JP2007077268A - Resin composition for inner coating of can and metal plate for can inner coated with the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for inner coating of a can and to provide a metal plate for a can inner coated with the same, having processability and deterioration resistance with the passage of time. <P>SOLUTION: The invention relates to the resin composition comprising a copolyester resin (A) obtained by polymerization using a polymerization catalyst containing an aluminum compound, and comprising 75-100 mol% of an aromatic dicarboxylic acid as the acid components, 30-100 mol% of at least one of polyalcohol components represented by formula (1) and/or a 1, 4-cyclohexanedimethanol, and (B) a crosslinking agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a can inner surface coating resin composition comprising a copolymer polyester resin obtained by using a polymerization catalyst containing an aluminum compound as an active ingredient, and a can inner surface coated metal sheet coated with the same.

  The paint for the inner surface of the can is supplied assuming that the flavor and flavor of the contents of the can are not impaired and used in a wide variety of cans. In recent years, the required properties are (1) heavy metal ( Catalyst, etc.), no toxicity of environmental hormones and environmental pollution, (2) resistance to heat sterilization (retort) treatment, (3) excellent adhesion and workability, (4) salt and Excellent blister resistance and whitening resistance (content resistance) when heat-sterilized contents showing acidity, (5) No deterioration of workability due to excessive baking during canning (aging resistance over time) ) And the like.

  Conventionally, vinyl chloride resins and epoxy-phenolic resins are often used as resins for can inner surface coatings, both of which have been pointed out the problem of environmental hormones. In particular, in the case of a vinyl chloride resin, it has been pointed out that the vinyl chloride monomer remaining in the resin is a substance having a serious sanitary problem such as carcinogenicity. In addition, the epoxy-phenolic resin has a high baking temperature, and the generation of environmental hormones becomes a problem as described above. On the other hand, as a solution to these problems, proposals have been made to use a copolymerized polyester resin based on a titanium polymerization catalyst without using a vinyl chloride resin or a bisphenol type epoxy resin (Patent Document 1 and Patent Document 2). There are many patent documents relating to polymerization catalysts for polyethylene terephthalate. As one example, an aluminum compound and a phosphorus compound have been proposed (Patent Document 3), but the use of a copolyester resin has not been known yet.

JP 2001-106969 A Japanese Patent No. 2526663 JP 2004-256633 A

As a polymerization catalyst for the copolyester, antimony, titanium, germanium, tin and the like are known. However, with respect to the production of such a copolyester resin for a can inner surface paint of a metal plate, the following problems remain in these polymerization catalyst species.
(1) Polymerization catalysts such as tin compounds and antimony compounds contain heavy metals and polyesters that do not contain these metals are desired.
(2) When antimony compounds are dissolved in a solvent and the resulting copolyester resin is made into a varnish, aggregates containing reduced antimony and antimony settle out and have problems as paints. Dullness can be seen.
(3) When a titanium compound is used as a polymerization catalyst, the copolymerized polyester resin is colored. When an aliphatic dicarboxylic acid such as adipic acid or sebacic acid is used as the copolymerization component, the heat resistance is poor. The resin is highly colored and the white color cannot be obtained with white paint.
(4) The germanium compound can be used effectively as the polymerization catalyst, but the price is extremely high.
and so on.

  From such a technical background, the inner surface paint of the can which is mainly composed of an aluminum compound as a polymerization catalyst, has sufficient polymerization activity, is inhibited from coloring due to poor thermal stability of the obtained copolyester resin, and has few foreign matters derived from aluminum. There is a need for copolyester resins.

  In view of the above-mentioned conventional problems, the present invention provides a resin composition for can inner surface coatings, in which environmental problems are considered, polymerization activity is excellent, resin coloring is suppressed, and foreign substances derived from aluminum are reduced. It is an object of the present invention to provide a coated metal sheet that is coated and has workability and resistance to deterioration over time.

  In order to achieve the above object, the coating resin composition for inner surfaces of cans of the present invention is polymerized in the presence of a polymerization catalyst containing an aluminum compound, and the acid component is 75 to 100 mol% of an aromatic dicarboxylic acid, aliphatic and And / or alicyclic dicarboxylic acid in an amount of 0 to 25 mol%, and the polyalcohol component is at least one polyalcohol having a side chain represented by (Formula 1) and / or 1,4-cyclohexanedimethanol in an amount of 30 to 100 It is characterized by comprising a copolyester resin (A) and a cross-linking agent (B) that are 0% to 70% by mole of other polyalcohols.

(Wherein n = 0 or 1, R ¹ : H, methyl or ethyl group, R ² : H, or an alkyl group having 1 or more carbon atoms, R ³ : H or an alkyl group having 1 or more carbon atoms). Also, at least one of R ¹ , R ² and R ³ is an alkyl group.)

  In this case, the polyalcohol component represented by (Formula 1) preferably contains at least one kind of 1,2-propanediol or 2-methyl-1,3-propanediol.

  Moreover, it is preferable that the polymerization catalyst containing an aluminum compound is composed of at least one selected from the group consisting of aluminum compounds and at least one selected from the group consisting of phosphorus compounds.

  Further, the polymerization catalyst containing an aluminum compound is composed of at least one selected from the group consisting of aluminum compounds and at least one selected from the group consisting of alkali metals, alkaline earth metals and their compounds. Is preferred.

  Moreover, it is preferable that an aluminum compound is a carboxylic acid containing compound.

  Moreover, it is preferable that a phosphorus compound is aromatic phosphonic acid and derivatives thereof.

  Moreover, it is preferable that an alkali metal is Li and Na, an alkaline earth metal is Mg, and an alkali metal compound and an alkaline earth metal compound are compounds of Li, Na, and Mg.

  In addition, organic sulfonic acid as a curing catalyst (C) is added to the above-mentioned paint resin composition for the inner surface of the can [(A) + (B)] / (C) = 100 / 0.01 to 1.0 (weight ratio). It is preferable to blend in the range.

  Moreover, it is preferable that the filtration time of the aluminum-type foreign material insoluble in copolymer polyester resin in copolymer polyester resin (A) which comprises the paint resin composition for can inner surfaces is 5 hours or less.

  Here, the aluminum-based foreign matter filtration time insoluble in the copolymerized polyester resin means that the copolymerized polyester resin dissolved in the mixed solution is a polytetrafluoroethylene membrane filter having a pore diameter of 1.0 μm by the method described below. This is the filtration time until filtration is completed when filtration is performed under a pressure of 0.15 MPa.

  Furthermore, the paint resin composition for can inner surfaces can be applied to a metal plate to form a coated metal plate.

  In addition, a paint resin composition for a can inner surface can be obtained by applying a paint resin composition for the inner surface of a can containing a curing catalyst to a metal plate.

  According to the resin composition for a can inner surface paint and the coated metal plate for a can inner surface of the present invention, the can inner surface paint is excellent in polymerization activity, suppressed coloring of the resin, and further solved the problem of foreign matters derived from aluminum. And a coated metal plate for the inner surface of the can excellent in workability and resistance to deterioration over time can be obtained.

  Hereinafter, embodiments of the resin composition for a can inner surface coating of the present invention and a coated metal plate for a can inner surface coated with the same will be described in detail.

  The resin composition for can inner surface coating of the present invention is copolymerized in the presence of a polymerization catalyst containing an aluminum compound, and the acid component is 75 to 100 mol% of an aromatic dicarboxylic acid, an aliphatic and / or alicyclic dicarboxylic acid. The acid is 0 to 25 mol%, the polyalcohol component is at least one polyalcohol having a side chain represented by the above (formula 1) and / or 1,4-cyclohexanedimethanol in an amount of 30 to 100 mol%, other It consists of a copolyester resin (A) and a cross-linking agent (B) that are 0 to 70 mol% of polyalcohol.

  As an aluminum compound used as a polymerization catalyst of the copolyester resin constituting the present invention, known aluminum compounds can be used without limitation in addition to metallic aluminum.

  Specific examples of the aluminum compound include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, and aluminum lactate. , Carboxylates such as aluminum citrate, aluminum salicylate, inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum Aluminum such as n-propoxide, aluminum-iso-propoxide, aluminum-n-butoxide, aluminum t-butoxide Aluminum chelate compounds such as aluminum alkoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate di-iso-propoxide, organoaluminum compounds such as trimethylaluminum and triethylaluminum, and partial hydrolysis of these Products, aluminum oxide and the like. Of these, carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

  As the usage-amount of the aluminum compound used by this invention, 0.001-1.0 mol% is preferable with respect to the number-of-moles of all the structural units of carboxylic acid components, such as dicarboxylic acid and polyhydric carboxylic acid of polyester obtained, More preferably, it is 0.005-0.5 mol%. Thus, the amount of the aluminum component to be added is required to be wide because the catalytic activity varies greatly depending on the type and combination of polyvalent carboxylic acid and diol used, and the polymerization method. This shows the same tendency with other polymerization catalysts. In particular, when polymerization is not carried out under reduced pressure, it is necessary to greatly increase the amount of polymerization catalyst. Since the polymerization catalyst used in the present invention exhibits sufficient catalytic activity, as a result, the resulting polyester has excellent thermal stability, thermal oxidation stability, and hydrolysis resistance, and the generation and coloring of foreign matters due to aluminum are suppressed. The

  Below, the specific example of the preparation method of the same solution using basic aluminum acetate as an aluminum compound is shown. Examples of preparation of an aqueous solution of basic aluminum acetate are as follows. That is, water is added to basic aluminum acetate and sufficiently diffused at room temperature, and then dissolved at room temperature to 100 ° C. to prepare an aqueous solution. In this case, the temperature is preferably low, and the heating is preferably short. The concentration of the aqueous solution is preferably 10 to 30 g / l, particularly preferably 15 to 20 g / l.

Furthermore, in order to suppress the heat shock at the time of catalyst addition, it is preferable that the basic aluminum acetate aqueous solution is the same ethylene glycol solution. That is, ethylene glycol is added to the aqueous solution. The amount of ethylene glycol added is preferably 0.5 to 5.0 times the volume ratio of the aqueous solution. More preferably, the amount is 0.8 to 2.0 times. After stirring the solution to obtain a uniform water / ethylene glycol mixed solution, the solution is heated and water is distilled off to obtain an ethylene glycol solution. The temperature is preferably 70 ° C. or higher, and preferably 130 ° C. or lower. More preferably, the water is distilled off by heating and stirring at 80 to 120 ° C. More preferably, heating is performed under reduced pressure and / or an inert gas atmosphere such as nitrogen or argon, and water is distilled off to prepare a catalyst solution.
The above ethylene glycol is an example, and other alkylene glycols can be used in the same manner.

    The above basic aluminum acetate is used solubilized in a solvent such as water or glycol, and particularly used from water and / or ethylene glycol from the viewpoint of reducing catalytic activity and reducing foreign matter in the resulting copolymerized polyester. preferable.

In the present invention, a metal polymerization catalyst such as a tin compound, an antimony compound, a germanium compound and a titanium compound is substantially not used.

  Although it does not specifically limit as a phosphorus compound which comprises the polymerization catalyst used by this invention, Phosphate esters, such as phosphoric acid and trimethyl phosphoric acid, triethyl phosphoric acid, phenyl phosphoric acid, triphenyl phosphoric acid, phosphorous acid, and trimethyl Phosphite, triethyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphite And the like.

