JP2008239856A - Flame-retardant resin aqueous emulsion and method for producing the same - Google Patents
Flame-retardant resin aqueous emulsion and method for producing the same Download PDFInfo
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本発明は、自動車や家屋の内装材、事務所等の床部のカーペット等に塗布したり、接着剤、充填材として使用することにより、被塗物などに難燃性を付与する樹脂水性エマルジョンおよびその製造法に係り、特に火災時にハロゲン含有ガス等の有毒ガスが発生することなく、且つ平時は揮発分の付着による窓ガラス等の曇化のないバッキング材、接着剤、充填材などとして使用できる難燃性樹脂水性エマルジョンおよびその製造法に関する。 The present invention is an aqueous resin emulsion that imparts flame retardancy to an object to be coated by applying it to interior materials of automobiles and houses, carpets on floors of offices, etc., or as an adhesive or filler. In addition, it does not generate toxic gases such as halogen-containing gases in the event of a fire, and it is used as a backing material, adhesive, filler, etc. that does not cause fogging such as window glass due to adhesion of volatile matter during normal times. The present invention relates to a flame retardant resin aqueous emulsion that can be produced and a method for producing the same.
近年の自動車の数の増大や住宅の密集化に伴い、それらの火災に対する対策は極めて重要である。特に各種の車両や家屋の内装材についての難燃化の要望が大きく、難燃化技術が種々提案されている。自動車内装に使用されている繊維製品の難燃化については繊維製品の補強剤として使用されるバッキング剤に塩化ビニル系、塩化ビニリデン系等のハロゲン含有の難燃性共重合体エマルジョンを用いたり、あるいは通常の合成ゴム系、アクリル系、アクリル・スチレン系、エチレン酢酸ビニル系などの共重合体エマルジョン及びこれらのブレンド物に難燃剤を配合し、それを繊維製品に塗布することにより難燃化する方法が提案されている（特許文献1）。この様な難燃剤としては、液状又は粉末状のリン酸エステル系、ハロゲン化リン酸エステル系、ハロゲン化合物系などの有機難燃剤（特許文献２から４）、アンチモン系（特許文献５）、アルミニウム系（特許文献６）、ほう素系（特許文献７）などの無機難燃剤等がそれぞれ単独で、または適宜併用して使用されている。 With the recent increase in the number of cars and the concentration of houses, countermeasures against these fires are extremely important. In particular, there is a great demand for flame retardancy for various vehicles and interior materials of houses, and various flame retarding techniques have been proposed. For flame retardant of textile products used in automobile interiors, halogen-containing flame retardant copolymer emulsions such as vinyl chloride and vinylidene chloride are used as backing agents used as reinforcing agents for textile products, Or, it is made flame retardant by blending a flame retardant with ordinary synthetic rubber-based, acrylic-based, acrylic / styrene-based, copolymer emulsions such as ethylene vinyl acetate, and blends thereof, and applying them to textiles. A method has been proposed (Patent Document 1). Examples of such flame retardants include organic or flame retardants such as phosphoric acid esters, halogenated phosphoric acid esters, and halogen compounds (Patent Documents 2 to 4), antimony (Patent Document 5), and aluminum in liquid or powder form. Inorganic flame retardants such as a system (Patent Document 6) and a boron system (Patent Document 7) are used alone or in combination as appropriate.
しかしながら、上記のハロゲン含有難燃性共重合体エマルジョンやハロゲン系難燃剤は、火災時あるいは熱リサイクル等の燃焼時にハロゲンガス等の有毒ガスを発生させて人体に重篤な害をもたらせ、また大気汚染や焼却炉の劣化を招く等の欠点を有している。またこれらの難燃剤はその強い難燃付与性のため火災時、繊維製品やバッキング剤が不完全燃焼して却って一酸化炭素の発生量を増加させることが知られている。さらに、平時でもこれらの難燃剤が自動車の内装材に用いられている場合、含有しているハロゲン化合物の分解等によって発生するハロゲン化水素とカーシートの緩衝材であるウレタンフォーム中のアミン類との反応生成物が窓ガラスを曇化させるという問題点も有している。また、ハロゲン系以外の難燃剤として一般的なリン系難燃剤も赤潮の原因物質として環境への影響が懸念されるという問題点がある。 However, the above halogen-containing flame-retardant copolymer emulsion and halogen-based flame retardant cause toxic gas such as halogen gas at the time of fire or combustion such as heat recycling, causing serious harm to human body, In addition, it has drawbacks such as air pollution and deterioration of the incinerator. In addition, these flame retardants are known to increase the amount of carbon monoxide generated due to incomplete combustion of textile products and backing agents in the event of a fire due to their strong flame retardancy. Furthermore, when these flame retardants are used in automobile interior materials even during normal times, hydrogen halides generated by decomposition of halogen compounds contained therein and amines in urethane foam that is a cushioning material for car seats This reaction product also has a problem that the window glass is fogged. In addition, phosphorous flame retardants, which are general as flame retardants other than halogen-based flame retardants, have a problem in that they are concerned about environmental impact as causative substances of red tide.
本発明者らは、自動車の火災時における人身事故は、火の廻りが早く脱出の機会が失われたり、発生する有害ガスや一酸化炭素によって人が中毒に陥った場合が多いことに鑑み、充分な難燃性を有し且つ火災時有害ガスが発生しないバッキング材、接着剤、充填材を得ることを第一の目的として鋭意研究を行った結果、ビニル系樹脂水性エマルジョンにケイ酸ナトリウムを配合することにより得られる樹脂水性エマルジョン組成物が、この課題を悉く解決することを見出し、さらに研究を重ねて本発明を完成した。 In view of the fact that human accidents in the event of a fire in an automobile often cause the person to become addicted by the toxic gas and carbon monoxide that are generated due to the early fire and the opportunity to escape. As a result of intensive research aimed at obtaining backing materials, adhesives and fillers that have excellent flame retardancy and do not generate harmful gases in the event of fire, sodium silicate was added to the vinyl resin aqueous emulsion. The present inventors have found that an aqueous resin emulsion composition obtained by doing so solves this problem, and further researched to complete the present invention.
