JP2019172831A - Anchor coat for metal, laminate, battery and packaging body - Google Patents

Abstract

To provide an anchor coat for metal capable of enhancing adhesive strength, a laminate, a battery, and a packaging body.SOLUTION: An anchor coat for metal contains a polyvalent phenol compound, and an amine compound. The polyvalent phenol compound contains an aromatic ring, 2 hydroxyl groups directly bound to 2 carbon atoms neighboring each other in the aromatic ring each other, and at least one selected from a group consisting of a COO bond and a carboxyl group. The amine compound has weight average molecular weight of 1×10or more, and contains primary amino group.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a metal primer, a laminate, a battery, and a package.

  Conventionally, a laminate in which an adherend is bonded to a metal substrate (metal foil) via an adhesive layer is known.

  Moreover, in patent document 1, the surface of a metal base material is subjected to chemical conversion treatment, and then an adhesive layer is laminated on the surface subjected to chemical conversion treatment on the metal substrate. Thereby, the adhesive strength of the adhesive layer of the metal substrate is improved.

WO2014 / 123183 Publication

  However, further improvement in the adhesive strength of the adhesive layer to the metal substrate is required.

  The present invention provides a metal primer, a laminate, a battery, and a package that can improve adhesive strength.

The present invention (1) includes a polyhydric phenol compound and an amine compound, and the polyhydric phenol compound includes an aromatic ring and two hydroxyl groups directly connected to two carbon atoms adjacent to each other in the aromatic ring. And at least one selected from the group consisting of a COO bond and a carboxyl group, and the amine compound has a weight average molecular weight of 1 × 10 ³ or more and contains a primary amino group. Contains agents.

  The present invention (2) includes the metal primer according to (1), which contains three hydroxyl groups directly bonded to the aromatic ring.

  In the present invention (3), the ratio of the polyhydric phenol compound is 20% by mass or more and 80% by mass or less based on the total of the polyhydric phenol compound and the amine compound. (1) or (2) The primer for metals described in 1. is included.

  This invention (4) contains the metal primer as described in any one of (1)-(3) which further contains an organic acid.

  This invention (5) contains the primer for metals as described in (4) whose pH is 1 or more and 4 or less.

This invention (6) contains the metal primer as described in any one of (1)-(5) whose weight average molecular weights of the said amine compound are 100x10 < ³ > or less.

  This invention (7) contains the metal primer as described in any one of (1)-(6) whose amine value of the said amine compound is 4-30.

  The present invention (8) includes a metal substrate and an undercoat layer formed on one surface of the metal substrate and prepared from the metal primer according to any one of (1) to (7). Includes laminates.

  This invention (9) contains the laminated body as described in (8) further provided with the adhesive bond layer arrange | positioned at the one surface of the said undercoat.

  This invention (10) contains the laminated body as described in (9) further provided with the to-be-adhered body arrange | positioned at the one surface of the said adhesive bond layer.

  This invention (11) contains the laminated body as described in (10) which is a packaging material for battery cases.

  The present invention (12) includes the laminate according to (11), which is a battery case packaging material, and the electrolytic solution packaged in the battery case packaging material, and the attachment of the battery case packaging material At least a portion of the body includes a battery in contact with the electrolyte.

  This invention (13) contains the laminated body as described in (10) which is a packaging material for high alkali solutions.

  This invention (14) contains a package provided with the laminated body as described in (13) which is a packaging material for high alkali solutions, and the solution of pH9 or more packaged by the said packaging material for high alkali solutions.

  This invention (15) contains the laminated body as described in (10) which is a packaging material for alcohol containing solutions.

  This invention (16) contains a package provided with the laminated body as described in (15) which is a packaging material for alcohol containing solutions, and the alcohol containing solution packaged in the said packaging material for alcohol containing solutions.

  In the metal primer of the present invention, a strong amide bond is formed by reacting with at least one selected from the group consisting of a COO bond and a carboxyl group in a polyhydric phenol compound and a primary amino group in an amine compound. Can do.

  On the other hand, in the polyhydric phenol compound, the two hydroxyl groups are directly bonded to the two carbon atoms adjacent to each other in the aromatic ring. Can do.

  Therefore, this metal primer can increase the strength of the resulting primer layer. Therefore, in a laminate in which a metal primer is applied to one side of the metal to form an undercoat layer, and the adhesive layer and the adherend are disposed on one side of the metal, the adherend to the metal is adhered. Strength can be improved.

  Since the battery of the present invention includes the above-described laminate, it is possible to prevent a decrease in adhesive strength in the laminate due to contact with the electrolytic solution.

  Since the package of the present invention includes the above-described laminate, it is possible to prevent a decrease in adhesive strength in the laminate caused by contact with the highly alkaline solution.

  Since the package of the present invention includes the above-described laminate, it is possible to prevent a decrease in adhesive strength in the laminate due to contact with the alcohol-containing solution.

FIG. 1 shows a cross-sectional view of a first laminate which is an embodiment of the laminate of the present invention. FIG. 2 shows a cross-sectional view of a second laminate which is an embodiment of the laminate of the present invention. FIG. 3 shows a cross-sectional view of a third laminate which is an embodiment of the laminate of the present invention. FIG. 4 shows a cross-sectional view of a battery case packaging material according to an embodiment of the laminate of the present invention. FIG. 5 shows a cross-sectional view of one embodiment of the battery of the present invention. FIG. 6 shows a cross-sectional view of an embodiment of the packaging material for high alkali solution or the packaging material for alcohol-containing solution of the present invention. FIG. 7: shows sectional drawing of one Embodiment of the package body of this invention.

Metal Undercoat One embodiment of the metal undercoat of the present invention will be described.

The metal primer for use in the present invention is a primer (primer) that is used to form a primer layer by applying to a metal. The metal undercoat contains a polyhydric phenol compound and an amine compound.
Polyhydric phenol compound The polyhydric phenol compound contains an aromatic ring, two hydroxyl groups directly bonded to the aromatic ring, and at least one selected from the group consisting of a COO bond and a carboxyl group.

  The aromatic ring may specifically be either a single ring or a polycycle (including a condensed ring in which a single ring is condensed), preferably a single ring, and specifically a benzene ring. .

  The number of aromatic rings in the polyhydric phenol compound is not particularly limited, and may be either singular or plural. The number of aromatic rings in the polyhydric phenol compound is preferably plural from the viewpoint of increasing the adhesion point.

  Each of the two hydroxyl groups is directly connected to each of two adjacent carbon atoms in one aromatic ring.

  When the number of aromatic rings in the polyhydric phenol compound is plural, for example, each of the two hydroxyl groups is directly connected to each of the aromatic rings. In addition, among a plurality of aromatic rings, two hydroxyl groups are directly connected to some of the aromatic rings (each), and only one hydroxyl group is directly connected to the remaining aromatic ring (each), for example, Alternatively, two hydroxyl groups may be bonded via a divalent hydrocarbon group (described later). Furthermore, when the number of aromatic rings in the polyhydric phenol compound is plural, the polyhydric phenol compound can also include, for example, an aromatic ring that is not bonded to a hydroxyl group. Preferably, for each of all aromatic rings, each of the two hydroxyl groups is directly linked.

