CN109135425A

CN109135425A - Laser labelling ink composition and packaging material

Info

Publication number: CN109135425A
Application number: CN201810614739.XA
Authority: CN
Inventors: 上原茧
Original assignee: Dainichiseika Color and Chemicals Mfg Co Ltd
Current assignee: Dainichiseika Color and Chemicals Mfg Co Ltd
Priority date: 2017-06-16
Filing date: 2018-06-14
Publication date: 2019-01-04

Abstract

The present invention relates to laser labelling ink composition and packaging materials.The issue of the present invention is to provide: in the Laser labeling layer of formation, it can be carried out the laser labelling ink composition of distincter and visual excellence laser labelling.Laser labelling ink composition of the invention is the ink composition for being used to form Laser labeling layer, and the ink composition contains: binder resin；Laser colour development material generates colour developing by the irradiation of laser beam in Laser labeling layer；With flakey filler is functioned as the auxiliary agent to be developed the color using laser colour development material.

Description

Laser labelling ink composition and packaging material

Technical field

The present invention relates to laser labelling ink composition and packaging materials.

Background technique

In the various packing containers and film of storage food, beverage, drug, quasi drug and cosmetics etc. and paper etc. It is usually proceeded as follows on packaging materials of various packaging raw material etc. etc.: record trade name, lot number, manufacture date, most The various information such as good edible date, service life and manufacturer's title.As such method recorded is carried out, in recent years, just Universal by irradiating laser beam to object to be recorded the laser labelling mode of (so-called laser printing).

Laser labelling mode due to be so-called contactless, have the advantages that as follows: can be carried out high-precision record； It can be carried out high-speed record；With can be recorded in the various surface shapes of object.In turn, laser labelling mode and base It is compared in the record of hot padding mode, ink-jet mode, there are also become the advantages of capable of being difficult to the record eliminated.

It in above-mentioned packaging material etc., usually proceeds as follows: being swashed on the substrate for constituting packaging material with formation such as ink Signal layer irradiates laser beam to the Laser labeling layer, implements label.Such as a kind of recording materials are disclosed in patent document 1, It contains the material selected from one or more of pigment, dyestuff and inorganic material, and has and have at 700~12000nm of wavelength The laser colour rendering printer's ink coating layer and sealer of absorption.In addition, being disclosed in patent document 2, develop the color containing laser The laser labelling of material and specific polyurethane resin ink composition and by the drying overlay film of the ink composition formed swash The recording materials of resin layer are laminated on signal layer and substrate.

On the other hand, in order to can be carried out distincter laser printing, a kind of packaging material is proposed, laser labelling is equipped with Layer of ink, and it is equipped with the layer to the layer of ink reflection laser beam (hereinafter, sometimes referred to as " laser reflection layer ").Such as patent document 3 In disclose a kind of packaging material, at least part of substrate have be sequentially laminated with ink and color layer and pasted using aluminium The laser printing region of the silver color layer of ink (laser reflection layer) of the metallic pigments such as agent, aluminium powder.It is recorded in patent document 3 in following Hold: in the packaging material, by means of reaching the laser beam of ink and color layer through substrate and reflecting from laser reflection layer Laser beam, ink and color layer transparence, can the arbitrary figure of laser printing.In addition, disclosing a kind of packing timber in patent document 4 Material, be successively arranged: laser labelling layer of ink is developed the color in the back side of transparent substrate layer by the irradiation of laser beam；With, Layer of ink (laser reflection layer) containing Aluminum Paste promotes the colour developing of aforementioned layer of ink and having the function of reflection laser beam.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2007-055110 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2010-047681 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2011-148197 bulletin

Patent document 4: Japanese Unexamined Patent Publication 2015-020796 bulletin

Summary of the invention

Problems to be solved by the invention

For Laser labeling layer, the available photograph for for example passing through laser beam from the bottom (white background) of the tone with white color system Penetrate and develop the color for mode of the tone of black system etc. like that, the contrast of the colour developing of background color and the irradiation based on laser beam clearly The record of visual excellence.

On the other hand, it the packaging material as disclosed in above patent document 3 and 4, stacks gradually over the transparent substrate In the case where the Laser labeling layer of white background and the layer of ink containing Aluminum Paste, Laser labeling layer can not be hidden completely contains Aluminum Paste under it Layer of ink.From transparent substrate side when such packaging material, the bottom of Laser labeling layer is easy to be considered as with grey Tone, beautiful, label visuality are easily reduced.In addition, if such packaging material is used for food packaging material, Since packaging material includes the metals such as Aluminum Paste, for being put into the product after food in packaging material, there are following feelings Condition: it is difficult to that the inspection of foreign substance using metal detector is effectively performed；It is unsuitable for micro-wave oven.Therefore, above-mentioned packaging material In the case of, purposes is restricted.

Therefore, the present invention wants to provide: even if being not provided with the laser reflection layer containing metallic pigments such as Aluminum Pastes, in institute's shape At Laser labeling layer in, also can be carried out the laser labelling ink composition of distincter and visual excellence record.

The solution to the problem

The inventors of the present invention are without using laser reflection layer containing metallic pigments such as Aluminum Pastes, to being used to form The ink composition that can be carried out the Laser labeling layer of distincter and visual excellence record has made intensive studies.As a result, this The discovery such as inventor: the laser colour development material is used as by containing laser colour development material in ink composition and not having substantially The flakey filler of function so far complete the present invention to can unexpectedly form target laser mark layer.

That is, the present invention provides a kind of laser labelling ink composition, it is the ink composition for being used to form Laser labeling layer, The ink composition contains: binder resin；Laser colour development material, by the irradiation of laser beam in aforementioned laser mark layer Middle generation colour developing；With, flakey filler, the auxiliary agent as the colour developing functions, it is described colour developing for using it is described swash The colour developing that light colour development material carries out.

The effect of invention

According to the present invention it is possible to provide: in being formed by Laser labeling layer, can be carried out distincter and visual excellence The laser labelling ink composition of record.

Specific embodiment

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments and the accompanying drawings.

< ink composition >

By the laser labelling of an embodiment of the invention with ink composition (hereinafter, being simply recorded as " ink combination sometimes Object ") it is used to form Laser labeling layer.The ink composition contains: binder resin；Laser colour development material passes through laser beam It irradiates and generates colour developing in Laser labeling layer；With flakey filler, the auxiliary agent as the colour developing functions, institute Stating colour developing is the colour developing carried out using the laser colour development material.

By above-mentioned ink composition, can be formed containing binder resin, laser colour development material and flakey filler Laser labeling layer.The substrate of the object of the Laser labeling layer is set for becoming, such as even if further setting is not pasted containing aluminium Other layers such as laser reflection layer of the metallic pigments such as agent, aluminium powder are also able to carry out distincter and visual in Laser labeling layer Excellent record.Therefore, by using the Laser labeling layer based on ink composition to the object for implementing laser labelling, thus also It can be conducive to the beauty for improving object, the visuality for improving label.It in turn, can also using the Laser labeling layer of ink composition To become the layer without containing metal (pure metal and alloy) as above-mentioned metallic pigments.Therefore, such Laser labeling layer exists When object is the situation of packaging material for food etc., the product being put into after content in packaging material can also be advantageously implemented Using metal detector inspection of foreign substance, reply microwave stove heating.Therefore, ink composition can be used for being formed extensive purposes Laser labeling layer.

Laser colour development material " generating colour developing in Laser labeling layer by the irradiation of laser beam " includes following situation: logical Cross the irradiation of laser beam and laser colour development material itself develops the color；Itself does not develop the color and makes neighbouring resin, arbitrary additive Colour developing；With both.For example: when irradiating laser beam to Laser labeling layer, the energy of laser beam is laser marked Laser colour development material in layer absorbs, and using its fuel factor, molecular density is improved, and agglomerates and changes colour as dark color；The resin of surrounding (macromolecule) occurs carbonization, decomposes or gasify and develop the color.Furthermore it is possible to enumerate: passing through the irradiation laser colour developing material of laser beam Material occurs chemical change and develops the color.

