JP6024244B2 - Vinyl chloride polymer latex and fiber composite for flame retardant - Google Patents
Vinyl chloride polymer latex and fiber composite for flame retardant Download PDFInfo
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Description
本発明は、難燃剤用塩化ビニル系ポリマーラテックス及び繊維複合体に関する。 The present invention relates to a vinyl chloride polymer latex for a flame retardant and a fiber composite.
従来より、車両内装材、インテリア材として使用されるプラスチック材料に対して、安全上の問題から難燃化の要求が強く、種々の難燃性規格が定められている。これに対応して繊維に難燃性を付与する方法が種々提案されている（特許文献１）。 Conventionally, with respect to plastic materials used as vehicle interior materials and interior materials, there has been a strong demand for flame retardance due to safety problems, and various flame retardancy standards have been established. In response to this, various methods for imparting flame retardancy to fibers have been proposed (Patent Document 1).
その一つとして、ハロゲン系難燃剤を配合する方法がある。臭素系難燃剤は優れた難燃性が得られるものの、難燃処理液の安定性が悪く沈降することから常時攪拌、振とうさせる必要があり、処理作業時のハンドリング性能に問題があった。 One of them is a method of blending a halogen-based flame retardant. Although brominated flame retardants have excellent flame retardancy, they have a problem in handling performance at the time of processing because they need to be constantly stirred and shaken due to poor stability of the flame retardant treatment solution and settling.
臭素系難燃剤を使用しない方法として、繊維に水酸化アルミニウム、水酸化マグネシウムなどの水和金属化合物を添加する方法が知られているが、十分な難燃性を得るためには、上記水和金属化合物を多量に添加する必要があり、繊維本来の特性が失われるという欠点を有していた。 As a method not using a brominated flame retardant, a method of adding a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide to a fiber is known. It was necessary to add a large amount of a metal compound, which had the disadvantage that the original properties of the fiber were lost.
本発明は、上記課題に鑑みてなされたものであり、塩化ビニル系ポリマーエマルジョンを用いることで、優れた難燃性、貯蔵安定性に優れた難燃剤用塩化ビニル系ポリマーラテックス、かつ色合いが良く、難燃処理作業時に良好なハンドリング性能がある繊維複合体を提供するものである。 The present invention has been made in view of the above problems. By using a vinyl chloride polymer emulsion, the vinyl chloride polymer latex for a flame retardant having excellent flame retardancy and storage stability is excellent in color. The present invention provides a fiber composite having good handling performance during a flame retardant treatment operation.
本発明者らは、上記の課題を解決するため、鋭意研究を重ねた結果、塩化ビニル系ポリマー１００重量部に対して、アルキルベンゼンスルホン酸塩１.５〜５重量部及び高級脂肪酸塩０．０５〜２.５重量部を含有し、平均粒子径が０．１２μｍ以下である難燃剤用の塩化ビニル系ポリマーラテックスは、ラテックスの貯蔵安定性に優れ、この塩化ビニル系ポリマーラテックスを用いた繊維複合体は優れた難燃性、配合安定性、色合いを持ち、ハンドリング性能の良いことを有することを見出し、本発明に至った。すなわち、本発明は、塩化ビニル系ポリマー１００重量部に対して、アルキルベンゼンスルホン酸塩１.５〜５重量部及び高級脂肪酸塩０．０５〜２.５重量部を含有し、平均粒子径が０．１２μｍ以下であることを特徴とする難燃剤用塩化ビニル系ポリマーラテックス、並びに繊維複合体である。
As a result of intensive studies to solve the above problems, the inventors of the present invention have found that 1.5 to 5 parts by weight of an alkylbenzene sulfonate and 0.05 to a higher fatty acid salt with respect to 100 parts by weight of a vinyl chloride polymer. The vinyl chloride polymer latex for flame retardant containing ˜2.5 parts by weight and having an average particle diameter of 0.12 μm or less is excellent in latex storage stability, and fibers using this vinyl chloride polymer latex The composite has been found to have excellent flame retardancy, blending stability, hue, and good handling performance, leading to the present invention. That is, the present invention contains 1.5 to 5 parts by weight of alkylbenzene sulfonate and 0.05 to 2.5 parts by weight of higher fatty acid salt with respect to 100 parts by weight of vinyl chloride polymer, and the average particle size is 0. A vinyl chloride polymer latex for a flame retardant, and a fiber composite, characterized by being .12 μm or less.
以下に本発明について詳細に説明する。 The present invention is described in detail below.
本発明の難燃剤用塩化ビニル系ポリマーラテックスは、塩化ビニル系ポリマー１００重量部に対して、アルキルベンゼンスルホン酸塩１〜１０重量部及び高級脂肪酸塩０．０５〜２．５重量部を含有するものである。 The vinyl chloride polymer latex for flame retardant of the present invention contains 1 to 10 parts by weight of alkylbenzene sulfonate and 0.05 to 2.5 parts by weight of higher fatty acid salt with respect to 100 parts by weight of vinyl chloride polymer. It is.
塩化ビニル系ポリマーは、塩化ビニルモノマー単独で重合させたもの、又は塩化ビニルモノマー及び塩化ビニルモノマーと共重合可能なモノマー（以下、共重合モノマーと略すことがある）を共重合させたものである。 The vinyl chloride polymer is obtained by polymerizing a vinyl chloride monomer alone or by copolymerizing a vinyl chloride monomer and a monomer copolymerizable with the vinyl chloride monomer (hereinafter sometimes abbreviated as a copolymerization monomer). .
