JPH07113100B2 - Printing ink composition for plastics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial field of application) The present invention is superior to plastics, especially plastic films such as polypropylene, polyester and nylon even when used in a one-pack type. The present invention relates to a printing ink composition having adhesiveness, printability, laminating suitability, and boil / retort resistance.

(Prior Art) As a printing ink composition used for plastics, in particular, plastic films such as polypropylene, polyester, nylon, etc., a one-component type containing a linear polyurethane resin soluble in an organic solvent as a main binder And a two-component type having a mixture of a linear polyurethane resin soluble in an organic solvent and a polyisocyanate compound as a main binder are used, and they are properly used depending on the type and application of the material to be printed.

Among them, the one-pack type printing ink composition has good adhesiveness to plastics and suitability for laminating to plastic film, but is sufficient for applications requiring high resistance such as boiling sterilization and retort sterilization. There was a drawback that we could not deal with it.

In addition, although the two-component type can sufficiently support applications requiring high resistance, from the viewpoint of storage stability, a polyisocyanate compound must be added to and mixed with the component containing the linear polyurethane resin immediately before use. However, there were drawbacks such as complicated work, lack of stability of residual meat, and difficulty of reuse of residual meat.

As a means for improving these drawbacks, JP-A-57-149323 has been proposed.
Japanese Patent Application Laid-Open No. 2003-242242 proposes a printing ink binder comprising a polyurethane resin formed from an organic diisocyanate and a polyol having an amide bond and an ester bond obtained from polymerized fatty acid, organic diamine and polyhydric alcohol. When such a binder for printing ink is used as a one-pack type, the stability of the residual thickness of the printing ink, the adhesion to the plastic film, the blocking resistance, and the laminating strength when used as a laminating ink are improved, It was still inadequate, and when used as a laminate ink, it had the drawbacks of poor boiling resistance and retort resistance.

(Problems to be Solved by the Invention) The present invention, even when used in a one-pack type, has excellent adhesiveness, printability, laminating suitability to plastics, especially plastic films such as polypropylene, polyester, and nylon. And a printing ink composition having boil retort resistance.

[Structure of Invention]

(Means for Solving the Problems) The present invention provides (A) dimer diol and / or
(B) Polymerized fatty acid polyester polyol having no amide bond, (C) if necessary (A) and (B)
Other than polyol, (D) organic diisocyanate, and (E) chain extender and / or (F) as required
A printing ink composition for plastics, comprising as a main binder a polyurethane resin obtained by reacting a terminal stopper.

In the present invention, the (A) dimer diol refers to one having a diol obtained by reducing a polymerized fatty acid as a main component. Further, (B) an amide bond-free polymerized fatty acid polyester polyol is reacted with a polymerized fatty acid, a polycarboxylic acid other than the polymerized fatty acid or an anhydride thereof, a diol, and a polyol other than the diol, if necessary. It is obtained by doing. Polymerized fatty acids include C ₁₈ unsaturated fatty acids such as oleic acid and linoleic acid, drying oil fatty acids or semi-drying oil fatty acids, and lower monoalcohol esters of these fatty acids in the presence or absence of a catalyst. Molecularly polymerized products are available, and various products are commercially available. Typical examples are C ₁₈ monocarboxylic acid 0 to 5% by weight, C ₃₆ dimer acid 70
˜98% by weight, and 0 to 30% by weight of C ₅₄ trimer acid. Polycarboxylic acids other than polymerized fatty acids or their anhydrides include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid,
These are dicarboxylic acids such as suberic acid, azelaic acid and sebacic acid or their anhydrides, and trifunctional or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid or their anhydrides. From the viewpoint of solubility of the resulting polyurethane resin, it is preferable to use polycarboxylic acids other than polymerized fatty acids or their anhydrides. Examples of the diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-
Saturated or unsaturated low molecular weight diols such as butanediol, neopentyl glycol, pentanediol, hexanediol, octanediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, dimer diol, or these It is a diol obtained by reacting a low molecular weight diol with the above dicarboxylic acid or an anhydride thereof.
Examples of polyols other than diols include trifunctional or higher polyols such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-butanetriol, pentaerythritol, and sorbitol, or dicarboxylic acids or their anhydrides. Examples thereof include a polyol obtained by the reaction and a polyol obtained by reacting a diol with a polycarboxylic acid having three or more functional groups or an anhydride thereof. From the viewpoint of hardness and solvent resistance of the obtained printing ink film, it is preferable to use a polyol other than the diol.

