JP2001089283A - Coating material for coated granular fertilizer and coated granular fertilizer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating material which has good elution controllability in soil and can avert the accumulation of the coat in an ecosystem by the degradation of the films in and out of the soil and a coated fertilizer by the same. SOLUTION: The coating material containing aliphatic aromatic polyester formed of an aliphatic compound component (for example, aliphatic glycol and aliphatic dicarboxylic acid) and an aromatic compound component (for example, aromatic dicarboxylic acid) as at least one component in the main chain and the coated granular fertilizer coated by using this material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating material mainly composed of a biodegradable aliphatic aromatic polyester and a granular fertilizer coated with the coating material. More specifically, the present invention has good controllability of elution of fertilizer components in soil, and the aliphatic aromatic polyester in the film is decomposed inside and outside the soil to cause the film to disintegrate and accumulate in the ecosystem. No coating granular fertilizer and a coating material used for the coating.

[0002]

[Prior art]

[0003] In order to physically control the dissolution of fertilizer components applied to soil, studies have been widely made to coat the surface of a granular fertilizer with a film containing a dissolution rate regulator.
In particular, JP-A-50-99858, JP-B-60-304
0, the production method of a coated fertilizer using a polyolefin resin or the like as a coating material disclosed in Japanese Examined Patent Publication No. 60-37074 has reached practical use. However, in recent years, there have been voices of concern about the environmental load due to the non-disintegrability of the coating. Therefore, an ethylene / carbon monoxide copolymer (JP-B-2-235)
16) or the use of ethylene / vinyl acetate / carbon monoxide copolymer (JP-B-2-23515) for the coating has been proposed to impart the disintegration property of the coating by photolysis, but the mechanism does not work in soil. Therefore, no substantial effect was achieved.

On the other hand, as an example in which a resin having biodegradability is used for a film of a granular fertilizer, a coated fertilizer which is coated with a film of an aliphatic polyester composed of an aliphatic dicarboxylic acid and a glycol component has been proposed ( JP-A-7-31
5976, JP-A-8-157290). An aliphatic polyester using an aliphatic hydroxycarboxylic acid in addition to an aliphatic dicarboxylic acid and a glycol component has also been proposed (JP-A-9-249777). However, since these biodegradable polyesters are rapidly decomposed, the film collapses during the elution period of the fertilizer, and it is difficult to control elution. Further, in general, a film made of a biodegradable aliphatic polyester has a drawback that only a film having a very short elution period can be obtained even in sterile water which is not affected by microorganisms. Therefore, Japanese Patent Application Laid-Open Nos. 3-146192 and 4
-89384, 7-315976, 9-26347
No. 6 proposes a film composition in which a biodegradable aliphatic polyester is blended with a polyolefin, a wax or the like. However, these did not achieve both the control of dissolution and the sufficient biodegradability.

[0005] Japanese Patent Application Laid-Open Nos. 9-194280 and 9-3
In 09784, a blend of a biodegradable aliphatic polyester and another polymer is mixed with a substance that promotes oxidative degradation to achieve both dissolution controllability and biodegradability. However, the compatibility between biodegradable aliphatic polyester and polyolefin is poor, and the film formed from the mixture is very brittle, has low strength, and cannot withstand the physical load during the use process. . Further, Japanese Patent Application Laid-Open No. 10-25180 proposes a method of achieving both biodegradability and dissolution controllability by using copolyesterethylene having a prescribed ester group content. However, it is industrially difficult to introduce a polar group such as an ester group into the main chain of polyethylene, and its utility is extremely low. For example, in JP-A-4-50224 and JP-A-4-50225, polymerization of polyester ethylene in which an ester group has been introduced into polyethylene is attempted, but the polymerization requires a long reaction time in a solvent, resulting in high polymerization. Since it is difficult to obtain a polymer, it has low industrial practicality. In addition, when an ester group is introduced into the side chain of polyethylene, as in the case of an ethylene-vinyl acetate copolymer, the biodegradability is still very slow and a biodegradable film cannot be formed. BASF Patent (DE 196
According to 40269 A1), an aliphatic aromatic polyester is used for a coating fertilizer. The method of dissolving it in an organic solvent and then dispersing it in water to coat it. In this method, when water-soluble fertilizer particles are coated, there is a disadvantage that the fertilizer component is mixed into the film as the film is dried, thereby impairing the function of the film. Further, after drying, water remains in the film to promote hydrolysis of the ester group, thereby causing deterioration of the film.

[0006]

An object of the present invention is to provide a coated granular fertilizer having good controllability of dissolution in soil, and a polymer in the film is biodegraded in the soil, so that it can be used in a field. Avoiding accumulation and easily disintegrating the film as it decomposes, suppressing the floating of hollow particles and outflow outside the field, and furthermore, decomposing the outflowing film by ecological microorganisms, It is not accumulated. In other words, the purpose is to provide a coated granular fertilizer with good elution control without a substantial environmental load due to the film and a coating material therefor. In addition, the film deteriorates during storage, and the elution control becomes unstable. It is also an issue to prevent them from doing so.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the gist of the present invention is that the main chain is mainly composed of an aliphatic compound component and an aromatic compound component. The present invention relates to a coating material for a coated granular fertilizer containing an aromatic polyester as at least one component, and a coated granular fertilizer coated with the coating material.

In a preferred embodiment of the present invention, the aliphatic aromatic polyester which is the main component of the coating material of the present invention is mainly composed of an aliphatic glycol (for example, 1,4-butanediol), an aliphatic dicarboxylic acid or an ester thereof ( For example, it is formed from succinic acid and / or adipic acid) and an aromatic dicarboxylic acid or an ester thereof (for example, terephthalic acid). Further, the aliphatic aromatic polyester is defined by X-ray absorption fine structure analysis (XAFS). Specific physical properties and reduced viscosity. Also, a preferred embodiment is a coated granular fertilizer in which a solution obtained by dissolving the aliphatic aromatic polyester in an organic solvent is coated on a fertilizer by spraying and drying.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The aliphatic aromatic polyester of the present invention (hereinafter, sometimes abbreviated as polyester) is one whose main chain is mainly formed of an aliphatic compound component and an aromatic compound component, and forms the polyester. It is produced using an aliphatic compound and / or an alicyclic compound having at least two OH groups and an aliphatic compound and an aromatic compound having at least two COOH groups or carboxylic ester groups as main monomers. (Although lactones may be included). Thus, the polyester, corresponding to its monomer component,
The following formulas (1), (2), mainly comprising the constituent units represented by (3), including a constituent unit represented by the formula (4) derived from an oxycarboxy compound optionally added optionally You can be there.

