JP4478785B2 - Highly dispersible hydroxide resin compounding agent and resin composition - Google Patents
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本発明は、新規で有用な層状複水酸化物、該複合物を水中で分散させたコロイド溶液、該コロイド溶液を使用した樹脂組成物、及びこれらの製造方法に関する。 The present invention relates to a novel and useful layered double hydroxide, a colloidal solution in which the composite is dispersed in water, a resin composition using the colloidal solution, and a method for producing them.
層状複水酸化物またはハイドロタルサイトと呼ばれる化合物は、以下の一般式で表される層状化合物である。
[M2+ 1-xM3+ x(OH)2][An- x/n・mH2O]または[Li＋ 1/3Al3+ 2/3(OH)2][An- 1/3n・mH2O〕
ここで M2+ は2価金属、 M3+ は3価金属（3価金属の一部を4価金属に置き換えることも可能）、An- は層間陰イオンで、mは適当な有理数、nは整数、xは1を超えない有理数である。一般式において前半部の[M2+ 1-xM3+ x(OH)2]または[Li＋ 1/3Al3+ 2/3(OH)2]は、層状複水酸化物の基本層またはホスト層と呼ばれる金属水酸化物層であり、この基本層が一般式後半部の陰イオンと水分子から成る中間層またはゲスト層と呼ばれる層と交互に積み重なっている。
A compound called layered double hydroxide or hydrotalcite is a layered compound represented by the following general formula.
[M 2+ 1-x M 3+ x (OH) 2] [A n- x / n · mH 2 O] or [Li + 1/3 Al 3+ 2/3 ( OH) 2] [A n- (1 / 3n・ mH 2 O)
Here M 2+ is a divalent metal, M 3+ is (also possible to replace some of the trivalent metal tetravalent metal) trivalent metal, A n-in interlayer anion, m is an appropriate rational number, n is an integer and x is a rational number not exceeding 1. In the general formula, [M 2+ 1-x M 3+ x (OH) 2 ] or [Li + 1/3 Al 3+ 2/3 (OH) 2 ] in the first half is the base layer of the layered double hydroxide Alternatively, it is a metal hydroxide layer called a host layer, and this basic layer is alternately stacked with a layer called an intermediate layer or guest layer consisting of anions and water molecules in the latter half of the general formula.
層状複水酸化物は、難燃化剤、安定剤、成型改質剤および保温性改良剤などとして樹脂に添加され利用されてきた。特に、環境への配慮から毒性のない金属より構成されているMg-Al系層状複水酸化物は、層状複水酸化物のなかでも最もよく利用されている。しかし、樹脂練り込み時の分散性は悪く、このための様々な検討がなされてきた（特許文献１〜３参照）。 過去のこうした検討は、ある程度の分散性向上を達成してはいるが、技術の進歩に伴い、分散性への要求はさらに厳しくなることは必至である。 Layered double hydroxides have been added to resins and used as flame retardants, stabilizers, molding modifiers, and heat retention improvers. In particular, Mg—Al-based layered double hydroxides composed of non-toxic metals from the viewpoint of the environment are most often used among layered double hydroxides. However, the dispersibility at the time of resin kneading is poor, and various studies for this purpose have been made (see Patent Documents 1 to 3). These past studies have achieved some degree of improvement in dispersibility, but with the advancement of technology, the demand for dispersibility will inevitably become stricter.
分散性向上の技術開発として、１つには、層状複水酸化物自体を直接樹脂中においてナノメーターレベルで分散する技術が報告されている。イオンのモノマー（フェノール性水酸基を有する化合物）を層状複水酸化物の層間陰イオンとして含有させたものを、フェノール樹脂又は変性フェノール樹脂の合成段階で混合させることによって、層状複水酸化物を剥離した状態で分散させた樹脂組成物が発明されている（特許文献４〜７参照）。これは、層状複水酸化物の層間に存在するモノマーが重合して分子量が増大することにより層間を非常に大きく押し広げたため、層状複水酸化物が樹脂合成過程において剥離状態で分散したものである。 As a technical development for improving dispersibility, one technique has been reported in which a layered double hydroxide itself is directly dispersed in a resin at a nanometer level. Peeling layered double hydroxide by mixing ionic monomer (compound having phenolic hydroxyl group) as interlayer anion of layered double hydroxide at the synthesis stage of phenolic resin or modified phenolic resin Invented resin compositions dispersed in such a state (see Patent Documents 4 to 7). This is because the layered double hydroxide was dispersed in the exfoliated state during the resin synthesis process because the monomers present between the layers of the layered double hydroxide were polymerized and the molecular weight increased and the layer was greatly expanded. is there.
ただし、このような手法は、陰イオンモノマーが存在する樹脂のみに適用が限られ、一般的には、他の層状無機化合物の例と同様、熱硬化性樹脂との樹脂組成物に限られ、熱可塑性樹脂に層状複水酸化物を剥離状態で分散させることは不可能である。また、剥離の機構及び剥離の状態は明らかではないが、特許文献８においては、層状複水酸化物をグリセロールと反応させて層間距離を14.2オングストロームに広げたものをエチレン−酢酸ビニル共重合体と混錬することによって、層状複水酸化物を樹脂中で剥離した状態で分散した樹脂組成物を得たと報告している。 However, such a method is limited to application only to a resin in which an anionic monomer is present, and is generally limited to a resin composition with a thermosetting resin, as in the case of other layered inorganic compounds, It is impossible to disperse the layered double hydroxide in a peeled state in the thermoplastic resin. In addition, although the mechanism of peeling and the state of peeling are not clear, in Patent Document 8, a layered double hydroxide reacted with glycerol to expand the interlayer distance to 14.2 angstroms is referred to as an ethylene-vinyl acetate copolymer. It is reported that by kneading, a resin composition was obtained in which the layered double hydroxide was dispersed in a state of being peeled in the resin.
