JP3188905B2 - Polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to productivity, moldability,
The present invention relates to a polyester resin composition used for yarns, films, sealants, molding materials, and the like having excellent workability and mechanical properties.

[0002]

2. Description of the Related Art Organic polymer materials used in yarns, films, sealants, molding materials and the like have been used in the past for the purpose of improving mechanical strength and heat resistance. Mixing and kneading of materials are performed. However, since these inorganic materials are not easily dispersed into fine particles by merely mixing and kneading, there is no material having satisfactory properties. For this reason, many patent applications have been filed for inventions aiming at uniform dispersion in an organic polymer material, in which montmorillonite and a fluoromica-based swelling clay mineral are chemically treated to form fine particles. Examples thereof are described in JP-A-62-749.
No. 57, Japanese Unexamined Patent Application Publication No. 2-173160, Japanese Unexamined Patent Application Publication No.
-7729, JP-A-3-41149, JP-A-8-3310, JP-A-8-59822,
JP-A-8-120071 and JP-A-8-13420
No. 5 publication. However, at present, the dispersibility of the inorganic material is not sufficient in these methods.

[0003]

The object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to improve the dispersibility of an inorganic material and thereby to expect higher mechanical strength and heat resistance. To a polyester resin composition to be prepared.

[0004]

The present inventors have discovered that certain inorganic materials, namely swellable layered silicates, phosphates,
By using a composite obtained by mixing or reacting with at least one compound selected from a polyphosphate, a polyvalent metal salt and a polynuclear metal complex, the dispersibility of the swellable layered silicate is good. It has been found that such a polyester resin composition as follows can be obtained, and the present invention has been completed.

That is, the present invention is as follows. (1) A composition containing a polyester resin and an inorganic material, wherein the inorganic material is a swellable layered silicate (a),
A polyester resin composition, which is a complex obtained by mixing or reacting with at least one compound (b) selected from phosphates, polyphosphates, polyvalent metal salts and polynuclear metal complex salts. (2) Compound (b) is at least one compound selected from phosphates and polyphosphates (b-1) and at least one compound selected from polyvalent metal salts and polynuclear metal complex salts
The polyester resin composition according to the above (1), which is a compound (d) containing phosphoric acid and a metal element generated by the reaction with (b-2).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail.
The polyester resin composition of the present invention contains a polyester resin and an inorganic material.

A polyester resin is a resin containing an ester bond in the main chain, and is obtained by a condensation reaction of an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid or an ester derivative thereof with a polyhydric alcohol or an ester derivative thereof. It is a copolymer.

The aromatic dicarboxylic acids include, for example, phthalic acid, terephthalic acid, isophthalic acid, naphthalene-
2,6-dicarboxylic acid, α, β- (4-carboxyphenoxy) ethane, 4,4′-dicarboxydiphenyl,
5-sodium sulfoisophthalic acid or ester derivatives thereof. Examples of the aliphatic dicarboxylic acid include succinic acid, maleic acid, fumaric acid, itaconic acid, malic acid, oxaloacetic acid and ester derivatives thereof.

Examples of the glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6
-Hexanediol, decamethylene glycol, cyclohexanediol, cyclohexanedimethanol, glycerin, pentaerythritol and the like.

Specific examples of the polyester resin used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate,
Examples include aromatic polyesters such as polycyclohexane dimethylene terephthalate, polyhexamethylene terephthalate, and polyethylene naphthalate, unsaturated polyesters, and alkyd resins.

The composition of the present invention contains an inorganic material in addition to the above polyester resin. This inorganic material
Swellable layered silicate (a), phosphate, polyphosphate,
A complex in which at least one compound (b) selected from a polyvalent metal salt and a polynuclear metal complex is mixed or reacted.

Swellable phyllosilicate used in composites
(a) is natural or synthetic, hectorite, saponite, stevensite, hyderite, montmorillonite, non-trite, smectite clay minerals such as bentonite, Na-type tetrasilicic mica, Li-type tetrasilicic mica, Swelling mica clay minerals such as Na-type fluorine teniolite and Li-type fluorine teniolite, and vermiculite or a mixture thereof.