By the Laser labeling layer containing binder resin, laser colour development material and flakey filler, swash with only containing Light colour development material is compared with the overlay film of any one of flakey filler, can be carried out distincter and visual excellence record (laser labelling).Think, when irradiating laser beam to Laser labeling layer, it is aobvious that the laser beam entered in Laser labeling layer reaches laser Color material and flakey filler, are reflected by flakey filler.And think, the flakey being laser marked in layer is filled out The a part for filling the laser beam of agent reflection reaches laser colour development material.Result, it is believed that by containing laser colour development material and scale The Laser labeling layer of shape filler also can be such that laser colour development material further absorbs even if not improving the output power of laser beam The energy of laser beam, so as to improve colour rendering.Its result thinks, can be carried out distincter and visual excellence record.

The laser colour development material for generating colour developing in Laser labeling layer as the irradiation by laser beam, can enumerate Machine pigment, inorganic pigment, dyestuff and inorganic material in addition to pigment etc..It can be used alone in these laser colour development materials 1 kind or combine two or more use.Can according to the use purpose and purposes of the Laser labeling layer formed by ink composition, with And use environments such as laser species that Laser labeling layer is used etc. and be suitable for select the laser contained in ink composition develop the color material Material.

As organic pigment, for example, yellow uitramarine, orange pigment, red pigment, violet pigment, blue face Material and viridine green etc..As yellow uitramarine, for example, Fast Yellow G；10G；FGL, dual-azo yellow AAA；AAOT； AAMX；H10G；Special Huang (the Flavanthrone yellow) and Chromophthal yellow GR etc. of HR, indanthrene.As Orange pigment, for example, pyrazolone orange, dianisidine are orange, benzimidazolone orange HL and purple cyclic ketones orange etc..As red Color pigment, for example, C lake red CAN'T 4R；C, naphthol reds BS；FRR；M, naphthols fuchsin (Naphthol carmine) FB and heavily fortified point Firm brilliant scarlet G (Brilliant fast scarlet) etc..As violet pigment, for example, Methyl Violet Lake, rhodamine The color lake B and dioxazine violet etc..As blue pigment, for example, phthalocyanine blue R；G, Victoria Blue Lake and green rust Form sediment etc..As viridine green, for example, brilliant green color lake, malachite green color lake and phthalocyanine green 6Y etc..

As inorganic pigment, the white face such as titanium oxide, basic lead sulfates, zinc oxide, zinc sulphide and antimony oxide can be enumerated Material.In addition, can enumerate settleability barium sulfate as inorganic pigment, barium carbonate, settleability calcium carbonate, diatomite, talcum, glue The extender pigments such as native, basic magnesium carbonate and aluminium are white, can also use using these extender pigments as white pigment.In turn, as Inorganic pigment can enumerate the black pigments such as the carbon blacks such as furnace black, channel black, acetylene black, thermal black and lampblack.

As dyestuff, the colour rendering compound used in common thermal photography as electron donor can be used for example. As such dyestuff, for example, fluorane system, phenthazine system, spiro-pyrans system, triphenylmenthane base phthalide system and rhodamine The leuco dyes such as lactams system (Leuco dye).

As inorganic material, the oxide of the simple substance of metal, the salt of metal, the hydroxide of metal and metal can be enumerated Deng.As the simple substance of metal, for example, iron, zinc, tin, nickel, copper, silver and gold etc..As the salt of metal, such as can lift Copper carbonate, nickelous carbonate, manganese carbonate, cobalt carbonate, lanthanum carbonate, magnesium nitrate, manganese nitrate, ferric nitrate, cadmium nitrate, zinc nitrate, nitric acid out Cobalt, plumbi nitras, nickel nitrate, copper nitrate, palladium nitrate, lanthanum nitrate, magnesium acetate, manganese acetate, cadmium acetate, zinc acetate, cobalt acetate, acetic acid Lead, nickel acetate, copper acetate, acid chloride, copper chloride, iron chloride, cobalt chloride, nickel chloride, silver chlorate, zinc chloride, cupric phosphate, phosphoric acid Iron, cobalt phosphate, cupric pyrophosphate, copper sulphate, ferric sulfate, cobaltous sulfate, cupric oxalate, ferric oxalate, cobalt oxalate, copper benzoate, benzoic acid Iron, cobalt benzoate, phosphonic acids copper with aromatic rings etc..

As the hydroxide of metal, for example, Kocide SD, aluminium hydroxide, magnesium hydroxide, zinc hydroxide, hydrogen Antimony oxide, cobalt hydroxide, nickel hydroxide, iron hydroxide and lanthanum hydroxide etc..As the oxide of metal, oxidation can be enumerated Silicon, aluminium oxide, iron oxide, calcium oxide, magnesia, cobalt oxide, lead oxide, tin oxide, indium oxide, manganese oxide, molybdenum oxide, oxidation Nickel, copper oxide, palladium oxide, lanthana, antimony-doped tin oxide (ATO), indium doping tin oxide (ITO), synthetic zeolite, natural boiling Stone, copper-molybdenum composite oxides etc..As the oxide of metal, with layer structure, mica, montmorillonite also can be used (Montmorillonite) and smectite (Smectite) etc..

Laser colour development material is preferably, and can form Laser labeling layer on the white background of the tone with white color system, and Irradiation on the white background by laser beam generates the substance of the colour developing of the tone of black system.Contrast becomes apparent from as a result, can To obtain visual superior record.As such laser colour development material, such as can be suitble to using white face above-mentioned The inorganic material (such as aluminium oxide, calcium oxide, silver chlorate, molybdenum compound etc.) of material and extender pigment and white color system.Wherein, More preferably use at least one of titanium oxide and molybdenum compound.By by the conduct of at least one of titanium oxide and molybdenum compound Part or all of use of the colorant contained in ink composition, can form and can be carried out distincter and visual excellence note The Laser labeling layer of record.In turn, by using titanium oxide as laser colour development material, it can be conducive to inhibit ink composition, make With the manufacturing cost of its product.In addition, by using molybdenum compound as laser colour development material, even for precisions such as Chinese characters Text can also be conducive to carry out distinct and visual excellence record.

Titanium oxide is further preferably used as and uses YVO₄The ink combination of the laser labelling of laser, YAG laser or optical-fiber laser The laser colour development material that contains in object and use.As titanium oxide, any one of Detitanium-ore-type and rutile-type can be used , more preferably use rutile-type.

Molybdenum compound is further preferably used as and uses CO₂The laser colour developing contained in the laser labelling ink composition of laser Material and use.As the suitable concrete example of molybdenum compound, aforementioned oxidation molybdenum (molybdenum trioxide) and copper-molybdenum composite oxides are removed Except, calcium molybdate, sodium molybdate, ammonium heptamolybdate and ammonium octamolybdate etc. can be enumerated.Wherein, more preferable sodium molybdate, ammonium octamolybdate and Copper-molybdenum composite oxides.

It, will from the viewpoint of the intensity of Laser labeling layer and aggregation force and the colour rendering of the irradiation based on laser beam The gross mass of the solid component of ink composition is as benchmark, the content of laser colour development material preferably 0.1~80 mass %.From obtaining From the perspective of the Laser labeling layer with appropriate intensity and aggregation force and to bending with good patience, ink composition The above-mentioned content of laser colour development material in all solids ingredient preferably 80 mass % or less, more preferable 70 mass % or less, into One step preferably 60 mass % or less, particularly preferred 50 mass % or less.On the other hand, from obtaining the irradiation body by laser beam From the perspective of the Laser labeling layer of existing good colour rendering, laser colour development material in all solids ingredient of ink composition Above-mentioned content preferably 0.1 mass % or more, more preferable 1 mass % or more, further preferred 5 mass % or more, further it is excellent Select 10 mass % or more, particularly preferred 20 mass % or more.