  A more preferable phosphorus compound used in the present invention is at least one selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. It is a kind of phosphorus compound. By using these phosphorus compounds, an effect of improving the catalytic activity is seen, and an effect of improving physical properties such as thermal stability of the polyester is seen. Among these, use of a phosphonic acid compound is preferable because of its great effect of improving physical properties and improving catalytic activity. Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

  The phosphonic acid-based compound, phosphinic acid-based compound, phosphine oxide-based compound, phosphonous acid-based compound, phosphinic acid-based compound, and phosphine-based compound referred to in the present invention are represented by the following formulas (Chemical Formula 3) to (Chemical Formula 8), respectively. It refers to a compound having the structure represented.

  Examples of the phosphonic acid compounds used in the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate and the like. Examples of the phosphinic acid compound used in the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, and phenylphenylphosphinate. Examples of the phosphine oxide compound used in the present invention include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide.

  Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds, the phosphorus compounds of the present invention are represented by the following formulas (Chemical Formula 9) to (Chemical Formula 14). Are preferred.

  Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

  Moreover, as a phosphorus compound used by this invention, when the compound represented by the following general formula (Formula 15)-(Formula 17) is used, the physical property improvement effect and the catalyst activity improvement effect are especially large and preferable.

Wherein R ¹ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group or an amino group. Represents a hydrocarbon group having 1 to 50 carbon atoms including R ² and R ³ each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl.)

The phosphorus compound of the present invention is particularly preferably a compound in which R ¹ , R ⁴ , R ⁵ , and R ⁶ are groups having an aromatic ring structure in the above formulas (Chemical Formula 15) to (Chemical Formula 17).

  Examples of the phosphorus compound used in the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl phosphophosphonate, diethyl benzylphosphonate, diphenylphosphinic acid, diphenylphosphine. Examples include methyl acid, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide. Of these, dimethyl phenylphosphonate and diethyl benzylphosphonate are particularly preferred.

  Among the phosphorus compounds described above, a phosphorus metal salt compound is particularly preferable as the phosphorus compound in the present invention. The phosphorus metal salt compound is not particularly limited as long as it is a metal salt of a phosphorus compound. However, when a metal salt of a phosphonic acid compound is used, the physical properties improving effect and catalytic activity improving effect of the polyester, which are the problems of the present invention, are improved. Largely preferred. Examples of the metal salt of the phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

  Further, among the above-described phosphorus compounds, when the metal part of the metal salt is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn, the catalytic activity is improved. Is preferable. Of these, Li, Na, and Mg are particularly preferable.

  As the phosphorus metal salt compound used in the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula (Chemical Formula 18) because the effect of improving physical properties and the effect of improving catalytic activity are large.

(In the formula (Chemical Formula 18), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group having 1 to 50 carbon atoms. R ² represents , Hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and a hydrocarbon group having 1 to 50 carbon atoms, R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. A hydrocarbon group having 1 to 50 carbon atoms including a group or carbonyl, l is an integer of 1 or more, m is 0 or an integer of 1 or more, l + m is 4 or less, M is (l + m And n represents an integer greater than or equal to 1. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

Examples of R ¹ include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R ² include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, substituted phenyl and naphthyl, and a group defined as -CH ₂ CH ₂ OH and the like. Examples of R ³ O ⁻ include hydroxide ions, alcoholate ions, acetate ions, and acetylacetone ions.

  Among the compounds represented by the general formula (Formula 18), it is preferable to use at least one selected from the compounds represented by the following general formula (Formula 19).

(In formula (Chemical Formula 19), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group having 1 to 50 carbon atoms. R ³ represents , Hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl, l is an integer of 1 or more, and m is 0 or an integer of 1 or more. , L + m is 4 or less, M represents a (l + m) -valent metal cation, and the hydrocarbon group contains an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl. May be good.)

Examples of R ¹ include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R ³ O ⁻ include hydroxide ions, alcoholate ions, acetate ions, and acetylacetone ions.

  Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

  Among the above formulas (Chemical formula 19), when M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn, the effect of improving the catalytic activity is large and preferable. Of these, Li, Na, and Mg are particularly preferable.

  Examples of the metal salt compound of phosphorus according to the present invention include lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [ethyl (1-naphthyl) methylphosphonate], potassium [ (2-naphthyl) methylphosphonate ethyl], magnesium bis [(2-naphthyl) methylphosphonate ethyl], lithium [benzylphosphonate ethyl], sodium [benzylphosphonate ethyl], magnesium bis [benzylphosphonate ethyl], beryllium bis [Ethyl benzylphosphonate], strontium bis [ethyl benzylphosphonate], manganese bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid], sodium [(9-anths L) ethyl methylphosphonate], magnesium bis [(9-anthryl) methylphosphonate ethyl], sodium [ethyl 4-hydroxybenzylphosphonate], magnesium bis [4-hydroxybenzylphosphonate ethyl], sodium [4-chlorobenzylphosphone] Acid phenyl], magnesium bis [4-chlorobenzylphosphonate ethyl], sodium [methyl 4-aminobenzylphosphonate], magnesium bis [4-aminobenzylphosphonate methyl], sodium phenylphosphonate, magnesium bis [phenylphosphonic acid] Ethyl], zinc bis [ethyl phenylphosphonate] and the like. Among these, lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [ethyl (1-naphthyl) methylphosphonate], lithium [ethyl benzylphosphonate], Sodium [ethyl benzylphosphonate], magnesium bis [ethyl benzylphosphonate], sodium benzylphosphonate and magnesium bis [benzylphosphonic acid] are particularly preferred.

Among the phosphorus compounds described above, in the present invention, a phosphorus compound having at least one P—OH bond is particularly preferable as the phosphorus compound. In addition to particularly enhancing the physical properties improving effect of the polyester by containing these phosphorus compounds, the catalytic activity is improved by using these phosphorus compounds together with the aluminum compound used in the present invention during the polymerization of the polyester. Is seen greatly.
The phosphorus compound having at least one P—OH bond is not particularly limited as long as it is a phosphorus compound having at least one P—OH in the molecule. Among these phosphorus compounds, use of a phosphonic acid compound having at least one P-OH bond facilitates formation of a complex with an aluminum compound, and is highly preferable for improving the physical properties and improving the catalytic activity of the polyester.

  Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

  As the phosphorus compound having at least one P—OH bond of the present invention, when at least one selected from the compounds represented by the following general formula (Chemical Formula 20) is used, the physical property improving effect and the catalytic activity improving effect are large. preferable.

(In the formula (Chemical Formula 20), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group having 1 to 50 carbon atoms. R ² represents , Hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, n represents an integer of 1 or more, and the hydrocarbon group is an alicyclic structure such as cyclohexyl. And may contain an aromatic ring structure such as a branched structure or phenyl or naphthyl.)

Examples of R ¹ include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R ² include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, substituted phenyl and naphthyl, and a group defined as -CH ₂ CH ₂ OH and the like.

  Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

  Examples of phosphorus compounds having at least one P-OH bond used in the present invention include ethyl (1-naphthyl) methylphosphonate, (1-naphthyl) methylphosphonic acid, ethyl (2-naphthyl) methylphosphonate, ethyl benzylphosphonate, benzyl Phosphonic acid, ethyl (9-anthryl) methylphosphonate, ethyl 4-hydroxybenzylphosphonate, ethyl 2-methylbenzylphosphonate, phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate, 4-methoxybenzylphosphonic acid Examples include ethyl. Of these, ethyl (1-naphthyl) methylphosphonate and ethyl benzylphosphonate are particularly preferred.

  A preferable phosphorus compound of the present invention is a phosphorus compound represented by the chemical formula (Formula 21).

(In the formula (Chemical Formula 21), R ¹ represents a hydrocarbon group having ¹ to 49 carbon atoms, or a hydrocarbon group having ¹ to 49 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and R ² , R ³ each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, which has an alicyclic structure, a branched structure or an aromatic ring structure. May be included.)

More preferably, at least one of R ¹ , R ² and R ^{3 in} the chemical formula (Chemical Formula 21) is a compound containing an aromatic ring structure.

  Specific examples of these phosphorus compounds are shown below.

  Moreover, since the phosphorus compound used by this invention has a large effect, since the thing with a large molecular weight is hard to be distilled off at the time of superposition | polymerization.

  The phosphorus compound of the present invention is preferably a phosphorus compound having a phenol moiety in the same molecule. In addition to enhancing the physical properties of polyester by containing a phosphorus compound having a phenol moiety in the same molecule, the effect of increasing catalytic activity by using a phosphorus compound having a phenol moiety in the same molecule during polymerization of the polyester Is larger, and therefore the productivity of polyester is excellent.

  The phosphorus compound having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but a phosphonic acid compound, phosphinic acid compound, phosphine oxide compound having a phenol moiety in the same molecule. When one or more compounds selected from the group consisting of a compound, a phosphonous acid compound, a phosphinic acid compound, and a phosphine compound are used, the physical property improving effect and the catalytic activity improving effect of the polyester are greatly preferred. Among these, when a phosphonic acid compound having one or two or more phenol moieties in the same molecule is used, the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are particularly large and preferable.

  As a phosphorus compound which has the phenol part used by this invention in the same molecule | numerator, the compound represented by the following general formula (Formula 28)-(Formula 30) is preferable.

(In the formulas (Chemical Formula 28) to (Chemical Formula 30), R ¹ is a carbon having 1 to 50 carbon atoms including a phenol moiety, a substituent such as a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a phenol moiety. R ⁴ , R ⁵ and R ⁶ each independently represents a substituent such as hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group or an amino group. Represents a hydrocarbon group having 1 to 50 carbon atoms, R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and the like. Represents a hydrocarbon group, provided that the hydrocarbon group may contain a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl, and the ends of R ² and R ⁴ are bonded to each other. May be good.)

  Examples of the phosphorus compound having the phenol moiety of the present invention in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, diphenyl p-hydroxyphenylphosphonate, bis (P-hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate, p-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, p- Phenyl hydroxyphenylphenylphosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, bis (p-hydroxyphenyl Yl) phosphine oxide, tris (p- hydroxyphenyl) phosphine oxide, bis (p- hydroxyphenyl) methyl phosphine oxide, and the following formula (Formula 31), and the like compounds represented by to (Formula 34). Among these, a compound represented by the following formula (Chemical Formula 31) and dimethyl p-hydroxyphenylphosphonate are particularly preferable.

  As a compound represented by the above formula (Chemical Formula 33), SANKO-220 (manufactured by Sanko Co., Ltd.) is available.

  Among the phosphorus compounds having a phenol moiety used in the present invention in the same molecule, at least one selected from a metal salt compound of a specific phosphorus represented by the following general formula (Formula 35) is particularly preferable.

((In formula (Formula 35), R ^1, R ² are each independently hydrogen, .R ³ representing a hydrocarbon group having 1 to 30 carbon atoms, hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or R ⁴ represents a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group, R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a carbonyl group including carbonyl. Examples of R ⁴ O ⁻ include hydroxide ion, alcoholate ion, acetate ion, acetylacetone ion, etc. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m represents M is an (l + m) -valent metal cation, n is an integer of 1 or more, and the hydrocarbon group is an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. May be included.)

  Among these, at least one selected from compounds represented by the following general formula (Formula 36) is preferable.

(In the formula (Formula 36), M ^{n +} represents an n-valent metal cation. N represents 1, 2, 3 or 4.)

  Among the above formulas (Chemical Formula 35) or (Chemical Formula 36), when M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, Zn, the catalytic activity is improved. The effect is large and preferable. Of these, Li, Na, and Mg are particularly preferable.