In the present invention, (C) polyols other than (A) and (B) above include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butane. Saturated or unsaturated low molecular weight diols such as diol, neopentyl glycol, pentane diol, hexane diol, octane diol, 1,4-butylene diol, diethylene glycol, triethylene glycol, dipropylene glycol; or these low molecular diols , Glycerin, trimethylolpropane, trimethylolethane, 1,2,6-
Trifunctional or higher functional polyols such as butanetriol, pentaerythritol, sorbitol, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberin Acid, azelaic acid, dicarboxylic acids such as sebacic acid or their anhydrides, and, if necessary, trifunctional or higher polycarboxylic acids such as trimellitic acid or pyromellitic acid, or their anhydrides by dehydration condensation or polymerization Polyester polyols obtained by the above; polyester polyols obtained by ring-opening polymerization of a cyclic ester compound; polycarbonate polyols; polybutadiene glycols; glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A, etc. It can be exemplified polymer polyols conventionally used for producing polyurethane resins.
When only (A) and / or (B) having an average molecular weight of less than 1000 is used as (A) and / or (B), dispersion stability of the pigment, oil resistance when used as a laminating ink From the aspect of, average molecular weight as (C)
It is preferable to use one having 1000 or more polymer polyols as a main component, particularly one having polycaprolactone polyol or polypropylene adipate as a main component. Further, the high molecular weight polyol having an average molecular weight of 1000 or more is preferably used in a ratio of 30 to 100 parts by weight of the high molecular weight polyol with respect to 50 parts by weight of (A) and / or (B) having an average molecular weight of less than 1,000.

The organic diisocyanate (D) is an aromatic diisocyanate, an aliphatic diisocyanate, an alicyclic diisocyanate, or a mixture thereof, for example, 1,5-
Naphthylene diisocyanate, 4,4-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 4,4-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate , Tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1,4-diisocyanate,
Examples include xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, and dimeryl diisocyanate.

Examples of the chain extender (E) include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4-diamine, and the like.
Amines having a hydroxyl group such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxypropylethylenediamine and di-2-hydroxypropylethylenediamine can also be used. Further, as the (E) terminal stopper, a dialkylamine such as di-n-butylamine can be used.

The polyurethane resin used in the present invention is
(A) and / or (B), if necessary (C),
And (D) are reacted at an excess ratio of isocyanate groups to obtain a prepolymer having a terminal isocyanate group, and if necessary, the obtained prepolymer is added in a suitable solvent,
That is, it is usually used as a solvent for printing ink,
Aromatic solvents such as benzene, toluene, xylene; ester solvents such as ethyl acetate, butyl acetate; alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone Or in a mixture of these, (E) and / or
Two-step method of reacting with (F), or (A) and / or (B), if necessary (C), (D), and if necessary, (E) and (or) (F) It is produced by a one-step method of reacting all at once in a different solvent. Among these methods, in order to obtain a uniform polyurethane resin,
The two-step method is preferred. When the polyurethane resin is produced by the two-step method, (E) and / or
(F) relative to the prepolymer, the total (equivalent ratio) of isocyanate groups / (E) and / or (F) amino groups of the prepolymer is 1 / 0.90 to 1.30, preferably 1.01 to 1.2.
It is desirable to react so that the ratio becomes 0. When the equivalent ratio of isocyanate group to amino group is less than 1 / 1.30, (E) and / or (F) remain unreacted, the polyurethane resin turns yellow, and odor is generated after printing. It may happen. The molecular weight of the polyurethane resin thus obtained is preferably in the range of 5,000 to 100,000. When the molecular weight of the polyurethane resin is less than 5,000, the drying property of the obtained printing ink composition for plastics, the strength of the printed film and the oil resistance tend to be slightly lower, and when it exceeds 100,000, the obtained plastic is obtained. There is a tendency that the viscosity of the printing ink composition for printing becomes high, the re-solubility becomes slightly low, and the gloss of the printing film becomes slightly low.

In the printing ink composition for plastics of the present invention, in addition to the main binder made of the above polyurethane resin, if necessary, nitrocellulose resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, polyamide resin, acrylic resin. Sub-binder such as is blended.

