Composite, method for producing composite, resin composition comprising composite, and method for producing resin composition

Abstract

To provide a composite comprising a layered double hydroxide that can contribute to crystallization of resin, and a method for producing the same, and provide a resin composition comprising such a composite and a method for producing the same.SOLUTION: A composite comprises a layered double hydroxide and an outer layer covering the layered double hydroxide. The layered double hydroxide comprises a compound represented by the formula: [[M12+]1-x[M23+]x(OH)2](An-)x / n mH2O (I) [where M12+ is one or more kinds of divalent metal ions, M23+ is one or more kinds of trivalent metal ions, An- is one or more n-valent anions, m is 0 or more and less than 2, n is 1 or more and 5 or less, and x is more than 0 and 0.6 or less], the outer layer comprises an organic acid derivative or a salt thereof, and when the composite is washed with pure water 100 times the mass of the composite, a residual ratio of the organic acid derivative or the salt thereof after the washing is 56 mass% or more compared to that before the washing.SELECTED DRAWING: Figure 7

Description

[Technical Field]

[0001] The present disclosure relates to a layered double hydroxide composite, a method for producing the composite, a resin composition containing the composite, and a method for producing the resin composition. [Background technology]

[0002] Layered double hydroxides are widely used as additives for resins and the like. Non-patent document 1 states that MoO x It is stated that a three-dimensional pillared MgAl layered double hydroxide containing nanoparticles was obtained. Non-Patent Document 2 describes that a ZnAl layered double hydroxide modified with citric acid was obtained. Non-Patent Document 3 describes that a layered double hydroxide modified with N-tetrabromophthaloyl glutamic acid was obtained. Non-Patent Document 4 describes that the surface of a layered double hydroxide was modified by electrostatic interaction using an anionic surfactant. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Li Jin et al., "Organic modification of Mo-decorated MgAl layered double hydroxide for polymer flame retardancy", Composites Part A: Applied Science and Manufacturing, volume 129, 2020, 105717 [Non-patent document 2] Mohammad Dinari et al., "Citric acid-modified layered double hydroxides as a green reinforcing agent for improving thermal and mechanical properties of poly(vinyl alcohol)-based nanocomposite films", Polymer Composites, volume 37, issue 51, 2017, E128 [Non-patent document 3] Shadpour Mallakpour et al., "Exfoliation and dispersion of LDH modified with N-tetrabromophthaloyl-glutamic in poly(vinyl alcohol): Morphological and thermal studies", Journal of Chemical Sciences, volume 127, 2015, 519 [Non-patent document 4] Jae-Hun Yang et al., "Influence of anionic surface modifiers on the thermal stability and mechanical properties of layered double hydroxide / polypropylene nanocomposites", Journal of Materials Chemistry A, volume 3, issue 45, 2015, 22730 Summary of the Invention [Problem to be solved by the invention]

[0004] However, Non-Patent Documents 1 to 4 do not consider at all the relationship between the modified layered double hydroxide and the crystallization of a resin when the modified layered double hydroxide is mixed with the resin.

[0005] Therefore, an object of the present disclosure is to provide a composite containing a layered double hydroxide that can contribute to the crystallization of a resin. Another object of the present disclosure is to provide a method for producing such a composite. Another object of the present disclosure is to provide a resin composition containing such a composite and a method for producing the same. [Means for solving the problem]

[0006] A first embodiment of the present disclosure provides a composite comprising a layered double hydroxide and an outer layer covering the layered double hydroxide. The layered double hydroxide includes a compound represented by the following formula (I): [[M1 2+ ] 1-x [M2 3+ ] x (OH)2](A n- ) x / n mH2O (I) In formula (I), M1 2+ represents one or more divalent metal ions. 3+ represents one or more trivalent metal ions. n- represents one or more kinds of n-valent anions. m is 0 or more and less than 2. n is 1 or more and 5 or less. x is more than 0 and 0.6 or less. The outer layer comprises an organic acid derivative or a salt thereof. When the complex is washed with pure water in an amount 100 times by mass of the complex, the remaining rate of the organic acid derivative or its salt after the washing is 56% by mass or more compared to before the washing.

[0007] In the second embodiment of the present disclosure, in the first embodiment, the outer layer may have an adhesion rate to the layered double hydroxide of 1% by mass or more.

[0008] In a third embodiment of the present disclosure, in any one of the first and second embodiments, in formula (I), M1 2+ is Mg 2+ , Zn 2+ , Ca 2+ , Sr 2+ , Fe 2+ , Mn2+ , Co 2+ , Ni 2+ , Sn 2+ , Pb 2+ , Cd 2+ and Ba 2+ The composition may contain one or more selected from the group consisting of: M2 3+ Al 3+ and Fe 3+ The composition may contain one or more selected from the group consisting of:

[0009] In a fourth embodiment of the present disclosure, in any one of the first to third embodiments, in formula (I), 2×(1−x) / x can be 1.5 or more and 7.5 or less.

[0010] In a fifth embodiment of the present disclosure, in any one of the first to fourth embodiments, the content of Fe in the composite can be 0 ppm by mass or more and 500 ppm by mass or less.

[0011] In a sixth embodiment of the present disclosure, in any one of the first to fifth embodiments, the zeta potential of the complex may be 0 mV or more and 50 mV or less.

[0012] In a seventh embodiment of the present disclosure, in any one of the first to sixth embodiments, the BET specific surface area of ​​the composite is 5 m 2 / g or more 100m 2 / g or less.

[0013] In an eighth embodiment of the present disclosure, in any one of the first to seventh embodiments, the average aspect ratio of the composite may be 2 or more and 150 or less.

[0014] In a ninth embodiment of the present disclosure, in any one of the first to eighth embodiments, the loss on drying of the composite may be 0% by mass or more and 1.5% by mass or less.

[0015] A tenth embodiment of the present disclosure provides a method for producing a composite comprising a layered double hydroxide and an outer layer covering the layered double hydroxide. The layered double hydroxide includes a compound represented by the following formula (I): [[M1 2+ ] 1-x [M2 3+ ] x (OH)2](A n- ) x / n mH2O (I) In formula (I), M1 2+ represents one or more divalent metal ions. 3+ represents one or more trivalent metal ions. n- represents one or more kinds of n-valent anions. m is 0 or more and less than 2. n is 1 or more and 5 or less. x is more than 0 and 0.6 or less. The outer layer comprises an organic acid derivative or a salt thereof. The production method includes a slurry production step of producing a slurry of the layered double hydroxide. The production method includes a mixing step of mixing a slurry of the layered double hydroxide with the organic acid derivative or a salt thereof. The production method includes a heating step of heating the layered double hydroxide and the organic acid derivative or its salt mixed in the mixing step.

[0016] An eleventh embodiment of the present disclosure provides a resin additive including any one of the composites according to the first to ninth embodiments.

[0017] A twelfth embodiment of the present disclosure provides a resin composition including the resin additive according to the eleventh embodiment and a resin. [Effects of the Invention]

[0018] The composite of the present disclosure can contribute to the crystallization of a resin. The present disclosure also provides a method for producing a composite that can contribute to the crystallization of a resin. [Brief explanation of the drawings]

[0019] [Figure 1] 1 is a schematic diagram showing the arrangement of a layered double hydroxide and an organic acid derivative or its salt, where (a) is a schematic diagram of the composite of the present disclosure, and (b) is a schematic diagram of a case where the residual rate is lower than that of the composite. [Figure 2] FIG. 2 is a graph showing the yellowness index results of the heat resistance test of the resin composition. [Figure 3] FIG. 3 is a graph of thermal shrinkage showing the results of a heat resistance test of the resin composition. [Figure 4] 4 is a photograph showing the state of foaming in the flat plate. (a) shows the flat plate using sample A, and (b) shows the flat plate using sample B. [Figure 5] FIG. 5 is a graph showing the relationship between the moisture content of the composite and the yellowness of the resin compound. [Figure 6] 6 shows spectra obtained by infrared absorption measurement. (a) shows the spectrum of composite 7, which is the treated product of Test Example 7, and the spectrum of layered double hydroxide 2, which is the untreated product of Test Example 7. (b) shows the spectrum of composite 11, which is the treated product of Test Example 11, and the spectrum of layered double hydroxide 4, which is the untreated product of Test Example 11. [Figure 7] 7 shows scanning electron microscope images, where (a) is an image of Test Example 7 and (b) is an image of Test Example 11. [Figure 8] 8 shows spectra obtained by X-ray diffraction measurement. (a) shows the spectrum of composite 7, which is the treated product of Test Example 7, and the spectrum of layered double hydroxide 2, which is the untreated product of Test Example 7. (b) shows the spectrum of composite 11, which is the treated product of Test Example 11, and the spectrum of layered double hydroxide 4, which is the untreated product of Test Example 11. [Figure 9] FIG. 9 is a graph showing the relationship between the amount of cis-1,2-cyclohexanedicarboxylic acid and the crystallization temperature. DETAILED DESCRIPTION OF THE INVENTION

[0020] The composite of the present disclosure comprises a layered double hydroxide and an outer layer, wherein the layered double hydroxide comprises a compound represented by formula (I). [[M1 2+ ] 1-x [M2 3+ ] x (OH)2](A n- ) x / n mH2O (I) In formula (I), M1 2+ represents one or more divalent metal ions. 3+ represents one or more trivalent metal ions. n- represents one or more n-valent anions. m is 0 or greater and less than 2. n is 1 or greater and 5 or less. x is greater than 0 and 0.6 or less. The outer layer contains an organic acid derivative or a salt thereof. When the composite is washed with pure water in an amount 100 times the mass of the composite, the residual rate of the organic acid derivative or the salt thereof after the washing is 56% by mass or greater compared to before the washing.

[0021] The composite of the present disclosure can contribute to the crystallization of a resin. In a preferred embodiment, the composite of the present disclosure can promote the crystallization of a resin. In a more preferred embodiment, the composite of the present disclosure is also expected to adsorb anions present in the resin. Furthermore, the composite of the present disclosure is also expected to promote the crystallization of a resin, thereby improving the mechanical strength of the resin composition. Although the present disclosure should not be interpreted as being limited to a particular theory, the reason why the composite of the present disclosure can exhibit such an effect is thought to be as follows.