  Specific phosphorus metal salt compounds of the present invention include lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzyl]. Ethyl phosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], potassium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3 , 5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-tert- Butyl-4-hydroxybenzylphosphonate methyl], strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-di-tert-butyl] Phenyl-4-hydroxybenzylphosphonate], manganese bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-4-hydroxybenzyl] Ethyl phosphonate], copper bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], zinc bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] and the like. Can be mentioned. Among these, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [ Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

  Among phosphorus compounds having a phenol moiety in the same molecule used in the present invention, at least one selected from specific phosphorus compounds having at least one P—OH bond represented by the following general formula (Formula 37) is particularly used. preferable.

(In the formula (Chemical Formula 37), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or Represents a C1-C50 hydrocarbon group containing an alkoxyl group, n represents an integer of 1 or more, and the hydrocarbon group includes an alicyclic structure such as cyclohexyl, a branched structure, and an aromatic ring structure such as phenyl or naphthyl. May be.)

  Among these, at least one selected from the compounds represented by the following general formula (Formula 38) is preferable.

(In formula (Chemical Formula 38), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group is a fatty acid such as cyclohexyl. (It may contain a ring structure, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

Examples of R ³ include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, substituted phenyl and naphthyl, and a group defined as -CH ₂ CH ₂ OH and the like.

  Specific phosphorus compounds having at least one P-OH bond of the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxy Methyl benzylphosphonate, isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, phenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl Examples include octadecyl -4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and the like. Of these, ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

  Among the phosphorus compounds having a phenol moiety used in the present invention in the same molecule, at least one phosphorus compound selected from specific phosphorus compounds represented by the following general formula (Formula 39) is preferable.

(In the above formula (Chemical Formula 39), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ and R ⁴ are each independently hydrogen and carbon atoms having 1 to 50 carbon atoms. Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrogen group, a hydroxyl group or an alkoxyl group, n represents an integer of 1 or more, and the hydrocarbon group is an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic such as phenyl or naphthyl. It may contain a ring structure.)

  Among the above general formulas (Chemical Formula 39), it is preferable to use at least one selected from the compounds represented by the following General Formula (Chemical Formula 40) because the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are high.

(In the above formula (Formula 40), R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, including a hydroxyl group or an alkoxyl group. The group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

Examples of R ³ and R ⁴ include short chain aliphatic groups such as hydrogen, methyl and butyl groups, long chain aliphatic groups such as octadecyl, phenyl groups, naphthyl groups, substituted phenyl groups and naphthyl groups. An aromatic group such as a group, a group represented by —CH ₂ CH ₂ OH, and the like.

  Specific phosphorus compounds used in the present invention include diisopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-n-butyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate. , Dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, and the like. Of these, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

  Among phosphorus compounds having a phenol moiety in the same molecule used in the present invention, a particularly desirable compound in the present invention is at least one phosphorus compound selected from compounds represented by chemical formulas (Chemical Formula 41) and (Chemical Formula 42) It is.

  As the compound represented by the above chemical formula (Chemical Formula 41), Irganox 1222 (manufactured by Ciba Specialty Chemicals) is commercially available. Chemicals) is commercially available and can be used.

  Other phosphorus compounds that are preferably used in the present invention are represented by the following phosphonic acid compounds having a linking group (X) represented by (Chemical Formula 43) or (Chemical Formula 44) or (Chemical Formula 45). Examples thereof include phosphonic acid compounds having no linking group (X).

[In the formula (Chemical Formula 43), R ¹ represents an aromatic ring structure having 6 to 50 carbon atoms or a heterocyclic structure having 4 to 50 carbon atoms, and the aromatic ring structure or the heterocyclic structure may have a substituent. Good. X is a linking group, an aliphatic hydrocarbon having 1 to 10 carbon atoms (which may be linear, branched or alicyclic), or an aliphatic group having 1 to 10 carbon atoms containing a substituent. Hydrocarbon (which may be linear, branched or alicyclic), —O—, —OCH ₂ —, —SO ₂ —, —CO—, —COCH ₂ —, —CH ₂ OCO—, It is selected from —NHCO—, —NH—, —NHCONH—, —NHSO ₂ —, —NHC ₃ H ₆ OCH ₂ CH ₂ O—. R ² and R ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ]

  The substituent of the aromatic ring structure and heterocyclic structure of the phosphorus compound represented by the formula (Chemical Formula 43) is a hydrocarbon group having 1 to 50 carbon atoms (an alicyclic structure, a branched structure, an aromatic ring even if it is linear) Or a hydroxyl group, a halogen group, a C1-C10 alkoxyl group or an amino group (C1-C10 alkyl or alkanol-substituted). Or nitro group, carboxyl group, aliphatic carboxylic acid ester group having 1 to 10 carbon atoms, formyl group, acyl group, sulfonic acid group, sulfonic acid amide group (alkyl group having 1 to 10 carbon atoms or alkanol substitution) 1 or 2 selected from a phosphoryl-containing group, a nitrile group, and a cyanoalkyl group. More than a seed.

  Examples of the phosphorus compound represented by the formula (Chemical Formula 43) include the following. Specifically, benzylphosphonic acid, benzylphosphonic acid monoethyl ester, 1-naphthylmethylphosphonic acid, 1-naphthylmethylphosphonic acid monoethyl ester, 2-naphthylmethylphosphonic acid, 2-naphthylmethylphosphonic acid monoethyl ester, 4-phenyl, Benzylphosphonic acid, 4-phenyl, benzylphosphonic acid monoethyl ester, 2-phenyl, benzylphosphonic acid, 2-phenyl, benzylphosphonic acid monoethyl ester, 4-chloro, benzylphosphonic acid, 4-chloro, benzylphosphonic acid mono Ethyl ester, 4-chloro, benzylphosphonic acid diethyl ester, 4-methoxy, benzylphosphonic acid, 4-methoxy, benzylphosphonic acid monoethyl ester, 4-methoxy, benzylphosphonic acid diethyl ester, 4-methyl, benzyl Sulphonic acid, 4-methyl, benzylphosphonic acid monoethyl ester, 4-methyl, benzylphosphonic acid diethyl ester, 4-nitro, benzylphosphonic acid, 4-nitro, benzylphosphonic acid monoethyl ester, 4-nitro, benzylphosphonic acid Diethyl ester, 4-amino, benzylphosphonic acid, 4-amino, benzylphosphonic acid monoethyl ester, 4-amino, benzylphosphonic acid diethyl ester, 2-methyl, benzylphosphonic acid, 2-methyl, benzylphosphonic acid monoethyl ester 2-methyl, benzylphosphonic acid diethyl ester, 10-anthranylmethylphosphonic acid, 10-anthranylmethylphosphonic acid monoethyl ester, 10-anthranylmethylphosphonic acid diethyl ester, (4-methoxyphenyl-, ethoxy-) me Ruphosphonic acid, (4-methoxyphenyl-, ethoxy-) methylphosphonic acid monomethyl ester, (4-methoxyphenyl-, ethoxy-) methylphosphonic acid dimethyl ester, (phenyl-, hydroxy-) methylphosphonic acid, (phenyl-, hydroxy-) Methylphosphonic acid monoethyl ester, (phenyl-, hydroxy-) methylphosphonic acid diethyl ester, (phenyl-, chloro-) methylphosphonic acid, (phenyl-, chloro-) methylphosphonic acid monoethyl ester, (phenyl-, chloro-) methylphosphonic acid Diethyl ester, (4-chlorophenyl) -iminophosphonic acid, (4-chlorophenyl) -iminophosphonic acid monoethyl ester, (4-chlorophenyl) -iminophosphonic acid diethyl ester, (4-hydroxyphenyl-, diphenyl-) Tylphosphonic acid, (4-hydroxyphenyl-, diphenyl-) methylphosphonic acid monoethyl ester, (4-hydroxyphenyl-, diphenyl-) methylphosphonic acid diethyl ester, (4-chlorophenyl-, hydroxy-) methylphosphonic acid, (4- Chlorphenyl-, hydroxy-) methylphosphonic acid monomethyl ester, (4-chlorophenyl-, hydroxy-) methylphosphonic acid dimethyl ester, and other phosphorus compounds containing a heterocyclic ring include 2-benzofuranylmethylphosphonic acid diethyl ester, 2 -Benzofuranylmethylphosphonic acid monoethyl ester, 2-benzofuranylmethylphosphonic acid, 2- (5-methyl) benzofuranylmethylphosphonic acid diethyl ester, 2- (5-methyl) benzofuranylmethylphosphonic acid monoe Glycol ester, such as 2- (5-methyl) benzo furanyl methyl phosphonic acid. The phosphorus compound which has said coupling group is a preferable aspect at the point of polymerization activity.

  Examples of other compounds having a linking group (X) that are preferably used in the present invention include phosphorus compounds represented by the formula (Formula 44).

[In the formula (Chemical Formula 44), R ⁰ is a hydroxyl group, a C1-C10 alkyl group, —COOH group or —COOR ⁴ (R ⁴ represents a C1-C4 alkyl group), alkylene glycol group or monoalkoxyalkylene. Represents a glycol group (monoalkoxy represents C1-C4, alkylene glycol represents C1-C4 glycol). R ¹ represents an aromatic ring structure such as benzene, naphthalene, biphenyl, diphenyl ether, diphenylthioether, diphenylsulfone, diphenylmethane, diphenyldimethylmethane, diphenylketone, anthracene, phenanthrene, and pyrene. R ² and R ³ each independently represents a hydrogen atom, a C1-C4 hydrocarbon group, a hydroxyl group, or a C1-C4 hydrocarbon group having an alkoxyl group. m represents an integer of 1 to 5, and when R ⁰ is plural, the same substituent or a combination of different substituents may be used. n represents 0 or an integer of 1 to 5. ]

  Among the phosphorus compounds represented by the formula (Formula 44) used in the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure as benzene include the following. That is, 2-hydroxybenzylphosphonic acid diethyl ester, 2-hydroxybenzylphosphonic acid monoethyl ester, 2-hydroxybenzylphosphonic acid, 4-hydroxybenzylphosphonic acid diethyl ester, 4-hydroxybenzylphosphonic acid monoethyl ester, 4-hydroxy Benzylphosphonic acids, 6-hydroxybenzylphosphonic acid diethyl ester, 6-hydroxybenzylphosphonic acid monoethyl ester, 6-hydroxybenzylphosphonic acid, and the like include, but are not limited to, benzylphosphonic acids having a hydroxyl group introduced into the benzene ring. It is not a thing.

  Also, 2-n-butylbenzylphosphonic acid diethyl ester, 2-n-butylbenzylphosphonic acid monomethyl ester, 2-n-butylbenzylphosphonic acid, 3-n-butylbenzylphosphonic acid diethyl ester, 3-n-butylbenzyl Phosphonic acid monoethyl ester, 3-n-butylbenzylphosphonic acid, 4-n-butylbenzylphosphonic acid diethyl ester, 4-n-butylbenzylphosphonic acid monoethyl ester, 4-n-butylbenzylphosphonic acid, 2,5 -N-dibutylbenzylphosphonic acid diethyl ester, 2,5-n-dibutylbenzylphosphonic acid monoethyl ester, 2,5-n-dibutylbenzylphosphonic acid, 3,5-n-dibutylbenzylphosphonic acid diethyl ester, 3, 5-n-dibutylbenzylphosphonic acid monoethyl ester, 3,5-n-dibutylben Benzyl phosphonic acids was introduced alkyl benzene ring such as Ruhosuhon acid but not limited thereto.

