JP2000290574A - Vehicle for printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vehicle for a printing ink having excellent adhesion to any of a treated polypropylene film, a polyester film, a nylon film and a metal foil as a printing material. SOLUTION: The main component of the vehicle is a polyurethane polyurea resin solution having an amino group at a terminal, the content of the amino group per 1 g of the polyurethane polyurea resin is 15 to 100 μg, and the polyurethane polyurea resin solution is substantially A vehicle for printing inks, characterized in that it contains no chlorine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a vehicle for a printing ink comprising a polyurethane polyurea resin solution. The printing ink using the printing ink vehicle of the present invention can be applied to various plastic films used as a printing material, in particular, a film for a soft packaging material such as a treated polypropylene film, a polyester film, and a nylon film. It is suitable for applications where film and metal foil are attached to each other.

[0002]

2. Description of the Related Art In many cases, it has been proposed to use polyurethane polyurea as a vehicle for a printing ink used for a plastic film as a packaging material. However, any of a treated polypropylene film, a polyester film and a nylon film as a material to be printed is proposed. None have excellent adhesion (adhesion).

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a vehicle for a printing ink which has excellent adhesion to any of a treated polypropylene film, a polyester film and a nylon film as an object to be printed. It is. The present inventors have conducted intensive studies to achieve the above object.As a result, a solution of a polyurethane polyurea resin containing substantially no chlorine and having a specific amount of an amino group bonded to a terminal is used as a vehicle. The present inventors have found that a printing ink having excellent adhesion to a film can be obtained, and completed the present invention.

[0004]

The above object is achieved by the present invention described below. That is, the present invention relates to a polyurethane polyurea resin solution in which the main component of the vehicle has an amino group at the terminal,
A printing ink vehicle characterized in that the content of amino groups per g is 15 to 100 µg equivalent, and the polyurethane polyurea resin solution contains substantially no chlorine.

[0005]

Next, the present invention will be described in more detail with reference to preferred embodiments of the present invention. Printing inks usually consist of a colorant consisting of pigments and / or dyes, a vehicle consisting of oils, resins, plasticizers, waxes and solvents and auxiliaries (viscosity control, color control, dispersibility control, drying control, etc.). Be composed. The present invention is characterized in that a solution of the above-mentioned polyurethane polyurea resin is used as a main component of a vehicle for a printing ink. The polyurethane polyurea resin used in the present invention is a resin obtained by reacting a polyol and a polyisocyanate to form a prepolymer and reacting the prepolymer with a polyamine as a chain extender according to a conventional method.

In producing the polyurethane polyurea resin of the present invention, a conventionally known polymer polyol can be used as the polyol component. The polymer polyol preferably has a number average molecular weight of 500 or more and 6000 or less. If it is less than 500, the resolubility of the polyurethane polyurea resin in the solvent is poor, and it is difficult to obtain high-speed printability of the printing ink. , It becomes difficult to obtain blocking resistance during winding. A more preferred number average molecular weight is from 2,000 to 4,000.

The polyisocyanate used in the present invention is preferably a diisocyanate compound. As the diisocyanate compound, conventionally known diisocyanate compounds can be used, but most of the diisocyanate compounds currently industrially supplied are produced by the phosgene method and contain chlorine as an impurity. In order that the printing ink using the vehicle of the present invention can be used for printing food packaging materials, the use of a diisocyanate compound containing chlorine as an impurity is not preferred, and phosgene is not used, and a method containing no chlorine as an impurity is used. For example, m-tetramethylxylylene diisocyanate (for example, there is a product of American Cyanamide Co., Ltd. as a commercially available product, hereinafter abbreviated as m-TMXDI) or 1, which is produced by a dimethyl carbonate method or the like.
Preferred examples thereof include 3-bis (isocyanatomethyl) cyclohexane (for example, a commercially available product of Mitsubishi Gas Chemical Co., Ltd .; hereinafter, abbreviated as 1,3-BIC).

