WO2015068412A1 - 印刷インキ用バインダー、軟包装用ラミネートインキ組成物及び印刷物 - Google Patents
印刷インキ用バインダー、軟包装用ラミネートインキ組成物及び印刷物 Download PDFInfo
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- WO2015068412A1 WO2015068412A1 PCT/JP2014/059871 JP2014059871W WO2015068412A1 WO 2015068412 A1 WO2015068412 A1 WO 2015068412A1 JP 2014059871 W JP2014059871 W JP 2014059871W WO 2015068412 A1 WO2015068412 A1 WO 2015068412A1
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- peg
- binder
- ink
- polyurethane resin
- printing
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a binder for printing ink, a laminate ink composition for soft packaging, and a printed matter.
- plastic films have been used in various fields as packaging materials. Printing on such a plastic film is performed by gravure printing or flexographic printing. With the diversification of packaging base materials, the performance required for printing inks and coating agents used for decoration or surface protection is becoming increasingly sophisticated.
- a printing ink for plastic film needs to have excellent printability, adhesion, anti-blocking property, gloss and the like for a wide variety of films. Furthermore, in the field of food packaging containers, ink is not in direct contact with the contents, and sanitary laminated packaging containers are used.
- an ink is printed using various plastic films as a printing substrate
- an extrusion laminating method in which molten polyolefin or the like is laminated on the printing surface via an anchor coating agent
- a plastic film is laminated on the printing surface via an adhesive. This is a dry laminating method.
- the ink used in the laminating method must adhere well to printing substrates such as various plastic films, and must have excellent adhesion to the laminated plastic film, printability, and laminate strength.
- boil or retort treatment is applied to wrap the whole packaging container laminated in hot water, suitability for boil and retort that does not cause laminating float or wrinkle during treatment Is required.
- binder resin Since most of the above ink performance mainly depends on the performance of the binder resin, various binder resins are used depending on the required performance. In general, a polyurethane resin is used as a binder resin for laminating ink (see Patent Documents 1 to 3).
- a polyurethane resin with a molecular urethane bond concentration as high as possible is used as the binder resin for laminating inks.
- the urethane bond concentration increases, the ink boil and retort suitability tends to be poor, and methyl ethyl ketone
- solvents such as ethyl acetate, isopropyl alcohol, etc. decreases, and when these solvents are used, printing of the image area is caused by the phenomenon that the solid matter of ink accumulates in the plate, which is called plate clogging. There is a problem that a defect occurs (decrease in printability).
- the polyurethane resin skeleton is hardened to improve blocking resistance.
- chlorinated PP polypropylene
- boil / retort suitability, laminate strength, An ink having good printability, adhesion and anti-blocking properties can be obtained.
- aromatic organic solvents and organic solvents that do not contain ketone organic solvents such as methyl ethyl ketone is being promoted (such as non-tolueneization).
- these polyurethane resins alone it has been difficult for inks obtained with organic solvents not containing aromatic organic solvents to meet a wide variety of film requirements.
- An object of the present invention is to provide a printing ink binder for obtaining an ink excellent in printability, laminate strength and boil / retort property. Moreover, it is providing the laminate ink composition for soft packaging which uses the binder for printing inks, and its printed matter.
- PEG polyethylene glycol
- the present invention is a printing ink binder comprising a PEG-containing polyurethane resin and a vinyl chloride vinyl acetate copolymer resin as components, wherein the PEG-containing polyurethane resin comprises at least (A) a polyester polyol having a number average molecular weight of 1000 to 6000, (B) is obtained by reacting PEG, (C) diisocyanate compound and (D) chain extender, and (B) the content ratio of PEG is 100 parts by mass of PEG-containing polyurethane resin,
- the present invention relates to a printing ink binder in the range of 1 to 40 parts by mass.
- the present invention also relates to the above-mentioned binder for printing ink, wherein (B) PEG has a number average molecular weight of 200 to 4000. (B) When the number average molecular weight of PEG is within the above range, effects such as improvement in laminate strength can be obtained.
