認性を制御することができる。例えば、線幅を0.2mm、線数を４本とすると0.2mm幅の間に４本の印字が施され、結果的に印字が濃くなり、視認性が良化する。しかしながら、本数を増やす分、印字時間が長くなり、生産効率が低下する問題があった。
Laser printing by laser irradiation occurs due to discoloration of the color former in the laser coloring layer, carbonization, decomposition, and vaporization of the surrounding resin. Therefore, it is assumed that a certain color can be obtained if given energy is given to the laser coloring layer with a specific thickness. However, depending on the structure of the laminate, a phenomenon in which visibility changes may occur. However, there was a problem that an unstable phenomenon occurred. In laser printing, the visibility of printing can be controlled by the number of characters when printing characters. For example, if the line width is 0.2 mm and the number of lines is 4, four prints are applied within the 0.2 mm width, resulting in darker prints and improved visibility. However, there is a problem that the printing time is increased by increasing the number of lines and the production efficiency is lowered.
そこで、本発明は、レーザ発色層を有するレーザマーキング用積層体において、印字濃度が高く、視認性が良好で、またレーザ印字の生産性の高いレーザ印字積層体を得ることを目的とする。 Therefore, an object of the present invention is to obtain a laser printing laminate having a high printing density, good visibility, and high laser printing productivity in a laser marking laminate having a laser coloring layer.
すなわち、本発明は、
フィルム層（Ａ）、レーザ発色層（Ｂ）、接着層（Ｃ）、および基材層（Ｄ）を順に積層してなるレーザ印字積層体の製造方法、
あるいは、フィルム層（Ａ）、レーザ発色層（Ｂ）および基材層（Ｄ）を順に積層してなるレーザ印字積層体の製造方法であって、
下記（２）の方法で印字することを特徴とするレーザ印字積層体の製造方法に関する。
（２) フィルム層（Ａ）の、レーザ発色層（Ｂ）と接する面の濡れ表面張力が４５ｍＮ／ｍを超える場合、フィルム層（Ａ）と基材層（Ｄ）間で剥離処理を行った際に、レーザ発色層（Ｂ）と、接着層（Ｃ）もしくは基材層（Ｄ）で層間剥離することを確認後、下記（ハ）でレーザ印字する。
（ハ）基材層がレーザ光を透過する場合は、基材層（Ｄ）側から正文字をレーザ印字する、または、フィルム層（Ａ）側から鏡文字をレーザ印字する
さらに、本発明は、フィルム層（Ａ）が、コロナ未処理面を有するフィルムであり、そのコロナ未処理面にレーザ発色層（Ｂ）を設けた前記レーザ印字積層体の製造方法に関する。
さらに、本発明は、レーザ発色層（Ｂ）が、酸化チタン、アンチモンドープ酸化物および銅モリブデン複合酸化物から選ばれる１種以上を含有することを特徴とする前記レーザ印字積層体の製造方法に関する。
さらに、本発明は、レーザ発色層（Ｂ）のバインダー樹脂が、ポリウレタン樹脂、塩化ビニル／酢酸ビニル共重合体および硝化綿から選ばれる１種類以上の樹脂を含有していることを特徴とする前記レーザ印字積層体の製造方法に関する。
That is, the present invention
A method for producing a laser-printed laminate comprising a film layer (A), a laser coloring layer (B), an adhesive layer (C), and a base material layer (D),
Alternatively, a method for producing a laser-printed laminate in which a film layer (A), a laser coloring layer (B), and a base material layer (D) are sequentially laminated,
It is related with the manufacturing method of the laser-printing laminated body characterized by printing by the method of following (2) .
( 2) When the wet surface tension of the surface of the film layer (A) in contact with the laser coloring layer (B) exceeds 45 mN / m, a peeling treatment was performed between the film layer (A) and the base material layer (D). At this time, after confirming that the laser color-developing layer (B) and the adhesive layer (C) or the base material layer (D) are delaminated, laser printing is performed according to the following (c).
(C) When the base material layer transmits laser light, positive characters are laser-printed from the base material layer (D) side, or mirror characters are laser-printed from the film layer (A) side. The film layer (A) is a film having a corona-untreated surface, and relates to a method for producing the laser-printed laminate in which a laser coloring layer (B) is provided on the corona-untreated surface.
Furthermore, the present invention relates to the method for producing a laser-printed laminate, wherein the laser coloring layer (B) contains one or more selected from titanium oxide, antimony-doped oxide and copper-molybdenum composite oxide. .
Furthermore, the present invention is characterized in that the binder resin of the laser coloring layer (B) contains at least one resin selected from polyurethane resin, vinyl chloride / vinyl acetate copolymer and nitrified cotton. The present invention relates to a method for manufacturing a laser-printed laminate.
本願のレーザマーキング用積層体は、レーザ照射により、積層体の接着力が弱い層間が剥離を起こすことを利用したもので、積層体に対するレーザ照射方向、レーザ印字の形態（正文字、鏡文字）、積層体の構成を制御することにより、視認性の良好なレーザ印字された積層体を得ることが出来る。本願発明の完成により、コントラストが鮮明な文字、図形、情報を有すコード等を記録でき、商品、製品の製造管理、流通管理、販売において管理、広告、宣伝機能を十分に発揮することができる。 The laminated body for laser marking of the present application utilizes the fact that the layer where the adhesive strength of the laminated body is weak due to laser irradiation is peeled off. The laser irradiation direction to the laminated body, the form of laser printing (correct characters, mirror characters) By controlling the configuration of the laminate, a laser-printed laminate with good visibility can be obtained. By completing the invention of the present application, it is possible to record characters, graphics, codes having information with clear contrast, etc., and to fully exhibit management, advertising, and advertising functions in product management, product manufacturing management, distribution management, and sales. .
以下、本発明について、更に詳しく説明するが、本発明の技術的思想を逸脱しない限り、本発明はこれらの実施の形態に限定されるものではない。
先ず、レーザマーキング用積層体について説明する。
レーザマーキング用積層体は、フィルム層（Ａ）上にレーザ発色層（Ｂ）、必要に応じて接着層（Ｃ）、基材層（Ｄ）を形成することで得られる。レーザ発色層（Ｂ）はレーザ発色剤を含有するレーザ発色性印刷インキ、もしくはレーザ発色性塗料を印刷、塗工することで形成される。
Hereinafter, the present invention will be described in more detail, but the present invention is not limited to these embodiments without departing from the technical idea of the present invention.
First, the laminated body for laser marking will be described.
The laminate for laser marking can be obtained by forming a laser coloring layer (B) and, if necessary, an adhesive layer (C) and a base material layer (D) on the film layer (A). The laser color-developing layer (B) is formed by printing and coating a laser color-developing printing ink containing a laser color-developing agent or a laser color-developing coating.
積層体の基本構成は、１） フイルム層（ Ａ ） ／レーザ発色層（Ｂ） ／ 接着層（Ｃ）／基材層（Ｄ）、２）フイルム層（ Ａ ） ／レーザ発色層（Ｂ） ／基材層（Ｄ）である。
本発明においては、前述のレーザマーキング用積層体のレーザ発色層が隣接する二つの界面、即ち（１）フイルム層（Ａ）／レーザ発色層（Ｂ）、（２）レーザ発色層（Ｂ）／接着剤層（Ｃ）もしくは基材層（Ｄ）の相対的接着強度の違いに基付き、印字方向、印字の形態を適宜選択することにより印字の視認性が大きく向上することを見出したものである。
The basic structure of the laminate is 1) film layer (A) / laser color layer (B) / adhesive layer (C) / base material layer (D), 2) film layer (A) / laser color layer (B) / It is a base material layer (D).
In the present invention, the laser coloring layer of the above-mentioned laminate for laser marking is adjacent to two interfaces, namely (1) film layer (A) / laser coloring layer (B), (2) laser coloring layer (B) / Based on the difference in the relative adhesive strength of the adhesive layer (C) or the base material layer (D), it has been found that the visibility of printing is greatly improved by appropriately selecting the printing direction and the printing form. is there.
具体的には、レーザ印字前の積層体において、フイルム層（Ａ）と基材層（Ｄ）間で剥離処理を行なった際、層間剥離の生じる界面により、そして基材層（Ｄ）のレーザ光透過性により、レーザ印字を行なう面、レーザ印字が正文字印字、或いは鏡文字印字であるかを適宜選択することにより印字濃度の高く、視認性に優れた印刷物を得ることができる。本発明により、種々の積層構成を有する積層体に対して印字濃度が高く、視認性に優れたレーザ印字物を得ることが可能となった。
また、レーザ印字濃度、視認性を高める方法として、複数の線数を印字する方法が知られているが、レーザ印字に時間を要し、生産効率が劣る。本発明により最小回数のレーザ印字により、優れた視認性が得られ、生産効率も向上させることができる。
Specifically, in the laminate before laser printing, when the peeling treatment is performed between the film layer (A) and the base material layer (D), the laser of the base material layer (D) is caused by the interface at which delamination occurs. By appropriately selecting whether to perform laser printing or whether the laser printing is normal character printing or mirror character printing, the printed matter with high printing density and excellent visibility can be obtained. According to the present invention, it is possible to obtain a laser print having a high print density and excellent visibility with respect to a laminate having various laminate configurations.