(1) —O—R _a —O— (wherein, R _a mainly represents a chain alkylene group having 2 to 10 carbon atoms and / or an alicyclic alkylene group having 6 to 10 carbon atoms.) (2) -OC- _Rb- CO- (wherein, _Rb mainly means a chain alkylene group having 0 to 20 carbon atoms and / or an alicyclic alkylene group having 6 to 10 carbon atoms). .. to) (3) -OC-Ar _b -CO- (wherein, Ar _b is primarily to mean a divalent aromatic group having 6 to 18 carbon _{atoms) (4) -O-R c} - CO- (wherein, R _c is primarily meant good chain alkylene group which may be branched having 1 to 10 carbon atoms.)

Accordingly, the aliphatic aromatic polyester of the present invention comprises, for example, both an aliphatic glycol compound as a dioxy compound and an aromatic carboxylic acid compound and an aliphatic carboxylic acid compound as a dicarboxy compound. Means that the oxycarboxy compound optionally used is an aliphatic compound, and the above formula (1),
This indicates that all the constituent units (2) and (3) are included, and that (4) may or may not be included.

The constituent unit represented by the formula (1) is derived from an aliphatic compound and / or an alicyclic compound monomer having at least two OH groups, wherein _Ra is mainly a group having 2 carbon atoms.
A chain alkylene group of 10 to 10 and / or an alicyclic alkylene group having 6 to 10 carbon atoms. From the viewpoint of heat resistance, _Ra is preferably an alkylene group having 2 to 6 carbon atoms and an alicyclic alkylene group having 8 carbon atoms, and more preferably an alkylene group having 3, 4 or 6 carbon atoms and an alicyclic group having 8 carbon atoms. Formula alkylene groups are preferred and alkylene groups having 4 carbon atoms are most preferred.

Specifically, dioxy compounds (monomers)
Examples thereof include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanedimethanol, cyclohexaneglycol, and neopentylglycol.
In addition, these glycols are used in a small amount of diethylene glycol, triethylene glycol, polyethylene glycol.
, Polyoxyethylene glycol and polytetramethylene glycol. In the above glycol, 1,3-
Propylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol are preferred, and 1,4-butanediol is particularly preferred. Further, if necessary, a small amount of 3
It may contain a functional or higher glycol (eg, glycerin, erythritol, etc.) or an epoxy compound.

The constituent unit represented by the formula (2) is derived from an aliphatic compound monomer having at least two COOH groups or carboxylic acid ester groups, wherein R _b is mainly a C0-20 carbon atom. Chain alkylene group and / or carbon number 6-1
0 means an alicyclic alkylene group. R _b is particularly preferably an alkylene group having 2 to 6 carbon atoms, and most preferably an unsubstituted linear alkylene group having 2 and / or 4 carbon atoms. As the dicarboxy aliphatic compound, specifically,
Succinic acid, adipic acid, oxalic acid, glutaric acid, sebacic acid, azelaic acid, suberic acid, fumaric acid, maleic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid,
Tridecane dicarboxylic acid, tetradecane dicarboxylic acid,
Examples thereof include saturated and unsaturated aliphatic carboxylic acids such as pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, and eicosandicarboxylic acid, and lower alkyl esters thereof. Of these, succinic acid and adipic acid are particularly preferred. Examples of the dicarboxy alicyclic compound include cyclohexanedicarboxylic acid and dialkyl esters thereof. Further, these dicarboxy compounds may contain a small amount of trifunctional or higher-functional polybasic acid compounds (for example, hydroxypolycarboxylic acids such as malic acid and citric acid) so that the polyester has a branched structure if necessary.

The constituent unit represented by the formula (3) is derived from an aromatic compound monomer having at least two COOH groups or carboxylic acid ester groups, wherein Ar _b is mainly composed of 6 to 18 carbon atoms. Means a divalent aromatic group. Ar _b is an aromatic group having 6 to 18 carbon atoms, and examples thereof include a phenylene group and a naphthalene group. Particularly, 1,4-phenylene group and 2,6
Those having a bond to a carboxyl group at a structural symmetry position, such as a naphthalene group, are preferred. As the dicarboxy aromatic compound, specifically, terephthalic acid, dimethyl terephthalate, which is one of lower alkyl esters,
Examples thereof include 2,6-naphthalenedicarboxylic acid and its lower alkyl ester, dimethylnaphthalate and isophthalic acid. Particularly, terephthalic acid and dimethyl terephthalate are preferred. Further, these dicarboxylic acids may contain a small amount of a trifunctional or higher-functional polybasic acid compound (for example, trimellitic acid, pyromellitic acid, etc.) in order to make the polyester have a branched structure as required.

The constituent unit represented by the formula (4) is derived from an oxycarboxy compound monomer component optionally added, wherein R _c mainly represents a side chain such as a methyl group having 1 to 10 carbon atoms. It means a chain alkylene group which may be possessed. As the oxycarboxy compound, specifically, lactic acid, monohydroxymonocarboxylic acid such as glycolic acid,
Lactones such as caprolactone, butyrolactone, and pivalolactone can also be mentioned. In order to form a branched structure, the oxycarboxy compound may include a small amount of a compound having three or more functional groups, and the polyfunctional compound may include both an OH group and a COOH group, Further, it may be an aromatic compound (for example, trimellitic acid, pyromellitic acid, etc.).

The aliphatic aromatic polyester of the present invention may contain a small amount (20 mol% or less, especially 10 mol% or less) of a carbonate structure or an amide structure in addition to the above structural units. These structures can be introduced by using, for example, oxyamine, aminocarboxylic acid and the like. Further, in order to improve the molecular weight at the time of production, the chain may be extended with a diisocyanate compound or an oxazoline compound.

The aliphatic aromatic polyester of the present invention can be prepared, for example, by using succinic acid (or adipic acid) as an aliphatic difunctional carboxylic acid component and terephthalic acid as an aromatic difunctional carboxylic acid component. Usually 75 mol%
Those having 1,4-butylene succinate (or adipate) terephthalate bonds as described above, preferably those having 1,4-butylene succinate (or adipate) terephthalate bonds of 80 mol% or more. And more preferably 90 mol% or more of 1,4-
It has butylene succinate (or adipate) terephthalate bond.

