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

Abstract

The purpose of the present disclosure is to provide a composite containing a layered double hydroxide that can contribute to crystallization of a resin. The purpose of the present disclosure is also to provide a method for producing such a composite. The purpose of the present disclosure is also to provide a resin composition containing such a composite, and a method for producing the same.　The composite comprises a layered double hydroxide and an outer layer covering the layered double hydroxide. The layered double hydroxide contains a compound represented by formula (I). Formula (1): [[M12+]1-x[M23+]x(OH)2](An-)x / n∙mH2O [In formula (I), M12+ represents one or more divalent metal ions, M23+ represents one or more trivalent metal ions, An- represents one or more n-valent anions, m is 0 to less than 2, n is 1-5, and x is more than 0 to 0.6.] 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 ratio of the organic acid derivative or salt thereof after the washing is 56 mass% or more as compared with before the washing.

Description

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

[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.

[0002] Layered double hydroxides are widely used as additives for resins, etc. ｘ It is described 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.

[0003] 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, 105717Mohammad 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 519Jae-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

[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.

[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 comprises a compound represented by the following 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. 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.

[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 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＋ , Mn ２＋ , Co ２＋ , Ni ２＋ , Sn ２＋ , Pb ２＋ , Cd２＋ and Ba ２＋ M2 may contain one or more selected from the group consisting of: ３＋ is Al ３＋ and Fe ３＋ The compound may contain one or more compounds 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 may 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 Fe content in the composite may 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 comprises a compound represented by the following formula (I): [[M1 ２＋ ] １－ｘ [M2 ３＋ ] ｘ (OH) ２ ](A ｎ－ ) ｘ／ｎ ・mH２ O (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. 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 the 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 a salt thereof mixed in the mixing step.

[0016] An eleventh embodiment of the present disclosure provides a resin additive including any one of the composites described in 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.

[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.

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

[0020] The composite of the present disclosure comprises a layered double hydroxide and an outer layer. The layered double hydroxide comprises a compound represented by 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. 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 post-washing survival rate. While the reason for this enhanced post-washing survival rate 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, 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 likely enhances compatibility with the resin crystal lattice and promotes 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 have particularly favorable crystal nucleation ability. While the reason why the organic acid derivative or its salt is retained strongly 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 held in close proximity in the composite of the present disclosure allows the composite to function as a crystal nucleating agent. When a magnesium 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 the magnesium salt of cis-1,2-cyclohexanedicarboxylic acid is small, and the function as a crystal nucleating agent is not substantially exhibited. Furthermore, when a magnesium salt of cis-1,2-cyclohexanedicarboxylic acid and a layered double hydroxide are each added to polypropylene and kneaded, the crystallization temperature increases by approximately 1.7°C compared to the polypropylene before addition. Even when both the Mg salt of cis-1,2-cyclohexanedicarboxylic acid and the layered double hydroxide are added, the increase in crystallization temperature is small, and the performance of the compound as a crystal nucleating agent is insufficient. On the other hand, when the composite of the present disclosure is added to polypropylene and kneaded, the crystallization temperature rises by approximately 7.9°C compared to the polypropylene before addition. The addition of the composite significantly increases the crystallization temperature of polypropylene compared to when the Mg salt of cis-1,2-cyclohexanedicarboxylic acid and the layered double hydroxide are added separately. This is considered to be evidence that the organic acid derivative or its salt does not function as a crystal nucleating agent unless it is present in the vicinity of the layered double hydroxide.

[0025] Furthermore, when an organic acid derivative or its salt is retained on the surface of a layered double hydroxide through chemical or physical interaction, its survival rate after washing is increased. When an organic acid derivative or its salt is retained on the surface of a layered double hydroxide through chemical or physical interaction, it is unlikely to be detached from the layered double hydroxide when kneaded with a resin, and its function as a crystal nucleating agent is believed to be 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 its survival rate after washing is believed to be low.

