JP3680988B2 - Sulfonic acid metal salt copolymer lactic acid resin - Google Patents
Sulfonic acid metal salt copolymer lactic acid resin Download PDFInfo
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- JP3680988B2 JP3680988B2 JP2000146633A JP2000146633A JP3680988B2 JP 3680988 B2 JP3680988 B2 JP 3680988B2 JP 2000146633 A JP2000146633 A JP 2000146633A JP 2000146633 A JP2000146633 A JP 2000146633A JP 3680988 B2 JP3680988 B2 JP 3680988B2
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- JP
- Japan
- Prior art keywords
- lactic acid
- metal salt
- resin
- sulfonic acid
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Description
【0001】
【発明の属する技術分野】
本発明は、乳酸系ポリエステルにスルホン酸金属塩を共重合させることにより、無機顔料、着色顔料、フィラー等の分散性を向上させることにより、塗料、コ−ティング材、インキ等に有用な生分解性樹脂に関する。
【0002】
【従来技術・発明が解決しようとする課題】
近年の環境問題に対する意識の高まりから、天然素材または生分解性合成素材を利用した商品の開発が盛んに行われている。ポリ乳酸系樹脂も各種用途開発が盛んに進められているが、無機顔料、着色顔料、フィラー等の分散性が悪いため、塗料、コーティング材、インキ、接着剤等への展開が阻まれていた。
【0003】
【課題を解決するための手段】
本発明者らは、以上の実情に鑑み、乳酸系樹脂にスルホン酸金属塩を導入することを鋭意検討し、特定のスルホン酸金属塩構造を導入することにより、無機顔料、着色顔料、フィラー等の分散性が飛躍的に向上することを発見し、本発明を完成させた。
【0004】
即ち、本発明は、スルホン酸金属塩を10〜200eq/106gの濃度でする脂肪族ポリエステルであり、かつ、乳酸残基を80モル%以上含有し、そのうちL乳酸とD乳酸のモル比(L/D)が1〜9であることを特徴とするスルホン酸金属塩共重合乳酸系樹脂と溶剤からなる組成物に関する。
【0005】
本発明における乳酸系樹脂は、乳酸残基を80モル%以上含有していることが必要であり、好ましくは、90モル%以上である。80モル%未満では、良好な生分解性および塗膜物性は得られない。
【0006】
また、L乳酸とD乳酸のモル比(L/D)が1〜9であることも必要であり、好ましくは1〜5.6である。L/Dが9を超えると、汎用溶剤に対する当該ポリエステルの溶解性が悪くなり、塗料、インキ、接着剤として使用できなくなる。L/Dが1未満(D乳酸過剰)であると原料コストが高くなる。
なお、乳酸としては、L乳酸、D乳酸、DL乳酸のいずれも用いることができる。
【0007】
本発明の乳酸系樹脂におけるスルホン酸金属塩濃度は10〜200eq/106gの濃度範囲で共重合させる必要がある。10eq/106g以下であると、良好な無機顔料、有機顔料等の分散性が得られないことがある。また、200eq/106gを超えると、樹脂溶液粘度が高くなりすぎて、塗料、インキ、接着剤などにおける良好なコーティング適性が得られないことがある。
【0008】
本発明の乳酸系樹脂にスルホン酸金属塩を導入させる方法としては、ポリ乳酸と共重合可能なスルホン酸金属塩基を持った化合物を共重合させる方法、得られたポリ乳酸系樹脂を公知の方法でスルホン化する方法、等挙げられるが、特に限定するものではないが、ポリ乳酸と共重合可能なスルホン酸金属塩基を持った化合物を共重合させる方法が好ましい。
【0009】
ポリ乳酸と共重合可能なスルホン酸金属塩基を持った好ましい化合物としては、下記式(I)、又は(II)で挙げる化合物が挙げられる。
【化1】
(但し、R1、R2は炭素数20以下のアルキル基であり、MはLi、Na、Kを表す。)
HO−R3−SO3M 式(II)
(但し、R3、はそれぞれ、炭素数20以下のアルキル基を表し、MはLi、Na、Kを表す。)
【0010】
本発明における乳酸系樹脂の還元粘度は0.3〜1.5dl/gの範囲であることが好ましい。還元粘度が0.3dl/gよりも低いと、塗膜物性が低下してしまい、塗料、インキ、接着剤等で使用する場合問題が生じることがある。また還元粘度が高すぎると、塗料、インキ、接着剤等の溶液粘度が増大し、良好なコーティング適性が得られないことがある。