- the present invention further relates to the printing ink binder described above, wherein the PEG-containing polyurethane resin is obtained by reacting dimethylolpropionic acid. Further, by using a dimethylolpropionic acid (hereinafter referred to as DMPA) -containing polyurethane resin as a component, effects such as improvement in laminate strength and suitability for boil and retort can be obtained.
- DMPA dimethylolpropionic acid
- the present invention also relates to a laminate ink composition for soft packaging comprising the above-mentioned printing ink binder, colorant and organic solvent as components.
- the present invention also relates to the laminate ink composition for soft packaging, wherein the organic solvent does not contain an aromatic organic solvent or a ketone organic solvent.
- the printing ink binder of the present invention is particularly suitable for a laminate ink composition for soft packaging that does not use an aromatic organic solvent or a ketone organic solvent, but uses an aromatic organic solvent or a ketone organic solvent. It can also be used in laminated ink compositions for soft packaging, and exhibits excellent properties.
- the present invention also relates to a printed matter obtained by printing the above-mentioned laminated ink composition for soft packaging.
- a printing ink binder for obtaining an ink excellent in printability, laminate strength, and boil / retort suitability.
- the binder for printing ink of the present invention is a binder for printing ink comprising a PEG-containing polyurethane resin and a vinyl chloride-vinyl acetate copolymer resin as components, and the PEG-containing polyurethane resin has at least (A) a number average molecular weight of 1000 to 6000.
- diol component constituting the (A) polyester polyol used in the present invention examples include ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, triethylene glycol, 1- or 2-methyl -1,3-butylene glycol, 1- or 2-methyl-1,4-pentylene glycol, 2,4-diethyl-1,5-pentanediol, tripropylene glycol, 1,2-propylene glycol, 1,3 Alkylene oxides such as butanediol, 1-, 2- or 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, ethylene oxide of bisphenol A, propylene oxide, ethylene propylene oxide, etc. Addendum, Neope Chill glycol, butyl ethyl propanediol. Of these, particularly preferred are 3-methyl-1,5-pentanediol and neopen
- polyfunctional polyols can be used for some of the diol components.
- examples of the polyfunctional polyol include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanol, sorbitol, pentaerythritol and the like. It is done.
- dicarboxylic acid constituting the polyester polyol examples include adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid and the like, and mixtures of two or more thereof. Of these, particularly preferred are adipic acid and sebacic acid. Also included are anhydrides of the dicarboxylic acids and esterified products of lower alcohols having 1 to 5 carbon atoms.
- the polyester polyol in the present invention can be obtained by a method similar to a conventionally known polyester production method.
- a polyester polyol can be obtained by dehydrating and condensing the diol component and the dicarboxylic acid or acid anhydride.
- the polyester polyol (A) used in the present invention has a number average molecular weight of 1000 to 6000. If the number average molecular weight is less than 1000, the urethane bond concentration in the molecule is high, and the ink boil and retort suitability tends to be poor, and methyl ethyl ketone. And solubility in solvents such as ethyl acetate and isopropyl alcohol tends to be lowered. On the other hand, when the number average molecular weight exceeds 6000, the urethane bond concentration in the molecule is lowered, and the adhesiveness, the laminate strength, and the blocking resistance are liable to be lowered.
- the number average molecular weight of the polyester polyol is preferably 1500 to 5000, and more preferably 2000 to 4000.
- the number average molecular weight can be measured by gel permeation chromatography (GPC) (in terms of standard polystyrene).
- (B) PEG used in the present invention preferably has a number average molecular weight of 200 to 4000, more preferably 400 to 3000, and still more preferably 500 to 2000.
- the number average molecular weight is 200 to 4000, effects such as improvement in laminate strength can be obtained.
- the range is 1 to 40 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the PEG-containing polyurethane resin.
- (B) When the content ratio of PEG is in the range of 1 to 40 parts by mass, effects such as improved boil / retort suitability and printability can be obtained.
- Examples of the (C) diisocyanate compound used in the present invention include alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate.
- alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate.
- Fragrances such as aliphatic diisocyanates such as dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, tolylene diisocyanate, xylylene diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate Examples thereof include aliphatic diisocyanates and modified products of these diisocyanate compounds. These polyisocyanate compounds may be used alone or in combination of two or more. Of these, alicyclic diisocyanates are preferred, and isophorone diisocyanate (IPDI) is particularly preferred.
