JP7031368B2 - Binders for printing inks, printing inks and printed matter - Google Patents

Description

The present invention relates to a binder for printing ink and a printing ink having excellent adhesion to a poorly adherent substrate such as polyethylene and polypropylene, and a binder for the printing ink or a printed matter produced by using the printing ink.

In recent years, various plastic films such as polyester (PET), nylon (NY), polyethylene (PE), polypropylene (PP) and the like have been used as packaging materials depending on their use. Among them, PE and PP films having excellent moisture resistance and chemical stability are preferably used for food packaging.

PE and PP have low adhesion. That is, it is difficult to adhere. Therefore, in order to use such a resin as a base material and improve the adhesion of ink (including paint) to the base material, a technique is required.

Patent Document 1 is available as a high adhesion technique for reliably adhering ink to such a resin base material.

Patent Document 1 discloses a polypropylene resin coating composition comprising a chlorinated polypropylene resin and a terpene phenol copolymer.

Patent Document 2 describes a terpenephenol-based resin, a polymer polyol, and a diisocyanate compound as main components, which have excellent adhesiveness to various plastics such as PET, NY, PE, and PP, and are composed of a non-chlorine-based resin. A binder for printing ink using a polyurethane resin obtained by reacting with the above is disclosed.

Patent Document 3 describes a high molecular weight polyol having a predetermined molecular weight and a low molecular weight ink having excellent boil / retort suitability and printability even in a one-component ink, and particularly useful as a binder for gravure printing ink and flexographic printing ink. A binder for printing ink, which is a polyurethane resin obtained by reacting a polyol, an organic diisocyanate, and a chain extender and having a predetermined number average molecular weight, is disclosed.

Japanese Unexamined Patent Publication No. 58-136627 Japanese Patent No. 4134401 Japanese Patent No. 5523744

Since the chlorinated polypropylene resin used in the polypropylene resin coating composition described in Patent Document 1 contains chlorine, there is a problem that hydrogen chloride and chlorine gas are generated by recycling the packaging material and heating in the incineration process. was there.

Since the binder for printing ink described in Patent Document 2 uses copolymerization, there is room for improvement in that it takes time to develop various inks having different required characteristics.

Although Patent Document 3 describes the printability for PET as an ink, the adhesiveness (adhesion) to PE and PP has not been sufficiently investigated.

An object of the present invention is a non-chlorine-based binder having improved adhesion to PE and PP without changing the chemical structure of a polyurethane resin widely used as a binder for printing inks, and a printing ink containing this binder. Is to provide.

The binder for printing ink of the present invention includes a terpene phenol resin having a terpene chain having an average carbon number of 11 or more and less than 19 per phenol skeleton, and a polyurethane resin.

According to the present invention, it is possible to improve the adhesion of the binder and the printing ink to PE and PP without using chlorine without changing the chemical structure of the current polyurethane resin.

It is sectional drawing which shows the printed matter which concerns on 1st Embodiment of this invention. It is sectional drawing which shows the printed matter which concerns on the 2nd Embodiment of this invention. It is a figure which shows the standard of adhesion evaluation of an Example.

The present inventor investigated the effect of improving the adhesion by the additive (hereinafter, also referred to as "adhesion improving effect") without changing the chemical structure of the current polyurethane resin. As a result, when a specific terpene phenol resin having a terpene chain having an average carbon number of 11 or more and less than 19 is used as an additive for one phenol skeleton, the adhesion between the printing ink binder or the printing ink and PE or PP. Was found to improve dramatically.

The binder for printing ink of the present invention contains a polyurethane resin and a predetermined terpene phenol resin as main components. This binder can also be used as a colorless and transparent clear paint without adding a pigment. Clear paint is also a type of printing ink.

If a pigment is added to the binder, it can be used as an ink (printing ink) for producing a printed matter having a color that can be visually perceived.

A printed matter can be produced by applying the printing ink component to the surface of the substrate to be printed so that the components of the printing ink remain. That is, the printed matter is coated so that the components of the printing ink are in contact with the surface of the base material.

