WO2015019750A1 - Poly(lactic acid) resin, poly(lactic acid) resin composition, and ship bottom paint - Google Patents

Poly(lactic acid) resin, poly(lactic acid) resin composition, and ship bottom paint Download PDF

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WO2015019750A1
WO2015019750A1 PCT/JP2014/067496 JP2014067496W WO2015019750A1 WO 2015019750 A1 WO2015019750 A1 WO 2015019750A1 JP 2014067496 W JP2014067496 W JP 2014067496W WO 2015019750 A1 WO2015019750 A1 WO 2015019750A1
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lactic acid
resin
polylactic acid
acid
poly
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French (fr)
Japanese (ja)
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宮本　貴志
奈央子 篠沢
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東洋紡株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
    • C09D193/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable

Definitions

  • the present invention relates to a polylactic acid resin obtained by copolymerizing an abietic acid compound, and a polylactic acid resin composition obtained by blending a rosin compound with these polylactic acid resins, and a solvent solution. It can be used in the coating field such as ship bottom paint.
  • rosin compounds are natural compounds that have been known for a long time, and it has been studied that they are blended with polylactic acid resins to impart various properties while utilizing the properties of biomass materials.
  • An object of the present invention is to provide an abietic acid copolymerized polylactic acid-based resin that has good miscibility with the rosin compound (B) and does not cause a phenomenon such as separation even in a solvent solution.
  • a polylactic acid resin using an abietic acid compound (A) having one or more hydroxyl groups as a polymerization initiator is a solvent compared to a normal polylactic acid resin. It was discovered that the rosin compound (B) and the polylactic acid resin can be stably mixed even in the lysate, thereby completing the present invention.
  • this invention consists of the following structures.
  • the polylactic acid resin according to (1) wherein the D-lactic acid residue contains a meso-lactide-derived D-lactic acid residue as a main component.
  • a polylactic acid resin composition comprising the rosin compound (B) and the polylactic acid resin described in (1) or (2), wherein the rosin compound (B) / polylactic acid resin is in a weight ratio.
  • the polylactic acid resin composition (5) or (4), wherein the polylactic acid resin composition according to (3) is a resin-dissolved composition further containing a solvent (C). Ship bottom paint using a polylactic acid resin composition.
  • Examples of the abietic acid compound (A) having one or more hydroxyl groups in the present invention include compounds listed in structural formulas I, II, III, IV, and V, but are not particularly limited thereto. .
  • abietic acid-based compound (A) having a hydroxyl group in the present invention a compound having a structure similar to that of abietic acid, such as parastrinic acid, neoabietic acid, pimaric acid, isopimaric acid, and one or more hydroxyl groups Can also be used.
  • abietic acid compound (A) compounds of the following structural formulas I to V are preferable.
  • R represents a linear or branched alkylene group having 1 to 10 carbon atoms
  • R1 and R2 may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms or a —CH 2 OH group.
  • the concentration of abietic acid in the polylactic acid-based resin in the present invention is in the range of 70 to 600 eq / 10 6 g. Stability cannot be ensured in solvent-based melts. On the other hand, if it exceeds 600 eq / 10 6 g, the molecular weight of the polylactic acid resin becomes low, and the film strength cannot be ensured.
  • lactic acid residue of the lactic acid resin in the present invention 70 wt% is required, and preferably 80 wt%. If the lactic acid residue is 70 wt% or more, good biodegradability can be secured.
  • the polylactic acid resin in the present invention needs to have a molar ratio (L / D) of L-lactic acid to D-lactic acid in the range of 50/50 to 85/15.
  • L-lactic acid is excessive, the solvent solubility of the resin is lowered and it cannot be used as a resin-dissolved material for paints.
  • the origin of the D-lactic acid residue in the present invention is preferably not composed of D-lactide but mainly composed of mesolactide, and more preferably composed only of mesolactide.
  • mesolactide as a main component means that a D-lactic acid residue contains 50% by weight or more of a mesolactide-derived D-lactic acid residue.
  • the reduced viscosity of the polylactic acid resin in the present invention is preferably in the range of 0.15 dl / g to 0.7 dl / g, and if it is less than 0.15 dl, the coating film strength and adhesive strength are insufficient. There is a problem, and when it is 0.7 dl / g or more, there is a problem that the coating suitability is poor.