In the present invention, since the polyurethane polyurea resin is used as a solution, for example, the resin can be used after being separated from a solution of the resin produced in a solvent, but a solution of the resin is used. Is advantageous in various respects. Therefore, in order to obtain a polyurethane polyurea resin solution containing substantially no chlorine, it is preferable to use a diisocyanate compound having a chlorine content of 10 ppm or less. In this case, chlorine is not substantially contained in the polyurethane polyurea resin separated from the solution.
In the present invention, the chlorine content of the diisocyanate compound means the content of chlorine bonded to the diisocyanate compound and the total chlorine such as chlorine compounds mixed in the diisocyanate compound in other forms.

[0009] As a chain extender, an amino group is added to the molecule.
Conventionally known amines having at least one amine (e.g., isophoronediamine, ethylenediamine, hexamethylenediamine, diaminopropylamine, pentaethylenehexamine, N-aminoethylpiperazine, m-xylenediamine, hydrazine, etc.) can be used. If necessary, diols and monoamines as a reaction terminator can be used in combination. In the present invention, the terminal of the polyurethane polyurea resin obtained by reacting the above-mentioned raw material components has an amino group in an amount of 15 to 100 per gram of the resin.
The μg equivalent binding is necessary to ensure sufficient adhesion between the printing ink and the substrate, such as a treated polypropylene film, polyester film, or nylon film. When the amino group content is less than 15 μg equivalent, the adhesiveness to the above-mentioned printing material becomes poor, and when it exceeds 100 μg equivalent, the suitability for boiling after lamination processing becomes poor, which is not preferable. Preferably, it is 30 to 60 μg equivalent. The content of the terminal amino group can be adjusted by the mixing ratio of the urethane prepolymer, the diamine as the chain extender and the reaction terminator.

Examples of the solvent used for producing the polyurethane polyurea resin of the present invention include, for example, aromatic hydrocarbon solvents such as benzene, toluene and xylene which are well known as solvents for printing inks; cyclohexane, methylcyclohexaneethyl Saturated hydrocarbon solvents such as cyclohexane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, isopropanol and butanol. And these can be used alone or in combination.

[0011] The vehicle for a printing ink of the present invention containing the above-mentioned polyurethane polyurea resin solution as a main component may contain, if necessary, a vehicle resin other than the polyurethane polyurea resin of the present invention as long as the object of the present invention is not impaired. It can also be added. A printing ink is produced by mixing the printing vehicle of the present invention with a colorant and various auxiliaries according to a conventional method. Although the concentration of the polyurethane polyurea resin in the vehicle is not particularly limited, it is usually 10 to 4%.
0% by weight. In the printing ink using the printing ink vehicle of the present invention, since no harmful chlorine is present around the urethane, urea group and terminal amino group in the polyurethane urea resin molecule used in the present invention, the printing material film of the printing ink is used. It is considered that excellent adhesiveness, laminating strength, and post-processing suitability are exhibited.

[0012]

Next, the present invention will be described more specifically with reference to examples. Parts in the text are based on weight unless otherwise specified.

Example 1 A reaction vessel was charged with 500 parts of a polyesterdiol having a number average molecular weight of 2,000 obtained from adipic acid and neopentyl glycol and 122 parts of m-TMXDI (manufactured by American Cyanamide Co.), and heated to 100 ° C. under a nitrogen stream. For 5 hours to obtain a urethane prepolymer having an NCO group content of 3.07%. This urethane prepolymer was dissolved in ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 63%. A mixed solution comprising 37.1 parts of isophoronediamine, 5.85 parts of di-n-butylamine, 386 parts of isopropyl alcohol and 772 parts of methylcyclohexane was prepared, and the above urethane prepolymer solution was added dropwise to this solution while stirring. Non-volatile content 30%, viscosity 1050
mPa. s, a polyurethane polyurea solution having a terminal amino group content of 12 μg equivalent was obtained. No chlorine was detected from this polyurethaneurea solution.

