JP5137102B2 - Antistatic adhesive base solution, antistatic dry laminate adhesive and antistatic composite film - Google Patents

Description

  The present invention relates to a solution for the main agent of the adhesive that imparts antistatic performance to the adhesive for dry laminate, an adhesive for dry laminate prepared by this solution, and an antistatic composite that has been dry laminated using the adhesive More specifically, the intermediate adhesive layer of the laminate film is free of moisture and the laminate adhesive is capable of effectively suppressing frictional charging on both outer surfaces of the laminate film by ionic conductivity. The present invention relates to a main agent solution, an adhesive prepared with this solution, and an antistatic composite film dry-laminated using this adhesive.

In the case of a plastic film, it has a defect that it is charged due to its dielectric property, and it is well known that electrostatic charges are caused by various charges in the plastic film due to the charged static electricity.
For example, discharge troubles due to static electricity occur in recording media and electronic components that record various types of information. In the packaging field of foods and medical products, there arises a sanitary problem that dust or dust adheres to the package due to electrification.

Usually, a plastic film is used as a composite film in which other plastic films are bonded to a base film to give various functions.
As described above, a dry laminating method using a dry laminator is generally used for manufacturing a composite film having various functionalities.

  And as a method of imparting antistatic performance to the composite film by this dry laminating method, a method of kneading an antistatic agent into two types of composite films or a method of applying an antistatic agent to the outer surface of the two types of film Any one of these is generally used, and there is no method to suppress the generation of static electricity on both outer surfaces of the composite film by providing an antistatic performance to the adhesive for dry laminating. .

Generally, the material used for the adhesive for solvent-type dry laminate is polyether polyol or polyester polyol as the main agent, and the crosslinking reaction with the isocyanate curing agent functions as an adhesive. In this reaction system, the presence of moisture is zero. There is an absolute condition.
On the other hand, the antistatic agent is a condition contrary to the condition of zero moisture in the adhesive reaction system because ionic conductivity by ionic electrolysis is the main operation of the antistatic performance due to the presence of moisture. A problem to be solved is to impart an ion conductive antistatic function to the laminating adhesive.

The present inventor thought that finding a non-aqueous ionic electrolyte with another solvent compatible with an ethyl acetate solvent used in an adhesive for solvent-based dry lamination was a solution to this problem, and repeated research. As a result, it was found to be propylene carbonate according to claim 1. In addition to being a non-aqueous ionic electrolyte, the characteristics of this solvent are that it is optionally compatible with the ethyl acetate solvent of the solvent-type dry laminate adhesive, and has a boiling point higher than the boiling point of ethyl acetate (77.1 ° C.) 241.7 ° C.) is one of the extremely important conditions. Add and dissolve alkyl quaternary ammonium etosulphate in a mixed solution of propylene carbonate and ethyl acetate having these characteristics, add this solution to the adhesive main component for dry laminating, and obtain a dry laminating adhesive. When the plastic film is coated and passed through the drying process, only ethyl acetate out of the two solvents evaporates, and the ionic electrolyte propylene carbonate in which the antistatic agent is dissolved remains in the molecular space of the adhesive. It was confirmed that the antistatic function of the agent layer expresses the ability to suppress the generation of static electricity on the composite laminate film surface.

  The present invention can be applied to all adhesives for dry laminates using ethyl acetate as the organic solvent as the main agent of the adhesive. The dry laminating film can be applied to all known composite films.

In the present invention, propylene carbonate is added to an ethyl acetate solution that dissolves the main component of an ordinary solvent-type dry laminate adhesive that does not contain moisture, and further, an alkyl quaternary ammonium ethosulphate is added to make the main component of the adhesive. The adhesive cured with an isocyanate curing agent exhibits performance not inferior to the antistatic effect due to ionic conductivity due to the presence of moisture.
In particular, propylene carbonate is a colorless, odorless, and less hygroscopic liquid having a freezing point = −49.2 ° C., a boiling point = 241.7 ° C., and a dielectric constant of 69.0 at 23 ° C. It is a harmless organic solvent that dissolves polar substances well because of its high dielectric constant.

  Also, since the propylene carbonate solution of quaternary ammonium salt has a high boiling point, only the ethyl acetate is evaporated even after the heat drying process after applying the ethyl acetate / propylene carbonate solution of the adhesive to the base film of the dry laminate. When the base film and the sealant film are combined with this adhesive, the composite film has friction on both sides. An excellent antistatic effect showing a low voltage in the charged voltage can be exhibited.