In the aliphatic aromatic polyester of the present invention, the ratio of the constituent units represented by the following formulas (2) and (3) derived from the aliphatic and aromatic bifunctional carboxylic acids constituting the polyester is as follows: Although not particularly limited, usually 1/9
<(2) / (3) (equivalent ratio) <9/1 is preferred, and 2/8 ≦
(2) / (3) (equivalent ratio) ≦ 8/2 is particularly preferred.
≦ (2) / (3) (equivalent ratio) ≦ 7/3 is more preferable, and 4/6
≦ (2) / (3) (equivalent ratio) ≦ 6/4 is most preferred in terms of melting point. (2) -OC-R _b -CO- (3) -OC-Ar _b -CO-

From the viewpoint of mechanical strength, the viscosity of the aliphatic aromatic polyester of the present invention is reduced viscosity (η _sp / c) ≧ 0.
It is essential that the viscosity be 6 (hereinafter, unless otherwise specified, the viscosity means reduced viscosity (η _sp / c)). In consideration of moldability, 1.0 ≦ viscosity (η _sp /c)≦3.6 is preferable, and 1.5 ≦ viscosity (η _sp /c)≦3.3 is more preferable. More preferably, 1.7 ≦ viscosity (η _sp / c) ≦ 3.
0, most preferably 2.1 ≦ viscosity (η _sp / c) ≦ 2.
9 Although the terminal vinyl group is not essential, usually 4 eq
/ Ton or more is preferred. If the terminal vinyl group is 4 eq / ton or more, it is excellent in biodegradability. Preferably, the terminal vinyl group is at least 6 eq / ton, more preferably at least 8 eq / ton, most preferably at least 10 eq / ton.

In the aliphatic aromatic polyester of the present invention, the number of terminal COOH groups is not particularly limited.
5 eq / ton or more is preferable. More preferably, 22e
q / ton or more, more preferably 30 eq / ton or more. In particular, 40 eq / ton or more is preferable, and 50 eq / ton is preferable.
/ Ton or more is most preferred. As the number of terminal COOH groups increases, hydrolysis and biodegradability are promoted.

The aliphatic aromatic polyester of the present invention is characterized by having a moderate rate of biodegradability, and is suitable as a coating material for coated granular fertilizer. X-ray absorption fine structure analysis (XAF
Aliphatic aromatic polyesters having the physical properties and reduced viscosity specified in S) are more suitable as a coating material for fertilizers because their biodegradability is further improved and the rate of change in biodegradability is small. . Such an aliphatic aromatic polyester of the present invention may be produced with any catalyst as long as it has the specified physical properties.However, those obtained using a Ti compound as a catalyst have a high biodegradability from the viewpoint of polymerization rate. It is preferable also from the point of raising. Among them, further, a specific state, in other words, the arrangement with other atoms present near Ti has a specific state of Ti, and the reduced viscosity (η _sp / c) ≧
Aliphatic aromatic polyesters of 0.6 are preferred.

That is, the Ti-containing aliphatic aromatic polyether of the present invention
First, X-ray absorption fine structure analysis of esters
(XAFS; X-ray Absorption fi
X-ray near absorption edge structure (XAN)
ES; X-ray Absorption Near-
Edge Structure)
In the subtracted spectrum, the titanium absorption K
4.965 to 4.9 near the absorption edge with respect to the pump height
Of the main peak among the pre-edge peaks around 72 keV
The ratio of strength is R₁And the jump height at the K absorption edge of titanium
The difference between the maximum slope and the minimum slope of the main peak with respect to₁
And the Ti-containing composite catalyst C_AAliphatic aromatic compound synthesized by
Riester R₁And r₁To R_1AAnd r_1AAnd the
Ti-only catalyst C having the same Ti molarity as the combined catalyst_BSynthesized with
Of aromatic aromatic polyester₁And r₁To R_1B
And r_1BIn formula (i): R_1A/ R_1B> 1.05
And formula (ii): r_1A/ R_1B> 1.05 at least
R having the relationship_1AAnd r_1A Is to give.

Secondly, the Ti-containing aliphatic aromatic polyester of the present invention is obtained by X-ray absorption fine structure analysis (XAFS).
In the spectrum from which the background of the near-line absorption edge structure (XANES) has been subtracted, when the background is subtracted and the first-order differentiation is performed, the high energy side of the splitting peak near 4.98 keV corresponding to the K absorption edge of titanium
(4.982KeV near) the low energy side to the peak intensity N _H (near 4.978KeV) the ratio of the peak intensities N _L and _{R 2 (= N L / N} H), aliphatic synthesized in Ti-containing complex catalyst C _A the R ₂ of the aromatic polyester and R _2A, if the R ₂ of synthetic aliphatic aromatic polyesters Ti alone catalyst C _B of the composite catalyst of the same Ti molar concentration of R _2B,
Formula (iii): R _2A > 0.90 and Formula (iv): R _2A / R _2B
> 1.05 is what gives the R _2A satisfying at least one of relationships. However, the above C _B, when C _A is more additives catalyst containing Ti, it refers to Ti alone catalyst therein, and when C _A is a complex compound with other metals consisting of Ti, T used to synthesize the composite compound
i refers to a compound of a single metal. For example, if C _A is a tetrabutyl titanate / magnesium acetate catalyst, then C _B is tetrabutyl titanate.

This pre-edge peak seen in the XAFS XANES spectrum is attributed to the transition process of Ti from 1s to 3d orbital, and the point-symmetric octahedral structure of the atoms coordinated and bonded near the Ti element is distorted and different. When the coordination structure changes, its strength becomes stronger (Journal
of Non-Crystalline Solid
s, 81 (1986) 201, and others). That is, the intensity of the pre-edge peak indicates the degree of the change. Ti catalyst for the production of the aliphatic aromatic polyester of the present invention,
It breaks the perfectly symmetric coordination / bonding structure of octahedral of Ti catalyst and realizes a specific structure that makes it easy to generate a specific active site of the main reaction such that the molecules of the reaction raw material can interact with Ti atoms during the reaction. is there. With respect to the coordination / bonding structure of Ti catalyzed only by the compound of Ti alone metal, the structure deviates from the octahedral property which is more point symmetric, that is, the present pre-edge peak (4.965 to 4.965).
A state in which the intensity of the main peak (around 972 keV) is larger than that of the Ti-only catalyst has a catalyst structure that realizes a polymer having high polymerization activity and a high degree of polymerization. When the intensity of the main peak increases, the difference between the maximum inclination and the minimum inclination tends to increase, and it may be easy to understand the intensity based on the difference.

Furthermore, in the present invention, specific strong acidic sites of Ti which are not uniform can be suppressed, and generation of unnecessary by-products can be suppressed. Unnecessary by-products include formation of tetrahydrofuran or a terminal vinyl group by various decomposition reactions of a terminal hydroxybutyl group, and generation of a carboxyl group by a decomposition reaction of an ester group. This Ti
The electronic state of Ti related to the specific acid-base property is shown in the XANES region of XAFS. 4.98 keV of Ti
There are mainly two types of jumps in the vicinity of the K absorption edge. There are a jump on the high energy side (near 4.982 keV) and a jump on the low energy side (near 4.978 keV). It can be seen from FIG. 7 that the difference between the two transition intensities on the low energy side and the high energy side is different. Ratio of the slope of the low-energy side jump for the slope of the high-energy side jump (easy compared to see at a rate R ₂ of the maximum slope.) Is how strong transitions low energy side is the transition of the high-energy side It is a measure of whether it is. Generally, when the electron density of the measurement element increases, the position of the absorption edge jump shifts to a lower energy side. Therefore, this R ₂ is a specific electron density magnitude of Ti, Ti
Shows the degree of suppression of the acid properties of the specific site. The present invention relates to Ti
An aliphatic aromatic polyester having a degree of inhibition of the acidity of a specific site of XANES, in which R _{2 of} XANES exceeds 0.90,
It is based on the finding that it has good polymerization activity in which unnecessary by-products are suppressed, and as a result, a product with a high degree of polymerization can be produced.