Hereinafter, embodiments for carrying out the present invention (the present embodiment) will be described. However, the contents described below are merely examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In addition, each figure to be referred to may be enlarged or reduced as appropriate for the convenience of illustration, and the relative size of each member may differ from the actual one.

FIG. 1 shows a cross section of a printed matter or a painted matter of the first embodiment.

As shown in this figure, the printed matter (or painted matter) has an ink layer 1 formed on the surface of the base material 2.

The substrate 2 includes a PE film (including biaxially stretched polyethylene film (abbreviated as OPE: Oriented polypropylene films)) or a PP film (including biaxially stretched polypropylene film (abbreviated as OPP: Oriented polypropylene films)) or These molded bodies can be used. These films and molded products may contain additives. Further, the surface of the base material 2 may be subjected to surface treatment such as UV ozone treatment, corona treatment, and plasma treatment in order to improve the adhesion to the ink.

The ink layer 1 contains a polyurethane resin and a terpene phenol resin having a specific structure as essential components. A desired colorant can be added to the ink layer 1 if necessary.

The terpene phenol resin having a specific structure in the present invention has a terpene chain having an average carbon number of 11 or more and less than 19 for one phenol skeleton. Its typical structure is shown in the following chemical formula (1).

In the formula, m and n represent integers of 1 or more.

A more preferable average number of carbon atoms in the terpene chain is 11 to 13. When a terpene phenol resin in this range is added, the effect of remarkably improving the adhesion can be obtained.

The average number of carbon atoms in the phenol skeleton and the terpene chain can be determined by proton NMR.

In the above chemical formula (1), when m is 1, the number of protons derived from the phenol skeleton is 3, and the number of protons derived from the terpene chain is 15. The terpene chain at that time has 10 carbon atoms.

Specifically, the integral value of the spectrum derived from the proton of the phenol skeleton at 6.3 to 7.5 ppm observed by proton NMR is set to 3, and the proton derived from the terpene chain observed at 0.7 to 5.0 ppm. The integral value of the spectrum of is divided by 15, and the value obtained by dividing is multiplied by 10, so that the average number of carbon atoms in the terpene chain for one phenol skeleton is obtained. The average carbon number of the terpene chain of the terpene phenol resin is not a multiple of 10, because the terpene phenol resin is a mixture of a plurality of compounds having different molecular weights.

The molecular weight of the terpene phenol resin preferable in the present invention is such that the styrene-equivalent number average molecular weight is 600 or more and 800 or less, and the styrene-equivalent mass average molecular weight is 800 or more and 1100 or less.

The molecular weight described in the present specification was determined by observing gel permeation chromatography (GPC) under the following conditions.

A gel pack GL-R420, GL-R430, and GL-R440 manufactured by Hitachi High-Tech Science Corporation were used in combination for the analysis column, and the differential refractometer (RI) detector L-3300 of the same company was used for detection. 20 mg of terpene phenol resin was dissolved in 2 mL of tetrahydrofuran as an eluent, the injection amount into the column was 50 μL, the eluent flow rate was 1.75 mL / min, and the column temperature was 25 ° C.

From this observation, it was found that the particularly preferable terpene phenol resin is the one in which the maximum peak (peak top) is between 29 minutes and 30 minutes among the plurality of peaks of GPC observed under the above-mentioned conditions. That is, a terpene phenol resin containing a large amount of such a low molecular weight substance is particularly preferable, and its adhesion improving effect is particularly high.

In the case where the styrene-equivalent number average molecular weight is 600 or more and 800 or less and the styrene-equivalent mass average molecular weight is 800 or more and 1100 or less, which is the range of the molecular weight of the terpene phenol resin preferable in the present invention, the terpene chain is used for one phenol skeleton. A terpenphenol resin having an average carbon number of 11 or more and 13 or less is preferable because it has a higher adhesion improving effect.