一方、上述の層状複水酸化物自体を樹脂に直接分散させるような方法とは全く異なり、層状複水酸化物の主要構成成分である金属水酸化物層を構造中に有する微小粒子を合成してから、これを樹脂に高度に分散させる手法が考えられている。すなわち、高度に薄片化してコロイド粒子に転化した層状複水酸化物誘導体を作製し、この誘導体と樹脂との組成物を得る方法が報告されるようになった。これが可能となった背景には、最近の２つの論文において（１つは本発明者によるもの）、層状複水酸化物を有機溶媒中で、層剥離させて分散させる報告があったためである。この技術を利用すれば、溶媒中で層状複水酸化物が層剥離して薄片化したコロイド粒子化層状複水酸化物誘導体が得られ、溶媒に溶かした樹脂と溶液中で分子レベルまたは分子レベルに近い状態で混合可能である。 On the other hand, unlike the above-described method in which the layered double hydroxide itself is directly dispersed in the resin, fine particles having a metal hydroxide layer, which is the main component of the layered double hydroxide, in the structure are synthesized. Then, a method of highly dispersing this in a resin has been considered. That is, a method of producing a layered double hydroxide derivative that has been highly exfoliated and converted into colloidal particles and obtaining a composition of this derivative and a resin has been reported. This is because the recent two papers (one by the present inventor) reported that the layered double hydroxide was dispersed and separated in an organic solvent. If this technology is used, a layered double hydroxide derivative in which a layered double hydroxide is exfoliated and exfoliated in a solvent is obtained, and a molecular level or molecular level is obtained in a resin and a solution dissolved in a solvent. Can be mixed in a state close to.
この方法は、層状複水酸化物を直接樹脂または樹脂の前駆体に投入するのではなく、一旦、層状複水酸化物複合物を溶媒中で層剥離して安定なコロイド粒子化した特殊な層状複水酸化物誘導体を作製するため、特許文献４−８に記述の方法とは全く異なる。しかし、層状複水酸化物誘導体は層状複水酸化物の主要構成成分である金属水酸化物成分を有しているため、樹脂に添加した際に層状複水酸化物と同様の特性向上（難燃化、安定化、成型性改良および保温性改良など）が期待できる。溶媒中に剥離・分散に要する条件は、前者（非特許文献１参照）は溶媒としてホルムアミドを用いて室温で即時反応、後者（非特許文献２参照）では、ブタノールを用いて120℃−16時間還流を必要とするため、反応は前者が極めて簡便である。前者はMg-Al-系層状複水酸化物において、層間陰イオンとしてグリシンを用い、後者は、Zn-Al系層状複水酸化物においてドデシル硫酸を用いている。 In this method, the layered double hydroxide is not directly added to the resin or the resin precursor, but once the layered double hydroxide composite is separated in a solvent to form a stable colloidal particle. In order to produce a double hydroxide derivative, it is completely different from the method described in Patent Documents 4-8. However, since the layered double hydroxide derivative has a metal hydroxide component that is a main component of the layered double hydroxide, the same characteristic improvement as the layered double hydroxide when added to the resin (difficulty) Combustion, stabilization, moldability improvement, heat retention improvement, etc.) can be expected. The conditions required for peeling and dispersion in a solvent are as follows: the former (see Non-patent Document 1) uses formamide as a solvent and immediately reacts at room temperature; the latter (see Non-Patent Document 2) uses butanol at 120 ° C. for 16 hours. Since the reflux is required, the former is very simple. The former uses glycine as an interlayer anion in the Mg-Al-based layered double hydroxide, and the latter uses dodecyl sulfate in the Zn-Al-based layered double hydroxide.
前者の手段に関しては、グリシン以外のアミノ酸を層状複水酸化物に挿入してもホルムアミド中でグリシンと同様の層剥離が起こることを本発明者らはすでに見出している（特許文献９−１１）。グリシンを層間陰イオンとした層状複水酸化物をホルムアミドに分散させ、溶媒に溶かした樹脂と溶液中で混合し、溶媒の除去によって樹脂とのナノコンポジットを作製した例は、樹脂としてポリビニルアルコール及び、ポリメチルメタクリ酸メチルを使用した例において報告がある（非特許文献３，４）。しかし、層状複水酸化物からコロイド粒子に転化した層状複水酸化物誘導体を作製するために用いる適当な溶媒は非特許文献1に類した方法ではホルムアミド、非特許文献2に類した方法では高級アルコールまたはキシレンが知られているにすぎず、環境への有害性のない溶媒を用いて作製する類似の樹脂用配合剤は知られていなかった。 As for the former means, the present inventors have already found that delamination similar to glycine occurs in formamide even when an amino acid other than glycine is inserted into the layered double hydroxide (Patent Documents 9-11). . An example in which a layered double hydroxide having glycine as an interlayer anion is dispersed in formamide, mixed with a resin dissolved in a solvent in a solution, and a nanocomposite with the resin by removing the solvent is used as a resin. There is a report in an example using methyl polymethyl methacrylate (Non-patent Documents 3 and 4). However, a suitable solvent used for preparing a layered double hydroxide derivative converted from layered double hydroxide to colloidal particles is formamide in the method similar to Non-Patent Document 1, and high-grade in the method similar to Non-Patent Document 2. Only alcohols or xylenes are known, and no similar resin compounding agents made with solvents that are not harmful to the environment have been known.
これに対して、本発明者は水溶媒で、層状複水酸化物をコロイド粒子に転化する方法を見出したが（特許文献１２）、コロイド粒子が安定的である配合では、コロイド粒子に転化する熟成期間が長く、逆にコロイド粒子に転化する熟成期間が短い配合では、条件が特定されないが、コロイド粒子が凝集して沈降してしまうことがあり、コロイド粒子の安定性が悪かった。このため、層状複水酸化物を樹脂中に高分散させるために、効率的で安定的なコロイド粒子に環境に優しい溶媒で転化させる技術は未だ確立されていない状況であった。 On the other hand, the present inventor found a method for converting a layered double hydroxide into colloidal particles with an aqueous solvent (Patent Document 12). However, when the colloidal particles are stable, they are converted into colloidal particles. When the aging period is long and conversely the aging period for converting to colloidal particles is short, the conditions are not specified, but the colloidal particles may aggregate and settle, and the stability of the colloidal particles is poor. For this reason, in order to highly disperse the layered double hydroxide in the resin, a technology for converting the efficient and stable colloidal particles into an environment-friendly solvent has not yet been established.