  • 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.
  • the reduced viscosity of the polylactic acid resin in the present invention is in the range of 0.15 dl / g to 0.4 dl / g from the viewpoint of the balance of film strength, suitability for overcoating, and self-polishing speed. To preferred.
  • the blending amount of the rosin compound (B) blended in the present invention is preferably 20/80 to 60/40 in the weight ratio of rosin / polylactic acid resin. If the rosin compound is less than 20, the self-polishing property is insufficient and the antifouling property is deteriorated. If it exceeds 60, the film strength is insufficient.
  • rosin compound (B) having no hydroxyl group in the present invention tall oil rosin, gum rosin, mainly composed of resin acid such as abietic acid, parastrinic acid, neoabietic acid, pimaric acid, isopimaric acid, or dehydroabietic acid, Examples include, but are not limited to, unmodified rosin such as wood rosin, disproportionated rosin, polymerized rosin, hydrogenated rosin, and other chemically modified rosins.
  • the solvent (C) in the present invention is preferably a single solvent such as ethyl acetate, propyl acetate, methyl ethyl ketone, toluene, xylene, or a mixed solvent containing these solvents as a main component from the viewpoint of solubility, drying property, and the like. In particular, it is not limited to these. In ship bottom coating applications, it is particularly preferable to use xylene as the solvent (C).
  • a resin-dissolving composition containing the solvent (C) in the present invention a resin-dissolving composition that does not cause the phenomenon of complete separation in the evaluation methods of Examples described later is referred to as a resin-dissolving composition.
  • usable copolymerization components other than lactic acid include ⁇ -caprolactone, glycolic acid, 2-hydroxyisobutyric acid, 3-hydroxybutyric acid, 16-hydroxyhexadecanoic acid, 2-hydroxy-2 Examples thereof include oxyacids such as methylbutyric acid, 10-hydroxystearic acid, malic acid and citric acid, dicarboxylic acids such as succinic acid, and glycols such as ethylene glycol and propylene glycol.
  • Example 1 Polymerization of polylactic acid resin A 600 g of L-lactide, 400 g of meso-lactide, 50 g of abietic acid compound (structural formula VI) and 250 mg of tin octylate are added to a flask, heated to 180 ° C. in a nitrogen atmosphere, and subjected to ring-opening polymerization for 2 hours. Then, polylactic acid resin A was obtained by distilling off the unreacted monomer under reduced pressure. The analysis results are shown in Table 1.
  • rosin lysate 500 g of abietic acid and 500 g of xylene were added to a flask and stirred at 60 ° C. for 5 hours to obtain a rosin compound A lysate.
  • Example 2 Polymerization of polylactic acid resin B: L-lactide 600 g, meso-lactide 400 g, abietic acid compound (structural formula III) 200 g, and tin octylate 250 mg were added to the flask, and subjected to ring-opening polymerization at 180 ° C. for 2 hours in a nitrogen atmosphere. Was distilled off under reduced pressure to obtain polylactic acid resin B. The analysis results are shown in Table 1.
  • Preparation of dissolved polylactic acid resin B A polylactic acid resin B solution was obtained by adding 500 g of polylactic acid resin B and 500 g of xylene to the flask and stirring under heating at 60 ° C. for 5 hours.
  • Comparative Example 1 Add 600 g of L-lactide, 400 g of meso-lactide, 1.5 g of ethylene glycol and 250 mg of tin octylate to the flask, carry out ring-opening polymerization at 180 ° C. for 2 hours in a nitrogen atmosphere, and then distill off unreacted monomers under reduced pressure. By doing so, a polylactic acid resin C was obtained.
  • the analysis results are shown in Table 1.
  • a polylactic acid-based resin C melt was obtained by adding 600 g of polylactic acid-based resin C and 400 g of xylene to the flask and stirring with heating at 60 ° C for 5 hours.
  • the rosin copolymer polylactic acid resin of the present invention can be used for applications such as coating agents, inks, and adhesives.