Further, since the ink is usually dried at 60 ° C to 100 ° C after application, the softening point of the terpene phenol resin is preferably higher than 100 ° C in order to suppress blocking of printed matter.

Specifically, as such a terpene phenol resin, YS Polystar K125 manufactured by Yasuhara Chemical Co., Ltd. (average carbon number 11.2 in the terpene chain for one phenol skeleton, styrene equivalent number average molecular weight 695, styrene equivalent mass average molecular weight) 932, GPC peak top 29.7 minutes, softening temperature about 125 ° C), YS Polystar N125 manufactured by the same company (average carbon number 12.4 in terpen chain for one phenol skeleton, styrene equivalent number average molecular weight 646, styrene equivalent mass) Average molecular weight 840, peak top of GPC 29.7 minutes, softening temperature about 125 ° C), YS Polystar S145 manufactured by the same company (average number of carbon atoms in terpene chain for one phenol skeleton 18.9, styrene equivalent number average molecular weight 781, styrene The converted mass average molecular weight is 1086, the peak top of GPC is 27.8 minutes, and the softening temperature is about 145 ° C.). Examples of slightly larger molecular weights include YS Polystar G125 manufactured by Yasuhara Chemical Co., Ltd. (average carbon number 17.1 in the terpene chain for one phenol skeleton, styrene-equivalent number average molecular weight 812, styrene-equivalent mass average molecular weight 1184, GPC peak. There is a top 27.9 minutes, softening temperature about 125 ° C.).

The binder for printing ink and the printing ink of the present invention contain a polyurethane resin. This polyurethane resin is a polyurethane resin obtained by reacting a polyol component, an organic diisocyanate component, a chain extender and / or a chain terminator, and the ratio of the polyol component to the organic diisocyanate is [NOC] / [OH]. It is characterized by being 1.2 to 2.4. This ratio represents the ratio of the monomers.

Examples of the binder for printing ink in which the polyurethane resin is dissolved in an organic solvent include binder solutions such as TA24-530E, TA24-538D, and TA24-549H manufactured by Hitachi Chemical Co., Ltd. The solid content concentration of this binder solution is 30% by mass. The solvent is a mixed solvent of ethyl acetate and isopropanol.

As the solvent, any other solvent can be applied as long as it dissolves the polyurethane resin.

The blending ratio of the polyurethane resin and the terpenephenol resin in the binder for printing ink and the printing ink may be arbitrarily set according to the desired adhesion, printing conditions, etc., but with respect to 100 parts by mass of the polyurethane resin, it may be set arbitrarily. It is preferable to add the terpenphenol resin in the range of 10 parts by mass or more and 450 parts by mass or less. When the amount of the terpene phenol resin is 10 parts by mass or more, the effect of improving adhesion tends to be excellent, and when the amount is 450 parts by mass or less, the occurrence of cracks in the printing ink layer can be prevented.

The binder for printing ink of the present invention can be used as a base material for ink, as well as as a clear paint or an adhesive layer.

As the base material, a PP molded product and OPP, which are inexpensive and have a relatively high softening temperature, are particularly preferably used.

The printing ink of the present invention is produced by adding various colorants to the above-mentioned binder for printing ink.

FIG. 2 shows a cross section of a printed matter or a painted matter of the second embodiment.

In this figure, the printed matter (or painted matter) has an ink layer 1 formed on the surface of the base material 2 and further provided with a protective layer 3.

The protective layer 3 protects the ink layer 1 from scratches and various chemicals, and also prevents the ink layer 1 from coming into contact with food in the food packaging field. From the viewpoint of decorativeness, safety, hygiene, etc., it is preferable to install the protective layer 3. The method of installing the protective layer 3 may be arbitrarily selected. For example, in the case of a film, a laminating process using an adhesive can be used, and in the case of a molded product, a clear paint coating can be used. As the material of the protective layer 3, Lumirer (registered trademark) T60 manufactured by Toray Industries, Inc. is preferably used.