本発明の課題は、上記従来の層状複水酸化物の樹脂に対する分散性の低さに関する問題点を、環境に優しい手段を用いて解消し、具体的には、水中でより効率的かつ安定的にコロイド粒子に転化しうる層状複水酸化物複合物、これを用いた樹脂配合剤、及び該コロイド粒子化金属水酸化物が高度に分散された樹脂組成物を提供しようとするものである。 The problem of the present invention is to solve the above-mentioned problems related to low dispersibility of the conventional layered double hydroxide resin by using environmentally friendly means, specifically, more efficient and stable in water. It is intended to provide a layered double hydroxide composite that can be converted into colloidal particles, a resin compounding agent using the same, and a resin composition in which the colloidal particle metal hydroxide is highly dispersed.
本発明者は、上記従来技術の層状複水酸化物の樹脂に対する分散性の低さに関する問題点を環境に優しい手段を用いて解消するため鋭意研究の結果、層状複水酸化物における中間層を構成する層間イオンとして、カルボン酸イオンを含有させる手段により、層状複水酸化物複合物を新たに得るとともに、このようにして得られた層状複水酸化物複合物が、有機溶媒を使用せずに、水のみでも容易に、かつ従来と比較してより効率的かつ安定的に分散し、層剥離してコロイド粒子に転化しうることを見いだし、本発明を完成させるに至ったものである。
すなわち、本発明は以下に示すとおりのものである。
As a result of earnest research, the present inventor has solved an intermediate layer in the layered double hydroxide in order to solve the above-described problems related to the low dispersibility of the layered double hydroxide in the resin using an environmentally friendly means. A layered double hydroxide composite is newly obtained by means of containing carboxylate ions as interlayer ions to constitute, and the layered double hydroxide composite thus obtained does not use an organic solvent. In addition, the present inventors have found that it can be easily dispersed with water alone more efficiently and stably as compared with the prior art, and can be separated into layers and converted into colloidal particles, thereby completing the present invention.
That is, the present invention is as follows.
（１） 金属水酸化物からなる基本層と、陰イオン及び水分子とからなる中間層が交互に積層した層状複水酸化物において、中間層を構成する層間イオンとして、乳酸イオンを含有する層状複水酸化物を水中に分散させたコロイド溶液であって、該溶液中において層状複水酸化物が層剥離によって薄片化されたコロイド粒子に転化されていることを特徴とする、上記コロイド溶液。
（２） 上記（１）に記載の層状複水酸化物複合物を水中に分散させることにより形成されたコロイド粒子が樹脂中に含有されていることを特徴とする、樹脂組成物。
（３） 上記（１）に記載のコロイド溶液を、樹脂と溶液状態で混合し、溶媒を除去することにより得られたものであることを特徴とする、上記（２）に記載の樹脂組成物。
（４） 上記（１）に記載のコロイド溶液を含有することを特徴とする、樹脂配合剤。
（５） 異なる価数の金属の組み合わせを含む２種以上の金属の塩と乳酸塩とをアルカリ条件下溶液状態で混合させることにより、または、異なる価数の金属の組み合わせを含む乳酸の金属塩をアルカリ溶液に混合させることにより共沈澱させ、得られた層状複水酸化物を水中に分散させ、層状複水酸化物を層剥離によって薄片化されたコロイド粒子に転化させることを特徴とする、コロイド溶液の製造方法。
（６） 上記（５）に記載のコロイド溶液を樹脂溶液と混合し、溶媒を除去することを特徴とする、樹脂組成物の製造方法。
（７） 上記（２）又は（３）に記載の樹脂組成物を樹脂配合剤として樹脂に配合してなる樹脂組成物。
(1) In a layered double hydroxide in which a basic layer made of a metal hydroxide and an intermediate layer made of an anion and a water molecule are alternately laminated, a layered form containing lactate ions as interlayer ions constituting the intermediate layer A colloidal solution in which a double hydroxide is dispersed in water, wherein the layered double hydroxide is converted into colloidal particles that have been exfoliated by delamination in the solution.
(2) A resin composition comprising colloidal particles formed by dispersing the layered double hydroxide composite according to (1) in water.
(3) The resin composition according to (2) above, which is obtained by mixing the colloidal solution according to (1) with a resin in a solution state and removing the solvent. .
(4) A resin compounding agent comprising the colloid solution described in (1 ) above .
(5) A metal salt of lactic acid containing a combination of two or more metal salts containing a combination of metals having different valences and a lactate in a solution state under alkaline conditions, or a combination of metals having different valences Is co-precipitated by mixing with an alkaline solution , the obtained layered double hydroxide is dispersed in water, and the layered double hydroxide is converted into flaky colloidal particles by delamination, A method for producing a colloidal solution.
(6) A method for producing a resin composition, comprising mixing the colloidal solution according to (5 ) above with a resin solution and removing the solvent.
(7) The resin composition formed by mix | blending resin with the resin composition as described in said (2) or (3) as a resin compounding agent.
本発明の層状複水酸化物複合物は、有機溶媒を使用する従来技術とは異なり、水のみで容易に層剥離、薄片化して分散し、効率的かつ安定的にコロイド粒子に転化する。また、このコロイド粒子化溶液は樹脂配合剤として、樹脂溶液と混合することにより、上記複合物の主要構成成分である金属水酸化物成分が高度に分散した樹脂組成物を製造することができる。したがって、本発明は、従来技術の環境上の問題を解消するとともに、上記金属水酸化物成分の樹脂への分散に起因する、難燃性、安定性、成型性、機械的強度および保温性等の様々な特性に優れる樹脂組成物を提供することが可能になる。 Unlike the conventional technique using an organic solvent, the layered double hydroxide composite of the present invention is easily separated and separated into thin pieces with water alone and dispersed into colloidal particles efficiently and stably. Moreover, this colloid particle-ized solution can be mixed with a resin solution as a resin compounding agent to produce a resin composition in which a metal hydroxide component, which is a main constituent of the composite, is highly dispersed. Therefore, the present invention solves the environmental problems of the prior art, and flame retardancy, stability, moldability, mechanical strength, heat retention, etc. due to dispersion of the metal hydroxide component into the resin. It becomes possible to provide a resin composition excellent in various properties.
