JP3006129B2 - Anchor coating agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel anchor coating agent for a laminated film, and a film or sheet coated with the anchor coating agent.

[0002]

2. Description of the Related Art Films and sheets (hereinafter referred to as films, etc.) used for packaging materials have barrier properties against water, water vapor, various gases, light, aroma, odor, etc., tensile strength, impact strength, puncture strength and the like. Various quality characteristics such as stability such as various mechanical strengths, chemical resistance, heat resistance, and cold resistance, hygiene, safety, workability, appearance, and economy are required.
Although materials for various types of films and the like are supplied today, it is not possible to satisfy all of these quality characteristics with a film or the like consisting of only one type of material. As a countermeasure against such a problem, it is well known that two or more films of different types are laminated and used as a so-called laminate film or the like. One of the methods for manufacturing a laminated film is an extrusion lamination method. This method is a method in which another plastic, for example, polyethylene, is extruded at a relatively high temperature, laminated and integrated with a base film such as a plastic film or an aluminum foil. In this case, in order to increase the adhesive strength between the base film and the like having different properties and the laminated film, a base film or the like to which an anchor coating agent is applied in advance is used.

Typical anchor coating agents include (1) isocyanate anchor coating agents, (2) organotitanium anchor coating agents, (3) polybutadiene anchor coating agents, and (4) polyethyleneimine anchor coating agents. it can. The characteristics required of the anchor coating agent are (a) to increase the adhesive force between the films, which is the original purpose, and (b) to at least not adversely affect the above-mentioned quality characteristics required for the laminated film. The production of laminated films is easy, safe and economical. Among them, the polyethyleneimine-based anchor coating agent does not have sufficient water resistance, but does not require aging after processing, unlike the isocyanate-based anchor coating agent, and can process efficiently. Also, there is no need to use an organic solvent, so there is no problem of pollution. Further, it is a chemically stable substance, and does not cause a problem that the pot life is short as in the case of the organic titanium anchor coating agent. For this reason, it is widely used in fields that do not require much water resistance. However, extrusion lamination is performed at a relatively high temperature, and polyethyleneimine is easily colored brown when heated.Therefore, there is a problem that a laminate film produced using this anchor coating agent is colored and impairs economic value. is there. Furthermore, carcinogenicity has been pointed out for ethyleneimine which may remain in polyethyleneimine.

[0004]

SUMMARY OF THE INVENTION The present invention relates to an anchor coat which is easy to handle in the production of a laminated film, is safe, can be efficiently produced, and can produce a laminated film having excellent adhesive strength and appearance. An object of the present invention is to provide a film and a sheet to which an agent and an anchor coat agent are applied.

[0005]

The present invention provides an allylamine polymer, a copolymer of allylamine and diallylamine,
And an anchor coating agent containing, as a main component, at least one selected from the group consisting of partially neutralized products of the polymer or copolymer. The present invention also provides an anchor coating agent containing as a main component at least one selected from the group consisting of an allylamine polymer, a copolymer of allylamine and diallylamine, and a partially neutralized product of the polymer or the copolymer. The gist is also a film or a sheet to which is applied. Hereinafter, the present invention will be described in detail.

The allylamine polymer used as the anchor coating agent of the present invention is

[0007]

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And a repeating unit represented by The molecular weight is not limited, but is preferably 300 to 1,000,000.
00. This polymer is produced, for example, by adding a strong base such as sodium hydroxide to an allylamine mineral acid polymer obtained by polymerization of an allylamine mineral acid salt (for example, hydrochloride) and deoxidizing the polymer. It is preferable to remove salts (eg, salt) by-produced during deacidification by means such as dialysis. The allylamine and diallylamine copolymer used as the anchor coating agent of the present invention comprises a structural unit represented by the following formula (1) and (2) or (3).

[0009]

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The molecular weight is not critical but is preferably 30.
0 to 1,000,000. The mole% of the structural unit (1) is 100 to 20, preferably 100 to 30, and the mole% of the structural unit (2) or (3) is 0 to 80, preferably 0 to 70. This copolymer is obtained, for example, by adding a copolymer of allylamine mineral acid salt (eg, hydrochloride) and diallylamine mineral acid salt (eg, hydrochloride) to a copolymer of allylamine mineral acid salt and diallylamine mineral acid. It is prepared by adding a strong base such as sodium oxide and deoxidizing. It is preferable to remove salts (for example, salt) by-produced during deacidification by means such as dialysis. The above-mentioned allylamine polymer or a partially neutralized product of an allylamine and diallylamine copolymer with an acid can also be used as the anchor coating agent of the present invention. The type of acid is not limited and may be any organic or inorganic acid. The degree of neutralization is in the range of 0 to 50 mol% based on the total of repeating units or structural units of the polymer or copolymer.