- IPDI isophorone diisocyanate
- the PEG-containing polyurethane resin used in the present invention is preferably further reacted with a low molecular diol.
- a low molecular diol dimethylolpropionic acid (DMPA) is particularly preferable.
- the content of dimethylolpropionic acid (DMPA) is preferably in the range of 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass with respect to 100 parts by mass of the PEG-containing polyurethane resin. More preferably, it is 0.1 to 3 parts by mass.
- (D) chain extender used in the present invention various known ones can be used. Examples thereof include ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, dimer diamine and the like. Other molecules such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc.
- chain extenders include diols having a tertiary amine structure such as methyldiethanolamine, methyldiisopropanolamine, phenyldiisopropanolamine, 4-methylphenyldiisopropanolamine, 4-methylphenyldiethanolamine, and 2 A mixture of more than one type can be mentioned.
- chain elongation terminator can be used as necessary.
- chain elongation terminators include monoalcohols (methanol, propanol, butanol, 2-ethylhexanol, etc.), monoamines (mono- or dialkylamines having 2 to 8 carbon atoms (butylamine, dibutylamine, etc.), mono-carbons having 2 to 6 carbon atoms.
- dialkanolamine monoethanolamine, diethanolamine, propanolamine, isopropanolamine, etc.
- the PEG-containing polyurethane resin used in the present invention is a conventionally known method, for example, JP-A-62-153366, JP-A-62-153367, JP-A-1-236289, JP-A-2-64173. No. 2, 64,174, and No. 2-64175, and the like.
- polypropylene glycol and a combination polyol and a diisocyanate compound are reacted in an excess ratio of isocyanate groups to obtain a prepolymer of a terminal isocyanate group, and the resulting prepolymer is placed in a suitable solvent, that is, non-toluene.
- a suitable solvent that is, non-toluene.
- Ester solvents such as ethyl acetate, propyl acetate, butyl acetate, etc .
- ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone
- Alcohol solvents such as methylcyclohexane and ethylcyclohexane; or a mixed solvent such as a two-stage method of reacting with a chain extender and / or endblocker, or polypropylene Call and combination polyol, diisocyanate compound, a chain extender and (or) endblocker is produced by one-step process of reacting at a time in a suitable solvent of the above.
- the vinyl chloride vinyl acetate copolymer resin having a hydroxyl group used in the present invention can be obtained by two kinds of methods. One is obtained by copolymerizing vinyl chloride monomer, vinyl acetate monomer and vinyl alcohol in appropriate proportions. The other is obtained by copolymerizing vinyl chloride and vinyl acetate and then partially saponifying vinyl acetate.
- the properties of the resin film and the resin dissolution behavior are determined by the monomer ratio of vinyl chloride, vinyl acetate and vinyl alcohol. That is, vinyl chloride imparts toughness and hardness of the resin coating, vinyl acetate imparts adhesion and flexibility, and vinyl alcohol imparts good solubility in polar solvents.
- a laminating ink composition (printing ink) for soft packaging can be produced by mixing appropriately and kneading using a normal ink production apparatus such as a ball mill, an attritor, or a sand mill.
- the blending amount of the binder of the present invention in the soft packaging laminate ink composition (printing ink) is 3 to 20% by mass in terms of the resin solid content in the soft packaging laminate ink composition (printing ink). It is preferable to blend in.
- organic solvent used for a laminating ink composition for soft packaging (printing ink) it is preferable not to include an aromatic organic solvent or a ketone organic solvent from the point of use environment, for example, methanol, ethanol, isopropanol, Examples include alcohol solvents such as n-propanol and methoxypropanol, and ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate. These are used alone or as a mixture of two or more.
- the laminate ink composition for soft packaging of the present invention is suitable as a printing ink for a plastic film as a packaging material, and printing on such a plastic film may be performed by gravure printing or flexographic printing, which are generally performed. . And, for example, an extrusion laminating method in which various plastic films are used as printing bases, ink (laminated ink composition for soft packaging) is printed, and molten polyolefin is laminated on the printed surface via an anchor coat agent, or A dry laminate process is performed in which a plastic film is laminated on the printing surface via an adhesive to produce a printed matter.