Commercial products include Laponite XLG (synthetic hectorite-like substance manufactured by LaPorte, UK), Laponite RD (synthetic hectorite-like substance manufactured by Laporte, UK), and Thermabis (similar to hectorite manufactured by Henkel, Germany) Substance), smecton SA-1 (a saponite-like substance manufactured by Kunimine Industry Co., Ltd.), wenger (natural montmorillonite sold by Toysun Yoko Co., Ltd.), kunivia F (natural montmorillonite sold by Kunimine Industry Co., Ltd.), veegum (US Natural hectorite manufactured by Vanderbilt Co., Ltd., dimonite (synthetic swelling mica manufactured by Topy Industries, Ltd.), somasif (synthetic swelling mica manufactured by Corp Chemical Co., Ltd.), SWN (manufactured by Corp Chemical Co., Ltd.) Synthetic smectite) and SWF (synthetic smectite manufactured by Corp Chemical Co., Ltd.).

Among them, a fine powder obtained by mixing talc with sodium and / or lithium silicofluoride is used as a powder.
It is preferable to use an alkali metal selected from sodium and lithium, which is obtained by heating to 00 ° C. to 1200 ° C., and magnesium, silicon, oxygen and fluorine as main constituent elements. Somasif (synthetic swellable mica manufactured by Corp Chemical Co., Ltd.).

In the present invention, “swelling” means “swelling”.
Water or a solvent such as alcohol or ether enters between crystal layers and swells.

Among the compounds (b) used in the complex, the phosphate includes alkali metal or ammonium salts of orthophosphoric acid and other water-soluble phosphates, such as disodium hydrogen phosphate, There is sodium dihydrogen phosphate.

Among the compounds (b) used in the composite, the polyphosphates include alkali metal or ammonium salts of pyrophosphate, alkali metal or ammonium salts of tripolyphosphate, alkali metal or ammonium salts of trimetaphosphate, Examples thereof include alkali metal or ammonium salts of metaphosphoric acid and other water-soluble polyphosphates, such as sodium pyrophosphate, disodium dihydrogen pyrophosphate, and sodium tripolyphosphate. In the present invention, it is particularly preferable to use a polyphosphate such as sodium pyrophosphate, disodium dihydrogen pyrophosphate, and sodium tripolyphosphate.

Among the compounds (b) used in the composite, the polyvalent metal salt refers to a divalent or higher, preferably trivalent or tetravalent, metal salt, for example, an Al salt, a Zr salt, a Ti salt, Price F
e salt and Cr salt. Preferred specific examples include:
Examples include aluminum nitrate (Al (NO ₂ ) ₂ ), aluminum chloride (AlCl ₃ ), and zirconium oxychloride.

Among the compounds (b) used in the composite, the polynuclear metal complex salt is a metal complex salt having two or more, preferably three or four nuclei, such as an Al complex salt, a Zr complex salt,
Examples of the complex include a Ti complex salt, a trivalent Fe complex salt, and a Cr complex salt.

The compound (b) may be at least one compound (b-1) selected from phosphate and polyphosphate.
And at least one compound selected from a polyvalent metal salt and a polynuclear metal complex (b-2).
A composite obtained by mixing or reacting (d) and the swellable layered silicate (a) may be used as the inorganic material. It is preferable to include such a composite in the polyester resin composition, since the dispersibility of the swellable layered silicate (a) in the polyester becomes better.

The above polyester resin composition is produced, for example, by the following method. First, the swellable layered silicate (a) is dispersed in a solvent. The solvent used here is usually water, but depending on the case, lower alcohols such as alcohol, methanol, ethanol and propanol and / or
Alternatively, a polyhydric alcohol may be mixed. The concentration of the swellable layered silicate (a) is not particularly limited, but is usually 1 to 50.
% By weight, preferably 1 to 40% by weight, more preferably 1 to 20% by weight. Stirring is performed sufficiently to improve the dispersion.

Next, at least one compound (b) selected from phosphate, polyphosphate, polyvalent metal salt and polynuclear metal complex salt is added to the dispersion containing the swellable layered silicate. To form a complex. Here, the compounding amount of the compound (b) is usually 0.01 to 1 mol per 1 mol of the swellable layered silicate.
An amount is added so as to be 20.00 mol, preferably 0.10 to 20.00 mol, and more preferably 0.10 to 10.00 mol. Since the added compound (b) needs to be dissolved in a solvent, it is added if the solvent is insufficient.
Alternatively, compound (b) may be added after dissolving in a solvent.