Comparative Example 1 A reaction vessel was charged with 500 parts of a polyester diol having a number average molecular weight of 2,000, obtained from adipic acid and neopentyl glycol, and 111 parts of isophorone diisocyanate (Phusgene method, manufactured by Huls Co.).
The reaction was carried out at 0 ° C. for 5 hours to obtain a urethane prepolymer having an NCO group content of 3.12%. This urethane prepolymer was dissolved in ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 63%. 37.0 parts of isophorone diamine,
A mixture was prepared by mixing 5.86 parts of di-n-butylamine, 385 parts of isopropyl alcohol and 771 parts of methylcyclohexane, and the above urethane prepolymer solution was added dropwise with stirring to obtain a nonvolatile content of 30% and a viscosity of 30%. 1150 mPa. s, terminal amino group content 12 μg
An equivalent amount of a polyurethane polyurea solution was obtained. From this polyurethane polyurea solution, 8.4 ppm of chlorine was detected.

Example 2 300 parts of polytetramethylene glycol having a number average molecular weight of 3000, 200 parts of polycaprolactone diol having a number average molecular weight of 2000, and 1.3-BIC68.
Five parts were charged and reacted at 100 ° C. for 5 hours under a nitrogen stream to obtain a urethane prepolymer having an NCO group content of 2.10%. This urethane prepolymer was dissolved in ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 63%.
A solution was prepared by mixing 25.9 parts of isophoronediamine, 347 parts of isopropyl alcohol and 693 parts of methylcyclohexane, and the above urethane prepolymer solution was added dropwise to this solution while stirring, and the nonvolatile content was 30% and the viscosity was 1000 mPa.s. As a result, a polyurethane polyurea solution having a terminal amino group content of 25 μg equivalent was obtained. No chlorine was detected from this polyurethane polyurea solution.

Comparative Example 2 In a reaction vessel, 300 parts of polytetramethylene glycol having a number average molecular weight of 3000, 200 parts of polycaprolactone diol having a number average molecular weight of 2,000 and dicyclohexylmethane-4,4'diisocyanate (Desmodur W, manufactured by Bayer AG) : Phosgene method) 92.5 parts were charged and reacted at 100 ° C for 5 hours under a nitrogen stream to obtain an NCO group content of 2.0.
3% urethane prepolymer was obtained. This urethane prepolymer was dissolved in ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 63%. Isophorone diamine 2
6.2 parts, 361 parts of isopropyl alcohol and 721 parts of methylcyclohexane were mixed to obtain a solution, and a urethane prepolymer solution was added dropwise to this solution while stirring, so that the nonvolatile content was 30% and the viscosity was 1450 mPa.s. As a result, a polyurethaneurea solution having a terminal amino group content of 26 μg equivalent was obtained. 34.4p from this polyurethane polyurea solution
pm chlorine was detected.

Example 3 A reaction vessel was charged with 500 parts of a polyester diol having a number average molecular weight of 4,000 obtained from adipic acid and 3-methyl-1,5-pentanediol and 53.3 parts of 1,3-BIC, and then charged under a nitrogen stream. For 5 hours at 100 ° C
A urethane prepolymer having an O group content of 2.06% was obtained.
This urethane prepolymer was dissolved in ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 63%. 25.2 parts of isophoronediamine, isopropyl alcohol 33
7 parts and 673 parts of methylcyclohexane were mixed to obtain a solution, and the above-mentioned urethane prepolymer solution was added dropwise to this solution while stirring, so that the nonvolatile content was 30% and the viscosity was 1000 mP.
a. s, a polyurethane polyurea solution having a terminal amino group content of 18 μg equivalent was obtained. No chlorine was detected from this polyurethane polyurea solution.

Comparative Example 3 In a reaction vessel, 500 parts of a polyester diol having a number average molecular weight of 4000 obtained from adipic acid and 3-methyl-1,5-pentanediol and 1,3-bis (isocyanatomethyl) cyclohexane (manufactured by Takeda Chemical Industries, Ltd.) Takenate 6
00: phosgene method) 53.3 parts were charged and reacted at 100 ° C. for 5 hours under a nitrogen stream to obtain an NCO group content of 2.06%.
Was obtained. This urethane prepolymer was dissolved in ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 63%. Isophorone diamine 25.2
Of a solution consisting of 337 parts of isopropyl alcohol and 673 parts of methylcyclohexane, the above urethane prepolymer solution was added dropwise with stirring, and the nonvolatile content was 30% and the viscosity was 1150 mPa.s. s, a polyurethane polyurea solution having a terminal amino group content of 18 μg equivalent was obtained. From this polyurethane polyurea solution, 106.
4 ppm of chlorine was detected.