Further, as a method for improving the laser printing density and visibility, a method of printing a plurality of lines is known, but it takes time for the laser printing and the production efficiency is inferior. According to the present invention, excellent visibility can be obtained and the production efficiency can be improved by the minimum number of times of laser printing.
その他の構成として（３） フイルム層（ Ａ ） ／レーザ発色層（Ｂ） ／印刷インキ層／基材層（Ｄ）、（４） フイルム層（ Ａ ） ／レーザ発色層（Ｂ） ／印刷インキ層／接着層（Ｃ）／基材層（Ｄ）等が挙げられる。これらにおいても同様であり、フィルム層（Ａ）側から見て視認性が良好であるためには、フイルム層（ Ａ ） ／レーザ発色層（Ｂ）で層間剥離することが必要である。 Other configurations are (3) Film layer (A) / Laser color layer (B) / Printing ink layer / Base material layer (D), (4) Film layer (A) / Laser color layer (B) / Printing ink layer / Adhesive layer (C) / base material layer (D) and the like. The same applies to these, and in order to achieve good visibility when viewed from the film layer (A) side, it is necessary to delaminate the film layer (A) / laser coloring layer (B).
本発明におけるフィルム層（Ａ）と基材層（Ｄ）間で剥離処理は、ラミネート物の引張り強度試験に用いられる公知の方法、装置により行なうことができる、例えばラミネート物を定形に切り出し、その一部を前もって剥離させ、引っ張り試験機で剥離強度を測定する方法である。市販の装置としてはインテスコ製２０１万能引張り試験機がある。 The peeling treatment between the film layer (A) and the base material layer (D) in the present invention can be performed by a known method and apparatus used for the tensile strength test of the laminate, for example, the laminate is cut into a fixed shape, In this method, a part is peeled in advance and the peel strength is measured with a tensile tester. As a commercially available apparatus, there is a 2011 universal tensile tester manufactured by Intesco.
本態様に用いられるフィルム層（Ａ）としては、レーザ光を透過する透明なプラスチックフィルムを使用する。プラスチックフィルムとしては、ポリエステル系フィルム、ポリアミド系フィルム、ポリオレフィン系フィルム等がある。ポリエステル系フィルムとしてはポリエチレンテレフタレート（ＰＥＴ）、ポリアミド系フィルムとしてはナイロン（Ｎｙ）、ポリオレフィン系フィルムとしては低密度ポリエチレン、無延伸および延伸ポリプロピレン（ＯＰＰ）等が挙げられる。
その他の透明プラスチックフィルムとしては、ポリ塩化ビニル、ポリカーボネイト、ポリビニルアルコールフイルム等、及びポリ塩化ビニリデン等をコーテイングしたポリプロピレン、ポリエステル、ナイロン、セロファン等のフイルムも挙げられる。また、プラスチックフイルムとして熱収縮フイルムを使用することもできる。熱収縮性フイルムとしては、ポリエステル系、スチレン系等がある。また、これらフイルム等にアルミナ、シリカ等を蒸着した蒸着フイルム等も使用できる。
As the film layer (A) used in this embodiment, a transparent plastic film that transmits laser light is used. Examples of the plastic film include a polyester film, a polyamide film, and a polyolefin film. Examples of the polyester film include polyethylene terephthalate (PET), the polyamide film includes nylon (Ny), and the polyolefin film includes low density polyethylene, unstretched and stretched polypropylene (OPP), and the like.
Examples of other transparent plastic films include polyvinyl chloride, polycarbonate, polyvinyl alcohol films, and films such as polypropylene, polyester, nylon, cellophane, etc. coated with polyvinylidene chloride. Moreover, a heat shrink film can also be used as a plastic film. Examples of the heat-shrinkable film include polyester and styrene. Further, a vapor deposition film obtained by vapor-depositing alumina, silica or the like on these films can also be used.
本発明においては、フィルム層（Ａ）を構成するプラスチックフィルムは透明であることが必要である。透明であるとは、レーザマーキング用積層体において該プラスチックフィルムを通してレーザ発色層（Ｂ）の印字、或いはレーザ層発色（Ｂ）以外の通常の印刷インキ層部分が十分に認識できることをいう。一般に見た目で透明なプラスチックフィルムは本発明において使用できるが、プラスチックフィルムに着色剤を練り込んで透明さが低下したもの、透明なプラスチックフィルム上に不透明な膜が蒸着、コーテイングされているものは適さない。 In the present invention, the plastic film constituting the film layer (A) needs to be transparent. To be transparent means that the laser marking layer (B) can be printed through the plastic film in the laser marking laminate, or a normal printing ink layer other than the laser layer coloring (B) can be sufficiently recognized. In general, a transparent plastic film that can be used in the present invention can be used in the present invention. However, it is suitable to use a plastic film in which a colorant is kneaded to reduce transparency, or an opaque film deposited and coated on a transparent plastic film. Absent.
フィルム層（Ａ）を構成する透明なプラスチックフイルムの厚みは特に限定されないが、通常印刷に用いられるフイルムがそのまま適用できる。例えばＰＥＴの場合、１２〜４０μｍ、ナイロンの場合は１５〜４０μｍ、ＯＰＰの場合は２０〜５０μｍが好適に用いられる。 Although the thickness of the transparent plastic film which comprises a film layer (A) is not specifically limited, The film normally used for printing can be applied as it is. For example, 12 to 40 μm is suitably used for PET, 15 to 40 μm for nylon, and 20 to 50 μm for OPP.
フィルム層（Ａ）とレーザ発色層（Ｂ）が層間剥離するためには、使用するプラスチックフィルムがポリエステル系フィルム、ポリアミド系フィルム、ポリオレフィン系フィルムであり、その印刷面の表面張力が４５ｍＮ／ｍ以下であることが好ましい。これらのプラスチックフィルムはレーザ発色層（Ｂ）に対して接着性が劣る傾向であり、レーザ照射を行なうとフィルム層（Ａ）とレーザ発色層（Ｂ）が層間剥離し易く、フィルム層（Ａ）側から見た場合、視認性に優れたレーザ印字積層体が得られる。フィルム層（Ａ）の表面張力は、例えば、濡れ指数としてＪＩＳ Ｋ６７６８（ポリエチレン及びポリプロピレンフィルムの濡れ試験方法）で求められる。 In order for the film layer (A) and the laser coloring layer (B) to be delaminated, the plastic film used is a polyester film, a polyamide film, or a polyolefin film, and the surface tension of the printed surface is 45 mN / m or less. It is preferable that These plastic films tend to have poor adhesion to the laser coloring layer (B). When the laser irradiation is performed, the film layer (A) and the laser coloring layer (B) are easily separated from each other, and the film layer (A) When viewed from the side, a laser-printed laminate having excellent visibility can be obtained. The surface tension of the film layer (A) is determined, for example, by JIS K6768 (wetting test method for polyethylene and polypropylene films) as a wetting index.
また、本発明において、プラスチック層（Ａ）をなすプラスチックフィルムは、ポリエステル系フィルム、ポリアミド系フィルム、ポリオレフィン系フィルムでありコロナ処理を施していないコロナ未処理面を有していることが好ましい。レーザ発色層（Ｂ）をフィルム層（Ａ）のコロナ未処理面側に形成し、レーザマーキング用積層体を製造すると、フィルム層（Ａ）とレーザ発色層（Ｂ）での層間剥離が起こり易く、フィルム層（Ａ）側から見た場合印字濃度の高く、視認性の良好なレーザ印字積層体を得ることができる。 In the present invention, the plastic film forming the plastic layer (A) is preferably a polyester film, a polyamide film, or a polyolefin film and has a corona-untreated surface that has not been subjected to corona treatment. When the laser coloring layer (B) is formed on the non-corona-treated surface side of the film layer (A) and a laminate for laser marking is produced, delamination between the film layer (A) and the laser coloring layer (B) is likely to occur. When viewed from the film layer (A) side, it is possible to obtain a laser printing laminate having a high printing density and good visibility.
本発明の原理を推察も含めて更に説明する。前述したようにレーザ照射するとレーザ発色層（Ｂ）内で発色剤の変色、発色剤近傍のバインダー樹脂の炭化に伴い、分解ガス、気化ガスが発生する。これらはレーザ照射スポット付近に膨れが生じ、凸が形成されることでも分かる。 The principle of the present invention will be further described including inference. As described above, when laser irradiation is performed, decomposition gas and vaporized gas are generated in the laser coloring layer (B) due to discoloration of the color former and carbonization of the binder resin near the color former. These can also be seen from the fact that swelling occurs in the vicinity of the laser irradiation spot and the projection is formed.