The present invention was formed of a binder for printing ink and a printing ink, and PE or PP which is a poor adhesion material, by adding a terpene phenol resin having a specific structure without changing the structure of a conventional polyurethane resin. It improves the adhesion to the substrate, and can be suitably used in the fields of printing and painting on a poorly adherent substrate such as food packaging.

Hereinafter, the present invention will be described in more detail with reference to examples.

The molecular weight of the terpene phenol resin as a test sample and the average carbon number of the terpene chain were determined as follows.

The molecular weight was determined by observing gel permeation chromatography (GPC) under the following conditions. A gel pack GL-R420, GL-R430, and GL-R440 manufactured by Hitachi High-Tech Science Corporation were used in combination for the analysis column, and the differential refractometer (RI) detector L-3300 of the same company was used for detection. 20 mg of terpene phenol resin was dissolved in 2 mL of tetrahydrofuran as an eluent, the injection amount into the column was 50 μL, the eluent flow rate was 1.75 mL / min, and the column temperature was 25 ° C.

The average number of carbon atoms in the terpene chain of the terpene phenol resin is 0.7 to 5.0 ppm, where 3 is the integrated value of the proton-derived spectrum of the phenol skeleton at 6.3 to 7.5 ppm observed by proton NMR. The average number of carbon atoms in the terpene chain for one phenol skeleton was obtained by dividing the integrated value of the spectrum of protons derived from the terpene chain observed in 1 by 15 and multiplying the value obtained by dividing by 10. .. The average number of carbon atoms in the terpene chain of the terpene phenol resin is not a multiple of 10, because the terpene phenol resin is a mixture of a plurality of compounds having different molecular weights.

<Test sample>
(1) Terpene phenol resin-YS Polystar K125 manufactured by Yasuhara Chemical Co., Ltd. (average carbon number 11.2 in terpene chain for one phenol skeleton, styrene-equivalent number average molecular weight 695, styrene-equivalent mass average molecular weight 932, peak top of GPC 29.7 minutes, softening temperature about 125 ° C)
YS Polystar N125 manufactured by Yasuhara Chemical Co., Ltd. (average carbon number 12.4 in terpene chain for one phenol skeleton, styrene-equivalent number average molecular weight 646, styrene-equivalent mass average molecular weight 840, GPC peak top 29.7 minutes, softening Temperature approx. 125 ° C)
YS Polystar S145 manufactured by Yasuhara Chemical Co., Ltd. (average carbon number 18.9 in terpene chain for one phenol skeleton, styrene-equivalent number average molecular weight 781, styrene-equivalent mass average molecular weight 1086, GPC peak top 27.8 minutes, softening Temperature about 145 ° C)
YS Polystar G125 manufactured by Yasuhara Chemical Co., Ltd. (average carbon number 17.1 in terpene chain for one phenol skeleton, styrene-equivalent number average molecular weight 812, styrene-equivalent mass average molecular weight 1184, GPC peak top 27.9 minutes, softening Temperature approx. 125 ° C)
YS Polystar U130 manufactured by Yasuhara Chemical Co., Ltd. (average carbon number 42.1 in terpene chain for one phenol skeleton, styrene-equivalent number average molecular weight 794, styrene-equivalent mass average molecular weight 1245, GPC peak top 27.2 minutes, softening Temperature approx. 125 ° C)
YS Polystar T130 manufactured by Yasuhara Chemical Co., Ltd. (average carbon number 30.2 in terpene chain for one phenol skeleton, styrene-equivalent number average molecular weight, styrene-equivalent mass average molecular weight not evaluated, softening temperature about 130 ° C)
(2) Binder solution for printing ink containing 30% by mass of polyurethane resin-TA24-538D manufactured by Hitachi Kasei Co., Ltd.
・ TA24-530E manufactured by Hitachi Kasei Co., Ltd.
・ TA24-549H manufactured by Hitachi Kasei Co., Ltd.
(3) White ink containing white pigment (contains 7.7 parts by mass of polyurethane resin, 26.8 parts by mass of white pigment, and 65.5 parts by mass of solvent).
・ TA24-538D manufactured by Hitachi Kasei Co., Ltd. (white ink)
・ TA24-530E (white ink) manufactured by Hitachi Kasei Co., Ltd.
・ TA24-549H (white ink) manufactured by Hitachi Kasei Co., Ltd.
(4) White pigment-Titanium oxide (5) Biaxially stretched polypropylene film (OPP film)
・ Toray Industries, Inc. Trefan (registered trademark) type 2578, thickness 30 μm, with corona treatment ・ Toray Industries, Ltd. Trefan (registered trademark) type 2500H, thickness 30 μm, without corona treatment (6) For peeling test Tape-Cellotape (registered trademark) type CT405AP manufactured by Nichiban Co., Ltd.
<Adhesion evaluation>
A predetermined printing ink binder or printing ink was applied onto the OPP film using a bar coater (No. 7), and dried under the conditions described below. The ink thickness after drying was 3 to 6 μm. The peeling test tape was strongly pressed against the printed surface with a fingertip to be attached, and the tape was peeled off in a direction of approximately 180 ° to evaluate the adhesion.

