JP4545224B2 - One-component, moisture-curing type bed bed stabilizer - Google Patents
One-component, moisture-curing type bed bed stabilizer Download PDFInfo
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Description
本発明は、一液湿気硬化型道床安定剤に関する。 The present invention relates to a one-component moisture curing type bed bed stabilizer.
バラスト軌道では、主に枕木及びバラストにより道床が構成される。従来、バラストに道床安定剤を散布してバラストを固定することにより、道床抵抗力を高め、またバラストの飛散を防止している。夏のレール膨張を抑え、冬の降雪、凍結、暴風等の自然災害からレールを守るためにもバラストの固定は重要である。一方、半年程度経過後の短期間での保守作業においては、バラストの突き崩しが容易であることが求められる。
道床安定剤として、ポリウレタンプレポリマーを含有する一液湿気硬化型のものが周知である（例えば、特許文献１〜３）。しかし、これらの道床安定剤では、ポリウレタンの湿気硬化の速度、硬化方法をコントロールするために、ポリウレタンプレポリマーにオキシエチレン基を含有するポリオールあるいはモノオールの導入や、親水性を持った希釈剤を使用するなどの使用原料に制限があり、第３級アミン類や有機金属化合物のような人体に有毒なウレタン化触媒が添加されていたりする。
In the ballast track, the roadbed is mainly composed of sleepers and ballast. Conventionally, a ballast is sprayed onto the ballast to fix the ballast, thereby increasing the resistance to the bed and preventing the ballast from scattering. Fixing ballast is also important in order to suppress rail expansion in summer and protect the rail from natural disasters such as snowfall, freezing, and windstorms in winter. On the other hand, in maintenance work in a short period after about half a year has passed, it is required that the ballast be easily broken.
As the bed bed stabilizer, a one-component moisture-curing type containing a polyurethane prepolymer is well known (for example, Patent Documents 1 to 3). However, in these road bed stabilizers, in order to control the moisture curing speed and the curing method of polyurethane, the introduction of polyols or monools containing oxyethylene groups into the polyurethane prepolymer, or hydrophilic diluents are used. There are restrictions on the raw materials used, and urethanization catalysts that are toxic to the human body such as tertiary amines and organometallic compounds are added.
本発明は、非水溶性のため降雨時などにも自然界に溶け出さないため安全性が高く、バラストの突き崩しが容易となる一液湿気硬化型道床安定剤を提供することを主な課題とする。 The main object of the present invention is to provide a one-part moisture-curing type bed bed stabilizer that is water-insoluble and therefore has high safety because it does not dissolve in the natural environment even during rainfall, etc. To do.
本発明者は上記課題を解決するために研究を重ね、以下の知見を得た。即ち、（ａ）ポリ又はモノイソシアネートと（ｂ）活性水素含有モノマー又はポリマーとを反応させて得られるイソシアネート含有ポリウレタンプレポリマー、分解促進剤、及び減粘剤を含有する道床安定剤を用いることにより、空気中の湿分を用いたポリウレタンの湿気硬化反応をコントロールすることができると共に、硬化したウレタンプレポリマーの分解を促進する効果を生じさせることを知見した。当該道床安定剤は、引火点が高い非水溶性の減粘剤を使用することができ、人体に有毒な触媒を添加する必要がないので、安全性も高いという利点を有する。 The present inventor repeated researches to solve the above problems, and obtained the following knowledge. That is, by using a road bed stabilizer containing an isocyanate-containing polyurethane prepolymer obtained by reacting (a) poly or monoisocyanate and (b) an active hydrogen-containing monomer or polymer, a decomposition accelerator, and a viscosity reducing agent. It has been found that the moisture curing reaction of polyurethane using moisture in the air can be controlled and the effect of promoting the decomposition of the cured urethane prepolymer is produced. The road bed stabilizer has an advantage of high safety because it can use a water-insoluble thinning agent having a high flash point and it is not necessary to add a toxic catalyst to the human body.
本発明は、上記知見に基づき完成されたものであり、下記の一液湿気硬化型道床安定剤を提供する。
［１］ （ａ）ポリ又はモノイソシアネートと（ｂ）活性水素含有モノマー又はポリマーとを反応させて得られるイソシアネート含有ポリウレタンプレポリマー、分解促進剤、及び減粘剤を含有する一液湿気硬化型道床安定剤。
［２］ 塩を含有するモノマーまたはポリマーをさらに含有することを特徴とする［１］記載の一液湿気硬化型道床安定剤。
［３］ 分解促進剤が有機金属化合物であることを特徴とする［１］又は［２］記載の一液湿気硬化型道床安定剤。
［４］ 減粘剤が、炭素数６〜２２の高級脂肪酸エステル、植物油もしくは動物油脂肪酸の炭素数１〜２２のアルキルエステル、炭素数６〜２２の高級脂肪酸のモノ、ジもしくはトリグリセライド、炭素数６〜２２の多塩基酸もしくは酸無水物のエステル、並びに炭素数６〜２２の多塩基酸もしくは酸無水物のモノ、ジもしくはトリグリセライドからなる群より選ばれる少なくとも１種であり、２０℃での水に対する溶解度が１．０重量％未満の疎水性であることを特徴とする［１］〜［３］記載の一液湿気硬化型道床安定剤。
［５］ 活性水素含有モノマー又はポリマーがオキシエチレン基を含有しないことを特徴とする［１］〜［４］のいずれかに記載の一液湿気硬化型道床安定剤。
［６］ ２０℃での水に対する溶解度が１．０重量％未満の疎水性であり、引火点が２００℃を越え、消防法上の危険物第４類第４石油類であることを特徴とする［１］〜［５］のいずれかに記載の一液湿気硬化型道床安定剤。
［７］ 湿気硬化に際してウレタン化触媒を含有しないことを特徴とする［１］〜［６］のいずれかに記載の一液湿気硬化型道床安定剤。
The present invention has been completed based on the above findings, and provides the following one-component moisture-curing type bed bed stabilizer.