  In addition to the two hydroxyl groups described above, another hydroxyl group can be directly linked to one aromatic ring. That is, in addition to the first hydroxyl group and the second hydroxyl group, which are two hydroxyl groups directly connected to two adjacent carbon atoms in one aromatic ring, the polyhydric phenol compound is adjacent to each other in one aromatic ring. A third hydroxyl group directly attached to a carbon atom other than the two carbon atoms.

  The polyhydric phenol compound containing the first hydroxyl group, the second hydroxyl group and the third hydroxyl group contains a first hydroxyl group and a second hydroxyl group, and does not contain a third hydroxyl group. Compared to a polyhydric phenol compound, it contains a third hydroxyl group, so that it can form a hydrogen bond even more firmly with the metal.

The carbon atom to which the third hydroxyl group is directly bonded, that is, the third carbon atom is the above-mentioned two carbon atoms, that is, the first carbon atom to which the first hydroxyl group is directly bonded, and the second hydroxyl group. May be adjacent to one of the second carbon atoms directly connected to each other, or may be adjacent to one of the above through another carbon atom without being adjacent. Preferably, the third carbon atom is adjacent to the second carbon atom. In this case, the first carbon atom, the second carbon atom, and the third carbon atom are continuously located in the aromatic ring. Specifically, the first carbon atom, the second carbon atom, and the third carbon atom are located at the 1st, 2nd, and 3rd positions in the aromatic ring, respectively.
COO bond and carboxyl group At least one selected from the group consisting of a COO bond and a carboxyl group (COOH) is a COO-containing moiety. Such a COO-containing moiety may be directly bonded to the aromatic ring, or may not be directly bonded and may be bonded via a divalent hydrocarbon group (described later). Preferably, the COO-containing portion is directly connected to the aromatic ring.

Among the COO-containing moieties, any one of the carbon atoms constituting the carbonyl group (> C═O), that is, the carbonyl carbon atom and the oxygen atom bonded to the carbonyl carbon atom with a single bond is, for example, an aromatic ring. Preferably, the carbonyl carbon atom is bonded to the aromatic ring, more preferably the carbonyl carbon atom is directly connected to the aromatic ring. That is, the structure shown in Formula (1) is configured.
Formula (1):

  The COO-containing portion is preferably a COO bond from the viewpoint of solubility.

  The carbon atoms bonded to the COO bond in the aromatic ring (preferably the carbon atoms directly bonded to the COO bond in the aromatic ring) are COO-bonded carbon atoms (preferably the COO directly bonded carbon atoms), and It may be adjacent to at least one of the adjacent first carbon atom and the second carbon atom, or may be adjacent to one of the above through another carbon atom without being adjacent.

  Specifically, when the first carbon atom and the second carbon atom adjacent to each other in the aromatic ring are located at the 1-position and the 2-position (ortho position), respectively, the COO-bonded carbon atom is, for example, the 3-position It is located in any of the 4th, 5th and 6th positions, preferably located in any of the 3rd, 4th and 5th positions, and more preferably located in the 4th (para) position.

More preferably, when the first carbon atom, the second carbon atom, and the third carbon atom are located at the 1-position, 2-position, and 3-position, respectively, the COO-bonded carbon atom is, for example, at the 4-position, 5-position, It is located in either the position or the 6th position, preferably in the 5th position. That is, the structure shown in Formula (2) is configured.
Formula (2):

  On the other hand, in the COO-containing moiety, when the carbonyl carbon atom is bonded to the aromatic ring, the oxygen atom bonded to the carbonyl carbon atom with a single bond is bonded to, for example, an organic group, and preferably an oxo ring is bonded. It binds to the organic group it has.

Examples of the organic group having an oxo ring include a first organic group represented by the formula (3). In this case, the polyhydric phenol compound is specifically represented by the formula (4).
Formula (3)

Formula (4)

(In the formula, n represents an integer of 1 or more.)
n is preferably 2 or more, more preferably 4 or more, and is, for example, 7 or less, preferably 6 or less. Most preferably, n is 5.

Examples of the organic group having an oxo ring include a second organic group represented by the formula (5). In this case, the polyhydric phenol compound is specifically represented by the formula (6). Has a structure.
Formula (5)

Formula (6)

  The organic group having an oxo ring is preferably the first organic group represented by the formula (3).

  The carboxyl group is preferably directly connected to an aromatic ring directly connected to two hydroxyl groups adjacent to each other.

  In the case where the carboxyl group is not directly connected to the aromatic ring, for example, the carboxyl group is directly connected to the aromatic ring via a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include alkylene having 1 to 12 carbon atoms (divalent saturated hydrocarbon group) such as methylene, ethylene and propylene, for example, 2 carbon atoms such as vinylene, propenylene and butenylene. The alkenylene (divalent unsaturated hydrocarbon group) of 12 or less is mentioned. Alkenylene is preferable, and vinylene is more preferable.

The carbon atom bonded to the carboxyl group (carboxyl group-bonded carbon atom) and the first carbon atom and the second carbon atom adjacent to each other in the aromatic ring are carbon atoms that are not directly connected to the carboxyl group in the aromatic ring. It may be located via. Specifically, in the aromatic ring, when the carbon atoms directly connected to the two hydroxyl groups are located at the 1-position and the 2-position, the carboxyl group-bonded carbon atoms are, for example, the 3-position, the 4-position, the 5-position, It can also be located in any of the 6th positions, preferably in the 3rd, 4th, 5th positions, more preferably in the 4th position. That is, the structure shown in Expression (7) is configured.
Formula (7):

More preferably, when the first carbon atom, the second carbon atom, and the third carbon atom are located at the 1-position, 2-position, and 3-position, the carboxyl group-bound carbon atom is, for example, at the 4-position, 5-position, It can also be located in either the position or the 6th position, and is preferably located in the 5th position. That is, the structure shown in Formula (8) is configured.
Formula (8):

Specifically, the polyhydric phenol compound has a structure represented by Formula (9).
Formula (9):

(In the formula, A represents a hydrogen atom or a hydroxyl group. B represents a structure having at least one selected from the group consisting of a COO bond and a carboxyl group.)
Two hydroxyl groups (OH) are the above-mentioned first hydroxyl group and second hydroxyl group, respectively.

  The hydroxyl group represented by A is the above-described third hydroxyl group. The third hydroxyl group is preferably bonded to a third carbon atom adjacent to the second carbon atom.

  At least one selected from the group consisting of a COO bond and a carboxyl group represented by B is the above-described COO-containing moiety. The carbonyl carbon atom in the COO-containing moiety is preferably a carbon atom other than the first and second carbon atoms adjacent to each other in the aromatic ring (more preferably, the first carbon atom, the second carbon atom and Carbon atom other than the third carbon atom).

  As the structure represented by the formula (9), a galloyl group is preferable.

The galloyl group is a 3,4,5-trihydroxybenzoyl group, and specifically represented by the formula (10).
Formula (10):

  More specifically, examples of the polyhydric phenol compound having a COO bond as a COO-containing moiety include, for example, tannic acid, and a polyhydric phenol compound having a carboxyl group as a COO-containing moiety. Examples of these include, for example, polyhydric phenol acids.

  Examples of tannic acid include hydrolyzable tannin represented by formula (11) and condensed tannin represented by formula (12).

Formula (11):

Formula (12):

(Wherein R includes at least the galloyl group described above)
R may further contain a hydroxyl group.