The compound (b) comprises at least one compound (b-1) selected from phosphates and polyphosphates and at least one compound selected from polyvalent metal salts and polynuclear metal complexes ( In the case of the compound (d) containing phosphoric acid and a metal element generated by the reaction with b-2), first, a phosphate and a polyphosphate are added to the dispersion containing the swellable layered silicate described above. At least one compound selected from salts (b-1)
Is added. The amount of the compound (b-1) to be added is generally 0.01 to 20.00 mol, preferably 0.05 to 10.00 mol, more preferably 0.05 to 5 mol, per 1 mol of the swellable layered silicate. 0.000 mol. Compound
Since (b-1) needs to be dissolved in a solvent, it is added if the solvent is insufficient. Compound (b-1) may be added after dissolving in a solvent. Examples of the solvent in this case include those used as a solvent in which the swellable layered silicate (a) is dispersed.

Next, at least one compound selected from a polyvalent metal salt and a polynuclear metal complex (b-
2) is added. When the compound (b-2) is added as a powder, a good dispersion cannot be obtained. Therefore, the compound (b-2) is preferably added as a solution dissolved in a solvent, and is preferably added little by little while mixing. The amount of the compound (b-2) to be added is usually 0.01 to 20.00 mol per 1 mol of the swellable layered silicate,
The amount is preferably from 0.05 to 10.00 mol, more preferably from 0.1 to 10.00 mol. Examples of the solvent in this case include those used as a solvent in which the swellable layered silicate (a) is dispersed.

In the dispersion thus obtained, a compound (b-1) contains a phosphorus element and a compound (d) containing the metal element contained in the compound (b-2). It is determined that a complex was formed with the swellable phyllosilicate (a) and dispersed in the liquid as a fine solid. The basis is that the solid content of the dispersion is centrifuged, washed with water, dried at 50-90 ° C, and left at room temperature. The presence of the element can be confirmed, and in the X-ray diffraction spectrum by the powder method, the reflection peak value in the vicinity of the (001) diffraction line region, which is the bottom spacing value (d001) specific to the raw material swellable phyllosilicate (a), is shown. (9.5 to 15 °) is that the obtained solid (e) is 3 to 30 ° larger than the value of the raw material swellable phyllosilicate (a). The results show that the compound (d) exists between the crystal layers, and the presence of the compound (d) between the crystal layers indicates that the swellable layered silicate is present.
This is the result of the application of some bonding force to (a), and it can be determined that a complex of the swellable layered silicate (a) and the compound (d) has been formed. The compound (d) may exist alone without forming a complex with the swellable layered silicate (a) depending on the reaction conditions.

The compound (d) has a clear composition formula.
However, for example, as a compound (b-1), NaH_TwoPO
_Four, Na_FourP_TwoO₇Or Na_FiveP_ThreeO_TenUsing
Al (NO) as product (b-2)_Three)_ThreeIf you use
Such compounds are presumed. NaH_TwoPO_FourAnd Al (NO_Three)_ThreeIn combination with Al_1-XNa_Y(H_TwoO)_ZPO_Four(0 ≦ X <1, X +
Y = 3X) Na_FourP_TwoO₇And Al (NO_Three)_ThreeIn the case of combination with AlNa_1-X(H_TwoO) XP_TwoO₇(X = 0-1) Na_FiveP_TwoO_TenAnd Al (NO_Three)_ThreeIn the case of combination with AlNa_2-X(H_TwoO) XP_TwoO_Ten(X = 0-2) In the case of other combinations, the metal elements are different,
Compounds similar to are envisioned. In addition,
(PO) of the compound (b-1) exemplified in_Four), (P
_TwoO₇), (P_TwoO_TenPart of the moiety is replaced with an OH group
And when using polyphosphates, some
With a lower degree of polymerization polyphosphate or orthophosphate
After that, compound (d) may be formed.