レーザ照射を行なった場合、分解、気化ガスの発生が全く、或いは殆どない場合、レーザマーキング積層体のレーザ照射スポット付近では膨れは起こらなく、発色した発色剤、炭化したバインダー樹脂は、基本的にはレーザ発色層（Ｂ）内でレーザ光のビーム径の透過体積内にのみ存在すると考えられる。（図１）そのため、フィルム層（Ａ）、または基材層（Ｄ）から見た場合、視認できる印字面積は、ほぼレーザビーム径にほぼ等しいと言える。 When laser irradiation is performed, there is no or almost no decomposition or generation of vaporized gas, and no swelling occurs near the laser irradiation spot of the laser marking laminate. Colored color former and carbonized binder resin are basically Is considered to exist only in the transmission volume of the beam diameter of the laser beam in the laser coloring layer (B). (FIG. 1) Therefore, when viewed from the film layer (A) or the base material layer (D), it can be said that the visible print area is substantially equal to the laser beam diameter.
しかし、本発明に示したように特定の層間剥離を起こす積層体、例えば、フィルム層（Ａ）とレーザ発色層（Ｂ）間が層間剥離し易い構成の場合、レーザ照射を行なうと、１）レーザ発色層（Ｂ）内で発生した分解、気化ガスが“内部圧力”となり、レーザ照射スポットを含む領域で接着強度がより弱い層間、すなわちフィルム層（Ａ）／レーザ発色層（Ｂ）間に層間剥離を引き起こさせる。２）また、同時に発色した発色剤、炭化したバインダー樹脂は、レーザ径の透過体積内にとどまらず、層間剥離に伴いあらたに発生した“空間内”に“飛散”した状態になる。（図２）フィルム層（Ａ）側から見るとレーザ照射スポットを含む領域は、層間剥離し、レーザ発色層（Ｂ）のその部分はあたかも“口を開いた”状態であり、しかも発色した発色剤、炭化した樹脂がレーザスポット径以上に拡がった状態、すなわち印字スポット面積がより大きく拡がった状態に見える。 これは、あたかもビーム径のより大きいレーザ光を照射した印字物、レーザ照射の本数を増やした印字物と同等な状態であり、視認性が極めて高い印字物が得られる。 この場合、基材層（Ｄ）が透明なフィルムとすると、基材層（Ｄ）側からみると、レーザ発足層（Ｂ）／接着剤層（Ｃ）、或いは接着剤層（Ｃ）／基材層（Ｄ）で層間剥離していないため、僅かレーザのスポット径に相当する領域のみが発色したように見えるのみで、基材層（Ｄ）側からの視認性は乏しい。 However, as shown in the present invention, in the case of a laminate that causes specific delamination, for example, when the film layer (A) and the laser coloring layer (B) are easily delaminated, when laser irradiation is performed, 1) The decomposition and vaporized gas generated in the laser coloring layer (B) becomes “internal pressure”, and the adhesive strength is weaker in the region including the laser irradiation spot, that is, between the film layer (A) / the laser coloring layer (B). Cause delamination. 2) In addition, the color former that has developed color and the carbonized binder resin do not stay within the transmission volume of the laser diameter, but are “scattered” in the “space” newly generated due to delamination. (FIG. 2) When viewed from the film layer (A) side, the region including the laser irradiation spot is delaminated, and that portion of the laser coloring layer (B) is in an “open-mouthed” state, and the colored color developed. It appears that the agent and the carbonized resin have expanded beyond the laser spot diameter, that is, the printing spot area has expanded more. This is a state equivalent to a printed matter irradiated with a laser beam having a larger beam diameter or a printed matter with an increased number of laser irradiations, and a printed matter with extremely high visibility can be obtained. In this case, when the base layer (D) is a transparent film, the laser launch layer (B) / adhesive layer (C) or adhesive layer (C) / base is seen from the base layer (D) side. Since there is no delamination in the material layer (D), only a region corresponding to a slight laser spot diameter appears to be colored, and visibility from the base material layer (D) side is poor.
本発明においては、視認する側は剥離が起こっている界面に近い側である。具体的には フィルム層
（Ａ）とレーザ発色層（Ｂ）が層間剥離する場合には、フィルム層側から視認する。レーザ発色層（Ｂ）と、接着層（Ｃ）もしくは基材層（Ｄ）で層間剥離する場合は、基材層（Ｄ）側から視認する。
レーザ発色層（Ｂ）／接着層（Ｃ）で層間剥離する場合、接着層（Ｃ）は元々透明であるため、また基材層（Ｄ）も透明であるため基材層（Ｄ）側から見れば上記の例の説明がそのまま当てはまる。
In the present invention, the side to be viewed is the side close to the interface where peeling occurs. Specifically, when the film layer (A) and the laser coloring layer (B) are peeled from each other, the layer is visually recognized from the film layer side. When delamination is performed between the laser coloring layer (B) and the adhesive layer (C) or the substrate layer (D), the layer is visually recognized from the substrate layer (D) side.
In the case of delamination at the laser coloring layer (B) / adhesive layer (C), since the adhesive layer (C) is originally transparent and the base layer (D) is also transparent, from the base layer (D) side. If you look at it, the explanation of the above example applies as it is.
本発明を更に説明すると、（１）フィルム層（Ａ）と基材層（Ｄ）間で剥離処理を行った際に、フィルム層（Ａ）とレーザ発色層（Ｂ）が層間剥離する場合には、下記（イ）、（ロ）のいずれかでレーザ印字する。
(イ)基材層がレーザ光を透過しない場合はフィルム層（Ａ）側から正文字をレーザ印字する。
この場合視認が高いのは、フィルム層（Ａ）側である。正文字を印字するので、印字状態を把握しながら印字し易く、特に好ましい。
（ロ）基材層がレーザ光を透過する場合は、基材層（Ｄ）側から鏡文字をレーザ印字する。または、フィルム層（Ａ）側から正文字をレーザ印字する
この場合基材層（Ｄ）もレーザ光を透過するため、基材層（Ｄ）側からも印字可能であるが、視認性が良好なのは剥離面により近いフィルム層（Ａ）側である。フィルム層（Ａ）側から視認するためには基材層（Ｄ）側から鏡文字としてレーザ印字する必要がある。これら鏡文字はフィルム層（Ａ）側から見ると通常の正文字として認識できる。
The present invention will be further described. (1) When the film layer (A) and the laser coloring layer (B) are delaminated when the peeling process is performed between the film layer (A) and the base material layer (D). Performs laser printing in either of the following (A) or (B).
(A) When the base material layer does not transmit laser light, positive characters are laser-printed from the film layer (A) side.
In this case, it is the film layer (A) side that is highly visible. Since correct characters are printed, printing is easy while grasping the printing state, which is particularly preferable.
(B) When the base material layer transmits laser light, a mirror character is laser-printed from the base material layer (D) side. Or, in this case, positive characters are laser-printed from the film layer (A) side. Since the base material layer (D) also transmits laser light, printing is possible from the base material layer (D) side, but the visibility is good. What is the film layer (A) side closer to the release surface. In order to visually recognize from the film layer (A) side, it is necessary to perform laser printing as a mirror character from the base material layer (D) side. These mirror characters can be recognized as normal positive characters when viewed from the film layer (A) side.
（２) フィルム層（Ａ）と基材層（Ｄ）間で剥離処理を行った際に、レーザ発色層（Ｂ）と、接着層（Ｃ）もしくは基材層（Ｄ）で層間剥離する場合は、下記（ハ）でレーザ印字する
（ハ）基材層がレーザ光を透過する場合は、基材層（Ｄ）側から正文字をレーザ印字する、または、フィルム層（Ａ）側から鏡文字をレーザ印字する
何れの方向から印字しても視認性が良好なのは基材層（Ｄ）側である。フィルム層（Ａ）側から見ると、フィルム層（Ａ）側は剥離面がないため、僅かレーザスポット径のみの印字面積であり、視認性は劣る。
(2) When peeling between the film layer (A) and the base material layer (D), the laser coloring layer (B) and the adhesive layer (C) or the base material layer (D) are delaminated. (C) Laser printing is performed in the following (c) (c) When the base material layer transmits laser light, positive characters are laser-printed from the base material layer (D) side or mirrored from the film layer (A) side. It is the base material layer (D) side that has good visibility no matter which direction the character is laser printed. When viewed from the film layer (A) side, the film layer (A) side has no peeled surface, so it is a print area with only a small laser spot diameter, and the visibility is poor.
レーザ発色層（Ｂ）は、レーザ発色性の印刷インキおよび／または塗工液より形成され、印刷インキであることが好ましい。レーザ発色性の印刷インキは、レーザ発色性を有する材料から選択される１種以上の材料の他に、通常はバインダー樹脂を含有し、さらに必要に応じて、インキ適性、印刷適性などを向上させる添加剤などを含有する。レーザ発色性を有する材料としては、無機材料、有機材料がある。本態様に用いられる無機材料は、例えば、（１）金属単体、（２）金属塩、（３）金属水酸化物、（４）金属の酸化物等を示す。 The laser coloring layer (B) is formed from a laser coloring printing ink and / or coating liquid, and is preferably a printing ink. Laser-colorable printing inks usually contain a binder resin in addition to one or more materials selected from laser-colorable materials, and further improve ink suitability, printability, and the like as necessary. Contains additives. Examples of the material having laser colorability include inorganic materials and organic materials. The inorganic material used in this embodiment is, for example, (1) simple metal, (2) metal salt, (3) metal hydroxide, (4) metal oxide, or the like.