[0026] In the method for producing a composite of the present disclosure, it is believed that heating and mixing an organic acid derivative or its salt with a layered double hydroxide results in the organic acid derivative or its salt and the layered double hydroxide being 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. A stronger chemical or physical interaction between the organic acid derivative or its salt and the layered double hydroxide can more firmly hold the organic acid derivative or its salt and the layered double hydroxide together. Heating at a lower temperature within the production temperature range of the present disclosure tends to produce a mixture of the organic acid derivative or its salt and the layered double hydroxide. Even in a mixture of an organic acid derivative or its salt and a layered double hydroxide, the proximity effect allows the mixture to function as a crystal nucleating agent. The lower heating temperature of a mixture of an organic acid derivative or its salt and a layered double hydroxide allows for production 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 be easily 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, a layered double hydroxide refers to a compound containing a basic layer of a metal hydroxide containing at least one or more divalent metal ions and one or more trivalent metal ions, and an anion and water present between the basic 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 basic 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 ・mH ２ O (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 more and less than 2. n is 1 or more and 5 or less. x is more than 0 and 0.6 or less.

[0032] M1 ２＋ represents one or more divalent metal ions. ２＋ is Mg２＋ , 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: ２＋ However, the above metal ions, especially Mg ２＋ and Zn ２＋ By including one or more selected from the group consisting of: 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＋ is Al ３＋ , Fe ３＋ , Sc ３＋ , Y ３＋ , Ti ３＋ , Cr ３＋ , Fe ３＋ , Al ３＋ , Ga ３＋ , In ３＋ and La ３＋ Preferably, the compound contains one or more selected from the group consisting of Al ３＋ and Fe３＋ It is more preferable that the compound contains one or more selected from the group consisting of Al ３＋ It is more preferable that M2 ３＋ However, the above metal ions, especially Al ３＋ and Fe ３＋ By including one or more selected from the group consisting of: 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 within this range, the stability and crystal nucleation ability of the composite may 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, 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 for ２＋ The ratio of the amount of substance (M 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 organic acid derivative is in the range of M1 in the layered double hydroxide is as follows. ２＋ It is thought that the salt easily reacts with the organic acid to form a salt, which is dissolved or deposited on the layered double hydroxide. ３＋ That is, M1 ２＋ Since the organic acid does not form a salt compared to the layered double hydroxide, it is thought that elution is suppressed and the organic acid is easily immobilized on the surface of the layered double hydroxide. ２＋ / M2 ３＋) is in 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 material 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 may be performed by powder X-ray diffraction. In one embodiment, measurement may be performed using CuKα radiation (λ=1.54 Å) as an X-ray source, with a 2θ measurement interval of 0.026°, an accumulation time of 296.565 seconds, an acceleration voltage of 45 kV, an acceleration current of 40 mA, a focal length of 12.0 mm, and a take-off angle of 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): (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 represents a single bond or NR １２ represents -, R １ represents a hydroxyl group, a carboxyl group, R １０ -OCO-, R １１ -CO-NR １２ -, NR １２ ２ -, NR １２ ２ -CO-, C １－６ R represents one or more groups selected from the group consisting of an alkyl group, a hydroxyphosphoryl group, a heterocyclic group, and an aryl group; ２ represents one atom selected from the group consisting of a carbon atom, a phosphorus atom, and a sulfur atom; 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 ２is a phosphorus atom, a hydroxy group or C １－６ represents an alkyl group, and R １ When 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, and n3 represents an integer of 1 to 3. Examples of the organic acid include organic acids represented by the formula (I), derivatives thereof, and salts thereof.

[0045] The above formula (II) is preferably the following formula (III): [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 an alicyclic hydrocarbon group, an aromatic group, and a heterocyclic group. A is 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 is preferably 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 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 includes C ３－１０ Heterocyclic groups are preferred, and C ３－５Heterocyclic 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 - is.

[0052] R １ represents 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 １－６ It 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 be preferably 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 preferably be 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 one embodiment, R ３ is a hydroxy group. ３ is C １－６ It is an alkyl group.

[0055] R ４ is R ２ is a phosphorus atom, a hydroxy group or C １－６ represents an alkyl group, and R １ When is a sulfur atom, R ２ represents an oxygen atom forming a double bond with R.２ 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] The 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] The above R １１ The aryl group represented by the formula: ６－２０ An aryl group is preferred, and C ６－１０ An 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, 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, preferably 1.

[0062] The N-substituted isocyanurate may include 1,3,5-triazine-2,4,6-triol.