The swellable layered silicate (a) and the compound
In the formation of the complex with (d), the pH of the liquid is generally adjusted to 1 to 5 because the hydrogen ion concentration (pH) of the dispersion influences.
It is necessary to adjust the pH to about 6. For example, when an Al salt, a Zr salt, a Ti salt, a Cr salt, a trivalent Fe salt, or the like is used as the compound (b-2), the pH is preferably about 1 to 4. . Therefore, in some cases, before or after the addition of compound (b-2), it is necessary to adjust the pH by adding an alkaline solution such as a NaOH or KOH solution.

In the above series of operations, there is no particular problem if the liquid temperature is 0 to 100 ° C., preferably 0 to 60 ° C. Further, as a characteristic of the dispersion, a dispersion obtained by dispersing only the swellable layered silicate (a) in a solvent mainly composed of water has a card house structure. The reflection peak value (9.5 to 9.5) near the (001) diffraction line region which is the bottom surface interval value (d001) of a)
Although 15 °) is not recognized, in the X-ray diffraction spectrum of the dispersion in which the complex is formed, the reflection peak value near the (001) diffraction line region is 1% smaller than the reflection peak value of the solid (e).
Å15 ° greater value. This indicates that in addition to the compound (d), the solvent was intercalated between the crystal layers, and that the layers were regularly stacked.
This is considered to be a remarkable property of this dispersion, and it is judged that this property greatly affects the good dispersibility of the dispersion.

[0029] Further, since the dispersed liquid after the formation of the complex contains dissolved electrolytes, they may be separated if judged to be disadvantageous substances. The separation may be performed by a conventional means such as centrifugation, decantation, filtration and the like. If a certain amount of dissolved electrolyte is to be removed, it may be removed by decantation. Since the separated solid contains an attached electrolyte, the solid substance is washed with water when it is desired to sufficiently remove the attached electrolyte. The solid thus obtained is mainly composed of a composite.

Next, a part of one of the glycol component and the dicarboxylic acid component constituting the polyester is previously blended with the dispersion in which the complex is formed. The glycol component and the dicarboxylic acid component to be blended here are the same as the glycol component and the dicarboxylic acid component of the polyester resin in which the composite is dispersed, but the glycol component is particularly preferable. For example, if the polyester resin is polyethylene terephthalate, ethylene glycol is used. If these components are liquid, they are used as they are. If they are solid, they are used by dissolving or heating in an appropriate solvent. The mixing ratio between the dispersion and the component can be arbitrarily selected depending on the purpose. Generally, the ratio is 1 to 5000 (weight ratio), preferably 5 to 5000, more preferably 1 to the swellable layered silicate 1 as a raw material. 5-
1000.

After the complex is once isolated and purified from the dispersion, the complex may be blended with a part of the glycol component or the dicarboxylic acid component. In this case, when the component is a liquid, the solvent may not be used. The mixing ratio of the separated complex and the component can be arbitrarily selected depending on the purpose, but generally, for example, when the swellable layered silicate 1 used as a raw material contained in the separated complex is a glycol component, Is 1 to 5000 (weight ratio), preferably 5 to 5000, and more preferably 5 to 1000.
In many cases, dispersion of the separated complex and the component does not go well. In general, the separated complex is first dispersed in the above-described solvent (the dispersion concentration of the complex is not particularly limited; 80% by weight, preferably 1 to 50% by weight), after which the components are mixed. When the complex is dispersed in the solvent, a small amount (5% by weight or less of the solvent) is added to the solvent.
May be dissolved and then dispersed.

In the same manner as described above, in the case of a dispersion of a composite containing a glycol component, a dispersion in which only the swellable layered silicate (a) is dispersed in a water-based solvent has a swelling property in the X-ray diffraction spectrum. Bottom spacing value of layered silicate (a) (d00
Although the reflection peak value (9.5 to 15 °) near the (001) diffraction line region which is 1) is not recognized, the (001) diffraction line region is observed in the X-ray diffraction spectrum of the dispersion in which the composite is formed. The near reflection peak value is obtained as a value 1 to 15 ° larger than the reflection peak value of the solid (e).

Next, the polyester is polymerized using the dispersion. In the polyester resin composition of the present invention thus obtained, the composite is preferably 0.01 to 50% by weight, more preferably 1 to 30% by weight in the composition.
% By weight, particularly preferably 1 to 10% by weight.