１）金属の単体としては、鉄、亜鉛、スズ、ニッケル、銅、銀、金等が挙げられる。 1) Examples of simple metals include iron, zinc, tin, nickel, copper, silver, and gold.
（２）金属の塩としては、炭酸銅、炭酸ニッケル、炭酸マンガン、炭酸コバルト、炭酸ランタン、硝酸マグネシウム、硝酸マンガン、硝酸鉄、硝酸カドミウム、硝酸亜鉛、硝酸コバルト、硝酸鉛、硝酸ニッケル、硝酸銅、硝酸パラジウム、硝酸ランタン、酢酸マグネシウム、酢酸マンガン、酢酸カドミウム、酢酸亜鉛、酢酸コバルト、酢酸鉛、酢酸ニッケル、酢酸銅、酢酸パラジウム、塩化銅、塩化鉄、塩化コバルト、塩化ニッケル、塩化銀、塩化亜鉛、リン酸銅、リン酸鉄、リン酸コバルト、ピロリン酸銅、硫酸銅、硫酸鉄、硫酸コバルト、シュウ酸銅、シュウ酸鉄、シュウ酸コバルト、安息香酸銅、安息香酸鉄、安息香酸コバルト、芳香環を有するホスホン酸銅などが挙げられる。 (2) Metal salts include copper carbonate, nickel carbonate, manganese carbonate, cobalt carbonate, lanthanum carbonate, magnesium nitrate, manganese nitrate, iron nitrate, cadmium nitrate, zinc nitrate, cobalt nitrate, lead nitrate, nickel nitrate, copper nitrate , Palladium nitrate, lanthanum nitrate, magnesium acetate, manganese acetate, cadmium acetate, zinc acetate, cobalt acetate, lead acetate, nickel acetate, copper acetate, palladium acetate, copper chloride, iron chloride, cobalt chloride, nickel chloride, silver chloride, chloride Zinc, copper phosphate, iron phosphate, cobalt phosphate, copper pyrophosphate, copper sulfate, iron sulfate, cobalt sulfate, copper oxalate, iron oxalate, cobalt oxalate, copper benzoate, iron benzoate, cobalt benzoate And copper phosphonate having an aromatic ring.
（３）金属の水酸化物としては、水酸化銅、水酸化アルミニウム、水酸化マグネシウム、水酸化亜鉛、水酸化アンチモン、水酸化コバルト、水酸化ニッケル、水酸化鉄、水酸化ランタン等が挙げられる。 (3) Examples of metal hydroxides include copper hydroxide, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, antimony hydroxide, cobalt hydroxide, nickel hydroxide, iron hydroxide, and lanthanum hydroxide. .
（４）金属の酸化物としては、酸化チタン、酸化ケイ素、酸化アルミニウム、酸化鉄、酸化マグネシウム、酸化コバルト、酸化鉛、酸化スズ、酸化インジウム、酸化マンガン、酸化モリブテン、酸化ニッケル、酸化銅、酸化パラジウム、酸化ランタン、アンチモンドープ酸化スズ（ＡＴＯ）、インジウムドープ酸化スズ（ＩＴＯ）、合成ゼオライト、天然ゼオライト、銅−モリブテン複合酸化物（４２−９０3Ａ、東缶マテリアル・テクノロジー株式会社製）等が挙げられる。 その他の金属酸化物としては、層状構造を有する、マイカ、モンモリロナイト、スメクタイト等を用いることもできる。 (4) As metal oxides, titanium oxide, silicon oxide, aluminum oxide, iron oxide, magnesium oxide, cobalt oxide, lead oxide, tin oxide, indium oxide, manganese oxide, molybdenum oxide, nickel oxide, copper oxide, oxidation Palladium, lanthanum oxide, antimony-doped tin oxide (ATO), indium-doped tin oxide (ITO), synthetic zeolite, natural zeolite, copper-molybten complex oxide (42-903A, manufactured by Tocan Material Technology Co., Ltd.), etc. It is done. As other metal oxides, mica, montmorillonite, smectite, etc. having a layered structure can also be used.
無機材料の中では、銅化合物、モリブデン化合物、酸化チタン、アンチモン化合物、鉄化合物、ニッケル化合物、クロム化合物、またはジルコニウム化合物、から選ばれる１種以上の材料、より好ましくは、銅化合物、モリブデン化合物、酸化チタン、アンチモン化合物、クロム化合物、ニッケル化合物を有する材料、さらに好ましくは、酸化チタン、アンチモンドープ酸化物、銅−モリブデン複合酸化物から選ばれる1種以上である。特に、銅−モリブテン複合酸化物は自己発色性が強く、また銅−モリブデン複合酸化物自身の近傍の樹脂なども黒化させやすいため、視認性の優れた印字物が得られる。また、それ自身は黒色化しないものの、近傍の樹脂を黒化し易いアンチモンドープ酸化スズ、発色層中に高濃度で含有させることが出来る酸化チタンも発色性、バックグランドが元々白色であることから視認性が非常に高く、好適に用いられる。酸化チタンとしてはアナターゼ、ルチル型共に使用できる。 Among inorganic materials, one or more materials selected from copper compounds, molybdenum compounds, titanium oxide, antimony compounds, iron compounds, nickel compounds, chromium compounds, or zirconium compounds, more preferably copper compounds, molybdenum compounds, A material having titanium oxide, an antimony compound, a chromium compound, or a nickel compound, more preferably at least one selected from titanium oxide, antimony-doped oxide, and copper-molybdenum composite oxide. In particular, the copper-molybten complex oxide has strong self-coloring properties, and the resin in the vicinity of the copper-molybdenum complex oxide itself can be easily blackened, so that a printed matter with excellent visibility can be obtained. Antimony-doped tin oxide, which does not blacken itself, but tends to blacken nearby resin, and titanium oxide that can be contained in a high concentration in the color-developing layer is also visible due to its color development and white background. The property is very high and is preferably used. Both anatase and rutile types can be used as titanium oxide.
レーザ発色層（Ｂ）にはレーザ発色剤の他、着色顔料を用いると印字物のバックグランドとして鮮明性、コントラスト、視認性を向上させることができる。本発明に使用するレーザ発色剤においては、黄色、紅色、藍色、もしくは白色顔料等の着色顔料を必要に応じて併用することにより視認性の高いレーザ発色層（Ｂ）を得ることができる。 When a color pigment other than the laser color former is used for the laser color development layer (B), it is possible to improve the clarity, contrast and visibility as the background of the printed matter. In the laser color former used in the present invention, a highly visible laser color layer (B) can be obtained by using a color pigment such as yellow, red, indigo, or white pigment in combination as necessary.
レーザ発色性印刷インキに用いるバインダー樹脂として、例えばセルロース、メチルセルロース、メトキシセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、ポリビニルアルコール、ポリアクリルアミド、ポリアクリル酸、カゼイン、ゼラチン、スチレン／無水マレイン酸共重合体塩、イソブチレン／無水マレイン酸共重合体塩、ポリアクリル酸エステル、ポリウレタン樹脂、アクリル／スチレン樹脂等が挙げられる。溶剤型樹脂としてはスチレン／マレイン酸、アクリル／スチレン樹脂、ポリスチレン、ポリエステル、ポリカーボネイト、エポキシ樹脂、ポリウレタン樹脂、ポリブチラール樹脂、ポリアクリル酸エステル、スチレン／ブタジエン共重合体、スチレン／ブタジエン／アクリル酸共重合体、ポリ酢酸ビニル、塩化ビニル／酢酸ビニル共重合体、硝化綿等がある。これらの樹脂は単独、または２種以上混合することで得られる。
これら樹脂の中でポリウレタン樹脂、塩化ビニル／酢酸ビニル共重合体、硝化綿から選ばれる１種以上の樹脂を用いることが好ましい。特にポリウレタン樹脂はフイルムへの密着性が良く、熱的緩和性にも優れていることから積層体として好適に用いられる。また、塩化ビニル／酢酸ビニル共重合体、硝化綿は、レーザによる発色性が良好で、レーザ発色剤のレーザ吸収性が乏しくても、印刷層、塗工層としての発色性を向上させる。
Examples of binder resins used in laser-colorable printing inks include cellulose, methylcellulose, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyacrylamide, polyacrylic acid, casein, gelatin, styrene / maleic anhydride copolymer salt, and isobutylene. / Maleic anhydride copolymer salt, polyacrylic acid ester, polyurethane resin, acrylic / styrene resin and the like. Solvent type resins include styrene / maleic acid, acrylic / styrene resin, polystyrene, polyester, polycarbonate, epoxy resin, polyurethane resin, polybutyral resin, polyacrylate ester, styrene / butadiene copolymer, styrene / butadiene / acrylic acid copolymer Examples include polymers, polyvinyl acetate, vinyl chloride / vinyl acetate copolymers, and nitrified cotton. These resins can be obtained singly or by mixing two or more.