FIG. 3 shows the criteria for evaluating the adhesion of the examples.

As shown in this figure, the adhesion of the printed ink was evaluated by observing and measuring the state of the peeled portion.

The evaluation index of adhesion is 5 points when no peeling occurs, 4 points when there is only point-like peeling, 3 points when the peeling area of the evaluation surface is 1% or more and less than 10%, and the peeling area is. Two points were given when the content was 10% or more and less than 50%, and one point was given when the peeling area was 50% or more.

(Example 1)
In Example 1, the terpene phenol resin YS Polystar K125, which has 11.2 average carbon atoms in the terpene chain for one phenol skeleton, was added to 1 part by mass of the polyurethane resin in the printing ink binder solution TA24-530E. This is an example of a binder for printing ink to which 0.11 part by mass is added. The binder solution was applied to the OPP film and dried at room temperature for 24 hours, and then the adhesion was evaluated.

As a result, the adhesion was 5 points regardless of the presence or absence of surface treatment on the OPP film. By adding an appropriate terpene phenol resin, the adhesion of the binder for printing ink was dramatically improved. The binder for the present printing ink is preferable as the binder for the printing ink of the OPP film.

(Example 2)
In Example 2, a terpene phenol resin YS Polystar S145 having an average carbon number of 18.9 in a terpene chain for one phenol skeleton was added to 1 part by mass of a polyurethane resin in a binder solution TA24-530E for printing ink. This is an example of a binder for printing ink to which 0.11 part by mass is added. The adhesion evaluation was carried out in the same manner as in Example 1.

As a result, the adhesion was 5 points regardless of the presence or absence of surface treatment on the OPP film. By adding an appropriate terpene phenol resin, the adhesion of the binder for printing ink was dramatically improved. The binder for the present printing ink is preferable as the binder for the printing ink of the OPP film.

(Comparative Example 1)
In Comparative Example 1, a terpene phenol resin YS Polyster U130 having an average number of carbon atoms in a terpene chain of 40.2 for one phenol skeleton was added to 1 part by mass of a polyurethane resin in a binder solution TA24-530E for printing ink. This is an example of a binder for printing ink to which 0.11 part by mass is added. The adhesion evaluation was carried out in the same manner as in Example 1.

As a result, the adhesion was 1 point regardless of the presence or absence of surface treatment on the OPP film. It was found that the terpene phenol resin having a large average carbon number in the terpene chain has a low effect of improving the adhesion between the binder for printing ink and the OPP film.

(Comparative Example 2)
In Comparative Example 2, the terpene phenol resin YS Polyster T130, which has an average carbon number of 30.2 in the terpene chain for one phenol skeleton, was added to 1 part by mass of the polyurethane resin in the printing ink binder solution TA24-530E. This is an example of a binder for printing ink to which 0.11 part by mass is added. The adhesion evaluation was carried out in the same manner as in Example 1.