[0063] As the organic acid derivative, a compound represented by the formula (II) is preferred, a compound represented by the formula (III) is more preferred, and C １－１２ Aliphatic monocarboxylic acids, C１－１２ 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 acid, C ３－８ Cycloalkanedicarboxylic acids and C ３－８ More preferably, the carboxylic acid is one or more selected from the group consisting of cycloalkanetricarboxylic acids, １－１２ Aliphatic dicarboxylic acids, C １－１２ Aromatic dicarboxylic acids and C ３－８ Cycloalkanedicarboxylic acids are even more preferred, C ３－８ 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., 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 tricarboxylic acid, 4-(benzoylamino)benzoic acid, disodium malonate, sodium acetate, 1-octanesulfonic acid, 2,3-pyridinedicarboxylic acid, 2-carboxyethyl(phenyl)phosphinic acid, 2-naphthalenecarboxylic acid, 2-tert-butylbenzoic acid, 4-aminobenzoic acid, 4-biphenylcarboxylic acid, 4-toluenesulfonic acid, bis(2-ethylhexyl)hydrogenphosphate, butylphosphonic acid, 4-phthalimidobenzoic acid, 4-tert-butylbenzoic acid, 1,4-cyclohexanedicarboxylic acid and / or 4-propylcyclohexanecarboxylic acid. More preferred examples of the organic acid or derivative thereof include 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, and 1,4-cyclohexanedicarboxylic acid and / or 4-propylcyclohexanecarboxylic acid. 1,2-cyclohexanedicarboxylic acid or its anhydride (in one embodiment, cis-1,2-cyclohexanedicarboxylic acid or its anhydride) 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 % or more and 100 mol % or less, more preferably 70 mol % or more and 100 mol % or less, and even more preferably 90 mol % or more and 100 mol % or less, 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 adhesion ratio of cis isomer may be calculated based on 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.

[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 the anhydride of an organic acid does not form a salt with the metal species in the layered double hydroxide in its anhydrous state. It is believed that the 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 the use of an anhydride of an organic acid results in more uniform immobilization on the layered double hydroxide than the case where 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 % or more and 100 mol % or less, more preferably 70 mol % or more and 100 mol % or less, and even more preferably 90 mol % or more and 100 mol % or less, based on the total amount of 1,2-cyclohexanedicarboxylic acid or anhydride.

[0070] The inclusion of the above-mentioned compound, particularly cis-1,2-cyclohexanedicarboxylic acid, as the organic acid or its derivative is believed to facilitate the presence of such compound on the surface of the base layer of the metal hydroxide. As a result, it is believed that the functionality of the layered double hydroxide, such as its anion-trapping ability, is more easily maintained. This point can also be confirmed by the fact that, in XRD measurement 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 the 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] 5 mL of 1 mol / L hydrochloric acid is added to 0.1 g of the complex before washing, and the mixture is stirred at 60°C for 4 hours. 5 mL of methanol is added to the stirred solution. This solution is diluted with phosphate buffer (pH 2). The diluted solution is subjected to high performance liquid chromatography (HPLC) under the following conditions to determine the amount of organic acid derivative adhesion, m １ The amount of treatment m is determined from an external calibration curve created using an organic acid derivative solution of known concentration. １ The amount of layered double hydroxide in the composite, m ０Based on this, adhesion rate = m １ / m ０ Column: C18 reverse phase column Column temperature: 35°C 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 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 in a proportion of 500 ppm by mass with respect to the resin, and kneading the mixture using a twin-screw kneader so that the resin temperature is 210° C. or higher and 230° C. or lower. As the resin, polypropylene (for example, “PX-600N” manufactured by SunAllomer) can be used.

[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 the 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 is prepared by mixing 5 g of the composite 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 is stirred at a rotation speed of 400 to 600 rpm for 2 hours using a fluid jet stirrer (product name: Jet Stirrer Ajiter, manufactured by Shimazaki Engineering Co., Ltd.) with stirring blades having a diameter of 5 cm, to perform washing. After washing, the mixture is filtered and then dried at 70°C for 12 hours to obtain a washed composite.

