JP5365082B2 - Polyhydrazone compound, method for producing the same, and metal rust preventive comprising polyhydrazone compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer which is a decomposable polymer and has an anticorrosive effect on metals, and to provide a method for producing the same. <P>SOLUTION: A polymer is provided which includes using, as anticorrosive agents for metals, a polyhydrazone compound represented by general formula (1) obtained by dehydration condensation of a polycarbonyl compound with a hydrazine derivative. [Wherein, X, Y, R<SB>1</SB>, and R<SB>2</SB>each independently represents a hydrogen atom, 1-18C alkyl group, 5-10C aromatic group, 5-10C aromatic group in which 1-3 hydrogen atoms on its aromatic ring are substituted with a 1-4C alkyl group, or 1-4C alkyl group in which 1-3 hydrogen atoms are substituted with a 5-10C aromatic group]. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a polyhydrazone compound, a method for producing the same, and a metal rust preventive comprising the polyhydrazone compound.

  A method of coating a metal surface with a polymer for the purpose of preventing rust on the metal surface is well known. The coating with polymer has various functions such as antifouling, abrasion stability, antistatic, adhesiveness, antibacterial, paint adhesion, water repellency, oil repellency, gas barrier property, etc. on the metal surface at the same time. Can be granted. The polymer used as the coating agent varies depending on the function to be imparted to the metal surface, but includes, for example, fluororesin, acrylic resin, silicone, polyamide, polyester, polyurethane, and the like.

  However, the removability of the coating itself is not generally considered, and there is a problem that such a coating layer cannot be easily removed in a scene where the base metal is to be recycled or discarded.

  Therefore, a method using a degradable polymer as a coating agent has been studied.

  For example, a method of providing an aliphatic polyester resin layer known as a biodegradable polymer on a paper substrate (for example, see Patent Document 1), a method of applying a polylactic acid resin to an underwater structure (for example, see Patent Document 2) Etc.

  However, since these biodegradable polymers do not have hetero atoms that enhance adhesion to metals in their molecular structure, they have a problem that they have poor gas barrier properties and cannot be expected to have a rust prevention effect.

  In addition, a method of using an acrylic copolymer known as a photodegradable polymer as a pressure sensitive adhesive for semiconductor parts or the like (for example, see Patent Document 3) is also known.

  However, even in the case of this polymer, the adsorptive power to metal is not sufficient, and there has been no use as a metal rust preventive.

Japanese Patent Application Laid-Open No. 07-266752 Japanese Patent Laid-Open No. 04-120183 JP-A-63-260912

  This invention is made | formed in view of said background art, The objective is to provide the polymer which is a degradable polymer and has the antirust effect with respect to a metal.

  As a result of intensive studies on a polymer that is a degradable polymer and has a rust-preventing effect on metals, the inventor has obtained a specific polyhydrazone compound obtained by dehydration condensation of a specific polycarbonyl compound and a hydrazine derivative. It has been found that the above-mentioned problems can be solved by using it as a rust inhibitor for metals, and the present invention has been completed.

  That is, this invention is a rust preventive agent for metals which consists of a polyhydrazone compound as shown below, its manufacturing method, and a polyhydrazone compound.

  [1] A polyhydrazone compound containing one or more structural units represented by the following general formula (1) and having a number average molecular weight (Mn) in the range of 100 to 1,000,000 in terms of polystyrene.

[In General Formula (1), X, Y, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or 1 carbon atom. An aromatic group having 5 to 10 carbon atoms in which 1 to 3 hydrogen atoms on the aromatic ring are substituted with 1 to 4 alkyl groups, or carbon in which 1 to 3 hydrogen atoms are substituted with an aromatic group having 5 to 10 carbon atoms The alkyl group of number 1-4 is represented. ]
[2] In the general formula (1), X, Y, R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic group having 3 to 18 carbon atoms. An alkyl group, an aromatic group having 5 to 10 carbon atoms, an aromatic group having 5 to 10 carbon atoms in which hydrogen on the aromatic ring is substituted by 1 to 3 by a methyl group, and a hydrogen atom having 1 to 3 substituents by a phenyl group The polyhydrazone compound as described in [1] above, which represents a methyl group or an ethyl group in which a hydrogen atom is substituted by 1 to 3 with a phenyl group.

[3] In the general formula (1), X, Y, and R ₁ each independently represent a hydrogen atom or a methyl group, and R ₂ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or i-propyl. Group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, i-hexyl Group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclohexyl group, phenyl group, 4-methylphenyl group, benzyl group, or 2- The polyhydrazone compound as described in [1] or [2] above, which represents a phenylethyl group.

  [4] The following general formula (2)

[In General Formula (2), X and Y are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An aromatic group having 5 to 10 carbon atoms in which 1 to 3 hydrogen atoms on the aromatic ring are substituted, or an alkyl having 1 to 4 carbon atoms in which 1 to 3 hydrogen atoms are substituted with an aromatic group having 5 to 10 carbon atoms Represents a group. ]
And a polycarbonyl compound having a number average molecular weight (Mn) in the range of 100 to 1,000,000 in terms of polystyrene, and the following general formula (3):

[In General Formula (3), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or an alkyl having 1 to 4 carbon atoms. Group having 5 to 10 carbon atoms substituted with 1 to 3 hydrogen atoms on the aromatic ring, or 1 to 4 carbon atoms having 1 to 3 hydrogen atoms substituted with an aromatic group having 5 to 10 carbon atoms Represents an alkyl group. ]
The method for producing a polyhydrazone compound according to any one of the above [1] to [3], wherein the dehydration condensation is performed with a hydrazine derivative represented by the formula:

[5] In the general formula (2), X and Y are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, and a carbon number of 5 10 to 10 aromatic groups, an aromatic group having 5 to 10 carbon atoms in which hydrogen on the aromatic ring is substituted by 1 to 3 with a methyl group, a methyl group in which 1 to 3 hydrogen atoms are substituted with a phenyl group, or a phenyl group And in the general formula (3), R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, or a straight chain having 3 to 18 carbon atoms. A chain, branched or cyclic alkyl group, an aromatic group having 5 to 10 carbon atoms, an aromatic group having 5 to 10 carbon atoms in which hydrogen on the aromatic ring is substituted by 1 to 3 methyl groups, and a phenyl group. A methyl group substituted with 1 to 3 hydrogen atoms, or ethyl substituted with 1 to 3 hydrogen atoms with a phenyl group Method for producing Porihidorazon compound according to [4], which represents a.