すなわち本発明は、
（１）
ビニル系樹脂水性エマルジョンと、その樹脂分１００重量部に対して式（１）で示されるケイ酸ナトリウム３０〜３５０重量部を含み、ｐＨが１０〜１３の難燃性樹脂水性エマルジョン組成物、
Ｎａ２Ｏ・ｎＳｉＯ２ （１）
（ただしｎは２．５〜４．５の数）
（２）
組成物中のビニル系樹脂とケイ酸ナトリウムの合計重量が２０〜６０重量％である（１）記載の難燃性樹脂水性エマルジョン組成物、
（３）
更にセルロースエーテルを樹脂分に対し固形分として０．０５〜１０重量％配合してなる（１）または（２）記載の難燃性樹脂水性エマルジョン組成物、
（４）
ビニル系樹脂水性エマルジョンと、その樹脂分１００重量部に対して式（１）で示されるケイ酸ナトリウム３０〜３５０重量部を含む水溶液を５０℃以下で混合するｐＨが１０〜１３の難燃性樹脂水性エマルジョンの製造法、
Ｎａ２Ｏ・ｎＳｉＯ２ （１）
（ただしｎは２．５〜４．５の数）
である。
That is, the present invention
(1)
A flame-retardant resin aqueous emulsion composition comprising 30 to 350 parts by weight of a sodium silicate represented by the formula (1) with respect to 100 parts by weight of the resin-based vinyl emulsion and a pH of 10 to 13;
Na 2 O · nSiO 2 (1)
(Where n is a number from 2.5 to 4.5)
(2)
The flame retardant resin aqueous emulsion composition according to (1), wherein the total weight of the vinyl resin and sodium silicate in the composition is 20 to 60% by weight,
(3)
Furthermore, the flame retardant resin aqueous emulsion composition according to (1) or (2), wherein cellulose ether is blended in an amount of 0.05 to 10% by weight as a solid content with respect to the resin content,
(4)
Flame retardant having a pH of 10 to 13 in which an aqueous vinyl resin emulsion and an aqueous solution containing 30 to 350 parts by weight of sodium silicate represented by the formula (1) with respect to 100 parts by weight of the resin are mixed at 50 ° C. or lower Manufacturing method of resin aqueous emulsion,
Na 2 O · nSiO 2 (1)
(Where n is a number from 2.5 to 4.5)
It is.
ここにいう「難燃性」とは、JIS D 1201-1977の「自動車室内用有機資材の燃焼性試験方法」において燃焼性区分として用いられている「遅燃性」を意味する。すなわち、無風の大気中（７０度Ｆ 湿度７０％）で一旦着火した資材（４×１４インチ）が着火源を取り去った後炎が標線を越えて、燃焼速度が４インチ／ｍｉｎ以下のものについていう。この JIS D 1201-1977の燃焼性試験方法は、米国自動車安全基準（Federal Motor Vehicle Safety Standard）FMVSS-302に規定されている燃焼試験に準拠したものである。 The term “flame retardant” as used herein means “slow flame retardant” used as a flammability category in “Test method for flammability of organic materials for automobile interior” of JIS D 1201 -1977 . That is, after the material (4 × 14 inches) once ignited in a windless atmosphere (70 ° F. humidity 70%) removed the ignition source, the flame exceeded the marked line, and the combustion speed was 4 inches / min or less. Say about things. This JIS D 1201-1977 flammability test method complies with the combustion test defined in the Federal Motor Vehicle Safety Standard FMVSS-302.
本発明でいうビニル系樹脂水性エマルジョンとは、重合性ビニル系単量体の１種または２種以上を界面活性剤及び／又は保護コロイドの存在下又は不存在下、水性媒体中で乳化重合したり、乳化重合以外の方法により重合した重合体を後乳化したりして得られる単独重合体または共重合体の水性エマルジョンの単独物、又は、複数の重合体エマルジョンのブレンド物をいい、製造の容易性、経済性等の理由から、通常重合性ビニル系単量体の乳化重合によってえられる単独または共重合体エマルジョンの単独物又は複数の重合体エマルジョンのブレンド物であるのが好ましい。 The aqueous vinyl resin emulsion referred to in the present invention is an emulsion polymerization of one or more polymerizable vinyl monomers in an aqueous medium in the presence or absence of a surfactant and / or protective colloid. Refers to a homopolymer or copolymer aqueous emulsion obtained by post-emulsifying a polymer polymerized by a method other than emulsion polymerization, or a blend of a plurality of polymer emulsions. For reasons such as ease and economy, a single or copolymer emulsion or a blend of a plurality of polymer emulsions usually obtained by emulsion polymerization of a polymerizable vinyl monomer is preferred.
重合性ビニル系単量体としては、例えば、メチルアクリレート、エチルアクリレート、ｎ−ブチルアクリレート、イソブチルアクリレート、２−エチルヘキシルアクリレート、ｎ−オクチルアクリレート、イソノニルアクリレート、ラウリルアクリレート、ステアリルアクリレート等のアクリル酸アルキルエステル系単量体、例えばメチルメタクリレート、エチルメタクリレート、ｎ−ブチルメタクリレート、２−エチルヘキシルメタクリレート、ステアリルメタクリレート等のメタクリル酸アルキルエステル単量体、例えば、スチレン、α−メチルスチレン、ビニルトルエン、エチルビニルベンゼン等の芳香族ビニル系単量体、例えば、酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニル等の飽和脂肪酸ビニル系単量体、例えば、アクロニトリル、メタクリロニトリル等のシアン化ビニル系単量体、例えば、エチレン、プロピレン、ブタジエン等のオレフィン系単量体、例えば、アクリル酸、メタクリル酸、クロトン酸、シトラコン酸、イタコン酸、マレイン酸、フマル酸等のエチレン系カルボン酸、例えば、無水マレイン酸等のエチレン系カルボン酸無水物、例えばモノブチルマレイン酸などのエチレン系ジカルボン酸のモノアルキルエステル、及びこれらのアンモニウム塩もしくはアルカリ金属塩等のエチレン系カルボン酸塩類、例えば、アクリルアミド、メタクリルアミド、ジアセトンアクリルアミド等のエチレン系カルボン酸の酸アミド類、例えば、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、メチロール化ジアセトンアクリルアミド及び、これらの単量体と炭素数１〜８個のアルコール類とのエーテル化物（例えば、Ｎ−イソブトキシメチルアクリルアミド）等のエチレン系カルボン酸アミド類のメチロール化物及びその誘導体、例えば、グリシジルアクリレート、グリシジルメタクリレート等のエチレン系カルボン酸とエポキシ基を有するアルコールとのエステル類、例えば、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシメタクリレート等のエチレン系カルボン酸のヒドロキシアルキルエステル類、例えば、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルメタクリレート等のエチレン系カルボン酸とアミノ基を有するアルコールとのエステル類など、エチレン性不飽和結合を１個有する単量体や、例えばジビニルベンゼン、ジアリルフタレート、トリアリルシアヌレート、ジエチレングリコールジメタクリレート等の２個以上の非共役性不飽和結合を有する単量体を挙げることができる。 