In the printing ink composition for plastics of the present invention, in addition to the above-mentioned binder, if necessary, a colorant such as a pigment, an organic solvent, a surfactant for improving the fluidity and film state of the ink, a wax and the like are added. The agent is appropriately mixed, printed on a plastic such as a plastic film by a method such as gravure printing or flexographic printing, and dried. Printed plastics include cellophane, moisture-proof cellophane, olefin resins such as polyethylene and polypropylene,
Polyester such as polyethylene terephthalate and polybutylene terephthalate, vinyl chloride resin, vinylidene chloride resin, styrene resin, vinyl acetate resin, vinyl alcohol resin, polyamide, etc., uniaxially or biaxially stretched or stretched Film or sheet, a film or sheet that has or has not been surface-treated such as corona discharge treatment, low-temperature plasma treatment, or a laminate of these. Moreover, the drying temperature is usually about 40 to 60 ° C.

When the printing ink composition for plastics of the present invention is used as a laminate ink, the printing ink composition of the present invention is printed on the plastic film or sheet, and the printed surface of the printed film or sheet is anchor-coated. Another film or sheet or aluminum foil is attached or extrusion laminated with or without an agent or a urethane-based or modified polyolefin-based adhesive to form a laminate. For retort sterilized applications, polyester film / polypropylene film, polyamide film /
A laminate having a structure such as a polypropylene film, a polyester film, or an aluminum foil / polypropylene film is suitable, and a laminate having a structure such as a polyester film / polyethylene film or a polyamide film / polyethylene film is suitable for use for sterilization by boiling. Anchor coat agents include organotitanium-based, polyisocyanate-based, polyethyleneimine-based, polybutadiene-based, etc., and resin to be extrusion laminated is low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene. , Ethylene-vinyl acetate copolymer or saponified products thereof, ethylene-ethyl acrylate copolymer, ethylene-
Examples include acrylic acid copolymer, polyethylene terephthalate, polyamide, polymethylpentene-1, and iomer. Extrusion lamination is performed by applying an extrusion coating on the printed surface of the film by heating the resin melted by heating at 120 to 310 ° C. and immediately cooling it with a cooling means such as a cooling roll. The laminated body thus obtained is formed into a container shape such as a bag shape, filled with foods and drinks, pharmaceuticals, medical instruments and the like, and heat-sterilized. The conditions of heat sterilization are usually 85 ℃ for 30 minutes for low temperature boiling sterilization, 100 ℃ for 30 minutes for high temperature boiling sterilization, 120 to 130 ℃ for 30 minutes for retort sterilization, and 140 to 145 ℃ 10 minutes for high retort sterilization. It is a degree.

(Examples) Hereinafter, the present invention will be described with reference to Examples. In the examples, "part" means "part by weight" and "%" means "% by weight".

Synthetic Example 1 Polymerized fatty acid "Versadym 216" (Henkel Hakusui Co., Ltd.)
Manufactured, trade name) and 100 parts of a polyester polyol having an average molecular weight of 2000 obtained from 1,4-butanediol and 18 parts of isophorone diisocyanate are reacted at 100 ° C. for 6 hours to obtain a prepolymer of an end isocyanate. Toluene (97 parts) was added to obtain a solvent solution of the terminal isocyanate prepolymer.

Next, 6 parts of isophoronediamine and di-n-butylamine
To a mixture of 0.5 part, 97 parts of methyl ethyl ketone and 97 parts of isopropyl alcohol, 215 parts of a solvent solution of the obtained terminal isocyanate prepolymer was added, and the mixture was mixed at 50 ° C. for 3 days.
After reacting for a time, a polyurethane resin solution a having a solid content of 30% and a viscosity of 400 cP at 25 ° C. was obtained.

Synthetic Example 2 From the following raw materials, in the same manner as in Synthetic Example 1, solid content 30%, 2
A polyurethane resin solution b having a viscosity of 500 cP at 5 ° C. was obtained.

"Versadym 216", polyester polyol obtained from adipic acid and 1,6-hexanediol with an average molecular weight of 2000 100 parts 1,3-bis (isocyanatomethyl) cyclohexane 18
Parts Toluene 97 parts Isophoronediamine 7 parts Di-n-butylamine 0.6 parts Methyl ethyl ketone 97 parts Isopropyl alcohol 97 parts Synthesis Example 3 Solid content 30%, 2 from the following raw materials in the same manner as Synthesis Example 1
A polyurethane resin solution c having a viscosity of 300 cP at 5 ° C. was obtained.