[0078] 5 mL of 1 mol / L hydrochloric acid is added to 0.1 g of the complex before washing, and the mixture is stirred at 60°C for 4 hours. 5 mL of methanol is added to the stirred solution. This solution is diluted with phosphate buffer (pH 2). The amount of organic acid derivative treated with the diluted solution is quantified by high performance liquid chromatography (HPLC) under the following conditions. The amount of treated organic acid derivative m is determined from an external calibration curve created using organic acid derivative solutions of known concentrations. １ The amount of layered double hydroxide in the composite m ０ Based on this, the amount of treatment before cleaning (m １ / m ０ ) is determined. Column: C18 reverse phase column Column temperature: 35°C Mobile phase: 20% acetonitrile, 80% phosphate buffer (pH 2), flow rate 1.0 mL / min Detector: UV (225 nm) The complex after washing was also treated in the same manner. ２ The amount of layered double hydroxide in the composite m ０ Based on this, the amount of processing after cleaning (m ２ / m ０ The residual rate is calculated as follows: residual rate = (treatment amount after washing / treatment 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 aspect, the composite preferably does not have a peak in the 2θ range of 4° to 9° in X-ray diffraction (XRD) measurement. Absence of a peak in this range is believed to indicate 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, high compatibility between the composite and the resin and high dispersibility are expected. In another aspect, the composite may have a peak in the 2θ range of preferably 4° to 9°, more preferably 5° to 8°, and even more preferably 6° to 7.5° in XRD measurement. The 2θ is preferably 4° C. or higher, more preferably 5° or higher, and even more preferably 6° or higher, and is preferably 9° to 8°, and even more preferably 7.5° or lower. A peak in this range is believed to indicate that the salt of the organic acid derivative or its salt and the metal eluted from the layered double hydroxide is precipitated in a non-uniform state on the surface of the layered double hydroxide. In this case, mixing the resin with such a complex makes it easier to ensure an anion capture pathway in the resin, and it is expected that a high acid-accepting capacity can be exhibited.

[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 when the composite of the present disclosure is mixed with a resin is good. 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, even more preferably 15 mV or more, and preferably 50 mV or less, 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, followed by the addition of 25 mL of ethanol 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 coloration is more likely to be suppressed during kneading and molding 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, even more preferably 0.2 μm or more, and 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 can have good dispersibility when mixed with a resin. The average secondary particle diameter of the composite means the cumulative 50% volume diameter, i.e., 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 composite. 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 observed using a scanning electron microscope. In a specific embodiment, they can be measured, for example, by the following method. [Method for Measuring Average Aspect Ratio, Average Diameter, and Average Thickness] The composite is ultrasonicated 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 observed at a magnification of 5,000x or 10,000x, and calculated as the average of the longest diameters of the primary particles of the composite. The arithmetic mean value of the diameters measured for the primary particles of any 20 composites is taken as the average diameter. The thickness is observed at a magnification of 100,000x, and the thickness of the primary particles of any 14 composites is measured, and the arithmetic mean value is taken as the average thickness. 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] A sample is placed in a weighing bottle (diameter 40 mm) of known mass so that the sample has a thickness of 3 to 5 mm, and the mass (sample mass) is measured using a precision balance. The sample is dried in a thermostatic oven at 105±2°C for 1 hour, allowed to cool in a desiccator, and then the mass is measured using a precision balance. The loss on drying is calculated based on the following formula: Loss on drying (%) = (sample mass - sample mass after drying) × 100 / sample mass.

[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 moisture content of the 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 the weight before heating may be taken as the moisture 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, a mixing step of mixing the slurry of the layered double hydroxide with the organic acid derivative or its salt, and a heating step of heating the layered double hydroxide and the organic acid or its derivative 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 or higher and 90°C or lower, more preferably 60°C or higher and 90°C or lower, and even more preferably 65°C or higher and 90°C or lower. When the heating temperature is within this range, the organic acid or derivative thereof is fixed 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 to 5 hours, more preferably 1 hour to 3 hours.