Flakey filler is functioned as the auxiliary agent to be developed the color using aforementioned laser colour development material.Pass through the scale Shape filler is contained in Laser labeling layer together with laser colour development material, and the dense of the colour developing based on laser colour development material can be improved Degree, as a result, can be carried out distincter and visual excellence record.

Even if flakey filler itself does not have the function as laser colour development material substantially, can also play above-mentioned Effect.It is from the viewpoint of absorbing the energy of laser beam further by laser colour development material, it is preferable to use basic without logical The flakey filler crossed the irradiation of laser beam and generate the function of colour developing in Laser labeling layer (embodies the scale of non-colour rendering Shape filler).The flakey filler and laser of non-colour rendering will be embodied on Laser labeling layer by the irradiation of laser beam Colour development material is contained in ink composition together, so as to form the laser that can be carried out distincter and visual excellence record Mark layer.

Flakey filler " non-colour rendering is embodied in Laser labeling layer by the irradiation of laser beam " refers to, substantially not The function of colour developing is generated in Laser labeling layer with the irradiation by laser beam.Specifically, referring to, to solid component packet The portion for having irradiated laser beam in the case where irradiating laser beam containing the overlay film of binder resin and flakey filler, in the overlay film The reflection density (DB) divided is lower than 0.5.More specifically, refer to, fluid composition as shown below is coated on 12 μm of thickness PET film, form about 3 μm of thickness of overlay film and the laser of condition as shown below irradiated from PET film side for the overlay film In the case where beam, the part for having irradiated laser beam in overlay film with reflection of the concentration (trade name " Spectro Eye ", Gretag Macbeth corporation) measurement reflection density (DB) be lower than 0.5.Reflection density (DB) at this time is more preferably less than 0.2, it is even more preferably below 0.1.

(fluid composition)

51 mass % of polyurethane resin solution, the scale for being 30 mass % comprising solid component used in aftermentioned embodiment 17 mass % of shape filler, 9 mass % of ethyl acetate and ethyl acetate/propyl acetate/isopropanol mass ratio be 6/2/2 it is mixed The fluid composition of 23 mass % of bonding solvent.

(laser beam (1))

Laser species: optical-fiber laser

Device: trade name " Videojet7510 " (Videojet Tchnologies corporation)

Scanning speed: 1000mm/ seconds

Average output power: 8.5W

Pulse frequency: 20kHz

The irradiation patterns of laser beam: the whole face of the round of diameter 5mm is coated with image.

(laser beam (2))

Laser species: CO₂Laser

Device: trade name " ML-Z9520 " (Keyence Corporation system)

Scanning speed: 1000mm/ seconds

Average output power: 7.5W

The irradiation patterns of laser beam: the whole face of the square shape of 8mm square is coated with image.

As flakey filler, for example, natural mica (natural Mica), synthetic mica (synthesis Mica), squama Flaky silicon dioxide (SiO₂Thin slice), flaky alumina (Al₂O₃Thin slice), flakey titanium oxide (TiO₂Thin slice), glass flake Pearlescent pigment obtained from covering them with Bismuth Oxychloride (BiOCl) etc. and with metal oxide layer etc..As composition pearly-lustre The metal oxide of coating in pigment, for example, TiO₂、ZrO₂、Fe₂O₃、Fe₃O₄、Cr₂O₃, ZnO and SnO₂Deng. One kind or two or more mixture in them can be used for metal oxide layer.In addition, metal oxide layer can be 1 layer It may be 2 layers or more.It can contain in ink composition one kind or two or more in above-mentioned flakey filler.

Preferably make from the viewpoint of further increasing the function of aforementioned flakey filler as flakey filler With at least one kind of in the group being made of natural mica, synthetic mica and pearlescent pigment.In natural mica, more preferable white clouds Female and phlogopite, in synthetic mica, more preferable fluorophologopite, four silicon muscovites and four silicon paragonites.In addition, in pearlescent pigment, The mica of more preferably coating titanium oxide.Wherein, flakey filler further preferably includes selected from by muscovite, phlogopite, fluorine It is at least one kind of in the group of the mica of phlogopite and coating titanium oxide composition.

Preferably 1~30 μm of the average grain diameter of flakey filler.From obtaining can be carried out distincter and visual excellence note From the perspective of the Laser labeling layer of record, preferably 1 μm or more, more preferable 3 μm of the average grain diameter of flakey filler or more.It is another Aspect, from being easy to be prepared as ink composition to be suitable for forming the intaglio printing of Laser labeling layer with black, flexible version printing is black From the perspective of, preferably 30 μm or less, more preferable 20 μm of the average grain diameter of flakey filler or less, it is further preferred 10 μm with Under.Especially in the case where fluorophologopite, from the viewpoint of obtaining distincter record, preferably its average grain diameter is 8 μm Below.In this specification, average grain diameter is the granularity found out by the sedimentograph based on laser diffraction scattering method Partial size at the accumulated value 50% of volume reference in distribution.

From the viewpoint of the intensity of Laser labeling layer and colour rendering, using the gross mass of the solid component of ink composition as Benchmark, the content of flakey filler preferably 1~60 mass %.Have from the intensity and aggregation force that obtain with appropriateness and to bending From the perspective of the Laser labeling layer for having good patience, the above-mentioned content of flakey filler preferably 60 mass % or less, more It is preferred that 50 mass % or less, further preferred 40 mass % or less.On the other hand, from further increasing based on laser colour development material Colour developing concentration from the perspective of, the above-mentioned content of flakey filler preferably 1 mass % or more, more preferable 5 mass % with Upper, further preferred 10 mass % or more, particularly preferred 20 mass % or more.

In addition, the above-mentioned content of flakey filler is using the gross mass of the solid component of ink composition as benchmark with phase Quality ratio meter for the content of aforementioned laser colour development material is preferably 0.1~2.0 times.Pass through flakey filler and laser Colour development material is contained in all solids ingredient of ink composition with above-mentioned ratio, can advantageously form can be carried out it is distincter and The Laser labeling layer of the record of visual excellence.From the concentration for improving the colour developing based on laser colour development material and can be carried out From the perspective of the Laser labeling layer of distincter and visual excellence record, the above-mentioned content of flakey filler with relative to The quality ratio meter of the content of laser colour development material is preferably 0.2 times or more, more preferable 0.3 times or more, 0.5 times further preferred Above, particularly preferred 0.6 times or more.In addition, from the viewpoint of being easy to prepare ink composition, above-mentioned quality ratio preferably 2.0 Times or less, more preferable 1.5 times or less, further preferred 1.0 times or less.

Binder resin used in ink composition is not particularly limited.As preferred binder resin, such as can be with It is total to enumerate (methyl) acrylic resin, urethane-modified (methyl) acrylic resin, styrene-(methyl) acrylic acid Poly resin, ethylene-(methyl) acrylic copolymeric resin, polyurethane resin, polyester resin, polystyrene resin, Abietyl modified horse Come acid resin, Chlorovinyl-acetate vinyl copolymer resins, ethylene-vinyl acetate c resin, polyvinyl acetal resin and Cellulose-based resins such as polyamide and hydroxyethyl cellulose, hydroxypropyl cellulose and NC Nitroncellulose etc..It can be independent Using a kind in them or combine two or more use.In above-mentioned resin, binder resin more preferably includes selected from by polyurethane Resin；(methyl) acrylic resin；Polyester resin；Chlorovinyl-acetate vinyl copolymer resins；And polyamide and nitre Change at least one kind of in the group of the hybrid resin composition of cotton.It should be noted that in this specification, term " (methyl) acrylic acid " In comprising " acrylic acid " and " methacrylic acid " the two term.

As binder resin, the curability trees such as light-cured resin (such as uv curing resin) also can be used Rouge.As light-cured resin, for example, unsaturated polyester resin, (methyl) acrylic resin, carbamic acid Ester modified (methyl) acrylic resin, epoxy-modified (methyl) acrylic resin and epoxy system resin etc..It can be used And photo-curable monomer and oligomer and Photoepolymerizationinitiater initiater etc. as needed.