層状複水酸化物は、上記したように金属水酸化物からなる基本層と、陰イオン及び水分子とからなる中間層が交互に積層した化合物である。
本発明に用いる樹脂配合剤前駆体としての層状複水酸化物は、１種または２種以上の２価金属塩及び１種または２種以上の３価金属塩、あるいはさらに３価金属塩の一部を４価金属塩としたもの、若しくは一価金属塩と３価金属塩の組み合わせからなるものと、さらに中間層を形成する層間イオン成分として、１種または２種以上のカルボン酸とを、アルカリ条件下、溶液状態で混合することにより共沈殿させることにより得られる。このようにして得られた層状複水酸化物は水のみでも層剥離により薄片化し、コロイド粒子に転化する。
A layered double hydroxide is a compound in which a basic layer made of a metal hydroxide and an intermediate layer made of an anion and a water molecule are alternately laminated as described above.
The layered double hydroxide as a resin compounding agent precursor used in the present invention is one or more divalent metal salts and one or more trivalent metal salts, or further one of trivalent metal salts. A part of which is a tetravalent metal salt, or a combination of a monovalent metal salt and a trivalent metal salt, and further, one or more carboxylic acids as an interlayer ion component for forming an intermediate layer, It can be obtained by coprecipitation by mixing in solution under alkaline conditions. The layered double hydroxide thus obtained is thinned by delamination even with water alone and converted into colloidal particles.
上記本発明の層状複水酸化物の製造において使用するカルボン酸としては、乳酸、酢酸、酪酸、マロン酸、コハク酸、アジピン酸、ピメリン酸等の有機カルボン酸が挙げられるが、これらの中では一価の有機カルボン酸が好ましい。
本発明における前駆体としての層状複水酸化物を一般式で表すと、以下の通りである。
[M2+ 1-xM3+ x(OH)2][An- x/n・mH2O]
ここで M2+ は2価金属、 M3+ は3価金属（3価金属の一部を4価金属に置き換えることも可能）、An- は層間陰イオンで、mは適当な有理数、nは整数、xは1を超えない有理数である。一般式において前半部の[M2+ 1-xM3+ ｘ(OH)2]は、層状複水酸化物の基本層またはホスト層と呼ばれる金属水酸化物層であり、この基本層が一般式後半部の陰イオンと水分子から成る中間層またはゲスト層と呼ばれる層と交互に積み重なっている。同後半部の[An- x/n・mH2O]は、陰イオン群と水分子からなる中間層であり、An-は、１種または２種以上の有機酸のカルボン酸イオン、金属塩由来の陰イオン及びその他上記共沈殿溶液中に含まれる水酸化物イオン、製造過程で混入する炭酸イオン等の各陰イオンを表す。
Examples of the carboxylic acid used in the production of the layered double hydroxide of the present invention include organic carboxylic acids such as lactic acid, acetic acid, butyric acid, malonic acid, succinic acid, adipic acid, and pimelic acid. Monovalent organic carboxylic acids are preferred.
The layered double hydroxide as a precursor in the present invention is represented by the following general formula.
[M 2+ 1-x M 3+ x (OH) 2 ] [A n- x / n・ mH 2 O]
Here M 2+ is a divalent metal, M 3+ is (also possible to replace some of the trivalent metal tetravalent metal) trivalent metal, A n-in interlayer anion, m is an appropriate rational number, n is an integer and x is a rational number not exceeding 1. [M 2+ 1-x M 3+ x (OH) 2 ] in the first half of the general formula is a metal hydroxide layer called a base layer or a host layer of a layered double hydroxide. In the latter half of the formula, the layers are alternately stacked with an intermediate layer or guest layer composed of anions and water molecules. [A n− x / n · mH 2 O] in the latter half is an intermediate layer composed of anion groups and water molecules, and A n− is a carboxylate ion of one or more organic acids, It represents anions derived from metal salts and other anions such as hydroxide ions contained in the coprecipitation solution and carbonate ions mixed in the production process.
本発明の層状複酸化物をさらに具体的に説明すると、上記２価金属イオンは、具体的には、Mg2+、Zn2+、Co2+、Ni2+及びCu2+等であり、同３価金属イオンは、Al3+、Fe3+、Cr3+及びCo3+等で、４価金属イオンはZr4+やSn4+等である。また、上記金属塩由来の陰イオンには、Cl-、NO3 -及びSO4 2-等の無機酸イオン等が挙げられる。 本発明の層状酸化物としては、Mg-Al系層状複酸化物、Ni-Al系層状複酸化物、Co-Al系層状複酸化物あるいはZn-Al系層状複酸化物が挙げられるが、特にこれらに限定されるものではない。また、上記構造式中ｘは0.15〜0.33が好ましい。 The layered double oxide of the present invention will be described more specifically. Specifically, the divalent metal ions are Mg 2+ , Zn 2+ , Co 2+ , Ni 2+, Cu 2+ and the like, The trivalent metal ions are Al 3+ , Fe 3+ , Cr 3+ and Co 3+ , and the tetravalent metal ions are Zr 4+ and Sn 4+ . Examples of the anion derived from the metal salt include inorganic acid ions such as Cl − , NO 3 − and SO 4 2− . Examples of the layered oxide of the present invention include Mg-Al-based layered double oxide, Ni-Al-based layered double oxide, Co-Al-based layered double oxide, or Zn-Al-based layered double oxide. It is not limited to these. In the above structural formula, x is preferably 0.15 to 0.33.