[1] A one-part moisture-curing type roadbed containing an isocyanate-containing polyurethane prepolymer obtained by reacting (a) poly or monoisocyanate with (b) an active hydrogen-containing monomer or polymer, a decomposition accelerator, and a thickener. Stabilizer.
[2] The one-part moisture curing type bed bed stabilizer according to [1], further comprising a monomer or polymer containing a salt.
[3] The one-part moisture curing type bed bed stabilizer according to [1] or [2], wherein the decomposition accelerator is an organometallic compound.
[4] The viscosity reducing agent is a higher fatty acid ester having 6 to 22 carbon atoms, an alkyl ester having 1 to 22 carbon atoms of vegetable oil or animal oil fatty acid, a mono-, di- or triglyceride of higher fatty acids having 6 to 22 carbon atoms, 6 carbon atoms. At least one selected from the group consisting of esters of polybasic acids or acid anhydrides of -22 and mono, di or triglycerides of polybasic acids or acid anhydrides of 6 to 22 carbon atoms, and water at 20 ° C. The one-part moisture-curing type bed bed stabilizer according to [1] to [3], wherein the one-part moisture-curing type bed bed stabilizer has a hydrophobicity of less than 1.0% by weight.
[5] The one-component moisture-curing bed bed stabilizer according to any one of [1] to [4], wherein the active hydrogen-containing monomer or polymer does not contain an oxyethylene group.
[6] Hydrophobic with water solubility at 20 ° C. of less than 1.0% by weight, flash point exceeding 200 ° C. The one-component moisture curing type bed bed stabilizer according to any one of [1] to [5].
[7] The one-part moisture curing type bed bed stabilizer according to any one of [1] to [6], which does not contain a urethanization catalyst during moisture curing.
本発明によれば、安全性が高く、バラストの突き崩しが容易となる一液湿気硬化型道床安定剤を提供することができる。 According to the present invention, it is possible to provide a one-component moisture-curing road bed stabilizer that is high in safety and easy to break down ballast.
以下、本発明を詳細に説明する。
本発明の一液湿気硬化型道床安定剤は、（ａ）ポリ又はモノイソシアネートと（ｂ）活性水素含有モノマー又はポリマーとを反応させて得られるイソシアネート含有ポリウレタンプレポリマー、分解促進剤、及び減粘剤を含有する。
Hereinafter, the present invention will be described in detail.
The one-component moisture-curing road bed stabilizer of the present invention comprises: (a) an isocyanate-containing polyurethane prepolymer obtained by reacting a poly or monoisocyanate and (b) an active hydrogen-containing monomer or polymer; a decomposition accelerator; Contains agents.
［ポリ又はモノイソシアネート］
ポリ又はモノイソシアネートとしては、例えば分子中に平均１個以上、好ましくは平均１〜３個程度のイソシアネート基を有する脂肪族、芳香族、脂環族、等のポリ又はモノイソシアネートが挙げられる。具体的には、ジフェニルメタンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、ｐ−フェニレンジイソシアネート、イソホロンジイソシアネート、ポリメチレンポリフェニレンポリイソシアネート等のポリイソシアネート；フェニルイソシアネート、ｐ−クロロフェニルイソシアネート、ベンゼンスルホニルイソシアネート、ｐ−トルエンスルホニルイソシアネート、イソシアネートエチルメタクリレート等のモノイソシアネートが挙げられる。これらのポリ又はモノイソシアネートは、単独で、又は２種以上を混合して使用することができる。
[Poly or monoisocyanate]
Examples of the poly or monoisocyanate include aliphatic or aromatic or alicyclic poly or monoisocyanate having an average of 1 or more, preferably an average of 1 to 3 isocyanate groups in the molecule. Specifically, polyisocyanates such as diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate, polymethylene polyphenylene polyisocyanate; phenyl isocyanate, p-chlorophenyl isocyanate, Examples thereof include monoisocyanates such as benzenesulfonyl isocyanate, p-toluenesulfonyl isocyanate, and isocyanate ethyl methacrylate. These poly or monoisocyanates can be used alone or in admixture of two or more.