Examples of the polymerizable vinyl monomer include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, and stearyl acrylate. Ester monomers such as alkyl methacrylate monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and stearyl methacrylate, such as styrene, α-methylstyrene, vinyl toluene, ethyl vinyl benzene Aromatic vinyl monomers such as vinyl acetate, vinyl propionate, vinyl versatate, and other saturated fatty acid vinyl monomers such as vinyl Vinyl cyanide monomers such as nitrile and methacrylonitrile, for example, olefin monomers such as ethylene, propylene, and butadiene, such as acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, Ethylene carboxylic acids such as fumaric acid, for example, ethylene carboxylic anhydrides such as maleic anhydride, monoalkyl esters of ethylene dicarboxylic acid such as monobutyl maleic acid, and ammonium salts or alkali metal salts thereof. Ethylene carboxylates, for example, acid amides of ethylene carboxylic acids such as acrylamide, methacrylamide, diacetone acrylamide, such as N-methylol acrylamide, N-methylol methacrylamide, methylolated diacetone acrylamide, and Methylolated products of ethylene-based carboxylic acid amides such as etherified products of these monomers and alcohols having 1 to 8 carbon atoms (for example, N-isobutoxymethylacrylamide) and derivatives thereof such as glycidyl acrylate, glycidyl Esters of ethylene carboxylic acid such as methacrylate and alcohol having an epoxy group, for example, hydroxyalkyl esters of ethylene carboxylic acid such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy methacrylate, Monomers having one ethylenically unsaturated bond such as esters of ethylenic carboxylic acid and amino group-containing alcohols such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; Benzene, diallyl phthalate, triallyl cyanurate, may be mentioned a monomer having two or more nonconjugated unsaturated bonds such as diethylene glycol dimethacrylate.
これらは単独であるいは２種以上を組み合わせて用いることができる。これらの中では、（メタ）アクリル酸アルキルエステルが好ましく、メタクリル酸メチル、アクリル酸エチル、アクリル酸ブチルが特に好ましく、またそれらとアクリロニトリルとの共重合体も好ましい。
これらの共重合性ビニル系モノマーに、その１００重量に対して０．１〜３重量部、好ましくは０．５〜２重量部の、例えばジビニルベンゼン、ジアリルフタレート、エチレングリコールジメタクリレート、アリルメタクリレート等の架橋剤を併用してもよい。
These can be used alone or in combination of two or more. Among these, (meth) acrylic acid alkyl esters are preferable, methyl methacrylate, ethyl acrylate, and butyl acrylate are particularly preferable, and a copolymer of these with acrylonitrile is also preferable.
In these copolymerizable vinyl monomers, 0.1 to 3 parts by weight, preferably 0.5 to 2 parts by weight, for example, divinylbenzene, diallyl phthalate, ethylene glycol dimethacrylate, allyl methacrylate, etc. These crosslinking agents may be used in combination.
本発明に用いられるビニル系樹脂水性エマルジョンは、自体公知の共重合可能なビニル系単量体の乳化重合により製造することができる。
この乳化重合に用いられる重合開始剤としては過硫酸アンモニウム、過硫酸ナトリウム等の過硫酸塩、過酸化水素水、ｔ−ブチルハイドロパーオキサイド等の水性ラジカル重合開始剤またはこれらの混合物が挙げられ、使用量はモノマー全重量に対して通常は０．１〜５重量部、好ましくは０．１〜２重量部である。このような開始剤はまた、還元剤と組み合わせレドックス系を形成することができる。そのような還元剤としては亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、ホルムアルデヒドスルホン酸塩等のアルカリ金属塩やアンモニウム塩、Ｌ−アスコルビン酸、酒石酸などのカルボン酸類が挙げられ、使用量はモノマー全重量に対して０．１〜５重量部、好ましくは０．１〜２重量部である。
なお、本発明の共重合体の製造法においては、硫酸第一鉄、硫酸アンモニウム第一鉄、ナフテン酸第一銅などの鉄、銅、ニッケル、コバルト、クロモ、モリブテン、バナジウム、セリウムのような遷移金属の塩なども用いることができるが、組成物に着色などが観られる場合がある。
The aqueous vinyl resin emulsion used in the present invention can be produced by emulsion polymerization of a copolymerizable vinyl monomer known per se.
Examples of the polymerization initiator used in this emulsion polymerization include persulfates such as ammonium persulfate and sodium persulfate, aqueous radical polymerization initiators such as hydrogen peroxide, t-butyl hydroperoxide, and mixtures thereof. The amount is usually 0.1 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on the total weight of the monomers. Such initiators can also be combined with a reducing agent to form a redox system. Examples of such reducing agents include alkali metal salts such as sulfites, hydrogen sulfites, pyrosulfites, and formaldehyde sulfonates, and carboxylic acids such as L-ascorbic acid and tartaric acid. It is 0.1-5 weight part with respect to a weight, Preferably it is 0.1-2 weight part.
In the method for producing the copolymer of the present invention, transitions such as iron, copper, nickel, cobalt, chromo, molybdenum, vanadium, cerium such as ferrous sulfate, ferrous ammonium sulfate and cuprous naphthenate are used. Metal salts and the like can also be used, but coloring or the like may be observed in the composition.