また、金属水酸化物層が１価金属と３価金属からなる場合として、例えば、リチウムとアルミニウムからなる金属水酸化物層を有する層状複水酸化物は、以下の式で表される。
[Li＋ 1/3Al3+ 2/3(OH)2][An- 1/3n・mH2O]
ここで上記式中の符号の意味は、前記一般式と同様である。
水酸化物層がリチウムとアルミニウムの層状複水酸化物である場合には、その製法において金属塩として、アルミニウム塩とリチウム塩を使用するが、水酸化アルミニウムの副生を防ぐため、共沈時にはリチウム塩は過剰に投入する。これらの層状複水酸化物は、リチウムとアルミニウムの水酸化物からなる基本層と、陰イオン及び水分子とからなる中間層が交互に積層しており、中間層を構成する層間イオンとして、１種または２種以上の有機酸のカルボン酸イオンを含有するものである。
Moreover, as a case where the metal hydroxide layer is composed of a monovalent metal and a trivalent metal, for example, a layered double hydroxide having a metal hydroxide layer composed of lithium and aluminum is represented by the following formula.
[Li + 1/3 Al 3+ 2/3 (OH) 2 ] [A n- 1 / 3n・ mH 2 O]
Here, the meanings of the symbols in the above formula are the same as those in the general formula.
When the hydroxide layer is a layered double hydroxide of lithium and aluminum, an aluminum salt and a lithium salt are used as the metal salt in the production method, but in order to prevent by-production of aluminum hydroxide, An excessive amount of lithium salt is added. In these layered double hydroxides, a basic layer made of lithium and aluminum hydroxide and an intermediate layer made of anions and water molecules are alternately laminated, and the interlayer ions constituting the intermediate layer are 1 It contains a carboxylate ion of a seed or two or more organic acids.
本発明に用いる前駆体である層状複水酸化物の合成法は、例えば、マグネシウム、亜鉛、コバルト、ニッケル等の２価金属、及びアルミニウム、鉄、クロム等の３価金属の硝酸塩、塩化物、硫酸塩の水溶液、あるいはこれら金属のカルボン酸塩を溶かした水溶液と、１種または２種以上のカルボン酸を溶かした水溶液を調整し、この２つの水溶液をアルカリ性条件下でゆっくりと混合する方法が好適である。合成後の層状複水酸化物は、層剥離性、分散性の点で乾燥させないことが好ましい。
本発明により得られた樹脂配合剤前駆体としての層状複水酸化物は、合成時に副生する多量の塩を純水にて洗浄除去した後、そのまま水中に静置することによって、層剥離により薄片化したコロイド粒子となって分散し、コロイド粒子化した層状複水酸化物誘導体（コロイド粒子化水酸化物系複合物）に転化する。コロイド粒子化までの時間は、分散させる量や組成によって変化するが、早い系では12時間程度で転化する。また、得られたコロイド溶液は、空気中での取り扱いや保存中に再凝集して沈殿することはない。
The method for synthesizing the layered double hydroxide used as a precursor for the present invention includes, for example, divalent metals such as magnesium, zinc, cobalt and nickel, and nitrates, chlorides of trivalent metals such as aluminum, iron and chromium. There is a method in which an aqueous solution of sulfate or an aqueous solution in which these metal carboxylates are dissolved and an aqueous solution in which one or more carboxylic acids are dissolved are prepared, and these two aqueous solutions are slowly mixed under alkaline conditions. Is preferred. The layered double hydroxide after synthesis is preferably not dried in terms of delamination and dispersibility.
The layered double hydroxide as a resin compounding agent precursor obtained by the present invention is obtained by removing a large amount of salt produced as a by-product at the time of synthesis by washing with pure water, and then leaving it in water as it is, thereby peeling off the layer. It is dispersed as exfoliated colloidal particles and converted into a colloidal layered layered double hydroxide derivative (colloidalized hydroxide-based composite). The time until colloidal particles changes depending on the amount and composition to be dispersed, but in a fast system, the conversion takes about 12 hours. Moreover, the obtained colloidal solution does not re-aggregate and precipitate during handling and storage in air.
本発明によるコロイド粒子化水酸化物系複合物は、コロイド溶液状態のまま、溶媒に溶かした樹脂と混合して、その後、溶媒を除去すると、ナノメーターから数百ナノメーターレベルでコロイド粒子化水酸化物系複合物が樹脂中に分散された形態で樹脂と複合化した樹脂組成物を得ることができる。
本発明のコロイド粒子化水酸化物系複合物が配合される樹脂としては、水溶性ポリマーや、水酸基等の親水性基あるいは水溶性を付与する基を導入して水に可溶にした変性ポリエチレン、変性ポリプロピレン、変性ポリスチレン、変性ポリ塩化ビニル、変性ポリ乳酸及びそれらのポリマーアロイなどが挙げられる。水中で薄片化したコロイド粒子化水酸化物系複合物の液状物と変性ポリマー溶液を混合した後、溶媒を除去することによってナノメーターから数百ナノメーターレベルでコロイド粒子化水酸化物系複合物が樹脂中に分散された形態で樹脂と複合化した樹脂組成物を得ることができる。
The colloidal particulate hydroxide-based composite according to the present invention is mixed in a colloidal solution with a resin dissolved in a solvent, and then the solvent is removed. A resin composition in which an oxide composite is combined with a resin in a form dispersed in the resin can be obtained.
Examples of the resin compounded with the colloidal particle hydroxide-based composite of the present invention include a water-soluble polymer, a modified polyethylene that has been made water-soluble by introducing a hydrophilic group such as a hydroxyl group or a group that imparts water solubility. , Modified polypropylene, modified polystyrene, modified polyvinyl chloride, modified polylactic acid, and polymer alloys thereof. Colloidalized hydroxide-based composite at the nanometer to hundreds of nanometer level by mixing the modified polymer solution with the liquid of colloidalized hydroxide-based composite exfoliated in water Can be obtained by combining the resin with the resin dispersed in the resin.