- part represents “part by mass”
- % represents “% by mass”.
- Synthesis Example 1 (Synthesis of polyurethane resin a) In a round bottom flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, 295 parts of a polyester polyol (adipate of 3-methyl-1,5-pentanediol) having a number average molecular weight of 3000 as component (A), (B) As a component, 5 parts of polyethylene glycol having a number average molecular weight of 400 and 49.3 parts of isophorone diisocyanate (IPDI) as a component (C) were charged and reacted at 105 ° C. for 6 hours under a nitrogen stream to obtain an isocyanate group content of 2.67%.
- a polyester polyol adipate of 3-methyl-1,5-pentanediol having a number average molecular weight of 3000
- component (B) As a component, 5 parts of polyethylene glycol having a number average molecular weight of 400 and 49.3
- polyurethane resin a The polyurethane resin thus obtained (hereinafter referred to as polyurethane resin a) had a resin solid content concentration of 30% by mass, a viscosity of 500 mPa ⁇ s (25 ° C.), and an amine value of 0.8 mgKOH / g.
- Example 1 to 10 and Comparative Examples 1 to 3 Regarding color pigment dispersibility, 28 parts of polyurethane resin of Synthesis Examples 1 to 13, 10 parts of vinyl chloride vinyl acetate copolymer resin (15% solution in ethyl acetate), 10 parts of cyanine blue, mixed solvent ethyl acetate / isopropyl
- a laminated ink composition for soft wrapping composed of 52 parts of alcohol 7/3 (mass ratio) was dispersed for 3 hours using a pigment disperser (paint shaker), and then mixed with Zahn Cup No. 1 using a mixed solvent. 3 was adjusted to 15 seconds, and the laminated ink composition for soft packaging was evaluated for the following (1) color pigment dispersibility.
- PET film polyethylene terephthalate film
- ink cyanine blue
- X Color unevenness occurs in the coating film, and pigment dispersion is inferior.
- Boil suitability test After applying an isocyanate adhesive on the ink surface of a printed material obtained by printing the ink (titanium white) described above on a PET film or nylon film (abbreviated as NY film), 60 ⁇ m by a dry laminating machine. The unstretched polyethylene film was laminated to obtain a laminated product. The laminated product was made into a bag, a water / oil mixture was sealed inside, sealed, heated in 95 ° C. hot water for 30 minutes, and the floating state of the laminated product was observed to evaluate the boil suitability. “O”: The laminated product does not float at all. “ ⁇ ”: A part of the laminate processed product that is partially lifted. “ ⁇ ”: A float occurred on the entire surface of the laminated product.
- Retort suitability test After applying an isocyanate adhesive to the ink surface of the printed matter obtained by printing the ink (titanium white) described above on a PET film or NY film, a 60 ⁇ m unstretched polypropylene film was applied by a dry laminating machine. Lamination was performed to obtain a laminated product. This laminated product is made into a bag, sealed with a water / oil mixture inside, heated in pressurized hot water at 120 ° C for 30 minutes, and evaluated for retort suitability by observing the floating state of the laminated product. did. “O”: The laminated product does not float at all. “ ⁇ ”: A part of the laminate processed product that is partially lifted. “ ⁇ ”: A float occurred on the entire surface of the laminated product.
- Adhesion Printing was performed on the PET film using the ink (titanium white) described above.
- the print film was allowed to stand for 24 hours, and then a cellophane tape was affixed to the print surface, and the coating state of the print surface when it was rapidly peeled off was observed and evaluated.
- ⁇ ” 50% or less of the printed film remains on the film.
- Blocking resistance Printing was performed on the PET film using the ink (titanium white) described above to produce a printed film.
- the printed surface of the printed film was overlapped, and the adhesion state of the printed surface after standing at 40 ° C. with a load of 4 ⁇ 10 5 Pa for 15 hours was observed.
- ⁇ 0% to less than 20% of the contact area is adhered.
- ⁇ Adhesion of 20% to less than 50% of the contact area.
- ⁇ There is adhesion of 50% or more of the contact area.