[6] In general formula (2), represents a hydrogen atom or a methyl group, and in general formula (3), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, a methyl group, an ethyl group, n -Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neo-pentyl group, t-pentyl group, n -Hexyl group, i-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclohexyl group, phenyl group, 4-methylphenyl group , A benzyl group, or a 2-phenylethyl group, The method for producing a polyhydrazone compound according to the above [4].

  [7] A metal rust preventive containing the polyhydrazone compound according to any one of [1] to [3].

  The present invention provides a polyhydrazone compound, a method for producing the same, and a metal rust preventive comprising the polyhydrazone compound. The polyhydrazone compound of the present invention can be used as a rust preventive for metals and is an industrially extremely useful compound.

  The method for producing the polyhydrazone compound of the present invention does not require the installation of a special reaction apparatus, and can reduce capital investment and utility costs.

  Moreover, in this invention, since the polycarbonyl compound and the hydrazine derivative which can be obtained and manufactured at low cost are utilized as a raw material, it is excellent in cost performance.

  The present invention is described in further detail below.

  The polyhydrazone compound of the present invention is a compound containing one or more structural units represented by the general formula (1).

In the polyhydrazone compound of the present invention, when considering its decomposability and removability of decomposition products, in the structural unit represented by the general formula (1), X, Y, R ₁ and R ₂ are each independently A hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, and a methyl group having 1 to 3 hydrogen atoms on the aromatic ring It preferably represents a substituted aromatic group having 5 to 10 carbon atoms, a methyl group having 1 to 3 hydrogen atoms substituted with a phenyl group, or an ethyl group having 1 to 3 hydrogen atoms substituted with a phenyl group, In the general formula (1), X, Y, and R ₁ each independently represent a hydrogen atom or a methyl group, and R ₂ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n -Butyl group, i-butyl group, sec-butyl group, t- Tyl group, n-pentyl group, i-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n- More preferably, it represents a decyl group, an n-undecyl group, an n-dodecyl group, a cyclohexyl group, a phenyl group, a 4-methylphenyl group, a benzyl group, or a 2-phenylethyl group.

In the polyhydrazone compound of the present invention, specific examples of the polyhydrazone compound represented by the general formula (1) are not particularly limited. For example, the substituents X, Y, and R ₁ are hydrogen atoms. Specific examples include poly (propenaldehyde hydrazone), poly (propenaldehyde methyl hydrazone), poly (propenaldehyde ethyl hydrazone), poly (propenaldehyde n-propyl hydrazone), poly (propenaldehyde i-propyl hydrazone). , Poly (propenaldehyde n-butylhydrazone), poly (propenaldehyde i-butylhydrazone), poly (propenaldehyde sec-butylhydrazone), poly (propenaldehyde t-butylhydrazone), poly (propenaldehyde n-pentylhydrazone) ), Poly (propenaldehyde i-pentylhydrazone), poly (propenaldehyde neo-pentylhydrazone), poly (propenaldehyde t-pentylhydrazone), poly (propenaldehyde n-hexylhydrazone), poly (propenaldehyde i-hexylhydrazone) ), Poly (propenaldehyde n-heptylhydrazone), poly (propenaldehyde n-octylhydrazone), poly (propenaldehyde n-nonylhydrazone), poly (propenaldehyde n-decylhydrazone), poly (propenaldehyde n-undecyl) Hydrazone), poly (propenaldehyde n-dodecylhydrazone), poly (propenaldehyde cyclohexyl hydrazone), poly (propenaldehyde phenylhydrazone), poly [prope Aldehyde (4-methyl) phenylhydrazone], poly (propene aldehyde benzylhydrazone), poly [propene aldehyde (2-phenyl) ethyl hydrazone] and the like.

In the general formula (1), for example, the substituent X is a hydrogen atom, Y is a methyl group, and R ₁ is a hydrogen atom. Specifically, poly (2-methyl-2-propenaldehyde hydrazone) ), Poly (2-methyl-2-propenaldehyde methylhydrazone), poly (2-methyl-2-propenaldehyde ethylhydrazone), poly (2-methyl-2-propenaldehyde n-propylhydrazone), poly (2- Methyl-2-propenaldehyde i-propylhydrazone), poly (2-methyl-2-propenaldehyde n-butylhydrazone), poly (2-methyl-2-propenaldehyde i-butylhydrazone), poly (2-methyl- 2-propenaldehyde sec-butylhydrazone), poly (2-methyl-2-propenaldehyde t-butyl) Tilhydrazone), poly (2-methyl-2-propenaldehyde n-pentylhydrazone), poly (2-methyl-2-propenaldehyde i-pentylhydrazone), poly (2-methyl-2-propenaldehyde neo-pentylhydrazone) ), Poly (2-methyl-2-propenaldehyde t-pentylhydrazone), poly (2-methyl-2-propenaldehyde n-hexylhydrazone), poly (2-methyl-2-propenaldehyde i-hexylhydrazone), Poly (2-methyl-2-propenaldehyde n-heptylhydrazone), poly (2-methyl-2-propenaldehyde n-octylhydrazone), poly (2-methyl-2-propenaldehyde n-nonylhydrazone), poly ( 2-Methyl-2-propenaldehyde n-decylhi Razone), poly (2-methyl-2-propenaldehyde n-undecylhydrazone), poly (2-methyl-2-propenaldehyde n-dodecylhydrazone), poly (2-methyl-2-propenaldehyde cyclohexylhydrazone), Poly (2-methyl-2-propenaldehyde phenylhydrazone), poly [2-methyl-2-propenaldehyde (4-methyl) phenylhydrazone], poly (2-methyl-2-propenaldehyde benzylhydrazone), poly [2 -Methyl-2-propenaldehyde (2-phenyl) ethylhydrazone] and the like.