  As the tannic acid, a hydrolyzable tannin represented by the formula (11) is preferably used from the viewpoint of compatibility with an amine compound and / or reactivity.

  Examples of polyhydric phenol acids include monocarboxylic acids (described later), such as dihydroxyphthalic acid (dihydroxydicarboxylic acid), trihydroxyphthalic acid (trihydroxydicarboxylic acid), and tetrahydroxyphthalic acid (tetrahydroxydicarboxylic acid). Examples thereof include tricarboxylic acids such as dicarboxylic acid, dihydroxytricarboxylic acid, and trihydroxytricarboxylic acid, such as dihydroxytetracarboxylic acid.

  As polyhydric phenol acid, Preferably, monocarboxylic acid is mentioned.

  Examples of the monocarboxylic acid include dihydroxybenzoic acid (dihydroxymonocarboxylic acid) such as 2,3-dihydroxybenzoic acid and 3,4-dihydroxybenzoic acid, and tricyclic such as 3,4,5-trihydroxybenzoic acid. Examples include hydroxybenzoic acid (trihydroxymonocarboxylic acid), for example, tetrahydroxybenzoic acid (tetrahydroxymonocarboxylic acid) such as 2,3,4,5-tetrahydroxybenzoic acid. Preferably, polyhydric phenol acids having 3 or more hydroxyl groups such as trihydroxybenzoic acid and tetrahydroxybenzoic acid can be used, and more preferably, from the viewpoint of compatibility with amine compounds and / or adhesion to metals, Trihydroxybenzoic acid, more preferably 3,4,5-trihydroxybenzoic acid (gallic acid) represented by the formula (13) is mentioned.

Formula (13):

  In addition, examples of polyhydric phenol acids include, for example, dihydroxyphenyl monophenyl, in which a carboxyl group is bonded to an aromatic ring via a divalent hydrocarbon group (preferably a divalent unsaturated hydrocarbon group). Monoacrylic acid such as acrylic acid, trihydroxyphenyl monoacrylic acid, tetrahydroxyphenyl monoacrylic acid, pentahydroxyphenyl monoacrylic acid, for example, dihydroxyphenyl diacrylic acid, trihydroxyphenyl diacrylate Acrylic acid, diacrylic acid such as tetrahydroxyphenyl diacrylic acid, for example, triacrylic acid such as dihydroxyphenyl triacrylic acid, trihydroxyphenyl triacrylic acid, for example, tetrahydroxy such as dihydroxyphenyl tetraacrylic acid Acrylic acid is mentioned.

  As polyhydric phenol acid, Preferably, monoacrylic acid is mentioned.

  Specific examples of monoacrylic acid include dihydroxycinnamic acid (dihydroxyphenyl monoacrylic acid), trihydroxycinnamic acid (trihydroxyphenyl monoacrylic acid), and tetrahydroxycinnamic acid (tetrahydroxyphenyl monoacrylic). Acid) and pentahydroxycinnamic acid (pentahydroxyphenyl monoacrylic acid).

  The monoacrylic acid is preferably dihydroxycinnamic acid (dihydroxyphenyl monoacrylic acid).

  Examples of dihydroxycinnamic acid include 2,3-dihydroxy cinnamic acid and 3,4-dihydroxy cinnamic acid.

Preferably, from the viewpoint of compatibility with amine compounds and / or adhesion to metals, 3,4-dihydroxycinnamic acid (caffeic acid or caffeic acid) represented by formula (14) is preferable.
Formula (14):

  Such a polyhydric phenol compound is a natural product-derived component extracted from a natural product, for example, a plant-derived component extracted from a plant such as a pentaploid or a gallic pod. On the other hand, the polyphenol compound may be an artificially synthesized component.

  The polyhydric phenol compound may contain a trace amount of impurities derived from plants (heavy metals such as arsenic and lead). The purity in the polyhydric phenol compound is, for example, 90% by mass or more, preferably 95% by mass or more, and for example, 100% by mass or less, preferably 98% by mass or less.

  A commercially available product can be used as the polyhydric phenol compound, for example, tannic acid AL (manufactured by Fuji Chemical Industry Co., Ltd.) as hydrolyzed tannin, tannic acid KT (manufactured by Fuji Chemical Industry Co., Ltd.), etc. as condensed tannin. Used.

  The weight average molecular weight of the polyhydric phenol compound is, for example, 150 or more, 1000 or more, and 1900 or more, and is 4000 or less, preferably 3000 or less, more preferably 2500 or less. The weight average molecular weight of the polyhydric phenol compound is determined by GPC measurement.

  The ratio of the polyhydric phenol compound is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% with respect to the total of the polyhydric phenol compound and the amine compound. % By mass or more, particularly preferably 35% by mass or more, most preferably 40% by mass or more, and for example, 95% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, More preferably, it is 70 mass% or less, Most preferably, it is less than 50 mass%, Most preferably, it is 45 mass% or less.

  The content ratio of the polyhydric phenol compound in the component excluding the solvent (described later) in the metal primer is, for example, 5% by mass or more, preferably 20% by mass or more, and for example, 95% by mass or less, preferably Is 50 mass% or less.

  If the ratio of the polyhydric phenol compound is equal to or more than the lower limit described above, the amount of unreacted amine compound that does not contribute to the amide bond formation reaction can be reduced, thereby suppressing the decrease in adhesive strength caused by the unreacted amine compound. can do.

If the ratio of the polyhydric phenol compound is not more than the above upper limit, the amount of the unreacted polyhydric phenol compound that does not contribute to the amide bond formation reaction can be reduced, and therefore, the adhesive strength caused by the unreacted polyhydric phenol compound. Can be suppressed.
Amine compound An amine compound is a high molecular weight compound containing a primary amino group (—NH ₂ ) and having a weight average molecular weight of 1 × 10 ³ or more. The number of primary amino groups in one molecule of the amine compound is not particularly limited, and may be either singular or plural. Preferably, there are a plurality.

  Further, the amine compound can further contain a secondary amino group and / or a tertiary amino group in addition to the above-mentioned primary amino group. Alternatively, the amine compound may contain only primary amino groups.

The amine compound is preferably a first amine compound containing both a primary amino group and a secondary amino group, and a second amine compound containing a primary amino group and not containing a secondary amino group. .
First Amine Compound Examples of the first amine compound include polyethyleneimine represented by the formula (15).
Formula (15):
_{H 2 N- (CH 2 -CH 2} -NH) k -H
(15)
(In the formula, k represents an integer of 16 or more.)
Specifically, the polyethyleneimine is, for example, the formula (16) represented by the formula (16):

Polyethyleneimine is a polymer obtained by polymerizing ethyleneimine represented by the formula (17).
Formula (17):

In the first amine compound, the molar ratio of the primary amino group to the total amino groups (the total of the primary amino group, the secondary amino group, and the tertiary amino group) is, for example, 4 mol% or more, 100 mol% or less.
Second Amine Compound Examples of the second amine compound include polyallylamine represented by the formula (18).

Formula (18):

(In the formula, n represents an integer of 17 or more.)
Polyallylamine is a polymer obtained by polymerizing allylamine (CH ₂ ═C (CH ₂ NH ₃ ) H).