  Further, 2-carboxybenzylphosphonic acid diethyl ester, 2-carboxybenzylphosphonic acid monoethyl ester, 2-carboxybenzylphosphonic acid, 3-carboxybenzylphosphonic acid diethyl ester, 3-carboxybenzylphosphonic acid monoethyl ester, 3-carboxy Benzylphosphonic acid, 4-carboxybenzylphosphonic acid diethyl ester, 4-carboxybenzylphosphonic acid monoethyl ester, 4-carboxybenzylphosphonic acid, 2,5-dicarboxybenzylphosphonic acid diethyl ester, 2,5-dicarboxybenzylphosphone Acid monoethyl ester, 2,5-dicarboxybenzylphosphonic acid, 3,5-dicarboxybenzylphosphonic acid diethyl ester, 3,5-dicarboxybenzylphosphonic acid Ethyl ester, 3,5-dicarboxybenzylphosphonic acid, 2-methoxycarbonylbenzylphosphonic acid diethyl ester, 2-methoxycarbonylbenzylphosphonic acid monoethyl ester, 2-methoxycarbonylbenzylphosphonic acid, 3-methoxycarbonylbenzylphosphonic acid diethyl Ester, 3-methoxycarbonylbenzylphosphonic acid monoethyl ester, 3-methoxycarbonylbenzylphosphonic acid, 4-methoxycarbonylbenzylphosphonic acid diethyl ester, 4-methoxycarbonylbenzylphosphonic acid monoethyl ester, 4-methoxycarbonylbenzylphosphonic acid, 2,5-dimethoxycarbonylbenzylphosphonic acid diethyl ester, 2,5-dimethoxycarbonylbenzylphosphonic acid monoethyl ester Carboxyl on the benzene ring such as 2,5-dimethoxycarbonylbenzylphosphonic acid, 3,5-dimethoxycarbonylbenzylphosphonic acid diethyl ester, 3,5-dimethoxycarbonylbenzylphosphonic acid monoethyl ester, 3,5-dimethoxycarbonylbenzylphosphonic acid, etc. Benzylphosphonic acids into which a group or a carboxylic acid ester group has been introduced may be mentioned, but the invention is not limited thereto.

  Further, 2- (2-hydroxyethoxy) benzylphosphonic acid diethyl ester, 2- (2-hydroxyethoxy) benzylphosphonic acid monoethyl ester, 2- (2-hydroxyethoxy) benzylphosphonic acid, 3- (2-hydroxyethoxy) ) Benzylphosphonic acid diethyl ester, 3- (2-hydroxyethoxy) benzylphosphonic acid monoethyl ester, 3- (2-hydroxyethoxy) benzylphosphonic acid, 4- (2-hydroxyethoxy) benzylphosphonic acid diethyl ester, 4- (2-hydroxyethoxy) benzylphosphonic acid monoethyl ester, 4- (2-hydroxyethoxy) benzylphosphonic acid, 2,5-di (2-hydroxyethoxy) benzylphosphonic acid diethyl ester, 2,5-di (2- Hydroxyethoxy) benzylphosphonic acid monoethyl Ester, 2,5-di (2-hydroxyethoxy) benzylphosphonic acid, 3,5-di (2-hydroxyethoxy) benzylphosphonic acid diethyl ester, 3,5-di (2-hydroxyethoxy) benzylphosphonic acid monoethyl Ester, 3,5-di (2-hydroxyethoxy) benzylphosphonic acid, 2- (2-methoxyethoxy) benzylphosphonic acid diethyl ester, 2- (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 1- (2 -Methoxyethoxy) benzylphosphonic acid, 3- (2-methoxyethoxy) benzylphosphonic acid monomethyl ester, 3- (2-methoxyethoxy) benzylphosphonic acid diethyl ester, 3- (2-methoxyethoxy) benzylphosphonic acid monoethyl ester 3- (2-methoxyethoxy) benzylphosphonic acid, 4 (2-methoxyethoxy) benzylphosphonic acid diethyl ester, 4- (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 4- (2-methoxyethoxy) benzylphosphonic acid, 2,5-di (2-methoxyethoxy) Benzylphosphonic acid diethyl ester, 2,5-di (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 2,5-di (2-methoxyethoxy) benzylphosphonic acid, 3,5-di (2-methoxyethoxy) Benzenephosphonic acid diethyl ester, 3,5-di (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 3,5-di (2-methoxyethoxy) benzylphosphonic acid and other benzene rings such as alkylene glycol groups or monoalkoxylation And benzylphosphonic acids introduced with an alkylene glycol group. The

  Among the phosphorus compounds represented by (Chemical Formula 44), the phosphorus compound whose aromatic ring structure having a substituent is benzene is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Formula 44) used in the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure of naphthalene include the following. 1- (5-hydroxy) naphthylmethylphosphonic acid diethyl ester, 1- (5-hydroxy) naphthylmethylphosphonic acid monoethyl ester, 1- (5-hydroxy) naphthylmethylphosphonic acid, 1- (5-hydroxy) naphthylmethylphosphonic acid Diethyl ester, 1- (5-hydroxy) naphthylmethylphosphonic acid monoethyl ester, 1- (5-hydroxy) naphthylmethylphosphonic acid, 1- (5-n-butyl) naphthylmethylphosphonic acid diethyl ester, 1- (5-n- Butyl) naphthylmethylphosphonic acid monoethyl ester, 1- (5-n-butyl) naphthylmethylphosphonic acid, 1- (4-carboxy) naphthylmethylphosphonic acid diethyl ester, 1- (4-carboxy) naphthylmethylphosphonic acid monoethyl ester Ter, 1- (4-carboxy) naphthylmethylphosphonic acid, 1- (4-methoxycarbonyl) naphthylmethylphosphonic acid diethyl ester, 1- (4-methoxycarbonyl) naphthylmethylphosphonic acid monoethyl ester, 1- (4-methoxycarbonyl) Naphthylmethylphosphonic acid, 1- [4- (2-hydroxyethoxy)] naphthylmethylphosphonic acid diethyl ester, 1- [4- (2-hydroxyethoxy)] naphthylmethylphosphonic acid monoethyl ester, 1- [4- (2-hydroxy) Ethoxy)] naphthylmethylphosphonic acid, 1- (4-methoxyethoxy) naphthylmethylphosphonic acid diethyl ester, 1- (4-methoxyethoxy) naphthylmethylphosphonic acid monoethyl ester, 1- (4-methoxyethoxy) naphthylmethylphosphonic acid Acid, 1- (5-hydroxy) naphthylmethylphosphonic acid diethyl ester, 2- (6-hydroxy) naphthylmethylphosphonic acid diethyl ester, 2- (6-hydroxy) naphthylmonoethylphosphonic acid, 2- (6-hydroxy) naphthylmethylphosphonic acid Acid, 2- (6-n-butyl) naphthylmethylphosphonic acid diethyl ester, 2- (6-n-butyl) naphthylmethylphosphonic acid monoethyl ester, 2- (6-n-butyl) naphthylmethylphosphonic acid, 2- (6 -Carboxy) naphthylmethylphosphonic acid diethyl ester, 2- (6-carboxy) naphthylmethylphosphonic acid monoethyl ester, 2- (6-carboxy) naphthylmethylphosphonic acid, 2- (6-methoxycarbonyl) naphthylmethylphosphonic acid diethyl ester, 2- ( 6-methoxycarbonyl) naphthylmethylphosphonic acid monoethyl ester, 2- (6-methoxycarbonyl) naphthylmethylphosphonic acid, 2- [6- (2-hydroxyethoxy)] naphthylmethylphosphonic acid diethyl ester, 2- [6- (2- Hydroxyethoxy)] naphthylmethylphosphonic acid monoethyl ester, 2- [6- (2-hydroxyethoxy)] naphthylmethylphosphonic acid, 2- (6-methoxyethoxy) naphthylmethylphosphonic acid diethyl ester, 2- (6-methoxyethoxy) naphthyl Alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monoalkoxyalkylene glycol on naphthalene ring such as methylphosphonic acid monoethyl ester and 2- (6-methoxyethoxy) naphthylmethylphosphonic acid Although like phosphonic acids and the like are introduced is not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44), the phosphorus compound in which the aromatic ring structure having a substituent is naphthalene is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Formula 44) used in the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure of biphenyl include the following. That is, 4- (4-hydroxyphenyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyl) benzylphosphonic acid, 4- (4-n- Butylphenyl) benzylphosphonic acid diethyl ester, 4- (4-n-butylphenyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenyl) benzylphosphonic acid, 4- (4-carboxyphenyl) benzylphosphone Acid diethyl ester, 4- (4-carboxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyl) benzylphosphonic acid, 4- (4-methoxycarbonylphenyl) benzylphosphonic acid diethyl ester, 4- (4 -Methoxycarbonylph Nyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyl) benzylphosphonic acid, 4- (4-hydroxyethoxyphenyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxyethoxyphenyl) benzylphosphonic acid mono Ethyl ester, 4- (4-hydroxyethoxyphenyl) benzylphosphonic acid, 4- (4-methoxyethoxyphenyl) benzylphosphonic acid diethyl ester, 4- (4-methoxyethoxyphenyl) benzylphosphonic acid monoethyl ester, 4- ( 4-methoxyethoxyphenyl) phosphones in which an alkyl group, a carboxyl group, a carboxylic ester group, an alkylene glycol group, a monomethoxyalkylene glycol group or the like is introduced into a biphenyl ring such as benzylphosphonic acid Although s and the like are not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44), the phosphorus compound in which the aromatic ring structure having a substituent is biphenyl is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44) used in the present invention, the following can be given as phosphorus compounds in which the aromatic ring structure having a substituent is diphenyl ether. That is, 4- (4-hydroxyphenyloxy) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyloxy) benzylphosphonic acid, 4- (4 -N-butylphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-butylphenyloxy) benzylphosphonic acid, 4- (4- Carboxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyloxy) benzylphosphonic acid, 4- (4-methoxycarbonylphenyloxy) Benji Phosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyloxy) benzylphosphonic acid, 4- (4-hydroxyethoxyphenyloxy) benzylphosphonic acid Monoethyl ester, 4- (4-hydroxymethoxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenyloxy) benzylphosphonic acid, 4- (4-methoxyethoxyphenyloxy) benzylphosphonic acid monoethyl An alkyl group on a diphenyl ether ring such as ester, 4- (4-methoxyethoxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenyloxy) benzylphosphonic acid, Rubokikishiru group, a carboxylic acid ester group, an alkylene glycol group, and a phosphonic acids like are introduced monomethoxy polyalkylene glycol groups are not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44), the phosphorus compound whose aromatic ring structure having a substituent is diphenyl ether is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44) used in the present invention, examples of the phosphorus compounds in which the aromatic ring structure having a substituent is diphenithioether include the following. That is, 4- (4-hydroxyphenylthio) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenylthio) benzylphosphonic acid, 4- (4 -N-butylphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-butylphenylthio) benzylphosphonic acid, 4- (4- Carboxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylthio) benzylphosphonic acid, 4- (4-methoxycarbonylphenylthio) Benzylphosphonic acid monoethyl Ester, 4- (4-methoxycarbonylphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenylthio) benzylphosphonic acid, 4- (4-hydroxyethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenylthio) benzylphosphonic acid, 4- (4-methoxyethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylthio) benzylphosphonic acid and other diphenylthioether rings have an alkyl group, a carboxyl group, a carboxylic acid ester Group, alkylene glycol group, and a phosphonic acids like are introduced monomethoxy polyalkylene glycol groups are not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44), the phosphorus compound in which the aromatic ring structure having a substituent is diphenylthioether is not limited to the above-mentioned single substituent species. A mixture of a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Formula 44) used in the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure of diphenylsulfone include the following. 4- (4-hydroxyphenylsulfonyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenylsulfonyl) benzylphosphonic acid, 4- (4-n -Butylphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-butylphenylsulfonyl) benzylphosphonic acid, 4- (4-carboxyphenyl) Sulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylsulfonyl) benzylphosphonic acid, 4- (4-methoxycarbo) Ruphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenylsulfonyl) benzylphosphonic acid, 4- (4-hydroxyethoxyphenyl) Sulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenylsulfonyl) benzylphosphonic acid, 4- (4-methoxyethoxyphenylsulfonyl) Benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylsulfonyl) ) Examples include, but are not limited to, phosphonic acids in which an alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monomethoxyalkylene glycol group or the like is introduced into a diphenylsulfone ring such as benzylphosphonic acid. .