共重合モノマーとしては、例えば、エチレン、プロピレン、１―ブテン、２−ブテン、１−ペンテン、１−ヘキセン、１−ヘプタン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、３−メチル−１−ブテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、４−メチル−１−ヘキセン、４．４−ジメチル−１−ヘキセン、４．４−ジメチル−１−ペンテン、４−エチル−１−ヘキセン、３−エチル−１−ヘキセン等などのα−オレフィンモノマー；スチレン、α−メチルスチレンなどの芳香族系モノマー；アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸プロピル、メタアクリル酸メチル、メタアクリル酸エチル、メタアクリル酸ブチル、メタアクリル酸プロピル、マレイン酸ジメチル、マレイン酸ジエチル、マレイン酸ジプロピル、マレイン酸ジ−ｎ−ブチル、マレイン酸ジイソブチル、マレイン酸ジ−ｎ−ペンチル、マレイン酸ジ−ｎ−ヘキシル、マレイン酸ジ−２−エチルヘキシル、フマル酸ジメチル、フマル酸ジエチル、フマル酸ジプロピル、フマル酸ジ−ｎ−ブチル、フマル酸ジイソブチル、フマル酸ジ−ｎ−ペンチル、フマル酸ジ−ｎ−ヘキシル、フマル酸ジ−２−エチルヘキシル、イタコン酸ジメチル、イタコン酸ジエチル、イタコン酸ジプロピル、イタコン酸ジ−ｎ−ブチル、イタコン酸ジイソブチル、イタコン酸ジ−ｎ−ペンチル、イタコン酸ジ−ｎ−ヘキシル、イタコン酸ジ−２−エチルヘキシル、シトラコン酸ジメチル、シトラコン酸ジエチル、シトラコン酸ジプロピル、シトラコン酸ジ−ｎ−ブチル、シトラコン酸ジイソブチル、シトラコン酸ジ−ｎ−ペンチル、シトラコン酸ジ−ｎ−ヘキシル、シトラコン酸ジ−２−エチルヘキシル、メサコン酸ジメチル、メサコン酸ジエチル、メサコン酸ジプロピル、メサコン酸ジ−ｎ−ブチル、メサコン酸ジイソブチル、メサコン酸ジ−ｎ−ペンチル、メサコン酸ジ−ｎ−ヘキシル、メサコン酸ジ−２−エチルヘキシル、グルタコン酸ジメチル、グルタコン酸ジエチル、グルタコン酸ジプロピル、グルタコン酸ジ−ｎ−ブチル、グルタコン酸ジイソブチル、グルタコン酸ジ−ｎ−ペンチル、グルタコン酸ジ−ｎ−ヘキシル、グルタコン酸ジ−２−エチルヘキシル、アリルマロン酸ジメチル、アリルマロン酸ジエチル、アリルマロン酸ジプロピル、アリルマロン酸ジ−ｎ−ブチル、アリルマロン酸ジイソブチル、アリルマロン酸ジ−ｎ−ペンチル、アリルマロン酸ジ−ｎ−ヘキシル、アリルマロン酸ジ−２−エチルヘキシル、テラコン酸ジメチル、テラコン酸ジエチル、テラコン酸ジプロピル、テラコン酸ジ−ｎ−ブチル、テラコン酸ジイソブチル、テラコン酸ジ−ｎ−ペンチル、テラコン酸ジ−ｎ−ヘキシル、テラコン酸ジ−２−エチルヘキシルなどのエチレン性不飽和カルボン酸アルキルエステル；酢酸ビニル、プロピオン酸ビニルなどのビニルエステルモノマー；アクリルアミド、メタクリルアミドなどのα，β−エチレン性不飽和モノカルボン酸アミド；ビニルメチルエーテル、ビニルセチルエーテルなどのビニルエーテルモノマー；塩化ビニリデンなどのビニリデン化合物等を挙げることができる。 Examples of the copolymerization monomer include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptane, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- Dodecene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4.4-dimethyl-1-hexene, 4.4-dimethyl- Α-olefin monomers such as 1-pentene, 4-ethyl-1-hexene and 3-ethyl-1-hexene; aromatic monomers such as styrene and α-methylstyrene; methyl acrylate, ethyl acrylate, acrylic acid Butyl, propyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, dimethyl methacrylate , Diethyl maleate, dipropyl maleate, di-n-butyl maleate, diisobutyl maleate, di-n-pentyl maleate, di-n-hexyl maleate, di-2-ethylhexyl maleate, dimethyl fumarate, Diethyl fumarate, dipropyl fumarate, di-n-butyl fumarate, diisobutyl fumarate, di-n-pentyl fumarate, di-n-hexyl fumarate, di-2-ethylhexyl fumarate, dimethyl itaconate, itaconic acid Diethyl, dipropyl itaconate, di-n-butyl itaconate, diisobutyl itaconate, di-n-pentyl itaconate, di-n-hexyl itaconate, di-2-ethylhexyl itaconate, dimethyl citraconic acid, diethyl citraconic acid, Dipropyl citraconic acid, di-n-butyl citraconic acid , Diisobutyl citraconic acid, di-n-pentyl citraconic acid, di-n-hexyl citraconic acid, di-2-ethylhexyl citraconic acid, dimethyl mesaconic acid, diethyl mesaconic acid, dipropyl mesaconic acid, di-n-butyl mesaconic acid, mesacone Diisobutyl acid, di-n-pentyl mesaconate, di-n-hexyl mesaconate, di-2-ethylhexyl mesaconate, dimethyl glutaconate, diethyl glutaconate, dipropyl glutaconate, di-n-butyl glutaconate, diisobutyl glutaconate Di-n-pentyl glutaconate, di-n-hexyl glutaconate, di-2-ethylhexyl glutaconate, dimethyl allyl malonate, diethyl allyl malonate, dipropyl allyl malonate, di-n-butyl allyl malonate, diallyl malonate Sobutyl, di-n-pentyl allylmalonate, di-n-hexyl allylmalonate, di-2-ethylhexyl allylmalonate, dimethyl teraconic acid, diethyl teraconic acid, dipropyl teraconic acid, di-n-butyl teraconic acid, diisobutyl teraconic acid, Ethylenically unsaturated carboxylic acid alkyl esters such as di-n-pentyl teraconic acid, di-n-hexyl teraconic acid, di-2-ethylhexyl teraconic acid; vinyl ester monomers such as vinyl acetate and vinyl propionate; acrylamide, methacrylamide Α, β-ethylenically unsaturated monocarboxylic acid amides such as: vinyl ether monomers such as vinyl methyl ether and vinyl cetyl ether; vinylidene compounds such as vinylidene chloride.