[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 a resin additive. 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 believed to have crystal nucleation ability. Furthermore, unlike the composite, particles of organic compounds conventionally used as crystal nucleating agents have a uniform composition, and therefore may contain organic acids or derivatives thereof within the particles. However, in the case of such organic compound particles, the organic matter within the particles that cannot come into contact with the resin does not function as a crystal nucleating agent. Therefore, the use of the composite of the present disclosure is believed to have the advantage of reducing the amount of organic matter used as an additive compared to using calcium salts of organic compounds conventionally used as crystal nucleating agents. Furthermore, the composite of the present disclosure is expected to have good crystal nucleation ability for resins and good anion capture performance. Therefore, the amount of additive used can be reduced compared to simply mixing a crystal nucleating agent and an anion scavenger. Therefore, resin additives containing the composite of the present disclosure are also within 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 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 mass ppm or more and 1,000 mass ppm or less, more preferably 0.1 mass ppm or more and 500 mass ppm or less, and even more preferably 1 mass ppm or more and 250 mass ppm 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 an increased crystallization temperature T ｃ０ and the crystallization temperature T of the mixture. ｃ１ The crystallization temperature difference (T ｃ１ -Tｃ０ ) 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.

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

[0119] Production Example 2: Production method for layered double hydroxide 2 (2 × (Mg / Al) = 4) (Slurry generation step) A 4.2 mol / L aqueous magnesium chloride solution and a 2.4 mol / L aqueous aluminum chloride 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 aqueous sodium hydroxide 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 an aqueous sodium carbonate solution and then with pure water. The obtained cake was removed, pure water was added, and the mixture was re-emulsified using a homogenizer to obtain a slurry. The obtained slurry was 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: Production method for layered double hydroxide 3 (2 × (Mg / Al) = 6) (Slurry production step) 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 aqueous magnesium chloride solution to the 2.4 mol / L aqueous aluminum chloride solution was changed to 100:60 instead of 100:88, and the volume ratio of the mixed solution to the 6.3 mol / L aqueous sodium hydroxide solution was changed to 100:58 instead of 100:50.

[0121] Production Example 4: Production method for layered double hydroxide 4 (2 × (Mg / Al) = 8) (Slurry production step) 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 aqueous magnesium chloride solution to the 2.4 mol / L aqueous aluminum chloride solution was changed to 100:43 instead of 100:88, and the volume ratio of the mixed solution to the 6.3 mol / L aqueous sodium hydroxide 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) 1.03 mol / L magnesium chloride aqueous solution, 0.64 mol / L sodium aluminate aqueous solution, 2.7 mol / L sodium hydroxide aqueous solution, and 0.7 mol / L sodium carbonate aqueous solution were poured into a vessel at atmospheric pressure and 25°C in a volume ratio of 100:80:24:47 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 obtained cake was removed, and pure water was added. The mixture was re-emulsified using a homogenizer to obtain a slurry. The obtained slurry was heat-treated in an autoclave at 170°C for 13 hours to obtain a slurry of layered double hydroxide 5. A portion of the obtained slurry of layered double hydroxide 1 was filtered, and the obtained cake was dried at 70°C for 12 hours. After drying, the sample was sieved through a 150 mesh sieve and used for analysis.

[0123] Test Example 1 (Mixing Step) To an 8-12 mass% slurry of 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 in the range of 15°C to 25°C. (Heating Step) The mixture was heated to 80°C with stirring, and heated at 80°C for 2 hours. The resulting mixture was cooled. (Dehydration Step) After cooling, the resulting mixture was filtered to obtain a cake. (Drying Step) The resulting cake was dried at 70°C for 12 hours. The dried cake was pulverized and then sieved through a 150 mesh sieve to obtain a composite.

[0124] Test Examples 2 to 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 a rotation speed of 400 to 600 rpm for 2 hours using a fluid jet-type stirrer (product name: Jet Stirrer Ajiter, manufactured by Shimazaki Engineering Co., Ltd.) with a stirring blade having a diameter of 5 cm, and then washed. After washing, the mixture was filtered and dried overnight at 70°C to obtain a washed composite. 0.1 g of the composite before washing was stirred with 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 quantified using an external calibration curve prepared using a cis-1,2-cyclohexanedicarboxylic acid solution of known concentration, and the amount of cis-1,2-cyclohexanedicarboxylic acid treated was determined. １ The sample and processing amount m １ From the amount of layered double hydroxide in the composite, m ０ From this, the treatment amount before cleaning (m １ / m ０ The amount of treatment before washing (m １ / m ０ ) is also understood as the adhesion rate. Column: C18 reversed-phase column Column temperature: 35°C Mobile phase: 20% acetonitrile, 80% phosphate buffer (pH 2), flow rate 1.0 mL / min Detector: UV (225 nm)