  A commercially available product can be used as the amine compound. For example, as the first amine compound, the Epomin series (manufactured by Nippon Shokubai Co., Ltd.), for example, as the second amine compound, the PAA series (manufactured by Nitto Bo Medical Co., Ltd.), etc. Used.

  Of these amine compounds, the first amine compound is more preferable from the viewpoint of reactivity.

The weight average molecular weight of the amine compound is 1 × 10 ³ or more, preferably 1.5 × 10 ³ or more, more preferably 3.0 × 10 ³ or more, and further preferably 5.0 × 10 ³ or more. Also, for example, it is 300 × 10 ³ or less, preferably 200 × 10 ³ or less, and more preferably 10 × 10 ³ or less. The weight average molecular weight of the amine compound is determined by GPC measurement, boiling point increase method, or viscosity method.

  If the weight average molecular weight of the amine compound is equal to or higher than the above lower limit, the film strength of the undercoat layer prepared from the metal undercoat is increased, so that the adhesion strength between the metal (for example, a metal substrate) and the undercoat layer is improved. be able to.

  If the weight average molecular weight of an amine compound is below the above-mentioned upper limit, a stable liquid mixture with a polyhydric phenol compound can be prepared.

  The amine value of the amine compound is, for example, 4 or more, preferably 10 or more, and for example, 30 or less, preferably 20 or less.

  When the amine value of the amine compound is equal to or higher than the lower limit described above, the number of reaction points with the polyhydric phenol compound increases, and the adhesive strength with a metal (for example, a metal substrate) can be improved. On the other hand, if the amine value of an amine compound is below the above-mentioned upper limit, a stable compounding liquid with a polyhydric phenol compound can be prepared.

  The amine value indicates the amount of all amino groups in the amine compound. The amine value is mg of potassium hydroxide equivalent to the acid required to neutralize all amino groups in 1 g of the amine compound. The amine value of the amine compound is measured according to the description of JISK 7237-1995.

  The content ratio of the amine compound in the component excluding the solvent (described later) in the metal primer is, for example, 5% by mass or more, preferably 20% by mass or more, more preferably 50% by mass or more. It is 95 mass% or less, Preferably, it is 80 mass% or less.

  Moreover, the metal undercoat can contain a pH adjuster.

  Examples of the pH adjuster include acids such as organic acids (excluding the above-described polyhydric phenol acids), and bases such as organic bases. The metal primer containing only the polyhydric phenol compound and the amine compound in the above-described content ratio usually exhibits basicity, and from the viewpoint of neutralizing this, preferably an acid, more preferably, Organic acids are mentioned. Examples of the organic acid include monocarboxylic acids such as formic acid, lactic acid, and acetic acid, and more preferably formic acid.

  The content of the pH adjusting agent (preferably, an organic acid) is, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more in the metal primer. 15 mass% or less, preferably 10 mass% or less. If the content of the pH adjusting agent is not less than the above lower limit and not more than the above upper limit, the pH of the metal primer can be set in the range described below.

  If the metal primer contains the pH adjuster described above, the pH of the metal primer is set to, for example, 1 or more, preferably 1.5 or more, and for example, 5 or less, preferably 4 or less. To do.

  When the pH of the metal primer is not less than the above lower limit and not more than the above upper limit, the stability of the metal primer can be improved (specifically, the occurrence of precipitates can be suppressed).

  Moreover, in order to produce this metal primer, for example, a polyhydric phenol compound, an amine compound, and, if necessary, a pH adjuster are blended. Preferably, a polyhydric phenol compound, an amine compound, and, if necessary, a pH adjuster and a solvent are blended to prepare a metal primer as a composition solution (varnish). Examples of the solvent include an aqueous solvent such as water, an alcohol such as methanol and ethanol, a ketone solvent such as methyl ethyl ketone, and an ester solvent such as ethyl acetate, preferably an aqueous solvent, more preferably Water is mentioned.

  Specifically, a polyhydric phenol compound, an amine compound, and, if necessary, a pH adjuster are dissolved in a solvent to prepare a metal primer as an aqueous composition solution.

  The solvent is blended in the metal primer so as to be, for example, 60% by mass or more, preferably 70% by mass or more, and for example, 99% by mass or less, preferably 95% by mass or less.

It should be noted that the metal undercoat can be added with an additive at an appropriate ratio within a range that does not impair the effects of the present invention. Additives are not particularly limited, for example, epoxy resins, curing catalysts, leveling agents, antifoaming agents, stabilizers such as antioxidants and UV absorbers, plasticizers, surfactants, pigments, fillers, organic Alternatively, inorganic fine particles, antifungal agents, silane coupling agents and the like can be mentioned.
Laminated body Next, the various laminated body provided with the undercoat layer prepared using the above-mentioned undercoat for metals is demonstrated with reference to FIGS.
1st laminated body As shown in FIG. 1, the 1st laminated body 11 has a sheet | seat shape (film shape or plate shape) extended in the direction orthogonal to the thickness direction. The first stacked body 11 includes a metal layer 1 as an example of a metal and an undercoat layer 2. Preferably, the first laminated body includes only the metal layer 1 and the undercoat layer 2.

  The metal layer 1 has a sheet shape (film shape or plate shape) extending in a direction orthogonal to the thickness direction. Examples of the material of the metal layer 1 include metals such as aluminum, iron, and alloys thereof (for example, aluminum alloys), preferably aluminum-based metals such as aluminum and aluminum alloys, and more preferably. And aluminum. The thickness of the metal layer 1 is not specifically limited, For example, they are 1 micrometer or more and 10 mm or less.

  The undercoat layer 2 is directly disposed on one surface of the metal layer 1 (specifically, one surface in the thickness direction, the same applies hereinafter). Specifically, the undercoat layer 2 is in contact with one surface of the metal layer 1. The undercoat layer 2 has a thin film shape that extends along one surface of the metal layer 1.

  The undercoat layer 2 is prepared from the above-described metal undercoat. Specifically, the undercoat layer 2 is a reaction product of a metal undercoat. Specifically, the hydroxyl group of the polyhydric phenol compound forms a hydrogen bond with the metal layer 1 and reacts with the COO-containing portion of the polyhydric phenol compound and the primary amino group of the amine compound to form an amide bond. Reaction product.

  The molar ratio (N / C) of nitrogen atoms to carbon atoms in the undercoat layer 2 is, for example, 0.2 or more, preferably 0.3 or more, and, for example, 0.5 or less, preferably 0.45 or less. The above molar ratio (N / C) is determined by XPS analysis. If the molar ratio of the nitrogen atom to the carbon atom is equal to or greater than the lower limit described above, a reaction product of a polyhydric phenol compound and an amine compound that is excellent in adhesiveness with a metal can be obtained. If the molar ratio of the nitrogen atom to the carbon atom is equal to or less than the above upper limit, a reaction product of a polyhydric phenol compound and an amine compound that is excellent in adhesiveness with a metal can be obtained.

The thickness of the undercoat layer 2 is, for example, 1 nm or more, preferably 10 nm or more, and for example, 5 μm or less, preferably 1 μm or less. The basis weight of the undercoat layer 2 is, for example, 0.01 g / m ² or more, preferably 0.1 g / m ² or more, and for example, 5 g / m ² or less, preferably 1 g / m ^2. It is as follows.