  Among the phosphorus compounds represented by the formula (Chemical Formula 44), the phosphorus compound in which the aromatic ring structure having a substituent is diphenylsulfone is not limited to the above-mentioned single substituent species. A mixture of a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44) used in the present invention, examples of the phosphorus compounds having an aromatic ring structure having a substituent as diphenylmethane include the following. That is, 4- (4-hydroxybenzyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxybenzyl) benzylphosphonic acid, 4- (4-n- Butylbenzyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylbenzyl) benzylphosphonic acid monoethyl ester, 4- (4-butylbenzyl) benzylphosphonic acid, 4- (4-carboxybenzyl) benzylphosphonic acid Monoethyl ester, 4- (4-carboxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxybenzyl) benzylphosphonic acid, 4- (4-methoxycarbonylbenzyl) benzylphosphonic acid monoethyl ester, 4- ( 4-methoxycarbonyl Benzyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylbenzyl) benzylphosphonic acid, 4- (4-hydroxyethoxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxybenzyl) benzylphosphonic acid Monoethyl ester, 4- (4-hydroxymethoxybenzyl) benzylphosphonic acid, 4- (4-methoxyethoxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxybenzyl) benzylphosphonic acid monoethyl ester, 4 An alkyl group, a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group or the like is introduced into a diphenylmethane ring such as-(4-methoxyethoxybenzyl) benzylphosphonic acid. And the like phosphonic acids include but are not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44), the phosphorus compound in which the aromatic ring structure having a substituent is diphenylmethane is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Formula 44) used in the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure of diphenyldimethylmethane include the following. That is, 4- (4-hydroxyphenyldimethylmethyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyldimethylmethyl) benzylphosphonic acid, 4 -(4-n-butylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-butylphenyldimethylmethyl) benzylphosphonic acid 4- (4-carboxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyldimethylmethyl) Benzylphosphonic acid, 4- (4-methoxycarbonylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyldimethylmethyl) ) Benzylphosphonic acid, 4- (4-hydroxyethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenyldimethyl) Methyl) benzylphosphonic acid, 4- (4-methoxyethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenyldimethylmethyl) benzene Alkyl groups, carboxyxyl groups, carboxylic acid ester groups, alkylene glycol groups, monomethoxyalkylene glycol groups, etc. were introduced into diphenylmethane rings such as diphosphonic acid monoethyl ester and 4- (4-methoxyethoxyphenyldimethylmethyl) benzylphosphonic acid. Examples thereof include, but are not limited to, phosphonic acids.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44), the phosphorus compound whose aromatic ring structure having a substituent is diphenyldimethylmethane is not limited to the above-mentioned single substituent species. , A hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group may be used.

  Among the phosphorus compounds represented by the formula (Formula 44) used in the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure of diphenyl ketone include the following. That is, 4- (4-hydroxybenzoyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxybenzoyl) benzylphosphonic acid, 4- (4-n- Butylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-butylbenzoyl) benzylphosphonic acid, 4- (4-carboxybenzoyl) benzylphosphonic acid Monoethyl ester, 4- (4-carboxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxybenzoyl) benzylphosphonic acid, 4- (4-methoxycarbonylbenzoyl) benzylphosphonic acid monoethyl ester, 4- ( 4 Methoxycarbonylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylbenzoyl) benzylphosphonic acid, 4- (4-hydroxyethoxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxybenzoyl) benzyl Phosphonic acid monoethyl ester, 4- (4-hydroxymethoxybenzoyl) benzylphosphonic acid, 4- (4-methoxyethoxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxybenzoyl) benzylphosphonic acid monoethyl ester , 4- (4-methoxyethoxybenzoyl) benzylphosphonic acid and the like on an alkyl group, a carboxy group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxy group Although such phosphonic acids such as alkylene glycol group is introduced are exemplified but not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44), the phosphorus compound in which the aromatic ring structure having a substituent is diphenyl ketone is not limited to the above-mentioned single substituent species. A mixture of a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44) used in the present invention, examples of the phosphorus compounds having an anthracene substituted aromatic ring structure include the following. That is, 9- (10-hydroxy) anthrylmethylphosphonic acid diethyl ester, 9- (10-hydroxy) anthrylmethylphosphonic acid monoethyl ester, 9- (10-hydroxy) anthrylmethylphosphonic acid, 9- (10-n- Butyl) anthrylmethylphosphonic acid diethyl ester, 9- (10-n-butyl) anthrylmethylphosphonic acid monoethyl ester, 9- (10-n-butyl) anthrylylmethylphosphonic acid, 9- (10-carboxy) anthryl Methylphosphonic acid diethyl ester, 9- (10-carboxy) anthrylmethylphosphonic acid monoethyl ester, 9- (10-carboxy) anthrylmethylphosphonic acid, 9- (10-carboxy) 9- (2-hydroxyethoxy) anthrylmethylphosphone Acid di Chill ester, 9- (2-hydroxyethoxy) anthrylmethylphosphonic acid monoethyl ester, 9- (2-hydroxyethoxy) anthrylmethylphosphonic acid, 9- (2-methoxyethoxy) anthrylmethylphosphonic acid diethyl ester, 9- (2 -Methoxyethoxy) anthrylmethylphosphonic acid monoethyl ester, 9- (2-methoxyethoxy) anthrylmethylphosphonic acid, 9- (2-methoxycarbonyl) anthrylmethylphosphonic acid diethyl ester, 9- (2-methoxycarbonyl) anthryl Anthracene rings such as methylphosphonic acid monoethyl ester and 9- (2-methoxycarbonyl) anthrylmethylphosphonic acid have alkyl groups, carboxyxyl groups, carboxylic acid ester groups, alkylene glycol groups, monomethoxy groups. Although such phosphonic acids such as alkylene glycol group is introduced are exemplified but not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44), the phosphorus compound whose aromatic ring structure having a substituent is anthracene is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44) used in the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure being phenanthrene include the following. 1- (7-n-butyl) phenanthrylmethylphosphonic acid diethyl ester, 1- (7-n-butyl) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-n-butyl) phenanthrylmethylphosphone Acid, 1- (7-carboxy) phenanthrylmethylphosphonic acid diethyl ester, 1- (7-carboxy) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-carboxy) phenanthrylmethylphosphonic acid, 1- (7 -Hydroxyethoxy) phenanthrylmethylphosphonic acid diethyl ester, 1- (7-hydroxyethoxy) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-hydroxyethoxy) phenanthrylmethylphosphonic acid, 1- (7-methoxyethoxy) ) Phenanthryl 1- (7-methoxyethoxy) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-methoxyethoxy) phenanthrylmethylphosphonic acid, 1- (7-methoxycarbonyl) phenanthrylmethylphosphonic acid diethyl ester Ester, 1- (7-methoxycarbonyl) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-methoxycarbonyl) phenanthrylmethylphosphonic acid, etc., phenanthrene ring, alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol Examples thereof include, but are not limited to, phosphonic acids into which a group or a monomethoxyalkylene glycol group has been introduced.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44), the phosphorus compound in which the aromatic ring structure having a substituent is phenanthrene is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Formula 44) used in the present invention, examples of the phosphorus compounds having an aromatic ring structure having a substituent as pyrene include the following. 1- (5-hydroxy) pyrenylmethylphosphonic acid diethyl ester, 1- (5-hydroxy) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-hydroxy) pyrenylmethylphosphonic acid, 1- (5-n- Butyl) pyrenylmethylphosphonic acid diethyl ester, 1- (5-n-butyl) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-n-butyl) pyrenylmethylphosphonic acid, 1- (5-carboxy) pyrenyl Methylphosphonic acid diethyl ester, 1- (5-carboxy) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-carboxy) pyrenylmethylphosphonic acid, 1- (5-hydroxyethoxy) pyrenylmethylphosphonic acid diethyl ester, 1- ( 5-hydroxyethoxy) pyrenylmethylphosphonate Ethyl ester, 1- (5-hydroxyethoxy) pyrenylmethylphosphonic acid, 1- (5-methoxyethoxy) pyrenylmethylphosphonic acid diethyl ester, 1- (5-methoxyethoxy) pyrenylmethylphosphonic acid monoethyl ester, 1- ( 5-methoxyethoxy) pyrenylmethylphosphonic acid, 1- (5-methoxycarbonyl) pyrenylmethylphosphonic acid diethyl ester, 1- (5-methoxycarbonyl) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-methoxycarbonyl) Examples include, but are not limited to, phosphonic acids in which an alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monomethoxyalkylene glycol group, etc. are introduced into a pyrene ring such as pyrenylmethylphosphonic acid. No.

  Among the phosphorus compounds represented by the formula (Chemical Formula 44), the phosphorus compound in which the aromatic ring structure having a substituent is pyrene is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Substituents such as hydroxyl groups, alkyl groups, carboxyl groups, carboxyester groups, 2-hydroxyethoxy groups, 2-methoxyethoxy groups introduced into the series of aromatic rings are complexed with aluminum atoms during polymerization of the polyester. It is estimated to be deeply related to In addition, a carboxyl group or a hydroxyl group that is a functional group at the time of polyester formation is also included, and it is easily dissolved or taken into the polyester matrix.

Compared to an unsubstituted group in which R ⁰ is a hydrogen atom bonded to an aromatic ring structure (R ¹ ), a C1-C10 alkyl group, —COOH group or —COOR ⁴ (R ⁴ is a C1-C4 group) used in the present invention. A phosphorus compound substituted with an alkyl group), an alkylene glycol group or a monoalkoxyalkylene glycol group (monoalkoxy represents C1-C4, alkylene glycol represents a C1-C4 glycol) only improves the catalytic activity. This is preferable in terms of the effect of reducing foreign matter.

  Examples of the substituent bonded to the aromatic ring structure include C1-C10 alkyl groups, carboxyl and carboxyl ester groups, alkylene glycols and monoalkoxy alkylene glycols. From the viewpoint of the effect of reducing foreign matter, carboxyl and carboxyl ester groups, alkylene glycols and monoalkoxy alkylene glycols are more preferable. The reason for this is unknown, but it is assumed that the compatibility with the alkylene glycol, which is a medium for the polyester and the catalyst, is improved.

  The phosphorus compound (Chemical Formula 45) having no linking group (X) that is preferably used in the present invention is as follows.

(In formula (Formula 45), R ¹ represents a heterocyclic structure aromatic ring structure or 4-50 carbon atoms having 6 to 50 carbon atoms, aromatic ring structure or a heterocyclic structure which may have a substituent R ² and R ³ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, or a hydrocarbon group containing 1 to 20 carbon atoms, which is an alicyclic structure. And may have a branched structure or an aromatic ring structure.)