[0022] That is, the composite of the present disclosure contains an organic acid derivative or its salt in the outer layer and exhibits an enhanced retention rate after washing. While the reason for this enhanced retention rate after washing is unclear, it is believed to be due to the organic acid derivative or its salt being present in an orderly layered form on the surface of the layered double hydroxide in the present disclosure, as shown in Figure 1(a). Therefore, even when the composite of the present disclosure is mixed with a resin, the organic acid derivative or its salt is believed to remain in the outer layer of the layered double hydroxide. This facilitates enhanced alignment with the resin crystal lattice, facilitating crystal growth (epitaxial growth) of the resin. Furthermore, the retention of the organic acid or its salt derivative on the layered double hydroxide surface is believed to improve the compatibility between the resin and the composite, improve the dispersibility of the composite in the resin, increase the crystallization temperature of the resin, and promote uniform and rapid crystallization of the resin. Uniform and rapid crystallization may result in improved transparency and physical properties of the resulting resin structure. Furthermore, the composite of the present disclosure is also expected to adsorb anions present in the resin. It is also expected that costs will be reduced since there is no need to separately add an anion adsorbent.

[0023] When the surface of a layered double hydroxide is modified with an organic substance, the modification is typically present on the outermost surface. During kneading with a resin, the modification is easily detached and disintegrated due to shear forces, frictional heat, and other factors. However, in the composite of the present disclosure, the organic acid derivative or its salt is retained strongly on the layered double hydroxide, contributing to crystallization when mixed with a resin, and is thought to improve crystal nucleation ability in particular. While the reason for the strong retention of the organic acid derivative or its salt on the layered double hydroxide is unclear, it is thought to be due to the formation of a salt between the organic acid derivative and divalent metal ions eluted from the layered double hydroxide and the divalent metal ions eluted from the layered double hydroxide, resulting in the formation of a precipitate. These precipitates are thought to be regularly layered on the surface of the layered double hydroxide. As a result, even when the composite of the present disclosure is kneaded with a resin, the precipitates are not disintegrated, ensuring their function as a crystal nucleating agent.

[0024] In the composite of the present disclosure, the organic acid derivative or its salt is held in the vicinity of the layered double hydroxide through chemical or physical interactions. It is believed that the proximity effect of the organic acid derivative or its salt and the layered compound in the composite of the present disclosure allows the composite to function as a crystal nucleating agent. When Mg salt of cis-1,2-cyclohexanedicarboxylic acid is added to polypropylene and kneaded, the crystallization temperature increases by approximately 1.2°C compared to the polypropylene before addition. In other words, the increase in crystallization temperature with Mg salt of cis-1,2-cyclohexanedicarboxylic acid is small, and the function as a crystal nucleating agent is not substantially exhibited. Furthermore, when Mg salt of cis-1,2-cyclohexanedicarboxylic acid and a layered double hydroxide are added to polypropylene and kneaded, the crystallization temperature increases by approximately 1.7°C compared to the polypropylene before addition. Even when both the magnesium salt of cis-1,2-cyclohexanedicarboxylic acid and the layered double hydroxide were added, the increase in crystallization temperature was small, and the performance of the nucleating agent was insufficient. On the other hand, when the composite of the present disclosure was added to polypropylene and kneaded, the crystallization temperature increased by approximately 7.9°C compared to the polypropylene before addition. The addition of the composite significantly increased the crystallization temperature of polypropylene compared to when the magnesium salt of cis-1,2-cyclohexanedicarboxylic acid and the layered double hydroxide were added separately. This is considered to be evidence that the organic acid derivative or its salt does not function as a nucleating agent unless it is present in the vicinity of the layered double hydroxide.

[0025] In addition, the chemical or physical interactions of layered double hydroxides When an organic acid derivative or its salt is retained on the surface, the residual rate after washing is increased. When an organic acid derivative or its salt is retained on the surface of a layered double hydroxide due to chemical or physical interaction, it is unlikely to be detached from the layered double hydroxide when kneaded with a resin, and it is believed that its function as a crystal nucleating agent is ensured when mixed with a resin. When the organic acid derivative or its salt and the layered double hydroxide exist separately, the chemical or physical interaction between the organic acid derivative or its salt and the layered double hydroxide is weak, and the residual rate after washing is thought to be low.

[0026] In the method for producing a composite of the present disclosure, it is believed that by heating and mixing an organic acid derivative or its salt with a layered double hydroxide, the organic acid derivative or its salt and the layered double hydroxide are held in close proximity to each other. Heating at a higher temperature within the production temperature range of the present disclosure strengthens the chemical or physical interaction between the organic acid derivative or its salt and the layered double hydroxide. If the chemical or physical interaction between the organic acid derivative or its salt and the layered double hydroxide is strengthened, the organic acid derivative or its salt and the layered double hydroxide can be held more firmly together. By heating at a low temperature within the manufacturing temperature range of the present disclosure, the product tends to be a mixture of an organic acid derivative or its salt and a layered double hydroxide. Even in a mixture of an organic acid derivative or its salt and a layered double hydroxide, the function as a crystal nucleating agent is exhibited due to the proximity effect. In the case of a mixture of an organic acid derivative or its salt and a layered double hydroxide, the heating temperature is low, so it can be produced with less energy.

[0027] On the other hand, when the organic acid or its salt is irregularly arranged on the layered double hydroxide, as shown in Figure 1(b), it is thought that the organic acid or its salt can easily be released by the application of external stress, etc. If the organic acid derivative or its salt is not regularly arranged, even if it remains on the surface of the layered double hydroxide during resin kneading, mismatch with the resin crystal lattice may occur, which is thought to be disadvantageous to the epitaxial growth of the resin crystals compared to when it is regularly arranged.

[0028] In this disclosure, layered double hydroxide refers to a compound containing a metal hydroxide base layer containing at least one or more divalent metal ions and one or more trivalent metal ions, and an anion and water present between the base layers. The anion is also referred to as an intercalator. The layer that can be formed by the anion and water is also referred to as an intermediate layer. By having the base layer, the layered double hydroxide can function as an anion scavenger.

[0029] The layered double hydroxide may contain metal ions other than the divalent and trivalent metal ions, i.e., the layered double hydroxide may contain metal ions other than those constituting the metal hydroxide in the base layer, the intermediate layer, or between the base layer and the intermediate layer.

[0030] The organic acid derivative or salt thereof in the outer layer may be one or more selected from organic acids, counter anions of the organic acids (i.e., deprotonated anions of the organic acids), amides, esters, thioesters, and phosphates. The organic acid derivative may also be a salt of the counter anions, amides, esters, and thioesters.

[0031] The layered double hydroxide is represented by the following formula (I). [M1 2+ ] 1-x [M2 3+ ] x (OH)2](A n- ) x / n mH2O (I) In formula (I), M1 2+ represents one or more divalent metal ions. M2 3+ represents one or more trivalent metal ions. A n- represents one or more n-valent anions. m is greater than or equal to 0 and less than 2. n is between 1 and 5 inclusive. x is greater than 0 and equal to or less than 0.6.

[0032] M1 2+ represents one or more divalent metal ions. 2+ is Mg 2+ , Zn 2+ , Ca 2+ , Sr 2+ , Cu 2+ , Fe 2+ , Mn 2+ , Co 2+ , Ni 2+ , Sn 2+ , Pb 2+ , Cd 2+ and Ba 2+ Preferably, the material contains one or more selected from the group consisting of Mg 2+ , Zn 2+ , Cu 2+ , Fe 2+ , Mn 2+ , Co 2+ , Ni 2+ , and Cd 2+ More preferably, it contains one or more selected from the group consisting of Mg 2+ and Zn 2+ It is more preferable that the compound contains one or more selected from the group consisting of M1 2+ However, the above metal ions, especially Mg 2+ and Zn 2+ By including one or more compounds selected from the group consisting of: the compound represented by formula (I) is more likely to undergo crystal growth by heat treatment during production, facilitating production. In one embodiment, M1 2+ may contain two or more metal ions. 2+ consists of one type of metal ion.

[0033] M2 3+ represents one or more trivalent metal ions. 3+ Al 3+ , Fe 3+ ,Sc. 3+ , Y 3+ , Ti 3+ , Cr 3+, Fe 3+ , Al 3+ , Ga 3+ , In 3+ and La 3+ It is preferable that the material contains one or more selected from the group consisting of Al 3+ and Fe 3+ It is more preferable that the material contains one or more selected from the group consisting of Al 3+ More preferably, M2 3+ However, the above metal ions, especially Al 3+ and Fe 3+ By including one or more selected from the group consisting of: the stability of the compound represented by formula (I) can be improved. In one embodiment, M2 3+ may contain two or more metal ions. 3+ consists of one type of metal ion.

[0034] In formula (I), 2×(1−x) / x is preferably 1.5 or more and 7.5 or less, more preferably 2.5 or more and 7 or less, and even more preferably 3.5 or more and 6.5 or less. When 2×(1−x) / x is in this range, the stability and crystal nucleation ability of the composite can be good when mixed with a resin. In formula (I), 2×(1−x) / x is preferably 1.5 or more, more preferably 2.5 or more, and even more preferably 3.5 or more, and is preferably 7.5 or less, more preferably 7 or less, and even more preferably 6.5 or less. 2×(1−x) / x is the ratio of M2 3+ M1 against 2+ The ratio of the amount of substance (M1 2+ / M2 3+ ) is doubled.

[0035] Although the present disclosure should not be construed as being limited to any particular theory, it is believed that the above ratio (M 2+ / M2 3+ The reason why the above effect can be achieved when the M1 in the layered double hydroxide is in this range is considered to be as follows. 2+It is thought that the salts easily react with the organic acids to form salts, which are dissolved or deposited on the layered double hydroxide. 3+ That is, M1 2+ It is thought that because the organic acid does not form a salt compared to the layered double hydroxide, elution is suppressed and the organic acid is easily immobilized on the surface of the layered double hydroxide. 2+ / M2 3+ ) is within the above range, M1 2+ It is believed that the above-mentioned effects can be achieved by preventing the organic acid from being desorbed and immobilizing the organic acid on the surface of the layered double hydroxide.

