JP2008007716A - (meth) acrylic-modified oily alkyd resin, resin composition for water-based alkyd coating and method for producing them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition for a water-based alkyd coating, more in detail, a resin composition which contains no tin, no lead and no zinc compounds so as to deal with resource saving and markets desiring environmental conservation, controls resin discoloration caused by deficiency of thermal stability being a drawback of a titanium-based catalyst and has excellent heat resistance, especially useful for coating. <P>SOLUTION: The (meth)acrylic modified oily alkyd resin is obtained by using a natural fatty acid ester and a polycarboxylic acid anhydride as acid components and a 2-50C polyhydric alcohol as an alcohol component in the presence of a polymerization catalyst containing at least an aluminum compound to give an oily alkyd resin and subjecting the oily alkyd resin to graft polymerization with a polymerizable monomer and has an acid value of ≥50eq/10<SP>6</SP>g. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition for water-based alkyd paints and a method for producing the same, and more particularly relates to a water-based alkyd resin paint composition which is environmentally friendly and has improved colorability, water resistance and chemical resistance, and a method for producing the same.

  The alkyd resin coating material means a coating material mainly composed of an ester composed of a polybasic acid and a polyhydric alcohol, and a resin obtained by modifying the ester with a fatty acid or oil, and has been widely used. Alkyd resin paints have such advantages as a tough coating film and good color and gloss, but water resistance and chemical resistance are not necessarily sufficient. For this reason, various proposals have been made to solve these problems, but no satisfactory one has yet appeared.

  Oily alkyd resin is a method in which polyhydric alcohol is mixed with animal and vegetable oils, derived into a partial fatty acid ester of polyhydric alcohol by a known transesterification reaction, and then reacted by adding polyvalent carboxylic acid (as a modifier). By a method using crude oil derived from animals and plants) or a method of reacting three components of a mixed fatty acid, a polyvalent carboxylic acid and a polyhydric alcohol obtained by decomposing animal and vegetable oils (a method using a fatty acid as a modifier). It is manufactured.

  Crude oil or its fatty acid raw materials used as denaturing agents include palm oil, soybean oil, rice bran oil, dehydrated castor oil, flaxseed oil, cottonseed oil, etc., but these crude oils contain fine particles derived from the tissues of raw material animals and plants. , Pigments, proteins, phospholipids and other so-called gums. For this reason, when these crude oils are used as modified oils as they are, there are problems such as deterioration of resin color tone and deterioration of weather resistance.

  For this reason, oil refined by deoxidation (alkali refining), decolorization, etc. of crude oil is used as a denaturing agent, or fatty acids obtained by decomposing animal and vegetable oils are purified by distillation and used as a denaturing agent.

  However, even if the crude oil is deacidified and decolorized, it is difficult to remove these colored substances, and the fatty acid obtained by decomposing animal and vegetable oils has a high boiling point, so that the distillation temperature required for refining is also high. As a result, a heat-deteriorated product is generated and the color tone and weather resistance of the resin product are inevitably lowered.

  Furthermore, in oil-modified alkyd resins that are blended with amino resins such as melamine resin and urea resin as a cross-linking agent and used as a baked paint, a baking condition of 20 to 30 minutes at a temperature of 130 to 150 ° C. is generally employed. ing.

  However, at that time, depending on the baking conditions, the coating surface tends to yellow due to heat deterioration, and the product value decreases when used as an electric washing machine, electric refrigerator, automobile solid color, etc. as a white paint. There was a problem.

  Further, as a conventional technique related to biodegradable polyester in consideration of environmental aspects, those using tin, lead and zinc compounds as polymerization catalysts are mainly used (for example, Patent Document 1). Examples of other techniques include a titanium-based compound (for example, Patent Document 2) and trisacetylacetonato aluminum as a polymerization catalyst (for example, Patent Document 3). However, there are also arguments that tin compounds and the like may affect the environment, and there are voices in the market for products that do not contain them from the viewpoint of environmental protection. On the other hand, in the case of a titanium-based compound, the thermal stability is not sufficient, and the problem of coloring during molding is pointed out, and the problem that trisacetylacetonato aluminum is expensive is pointed out.

JP-A-6-49191 JP-A-8-73582 Japanese Patent Laid-Open No. 10-287735

  An object of the present invention is to provide a stable resin composition for aqueous alkyd paints that is environmentally friendly, has good adhesion, is excellent in color tone and weather resistance, has little heat discoloration.

  In view of these problems, the present inventors have made extensive studies on a resin composition that is environmentally friendly, has good adhesion, has little coloration, and has little heat discoloration and is suitable for water-based alkyd paints. Reached completion.

That is, the present invention
(1) An oily alkyd resin obtained using a natural fatty acid ester and a polycarboxylic acid anhydride as an acid component and a polyhydric alcohol having 2 to 50 carbon atoms as an alcohol component in the presence of a polymerization catalyst containing at least an aluminum compound (A) A (meth) acrylic-modified oily alkyd resin (B) having an acid value of 50 eq / 10 ⁶ g or more obtained by graft polymerization of a polymerizable monomer.
(2) The polymerization catalyst described in (1) above, wherein the polymerization catalyst is a polymerization catalyst composed of at least one selected from the group consisting of aluminum compounds and one selected from the group consisting of phosphorus compounds. (Meth) acrylic modified oily alkyd resin (B).
(3) The (meth) acryl as described in (1) above, wherein the polymerization catalyst comprises at least one selected from the group consisting of at least an aluminum compound, and an alkali metal and / or an alkaline earth metal. Modified oily alkyd resin (B).
(4) The (meth) acryl-modified oil-based alkyd resin (B) according to (1) above, wherein the polymerization catalyst comprises an aluminum compound, a phosphorus compound and an alkali metal and / or an alkaline earth metal.
(5) The aluminum compound as a constituent component of the polymerization catalyst is at least one selected from aluminum acetate, basic aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide chloride, and polyaluminum chloride. (Meth) acrylic-modified oily alkyd resin (B) according to any one of (1) to (4).
(6) The phosphorus compound that is a constituent component of the polymerization catalyst is selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. The (meth) acrylic-modified oily alkyd resin (B) according to any one of the above (2), (4) and (5), characterized in that it is at least one.
(7) The above (3), (4) and (5), wherein the alkali metal and / or alkaline earth metal is at least one selected from Li, Na, Ca, Mg or a compound thereof. The (meth) acryl-modified oily alkyd resin (B) according to any one of the above.
(8) The (meth) acryl-modified oily alkyd resin (B) according to any one of the above (1) to (7), wherein the polymerizable monomer contains at least (meth) acrylic acid.
(9) The neutralization agent (C) is used for the (meth) acryl-modified oily alkyd resin (B) according to any one of (1) to (8), and the acid value of the resin (B) is medium. A resin composition for aqueous alkyd paints, which is an aqueous dispersion prepared so as to satisfy a sum ratio of 1 to 2000%.
(10) The water-based alkyd paint resin composition according to (9), which contains a curing agent (D) capable of reacting with the (meth) acryl-modified oily alkyd resin (B).
(11) The resin composition for aqueous alkyd paints according to (10), wherein the curing agent (D) is at least one selected from alkyl etherified aminoformaldehyde resins, epoxy compounds and isocyanate compounds.
(12) The method for producing the (meth) acryl-modified oily alkyd resin according to any one of (1) to (8) above.
(13) A method for producing a resin composition for aqueous alkyd paints according to any one of (9) to (11) above.