- Comparative Examples 1 to 3 in which the content ratio of (B) PEG is not in the range of 1 to 40 parts by mass with respect to 100 parts by mass of the PEG-containing polyurethane resin are: Printability, boilability, retort suitability, adhesion, and blocking resistance are all poor.
- Examples 1 to 10 in which the polyurethane resin having a content ratio of (B) PEG in the range of 1 to 40 parts by mass with respect to 100 parts by mass of the PEG-containing polyurethane resin is a color pigment dispersibility. It can be seen that the printability, boilability, retortability, adhesiveness, and blocking resistance are all excellent.
- the ink using the binder for printing ink of the present invention has good color pigment dispersibility and excellent solubility in a solvent without using an aromatic organic solvent or a ketone organic solvent. Suppressing and printing defects in the image area do not occur.
- the binder for printing inks of this invention is excellent in printability, and also excellent in boil and retort suitability, it is very useful as a binder for printing inks used for food packaging containers and the like.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
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- Polyurethanes Or Polyureas (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明の印刷インキ用バインダーは、PEG含有ポリウレタン樹脂及び塩化ビニル酢酸ビニル共重合樹脂を成分とする印刷インキ用バインダーであって、前記PEG含有ポリウレタン樹脂が、少なくとも(A)数平均分子量1000~6000のポリエステルポリオールと、(B)PEGと、(C)ジイソシアネート化合物と、(D)鎖伸長剤とを反応させて得られるものであり、(B)PEGの含有比率が、PEG含有ポリウレタン樹脂100質量部に対して、1~40質量部の範囲である。
撹拌機、温度計および窒素ガス導入管を備えた丸底フラスコに、(A)成分として数平均分子量3000のポリエステルポリオール(3-メチル-1,5-ペンタンジオールのアジペート)295部、(B)成分として数平均分子量400のポリエチレングリコール5部、および(C)成分としてイソホロンジイソシアネート(IPDI)49.3部を仕込み、窒素気流下、105℃で6時間反応させ、イソシアネート基含量2.67%のプレポリマーを製造した後、酢酸エチル233部を加えてウレタンプレポリマーの均一溶液とした。続いて(D)成分としてイソホロンジアミン(IPDA)20部、ジ-n-ブチルアミン(DBA)1.7部、酢酸エチル373部およびイソプロピルアルコール260部からなる混合物に前記ウレタンプレポリマー溶液582部を加え、次いで60℃で3時間反応させた。こうして得られたポリウレタン樹脂(以下、ポリウレタン樹脂a)は、樹脂固形分濃度が30質量%、粘度が500mPa・s(25℃)、アミン価が0.8mgKOH/gであった。
表1~2に示す原料を用い、合成例1と同様にして、ポリウレタン樹脂溶液b~mを得た。