［活性水素含有ポリマー又はモノマー］
活性水素含有ポリマー又はモノマーとしては、例えば、水酸基、アミノ基、メルカプト基等の活性水素含有基を平均１個以上、好ましくは平均１〜４個程度含有するポリマー又はモノマーが用いられる。具体的には、１，４−ブタンジオール、１，６−ヘキサンジオール、３−メチル１，５−ペンタンジオール、ジメチロールプロピオン酸等のアルキルポリオール；ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、エチレンオキサイド変性ビスフェノールＡ、ペンタエリスリトール、ＤＰＰＡ等のポリエーテルポリオール；多価アルコール（例えば、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、トリメチロールプロパン、トリシクロデカンジメチロール等）と多塩基酸（例えば、コハク酸、フタル酸、ヘキサヒドロ無水フタル酸、テレフタル酸、アジピン酸、アゼライン酸、テトラヒドロ無水フタル酸等）との反応によって得られるポリエステルポリオール；ポリカーボネートポリオール等のポリオール、ポリアミン、ポリチオール等が挙げられる。これらの活性水素含有ポリマー又はモノマーは、単独で、又は２種以上を混合して使用することができる。
活性水素含有ポリマー又はモノマーはオキシエチレン基を含有しないことが好ましい。
（ａ）ポリ又はモノイソシアネートと（ｂ）活性水素含有モノマー又はポリマーとの反応は、例えば、重量比１００：１００〜１００：１程度、好ましくは１００：５０〜１００：１０程度で行えばよい。
[Active hydrogen-containing polymer or monomer]
As the active hydrogen-containing polymer or monomer, for example, a polymer or monomer containing an average of one or more active hydrogen-containing groups such as a hydroxyl group, an amino group, or a mercapto group, preferably about 1 to 4 on average is used. Specifically, alkyl polyols such as 1,4-butanediol, 1,6-hexanediol, 3-methyl 1,5-pentanediol, dimethylolpropionic acid; polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene Polyether polyols such as oxide-modified bisphenol A, pentaerythritol, DPPA; polyhydric alcohols (for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, tricyclodecane dimethylol) Etc.) and a polybasic acid (for example, succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc.) Triol; polyols such as polycarbonate polyols, polyamines, polythiols, and the like. These active hydrogen-containing polymers or monomers can be used alone or in admixture of two or more.
The active hydrogen-containing polymer or monomer preferably does not contain oxyethylene groups.
The reaction between (a) poly or monoisocyanate and (b) active hydrogen-containing monomer or polymer may be performed, for example, at a weight ratio of about 100: 100 to 100: 1, preferably about 100: 50 to 100: 10.
［塩を含有するモノマーまたはポリマー］
塩を含有するモノマーまたはポリマーとしては、例えば無機酸の塩（例えば、塩化ナトリウム、塩化カリウム等）、有機酸の塩（例えば、酢酸ナトリウム、アスコルビン酸ナトリウム等）を含有するモノマーまたはポリマーが使用できる。好ましくは、ウレタンプレポリマーとの溶解性から、有機酸の塩を含有するモノマーまたはポリマーを用いるが、雨などにより自然界に溶け出さないためにはウレタン化する必要があり、ヒドロキシ酸の塩を含有するモノマーまたはポリマー用いるのがより好ましい。
ヒドロキシ酸としては、具体的には、グリコール酸、乳酸、タルトロン酸、グリセリン酸、ヒドロキシ酪酸、リンゴ酸、酒石酸、シトラマル酸、クエン酸、イソクエン酸、ロイシン酸、メバロン酸、パントイン酸、リシノール酸、リシネライジン酸、セレブロン酸、キナ酸、シキミ酸等の脂肪族ヒドロキシ酸；サリチル酸、クレオソート酸、バニリン酸、シリング酸、ピロカテク酸、レソルシル酸、プロトカテク酸、ゲンチジン酸、オルセリン酸、没食子酸、マンデル酸、ベンジル酸、アトロラクチン酸、メリロト酸、フロレト酸、クマル酸、ウンベル酸、コーヒー酸、フェルラ酸、シナピン酸等の芳香族ヒドロキシ酸等が挙げられる。塩としては、具体的には、アルカリ金属塩（カリウム、ナトリウム等）、アルカリ土類金属塩（カルシウム、マグネシウム等）、アンモニューム塩等が挙げられる。
塩を含有するモノマーまたはポリマーの含有量は、ウレタンプレポリマー全体に対して０．１〜３０重量％程度、好ましくは０．１〜１０重量％、より好ましくは０．１〜５重量％である。上記範囲であれば、空気中からの吸湿量が適切であり、ウレタンプレポリマーの硬化が均一に行われるので、バラスト固定力の低下が抑えられる。
[Monomer or polymer containing salt]
As the monomer or polymer containing a salt, for example, a monomer or polymer containing a salt of an inorganic acid (eg, sodium chloride, potassium chloride, etc.) or a salt of an organic acid (eg, sodium acetate, sodium ascorbate, etc.) can be used. . Preferably, from the viewpoint of solubility with the urethane prepolymer, a monomer or polymer containing a salt of an organic acid is used. However, in order not to dissolve in nature due to rain or the like, it is necessary to urethanize, and a salt of a hydroxy acid is contained. More preferably, a monomer or polymer is used.