In the above general formula (1), for example, the substituents X and Y are hydrogen atoms and R ₁ is a methyl group. Specifically, poly (propenaldehyde-2,2-dimethylhydrazone), poly (Propenaldehyde-2-methyl-2-ethylhydrazone), poly (propenaldehyde-2-methyl-2-n-propylhydrazone), poly (propenaldehyde-2-methyl-2-i-propylhydrazone), poly ( Propenaldehyde-2-methyl-2-n-butylhydrazone), poly (propenaldehyde-2-methyl-2-i-butylhydrazone), poly (propenaldehyde-2-methyl-2-sec-butylhydrazone), poly (Propenaldehyde-2-methyl-2-t-butylhydrazone), poly (propenaldehyde-2-methyl) -2-n-pentylhydrazone), poly (propenaldehyde-2-methyl-2-i-pentylhydrazone), poly (propenaldehyde-2-methyl-2-neo-pentylhydrazone), poly (propenaldehyde-2- Methyl-2-t-pentylhydrazone), poly (propenaldehyde-2-methyl-2-n-hexylhydrazone), poly (propenaldehyde-2-methyl-2-i-hexylhydrazone), poly (propenaldehyde-2) -Methyl-2-n-heptylhydrazone), poly (propenaldehyde-2-methyl-2-n-octylhydrazone), poly (propenaldehyde-2-methyl-2-n-nonylhydrazone), poly (propenaldehyde- 2-methyl-2-n-decylhydrazone), poly (propene aldehyde) -2-methyl-2-n-undecylhydrazone), poly (propenaldehyde-2-methyl-2-n-dodecylhydrazone), poly (propenaldehyde-2-methyl-2-cyclohexylhydrazone), poly (propenaldehyde) -2-methyl-2-phenylhydrazone), poly [propenaldehyde-2-methyl-2- (4-methyl) phenylhydrazone], poly (propenaldehyde-2-methyl-2-benzylhydrazone), poly [propenaldehyde -2-methyl-2- (2-phenyl) ethylhydrazone] and the like.

In the general formula (1), for example, the substituent X is a methyl group, Y, and R ₁ is a hydrogen atom. Specifically, poly (methyl vinyl ketone hydrazone), poly (methyl vinyl ketone methyl) Hydrazone), poly (methyl vinyl ketone ethyl hydrazone), poly (methyl vinyl ketone n-propyl hydrazone), poly (methyl vinyl ketone i-propyl hydrazone), poly (methyl vinyl ketone n-butyl hydrazone), poly (methyl vinyl ketone) i-butyl hydrazone), poly (methyl vinyl ketone sec-butyl hydrazone), poly (methyl vinyl ketone t-butyl hydrazone), poly (methyl vinyl ketone n-pentyl hydrazone), poly (methyl vinyl ketone i-pentyl hydrazone), Poly (methyl vinyl ketone neo-pen Tilhydrazone), poly (methyl vinyl ketone t-pentyl hydrazone), poly (methyl vinyl ketone n-hexyl hydrazone), poly (methyl vinyl ketone i-hexyl hydrazone), poly (methyl vinyl ketone n-heptyl hydrazone), poly ( Methyl vinyl ketone n-octyl hydrazone), poly (methyl vinyl ketone n-nonyl hydrazone), poly (methyl vinyl ketone n-decyl hydrazone), poly (methyl vinyl ketone n-undecyl hydrazone), poly (methyl vinyl ketone n- Dodecylhydrazone), poly (methyl vinyl ketone cyclohexyl hydrazone), poly (methyl vinyl ketone phenyl hydrazone), poly [methyl vinyl ketone (4-methyl) phenyl hydrazone], poly (methyl vinyl ketone benzyl hydrazone) Poly [methyl vinyl ketone (2-phenyl) ethyl hydrazone] and the like.

In the above general formula (1), for example, the substituents X and Y are methyl groups and R ₁ is a hydrogen atom. Specifically, poly (methyl isopropenyl ketone hydrazone), poly (methyl isopropenyl) Ketone (methyl hydrazone), poly (methyl isopropenyl ketone ethyl hydrazone), poly (methyl isopropenyl ketone n-propyl hydrazone), poly (methyl isopropenyl ketone i-propyl hydrazone), poly (methyl isopropenyl ketone n-butyl hydrazone) Poly (methyl isopropenyl ketone i-butyl hydrazone), poly (methyl isopropenyl ketone sec-butyl hydrazone), poly (methyl isopropenyl ketone t-butyl hydrazone), poly (methyl isopropenyl ketone n-pentyl hydrazone), poly ( Methyl isopropenyl ketone i-pentyl hydrazone), poly (methyl isopropenyl ketone neo-pentyl hydrazone), poly (methyl isopropenyl ketone t-pentyl hydrazone), poly (methyl isopropenyl ketone n-hexyl hydrazone), poly (methyl iso Propenyl ketone i-hexyl hydrazone), poly (methyl isopropenyl ketone n-heptyl hydrazone), poly (methyl isopropenyl ketone n-octyl hydrazone), poly (methyl isopropenyl ketone n-nonyl hydrazone), poly (methyl isopropenyl ketone) n-decylhydrazone), poly (methyl isopropenyl ketone n-undecyl hydrazone), poly (methyl isopropenyl ketone n-dodecyl hydrazone), poly (methyl isopropenyl ketone) Chlohexyl hydrazone), poly (methyl isopropenyl ketone phenyl hydrazone), poly [methyl isopropenyl ketone (4-methyl) phenyl hydrazone], poly (methyl isopropenyl ketone benzyl hydrazone), poly [methyl isopropenyl ketone (2-phenyl) ) Ethyl hydrazone] and the like.