色顔料分散性については、合成例1~13のポリウレタン樹脂28部、塩化ビニル酢酸ビニル共重合樹脂(酢酸エチルで15%溶液にしたもの)10部、シアニンブルー10部、混合溶剤酢酸エチル/イソプロピルアルコール=7/3(質量比)52部からなる組成の軟包装用ラミネートインキ組成物を、顔料分散機(ペイントシェイカー)を用いて3時間分散した後、混合溶剤を用いてザーンカップNo.3で15秒となるよう粘度調整し、軟包装用ラミネートインキ組成物について、下記(1)色顔料分散性の評価を行った。
ポリエチレンテレフタレートフィルム(PETフィルムと略す)に上記に記載のインキ(シアニンブルー)を用いて印刷を施し、印刷フィルムを作製し、印刷物の塗膜の状態を目視観察で判定した。評価基準は以下の通り。
「○」…塗膜に色むらがなく、顔料分散が良好なもの。
「△」…塗膜に一部色むらがあり、顔料分散が若干劣るもの。
「×」…塗膜に色むらが生じており、顔料分散が劣るもの。
上記に記載のインキ(チタン白)により小型グラビア印刷試験機を用いてPETフィルム印刷した印刷パターンの状態、すなわち、版のドクター切れの状態、およびセル詰りに関連する印刷パターンの欠落を目視観察で判定した。評価基準は以下の通り。
「○」…印刷適性が良好なもの。
「△」…印刷適性が不十分なもの。
「×」…印刷適性が極めて劣るもの。
上記に記載のインキ(チタン白)をPETフィルム、ナイロンフィルム(NYフィルムと略す)に印刷した印刷物のインキ面に、ウレタン系接着剤を使用し、ドライラミネート機によってCPP(無延伸ポリプロピレン)フィルムを積層し、40℃で2日間エージング後、ラミネート後3日目に試料を15mm幅に切断し、180°剥離強度を測定した。
上記に記載のインキ(チタン白)をPETフィルム、ナイロンフィルム(NYフィルムと略す)に印刷した印刷物のインキ面に、イソシアネート系接着剤を塗布した後、ドライラミネート機によって60μmの無延伸ポリエチレンフィルムを積層し、ラミネート加工物を得た。このラミネート加工物を製袋し、内部に水/油の混合物を入れて密封後、95℃の熱水中で30分間加熱し、ラミネート加工物の浮き状態を観察してボイル適性を評価した。
「○」:ラミネート加工物に全く浮きのないもの。
「△」:ラミネート加工物に部分的に浮きが生じたもの。
「×」:ラミネート加工物の全面で浮きが生じたもの。
上記に記載のインキ(チタン白)をPETフィルム、NYフィルムに印刷した印刷物のインキ面に、イソシアネート系接着剤を塗布した後、ドライラミネート機によって60μmの無延伸ポリプロピレンフィルムを積層し、ラミネート加工物を得た。このラミネート加工物を製袋し、内部に水/油の混合物を入れて密封後、120℃の加圧熱水中で30分間加熱し、ラミネート加工物の浮き状態を観察してレトルト適性を評価した。
「○」:ラミネート加工物に全く浮きのないもの。
「△」:ラミネート加工物に部分的に浮きが生じたもの。
「×」:ラミネート加工物の全面で浮きが生じたもの。
PETフィルムに上記に記載のインキ(チタン白)を用いて印刷を施し、印刷フィルムを作製した。前記印刷フィルムを24時間放置後、印刷面にセロファンテープを貼り付け、これを急速に引き剥したときの印刷面の塗膜状態を観察評価した。
「○」…印刷皮膜の80%以上がフィルムに残る。
「△」…印刷皮膜の50~80%がフィルムに残る。
「×」…印刷皮膜の50%以下がフィルムに残る。
PETフィルムに上記に記載のインキ(チタン白)を用いて印刷を施し、印刷フィルムを作製した。前記印刷フィルムの印刷面を重ね合わせ、4×105Paの荷重にて40℃で15時間静置した後の印刷面の付着状態を観察した。
「○」…接触面積のうち0%~20%未満の付着あり。
「△」…接触面積のうち20%以上~50%未満の付着あり。
「×」…接触面積のうち50%以上の付着あり。
Claims (6)
- ポリエチレングリコール(以下「PEG」という)含有ポリウレタン樹脂及び塩化ビニル酢酸ビニル共重合樹脂を成分とする印刷インキ用バインダーであって、前記PEG含有ポリウレタン樹脂が、少なくとも(A)数平均分子量1000~6000のポリエステルポリオールと、(B)PEGと、(C)ジイソシアネート化合物と、(D)鎖伸長剤とを反応させて得られるものであり、(B)PEGの含有比率が、PEG含有ポリウレタン樹脂100質量部に対して、1~40質量部の範囲である印刷インキ用バインダー。
- (B)PEGの数平均分子量が200~4000である請求項1に記載の印刷インキ用バインダー。
- さらにPEG含有ポリウレタン樹脂が、ジメチロールプロピオン酸を反応させたものである請求項1又は2に記載の印刷インキ用バインダー。
- 請求項1~3いずれかに記載の印刷インキ用バインダー、着色剤及び有機溶剤を成分とする軟包装用ラミネートインキ組成物。
- 有機溶剤が芳香族系有機溶剤又はケトン系有機溶剤を含まない請求項4に記載の軟包装用ラミネートインキ組成物。
- 請求項4又は5に記載の軟包装用ラミネートインキ組成物を印刷してなる印刷物。
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