  The resin composition for water-based alkyd paints according to the present invention has a high required quality in the field of paints, particularly in the automobile field by having not only weatherability and water resistance but also low coloring and excellent heat discoloration characteristics. I can answer.

  As an aluminum compound which comprises the polymerization catalyst of this invention, a well-known aluminum compound other than metallic aluminum can be used without limitation.

  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 alkoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethyl acetoacetate diiso-propoxide, organoaluminum compounds such as trimethylaluminum, triethylaluminum and their partial hydrolysates And aluminum oxide. 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.

  The amount of the aluminum compound used in the present invention is 1 to 200 ppm in terms of aluminum atom, based on the total weight of the carboxylic acid component such as a natural fatty acid ester of an oily alkyd resin or a polyvalent carboxylic acid. More preferably, it is 20-100 ppm. As described above, the amount of the aluminum component to be added is required to vary widely because the catalytic activity varies greatly depending on the types and combinations of natural fatty acid esters, polycarboxylic acids and diols used, and the polymerization method. The polymerization catalyst of the present invention exhibits sufficient catalytic activity. As a result, the resulting oily alkyd resin has excellent thermal stability, thermal oxidation stability and hydrolysis resistance, and suppresses the generation and coloring of foreign substances due to aluminum. Is done.

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 a preferable aspect that the basic aluminum acetate aqueous solution is the same ethylene glycol solution. That is, ethylene glycol is added to the above aqueous solution. The amount of ethylene glycol added is preferably 0.5 to 5 times the volume ratio of the aqueous solution. More preferably, the amount is 0.8 to 2 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. In particular, when alkylene glycol having a high melting point and solid at room temperature is used, it can be used as an aluminum compound / alkylene glycol solid solution.

  From the viewpoint of reducing catalytic activity and foreign matters of the resulting oily alkyd resin, it is preferable to use the above basic aluminum acetate solubilized in a solvent such as water or alkylene glycol, particularly those solubilized in water and / or alkylene glycol. Is also preferable.

  The phosphorus compound constituting the polymerization catalyst of the present invention is not particularly limited, but phosphoric acid and phosphoric acid esters such as trimethyl phosphoric acid, triethyl phosphoric acid, phenyl phosphoric acid and triphenyl phosphoric acid, phosphorous acid and trimethyl phosphine. Phyto, triethyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphite, etc. And phosphite esters.

  More preferable phosphorus compounds of the present invention are at least one phosphorus compound 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. By using these phosphorus compounds, an effect of improving the catalytic activity is seen, and an effect of improving physical properties such as the thermal stability of the oily alkyd resin 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 (Formula 1) to (Formula 6), respectively. It refers to a compound having the structure represented.

  Examples of the phosphonic acid compound of 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 of the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenylphenylphosphinate and the like. Examples of the phosphine oxide compound of 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 7) to (Chemical Formula 12). 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.

  In addition, when the compounds represented by the following general formulas (Chemical Formula 13) to (Chemical Formula 15) are used as the phosphorus compound of the present invention, the physical property improving effect and the catalytic activity improving effect are particularly large and preferable.

(In the formulas (Chemical Formula 13) to (Chemical Formula 15), 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 containing an amino group. Represents a hydrocarbon group having 1 to 50. R2 and R3 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 hydrogen group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl.)

  As the phosphorus compound of the present invention, a compound in which R1, R4, R5, and R6 are groups having an aromatic ring structure in the above formulas (Chemical Formula 13) to (Chemical Formula 15) is particularly preferable.

  Examples of the phosphorus compound of the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, diphenylphosphinic acid, diphenylphosphinic acid. Examples include methyl, 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, in the present invention, a metal salt compound of phosphorus is particularly preferable as the phosphorus compound. 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 property improving effect and catalytic activity of the oily alkyd resin, which are the problems of the present invention, are improved. The effect is large and preferable. 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 of the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula (Chemical Formula 16) because the effect of improving the physical properties and the effect of improving the catalytic activity are large.

(In the formula (Chem. 16), R1 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. R2 represents hydrogen. Represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and R3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group or a carbonyl group. 1 represents an integer of 1 or more, m represents 0 or an integer of 1 or more, l + m is 4 or less, and M is a (l + m) valence. Represents a metal cation, n represents an integer of 1 or more, and 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 R1 include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R2 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, and substitution. And a phenyl group, a naphthyl group, a group represented by —CH 2 CH 2 OH, and the like. Examples of R3O- include hydroxide ion, alcoholate ion, acetate ion and acetylacetone ion.

  Among the compounds represented by the general formula (Chemical Formula 16), it is preferable to use at least one selected from the compounds represented by the following General Formula (Chemical Formula 17).

(In the formula (Chemical Formula 17), R1 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. R3 represents hydrogen. Represents 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, 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 may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl. .)

  Examples of R1 include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R3O- include hydroxide ion, alcoholate ion, acetate ion and acetylacetone ion.

  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 17), 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 of the present invention during the polymerization of the oily alkyd resin. The effect 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, the use of a phosphonic acid compound having at least one P-OH bond facilitates complex formation with an aluminum compound, and is highly preferable for improving the physical properties and improving the catalytic activity of oily alkyd resins. .

  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, it is preferable to use at least one selected from the compounds represented by the following general formula (Chemical Formula 18) because the physical property improving effect and the catalytic activity improving effect are large. .

(In the formula (Chemical Formula 18), R1 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. R2 represents hydrogen. Represents 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 or branched. The structure may include an aromatic ring structure such as phenyl or naphthyl.)