In the aliphatic aromatic polyester of the present invention, R _1A and r _1A in the above definition are those represented by the formulas (i) and / or (i)
Preferred aliphatic aromatic polyesters satisfying (i) are those whose ratio of R _1A to R ₁ , ie, R _{1B in} the case of a Ti-only catalyst, exceeds 1.05, more preferably exceeds 1.1. , More preferably above 1.2, most preferably above 1.25. R _1A is more than 1.05, more preferably more than 1.2, more preferably more than 1.3 in the ratio of r ₁ , ie, r _1B , in the case of a Ti-only catalyst. Further, although R _2A and R _2B in the above definition satisfy the formulas (iii) and / or (iv), preferred aliphatic aromatic polyesters are those having a value of more than 0.90, more preferably 0, for R _2A. More than 0.95, more preferably more than 0.98, most preferably more than 1.00. The ratio of R _2A to R _2B is greater than 1.05, more preferably greater than 1.1, even more preferably greater than 1.15.

The titanium in the specific state described above is generated from a specific catalyst system used in the polymerization, and the aliphatic aromatic polyester obtained by polymerization with the catalyst having titanium in such a state is a specific Ti-based. Since the catalyst has higher polymerization activity in the polymerization step and fewer side reactions than the Ti-based catalyst, it is obtained as a high polymer, has excellent color tone, and has excellent hydrolyzability and biodegradability.

The aliphatic aromatic polyester of the present invention can be produced, for example, by the following method. That is, a glycol component mainly containing 1,4-butanediol, a lower alkyl ester component of a difunctional aliphatic carboxylic acid mainly containing succinic acid ester and / or adipic acid ester, and a difunctional mainly containing dimethyl terephthalate. Reacting with a carboxylic acid (ester) component,
Or a glycol component mainly composed of 1,4-butanediol, an aliphatic carboxylic acid mainly composed of succinic acid and / or adipic acid, and a bifunctional carboxylic acid (ester) mainly composed of terephthalic acid and / or dimethyl terephthalate.
When the polyester is produced by reacting the components with each other, in the presence of a cocatalyst such as a titanium compound and a magnesium compound as a polymerization catalyst, the atomic ratio (Mg / Ti) of magnesium to titanium metal (Mg / Ti) is preferably 0.1 to 1
It can be produced by being present in the range of 0 and polymerizing.

As the glycol component used in the present invention, for example, 1,4-butanediol is mainly used, but ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol, decamethylene glycol, cyclohexane dimethanol, polyhexane One kind of alkylene glycols such as (oxy) ethylene glycol, polytetramethylene glycol, and polymethylene glycol, or two or more kinds thereof may be mixed, and may be arbitrarily selected depending on the purpose. Further, a small amount of a polyhydric alcohol component such as glycerin may be used. Also, a small amount of an epoxy compound may be used.

In the present invention, at least an aliphatic or aromatic difunctional carboxylic acid or a lower alkyl ester component thereof is used. Examples of the aliphatic dicarboxylic acid and its ester include succinic acid and / or adipic acid. , And their lower alkyl esters, but aliphatic dicarboxylic acids such as sebacic acid and oxalic acid and their lower alkyl esters can also be used as a mixture. In the present invention, it is preferable to use a carboxylic acid as the aliphatic dicarboxylic acid component rather than an ester thereof. In addition, as the aromatic dicarboxylic acid and its lower alkyl ester, terephthalic acid and its methyl ester are mainly used, but aromatic dicarboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, and diphenyldicarboxylic acid, and the like. One of lower alkyl esters,
Alternatively, two or more kinds may be mixed and may be arbitrarily selected depending on the purpose.

The lower alkyl ester components of aliphatic and aromatic carboxylic acids are mainly methyl esters, but one or more of ethyl esters, propyl esters, butyl esters and the like may be mixed. ,
It can be arbitrarily selected depending on the purpose.

When a polyester having a branched structure is desired, a small amount of an oxycarboxylic acid such as glycolic acid or lactic acid or a lactone such as caprolactone may be used.
A trifunctional or higher functional acid anhydride or carboxylic acid such as a functional or higher functional oxycarboxylic acid, trimellitic anhydride or pyromellitic anhydride may be used. Further, according to the method of the present invention without using a chain extender, a predetermined degree of polymerization can be achieved, but a diisocyanate, diphenyl carbonate, a chain extender such as dioxazoline may be used,
In particular, when diphenyl carbonate is used, 20
% Or less (especially 10% or less) to make a polyester carbonate. It is of course also possible to add a small amount of peroxide in order to increase the melt tension. Furthermore, in order to enhance the hydrophilicity of the formed polyester, a compound having a hydrophilic group such as a sulfone group or a phosphate group may be used, and these hydrophilic groups may be introduced into a side chain. Examples of the compound to be obtained include 4-sulfonated-2,6-isophthalic acid.

Examples of the titanium compound used in the production of the polyester of the present invention include potassium titanium oxalate, titanium halide, tetraalkyl titanate and titanium carbonate. Among them, tetraalkyl titanate is preferred. Tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-
Butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetrabenzyl titanate, or a mixed titanate thereof; Of these, tetra-n-propyl titanate, tetraisopropyl titanate and tetra-n-butyl titanate are particularly preferred, and tetra-n-butyl titanate is preferred.
Butyl titanate is most preferred. Further, two or more of these titanium compounds may be used in combination. The addition amount of the titanium compound is 30 to 200 ppm, preferably 40 to
It is 150 ppm, more preferably 50 to 130 ppm.

In the production of the polyester of the present invention, any other compound may be used in combination with the above-mentioned titanium compound as long as a polyester having the physical properties defined in claims 6 and 7 can be produced. And compounds such as calcium, and a magnesium compound is preferred. Examples of the magnesium compound to be used include magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alkoxide, magnesium hydrogen phosphate, and the like. Particularly, the polymerization rate and solubility in 1,4-butanediol (foreign matter formation) ) And the like are most preferred.