  In order to obtain the first laminate 11, for example, a varnish of a metal primer is applied to one surface of the metal layer 1 using a known coating device such as a bar coater.

  Thereafter, when the metal primer contains a solvent, the solvent is removed by heating and drying. The heating conditions are not particularly limited, and the temperature is, for example, 50 ° C. or higher, preferably 80 ° C. or higher, for example, 150 ° C. or lower, preferably 120 ° C. or lower, and the time is, for example, 0 1 minute or more, preferably 0.5 minutes or more, for example, 300 minutes or less, preferably 5 minutes or less.

  Thereby, the 1st laminated body 11 is obtained.

  The thickness of the 1st laminated body 11 is the sum total of the thickness of the metal layer 1 and the undercoat layer 2, for example, is 2 micrometers or more and 10 mm or less.

  This 1st laminated body 11 can be used as a 1st decorating film provided with the undercoat 2 as a 1st coating layer, for example.

The first laminated body 11 is, for example, a car interior / exterior member, for example, a surface cosmetic material such as an emblem, for example, various parts such as a case of an information appliance such as a mobile phone or a camera, a housing, a button, for example, a furniture exterior material. , For example, interior materials for buildings such as bathrooms, walls, ceilings, floors, etc., exterior walls such as siding, exterior materials for buildings such as fences, roofs, gates, windbreak boards, for example, window frames, doors, handrails, sills, It is used in various other applications such as surface decorative materials for furniture such as Kamoi, for example, members for interior and exterior of various vehicles other than automobiles such as trains, airplanes, and ships.
2nd laminated body As shown in FIG. 2, the 2nd laminated body 12 containing the adhesive bond layer 3 can be obtained using the 1st laminated body 11 subsequently.

  The second laminate 12 has a sheet shape (film shape or plate shape) extending in a direction orthogonal to the thickness direction. The 2nd laminated body 12 is equipped with the metal layer 1, the undercoat layer 2, and the adhesive bond layer 3 in order toward the thickness direction one side. Specifically, the second laminated body 12 includes a metal layer 1, an undercoat layer 2 disposed on one surface thereof, and an adhesive layer 3 disposed on one surface thereof. Preferably, the second laminate 12 includes only the metal layer 1, the undercoat layer 2, and the adhesive layer 3.

  It does not specifically limit as a material of the adhesive bond layer 3, Well-known adhesive agents (coating agent), such as a laminating adhesive agent, are mentioned. Specifically, as an adhesive, for example, polyolefin adhesive, acrylic adhesive, polyester adhesive, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, rubber adhesive, silicone, etc. System adhesives and the like. These can be used alone or in combination. Preferably, polyolefin adhesive is used.

  Examples of polyolefin adhesives include adhesives containing olefin polymers described in, for example, JP-A-8-319324 and WO2013 / 164976, such as WO2016 / 080297. And an adhesive containing a hydrocarbon-based synthetic oil, for example, an adhesive containing a modified olefin polymer, a polyisocyanate (curing agent), and a hydrocarbon-based synthetic oil, described in WO2014 / 123183, etc. Examples thereof include an adhesive containing a modified olefin polymer described in WO2017 / 126520 and a crosslinking agent. In addition, a polyolefin-type adhesive agent can contain an olefin polymer or a modified olefin polymer as an essential component among the above illustrations, and can contain other components in combination as appropriate.

  The thickness of the adhesive layer 3 is, for example, 0.5 μm or more, and is, for example, 20 μm or less, preferably 5 μm or less.

  The ratio of the thickness of the undercoat layer 2 to the thickness of the adhesive layer 3 (the thickness of the undercoat layer 2 / the thickness of the adhesive layer 3) is, for example, 0.00005 or more, preferably 0.002 or more. For example, it is 10 or less, preferably 2 or less.

  The adhesive layer 3 is directly formed on one surface of the undercoat layer 2. For example, an adhesive is applied to one surface of the undercoat layer 2 and then dried as necessary. Alternatively, after the adhesive layer 3 is formed on one surface of a release sheet (not shown), it can be attached (transferred) to one surface of the undercoat layer 2.

This 2nd laminated body 12 can be used as a 2nd decorating film provided with the adhesive bond layer 3 as a 2nd coating layer, for example.
3rd laminated body As shown in FIG. 3, the 3rd laminated body 13 containing the to-be-adhered body 4 can be obtained using the 2nd laminated body 12. As shown in FIG.

  The third laminated body 13 is an adhesive laminated body including an adherend 4 that is bonded and fixed to the metal layer 1 via the undercoat layer 2 and the adhesive layer 3. Specifically, the metal layer 1, the undercoat layer 2, the adhesive layer 3, and the adherend 4 are sequentially provided toward one side in the thickness direction. Specifically, the third laminated body 13 includes a metal layer 1, an undercoat layer 2 disposed on one surface thereof, an adhesive layer 3 disposed on one surface thereof, and an adherend 4 on one surface thereof. With. Preferably, the third laminate 13 includes only the metal layer 1, the undercoat layer 2, the adhesive layer 3, and the adherend 4.

  The adherend 4 has, for example, a sheet shape (film shape or plate shape) extending in a direction orthogonal to the thickness direction. The adherend 4 includes, for example, an adherend surface that is an example of the other surface facing the one surface of the metal layer 1 and an exposed surface that is an example of the one surface exposed on one side in the thickness direction. Note that the adherend surface may be subjected to a treatment such as a corona treatment.

  The material of the adherend 4 is not particularly limited. For example, a polyolefin material such as PP, for example, a polar resin such as ABS, PC, PET, PPS, and acrylic resin, for example, an ED steel plate, Mg alloy, SUS (stainless steel). ), Inorganic materials such as aluminum, aluminum alloys, and glass. The material of the adherend 4 is preferably a polyolefin material. The thickness of the adherend 4 is not particularly limited, and is, for example, 1 μm or more, preferably 2 μm or more, and for example, 10 mm or less, preferably 5 mm or less.

  In order to arrange the adherend 4 on one surface of the adhesive layer 3, the adherend surface of the adherend 4 is brought into contact with one surface of the adhesive layer 3. At this time, the contact may be performed while heating the undercoat layer 2 (and the adhesive layer 3). The heating temperature is, for example, 80 ° C. or higher, preferably 100 ° C. or higher, and for example, 200 ° C. or lower, preferably 180 ° C. or lower.

  As a result, the undercoat layer 2 and the adhesive layer 3 are interposed between the metal layer 1 and the adherend 4. That is, the 3rd laminated body 13 by which the metal layer 1, the undercoat layer 2, the adhesive bond layer 3, and the to-be-adhered body 4 are arrange | positioned in order at the thickness direction one side is obtained.

  The thickness of the 3rd laminated body 13 is 2 micrometers or more, for example, Preferably, it is 30 micrometers or more, for example, is 5 mm or less, Preferably, it is 15 mm or less.

  Alternatively, the adhesive layer 3 may be formed in advance on the other surface of the adherend 4 and bonded to the undercoat layer 2 in the first laminate 11 to obtain the third laminate 13.

  Thereafter, the third laminate 13 is heated to promote at least the reaction of the undercoat layer 2.