  Examples of R1 include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R2 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, and substitution. And a phenyl group, a naphthyl group, a group represented by —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 the phosphorus compound having at least one P—OH bond of the present invention include (1-naphthyl) methylphosphonic acid ethyl, (1-naphthyl) methylphosphonic acid, (2-naphthyl) methylphosphonic acid ethyl, benzylphosphonic acid ethyl, benzylphosphonic acid. Acid, ethyl (9-anthryl) methylphosphonate, ethyl 4-hydroxybenzylphosphonate, ethyl 2-methylbenzylphosphonate, phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate, ethyl 4-methoxybenzylphosphonate Etc. 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 19).

(In the formula (Chemical Formula 19), R1 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 R2 and R3 are respectively 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, which includes an alicyclic structure, a branched structure, or an aromatic ring structure. May be good.)

  More preferably, at least one of R1, R2, and R3 in the chemical formula (Formula 19) is a compound containing an aromatic ring structure.

  Specific examples of these phosphorus compounds are shown below.

  Moreover, since the phosphorus compound of the present invention has a large molecular weight, it is more effective because it is less likely to be distilled off during 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 polyester polymerization Is larger, and therefore the polyester productivity 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, a phosphinic acid compound, a phosphine oxide compound having a phenol moiety in the same molecule. When one or two 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 effect of improving the physical properties and catalytic activity of the oily alkyd resin is greatly preferred. Among these, the use of a phosphonic acid compound having one or two or more phenol moieties in the same molecule is particularly preferable because the effect of improving the physical properties and improving the catalytic activity of the oily alkyd resin are particularly large.

  As a phosphorus compound which has the phenol part of this invention in the same molecule | numerator, the compound represented by the following general formula (Formula 26)-(Formula 28) is preferable.

(In the formulas (Chemical Formula 26) to (Chemical Formula 28), R1 is a C1-C50 hydrocarbon group including a phenol part, a hydroxyl group, a halogen group, an alkoxyl group, an amino group or the like, and a carbon number including a phenol part. Represents a hydrocarbon group having 1 to 50. R4, R5 and R6 each independently represent 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 carbon number of 1 R 2 and R 3 each independently represents a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. However, 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 R2 and R4 may be bonded to each other.)

  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 29), and the like compounds represented by to (Formula 32). Among these, the compound represented by the following formula (Chemical Formula 29) and dimethyl p-hydroxyphenylphosphonate are particularly preferable.

  As a compound represented by the above formula (Chemical Formula 31), SANKO-220 (manufactured by Sanko Co., Ltd.) can be used.

  Among the phosphorus compounds having the phenol moiety of 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 33) is particularly preferable.

(In the formula (Chemical Formula 33), R1 and R2 each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R3 includes hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. R4 represents a hydrocarbon group having 1 to 50 carbon atoms, R4 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group or a carbonyl group containing 1 to 50 carbon atoms, R4O- Examples 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 is 4 or less. represents an (l + m) -valent metal cation, n represents an integer of 1 or more, and the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

  Among these, at least one selected from compounds represented by the following general formula (Formula 34) is preferable.

(In the formula (Chemical Formula 34), Mn + represents an n-valent metal cation. N represents 1, 2, 3 or 4.)

  Among the above formulas (Chemical Formula 33) or (Chemical Formula 34), 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 the phosphorus compounds having the phenol moiety of the present invention in the same molecule, at least one selected from specific phosphorus compounds having at least one P—OH bond represented by the following general formula (Formula 35) is particularly preferable.

(In the formula (Chemical Formula 35), R1 and R2 each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R3 includes hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. Represents a hydrocarbon group having 1 to 50 carbon atoms, n represents an integer of 1 or more, and the hydrocarbon group may include an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

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

(In the formula (Chemical Formula 36), 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 an alicyclic ring such as cyclohexyl. It may contain a structure, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

  Examples of R3 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 And a phenyl group, a naphthyl group, a group represented by —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 the phenol moiety of the present invention in the same molecule, at least one phosphorus compound selected from specific phosphorus compounds represented by the following general formula (Formula 37) is preferable.

(In the above formula (Chemical Formula 37), R1 and R2 each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R3 and R4 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, and a hydroxyl group. Or it 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. You may go out.)

  Among the above general formulas (Chemical Formula 37), it is preferable to use at least one selected from the compounds represented by the following General Formula (Chemical Formula 38) because the effects of improving the physical properties and the catalytic activity of the oily alkyd resin are high.

(In the above formula (Chemical Formula 38), R3 and R4 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. (It may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

  Examples of R3 and R4 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, a group represented by —CH 2 CH 2 OH, and the like.

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

  Among the phosphorus compounds having the phenol moiety of the present invention in the same molecule, a particularly desirable compound in the present invention is at least one phosphorus compound selected from compounds represented by chemical formulas (Chemical Formula 39) and (Chemical Formula 40).

  As the compound represented by the above chemical formula (Chemical Formula 39), Irganox 1222 (manufactured by Ciba Specialty Chemicals) is commercially available, and as the compound represented by the chemical formula (Chemical Formula 40), Irganox 1425 (Ciba Specialty Chemical). 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 41) or (Chemical Formula 42) or (Chemical Formula 43). Examples thereof include phosphonic acid compounds having no linking group (X).

Embedded image R1-X- (P = O) (OR2) (OR3)
[In the formula (Chemical Formula 41), R1 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. . 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-, -OCH2-, -SO2-, -CO-, -COCH2-, -CH2OCO-, -NHCO-,- Selected from NH-, -NHCONH-, -NHSO2-, -NHC3H6OCH2CH2O-. R2 and R3 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 the heterocyclic structure of the phosphorus compound represented by the formula (Chemical Formula 41) 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 phosphoryl-containing groups, nitrile groups, and cyanoalkyl groups. More than a seed.

  Examples of the phosphorus compound represented by the formula (Chemical Formula 41) 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, 2-chloro, benzylphosphonic acid, 2-chloro, benzylphosphonic acid mono Ethyl ester, 2-chloro, benzylphosphonic acid diethyl ester, 2-methoxy, benzylphosphonic acid, 2-methoxy, benzylphosphonic acid monoethyl ester, 2-methoxy, benzylphosphonic acid diethyl ester, 2-methyl, benzyl Sphonic acid, 2-methyl, benzylphosphonic acid monoethyl ester, 2-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, 4-methyl, benzylphosphonic acid, 4-methyl, benzylphosphonic acid monoethyl ester 4-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.