アルキルベンゼンスルホン酸塩としては、例えば、ドデシルベンゼンスルホン酸等と、ナトリウム、カリウム、アンモニア、トリエタノールアミン等のアルカリとの塩を挙げることができる。更にアルキル基の構造として直鎖状、分岐状どちらでも良い。入手が容易なことから、ドデシルベンゼンスルホン酸ナトリウムが好ましい。アルキルベンゼンスルホン酸塩が１重量部未満の場合は、ラテックスの貯蔵時にラテックスが凝集し沈殿物が発生し、貯蔵安定性に劣る。１０重量部を超える場合は、不純物が多くなり難燃効果が低下する。貯蔵安定性や難燃効果をより向上させるため、１．５〜５重量部が好ましい。 Examples of the alkylbenzene sulfonate include salts of dodecylbenzenesulfonic acid and the like with alkalis such as sodium, potassium, ammonia, triethanolamine and the like. Further, the structure of the alkyl group may be either linear or branched. Sodium dodecylbenzenesulfonate is preferred because it is readily available. When the alkylbenzene sulfonate is less than 1 part by weight, the latex agglomerates and precipitates during storage of the latex, resulting in poor storage stability. If it exceeds 10 parts by weight, the amount of impurities increases and the flame retardant effect decreases. In order to further improve storage stability and flame retardancy, 1.5 to 5 parts by weight is preferred.
高級脂肪酸塩としては、例えば、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸等と、ナトリウム、カリウム、アンモニア、トリエタノールアミン等のアルカリとの塩が挙げられる。入手が容易なことから、ラウリン酸カリウムが好ましい。高級脂肪酸塩の含有量は０．０５〜２．５重量部である。０．０５重量部未満だとラテックスの貯蔵時にラテックスの貯蔵安定性に劣り、２．５重量部を超えると不純物を多く含み、難燃効果が低下する。より好ましくは、０．１〜２．０重量部である。 Examples of the higher fatty acid salt include salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like with an alkali such as sodium, potassium, ammonia, triethanolamine and the like. Potassium laurate is preferred because it is easily available. The content of the higher fatty acid salt is 0.05 to 2.5 parts by weight. If it is less than 0.05 part by weight, the storage stability of the latex is inferior during storage of the latex, and if it exceeds 2.5 parts by weight, it contains a large amount of impurities and the flame retardant effect is lowered. More preferably, it is 0.1 to 2.0 parts by weight.
難燃剤用塩化ビニル系ポリマーラテックス中の塩化ビニル系ポリマーの平均粒子径は、０．２０μｍ以下である。平均粒子径が０．２０μｍを超えると長期貯蔵後に沈殿物が発生し、難燃処理作業時に、常にラテックスを攪拌、振とうするという問題がある。平均粒子径は、好ましくは０．１２μｍ以下であり、さらに好ましくは０．１０μｍ以下であり、特に好ましくは０．０５〜０．１０μｍである。 The average particle diameter of the vinyl chloride polymer in the vinyl chloride polymer latex for the flame retardant is 0.20 μm or less. When the average particle diameter exceeds 0.20 μm, precipitates are generated after long-term storage, and there is a problem that the latex is always stirred and shaken during the flame retardant treatment. The average particle diameter is preferably 0.12 μm or less, more preferably 0.10 μm or less, and particularly preferably 0.05 to 0.10 μm.
本発明の難燃剤用塩化ビニル系ポリマーラテックスは、連鎖移動剤、還元剤、緩衝剤、アルキルベンゼンスルホン酸塩及び高級脂肪酸塩以外の乳化剤等を含有していても良い。 The vinyl chloride polymer latex for flame retardant of the present invention may contain a chain transfer agent, a reducing agent, a buffering agent, an emulsifier other than alkylbenzene sulfonate and higher fatty acid salt, and the like.
ここに、連鎖移動剤とは、塩化ビニル単独重合体や塩化ビニルと共重合可能なモノマーとの共重合体の重合度を調整できるものであればよく、例えば、トリクロルエチレン、四塩化炭素などのハロゲン系炭化水素；２−メルカプトエタノール、３−メルカプトプロピオン酸オクチル、ドデシルメルカプタンなどのメルカプタン類；アセトン、ｎ−ブチルアルデヒドなどのアルデヒド類等が挙げられる。還元剤とは、例えば、亜硫酸ナトリウム、亜硫酸アンモニウム、亜硫酸水素ナトリウム、亜硫酸水素アンモニウム、チオ硫酸アンモニウム、メタ重亜硫酸カリウム、亜二チオン酸ナトリウム、ナトリウムホルムアルデヒドスルフォキシレート、Ｌ−アスコルビン酸、デキストローズ、硫酸第一鉄、硫酸銅等が挙げられる。緩衝剤とは、例えば、リン酸一または二水素アルカリ金属塩、フタル酸水素カリウム、炭酸水素ナトリウム等が挙げられる。アルキルベンゼンスルホン酸塩及び高級脂肪酸塩以外の乳化剤とは、例えば、ラウリル硫酸エステルナトリウム、ミリスチル硫酸エステルなどのアルキル硫酸エステル塩類；ジオクチルスルホコハク酸ナトリウム、ジヘキシルスルホコハク酸ナトリウムなどのスルホコハク酸塩類；ポリオキシエチレンアルキル硫酸エステル塩類；ポリオキシエチレンアルキルアリール硫酸エステル塩類等のアニオン系界面活性剤；ソルビタンモノオレート、ポリオキシエチレンソルビタンモノステアレート等のソルビタンエステル類；ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンアルキルエステル類、ポリアルキレングリコール類、ポリビニルアルコール、部分ケン化ポリビニルアルコール、部分ケン化ポリメタクリル酸メチル、ポリアクリル酸およびその塩等のノニオン系界面活性剤等が挙げられる。これらは単独でも、２種類以上含有していても良い。 Here, the chain transfer agent may be any one that can adjust the degree of polymerization of a vinyl chloride homopolymer or a copolymer with a monomer copolymerizable with vinyl chloride, such as trichloroethylene and carbon tetrachloride. Halogen-based hydrocarbons; mercaptans such as 2-mercaptoethanol, octyl 3-mercaptopropionate, and dodecyl mercaptan; aldehydes such as acetone and n-butyraldehyde. Examples of the reducing agent include sodium sulfite, ammonium sulfite, sodium hydrogen sulfite, ammonium hydrogen sulfite, ammonium thiosulfate, potassium metabisulfite, sodium dithionite, sodium formaldehyde sulfoxylate, L-ascorbic acid, dextrose, Examples thereof include ferrous sulfate and copper sulfate. Examples of the buffer include mono- or dihydrogen alkali metal phosphates, potassium hydrogen phthalate, sodium hydrogen carbonate, and the like. Examples of emulsifiers other than alkylbenzene sulfonate and higher fatty acid salt include alkyl sulfate esters such as sodium lauryl sulfate and myristyl sulfate; sulfosuccinates such as sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate; polyoxyethylene alkyl Sulfate esters; Anionic surfactants such as polyoxyethylene alkylaryl sulfate salts; Sorbitan esters such as sorbitan monooleate and polyoxyethylene sorbitan monostearate; Polyoxyethylene alkylphenyl ethers and polyoxyethylene alkyl esters , Polyalkylene glycols, polyvinyl alcohol, partially saponified polyvinyl alcohol, partially saponified polymethyl methacrylate, Riakuriru acid and nonionic surface active agents such salts thereof. These may be used alone or in combination of two or more.