Polyester polyol having an average molecular weight of 2000 obtained from "VERSADIME 216" and 1,4-butanediol 50 parts Isophorone diisocyanate 18 parts Toluene 97 parts Isophoronediamine 6 parts Di-n-butylamine 0.5 parts Methyl ethyl ketone 97 parts Isopropyl alcohol 97 parts Synthesis example 4 From the following raw materials, in the same manner as in Synthesis Example 1, solid content 30%, 2
A polyurethane resin solution d having a viscosity of 300 cP at 5 ° C. was obtained.

Poly (1,2-propylene adipate) glycol (average molecular weight 2000) 100 parts Isophorone diisocyanate 18 parts Toluene 97 parts Isophorone diamine 6 parts Di-n-butylamine 0.5 parts Methyl ethyl ketone 97 parts Isopropyl alcohol 97 parts Synthesis Example 5 From the following raw materials, In the same manner as in Synthesis Example 1, solid content 30%, 2
A polyurethane resin solution e having a viscosity of 1300 cP at 5 ° C. was obtained.

Polycaprolactone glycol (average molecular weight 2000) 100
Part Isophorone diisocyanate 18 parts Toluene 97 parts Isophorone diamine 6 parts Di-n-butylamine 0.5 part Methyl ethyl ketone 97 parts Isopropyl alcohol 97 parts Synthesis example 6 Poly (1,2-propylene adipate) with an average molecular weight of 2000
100 parts of glycol, dimer diol "Sobamol 650N"
S) (Henkel Hakusui Co., Ltd., trade name, hydroxyl value 190KOHm
g / g) 62 parts, isophorone diisocyanate 46 parts and toluene 168 parts were reacted at 100 ° C. for 6 hours to obtain a solvent solution of a terminal isocyanate prepolymer.

Next, 7 parts of 1,3-bis (aminomethyl) cyclohexane,
To a mixture of 0.5 parts of di-n-butylamine, 168 parts of methyl ethyl ketone and 168 parts of isopropyl alcohol was added 376 parts of the solvent solution of the obtained terminal isocyanate prepolymer, and the mixture was reacted at 50 ° C for 3 hours to give a solid content of 30%. , 2
A polyurethane resin solution f having a viscosity of 150 cP at 5 ° C. was obtained.

Synthesis Example 7 From the following raw materials, in the same manner as in Synthesis Example 6, solid content of 30%, 2
A polyurethane resin solution g having a viscosity of 200 cP at 5 ° C. was obtained.

"Versadime 216", polyester polyol obtained from azelaic acid and 1,4-butanediol with an average molecular weight of 2000 100 parts "Sobamol 650NS" 62 parts Isophorone diisocyanate 46 parts Toluene 169 parts Isophorone diamine 8 parts Di-n-butylamine 0.5 part Methyl ethyl ketone 169 parts Isopropyl alcohol 169 parts Synthesis Example 8 From the following raw materials, in the same manner as in Synthesis Example 6, solid content 30%, 2
A polyurethane resin solution h having a viscosity of 400 cP at 5 ° C. was obtained.

Polycaprolactone glycol (average molecular weight 1500) 100
Part "Sobamol 650NS" 50 parts Dimeryl diisocyanate "DDI1410" (Henkel Hakusui Co., Ltd., trade name) 181 parts Toluene 277 parts Isophorone diamine 22 parts Di-n-butylamine 3 parts Methyl ethyl ketone 277 parts Isopropyl alcohol 277 parts Synthesis Example 9 Polymerized fatty acid "Versadim 216" (Henkel Hakusui Co., Ltd.)
Made, trade name) 1000 parts, azelaic acid 86 parts, hexamethylenediamine 183 parts and dibutyltin dilaurate 6 parts were reacted at 200 ° C for 2 hours, cooled to 130 ° C, and then 1,6
-126 parts of hexanediol was added, the reaction was carried out at 200 ° C for 2 hours, and the vacuum was further maintained at 200 ° C for 1 hour at 20 mmHg to obtain a polyol having an amide bond and an ester bond. To 100 parts of the obtained polyol, 117 parts of toluene and 68 parts of ethyl acetate were added, dissolved by heating, 8 parts of tolylene diisocyanate was added, and the mixture was reacted at 80 ° C. for 4 hours. Further, 68 parts of isopropyl alcohol was added to solid content. A polyurethane resin solution i having a viscosity of 9600 cP at 30% and 25 ° C. was obtained.