[0036] Above A n- represents one or more kinds of n-valent anions, where n is 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less.

[0037] The n-valent anion preferably includes one or more selected from the group consisting of carbonate ion, chloride ion, nitrate ion, sulfate ion, phosphate ion, and bicarbonate ion, and more preferably includes one or more selected from carbonate ion, chloride ion, nitrate ion, and sulfate ion. In one embodiment, the n-valent anion may include carbonate ion.

[0038] In XRD measurement, the layered double hydroxide preferably has a peak in the range of 2θ of 22° or more and 24° or less, more preferably 22.5° or more and 24° or less, and even more preferably 23° or more and 24° or less.

[0039] In the present disclosure, X-ray diffraction measurement can be performed by powder X-ray diffraction. In one embodiment, CuKα radiation (λ=1.54 Å) is used as an X-ray source, and measurements can be performed under the following conditions: 2θ measurement interval: 0.026°; integration time: 296.565 seconds; acceleration voltage: 45 kV; acceleration current: 40 mA; focal length: 12.0 mm; take-off angle: 6°.

[0040] In the layered double hydroxide, the content of the compound represented by formula (I) may be preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less.

[0041] The composite comprises the layered double hydroxide and an outer layer covering the layered double hydroxide. The outer layer is typically disposed on the surface of the layered double hydroxide. That is, the outer layer may be disposed on the surface of the outermost basic layer of the metal hydroxide contained in the layered double hydroxide. The outer layer does not necessarily have to cover the entire layered double hydroxide, but may also cover only a portion of the layered double hydroxide.

[0042] In the above-mentioned complex, the bonding mode between the organic acid derivative or its salt and the layered double hydroxide may include a covalent bond, an ionic bond, a coordinate bond, a hydrogen bond, or van der Waals forces. Furthermore, the organic acid derivative or its salt may be not only chemically bonded to the layered double hydroxide but also physically adsorbed thereto.

[0043] The outer layer includes an organic acid derivative or a salt thereof. In the present disclosure, the organic acid derivative may include an organic acid and / or a derivative of an organic acid, and the salt of the organic acid derivative may include a salt of an organic acid and / or a salt of an organic acid derivative.

[0044] The organic acid derivative or its salt may be an N-substituted isocyanurate or a compound represented by the following formula (II): [ka] (II) [In formula (II), A represents one selected from the group consisting of an alicyclic hydrocarbon group, an aromatic group, and a heteroaromatic group; L is a single bond or NR 12 - represents R 1 is a hydroxyl group, a carboxyl group, R 10 -OCO-, R 11 -CO-NR 12 -, NR 122-, NR 12 2-CO-, C 1-6 represents one or more groups selected from the group consisting of an alkyl group, a hydroxyphosphoryl group, a heterocyclic group, and an aryl group; R 2 represents one atom selected from the group consisting of carbon atoms, phosphorus atoms, and sulfur atoms; R 3 represents a hydroxy group when L is a single bond, and represents C when L is -NH-. 1-6 represents an alkyl group, R 4 is R 2 If is a phosphorus atom, then a hydroxy group or C 1-6 represents an alkyl group, and R 1 If is a sulfur atom, R 2 represents an oxygen atom forming a double bond with R 10 is C 1-6 represents an alkyl group, R 11 represents an aryl group, R 12 is C 1-6 represents an alkyl group or a hydrogen atom, n1 represents an integer of 0 to 5, n2 is 0 or 1, n3 represents an integer of 1 to 3. and their derivatives, as well as salts thereof.

[0045] The above formula (II) is preferably the following formula (III): [ka] [In formula (III), R 1 , R 2 , R 4 , A, n1 and n2 are as defined above.] and salts thereof.

[0046] The above A represents one selected from the group consisting of alicyclic hydrocarbon groups, aromatic groups, and heterocyclic groups. A may be an n1+n3-valent group, preferably a monovalent to tetravalent group, and more preferably a monovalent to trivalent group.

[0047] The alicyclic hydrocarbon group represented by A above includes C 3-8 Alicyclic hydrocarbon groups are preferred. Specific examples of the alicyclic hydrocarbon groups include a norbornane ring group, a norbornene ring group, a cyclobutane ring group, a cyclopentane ring group, a cyclohexane ring group, and a cycloheptane ring group.

[0048] The aromatic group represented by A above is C 6-20 Aromatic groups are preferred, C 6-10 Aromatic groups are more preferred. Specific examples of the aromatic groups include benzene ring groups and naphthalene ring groups.

[0049] The heterocyclic group represented by A above includes C 3-10 Heterocyclic groups are preferred, and C 3-5 Heterocyclic groups are more preferred. Examples of the heterocyclic groups include a tetrahydrofuran ring group, a tetrahydrothiophene ring group, an azole ring group, a furan ring group, a thiophene ring group, a piperidine ring group, and a pyridine ring group.

[0050] A is preferably an alicyclic hydrocarbon group, and C 3-8 Alicyclic hydrocarbon groups are more preferred.

[0051] L is a single bond or NR 12 In one embodiment, L is a single bond. In another embodiment, L is -NR 12 -It is.

[0052] R 1 is a hydroxyl group, a carboxyl group, R 10 -OCO-, R 10 -COO-, R 11 -CO-NR 12 -, NR 12 2-, NR 12 2-CO-, C 1-6It represents one or more groups selected from the group consisting of an alkyl group, a hydroxyphosphoryl group, a heterocyclic group, and an aryl group, and may preferably be a carboxy group.

[0053] R 2 represents one or more atoms selected from the group consisting of carbon atoms, phosphorus atoms, and sulfur atoms, and may be preferably carbon atoms.

[0054] R 3 represents a hydroxy group when L is a single bond, and represents C when L is -NH-. 1-6 In some embodiments, R 3 is a hydroxy group. 3 is C 1-6 It is an alkyl group.

[0055] R 4 is R 2 If is a phosphorus atom, then a hydroxy group or C 1-6 represents an alkyl group, and R 1 If is a sulfur atom, R 2 represents an oxygen atom that forms a double bond with R. 2 If is a carbon atom, R 4 is not present. In some embodiments, R 4 is a hydroxy group or C 1-6 In another embodiment, R 4 is R 2 represents an oxygen atom forming a double bond with

[0056] Above R 1 , R 3 , R 4 , R 10 , R 12 C, represented by 1-6 The alkyl group is preferably C 1-3 It may be an alkyl group.

[0057] Above R 11 The aryl group represented by the formula C 6-20 An aryl group is preferred, and C 6-10An aryl group is more preferred. Specific examples of the aryl group include a phenyl group and a naphthyl group.

[0058] R 12 is C 1-6 represents an alkyl group or a hydrogen atom. 12 is C 1-6 In another embodiment, R 12 is a hydrogen atom.

[0059] n1 represents an integer of 0 to 5, and preferably an integer of 0 to 2.

[0060] n2 is 0 or 1. In some embodiments, n2 is 0. In other embodiments, n2 is 1.

[0061] n3 represents an integer of 1 to 3, and is preferably 1.

[0062] An example of the N-substituted isocyanurate is 1,3,5-triazine-2,4,6-triol.

[0063] The organic acid derivative is preferably a compound represented by the formula (II), more preferably a compound represented by the formula (III), and C 1-12 Aliphatic monocarboxylic acid, C 1-12 Aliphatic dicarboxylic acids, C 1-12 Aromatic monocarboxylic acids, C 1-12 Aromatic dicarboxylic acids, C 1-12 Alkyl sulfonyl hydroxide, C 1-12 Alkylphosphonic acid, C 1-12 Alkylphosphonates, C 3-8 Cycloalkane monocarboxylic acids, C 3-8 Cycloalkanedicarboxylic acids and C 3-8 More preferably, the compound is one or more selected from the group consisting of cycloalkanetricarboxylic acids, and C 1-12 Aliphatic dicarboxylic acids, C 1-12 Aromatic dicarboxylic acids and C 3-8 Cycloalkanedicarboxylic acids are more preferred, C3-8 Cycloalkanedicarboxylic acids are particularly preferred.

[0064] That is, the organic acid derivative or salt thereof in the outer layer may be one or more selected from the organic acid, anhydride of the organic acid, counter anion of the organic acid (i.e., the deprotonated anion of the organic acid), amide, ester, thioester, and phosphate. The organic acid derivative or salt thereof may further be a salt of the counter anion, amide, ester, or thioester. The salt may be preferably an alkali metal salt, more preferably a sodium salt.

[0065] The organic acid or a derivative thereof is preferably bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid or anhydride thereof (in one embodiment, cis-1,2-cyclohexanedicarboxylic acid or anhydride thereof), (1R,2S)-2-methoxycarbonylcyclohexanecarboxylic acid, 1,3,5-tris(2,2-dimethylpropionylamino)benzene, 2,6-naphthalenedicarboxylic acid, benzoic acid, pimelic acid, phenylphosphonic acid, 2,6-dihydroxypyrimidine-4-carboxylic acid, 4-pyridinecarboxylic acid, benzene-1,3,5 1,4-cyclohexanedicarboxylic acid and / or 4-propylcyclohexanecarboxylic acid. The organic acid or its derivative is more preferably bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid or its anhydride (in one embodiment, cis-1,2-cyclohexanedicarboxylic acid or its anhydride), pimelic acid, phenylphosphonic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and / or 4-propylcyclohexanecarboxylic acid. As the organic acid or a derivative thereof, 1,2-cyclohexanedicarboxylic acid or anhydride thereof (in one embodiment, cis-1,2-cyclohexanedicarboxylic acid or anhydride thereof) is particularly preferred.