[0127] After washing with pure water, the amount of cis-1,2-cyclohexanedicarboxylic acid treated with the complex was also determined. ２ The amount of layered double hydroxide m ０ Determine the amount of treatment after cleaning (m ２ / m ０ The residual rate was calculated as follows: residual rate = (amount treated after washing / amount treated 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 composite amount was 500 ppm and the antioxidant amount was 300 ppm. A sample for measuring the crystallization temperature was prepared by kneading the resulting sample. The obtained sample was measured using a differential scanning calorimeter (DSC). The measurement sample was 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, and the crystallization temperature during cooling was measured.

[0129] The results are shown in Table 1.

[0130]

[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 (Coloration) A resin compound containing 500 ppm of composite was prepared using a twin-screw kneader. The prepared compound was then molded into 90 mm square, 2 mm thick plates using an injection molding machine. The resulting plates were placed in an oven set to 120°C and heated. After 88 and 140 hours of heating, the plates were cooled to room temperature and their yellowness was measured using a colorimeter (ZE6000, manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Figure 2. The sample (composite) containing 1,000 ppm of Fe (869 ppm by XRF analysis) exhibited more coloration than the sample (composite) containing 500 ppm of Fe (460 ppm by XRF analysis). It is believed that Fe, when present in large amounts, acts as a catalyst for the degradation and decomposition of the resin. As a result, the composite containing 1,000 ppm of Fe exhibited poor heat resistance and thus exhibited resin coloration. When the nucleating agent is kneaded at a higher concentration, such as when used as a masterbatch, the coloring of the resin composition due to Fe is thought to become more pronounced due to heat, and therefore, when the nucleating agent contains a large amount of Fe, it may not be preferable to use it as a nucleating agent.

[0134] [Heat Resistance Test (Thermal Shrinkage)] Using the compound (500 ppm composite) prepared using a twin-screw kneader, a flat plate approximately 90 mm square and approximately 2 mm thick was prepared using an injection molding machine. The prepared flat plate was placed in an oven set to 100°C and heated for 24 hours. After cooling, the heated flat plate was measured for its length in the MD and TD directions. (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 PP crystallization temperature than the sample (composite) containing 500 ppm Fe (460 ppm by XRF analysis), resulting in thermal shrinkage of the molded product. Fe has a larger ionic radius than Mg and Al. Therefore, 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 Fe content is low, which is thought to prevent a high crystallization temperature from being achieved for PP. In composites containing a large amount of Fe, the precipitates of the salt of organic acid and Mg are less likely to be regularly arranged, and the residual rate of the organic acid derivative or its salt after washing is thought to be lower than when the Fe content is low. Even during injection molding, samples containing a large amount of Fe solidify without sufficient crystallization due to the above factors. Heating at 100°C is thought to align PP polymer chains in the amorphous PP, which is not sufficiently crystallized, and crystallization progresses, resulting in high thermal shrinkage. If shrinkage due to heat application after molding is likely to occur, dimensional stability is poor, making this industrially undesirable.

[0135] [Measurement of Loss on Drying] The composite was left to stand in a thermo-hygrostat set at 80°C and 85% RH, and the composite sample was collected two weeks after the start of standing to obtain a composite sample with a variable moisture content. The loss on drying of the obtained composite was measured by the following procedure.

[0136] The sample was placed in a weighing bottle (40 mm diameter) of known mass to a thickness of 3 to 5 mm, and the mass was measured using a precision balance. The sample 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 a precision balance. Loss on drying (%) = (sample mass - sample mass after drying) × 100 / sample mass

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

[0139] The resin compound thus obtained 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 FIG. 4.

[0140] It can be seen that the flat plate made with sample B (Fig. 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 (Fig. 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] [Measurement of Moisture Content] The composite was left to stand in a high-temperature, high-humidity environment (22°C, 85% RH), and composite samples were collected over a certain period of time to obtain composite samples with varying moisture contents. Five grams of the obtained 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 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 of the resin compound was measured using a colorimeter (DataColor, 850) according to ASTM E313. Composites with high water content tend to produce colored molded articles.