乳化重合に用いられる界面活性剤は少なくとも１種のアニオン性、ノニオン性、または両性界面活性剤、またはその混合物を用いることができる。アニオン性界面活性剤の例としてはアルキルまたはアルキルアリル硫酸塩、アルキルまたはアルキルアリルスルホン酸塩、ジアルキルスルホコハク酸塩、ポリオキシエチレンアルキルエーテル硫酸塩などのアルカリ金属塩、またはアンモニウム塩が挙げられる。ノニオン系界面活性剤としてはポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル等が挙げられる。両性界面活性剤としてはベタイン、アミノ酸の誘導体が挙げられる。これら界面活性剤の使用量はモノマー全重量に対して０．１〜５重量部、好ましくは０．３〜３重量部である。この使用量が０．１重量部よりも少ない場合は反応が不安定となり、凝集物が生成する場合がある。反対に５重量部よりも多い場合は乾燥性、耐水性が悪くなる場合がある。 As the surfactant used in the emulsion polymerization, at least one anionic, nonionic or amphoteric surfactant, or a mixture thereof can be used. Examples of anionic surfactants include alkali metal salts such as alkyl or alkyl allyl sulfates, alkyl or alkyl allyl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl ether sulfates, or ammonium salts. Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, and the like. Examples of amphoteric surfactants include betaine and amino acid derivatives. These surfactants are used in an amount of 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on the total weight of the monomers. When the amount used is less than 0.1 parts by weight, the reaction becomes unstable and aggregates may be generated. On the other hand, when the amount is more than 5 parts by weight, the drying property and water resistance may be deteriorated.
また、乳化重合は、必要に応じてエチレンジアミン４酢酸ナトリウムなどのキレート剤、ポリカルボン酸塩などの分散剤、リン酸塩、炭酸塩などの無機塩、チオール化合物、ハロゲン化合物などの連鎖移動剤の存在下に行ってもよい。
重合は通常０〜１００℃の温度で、単量体の添加率が９９％以上に達するまで行われる。
微粒子の平均粒子径は、通常０．５〜１００μｍ、好ましくは１〜５０μｍである。微粒子の形状は特に限定されないが、球形、回転楕円体などが好ましい。
In addition, emulsion polymerization can be carried out by using a chain transfer agent such as a chelating agent such as sodium ethylenediaminetetraacetate, a dispersing agent such as polycarboxylate, an inorganic salt such as phosphate or carbonate, a thiol compound, or a halogen compound. You may go in the presence.
The polymerization is usually carried out at a temperature of 0 to 100 ° C. until the monomer addition rate reaches 99% or more.
The average particle diameter of the fine particles is usually 0.5 to 100 μm, preferably 1 to 50 μm. The shape of the fine particles is not particularly limited, but a spherical shape, a spheroid and the like are preferable.
上記の重合性ビニル系単量体の種類及び使用量は、特に限定されるものではなく、難燃加工の対象となるシート状繊維製品等が要求する各種の物性によって適宜選択することができる。例えば、自動車のフロアーやデッキ部等比較的硬い風合いを要求される分野では、硬化物のガラス転移点（Ｔｇ）が１０℃以上である重合性ビニル単量体の使用が好ましく、またシートなどの比較的軟らかい風合いを要求される分野では硬化物のガラス転移点が０℃以下である重合性ビニル単量体の使用が好ましい。 The kind and amount of the polymerizable vinyl monomer are not particularly limited, and can be appropriately selected according to various physical properties required by the sheet-like fiber product to be subjected to flame retardant processing. For example, in fields where a relatively hard texture is required, such as automobile floors and deck parts, it is preferable to use a polymerizable vinyl monomer having a glass transition point (Tg) of a cured product of 10 ° C. or higher. In a field where a relatively soft texture is required, it is preferable to use a polymerizable vinyl monomer having a cured product having a glass transition point of 0 ° C. or lower.
乳化重合の際利用し得る保護コロイドとしては、例えば、ポリビニルアルコール類、セルロース誘導体等が挙げられ、これらは単独又は複数で使用できる。その使用量は適宜に選択でき、例えば、使用する重合性ビニル単量体の全量に対して、約０.５〜１０重量％の使用量を例示することができる。本発明に用いる重合性ビニル重合体水性エマルジョンの固形分は特に限定されないがその生産性と製造の容易さより約３０〜６５重量％であるのが好ましい。 Examples of protective colloids that can be used in emulsion polymerization include polyvinyl alcohols and cellulose derivatives, and these can be used alone or in combination. The amount used can be appropriately selected. For example, the amount used is about 0.5 to 10% by weight based on the total amount of the polymerizable vinyl monomer used. The solid content of the polymerizable vinyl polymer aqueous emulsion used in the present invention is not particularly limited, but is preferably about 30 to 65% by weight because of its productivity and ease of production.
本発明においては、上記重合性ビニル重合体水性エマルジョンに式（１）
Ｎａ２Ｏ・ｎＳｉＯ２ （１）
（ただしｎは２．５〜４．５の数）
で示されるケイ酸ナトリウムの水溶液を配合する。
式（１）で表される物質は、ケイ酸ナトリウムとも称され、そのモル比ｎによって連続的に変化する。本発明において用いられるのは、ｎが２．５〜４．５、好ましくは３．０〜４．０のものである。商品としても各種組成の化合物があるが、その中でJIS K1408により定められた２号、３号、４号のケイ酸ソーダが使用できる。このケイ酸ナトリウムの水溶液は水ガラスと呼ばれ、無色で、濃厚液は粘度が高く増粘剤、粘着剤などとして用いられている。
In the present invention, the polymerizable vinyl polymer aqueous emulsion has the formula (1).
Na 2 O · nSiO 2 (1)
(Where n is a number from 2.5 to 4.5)
An aqueous solution of sodium silicate shown in FIG.
The substance represented by the formula (1) is also called sodium silicate, and continuously changes depending on the molar ratio n. In the present invention, n is 2.5 to 4.5, preferably 3.0 to 4.0. There are compounds of various compositions as commercial products, among which sodium silicates of No. 2, No. 3, No. 4, and No. 4 defined by JIS K1408 can be used. This aqueous solution of sodium silicate is called water glass and is colorless, and the concentrated liquid has a high viscosity and is used as a thickener, an adhesive or the like.