In the general formula (1), for example, the substituents X, Y, and R ₁ are each a methyl group. Specifically, poly (methyl isopropenyl ketone-2,2-dimethylhydrazone), poly ( Methyl isopropenyl ketone-2-methyl-2-ethylhydrazone), poly (methyl isopropenyl ketone-2-methyl-2-n-propyl hydrazone), poly (methyl isopropenyl ketone-2-methyl-2-i-propyl) Hydrazone), poly (methyl isopropenyl ketone-2-methyl-2-n-butyl hydrazone), poly (methyl isopropenyl ketone-2-methyl-2-i-butyl hydrazone), poly (methyl isopropenyl ketone-2- Methyl-2-sec-butylhydrazone), poly (methyl isopropenyl ketone-2-methyl-2-t-butyl) Tilhydrazone), poly (methylisopropenylketone-2-methyl-2-n-pentylhydrazone), poly (methylisopropenylketone-2-methyl-2-i-pentylhydrazone), poly (methylisopropenylketone-2) -Methyl-2-neo-pentylhydrazone), poly (methylisopropenylketone-2-methyl-2-t-pentylhydrazone), poly (methylisopropenylketone-2-methyl-2-n-hexylhydrazone), poly (Methyl isopropenyl ketone-2-methyl-2-i-hexyl hydrazone), poly (methyl isopropenyl ketone-2-methyl-2-n-heptyl hydrazone), poly (methyl isopropenyl ketone-2-methyl-2- n-octylhydrazone), poly (methyl isopropenyl ketone-2) Methyl-2-n-nonylhydrazone), poly (methylisopropenylketone-2-methyl-2-n-decylhydrazone), poly (methylisopropenylketone-2-methyl-2-n-undecylhydrazone), poly (Methyl isopropenyl ketone-2-methyl-2-n-dodecylhydrazone), poly (methyl isopropenyl ketone-2-methyl-2-cyclohexyl hydrazone), poly (methyl isopropenyl ketone-2-methyl-2-phenylhydrazone) ), Poly [methyl isopropenyl ketone-2-methyl-2- (4-methyl) phenylhydrazone], poly (methyl isopropenyl ketone-2-methyl-2-benzylhydrazone), poly [methyl isopropenyl ketone-2- Methyl-2- (2-phenyl) ethylhydrazone] and the like It is.

  In the present invention, among these, in consideration of the rust prevention effect and cost, poly (propenaldehyde hydrazone), poly (propenaldehyde phenylhydrazone), poly (2-methyl-2-propenaldehyde hydrazone), poly (2 -Methyl-2-propenaldehyde phenylhydrazone), poly (propenaldehyde-2,2-dimethylhydrazone), poly (methyl vinyl ketone hydrazone), poly (methyl vinyl ketone phenyl hydrazone), poly (methyl isopropenyl ketone hydrazone), It is more preferable to use one or a combination of two or more selected from the group consisting of poly (methyl isopropenyl ketone phenylhydrazone) and poly (methyl isopropenyl ketone-2,2-dimethylhydrazone).

  The polyhydrazone compound of the present invention has a number average molecular weight (Mn) in the range of 100 to 1,000,000 in terms of polystyrene, preferably a number average molecular weight (Mn) in the range of 1000 to 50,000. By setting the number average molecular weight (Mn) to 100 or more, operations such as crystallization can be simplified during the production of the polyhydrazone compound, and the adsorptive power to the metal is improved and a sufficient rust prevention effect is obtained. To express. On the other hand, by setting the number average molecular weight (Mn) to 1,000,000 or less, the decomposition of the polymer proceeds smoothly during the decomposition treatment, and the time required for the decomposition can be within the industrial range.

  The polyhydrazone compound of the present invention contains one or more structural units represented by the general formula (1), but further includes other structural units in addition to the structural unit represented by the general formula (1). May be. Other structural units are not particularly limited. For example, ethylene, propylene, isobutylene, styrene, α-methylstyrene, acrylic esters, methacrylic esters, maleimides, acrylonitrile, vinyl ethers, vinyl alcohol And structural units derived from monomers such as vinyl acetate.

  The polyhydrazone compound of the present invention has degradability. That is, the polyhydrazone compound of the present invention is decomposed by heat or light to lower the molecular weight.

In the polyhydrazone compound of the present invention, the temperature at which decomposition occurs is usually in the range of 100 to 400 ° C., and the light at which decomposition occurs is usually in the range of about 10 to 1000 mW / cm ² and a wavelength of 250 to 800 nm. Are exemplified.

  The degradation of the polyhydrazone compound of the present invention is promoted in the presence of water. Therefore, when decomposing, it is preferable to contact the polyhydrazone compound with water. The amount of water to be contacted is usually in the range of 1 to 100 molar equivalents and preferably in the range of 2 to 20 molar equivalents with respect to 1 molar equivalent of the hydrazone group of the polyhydrazone compound. If the amount of water is 1 molar equivalent or more, it contributes sufficiently to the promotion of polymer degradation. Moreover, even if it uses exceeding 20 molar equivalent, the decomposition promotion effect only added is not acquired.

  The decomposition of the polyhydrazone compound of the present invention is further promoted by allowing an acid catalyst to coexist in the presence of water. Therefore, when decomposing, it is more preferable to contact the polyhydrazone compound with a mixture of water and an acid catalyst.

  The acid catalyst is not particularly limited as long as it is an acidic compound. Specific examples include hydrochloric acid, hydrogen chloride gas, hydrobromic acid, sulfuric acid, phosphoric acid, phosphorus oxychloride, methanesulfonic acid, trifluoromethane. Examples include sulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, chlorosulfonic acid, formic acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, benzoic acid and the like. Among these, when it is assumed to be used in the field of electronic materials, it is preferable to avoid mixing of halogen atoms and sulfur atoms, so one or more selected from the group consisting of formic acid, acetic acid, and propionic acid The acid catalyst can be preferably used.

  The amount of the acid catalyst is usually 0.0001 to 0.1 molar equivalents, preferably 0.001 to 0.01 molar equivalents, based on 1 molar equivalent of the hydrazone group of the polyhydrazone compound. It is. When the amount of the acid catalyst is 0.0001 molar equivalent or more, it sufficiently contributes to the promotion of polymer decomposition. Moreover, even if it uses exceeding 0.1 molar equivalent, the decomposition promotion effect only added is not acquired.

  The polyhydrazone compound of the present invention is produced by dehydrating and condensing a polycarbonyl compound containing one or more structural units represented by the general formula (2) with a hydrazine derivative represented by the general formula (3). can do.

In the production method of the polyhydrazone compound of the present invention, considering its decomposability and removability of decomposition products, in general formula (2), X and Y are each independently a hydrogen atom, a methyl group, an ethyl group, A C3-C18 linear, branched or cyclic alkyl group, a C5-C10 aromatic group, a C5-C10 hydrogen substituted with 1-3 hydrogen on the aromatic ring with a methyl group An aromatic group, a methyl group substituted with 1 to 3 hydrogen atoms with a phenyl group, or an ethyl group substituted with 1 to 3 hydrogen atoms with a phenyl group, and in the general formula (3), R ₁ , R ₂ Are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or a methyl group on an aromatic ring. An aromatic group having 5 to 10 carbon atoms in which 1 to 3 hydrogen atoms are substituted, phenyl In the general formula (2), a hydrogen atom or a methyl group in which the hydrogen atom is substituted with 1 to 3 or a phenyl group is preferable. In the general formula (3), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, n-heptyl group, n-octyl group, More preferably, it represents an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, a cyclohexyl group, a phenyl group, a 4-methylphenyl group, a benzyl group, or a 2-phenylethyl group.