Example 1 Composition of white printing ink Titanium white 30 parts Polyurethane resin solution a 50 parts Toluene 10 parts Isopropyl alcohol 10 parts Aiiro printing ink composition Phthalocyanine blue "Rionol Blue" (trade name, manufactured by Toyo Ink Mfg. Co., Ltd.) 10 parts Polyurethane resin solution a 40 parts Toluene 20 parts Isopropyl alcohol 10 parts Each mixture of the above composition was kneaded with a ball mill to obtain white printing ink and tinted printing ink, and for each 100 parts of the printing ink obtained, The viscosity was adjusted by adding 35 parts of toluene and 15 parts of isopropyl alcohol, and the two-color gravure rotary printing machine equipped with two gravure plates with a plate depth of 35 μm was used to print the white-colored printing ink in the first unit. The second unit is a 20 μm thick corona discharge treated stretched polypropylene film “Pyrene 21”.
61 "(manufactured by Toyobo Co., Ltd., trade name, abbreviated as PP below) and corona discharge treated nylon filom“ emblem ”with a thickness of 15 μm (manufactured by Unitika Co., Ltd., trade name below)
Abbreviated as NY. ) And 11 μm thick corona discharge treated polyethylene terephthalate film “Ester E5100”
(Toyobo Co., Ltd., trade name, abbreviated as PET hereinafter)
Print on each processing surface at a printing speed of 100 m / min, 40 to 50
It was dried at ℃ and a printing film was obtained.

About the obtained printing film, the adhesiveness of printing ink,
Table 1 shows the results of evaluation of anti-blocking property and stability of printing ink residue over time. The evaluation method and the display of the evaluation result are as follows.

Adhesiveness of printing ink The adhesiveness of the printing ink in the overprinted portion of the white color printing ink and the white color printing ink of the obtained printing film was evaluated by the cellophane adhesive tape peeling test. The display of the evaluation result is 5: No peeling.

4: Area ratio of more than 0% and less than 20% peeled.

3: More than 20% and 50% or less of the area ratio peeled.

2: More than 50% and 70% or less of the area ratio peeled.

1: More than 70% and 100% or less of the area peeled.

Blocking resistance Of the printing films obtained, using printing PP, the printed surfaces were superposed and the printed and non-printed surfaces were superposed, respectively, under a load of 1 kg / cm, 40 ° C, relative After storing at 80% humidity for 24 hours, they were peeled off and evaluated for blocking resistance. As for the display of the evaluation result, 5: no blocking was observed.

4: There was resistance during peeling.

3: A small area was peeled off in a part, and the gloss of the printed surface became large.

2: Blocking occurred in large area.

1: Blocking occurred on the entire surface.

Stability of Printing Ink Residue Over Time The printing ink residue was stored at room temperature for 1 week, and the fluidity of the printing ink residue and changes in the state were evaluated. The display of the evaluation result is ◯: No change.

Δ: A slight increase in viscosity was observed, but there was no problem in practical use.

X: Remarkably thickened, part or all gelled, or
The change in hue was remarkable.

Examples 2 to 6 and Comparative Examples 1 to 3 Instead of the polyurethane resin solution a, a polyurethane resin solution b (Example 2) and a polyurethane resin solution c, respectively.
(Example 3), polyurethane resin solution f (Example 4),
Polyurethane resin solution g (Example 5), polyurethane resin solution h (Example 6), polyurethane resin solution i (Comparative Example 1), polyurethane resin solution d (Comparative Example 2), polyurethane resin solution e (Comparative Example 3) Example 1 except that it was used
Table 1 shows the results of obtaining a printing film in the same manner as described above, and evaluating the adhesiveness of the printing ink, the blocking resistance, and the temporal stability of the residual thickness of the printing ink.