なお、当該還元粘度は、サンプル濃度0.125g/25ml、測定溶剤クロロホルム、測定温度25℃で、ウベローデ粘度管を用いて測定した値である。
【0011】
当該乳酸系樹脂には、乳酸以外にも、例えば乳酸以外のオキシ酸系化合物、コハク酸等のジカルボン酸、プロピレングリコール等のジオール、グリセリン等のポリオール化合物等の生分解性を有する化合物を用いることができる。
なお、式(I)、(II)の構造がポリエステル中に10〜200eq/106gの範囲で共重合されていれば、乳酸以外の他の共重合成分は0%でもよい。
【0012】
乳酸以外のオキシ酸としては、例えば、グリコール酸、カプロラクトン、2−ヒドロキシイソ酪酸、3−ヒドロキシ酪酸、4−ヒドロキシ酪酸、16−ヒドロキシヘキサデカン酸、2−ヒドロキシ−2−メチル酪酸、10−ヒドロキシステアリン酸、リンゴ酸、クエン酸、グルコン酸等が挙げられる。
【0013】
本発明における乳酸系樹脂のTgは35〜60℃であることが必要であり、好ましくは、40〜55℃である。35〜60℃の範囲であれば、良好な塗膜物性が得られる。
Tgは、例えば、乳酸系樹脂中の共重合成分の割合を変化させることにより調製することができる。
なお、当該Tgは、DSC(示差走査熱量計)法により測定した値である。
【0014】
当該、乳酸系樹脂の製造方法としては、特に限定されず、従来公知の方法を用いることができる。例えば、乳酸の二量体であるラクチドと、乳酸以外の前期生分解性を有する化合物を溶融混合し、公知の開環重合触媒(例えばオクチル酸スズ、アルミニウムアセチルアセトナート等)を使用して加熱開環重合させる方法や、加熱および減圧による直接脱水重縮合を行う方法等が挙げられる。
【0015】
【実施例】
以下に実施例を挙げて本発明をより詳細に説明するが、本発明はこれらに限定されるものではない。
【0016】
実施例1
DL−ラクチド500部、5−ナトリウムスルホ−イソフタル酸のエチレングリコールエステル3.56部、開環重合触媒としてオクチル酸錫0.1部を4つ口フラスコに仕込み、窒素雰囲気下、190℃で1時間加熱し、開環重合させることによりポリ乳酸の主鎖中にスルホン酸金属塩を有する乳酸系樹脂(A)を得た。
次に、上記乳酸系樹脂(A)100部をトルエン200部に溶解させ、カーボンブラック10部とをボールミル中で混合分散化し、黒塗料を作製し、塗膜中におけるカーボンブラック分散性を評価した。結果を表2に示す。分散性評価にはグロスメーターを用いた。
【0017】
実施例2
DL−ラクチド500部、3−ナトリウムスルホ−n−プロパノール1.62部、開環重合触媒としてオクチル酸錫0.1部を4つ口フラスコに仕込み、窒素雰囲気下、190℃で1時間加熱し、開環重合させることにより、高分子鎖末端にスルホン酸金属塩を共重合させた乳酸系樹脂(B)を得た。
乳酸系樹脂(B)についても、実施例1と同様な方法でカーボンブラック分散性を評価した。結果を表2に示す。
【0018】
比較例1
DL−ラクチド500部、重合開始剤としてグリコ−ル2.25部、開環重合触媒としてオクチル酸錫0.1部を4つ口フラスコ内に仕込み、窒素雰囲気下、190℃で1時間、加熱開環重合を実施し乳酸系樹脂(C)を得た。
乳酸系樹脂(C)についても、実施例1と同様な方法でカーボンブラック分散性を評価した。結果を表2に示す。
【0019】
上記実施例および比較例で使用された乳酸系樹脂の組成および物性を表1に示す。
なお、還元粘度は、サンプル濃度0.125g/25ml、測定溶剤クロロホルム、測定温度25℃で、ウベローデ粘度管を用いて測定した。また、TgはDSC法により測定した。
【0020】
【表1】
【0021】
【表2】
【0022】
【発明の効果】
本発明のスルホン酸金属塩共重合乳酸系樹脂は、従来の生分解性樹脂では得られなかった優れた顔料分散性を有しており、生分解性の有る高機能な塗料、インキ、接着剤とした場合に優れた保存安定性を確保できるだけでなく、色調に優れ、基材との高い密着性を確保出来る。さらには乳酸系樹脂の持つ高い生分解性のため、自然環境下で速やかに分解することができ、スルホン酸塩部分による適度な親水性のため、生分解速度を適度な範囲に調整することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention improves the dispersibility of inorganic pigments, colored pigments, fillers, etc. by copolymerizing sulfonic acid metal salts with lactic acid-based polyesters, thereby making biodegradation useful for paints, coating materials, inks, etc. Relates to a functional resin.