When a magnesium compound is used, the amount used is not particularly limited. However, when the atomic ratio of metal to titanium, that is, the ratio of Mg / Ti is 0.1 to 10, the improvement in polymerization rate is high. And good color tone. Further, 0.2 to 5.0 is preferable, and 0.5 to 3.0 is preferable.
Is most preferred. In particular, when 0.5 ≦ Mg / Ti ≦ 3.0, the polymerization rate is extremely improved and the color tone is greatly improved.

The aliphatic aromatic polyester of the present invention includes those produced by a catalyst other than the combination of the Ti compound and the Mg compound as long as the above properties are satisfied, but is preferably a combination of the Ti compound and the Mg compound. And the viscosity (η _sp /c)≧0.6, the terminal COOH group is preferably 15 eq / ton or more, and the terminal vinyl may be absent, but preferably 4 eq / ton or more. .

The melt polymerization temperature can be set to any value.
The temperature is preferably higher than 220 ° C., particularly the internal temperature at the end of the melt polymerization (end stage) is higher than 220 ° C. The temperature is more preferably 230 ° C or higher, and further preferably 235 ° C or higher. 240 ° C. or higher is preferred, and most preferably 245 ° C.
As described above, the upper limit is 270 ° C. In this case, since the melt polymerization rate is high, additional charging can be performed, which can contribute to improvement in productivity. On the other hand, when the reaction is carried out at 220 ° C. or lower, the polymerization activity is low, the terminal vinyl group is hardly generated, and the terminal COOH group is reduced to less than 15 eq / ton, which is not preferable in terms of biodegradability.

In the present invention, an alkylene glycol component mainly composed of a 1,4-butylene glycol component, a lower alkyl ester component of an aliphatic difunctional carboxylic acid mainly composed of succinic acid and adipic acid component, and a terephthalic acid mainly. A transesterification reaction of an aromatic bifunctional carboxylic acid with a lower alkyl ester component, and / or 1,4
An esterification reaction step of an alkylene glycol component mainly composed of a butylene glycol component with an aliphatic difunctional carboxylic acid mainly composed of succinic acid and adipic acid components and an aromatic difunctional carboxylic acid mainly composed of terephthalic acid; The production of the aliphatic aromatic polyester is carried out via a subsequent polycondensation reaction step.These reaction conditions are not particularly limited, except for the temperature at the time of polymerization, and known reaction conditions can be applied as they are. Is done. In the method of the present invention, when a combination of an aliphatic dicarboxylic acid such as succinic acid and an ester of a difunctional carboxylic acid such as an aromatic dicarboxylic acid lower alkyl ester such as dimethyl terephthalate is used as a raw material of the produced polyester. , The esterification reaction and the transesterification reaction step are performed simultaneously.

The molar ratio of (alkylene glycol component) / (lower alkyl ester component of aliphatic and aromatic difunctional carboxylic acid) at the time of transesterification is 2.0 or less, preferably 1.0 to 1.6. 180 to 260 ° C., preferably 190 to 25 ° C., as a transesterification reaction.
Performed at 5 ° C. for 2-4 hours. In the case of the esterification reaction, the molar ratio of (alkylene glycol component) / (aliphatic and aromatic difunctional carboxylic acid component) is 2.0 or less,
It is preferably from 1.1 to 1.6, and the esterification reaction is from 180 ° C to 250 ° C, preferably from 185 to 23.
Performed at 0 ° C. for 2-4 hours. The subsequent polycondensation reaction may be performed at a temperature of 200 ° C. to 27
Conditions at 0 ° C. or lower and 2 to 6 hours can be adopted. In the late stage of polymerization in which the degree of polymerization increases, the melt viscosity increases with high degree of polymerization, so it is important to raise the set temperature and raise the internal temperature to a temperature exceeding 250 ° C.

The timing for adding the titanium compound is transesterification.
At the start of (or esterification), during transesterification, after transesterification, at the time of polycondensation, etc., it is preferable to add separately at the start of transesterification and before the polycondensation reaction. Other additives such as magnesium compounds may be added at the start of transesterification, during transesterification, after transesterification, at the time of polycondensation, etc. It is preferable from the point of view. In the case of an esterification method using succinic acid and / or adipic acid and terephthalic acid as main components, it is preferable to add a titanium compound and a magnesium compound during the polycondensation reaction. In this case, a tin compound or a zinc compound may be added at the time of esterification or polymerization, but the color tone may be slightly deteriorated in some cases. According to the production method of the present invention, the polymerization rate is greatly improved as compared with the conventional method, so that the productivity can be further improved by increasing the charge amount.

The granular fertilizer used in the present invention is not particularly limited, but urea, which has a high fertilizer component and has the most remarkable fertilizing effect, is particularly preferable from the viewpoint of elution control. Further, it is preferable to use a compound-type slow-release fertilizer such as isobutylidene diurea which has elution controllability in the fertilizer itself, because more various elution controllability can be obtained. Further, it is preferable that the fertilizer shape has a high sphericity, because the coating uniformity is high.

The coverage of the fertilizer of the present invention is not particularly limited, and is appropriately selected in consideration of economy, dissolution controllability and degradability. In order to increase economic efficiency, it is advantageous that the coverage is lower. On the other hand, in order to enhance the elution controllability, it is advantageous to have a higher coverage. In order to enhance the decomposability of the film, a low specific surface area and a low coverage are advantageous. Taking these into consideration, the coverage is in the range of 4 to 30%, preferably 6 to 20% by weight, based on the weight of the fertilizer to be coated. Most preferably, it is in the range of 8 to 15%. A structure having two or more layers may be used in consideration of dissolution controllability, decomposability, storage stability, and film strength.

The coating method of the film is not particularly limited, and it can be carried out by a conventional method. However, after the used coating material is dissolved or dispersed in a solvent and sprayed on the fertilizer, the solvent is dried instantaneously to obtain a uniform coating property. Is preferred because The solvent used may be any one that dissolves or disperses the coating material and is quick drying. Specifically, chlorinated hydrocarbons such as trichloroethylene and tetrachloroethylene, saturated hydrocarbons such as hexane and heptane, and aromatic hydrocarbons such as toluene and xylene are used.

The coated granular fertilizer coated with a coating composed of a coating material containing the aliphatic aromatic polyester as a main component of the present invention can provide an elution pattern suitable for the growth of crops and has good elution control in soil. In addition, the film is biodegraded. Further, the dissolution controllability does not become unstable during storage.