  • the biodegradable substrate biodegradable film or paper
  • the biodegradable substrate is highly useful in the field of adhesion and ship bottom coating.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

[Problem] To provide a resin based on poly(lactic acid) copolymerized with abietic acid, the resin having satisfactory miscibility with rosin compounds (B) and suffering no separation or no similar phenomenon even in solutions thereof in solvents. [Solution] The poly(lactic acid) resin is obtained by polymerization using, as a polymerization initiator, an abietic acid compound (A) having one or more hydroxy groups, and is characterized in that the concentration of residues of the abietic acid compound (A) is in the range of 70-600 eq/106 g, the lactic acid residues account for 70 wt% or more, the molar ratio of the L-lactic acid residues to the D-lactic acid residues in the lactic acid residues, L/D, is in the range of 50/50 to 85/15, and the reduced viscosity is in the range of 0.15-0.7 dl/g.

Description

ポリ乳酸系樹脂、ポリ乳酸系樹脂組成物および船底塗料Polylactic acid resin, polylactic acid resin composition, and ship bottom coating
　本発明は、アビエチン酸系化合物を共重合させたポリ乳酸系樹脂に関するものであり、これらのポリ乳酸系樹脂に対して、ロジン化合物をブレンドさせたポリ乳酸系樹脂組成物、溶剤溶解物であり、船底塗料等のコーティング分野での利用が可能である。 The present invention relates to a polylactic acid resin obtained by copolymerizing an abietic acid compound, and a polylactic acid resin composition obtained by blending a rosin compound with these polylactic acid resins, and a solvent solution. It can be used in the coating field such as ship bottom paint.
　近年の環境問題に対する意識の高まりから、天然素材またはバイオマス由来原料からなる合成樹脂を利用した商品の開発が盛んに行われている。ポリ乳酸系樹脂もとうもろこし澱粉等のバイオマスを発酵させて得られる乳酸を合成原料として重合される樹脂であることから、各種用途開発が実施されている。 Due to the recent increase in awareness of environmental issues, products using synthetic resins made of natural materials or biomass-derived materials are being actively developed. Development of various uses has been carried out because it is a resin that is polymerized using lactic acid obtained by fermenting biomass such as corn starch as a synthetic raw material.
　一方、ロジン化合物は、古くから知られている天然物系の化合物であり、ポリ乳酸系樹脂とブレンドし、バイオマス材料としての特性を活かしつつ、さまざまな特性を付与することが検討されてきた。（特許文献１，２，３） On the other hand, rosin compounds are natural compounds that have been known for a long time, and it has been studied that they are blended with polylactic acid resins to impart various properties while utilizing the properties of biomass materials. (Patent Documents 1, 2, 3)
　しかしながら、ポリ乳酸系樹脂とロジン化合物のブレンド性が悪く、任意に配合することが難しく、各種用途開発を阻害するという問題点があった。 However, there is a problem that the blendability of the polylactic acid resin and the rosin compound is poor, it is difficult to mix arbitrarily, and development of various uses is hindered.
特開２００４－２３１７９７号公報Japanese Patent Laid-Open No. 2004-231797 特開２００５－２１９９号公報JP 2005-2199 A 特開２００７－１３８１８７号公報JP 2007-138187 A
　本発明の課題は、ロジン化合物（Ｂ）との混合性が良く、溶剤溶解物においてさえも分離等の現象がおきない、アビエチン酸共重合ポリ乳酸系樹脂を提供することを課題とする。 An object of the present invention is to provide an abietic acid copolymerized polylactic acid-based resin that has good miscibility with the rosin compound (B) and does not cause a phenomenon such as separation even in a solvent solution.
　本発明者らは、鋭意検討の結果、１個以上の水酸基を有するアビエチン酸系化合物（Ａ）を重合開始剤として用いたポリ乳酸系樹脂が、通常のポリ乳酸系樹脂と比較して、溶剤溶解物中においてさえも、ロジン化合物（Ｂ）とポリ乳酸系樹脂が安定的に混合できることを発見し、本発明を完成させた。 As a result of intensive studies, the present inventors have found that a polylactic acid resin using an abietic acid compound (A) having one or more hydroxyl groups as a polymerization initiator is a solvent compared to a normal polylactic acid resin. It was discovered that the rosin compound (B) and the polylactic acid resin can be stably mixed even in the lysate, thereby completing the present invention.