Can according to become setting ink composition object substrate, on the substrate be arranged ink composition method, with And the Laser labeling layer formed by ink composition using purpose and purposes etc. is suitable for the bonding for selecting to contain in ink composition Agent resin.As binder resin, more preferable (methyl) acrylic resin and polyurethane resin, further preferred polyurethane tree Rouge.Polyurethane resin is easy to be closely sealed well with plastic film, is imbued with the elasticity for following film, in addition, hot wire-CVD is also excellent. Therefore, it can will contain formation, in turn of the polyurethane resin as the ink composition of binder resin suitable for plastic film Formation suitable for the Laser labeling layer in the packaging material for being set to plastic film.

The sight of aggregation force from Laser labeling layer and the adaptation to substrate and the colour rendering by the irradiation of laser beam Point sets out, using the gross mass of the solid component of ink composition as benchmark, the content of binder resin preferably 10~90 mass %. From the viewpoint of obtaining the Laser labeling layer of aggregation force and adaptation with appropriateness, in all solids ingredient of ink composition Binder resin above-mentioned content preferably 10 mass % or more, more preferable 15 mass % or more, further preferred 20 mass % More than.On the other hand, from the viewpoint of obtaining the irradiation by laser beam and embodying the Laser labeling layer of good colour rendering, ink The above-mentioned content of binder resin in all solids ingredient of composition preferably 90 mass % or less, more preferable 80 mass % with Under, further preferred 70 mass % or less.

For ink composition, curing agent can be contained while containing binder resin, at black group when also can be used It closes in object and adds curing agent.It, can as curing agent it is preferable to use polyisocyanate curing agent and carbodiimides curing agent It is one kind or two or more in them to use.

Ink composition can also contain liquid medium.As liquid medium, water and organic solvent etc. can be used.As having Solvent, for example, ethyl alcohol, isopropanol, ethyl acetate, propyl acetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), 1- methoxy Base -2- propyl alcohol, toluene and dimethylbenzene etc..It can be in ink composition containing independent one kind or two or more mixed in organic solvent Bonding solvent.

Various additives can also be contained in ink composition.As additive, for example, pigment dispersing agent, defoaming Agent, levelling agent, wax, coupling agent, antioxidant, ultraviolet absorbing agent, photostability, surfactant, preservative, antirust agent, Plasticizer, fire retardant and color developing agent etc..

From the viewpoint of be easy on substrate be arranged ink composition formed Laser labeling layer, ink composition is preferably prepared as Printing ink.Wherein, the aspect high from quality and productivity is more preferably prepared as intaglio printing ink, hectographic printing is used Ink, flexible version printing ink or silk-screen printing ink, are further preferably prepared as intaglio printing ink.

The substrate of object for becoming setting ink composition (Laser labeling layer) is not particularly limited, as its material, For example, plastics, rubber, ceramics, metal, timber and paper etc..In addition, as the purposes for using the substrate, such as can be with It enumerates: each for various packing containers and film of content and paper etc. with food, beverage, drug, quasi drug and cosmetics etc. The packaging materials such as kind packaging material.As the purposes for using substrate, and then electronic component, electric component, electrical system can be enumerated Product, automobile component, various sheet materials and card and the label being set on product and label etc..Ink composition is preferred for shape At the Laser labeling layer being set in packaging material.As the suitable substrate of the purposes, art paper (Art can be enumerated Paper), the paper such as art paper (Coated paper), good quality paper, intaglio plate paper and paper, paperboard and synthetic paper；The metals such as aluminium foil Foil；Plastic film；And the one kind or two or more laminated body etc. in them.As substrate, more preferably using such as plastic film Deng like that, through the substrate of the laser beam used.

As plastic film, for example, polyethylene terephthalate (PET), polybutylene terephthalate The polyester films such as ester (PBT) and polyethylene naphthalate (PEN)；Low density polyethylene (LDPE) (LDPE), linear low density polyethylene The polyolefin films such as alkene (LLDPE), high density polyethylene (HDPE) (HDPE), polypropylene (PP)；The cellophanes such as glassine paper；Polyphenyl second Alkene (PS) film；Ethylene-vinyl acetate c resin film；Ethylene-vinyl alcohol copolymer resin film；Polyamide film；It is poly- Carbonic ester film；Kapton；Polyvinyl chloride film etc..Such as it also can be used such as biaxial stretch-formed PP film and tensionless winkler foundation The plastic film of stretching and any one of tensionless winkler foundation as PP film etc..Aluminium-vapour deposition is equipped with alternatively, it is also possible to use The plastic film of equal metal vapor deposition layers, plastic film equipped with the transparent vapor deposition layer such as aluminium oxide and silica etc..In turn, may be used Implement Corona discharge Treatment, corona treatment, flame treatment (Flame treatment), molten with the surface to plastic film The various surface treatments such as agent processing and coating process and the various decorations based on the printing for using color ink etc. etc..

As the laser beam to the Laser labeling layer irradiation formed by ink composition, can be used, which can be used for so-called laser, is beaten The laser beam of print.As suitable laser beam, CO can be enumerated₂Laser (wavelength: 10600nm), YAG laser (wavelength: 1064nm)、YVO₄Laser (wavelength: 1064nm) and optical-fiber laser (wavelength: 1050~1090nm) etc..Ink composition preferably makes It is used with the laser labelling of either of which kind laser beam, more preferably uses optical-fiber laser or CO₂The laser labelling of laser is used.

In order to effectively play aforementioned each function in the laser colour development material and flakey filler contained in ink composition Can, ink composition is more preferably the optical-fiber laser or CO using following condition₂The laser labelling of laser is used.

(optical-fiber laser)

Scanning speed: 500~4000mm/ seconds, 800~3000mm/ seconds more preferable；

Average output power: 2~30W, more preferable 5~15W；

Pulse frequency: 5~150kHz, more preferable 10~50kHz.

〔CO₂Laser)

Scanning speed: 500~4000mm/ seconds, 800~3000mm/ seconds more preferable；

Average output power: 3~25W, more preferable 5~15W.

< packaging material >

The packaging material (hereinafter, being abbreviated as " packaging material " sometimes) of an embodiment of the invention has: substrate； Be set to the Laser labeling layer of substrate.Packaging material can also have the random layer in addition to substrate and Laser labeling layer.Make For random layer, for example, design level, coloring layer, protective layer, vapor deposition layer and adhesive layer etc., but it is not limited to these. In addition, the Laser labeling layer in packaging material can be directly arranged at the surface of substrate, it can also be for example by design level, coloring Layer etc. random layers and be arranged.

Laser labeling layer in packaging material is to be formed by aforementioned laser label with ink composition.Therefore, laser labelling Layer contains: binder resin；Laser colour development material generates colour developing by the irradiation of laser beam in Laser labeling layer；With, Flakey filler is functioned as the auxiliary agent for carrying out aforementioned colour developing using laser colour development material.The thickness of Laser labeling layer Degree preferably 0.1~100 μm, it is 0.5~20 μm more preferable, 1~5 μm further preferred.

Laser labeling layer preferably passes through laser colour development material and is formed on the white background of the tone with white color system, and preferably exists Irradiation on the white background by laser beam generates the colour developing of the tone of black system.By being swashed on such Laser labeling layer Signal, available contrast becomes apparent from, visual superior record.From this viewpoint, for laser labelling Layer, for example, preferably comprise selected from by aforementioned white pigment and extender pigment and white color system inorganic material (such as aluminium oxide, Calcium oxide, silver chlorate, molybdenum compound etc.) composition group at least one kind of be used as laser colour development material, further preferably titanium oxide At least one of with molybdenum compound.It, can be by the Laser labeling layer containing at least one of titanium oxide and molybdenum compound Distincter and visual excellence the record of row.

As the substrate in packaging material, it has been observed that it is preferred that paper, metal foil and plastic film and a kind in them Or laminated body of more than two kinds, more preferable aforementioned various plastic films.Preferably 5~500 μm of the thickness of substrate, more preferable 10~100 μm, it is 10~60 μm further preferred.