本発明の難燃剤用塩化ビニル系ポリマーラテックスは、塩化ビニルモノマー単独、又は塩化ビニルモノマーと共重合モノマーを、アルキルベンゼンスルホン酸塩１〜１０重量部、好ましくは１．５〜５重量部、及び高級脂肪酸塩０．０５〜２．５重量部の存在下、乳化重合によって得られる。 The vinyl chloride polymer latex for the flame retardant of the present invention is composed of vinyl chloride monomer alone or vinyl chloride monomer and copolymer monomer in an amount of 1 to 10 parts by weight, preferably 1.5 to 5 parts by weight, of alkylbenzene sulfonate. It is obtained by emulsion polymerization in the presence of 0.05 to 2.5 parts by weight of a fatty acid salt.
乳化重合は、水を分散媒とし、分散媒に対して５〜１５０重量％の塩化ビニルモノマー単独、又は塩化ビニルモノマーと共重合モノマーを、所定量のアルキルベンゼンスルホン酸塩及び高級脂肪酸塩の存在下、重合開始剤を用い、３０〜１００℃程度、好ましくは４０〜８０℃で３〜２４時間、攪拌下重合することにより行われる。 Emulsion polymerization uses water as a dispersion medium, and 5 to 150% by weight of vinyl chloride monomer alone or vinyl chloride monomer and copolymer monomer in the presence of a predetermined amount of alkylbenzene sulfonate and higher fatty acid salt. The polymerization is carried out using a polymerization initiator at about 30 to 100 ° C., preferably at 40 to 80 ° C. for 3 to 24 hours with stirring.
前記重合開始剤は、例えば、過硫酸カリウム、過硫酸アンモニウム等の水溶性開始剤、２、２’−アゾビスイソブチロニトリル、２、２’−アゾビス−２−メチルブチロニトリル、ラウロイルパーオキサイド、ｔ−ブチルペルオキシピバレート、ジアシルパーオキサイド、パーオキシエステル、パーオキシジカーボネート等の油溶性開始剤等を挙げることができる。 Examples of the polymerization initiator include water-soluble initiators such as potassium persulfate and ammonium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, lauroyl peroxide. , T-butyl peroxypivalate, diacyl peroxide, peroxy ester, peroxydicarbonate, and other oil-soluble initiators.
塩化ビニルモノマーの重合率は、全モノマーに対して８０〜９７重量％であることが好ましい。 The polymerization rate of the vinyl chloride monomer is preferably 80 to 97% by weight based on the total monomers.
重合の終了は、容器内の圧力を常圧、さらに減圧し、モノマーを回収することにより行う。重合禁止剤を添加して重合を終了させてもよい。 The polymerization is terminated by recovering the monomer by reducing the pressure in the vessel to normal pressure and further reducing the pressure. A polymerization inhibitor may be added to terminate the polymerization.
必要に応じ、重合終了後のラテックスに、塩化ビニル系ポリマー１００重量部に対してアルキルベンゼンスルホン酸スルホン酸塩１〜１０重量部及び高級脂肪酸塩０．０５〜２．５重量部を含有するように、これらの乳化剤を追加添加することができる。 If necessary, the latex after completion of polymerization contains 1 to 10 parts by weight of alkylbenzene sulfonic acid sulfonate and 0.05 to 2.5 parts by weight of higher fatty acid salt with respect to 100 parts by weight of the vinyl chloride polymer. These emulsifiers can be additionally added.
さらに、本発明の難燃剤用塩化ビニル系ポリマーラテックスを製造する際に、重合の安定化やスケ−ル発生量の低減を目的として、連鎖移動剤、還元剤、緩衝剤、アルキルベンゼンスルホン酸塩以外の乳化剤等を添加することもできる。 Furthermore, when producing the vinyl chloride polymer latex for flame retardant of the present invention, for the purpose of stabilizing the polymerization and reducing the amount of scale generated, other than chain transfer agent, reducing agent, buffering agent, alkylbenzene sulfonate. An emulsifier or the like can also be added.
本発明の繊維複合体は、本発明の難燃剤用塩化ビニル系ポリマーラテックスが繊維に含浸されているものである。本発明の繊維複合体は、本発明の難燃剤用塩化ビニル系ポリマーラテックスが繊維に含浸されていることにより、難燃性に優れるものとなる。繊維とは、例えば、ポリエステル繊維、ポリエチレン繊維、ポリプロピレン繊維、ポリアミド繊維、アクリル繊維、ウレタン繊維、ポリ塩化ビニル繊維、ポリ塩化ビニリデン繊維、アセテート繊維などの合成繊維；パルプ、木綿、羊毛、ヤシ繊維、麻繊維、竹繊維などの天然繊維；ガラス繊維、セラミック繊維、炭素繊維、金属繊維などの無機繊維等が挙げられる。 The fiber composite of the present invention is obtained by impregnating fibers with the vinyl chloride polymer latex for flame retardant of the present invention. The fiber composite of the present invention is excellent in flame retardancy when the vinyl chloride polymer latex for flame retardant of the present invention is impregnated in the fiber. Examples of fibers include polyester fibers, polyethylene fibers, polypropylene fibers, polyamide fibers, acrylic fibers, urethane fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, and acetate fibers; pulp, cotton, wool, palm fibers, Examples thereof include natural fibers such as hemp fiber and bamboo fiber; inorganic fibers such as glass fiber, ceramic fiber, carbon fiber, and metal fiber.