  In the method for producing a polyhydrazone compound of the present invention, the polycarbonyl compound containing one or more of the structural units represented by the general formula (2) is not limited to the structural unit represented by the general formula (2). Other structural units may be included. Other structural units are not particularly limited. For example, ethylene, propylene, isobutylene, styrene, α-methylstyrene, acrylic esters, methacrylic esters, maleimides, acrylonitrile, vinyl ethers, vinyl alcohol And structural units derived from monomers such as vinyl acetate.

  In the method for producing a polyhydrazone compound of the present invention, specific examples of the polycarbonyl compound containing one or more structural units represented by the general formula (2) are not particularly limited. (Propene aldehyde), poly (2-methyl-2-propenaldehyde), poly (methyl vinyl ketone), poly (methyl isopropenyl ketone) and the like are exemplified.

  In the method for producing a polyhydrazone compound of the present invention, the number average molecular weight (Mn) of a polycarbonyl compound containing one or more structural units represented by the general formula (2) is 100 to 1,000 in terms of polystyrene. The number average molecular weight (Mn) is preferably in the range of 1000 to 50,000. By setting the number average molecular weight (Mn) to 100 or more, operations such as crystallization of the produced polyhydrazone compound are simplified, and the adsorptive power to the metal is improved and the rust prevention effect is sufficiently exhibited. In addition, by setting the number average molecular weight (Mn) to 1,000,000 or less, the decomposition of the polymer proceeds smoothly during the decomposition treatment of the produced polyhydrazone compound, and the time required for the decomposition becomes an industrial range.

  In the method for producing a polyhydrazone compound of the present invention, the polycarbonyl compound containing one or more structural units represented by the general formula (2) may be a commercially available product or a compound synthesized by a known method. good. Moreover, although it does not specifically limit about purity, 95% or more is preferable and 99% or more is further more preferable on the assumption that it uses in the electronic material field | area.

  In the present invention, the method for producing a polycarbonyl compound containing one or more structural units represented by the general formula (2) may be any method such as radical polymerization, anionic polymerization, and cationic polymerization, Although not particularly limited, radical polymerization and anionic polymerization are preferably used (for example, AR Lyons, J. Polym. Sci. Part D, 6, 251 (1972), Yoshio Okamoto, “Polymer Experiment”). Gaku 4 addition polymerization and ring-opening polymerization ", see Kyoritsu Shuppan (1983), p. 150, JP-A-10-45837, etc.).

In the method for producing a polyhydrazone compound of the present invention, specific examples of the hydrazine derivative represented by the general formula (3) are not particularly limited. For example, the substituent R ₁ is a hydrogen atom. Specifically, hydrazine, methyl hydrazine, ethyl hydrazine, n-propyl hydrazine, i-propyl hydrazine, n-butyl hydrazine, i-butyl hydrazine, sec-butyl hydrazine, t-butyl hydrazine, n-pentyl hydrazine, i -Pentyl hydrazine, neo-pentyl hydrazine, t-pentyl hydrazine, n-hexyl hydrazine, i-hexyl hydrazine, n-heptyl hydrazine, n-octyl hydrazine, n-nonyl hydrazine, n-decyl hydrazine, n-undecyl hydrazine, n-dodecyl hydride Examples include azine, cyclohexyl hydrazine, phenyl hydrazine, (4-methyl) phenyl hydrazine, benzyl hydrazine, (2-phenyl) ethyl hydrazine and the like.

For example, specific examples of the hydrazine derivative represented by the general formula (3) in which the substituent R ₁ is a methyl group include 1,1-dimethylhydrazine, 1-methyl-1-ethylhydrazine, 1 -Methyl-1-n-propylhydrazine, 1-methyl-1-i-propylhydrazine, 1-methyl-1-n-butylhydrazine, 1-methyl-1-i-butylhydrazine, 1-methyl-1-sec -Butyl hydrazine, 1-methyl-1-t-butyl hydrazine, 1-methyl-1-n-pentyl hydrazine, 1-methyl-1-i-pentyl hydrazine, 1-methyl-1-neo-pentyl hydrazine, 1- Methyl-1-t-pentylhydrazine, 1-methyl-1-n-hexylhydrazine, 1-methyl-1-i-hexylhydrazine, 1-methyl-1-n -Heptylhydrazine, 1-methyl-1-n-octylhydrazine, 1-methyl-1-n-nonylhydrazine, 1-methyl-1-n-decylhydrazine, 1-methyl-1-n-undecylhydrazine, 1 -Methyl-1-n-dodecylhydrazine, 1-methyl-1-cyclohexylhydrazine, 1-methyl-1-phenylhydrazine, 1-methyl-1- (4-methyl) phenylhydrazine, 1-methyl-1-benzylhydrazine 1-methyl-1- (2-phenyl) ethylhydrazine and the like.

  In the method for producing a polyhydrazone compound of the present invention, the hydrazine derivative represented by the general formula (3) may be a commercially available product or a product synthesized by a known method. Known preparation methods include, for example, a method of reducing an aromatic diazonium salt with a reducing agent such as sulfite or tin (II) chloride, a method of catalytic reduction of hydrazone or azine using a platinum catalyst, reduction of acylhydrazine, Examples include reduction of N-nitrosamine, reductive coupling of aromatic nitro compounds, alkylation and arylation of hydrazine and azine, reaction of amine and chloramine (Reaching reaction), and the like. Further, the purity of the hydrazine derivative represented by the general formula (3) is not particularly limited, but is preferably 95% or more, and more preferably 99% or more in consideration of use in the field of electronic materials.

  In the method for producing a polyhydrazone compound of the present invention, the mixing ratio of the above-mentioned polycarbonyl compound and hydrazine compound may be appropriately selected according to various conditions such as the type of polycarbonyl compound and hydrazine compound used, and is particularly limited. The hydrazine compound is usually mixed in the range of 1 to 100 molar equivalents, preferably in the range of 1.0 to 10 molar equivalents, with respect to 1 molar equivalent of the carbonyl group of the polycarbonyl compound. . By using 1 mol equivalent or more of the hydrazine compound, all the carbonyl groups react, and even if the hydrazine compound is used in excess of 10 mol equivalent, the effect just added is not obtained.