[0066] The 1,2-cyclohexanedicarboxylic acid or anhydride thereof preferably contains cis-1,2-cyclohexanedicarboxylic acid or anhydride thereof (hereinafter also referred to as "cis isomer"). The proportion of the cis isomer attached to the outer layer is preferably 50 mol % to 100 mol %, more preferably 70 mol % to 100 mol %, and even more preferably 90 mol % to 100 mol %, based on the total amount of 1,2-cyclohexanedicarboxylic acid or anhydride. The cis isomer is thought to easily form a salt with the metal species in the layered double hydroxide and to be easily immobilized on the surface of the layered double hydroxide.

[0067] The attachment ratio of cis isomers is calculated using the following formula: Adhesion ratio of cis isomer (mol%) = Adhesion amount of cis isomer / (Adhesion amount of cis isomer + Adhesion amount of trans isomer) × 100 It may be calculated based on the

[0068] The organic acid derivative or its salt preferably contains an anhydride. The proportion of the anhydride attached to the outer layer is preferably 50 mol% to 100 mol%, more preferably 70 mol% to 100 mol%, and even more preferably 90 mol% to 100 mol%, based on the total amount of the organic acid derivative or its salt. It is believed that an anhydride of an organic acid does not form a salt with the metal species of the layered double hydroxide in its anhydride state. It is believed that an anhydride of an organic acid can form a salt by hydrolysis, and subsequently forms a salt after hydrolysis. Therefore, compared with the case where a non-anhydride organic acid is used, the concentration of the organic acid that can contribute to salt formation is lower, and the reaction is believed to proceed more gently. As a result, it is believed that when an anhydride of an organic acid is used, it is immobilized more uniformly on the layered double hydroxide than when a non-anhydride organic acid is used.

[0069] The 1,2-cyclohexanedicarboxylic acid or anhydride thereof preferably contains cis-1,2-cyclohexanedicarboxylic acid anhydride. The proportion of the cis anhydride attached to the outer layer is preferably 50 mol % to 100 mol %, more preferably 70 mol % to 100 mol %, and even more preferably 90 mol % to 100 mol %, based on the total amount of 1,2-cyclohexanedicarboxylic acid or anhydride.

[0070] The inclusion of the organic acid or its derivative, particularly cis-1,2-cyclohexanedicarboxylic acid, is believed to facilitate the presence of the compound on the surface of the base layer of the metal hydroxide. As a result, the functionality of the layered double hydroxide, such as its anion-trapping ability, is believed to be more easily maintained. This point is also confirmed by the fact that, in XRD measurements of the composite, there is no shift in the peak position observed in the 2θ range of 22° to 24° compared to the layered double hydroxide.

[0071] The adhesion rate of the outer layer to the layered double hydroxide is preferably 1% by mass or more, more preferably 1.3% by mass or more, even more preferably 1.6% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. The adhesion rate of the outer layer to the layered double hydroxide is preferably 1% by mass or more and 20% by mass or less, more preferably 1.3% by mass or more and 15% by mass or less, and even more preferably 1.6% by mass or more and 10% by mass or less. When the adhesion rate of the outer layer to the layered double hydroxide is within this range, the stability and crystal nucleation ability of the composite can be improved. The adhesion rate of the outer layer to the layered double hydroxide can be understood as the amount of organic acid derivative or its salt attached to the layered double hydroxide in the composite. The organic acid derivative or its salt may form a salt with an element in the layered double hydroxide. For example, the organic acid derivative may form a salt with a metal element eluted from the layered double hydroxide, and the salt may be attached to the layered double hydroxide. Such aspects are also included within the technical scope of the present disclosure.

[0072] The adhesion rate can be measured by the following method. [Method for measuring adhesion rate] Before washing, 0.1 g of the composite was added with 5 mL of 1 mol / L hydrochloric acid and stirred at 60°C for 4 hours. 5 mL of methanol was added to the stirred solution. This solution was diluted with phosphate buffer (pH 2). The diluted solution was subjected to high-performance liquid chromatography (HPLC) under the following conditions to quantify the amount of organic acid derivative attached, m1. The amount of treatment, m1, was quantified from an external calibration curve created using organic acid derivative solutions of known concentrations, and the attachment rate was calculated as m1 / m0, based on the amount of layered double hydroxide in the composite, m0. Column: C18 reversed phase column Column temperature: 35℃ Mobile phase: 20% acetonitrile, 80% phosphate buffer (pH 2), flow rate 1.0 mL / min Detector: UV (225 nm)

[0073] By including the above compound as the organic acid or its derivative, the crystal nucleation ability can be improved. The crystal nucleation ability can be measured, for example, by kneading a resin with 0.05 mass % (500 ppm) of the complex relative to the resin to prepare a mixture, measuring the crystallization temperature of the mixture, and determining the crystallization temperature T c0 and the crystallization temperature T of the mixture. c1 The crystallization temperature difference (T c1 -T c0 The difference in crystallization temperature (T) is preferably 5.0°C or higher, more preferably 5.5°C or higher, and even more preferably 6.5°C or higher, and may be, for example, 20°C or lower, 15°C or lower, or even 12°C or lower. c1 -T c0 ) may be preferably 5.0°C or higher and 20°C or lower, more preferably 5.5°C or higher and 15°C or lower, and even more preferably 6.5°C or higher and 12°C or lower.

[0074] The mixture can be prepared by blending the composite with the resin at a ratio of 500 ppm by mass, and kneading the mixture using a twin-screw kneader to a resin temperature of 210° C. to 230° C. Polypropylene (for example, "PX-600N" manufactured by SunAllomer) can be used as the resin.

[0075] The crystallization temperature can be measured by using a differential scanning calorimeter (DSC) to measure a sample by heating it from room temperature to 200°C at a heating rate of 10°C / min, holding it at 200°C for 10 minutes, and then cooling it from 200°C at a cooling rate of 10°C / min, and measuring the peak top temperature of the exothermic peak associated with crystallization.

[0076] When the composite of the present disclosure is washed with 100 times its mass of pure water, the residual rate of the organic acid derivative or its salt after the washing is 56% by mass or more compared to before the washing. When the residual rate is within this range, the composite of the present disclosure may have good crystal nucleation ability. The residual rate is preferably 57% by mass or more, more preferably 57.5% by mass or more, even more preferably 58% by mass or more, and may be, for example, 60% by mass or less.

[0077] Specifically, the residual rate can be measured by the following method. [Method for measuring residual rate] A mixture was prepared by mixing 5 g of the complex with 500 g of pure water. While maintaining the temperature of the mixture at 15°C to 25°C, the mixture was stirred at 400 to 600 rpm for 2 hours using a fluid jet agitator with a 5 cm diameter agitator blade (product name: Jet Agitator, manufactured by Shimazaki Engineering Co., Ltd.). After washing, the mixture was filtered and dried at 70°C for 12 hours to obtain the washed complex.

[0078] Before washing, 0.1 g of the composite was mixed with 5 mL of 1 mol / L hydrochloric acid and stirred at 60°C for 4 hours. 5 mL of methanol was added to the stirred solution. This solution was then diluted with phosphate buffer (pH 2). The amount of organic acid derivative treated with the diluted solution was quantified using high-performance liquid chromatography (HPLC) under the following conditions. The amount of treatment m1 was quantified using an external calibration curve created using a solution of organic acid derivative of known concentration, and the amount of treatment before washing (m1 / m0) was determined based on the amount of layered double hydroxide in the composite (m0). Column: C18 reversed phase column Column temperature: 35℃ Mobile phase: 20% acetonitrile, 80% phosphate buffer (pH 2), flow rate 1.0 mL / min Detector: UV (225 nm) The treated amount m2 of the washed composite is also quantified in the same way, and the amount of layered double hydroxide in the composite, m0, is used as the standard to determine the "treated amount after washing (m2 / m0)." The residual rate is calculated as follows: residual rate = (treated amount after washing / treated amount before washing).

[0079] The method for measuring the residual rate is an analogous procedure for measuring the stability of the layered double hydroxide itself and the strength of the interaction between the layered double hydroxide and the organic acid when the composite of the present disclosure is mixed with a resin, and it is believed that the functionality of such a composite can be evaluated based on the residual rate.

[0080] In one embodiment, the composite preferably does not have a peak in the 2θ range of 4° to 9° in X-ray diffraction (XRD) measurement. When there is no peak in this range, it is believed that the salt of the organic acid derivative or its salt and the metal eluted from the layered double hydroxide is precipitated in a more uniform state on the surface of the layered double hydroxide. In this case, it is expected that the composite will have high compatibility with the resin, resulting in high dispersibility. In another embodiment, the composite may have a peak in XRD measurement, with 2θ preferably in the range of 4° to 9°, more preferably 5° to 8°, and even more preferably 6° to 7.5°. The 2θ is preferably 4°C or higher, more preferably 5° or higher, and even more preferably 6° or higher, and is preferably 9° or lower, more preferably 8° or lower, and even more preferably 7.5° or lower. A peak in this range is considered to indicate that a salt of an organic acid derivative or its salt and a metal eluted from the layered double hydroxide is deposited in a non-uniform state on the surface of the layered double hydroxide. In this case, mixing such a composite with a resin makes it easier to secure anion capture pathways in the resin, and is expected to exhibit high acid-accepting ability.

[0081] The Fe content in the composite may be preferably 0 ppm by mass or more and 800 ppm by mass or less, more preferably 0 ppm by mass or more and 600 ppm by mass or less, and even more preferably 0 ppm by mass or more and 500 ppm by mass or less. When the Fe content in the composite is within this range, the stability of the resin is good when the composite of the present disclosure is mixed with the resin. In the present disclosure, the content of a specific element in a specific material can be measured by wavelength dispersive X-ray fluorescence spectroscopy (XRF).

[0082] The zeta potential of the complex may be preferably 0 mV or more and 50 mV or less, more preferably 10 mV or more and 50 mV or less, and even more preferably 15 mV or more and 45 mV or less. The zeta potential of the complex may be preferably 0 mV or more, more preferably 10 mV or more, and even more preferably 15 mV or more, and preferably 50 mV or less, and more preferably 45 mV or less. When the zeta potential of the complex is within this range, the complex of the present disclosure has good dispersibility when mixed with a resin. In the present disclosure, the zeta potential of a specific material can be measured in accordance with JIS Z 8836:2017. Specifically, 25 mL of ethanol is added to 0.05 g of the complex, and the mixture is ultrasonically dispersed. Then, 25 mL of ethanol is added to disperse the complex. The zeta potential is measured using the resulting dispersion.