本発明の繊維複合体は、本発明の難燃剤用塩化ビニル系ポリマーラテックスを繊維に含浸することにより得ることができる。含浸の方法としては、特に制限はなく、公知の含浸方法の中から適宜選択した方法により含浸させることができるが、例えば、浸漬法などが好適に挙げられる。 The fiber composite of the present invention can be obtained by impregnating the fiber with the vinyl chloride polymer latex for flame retardant of the present invention. The impregnation method is not particularly limited and can be impregnated by a method appropriately selected from known impregnation methods. For example, a dipping method and the like are preferable.
本発明では、貯蔵安定性に優れた難燃剤用塩化ビニル系ポリマーラテックス、難燃性、色合い、ハンドリング性能に優れた繊維複合体を提供することができる。 In the present invention, it is possible to provide a vinyl chloride polymer latex for flame retardants excellent in storage stability, and a fiber composite excellent in flame retardancy, hue and handling performance.
以下の実施例、比較例により、本発明をさらに具体的に説明するが、本発明はこれらの実施例により何らの制限を受けるものではない。 The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to these examples.
なお、以下の実施例、比較例における難燃剤用塩化ビニルラテックス組成物の評価法は以下のとおりである。 In addition, the evaluation method of the vinyl chloride latex composition for flame retardants in the following examples and comparative examples is as follows.
＜難燃剤用塩化ビニル系ポリマーラテックス（以下、ＰＶＣラテックスと略すことがある）の貯蔵安定性＞
ＰＶＣラテックスを水で希釈し、固形分を３０重量％に調整した。ＰＶＣラテックス５００ｇを透明なガラス瓶に入れ、室温下１ヶ月間静置し、ラテックス中の沈降物発生の有無を目視で確認し、以下の通り評価した。
<Storage stability of vinyl chloride polymer latex for flame retardant (hereinafter sometimes abbreviated as PVC latex)>
The PVC latex was diluted with water to adjust the solid content to 30% by weight. 500 g of PVC latex was placed in a transparent glass bottle and allowed to stand at room temperature for 1 month. The presence or absence of precipitates in the latex was visually confirmed and evaluated as follows.
○：沈降物の発生が全く無い。 ○: No sediment is generated.
△：僅かに発生が見られた。 Δ: Slight occurrence was observed.
×：多量の沈降物発生が見られた。 X: A large amount of sediment was observed.
＜ＰＶＣラテックス中のドデシルベンゼンスルホン酸ナトリウム量及びラウリン酸カリウム量＞
重合終了後のＰＶＣラテックスを重合器より採取し、４０℃で２４時間真空乾燥後の固形分測定によりビニルモノマーの重合転化率を求め、仕込み組成よりポリマー中のドデシルベンゼンスルホン酸ナトリウム量及びラウリン酸カリウム量を求めた。
<Amount of sodium dodecylbenzenesulfonate and amount of potassium laurate in PVC latex>
The PVC latex after the polymerization is collected from the polymerization vessel, the polymerization conversion rate of the vinyl monomer is obtained by measuring the solid content after vacuum drying at 40 ° C. for 24 hours, and the amount of sodium dodecylbenzenesulfonate and lauric acid in the polymer from the charged composition. The amount of potassium was determined.
＜ＰＶＣラテックスの平均粒子径の測定方法＞
ＰＶＣラテックスの平均粒子径は、粒径分布測定機（マイクロトラックＵＰＡ１５０、日機装社製）を用い、分散媒の屈折率を１．３３に設定し粒径分布を測定し、メジアン粒径を求め、各々の樹脂粒子の平均粒子径とした。
<Measuring method of average particle diameter of PVC latex>
The average particle size of the PVC latex is measured using a particle size distribution measuring device (Microtrac UPA150, manufactured by Nikkiso Co., Ltd.), the refractive index of the dispersion medium is set to 1.33, the particle size distribution is measured, and the median particle size is obtained. It was set as the average particle diameter of each resin particle.
＜燃焼速度の測定＞
１００×３５０ｍｍに裁断したポリエステル繊維からなる織布を用意した。
<Measurement of burning rate>
A woven fabric made of polyester fibers cut to 100 × 350 mm was prepared.
１２０ｍｌのＰＶＣラテックスを用意して、トレイに流し込んだ。その後、織布をトレイに１分間浸漬した。その後織布を裏返してさらに１分間浸漬した。その後、トレイから織布を取出し、手で絞液操作を行った。絞液操作は、織布の上端を持ち、４回絞液操作を行った。次に織布を逆にして４回絞液操作を行った。その後、１３０℃、５分で乾燥を行い、これを試験片とした。 120 ml of PVC latex was prepared and poured into a tray. Thereafter, the woven fabric was immersed in the tray for 1 minute. Thereafter, the woven fabric was turned over and immersed for another 1 minute. Thereafter, the woven fabric was taken out from the tray, and the squeezing operation was performed by hand. The drawing operation was performed four times with the upper end of the woven fabric. Next, the squeezing operation was performed 4 times with the woven fabric reversed. Thereafter, drying was performed at 130 ° C. for 5 minutes, and this was used as a test piece.
この繊維は１００ｇ／ｍ２となるように、ＰＶＣラテックス濃度を調整した。 The PVC latex concentration was adjusted so that this fiber was 100 g / m 2 .
得られた試験片について燃焼性を測定した。燃焼試験は、試験片（３５０×１００ｍｍ）を水平に保持し、３８ｍｍ炎を１５秒間接炎し、Ａ標線からＢ標線間２５４ｍｍに対する燃焼速度により判定を行った（自動車室内用有機資材の燃焼試験方法 ＦＭＶＳＳ−３０２法による）。 The combustibility of the obtained test piece was measured. In the combustion test, a test piece (350 × 100 mm) was held horizontally, a 38 mm flame was indirectly flamed for 15 seconds, and a determination was made based on the burning speed with respect to 254 mm between the A marked line and the B marked line (for organic materials for automobile interiors). Combustion test method FMVSS-302 method).