Hereinafter, a basic solution for imparting high antistatic performance to the adhesive in the adhesive for dry lamination according to the present invention will be described below.
As an antistatic agent, 200 g of alkyl quaternary ammonium etosulphate (solid content 40%) was selected, and 250 g of ethyl acetate and 50 g of propylene carbonate were mixed to obtain 500 g of a solution.

  10 parts of this antistatic agent solution (solid content 40% ethyl acetate / propylene carbonate mixed solution) is added to 100 parts dry adhesive main agent (solid content 26% ethyl acetate solution) to prepare an antistatic agent-containing dry solution. A laminating adhesive was prepared.

  The amount of propylene carbonate added to maintain the antistatic performance is desirably in the practical range of about 0.5 to 1.0 part with respect to 100 parts of the main agent of the adhesive. When the amount of the antistatic agent solution is increased, the antistatic performance increases, but the adhesive strength tends to decrease. Therefore, the above practical range is desirable.

[Test Example 1]
The results of performance when a laminated film for soft packaging is laminated (composite) using the solvent-based antistatic dry laminating adhesive prepared with the above solution will be described below.
“Dick Dry LX-415A / SP75” manufactured by Dainippon Ink & Chemicals, Inc. was selected as an adhesive for dry lamination whose main component is polyether polyol, and the brands in Table 1 were selected as films for bonding. However, AS agent = alkyl quaternary ammonium etsulfate.

The adhesive was prepared by mixing the main agent (LX-415A) and the curing agent (SP-75) 1: 1 and diluting with ethyl acetate to prepare a solution with a solid content of 26%. An AS agent (solid content 40%) was added thereto to obtain an antistatic adhesive shown in Table 2.

The solid content concentration of the AS agent in the solid content in each antistatic adhesive was 13.3% for (A) and 23.5% for (B).
The adhesive was applied to the corona discharge-treated surface of the base film (biaxially stretched PET12μ), and the sealant film (LLDPE 40μ) was bonded with a dry laminator, and stored and aged in a constant temperature room at 40 ° C. for 24 hours.
An engraving gravure plate was used as the coating plate, and the coating amount of the adhesive after drying was 2.3 to 2.5 g / m2.

The laminated film after storage aging was measured for properties such as laminate strength, heat seal strength, and frictional voltage value.
-Laminate strength measurement The base material and sealant film were peeled in a T-shape from the end of a sample piece cut to a width of 15 mm, and the strength when peeled at a pulling rate [300 mm / min] was measured using an autograph. . The results are shown in Table 3.

帯電防止性接着剤（Ａ）では安定した、帯電防止性接着剤（Ｂ）では若干弱いラミネート強度、ヒートシール強度結果を得た。 -Heat seal strength measurement The sealant film surfaces of the laminated film of the sample face each other [150 ° C, 1 kg /
cm 2, 1 second]. A sample piece obtained by cutting the heat-sealed portion to a width of 15 mm was set in an autograph in a T-shape, and the strength when peeled at a pulling speed [300 mm / min] was measured. The results are shown in Table 4.

The antistatic adhesive (A) was stable, and the antistatic adhesive (B) was slightly weak in laminate strength and heat seal strength.

何れも非常に優れた帯電防止効果を示した。 -Measurement of frictional voltage value The frictional voltage was measured in an environment of 19 ° C and 43% RH. The results are shown in Table 5.

All showed a very excellent antistatic effect.

[Test Example 2]
In the same manner as in Test Example 1, “Takelac A-969V / Takenate A-5” manufactured by Mitsui Takeda Chemical Co., Ltd. was used as an adhesive for dry laminating, the main agent of which is polyether polyol. I chose.

The adhesive was prepared as a solution having a solid content of 25% by mixing the main agent (A-969V) and the curing agent (A-5) in a ratio of 3: 1 and diluting with ethyl acetate. The solvent type AS agent (solid content 40%) was added there, and the antistatic adhesive of Table 7 was obtained.

The solid content concentration of the AS agent in the solid content of each antistatic adhesive was 13.8% for (C) and 24.2% for (D).
The adhesive was applied to the corona discharge-treated surface of the base film (biaxially stretched PET12μ), and the sealant film (LLDPE 40μ) was bonded with a dry laminator, and stored and aged in a constant temperature room at 40 ° C. for 24 hours.
An engraving gravure plate was used as the coating plate, and the coating amount of the adhesive after drying was 2.2 to 2.4 g / m2.