The anchor coating agent of the present invention is dissolved in a solvent and applied as a coating liquid to a base film or sheet.
As the base film or sheet, polyamide, polyester, polyimide, polypropylene, polyethylene,
Resin films such as polyvinyl chloride and polyvinylidene chloride, metal foils such as aluminum foil and copper foil, cellophane,
Examples include paper, nonwoven fabric, and woven fabric. As a solvent for dissolving the anchor coating agent of the present invention, water, methyl alcohol, ethyl alcohol, or a mixed solvent of water, alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol, dimethylformamide, dimethyl sulfoxide, or the like may be used. it can. Coating amount is 0.005~0.05g / m ² as an active ingredient, preferably made to be 0.01~0.03g / m ^2. The coating method may be a known method, for example, a roll coating method, a lot bar coating method, an air knife coating method, a spray coating method, a dipping method, or the like. After coating, air-dry or heat to dry to remove the solvent.

[0012] A resin film is laminated by extrusion lamination using the film or sheet-like material coated with the anchor coating agent of the present invention as a base material to produce a laminated film. As the extrusion lamination method, a conventionally known method can be used. Next, the present invention will be described in more detail with reference to examples, but it is needless to say that the present invention is not limited to these examples. In the examples,% represents% by weight.

[0013]

EXAMPLES Example 1 Allylamine hydrochloride polymer (molecular weight: 20,000) 1
8.71 g was dissolved in 79.49 g of water. 50
Then, 16.00 g of sodium hydroxide was added for deacidification.
Dialyze against ion-exchanged water for 96 hours, concentrate to a concentration of 1
74.61 g of a 5% aqueous solution of an allylamine polymer was obtained.
0.36 g of water and 14 parts of methyl alcohol
8.83 g was added to obtain a 5% polymer solution.

Example 2 21.38 g of a copolymer of allylamine hydrochloride and diallylamine hydrochloride (molar ratio 2: 1, molecular weight 30,000)
Was dissolved in 103.52 g of water. To this was added 16.00 g of 50% sodium hydroxide for deacidification. The mixture was dialyzed against ion-exchanged water for 96 hours, concentrated, and concentrated to obtain a copolymer of allylamine and diallylamine (concentration of 2:
92.05 g of an aqueous solution (1, molecular weight: 20,000) was obtained.
0.48 g of water and 18 parts of ethyl alcohol were added to this aqueous solution.
3.67 g was added to obtain a 5% copolymer solution.

Example 3 22.72 g of a copolymer of allylamine hydrochloride and diallylamine hydrochloride (molar ratio 1: 1, molecular weight 60,000)
Was dissolved in 115.58 g of water. To this was added 16.00 g of 50% sodium hydroxide for deacidification. The mixture was dialyzed against ion-exchanged water for 96 hours, concentrated and concentrated to obtain a copolymer of allylamine and diallylamine at a concentration of 15% (molar ratio 1: 1).
(1. molecular weight: 41,000) 100.81 g of an aqueous solution was obtained. To this aqueous solution, 0.49 g of water and 201.10 g of isopropyl alcohol were added to obtain a 5% copolymer solution.

Example 4 A 15% aqueous solution of an allylamine polymer obtained in Example 1 7
To 13.13 g, 10.42 g of 35% hydrochloric acid was added to obtain an aqueous solution of a partially neutralized allylamine polymer (degree of neutralization: 50 mol%, molecular weight: 17,000). 14.42 water is added to this aqueous solution.
g and 200.43 g of methyl alcohol were added to obtain a 5% polymer solution.

Example 5 To 93.43 g of a 15% aqueous solution of a copolymer of allylamine and diallylamine obtained in Example 2, 35% hydrochloric acid was added to 10.3 g of an aqueous solution.
By adding 42 g, a partially neutralized product of a copolymer of allylamine and diallylamine was obtained (neutralization degree: 50 mol%, molecular weight: 25,
000). 14.51 g of water and 235.94 g of ethyl alcohol were added to this aqueous solution to obtain a 5% copolymer solution.

EXAMPLE 6 35% hydrochloric acid (1) was added to 102.87 g of the aqueous 15% copolymer solution of allylamine and diallylamine obtained in Example 3
0.42 g was added to obtain a partially neutralized copolymer of allylamine and diallylamine (neutralization degree 50 mol%, molecular weight 5
1,000). To this aqueous solution, 14.55 g of water and 253.76 g of isopropyl alcohol were added to obtain a 5% copolymer solution.