As a result, the adhesion was 1 point regardless of the presence or absence of surface treatment on the OPP film. It was found that the terpene phenol resin having a large average carbon number in the terpene chain has a low effect of improving the adhesion between the binder for printing ink and the OPP film.

(Comparative Examples 3 and 4)
Comparative Examples 3 and 4 are examples in which the amount of the terpene phenol resin added in Comparative Examples 1 and 2 was increased to 0.44 parts by mass. The adhesion evaluation was carried out in the same manner as in Example 1.

As a result, the adhesion was 1 point regardless of the presence or absence of the surface treatment of the OPP film. Despite increasing the amount of terpene phenolic resin, the adhesion was not improved. It was reconfirmed that the terpene phenol resin having a large average carbon number in the terpene chain has a low effect of improving the adhesion between the binder for printing ink and the OPP film.

(Comparative Example 5)
Comparative Example 5 is an example in which the terpene phenol resin is not added. The adhesion was 1 point regardless of the presence or absence of corona treatment of the OPP film. It was confirmed that the addition of the terpene phenol resin having a specific structure of the present invention is effective for adhering the binder for printing ink using a polyurethane resin as a binder to a hydrocarbon-based substrate such as an OPP film.

Table 1 summarizes Examples 1 and 2 and Comparative Examples 1 to 5.

In this table, the component of the binder solution and the amount of the terpene phenol resin added indicate the value of "parts by mass", and the adhesion evaluation indicates the score of the adhesion evaluation index. The same applies to the other tables described later.

(Examples 3 to 5 and Comparative Example 6)
In Examples 3 to 5, terpene phenol resin YS polystar K125 having an average number of carbon atoms in a terpene chain of 11.2 for one phenol skeleton is added to TA24-538D (white ink) containing a white pigment. This is an example of a printing ink in which 0.39 to 4.48 parts by mass is added to 1 part by mass of resin. Further, in Examples 3 to 5, a predetermined amount of ethyl acetate was added as a solvent for adjusting the concentration. This is called an "additional solvent". The concentration was adjusted to be 34% by mass. The same applies to the examples described later.

On the other hand, Comparative Example 6 is an example in which the terpene phenol resin is not added.

Each ink was applied to a corona-treated OPP film and an untreated OPP film and dried at 80 ° C. for 10 seconds to prepare a sample for adhesion evaluation.

Table 2 shows the evaluation results of the ink composition and the adhesion.

The adhesion was observed immediately after drying (10s in the table is added) and 24 hours later (24h in the table is added). The total amount of the paint is a value including the polyurethane resin, the white pigment, the solvent, the terpene phenol resin and the additional solvent. The concentration in the table is the ratio of the polyurethane resin, the white pigment and the terpene phenol resin contained in the printing ink.

In Examples 3 to 5 in which 0.39 parts by mass or more of the terpene phenol resin was added, higher adhesion was achieved in all cases as compared with Comparative Example 6 in which the terpene phenol resin was not added, regardless of the type of OPP film. Indicated. The printing ink of this embodiment is preferable as the printing ink of the OPP film.

(Examples 6 to 8 and Comparative Example 7)
In Examples 6 to 8, terpene phenol resin YS polystar K125 having an average number of carbon atoms in a terpene chain of 11.2 for one phenol skeleton was added to TA24-530E (white ink) containing a white pigment. This is an example of a printing ink in which 0.26 to 4.48 parts by mass is added to 1 part by mass of resin.

On the other hand, Comparative Example 7 is an example in which the terpene phenol resin is not added.

Each ink was applied to a corona-treated OPP film and an untreated OPP film and dried at 80 ° C. for 10 seconds to prepare a sample for adhesion evaluation.

Table 3 shows the evaluation results of the ink composition and the adhesion.

The adhesion was observed immediately after drying (10s in the table is added) and 24 hours later (24h in the table is added).