　即ち、本発明は、以下の構成からなる。
（１）１個以上の水酸基を有するアビエチン酸系化合物（A）を重合開始剤として用いて重合されたポリ乳酸系樹脂であり、該アビエチン酸系化合物（A）残基濃度が、７０～６００ｅｑ／１０6ｇの範囲にあり、乳酸残基が７０重量％以上、かつ該乳酸残基中のＬ－乳酸残基とＤ－乳酸残基のモル比（Ｌ／Ｄ）が５０／５０～８５／１５の範囲にあり、還元粘度が０．１５ｄｌ／ｇ～０．７ｄｌ／ｇの範囲にあることを特徴とするポリ乳酸系樹脂。
（２）前記Ｄ－乳酸残基において、メソラクチド由来のＤ－乳酸残基を主成分とすることを特徴とする（１）記載のポリ乳酸系樹脂。
（３）ロジン化合物（Ｂ）と（１）又は（２）記載のポリ乳酸系樹脂が含有されてなるポリ乳酸系樹脂組成物であり、該ロジン化合物（Ｂ）／ポリ乳酸系樹脂が重量比で８０／２０～４０／６０の範囲で配合されたことを特徴とするポリ乳酸系樹脂組成物。
（４）（３）記載のポリ乳酸系樹脂組成物がさらに溶剤（Ｃ）を含有してなる樹脂溶解組成物であることを特徴とするポリ乳酸系樹脂組成物
（５）（４）に記載のポリ乳酸系樹脂組成物を用いてなる船底塗料。 That is, this invention consists of the following structures.
(1) A polylactic acid resin polymerized using an abietic acid compound (A) having one or more hydroxyl groups as a polymerization initiator, and the abietic acid compound (A) residue concentration is 70 to 600 eq. / 10 6 g, the lactic acid residue is 70% by weight or more, and the molar ratio (L / D) of L-lactic acid residue to D-lactic acid residue in the lactic acid residue is 50/50 to 85 / 15 and a reduced viscosity in the range of 0.15 dl / g to 0.7 dl / g.
(2) The polylactic acid resin according to (1), wherein the D-lactic acid residue contains a meso-lactide-derived D-lactic acid residue as a main component.
(3) A polylactic acid resin composition comprising the rosin compound (B) and the polylactic acid resin described in (1) or (2), wherein the rosin compound (B) / polylactic acid resin is in a weight ratio. A polylactic acid resin composition characterized by being blended in the range of 80/20 to 40/60.
(4) The polylactic acid resin composition (5) or (4), wherein the polylactic acid resin composition according to (3) is a resin-dissolved composition further containing a solvent (C). Ship bottom paint using a polylactic acid resin composition.
　本発明によれば、長期間保存した場合もポリ乳酸系樹脂とロジン化合物の分離現象が起こることのない溶剤溶解品を得ることができる。 According to the present invention, it is possible to obtain a solvent-dissolved product in which the separation phenomenon between the polylactic acid resin and the rosin compound does not occur even when stored for a long period of time.
　本発明における１個以上の水酸基を有するアビエチン酸系化合物（Ａ）としては、構造式Ｉ、II、III、IV、Ｖに挙げられる化合物等が該当するが、特にこれらに限定されるものでは無い。 Examples of the abietic acid compound (A) having one or more hydroxyl groups in the present invention include compounds listed in structural formulas I, II, III, IV, and V, but are not particularly limited thereto. .
　また、本発明における水酸基を有するアビエチン酸系化合物（A）としては、アビエチン酸と類似の構造を有するパラストリン酸、ネオアビエチン酸、ピマール酸、イソピマール酸等の構造と１個以上の水酸基を有する化合物も使用可能である。
　該アビエチン酸系化合物（A）としては、下記構造式Ｉ～Ｖの化合物が好ましい。 In addition, as the abietic acid-based compound (A) having a hydroxyl group in the present invention, a compound having a structure similar to that of abietic acid, such as parastrinic acid, neoabietic acid, pimaric acid, isopimaric acid, and one or more hydroxyl groups Can also be used.
As the abietic acid compound (A), compounds of the following structural formulas I to V are preferable.
Figure JPOXMLDOC01-appb-C000001
 （Ｒは、炭素数１～１０の直鎖状又は分岐状アルキレン基を示す）
Figure JPOXMLDOC01-appb-C000001
 (R represents a linear or branched alkylene group having 1 to 10 carbon atoms)
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
 （但しR1、R2は同一であっても異なっていてもよく、炭素１～３のアルキル基、又は－CH2OH基を示す）
Figure JPOXMLDOC01-appb-C000003
 (However, R1 and R2 may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms or a —CH 2 OH group.)