判定 ○：燃焼速度が１００ｍｍ／ｍｉｎ以下
×：燃焼速度が１００ｍｍ／ｍｉｎを超える
＜色合いの測定＞
色合いは目視で測定し、ポリエステル繊維と同等の色合いのものを○、ポリエステル繊維より色がポリマーにより白くなったものを×とした。
Judgment ○: Burning speed is 100 mm / min or less ×: Burning speed exceeds 100 mm / min <Measurement of hue>
The hue was measured visually, and a color having the same color as that of the polyester fiber was marked with ◯, and a color whitened by the polymer from the polyester fiber was marked with x.
実施例１
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム１５ｇ（モノマーに対して０．１重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．５６重量部、ラウリン酸カリウム：０．１１重量部）。平均粒子径を測定したところ０．１μｍであった。
Example 1
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.50 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 15 g of 5% by weight potassium laurate (0.1 part by weight with respect to the monomer) was added. A vinyl chloride polymer latex for a flame retardant was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 0.11 parts by weight based on 100 parts by weight of vinyl chloride homopolymer). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物○であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and storage stability. The results were burning rate ◯, hue ◯, and sediment ○.
実施例２
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム７５ｇ（モノマーに対して０．５重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．５６重量部、ラウリン酸カリウム：０．５６重量部）。平均粒子径を測定したところ０．１μｍであった。
Example 2
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.50 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 75 g of 5 wt% potassium laurate (0.5 parts by weight with respect to the monomer) was additionally added. A vinyl chloride polymer latex for a fuel was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 0.56 parts by weight based on 100 parts by weight of vinyl chloride homopolymer). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物○であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and storage stability. The results were burning rate ◯, hue ◯, and sediment ○.
実施例３
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、１５重量％ラウリン酸カリウム１００ｇ（モノマーに対して２．０重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．５６重量部、ラウリン酸カリウム：２．２２重量部）。平均粒子径を測定したところ０．１μｍであった。
Example 3
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.50 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, the unreacted vinyl chloride monomer was recovered, and 100 g of 15 wt% potassium laurate (2.0 parts by weight with respect to the monomer) was added. A vinyl chloride polymer latex for a fuel was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 2.22 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物○であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and storage stability. The results were burning rate ◯, hue ◯, and sediment ○.
実施例４
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ステアリン酸カリウム７５ｇ（モノマーに対して０．５重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．５６重量部、ステアリン酸カリウム：０．５６重量部）。平均粒子径を測定したところ０．１μｍであった。
Example 4
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.50 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 75 g of 5 wt% potassium stearate (0.5 parts by weight with respect to the monomer) was added and difficult. A vinyl chloride polymer latex for a fuel was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium stearate: 0.56 parts by weight with respect to 100 parts by weight of vinyl chloride homopolymer). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、付着量、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物○であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, adhesion amount, hue, and storage stability. As a result, the burning rate was o, the hue o, and the sediment o.
実施例５
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１６２ｇ（モノマーに対して１．０８重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム７５ｇ（モノマーに対して０．５重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：１．７６重量部、ラウリン酸カリウム：０．５６重量部）。平均粒子径を測定したところ０．１μｍであった。
Example 5
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.50 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and from 60 minutes after the start of polymerization, 162 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.08 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 75 g of 5 wt% potassium laurate (0.5 parts by weight with respect to the monomer) was additionally added. A vinyl chloride polymer latex for a fuel was obtained (sodium dodecylbenzenesulfonate: 1.76 parts by weight, potassium laurate: 0.56 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物○であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and storage stability. The results were burning rate ◯, hue ◯, and sediment ○.
実施例６
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム７５ｇ（モノマーに対して０．５重量部）、１５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１２５ｇ（モノマーに対して２．５０重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：５．３３重量部、ラウリン酸カリウム：０．５６重量部）。平均粒子径を測定したところ０．１μｍであった。
Example 6
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.50 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, 75 g of 5 wt% potassium laurate (0.5 wt part relative to the monomer), 15 wt% dodecylbenzene. 125 g of an aqueous sodium sulfonate solution (2.50 parts by weight with respect to the monomer) was additionally added to obtain a vinyl chloride polymer latex for flame retardant (sodium dodecylbenzenesulfonate with respect to 100 parts by weight of vinyl chloride homopolymer: 5.33). Parts by weight, potassium laurate: 0.56 parts by weight). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物○であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and storage stability. The results were burning rate ◯, hue ◯, and sediment ○.
実施例７
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム７．５ｇ（モノマーに対して０．０５重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．５６重量部、ラウリン酸カリウム：０．０６重量部）。平均粒子径を測定したところ０．１μｍであった。
Example 7
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.50 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 7.5 g of 5% by weight potassium laurate (0.05 parts by weight with respect to the monomer) was added. Thus, a vinyl chloride polymer latex for a flame retardant was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 0.06 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物○であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and storage stability. The results were burning rate ◯, hue ◯, and sediment ○.
実施例８
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１６２ｇ（モノマーに対して１．０８重量部）と５重量％ラウリン酸カリウム水溶液５７ｇ（モノマーに対して０．３８重量部）を２９０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム４０．５ｇ（モノマーに対して０．２７重量部）、５重量％濃度のラウリン酸カリウム１３．５ｇ（モノマーに対して０．０９重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：０．５２重量部）。平均粒子径を測定したところ０．１μｍであった。
Example 8
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.50 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. Keeping the temperature at 66 ° C., 60 minutes after the start of polymerization, 162 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.08 parts by weight based on the monomer) and 57 g of a 5 wt% potassium laurate aqueous solution (based on the monomer) 0.38 parts by weight) was continuously added over 290 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered. To this, 40.5 g of sodium dodecylbenzenesulfonate having a concentration of 5% by weight (0.27 parts by weight based on the monomer) and 13.5 g of potassium laurate having a concentration of 5% by weight (0.09 parts by weight based on the monomer) were added. Additional addition was performed to obtain a vinyl chloride polymer latex for flame retardant (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 0.52 parts by weight with respect to 100 parts by weight of vinyl chloride homopolymer). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物○であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and storage stability. The results were burning rate ◯, hue ◯, and sediment ○.