Examples 6 to 8 to which 0.26 parts by mass or more of the terpene phenol resin was added showed higher adhesion in each case as compared with Comparative Example 7 to which the terpene phenol resin was not added. The printing ink of this embodiment is preferable as the printing ink of the OPP film.

(Examples 9 to 11 and Comparative Example 8)
In Examples 9 to 11, terpene phenol resin YS polystar K125 having an average number of carbon atoms in a terpene chain of 11.2 for one phenol skeleton was added to TA24-549H (white ink) containing a white pigment. This is an example of a printing ink in which 0.52 to 4.48 parts by mass is added to 1 part by mass of resin.

On the other hand, Comparative Example 8 is an example in which the terpene phenol resin is not added.

Each ink was applied to a corona-treated OPP film and an untreated OPP film and dried at 80 ° C. for 10 seconds to prepare a sample for adhesion evaluation.

Table 4 shows the evaluation results of the ink composition and the adhesion.

The adhesion was observed immediately after drying (10s in the table is added) and 24 hours later (24h in the table is added).

Examples 9 to 11 to which 0.56 parts by mass or more of the terpene phenol resin was added showed higher adhesion in each case as compared with Comparative Example 8 to which the terpene phenol resin was not added. The printing ink of this embodiment is preferable as the printing ink of the OPP film.

(Examples 12 to 14 and Comparative Example 6)
In Examples 12 to 14, TA24-538D (white ink) containing a white pigment is provided with terpene phenol resin YS Polystar N125 having an average number of carbon atoms in a terpene chain of 12.4 for one phenol skeleton. This is an example of a printing ink in which 0.39 to 4.48 parts by mass is added to 1 part by mass of resin.

On the other hand, Comparative Example 6 is an example in which the terpene phenol resin is not added.

Each ink was applied to a corona-treated OPP film and an untreated OPP film and dried at 80 ° C. for 10 seconds to prepare a sample for adhesion evaluation.

Table 5 shows the evaluation results of the ink composition and the adhesion.

The adhesion was observed immediately after drying (10s in the table is added) and 24 hours later (24h in the table is added).

In Examples 12 to 14 in which 0.39 parts by mass or more of the terpene phenol resin was added, higher adhesion was achieved in all cases as compared with Comparative Example 6 in which the terpene phenol resin was not added, regardless of the type of OPP film. Indicated. The printing ink of this embodiment is preferable as the printing ink of the OPP film.

(Examples 15 to 17 and Comparative Example 7)
In Examples 15 to 17, terpene phenol resin YS polystar N125 having an average number of carbon atoms in a terpene chain of 12.4 for one phenol skeleton was added to TA24-530E (white ink) containing a white pigment. This is an example of a printing ink in which 0.26 to 4.48 parts by mass is added to 1 part by mass of resin.

On the other hand, Comparative Example 7 is an example in which the terpene phenol resin is not added.

Each ink was applied to a corona-treated OPP film and an untreated OPP film and dried at 80 ° C. for 10 seconds to prepare a sample for adhesion evaluation.

Table 6 shows the evaluation results of the ink composition and the adhesion.

The adhesion was observed immediately after drying (10s in the table is added) and 24 hours later (24h in the table is added).

Examples 15 to 17 to which 0.26 parts by mass or more of the terpene phenol resin was added showed higher adhesion in each case as compared with Comparative Example 7 to which the terpene phenol resin was not added. The printing ink of this embodiment is preferable as the printing ink of the OPP film.

(Examples 18 to 20 and Comparative Example 8)
In Examples 18 to 20, terpene phenol resin YS Polystar N125 having an average number of carbon atoms in a terpene chain of 12.4 for one phenol skeleton was added to TA24-549H (white ink) containing a white pigment. This is an example of a printing ink in which 0.52 to 4.48 parts by mass is added to 1 part by mass of resin.

On the other hand, Comparative Example 8 is an example in which the terpene phenol resin is not added.