この樹脂組成物は、そのまま樹脂組成物として用いても、他の樹脂組成物に対する添加剤として用いてもよい。添加剤として用いる場合は通常の溶融混錬で樹脂や樹脂組成物と複合化することが可能である。上記樹脂溶液の調製に使用する溶媒は、水あるいは有機溶媒であっても、水と混和性のある溶媒であれば使用できる。
したがって、本発明は、コロイド粒子化水酸化物系複合物を樹脂に極めて高分散で添加できるため、各種樹脂に対する難燃化、安定化、成型改質、高強度化および保温性改良等に極めて有用な樹脂組成物を提供するものである。
本発明の樹脂組成物は、あらかじめ層状複水酸化物を水中で分散させることにより、コロイド粒子化した水酸化物系複合物を、樹脂中に添加したものであって、上記従来技術に示されるようなモノマー陰イオンを有する層状複水酸化物を使用し、樹脂重合反応において該モノマーを反応させることにより樹脂中に分散させたものではない。このような方法では、配合する樹脂が限られ、層状複水酸化物の樹脂配合材としての用途は狭まる。
This resin composition may be used as it is as a resin composition or as an additive to other resin compositions. When used as an additive, it can be combined with a resin or resin composition by ordinary melt-kneading. The solvent used for preparing the resin solution may be water or an organic solvent as long as it is miscible with water.
Therefore, the present invention can add the colloidal particle hydroxide hydroxide compound to the resin with extremely high dispersion, so it is extremely effective for flame retardancy, stabilization, molding modification, high strength and heat retention improvement for various resins. A useful resin composition is provided.
The resin composition of the present invention is obtained by adding a hydroxide-based composite that has been formed into colloidal particles by dispersing a layered double hydroxide in water in advance into the resin. Such a layered double hydroxide having a monomer anion is used, and the monomer is reacted in a resin polymerization reaction to be dispersed in the resin. In such a method, the resin to mix | blend is restricted and the use as a resin compounding material of a layered double hydroxide becomes narrow.
これに対して、本発明においては、層状複合水酸化物を水中に分散させることにより、層剥離して薄片化し、コロイド粒子化した水酸化物系複合物を、樹脂に直接混合するものであり、この場合、樹脂溶液として親水性あるいは水溶性樹脂溶液を使用するのが好ましいものの、このようにして得られた層状複水酸化物が薄片化して分散した親水性あるいは水溶性樹脂は、疎水性樹脂その他の樹脂の配合剤として使用することができる。例えば、疎水性樹脂であっても、その構造の一部に親水性基あるいは水溶性付与基を導入して、上記親水性あるいは水溶性樹脂との親和性を向上させれば、本発明のコロイド粒子化水酸化物系複合物を含有する上記親水性あるいは水溶性樹脂中に分散された状態で配合することが可能であるし、逆にコロイド粒子化水酸化物系複合物を分散させた親水性あるいは水溶性樹脂に予め適度に疎水性を付与する基が適度に導入されていれば、この樹脂組成物をさらに疎水性樹脂に分散させることも可能であり、その適用範囲は広い。
以下に、本発明の実施例を示すが、本発明は特にこれにより限定されるものではない。
On the other hand, in the present invention, the layered composite hydroxide is dispersed in water, and the hydroxide-based composite that has been exfoliated and flakes into colloidal particles is directly mixed with the resin. In this case, it is preferable to use a hydrophilic or water-soluble resin solution as the resin solution. However, the hydrophilic or water-soluble resin in which the layered double hydroxide obtained in this way has been exfoliated and dispersed is hydrophobic. It can be used as a compounding agent for resins and other resins. For example, even if it is a hydrophobic resin, if the hydrophilic group or water-solubilizing group is introduced into a part of its structure to improve the affinity with the hydrophilic or water-soluble resin, the colloid of the present invention It can be blended in the state of being dispersed in the hydrophilic or water-soluble resin containing the particleized hydroxide-based composite, and conversely, the hydrophilicity in which the colloidal particle-formed hydroxide-based composite is dispersed. If a group imparting moderate hydrophobicity to the water-soluble or water-soluble resin is appropriately introduced in advance, this resin composition can be further dispersed in the hydrophobic resin, and its application range is wide.
Examples of the present invention are shown below, but the present invention is not particularly limited thereby.
〔実施例１〕
D,L-乳酸10.51gを、水で希釈した後、2N-NaOH水溶液を適量加えてpHを10に調整した。これとは別に、仕込比でマグネシウムとアルミニウムのモル比が2:1となるように、乳酸マグネシウム3水和物4.27gと乳酸アルミニウム2.45gを溶かした水溶液を用意し、上述の乳酸水溶液に250ml/hの速度で加えた。このとき、混合溶液は常にpHが10となるように、2N-NaOH水溶液を適宜加えた。以上により得られた共沈殿物を、水洗後、そのまま水中に静置して１晩から数日ほど熟成することによって系全体が半透明であるコロイド溶液となり、層状複水酸化物はコロイド粒子化水酸化物系複合物に転化した。これら一連の実験は、空気中からの炭酸イオンの混入を避けるため、合成および洗浄は、すべて窒素気流中で行い、使用する水も脱イオン・蒸留処理の後、JIS K 0102に従って炭酸を除去した。また、共沈殿物を乾燥させたもの、およびコロイド溶液化後、水を蒸発させて回収した固形物は、X線回折で分析したところ、いずれも層状複水酸化物特有の回折パターンを示した。
[Example 1]
After diluting 10.51 g of D, L-lactic acid with water, an appropriate amount of 2N-NaOH aqueous solution was added to adjust the pH to 10. Separately, prepare an aqueous solution in which 4.27 g of magnesium lactate trihydrate and 2.45 g of aluminum lactate are dissolved so that the molar ratio of magnesium to aluminum is 2: 1 in the charging ratio, and 250 ml of the above-mentioned aqueous lactic acid solution is added. Added at / h speed. At this time, 2N-NaOH aqueous solution was appropriately added so that the mixed solution always had a pH of 10. The coprecipitate obtained as described above is washed with water, left in water as it is, and aged for one to several days to become a semitransparent colloidal solution, and the layered double hydroxide is formed into colloidal particles. Conversion to a hydroxide-based composite. In order to avoid mixing carbonate ions from the air in these series of experiments, synthesis and washing were all performed in a nitrogen stream, and the water used was also deionized and distilled, and then the carbonate was removed according to JIS K 0102. . Moreover, when the coprecipitate was dried and the solid collected by evaporating water after colloidal solution was analyzed by X-ray diffraction, both showed a diffraction pattern peculiar to layered double hydroxides. .