比較例１
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．５６重量部）。平均粒子径を測定したところ０．１μｍであった。
Comparative Example 1
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.50 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride polymer latex (sodium dodecylbenzenesulfonate: 100 parts by weight of vinyl chloride homopolymer: 2 .56 parts by weight). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、沈降性を確認したところ、燃焼速度○、色合い○、沈降物×であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and sedimentation, and the burning rate was o, the hue o, and the sediment x.
比較例２
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム３ｇ（モノマーに対して０．０２重量部）を追加添加し、塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．５６重量部、ラウリン酸カリウム：０．０２重量部）。平均粒子径を測定したところ０．１μｍであった。
Comparative Example 2
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.50 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 3 g of 5% by weight potassium laurate (0.02 parts by weight with respect to the monomer) was additionally added. A vinyl polymer latex was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 0.02 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物×であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and storage stability. The results were burning rate ◯, hue ◯, and sediment x.
比較例３
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇを仕込み、温度を６６℃に上げた。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１５ｇ（モノマーに対して０．１０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム７５ｇ（モノマーに対して０．５０重量部）を追加添加し、塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：０．１１重量部、ラウリン酸カリウム：０．５６重量部）。平均粒子径を測定したところ０．２７μｍであった。
Comparative Example 3
A 2.5 L autoclave was charged with 830 g of deionized water, 750 g of vinyl chloride monomer, and 6.8 g of 3 wt% potassium persulfate, and the temperature was raised to 66 ° C. The temperature was kept at 66 ° C., and 60 g after the start of polymerization, 15 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (0.10 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 75 g of 5 wt% potassium laurate (0.50 parts by weight with respect to the monomer) was added and chlorinated. A vinyl polymer latex was obtained (sodium dodecylbenzenesulfonate: 0.11 part by weight, potassium laurate: 0.56 part by weight based on 100 parts by weight of the vinyl chloride homopolymer). When an average particle diameter was measured, it was 0.27 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い×、沈降物×であった。 Using the obtained vinyl chloride polymer latex, the burning rate, hue, and storage stability were confirmed, and the burning rate was o, tint x, and sediment x.
比較例４
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、１５重量％ラウリン酸カリウム１５０ｇ（モノマーに対して３．０重量部）を追加添加し、塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．５６重量部、ラウリン酸カリウム：３．３３重量部）。平均粒子径を測定したところ０．１μｍであった。
Comparative Example 4
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.50 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, the unreacted vinyl chloride monomer was recovered, and 150 g of 15 wt% potassium laurate (3.0 parts by weight with respect to the monomer) was additionally added. A vinyl polymer latex was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 3.33 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The average particle diameter was measured and found to be 0.1 μm.
調製した塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度×、色合い○、沈降物○であった。 Using the prepared vinyl chloride polymer latex, the burning rate, hue, and storage stability were confirmed, and the burning rate was x, the hue was o, and the precipitate was o.
比較例５
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液５０ｇ（モノマーに対して０．３３重量部）と５重量％ラウリン酸カリウム水溶液４６．０ｇ（モノマーに対して０．３１重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウムの量：０．９３重量部、ラウリン酸カリウムの量：０．３４重量部、平均粒子径を測定したところ０．１６μｍであった。
Comparative Example 5
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.50 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 50 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (0.33 parts by weight based on the monomer) and 46.0 g of a 5 wt% aqueous potassium laurate solution (into the monomer) (0.31 part by weight) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride polymer latex (amount of sodium dodecylbenzenesulfonate relative to 100 parts by weight of vinyl chloride homopolymer). : 0.93 part by weight, amount of potassium laurate: 0.34 part by weight, and the average particle diameter was measured to be 0.16 μm.
調製した塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い×、沈降物△であった。 Using the prepared vinyl chloride polymer latex, the burning rate, hue, and storage stability were confirmed, and the burning rate was o, the hue was x, and the sediment was Δ.
比較例６
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液５００ｇ（モノマーに対して３．３３重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液５００ｇ（モノマーに対して３．３３重量部）と５重量％ラウリン酸カリウム水溶液１３．５ｇ（モノマーに対して０．０９重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液５００ｇ（モノマーに対して３．３３重量部）を追加添加し、塩化ビニル系ポリマーラテックスを得た（塩化ビニルホモポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウムの量：１１．１１重量部、ラウリン酸カリウムの量：０．１０重量部、平均粒子径を測定したところ０．１０μｍであった。
Comparative Example 6
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 500 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (3.33 parts by weight with respect to the monomer) were charged. The temperature was raised to 66 ° C. to initiate emulsion polymerization. Maintaining the temperature at 66 ° C., 60 g after the start of polymerization, 500 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (3.33 parts by weight based on the monomer) and 13.5 g of a 5 wt% aqueous potassium laurate solution (into the monomer) 0.09 part by weight) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 500 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (3.33 parts by weight based on the monomer) was added. Thus, a vinyl chloride polymer latex was obtained (amount of sodium dodecylbenzenesulfonate with respect to 100 parts by weight of vinyl chloride homopolymer: 11.11 parts by weight, an amount of potassium laurate: 0.10 parts by weight, and an average particle size was measured. As a result, it was 0.10 μm.
調製した塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度×、色合い○、沈降物○であった。 Using the prepared vinyl chloride polymer latex, the burning rate, hue, and storage stability were confirmed, and the burning rate was x, the hue was o, and the precipitate was o.
実施例９
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７４４ｇ、酢酸ビニルモノマー６ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム１５ｇ（モノマーに対して０．１重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．５６重量部、ラウリン酸カリウム：０．１１重量部）。平均粒子径を測定したところ０．１μｍであった。
Example 9
In a 2.5 L autoclave, 830 g of deionized water, 744 g of vinyl chloride monomer, 6 g of vinyl acetate monomer, 6.8 g of 3 wt% potassium persulfate and 75 g of 5 wt% aqueous sodium dodecylbenzenesulfonate (0.50 wt. Part) and the temperature was raised to 66 ° C. to start emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 15 g of 5% by weight potassium laurate (0.1 part by weight with respect to the monomer) was added. A vinyl chloride polymer latex for a fuel was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 0.11 parts by weight with respect to 100 parts by weight of the vinyl chloride polymer). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物○であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and storage stability. The results were burning rate ◯, hue ◯, and sediment ○.