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　本発明におけるポリ乳酸系樹脂におけるアビエチン酸濃度は、７０～６００ｅｑ／１０6ｇの範囲であり、アビエチン酸濃度が低くすぎると、ロジン系化合物（Ｂ）との混合性がわるくなり、特に、キシレン溶剤系の溶解物において安定性が確保できない。また、６００ｅｑ／１０6ｇを越えると、ポリ乳酸系樹脂の分子量が低くなり、膜強度が確保できない。 The concentration of abietic acid in the polylactic acid-based resin in the present invention is in the range of 70 to 600 eq / 10 6 g. Stability cannot be ensured in solvent-based melts. On the other hand, if it exceeds 600 eq / 10 6 g, the molecular weight of the polylactic acid resin becomes low, and the film strength cannot be ensured.
　本発明における乳酸系樹脂の乳酸残基としては、７０ｗｔ％が必要であり、好ましくは、８０ｗｔ％である。乳酸残基が７０ｗｔ％以上であれば、良好な生分解性が確保できる。 As the lactic acid residue of the lactic acid resin in the present invention, 70 wt% is required, and preferably 80 wt%. If the lactic acid residue is 70 wt% or more, good biodegradability can be secured.
　本発明におけるポリ乳酸系樹脂は、Ｌ－乳酸とＤ－乳酸のモル比（Ｌ／Ｄ）が５０／５０～８５／１５の範囲にある必要がある。Ｌ－乳酸が過剰な場合、樹脂の溶剤溶解性が低下して、塗料用樹脂溶解物として使用できなくなる。 The polylactic acid resin in the present invention needs to have a molar ratio (L / D) of L-lactic acid to D-lactic acid in the range of 50/50 to 85/15. When L-lactic acid is excessive, the solvent solubility of the resin is lowered and it cannot be used as a resin-dissolved material for paints.
　本発明におけるＤ－乳酸残基の由来としては、Ｄ－ラクチドではなく、メソラクチドを主成分とすることが好ましく、メソラクチドのみでなることがより好ましい。該メソラクチドを主成分とするとは、Ｄ－乳酸残基中にメソラクチド由来のＤ－乳酸残基を５０重量％以上含有することをさす。メソラクチドを使用することにより、樹脂溶融粘度の低下や溶解性向上が期待できる。 The origin of the D-lactic acid residue in the present invention is preferably not composed of D-lactide but mainly composed of mesolactide, and more preferably composed only of mesolactide. The phrase “mesolactide as a main component” means that a D-lactic acid residue contains 50% by weight or more of a mesolactide-derived D-lactic acid residue. By using meso lactide, a decrease in resin melt viscosity and an improvement in solubility can be expected.
　本発明におけるポリ乳酸系樹脂の還元粘度としては、０．１５ｄｌ／ｇ～０．７ｄｌ／ｇの範囲にあることが好ましく、０．１５ｄｌ未満であると、コーティング膜強度や接着強度が不足するという問題があり、０．７ｄｌ／ｇ以上であると、コーティング適性が悪いという問題がある。尚、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。 The reduced viscosity of the polylactic acid resin in the present invention is preferably in the range of 0.15 dl / g to 0.7 dl / g, and if it is less than 0.15 dl, the coating film strength and adhesive strength are insufficient. There is a problem, and when it is 0.7 dl / g or more, there is a problem that the coating suitability is poor. 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.
　船底塗料用途の場合、本発明におけるポリ乳酸系樹脂の還元粘度は、０．１５ｄｌ／ｇ～０．４ｄｌ／ｇの範囲にあることが、膜強度、重ね塗り適性、セルフポリッシング速度のバランスの観点から好ましい。 In the case of ship bottom coating applications, the reduced viscosity of the polylactic acid resin in the present invention is in the range of 0.15 dl / g to 0.4 dl / g from the viewpoint of the balance of film strength, suitability for overcoating, and self-polishing speed. To preferred.