  As heating conditions, for example, 80 ° C. or less, preferably 70 ° C. or less, and for example, at a low temperature of 40 ° C. or more, for example, 1 day or more, preferably 3 days or more, for example, 7 days or less. A method of curing for a long time (low temperature curing method) can be mentioned.

  By the heating described above, the reaction of the adhesive layer 3 proceeds as necessary.

  And in the above-mentioned undercoat for metals, it can react with the COO containing part in a polyhydric phenol compound, and the primary amino group in an amine compound, and can form a firm amide bond.

  On the other hand, in the polyhydric phenol compound, the two hydroxyl groups are directly bonded to the two carbon atoms adjacent to each other in the aromatic ring. Can do.

  Therefore, this metal primer can increase the strength of the resulting primer layer 2. That is, the 1st laminated body 11, the 2nd laminated body 12, and the 3rd laminated body 13 provided with the undercoat 2 excellent in intensity | strength can be obtained.

  Therefore, a third laminate in which a metal undercoat is applied to one surface of the metal layer 1 to form an undercoat layer 2, and an adhesive layer 3 and an adherend 4 are disposed on one side of the metal layer 1. 13, the adhesion strength of the adherend 4 to the metal layer 1 can be improved.

  However, there is a need for a metal primer that does not contain heavy metals and has a low environmental impact. However, as described above, this metal primer has excellent strength without containing heavy metals. Therefore, it is used for various applications as a metal primer having a low environmental load.

  Moreover, in the 2nd laminated body 12, the adhesive strength of the adhesive bond layer 3 is excellent.

  Further, in the first laminated body 11, the undercoat layer 2 is bonded to the metal layer 1 of the adhesive layer 3 in the second laminated body 12, and in other words, the adhesion of the adherend 4 to the metal layer 1 in the third laminated body 13. Strength can be improved.

Battery case packaging material, high alkaline solution packaging material and alcohol-containing solution packaging material The third laminate 13 is, for example, a battery case packaging material excellent in adhesive strength and electrolytic solution resistance, and in adhesive strength and alkali resistance. It is suitably used as a packaging material for an excellent alkaline solution, and further as a packaging material for an alcohol-containing solution having excellent adhesive strength and alcohol resistance.
Battery Case Packaging Material Next, the battery case packaging material will be described with reference to FIG. In FIG. 4, the upper side on the paper surface will be described as the outside (an example on one side in the thickness direction), and the lower side on the paper surface will be described as the inner side (an example on the other side in the thickness direction).

  As shown in FIG. 4, the battery case packaging material 21 is interposed between the base material 5, the inner layer 6 bonded to the inside of the base material 5, and the base material 5 and the inner layer 6. 5 and the inner adhesive layer 7 that is interposed between the base material 5 and the inner layer 6 and that contacts the inner layer 6.

  The battery case packaging material 21 includes an outer layer 8 bonded to the outside of the base material 5 and an outer adhesive layer 9 interposed between the base material 5 and the outer layer 8.

  The substrate 5 is a metal substrate corresponding to the metal layer 1 described above. As the base material 5, Preferably, aluminum foil and stainless steel foil are mentioned.

  The inner layer 6 corresponds to the adherend described above. It does not specifically limit as a material of the inner layer 6, For example, a polyolefin film is mentioned.

  The undercoat layer 2 is in contact with the inner surface of the substrate 5.

  The inner adhesive layer 7 corresponds to the adhesive layer 3 described above. The inner adhesive layer 7 is in contact with the undercoat layer 2.

  The outer layer 8 is not particularly limited, and examples thereof include a polyester film, a polyamide film, and a polypropylene film.

  The outer adhesive layer 9 is not particularly limited, and examples thereof include an arbitrary adhesive layer such as an adhesive layer for dry lamination and a solventless adhesive layer.

  In this battery case packaging material 21, the inner layer 6, the inner adhesive layer 7, the undercoat layer 2, the base material 5, the outer adhesive layer 9 and the outer layer 8 are arranged in order from the inner side to the outer side.

The thickness of the battery case packaging material 21 is, for example, 60 μm or more and 160 μm or less.
Battery Next, a battery including a battery case packaging material will be described with reference to FIG.

  As shown in FIG. 5, the battery 10 includes a battery case packaging material 21 and an electrolytic solution 31 packaged in the battery case packaging material 21. Further, the battery 10 includes a positive electrode 17, a negative electrode 18, and a separator 19 that are accommodated in a battery case packaging material 21.

  The battery case packaging material 21 is configured in a bag shape so that the electrolyte solution 31 described below contacts the inner surface of the inner layer 6 of the battery case packaging material 21. Specifically, the battery case packaging material 21 wraps the electrolytic solution 31 so that the inner layer 6 contacts the electrolytic solution 31.

  The electrolytic solution 31 is not particularly limited, and includes, for example, lithium salts such as ethylene carbonate, diethyl carbonate and dimethyl carbonate, and lithium hexafluorophosphate.

  The positive electrode 17 and the negative electrode 18 are disposed opposite to each other so as to be in contact with the electrolytic solution 31 and spaced from each other. The separator 19 is disposed so as to be sandwiched between the positive electrode 17 and the negative electrode 18.

  The battery 10 described above is used as, for example, a lithium ion secondary battery, and in that case, the battery case packaging material 21 is used as a lithium ion secondary battery case packaging material.

  As shown in FIGS. 4 and 5, in the battery case packaging material 21 and the battery 10, the adhesive strength between the base material 5 and the inner layer 6 is excellent.

Specifically, as shown in FIG. 4, the undercoat layer 2 and the inner adhesive layer 7 in the battery case packaging material 21 have excellent electrolytic solution resistance. That is, even when the battery case packaging material 21 is used over a long period of time, in particular, it is possible to effectively prevent a decrease in the adhesive strength between the undercoat layer 2 and the inner adhesive layer 7. The battery case packaging material 21 is excellent in long-term reliability.
High Alkaline Solution Packaging and Package Next, the high alkaline solution packaging will be described with reference to FIG. In FIG. 6, the upper side of the paper surface will be described as the outside (an example of one side in the thickness direction), and the lower side of the paper surface will be described as the inner side (an example of the other side in the thickness direction).

  The packaging material 27 for high alkali solution is interposed between the base material 5, the inner layer 6 bonded to the inside of the base material 5, the base material 5 and the inner layer 6, and is in contact with the base material 5 as described above. An undercoat layer 2 and an inner adhesive layer 7 that is interposed between the base material 5 and the inner layer 6 and contacts the inner layer 6 are provided. The undercoat layer 2 and the inner adhesive layer 7 are in contact with each other.

  The base material 5, the inner layer 6, the undercoat layer 2, and the inner adhesive layer 7 have the same configurations as those in the battery case packaging material 21.

  In the packaging material 27 for high alkali solution, the inner layer 6, the inner adhesive layer 7, the undercoat layer 2, and the base material 5 are arranged in this order.

  The thickness of the highly alkaline solution packaging material 27 is, for example, 30 μm or more and 200 μm or less.

  Next, a packaging body provided with the above-described packaging material for a highly alkaline solution will be described with reference to FIG.

  As shown in FIG. 7, the package 15 includes a high alkaline solution packaging material 27 and a high alkaline solution 32 packaged in the high alkaline solution packaging material 27.

  The highly alkaline solution packaging material 27 is provided in a bag shape so that the highly alkaline solution 32 described below is in contact with the inner surface of the inner layer 6 of the packaging material for high alkali solution 27.