Example 7 The anchor coating agent produced in Examples 1 to 6 was applied to cellophane by a roll coater so as to have a solid content of 0.02 g / m ² , followed by hot-air drying. Next, a polyethylene having a thickness of 40 μm and a thickness of 290 were coated on the surface coated with the cellophane anchor coat agent by an extrusion in-line method.
The laminate was extruded and laminated at ℃ to produce a laminated film. For comparison, a laminate film was produced in the same manner using polyethyleneimine (PEI) as an anchor coating agent. The adhesive strength of the laminated film thus manufactured was measured by using a Tensilon tester (T-type peeling).
It measured using. In addition, 100
The appearance after heating at 4 ° C. for 4 hours is summarized in Table 1.

[0020]

[Table 1]

Example 8 The anchor coating agent produced in Examples 1 to 6 was coated on an aluminum foil with a roll coater at a solid content of 0.02 g /
m ² and dried with hot air. Next, polyethylene was extruded and laminated at 290 ° C. with a thickness of 40 μm on the surface of the aluminum foil to which the anchor coating agent was applied by an extrusion in-line method to produce a laminated film. For comparison, a laminate film was produced in the same manner using polyethyleneimine (PEI) as an anchor coating agent. Table 2 summarizes the adhesive strength of the laminate film measured by the method of Example 7 and the appearance after heating at 100 ° C. for 4 hours.

[0022]

[Table 2]

Example 9 The anchor coating agent produced in Examples 1 to 6 was coated on a nylon film with a roll coater to apply a solid content of 0.02 g.
/ M ² and dried with hot air. Next, 40 μm of polyethylene was applied to the surface of the nylon film to which the anchor coating agent was applied by an extrusion in-line method.
And extruded at 290 ° C. to produce a laminated film. For comparison, a laminate film was produced in the same manner using polyethyleneimine (PEI) as an anchor coating agent. Adhesive strength of laminated film, measured by the method of Example 7, 100
The appearance after heating at 4 ° C. for 4 hours is summarized in Table 3.

[0024]

[Table 3]

Example 10 The anchor coating agent prepared in Examples 1 to 6 was applied to a polyester film by a roll coater using a solid coating amount of 0.0
The coating was performed at ² g / m ² and dried with hot air. Next, polypropylene was extruded at 290 ° C. with a thickness of 40 μm on the surface of the polyester film coated with the anchor coating agent by an extrusion in-line method to produce a laminated film. For comparison, a laminate film was produced in the same manner using polyethyleneimine (PEI) as an anchor coating agent. Table 4 summarizes the adhesive strength of the laminate film measured by the method of Example 7 and the appearance after heating at 100 ° C. for 4 hours.

[0026]

[Table 4]

[0027]

According to the anchor coating agent and the film or sheet coated with the anchor coating agent of the present invention, a laminate film or sheet having excellent adhesive strength and no coloring can be produced. Further, since the anchor coating agent of the present invention is water-soluble, there is no need to use an organic solvent which is harmful to the human body even when producing a laminated film or sheet.

Claims (3)

(57) [Claims] An anchor coating agent comprising as a main component at least one selected from the group consisting of an allylamine polymer, a copolymer of allylamine and diallylamine, and a partially neutralized product of the polymer or the copolymer. . [However, the aliphatic polyepoxy compound having two or more epoxy groups in the molecule (A) is 0.3 to 98.6% by weight and the general formula: 99.7 polyallylamine (B) represented by the following basic skeleton:
To 1.4% by weight, excluding a treating agent for attaching to synthetic fibers] 2. An anchor coating agent comprising as a main component at least one selected from the group consisting of an allylamine polymer, a copolymer of allylamine and diallylamine, and a partially neutralized product of the polymer or the copolymer. Coated film or sheet. [However, the aliphatic polyepoxy compound having two or more epoxy groups in the molecule (A) is 0.3 to 98.6% by weight, and is represented by the general formula: 99.7 polyallylamine (B) represented by the following basic skeleton:
Excluding synthetic fibers to which a treating agent consisting of up to 1.4% by weight is attached] 3. An anchor coating agent containing as a main component at least one selected from the group consisting of an allylamine polymer, a copolymer of allylamine and diallylamine, and a partially neutralized product of the polymer or the copolymer. A method of manufacturing a laminated film by laminating a resin film by extrusion lamination using a film or a sheet-like material coated with a resin as a base. [However, as a substrate, 0.3 to 98.6% by weight of an aliphatic polyepoxy compound (A) having two or more epoxy groups in a molecule is represented by the general formula: 99.7 polyallylamine (B) represented by the following basic skeleton:
Excluding the case of using synthetic fibers to which a treating agent consisting of up to 1.4% by weight is attached]