The substituent of the aromatic ring structure and heterocyclic structure of the phosphorus compound represented by the formula (Chemical Formula 45) is a hydrocarbon group having 1 to 50 carbon atoms (even if it is a straight chain, an alicyclic structure, a branched structure, an aromatic ring Or a hydroxyl group, a halogen group, a C1-C10 alkoxyl group or an amino group (C1-C10 alkyl or alkanol-substituted). Or nitro group, carboxyl group, aliphatic carboxylic acid ester group having 1 to 10 carbon atoms, formyl group, acyl group, sulfonic acid group, sulfonic acid amide group (alkyl group having 1 to 10 carbon atoms or alkanol substitution) 1 type or 2 types selected from phosphoryl-containing groups, nitrile groups, and cyanoalkyl groups. That's it. The aromatic ring structure of (Chemical Formula 45) is selected from benzene, naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenylmethane, diphenyldimethylmethane, anthracene, phenanthrene and pyrene. And the heterocyclic structure is selected from furan, benzofuran, isobenzofuran, dibenzofuran, naphthalane and phthalide. Moreover, it is preferable that at least one of R ² and R ^{3 in} the above formula (Formula 45) is a hydrogen atom.

Examples of the phosphorus compound represented by the formula (Formula 45) that can be used in the present invention include the following phosphorus compounds. That is, (3-nitro, 5-methyl) -phenylphosphonic acid diethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid monoethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid, ( 3-nitro, 5-methoxy) -phenylphosphonic acid diethyl ester, (3-nitro, 5-methoxy) -phenylphosphonic acid monoethyl ester, (3-nitro, 5-methoxy) -phenylphosphonic acid, (4-chloro ) -Phenylphosphonic acid diethyl ester, (4-chloro,)-phenylphosphonic acid monoethyl ester, (4-chloro) -phenylphosphonic acid, (5-chloro,)-phenylphosphonic acid diethyl ester, (5-chloro, ) -Phenylphosphonic acid monoethyl ester, (5-chloro,)-phenylphosphonic acid, (3-nitro, 5-methyl) -phenylphospho Phosphonic acid diethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid monoethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid, (4-nitro) -phenylphosphonic acid diethyl ester, (4 -Nitro) -phenylphosphonic acid monoethyl ester, (4-nitro) -phenylphosphonic acid, (5-nitro) -phenylphosphonic acid diethyl ester, (5-nitro) -phenylphosphonic acid monoethyl ester, (5-nitro) ) -Phenylphosphonic acid, (6-nitro) -phenylphosphonic acid diethyl ester, (6-nitro) -phenylphosphonic acid monoethyl ester, (6-nitro) -phenylphosphonic acid, (4-nitro, 6-methyl) -Phenylphosphonic acid diethyl ester, (4-nitro, 6-methyl) -phenylphosphonic acid monoethyl ester, (4-nitro, 6-methyl)- Phenylphosphonic acid and other phosphorus compounds represented by the formula (Chemical Formula 44), such as benzene, naphthalene, biphenyl, diphenyl ether, diphenylthioether, diphenylsulfone, diphenylmethane, diphenyldimethylmethane, diphenylketone, anthracene, phenanthrene, and pyrene A methylene chain as a linking group, that is, a phosphorus compound group in which —CH ₂ — is removed from each structural formula having an aromatic ring structure, and a heterocyclic ring-containing phosphorus compound such as 5-benzofuranylphosphonic acid diethyl ester, 5- Benzofuranylphosphonic acid monoethyl ester, 5-benzofuranylphosphonic acid, 5- (2-methyl) benzofuranylphosphonic acid diethyl ester, 5- (2-methyl) benzofuranylphosphonic acid monoethyl ester Such as 5- (2-methyl) benzo furanyl phosphonic acid. The phosphorus compound having no linking group may be slightly inferior in polymerization activity compared to the above-described phosphorus compound having a linking group. However, when the catalyst preparation method used in the present invention is used, it is used as a copolymerized polyester polymerization catalyst. It is possible to do.

  Phosphorus compounds have been known as heat stabilizers for polyesters, but it has not been known so far that even when these compounds are used in combination with conventional metal-containing polyester polymerization catalysts, melt polymerization is greatly promoted. It was. Actually, when a polyester is melt-polymerized using a typical catalyst for polyester polymerization, such as an antimony compound, a titanium compound, a tin compound or a germanium compound, as a polymerization catalyst, the phosphorus compound used in the present invention is substantially added. It is not observed that the polymerization is accelerated to a useful level.

  As the usage-amount of the phosphorus compound used by this invention, 0.001-2.0 mol% is preferable with respect to the number-of-moles of all the structural units of the polycarboxylic acid component of the copolymerized polyester obtained, and 0.005-1. More preferably, it is 0 mol%. When the addition amount of the phosphorus compound is less than 0.001 mol%, the addition effect may not be exhibited. When the addition amount exceeds 2.0 mol%, the catalytic activity as a copolymerized polyester polymerization catalyst is reduced. The tendency of the reduction varies depending on the amount of aluminum used.

  On the other hand, in the present invention, it is preferable that at least one selected from a small amount of an alkali metal, an alkaline earth metal and a compound thereof in addition to aluminum or a compound thereof coexists as a second metal-containing component. The coexistence of such a second metal-containing component in the catalyst system increases the catalytic activity, and thus a catalyst component having a higher reaction rate can be obtained, which is effective in improving productivity.

When adding an alkali metal, an alkaline earth metal and a compound thereof, the amount M (mol%) used is 1 × 10 ⁻⁶ or more and 1.0 or more with respect to the number of moles of all polycarboxylic acid units constituting the polyester. It is preferably less than mol%, more preferably 5 × 10 ^{−6 to} 0.5 mol%, further preferably 1 × 10 ^{−5 to} 0.3 mol%, and particularly preferably 1 × 10 10. ^{-5 to} 0.1 mol%. Since the addition amount of alkali metal and alkaline earth metal is small, it is possible to increase the reaction rate without causing problems such as deterioration of thermal stability, generation of foreign substances, coloring, deterioration of hydrolysis resistance, etc. is there. When the amount M of the alkali metal, alkaline earth metal, or compound thereof is 1.0 mol% or more, the thermal stability is lowered, the generation of foreign matter and coloring, and the hydrolysis resistance are problems in product processing. A case occurs. When M is less than 1 × 10 ⁻⁶ , the effect is not clear even when added.

  In the present invention, the alkali metal or alkaline earth metal constituting the second metal-containing component preferably used in addition to aluminum or a compound thereof includes Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr. At least one selected from Ba, Ba is preferable, and at least one selected from Li, Na, Mg or a compound thereof is more preferable. Examples of the alkali metal and alkaline earth metal compounds include saturated aliphatic carboxylates such as formic acid, acetic acid, propionic acid, butyric acid, and succinic acid, and unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid. , Aromatic carboxylates such as benzoic acid, halogen-containing carboxylates such as trichloroacetic acid, hydroxycarboxylates such as lactic acid, citric acid and salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphorus Inorganic acid salts such as acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid and bromic acid, and organic sulfonates such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid , Organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butyl Alkoxides such as alkoxy, chelate compounds and the like acetylacetonate, hydrides, oxides, and hydroxides and the like.

  Among these alkali metals, alkaline earth metals or their compounds, when using strongly alkaline ones such as hydroxides, these tend to be difficult to dissolve in diols such as ethylene glycol or organic solvents such as alcohols. The solution must be added to the polymerization system in an aqueous solution, which may cause a problem in the polymerization process. Furthermore, when a strongly alkaline material such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during the polymerization, and the polymerized polyester tends to be colored, and the hydrolysis resistance also decreases. Tend to. Therefore, the alkali metal or their compounds or the alkaline earth metals or their compounds used in the present invention are preferably alkali metal or alkaline earth metal saturated aliphatic carboxylates, unsaturated aliphatic carboxylates, Aromatic carboxylate, halogen-containing carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromic acid Inorganic acid salts, organic sulfonates, organic sulfates, chelate compounds, and oxides selected from Among these, from the viewpoints of ease of handling and availability, use of saturated aliphatic carboxylates of alkali metals or alkaline earth metals, particularly acetates is preferred.

  The polymerization catalyst used in the present invention is a polymerization catalyst such as an antimony compound, a germanium compound, a titanium compound, or a tin compound, and the addition of these components causes problems in the products such as polyester characteristics, processability, and color tone as described above. Coexistence within the range of the addition amount that does not occur is preferable because it is effective in improving productivity by shortening the polymerization time.

  By using the phosphorus compound used in the present invention in combination, a catalyst that exhibits a sufficient catalytic effect can be obtained even if the amount added as aluminum in the polyester polymerization catalyst is small.

  Below, the specific example of the preparation method of the solution at the time of using basic aluminum acetate as an aluminum compound is shown.

(Polymerization catalyst preparation example)
(1) Preparation example of 1,2-propanediol solution of aluminum compound Basic aluminum acetate (hydroxyaluminum diacetate; manufactured by Aldrich) was dispersed in distilled water at a concentration of 20 g / l and stirred at 95 ° C. It was heated and dissolved for 2 hours. An equal amount (volume ratio) of 1,2-propanediol was charged into the flask together with the aqueous solution, and water was distilled off from the system while stirring at 70 to 90 ° C. under reduced pressure (133 Pa). A 1,2-propanediol solution of an aluminum compound was prepared.

(2) Preparation example of 1,2-propanediol solution of phosphorus compound Irganox 1222 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a phosphorus compound was charged into a flask together with 1,2-propanediol, and the liquid temperature was stirred while purging with nitrogen. The mixture was heated at 160 ° C. for 12 hours to prepare a 1,2-propanediol solution of 30 g / l phosphorus compound.

(3) Preparation Example of Mixture of Aluminum Compound 1,2-Propanediol Solution / Phosphorus Compound 1,2-Propanediol Solution Each of the aluminum compound preparation example 1 and the phosphorus compound preparation example 1 A 1,2-propanediol solution was charged into a flask, mixed at room temperature so that the molar ratio of aluminum atoms and phosphorus atoms was 1: 2, and stirred for 5 hours to prepare a catalyst solution.

(4) Preparation Example of 1,2-Propanediol Solution of Alkali Metal Compound Lithium acetate (manufactured by Nacalai Co., Ltd., reagent grade) as an alkali metal compound was charged into a flask together with 1,2-propanediol and stirred at room temperature while purging with nitrogen. A 1,2-propanediol solution of an alkali metal compound at 30 g / l was prepared.

(5) Preparation examples (1) of the above aluminum compound and preparation examples of the above alkali metal compound (1), each 1,2-propanediol solution obtained in (4) is charged into a flask, and aluminum atoms and lithium atoms are in a molar ratio. The mixture was mixed at room temperature so as to be 1: 1, and stirred for 5 hours to prepare a catalyst solution.

  As another embodiment of the polymerization catalyst used in the present invention, an alkali metal compound and / or an alkaline earth metal 1,2- It goes without saying that a propanediol solution can be used in combination.

  In the copolymerized polyester resin (A) used in the present invention, among the polycarboxylic acid components, the aromatic dicarboxylic acid is 75 to 100 mol%, preferably 80 to 100 mol%, more preferably 85 to 100 mol%. is there. By making the aromatic dicarboxylic acid 75 mol% or more of all the polycarboxylic acid components, the strength and flexibility of the coating film are improved, and the workability, overbaking resistance and aging resistance are excellent, Since the barrier is improved, retort resistance and can content resistance are also excellent. If the aromatic dicarboxylic acid content is less than 75 mol%, the strength and flexibility of the coating film will be reduced, and the processability, overbake resistance and aging resistance may not be satisfactory. When damage occurs, retort resistance and content resistance are remarkably inferior. Examples of the aromatic dicarboxylic acid include terephthalic acid, orthophthalic acid orthophthalic acid, naphthalenedicarboxylic acid, and the like. Among these, it is preferable that terephthalic acid is contained in an amount of 25 mol% or more in the total acid content.