[0083] The BET specific surface area of ​​the composite is preferably 5 m 2 / g or more 100m 2 / g or less, more preferably 8m 2 / g or more 80m 2 / g or less, more preferably 15m 2 / g or more 80m 2 The BET specific surface area of ​​the composite is preferably 5 m 2 / g or more, more preferably 8m 2 / g or more, more preferably 15m 2 / g or more, preferably 100m 2 / g or less, more preferably 80m 2 / g or less. When the BET specific surface area is within the above range, it is believed that the acid-accepting effect can be improved compared to when it is lower than the above range. Furthermore, when the BET specific surface area is within the above range, it is believed that the reaction of an antioxidant that may be contained in the resin is suppressed, and coloring during kneading and molding is more likely to be suppressed compared to when it is higher than the above range. In the present disclosure, the BET specific surface area can be measured by the BET method using nitrogen gas as the adsorbate.

[0084] The composite is preferably in the form of particles, more preferably in the form of flat particles. The average secondary particle diameter of the composite is preferably 0.05 μm or more and 5 μm or less, more preferably 0.1 μm or more and 2 μm or less, and even more preferably 0.2 μm or more and 1.5 μm or less. The average secondary particle diameter of the composite is preferably 0.05 μm or more, more preferably 0.1 μm or more, and even more preferably 0.2 μm or more, and may be preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1.5 μm or less. When the average secondary particle diameter of the composite is within this range, the composite of the present disclosure may have good dispersibility when mixed with a resin. The average secondary particle diameter of the above-mentioned complex means the cumulative 50% volume diameter, that is, D50, and can be measured by dynamic light scattering.

[0085] The average aspect ratio of the composite may be preferably 2 or more and 150 or less, more preferably 3 or more and 120 or less, and even more preferably 3 or more and 100 or less. The average aspect ratio of the composite may be preferably 2 or more, more preferably 3 or more, and preferably 150 or less, more preferably 120 or less, and even more preferably 100 or less. When the average aspect ratio of the composite is within this range, it is believed that the composite will have good dispersibility in the resin and good orientation in the resin.

[0086] In the present disclosure, the average aspect ratio refers to the average value of the aspect ratios of the composites. By evaluating the average aspect ratio rather than the aspect ratio of a single composite, it becomes easier to more accurately evaluate the properties of the composite as an aggregate.

[0087] The average diameter of the composite is preferably 0.01 μm or more and 10 μm or less, more preferably 0.05 μm or more and 5 μm or less, and even more preferably 0.1 μm or more and 3 μm or less. The average diameter of the composite is preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more, and is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. It is believed that when the average diameter of the composite is within this range, the composite has good dispersibility in the resin and good orientation in the resin.

[0088] The average thickness of the composite is preferably 5 nm or more and 500 nm or less, more preferably 10 nm or more and 300 nm or less, and even more preferably 20 nm or more and 200 nm or less. The average thickness of the composite is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more, and is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less. When the average thickness of the composite is within this range, it is believed that the composite has good dispersibility in the resin and good orientation in the resin. Furthermore, when the composite has a certain thickness or more, the particle structure of the composite can be maintained even when kneaded with the resin.

[0089] The average aspect ratio, average diameter, and average thickness can be measured using a scanning electron microscope. In a specific embodiment, the average aspect ratio, average diameter, and average thickness can be measured, for example, by the following method. [Methods for measuring average aspect ratio, average diameter, and average thickness] The composite is sonicated in alcohol for 1 minute. The structure of the primary particles of the composite is then observed using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and the diameter and thickness are measured. The diameter is calculated as the average of the longest diameters of the primary particles of the composite, observed at a magnification of 5,000x or 10,000x. The average diameter is calculated as the arithmetic mean of the diameters measured for the primary particles of 20 selected composites. The thickness is calculated as the arithmetic mean of the thicknesses measured for the primary particles of 14 selected composites, observed at a magnification of 100,000x. The average aspect ratio is calculated by dividing the average diameter by the average thickness.

[0090] The loss on drying of the composite is preferably 0% by mass or more and 1.5% by mass or less, more preferably 0% by mass or more and 1.1% by mass or less. When the loss on drying of the composite is small, the moisture content is small, and it is easy to suppress the generation of bubbles even when the composite is mixed with a resin and heated.

[0091] In the present disclosure, loss on drying can be measured, for example, by the following method. [Method for measuring loss on drying] The sample is placed in a weighing bottle (40 mm diameter) with a known mass so that the thickness is 3 to 5 mm, and the mass (sample mass) is measured using a precision balance. The sample is then dried in a thermostatic oven at 105±2°C for 1 hour, allowed to cool in a desiccator, and the mass is then measured using a precision balance. The loss on drying is calculated using the following formula: Loss on drying (%) = (sample mass - sample mass after drying) x 100 / sample mass Calculated based on the following.

[0092] The water content of the composite is preferably 0% by mass or more and 1.5% by mass or less, more preferably 0% by mass or more and 1.1% by mass or less. When the water content of the composite is low, it is easy to suppress coloration of a molded product using the composite.

[0093] In the present disclosure, the water content of a composite may be calculated based on the weight loss before and after heating. Specifically, 5 g of the composite is heated until no weight loss is observed during heating. The weight loss after heating compared to before heating may be taken as the water content.

[0094] The method for producing a composite of the present disclosure includes a slurry production step of producing a slurry of the layered double hydroxide. The production method includes a mixing step of mixing a slurry of the layered double hydroxide with the organic acid derivative or a salt thereof. The production method includes a heating step of heating the layered double hydroxide and the organic acid or derivative thereof mixed in the mixing step.

[0095] As the layered double hydroxide, it is preferable to use a compound in which, in the above formula (I), 2×(1−x) / x is preferably 1.5 or more and 7.5 or less, more preferably 2.5 or more and 7 or less, and even more preferably 3.5 or more and 6.5 or less. 2×(1−x) / x is preferably 1.5 or more, more preferably 2.5 or more, even more preferably 3.5 or more, and preferably 7.5 or less, more preferably 7 or less, and even more preferably 6.5 or less. When 2×(1−x) / x is within this range, the stability and crystal nucleation ability of the resulting composite can be good when mixed with a resin.

[0096] In the slurry production step, a slurry of the layered double hydroxide is prepared. In one embodiment, the slurrying of the layered double hydroxide can be carried out simultaneously with the production of the layered double hydroxide.

[0097] In one embodiment, the layered double hydroxide can be produced by a production method including the steps of mixing an aqueous solution of a water-soluble metal salt of a divalent metal, an aqueous solution of a water-soluble metal salt of a trivalent metal, and an alkali metal hydroxide in an aqueous medium to obtain a mixed solution, coprecipitating hydrotalcite in the mixed solution, and washing the hydrotalcite with an aqueous solution of an alkali metal carbonate to obtain a slurry containing the layered double hydroxide.

[0098] The slurry containing the layered double hydroxide may further be subjected to hydrothermal treatment. Hydrothermal treatment can promote crystal growth of the layered double hydroxide and suppress aggregation. In this case, the slurry after hydrothermal treatment can be subjected to the subsequent process. The hydrothermal treatment can be carried out using an autoclave. The temperature of the hydrothermal treatment is preferably 100°C or higher, more preferably 120 to 200°C, and the time of the hydrothermal treatment is preferably 1 hour or longer. The carbonate ion-containing hydrotalcite may be dehydrated, dried, pulverized, and classified as necessary.

[0099] In another embodiment, the slurry can be prepared by mixing the layered double hydroxide with a dispersion medium. The method for mixing the layered double hydroxide with the dispersion medium is not particularly limited, and the mixture can typically be mixed by stirring. Examples of the dispersion medium used in the slurry include water and hydrophilic organic solvents. Examples of the hydrophilic organic solvent include alcohol solvents such as methanol, ethanol, propanol, and ethylene glycol.

[0100] The amount of layered double hydroxide in the slurry is preferably 1% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 20% by mass or less. The amount of layered double hydroxide in the slurry is preferably 1% by mass or more, more preferably 5% by mass or more, and preferably 80% by mass or less, more preferably 20% by mass or less.

[0101] In the mixing step, the layered double hydroxide slurry is mixed with the organic acid derivative or its salt. The amount of the organic acid or its derivative is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less, per 100 parts by mass of the layered double hydroxide. The amount of the organic acid or its derivative is preferably 1 part by mass or more and more preferably 5 parts by mass or more, and preferably 30 parts by mass or less and more preferably 20 parts by mass or less, per 100 parts by mass of the layered double hydroxide.

[0102] The method for mixing the slurry and the organic acid or derivative thereof is not particularly limited, and typically, the mixture can be mixed by stirring.

[0103] In the heating step, the layered double hydroxide and the organic acid or derivative thereof mixed in the mixing step are heated. The heating temperature is preferably 50°C to 90°C, more preferably 60°C to 90°C, and even more preferably 65°C to 90°C. A heating temperature within this range can fix the organic acid or derivative thereof to the surface of the layered double hydroxide, thereby increasing the residual rate. The mixing step and the heating step may be carried out separately or simultaneously. That is, in one embodiment, the heating step may be carried out after the mixing step; in another embodiment, the heating step may be carried out after the mixing step; and in yet another embodiment, the mixing step and the heating step may be carried out simultaneously.

[0104] Although the present disclosure should not be interpreted as being limited to any particular theory, the reason why the above-mentioned effect can be achieved by setting the heating temperature within this range is thought to be as follows. Specifically, when the heating temperature is within this range, a larger amount of heat is applied during the reaction than when the heating temperature is lower. This may be because a heat amount greater than the activation energy required for the precipitation of a thermodynamically stable precipitate with an ordered molecular arrangement can be applied, which is thought to facilitate the more ordered precipitation of the precipitate, which is thought to be a salt of an organic acid derivative or its salt with a metal eluted from the layered double hydroxide. The more ordered precipitation of the precipitate is thought to suppress the detachment of the organic acid or its derivative. As a result, when the composite is mixed with a resin, the order of the precipitate is thought to promote crystal growth (epitaxial growth) of the resin. On the other hand, when the heating temperature is within this range, the precipitate is less likely to flow into the reaction solution and more likely to adhere to the surface of the layered double hydroxide than when the heating temperature is higher.