Packaging material is preferably also equipped with the protective layer being set to the substrate side in Laser labeling layer for opposite side.Change speech It, packaging material preferably includes the stepped construction at least successively having substrate, Laser labeling layer and protective layer.By protective layer, When carrying out laser labelling on packaging material, when the manufacture of packaging material and when using etc., the stripping of Laser labeling layer can be prevented From with abrasion etc..

In protective layer, it can be used for example and the same resin material, preceding enumerated in the explanation of foregoing adhesives resin The same resin material enumerated in the explanation of plastic film is stated, alternatively, it is also possible to use aforementioned substrates itself.Protective layer can be with It is directly arranged on Laser labeling layer, can also be arranged by anchor coating agent, bonding agent etc..The thickness of protective layer preferably 1~300 μm, it is 5~200 μm more preferable, 10~100 μm further preferred.

The manufacturing method of packaging material comprises the following steps: aforementioned ink composition being arranged on substrate, forms laser labelling Layer.The manufacturing method is preferably before the process for forming Laser labeling layer, the process including preparing ink composition.

It prepares in the process of ink composition, more preferably comprises the following steps: by binder resin, laser colour development material and squama The process (grinding process) that sheet filler and liquid medium as needed are kneaded；With combine ground ink Object is diluted with liquid medium, the process for obtaining dilution ink.It prepares in the process of ink composition, paint stirring can be used for example Device, roller mill (triple-roller mill), ball mill, sand mill and attritor and other agitating devices and dispersal device etc..

It is formed on substrate in the process of Laser labeling layer, as the method that ink composition is arranged on substrate, such as can To enumerate the methods of printing, dipping, spin coating.Go out from the viewpoint for being easy that ink composition is arranged on substrate and forms Laser labeling layer Hair, preferably in printing on substrates ink composition.From the high aspect of quality and productivity, the Laser labeling layer of printing is utilized Formed and more preferably carried out with intaglio printing, hectographic printing, flexible version printing or silk-screen printing, it is further preferred use intaglio printing into Row.Laser labeling layer can be set in the whole face of substrate, also can be set in comprising implement laser labelling desired position A part on.It is formed on substrate in the process of Laser labeling layer, after printing on substrates ink composition, can carry out making it Dry process makes the cured process of the binder resin in layer of ink etc..

It in the manufacturing method of packaging material, and then preferably includes following process: being with the substrate side in Laser labeling layer Protective layer is set on opposite side.As the method for setting protective layer, following method can be enumerated: for example, will protect containing being formed It is to keep it solid on opposite side that the fluid composition of the above-mentioned resin material of sheath, which is coated on the substrate side in Laser labeling layer, Change and forms protective layer.As the solidification form of fluid composition, for example: utilize the solidification and benefit of drying, heat etc. The solidification etc. irradiated with ultraviolet light isoreactivity energy-ray.

In addition, with the substrate side in Laser labeling layer be opposite side on, such as coating anchor coating agent, after making it dry, By the way that above-mentioned resin material (such as LDPE, HDPE and PP etc.) melting extrusion, lamination to be configured, protection can also be formed Layer.It in turn, is being such as coating adhesive, after making it dry, by making on opposite side with the substrate side in Laser labeling layer The dry lamination of the fittings such as aforementioned paper, metal foil and plastic film, also can be set protective layer.

As the specific mode of packaging material, for example, carton, wrapping paper, packing film, packaging bag and Plastic containers such as plastic casing and plastic bottle etc..In addition, the suitable purposes as packaging material, for example, beverage is used Packaging material, food packaging material, drug packaging material, quasi drug packaging material and packaging material used for cosmetic etc., Wherein, food packaging material is more suitable for.

By irradiating laser beam to the Laser labeling layer in packaging material, colour developing is generated in Laser labeling layer, can be carried out Laser labelling.As laser beam, it is preferable to use CO₂Laser, YAG laser, YVO₄Laser, optical-fiber laser, wherein more preferably use CO₂Laser or optical-fiber laser.These laser beams further preferably are irradiated to Laser labeling layer under the conditions of aforementioned be suitble to.

As the symbol type implemented by laser labelling, for example, text, figure, design, bar code and two Tie up code etc..In addition, as these symbols indicate information, for example, trade name, manufacturer's title, manufacture the date, Most preferably edible date, shelf-life, service life, quality assurance time limit, lot number, sequence number, raw material, ingredient, trade mark and pattern Deng.

As described in detail above like that, the laser labelling ink composition and packaging material of an embodiment of the invention use It is constituted using following.

[1] a kind of laser labelling ink composition is the ink composition for being used to form Laser labeling layer, the ink combination Object contains: binder resin；Laser colour development material is generated in aforementioned laser mark layer aobvious by the irradiation of laser beam Color；With, flakey filler, the auxiliary agent as the colour developing functions, it is described colour developing for utilize aforementioned laser develop the color material Expect the colour developing carried out.

[2] the laser labelling ink composition according to aforementioned [1], wherein aforementioned laser colour development material can have Aforementioned laser mark layer is formed on the white background of the tone of white color system, and is generated on aforementioned white background by the irradiation of aforementioned laser beam The colour developing of the tone of black system.

[3] the laser labelling ink composition according to aforementioned [1] or [2], wherein aforementioned flakey filler is put down Equal partial size is 1~30 μm.

[4] the laser labelling ink composition according to any one of aforementioned [1]~[3], wherein aforementioned flakey is filled out It includes at least one kind of in the group that the mica by muscovite, phlogopite, fluorophologopite and coating titanium oxide forms for filling agent.

[5] the laser labelling ink composition according to any one of aforementioned [1]~[4], wherein by aforementioned laser mark Note uses the gross mass of the solid component of ink composition as benchmark, and the content of aforementioned flakey filler is 1~60 mass %.

[6] the laser labelling ink composition according to any one of aforementioned [1]~[5], wherein by aforementioned laser mark Note uses the gross mass of the solid component of ink composition as benchmark, and the content of aforementioned flakey filler is relative to aforementioned laser The quality ratio of the content of colour development material is calculated as 0.5~2.0 times.

[7] the laser labelling ink composition according to any one of aforementioned [1]~[6], wherein foregoing adhesives tree Rouge include selected from by polyurethane resin, (methyl) acrylic resin, polyester resin, Chlorovinyl-acetate vinyl copolymer resins, And it is at least one kind of in the group of the hybrid resin composition of polyamide and nitrocotton.

[8] a kind of packaging material, has: substrate；With, the Laser labeling layer being set in aforementioned substrates, aforementioned laser Mark layer contains: binder resin；Laser colour development material is generated in aforementioned laser mark layer by the irradiation of laser beam Colour developing；With flakey filler, the auxiliary agent as the colour developing functions, and the colour developing is develops the color using aforementioned laser The colour developing that material carries out.

[9] a kind of packaging material, has: substrate；With, the Laser labeling layer being set in aforementioned substrates, aforementioned laser Mark layer is the layer that the laser labelling as described in any one of aforementioned [1]~[7] is formed with ink composition.

Embodiment

Hereinafter, embodiment and comparative example are enumerated, it is specific to the ink composition further progress of one embodiment of the present invention Illustrate, but the ink composition is not limited to the following embodiments.It should be noted that in text below, the note of " part " and " % " Carrying as long as no being particularly limited to is exactly quality criteria (respectively " mass parts " and " quality % ").

< test example A and B >

[preparation of binder resin]

As binder resin used in ink composition, the polyurethane tree for the use of solid component (evaporation surplus) being 30% Lipoprotein solution (trade name " Sanprene IB-971 ", Sanyo Chemical Industries, Ltd.'s system, viscosity: 1000mPaS, containing molten Agent: ethyl acetate and isopropanol).

[black preparation]

(ink 1)

It will be as the white pigment of laser colour development material (Titanium Dioxide Rutile Top grade, 0.29 μm of average grain diameter, trade name " Titanix JR-805 ", Tayca Corporation system) 30 parts, 60 parts of above-mentioned polyurethane resin solution and ethyl acetate 10 Part mixing grinds the mixture with paint shaker to obtain ink 1.