  The other dicarboxylic acid in the polycarboxylic acid component accounts for 0 to 25 mol%. In particular, aliphatic and / or alicyclic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid and other aliphatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid. And alicyclic dicarboxylic acids such as acid, tetrahydrophthalic acid, hexahydroisophthalic acid and 1,2-cyclohexene dicarboxylic acid, and unsaturated dicarboxylic acids such as fumaric acid, maleic acid and terpene-maleic acid adducts. Of these, one or more of them can be used within a range not affecting the coating film performance. In terms of hygiene, isophthalic acid, orthophthalic acid, adipic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, fumaric acid and maleic acid are preferred.

The copolymerized polyester resin (A) used in the present invention includes at least one polyalcohol having a side chain represented by (Formula 1) and / or 1,4-cyclohexanedimethanol among polyalcohol components. 30 to 100 mol%, preferably 40 to 90 mol%, and other polyalcohol components are in the range of 0 to 70 mol%, preferably 10 to 60 mol%.
Examples of the polyalcohol of (Formula 1) include propylene glycol (1,2-propanediol), 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, and neopentyl. Glycol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-dimethyl-1,3-pentanediol, 2,2-dimethyl-1 , 3-pentanediol, 2,2-dimethyl-1,3-butanediol, and the like can be used alone or in combination of two or more thereof.

  Examples of other polyalcohol components include ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3 -Pentanediol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1-methyl-1,8-octanediol, 3-propyl-1,5-pentanediol 3-methyl-1,6-hexanediol, 4-methyl-1,7-heptanediol, 4-methyl-1,8-octanediol, 4-propyl-1,8-octanediol, 1,9-nonane Aliphatic glycols such as diol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene Examples thereof include polyether glycols such as recall and polytetramethylene glycol, alicyclic polyalcohols such as 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecane glycols, and water-added bisphenols. One or two or more of these can be selected and used. Of these, preferred for hygiene are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, and diethylene glycol, and one or more of these can be mentioned. Can be used.

  Further, the copolymerized polyester resin (A) used in the present invention using an appropriate amount of 1,4-cyclohexanedimethanol and / or 1,2-propanediol as a glycol component, or 1,4-cyclohexanedimethanol and / or 2- The copolymerized polyester resins (K) to (M) used in the present invention using an appropriate amount of methyl-1,3-propanediol are capable of increasing the strength of the coating film while maintaining the flexibility, and thus have excellent workability and over-resistance. Bake, retort and content resistance are improved. 1,4-cyclohexanedimethanol is preferably used in the range of 10 to 30 mol% of the polyalcohol component. Further, 1,4-butanediol is a preferred glycol having good compatibility with the resol type phenol resin.

  In the copolymerized polyester resin (A) used in the present invention, a polycarboxylic acid component and / or polyalcohol having a functionality of 3 or more may be used in the polycarboxylic acid component and polyalcohol component as long as the processability is not deteriorated. Examples of the tri- or higher functional polycarboxylic acid component include trimellitic acid, pyromellitic acid, and benzophenone tetracarboxylic acid. Examples of the tri-functional or higher polyalcohol component include glycerin, trimethylol ethane, trimethylol propane, mannitol, Examples include sorbitol, pentaerythritol, α-methylglucoside and the like. For hygiene, trimellitic acid, trimethylolethane, trimethylolpropane, glycerin and the like are preferable. Preferably, it is used in the range of 0.1 to 3 mol%, and when these trifunctional components exceed 3 mol%, the flexibility of the copolyester resin (A) is lost and the processability is lowered.

  Among the properties of the copolyester resin (A) used in the present invention, the number average molecular weight is preferably 5,000 to 100,000, more preferably 8,000 to 30,000. A preferable glass transition temperature (Tg) is 15 to 120 ° C, more preferably 3050 to 100 ° C. If the number average molecular weight is less than 5,000, the coating film becomes brittle and the workability and hot water resistance are poor, and if it exceeds 100,000, the coating workability may be reduced. Further, when the glass transition temperature is less than 15 ° C., the retort resistance is inferior, and Tg of 30 ° C. or higher is desirable particularly for contents that require flavor properties. When Tg exceeds 120 ° C., workability and coating workability may deteriorate. The number average molecular weight referred to here is measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve, and the glass transition temperature (Tg) is measured by differential thermal analysis (DSC). It is.

The copolyester resin (A) used in the present invention may be given an acid value by any method. Examples of the purpose of giving the acid value include acceleration of curing of the cross-linking agent and improvement of adhesion with the metal material for cans. For these purposes, the preferred acid value range is 40 to 200 eq./10 ⁶ g.
If it exceeds 200 eq./10 ⁶ g, the retort resistance may be reduced or the acid addition component may elute into the contents. As a method for imparting an acid value, a depolymerization method in which a polyvalent carboxylic acid anhydride is added at a later stage of polymerization, a high acid value is added at the prepolymer (oligomer) stage, this is then polymerized, and a copolymer having an acid value is obtained. Although there is a method for obtaining a polymerized polyester resin, the former depolymerization method is preferred because it is easy to operate and a target acid value is easily obtained.

  Polyhydric carboxylic acid anhydrides used for acid addition in such depolymerization methods include phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, And ethylene glycol bistrimellitate dianhydride. Preferred are trimellitic anhydride and ethylene glycol bistrimellitate dianhydride.

  Examples of the crosslinking agent (B) used in the paint resin composition for a can inner surface of the present invention include amino resins, phenol resins, isocyanate compounds, and epoxy resins, but amino resins and phenol resins are preferred from the viewpoint of hygiene. In particular, amino resins are preferred for crosslinkability with polyester resins, processability, content resistance, and the like.

  As the above amino resins, methylolation obtained by reaction of amino components such as melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, and dicindiamide with aldehyde components such as formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde. An amino resin is mentioned. Those obtained by etherifying the methylol group of this methylolated amino resin with an alcohol having 1 to 6 carbon atoms are also included in the amino resin. Among these, it can be used alone or in combination. In terms of hygiene, amino resins using melamine and benzoguanamine are preferable, and amino resins using benzoguanamine which is excellent in retort resistance and extractability are more preferable.

  Examples of amino resins using benzoguanamine include methyl ether benzoguanamine resins in which some or all of the methylol groups of methylolated benzoguanamine resins are etherified with methyl alcohol, butyl etherified benzoguanamine resins butyl etherified with butyl alcohol, or methyl alcohol and butyl. A mixed etherified benzoguanamine resin mixed with methyl ether or butyl ether etherified with both alcohols is preferred. As said butyl alcohol, isobutyl alcohol and n-butyl alcohol are preferable.

  As the amino resin using melamine, a methylol group of the methylolated melamine resin is partially or entirely etherified with methyl alcohol, methyl etherified melamine resin, butyl etherified butyl ether with butyl alcohol, or methyl alcohol Preference is given to methyl ether etherified with both butyl alcohol and mixed etherified melamine resin with butyl ether.

  In addition, the phenol resin is not particularly limited, and examples thereof include a resol type resin obtained by reacting a phenol resin with an aldehyde in the presence of an alkali catalyst, and a novolak type obtained by reacting phenol with an aldehyde in the presence of an acidic catalyst. Particularly preferred as a crosslinking agent is a resole resin. The phenols used in these phenol resins are phenol, o-cresol, p-cresol, m-cresol, m-methoxyphenol, 2,3-xylenol, 2,5-xylenol, p-tert-butylphenol, p-ethyl. Examples include alkylphenols such as phenol, bisphenol-A, bisphenol-F, and the like, and alkylphenols that are excellent in compatibility with polyesters and not pointed out as environmental hormones are preferable. Mono- to trimethylolated products of these phenols, condensates thereof, or alkyl etherified products thereof, preferably butyl etherified products, or those modified in various ways such as epoxy modification, oil modification, melamine modification, amide modification, and acrylic modification. Etc. can be used.

  Further, for the purpose of further improving the curability, other crosslinking agents such as an epoxy resin and an isocyanate compound may be used in combination as long as the properties such as hygiene are not deteriorated.

  The coating resin composition for can inner surface of the present invention comprises a copolymerized polyester (A) and a crosslinking agent (B), preferably (A) / (B) = 60/40 to 95/5 in weight ratio, more preferably. Is 70/30 to 85/15. When the cross-linking agent (B) is less than the above component amount, a sufficient cured coating film cannot be obtained, processability, retort resistance, and content resistance cannot be obtained. Hygiene is reduced. Moreover, the hardening reaction of a coating film can be advanced with little heat energy by using a hardening | curing agent (C), and it becomes favorable coating film performance. It is desirable to use the curing agent (C) within the range of the following formula.

         [(A) + (B)] / (C) = 100 / 0.01 to 1.0 (weight ratio)

  If the amount is less than the above component amount, the effect of adding the curing catalyst cannot be obtained sufficiently, and processability, retort resistance, content resistance, and extractability may not be obtained. If the amount exceeds the above components, the cross-linking reaction may cause a reverse reaction or the copolyester resin may be decomposed, causing a phenomenon that the curability is remarkably reduced particularly during overbaking, and the workability, retort resistance, and content resistance Physical properties are reduced. Examples of the curing catalyst (C) used in the present invention include sulfuric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, camphor sulfonic acid, naphthalenesulfonic acid, and amine blocks thereof (partially neutralized by adding an amine). Among them, one or two or more of them can be used in combination, but dodecylbenzenesulfonic acid is preferable from the viewpoint of compatibility with the resin and hygiene. In particular, in the case of a combination of an amino resin and a sulfonic acid catalyst, in the case of baking at about 150 to 250 ° C. for 30 seconds to 15 minutes, the amount of catalyst is preferably 0.01 to 0.5, more preferably 0.8. It is 05-0.2.

  The resin composition for paints for cans of the present invention includes known inorganic pigments such as titanium oxide and silica, phosphoric acid and esterified products thereof, curing catalysts such as organotin compounds, surface smoothing agents, antifoaming agents, Known additives such as a dispersant can be blended.

  The resin composition for cans of the present invention is made into a paint in a state dissolved in a known organic solvent. Examples of organic solvents used for coating include solubility, evaporation rate from toluene, xylene, aromatic hydrocarbon compounds, ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexane, isophorone, methyl cellosolve, butyl cellosolve, ethylene glycol monoacetate, etc. It is selected in consideration of

  The paint resin composition for the inner surface of the can of the present invention can be applied to any metal plate that can be used for beverage cans, cans, lids, caps, etc., for example, tin plate, tin-free steel, aluminum And so on.

  The paint resin composition for inner surfaces of the can of the present invention can be applied by a known coating method such as roll coater coating or spray coating to obtain the coated metal plate of the present invention. The coating film thickness is not particularly limited, but is preferably 3 to 18 μm, more preferably 3 to 10 μm in terms of dry film thickness. The baking condition of the coating is usually about 100 to 300 ° C. for about 5 seconds to about 30 seconds, and further about 150 to 250 ° C. for about 1 to about 15 minutes. Is preferred.

  Hereinafter, the present invention will be specifically described with reference to examples. In the examples, the term “parts” means parts by weight. Each measurement item followed the following method.

1. Measurement of resin composition The molar ratio of the acid component and the alcohol component was determined by nuclear magnetic resonance spectroscopy and analysis by gas chromatography after alcoholysis.