The laminated film after storage aging was measured for properties such as laminate strength, heat seal strength, and frictional voltage value.
-Laminate strength measurement The base material and the sealant film were peeled off in a T-shape from the end of a sample piece cut to a width of 15 mm, and the strength when peeled at a pulling rate [300 mm / min] was measured using an autograph. The results are shown in Table 8.

帯電防止性接着剤（Ｃ）では安定した、帯電防止性接着剤（Ｄ）では若干弱いラミネート強度、ヒートシール強度結果を得た。 -Heat seal strength measurement The sealant film surfaces of the laminated film of the sample face each other [150 ° C, 1 kg /
cm 2, 1 second]. A sample piece obtained by cutting the heat-sealed portion into a width of 15 mm was set in an autograph in a T shape, and the strength when peeled at a pulling speed [300 mm / min] was measured. The results are shown in Table 9.

The antistatic adhesive (C) was stable, and the antistatic adhesive (D) was slightly weak in laminate strength and heat seal strength.

何れも非常に優れた帯電防止効果を示した。 Measurement of frictional voltage value The frictional voltage was measured in an environment of 21 ° C and 41% RH. The results are shown in Table 10.

All showed a very excellent antistatic effect.

[Test Example 3]
Next, “TM-595 / CAT-RT85” manufactured by Toyo Morton Co., Ltd. was selected as an adhesive for dry laminating whose main component is polyester polyol, and the brands shown in Table 11 were selected as films for bonding.

各々の帯電防止性接着剤の中の固形分に占めるＡＳ剤の固形分濃度は、（Ｅ）は１３．８％、（Ｆ）は２４．２％となった。
ベースフィルム（二軸延伸ＮＹＬＯＮ１５μ）のコロナ放電処理面に本接着剤を塗布し、シーラントフィルム（ＬＬＤＰＥ４０μ）をドライラミネーターにて貼り合わせ、４０℃の恒温室にて２４時間保管熟成した。
塗工版として彫刻グラビア版を用い、乾燥後の接着剤の塗布量は、２．３〜２．５ｇ／ｍ2であった。 The adhesive was prepared by mixing a main agent (TM-595) and a curing agent (CAT-RT85) at 100: 15, diluting with ethyl acetate, and preparing a solution with a solid content of 25%. The solvent type AS agent (solid content 40%) was added there, and the antistatic adhesive of Table 12 was obtained.

The solid content concentration of the AS agent in the solid content of each antistatic adhesive was 13.8% for (E) and 24.2% for (F).
This adhesive was applied to the corona discharge-treated surface of the base film (biaxially stretched NYLON 15 μ), and the sealant film (LLDPE 40 μ) was bonded with a dry laminator, and stored and aged in a constant temperature room at 40 ° C. for 24 hours.
An engraving gravure plate was used as the coating plate, and the coating amount of the adhesive after drying was 2.3 to 2.5 g / m2.

The laminated film after storage aging was measured for properties such as laminate strength, heat seal strength, and frictional voltage value.
-Laminate strength measurement The base material and sealant film were peeled in a T-shape from the end of a sample piece cut to a width of 15 mm, and the strength when peeled at a pulling rate [300 mm / min] was measured using an autograph. . The results are shown in Table 13.

帯電防止性接着剤（Ｅ）では安定した、帯電防止性接着剤（Ｆ）では若干弱いラミネート強度、ヒートシール強度結果を得た。 -Heat seal strength measurement The sealant film surfaces of the laminated film of the sample face each other [150 ° C, 1 kg /
cm 2, 1 second]. A sample piece obtained by cutting the heat-sealed portion to a width of 15 mm was set in an autograph in a T-shape, and the strength when peeled at a pulling speed [300 mm / min] was measured. The results are shown in Table 14.

The antistatic adhesive (E) was stable, and the antistatic adhesive (F) was slightly weak in laminate strength and heat seal strength.

何れも非常に優れた帯電防止効果を示した。 -Measurement of frictional band voltage value The frictional band voltage was measured in the environment of 20 degreeC and 42% RH. The results are shown in Table 15.

All showed a very excellent antistatic effect.

[Test Example 4]
As an adhesive for dry lamination whose main agent is a polyester polyol, “Takelac A-620 / Takenate A-65” manufactured by Mitsui Takeda Chemical Co., Ltd. shown in Table 16 was selected.