  Other compounds having a linking group (X) that are preferably used in the present invention include phosphorus compounds represented by the formula (Formula 42).

(R0) m-R1- (CH2) n- (P = O) (OR2) (OR3)
[In the formula (Chemical Formula 42), R0 represents a hydroxyl group, a C1-C10 alkyl group, -COOH group or -COOR4 (R4 represents a C1-C4 alkyl group), an alkylene glycol group or a monoalkoxyalkylene glycol group. (Monoalkoxy represents C1-C4, alkylene glycol represents C1-C4 glycol). R1 represents an aromatic ring structure such as benzene, naphthalene, biphenyl, diphenyl ether, diphenylthioether, diphenylsulfone, diphenylmethane, diphenyldimethylmethane, diphenylketone, anthracene, phenanthrene and pyrene. R2 and R3 each independently represent 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 R0 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 42) of the present invention, examples of the phosphorus compounds in which the aromatic ring structure having a substituent is 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 acid, 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 42), the phosphorus compound in which the 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 42) of 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 42), 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 42) of the present invention, examples of the phosphorus compound having a substituted 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 42), 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 (Formula 42) of the present invention, examples of the phosphorus compounds having an aromatic ring structure having a substituent as diphenyl ether include the following. 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 42), the phosphorus compound in which the 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 42) of the present invention, examples of the phosphorus compounds whose aromatic ring structure having a substituent is diphenythioether 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 42), 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 42) of the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure of diphenyl sulfone 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) ) Phosphonic acids in which an alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monomethoxyalkylene glycol group, etc. are introduced into a diphenylsulfone ring such as benzylphosphonic acid, but are not limited thereto. .

  Among the phosphorus compounds represented by the formula (Chemical Formula 42), 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 (Formula 42) of the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure of 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 42), 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 42) of 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 42), the phosphorus compound in which the 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 42) of the present invention, examples of the phosphorus compounds whose aromatic ring structure having a substituent is 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, carboxy group, carboxylic acid ester group, alkylene glycol group, 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 42), the phosphorus compound whose 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 42) of the present invention, examples of the phosphorus compound 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 42), the phosphorus compound whose aromatic ring structure having a substituent is anthracene is not limited to the above-mentioned single substituent species. A mixture 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 42) of the present invention, examples of the phosphorus compounds having an aromatic ring structure having a substituent as 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 42), 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 42) of 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 42), 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 since it is easily dissolved or taken into the polyester matrix, it is considered to be particularly effective for polymerization activity and foreign matter reduction.

Compared to an unsubstituted group in which R0 is a hydrogen atom bonded to the aromatic ring structure (R1), the C1-C10 alkyl group, -COOH group or -COOR4 of the present invention (R4 represents a C1-C4 alkyl group) A phosphorus compound substituted with an alkylene glycol group or a monoalkoxyalkylene glycol group (monoalkoxy represents C1-C4, alkylene glycol represents C1-C4 glycol) not only improves the catalytic activity, but also reduces foreign matters. This is preferable.
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 43) having no linking group (X) that is preferably used in the present invention is as follows.

Embedded image R1- (P = O) (OR2) (OR3)
(R1 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 heterocyclic structure may have a substituent. R2 and R3 are independent of each other. Represents a hydrocarbon group having 1 to 20 carbon atoms including a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group or an alkoxyl group, and the hydrocarbon group has an alicyclic structure, a branched structure or an aromatic ring structure. May be.)
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 type or 2 types selected from phosphoryl-containing groups, nitrile groups, and cyanoalkyl groups. That's it. The aromatic ring structure of (Chemical Formula 43) 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 R2 and R3 in the above formula (Formula 43) is a hydrogen atom.

  Examples of the phosphorus compound represented by the formula (Formula 43) 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 42), such as benzene, naphthalene, biphenyl, diphenyl ether, diphenylthioether, diphenylsulfone, diphenylmethane, diphenyldimethylmethane, diphenylketone, anthracene, phenanthrene, and pyrene. A methylene chain that is a linking group from each structural formula having an aromatic ring structure, that is, a phosphorus compound group in which —CH 2 — is removed, and a heterocyclic ring-containing phosphorus compound such as 5-benzofuranylphosphonic acid diethyl ester, 5-benzofuran Nylphosphonic 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 described above may have a slightly lower polymerization activity than the phosphorus compound having the linking group described above, but when the catalyst preparation method of the present invention is used, it is used as a copolymerized polyester polymerization catalyst. It is possible.

  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, even if the phosphorus compound of the present invention is added when the polyester is melt-polymerized by using an antimony compound, a titanium compound, a tin compound or a germanium compound, which is a typical catalyst for polyester polymerization, as a polymerization catalyst, it is substantially useful. It is not observed that polymerization is accelerated to a certain level.

  The amount of the phosphorus compound used in the present invention is 1 to 500 ppm in terms of P atom, based on the total weight of the carboxylic acid component such as the natural fatty acid ester of the oily alkyd resin and polyvalent carboxylic acid. Preferably, it is 10-200 ppm. When the addition amount of the phosphorus compound is less than 1 ppm, the addition effect may not be exhibited. When the addition amount exceeds 500 ppm, the catalytic activity may be reduced. The tendency of the decrease depends on the amount of aluminum used, etc. Change.

  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 the compound in addition to aluminum or a compound thereof coexists as the 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 alkali metals, alkaline earth metals and compounds thereof are added, the amount M (% by weight) used is based on the total constituent weight of carboxylic acid components such as natural fatty acid esters and polycarboxylic acids constituting the oily alkyd resin. In addition, it is preferably 1 to 200 ppm in terms of each metal atom, more preferably 5 to 100 ppm, and still more preferably 10 to 80 ppm. 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 used is 200 ppm or more, there are cases where deterioration in thermal stability, generation of foreign matter, increase in coloration, and decrease in hydrolysis resistance become problems in product processing. . If M is less than 1 ppm, the effect is not clear even if it is 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. , Ba is preferable, and among these, 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. However, it 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. Accordingly, the alkali metal or their compounds or alkaline earth metals or their compounds suitable for the present invention are preferably saturated aliphatic carboxylates, unsaturated aliphatic carboxylates, aromatics of alkali metals or alkaline earth metals. Aromatic carboxylates, halogen-containing carboxylates, hydroxycarboxylates, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromic acid Selected inorganic acid salts, organic sulfonates, organic sulfates, chelate compounds, and oxides. Among these, from the viewpoint of ease of handling, availability, and the like, it is preferable to use an alkali metal or alkaline earth metal saturated aliphatic carboxylate, particularly acetate.