Specific examples of the hydroxy acid include glycolic acid, lactic acid, tartronic acid, glyceric acid, hydroxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucine acid, mevalonic acid, pantoic acid, ricinoleic acid, Aliphatic hydroxy acids such as ricineraidic acid, cerebronic acid, quinic acid, shikimic acid; salicylic acid, creosote acid, vanillic acid, syringic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, orthoric acid, gallic acid, mandelic acid And aromatic hydroxy acids such as benzylic acid, atrolactic acid, mellilotic acid, furoletic acid, coumaric acid, umberic acid, caffeic acid, ferulic acid, and sinapinic acid. Specific examples of the salt include alkali metal salts (such as potassium and sodium), alkaline earth metal salts (such as calcium and magnesium), and ammonium salts.
The content of the salt-containing monomer or polymer is about 0.1 to 30% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on the entire urethane prepolymer. . If it is the said range, since the moisture absorption amount from air | atmosphere is suitable and hardening of a urethane prepolymer is performed uniformly, the fall of a ballast fixing force is suppressed.
［イソシアネート基を含有するポリウレタンプレポリマー］
イソシアネート基を含有するポリウレタンプレポリマーとしては、例えばイソシアネート基含有量を２〜５０％程度、好ましくは５〜２０％程度含有するポリウレタンプレポリマーが挙げられる。上記範囲であれば、フリーのイソシアネート基の量が適切であり、道床安定剤の貯蔵安定性に優れる。また、バラストに散布した後、イソシアネート基と水との反応による副生成物の炭酸ガスが多量に発生して、樹脂がスポンジ状に固まることもない。
一液湿気硬化型道床安定剤中のポリウレタンプレポリマーの含有量は、道床安定剤全体に対して、例えば３０〜９５重量％程度、好ましくは５０〜９０重量％程度、より好ましくは５０〜８０重量％程度にすればよい。
[Polyurethane prepolymer containing isocyanate groups]
Examples of the polyurethane prepolymer containing an isocyanate group include a polyurethane prepolymer containing an isocyanate group content of about 2 to 50%, preferably about 5 to 20%. If it is the said range, the quantity of a free isocyanate group is suitable and it is excellent in the storage stability of a road bed stabilizer. Further, after spraying on the ballast, a large amount of carbon dioxide as a by-product due to the reaction between the isocyanate group and water is not generated, and the resin does not harden in a sponge shape.
The content of the polyurethane prepolymer in the one-component moisture-curing type bed bed stabilizer is, for example, about 30 to 95% by weight, preferably about 50 to 90% by weight, and more preferably 50 to 80% by weight with respect to the whole bed bed stabilizer. %.
［分解促進剤］
分解促進剤としては、例えば、日光、紫外線、熱、水、酵素、微生物の作用によって熱可塑性樹脂や熱硬化性樹脂の分子結合を分断し最終的には水や二酸化炭素、コンポストなどの無害な物質にまで分解を促進させる重合体組成物を用いることができる。具体的には、熱可塑性樹脂や熱硬化性樹脂成分の分解を促進するための、脂肪酸、脂肪酸エステル、天然脂肪、天然もしくは合成ゴム、またはこれらの混合物から選ばれた酸化可能な成分と、酸化反応を開始させる遷移金属成分と、分解過程の開始を遅延させる非金属安定化成分とからなる酸化分解促進剤（特許第２９６１１３８号公報）等が挙げられる。具体的には、デグラノボンやＳ−ＡＷシロップ（ノボンジャパン株式会社製）等を用いることができる
一液湿気硬化型道床安定剤中の分解促進剤の含有量は、道床安定剤全体に対して、例えば０．１〜１０重量％程度、好ましくは０．１〜５重量％程度、より好ましくは０．１〜２重量％程度にすればよい。上記範囲であれば、分解促進速度が適切となり、バラスト固定から数ヵ月経過後の突き崩しが容易となる。
[Degradation accelerator]
As the decomposition accelerator, for example, the molecular bond of thermoplastic resin or thermosetting resin is broken by the action of sunlight, ultraviolet rays, heat, water, enzymes, microorganisms, and finally harmless such as water, carbon dioxide, compost etc. A polymer composition that promotes decomposition to a substance can be used. Specifically, an oxidizable component selected from fatty acids, fatty acid esters, natural fats, natural or synthetic rubbers, or mixtures thereof to promote the decomposition of thermoplastic resins and thermosetting resin components, and oxidation Examples thereof include an oxidative decomposition accelerator (Japanese Patent No. 29611138) composed of a transition metal component for initiating the reaction and a nonmetal stabilizing component for delaying the initiation of the decomposition process. Specifically, degranobon, S-AW syrup (manufactured by Novon Japan Co., Ltd.) and the like can be used. The content of the decomposition accelerator in the one-component moisture-curing type bed bed stabilizer is based on the whole bed bed stabilizer. For example, it may be about 0.1 to 10% by weight, preferably about 0.1 to 5% by weight, more preferably about 0.1 to 2% by weight. If it is the said range, decomposition | disassembly acceleration | stimulation speed | velocity | rate will become suitable and it will be easy to break down after several months pass from ballast fixation.