[0143] As shown in FIG. 5, the resin compound using a composite with a water content of 0.25% by 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 thickness was 1600 cm －１ A clear peak is observed around 1 / 3 of the normalized peak. 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 (JSM-7600F manufactured by JEOL Ltd.), the structures of the composites obtained in Test Examples 7 and 11 were observed at a magnification of 100,000. 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 radiation (λ = 1.54 Å), 2θ measurement interval: 0.026°, accumulation time: 296.565 seconds, acceleration voltage: 45 kV, acceleration current: 40 mA, focal length: 12.0 mm, 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 from the XRD chart. There was almost no change in the peak derived from the layered double hydroxide observed in the 2θ range of 22° to 24° between layered double hydroxide 2, which is shown as the untreated product, and composite 4, which is shown as the treated product, and it is believed 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 contained 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 a regular pattern on the surface of the layered double hydroxide. As a result, when the composite is mixed with a resin, the regularity of the precipitate can promote crystal growth (epitaxial growth) of the resin. On the other hand, trans-1,2-cyclohexanedicarboxylic acid can inhibit the regular precipitation of the salt due to the large torsion angle between the two carboxyl groups. Therefore, when trans-1,2-cyclohexanedicarboxylic acid is contained in a large proportion relative to the total amount of 1,2-cyclohexanedicarboxylic acid, it is believed that the regular precipitation of the salt on the surface of the layered double hydroxide becomes more difficult.

[0152] When cis-1,2-cyclohexanecarboxylic acid anhydride is used, hydrolysis proceeds gradually after addition to the slurry, and the amount of cis-1,2-cyclohexanecarboxylic acid in the system is thought to increase. When an anhydride is used, the initial organic acid concentration is lower than when cis-1,2-cyclohexanecarboxylic acid is added to the slurry, so the reaction is thought to proceed more gently, making it less likely that localized reactions will occur within the slurry and more likely to proceed uniformly. If the organic acid derivative is immobilized more uniformly on the layered double hydroxide, the surface area of ​​the composite, which effectively acts as a crystal nucleating agent when kneaded into a resin, will increase, 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 kneaded in a twin-screw kneader 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 Corporation, product name "PX-600N", crystallization temperature 115.4°C), and an antioxidant (manufactured by BASF, product name "Irganox 1010") were used and diluted and kneaded in a batch kneader so that the amount of the complex contained in the diluted resin compound was 5 ppm and the amount of the antioxidant was 300 ppm, thereby obtaining a resin compound containing 5 ppm of the 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 composites at 500 ppm, 5 ppm, and 1 ppm were measured using a differential scanning calorimeter (DSC). The measurement 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, and 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 agent effect is exerted even with a small amount of cis-1,2-cyclohexanedicarboxylic acid in the resin.

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

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

[0162] 1 Composite 10 Layered double hydroxide 11 Organic acid or derivative thereof

Claims

1. A composite comprising a layered double hydroxide and an outer layer covering the layered double hydroxide, wherein 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, 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, and x is more than 0 and 0.6 or less, wherein the outer layer contains an organic acid derivative or a salt thereof, and 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 more compared to that before the washing.

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＋ M2 ３＋ is Al ３＋ and Fe ３＋ The complex according to claim 1 or 2, comprising one or more species selected from the group consisting of:

4. The complex according to any one of claims 1 to 3, wherein in formula (I), 2×(1−x) / x is 1.5 or more and 7.5 or less.

5. The composite according to any one of claims 1 to 4, wherein the Fe content is 0 ppm by mass or more and 500 ppm by mass or less.

6. The complex according to any one of claims 1 to 5, 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 according to any one of claims 1 to 6, wherein the tensile strength is 1 / g or less.

8. The composite according to any one of claims 1 to 7, having an average aspect ratio of 2 or more and 150 or less.

9. The composite according to any one of claims 1 to 8, having a loss on drying of 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, wherein the layered double hydroxide is represented by 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, 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, and x is more than 0 and 0.6 or less, and the outer layer contains an organic acid derivative or a salt thereof, the method comprising: a slurry production step of producing a slurry of the layered double hydroxide; a mixing step of mixing the slurry of the layered double hydroxide with the organic acid derivative or the salt thereof; and a heating step of heating the layered double hydroxide and the organic acid derivative or the salt thereof 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.

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