[0105] Although the present disclosure should not be interpreted as being limited to any particular theory, the reason why the above-mentioned effect can be achieved by setting the heating temperature within this range is thought to be as follows: When the heating temperature is within this range, a larger amount of heat is applied during the reaction than when the heating temperature is lower. This increases the frequency with which the organic acid derivative or its salt comes into close proximity to the surface of the layered double hydroxide during the reaction. As a result, the organic acid derivative or its salt is more likely to be fixed closer to the surface of the layered double hydroxide, which is thought to increase intermolecular forces such as van der Waals forces between the layered double hydroxide and the organic acid derivative or its salt, thereby improving the retention rate after washing. On the other hand, when the heating temperature is within this range, the organic acid derivative or its salt is less likely to diffuse into the reaction solution than when the heating temperature is higher, which is thought to make it easier for the organic acid derivative or its salt to be fixed to the surface of the layered double hydroxide.

[0106] The time for contacting the layered double hydroxide with the organic acid or its derivative is preferably 30 minutes or more and 5 hours or less, more preferably 1 hour or more and 3 hours or less.

[0107] After contacting the layered double hydroxide with the organic acid or its derivative, the mixture may be subjected to treatments such as solid-liquid separation, washing, drying, etc., as needed, to obtain a dried composite.

[0108] The composite can be preferably used as an additive for resins. In a preferred embodiment, the composite can be preferably used as a crystal nucleating agent. In the composite, an organic acid derivative or its salt and a metal eluted from the layered double hydroxide form a salt and precipitate, and this precipitate is thought to have crystal nucleation ability. Furthermore, unlike the composite, particles of organic compounds conventionally used as crystal nucleating agents have a uniform composition, so the organic acid or its derivative may also be contained within the particles. However, in the case of particles of such organic compounds, the organic matter inside the particles that cannot come into contact with the resin does not function as a crystal nucleating agent. Therefore, when using the composite of the present disclosure, it is thought to have the advantage of being able to reduce the amount of organic matter used as an additive compared to when calcium salts of organic compounds conventionally used as crystal nucleating agents are used. Furthermore, the composite of the present disclosure is expected to have good resin crystal nucleation ability and good anion capture performance. Therefore, the content of additives used can be reduced compared to when a crystal nucleating agent and an anion scavenger are simply mixed. Therefore, resin additives containing the composite of the present disclosure are also included in the technical scope of the present disclosure.

[0109] The technical scope of the present disclosure further includes a resin composition containing the resin additive and a resin, and a method for producing a resin composition by mixing the resin additive and a resin.

[0110] Examples of the resin include polyolefin resin, polyvinyl chloride resin, polyvinyl alcohol, polylactic acid, and polyphenylene sulfide resin. Examples of the polyolefin resin include polypropylene and polyethylene. As the polyethylene, any of HDPE, LDPE, and LLDPE can be used.

[0111] The concentration of the composite of the present disclosure in the resin composition is preferably 1 ppm by mass or more and 10,000 ppm by mass or less, more preferably 50 ppm by mass or more and 5,000 ppm by mass or less, and even more preferably 100 ppm by mass or more and 3,000 ppm by mass or less. The concentration of the composite of the present disclosure in the resin composition is preferably 1 ppm by mass or more, more preferably 50 ppm by mass or more, and even more preferably 100 ppm by mass or more, and is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, and even more preferably 3,000 ppm by mass or less.

[0112] The concentration of the organic acid derivative or its salt in the resin composition is preferably 0.01 ppm by mass or more and 1,000 ppm by mass or less, more preferably 0.1 ppm by mass or more and 500 ppm by mass or less, and even more preferably 1 ppm by mass or more and 250 ppm by mass or less. By using the composite of the present disclosure, even when the amount of the organic acid derivative or its salt is small, the effect of the crystal nucleating agent can be exerted, and the moldability of the resin composition can be maintained. As a result, the amount of organic matter migrating from the resin molded body to the outside of the molded body during use (migration amount) can be suppressed.

[0113] The resin composition may further contain a solvent. Examples of such a solvent include water, an alcohol solvent, and an ester solvent. Examples of the alcohol solvent include ethanol and propanol. Examples of the ester solvent include ethyl acetate.

[0114] The resin composition of the present disclosure can be prepared by mixing a resin and a composite. The mixing method is not particularly limited, and a mixing method appropriate for the properties of the resin can be used. A method may be used in which a resin and a high-concentration composite are first mixed to prepare a masterbatch, and then the masterbatch and resin are further mixed.

[0115] The resin composition of the present disclosure has the following properties compared to the resin alone: The crystallization temperature T c0 and the crystallization temperature T of the mixture.c1 The crystallization temperature difference (T c1 -T c0 ) is preferably 5.0°C or higher, more preferably 5.5°C or higher, and even more preferably 6.5°C or higher, and may be, for example, 20°C or lower, 15°C or lower, or even 12°C or lower.

[0116] The composite of the present disclosure can contribute to the crystallization of resins and can be preferably used as a crystal nucleating agent. [Example]

[0117] The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0118] Production Example 1: Production method of layered double hydroxide 1 (2×(Mg / Al)=4.1) (Slurry production process) A 1.4 mol / L magnesium chloride aqueous solution and a 1.0 mol / L aluminum sulfate aqueous solution were mixed in a volume ratio of 100:30 to obtain a mixed solution. This mixed solution and a 1.4 mol / L sodium hydroxide aqueous solution were poured into a container in a volume ratio of 100:80 at atmospheric pressure and 25°C and reacted to obtain a hydrotalcite slurry. The obtained hydrotalcite slurry was filtered to obtain a cake. The obtained cake was washed with a sodium carbonate aqueous solution and then with pure water. The resulting cake was removed, pure water was added, and the mixture was re-emulsified using a homogenizer to obtain a slurry. The resulting slurry was then heat-treated in an autoclave at 170°C for 13 hours to obtain a slurry of layered double hydroxide 1. A portion of the resulting layered double hydroxide 1 slurry was filtered, and the resulting cake was dried at 70°C for 12 hours. After drying, the cake was sieved through a 150 mesh sieve and used for analysis.

[0119] Production Example 2: Method for producing layered double hydroxide 2 (2×(Mg / Al)=4) (Slurry production process) A 4.2 mol / L magnesium chloride aqueous solution and a 2.4 mol / L aluminum chloride aqueous solution were mixed in a volume ratio of 100:88, and then diluted with pure water to obtain a mixed solution. This mixed solution and a 6.3 mol / L sodium hydroxide aqueous solution were poured into a container in a volume ratio of 100:50 at atmospheric pressure and 25°C and reacted to obtain a hydrotalcite slurry. The obtained hydrotalcite slurry was filtered to obtain a cake. The obtained cake was washed with a sodium carbonate aqueous solution and then with pure water. The resulting cake was taken out, and pure water was added thereto, followed by re-emulsification using a homogenizer to obtain a slurry. The resulting slurry was then heat-treated in an autoclave at 150°C for 6 hours to obtain a slurry of layered double hydroxide 2. A portion of the obtained slurry of layered double hydroxide 2 was filtered, and the resulting cake was dried for 12 hours at 70° C. After drying, the cake was sieved through a 150 mesh sieve and used for analysis.

[0120] Production Example 3: Method for producing layered double hydroxide 3 (2×(Mg / Al)=6) (Slurry production process) A slurry of layered double hydroxide 3 was obtained in the same manner as in Production Example 2, except that the volume ratio of the 4.2 mol / L magnesium chloride aqueous solution to the 2.4 mol / L aluminum chloride aqueous solution was changed to 100:60 instead of 100:88, and the volume ratio of the mixed solution to the 6.3 mol / L sodium hydroxide aqueous solution was changed to 100:58 instead of 100:50.

[0121] Production Example 4: Method for producing layered double hydroxide 4 (2×(Mg / Al)=8) (Slurry production process) A slurry of layered double hydroxide 4 was obtained in the same manner as in Production Example 2, except that the volume ratio of the 4.2 mol / L magnesium chloride aqueous solution to the 2.4 mol / L aluminum chloride aqueous solution was changed to 100:43 instead of 100:88, and the volume ratio of the mixed solution to the 6.3 mol / L sodium hydroxide aqueous solution was changed to 100:79 instead of 100:50.

[0122] Production Example 5: Method for producing layered double hydroxide 5 (2 × (Mg / Al) = 4) A 1.03 mol / L magnesium chloride aqueous solution, a 0.64 mol / L sodium aluminate aqueous solution, a 2.7 mol / L sodium hydroxide aqueous solution, and a 0.7 mol / L sodium carbonate aqueous solution were poured into a vessel at a volume ratio of 100:80:24:47 at atmospheric pressure and 25°C and reacted to obtain a hydrotalcite slurry. The obtained hydrotalcite slurry was filtered to obtain a cake. The obtained cake was washed with a sodium carbonate aqueous solution and then with pure water. The resulting cake was removed, pure water was added, and the mixture was re-emulsified using a homogenizer to obtain a slurry. The resulting slurry was then heat-treated in an autoclave at 170°C for 13 hours to obtain a slurry of layered double hydroxide 5. A portion of the resulting slurry of layered double hydroxide 1 was filtered, and the resulting cake was dried at 70°C for 12 hours. After drying, the cake was sieved through a 150 mesh sieve and used for analysis.

[0123] Test Example 1 (Mixing process) To a slurry of 8 to 12 mass % layered double hydroxide 4, cis-1,2-cyclohexanedicarboxylic acid was added so that the amount was 10 mass % relative to the solid content of the slurry, and the mixture was mixed at a temperature in the range of 15°C to 25°C. (Heating process) The mixture was heated to 80° C. with stirring, and heated at 80° C. for 2 hours. The resulting mixture was cooled. (Dehydration process) After cooling, the resulting mixture was filtered to obtain a cake. (drying process) The resulting cake was dried for 12 hours at 70° C. The dried cake was pulverized and then sieved through a 150 mesh screen to obtain a composite.