The polyester resin composition of the present invention may contain a pigment, an antibacterial agent, an ultraviolet absorber and the like, if necessary, as long as its properties are not impaired.

[0035]

Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following examples, “parts” means “parts by weight”.

<Method for Forming Mixture or Composite> Reference Example 1 As a swellable layered silicate (a), Somasif (ME-100) manufactured by Corp Chemical Co., Ltd. was used. The general formula of Somasif is shown below. Na _{2X + 2a} Mg _3.0-X [(Si _4.0-a Mg _a ) O ₁₀ ]
(F, OH) ₂ (where 0 ≦ X ≦ 0.5, 0 ≦ a ≦ 0.50, 0.15
≦ X + a ≦ 0.5, and Na is a coordination number 12 between the layers.
Mg in Mg _3.0-X forms an octahedral sheet Cation having a coordination number of 6; Si and Mg in (Si _4.0-a Mg _a ) form a tetrahedral sheet It is a cation having a coordination number of 4. 4) Somasif and 96 parts of water were thoroughly mixed to prepare a 4% by weight Somasif dispersion. To 150 g of the dispersion, 3 g of sodium tripolyphosphate (Na ₅ P ₃ O ₁₀ ) was added and mixed well to completely dissolve the sodium tripolyphosphate. The solution was then added to aluminum nitrate (Al
_{(NO 3) 3 · 9H 2} O) 7.5g a 0.2mol / l
An aqueous solution equivalent to 100 ml was added and mixed in about 30 minutes to obtain a dispersion. The pH of the dispersion was 2.9. 25 parts of the dispersion was mixed with 30 parts of ethylene glycol to obtain a composite-containing dispersion 1. The molar ratio of somasif: sodium tripolyphosphate: aluminum nitrate when preparing the dispersion was 1: 0.5: 1.2. The mixing amount (weight ratio) of ethylene glycol is
It was 35 for Somasif 1.

Reference Example 2 In Reference Example 1, 3 g of sodium tripolyphosphate was added to 6
Except having changed to g, it carried out similarly to the reference example 1, and obtained the complex containing dispersion liquid 2. The molar ratio of somasif: sodium tripolyphosphate: aluminum nitrate when preparing the dispersion was 1: 1: 1.2. Further, the mixing amount (weight ratio) of ethylene glycol was 35 with respect to Somasif 1.

Reference Example 3 4 parts of Somasif was thoroughly mixed with 96 parts of water to prepare a 4% by weight Somasif dispersion. To 150 g of the dispersion, 0.5 g of sodium tripolyphosphate (Na ₅ P ₃ O ₁₀ ) was added and mixed well to completely dissolve the sodium tripolyphosphate. Next, 6.4 g of zirconium oxychloride (ZrCl ₂ O) was added to the solution as a 0.2 mol / l aqueous solution, and an equivalent amount of 100 ml was added and mixed in about 30 minutes to obtain a dispersion. The pH of the dispersion was 1.5. Dispersion 2
5 parts of ethylene glycol was mixed at a ratio of 30 parts to obtain a composite-containing dispersion liquid 3. The molar ratio of somasif: sodium tripolyphosphate: zirconium oxychloride when preparing the dispersion was 1: 0.17: 1.2. The amount of ethylene glycol mixed (weight ratio)
Was 35 for Somasif 1.

Reference Example 4 In Reference Example 3, sodium tripolyphosphate (Na ₅
A composite-containing dispersion 4 was obtained in the same manner as in Reference Example 3, except that 0.5 g of P ₃ O ₁₀ ) was changed to 1.5 g. The molar ratio of somasif: sodium tripolyphosphate: zirconium oxychloride in preparing the dispersion was 1: 0.
5: 1.2. Further, the mixing amount (weight ratio) of ethylene glycol was 35 with respect to Somasif 1.

Reference Example 5 In Reference Example 1, sodium tripolyphosphate (Na ₅
P ₃ O ₁₀₎ and aluminum nitrate _{(Al (NO 3) 3 ·} 9
Somasif-containing ethylene glycol dispersion 5 was obtained in the same manner as in Reference Example 1 except that H ₂ O) was not used. In addition, the mixing amount (weight ratio) of ethylene glycol was 35 with respect to Somasif 1.