  The polycondensation catalyst of the present invention has other polycondensation catalysts such as antimony compounds, germanium compounds, titanium compounds, tin compounds, etc. The addition of these components has problems with products such as polyester characteristics, processability, and color tone as described above. Coexistence within the range of the amount of addition that does not cause is effective in improving productivity by shortening the polymerization time, and is preferable.

  The natural fatty acid ester (hereinafter abbreviated as natural fatty acid) that can be used in the oily alkyd resin (A) in the present invention is not particularly limited as long as it is a naturally occurring fatty acid. Specifically, fatty acids derived from vegetable oils such as castor oil, palm oil, linseed oil, palm oil, palm kernel oil, safflower oil, soybean oil, kiri oil, tall oil, dehydrated castor oil and other fin whale oil Examples include fatty acids obtained from animal fats and oils, and fatty acids produced by microorganisms. Among these, fatty acids obtained from castor oil, coconut oil, linseed oil, palm oil, soybean oil, tung oil, dehydrated castor oil and the like are particularly preferable. Any of these natural fatty acids may be used alone, or two or more thereof may be used in combination.

  The natural fatty acid can be used in an amount of 30 to 90% by weight, preferably 40 to 80% by weight, more preferably 50 to 70% by weight, based on the weight of the oily alkyd resin obtained. If it is less than 30% by weight, the coating film performance such as hardness and adhesion is deteriorated, which is not preferable. On the other hand, if it is 90% by weight or more, in addition to deterioration of the coating film performance such as hardness and adhesion, yellowing progresses during high-temperature baking, which is not preferable.

In addition, polycarboxylic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be used in combination as an acid component as long as the effects of the present invention are not impaired.
The polycarboxylic acid anhydride can be used in an amount of 1 to 30% by weight, preferably 5 to 25% by weight, more preferably 8 to 20% by weight, based on the weight of the oily alkyd resin. If it is less than 1% by weight, the coating film performance such as hardness and adhesion is deteriorated, which is not preferable. On the other hand, if it is 30% by weight or more, the solubility in a solvent is insufficient in addition to the deterioration of the coating film performance such as hardness and adhesion.

  Specific examples of polyhydric alcohols having 2 to 50 carbon atoms that are alcohol components in the present invention include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, and 2,3-butanediol. 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3 -Propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, , 2-cyclohexanedimethanol, trimethylolethane, trimethylolpropane, glycerin, pe Such as data erythritol, and the like. Of these, trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol are preferable from the viewpoint of polymerization. Moreover, the C2-C50 polyhydric alcohol which is an alcohol component may be used independently, and may be used in combination of 2 or more type.

  The polyhydric alcohol can be used in an amount of 1 to 70% by weight, preferably 2 to 60% by weight, more preferably 5 to 50% by weight, based on the weight of the oily alkyd resin obtained. If it is less than 1% by weight, the coating film performance such as hardness and adhesion is lowered, which is not preferable. On the other hand, if it is 70% by weight or more, the coating film performance such as hardness, adhesion and water resistance is lowered, which is not preferable.

  Further, metal salts such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- [4-sulfophenoxy] isophthalic acid, 2-sulfo-1,4-butanediol, 2,5- A dicarboxylic acid or glycol containing a sulfonic acid metal base such as a metal salt such as dimethyl-3-sulfo-2,5-hexanediol may be used within a range of 15% by weight or less of the total acid or the total alcohol component.

  Further, after obtaining the resin in the oily alkyd resin (A) of the present invention, an acid anhydride such as succinic anhydride, 1,2-cyclohexanedicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride An acid, 1,8-naphthalic anhydride, or the like may be post-added to give an acid value.

In order to obtain the water-based alkyd resin of the present invention, the unsaturated double bond contained in the oily alkyd resin (A) is graft-polymerized using (meth) acrylic acid and a derivative thereof, and the acid value is 50 eq / 10 ^6. g or more is necessary.

In the present invention, the (meth) acrylate monomer represents at least one of acrylate monomer, methacrylate monomer, silicon acrylic type, and acrylic fluorine type.
Examples of the graft polymerization monomer include the following (meth) acrylate monomers. For example, carboxyl group-containing (meth) acrylic acids such as acrylic acid and methacrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyl group-containing (meth) acrylates such as (meth) acrylate, ionic group-containing monomers such as styrenesulfonic acid, (meth) acryloyloxyphosphonic acid, 2-hydroxy-3- (meth) acryloxypropyltrimethylammonium chloride, ( Examples thereof include nitrogen-containing monomers such as (meth) acrylamide, aminoethyl methacrylate and dimethylaminoethyl (meth) acrylate, and hydrophilic monomers such as polyethylene glycol (meth) acrylate.

  In addition, linear or branched alkyl (meth) acrylic such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Rate; cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, and hydrophobic poly such as polypropylene glycol (meth) acrylate Alkylene glycol (meth) acrylates, styrene monomers such as styrene, methyl styrene and chloromethyl styrene, vinyl ether monomers such as methyl vinyl ether and butyl vinyl ether, vinyl acetate , Hydrophobic monomer group such as a vinyl ester monomer such as vinyl propionate and the like are Kyora.

Silicon acryl-based materials include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acrylic. Examples thereof include hydrolyzable silyl group-containing vinyl monomers such as loxypropylmethyldiethoxysilane.
Examples of other monomers copolymerizable with the silicon-containing acrylic monomer include, for example, acrylic monomers used in the above-mentioned acrylic resin emulsions and other monomers copolymerizable with the acrylic monomers. A monomer etc. can be used without being specifically limited. When an acrylic silicon system is used, weather resistance, yellowing resistance, durability, chemical resistance, stain resistance, etc. are advantageous.

Moreover, as a fluorine acrylic type | system | group, what is obtained by radical copolymerization with a fluorine-containing monomer and the other monomer copolymerizable with a fluorine-containing monomer can be used.
Examples of the fluorine-containing monomer include fluoroolefins such as vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, pentafluoroethylene, and hexafluoropropylene; trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, Examples include fluorine-containing (meth) acrylates such as perfluorocyclohexyl (meth) acrylate. Examples of the other monomer copolymerizable with the fluorine-containing monomer include, for example, the acrylic monomers used in the above-mentioned acrylic series, and other monomers copolymerizable with the acrylic monomers. Can be used without any particular limitation. When a fluororesin acrylic is used, weather resistance, yellowing resistance, durability, chemical resistance, stain resistance, etc. are advantageous.