[0124] Test Examples 2-15 Composites 2 to 15 were obtained in the same manner as in Test Example 1, except that the layered double hydroxides shown in Table 1 were used and the heating temperatures shown in Table 1 were used.

[0125] The following measurements were carried out on Complexes 1 to 15.

[0126] [Measurement of residual rate] A mixture was prepared by mixing 5 g of the composite obtained in Test Examples 1 to 15 with 500 g of pure water. While maintaining the temperature of the mixture at 15°C or higher and 25°C or lower, the mixture was stirred at 400 to 600 rpm for 2 hours using a fluid jet stirrer with a 5 cm diameter stirring blade (product name: Jet Stirrer Ajiter, manufactured by Shimazaki Engineering Co., Ltd.). After washing, the mixture was filtered and then dried overnight at 70°C to obtain a washed composite. 0.1 g of the pre-washed composite was stirred in 5 mL of 1 mol / L hydrochloric acid at 60°C for 4 hours. 5 mL of methanol was added to the stirred solution. This solution was diluted with phosphate buffer (pH 2). The diluted solution was quantified by HPLC under the following conditions. The amount of cis-1,2-cyclohexanedicarboxylic acid treated was determined from an external calibration curve created using a cis-1,2-cyclohexanedicarboxylic acid solution of known concentration, and the amount of treatment m1 was determined. Furthermore, the amount of layered double hydroxide in the composite, m0, was determined from the sample used for measurement and the amount of treatment m1. From this, the amount of treatment before washing (m1 / m0) was calculated. The amount of treatment before washing (m1 / m0) can also be understood as the adhesion rate. Column: C18 reversed phase column Column temperature: 35℃ Mobile phase: 20% acetonitrile, 80% phosphate buffer (pH 2), flow rate 1.0 mL / min Detector: UV (225 nm)

[0127] The amount of cis-1,2-cyclohexanedicarboxylic acid treated on the composite after washing with pure water was also quantified to determine the amount of treatment (m2). The amount of layered double hydroxide (m0) was determined in the same manner as above, and the amount of treatment after washing (m2 / m0) was calculated. The residual ratio was calculated as the residual ratio = (amount of treatment after washing / amount of treatment before washing).

[0128] [Measurement of crystallization temperature] The composites obtained in Test Examples 1 to 15, polypropylene (manufactured by SunAllomer, product name "PX-600N", crystallization temperature 115.4°C), and an antioxidant (manufactured by BASF, product name "Irganox 1010") were mixed in a twin-screw mixer so that the blending amount of the composite was 500 ppm and the blending amount of the antioxidant was 300 ppm, thereby preparing samples for measuring the crystallization temperature. The obtained sample was measured using a differential scanning calorimeter (DSC) by heating the measurement sample from room temperature to 200°C at a heating rate of 10°C / min, holding it at 200°C for 10 minutes, and then cooling it from 200°C at a cooling rate of 10°C / min. The peak top temperature of the crystallization peak was read and the crystallization temperature during cooling was measured.

[0129] The results are shown in Table 1.

[0130] [Table 1]

[0131] Test Examples 2, 4, 6 to 10, 12, 14, and 15 correspond to examples of the present disclosure. In these test examples, it was confirmed that the crystallization temperature of the resin composition was higher than that of the raw material polypropylene, and that the composite can contribute to the crystallization of the resin.

[0132] Test Examples 1, 3, 5, 11, and 13 are examples in which the residual rate was less than 56 mass%, and correspond to comparative examples in the present disclosure. In these test examples, the increase in the crystallization temperature of the resin composition was suppressed compared to the raw material polypropylene, and the crystal nucleation ability was not fully satisfactory.

[0133] [Heat resistance test (coloring)] A resin compound containing 500 ppm of the composite was prepared using a twin-screw kneader. The compound was then molded into a 90 mm square, 2 mm thick plate using an injection molding machine. The plate was placed in an oven set to 120°C and heated. After heating for 88 and 140 hours, the plate was cooled to room temperature and the yellowness index was measured using a color difference meter (ZE6000, manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Figure 2. The sample (composite) containing 1,000 ppm Fe (869 ppm by XRF analysis) resulted in more coloring than the sample (composite) containing 500 ppm Fe (460 ppm by XRF analysis). When a large amount of Fe is contained, it is thought that Fe acts as a catalyst for the degradation and decomposition of the resin. As a result, a composite containing 1000 ppm of Fe has low heat resistance and is thought to result in discoloration of the resin. When a nucleating agent is kneaded at a higher concentration, such as when used as a masterbatch, it is thought that the discoloration of the resin composition due to Fe becomes even more pronounced due to heat. Therefore, when a nucleating agent contains a large amount of Fe, it may not be suitable for use as a nucleating agent.

[0134] [Heat resistance test (heat shrinkage)] Using the compound (composite blended at 500 ppm) produced in the twin-screw kneader, a flat plate approximately 90 mm square and 2 mm thick was produced in an injection molding machine. The produced flat plate was placed in an oven set at 100°C and heated for 24 hours. After cooling the heated flat plate, its length in the MD and TD directions was measured. (MD: direction of resin flow during injection molding, TD: direction perpendicular to MD) The results are shown in Figure 3. The sample (composite) containing 1000 ppm Fe (869 ppm by XRF analysis) had a lower crystallization temperature of PP than the sample (composite) containing 500 ppm Fe (460 ppm by XRF analysis), and the molded body also experienced thermal shrinkage. The ionic radius of Fe is larger than that of Mg and Al, and in composites containing a large amount of Fe, the presence of Fe on the surface of the layered double hydroxide (substrate) is thought to inhibit the regular arrangement of precipitates of the salt of cis-1,2-cyclohexanedicarboxylic acid and Mg. As a result, the effect of promoting resin crystallization is also inhibited compared to when the amount of Fe is low, and it is thought that a high crystallization temperature of PP could not be achieved. In complexes containing a large amount of Fe, it is difficult for the precipitates of salts of organic acids and Mg to be arranged in an orderly manner, and it is thought that the remaining rate of the organic acid derivatives or their salts after washing is lower than when the amount of Fe is low. Even during injection molding, samples containing a large amount of Fe solidified before crystallization had progressed sufficiently due to the factors mentioned above, and it is thought that heating at 100°C caused the PP polymer chains to align in the amorphous PP, which had not yet progressed in crystallization, and this progressed crystallization, resulting in a high rate of thermal shrinkage. If shrinkage is likely to occur due to heat application after molding, the dimensional stability is low, which is undesirable from an industrial standpoint.

[0135] [Measurement of loss on drying] The composite was placed in a thermo-hygrostat set at 80°C and 85% RH, and the composite sample was collected two weeks after the start of the placement to obtain composite samples with varying moisture content. The loss on drying of the obtained composite was measured using the following procedure.

[0136] The sample was placed in a weighing bottle (diameter 40 mm) of known mass to a thickness of 3 to 5 mm, and the mass was measured using a precision balance. This was then dried in a thermostatic oven at 105±2°C for 1 hour, allowed to cool in a desiccator, and the mass was then measured using the precision balance. Loss on drying (%) = (sample mass - sample mass after drying) x 100 / sample mass

[0137] The loss on drying of sample A before being placed in the thermo-hygrostat was 0.62%, and the loss on drying of sample B after being placed in the thermo-hygrostat was 1.71%.

[0138] The composite, polypropylene (manufactured by SunAllomer, product name "PX-600N", crystallization temperature 115.4°C), and antioxidant (manufactured by BASF, product name "Irganox 1010") were mixed in a twin-screw mixer so that the composite content was 500 ppm and the antioxidant content was 300 ppm, thereby obtaining a resin compound containing 500 ppm of the composite.

[0139] The resulting resin compound was compression molded in a 2 mm thick mold at 180°C for 5 minutes to obtain a plate containing 500 ppm of the composite. A photograph of the produced plate is shown in Figure 4.

[0140] It can be seen that the flat plate made with sample B (Figure 4(b)), which has a high moisture content and a large loss on drying, has more foaming than the flat plate made with sample A (Figure 4(a)), which has a low moisture content and a small loss on drying. In composites with a high amount of attached moisture, foaming due to moisture occurs during molding, which can cause concerns about poor appearance and reduced mechanical properties.

[0141] [Moisture content measurement] The composite was placed in a high-temperature, high-humidity environment (22°C, 85% RH), and composite samples were collected over a set period of time to obtain composite samples with varying moisture content. Five grams of the composite sample was heated at 105°C using a halogen moisture meter (Mettler Toledo, HX204) until no weight loss was observed during heating. The moisture content was measured from the weight loss after heating compared to the weight before heating.

[0142] Each composite was mixed with a polymer in a single-screw extruder to obtain a resin compound containing 500 ppm of composite. The yellowness index of the resin compound was measured using a colorimeter (DataColor, 850) according to ASTM E313. Composites with high water content tend to discolor the molded product.

[0143] As shown in FIG. 5, the resin compound using a composite with a water content of 0.25 mass % had a small yellowness index, and as the water content of the composite increased, the yellowness index of the resin compound increased.

[0144] [Infrared (IR) absorption measurement] 0.2 mg of each of the composites obtained in Test Examples 7 and 11 was mixed with 20 mg of KBr in a mortar. The mixed powder was molded and then subjected to infrared absorption measurement by the KBr method using a Fourier transform infrared spectrophotometer (FT / IR-4000, manufactured by JASCO Corporation). The results are shown in Figure 6.

[0145] In Test Example 7, the temperature was 1600 cm -1A clear peak is observed around 1 / 3. This peak is thought to be due to the C=O stretching of the carboxylate bonded to the metal in cis-1,2-cyclohexanedicarboxylic acid metal salt. This suggests that the formation of cis-1,2-cyclohexanedicarboxylic acid metal salt is more advanced in Test Example 7 than in Test Example 11.