Among these resins, it is preferable to use one or more resins selected from polyurethane resins, vinyl chloride / vinyl acetate copolymers, and nitrified cotton. In particular, a polyurethane resin is suitably used as a laminate because it has good adhesion to a film and is excellent in thermal relaxation. In addition, vinyl chloride / vinyl acetate copolymer and nitrified cotton have good color developability by laser and improve color developability as a printing layer and a coating layer even if laser absorbability of laser color former is poor.
更にレーザ発色層（Ｂ）には発色層の膜強度、耐熱性、耐水性、耐溶剤性等の向上を目的に硬化剤を併用することができる。硬化剤としてはイソシアネート系、オキサゾリン系、カルボジイミド系、エチレンイミン系等が使用できる。膜強度、膜物性の点からはイソシネート系硬化剤が好ましい。
イソシアネート系硬化剤としては、公知のヘキサメチレンジイソシアネート、イソポロンジイソシアネート、キシレンジイソシアネートなどのアダクトタイプ、ビュレットタイプおよびトリマータイプなどのポリイソシアネートプレポリマーが挙げられ、これらから１種または２種以上が使用される。イソシアネート系硬化剤の中でも３官能以上のものが特に良好である。これらイソシアネート系硬化剤は水酸基を有する樹脂と組み合わせれば、耐レーザ照射性が向上し、表面状態の優れた字物が得られるが、フィルム層との密着性が向上し、層間剥離が起こり難くなり、フィルム（Ａ）側の印字の視認性が低下する場合がある。
Further, a curing agent can be used in combination with the laser coloring layer (B) for the purpose of improving the film strength, heat resistance, water resistance, solvent resistance and the like of the coloring layer. As the curing agent, isocyanate, oxazoline, carbodiimide, ethyleneimine, and the like can be used. From the viewpoint of film strength and film physical properties, isocyanate-based curing agents are preferred.
Examples of the isocyanate-based curing agent include polyisocyanate prepolymers such as known adduct types such as hexamethylene diisocyanate, isopolone diisocyanate, and xylene diisocyanate, burette type, and trimer type, and one or more of these are used. The Of the isocyanate curing agents, those having 3 or more functional groups are particularly good. When these isocyanate-based curing agents are combined with a resin having a hydroxyl group, the laser irradiation resistance is improved and a character with excellent surface condition can be obtained, but the adhesion with the film layer is improved and delamination hardly occurs. Thus, the visibility of printing on the film (A) side may be reduced.
また、印刷適性、塗工適性、皮膜物性向上のため必要に応じて顔料分散剤、消泡剤、レベリング剤、ワックス、滑剤、シランカップリング剤、防腐剤、防錆剤、可塑剤、紫外線吸収剤、難燃剤などを挙げることができる。
これら添加剤の種類、使用量は、印刷方法、印刷基材、印刷条件により適宜選択できる。
In addition, pigment dispersants, antifoaming agents, leveling agents, waxes, lubricants, silane coupling agents, preservatives, rust preventives, plasticizers, UV absorbers as necessary to improve printability, coating suitability, and film properties Agents, flame retardants and the like.
The type and amount of these additives can be appropriately selected depending on the printing method, printing substrate, and printing conditions.
その他、レーザ発色性印刷インキとして光硬化性印刷インキも使用可能である。具体的には、不飽和ポリエステル系樹脂、アクリレート系樹脂、ポリエン／ポリチオール系樹脂、スピラン系樹脂、エポキシ系樹脂、アミノアルキッド系樹脂、ジアリルフタレート系樹脂、不飽和ポリエステル系樹脂、フラン系樹脂等、紫外線硬化性モノマー、プレポリマー、光重合開始剤、及びレーザ発色剤からなるものが使用される。 In addition, a photo-curable printing ink can also be used as the laser coloring printing ink. Specifically, unsaturated polyester resins, acrylate resins, polyene / polythiol resins, spirane resins, epoxy resins, aminoalkyd resins, diallyl phthalate resins, unsaturated polyester resins, furan resins, etc. An ultraviolet curable monomer, a prepolymer, a photopolymerization initiator, and a laser color former are used.
光硬化性印刷インキ）を硬化させるには、１）紫外線照射として超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク燈、メタルハライドランプ等が使用される。２）電子線照射の場合、コックロフトワルトン型、バンデグラフト型、共振変圧器型、絶縁コア変圧器型、或いは、直線型、ダイナミトロン型、高周波型等の各種電子線加速器を用い、１００〜１０００ｅＶのエネルギーを持つ電子を照射する。 In order to cure the photo-curable printing ink), 1) an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc lamp, a metal halide lamp or the like is used for ultraviolet irradiation. 2) For electron beam irradiation, various electron beam accelerators such as Cockloft Walton, Bandegraft, resonant transformer, insulated core transformer, linear type, dynamitron type, high frequency type, etc. Irradiate electrons with energy of 1000 eV.
レーザ発色層（Ｂ）は、レーザ発色性印刷インキ、もしくはレーザ発色性塗工液を用いてフィルム層（Ａ）をなすプラスチックフィルムの全体、或いは一部にベタ印刷し、使用に供される。レーザ発色性印刷インキ、もしくは塗工液を印刷後、溶剤乾燥、放射線硬化などの過程を経て形成される。このようなレーザ発色性印刷インキ、塗工液は、例えば、グラビア印刷用インキ、オフセット印刷用インキ、フレキソ印刷用インキ、シルクスクリーン印刷用インキなどとして調整することができる。必要に応じて、インクジェット、浸漬、スピンコーティングなどの方法を単独、又は併用して用いることができる。レーザ発色層（Ｂ）の形成をグラビア印刷法にて行う場合、１回の工程、もしくは数度の重ね印刷を行っても構わない。また、１回目に印刷するレーザ発色層と２回目以降のレーザ発色層で発色剤を同じものである必要はなく、意匠性を損なわない範囲で適宜選択される。
また、意匠性の観点から、レーザ発色層（Ｂ）を形成する前に、パターン柄を形成しても良い。パターン柄の形成には、例えばグラビア印刷の場合、黄、藍、マゼンタ、黒等のプロセスインキおよびパール顔料等を用いた特色インキ等が用いられるが、それらは公知公用のものが使用され、特に制限はなく、フィルム種類への適性、用途等により適宜選択される。
The laser color-developing layer (B) is solid-printed on the whole or a part of the plastic film forming the film layer (A) using a laser color-developing printing ink or a laser color-developing coating liquid, and used. It is formed through a process such as solvent drying and radiation curing after printing with a laser coloring printing ink or coating liquid. Such laser-colorable printing ink and coating liquid can be prepared as gravure printing ink, offset printing ink, flexographic printing ink, silk screen printing ink, and the like. As required, methods such as inkjet, dipping, and spin coating can be used alone or in combination. When the formation of the laser coloring layer (B) is performed by a gravure printing method, one step or several times of overprinting may be performed. Further, it is not necessary that the color forming agent is the same for the laser color forming layer printed at the first time and the laser color developing layer after the second time, and the color developing agent is appropriately selected within a range not impairing the design.
Further, from the viewpoint of design properties, a pattern pattern may be formed before forming the laser coloring layer (B). In the case of gravure printing, for example, in the case of gravure printing, process inks such as yellow, indigo, magenta, black, etc. and special color inks using pearl pigments, etc. are used. There is no restriction | limiting, It selects suitably by the aptitude to a film kind, a use, etc.
接着層（Ｃ）は必要に応じて設けられる層であるが、公知公用であるポリエステル系、ポリエーテル系等のドライラミネート型接着剤、ノンソルベント型接着剤、アクリル接着剤や押し出しラミネート用ＡＣ剤が用いられる。特に制限はないが、剥離面の制御するに際し、適宜選択される。 The adhesive layer (C) is a layer provided as necessary, but is a publicly known polyester-based or polyether-based dry laminate adhesive, non-solvent adhesive, acrylic adhesive or extrusion laminate AC agent. Is used. Although there is no restriction | limiting in particular, In controlling a peeling surface, it selects suitably.
基材層（Ｄ）にはフィルム層（Ａ）に挙げた透明なプラスチックフイルム以外に紙、金属箔、ガラス、木材等が用いられる。好ましくはプラスチックフィルム、紙、金属箔であり、更に好ましくはプラスチックフィルムである。
基材層（Ｄ）が透明な場合、基材層（Ｄ）側からもレーザ印字できる。
For the substrate layer (D), paper, metal foil, glass, wood and the like are used in addition to the transparent plastic film mentioned in the film layer (A). A plastic film, paper, and metal foil are preferable, and a plastic film is more preferable.
When the substrate layer (D) is transparent, laser printing can also be performed from the substrate layer (D) side.