　船底塗料用途の場合、本発明において配合されるロジン化合物（Ｂ）の配合量は、ロジン／ポリ乳酸系樹脂重量比において、２０／８０～６０／４０が好ましい。ロジン化合物が２０未満であるとセルフポリッシング性が不足し、防汚性が悪化するという問題が発生し、６０を越えると、膜強度が不足するという問題が発生する。 In the case of ship bottom paint use, the blending amount of the rosin compound (B) blended in the present invention is preferably 20/80 to 60/40 in the weight ratio of rosin / polylactic acid resin. If the rosin compound is less than 20, the self-polishing property is insufficient and the antifouling property is deteriorated. If it exceeds 60, the film strength is insufficient.
　本発明における水酸基を有しないロジン化合物（Ｂ）としては、アビエチン酸、パラストリン酸、ネオアビエチン酸、ピマール酸、イソピマール酸、或いはデヒドロアビエチン酸などの樹脂酸を主成分とするトール油ロジン、ガムロジン、ウッドロジンなどの未変性ロジンを初め、不均化ロジン、重合ロジン、水素化ロジン、或いはその他化学的に修飾されたロジンなどが挙げられるが特に限定されるものでは無い。 As the rosin compound (B) having no hydroxyl group in the present invention, tall oil rosin, gum rosin, mainly composed of resin acid such as abietic acid, parastrinic acid, neoabietic acid, pimaric acid, isopimaric acid, or dehydroabietic acid, Examples include, but are not limited to, unmodified rosin such as wood rosin, disproportionated rosin, polymerized rosin, hydrogenated rosin, and other chemically modified rosins.
　本発明における溶剤（Ｃ）としては、溶解性、乾燥性等の観点から、酢酸エチル、酢酸プロピル、メチルエチルケトン、トルエン、キシレン等の単独溶剤やこれらの溶剤が主成分である混合溶剤が好ましいが、特にこれらに限定されるものでは無い。船底塗料用途においては、キシレンを溶剤（Ｃ）として用いることが特に好ましい。なお、本発明における溶剤（Ｃ）を含有した樹脂溶解組成物において、後述の実施例の評価方法にて完全分離の現象が発生しないものを樹脂溶解組成物と称する。 The solvent (C) in the present invention is preferably a single solvent such as ethyl acetate, propyl acetate, methyl ethyl ketone, toluene, xylene, or a mixed solvent containing these solvents as a main component from the viewpoint of solubility, drying property, and the like. In particular, it is not limited to these. In ship bottom coating applications, it is particularly preferable to use xylene as the solvent (C). In the resin-dissolving composition containing the solvent (C) in the present invention, a resin-dissolving composition that does not cause the phenomenon of complete separation in the evaluation methods of Examples described later is referred to as a resin-dissolving composition.
　本発明におけるポリ乳酸系樹脂において、乳酸以外の使用可能な共重合成分としては、ε－カプロラクトン、グリコール酸、２－ヒドロキシイソ酪酸、３－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、クエン酸等のオキシ酸やコハク酸等のジカルボン酸、エチレングリコール、プロピレングリコール等のグリコール類が挙げられる。 In the polylactic acid resin of the present invention, usable copolymerization components other than lactic acid include ε-caprolactone, glycolic acid, 2-hydroxyisobutyric acid, 3-hydroxybutyric acid, 16-hydroxyhexadecanoic acid, 2-hydroxy-2 Examples thereof include oxyacids such as methylbutyric acid, 10-hydroxystearic acid, malic acid and citric acid, dicarboxylic acids such as succinic acid, and glycols such as ethylene glycol and propylene glycol.
　以下に、実施例にて、本発明を更に詳細に説明するが、本発明はこれらに限定されるものでは無い。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
実施例１
ポリ乳酸系樹脂Ａの重合
　Ｌラクチド６００ｇ、メソラクチド４００ｇ、アビエチン酸系化合物（構造式VI）５０ｇ、オクチル酸スズ２５０ｍｇをフラスコに加え、窒素雰囲気下、１８０℃に加熱、２時間開環重合をさせ、その後、未反応モノマーを減圧下留去させることにより、ポリ乳酸系樹脂Ａを得た。分析結果を表１に示す。 Example 1
Polymerization of polylactic acid resin A 600 g of L-lactide, 400 g of meso-lactide, 50 g of abietic acid compound (structural formula VI) and 250 mg of tin octylate are added to a flask, heated to 180 ° C. in a nitrogen atmosphere, and subjected to ring-opening polymerization for 2 hours. Then, polylactic acid resin A was obtained by distilling off the unreacted monomer under reduced pressure. The analysis results are shown in Table 1.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
ポリ乳酸系樹脂Ａ溶解物の調整
　上記ポリ乳酸系樹脂Ａ５００ｇとキシレン５００ｇをフラスコに加え、６０℃で５時間攪拌することにより、ポリ乳酸系樹脂Ａ溶解物を得た。 Preparation of polylactic acid-based resin A dissolved matter The above-mentioned polylactic acid-based resin A 500 g and xylene 500 g were added to a flask and stirred at 60 ° C. for 5 hours to obtain a polylactic acid-based resin A dissolved matter.