  The highly alkaline solution 32 is a solution having a pH of, for example, 9 or more, preferably 10 or more, and for example, 14 or less. Examples of the highly alkaline solution include alkaline detergents and hair treatment agents.

  Further, as shown in FIGS. 6 and 7, in the packaging material 27 for high alkali solution and the package 15 including the same, the adhesive strength between the base material 5 and the inner layer 6, and the packaging material 27 for high alkali solution Excellent alkali resistance.

Specifically, the undercoat layer 2 and the inner adhesive layer 7 in the packaging material 27 for the highly alkaline solution have excellent alkali resistance. That is, even if the packaging material 27 for the high alkaline solution is used for the packaging body 15 over a long period of time, in particular, it is possible to effectively prevent a decrease in the adhesive strength between the undercoat layer 2 and the inner adhesive layer 7. The highly alkaline solution packaging material 27 and the package 15 including the same are excellent in long-term reliability.
Next, an alcohol-containing solution packaging material will be described with reference to FIG.

  The alcohol-containing solution packaging material 28 includes a base material 5, an inner layer 6 bonded to the inside of the base material 5, and an undercoat layer interposed between the base material 5 and the inner layer 6 and in contact with the base material 5. 2 and an inner adhesive layer 7 that is interposed between the base material 5 and the inner layer 6 and contacts the inner layer 6.

  The base material 5, the inner layer 6, the undercoat layer 2, and the inner adhesive layer 7 have the same configurations as those in the battery case packaging material 21.

  The thickness of the packaging material 28 for an alcohol-containing solution is, for example, 30 μm or more and 200 μm or less.

  Next, a package including a packaging material for an alcohol-containing solution will be described with reference to FIG.

  As shown in FIG. 7, the package 15 includes an alcohol-containing solution packaging material 28 and an alcohol-containing solution 33 packaged in the alcohol-containing solution packaging material 28.

  The alcohol-containing solution packaging material 28 is provided in a bag shape so that the alcohol-containing solution 33 described below contacts the inner surface of the inner layer 6 of the alcohol-containing solution packaging material 28.

  Examples of the alcohol contained in the alcohol-containing solution 33 include methanol, ethanol, propanol, and ethylene glycol. The content ratio of the alcohol to the alcohol-containing solution 33 is, for example, 3% by mass or more, preferably 5% by mass or more, and for example, 95% by mass or less, preferably 80% by mass or less.

  Further, as shown in FIGS. 6 and 7, in the alcohol-containing solution packaging material 28 and the packaging body 15 including the same, the adhesive strength between the base material 5 and the inner layer 6, and the alcohol-containing solution packaging material 28. Excellent alcohol resistance.

  Specifically, the undercoat layer 2 and the inner adhesive layer 7 in the alcohol-containing solution packaging material 28 have excellent alcohol resistance. In other words, even when the alcohol-containing solution packaging material 28 is used for a long period of time in the package 15, it is possible to effectively prevent a decrease in the adhesive strength between the undercoat layer 2 and the inner adhesive layer 7 in particular. The alcohol-containing solution packaging material 28 and the package 15 including the same are excellent in long-term reliability.

Modified Examples In the following modified examples, members and processes similar to those of the above-described embodiment are given the same reference numerals, and detailed descriptions thereof are omitted. Moreover, each modification can have the same operational effects as those of the embodiment, unless otherwise specified. Furthermore, one embodiment and its modification examples can be combined as appropriate.

  In the above description, in the first stacked body 11, the second stacked body 12, and the third stacked body 13, the metal layer 1 is cited as an example of the metal. However, the metal is not limited to this, and is not illustrated, for example. However, metal particles may be used. The shape of the metal particles is not particularly limited, and examples thereof include a spherical shape and an indefinite shape.

  Although not shown, in this case, the undercoat layer 2 is disposed on the surface (circumferential surface) of the metal particles.

  Furthermore, the adhesive layer 3 can be disposed on the surface of the undercoat layer 2, and a coating layer as an adherend can be disposed on the surface of the adhesive layer 3. Thereby, the covering structure particle | grains provided with a metal particle, the undercoat layer 2, the adhesive bond layer 3, and a coating layer can also be obtained.

  Specific numerical values such as blending ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and the corresponding blending ratio (content ratio) ), Physical property values, parameters, etc. may be replaced with the upper limit values (numerical values defined as “less than” or “less than”) or lower limit values (numbers defined as “greater than” or “exceeded”). it can.

Production Example 1
(Production of maleic anhydride-modified propylene / 1-butene copolymer (C-1))
A maleic anhydride-modified propylene / 1-butene copolymer (C-1) was prepared according to the description in the examples of WO2016 / 080297. Specifically, it is as follows.

A 2 liter autoclave thoroughly purged with nitrogen was charged with 900 ml of hexane and 80 g of 1-butene, 1 mmol of triisobutylaluminum was added, the temperature was raised to 70 ° C., and propylene was supplied to give a total pressure of 7 kg / cm ² G Then, 0.30 mmol of methylaluminoxane, 0.001 mmol of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride in terms of Zr atom was added, and propylene was continuously added. The polymerization was carried out for 30 minutes while supplying and maintaining the total pressure at 7 kg / cm ² G. After the polymerization, the mixture was deaerated and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours to obtain a propylene / 1-butene copolymer. The content rate of the structural unit derived from propylene was 73.5 mol%.

  Subsequently, 3 kg of propylene / 1-butene copolymer was added to 10 L of toluene, and the temperature was raised to 145 ° C. in a nitrogen atmosphere to dissolve the propylene / 1-butene copolymer in toluene. Further, 382 g of maleic anhydride and 175 g of di-tert-butyl peroxide were supplied to the system over 4 hours under stirring, and then stirred at 145 ° C. for 2 hours. After cooling, a large amount of acetone was added to precipitate the maleic anhydride-modified propylene / 1-butene copolymer, filtered, washed with acetone, and then vacuum dried. Thereby, maleic anhydride-modified propylene / 1-butene copolymer (C-1) was obtained. The modification amount of maleic anhydride was 1% by mass in the maleic anhydride-modified propylene / 1-butene copolymer (C-1).

Production Example 2
(Synthesis of hydrocarbon-based synthetic oil (E-1))
A hydrocarbon-based synthetic oil (E-1) was prepared. Specifically, it is as follows.

To a continuous polymerization reactor equipped with stirring blades sufficiently purged with nitrogen, 1 liter of dehydrated and purified hexane was added, and ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl _1.5 ) adjusted to 96 mmol / L was added. After continuously supplying the hexane solution in an amount of 500 ml / h for 1 hour, a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 16 mmol / l as a catalyst was further added at 500 ml / h, and hexane was continuously supplied at 500 ml / h. Supplied. On the other hand, from the upper part of the polymerization vessel, the polymerization solution was continuously extracted so that the polymerization solution in the polymerization vessel was always 1 liter. Next, ethylene gas was supplied at a rate of 47 L / h, propylene gas at 47 L / h, and hydrogen gas at 20 L / h using a bubbling tube. A refrigerant was circulated through a jacket attached to the outside of the polymerization vessel to carry out a copolymerization reaction at 35 ° C. The obtained polymer solution was deashed with hydrochloric acid, poured into a large amount of methanol and precipitated, and then dried under reduced pressure at 130 ° C. for 24 hours to prepare a hydrocarbon-based synthetic oil composed of an ethylene / propylene copolymer ( E-1) was obtained. The content rate of the structural unit derived from ethylene was 55.9 mol%.