本発明においては、十分な難燃性とバインダー効果を付与するためケイ酸ナトリウムの使用量はビニル系樹脂水性エマルジョンの樹脂分１００重量部に対して無水ケイ酸ナトリウムを３０〜３５０重量部、好ましくは３５〜３００重量部、最も好ましくは４０〜２５０重量部である。使用量が３０重量部未満では、例えばJIS D 1201-1977の自動車室内用有機資材の燃焼性試験において、燃焼速度が 100mm／分を超え、易燃性となってしまう。また、３５０重量部を超えた場合には、本発明組成物の貯蔵安定性が低下するため、保存上の問題が生じる。 In the present invention, in order to impart sufficient flame retardancy and binder effect, the amount of sodium silicate used is 30 to 350 parts by weight of anhydrous sodium silicate, preferably 100 parts by weight of the resin content of the vinyl resin aqueous emulsion. Is 35 to 300 parts by weight, most preferably 40 to 250 parts by weight. When the amount used is less than 30 parts by weight, for example, in a flammability test of an organic material for automobile interior according to JIS D 1201 -1977 , the burning rate exceeds 100 mm / min, and it becomes flammable. Moreover, when it exceeds 350 weight part, since the storage stability of this invention composition falls, the problem on a preservation | save arises.
ビニル系樹脂水性エマルジョンと式（１）で示されるケイ酸ナトリウムの水溶液の混合は、まずケイ酸ナトリウムを水に溶解し、撹拌下、好ましくは、強い撹拌下にビニル重合体水性エマルジョンを少しずつ混合していく。混合の際、ケイ酸ナトリウムの水溶液の液温を５０℃以下、好ましくは０〜５０℃、より好ましくは５〜３５℃に保ちながら行うとよい。 The mixing of the aqueous vinyl resin emulsion and the aqueous solution of sodium silicate represented by the formula (1) involves first dissolving the sodium silicate in water, and gradually adding the aqueous vinyl polymer emulsion under stirring, preferably under strong stirring. Mix. When mixing, the temperature of the aqueous solution of sodium silicate is 50 ° C. or lower, preferably 0 to 50 ° C., more preferably 5 to 35 ° C.
ケイ酸ナトリウムを配合した樹脂エマルジョンの貯蔵安定性を向上させるためにエマルジョンにセルロースエーテルを配合することができる。使用できるセルロースエーテルとしては、例えばメチルセルロース、エチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース、ベンジルセルロースなどが挙げられる。これらのセルロースエーテルは、平均重合度１００〜７００、平均分子量30,000〜300,000のものが好ましく、特にメトキシ基１０〜４０、ヒドロキシプロポキシ基１．１〜２．５を有し、エーテル化度０．１〜３．０のものが好ましく用いられる。
これらのセルロースエーテルの使用割合は、樹脂分１００重量部に対し０．０５〜１０部重量部、好ましくは０．１〜５重量部である。
In order to improve the storage stability of the resin emulsion containing sodium silicate, a cellulose ether can be added to the emulsion. Examples of the cellulose ether that can be used include methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and benzyl cellulose. These cellulose ethers preferably have an average degree of polymerization of 100 to 700 and an average molecular weight of 30,000 to 300,000, particularly having 10 to 40 methoxy groups and 1.1 to 2.5 hydroxypropoxy groups, and an etherification degree of 0.1 The thing of -3.0 is used preferably.
The use ratio of these cellulose ethers is 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin content.
本発明の難燃性樹脂水性組成物は、前記のビニル重合体水性エマルジョンの他に物性の向上のために架橋剤を配合することもできる。該架橋剤としては、例えば、酸化亜鉛の水溶液又は水分散液、ブロック化イソシアネートの水溶液又は水分散液、メラミン−ホルムアルデヒド樹脂の水溶液又は水分散液等が挙げられる。これらの架橋剤の配合量はビニル重合体水性エマルジョンの固形分１００重量部に対して固形分で通常１〜２０重量部、好ましくは２〜１５重量部である。 The flame retardant resin aqueous composition of the present invention may contain a crosslinking agent in order to improve physical properties in addition to the vinyl polymer aqueous emulsion. Examples of the crosslinking agent include an aqueous solution or aqueous dispersion of zinc oxide, an aqueous solution or aqueous dispersion of blocked isocyanate, an aqueous solution or aqueous dispersion of melamine-formaldehyde resin, and the like. The compounding amount of these crosslinking agents is usually 1 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the solid content of the vinyl polymer aqueous emulsion.
更に本発明の難燃性樹脂水性組成物には、本発明の優れた効果を妨げない使用範囲において、他の難燃剤を併用することができる。該難燃剤としては、例えば、アンチモン系化合物、ほう素系化合物、アルミニウム系化合物、マグネシウム系化合物、ジルコニウム系化合物等平常はガラス等を曇化させず、火災時有毒ガスを発生させない難燃剤が挙げられる。これらの中ではアルミニウム系化合物、特に水酸化アルミニウムが好ましい。これらの難燃剤の使用量はエチレン系重合体水性エマルジョンの固形分１００重量部に対して、例えば、１〜２５０重量部程度を例示することができる。また、本発明の優れた効果を妨げない使用範囲において、無機充填剤、分散剤、増粘剤、湿潤剤、発泡剤、製泡剤、消泡剤、顔料、染料、可塑剤、老化防止剤、紫外線吸収剤、防腐剤等が使用できる。 Furthermore, the flame retardant resin aqueous composition of the present invention may be used in combination with other flame retardants within the range of use that does not hinder the excellent effects of the present invention. Examples of the flame retardant include flame retardants that do not normally fog glass or the like and do not generate toxic gases in a fire, such as antimony compounds, boron compounds, aluminum compounds, magnesium compounds, and zirconium compounds. It is done. Of these, aluminum compounds, particularly aluminum hydroxide, are preferred. The amount of these flame retardants used may be, for example, about 1 to 250 parts by weight with respect to 100 parts by weight of the solid content of the ethylene polymer aqueous emulsion. In addition, within the usage range that does not hinder the excellent effects of the present invention, inorganic fillers, dispersants, thickeners, wetting agents, foaming agents, foaming agents, antifoaming agents, pigments, dyes, plasticizers, anti-aging agents UV absorbers, preservatives and the like can be used.
以上の様にして得られた本発明の難燃性樹脂水性組成物の固形分、ｐＨ及び粘度は、該組成物の沈降、ゲル化からの安定性等の観点から、固形分は１０〜６０重量％、好ましくは２０〜６０重量％程度、ｐＨは１０〜１３．０、好ましくは１０．５〜１２、粘度（２０℃，１２ｒｐｍ）は１０００〜１００００ｍＰａ・ｓ、好ましくは１０００〜８０００ｍＰａ・ｓである。 The solid content, pH and viscosity of the flame retardant resin aqueous composition of the present invention obtained as described above are from 10 to 60 in terms of the stability of the composition from settling and gelation. % By weight, preferably about 20 to 60% by weight, pH is 10 to 13.0, preferably 10.5 to 12, viscosity (20 ° C., 12 rpm) is 1000 to 10000 mPa · s, preferably 1000 to 8000 mPa · s. is there.