［減粘剤］
減粘剤としては、例えば、炭素数６〜２２の高級脂肪酸、植物油又は動物油脂肪酸のエステル、モノグリセライド、ジグリセライド、トリグリセライド、多塩基酸又はその酸無水物等の炭素数１〜２２のアルキルエステル、脂肪族、脂環族、芳香族炭化水素これらの混合物等で、水に対する溶解度が１．０重量％未満の非水溶性かつ性状が常温液体であるものが挙げられる。
高級脂肪酸としては、例えば、直鎖又は分岐鎖をもつ炭素数６〜２２の飽和又は不飽和の高級脂肪酸が挙げられ、具体的にはカプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、オレイン酸、ノナデカン酸、ベヘニン酸、エルカ酸、１２−ヒドロキシステアリン酸、リシノール酸等が挙げられる。
植物油若しくは動物油脂肪酸としては、ヤシ油脂肪酸、綿実油脂肪酸、トウモロコシ油脂肪酸、牛脂脂肪酸、ババス脂肪酸、パーム核油脂肪酸、大豆油脂肪酸、あまに油脂肪酸、ひまし油脂肪酸、オリーブ油脂肪酸、鯨油脂肪酸等の植物油又は動物油脂肪酸等が挙げられる。
多塩基酸としては、蟻酸、マロン酸、シュウ酸、アジピン酸、セバシン酸、安息香酸、フタル酸、コハク酸、アジピン酸等が挙げられる。
脂肪族、脂環族、芳香族炭化水素としては、イソ、ノルマルパラフィン、石油ナフサ、メチルシクロヘキサン、イソホロン、ベンゼン、トルエン、キシレン等が上げられる。
減粘剤は、天然品又は天然品を常法により適宜精製した天然品由来のものでもよく、また石油由来などの合成品であってもよい。地球温暖化防止への取り組みが世界的規模で取り組まれ始めている昨今、炭酸ガスを排出しない天然素材を出発原料とした製品の開発が国内外から求められているという点から、天然品又は天然品由来のものが好ましい。
一液湿気硬化型道床安定剤中の減粘剤の含有量は、道床安定剤全体に対して、例えば５重量％以上、好ましくは１０〜５０重量％程度、より好ましくは２０〜５０重量％程度にすればよい。上記範囲であれば、道床安定剤の粘度が適切となり、バラスト表面にポリウレタン樹脂が適切量付着するので、バラストの固定強度に優れる。
[Thickener]
Examples of the thinning agent include alkyl esters having 1 to 22 carbon atoms such as higher fatty acids having 6 to 22 carbon atoms, esters of vegetable oils or animal oil fatty acids, monoglycerides, diglycerides, triglycerides, polybasic acids or acid anhydrides thereof, and fats. Aliphatic, alicyclic, aromatic hydrocarbons, and the like, which are water-insoluble with a solubility in water of less than 1.0% by weight and are liquid at room temperature.
Examples of higher fatty acids include linear or branched C6-C22 saturated or unsaturated higher fatty acids, specifically caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, Examples include palmitic acid, stearic acid, isostearic acid, oleic acid, nonadecanoic acid, behenic acid, erucic acid, 12-hydroxystearic acid, and ricinoleic acid.
Vegetable oil or animal oil fatty acids include coconut oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid, beef tallow fatty acid, babas fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, olive oil fatty acid, whale oil fatty acid, etc. And animal oil fatty acids.
Examples of the polybasic acid include formic acid, malonic acid, oxalic acid, adipic acid, sebacic acid, benzoic acid, phthalic acid, succinic acid, and adipic acid.
Examples of the aliphatic, alicyclic, and aromatic hydrocarbons include iso, normal paraffin, petroleum naphtha, methylcyclohexane, isophorone, benzene, toluene, and xylene.
The viscosity reducing agent may be a natural product or a natural product obtained by appropriately purifying a natural product by a conventional method, or may be a synthetic product such as petroleum. In recent years, efforts to prevent global warming have begun on a global scale, and the development of products that use natural materials that do not emit carbon dioxide as a starting material has been demanded both domestically and overseas. The thing of origin is preferable.
The content of the viscosity reducing agent in the one-component moisture curing type bed bed stabilizer is, for example, 5% by weight or more, preferably about 10 to 50% by weight, and more preferably about 20 to 50% by weight with respect to the whole bed bed stabilizer. You can do it. If it is the said range, since the viscosity of a road bed stabilizer will become appropriate and a suitable amount of polyurethane resin will adhere to the ballast surface, it is excellent in the fixed strength of a ballast.