  The above monomers can be used alone or in combination with various monomers.

(Meth) acid value of the acrylic-modified oil alkyd resin (B), in order to water-based alkyd resin is required more than 50 eq / 10 ⁶ g, preferably 75eq / 10 ⁶ g or more. When the acid value exceeds 500 eq / 10 ⁶ g, the water resistance and adhesion are deteriorated, which is not preferable. Water dispersibility is improved by securing an appropriate acid value and increasing the degree of acid dissociation with the neutralizing agent (C). As the polymerizable monomer, the above hydrophilic monomer and hydrophobic monomer may be used in combination.

  The neutralizing agent (C) is not particularly limited as long as it neutralizes the acid, and specific examples of the metal salt include salts such as Li, Na, K, Mg, Ca, Cu, and Fe. Organic substances include aqueous ammonia, methylethanolamine, diethylethanolamine, N-methyl-diethanolamine, bis-hydroxypropyl-methylamine, tri-n-butylamine, triethylamine, bis-2-hydroxypropylamine, N-methyl-ethanol. Amines such as amine, aminomethylpropanol, 3-amino-1-propanolamine, isopropanolamine, 2-amino-2-hydroxymethyl 1-3-propanediol, aminomethyl-propanediol, cyclohexylamine, t-butylamine, Examples thereof include salts of weak acids and strong bases such as sodium carbonate and potassium carbonate, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. When these neutralizing agents remain in the film after drying and curing, the physical properties of the film are adversely affected, and therefore, low boiling point amines such as ammonia water and dimethylethanolamine that do not volatilize and remain after drying and curing are preferred.

  The blending amount of the neutralizing agent (C) with respect to the (meth) acryl-modified oily alkyd resin (B) of the present invention is such that the neutralization ratio with respect to the acid value of the resin (B) is 1 to 2000%, preferably 10 to 200%. Range. If this ratio is less than 1%, the carboxyl group cannot be sufficiently dissociated, and good water dispersibility cannot be obtained. On the other hand, if it exceeds 2,000%, the hydrolysis resistance is adversely affected or the hydrolysis of the (meth) acryl-modified oily alkyd resin (B) during storage of the aqueous dispersion is adversely affected.

  The glass transition temperature of the (meth) acryl-modified oily alkyd resin (B) of the present invention is preferably 70 ° C. or less, more preferably 50 ° C. or less, from the viewpoints of adhesion, smoothness of the coating film surface, and the like. Preferably it is 30 degrees C or less. When the temperature exceeds 70 ° C., the coating film becomes not only brittle, but also the adhesiveness is lowered, which is not preferable. When the temperature is −60 ° C. or lower, the coating surface has adhesiveness, which causes a blocking problem.

  The aqueous alkyd resin composition of the present invention can be used by blending a curing agent (D) capable of reacting with the (meth) acryl-modified oily alkyd resin (B).

  Examples of the curing agent (D) that can react with the (meth) acryl-modified oily alkyd resin (B) include alkyl etherified aminoformaldehyde resins, epoxy compounds, and isocyanate compounds.

  Alkyl etherified aminoformaldehyde resin is, for example, formaldehyde or paraformaldehyde alkylated with an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, urea, N, N -Condensation products with ethylene urea, dicyandiamide, aminotriazine, etc., and methoxylated methylol-N, N-ethyleneurea, methoxylated methylol dicyandiamide, methoxylated methylol benzoguanamine, butoxylated methylol benzoguanamine, methoxylated methylol melamine, butoxylated Examples include methylol melamine, methoxylated / butoxylated mixed methylol melamine, and butoxylated methylol benzoguanamine. Et Preferred are methoxy methylol melamine, butoxy methylol melamine or methoxylated / butoxylated mixed melamine, may be used alone or in combination.

  Examples of epoxy compounds include diglycidyl ether of bisphenol A and oligomers thereof, diglycidyl ether of hydrogenated bisphenol A and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid diglyceride. Glycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 4-Butanediol glycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene group Diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether , Pentaerythritol tetraglycidyl ether, triglycidyl ether of a glycerol alcohol oxide adduct, and the like.

  Furthermore, the isocyanate compound includes aromatic and aliphatic diisocyanates, and trivalent or higher polyisocyanates, which may be either low molecular compounds or high molecular compounds. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess of these isocyanate compounds Amount and low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine or various polyester polyols, polyether polyols, polyamides Reacts with polymer active hydrogen compounds Terminal isocyanate group-containing compounds obtained Te are exemplified.

  The isocyanate compound may be a blocked isocyanate. As the isocyanate blocking agent, for example, phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, oximes such as acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, methanol, Alcohols such as ethanol, propanol and butanol, halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol, tertiary alcohols such as t-butanol and t-pentanol, and ε-caprolactam , Δ-valerolactam, γ-butyrolactam, β-propylolactam, and other lactams, and other aromatic amines, imides, acetylacetone Acetoacetic ester, active methylene compounds such as malonic acid ethyl ester, mercaptans, imines, ureas, and also such as diaryl compounds sodium bisulfite. The blocked isocyanate is obtained by subjecting the above isocyanate compound and an isocyanate blocking agent to an addition reaction by a conventionally known method.

  These crosslinking agents can be used in combination with a known curing agent or accelerator selected according to the type.

  The coating resin composition of the present invention is suitable for coating. In this case, the baking temperature is arbitrarily selected depending on the size, thickness, baking furnace capability, coating curability, etc. . For the production of the coating composition, a mixer such as a roll kneader, a ball mill or a blender is used. When painting, roller coating, roll coater, spray coating, electrostatic coating, etc. are selected as appropriate.

  The coating composition of the present invention may contain additives such as pigments such as titanium oxide, glass fibers, silica, and wax depending on the purpose and application.

  The present invention will be illustrated by the following examples, but the present invention is not limited thereto. In the examples, “parts” means “parts by weight”. In addition, each measurement item in an Example followed the following method.