  In the method for producing a polyhydrazone compound of the present invention, dehydration condensation can be performed by a conventionally known method, and is not particularly limited. For example, from the polycarbonyl compound represented by the general formula (2) as a raw material, One or two or more selected and one or two or more selected from the hydrazine derivative represented by the above general formula (3) can be dissolved in a solvent at the same time and then heated. At this time, in order to complete the reaction in a short time, it is preferable to carry out while distilling off the water produced as a by-product.

  In the method for producing a polyhydrazone compound of the present invention, a catalyst for promoting dehydration condensation can be added. The catalyst may be appropriately selected according to various conditions such as the type and amount of the polycarbonyl compound and hydrazine compound used, and is not particularly limited. For example, hydrochloric acid, hydrogen chloride gas, hydrobromic acid , Sulfuric acid, phosphoric acid, phosphorus oxychloride, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, chlorosulfonic acid, formic acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, benzoic acid, etc. Among these, one or two or more acid catalysts selected from the group consisting of methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, and acetic acid can be suitably used.

  The amount of the catalyst used may be appropriately selected according to various conditions such as the type and amount of the polycarbonyl compound and hydrazine compound used, and is not particularly limited, but 1 mol of the carbonyl group possessed by the polycarbonyl compound. It is usually used in the range of 0.0001 to 0.1 molar equivalent, preferably in the range of 0.001 to 0.01 molar equivalent relative to the equivalent. When the amount of the catalyst used is 0.0001 molar equivalent or more, the reaction can proceed at an industrial speed, and even if the amount used exceeds 0.1 molar equivalent, only the added effect is obtained. I can't get it.

  In the production method of the polyhydrazone compound of the present invention, any solvent can be used as long as it is inert to the reaction, and various types such as the type and amount of the polycarbonyl compound and hydrazine compound used. What is necessary is just to select suitably according to conditions, and it does not specifically limit. Specifically, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, pentanol, hexanol, heptanol, octanol, cyclohexanol, benzyl alcohol, terpineol Alcohols such as ethylene glycol, propylene glycol, butylene glycol, pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and other glycols, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol Diethyl ether, tetrahydrofuran, tetrahydropyra Ethers such as 1,4-dioxane, esters such as methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, and γ-butyrolactone, n -Hydrocarbons such as pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, cyclohexane, decalin, benzene, toluene, xylene, ethylbenzene, n- Examples include aromatic hydrocarbons such as propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, chlorobenzene and dichlorobenzene. These can be used alone or as a mixture of two or more compatible. Among these, one or two or more solvents selected from the group consisting of ethanol, i-propyl alcohol, tetrahydrofuran, 1,4-dioxane, and toluene can be suitably used.

  In the method for producing the polyhydrazone compound of the present invention, the amount of the solvent used is not particularly limited as long as it is at least the minimum amount at which the polycarbonyl compound used in the reaction dissolves, but the polycarbonyl used in the reaction is not particularly limited. It is usually used within a range of 200 to 10,000% by weight based on the compound. If the amount is less than 200% by weight, the solvent is also volatilized at the same time when the by-product water is distilled off, so the amount of the solvent may decrease during the reaction, and the polycarbonyl compound may be precipitated. When used, the time required to complete the reaction may not be industrial.

  In the method for producing the polyhydrazone compound of the present invention, the reaction temperature may be appropriately selected according to various conditions such as the type and amount of the polycarbonyl compound and hydrazine compound used, and is not particularly limited. For example, a range of 0 to 200 ° C. is preferable. If it is less than 0 ° C., the reaction may be extremely slow, and if it exceeds 200 ° C., the polycarbonyl compound, hydrazine compound and / or polyhydrazone compound may be decomposed, which is not practical.

  In the method for producing a polyhydrazone compound of the present invention, the reaction time may be appropriately selected according to various conditions such as the type and amount of the polycarbonyl compound and hydrazine compound to be used, and is not particularly limited. The reaction is complete within 1 to 1000 hours.

  In the method for producing the polyhydrazone compound of the present invention, the purification method is not particularly limited. For example, after completion of the reaction, the reaction solution is dropped into a solvent having low product solubility to crystallize the polyhydrazone compound. Can be taken up as. Examples of the solvent having low product solubility include n-pentane, n-hexane, n-heptane, methanol, acetonitrile, water and the like. These may be used alone or in combination of two or more compatible. Further, in order to improve the purity of the product, it may be re-dissolved in a soluble organic solvent and re-injected into a solvent having the low solubility of the product, and recrystallization may be performed.

  The polyhydrazone compound of the present invention can be used as a rust inhibitor for metals.

  The polyhydrazone compound of the present invention has an effect of protecting the metal surface and suppressing its corrosivity and preventing the occurrence of rust and the like.

  The metal rust preventive agent of the present invention contains the above-described polyhydrazone compound of the present invention.

  The antirust agent for metals of the present invention can be prepared by dissolving one or more compounds selected from the polyhydrazone compounds of the present invention described above in a soluble organic solvent.

  The rust preventive agent for metals of the present invention can further contain a surfactant, a stabilizer, a dispersant and the like depending on the application. Moreover, you may add and use for metal coating agents, such as a metal coating paint. Furthermore, it can also be used in combination with other rust inhibitor components for metals.

  In the metal rust preventive agent of the present invention, the concentration of the polyhydrazone compound of the present invention is preferably in the range of 0.001 to 50% by weight, preferably 0.1 to 20% by weight with respect to the metal rust preventive agent. A range is further preferred. By setting the concentration of the polyhydrazone compound to 0.001% by weight or more, the rust prevention effect can be sufficiently exhibited, and even if it is used in excess of 20% by weight, the rust prevention effect just used is exhibited. Not economically preferable.

  In the metal rust preventive agent of the present invention, the metal to be treated is not particularly limited. For example, copper and copper alloys such as copper, brass and white copper, aluminum and aluminum alloys, magnesium and magnesium alloys, nickel and Examples thereof include metals such as nickel alloys, chromium and chromium alloys, zinc and zinc alloys, iron and iron alloys such as iron, cast iron, carbon steel, and stainless steel, and metal products using these metals.