When the aliphatic aromatic polyester of the present invention is used as a coating material for a granular fertilizer, elution of the fertilizer is controlled by using various additives as in the conventional resin-coated fertilizer, as long as the purpose is not impaired. At the same time, one or more of a photodegradable material, a biodegradable material, an oxidation accelerating substance, a photodegradation accelerating substance, a sublimable substance and the like can be added to enhance the decomposability of the film. The aliphatic aromatic polyester of the present invention itself has sufficient biodegradability, but other biodegradable materials may be used in combination. Other biodegradable materials are not particularly limited, but include saccharide polymers and derivatives thereof, proteins and derivatives thereof, aliphatic polyesters, aliphatic polyesters into which aromatic or cyclic ethers are introduced, and water-soluble resins (for example, polyether, Polyvinyl alcohol and polymalic acid) are preferred. The amount of addition is appropriately determined in consideration of dissolution controllability, decomposability, and storage stability, but is generally 50% or less, preferably 20% or less, particularly preferably 10% or less, based on the entire polymer. . As a method of addition, if necessary, the resin of the present invention may be uniformly dispersed using a compatibilizer, or may be uniformly dispersed in a fine powder form.

Various substances can be added to the film as long as the object of the present invention is not impaired. For the purpose of promoting degradability, for example, photodegradable materials, oxidation promoting substances,
One or more of a photodegradation promoting substance and a sublimable substance can be added. The photodegradable material is not particularly limited, but a resin having a photosensitive functional group introduced therein, for example, a copolymer of carbon monoxide and olefins, a diene-based polymer, and a vinyl ketone-based copolymer is preferable. The amount to be added is appropriately determined in consideration of dissolution controllability, degradability, and storage stability.
It is particularly preferably at most 20%. As the addition method,
If necessary, the resin of the present invention may be dispersed uniformly using a compatibilizer, or may be dispersed in the form of fine powder.

There are no particular restrictions on the oxidation-promoting substance / photodegradation-promoting substance, but unsaturated fatty acids having carbon unsaturated bonds,
Preferred are unsaturated fatty acid esters, oils and fats, transition metals, transition metal compounds and transition metal complexes. The amount to be added is appropriately determined in consideration of dissolution controllability, decomposability, and storage stability.
0% or less, particularly preferably 5% or less. Although there is no particular limitation on the sublimable substance, naphthalene, camphor and sulfur are preferred. The addition amount is appropriately determined in consideration of dissolution controllability, decomposability, and storage stability, but is generally equal to or less than the total amount of the polymer, preferably 50% by weight or less, particularly preferably 20% by weight. Weight)% or less. In addition, a light stabilizer may be added in consideration of storage stability.

For the purpose of adjusting the elution pattern, one or more polyolefin polymers (eg, polyethylene) or copolymers containing polyolefin (eg, ethylene-vinyl acetate copolymer) can be added. In particular, low molecular weight polyethylene wax is preferable since it has biodegradability. The amount to be added is appropriately determined in consideration of dissolution controllability, decomposability, and storage stability, but is generally equal to or less than the total amount of the polymer, preferably 50% by weight or less, and particularly preferably 2% by weight or less.
0 (weight)% or less. Similarly, surfactants can be added for the purpose of adjusting the elution pattern. As the surfactant, any of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used. For example, nonionic surfactants such as polyoxyethylene nonylphenyl ether and polyoxyethylene alkyl ether can be used. Activators are preferred. The amount of addition is appropriately selected according to the intended pattern.

For the purpose of reducing the amount of expensive resin and reducing the temperature dependence, it is preferable to add, for example, an inorganic powder. In particular, natural inorganic minerals are preferable since they have high controllability of dissolution and are inexpensive even when they are added in a considerable amount. In particular,
Examples include talc, mica, sericite, glass flake, metal foil, graphite, plate-like iron oxide, plate-like aluminum hydroxide, hydrotalcite, charcoal, silica, clay, and the like, particularly talc, mica, charcoal, clay. Are preferred. If the amount of each of these natural inorganic minerals is too large, the film strength and crushing strength are extremely reduced, and the dissolution controllability is reduced. Considering these, the addition ratio of the natural inorganic mineral in the film is 0 to 8 by weight.
The range is 0%. In addition, any natural inorganic mineral preferably has a particle size that does not impair the continuity of the film and does not cause agglomeration of the powders, for example, a particle size of 1/2 or less of the film thickness. Also,
Agricultural materials such as other fertilizer components, pesticides, plant physiologically active substances, or plant growth promoting substances can be mixed in the film. There is no particular restriction on the dispersion position of these materials in the film.

Measurement and analysis method of XAFS in the aliphatic aromatic polyester of the present invention, reduced viscosity (η _sp / c),
The terminal vinyl group, terminal carboxyl group, and biodegradability were evaluated based on the following methods. (I) XAFS Measurement and Analysis Method XAFS XANES spectra were measured using the Beamline 12 of the Synchrotron Radiation Facility, High Energy Accelerator Research Organization.
C (BL12C) fluorescence XAFS measurement apparatus.
The spectral crystal is a Si (111) 2 crystal type, and the incident X-ray intensity I ₀ is a 17 cm ion chamber filled with a mixed gas He / N ₂ = 70/30, and the fluorescent X-ray intensity I
_f was measured using a fluorescent XAFS measurement chamber using Ar gas (commonly known as Lytle detector).

In the analysis, the least squares fitting is performed on the region before the absorption edge (flat pre-edge region) of the obtained spectrum I _f / I ₀ using the formula of Victorine or MacMaster, and the result is excluded. After subtracting the background by insertion, differentiation is performed. The energy value at the maximum value of the derivative of the XANES spectrum of Ti metal was determined to be 4.9645 keV, and calibration was performed. The following analysis was performed on this calibrated spectrum.

Normalized so that the K absorption edge jump height of Ti is equal, the pre-edge peak (4.965 to
(Approximately 4.972 keV) on the low energy side, a flat background area of 4.855 to 4.965 keV is linearly approximated (linear L) by the method of least squares, and the vertical axis component of the highest position of the main pre-edge peak And the difference between the vertical axis component and the same energy of the straight line L divided by the jump height was determined as R ₁ . : Differentiated, high energy side of K absorption edge jump of Ti
(Near 4.982 keV) and the low energy side (4.97 keV).
The maximum slope (at about 8 keV) (the height of the differential peak) was determined.

(II) Basic physical properties of aliphatic aromatic polyester (A) Reduced viscosity (η _sp / c) in phenol / tetrachloroethane (1: 1 weight ratio) at 30 ° C., solution concentration of 0.1
It was determined from the solution viscosity measured at 5 dl / g. (B) The terminal COOH group is a value obtained by dissolving an aliphatic aromatic polyester in benzyl alcohol and appropriately adjusting the concentration with 0.1 N NaOH, and is a carboxyl group equivalent per 1 × 10 ⁶ g. (C) The terminal vinyl group is obtained by converting aliphatic aromatic polyester to hexafluoroisopropanol / deuterated chloroform = 3.
/ 7 (vol ratio), 400 MHz ¹ H-NMR
And the vinyl group equivalent per 1 × 10 ⁶ g (tons).