Various measurements of the oily alkyd resin (A) were carried out according to the following methods.
1. Reduced viscosity (IV: dl / g)
Each oily alkyd resin (A) thus obtained was pulverized and dissolved in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane in 6/4 (weight ratio) at 80 to 100 ° C. over several hours. It measured at the temperature of 30 degreeC using the viscometer. Concentration was measured at several points centered on 4 g / l, and IV was determined according to a conventional method.
2. Glass transition temperature (Tg)
Measured with a differential thermal analyzer (DSC), RDC-220, manufactured by Seiko Electronics Industry Co., Ltd. The sample was heated at a rate of temperature increase of 20 ° C./minute, and 5 mg of the sample was placed in an aluminum press-lid container and crimped.
3. (1) Transparency and (2) Degree of Coloring of the Oily Alkyd Resin (A) In (1) and (2), the oily alkyd resin (A) was visually determined while having a plate shape with substantially the same thickness.
(1) Transparency of resin ○: Almost transparent Δ: Slightly turbid ×: Remarkably turbid (2) Degree of resin coloring ○: Almost not colored Δ: Slightly colored ×: Remarkably colored

4). Water dispersibility of solid content 30% of (meth) acryl-modified alkyd resin (B) The water dispersibility after 30 days at 25 ° C. was evaluated by visual judgment.
○: Good, ×: Insoluble content.

The evaluation method of the coating film is as follows. That is, the coating composition was applied to a 0.5 mm-thick zinc iron plate so as to have a film thickness of 30 μm, and then the test piece was dried and baked at 150 ° C. for 30 minutes.
5. Adhesiveness 100 pieces of 1 mm squares were made on the coating surface with a gobang cutter, and the cellophane tape was applied and peeled off five times. The adhesion number of the paints was evaluated by examining the number of peeled squares.
100/100: good adhesion, 0/100: poor adhesion Pencil hardness The hardness of a pencil ("Uni" manufactured by Mitsubishi Pencil Co., Ltd.) required to damage the coating surface of the test piece is indicated.

7). Weather resistance Evaluated by gloss retention before and after performing test for 48 hours with a super UV tester (acceleration test of aging) (measurement conditions: temperature 50 ° C., humidity 50%, UV lamp irradiation 100 mW) Went.
○: Gloss retention 90% or more Δ: Gloss retention 60% to less than 90% ×: Gloss retention 60% or less.
8). Water resistance The state after the test piece was immersed in warm water at 70 ° C. for 30 days was visually judged.
○: Almost no difference was observed compared to the state before immersion.
(Triangle | delta): It changed a little compared with the state before immersion.
X: It changed considerably compared with the state before immersion.
9. Yellowing resistance The color tone of the test piece before and after curing (baking) was visually determined.
○: Almost no difference was observed compared to the color tone before baking.
(Triangle | delta): It changed yellow a little compared with the color tone before baking.
X: Compared with the color tone before baking, it changed considerably yellow.
10. Measurement of AVo (acid value) The (meth) acryl-modified alkyd resin (B) is pulverized and dried under reduced pressure at 110 ° C. for 15 hours or more. Weigh precisely 1 g of sample and add 20 ml of chloroform to dissolve. After dissolution, 10 ml of pure water is added and allowed to cool to room temperature. Titrate with N / 10-NaOH ethanol solution using phenolphthalein as an indicator. Do the same for the blank without the sample.
AVo (equivalent / 10 ⁶ g) is calculated according to the following formula.
AVo = (A−B) × 0.1 × f × 1000 / W
(A = drop constant (ml), B = blank drop constant (ml), f = factor N / 10-NaOH, W = weight of sample (g))

Synthesis example of oil-based alkyd resin (A1) of the resin of the present invention:
Table 1 shows the total acid components at the time of charging 375 parts by weight of tung oil, 375 parts by weight of soybean oil, and the above aqueous solution of basic aluminum acetate and Irganox 1425 as a polymerization catalyst in a reaction vessel equipped with a stirrer, a condenser and a thermometer. The amount was charged, 50 parts of pentaerythritol was added, the temperature was raised from 100 ° C. to 200 ° C. in a nitrogen atmosphere, the ester exchange reaction was carried out at 200 ° C. for 1 hour, the temperature was lowered to 175 ° C., and trimellitic anhydride 200 Part by weight was added and the temperature was raised from 150 ° C. to 220 ° C. over 1 hour. Furthermore, dehydration reaction was performed at 220 ° C. for 1 hour. Table 1 shows the characteristics of the obtained oily alkyd resin (A1).
The properties of the obtained resin (A1) are shown in Table 1. The resin (A1) of the present invention was characterized by excellent resin transparency and low coloration.

Synthetic examples of the resin of the present invention (A2 to A4) and comparative resins (A5 and A6):
Synthesis examples of the resin of the present invention (A2 to A4) and comparative resin synthesis examples (A5 and A6) were also synthesized with the compositions shown in Table 1 by the method according to the synthesis example of A1. The resin group of the present invention is superior to the comparative resin in terms of transparency and coloring degree, and its performance is expected as a resin composition for a (meth) acryl-modified alkyd paint.

Synthesis example of (meth) acrylic modified alkyd resin (B1) of the present invention and preparation example of 30% solid content aqueous dispersion (b1):
75 parts of the oily alkyd resin (A1), 56 parts of methyl ethyl ketone and 19 parts of isopropyl alcohol were placed in a reactor equipped with a stirrer, a thermometer, a reflux device and a quantitative dropping device, and the resin was dissolved by heating and stirring at 65 ° C. . After the resin is completely dissolved, a mixture of 15 parts of butyl methacrylate, 6 parts of 2-hydroxyethyl methacrylate and 2 parts of methacrylic acid and a solution of 1.2 parts of azobisdimethylvaleronitrile dissolved in 25 parts of methyl ethyl ketone. The solution was dropped into the oily alkyd resin (A1) and the monomer solution at 0.2 ml / min, and stirring was further continued for 2 hours. The polymerization solution was added dropwise to 3 liters of diethyl ether with stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain a (meth) acryl-modified alkyd resin (B1). Next, 300 parts of (meth) acryl-modified alkyd resin (B1) and 700 parts of methyl ethyl ketone were charged into a four-necked flask equipped with a thermometer and a condenser and dissolved at 70 ° C. To this was charged 175 parts of isopropyl alcohol, and 700 parts of warm water obtained by adding 0.7 g of ammonia water to ion exchange water at 50 ° C. was gradually added with stirring. Then, the system was gently evacuated and the solvent was distilled off at 50 ° C. to obtain an aqueous dispersion (b1) of the resin (B1). This dispersion (b1) was a translucent stable solution having a solid content of 30%. Table 2 shows the results of the resin (B1) and the aqueous dispersion (b1).