〔実施例２〕
D,L-乳酸10.13gを、水で希釈した後、2N-NaOH水溶液を適量加えてpHを10に調整した。これとは別に、仕込比でマグネシウムとアルミニウムのモル比が3:1となるように、乳酸マグネシウム3水和物4.81gと乳酸アルミニウム1.84gを溶かした水溶液を用意し、上述の乳酸水溶液に250ml/hの速度で加えた。このとき、混合溶液は常にpHが10となるように、2N-NaOH水溶液を適宜加えた。以上により得られた共沈殿物を、水洗後、そのまま水中に静置して１晩から数日ほど熟成することによって系全体が半透明であるコロイド溶液となり、層状複水酸化物はコロイド粒子化水酸化物系複合物に転化した。これら一連の実験は、空気中からの炭酸イオンの混入を避けるため、合成および洗浄は、すべて窒素気流中で行い、使用する水も脱イオン・蒸留処理の後、JIS K 0102に従って炭酸を除去した。また、共沈殿物を乾燥させたもの、およびコロイド溶液化後、水を蒸発させて回収した固形物は、X線回折で分析したところ、いずれも層状複水酸化物特有の回折パターンを示した（図１）。
[Example 2]
After diluting 10.13 g of D, L-lactic acid with water, an appropriate amount of 2N-NaOH aqueous solution was added to adjust the pH to 10. Separately, prepare an aqueous solution in which 4.81 g of magnesium lactate trihydrate and 1.84 g of aluminum lactate were dissolved so that the molar ratio of magnesium and aluminum was 3: 1 in the feed ratio, and 250 ml of the above-mentioned aqueous lactic acid solution was added. Added at / h speed. At this time, 2N-NaOH aqueous solution was appropriately added so that the mixed solution always had a pH of 10. The coprecipitate obtained as described above is washed with water, left in water as it is, and aged for one to several days to become a semitransparent colloidal solution, and the layered double hydroxide is formed into colloidal particles. Conversion to a hydroxide-based composite. In order to avoid mixing carbonate ions from the air in these series of experiments, synthesis and washing were all performed in a nitrogen stream, and the water used was also deionized and distilled, and then the carbonate was removed according to JIS K 0102. . Moreover, when the coprecipitate was dried and the solid collected by evaporating water after colloidal solution was analyzed by X-ray diffraction, both showed a diffraction pattern peculiar to layered double hydroxides. (FIG. 1).
〔実施例３〕
D,L-乳酸9.90gを、水で希釈した後、2N-NaOH水溶液を適量加えてpHを10に調整した。これとは別に、仕込比でマグネシウムとアルミニウムのモル比が4:1となるように、乳酸マグネシウム3水和物5.13gと乳酸アルミニウム1.47gを溶かした水溶液を用意し、上述の乳酸水溶液に250ml/hの速度で加えた。このとき、混合溶液は常にpHが10となるように、2N-NaOH水溶液を適宜加えた。以上により得られた共沈殿物を、水洗後、そのまま水中に静置して１晩から数日ほど熟成することによって系全体が半透明であるコロイド溶液となり、層状複水酸化物はコロイド粒子化水酸化物系複合物に転化した。これら一連の実験は、空気中からの炭酸イオンの混入を避けるため、合成および洗浄は、すべて窒素気流中で行い、使用する水も脱イオン・蒸留処理の後、JIS K 0102に従って炭酸を除去した。また、共沈殿物を乾燥させたもの、およびコロイド溶液化後、水を蒸発させて回収した固形物は、X線回折で分析したところ、いずれも層状複水酸化物特有の回折パターンを示した。
Example 3
After diluting 9.90 g of D, L-lactic acid with water, an appropriate amount of 2N-NaOH aqueous solution was added to adjust the pH to 10. Separately, prepare an aqueous solution in which 5.13 g of magnesium lactate trihydrate and 1.47 g of aluminum lactate are dissolved so that the molar ratio of magnesium to aluminum is 4: 1 in the charging ratio, and 250 ml of the above-mentioned aqueous lactic acid solution is added. Added at / h speed. At this time, 2N-NaOH aqueous solution was appropriately added so that the mixed solution always had a pH of 10. The coprecipitate obtained as described above is washed with water, left in water as it is, and aged for one to several days to become a semitransparent colloidal solution, and the layered double hydroxide is formed into colloidal particles. Conversion to a hydroxide-based composite. In order to avoid mixing carbonate ions from the air in these series of experiments, synthesis and washing were all performed in a nitrogen stream, and the water used was also deionized and distilled, and then the carbonate was removed according to JIS K 0102. . Moreover, when the coprecipitate was dried and the solid collected by evaporating water after colloidal solution was analyzed by X-ray diffraction, both showed a diffraction pattern peculiar to layered double hydroxides. .
〔実施例４〕
D,L-乳酸10.13gを、水で希釈した後、2N-NaOH水溶液を適量加えてpHを10に調整した。これとは別に、仕込比でマグネシウムとアルミニウムのモル比が3:1となるように、乳酸マグネシウム3水和物4.81gと乳酸アルミニウム1.84gを溶かした水溶液を用意し、上述の乳酸水溶液に250ml/hの速度で加えた。このとき、混合溶液は常にpHが10となるように、2N-NaOH水溶液を適宜加えた。以上により得られた共沈殿物を、水洗後、遠心分離により固液分離し、ペースト状の固相のみ乾燥しないように密封して保存した。このように保湿した状態での保存後も、このペースト状の層状複水酸化物は、水中に攪拌して静置すると、１晩から数日ほどで系全体が半透明であるコロイド溶液となり、層状複水酸化物はコロイド粒子化水酸化物系複合物に転化した。これら一連の実験は、空気中からの炭酸イオンの混入を避けるため、合成および洗浄は、すべて窒素気流中で行い、使用する水も脱イオン・蒸留処理の後、JIS K 0102に従って炭酸を除去した。
Example 4
After diluting 10.13 g of D, L-lactic acid with water, an appropriate amount of 2N-NaOH aqueous solution was added to adjust the pH to 10. Separately, prepare an aqueous solution in which 4.81 g of magnesium lactate trihydrate and 1.84 g of aluminum lactate were dissolved so that the molar ratio of magnesium and aluminum was 3: 1 in the feed ratio, and 250 ml of the above-mentioned aqueous lactic acid solution was added. Added at / h speed. At this time, 2N-NaOH aqueous solution was appropriately added so that the mixed solution always had a pH of 10. The coprecipitate obtained above was washed with water, solid-liquid separated by centrifugation, sealed and stored so as not to dry only the pasty solid phase. Even after storage in such a moisturized state, this paste-like layered double hydroxide, when stirred in water and left to stand, becomes a colloidal solution in which the entire system is translucent in about one to several days, The layered double hydroxide was converted into colloidal granulated hydroxide composite. In order to avoid mixing carbonate ions from the air in these series of experiments, synthesis and washing were all performed in a nitrogen stream, and the water used was also deionized and distilled, and then the carbonate was removed according to JIS K 0102. .