基材層（Ｄ）に透明なプラスチックフィルムを用いる場合は、前記したフィルム、及びその厚みがそのまま適用できる。またエクストルーダー方式による押し出しポリエチレン，ポリプロピレン等も使用できる。
レーザ印字積層体から包装袋とする場合は 基材層（Ｄ）はポリエチレン、ポリプロピレン等のシーラントと呼ばれるヒートシール可能なフィルムがより好ましい。
When using a transparent plastic film for a base material layer (D), an above-described film and its thickness can be applied as it is. Extruded polyethylene, polypropylene, etc. can also be used.
When a laser printed laminate is used as a packaging bag, the base material layer (D) is more preferably a heat-sealable film called a sealant such as polyethylene or polypropylene.
紙としては、アート紙、コート紙、上質紙、和紙、合成紙等が使用できる。 As paper, art paper, coated paper, high-quality paper, Japanese paper, synthetic paper, and the like can be used.
金属箔としてはアルミ箔が好ましく、印刷に適した厚さのもの、例えば厚みが５〜１５０μｍのものが使用できる。 As the metal foil, an aluminum foil is preferable, and one having a thickness suitable for printing, for example, one having a thickness of 5 to 150 μm can be used.
レーザ照射によるレーザ印字方法は、公知のレーザ印字装置、レーザマーカで行われる。例えば、炭酸ガスレーザ（１０６４０ｎｍ）、ＹＡＧレーザ（１０６４ｎｍ）、ＹＶＯ4レーザ（１０６４ｎｍ）、ファイバーレーザ（１０６４ｎｍ）、グリーンレーザ（５３２ｎｍ）等を使用できる。特にレーザ光の波長が５３２ｎｍ〜１０６４ｎｍであると、より鮮明な印字が可能となる。 The laser printing method by laser irradiation is performed with a known laser printing apparatus or laser marker. For example, a carbon dioxide laser (10640 nm), a YAG laser (1064 nm), a YVO 4 laser (1064 nm), a fiber laser (1064 nm), a green laser (532 nm), or the like can be used. In particular, when the wavelength of the laser light is 532 nm to 1064 nm, clearer printing is possible.
好ましくは、ＹＡＧレーザ、ＹＶＯ4レーザ、ファイバーレーザであり、更に好ましくはレーザ光の強度分布がシングルモードのパワー分布であるＹＶＯ4レーザである。 A YAG laser, a YVO4 laser, and a fiber laser are preferable, and a YVO4 laser in which the intensity distribution of laser light is a single-mode power distribution is more preferable.
ＹＡＧレーザ、若しくはＹＶＯ4レーザは１）ＬＤ％、２）Ｑ−スイッチ周波数、及び３）走査速度等の条件により対象物の印字品質を制御できる。例えば、キーエンス社製のＭＤ−Ｖ９６００。
ＬＤ％は、レーザ出力を表す。ＬＤ％によりレーザパワーを制御できるが、大きくし過ぎるとレーザマーキング用積層体がダメージを受けやすい。また、小さすぎると印字が不鮮明になる。
Ｑ−スイッチ周波数は、パルスを発生させる周波数を表す。Ｑ−スイッチ周波数も印字品質に影響を及ぼし、大きすぎても、小さすぎても印字品質が低下する。
走査速度は印字ドットの間隔、印字時間等を制御するもので遅過ぎると印字ドットが集中し、場合によってはレーザマーキング用積層体がダメージを受ける。また、速過ぎると、印字ドット間が広くなり場合によっては印字濃度、印字品質の低下がみられる。
レーザによる印字では、文字を印字するにあたって、走査するレーザ本数により印字の視認性を制御することができる。例えば、線幅を0.2mm、線数を４本とすると0.2mm幅の間に４本の印字が施され、結果的に印字が濃くなり、視認性が良化する。しかしながら、本数を増やす分、印字時間が長くなり、生産効率が低下するため、より少ない本数で視認性の良い印字を行うことが好ましい。本発明においてはレーザマーキング用積層体の剥離界面を考慮し、レーザ印字面、印字文字の形態（正文字、鏡文字）を適宜選択し、印字することから、少ない印字本数で印字濃度が高く、視認性の高いレーザ印字物を得ることができる。
With YAG laser or YVO4 laser, the print quality of the object can be controlled by conditions such as 1) LD%, 2) Q-switch frequency, and 3) scanning speed. For example, MD-V9600 manufactured by Keyence Corporation.
LD% represents the laser output. The laser power can be controlled by LD%, but if it is too large, the laser marking laminate is easily damaged. If it is too small, the print becomes unclear.
The Q-switch frequency represents the frequency at which pulses are generated. The Q-switch frequency also affects the print quality. If it is too large or too small, the print quality will deteriorate.
The scanning speed controls the interval between printing dots, printing time, and the like. If the scanning speed is too slow, the printing dots are concentrated, and in some cases, the laser marking laminate is damaged. On the other hand, if the speed is too high, the space between the print dots becomes wide, and in some cases, the print density and the print quality are lowered.
In printing by laser, when printing a character, the visibility of printing can be controlled by the number of lasers to be scanned. For example, if the line width is 0.2 mm and the number of lines is 4, four prints are applied within the 0.2 mm width, resulting in darker prints and improved visibility. However, as the number is increased, the printing time becomes longer and the production efficiency is lowered. Therefore, it is preferable to perform printing with less visibility with a smaller number. In the present invention, considering the peeling interface of the laminate for laser marking, the laser printing surface and the form of printed characters (correct characters, mirror characters) are appropriately selected and printed, so the print density is high with a small number of prints, A laser printed matter with high visibility can be obtained.
レーザ印字における鏡文字の印刷については、例えば、ＹＶＯ4レーザ「キーエンス社製ＭＤ-９６００」では、「ミラー反転あり」モードにすることで印字できる。鏡文字はレーザ印字面と反対の面から見ると通常の正文字となり、認識可能となる。 With respect to the printing of mirror characters in laser printing, for example, the YVO4 laser “MD-9600 manufactured by Keyence Corporation” can be printed in the “with mirror inversion” mode. The mirror character becomes a normal regular character when viewed from the side opposite to the laser printing surface and can be recognized.
本発明のレーザ印字積層体を用い、食品、医薬品、化粧品等を内容物とした包装体にすると、内容物の賞味期限、消費期限、製造年月日、ロット番号等の可変情報を提供でき生産者、消費者等に資することができる。本発明においてはレーザ印字はレーザマーキング用積層体に先にレーザ印字を行い、レーザ印字積層体を得て、その後に製袋する他、レーザマーキング用積層体を用途にあった筒状、箱状の筐体にし、その後にレーザ印字することも可能である。包装体として利用する時は、層間剥離面が包装体の外側（視認する側）になるようレーザマーキング用積層体を設計しておけば、内容物の可変情報を生産者、中間業者、消費者等が流通過程、店頭で視認しやすい。
また、本発明のレーザ印字積層体は、視認性に優れ、改竄ができなく、セキュリテイ上でも有用であることからカード、ラベル等にも適用できる。
Using the laser-printed laminate of the present invention to produce a package with food, medicine, cosmetics, etc. as contents, variable information such as the expiration date, expiry date, date of manufacture, and lot number of the contents can be provided and produced Can contribute to consumers and consumers. In the present invention, laser printing is performed first on the laser marking laminate, to obtain a laser printing laminate, and then to form a bag. It is also possible to carry out laser printing after that. If the laminate for laser marking is designed so that the delamination surface is on the outside (viewing side) of the package when used as a package, the variable information of the contents can be used by producers, middlemen, and consumers. Etc. are easily visible in the distribution process and in stores.
Further, the laser-printed laminate of the present invention is excellent in visibility, cannot be tampered with, and is also useful in terms of security, so that it can be applied to cards, labels, and the like.
以上のように本発明においては、積層体が有する固有の層間剥離面を事前に引っ張り試験などで把握したり、最初からある特定の界面で層間剥離するようにフイルム層（Ａ）、基材層（Ｄ）等の材質、表面処理を適宜選択することにより視認性の高いレーザ印字積層体が得られる。 As described above, in the present invention, the film layer (A) and the base material layer are formed so that the inherent delamination surface of the laminate can be grasped in advance by a tensile test or delamination is performed at a specific interface from the beginning. By appropriately selecting the material such as (D) and the surface treatment, a highly visible laser print laminate can be obtained.
以下、実施例に基づき本態様をさらに詳しく説明する。実施例中、部は重量部を表し、％は重量％を表す。 Hereinafter, this embodiment will be described in more detail based on examples. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.
以下、実施例に基づき本態様をさらに詳しく説明する。実施例中、部は重量部を表す。尚、％は特に指定のない限り重量％を示す。 Hereinafter, this embodiment will be described in more detail based on examples. In the examples, parts represent parts by weight. % Indicates% by weight unless otherwise specified.