[0002]
[Prior art / problems to be solved by the invention]
Due to the recent increase in awareness of environmental issues, products using natural materials or biodegradable synthetic materials have been actively developed. Development of various uses for polylactic acid resins has been actively promoted, but due to poor dispersibility of inorganic pigments, colored pigments, fillers, etc., development of paints, coating materials, inks, adhesives, etc. has been hindered. .
[0003]
[Means for Solving the Problems]
In view of the above circumstances, the present inventors have intensively studied the introduction of a sulfonic acid metal salt into a lactic acid-based resin, and introduced a specific sulfonic acid metal salt structure, whereby an inorganic pigment, a coloring pigment, a filler, and the like. The present invention has been completed by discovering that the dispersibility of the resin is greatly improved.
[0004]
That is, the present invention is an aliphatic polyester containing a sulfonic acid metal salt at a concentration of 10 to 200 eq / 10 6 g, and contains 80 mol% or more of lactic acid residues, of which L lactic acid and D lactic acid have a molar ratio. The present invention relates to a composition comprising a sulfonic acid metal salt copolymerized lactic acid resin and a solvent, wherein (L / D) is 1 to 9.
[0005]
The lactic acid-based resin in the present invention needs to contain 80 mol% or more of lactic acid residues, and preferably 90 mol% or more. If it is less than 80 mol%, good biodegradability and physical properties of the coating film cannot be obtained.
[0006]
Moreover, it is also necessary that the molar ratio (L / D) of L lactic acid to D lactic acid is 1 to 9, and preferably 1 to 5.6. When L / D exceeds 9, the solubility of the polyester in a general-purpose solvent is deteriorated and cannot be used as a paint, ink, or adhesive. When L / D is less than 1 (D lactic acid excess), the raw material cost increases.
As lactic acid, any of L lactic acid, D lactic acid and DL lactic acid can be used.
[0007]
The sulfonic acid metal salt concentration in the lactic acid resin of the present invention needs to be copolymerized within a concentration range of 10 to 200 eq / 10 6 g. If it is 10 eq / 10 6 g or less, good dispersibility of inorganic pigments and organic pigments may not be obtained. On the other hand, if it exceeds 200 eq / 10 6 g, the resin solution viscosity becomes too high, and good coating suitability in paints, inks, adhesives, etc. may not be obtained.
[0008]
Examples of the method for introducing a sulfonic acid metal salt into the lactic acid resin of the present invention include a method of copolymerizing a compound having a sulfonic acid metal base copolymerizable with polylactic acid, and a known method for obtaining the obtained polylactic acid resin. Although it does not specifically limit, the method of copolymerizing the compound with the sulfonic acid metal base copolymerizable with polylactic acid is preferable.
[0009]
Preferable compounds having a sulfonic acid metal base copolymerizable with polylactic acid include compounds represented by the following formula (I) or (II).
[Chemical 1]
(However, R 1 and R 2 are alkyl groups having 20 or less carbon atoms, and M represents Li, Na, or K.)
HO—R 3 —SO 3 M Formula (II)
(However, R 3 represents an alkyl group having 20 or less carbon atoms, and M represents Li, Na, or K.)
[0010]
The reduced viscosity of the lactic acid resin in the present invention is preferably in the range of 0.3 to 1.5 dl / g. When the reduced viscosity is lower than 0.3 dl / g, the physical properties of the coating film are deteriorated, which may cause a problem when used in paints, inks, adhesives and the like. On the other hand, if the reduced viscosity is too high, the solution viscosity of paints, inks, adhesives and the like increases, and good coating suitability may not be obtained.
The reduced viscosity is a value measured using an Ubbelohde viscosity tube at a sample concentration of 0.125 g / 25 ml, a measurement solvent chloroform, and a measurement temperature of 25 ° C.
[0011]
In addition to lactic acid, biodegradable compounds such as oxyacid compounds other than lactic acid, dicarboxylic acids such as succinic acid, diols such as propylene glycol, and polyol compounds such as glycerin are used for the lactic acid resin. Can do.