(III) Measurement of biodegradability (A) Changes in soil Sample preparation method A film (thickness: 30) of each polymer was formed by a pressure press machine.
μm) was prepared and cut into 10 cm pieces to obtain test samples. (B) Biodegradability Evaluation is performed using a lipase using a powdered product (pulverized with a freezer mill).

[0056]

Hereinafter, the present invention will be described in more detail with reference to Production Examples and Examples.
The present invention is not limited to the following embodiments. In the examples, "parts" means "parts by weight".

(1) Production of Aliphatic Aromatic Polyester Production Example 1 49.2 parts of 1,4-butanediol and 28.1 succinic acid were placed in a glass polymerization tube equipped with a stirring blade, a pressure reducing port, and a nitrogen inlet.
And 46.2 parts of dimethyl terephthalate, and the atmosphere in the system was changed to a nitrogen atmosphere by nitrogen-vacuum substitution. Next, the temperature was raised to 185 ° C. while stirring the system, and the system was maintained for 30 minutes. Thereafter, the temperature was raised to 220 ° C. over 1 hour and 30 minutes, water as a reaction product was distilled off, and an esterification reaction was performed. Here, 0.071 g of tetrabutyl titanate and 0.045 g of magnesium acetate tetrahydrate were dissolved as catalysts in 1,4-butanediol and added to the system. Next, the temperature was raised to 260 ° C. over 1 hour, and simultaneously, the pressure was gradually reduced to 0.5 mmHg over 1 hour and 30 minutes. 2
The polymerization reaction was terminated 3 hours after the temperature reached 60 ° C.
The viscosity (ηsp / c) of the obtained polyester was 2.17. The amount of terminal carboxyl groups was 31.4 eq / ton. The terminal vinyl group was 7.2 eq / ton.

Production Example 2 Polymerization was carried out in the same manner as in Production Example 1 except that only 0.071 g of tetrabutyl titanate was used as a catalyst. The viscosity (ηsp / c) of the obtained polyester was 1.61. The amount of terminal carboxyl groups was 46.9 eq / ton. Figure 1 shows the XAFS measurement results of Production Example 1 and Production Example 2.
1 and 2. R _1A / R _1B in FIGS. 1 and 2 =
1.31, _r1A / _r1B = 1.36, _R2A = 1.05, R
_2A / _R2B = 1.24.

Preparation Example 3 In Preparation Example 1, adipic acid was used instead of succinic acid.
An aliphatic aromatic polyester was obtained in the same manner as in Production Example 1, except that 7 parts were used. Polyester viscosity (ηsp /
c) is 2.03 and the amount of terminal carboxyl groups is 3
It was 5.4 eq / ton.

Production Example 4 In Production Example 2, adipic acid was replaced by 3 in place of succinic acid.
An aliphatic aromatic polyester was obtained in the same manner as in Production Example 2 except for using 4.7 parts. The viscosity (ηsp / c) of the obtained polyester was 1.47, and the amount of terminal carboxyl groups was 40.7 eq / ton. X of Production Examples 3 and 4
From the AFS measurement results (not shown), R _1A / R _1B = 1.
26, r _1A / r _1B = 1.35, R _2A = 1.02, R _2A /
R _2B = 1.17.

(2) Measurement of Biodegradability Table 1 shows the measurement results of the aliphatic aromatic polyesters produced in Production Examples 1 to 4 by the above-mentioned measurement method (A) relating to the measurement of biodegradability.

[Table 1]

(3) Production of coated fertilizer Examples 1-4 and Comparative Examples 1-4 The polyesters produced in Production Examples 1-4 and the control resins (Comparative Examples 1-4) shown in Table 2 below were each toluene Or spray liquid dissolved in trichlorethylene (concentration 2-5 w / v
%)) Into 2 kg of urea particles having a particle size of 2 to 4 mm.
Using a jet-type coating apparatus shown in FIG. 3, spray coating was performed at a drying air (flowing gas) temperature of 70 to 90 ° C. and an air flow of 100 m ³ N ₂ / hour to obtain a coated granular fertilizer having a coverage of 10% (to fertilizer). . A known method (DE using the resin of Production Example 1) was used.
According to 19640269 A1), a coated granular fertilizer was obtained in the same manner as described above except that an aqueous dispersion was prepared and used as a spray liquid (Comparative Example 5). In the apparatus shown in FIG. 3, while spraying the granular fertilizer 1 filled in the tank with the drying air (flowing gas) 3 from below, the spray liquid 2 in which the coating material is dissolved or dispersed is sprayed. It covers the fertilizer.

[0063]

[Table 2]

(4) Evaluation of Dissolution Characteristics of Coated Fertilizer a) Dissolution Measurement Method in Water 7 g / 2 of the coated fertilizer produced in (3) in 25 ° C. constant temperature water.
At a rate of 00 cc, urea nitrogen in water was quantified over time. Table 3 shows the results. b) Method for measuring dissolution in water after aging treatment The coated fertilizers of Example 1 and Comparative Example 5 produced in (3) were allowed to stand in a thermo-hygrostat (temperature: 40 ° C., relative humidity: 60%) for one month, and then a ). Table-
3 is shown. c) Dissolution measurement method in soil The coated fertilizer produced in (3) was added to 200 g of alluvial soil dry soil, 60 mg of nitrogen was added, 350 cc of water was added, and the mixture was allowed to stand still at 25 ° C. Over time, the coated fertilizer was taken out of the soil, residual nitrogen was quantified, and the elution amount was calculated. Table 3 shows the results. As the dissolution characteristics, the dissolution rate (in terms of dissolution rate in soil) for 40 days is preferably 30% or less. If the dissolution rate is low, various dissolution patterns can be created by the above-mentioned method, for example, by adding an inorganic filler or a surfactant. The difference between the water dissolution rate and the soil dissolution rate is ± 5
It is preferably within 3 days, particularly preferably within 3 days. The small difference means that the dissolution rate in soil can be predicted from the dissolution rate in water, and fertilization can be performed so as to be compatible with the growth of the crop.