　ロジン溶解物の調整
　アビエチン酸５００ｇとキシレン５００ｇをフラスコに加え、６０℃で５時間攪拌することにより、ロジン化合物Ａ溶解物を得た。 Preparation of rosin lysate 500 g of abietic acid and 500 g of xylene were added to a flask and stirred at 60 ° C. for 5 hours to obtain a rosin compound A lysate.
ロジンとポリ乳酸系樹脂の混合性評価：
　上記ポリ乳酸系樹脂Ａ溶解物８０ｇとアビエチン酸溶解物２０ｇを２５℃において、フラスコ中で攪拌し、混合物を取り出し、室温、静置下において、１週間後の溶液状態を目視にて観察し評価。結果を表２に示す。 Evaluation of mixing of rosin and polylactic acid resin:
80 g of the above polylactic acid-based resin A solution and 20 g of abietic acid solution were stirred in a flask at 25 ° C., the mixture was taken out, and the solution state after one week was visually observed and evaluated at room temperature and standing still. . The results are shown in Table 2.
実施例２
ポリ乳酸系樹脂Ｂの重合：
　Ｌラクチド６００ｇ、メソラクチド４００ｇ、アビエチン酸系化合物（構造式III）２００ｇ、オクチル酸スズ２５０ｍｇをフラスコに加え、窒素雰囲気下、１８０℃にて、２時間開環重合を実施させ、その後、未反応モノマーを減圧下留去させることによりポリ乳酸系樹脂Ｂを得た。分析結果を表１に示す。 Example 2
Polymerization of polylactic acid resin B:
L-lactide 600 g, meso-lactide 400 g, abietic acid compound (structural formula III) 200 g, and tin octylate 250 mg were added to the flask, and subjected to ring-opening polymerization at 180 ° C. for 2 hours in a nitrogen atmosphere. Was distilled off under reduced pressure to obtain polylactic acid resin B. The analysis results are shown in Table 1.
ポリ乳酸系樹脂Ｂ溶解物の調整：
　ポリ乳酸系樹脂Ｂ５００ｇとキシレン５００ｇをフラスコに加えて６０℃にて５時間加熱攪拌することによりポリ乳酸系樹脂Ｂ溶解物を得た。 Preparation of dissolved polylactic acid resin B:
A polylactic acid resin B solution was obtained by adding 500 g of polylactic acid resin B and 500 g of xylene to the flask and stirring under heating at 60 ° C. for 5 hours.
ロジンとポリ乳酸系樹脂の混合性評価
　実施例１の評価と同様の評価を実施した。結果を表２に示す。 Evaluation of Mixability of Rosin and Polylactic Acid Resin The same evaluation as in Example 1 was performed. The results are shown in Table 2.
比較例１
　Ｌラクチド６００ｇ、メソラクチド４００ｇ、エチレングリコール１．５ｇ、オクチル酸スズ２５０ｍｇをフラスコに加え、窒素雰囲気下、１８０℃にて、２時間環開重合を実施させ、その後、未反応モノマーを減圧下留去させることにより、ポリ乳酸系樹脂Ｃを得た。分析結果を表１に示す。 Comparative Example 1
Add 600 g of L-lactide, 400 g of meso-lactide, 1.5 g of ethylene glycol and 250 mg of tin octylate to the flask, carry out ring-opening polymerization at 180 ° C. for 2 hours in a nitrogen atmosphere, and then distill off unreacted monomers under reduced pressure. By doing so, a polylactic acid resin C was obtained. The analysis results are shown in Table 1.