（合成例１）ポリウレタン樹脂の合成
攪拌機、温度計、還流冷却器、および窒素ガス導入管を備えた四つ口フラスコに３−メチル−１，５―ペンタンジオールとアジピン酸からなるポリエステルジオール（分子量２０００、分子量はゲルパーミエーションクロマトグラフイで測定される数平均分子量を示す）１０００部、とイソホロンジイソシアネート２２２部を仕込み、窒素雰囲気下、８５℃で５時間反応させた。次いで、４０℃に冷却後イソホロンジアミン８２部、ジ−ｎ−ブチルアミン７．８部、トルエン１２４４部、メチルエチルケトン１２４４部およびイソプロピルアルコール５７３部を添加し、攪拌下４０℃で５時間反応させた。このようにして得られたポリウレタン樹脂（樹脂１）の固形分は３０％、粘度は４００ｃｐｓ（２５℃）であった。
(Synthesis example 1) Polyester diol (molecular weight consisting of 3-methyl-1,5-pentanediol and adipic acid in a four-necked flask equipped with a polyurethane resin synthesis stirrer, thermometer, reflux condenser, and nitrogen gas introduction tube 1000 parts (2000, molecular weight indicates number average molecular weight measured by gel permeation chromatography) and 222 parts of isophorone diisocyanate were charged and reacted in a nitrogen atmosphere at 85 ° C. for 5 hours. Subsequently, after cooling to 40 ° C., 82 parts of isophorone diamine, 7.8 parts of di-n-butylamine, 1244 parts of toluene, 1244 parts of methyl ethyl ketone and 573 parts of isopropyl alcohol were added and reacted at 40 ° C. for 5 hours with stirring. The polyurethane resin (resin 1) thus obtained had a solid content of 30% and a viscosity of 400 cps (25 ° C.).
（調整例１）塩化ビニル／酢酸ビニル共重合体の調整
塩化ビニル／酢酸ビニル共重合体ＳＯＬＢＩＮ Ｃ ３０部（日信化学工業社製）をメチルエチルケトン７０部に溶解し、３０％溶液に調整した（樹脂２）
(Adjustment Example 1) Preparation of vinyl chloride / vinyl acetate copolymer 30 parts of vinyl chloride / vinyl acetate copolymer SOLBIN C (manufactured by Nissin Chemical Industry Co., Ltd.) was dissolved in 70 parts of methyl ethyl ketone to prepare a 30% solution ( Resin 2)
（製造例１）レーザ発色性印刷インキ（ｂ１）の製造
酸化チタン（チタニックスＪＲ８０５、テイカ株式会社製）６０部、銅・モリブデン複合酸化物（トマテック４２−９０３Ａ、東罐マテリアル・テクノロジー株式会社製）１０部、合成例１で得たポリウレタン樹脂１５部、塩化ビニル／酢酸ビニル共重合体樹脂２）１５部、メチルエチルケトン６０部の混合物をペイントシェーカで練肉し、印刷インキを得た。得られた印刷インキを更に、メチルエチルケトン、酢酸エチル及びイソプロピルアルコールの混合溶剤（重量比50：40：10）で希釈し、ザーンカープ＃３（離合社製）で17秒（２５℃）に調整し、レーザ発色性印刷インキ（ｂ１）を得た。
(Production Example 1) Production of Laser Coloring Printing Ink (b1) 60 parts of titanium oxide (Titanics JR805, manufactured by Teika Co., Ltd.), copper / molybdenum composite oxide (Tomatec 42-903A, manufactured by Toago Material Technology Co., Ltd.) 10 parts, 15 parts of the polyurethane resin obtained in Synthesis Example 1, vinyl chloride / vinyl acetate copolymer resin 2) A mixture of 15 parts and 60 parts of methyl ethyl ketone was kneaded with a paint shaker to obtain a printing ink. The obtained printing ink was further diluted with a mixed solvent of methyl ethyl ketone, ethyl acetate and isopropyl alcohol (weight ratio 50:40:10), and adjusted to 17 seconds (25 ° C.) with Zahn Carp # 3 (manufactured by Ransha Co., Ltd.) Laser-colorable printing ink (b1) was obtained.
（製造例２）レーザ発色印刷インキ（ｂ２）
酸化チタン（チタニックスＪＲ８０５、テイカ株式会社製）７０部、合成例１で得たポリウレタン樹脂１５部、塩化ビニル／酢酸ビニル共重合体（樹脂２）１５部、メチルエチルケトン６０部の混合物をペイントシェーカで練肉し、印刷インキを得た。得られた印刷インキを更に、メチルエチルケトン、酢酸エチル及びイソプロピルアルコールの混合溶剤（重量比50：40：10）で希釈し、ザーンカープ＃３（離合社製）で17秒（２５℃）に調整し、レーザ発色性印刷インキ（ｂ２）を得た。
(Production Example 2) Laser color printing ink (b2)
A paint shaker was used to mix a mixture of 70 parts of titanium oxide (Titanics JR805, manufactured by Teika Co., Ltd.), 15 parts of the polyurethane resin obtained in Synthesis Example 1, 15 parts of vinyl chloride / vinyl acetate copolymer (Resin 2), and 60 parts of methyl ethyl ketone. Kneaded to obtain printing ink. The obtained printing ink was further diluted with a mixed solvent of methyl ethyl ketone, ethyl acetate and isopropyl alcohol (weight ratio 50:40:10), and adjusted to 17 seconds (25 ° C.) with Zahn Carp # 3 (manufactured by Ransha Co., Ltd.) Laser-colorable printing ink (b2) was obtained.
（製造例３）
アンチモンドープ酸化チタン（レーザーフレア ８２０、メルク社製）７０部、合成例１で得たポリウレタン樹脂１５部、塩化ビニル／酢酸ビニル共重合体（樹脂２）１５部、メチルエチルケトン６０部の混合物をペイントシェーカで練肉し、印刷インキを得た。得られた印刷インキを更に、メチルエチルケトン、酢酸エチル及びイソプロピルアルコールの混合溶剤（重量比50：40：10）で希釈し、ザーンカープ＃３（離合社製）で17秒（２５℃）に調整し、レーザ発色性印刷インキ（ｂ３）を得た。
表１に以上のレーザ発色性インキの組成表（固形重量比）を示す。
(Production Example 3)
Paint shaker was prepared by mixing 70 parts of antimony-doped titanium oxide (Laser Flare 820, manufactured by Merck), 15 parts of the polyurethane resin obtained in Synthesis Example 1, 15 parts of vinyl chloride / vinyl acetate copolymer (Resin 2), and 60 parts of methyl ethyl ketone. And kneaded to obtain printing ink. The obtained printing ink was further diluted with a mixed solvent of methyl ethyl ketone, ethyl acetate and isopropyl alcohol (weight ratio 50:40:10), and adjusted to 17 seconds (25 ° C.) with Zahn Carp # 3 (manufactured by Ransha Co., Ltd.) Laser-colorable printing ink (b3) was obtained.
Table 1 shows a composition table (solid weight ratio) of the above laser color forming ink.
（実施例１）
本明細書において、実施例７、８、および１０以外の実施例は参考例である。
Example 1
In this specification, Examples other than Examples 7, 8, and 10 are reference examples.
フィルム層（Ａ）として、ＰＥＴ（東洋紡績社製「エステルＥ５１０２」、膜厚１２μｍ）の未処理面を弱コロナ処理を行い、その面に版深３０μｍのグラビア版を用いて印刷速度５０ｍ／分、乾燥温度６０℃でレーザ発色性印刷インキ（ｂ１）を印刷した。この時フィルム層の濡れ指数は４０ｍＮ／ｍであった。 As the film layer (A), an untreated surface of PET (“Ester E5102” manufactured by Toyobo Co., Ltd., film thickness: 12 μm) is subjected to a weak corona treatment, and a gravure plate having a plate depth of 30 μm is used on the surface, and the printing speed is 50 m / min. The laser-colorable printing ink (b1) was printed at a drying temperature of 60 ° C. At this time, the wetting index of the film layer was 40 mN / m.
得られたＰＥＴ印刷物を接着剤ｃ１（ＴＭ３２９／ＣＡＴ−８Ｂ、東洋モートン社製）を用いドライラミネーションにより低密度ポリエチレン「ＴＵＸ−ＦＣＤ」（トーセロ社製、膜厚４０μｍ）を貼り合わせた。得られたラミネート物は４０℃で３日間エージングを施し、最終的にフイルム層（Ａ）／レーザ発色層（Ｂ）/接着剤層（Ｃ）/ポリエチレンの基材層（Ｄ）を有するレーザマーキング用積層体Ｌ１を得た。 Low-density polyethylene “TUX-FCD” (manufactured by Tosero Corp., film thickness 40 μm) was bonded to the obtained PET printed matter by dry lamination using an adhesive c1 (TM329 / CAT-8B, manufactured by Toyo Morton Co., Ltd.). The obtained laminate was aged at 40 ° C. for 3 days, and finally the laser marking having a film layer (A) / laser coloring layer (B) / adhesive layer (C) / polyethylene substrate layer (D) A laminated body L1 was obtained.