The above polyurethane polyurea solution is added to
Evaluation of the printing ink used as the ink 40 parts of each of the polyurethane polyurea solutions of Examples 1 to 3 and Comparative Examples 1 to 3, 35 parts of rutile type titanium white, 10 parts of methylcyclohexane, and isopropyl alcohol 1
A mixed solution having a composition of 5 parts was kneaded to prepare a white ink, and the viscosity was adjusted with a mixed solvent of methylcyclohexane, methyl ethyl ketone and isopropyl alcohol (weight ratio 50:30:20) to a # 3 Zahn cup for 20 seconds. To produce a printing ink. Using this printing ink,
By a gravure printing machine equipped with a gravure plate having a plate depth of 35μ, a corona discharge-treated biaxially oriented polypropylene film (hereinafter abbreviated as OPP) having a thickness of 40μ, a biaxially oriented polyethylene terephthalate film (hereinafter abbreviated as PET) having a thickness of 12μ and A 15 μm thick corona discharge treated biaxially stretched nylon film (hereinafter abbreviated as ONY) was overprinted twice and dried at 50 ° C. to obtain a white printed film. Each white printing film was evaluated by the following method, and the evaluation results are shown in Table 1.

(1) Adhesion The adhesion of the obtained white printed film after standing for one day was measured by attaching a cellophane tape to the printed surface and measuring 5 mm at an angle of 60 degrees.
The state of the printed surface when peeled off at a slow speed of about / min was visually determined. The criteria were as follows. ◎ ・ ・ ・ ・ ・ Ink did not come off at all ○ ・ ・ ・ ・ ・ 80% or more of ink remained on film △ ・ ・ ・ ・ ・ 50% or more of ink remained on film × ・ ・ ・ ・ ・50% or more of the ink was peeled off. (2) Boilability A toluene solution of an isocyanate-based anchor coating agent was applied on the printing surface of a printing film of ONY so that the dry film became 0.2 μm, and dried at 50 ° C. Was extruded and laminated. The polyethylene side of the obtained laminated film is heat-fused to make a pouch,
A mixture of salad oil / vinegar / water = 1/1/5 (weight ratio) was filled as the content, and the appearance after sterilizing by boiling at 100 ° C. for 30 minutes was evaluated. The criteria are as follows. ○ ・ ・ ・ ・ ・ ・ No abnormality in appearance △ ・ ・ ・ ・ Blister is generated in part × ・ ・ ・ ・ ・ Delamination is generated

Table 1

[0022]

According to the present invention described above, the use of the printing ink vehicle of the present invention provides a printing ink having excellent adhesion to a substrate (such as a plastic film for food packaging or a metal foil). Manufacturing is possible. In addition, by using a printing material on which the printing ink is printed, a food packaging material having excellent boilability is provided.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masafumi Saito 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Nissei Chemical Industry Co., Ltd. (72) Inventor Toru 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo F-term (reference) in Dai Nissei Chemical Co., Ltd. 4J034 BA01 CA15 CB05 CB07 CC26 DA01 DF01 HA07 HC12 HC22 JA41 KD12 KE02 RA06 SA02 SA06 4J039 AE04 BC02 BC03 BC07 BC16 BC20 BE12 CA04 CA07 EA37 EA38 EA43 EA48 FA01 FA02

Claims (3)

[Claims] 1. The polyurethane polyurea resin solution wherein the main component of the vehicle is a polyurethane polyurea resin solution having an amino group at a terminal, wherein the content of amino groups per 1 g of the polyurethane polyurea resin is 15 to 100 μg equivalent. Is a vehicle for printing ink, which is substantially free of chlorine. 2. The polyurethane polyurea resin described above,
The printing ink vehicle according to claim 1, wherein the vehicle is produced using a polyisocyanate having a chlorine content of 10 ppm or less as a raw material component. 3. The printing ink vehicle according to claim 1, which is used for printing ink for plastic films and metal foils for food packaging materials.