Synthesis of (meth) acrylic modified alkyd resins (B2 to B4) of the present invention and preparation examples of 30% solids aqueous dispersions (b2 to b4) of the present resin:
A (meth) acryl-modified alkyd resin (B2 to B4) was synthesized with the composition shown in Table 2 by a method according to the synthesis example of B1. Moreover, the aqueous dispersion (b2-b4) of this invention was obtained by the method according to the preparation example of said b1. Table 2 shows the evaluation results of the obtained (meth) acryl-modified alkyd resin and aqueous dispersion of the present invention.

Synthesis of comparative (meth) acryl-modified alkyd resins (B5 and B6) and preparation examples of comparative resin 30% solids aqueous dispersions (b5 and b6):
Comparative (meth) acryl-modified alkyd resins (B5 and B6) were synthesized with the compositions shown in Table 2 by a method according to the synthesis example of B1. Moreover, the aqueous dispersion (b5 and b6) of the comparison resin was obtained by the method according to the preparation example of said b1. Table 2 shows the evaluation results of the obtained comparative (meth) acryl-modified alkyd resin and the comparative aqueous dispersion. In all cases, good water dispersibility was exhibited.

(Example 1)
(Meth) acrylic modified alkyd resin 30% solids dispersion (b1) 100 parts by weight, Cymel 254 (Mitsui Cyanamid Co., Ltd., aminoformaldehyde resin) 25 parts, p-toluenesulfonic acid (Nacalai Co., Ltd.) , Reagent) 0.25 parts, titanium oxide CR93 (Ishihara Sangyo Co., Ltd., white pigment) 125 parts, acrylic beads (Japan Exlan Industrial Co., Ltd., particle size 5-40 μm) 140 parts after blending and stirring. Shake and disperse for 4 hours with a paint shaker to obtain a resin composition for aqueous alkyd paint. The obtained resin composition for water-based alkyd paints was applied to a 0.5 mm thick zinc iron plate so as to have a film thickness of 30 μm, followed by drying and baking at 150 ° C. for 30 minutes. Table 3 shows the evaluation results of the obtained test pieces. The physical properties of the coating film obtained from the resin composition for aqueous alkyd paints using an aluminum / phosphorus catalyst showed good adhesion, pencil hardness, weather resistance, water resistance, and excellent yellowing resistance.

(Examples 2 to 8)
Hereinafter, in the same manner as in Example 1, the compositions of Examples 2 to 8 were prepared according to the compositions shown in Table 3, and coating films were prepared. The test results obtained are shown in Table 3. As is apparent from the results in Table 3, the test pieces obtained in Examples 2 to 8 exhibited good adhesion, pencil hardness, weather resistance, water resistance, and excellent yellowing resistance.

(Comparative Example 1)
In Example 1, it carried out similarly to Example 1 except having changed into the resin composition for comparative water-based alkyd paints of the composition shown in Table 4. The obtained test results are shown in Table 4. As is clear from the results in Table 4, the test piece obtained in Comparative Example 1 showed good adhesion, pencil hardness, weather resistance, and water resistance, while the resin composition for aqueous alkyd paints of the present invention was used. Compared with yellowing resistance, it was inferior.

(Comparative Examples 2-6)
In Comparative Example 1, the same procedure as in Comparative Example 1 was performed except that the resin composition for comparative aqueous alkyd paint having the composition shown in Table 4 was changed. The obtained test results are shown in Table 4. As is clear from the results in Table 4, the test pieces obtained in Comparative Examples 2 to 6 exhibit good adhesion, pencil hardness, weather resistance, and water resistance, respectively, while the aqueous alkyd paint resin of the present invention. It was inferior in yellowing resistance compared to the composition.

The present invention relates to a resin composition for water-based alkyd paints and a method for producing the same, and more specifically, provides a resin composition for water-based alkyd paints that is environmentally friendly, has little colorability, and has improved thermal stability.

Claims (13)

Oily alkyd resin (A) obtained by using a natural fatty acid ester and a polycarboxylic acid anhydride as an acid component and a polyhydric alcohol having 2 to 50 carbon atoms as an alcohol component in the presence of a polymerization catalyst containing at least an aluminum compound (Meth) acryl-modified oily alkyd resin (B) having an acid value of 50 eq / 10 ⁶ g or more obtained by graft polymerization of a polymerizable monomer. 2. The (meta) of claim 1, wherein the polymerization catalyst is a polymerization catalyst composed of at least one selected from the group consisting of aluminum compounds and one selected from the group consisting of phosphorus compounds. Acrylic modified oily alkyd resin (B). 2. The (meth) acryl-modified oil-based alkyd resin according to claim 1, wherein the polymerization catalyst comprises at least one selected from the group consisting of at least an aluminum compound, and an alkali metal and / or an alkaline earth metal. (B). The (meth) acryl-modified oily alkyd resin (B) according to claim 1, wherein the polymerization catalyst comprises an aluminum compound, a phosphorus compound, and an alkali metal and / or an alkaline earth metal. The aluminum compound as a component of the polymerization catalyst is at least one selected from aluminum acetate, basic aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide chloride, and polyaluminum chloride. 4. The (meth) acryl-modified oily alkyd resin (B) according to any one of 4 above. The phosphorus compound as a constituent component of the polymerization catalyst 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. The (meth) acryl-modified oil-based alkyd resin (B) according to any one of claims 2, 4 and 5, wherein 6. The (meta) according to claim 3, wherein the alkali metal and / or alkaline earth metal is at least one selected from Li, Na, Ca, Mg or a compound thereof. Acrylic modified oily alkyd resin (B). The (meth) acrylic-modified oily alkyd resin (B) according to any one of claims 1 to 7, wherein the polymerizable monomer contains at least (meth) acrylic acid. The neutralization ratio with respect to the acid value of the resin (B) is 1 to 8 with respect to the (meth) acryl-modified oily alkyd resin (B) according to any one of claims 1 to 8. A resin composition for aqueous alkyd paints, which is an aqueous dispersion prepared to satisfy 2000%. The resin composition for water-based alkyd paints according to claim 9, comprising a curing agent (D) capable of reacting with the (meth) acryl-modified oily alkyd resin (B). The resin composition for water-based alkyd paints according to claim 10, wherein the curing agent (D) is at least one selected from alkyl etherified amino formaldehyde resins, epoxy compounds and isocyanate compounds. The method for producing a (meth) acryl-modified oily alkyd resin according to any one of claims 1 to 8. The manufacturing method of the resin composition for water-based alkyd paints in any one of the said Claims 9-11.