（実施例２〜１０、比較例１）
実験例２〜１０、比較例１については、実施例１と同じ方法で、表２に示したプラスチックフィルム、レーザ発色性印刷インキ、必要に応じて接着剤を用い、レーザマーキング用積層体Ｌ２〜Ｌ１１を得た。使用したプラスチックフィルム、接着剤、基材は下記の通りである。
（プラスチックフィルム）
ＰＥＴ ： ポリエステル、エステルＥ５１０２（東洋紡績社製、膜厚１２μｍ）
Ｎｙ： ナイロン、ＯＮ−ＲＴ（ユニチカ株式会社製、膜厚１５μｍ）
ＯＰＰ：延伸ポリプロピレン、パイレンＰ２１６１（東洋紡績社製、膜厚４０μｍ）
（接着剤）
ｃ１：ＴＭ３２９／ＣＡＴ８Ｂ ：東洋モートン社製 エーテルル系ドライラミネート用接着剤
ｃ２：ＥＬ５４０／ＣＡＴ−ＲＴ８０ 東洋モートン社製 エクストルーダー用ＡＣ剤
ｃ３：ＴＭ５５０／ＣＡＴＲＴ−３７：東洋モートン社製 エステル系ドライラミネート用接着
剤
フィルムの濡れ指数はＪＩＳ Ｋ６７６８の方法に準拠した。表２にその値を示す。
（基材）
ＰＥ：ポリエチレン、ＴＵＸ−ＦＣＤ（東セロ株式会社製、膜厚４０μｍ）
ＰＰ：未延伸ポリプロピレン
尚、実施例７、比較例１においてはイソシアネート硬化剤（ヘキサメチレンジイソシアネートのビュッレトタイプ）を使用した。
(Examples 2 to 10, Comparative Example 1)
For Experimental Examples 2 to 10 and Comparative Example 1, in the same manner as in Example 1, using the plastic film shown in Table 2, the laser-coloring printing ink, and an adhesive as necessary, the laser marking laminate L2 L11 was obtained. The plastic film, adhesive, and base material used are as follows.
(Plastic film)
PET: Polyester, ester E5102 (Toyobo Co., Ltd., film thickness 12 μm)
Ny: Nylon, ON-RT (manufactured by Unitika Ltd., film thickness 15 μm)
OPP: Stretched polypropylene, Pyrene P2161 (Toyobo Co., Ltd., film thickness 40 μm)
(adhesive)
c1: TM329 / CAT8B: Toyo Morton's ethereal dry laminate adhesive c2: EL540 / CAT-RT80 Toyo Morton's extruder AC agent c3: TM550 / CATRT-37: Toyo Morton's ester-based dry laminate The wetting index of the adhesive film conformed to the method of JIS K6768. Table 2 shows the values.
(Base material)
PE: polyethylene, TUX-FCD (manufactured by Tosero Co., Ltd., film thickness 40 μm)
PP: unstretched polypropylene In Example 7 and Comparative Example 1, an isocyanate curing agent (hexamethylene diisocyanate buret type) was used.
実施例１〜１０および比較例１で得られたレーザマーキング用積層体Ｌ１〜Ｌ１１について、層間剥離する界面、剥離強度を調べるため剥離試験を行なった。前記レーザマーキング用積層体を幅１５ｍｍ、長さ１００ｍｍに裁断し、剥離試験用のサンプルを得、インテスコ社製２０１万能引張り試験機で剥離面とその剥離強度を測定した。層間剥離面は下記のように記した
（Ａ）／（Ｂ）：フィルム層（Ａ）／レーザ発色層（Ｂ）で層間剥離
（Ｂ）／（Ｄ）：レーザ発色層（Ｂ）／基材層（Ｄ）で層間層間剥離
（Ｂ）／（Ｃ）：レーザ発色層（Ｂ）／接着剤層（Ｃ）で層間剥離
＊（Ｂ）：レーザ発色層の凝集破壊
For the laser marking laminates L <b> 1 to L <b> 11 obtained in Examples 1 to 10 and Comparative Example 1, a peel test was performed to examine the interface between layers to be peeled and peel strength. The laser marking laminate was cut into a width of 15 mm and a length of 100 mm to obtain a sample for a peel test, and the peel surface and the peel strength thereof were measured with an Intesco's 2010 universal tensile tester. The delamination surface was described as follows: (A) / (B): film layer (A) / laser color developing layer (B), delamination (B) / (D): laser color developing layer (B) / substrate Layer (D) delamination between layers (B) / (C): Laser color development layer (B) / layer separation at adhesive layer (C) * (B): Cohesive failure of laser color development layer
得られたレーザマーキング用積層体についてレーザ印字を行ない、レーザ印字積層体を得た。レーザ印字はＹＶＯ4レーザ「キーエンス社製ＭＤ-９６００」を使用して行った。印字内容は、「Ｌｏｔ．ＡＢＣ１２３」であり、印字条件は下記の通りである。鏡文字は「ミラー反転あり」モードで印字した。
（１）走査速度＝５００ｍｍ／秒
（２）Ｑ−スイッチ周波数＝１０ｋＨｚ
（３）レーザパワー３０％
（４）線数 １本
である。
Laser printing was performed on the obtained laser marking laminate to obtain a laser printing laminate. Laser printing was performed using a YVO4 laser “MD-9600 manufactured by Keyence Corporation”. The print contents are “Lot.ABC123”, and the print conditions are as follows. Mirror characters were printed in “with mirror inversion” mode.
(1) Scanning speed = 500 mm / sec (2) Q-switch frequency = 10 kHz
(3) Laser power 30%
(4) The number of lines is one.
得られたレーザ印字積層体について視認性を評価した。視認性はレーザ印字積層体のフィルム層（Ａ）側と基材層（Ｄ）側について行なった。表２にその視認性とレーザ照射側を記す。
視認性の評価は下記の通りである。
視認性：印字濃度５段階で目視評価した。
◎：印字濃度が極めて高く、視認性が極めて良好。
〇：印字濃度が高く、視認性が良好。
〇△：印字濃度が十分であり、視認性が比較的良好。
△：印字濃度が不十分であり、視認性が不良。
×：印字濃度が殆どなく、視認性が極めて不良。
尚、実用レベルは〇△以上である
Visibility was evaluated about the obtained laser-printed laminated body. Visibility was performed on the film layer (A) side and the base material layer (D) side of the laser-printed laminate. Table 2 shows the visibility and laser irradiation side.
The visibility evaluation is as follows.
Visibility: Visual evaluation was carried out at 5 print density levels.
A: The print density is extremely high and the visibility is very good.
◯: Print density is high and visibility is good.
○ Δ: The print density is sufficient and the visibility is relatively good.
Δ: Print density is insufficient and visibility is poor.
X: There is almost no printing density and visibility is very poor.
The practical level is △△ or more.
表２から明らかな様に、印字を読み取る方向が層間剥離すると、印字の視認性が高まる結果となった。レーザ印字に対して、剥離界面を制御した積層体とすることで、視認性の良好な積層体を得ることができる。 As is clear from Table 2, when the direction in which the print is read is delaminated, the visibility of the print is increased. A laminated body with good visibility can be obtained by using a laminated body in which the peeling interface is controlled for laser printing.
Claims (4)
あるいは、フィルム層（Ａ）、レーザ発色層（Ｂ）および基材層（Ｄ）を順に積層してなるレーザ印字積層体の製造方法であって、
下記（２）の方法で印字することを特徴とするレーザ印字積層体の製造方法。
（２) フィルム層（Ａ）の、レーザ発色層（Ｂ）と接する面の表面張力が４５ｍＮ／ｍを超える場合、フィルム層（Ａ）と基材層（Ｄ）間で剥離処理を行った際に、レーザ発色層（Ｂ）と、接着層（Ｃ）もしくは基材層（Ｄ）で層間剥離することを確認後、下記（ハ）でレーザ印字する。
（ハ）基材層がレーザ光を透過する場合は、基材層（Ｄ）側から正文字をレーザ印字する、または、フィルム層（Ａ）側から鏡文字をレーザ印字する A method for producing a laser-printed laminate comprising a film layer (A), a laser coloring layer (B), an adhesive layer (C), and a base material layer (D),
Alternatively, a method for producing a laser-printed laminate in which a film layer (A), a laser coloring layer (B), and a base material layer (D) are sequentially laminated,
A method for producing a laser-printed laminate, wherein printing is performed by the following method (2) .
( 2) When the surface tension of the surface of the film layer (A) in contact with the laser coloring layer (B) exceeds 45 mN / m, when the peeling treatment is performed between the film layer (A) and the base material layer (D) Then, after confirming that the laser color-developing layer (B) and the adhesive layer (C) or the base material layer (D) are delaminated, laser printing is performed according to the following (c).
(C) When the base material layer transmits laser light, positive characters are laser-printed from the base material layer (D) side, or mirror characters are laser-printed from the film layer (A) side.
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| JP2018076080A (en) * | 2016-11-07 | 2018-05-17 | 株式会社京都製作所 | Printing device |
| JP6483198B2 (en) * | 2017-06-16 | 2019-03-13 | 大日精化工業株式会社 | Laser marking ink composition and packaging material |
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| JP6562145B1 (en) * | 2018-11-13 | 2019-08-21 | 東洋インキＳｃホールディングス株式会社 | Ultraviolet laser marking composition, printed matter and laminate using the same |
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