(ink 2)

For 100 parts of ink 1, pearlescent pigment (mica of coating titanium oxide) (mica as flakey filler is added 61.0~67.1%, titanium oxide 33.0~39.0%), 9 μm of average grain diameter, trade name " Magna Pearl 2000 ", BASF system) 20 parts, ink 2 is stirred to get with dissolvers.

(ink 3)

For 100 parts of ink 1, fluorophologopite (6 μm of average grain diameter, trade name " PDM- as flakey filler are added 5B ", TOPY Industries, Ltd. system；Hereinafter, being recorded as " fluorophologopite 1 ") 20 parts, ink 3 is stirred to get with dissolvers.

(ink 4)

For 100 parts of ink 1, fluorophologopite (10 μm of average grain diameter, trade name as flakey filler are added " PDM-800 ", TOPY Industries, Ltd. system；Hereinafter, being recorded as " fluorophologopite 2 ") 20 parts, it is stirred to get with dissolvers Ink 4.

(ink 5)

For 100 parts of ink 1, add as flakey filler muscovite (4 μm of average grain diameter, trade name " M-XF ", Repco Co., Ltd. system) 20 parts, ink 5 is stirred to get with dissolvers.

(ink 6)

For 100 parts of ink 1, add as flakey filler phlogopite (3 μm of average grain diameter, trade name " S-XF ", Repco Co., Ltd. system) 20 parts, ink 6 is stirred to get with dissolvers.

(ink 7)

It will be with 20 parts of identical pearlescent pigment, 60 parts of above-mentioned polyurethane resin solution and ethyl acetate 10 used in ink 2 The mixture is stirred to get ink 7 with dissolvers by part mixing.

(ink 8)

It will be with 20 parts of identical " fluorophologopite 1 ", 60 parts of above-mentioned polyurethane resin solution and ethyl acetate used in ink 3 The mixture is stirred to get ink 8 with dissolvers by 10 parts of mixing.

(ink 9)

It will be with 20 parts of identical muscovite used in ink 5,60 parts of above-mentioned polyurethane resin solution and 10 parts of ethyl acetate The mixture is stirred to get ink 9 with dissolvers by mixing.

(ink 10)

It will be with 20 parts of identical phlogopite used in ink 6,60 parts of above-mentioned polyurethane resin solution and 10 parts of ethyl acetate The mixture is stirred to get ink 10 with dissolvers by mixing.

(ink 11)

The amount of muscovite used in the preparation of ink 5 is changed to 15 parts by 20 parts, it is in addition to this, same with preparing for ink 5 Obtain to sample ink 11.

(ink 12)

The amount of muscovite used in the preparation of ink 5 is changed to 18 parts by 20 parts, it is in addition to this, same with preparing for ink 5 Obtain to sample ink 12.

(ink 13)

The amount of white pigment (titanium oxide) used in the preparation of ink 5 is changed to 20 parts by 30 parts, and by muscovite Amount is changed to 30 parts by 20 parts, and in addition to this, the preparation with ink 5 gets similarly ink 13.

(ink 14)

The amount of white pigment (titanium oxide) used in the preparation of ink 5 is changed to 20 parts by 30 parts, and by muscovite Amount is changed to 40 parts by 20 parts, and in addition to this, the preparation with ink 5 gets similarly ink 14.

(ink 15)

In the preparation of ink 1, " white pigment " that uses as laser colour development material is changed to as CO₂Laser colour developing face The molybdenum compound (ammonium octamolybdate, trade name " PRIME100 ", Dataracing company system) of material, in addition to this, with ink 1 Preparation gets similarly ink 15.

(ink 16)

For 100 parts of ink 15, addition and 20 parts of identical pearlescent pigment used in ink 2 are stirred to get with dissolvers Ink 16.

(ink 17)

For 100 parts of ink 15, addition is stirred with used in ink 3 20 parts of identical " fluorophologopite 1 " with dissolvers To ink 17.

(ink 18)

For 100 parts of ink 15, addition is stirred with used in ink 4 20 parts of identical " fluorophologopite 2 " with dissolvers To ink 18.

(ink 19)

For 100 parts of ink 15, addition and 20 parts of identical muscovite used in ink 5 stir to get ink with dissolvers 19。

(ink 20)

For 100 parts of ink 15, addition and 20 parts of identical phlogopite used in ink 6 stir to get ink with dissolvers 20。

(ink 21)

The amount of muscovite used in the preparation of ink 19 is changed to 15 parts by 20 parts, in addition to this, the preparation with ink 19 Get similarly ink 21.

(ink 22)

The amount of muscovite used in the preparation of ink 19 is changed to 18 parts by 20 parts, in addition to this, the preparation with ink 19 Get similarly ink 22.

(ink 23)

The amount of molybdenum compound used in the preparation of ink 19 is changed to 20 parts by 30 parts, and by the amount of muscovite by 20 parts 30 parts are changed to, in addition to this, the preparation with ink 19 gets similarly ink 23.

(ink 24)

The amount of molybdenum compound used in the preparation of ink 19 is changed to 20 parts by 30 parts, and by the amount of muscovite by 20 parts 40 parts are changed to, in addition to this, the preparation with ink 19 gets similarly ink 24.

[preparation of dilution ink]

(dilution ink 1~24)

For gained ink 1~24, respectively and then ethyl acetate (60%)/propyl acetate (20%)/isopropanol (20%) is used Mixed solvent dilution, with Zahn cup No.3 (clutch society of Co., Ltd. system) adjust to become 17 seconds (25 DEG C) viscosity, obtain To dilution ink 1~24.

[production of lamination printed article]

(lamination printed article 1)

Using deep 35 μm of the gravure of version, black 1 intaglio printing will be diluted in the Corona discharge Treatment PET as base film On the processing surface side of film (Co. Ltd. system, 12 μm of thickness are spun by trade name " Ester E5102 ", Japan).In this way, obtaining in base The printed article of the layer of ink (3 μm of thickness) based on dilution ink 1 is formed on material film.Later, it is applied at the layer of ink side of the printed article Cloth polyethyleneimine amine system anchor coating agent (trade name " SEIKADYNE 4100 ", Dainichiseika Color Chem's system) simultaneously drying, shape At anchor coating (0.03 μm of thickness).It then, will be as the LDPE of middle layer (trade name " Novatec on the anchor coating LC600A ", Japan Polyethylene Corp.'s system) melting extrusion, and be laminated LLDPE film (trade name " T.U.X FC-D ", Mitsui Chemicals Tohcello, Inc. system).In this way, obtaining the layer of ink being arranged on the base film in printed article 1 On be laminated with LDPE layer (about 30 μm of thickness) and LLDPE layers (30 μm of thickness) protective layer (about 60 μm of thickness gauge) lamination printing Object 1.

(lamination printed article 2~24)

It will be laminated and dilute black 1 table 1 (table 1-1 and table 1-2) as be described hereinafter and (the table 2- of table 2 used in the production of printed article 1 1 and table 2-2) shown in, any one of be changed to above-mentioned dilution ink 2~24, in addition to this, utilize the system with lamination printed article 1 Make the same method of method, obtains lamination printed article 2~24.It should be noted that as shown in Table 1 and Table 2, for using dilution The lamination printed article 7~10 of 7~10 production of ink, in order to for the test example based on aftermentioned optical-fiber laser and based on CO₂Laser Both test examples prepare 2 respectively.

< test example A1~A14 >

For gained be laminated printed article 1~14, carry out the laser labelling using optical-fiber laser respectively, obtain record object A1~ A14.Specifically, being used up for the region equipped with layer of ink in lamination printed article from the PET film side being laminated in printed article Fine laser marker (trade name " Videojet7510 ", Videojet Tchnologies corporation) irradiation optical fiber laser (wave It is long: 1060~1070nm), obtain record object.The irradiation patterns for forming optical-fiber laser are the text (text of " 2017.06.01 " It is high: 5mm) and diameter 5mm the round image all filled, record these writings and images.The irradiation condition of optical-fiber laser is such as Under: for two kinds of irradiation patterns of writings and image, scanning speed is set as 1000mm/ seconds and pulse frequency is set as 20kHz, in addition, the average output power of the irradiation patterns of text to be set as to the average output work of the irradiation patterns of 10W, image Rate is set as 8.5W.