本発明の一液湿気硬化型道床安定剤は、２０℃での水に対する溶解度が１．０重量％未満の疎水性であり、引火点が２００℃を越え、消防法上の危険物第４類第４石油類であることが好ましい。また、湿気硬化に際して従来用いられる第３級アミン類、有機金属化合物などのウレタン化触媒を含有しないことが好ましい。
本発明の一液湿気硬化型道床安定剤は、イソシアネート含有ポリウレタンプレポリマー、分解促進剤、及び減粘剤を公知の方法で混合することにより製造可能である。道床安定剤は、じょうろ等の公知の散布器により散布が可能である。
The one-component moisture-curing type bed bed stabilizer of the present invention is hydrophobic with a water solubility at 20 ° C. of less than 1.0% by weight, a flash point exceeding 200 ° C. The fourth petroleum is preferable. Moreover, it is preferable not to contain urethanization catalysts such as tertiary amines and organometallic compounds conventionally used for moisture curing.
The one-component moisture-curing road bed stabilizer of the present invention can be produced by mixing an isocyanate-containing polyurethane prepolymer, a decomposition accelerator, and a viscosity reducing agent by a known method. The bed bed stabilizer can be sprayed by a known sprayer such as a watering can.
以下に、本発明の実施例及び比較例を提示する。 Below, the Example and comparative example of this invention are presented.
実施例１
攪拌羽根、還流装置、温度計を設置した加温装置付き四つ口セパラブルフラスコに窒素ガス雰囲気下、ポリメリックＭＤＩを７２重量部投入し、液温を５０℃に調整した。次に攪拌しながらポリエーテルポリオール（株式会社ＡＤＥＫＡ製Ｐ−３０００＝平均数分子量３０００、２官能ポリプロピレングリコール）１５重量部、リシノール酸トリグリセリド１０重量部、リシノール酸Ｎａ２重量部を投入し８０℃で３時間反応させた。反応終了後液温を５０℃まで下げた後、分解促進剤１重量部を投入して１５分間攪拌後ポリサイザー Ｗ−２３０−Ｈ（ＤＩＣ株式会社製、引火点２５０℃以上） ６７重量部投入して１５分間攪拌した。得られたウレタンプレポリマー溶液は２５℃で粘度が５００ｍＰａ・ｓ、固形分６０％のやや霞のある褐色粘稠液であった。
Example 1
Under a nitrogen gas atmosphere, 72 parts by weight of polymeric MDI was charged into a four-necked separable flask equipped with a heating device equipped with a stirring blade, a reflux device, and a thermometer, and the liquid temperature was adjusted to 50 ° C. Next, 15 parts by weight of polyether polyol (P-3000 manufactured by ADEKA Co., Ltd. = average number molecular weight 3000, bifunctional polypropylene glycol), 10 parts by weight of ricinoleic acid triglyceride, and 2 parts by weight of ricinoleic acid Na were added while stirring. Reacted for hours. After the completion of the reaction, the temperature of the solution was lowered to 50 ° C., 1 part by weight of a decomposition accelerator was added, and the mixture was stirred for 15 minutes. And stirred for 15 minutes. The obtained urethane prepolymer solution was a slightly viscous brown viscous liquid having a viscosity of 500 mPa · s and a solid content of 60% at 25 ° C.
比較例１
実施例１と同様に加温装置付き四つ口セパラブルフラスコに窒素ガス雰囲気下、ポリメリックＭＤＩを６５重量部投入し、液温を５０℃に調整した。次に攪拌しながらポリエーテルポリオール（株式会社ＡＤＥＫＡ製Ｐ−３０００＝平均数分子量３０００、２官能ポリプロピレングリコール）１２重量部、ポリオキシエチレン含有ポリエーテルポリオール（株式会社ＡＤＥＫＡ製ＰＲ−３００７＝数平均分子量３０００、２官能、ポリオキシエチレン：ポリオキシプロピレンの重量比７：３のランダム重合ポリエーテルポリオール）２０重量部、リシノール酸Ｎａ２重量部を投入し、８０℃で３時間反応させた。反応終了後液温を５０℃まで下げた後、分解促進剤１重量部を投入して１５分間攪拌後、プロピレンカーボネート４３重量部投入して１５分間攪拌した。得られたウレタンプレポリマー溶液は２５℃で粘度が２００ｍＰａ・ｓ、固形分７０％のやや霞のある褐色粘稠液であった。
Comparative Example 1
In the same manner as in Example 1, 65 parts by weight of polymeric MDI was charged into a four-necked separable flask equipped with a heating device in a nitrogen gas atmosphere, and the liquid temperature was adjusted to 50 ° C. Next, 12 parts by weight of polyether polyol (P-3000 manufactured by ADEKA = average number molecular weight 3000, bifunctional polypropylene glycol) with stirring, polyoxyethylene-containing polyether polyol (PR-3007 manufactured by ADEKA Corporation = number average molecular weight) 3000 parts of bifunctional, polyoxyethylene: polyoxypropylene (7: 3 random polymerization polyether polyol) 20 parts by weight and 2 parts by weight of ricinoleic acid Na were added and reacted at 80 ° C. for 3 hours. After the completion of the reaction, the liquid temperature was lowered to 50 ° C., 1 part by weight of a decomposition accelerator was added and stirred for 15 minutes, and 43 parts by weight of propylene carbonate was added and stirred for 15 minutes. The obtained urethane prepolymer solution was a slightly viscous brown viscous liquid having a viscosity of 200 mPa · s and a solid content of 70% at 25 ° C.