各々の帯電防止性接着剤の中の固形分に占めるＡＳ剤の固形分濃度は、（Ｇ）は０％、（Ｈ）は１３．８％となった。
次に、貼り合わせ用のフィルムとして表１８の銘柄を選んだ。

シーラントフィルムとして、表１９を選んだ。

上記フィルムについて、各々のコロナ放電処理面に本接着剤を塗布し、ドライラミネーターにて貼り合わせ、４０℃の恒温室にて２４時間保管熟成した。
塗工版として彫刻グラビア版を用い、乾燥後の接着剤の塗布量は、２．３〜２．６ｇ／ｍ2であった。 The adhesive was prepared as a solution having a solid content of 25% by mixing the main agent (A-620) and the curing agent (A-65) in a ratio of 16: 1 and diluting with ethyl acetate. The adhesive (blank) and the solvent-type AS agent (solid content 40%) were added as they were to obtain the antistatic adhesive shown in Table 17.

The solid content concentration of the AS agent in the solid content of each antistatic adhesive was 0% for (G) and 13.8% for (H).
Next, the brands shown in Table 18 were selected as films for bonding.

Table 19 was selected as the sealant film.

About the said film, this adhesive agent was apply | coated to each corona discharge treatment surface, it bonded together with the dry laminator, and it stored and matured for 24 hours in a 40 degreeC thermostat.
An engraving gravure plate was used as the coating plate, and the coating amount of the adhesive after drying was 2.3 to 2.6 g / m2.

The laminate film after storage aging was measured for performance such as laminate strength, heat seal strength, and frictional voltage value.
-Laminate strength measurement The base material and the sealant film were peeled off in a T-shape from the end of a sample piece cut to a width of 15 mm, and the strength when peeled at a pulling rate [300 mm / min] was measured using an autograph. The results are shown in Table 20.

接着剤（Ｇ）ブランクでも、帯電防止性接着剤（Ｈ）でも安定したラミネート強度、ヒートシール強度結果を得た。 -Heat seal strength measurement The sealant film surfaces of the sample laminated film face each other [150 ° C, 1 kg
/ Cm 2, 1 second]. A sample piece obtained by cutting the heat-sealed portion to a width of 15 mm was set in an autograph in a T shape, and the strength when peeled off at a pulling speed [300 mm / min] was measured. The results are shown in Table 21.

Stable laminate strength and heat seal strength results were obtained with either the adhesive (G) blank or the antistatic adhesive (H).

《帯電防止性接着剤（Ｈ）》

帯電防止性接着剤（Ｈ）では何れも非常に優れた帯電防止効果を示した。 Measurement of frictional voltage value The frictional voltage was measured in an environment of 21 ° C and 40% RH. The results are shown in Tables 22 and 23.
<< Adhesive (G) Blank >>

<Antistatic adhesive (H)>

All of the antistatic adhesives (H) exhibited a very excellent antistatic effect.

Examples of application fields of the composite film of the present invention are as follows.
Packaging materials field: Foods and chemicals packaging materials, especially in the materials field where contamination of contents due to antistatic treatment using surfactants is regarded as a problem, and a higher clean environment is required. Packaging material manufacturing field.
Paper product field: Composite material of paper and plastic film, especially anti-static film material field related to printable and printable film, and combination of paper cardboard base paper and laminated film.
Printing-related fields: Improvement measures for paper feeding suitability and paper delivery suitability for plastic film offset printing.
Building material field: Application to plastic film used for wall material, especially thermal transfer printing film, or flooring field.
Advertising billboard material field:
Adhesive tape field:
Liquid crystal polarizing plate field:

Claims (4)

A mixed solution of ethyl acetate and propylene carbonate, and a main solution of an adhesive for antistatic dry laminate obtained by mixing an alkyl quaternary ammonium etosulphate with the mixed solution. The main agent solution for an antistatic dry laminate adhesive according to claim 1, wherein the main agent of the adhesive is a polyether polyol or a polyester polyol. An antistatic dry laminate prepared by mixing a mixed solution of ethyl acetate and propylene carbonate and an antistatic solution obtained by mixing the mixed solution with an alkyl quaternary ammonium ethosulphate and a main component comprising a polyether polyol or a polyester polyol. Adhesive. An antistatic dry laminate prepared by mixing a mixed solution of ethyl acetate and propylene carbonate and an antistatic solution obtained by mixing the mixed solution with an alkyl quaternary ammonium ethosulphate and a main component comprising a polyether polyol or a polyester polyol. Antistatic composite film that is dry-laminated with adhesive.