< test example B1~B14 >

Printed article 15~20,7~10 and 21~24 is laminated for gained, carries out using CO respectively₂The laser labelling of laser, Obtain record object B1~B14.Specifically, for the region equipped with layer of ink in lamination printed article, from lamination printed article PET film side, uses CO₂Laser marker (trade name " ML-Z9520 ", Keyence Corporation system) irradiates CO₂Laser (wavelength: 10600nm) obtains record object.CO₂The irradiation patterns of laser form the text of " best edible date 2017.06.01 " The image that (text height: 5mm) and the square of 8mm square all fill, records these writings and images.CO₂The irradiation of laser Condition is as follows: for the irradiation patterns of text, being set as 2 kinds of irradiation conditions 1 and 2 as shown below, for the irradiation figure of image Case is set as irradiation condition 3 as shown below.

(irradiation condition 1 of text)

Scanning speed: 3000mm/ seconds, average output power: 10W

(irradiation condition 2 of text)

Scanning speed: 2000mm/ seconds, average output power: 10W

(irradiation condition 3 of image)

Scanning speed: 1000mm/ seconds, average output power: 7.5W

For recording object A1~A14 and B1~B14 obtained in test example A1~A14 and B1~B14, carry out as shown below Evaluation.

(record concentration)

Use reflection of the concentration (trade name " Spectro Eye ", Gretag Macbeth corporation), measurement record object A1 The reflection density (DB) of filling image (round or square) in~A14 and B1~B14, according to evaluation criteria as shown below Record concentration is evaluated.In evaluation criteria as shown below, by " A " and " B " as the level that can be actually used, by " C " " D " is as the level that can not be actually used.Show the results of the evaluation the lower section of Tables 1 and 2.It should be noted that test example Each of A7~A10 and B7~B10, DB are below 0.1.

A:DB is 1.0 or more.

B:DB is 0.5 more than or lower than 1.0.

C:DB is 0.2 more than or lower than 0.5.

D:DB is lower than 0.2.

(vividness of text)

With the text (number) of " 2017.06.01 " in visual confirmation record object A1~A14, the fuzzy feelings of text are considered Condition and deep or light, evaluates the vividness of text according to evaluation criteria (A~D) as shown below.In addition, for test example B1 The text (number and Chinese character) of " best edible date 2017.06.01 " in~B14, similarly, is commented according to as shown below Valence benchmark (AA~D) evaluates the vividness of text.In evaluation criteria as shown below, by " AA ", " A " and " B " conduct The level that can be actually used, by " C " and " D " as the level that can not be actually used.It shows the results of the evaluation under Tables 1 and 2 Section.

AA: without apparent fuzzy, and text did not had light, can clearly identify Chinese character and number.

A: without apparent fuzzy, and text did not had light, can clearly identify number.

B: text is fuzzy, and has light part, but can identify text.

C: most text is fuzzy, and very light, accordingly, it is difficult to identify text.

D: substantially non-shorthand can not identify text.

Table 1-1 uses the test example of the laser labelling of optical-fiber laser

Table 1-2 uses the test example of the laser labelling of optical-fiber laser

Table 2-1 uses CO₂The test example of the laser labelling of laser

Table 2-2 uses CO₂The test example of the laser labelling of laser

As shown in Table 1 and Table 2, the laser colour development material in laser colour development material and flakey filler is only used for layer of ink Test example A1 and B1 in, the vividness of text is insufficient.In addition, only by the squama in laser colour development material and flakey filler Sheet filler is used in the test example A7~A10 and B7~B10 of layer of ink, basic without carrying out laser labelling.It is true by the result Accept, the flakey filler used do not have substantially by using laser beam irradiation and the function of colour developing is generated in layer of ink Energy.

In contrast, by both laser colour development material and flakey filler be used for layer of ink test example A2~A6 and In A11~A14 and B2~B6 and B11~B14, the record of black system can be carried out on white background, has obtained record concentration and text The good result of vividness both of which of word.Therefore confirmed, the layer of ink formed in test example A2~A6 and B2~B6 can be with Using as the Laser labeling layer that can be carried out distincter and visual excellence record.Especially it confirmed, test example B2~B6 In B11~B14, can use as even for Chinese character complicated as " best edible date " also can be carried out it is distinct and The Laser labeling layer of the record of visual excellence.It confirmed by the result of above each test example, the flakey filler used It functions, can be improved using sharp as the auxiliary agent to be developed the color using laser colour development material in layer of ink (Laser labeling layer) The concentration of the colour developing of light colour development material.

In turn, confirmed by the result and test example B5 of test example A5 and A11~14 and the result of B11~14, black group It closes in object, the content (%) of muscovite is with the quality of the content (%) relative to laser colour development material (titanium oxide, molybdenum compound) In the case that ratio is calculated as 0.6~2.0 times, the excellent result of vividness both of which of record concentration and text has been obtained.It is right In using other flakey filler (pearlescent pigment, fluorophologopite 1 and 2 and phlogopite) in addition to muscovite the case where It confirms and is similarly inclined to the effect.

< test example C and D >

[preparation of binder resin]

In test example C and D, binder resin below is used in ink composition.

Polyurethane resin；Polyurethane resin solution (solid component 30%) used in test example A and B

Acrylic resin；Acrylic resin solution (the trade name that solid component (evaporation surplus) is 50% " Dianal LR-186 ", Mitsubishi Chemical Corporation system, Tg52 DEG C, weight average molecular weight (Mw) 35000)

Polyester resin；It is by solid component (evaporation surplus) with toluene (50%)/methyl ethyl ketone (50%) mixed solvent 100% polyester resin (trade name " Polyester TP-220 ", Japan synthesis Chemical Co., Ltd. system, Tg70 DEG C, number divide equally Son amount (Mn) 16000) obtained from the dissolution, polyester resin solution that solid component (evaporation surplus) is 30%

Chlorovinyl-acetate vinyl is copolymerized (PVC-PVAc) resin；With the mixing of toluene (50%)/methyl ethyl ketone (50%) Chlorovinyl-acetate vinyl copolymer resins (trade name " the VINNOL E15- that solid component (evaporation surplus) is 100% by solvent 48A ", Wacker corporation, Tg69 DEG C, molecular weight (Mn) 22000) obtained from dissolution, solid component (evaporation surplus) is 30% Chlorovinyl-acetate vinyl copolymer resins solution

Polyamide: use the mixed solvent of isopropanol (70%)/toluene (30%) by solid component (evaporation surplus) For 100% polyamide (trade name " Reomaido S-2800 ", Kao Corp's system, 112~120 DEG C of softening point) The polyamide resin lipoprotein solution that obtained from dissolution, solid component is 30%

Nitrocotton: use toluene (50%)/isopropanol (30%)/ethyl acetate (20%) mixed solvent by solid component Obtained from nitrocotton (trade name " H (RS) -1/2 ", the South Korea's CNC corporation) dissolution that (evaporation surplus) is 70%, solid at Divide the nitrocellulose solution that (evaporation surplus) is 20%

[black preparation]

(ink 26~29)

60 parts of above-mentioned polyurethane resin solution used in preparation for the ink 1 in test example A (is calculated as with solid component 18 parts), it is changed to 36 parts of above-mentioned acrylic resin solution (being calculated as 18 parts with solid component) in ink 26, is changed in ink 27 For 60 parts of above-mentioned polyester resin solution (being calculated as 18 parts with solid component), ink 28 in be changed to above-mentioned PVC-PVAc resin solution 60 parts (being calculated as 18 parts with solid component), in ink 29 be changed to 42 parts of above-mentioned polyamide resin lipoprotein solution and (be calculated as with solid component 12.6 parts) and 27 parts of nitrocellulose solution (being calculated as 5.4 parts by solid component) mixed resin solution (in terms of solid component 18 parts), remove Except this, the preparation with ink 1 gets similarly ink 26~29.