本発明は該組成物を繊維製品のバッキング剤として用いる場合は、難燃性に優れた繊維製品を得ることができる。本発明に用いられる繊維製品の生地としては火災時有害ガスの発生のないものであれば特に限定されないが、例えば、ポリエステル、ポリプロピレン、ナイロン、アクリル等を原料とする合成繊維、羊毛等の天然繊維および合成繊維と天然繊維の混紡繊維等が挙げられる。そして本発明の難燃性樹脂水性組成物により裏打ちされた繊維製品は、特に自動車内装材、たとえば、天井、ドア、座席の表張り材料として、またはデッキや床のカーペット材として好適に使用される。また、床部のニードルパンチカーペットの成形性、遮水性を向上させるために、該組成物をバッキング層としたニードルパンチカーペットに、ポリエチレン等の熱可塑性樹脂による溶融押し出しラミネートバッキングを施した場合でも、充分な難燃性が発揮される。 In the present invention, when the composition is used as a backing agent for a textile product, a textile product having excellent flame retardancy can be obtained. The fabric of the textile product used in the present invention is not particularly limited as long as no harmful gas is generated at the time of fire. For example, synthetic fibers made from polyester, polypropylene, nylon, acrylic, etc., natural fibers such as wool And a mixed fiber of synthetic fiber and natural fiber. The textile product lined with the flame retardant resin aqueous composition of the present invention is particularly suitably used as an automotive interior material, for example, as a covering material for ceilings, doors, seats, or as a carpet material for decks or floors. . Further, in order to improve the moldability of the needle punch carpet in the floor portion, the water barrier property, even when the needle punch carpet having the composition as a backing layer is subjected to melt extrusion lamination backing with a thermoplastic resin such as polyethylene, Sufficient flame retardancy is exhibited.
該組成物のバッキング層としての塗布量は、２０〜４００ｇ／ｍ2（固形分）、好ましくは３０〜２５０ｇ／ｍ2で、該組成物を塗布したシート状繊維製品は、前述の JIS D 1201-1977の自動車室内用有機資材の燃焼性試験方法において燃焼性区分として用いられている難燃性を示す。該組成物の塗布量が３０ｇ／ｍ2未満では、硬目の風合い及び難燃性が不十分で２５０ｇ／ｍ2を超えた場合は、粉落ちが発生したり、また経済的にも問題が生じる。 The coating amount of the composition as a backing layer is 20 to 400 g / m 2 (solid content), preferably 30 to 250 g / m 2 , and the sheet-like fiber product coated with the composition is the above-mentioned JIS D 1201 -Shows the flame retardancy used as a flammability category in the 1977 flammability test method for organic materials for automobile interiors. When the coating amount of the composition is less than 30 g / m 2 , the texture and flame retardancy of the hard are insufficient, and when it exceeds 250 g / m 2 , powder falling occurs, and there is a problem in terms of economy. Arise.
前述した通り、本発明によるケイ酸樹脂組成物はケイ酸ナトリウムと各種樹脂を極めて安定的にコンパウンド出来る事から、従来２液に分けて加工していた行程を１液での加工が可能となり、作業性を飛躍的に向上させると同時にコストメリットが大きくなる。 As described above, since the silicate resin composition according to the present invention can compound sodium silicate and various resins very stably, it is possible to process the process that has been processed separately into two liquids with one liquid, Workability is dramatically improved and cost merit is increased.
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例によって何ら限定されるものではない。 Examples The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
ステンレス製反応釜にアクリル酸エチル・アクリロニトリル共重合体水性エマルジョン（ガンツ化成製：ＡＮＸ−１５０）を樹脂分１００重量部相当分とメチルセルロース（第一工業製薬製：品名ＡＧガム 平均重合度５４０平均分子量127,000）を乾燥重量で１部を加え、T.K. HOMO DISPER モテ゛ルLを用いて回転数１０００ｒｐｍでよく攪拌し、均一な粘稠溶液を得た。
別の攪拌容器に乾燥重量で１２０部のケイ酸ナトリウム（大阪珪曹：ＳＰ−７０、ｎ＝３．６）を溶解した液温２０℃のケイ酸ナトリウム溶液を調製し、これを撹拌器（T.K. HOMO DISPER モテ゛ルL）に入れて回転数１０００ｒｐｍで攪拌し、そこに上記条件で得られた粘稠溶液を少量ずつ加えて１５分以上撹拌して全固形分３５％、粘度５００ｃｐｓ、ｐＨ１１．６のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。
In a stainless steel reaction kettle, ethyl acrylate / acrylonitrile copolymer aqueous emulsion (manufactured by Ganz Kasei: ANX-150) is equivalent to 100 parts by weight of resin and methylcellulose (Daiichi Kogyo Seiyaku Co., Ltd .: product name AG gum average polymerization degree 540 average molecular weight) 127,000) was added in 1 part by dry weight, and the mixture was thoroughly stirred using a TK HOMO DISPER model L at a rotation speed of 1000 rpm to obtain a uniform viscous solution.
In a separate stirring vessel, a sodium silicate solution having a liquid temperature of 20 ° C. in which 120 parts of sodium silicate (Osaka Silica: SP-70, n = 3.6) was dissolved by dry weight was prepared. TK HOMO DISPER model L) and stirred at a rotational speed of 1000 rpm. The viscous solution obtained under the above conditions was added little by little and stirred for 15 minutes or more. Total solid content 35%, viscosity 500 cps, pH 11.6. An aqueous resin emulsion containing sodium silicate was obtained.
実施例１のケイ酸ナトリウム溶液（大阪珪曹：ＳＰ−７０ ｎ＝３．６）の液温を５０℃とした以外は実施例１と同様にして、全固形分３５％、粘度７００ｃｐｓ、ｐＨ１１．６のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。 Except that the liquid temperature of the sodium silicate solution of Example 1 (Osaka Silica: SP-70 n = 3.6) was 50 ° C., the same as Example 1, except that the total solid content was 35%, the viscosity was 700 cps, the pH was 11 6 aqueous resin emulsion containing sodium silicate was obtained.