比較例２
実施例１と同様に加温装置付き四つ口セパラブルフラスコに窒素ガス雰囲気下、ポリメリックＭＤＩを６８重量部投入し、液温を５０℃に調整した。次に攪拌しながらポリエーテルポリオール（株式会社ＡＤＥＫＡ製Ｐ−３０００＝平均数分子量３０００、２官能ポリプロピレングリコール）１２重量部、ポリオキシエチレン含有ポリエーテルポリオール（株式会社ＡＤＥＫＡ製ＰＲ−３００７＝数平均分子量３０００、２官能、ポリオキシエチレン：ポリオキシプロピレンの重量比７：３のランダム重合ポリエーテルポリオール）２０重量部を投入し、８０℃で３時間反応させた。反応終了後液温を５０℃まで下げた後、プロピレンカーボネート４３重量部投入して１５分間攪拌した後、硬化促進のためウレタン化触媒としてＤＭＤＥＥを０．３重量部混合した。得られたウレタンプレポリマー溶液は２５℃で粘度が２００ｍＰａ・ｓ、固形分７０％でやや霞のある褐色粘稠液であった。
Comparative Example 2
In the same manner as in Example 1, 68 parts by weight of polymeric MDI was introduced into a four-necked separable flask equipped with a heating device in a nitrogen gas atmosphere, and the liquid temperature was adjusted to 50 ° C. Next, 12 parts by weight of polyether polyol (P-3000 manufactured by ADEKA = average number molecular weight 3000, bifunctional polypropylene glycol) with stirring, polyoxyethylene-containing polyether polyol (PR-3007 manufactured by ADEKA Corporation = number average molecular weight) 3000 parts of bifunctional, polyoxyethylene: polyoxypropylene random polymerization polyether polyol (7: 3 weight ratio) was added and reacted at 80 ° C. for 3 hours. After the completion of the reaction, the liquid temperature was lowered to 50 ° C., 43 parts by weight of propylene carbonate was added and stirred for 15 minutes, and 0.3 part by weight of DMDEE was mixed as a urethanization catalyst to accelerate curing. The obtained urethane prepolymer solution had a viscosity of 200 mPa · s at 25 ° C., a solid content of 70%, and a slightly viscous brown liquid.
比較例３
実施例１と同様に加温装置付き四つ口セパラブルフラスコに窒素ガス雰囲気下、ポリメリックＭＤＩを６８重量部投入し、液温を５０℃に調整した。次に攪拌しながらポリエーテルポリオール（株式会社ＡＤＥＫＡ製Ｐ−３０００＝平均数分子量３０００、２官能ポリプロピレンポリオール）１２重量部、ポリオキシエチレン含有ポリエーテルポリオール（株式会社ＡＤＥＫＡ製ＰＲ−３００７＝数平均分子量３０００、２官能、ポリオキシエチレン：ポリオキシプロピレンの重量比７：３のランダム重合ポリエーテルポリオール）２０重量部を投入し８０℃で３時間反応させた。反応終了後液温を５０℃まで下げた後、キシレン２１重量部、ソルフィットＡＣ２２重量部の混合液を投入して１５分間攪拌した後、硬化促進のためのウレタン化触媒ＤＭＤＥＥを０．３重量部混合した。得られたウレタンプレポリマー溶液は２５℃で粘度が５００ｍＰａ・ｓ、固形分７０％の褐色透明な粘稠液であった。
Comparative Example 3
In the same manner as in Example 1, 68 parts by weight of polymeric MDI was introduced into a four-necked separable flask equipped with a heating device in a nitrogen gas atmosphere, and the liquid temperature was adjusted to 50 ° C. Next, 12 parts by weight of polyether polyol (P-3000 manufactured by ADEKA Co., Ltd. = average number molecular weight 3000, bifunctional polypropylene polyol) and polyoxyethylene-containing polyether polyol (PR-3007 manufactured by ADEKA Co., Ltd. = number average molecular weight) with stirring. 3000 parts of a bifunctional, polyoxyethylene: polyoxypropylene random polymerization polyether polyol (7: 3 weight ratio) was added and reacted at 80 ° C. for 3 hours. After the completion of the reaction, the liquid temperature was lowered to 50 ° C., and then a mixed solution of 21 parts by weight of xylene and 22 parts by weight of Solfit AC was added and stirred for 15 minutes. Mixed. The obtained urethane prepolymer solution was a brown transparent viscous liquid having a viscosity of 500 mPa · s and a solid content of 70% at 25 ° C.