〔実施例５〕
実施例１で得られたコロイド粒子化水酸化物系複合物を含有するコロイド溶液をポリビニルアルコール水溶液と固形分で水酸化物系複合物がポリビニルアルコールに対して5wt%となるように混合し、室温で水を蒸発させて除去することにより、透明な樹脂組成物が得られた。得られた樹脂組成物をX線回折で分析したところ、この樹脂組成物は、層状複水酸化物に相当する反射ピークは観測されず、層状複水酸化物が樹脂中に高度に分散されていることが示唆された。
Example 5
The colloidal solution containing the colloidalized hydroxide-based composite obtained in Example 1 was mixed with an aqueous polyvinyl alcohol solution so that the hydroxide-based composite was 5 wt% with respect to the polyvinyl alcohol. A transparent resin composition was obtained by evaporating and removing water at room temperature. When the obtained resin composition was analyzed by X-ray diffraction, no reflection peak corresponding to the layered double hydroxide was observed in this resin composition, and the layered double hydroxide was highly dispersed in the resin. It was suggested that
〔実施例６〕
実施例２で得られたコロイド粒子化水酸化物系複合物を含有するコロイド溶液をポリビニルアルコール水溶液と固形分で水酸化物系複合物がポリビニルアルコールに対して5wt%となるように混合し、室温で水を蒸発させて除去することにより、透明な樹脂組成物が得られた。得られた樹脂組成物をX線回折で分析したところ、この樹脂組成物は、層状複水酸化物の底面反射ピークがごくわずかに観測されるだけで、層状複水酸化物が樹脂中に高度に分散されていることが示唆された。
Example 6
The colloidal solution containing the colloid-particle-formed hydroxide composite obtained in Example 2 was mixed with an aqueous polyvinyl alcohol solution so that the hydroxide composite was 5 wt% with respect to polyvinyl alcohol in a solid content. A transparent resin composition was obtained by evaporating and removing water at room temperature. The obtained resin composition was analyzed by X-ray diffraction. As a result, only a slight bottom reflection peak of the layered double hydroxide was observed in this resin composition. It was suggested that they are dispersed.
〔実施例７〕
実施例３で得られたコロイド粒子化水酸化物系複合物を含有するコロイド溶液をポリビニルアルコール水溶液と固形分で水酸化物系複合物がポリビニルアルコールに対して5wt%となるように混合し、室温で水を蒸発させて除去することにより、透明な樹脂組成物が得られた。得られた樹脂組成物をX線回折で分析したところ、この樹脂組成物は、層状複水酸化物の弱い底面反射ピークが観測されるだけで、層状複水酸化物が樹脂中に、ほぼ高度に分散されていることが示唆された。
Example 7
The colloidal solution containing the colloidalized hydroxide-based composite obtained in Example 3 was mixed with an aqueous polyvinyl alcohol solution so that the hydroxide-based composite was 5 wt% with respect to the polyvinyl alcohol. A transparent resin composition was obtained by evaporating and removing water at room temperature. The obtained resin composition was analyzed by X-ray diffraction. As a result, the resin composition was observed only with a weak bottom reflection peak of the layered double hydroxide. It was suggested that they are dispersed.
〔比較例1〕
実施例1,2および3の共沈殿に準拠して作製した硝酸イオン含有層状複水酸化物を、水洗後、そのまま水中に静置して熟成したが、分散は悪く、層状複水酸化物は容器下部に沈殿し、半透明なコロイド溶液である液状物は得られなかった。
(Comparative Example 1)
The nitrate ion-containing layered double hydroxide prepared in accordance with the coprecipitation of Examples 1, 2 and 3 was aged by standing in water as it was after washing, but the dispersion was poor, and the layered double hydroxide was A liquid which was precipitated at the bottom of the container and was a translucent colloidal solution was not obtained.
〔比較例2〕
実施例1,2および3の共沈殿に準拠して作製した炭酸イオン含有層状複水酸化物を水洗・乾燥後水中に浸したが、分散は悪く、層状複水酸化物は容器下部に沈殿し、半透明なコロイド溶液である液状物は得られなかった。このため、無理に水と炭酸イオン含有層状複水酸化物の混合物をポリビニルアルコール水溶液に加えて溶媒を蒸発させたが、層状複水酸化物の粒子がポリビニルアルコール樹脂中に凝集していることが肉眼でも観察できるほど、固体粉末の分散性が極めて悪い樹脂組成物しか得られなかった。
(Comparative Example 2)
The carbonate ion-containing layered double hydroxide prepared in accordance with the coprecipitation of Examples 1, 2 and 3 was immersed in water after washing and drying, but the dispersion was poor and the layered double hydroxide precipitated at the bottom of the container. A liquid which is a translucent colloidal solution was not obtained. For this reason, the solvent was evaporated by forcibly adding a mixture of water and carbonate ion-containing layered double hydroxide to the polyvinyl alcohol aqueous solution, but the layered double hydroxide particles were agglomerated in the polyvinyl alcohol resin. Only a resin composition with extremely poor dispersibility of the solid powder was obtained so that it could be observed with the naked eye.
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