2. Measurement of number average molecular weight The number average molecular weight was measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.

3. Measurement of reduced viscosity 0.10 g of polyester resin was dissolved in 25 cc of a mixed solvent of phenol / tetrachloroethane (weight ratio 6/4) and measured at 30 ° C.

4). Measurement of glass transition temperature It measured with the temperature increase rate of 20 degree-C / min using the differential scanning calorimeter (DSC).

5. Measurement of Acid Value 0.2 g of polyester was dissolved in 20 ml of chloroform and titrated with a 0.1N KOH ethanol solution to obtain the equivalent (eq / 10 ⁶ g) per 10 ⁶ g of resin.

6). Evaluation Method for Aluminum Foreign Body Insoluble in Copolyester 30 g of copolymer polyester pellets after melt polymerization and 300 ml of parachlorophenol / tetrachloroethane (3/1: weight ratio) mixed solution are put into a round bottom flask equipped with a stirrer, The pellet was stirred and dissolved in the mixed solution at 100 to 105 ° C. for 2 hours. The solution was allowed to cool to room temperature, and a polytetrafluoroethylene membrane filter (Advantec PTFE membrane filter, product name: T100A047A) having a diameter of 47 mm / pore size of 1.0 μm was used, and the total amount was under a pressure of 0.15 MPa. The foreign matter was filtered off with an effective filtration diameter of 37.5 mm.
The foreign matter was evaluated by filtration time as follows.
◯: Filtration time 5 hours or less △: Filtration time 5 hours to 24 hours ×: Filtration time 1 day or more

  When the filtration time exceeds 1 day, the content of fine foreign substances insoluble in the polyester increases, which leads to problems such as increased filter clogging during the filtration of the polyester in the polymerization process or molding process, which is not preferable. .

7). Transparency of Copolyester Resin (1) Transparency, (2) Degree of Coloring (1) and (2) were visually determined while the copolyester resin was in the form of a plate having substantially the same thickness.

(1) Transparency of resin ○: Almost transparent △: Slightly turbid ×: Remarkably turbid

(2) Degree of resin coloring ○: Almost not colored △: Slightly colored ×: Remarkably colored

8). Preparation of test piece The paint resin composition for the inner surface of the can was coated on a tin plate (70 mm x 150 mm x 0.3 mm) with a bar coater so that the film thickness would be 4-8 μm, cured and baked. did. As a baking condition, the coated tin plate was placed for 10 minutes in a drier at an atmospheric temperature of 210 ° C. to form a coating film.

9. Workability A sheet of tin plate with the same thickness as the test piece is sandwiched and bent in the direction of 180 degrees. This processed part was contacted with a sponge immersed in a 1% NaCl aqueous solution and evaluated by an energization value when a voltage of 5.5 V was applied. A smaller energization value is better.

10. Resistance to aging resistance The test piece was allowed to stand at room temperature for one month, and the workability was evaluated by the same method as in the above item 9.

11. Overbaking property The test piece was again heat-treated at 210 ° C. for 10 minutes, and this was evaluated for workability by the same method as in item 9 above.

12 Retort resistance Put a test piece in a stainless steel cup and pour ion-exchanged water up to half the height of the test piece. This is installed in a pressure cooker and a retort treatment is performed at 125 ° C. for 30 minutes. The evaluation after the treatment is performed for the underwater portion and the steam portion, and the degree of whitening is determined visually as follows.
◎: Good ○: Slightly whitened but no blisters △: Slightly whitened or slightly blistered ×: Significantly whitened or markedly blistered

13. Content Resistance Property After the test piece was immersed in an aqueous solution containing 3 wt% of sodium chloride and 3 wt% of lactic acid and treated at 125 ° C. for 30 minutes, the whitening of the coating film and the state of the blister were visually determined.
◎: Good ○: Slightly whitened but no blisters △: Slightly whitened or slightly blistered ×: Significantly whitened or markedly blistered

14 Extractability The extract after the retort test shown in item 12 above was titrated with potassium permanganate to quantify the amount of organic matter extracted from the coating film. A smaller number is better.

Synthesis example of the resin of the present invention: (A)
In a stainless steel reaction kettle equipped with a stirrer, a condenser, and a thermometer, terephthalic acid, trimellitic anhydride as an acid component, 1,2-propanediol as a polyalcohol component, 1, A 10 L autoclave was charged with a polymerization catalyst solution consisting of a mixture of 4-cyclohexanedimethanol and a 1,2-propanediol solution of the above aluminum compound / 1,3-propanediol solution of a phosphorus compound, and 3.5 Kg / cm · The temperature was gradually raised to 235 ° C. over 3 hours under nitrogen pressure of G to carry out esterification. Subsequently, the polymerization was performed under reduced pressure up to 1333 Pa over 1 hour, the temperature was raised to 250 ° C., and the latter polymerization was carried out at 133.3 Pa or lower for 120 minutes to obtain a polyester resin (A) used in the present invention. Table 1 shows the composition and characteristic values of the obtained copolyester resin (A). The obtained resin was cyclohexanone / solvesso-150 = 1/1 solvent as a resin varnish (a) having a solid content of 40%, and this was used to prepare the coating resin composition for can inner surfaces of the present invention.

Synthesis Examples of Resin of the Present Invention: (B), (C) and Synthesis Examples of Comparative Resins: (D) to (F)
The copolymer polyester resins (B), (C) and (D), (E), (F) using the respective polymerization catalyst species by a method according to the synthesis of the copolymer polyester resin (A) used in the present invention. Got. Table 1 shows the composition and characteristic values of each obtained copolyester resin.
In the case of an aluminum compound-only catalyst (C), the polymerization activity is slightly lower than that of the composite system (A) or (B), and the same good appearance is obtained in terms of transparency and coloring, except for a slight amount of foreign matter. Indicated. The antimony polymerization catalyst (D) was cloudy in addition to coloring. The titanium-based catalyst (E) is remarkably colored, and the tin-based polymerization catalyst (F) is relatively transparent and has little coloration. It is desired.

Synthesis examples of the resin of the present invention: (G) to (M)
The respective copolyester resins (G) to (M) were obtained by a method according to the synthesis of the copolyester resin (A) used in the present invention. Table 2 shows the composition and characteristic values of each obtained copolyester resin. The obtained resin was cyclohexanone / solvesso-150 = 1/1 resin varnish (g) to (m) having a solid content of 40%, and this was used to prepare the coating resin composition for can inner surfaces of the present invention. did.

Comparative resin synthesis example: (O) to (Q)
A comparative copolyester resin was obtained by a method according to the synthesis of the copolyester resin (A) used in the present invention. Table 3 shows the composition and characteristic values of the obtained comparative copolyester resins (O) to (Q). The obtained resin was cyclohexanone / solvesso-150 = 1/1 solvent varnish (o) to (q) having a solid content of 40%, and this was used to prepare the coating resin composition for the inner surface of the can according to the present invention. did.

(Example 1) 20 parts of resin varnish (a), 2.6 parts of Mycoat 106 (manufactured by Mitsui Cytec Co., Ltd.) and 0.01 part of dodecylbenzenesulfonic acid were added, and then cyclohexanone / solvesso-150 = 1/1. Was diluted to a viscosity suitable for coating to obtain a paint resin composition for can inner surfaces of the present invention. This was applied and baked by the method described above to obtain a test piece of the coated metal plate of the present invention. Table 4 shows the composition and the results of evaluating the test pieces.

(Examples 2 to 7)
After obtaining the paint resin composition for inner surfaces of cans of the present invention shown in Examples 2 to 7 in the same manner as in Example 1, application and baking were also performed in the same manner as described above to obtain a test piece of the coated metal plate of the present invention. It was. Table 4 shows the composition and the results of evaluating the test pieces.

(Comparative Examples 1-4)
In the same manner as in Example 1, after obtaining the paint resin composition for the inner surface of the can shown in Comparative Examples 1 to 3, application and baking were performed by the same method as described above to obtain a test piece of Comparative Example. Table 5 shows the composition and the results of evaluating the test pieces. Incidentally, Comparative Example 4 reproduces an epoxy-phenol resin paint.

  As is apparent from Tables 4 to 5, the metal plate coated with the resin composition for can coating of the present invention has processability, retort resistance, content resistance, overbaking resistance, aging resistance, and extractability. Is excellent in terms of.

  As mentioned above, although the coating resin composition for can inner surfaces of this invention and the coating metal plate which apply | coated this were demonstrated based on several Example, this invention is not limited to the structure described in the said Example. The configuration can be appropriately changed within a range not departing from the gist, such as appropriately combining the configurations described in the embodiments.

  The present invention uses a polymerization catalyst mainly containing an aluminum compound, and an inner surface of a can having a copolyester resin obtained without using a metal polymerization catalyst such as a tin compound, an antimony compound, a germanium compound and a titanium compound as an active ingredient Paint resin composition and a coated metal plate for the inner surface of a can coated with the same, and can be widely used in food and beverage metal cans.

Claims (10)

Polymerized in the presence of a polymerization catalyst containing an aluminum compound, the acid component is 75 to 100 mol% of an aromatic dicarboxylic acid, 0 to 25 mol% of an aliphatic and / or alicyclic dicarboxylic acid, and a polyalcohol component Is a copolyester resin in which at least one polyalcohol having a side chain represented by (Formula 1) and / or 1,4-cyclohexanedimethanol is 30 to 100 mol%, and other polyalcohol is 0 to 70 mol% A paint resin composition for a can inner surface, comprising (A) and a crosslinking agent (B).

(Wherein n = 0 or 1, R ¹ : H, methyl or ethyl group, R ² : H, or an alkyl group having 1 or more carbon atoms, R ³ : H or an alkyl group having 1 or more carbon atoms). Also, at least one of R ¹ , R ² and R ³ is an alkyl group.)   The paint resin composition for inner surfaces of cans according to claim 1, wherein the polyalcohol component represented by (Formula 1) is at least 1,2-propanediol or 2-methyl-1,3-propanediol.   3. The polymerization catalyst containing an aluminum compound comprises at least one selected from the group consisting of aluminum compounds and at least one selected from the group consisting of phosphorus compounds. The paint resin composition for inner surfaces of cans as described in 1.   The polymerization catalyst containing an aluminum compound is composed of at least one selected from the group consisting of aluminum compounds and at least one selected from the group consisting of alkali metals, alkaline earth metals and their compounds. The paint resin composition for can inner surfaces according to any one of claims 1 to 3.   The paint resin composition for inner surfaces of cans according to any one of claims 1 to 4, wherein the aluminum compound is a carboxylic acid-containing compound.   The paint resin composition for inner surfaces of cans according to claim 3, wherein the phosphorus compound is an aromatic phosphonic acid or a derivative thereof.   The paint resin composition for a can inner surface according to claim 4, wherein the alkali metal is Li, Na, and the alkaline earth metal is Mg.   The organic sulfonic acid is used as the curing catalyst (C) [(A) + (B)] / (C) = 100 / 0.01 to the paint resin composition for the inner surface of the can according to claim 1. A paint resin composition for the inner surface of a can, which is blended in a range of 1.0 (weight ratio).   The coating resin for inner surfaces of cans according to any one of claims 1 to 8, wherein the filtration time of aluminum-based foreign matters insoluble in the copolymerized polyester resin in the copolymerized polyester resin (A) is 5 hours or less. Composition.   A coated metal plate for a can inner surface, wherein the paint resin composition for a can inner surface according to any one of claims 1 to 9 is applied to a metal plate.