[0065]

[Table 3]

In each of the aliphatic aromatic polyesters of the present invention obtained in each of the production examples, moderate propagation of mold was observed. Among them, the succinic acid type is slightly more prominent for mold growth, and in the same type, the polyester which satisfies the provisions of claim 6 and / or 7 has slightly more fungal multiplication and biodegradability. (Table 1). In all the examples, the dissolution rate in soil was 30% or less, and the difference between the dissolution rates in water and soil was within 5 days. (Table-3)
That is, it turned out that the performance of the coating material for fertilizer was imparted and biodegradable. On the other hand, in Comparative Examples 1 to 4, there is a large difference in the dissolution rate (%) between water and soil after 40 days, and the dissolution controllability is unstable, that is, the dissolution pattern in soil cannot be predicted. This is because in about 40 days in the soil, the film was significantly deteriorated by biodegradation. Furthermore, in Comparative Examples 1 to 4, the dissolution rate in soil exceeded 50% in all cases on day 40, and did not satisfy the performance as a slow-release fertilizer. In Comparative Example 5, the water-based coating increased the dissolution rate to 32% (Example 1: 21%), and the dissolution rate in water on the 40th day after the aging treatment was increased to 40%. It is unstable and does not fulfill its function as a coated fertilizer.

[0067]

The aliphatic aromatic polyester, which is the main component of the coating material of the present invention, has a moderate biodegradability and, as is evident from Table 3, there is no great difference in the elution between water and soil. In addition, since the elution stopping ability is good,
Coated fertilizer coated with the coating material is extremely useful.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 In the spectra of the near-X-ray absorption edge structure of the X-ray absorption fine structures of the aliphatic aromatic polyesters of Production Examples 1 and 2, after subtracting the background, the K absorption edge jump of Ti Charts normalized so that heights are equal (solid line (Production Example 1), dotted line (Production Example 2)).

FIG. 2 shows the spectra of the aliphatic aromatic polyesters of Production Example 1 and Production Example 2 in the near-X-ray absorption edge structure of the X-ray absorption edge fine structure, after the background has been subtracted, and the first-order differentiation. (Solid line (Production Example 1), dotted line (Production Example 2)). R in FIGS. 1 and 2
_1A / _R1B = 1.31, _r1A / _r1B = 1.36, _R2A =
1.05, _R2A / _R2B = 1.24.

FIG. 3 is a schematic diagram showing a jet-type coating apparatus used for producing the coated fertilizer of the example.

[Explanation of symbols]

 Reference Signs List 1 granular fertilizer 2 coating solution 3 dry air (flowing gas) 4 guide tube

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hisato Saito 1-1 Kurosaki Shiroishi, Yawatanishi-ku, Kitakyushu City, Fukuoka Prefecture Inside the Kurosaki Office of Mitsubishi Chemical Corporation (72) Inventor Toyohiko Shike 1 Kurosaki Shiroishi, Yawatanishi-ku, Kitakyushu-shi, Fukuoka Prefecture No. 1 Mitsubishi Chemical Corporation Kurosaki Works F-term (reference) 4H061 AA01 DD04 DD18 EE35 FF08 FF15 HH02 HH28 HH32 LL13 LL30 4J029 AA03 AB07 AC02 AD01 AD02 AE18 BA02 BA05 BA08 BA10 BD03A BD07A BF09 CA03 FC03 CA03 FC01 FC08 JA011 JB131 JE182 JF321 KB02 KB05 4J038 DD051 PB02

Claims (10)

[Claims] 1. A coating material for coated granular fertilizer, characterized in that at least one component is an aliphatic aromatic polyester whose main chain is mainly formed from an aliphatic compound component and an aromatic compound component. 2. The coated granular fertilizer according to claim 1, wherein the aliphatic aromatic polyester is mainly formed from aliphatic glycol, aliphatic dicarboxylic acid or its ester and aromatic dicarboxylic acid or its ester. -Ting materials. 3. The aliphatic compound residue in the main chain of the aliphatic aromatic polyester mainly comprises a 1,4-butanediol residue and a succinic acid and / or adipic acid residue. 3. The coating material for coated granular fertilizer according to claim 1, which mainly comprises terephthalic acid residues. 4. A coated granular fertilizer wherein the main chain is coated with a material containing at least one aliphatic aromatic polyester formed mainly from an aliphatic compound component and an aromatic compound component. 5. A coated granular fertilizer according to claim 4, which is coated with the coating material according to claim 2. 6. The X-ray absorption near-edge structure (XANE) of X-ray absorption fine structure analysis (XAFS)
In the spectrum after subtracting the background of S), the ratio of the intensity of the main peak among the pre-edge peaks around 4.965 to 4.972 keV near the absorption edge to the jump height of the K absorption edge of titanium is shown as R ₁
And it represents the difference between the maximum inclination and the minimum inclination of the main peak to the jump height of the K absorption edge of titanium as r _1, the aliphatic aromatic polyester synthesized in Ti-containing complex catalyst C _A R ₁ and r ₁ respectively R _1A and r _1A, and a Ti-only catalyst C _B having the same Ti molar concentration as the composite catalyst (in the case where C _A is a plurality of addition-type catalysts containing Ti, refer to a Ti-only catalyst among them;
When C _A is a composite compound of Ti and another metal, it refers to a compound of a single metal of Ti used for synthesizing the composite compound. )), When R ₁ and r ₁ of the aliphatic aromatic polyester synthesized in the above are R _1B and r _1B respectively,
2. The coated granular fertilizer according to claim 1, wherein R _1A and r _1A satisfying the relationship of (i) and / or (ii) are provided, and the reduced viscosity (η _sp /c)≧0.6. Coating material. R _1A / R _1B > 1.05 (i) r _1A / r _1B > 1.05 (ii) 7. The X-ray absorption near-edge structure (XANE) of X-ray absorption fine structure analysis (XAFS)
In the spectrum of S), when the background is subtracted and the first-order differentiation is performed, the spectrum corresponds to the K absorption edge of titanium4.
The high energy side of the fission peak near 98 keV (4.9
The ratio of the peak intensity N _L on the low energy side (around 4.978 keV) to the peak intensity N _H is represented by R
And _{2 (= N L / N H} ), the R ₂ of aliphatic aromatic polyester synthesized in Ti-containing complex catalyst C _A and R _2A, was synthesized with Ti alone Catalyst C _B of the composite catalyst of the same Ti molar concentration When R ₂ of the aliphatic aromatic polyester is R _2B , the formula (i)
2. The coated material for coated granular fertilizer according to claim 1, wherein R _2A satisfying the relationship of ii) and / or (iv) is provided and the reduced viscosity (η _sp /c)≧0.6. . R _2A > 0.90 (iii) R _2A / R _2B > 1.05 (iv) 8. A coated granular fertilizer according to claim 4, which is coated with the coating material according to claim 6. 9. A fertilizer is coated by spraying and drying a solution obtained by dissolving an aliphatic aromatic polyester formed mainly of an aliphatic compound component and an aromatic compound component in an organic solvent onto a fertilizer. The coated granular fertilizer according to claim 4, wherein 10. The aliphatic compound residue in the main chain of the aliphatic aromatic polyester mainly comprises a 1,4-butanediol residue and a succinic acid and / or adipic acid residue. The coated granular fertilizer according to claim 9, comprising mainly terephthalic acid residues.