[0146] [Scanning electron microscope (SEM) observation] Using a scanning electron microscope (JEOL JSM-7600F), the structures of the complexes obtained in Test Examples 7 and 11 were observed at a magnification of 100,000 times. The results are shown in FIG.

[0147] [Powder X-ray diffraction (XRD) measurement] The composites obtained in Test Examples 7 and 11 were crushed in an agate mortar and then subjected to X-ray diffraction measurement by powder X-ray diffraction using an X-ray diffractometer (EMPYREAN, manufactured by Malvern Panalytical). The results are shown in Figure 8. The measurement conditions were as follows: X-ray source: CuKα ray (λ=1.54Å) 2θ measurement interval: 0.026° Accumulation time: 296.565 seconds Accelerating voltage: 45 kV Accelerating current: 40mA Focal length: 12.0mm Take-off angle: 6°

[0148] In Test Example 7, a peak derived from cis-1,2-cyclohexanedicarboxylic acid metal salt was observed near 2θ=6.8°, and the formation of a cis-1,2-cyclohexanedicarboxylic acid metal salt precipitate was also confirmed in the XRD chart. The peak derived from the layered double hydroxide observed in the 2θ range of 22° to 24° showed almost no change between Layered Double Hydroxide 2 (shown as the untreated product) and Composite 4 (shown as the treated product), suggesting that the crystallinity of the layered double hydroxide was maintained.

[0149] (Test Example 16) To a 10% by mass slurry of layered double hydroxide, cis-1,2-cyclohexanecarboxylic anhydride was added at 40°C so that the amount was 10% by mass relative to the solid content of the slurry. For comparison, tests were also conducted in which the same total amounts of cis-1,2-cyclohexanedicarboxylic anhydride / trans-1,2-cyclohexanecarboxylic anhydride were added in cis / trans ratios of 70 / 30, 50 / 50, and 0 / 100.

[0150] The mixture was heated to 80°C with stirring and heated at 80°C for 2 hours. The resulting mixture was cooled to 30-40°C. After cooling, the resulting mixture was filtered to obtain a cake. The resulting cake was dried to obtain a composite.

[0151] When cis-1,2-cyclohexanedicarboxylic acid is present in a large proportion relative to the total amount of 1,2-cyclohexanedicarboxylic acid, it is believed that when a salt is formed between the metal species of the layered compound and 1,2-cyclohexanedicarboxylic acid, the salt is more likely to precipitate in an orderly manner on the surface of the layered double hydroxide. As a result, when the composite is mixed with a resin, the orderly precipitated structure can promote crystal growth (epitaxial growth) of the resin. On the other hand, trans-1,2-cyclohexanedicarboxylic acid can inhibit the orderly precipitation of the salt due to the large torsion angle between the two carboxyl groups. Therefore, when trans-1,2-cyclohexanedicarboxylic acid is present in a large proportion relative to the total amount of 1,2-cyclohexanedicarboxylic acid, it is believed that the orderly precipitation of the salt on the surface of the layered double hydroxide is more difficult.

[0152] When cis-1,2-cyclohexanecarboxylic acid anhydride is used, hydrolysis proceeds gradually after addition to the slurry, increasing the amount of cis-1,2-cyclohexanecarboxylic acid in the system. When an anhydride is used, the initial organic acid concentration is lower than when cis-1,2-cyclohexanecarboxylic acid is added to the slurry, which may allow the reaction to proceed more gently and more uniformly, preventing localized reactions within the slurry. The more uniformly the organic acid derivative is immobilized on the layered double hydroxide, the greater the surface area of ​​the complex that effectively acts as a crystal nucleating agent when kneaded into the resin, further promoting the crystallization of the resin.

[0153] (Test Example 17) The composite of Test Example 15, polypropylene (manufactured by SunAllomer, product name "PX-600N", crystallization temperature 115.4°C), and an antioxidant (manufactured by BASF, product name "Irganox 1010") were mixed in a twin-screw mixer so that the blending amount of the composite was 500 ppm and the blending amount of the antioxidant was 300 ppm, thereby obtaining a resin compound containing 500 ppm of the composite.

[0154] The obtained resin compound, polypropylene (manufactured by SunAllomer, product name "PX-600N", crystallization temperature 115.4°C), and antioxidant (manufactured by BASF, product name "Irganox 1010") were diluted and kneaded in a batch kneader so that the amount of complex contained in the diluted resin compound was 5 ppm and the amount of antioxidant contained in the diluted resin compound was 300 ppm, thereby obtaining a resin compound containing 5 ppm of complex.

[0155] Similar to the resin compound containing 5 ppm of the complex, a resin compound containing 1 ppm of the complex was obtained using a resin compound containing 500 ppm of the complex, so that the amount of the complex contained in the diluted resin compound was 1 ppm and the amount of the antioxidant was 300 ppm.

[0156] The samples containing the obtained complexes at 500 ppm, 5 ppm, and 1 ppm were measured using a differential scanning calorimeter (DSC). The samples were heated from room temperature to 200°C at a heating rate of 10°C / min, held at 200°C for 10 minutes, and then cooled from 200°C at a cooling rate of 10°C / min. The peak top temperature of the crystallization peak was read to measure the crystallization temperature during cooling.

[0157] The adhesion rate of cis-1,2-cyclohexanedicarboxylic acid in the composite was quantitatively measured using the method described above in [Method for measuring adhesion rate]. From the adhesion rate of cis-1,2-cyclohexanedicarboxylic acid in the composite, the amount of cis-1,2-cyclohexanedicarboxylic acid contained in the resin compound containing 500 ppm, 5 ppm, and 1 ppm of composite was calculated.

[0158] (Test Example 18) Resin compounds containing 500 ppm, 5 ppm, and 1 ppm of HPN-20E were prepared in the same manner as in Test Example 17, except that a crystal nucleating agent (HPN-20E manufactured by Milliken) was used instead of the above complex, and the crystallization temperature and the amount of cis-1,2-cyclohexanedicarboxylic acid were measured.

[0159] A graph plotting the crystallization temperature against the amount of cis-1,2-cyclohexanedicarboxylic acid is shown in Figure 9. It shows that in the composite, the salt of cis-1,2-cyclohexanedicarboxylic acid acts more effectively as a crystal nucleating agent, and that the crystal nucleating effect is exerted even with a small amount of cis-1,2-cyclohexanedicarboxylic acid in the resin.

[0160] If the effect of the nucleating agent can be achieved with a smaller amount of cis-1,2-cyclohexanedicarboxylic acid, it will be possible to produce molded articles that can maintain moldability while suppressing the amount of organic matter that migrates from the resin molded article to the outside of the molded article during use (migration amount). [Industrial Applicability]

[0161] The composite of the present disclosure can contribute to the crystallization of resins and can be preferably used as a crystal nucleating agent. [Explanation of symbols]

[0162] 1. Complex 10 Layered double hydroxides 11 Organic acids or their derivatives

Claims

1. A composite comprising a layered double hydroxide and an outer layer covering the layered double hydroxide, The layered double hydroxide has the formula (I): [[M1 ２＋ ] １－ｘ [M2 ３＋ ] ｘ (OH) ２ ](A ｎ－ ) ｘ／ｎ ・mH ２ O ・・・(I) [In formula (I), M1 ２＋ represents one or more divalent metal ions, M2 ３＋ represents one or more trivalent metal ions, A ｎ－ represents one or more n-valent anions, m is equal to or greater than 0 and less than 2; n is 1 or more and 5 or less, x is greater than 0 and equal to or less than 0.

6. The compound includes a compound represented by the outer layer comprises an organic acid derivative or a salt thereof, A complex, wherein when the complex is washed with pure water in an amount 100 times by mass of the complex, the residual rate of the organic acid derivative or its salt after the washing is 56% by mass or more compared to that before the washing.

2. 2. The composite according to claim 1, wherein the outer layer has an adhesion rate of 1% by mass or more to the layered double hydroxide.

3. In formula (I), M1 ２＋ is Mg ２＋ , Zn ２＋ , Ca ２＋ , Sr ２＋ , Fe ２＋ , Mn ２＋ , Co ２＋ , Ni ２＋ , Sn ２＋ , Pb ２＋ , Cd ２＋ and Ba ２＋ and M2 ３＋ is Al ３＋ and Fe ３＋ The complex according to claim 1, comprising one or more species selected from the group consisting of:

4. 2. The complex according to claim 1, wherein, in formula (I), 2×(1−x) / x is 1.5 or more and 7.5 or less.

5. The composite according to claim 1, wherein the Fe content is 0 ppm by mass or more and 500 ppm by mass or less.

6. The complex according to claim 1, having a zeta potential of 0 mV or more and 50 mV or less.

7. BET specific surface area is 5m ２ / g or more 100m ２ The composite of claim 1, wherein the tensile strength is 1 / g or less.

8. The composite according to claim 1 , wherein the average aspect ratio is 2 or more and 150 or less.

9. The composite according to claim 1, wherein the loss on drying is 0% by mass or more and 1.5% by mass or less.

10. A method for producing a composite comprising a layered double hydroxide and an outer layer covering the layered double hydroxide, comprising the steps of: The layered double hydroxide has the formula (I): [[M1 ２＋ ] １－ｘ [M2 ３＋ ] ｘ (OH) ２ ](A ｎ－ ) ｘ／ｎ ・mH ２ O ・・・(I) [In formula (I), M1 ２＋ represents one or more divalent metal ions, M2 ３＋ represents one or more trivalent metal ions, A ｎ－ represents one or more n-valent anions, m is equal to or greater than 0 and less than 2; n is 1 or more and 5 or less, x is greater than 0 and equal to or less than 0.

6. The compound includes a compound represented by the outer layer comprises an organic acid derivative or a salt thereof, a slurry production step of producing a slurry of the layered double hydroxide; a mixing step of mixing a slurry of the layered double hydroxide with the organic acid derivative or a salt thereof; The method for producing a composite includes a heating step of heating the layered double hydroxide and the organic acid derivative or its salt mixed in the mixing step.

11. A resin additive comprising the composite according to any one of claims 1 to 9.

12. A resin composition comprising the resin additive according to claim 11 and a resin.

Images