Comparative Example 4 100 parts of each of the white printing ink and the light-colored printing ink obtained in Comparative Example 3 were mixed with 3 parts of a triisocyanate curing agent obtained by reacting 1 mol of trimethylolpropane with 3 mol of isophorone diisocyanate. In addition, in the same manner as in Comparative Example 1, 35 parts of toluene and 15 parts of isopropyl alcohol were further added, the viscosity was adjusted, and printing was performed to obtain a printing film, and the adhesion of the printing ink, the blocking resistance, and the residual printing ink Table 1 shows the results of evaluation of stability over time.

Examples 7 to 12 and Comparative Examples 5 to 7 Example 7 is Example 1 and Example 8 is Example 2
In Example 9, in Example 3, in Example 10, in Example 4, in Example 11, in Example 5,
Example 12 is Example 6 and Comparative Example 5 is Comparative Example 1
In Comparative Example 6, in Comparative Example 2 and in Comparative Example 7, in Comparative Example 3, the printing surface of each of the printing films obtained, polyethyleneimine anchor coating agent (AC agent) "EL-420" (Toyo Morton (Trade name) or polyisocyanate-based anchor coating agent (AC
Agent) "EL-443A and B" (Toyo Morton Co., Ltd., trade name) is applied, and low-density polyethylene "Yukaron LK-30" (Mitsubishi Yuka Co., Ltd. trade name) is applied on the coated surface. Extrusion lamination was performed to obtain a laminate. For each of the obtained laminates, the laminate strength of the overprinted part of the white color printing ink and the white color printing ink was measured, and each of the laminates obtained using "EL-443A and B" was tested for low density polyethylene surface. Inside, 130 ℃, load 2k
Heat-seal at g / cm for 1 second to make a bag, and fill the resulting bag with water or vinegar / salad oil / tomato ketchup = 1/1/1 (weight ratio) soup. 30 minutes at 100 ° C for water, 85 for soup
Each was boiled for 30 minutes at ℃, and the appearance after treatment was evaluated. The evaluation was performed using 5 bags each of the test samples. Table 2 shows the results of the laminate strength measurement and the appearance evaluation after the boiling test.

In addition, the display of the appearance evaluation results after the boiling test was good in all of the 5 bags.

Δ: Delamination or blistering occurred in a part of 2 to 3 bags.

×: Delamination or blister occurred in all 5 bags.

Examples 13 to 18 and Comparative Examples 8 to 10 Example 13 is Example 1 and Example 11 is Example 2
In Example 12, Example 12 is in Example 3, Example 13 is in Example 4, and Example 14 is in Example 5.
Example 15 is Example 6 and Example 16 is Example 7
In Example 17, in Example 8, in Example 18, in Example 9, in Comparative Example 8, in Comparative Example 1,
Comparative Example 9 is Comparative Example 2 and Comparative Example 10 is Comparative Example 3.
Printing NY among the printing films obtained in
Apply the polyurethane dry laminate adhesive "AD900 and RT-5" (Toyo Morton Co., Ltd., trade name, solid content 25%) to the printing surface of each of the printed PET and the printing PET using a gravure plate with a plate depth of 60 μm. After drying and drying, the coated surface has a thickness of 60
A polypropylene film “Trefan 3701” (manufactured by Toray Industries, Inc., trade name) having a thickness of μm was dry laminated to obtain a laminate. The laminate strength of the obtained laminate was measured to evaluate the retort resistance. Table 3 shows the measurement results and evaluation results.

The unit of laminate strength is the same as in Table 2. As for the retort resistance, the obtained laminated body was heat-sealed with the "Trefan 3701" surface inside to form a bag, and the obtained bag had vinegar / salad oil / tomato ketchup = 1/1 / Filled with 1 (by weight) soup, 115
The appearance was evaluated after boiling at 30 ° C. for 30 minutes. Evaluation,
The number of test samples was 5 bags each. The display of the evaluation result is the same as in the case of Table 2.

[Effects of the Invention] According to the present invention, even when used in a one-pack type, it has excellent adhesion to plastics, particularly plastic films such as polypropylene, polyester, nylon, etc., printability, suitability for laminating, and boil retort. A printing ink composition having durability has been obtained.

Claims (1)

[Claims] 1. A dimer diol (A) and / or
(B) Polymerized fatty acid polyester polyol having no amide bond, (C) if necessary (A) and (B)
Other than polyol, (D) organic diisocyanate, and (E) chain extender and / or (F) as required
A printing ink composition for plastics, comprising as a main binder a polyurethane resin obtained by reacting a terminal stopper.