評価方法
＊樹脂の性状：ガラス容器を通して目視にて確認した。２４時間後に樹脂が分離、固化及び沈降物が発生していない場合を合格とした。
＊硬化性：５〜１０ｍｍ程度の花崗岩乾燥砕石を厚み２０ｍｍに敷き、各樹脂を２ｋｇ／ｍ２の量で均一に散布し２時間後完全に固着しているか否かを指蝕にて確認した。
＊接着性：５〜１０ｍｍ程度の花崗岩乾燥砕石を巾４５ｍｍ、厚み２０ｍｍに敷き、各樹脂を２ｋｇ／ｍ２の量で均一に散布し、２４時間後の圧縮破壊強度が２０Ｋｇｆ／ｃｍ２以上の場合を合格とした。
＊経時分解性：５〜１０ｍｍ程度の花崗岩乾燥砕石を巾４５ｍｍ、厚み２０ｍｍに敷き、各樹脂を２ｋｇ／ｍ２の量で均一に散布し、サンシャインウエザーメーター（スガ試験機株式会社製；型式；ＷＥＬ−ＳＵＮ−ＨＣＨ−Ｂ、放電電圧；電流５０Ｖ；６０Ａ、ブラックパネル温度；６３℃、スプレーサイクル；１８／１２０分）にて、３００時間、４００時間、５００時間暴露した後、圧縮破壊強度を測定した。初期強度の５０％以下になった時間が、３００から５００時間以内である場合を合格とした。結果を下記表１に示す。
Evaluation method * Property of resin: It confirmed visually through the glass container. The case where the resin was not separated, solidified, or sedimented after 24 hours was regarded as acceptable.
* Curability: A granite dry crushed stone of about 5 to 10 mm was laid on a thickness of 20 mm, each resin was evenly sprayed in an amount of 2 kg / m 2 , and after 2 hours, it was confirmed whether or not it was completely fixed by finger biting. .
* Adhesive: 5 to 10 mm approximately granite dried crushed stone the width 45 mm, laid in the thickness 20 mm, each resin was uniformly scattered in an amount of 2 kg / m 2, after 24 hours compression breaking strength is 20 Kgf / cm 2 or more The case was accepted.
* Degradability with time: A granite dry crushed stone of about 5 to 10 mm is spread over a width of 45 mm and a thickness of 20 mm, and each resin is uniformly sprayed in an amount of 2 kg / m 2 , and a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd .; model; WEL-SUN-HCH-B, discharge voltage; current 50V; 60A, black panel temperature; 63 ° C, spray cycle; 18/120 minutes), after 300 hours, 400 hours, and 500 hours exposure, the compression fracture strength It was measured. A case where the time when the initial strength was 50% or less was within 300 to 500 hours was regarded as acceptable. The results are shown in Table 1 below.
結果から明らかなように、比較例１、２の場合、樹脂の親水性が強く樹脂の含水量が多くなりすぎて、炭酸ガスの発生が多くなり樹脂が発泡して接着強度低下を引き起こしている。また、比較例２、３から明らかなように、分解促進剤を含有しない場合、経時分解の促進が図られず、当初の目的である線路の保守作業性の向上が図れていない。 As is clear from the results, in the case of Comparative Examples 1 and 2, the hydrophilicity of the resin is strong and the water content of the resin is excessive, so that the generation of carbon dioxide gas increases and the resin foams to cause a decrease in adhesive strength. . Further, as apparent from Comparative Examples 2 and 3, when no decomposition accelerator is contained, the degradation with time cannot be promoted, and the maintenance workability of the track, which is the original purpose, cannot be improved.
本発明の方法によれば、（ａ）ポリ又はモノイソシアネートと（ｂ）活性水素含有モノマー又はポリマーとを反応させて得られるイソシアネート含有ポリウレタンプレポリマー、分解促進剤、及び減粘剤を用いることにより、安全性が高く短期間の線路の保守が容易な一液湿気硬化型道床安定剤を得ることができる。 According to the method of the present invention, (a) by using an isocyanate-containing polyurethane prepolymer obtained by reacting a poly or monoisocyanate and (b) an active hydrogen-containing monomer or polymer, a decomposition accelerator, and a thickener. Thus, a one-component moisture-curing type bed bed stabilizer that is safe and easy to maintain for a short period of time can be obtained.
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| JPH06248191A (en) * | 1993-02-24 | 1994-09-06 | Asahi Glass Co Ltd | Moisture-curing composition |
| JP2003192888A (en) * | 2001-12-26 | 2003-07-09 | Dainippon Ink & Chem Inc | Grouting agent for roadbed macadam and method for stabilizing roadbed |
| JP2004060183A (en) * | 2002-07-25 | 2004-02-26 | Sumika Bayer Urethane Kk | Roadbed stabilizer |
| JP2004257123A (en) * | 2003-02-26 | 2004-09-16 | Totaku Industries Inc | Drain pipe for drainable pavement, and drainable paving body |
| WO2005040243A1 (en) * | 2003-10-28 | 2005-05-06 | Mitsui Chemicals Polyurethanes, Inc. | Flexible polyurethane foam and use thereof |
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| JP2010031280A (en) | 2010-02-12 |
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