  The metal rust preventive agent of the present invention is applied to the metal surface by dip coating, spin coating, spraying, etc., and then subjected to rust prevention treatment by natural drying or heat drying.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not construed as being limited in any way by these examples.

In the following examples, the number average molecular weight (Mn) was calculated in terms of polystyrene by gel permeation chromatography (Tosoh high-speed GPC system). ¹ H-NMR was measured with a Varian Gemini-200. IR was measured by 2000FT-IR manufactured by Perkin Elmer.

Reference Example 1 Preparation of poly (2-methyl-2-propenaldehyde).
In a 50 ml eggplant-shaped flask containing a magnetic stir bar, 7.0 g (100 mmol, produced by Tokyo Chemical Industry Co., Ltd.) of 2-methyl-2-propenaldehyde (methacrolein) produced by distillation was dissolved in 20 g of toluene, and azobis Isobutyronitrile 64 mg (0.2 mmol, manufactured by Kanto Chemical Co., Inc.) was added, heated to 50 ° C., and stirred for 2 hours. After completion of the reaction, the reaction solution was poured into 200 ml of methanol, and then the precipitate was collected by filtration. The obtained white solid was washed with water and then with methanol, and then dried under reduced pressure at room temperature to obtain 5.09 g of poly (2-methyl-2-propenaldehyde) (yield 72.7%).

Number average molecular weight (Mn) = 27.2 × 10 ² , Mw / Mn = 6.8.
¹ H-NMR (CDCl ₃ ) 9.78 (bs), 2.3 to 0.8 (bs).

Reference Example 2 Preparation of poly (methyl vinyl ketone).
In a 50 ml eggplant-shaped flask containing a magnetic stir bar, 3.5 g (50 mmol, produced by Tokyo Chemical Industry Co., Ltd.) of methyl vinyl ketone produced by distillation was dissolved in 10 g of toluene, and 32 mg (0.2 mmol) of azobisisobutyronitrile was dissolved. , Manufactured by Kanto Chemical Co., Ltd.), heated to 60 ° C., and stirred for 2 hours. After completion of the reaction, the reaction solution was poured into 200 ml of methanol, and then the precipitate was collected by filtration. The obtained white solid was washed with water and then with methanol, and dried under reduced pressure at room temperature to obtain 3.03 g of poly (methyl vinyl ketone) (yield: 86.7%).

Number average molecular weight (Mn) = 62.8 × 10 ² , Mw / Mn = 4.03.
¹ H-NMR (CDCl ₃ ) δ 2.6-1.9 (bs), 2.1 (bs), 1.68 (bs).

  Example 1 Preparation of poly (2-methyl-2-propenaldehyde phenylhydrazone). In a 50 ml eggplant-shaped flask containing a magnetic stirrer, 1.4 g of poly (2-methyl-2-propenaldehyde) synthesized in Reference Example 1 (ketone amount 20 mmol) was dissolved in 40 g of tetrahydrofuran to obtain 2.38 g of phenylhydrazine. (22 mmol, Wako Pure Chemical Industries, Ltd.) and 5 mg of p-toluenesulfonic acid were added, heated to 60 ° C. and stirred for 2 hours. After completion of the reaction, the reaction solution was poured into 200 ml of methanol, and then the precipitate was collected by filtration. The obtained white solid was washed with water and then with a small amount of methanol, and then dried under reduced pressure at room temperature to obtain 2.48 g of poly (2-methyl-2-propenaldehyde phenylhydrazone) (yield 70. 5%).

Number average molecular weight (Mn) = 38.1 × 10 ² , Mw / Mn = 3.05.
_{^{1 H-NMR (CDCl 3)}} δ7.19 (t), 7.08 (d), 6.74 (t), 9.78 (bs), 2.3~0.8 (bs).
IR (KBr) 3408, 2940, 1617, 1593, 1540, 1517, 1504, 1328, 1346, 1331, 1045, 928 cm ⁻¹ .

Example 2 Preparation of poly (methyl vinyl ketone dimethylhydrazone).
In a 50 ml eggplant type flask containing a magnetic stirrer, 1.4 g of poly (methyl vinyl ketone) synthesized in Reference Example 2 (ketone amount 20 mmol) was dissolved in 40 g of tetrahydrofuran, and 1.44 g of dimethylhydrazine (22 mmol, Tokyo Chemical Industry Co., Ltd.) Manufactured by Kogyo Co., Ltd.) and 5 mg of p-toluenesulfonic acid were added, heated to 60 ° C. and stirred for 2 hours. After completion of the reaction, the reaction solution was poured into 200 ml of methanol, and then the precipitate was collected by filtration. The obtained white solid was washed with water and then with a small amount of methanol, and then dried under reduced pressure at room temperature to obtain 2.12 g of poly (methyl vinyl ketone dimethylhydrazone) (yield 82.8%).

Number average molecular weight (Mn) = 58.2 × 10 ² , Mw / Mn = 4.32.
¹ H-NMR (CDCl ₃ ) δ 7.18 (t), 7.06 (d), 6.76 (t), 2.6 to 1.9 (bs), 2.1 (bs), 1.68 (Bs).
IR (KBr) 3405, 2940, 1619, 1594, 1538, 1519, 1502, 1338, 1356, 1334, 1045, 923 cm ⁻¹ .

Example 5 to Example 6, Comparative Example 1 to Comparative Example 3 Evaluation of rust prevention ability.
As a pretreatment, a pure copper plate having a length of 25 mm, a width of 15 mm, and a thickness of 3.2 mm, immersed in ethanol for 5 minutes, sandwiched in water and immersed in a 10% by weight hydrazine aqueous solution at 60 ° C., Table 1 The solution having the composition shown below was applied so as to form a film having a thickness of about 10 μm. Thereafter, the specimen was dried for 10 minutes at a temperature of 50 ° C. in a nitrogen atmosphere, and further cured at room temperature for 1 day to produce a rust-proof test specimen.

  Subsequently, each specimen was held at 60 ° C. for 72 hours in the atmosphere, and the oxygen amount on the surface of each specimen was evaluated by measuring with an EPMA (electron beam microanalyzer, manufactured by Horiba, Ltd., trade name “EMAX5770W”). .

  Subsequently, visual judgment was performed as a simple evaluation of the surface state of each specimen. The evaluation criteria were no change (◯), slight change (Δ), and considerable discoloration (×).

  Each evaluation result is shown in Table 1.