(ink 31~34)

For gained ink 26~29, muscovite 20 part are added used in the preparation of the ink 5 in test example A respectively, use is molten Device stirring is solved, ink 31~34 is respectively obtained.

(ink 37~40)

60 parts of above-mentioned polyurethane resin solution is (in terms of solid component used in preparation for the ink 15 in test example B It is 18 parts), it is changed to 36 parts of above-mentioned acrylic resin solution (being calculated as 18 parts with solid component) in ink 37, becomes in ink 38 More above-mentioned 60 parts of polyester resin solution (being calculated as 18 parts with solid component), to be changed to above-mentioned PVC-PVAc resin molten in ink 39 60 parts of liquid (being calculated as 18 parts by solid component) is changed to 42 parts of above-mentioned polyamide resin lipoprotein solution (in terms of solid component in ink 40 Be 12.6 parts) and the mixed resin solution of 27 parts of nitrocellulose solution (being calculated as 5.4 parts with solid component) (solid component is calculated as 18 Part), and 20 parts of muscovite are added, in addition to this, the preparation with ink 15 gets similarly ink 37~40.

[preparation of dilution ink]

(dilution ink 25,30,35 and 36)

For ink 1,5,15 and 19, the polyisocyanate curing agent that solid component (non-volatile content) is 30% is added respectively 10 parts of (trade name " Ramic B Hardener ", Dainichiseika Color Chem's system) (being calculated as 3 with solid component), in turn It is diluted with ethyl acetate (60%)/propyl acetate (20%)/isopropanol (20%) mixed solvent, with Zahn cup No.3 (strain Clutch society of formula commercial firm system) it adjusts to the viscosity for becoming 17 seconds (25 DEG C), respectively obtain dilution ink 25,30,35 and 36.

(dilution ink 26~28,31~33 and 37~39)

For ink 26~28,31~33 and 37~39,10 parts of above-mentioned polyisocyanate curing agent is added (in terms of solid component Be 3 parts), so with toluene (50%)/methyl ethyl ketone (50%) mixed solvent dilute, with Zahn cup No.3 (Co., Ltd. from Close society's system) it adjusts to the viscosity for becoming 17 seconds (25 DEG C), respectively obtain dilution ink 26~28,31~33 and 37~39.

(dilution ink 29,34 and 40)

It is dilute with toluene (50%)/isopropanol (30%)/ethyl acetate (20%) mixed solvent for ink 29,34 and 40 It releases, is adjusted with Zahn cup No.3 (clutch society of Co., Ltd. system) to the viscosity for becoming 17 seconds (25 DEG C), respectively obtain dilution ink 29,34 and 40.

[production of printed article]

(printed article 25)

Using deep 35 μm of the gravure of version, black 25 intaglio printings will be diluted in the Corona discharge Treatment as base film On the processing surface side of PET film (trade name " Ester E5102 ", Japan spin Co. Ltd. system, 25 μm of thickness), make to be printed Dilution ink 25 solidifies 24 hours under 40 DEG C of environment.It obtains being formed with the layer of ink (thickness based on dilution ink 25 on base film as a result, Degree 3 μm) printed article 25.

(printed article 26~28,30~33 and 35~39)

By shown in black 25 tables 3 and table 4 as be described hereinafter of dilution used in the production of printed article 25, it is changed to above-mentioned dilution ink 26 Any one of~28,30~33 and 35~39, in addition to this, using method same as the production method of printed article 25, obtain To printed article 26~28,30~33 and 35~39.

(printed article 29,34 and 40)

Respectively using dilution ink 29,34 and 40, printed article 29,34 and 40 is made.Specifically, recessed using deep 35 μm of version Printing plate will dilute black intaglio printing in Corona discharge Treatment biaxial stretch-formed polypropylene (OPP) film (commodity as base film Name " FOS ", Futamura Chemical Co, Ltd. system, 50 μm of thickness) processing surface side, obtain being formed on base film The printed article of layer of ink (3 μm of thickness) based on dilution ink.

< test example C1~C10 >

For gained printed article 25~34, carry out the laser labelling using optical-fiber laser respectively, obtain record object C1~ C10.Specifically, the region of the layer of ink for being equipped in printed article is beaten from the layer of ink side in printed article with above-mentioned optical-fiber laser Ink recorder irradiation optical fiber laser (wavelength: 1060~1070nm) obtains record object.The irradiation patterns and irradiation condition of optical-fiber laser are set For with afore-mentioned test example A identical conditions.

< test example D1~D6 >

For gained printed article 35~40, carry out using CO respectively₂The laser labelling of laser obtains record object D1~D6. Specifically, for the region for the layer of ink being equipped in printed article, from the layer of ink side in printed article, with above-mentioned CO₂Laser marker Irradiate CO₂Laser (wavelength: 10600nm) obtains record object.CO₂The irradiation patterns and irradiation condition of laser are set as and afore-mentioned test Example B identical conditions.

For record object D1 obtained in record object C1~C10 and test example D1~D6 obtained in test example C1~C10 ~D6 evaluates the vividness of record concentration and text using method same as the evaluation carried out in test example A and B. Show the results of the evaluation the lower section of table 3 and table 4.

Table 3 uses the test example of the laser labelling of optical-fiber laser

Table 4 uses CO₂The test example of the laser labelling of laser

It confirmed by the result of test example C6~C10 and D2~D6, use resin in addition to polyurethane resin as viscous It, can also by containing the ink composition of laser colour development material (titanium oxide, molybdenum compound) and muscovite in the case where tying agent resin To form the Laser labeling layer that can be carried out distincter and visual excellence laser labelling.For using its in addition to muscovite The case where his flakey filler (pearlescent pigment, fluorophologopite 1 and 2 and phlogopite) also confirms similarly inclines with the effect To.

Claims

1. a kind of laser labelling ink composition is the ink composition for being used to form Laser labeling layer,

The ink composition contains:

Binder resin；

Laser colour development material generates colour developing by the irradiation of laser beam in the Laser labeling layer；With,

Flakey filler, the auxiliary agent as the colour developing function, and the colour developing is to utilize the laser colour development material The colour developing of progress.

2. laser labelling ink composition according to claim 1, wherein the laser colour development material can have white The Laser labeling layer is formed on the white background of the tone of system, and black is generated by the irradiation of the laser beam on the white background The colour developing of the tone of system.

3. laser labelling ink composition according to claim 1 or 2, wherein the average grain of the flakey filler Diameter is 1~30 μm.

4. laser labelling ink composition according to claim 1, wherein the flakey filler includes selected from by white Mica, phlogopite, fluorophologopite and coating titanium oxide mica composition group in it is at least one kind of.

5. laser labelling ink composition according to claim 1, by the solid of the laser labelling ink composition at The gross mass divided is 1~60 mass % as benchmark, the content of the flakey filler.

6. laser labelling ink composition according to claim 1, wherein by consolidating for the laser labelling ink composition The gross mass of body ingredient is as benchmark, and the content of the flakey filler is with the content relative to the laser colour development material Quality ratio is calculated as 0.5~2.0 times.

7. laser labelling ink composition described according to claim 1~any one of 6, wherein the binder resin packet Containing selected from by polyurethane resin, (methyl) acrylic resin, polyester resin, Chlorovinyl-acetate vinyl copolymer resins and It is at least one kind of in the group of the hybrid resin of polyamide and nitrocotton composition.

8. a kind of packaging material, has: substrate；With, the Laser labeling layer being set on the substrate,

The Laser labeling layer contains: binder resin；Laser colour development material, by the irradiation of laser beam in the laser Colour developing is generated in mark layer；With, flakey filler, the auxiliary agent as the colour developing functions, it is described colour developing for utilize The colour developing that the laser colour development material carries out.