実施例１のケイ酸ナトリウム溶液の液温を５℃のものを用いた以外は実施例１と同様にして、全固形分３５％、粘度７００ｃｐｓ、ｐＨ１１．６のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。 A sodium silicate-containing resin aqueous emulsion having a total solid content of 35%, a viscosity of 700 cps, and a pH of 11.6 was obtained in the same manner as in Example 1 except that the solution temperature of the sodium silicate solution of Example 1 was 5 ° C. Obtained.
実施例１のメチルセルロースの代わりに、信越化学製「メトローズ９０ＳＨ３００００」（メトキシ基１９〜２４％ヒドロキシプロボキシ基４〜１２％）を用いた以外は実施例１と同様にして、全固形分３５％、粘度４００ｃｐｓ、ｐＨ１１．３のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。 In place of the methyl cellulose of Example 1, “Metros 90SH30000” (Methoxy group 19-24% hydroxypropoxy group 4-12%) manufactured by Shin-Etsu Chemical Co., Ltd. was used in the same manner as Example 1, except that the total solid content was 35%. An aqueous resin emulsion containing sodium silicate having a viscosity of 400 cps and a pH of 11.3 was obtained.
実施例１のアクリル酸エチル・アクリロニトリル共重合体水性エマルジョン（ガンツ化成製：ＡＮＸ−１５０）に代えて、天然ラテックス（ハイテックスNR、 樹脂分４７重量％）を用いた以外は実施例１と同様にして、全固形分３５％、粘度４００ｃｐｓ、ｐＨ１１．３のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。 The same procedure as in Example 1, except that natural latex (Hitex NR, resin content 47% by weight) was used instead of the aqueous ethyl acrylate / acrylonitrile copolymer emulsion of Example 1 (manufactured by Gantz Kasei: ANX-150). Thus, an aqueous resin emulsion containing sodium silicate having a total solid content of 35%, a viscosity of 400 cps, and a pH of 11.3 was obtained.
実施例１のケイ酸ナトリウム溶液に代えて、２号ケイ酸ナトリウム（ｎ＝２．５；大阪珪曹製）を用いて調製したケイ酸ナトリウム溶液を用いた以外は実施例１と同様にして、全固形分３５％、粘度４００ｃｐｓ、ｐＨ１３．０のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。 It replaced with the sodium silicate solution of Example 1, and it carried out similarly to Example 1 except having used the sodium silicate solution prepared using No. 2 sodium silicate (n = 2.5; made by Osaka Silica). An aqueous resin emulsion containing sodium silicate having a total solid content of 35%, a viscosity of 400 cps and a pH of 13.0 was obtained.
実施例１のアクリル酸エチル・アクリロニトリル共重合体水性エマルジョン（ガンツ化成製：ＡＮＸ−１５０）に代えて、ＳＢＲ(旭化成：スマーテックスＮＳＫ−４２０、樹脂分４７重量％）を用いた以外は実施例１と同様にして、全固形分３５％、粘度４００ｃｐｓ、ｐＨ１１．３のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。 Example except that SBR (Asahi Kasei: Smarttex NSK-420, resin content 47% by weight) was used in place of the ethyl acrylate / acrylonitrile copolymer aqueous emulsion of Example 1 (manufactured by Gantz Kasei: ANX-150). In the same manner as in Example 1, a sodium silicate-containing resin aqueous emulsion having a total solid content of 35%, a viscosity of 400 cps, and a pH of 11.3 was obtained.
実施例１のケイ酸アクリル樹脂組成物に分散剤としてトリポリリン酸ナトリウムを乾燥重量で１．５部、難燃性フィラーとして水酸化アルミニウムを３５０部、フィラーの沈降を防止する目的で強アルカリ下でも安定して増粘できるキタンサンガム（三唱製：ケルザンＡＳＸ）を乾燥重量で０．５部配合した以外は実施例１と同条件とし、全固形分４０％、粘度４５００ｃｐｓ、ｐＨ１１．６のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。 In the silicate acrylic resin composition of Example 1, 1.5 parts by weight of sodium tripolyphosphate as a dispersant, 350 parts of aluminum hydroxide as a flame retardant filler, even under strong alkali for the purpose of preventing the filler from settling Sodium silicate having the same conditions as in Example 1 except that 0.5 parts by weight of Kitansan gum (Sansho: Kelzan ASX) that can be stably thickened is blended, and having a total solid content of 40%, a viscosity of 4500 cps, and a pH of 11.6 A blended resin aqueous emulsion was obtained.
実施例１のセルロースエーテルを配合しなかった以外は実施例１と同様にして、全固形分３５％、粘度４００ｃｐｓ、ｐＨ１１．３のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。 A sodium silicate-containing resin aqueous emulsion having a total solid content of 35%, a viscosity of 400 cps, and a pH of 11.3 was obtained in the same manner as in Example 1 except that the cellulose ether of Example 1 was not blended.
実施例１のケイ酸ナトリウムを乾燥重量で４０部とした以外は実施例１と同様にして、全固形分３５％、粘度３００ｃｐｓ、ｐＨ１１．６のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。 A sodium silicate-containing resin aqueous emulsion having a total solid content of 35%, a viscosity of 300 cps, and a pH of 11.6 was obtained in the same manner as in Example 1 except that 40 parts by weight of sodium silicate of Example 1 was used.
実施例１のケイ酸ナトリウムを乾燥重量で２５０部とした以外は実施例１と同様にして、全固形分３５％、粘度５００ｃｐｓ、ｐＨ１１．６のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。 A sodium silicate-containing resin aqueous emulsion having a total solid content of 35%, a viscosity of 500 cps, and a pH of 11.6 was obtained in the same manner as in Example 1 except that the sodium silicate of Example 1 was changed to 250 parts by dry weight.
実施例１のケイ酸ナトリウム溶液に代えて、４号ケイ酸ソーダ（ｎ＝４．２；大阪珪曹製）を用いて調製したケイ酸ナトリウム溶液を用いた以外は実施例１と同様にして、全固形分３５％、粘度４００ｃｐｓ、ｐＨ１０．８のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。
〔比較例１〕
It replaced with the sodium silicate solution of Example 1, and carried out similarly to Example 1 except having used the sodium silicate solution prepared using No. 4 sodium silicate (n = 4.2; made by Osaka Silica). An aqueous resin emulsion containing sodium silicate having a total solid content of 35%, a viscosity of 400 cps and a pH of 10.8 was obtained.