<Production Method of Polyester Resin of the Present Invention> Examples 1 to 4 and Comparative Example 1 The dispersions 1 to 5 obtained above and ethylene glycol were introduced into an autoclave with stirring, kept at 90 ° C. After the transesterification reaction was performed by adding dimethyl acid to the system, the polymerization reaction was allowed to proceed by a conventional method to obtain a polyester resin composition. The composite was blended at 2% by weight with respect to the polyester resin.

For the dispersions 1 to 5 obtained in Reference Examples 1 to 5, the distance between the bottom surfaces (d001) of the composite before mixing with or before the reaction with ethylene glycol, the bottom surface of the composite after mixing with or after the reaction with ethylene glycol. Table 1 shows the interval (d001) and the dispersion state of the composite in the obtained polyester resin composition. However, the bottom distance (d001) of the raw material Somasif before forming the composite was measured in a solid state. For the bottom interval (d001), a reflection peak value near the (001) diffraction line region was measured. In addition, the dispersed state of the composite was observed by TEM (JEM2010). When the raw material-sized inorganic particles (swellable phyllosilicate) were not observed and the particles of 1 μm or less were uniformly dispersed, ○ indicates that the raw material-size inorganic particles (swellable phyllosilicate) were intact or micron. The state dispersed in the order was designated as x.

[0043]

[Table 1]

The bending strength, tensile strength, elongation and HDT of the obtained polyester resin composition were evaluated by the following methods. Table 2 shows the results. 1. Flexural strength Measured according to ASTM D-790. 2. Tensile strength was measured according to ASTM D-638. 3. Elongation Measured according to ASTM D-638. 4. HDT (Heat Distortion Temperature) Measured according to ASTM D-648.

[0045]

[Table 2]

From Tables 1 and 2, it can be seen that the polyester resin compositions obtained in Examples 1 to 4 are excellent in the dispersibility of the composite, and excellent in mechanical strength and heat resistance.

As is apparent from the above description, according to the present invention, it is possible to obtain a polyester resin composition in which an inorganic material is uniformly dispersed, has good moldability, and is excellent in mechanical strength and heat resistance. Can be.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08K 3:34) (72) Inventor Akira Yu Abiko 169-5 Takadacho, Tosu City, Saga Prefecture (72) Inventor Masaru Oi Suehirocho, Niigata City, Niigata Prefecture 9-32 (72) Inventor Haruo Asai 2-1-1 Katata, Otsu-shi, Shiga Toyo Spinning Co., Ltd. (72) Inventor Yoshiko Takino 2-1-1 Katata, Otsu-shi, Shiga Toyo Spinning Stock (72) Inventor Nobuyuki Kinan 2-1-1 Katata, Otsu-shi, Shiga Prefecture Examiner, Satoru Morikawa, Toyo Boseki Co., Ltd. (56) References JP-A-10-158431 (JP, A) ( 58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 67/00-67/04

Claims (3)

(57) [Claims] 1. A composition comprising a polyester resin and an inorganic material, wherein the inorganic material comprises at least one swellable layered silicate (a) and at least one selected from phosphates and polyphosphates.
Species of compound (b-1), at least one selected from polyvalent metal salts and polynuclear metal complex salts
A polyester resin composition, which is a complex obtainable from one kind of compound (b-2) . 2. A composition containing a polyester resin and an inorganic material.
Wherein the inorganic material comprises a swellable layered silicate (a) and at least one selected from phosphates and polyphosphates.
Compound (d) containing phosphoric acid and a metal element formed by the reaction of a kind of compound (b-1) with at least one kind of compound (b-2) selected from a polyvalent metal salt and a polynuclear metal complex salt And
A polyester resin composition, which is a mixed or reacted composite. (3) Contains polyester resin and inorganic material
A composition comprising: The inorganic material, a dispersion of the swellable layered silicate (a),
At least one selected from phosphates and polyphosphates
Seed compound (b-1) is added, and then the polyvalent metal salt and
At least one compound selected from nuclear metal complex salts (b-2)
Is a complex that can be obtained by adding
Rieester resin composition.