比較例７
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７４４ｇ、酢酸ビニルモノマー６ｇ、３重量％過硫酸カリウム６．８ｇを仕込み、温度を６６℃に上げた。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１５ｇ（モノマーに対して０．１０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム７５ｇ（モノマーに対して０．５０重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：０．１１重量部、ラウリン酸カリウム：０．５６重量部）。平均粒子径を測定したところ０．３１μｍであった。
Comparative Example 7
A 2.5 L autoclave was charged with 830 g of deionized water, 744 g of vinyl chloride monomer, 6 g of vinyl acetate monomer, and 6.8 g of 3% by weight potassium persulfate, and the temperature was raised to 66 ° C. The temperature was kept at 66 ° C., and 60 g after the start of polymerization, 15 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (0.10 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 75 g of 5 wt% potassium laurate (0.50 parts by weight with respect to the monomer) was additionally added. A vinyl chloride polymer latex for a fuel was obtained (sodium dodecylbenzenesulfonate: 0.11 part by weight, potassium laurate: 0.56 part by weight based on 100 parts by weight of the vinyl chloride polymer). The average particle diameter was measured and found to be 0.31 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い×、沈降物×であった。 Using the obtained vinyl chloride polymer latex, the burning rate, hue, and storage stability were confirmed, and the burning rate was o, tint x, and sediment x.
実施例１０
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７１２ｇ、ブチルアクリレートモノマー３８ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム１５ｇ（モノマーに対して０．１重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．５６重量部、ラウリン酸カリウム：０．１１重量部）。平均粒子径を測定したところ０．１μｍであった。
Example 10
In a 2.5 L autoclave, 830 g of deionized water, 712 g of vinyl chloride monomer, 38 g of butyl acrylate monomer, 6.8 g of 3 wt% potassium persulfate and 75 g of 5 wt% aqueous sodium dodecylbenzenesulfonate (0.50 wt. Part) and the temperature was raised to 66 ° C. to start emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 15 g of 5% by weight potassium laurate (0.1 part by weight with respect to the monomer) was added. A vinyl chloride polymer latex for a fuel was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 0.11 parts by weight with respect to 100 parts by weight of the vinyl chloride polymer). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物○であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and storage stability. The results were burning rate ◯, hue ◯, and sediment ○.
実施例１１
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー６７５ｇ、ブチルアクリレートモノマー７５ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム１５ｇ（モノマーに対して０．１重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．５６重量部、ラウリン酸カリウム：０．１１重量部）。平均粒子径を測定したところ０．１μｍであった。
Example 11
In a 2.5 L autoclave, 830 g of deionized water, 675 g of vinyl chloride monomer, 75 g of butyl acrylate monomer, 6.8 g of 3 wt% potassium persulfate and 75 g of 5 wt% sodium dodecylbenzenesulfonate aqueous solution (0.50 wt. Part) and the temperature was raised to 66 ° C. to start emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 15 g of 5% by weight potassium laurate (0.1 part by weight with respect to the monomer) was added. A vinyl chloride polymer latex for a fuel was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 0.11 parts by weight with respect to 100 parts by weight of the vinyl chloride polymer). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物○であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and storage stability. The results were burning rate ◯, hue ◯, and sediment ○.
実施例１２
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー６００ｇ、ブチルアクリレートモノマー１５０ｇ、３重量％過硫酸カリウム６．８ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液７５ｇ（モノマーに対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２７０ｇ（モノマーに対して１．８０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム１５ｇ（モノマーに対して０．１重量部）を追加添加し、難燃剤用塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．５６重量部、ラウリン酸カリウム：０．１１重量部）。平均粒子径を測定したところ０．１μｍであった。
Example 12
In a 2.5 L autoclave, 830 g of deionized water, 600 g of vinyl chloride monomer, 150 g of butyl acrylate monomer, 6.8 g of 3 wt% potassium persulfate and 75 g of 5 wt% aqueous sodium dodecylbenzenesulfonate (0.50 wt. Part) and the temperature was raised to 66 ° C. to start emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 15 g of 5% by weight potassium laurate (0.1 part by weight with respect to the monomer) was added. A vinyl chloride polymer latex for a fuel was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 0.11 parts by weight with respect to 100 parts by weight of the vinyl chloride polymer). The average particle diameter was measured and found to be 0.1 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い○、沈降物○であった。 The obtained vinyl chloride polymer latex was used to confirm the burning rate, hue, and storage stability. The results were burning rate ◯, hue ◯, and sediment ○.
比較例８
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニルモノマー７１２ｇ、ブチルアクリレートモノマー３８ｇ、３重量％過硫酸カリウム６．８ｇを仕込み、温度を６６℃に上げた。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１５ｇ（モノマーに対して０．１０重量部）を３６０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニルモノマーを回収し、５重量％ラウリン酸カリウム７５ｇ（モノマーに対して０．５０重量部）を追加添加し、塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：０．１１重量部、ラウリン酸カリウム：０．５６重量部）。平均粒子径を測定したところ０．２９μｍであった。
Comparative Example 8
A 2.5 L autoclave was charged with 830 g of deionized water, 712 g of vinyl chloride monomer, 38 g of butyl acrylate monomer, and 6.8 g of 3 wt% potassium persulfate, and the temperature was raised to 66 ° C. The temperature was kept at 66 ° C., and 60 g after the start of polymerization, 15 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (0.10 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 75 g of 5 wt% potassium laurate (0.50 parts by weight with respect to the monomer) was added and chlorinated. A vinyl polymer latex was obtained (sodium dodecylbenzenesulfonate: 0.11 part by weight and potassium laurate: 0.56 part by weight based on 100 parts by weight of the vinyl chloride polymer). The average particle size was measured and found to be 0.29 μm.
得られた塩化ビニル系ポリマーラテックスを使用して、燃焼速度、色合い、貯蔵安定性を確認したところ、燃焼速度○、色合い×、沈降物×であった。 Using the obtained vinyl chloride polymer latex, the burning rate, hue, and storage stability were confirmed, and the burning rate was o, tint x, and sediment x.
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