Example 1
2 g of polyhydric phenol compound (tannic acid AL) (hydrolyzable tannin represented by formula (11)) (A-1) described in Table 1 and amine compound (epomine P-1000) described in Table 2 (Polyethyleneimine represented by formula (16)) (B-1) 3 g and formic acid (pH adjuster) (F-1) 0.45 g were dissolved in distilled water 44.45 g to obtain a metal primer. A composition aqueous solution was prepared.

  Separately, 80 g of maleic anhydride-modified propylene / 1-butene copolymer (C-1) and 20 g of a hydrocarbon-based synthetic oil (E-1) were dissolved in 320 g of methylcyclohexane and 80 g of ethyl acetate. An olefin polymer varnish (1) was prepared, and 0.5 g of polyisocyanate (curing agent) (D-1) (Desmodur N 3300 (HDI Trimmer, manufactured by Covestro) was added to 50 g of the modified olefin polymer varnish (1). Mixing was performed to prepare a laminating adhesive.

Thereafter, an aqueous composition composition of the metal primer is applied to one surface of the metal layer 1 made of an aluminum foil having a thickness of 30 μm so that the basis weight of the primer layer 2 is 1 g / m ² using a bar coater. 25 ° C.), and the solvent was removed by drying at 100 ° C. for 1 minute to form an undercoat layer 2. That is, the 1st laminated body 11 provided with the metal layer 1 and the undercoat 2 was produced.

Subsequently, a laminating adhesive was applied to one surface of the undercoat layer 2 using a bar coater so that the basis weight of the resulting adhesive layer 3 was 3.3 g / m ² , and 100 ° C. for 1 minute. The adhesive layer 3 was formed on one surface of the undercoat layer 2 by drying. That is, the 2nd laminated body 12 provided with the metal layer 1, the undercoat layer 2, and the adhesive bond layer 3 was produced.

  Thereafter, the exposed surface of the obtained adhesive layer 3 and the corona-treated surface of the adherend 4 made of an unstretched polypropylene film (CPP, single-sided corona-treated product) having a thickness of 60 μm are pasted on a hot stage at 100 ° C. In addition, by curing at 60 ° C. for 3 days, the undercoat layer 2 and the adhesive layer 3 were reacted, and the substrate 1 and the adherend 4 were adhered. Thereby, the 3rd laminated body 13 by which the base material 1, the undercoat layer 2, and the adhesive bond layer 3 were laminated | stacked in order was obtained.

  In addition, the details (prescriptions, etc.) of each layer are described in Table 3 and later.

Examples 2 to 15 and Comparative Examples 1 to 12
A third laminate 13 was obtained in the same manner as in Example 1 except that the formulation was changed according to the descriptions in Tables 1 to 7.

  In addition, lignin (A-3), rutin (A-4), quercetin dihydrate (A-5), which are phenol compounds in the comparative examples (phenol compounds not included in the polyhydric phenol compound of the present invention) and The chemical formulas of 4-hydroxybenzoic acid (A-6) are represented by the following formulas (20) to (23), respectively.

Further, polyallylamine PAA-HCl-3L (B-5), polyamine PAS-21 (B-7), polyamine PAS-M-, which are amine compounds in the comparative examples (amine compounds not included in the amine compound of the present invention). Chemical formulas of 1 (B-8) and polyamine AS-410C (B-9) are represented by the following formulas (25) to (28), respectively.

Evaluation The following physical properties were measured. The results are shown in Tables 1-7.

Adhesive strength of the third laminated body The third laminated body 13 was cut into a size of 60 mm in length and 15 mm in width to produce a test piece, and this test piece was subjected to a crosshead speed of 50 mm / mm using a universal tensile measuring device. In minutes, a 180 ° peel test was performed to measure the initial bond strength of the third laminate 13.

The pH of the composition aqueous solution of the metal primer and the pH of the composition aqueous solution of the metal primer were measured with a pH meter. Moreover, about Examples 12-15, after leaving still the composition aqueous solution of a metal primer for 3 days at room temperature (25 degreeC), the state was observed visually and stability was evaluated on the following references | standards.
A: A clear solution.
Δ: Suspended solution.
X: Precipitation was observed.

N / C ratio of undercoat layer The molar ratio (N / C) of nitrogen atoms to carbon atoms in the undercoat layer 2 was determined by XPS analysis.

DESCRIPTION OF SYMBOLS 1 Metal layer 2 Undercoat layer 3 Adhesive layer 4 To-be-adhered body 11 The 1st laminated body 12 The 2nd laminated body 13 The 3rd laminated body 27 The packaging material for high alkali solutions 28 The packaging material for alcohol containing solutions 31 Electrolyte solution 32 High alkaline solutions 33 Alcohol-containing solution

Claims (16)

Containing a polyhydric phenol compound and an amine compound;
The polyhydric phenol compound is
An aromatic ring,
Two hydroxyl groups directly connected to two carbon atoms adjacent to each other in the aromatic ring;
Containing at least one selected from the group consisting of a COO bond and a carboxyl group,
The amine compound has a weight average molecular weight of 1 × 10 ³ or more and contains a primary amino group.   The metal primer according to claim 1, comprising three hydroxyl groups directly connected to the aromatic ring.   3. The metal according to claim 1, wherein a ratio of the polyhydric phenol compound is 20% by mass or more and 80% by mass or less based on a total of the polyhydric phenol compound and the amine compound. For undercoat.   The metal undercoat according to any one of claims 1 to 3, further comprising an organic acid.   The metal primer according to claim 4, wherein the pH is 1 or more and 4 or less. The metal primer according to claim 1, wherein the amine compound has a weight average molecular weight of 100 × 10 ³ or less.   The metal primer according to any one of claims 1 to 6, wherein the amine value of the amine compound is 4 or more and 30 or less. A metal substrate;
A laminate comprising an undercoat layer formed on one surface of the metal substrate and prepared from the metal undercoat according to any one of claims 1 to 7.   The laminate according to claim 8, further comprising an adhesive layer disposed on one surface of the undercoat layer.   The laminate according to claim 9, further comprising an adherend disposed on one surface of the adhesive layer.   It is a packaging material for battery cases, The laminated body of Claim 10 characterized by the above-mentioned. The laminate according to claim 11, which is a packaging material for a battery case,
An electrolyte solution packaged in the battery case packaging material,
At least a part of the adherend of the battery case packaging material is in contact with the electrolytic solution.   It is a packaging material for highly alkaline solutions, The laminated body of Claim 10 characterized by the above-mentioned. The laminate according to claim 13, which is a packaging material for a highly alkaline solution,
A packaging body comprising a solution having a pH of 9 or more that is packaged in the packaging material for a highly alkaline solution.   It is a packaging material for alcohol containing solutions, The laminated body of Claim 10 characterized by the above-mentioned. The laminate according to claim 15, which is a packaging material for an alcohol-containing solution,
A package comprising: an alcohol-containing solution packaged in the alcohol-containing solution packaging material.

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