In addition, as long as the structure of Formula (I) and (II) is copolymerized in the range of 10-200eq / 10 < 6 > g in polyester, 0% of other copolymerization components other than lactic acid may be sufficient.
[0012]
Examples of oxyacids other than lactic acid include glycolic acid, caprolactone, 2-hydroxyisobutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 16-hydroxyhexadecanoic acid, 2-hydroxy-2-methylbutyric acid, and 10-hydroxystearic acid. Examples include acid, malic acid, citric acid, and gluconic acid.
[0013]
The Tg of the lactic acid resin in the present invention is required to be 35 to 60 ° C, and preferably 40 to 55 ° C. If it is the range of 35-60 degreeC, a favorable coating-film physical property will be obtained.
Tg can be prepared, for example, by changing the proportion of the copolymer component in the lactic acid resin.
The Tg is a value measured by a DSC (Differential Scanning Calorimeter) method.
[0014]
The method for producing the lactic acid resin is not particularly limited, and a conventionally known method can be used. For example, lactide, which is a dimer of lactic acid, and a compound having early biodegradability other than lactic acid are melt-mixed and heated using a known ring-opening polymerization catalyst (eg, tin octylate, aluminum acetylacetonate, etc.). Examples thereof include a ring-opening polymerization method and a method of performing direct dehydration polycondensation by heating and reduced pressure.
[0015]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
[0016]
Example 1
500 parts of DL-lactide, 3.56 parts of ethylene glycol ester of 5-sodiumsulfo-isophthalic acid, and 0.1 part of tin octylate as a ring-opening polymerization catalyst were charged into a four-necked flask, and the temperature was 1 at 190 ° C. in a nitrogen atmosphere. By heating for a period of time and ring-opening polymerization, a lactic acid resin (A) having a sulfonic acid metal salt in the main chain of polylactic acid was obtained.
Next, 100 parts of the lactic acid resin (A) was dissolved in 200 parts of toluene, and 10 parts of carbon black was mixed and dispersed in a ball mill to produce a black paint, and the carbon black dispersibility in the coating film was evaluated. . The results are shown in Table 2. A gloss meter was used for dispersibility evaluation.
[0017]
Example 2
DL-lactide 500 parts, 3-sodium sulfo-n-propanol 1.62 parts, and 0.1 part tin octylate as a ring-opening polymerization catalyst were charged into a four-necked flask and heated at 190 ° C. for 1 hour in a nitrogen atmosphere. Then, ring-opening polymerization was performed to obtain a lactic acid resin (B) having a polymer chain terminal copolymerized with a sulfonic acid metal salt.
For the lactic acid resin (B), the carbon black dispersibility was evaluated in the same manner as in Example 1. The results are shown in Table 2.
[0018]
Comparative Example 1
500 parts of DL-lactide, 2.25 parts of glycol as a polymerization initiator, and 0.1 part of tin octylate as a ring-opening polymerization catalyst are charged into a four-necked flask and heated at 190 ° C. for 1 hour in a nitrogen atmosphere. Ring-opening polymerization was carried out to obtain a lactic acid resin (C).
For the lactic acid resin (C), the carbon black dispersibility was evaluated in the same manner as in Example 1. The results are shown in Table 2.
[0019]
Table 1 shows the composition and physical properties of the lactic acid resins used in the above Examples and Comparative Examples.
The reduced viscosity was measured using a Ubbelohde viscosity tube at a sample concentration of 0.125 g / 25 ml, a measurement solvent chloroform and a measurement temperature of 25 ° C. Tg was measured by DSC method.
[0020]
[Table 1]
[0021]
[Table 2]
[0022]
【The invention's effect】
The sulfonic acid metal salt copolymerized lactic acid resin of the present invention has excellent pigment dispersibility not obtained with conventional biodegradable resins, and is a biodegradable, highly functional paint, ink, and adhesive. In addition to ensuring excellent storage stability, the color tone is excellent and high adhesion to the substrate can be ensured. Furthermore, because of the high biodegradability of lactic acid-based resins, it can be quickly decomposed in the natural environment, and because of the moderate hydrophilicity due to the sulfonate portion, the biodegradation rate can be adjusted to an appropriate range. it can.
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JP2002097437A (en) * | 2001-09-17 | 2002-04-02 | Toyobo Co Ltd | Biodegradable polyester adhesive |
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WO2008146905A1 (en) | 2007-05-30 | 2008-12-04 | Toyo Boseki Kabushiki Kaisha | Phosphonium sulfoisophthalate structure-copolymerized lactic acid-based resin |
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