Example 7 Degradability evaluation of poly (2-methyl-2-propenaldehyde phenylhydrazone).
200 mg of poly (2-methyl-2-propenaldehyde phenylhydrazone) prepared in Example 1 was dissolved in 2 ml of dimethylformamide, and 0.2 g of trifluoroacetic acid dissolved in 1 ml of water was added. After stirring at room temperature for 30 minutes, the reaction solution was heated to 160 ° C. and held for 30 minutes, and then the molecular weight of the residue was measured by GPC. The number average molecular weight (Mn) = 16.1 × 10 ² and Mw / Mn = 2.59, which were lower than before the decomposition treatment.

Example 8 Evaluation of degradability of poly (methyl vinyl ketone dimethylhydrazone).
200 mg of poly (methyl vinyl ketone dimethylhydrazone) prepared in Example 2 was dissolved in 2 ml of dimethylformamide, and 0.2 g of trifluoroacetic acid dissolved in 1 ml of water was added. After stirring at room temperature for 30 minutes, the reaction solution was heated to 160 ° C. and held for 30 minutes, and then the molecular weight of the residue was measured by GPC. The number average molecular weight (Mn) = 4.1 × 10 ² and Mw / Mn = 1.71, which were lower than before the decomposition treatment.

Example 9 to Example 12 Removability evaluation.
As a pretreatment, a pure copper plate having a length of 25 mm, a width of 15 mm, and a thickness of 3.2 mm was immersed in ethanol for 5 minutes, washed with water, and immersed in a 10% by weight hydrazine aqueous solution at 60 ° C. for 20 minutes. The solution having the composition shown in 2 was applied so as to form a film having a thickness of about 100 μm. Then, it dried for 10 minutes at the temperature of 50 degreeC in nitrogen atmosphere, and also cured at room temperature for 1 day, and produced the test body.

  Next, each test specimen is immersed in 100 ml of pure water, kept in air at room temperature for 72 hours, and after removing the test specimen, water is completely distilled off and the weight of the residue (removed by washing with pure water). Represents the weight of the coated film) (hereinafter referred to as the residue weight A). Subsequently, each specimen removed from the pure water was washed with 100 ml of tetrahydrofuran to completely remove the film, and then the washing liquid was dried to determine the weight of the residue (the weight of the film that could not be removed by the pure water washing). (Referred to below as residue weight B). From these, the cleaning removal rate [= residue weight A ÷ (residue weight A + residue weight B) × 100 (% by weight)] of each test specimen was determined. The results are also shown in Table 2.

Claims (6)

Rust prevention for metals containing a polyhydrazone compound containing one or more structural units represented by the following general formula (1) and having a number average molecular weight (Mn) in the range of 100 to 1,000,000 in terms of polystyrene Agent .

[In General Formula (1), X, Y, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or 1 carbon atom. An aromatic group having 5 to 10 carbon atoms in which 1 to 3 hydrogen atoms on the aromatic ring are substituted with 1 to 4 alkyl groups, or carbon in which 1 to 3 hydrogen atoms are substituted with an aromatic group having 5 to 10 carbon atoms The alkyl group of number 1-4 is represented. ] In the general formula (1), X, Y, R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, An aromatic group having 5 to 10 carbon atoms, an aromatic group having 5 to 10 carbon atoms in which hydrogen on the aromatic ring is substituted by 1 to 3 with a methyl group, a methyl group in which 1 to 3 hydrogen atoms are substituted with a phenyl group, Or the rust preventive agent for metals containing the polyhydrazone compound of Claim 1 characterized by representing the ethyl group by which the hydrogen atom was substituted 1-3 by the phenyl group. In the general formula (1), X, Y, and R ₁ each independently represent a hydrogen atom or a methyl group, and R ₂ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n -Butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, n -Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclohexyl group, phenyl group, 4-methylphenyl group, benzyl group, or 2-phenylethyl group The metal rust preventive agent containing the polyhydrazone compound according to claim 1 or 2, wherein The following general formula (2)

[In General Formula (2), X and Y are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An aromatic group having 5 to 10 carbon atoms in which 1 to 3 hydrogen atoms on the aromatic ring are substituted, or an alkyl having 1 to 4 carbon atoms in which 1 to 3 hydrogen atoms are substituted with an aromatic group having 5 to 10 carbon atoms Represents a group. ]
And a polycarbonyl compound having a number average molecular weight (Mn) in the range of 100 to 1,000,000 in terms of polystyrene, and the following general formula (3):

[In General Formula (3), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or an alkyl having 1 to 4 carbon atoms. Group having 5 to 10 carbon atoms substituted with 1 to 3 hydrogen atoms on the aromatic ring, or 1 to 4 carbon atoms having 1 to 3 hydrogen atoms substituted with an aromatic group having 5 to 10 carbon atoms Represents an alkyl group. ]
The method for producing a rust inhibitor for metals containing a polyhydrazone compound according to any one of claims 1 to 3, wherein the hydrazine derivative represented by the formula (1) is subjected to dehydration condensation. In the general formula (2), X and Y are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, or a carbon atom having 5 to 10 carbon atoms. Aromatic group, C5-C10 aromatic group in which hydrogen on the aromatic ring is substituted with 1 to 3 by methyl group, Methyl group in which hydrogen atom is substituted by 1 to 3 phenyl group, or Hydrogen atom in phenyl group Represents an ethyl group having 1 to 3 substituents, and in the general formula (3), R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, a straight chain having 3 to 18 carbon atoms, A branched or cyclic alkyl group, an aromatic group having 5 to 10 carbon atoms, an aromatic group having 5 to 10 carbon atoms in which hydrogen on the aromatic ring is substituted by 1 to 3 methyl groups, and a hydrogen atom in a phenyl group. A methyl group substituted with 1 to 3 or an ethyl group substituted with 1 to 3 hydrogen atoms with a phenyl group Method for producing a metal anti-corrosion agent containing Porihidorazon compound according to claim 4, characterized in that. In the general formula (2), X and Y each independently represent a hydrogen atom or a methyl group, and in the general formula (3), R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents a hydrogen atom or methyl. Group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclohexyl group, phenyl group It represents a 4-methylphenyl group, a benzyl group, or a 2-phenylethyl group, The manufacturing method of the rust preventive agent for metals containing the polyhydrazone compound of Claim 4 characterized by the above-mentioned.