Each ink was applied to a corona-treated OPP film and an untreated OPP film and dried at 80 ° C. for 10 seconds, and used as a sample for adhesion evaluation.

Table 7 shows the evaluation results of the ink composition and the adhesion.

The adhesion was observed immediately after drying (10s in the table is added) and 24 hours later (24h in the table is added).

Examples 18 to 20 to which 0.56 parts by mass or more of the terpene phenol resin was added showed higher adhesion in each case as compared with Comparative Example 8 to which the terpene phenol resin was not added. The printing ink of this embodiment is preferable as the printing ink of the OPP film.

(Examples 21 to 23 and Comparative Example 6)
In Examples 21 to 23, TA24-538D (white ink) containing a white pigment is provided with terpene phenol resin YS Polystar S145 having an average number of carbon atoms in a terpene chain of 18.9 for one phenol skeleton. This is an example of a printing ink in which 0.78 to 4.48 parts by mass is added to 1 part by mass of resin.

On the other hand, Comparative Example 6 is an example in which the terpene phenol resin is not added.

Each ink was applied to a corona-treated OPP film and an untreated OPP film and dried at 80 ° C. for 10 seconds, and used as a sample for adhesion evaluation.

Table 8 shows the evaluation results of the ink composition and the adhesion.

The adhesion was observed immediately after drying (10s in the table is added) and 24 hours later (24h in the table is added).

In Examples 21 to 23 in which 0.78 parts by mass or more of the terpene phenol resin was added, higher adhesion was achieved in all cases as compared with Comparative Example 6 in which the terpene phenol resin was not added, regardless of the type of OPP film. Indicated. The printing ink of this embodiment is preferable as the printing ink of the OPP film.

(Examples 24 to 26 and Comparative Example 6)
In Examples 24 to 26, TA24-538D (white ink) containing a white pigment is provided with terpene phenol resin YS Polystar S145 having an average carbon number of 17.1 in the terpene chain for one phenol skeleton. This is an example of a printing ink in which 0.78 to 4.48 parts by mass is added to 1 part by mass of resin.

On the other hand, Comparative Example 6 is an example in which the terpene phenol resin is not added.

Each ink was applied to a corona-treated OPP film and an untreated OPP film and dried at 80 ° C. for 10 seconds, and used as a sample for adhesion evaluation.

Table 9 shows the evaluation results of the ink composition and the adhesion.

The adhesion was observed immediately after drying (10s in the table is added) and 24 hours later (24h in the table is added).

In Examples 24 to 26 in which 0.78 parts by mass or more of the terpene phenol resin was added, higher adhesion was achieved in all cases as compared with Comparative Example 6 in which the terpene phenol resin was not added, regardless of the type of OPP film. Indicated. The printing ink of this embodiment is preferable as the printing ink of the OPP film.

1: Ink layer 2: Base material 3: Protective layer.

Claims (7)

Contains binders for printing inks and pigments,
The printing ink binder is a printing ink containing a terpene phenol resin having a terpene chain having an average carbon number of 11 or more and less than 19 for one phenol skeleton, and a polyurethane resin . The printing ink according to claim 1, wherein the terpenphenol resin has a styrene-equivalent number average molecular weight of 600 or more and 800 or less, and a styrene-equivalent mass average molecular weight of 800 or more and 1100 or less. The printing ink according to claim 1, wherein the polyurethane resin has a ratio of a polyol component, which is a component thereof, and an organic diisocyanate of [NOC] / [OH] = 1.2 to 2.4. The printing ink according to claim 3, wherein the content of the terpene phenol resin is in the range of 10 to 450 parts by mass with respect to 100 parts by mass of the polyurethane resin. With the base material
Including the components of the printing ink according to claim 1 .
The component is a printed matter coated so as to be in contact with the surface of the base material. The printed matter according to claim 5 , wherein the base material is a polypropylene molded product or a biaxially stretched polypropylene film. The printed matter according to claim 5 , wherein the component of the printing ink applied to the surface of the substrate is covered with a protective layer.

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