ポリ乳酸系樹脂Ｃ溶解物の調整：
　ポリ乳酸系樹脂Ｃ６００ｇとキシレン４００ｇをフラスコに加えて６０℃にて５時間加熱攪拌することによりポリ乳酸系樹脂Ｃ溶解物を得た。 Preparation of dissolved polylactic acid resin C:
A polylactic acid-based resin C melt was obtained by adding 600 g of polylactic acid-based resin C and 400 g of xylene to the flask and stirring with heating at 60 ° C for 5 hours.
ロジンとポリ乳酸系樹脂との混合性評価
　実施例１と同様の評価を実施した。評価結果を表２に示す。 Evaluation of Mixability of Rosin and Polylactic Acid Resin The same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2.
（樹脂分析結果）
Figure JPOXMLDOC01-appb-T000007
 (Resin analysis results)
Figure JPOXMLDOC01-appb-T000007
（キシレン溶液での安定性）
Figure JPOXMLDOC01-appb-T000008
 (Stability in xylene solution)
Figure JPOXMLDOC01-appb-T000008
　本発明のロジン共重合ポリ乳酸系樹脂は、コーティング剤、インキ、接着剤等の用途に使用できる。特に、生分解性基材（生分解性フィルムや紙）の接着や船底塗料分野における利用価値が高い。 The rosin copolymer polylactic acid resin of the present invention can be used for applications such as coating agents, inks, and adhesives. In particular, the biodegradable substrate (biodegradable film or paper) is highly useful in the field of adhesion and ship bottom coating.

Claims (5)

  1. 　１個以上の水酸基を有するアビエチン酸系化合物（A）を重合開始剤として用いて重合
    されたポリ乳酸系樹脂であり、該アビエチン酸系化合物（A）残基濃度が、７０～６００ｅｑ／１０6ｇの範囲にあり、乳酸残基が７０重量％以上、かつ該乳酸残基中のＬ－乳酸残基とＤ－乳酸残基のモル比（Ｌ／Ｄ）が５０／５０～８５／１５の範囲にあり、還元粘度が０．１５ｄｌ／ｇ～０．７ｄｌ／ｇの範囲にあることを特徴とするポリ乳酸系樹脂。     A polylactic acid resin polymerized using an abietic acid compound (A) having one or more hydroxyl groups as a polymerization initiator, and the abietic acid compound (A) residue concentration is 70 to 600 eq / 10 6. g, the lactic acid residue is 70% by weight or more, and the molar ratio (L / D) of L-lactic acid residue to D-lactic acid residue in the lactic acid residue is 50/50 to 85/15. A polylactic acid resin having a reduced viscosity in a range of 0.15 dl / g to 0.7 dl / g.
  2. 　前記Ｄ－乳酸残基において、メソラクチド由来のＤ－乳酸残基を主成分とすることを特徴とする請求項１記載のポリ乳酸系樹脂。 2. The polylactic acid-based resin according to claim 1, wherein the D-lactic acid residue is mainly composed of a meso-lactide-derived D-lactic acid residue.
  3. 　ロジン化合物（Ｂ）と請求項１又は２記載のポリ乳酸系樹脂が含有されてなるポリ乳酸系樹脂組成物であり、該ロジン化合物（Ｂ）／ポリ乳酸系樹脂が重量比で８０／２０～４０／６０の範囲で配合されたことを特徴とするポリ乳酸系樹脂組成物。 A polylactic acid-based resin composition comprising the rosin compound (B) and the polylactic acid-based resin according to claim 1 or 2, wherein the rosin compound (B) / polylactic acid-based resin has a weight ratio of 80/20 to A polylactic acid resin composition characterized by being blended in a range of 40/60.
  4. 　請求項３記載のポリ乳酸系樹脂組成物がさらに溶剤（Ｃ）を含有してなる樹脂溶解組成物であることを特徴とするポリ乳酸系樹脂組成物。 A polylactic acid resin composition, wherein the polylactic acid resin composition according to claim 3 further comprises a solvent (C).
  5. 　請求項４に記載のポリ乳酸系樹脂組成物を用いてなる船底塗料。 Ship bottom paint using the polylactic acid resin composition according to claim 4.
PCT/JP2014/067496 2013-08-09 2014-07-01 Poly(lactic acid) resin, poly(lactic acid) resin composition, and ship bottom paint WO2015019750A1 (en)

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