[Comparative Example 1]
実施例１のケイ酸ナトリウムを乾燥重量で５００部とした以外は実施例１と同時にして、全固形分３５％、粘度４００ｃｐｓ、ｐＨ１１．６のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。
［比較例２］
A sodium silicate-containing resin aqueous emulsion having a total solid content of 35%, a viscosity of 400 cps, and a pH of 11.6 was obtained in the same manner as in Example 1 except that the sodium silicate of Example 1 was changed to 500 parts by dry weight.
[Comparative Example 2]
実施例１のケイ酸ナトリウムを乾燥重量で１部とした以外は実施例１と同様にして、全固形分３５％、粘度４００ｃｐｓ、ｐＨ１１．３のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。
［比較例３］
A sodium silicate-containing resin aqueous emulsion having a total solid content of 35%, a viscosity of 400 cps, and a pH of 11.3 was obtained in the same manner as in Example 1 except that the sodium silicate of Example 1 was changed to 1 part by dry weight.
[Comparative Example 3]
実施例１のケイ酸樹脂組成物に対して１０％の塩酸を添加し、ｐＨを９．５とした以外は実施例１と同様にして、全固形分３５％、粘度４００ｃｐｓ、ｐＨ１１．３のケイ酸ナトリウム配合樹脂水性エマルジョンを得た。
［比較例４］
10% hydrochloric acid was added to the silicate resin composition of Example 1 to adjust the pH to 9.5, and the same as in Example 1, except that the total solid content was 35%, the viscosity was 400 cps, and the pH was 11.3. An aqueous resin emulsion containing sodium silicate was obtained.
[Comparative Example 4]
実施例１で用いたと同じアクリル酸エチル・アクリロニトリル共重合体水性エマルジョン（ガンツ化成製：ＡＮＸ−１５０）に、それ以外のものを加えなかった。液のｐＨは、７．２であった。
［試験例１］
Nothing else was added to the same ethyl acrylate / acrylonitrile copolymer aqueous emulsion (Gantz Kasei: ANX-150) used in Example 1. The pH of the liquid was 7.2.
[Test Example 1]
実施例１〜１２、比較例１〜３で調製したそれぞれの樹脂液各２５０ｇをオープニング２７６ミクロンのろ布でろ過を行い残渣を確認する事で配合ショックや経時安定性の評価を行ない、その結果を表１に示した。 Each of the resin solutions prepared in Examples 1 to 12 and Comparative Examples 1 to 3 was filtered with an opening 276 micron filter cloth and the residue was confirmed to evaluate the compounding shock and stability over time. Is shown in Table 1.
［試験例２］
[Test Example 2]
試験例１で問題がなかった樹脂組成物について樹脂液を坪量３００ｇ／ｍ２のPET原反に塗布、乾燥させて、乾燥重量換算による上記組成物付着量７０ｇ／ｍ２となる本発明による難燃原反を得た。
ＦＭＳＳ規格による難燃性データーを表２に示す。
According to the present invention, the resin composition having no problem in Test Example 1 was applied to a PET raw material having a basis weight of 300 g / m 2 and dried to obtain the above composition adhesion amount of 70 g / m 2 in terms of dry weight. Obtained a flame-retardant material.
The flame retardancy data according to FMSS standard is shown in Table 2.
試験例１で配合直後からゲル化を起こした比較例３を除き、試験例２で平均難燃速度＋４σが８０以下であった樹脂組成物について樹脂のバインダー効果を確認するため試験１で作成した難燃原反９００ｃｍ2について樹脂面同士を２０回手もみし、粉落ちの状況について観察を行なった。
その結果、実施例１から１２の組成物を塗布した難燃原反は、いずれも粉落ちの重量が０．０５ｇ未満であった。しかし、比較例１の組成物を塗布した原反は、粉落ちの重量が０．２ｇ以上であった。
Except for Comparative Example 3 in which gelation occurred immediately after compounding in Test Example 1, a resin composition having an average flame retardancy rate + 4σ of 80 or less in Test Example 2 was prepared in Test 1 to confirm the binder effect of the resin. With respect to the flame-retardant raw fabric 900 cm 2 , the resin surfaces were gripped 20 times, and the state of powder falling was observed.
As a result, the flame retardant raw material coated with the compositions of Examples 1 to 12 had a weight of powder falling of less than 0.05 g. However, the raw fabric coated with the composition of Comparative Example 1 had a powder weight of 0.2 g or more.
本発明の特定のケイ酸ナトリウムを配合したビニル重合体水性エマルジョンを対象物、とくに繊維製品に含浸又は塗布することにより、安価に優れた難燃性を付与する事が出来る。 By impregnating or applying an aqueous vinyl polymer emulsion containing the specific sodium silicate of the present invention to an object, particularly a textile product, excellent flame retardancy can be imparted at low cost.
Claims (4)
Ｎａ２Ｏ・ｎＳｉＯ２ （１）
（ただしｎは２．５〜４．５の数） A flame retardant resin aqueous emulsion composition comprising 30 to 350 parts by weight of a sodium silicate represented by the formula (1) with respect to 100 parts by weight of the resin based resin emulsion and a pH of 10 to 13.
Na 2 O · nSiO 2 (1)
(Where n is a number from 2.5 to 4.5)
Ｎａ２Ｏ・ｎＳｉＯ２ （１）
（ただしｎは２．５〜４．５の数） Flame retardant having a pH of 10 to 13 in which an aqueous vinyl resin emulsion and an aqueous solution containing 30 to 350 parts by weight of sodium silicate represented by the formula (1) with respect to 100 parts by weight of the resin are mixed at 50 ° C. or lower A method for producing an aqueous resin emulsion.
Na 2 O · nSiO 2 (1)
(Where n is a number from 2.5 to 4.5)
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| JP2012102273A (en) * | 2010-11-12 | 2012-05-31 | Aica Kogyo Co Ltd | Flame-retardant aqueous resin composition |
| JP2013231092A (en) * | 2012-04-27 | 2013-11-14 | Aica Kogyo Co Ltd | Flame-retardant resin composition |
| FR3030550A1 (en) * | 2014-12-22 | 2016-06-24 | Saint-Gobain Adfors | AQUEOUS BINDER COMPOSITION FOR FIBERS AND FIBROUS PRODUCTS OBTAINED. |
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