JPH09202882A - Flame retardant composition - Google Patents
Flame retardant compositionInfo
- Publication number
- JPH09202882A JPH09202882A JP3276696A JP3276696A JPH09202882A JP H09202882 A JPH09202882 A JP H09202882A JP 3276696 A JP3276696 A JP 3276696A JP 3276696 A JP3276696 A JP 3276696A JP H09202882 A JPH09202882 A JP H09202882A
- Authority
- JP
- Japan
- Prior art keywords
- sulfamate
- flame retardant
- guanidine
- composition
- retardant composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 239000003063 flame retardant Substances 0.000 title claims abstract description 18
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 alkaline earth metal sulfamate Chemical class 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 8
- 238000004040 coloring Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 229920002994 synthetic fiber Polymers 0.000 abstract description 2
- 239000012209 synthetic fiber Substances 0.000 abstract description 2
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 abstract 1
- 230000003405 preventing effect Effects 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 abstract 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 9
- RSIPQRDGPVEGLE-UHFFFAOYSA-L calcium;disulfamate Chemical compound [Ca+2].NS([O-])(=O)=O.NS([O-])(=O)=O RSIPQRDGPVEGLE-UHFFFAOYSA-L 0.000 description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 6
- YZVJHCGMTYDKFR-UHFFFAOYSA-L magnesium;disulfamate Chemical compound [Mg+2].NS([O-])(=O)=O.NS([O-])(=O)=O YZVJHCGMTYDKFR-UHFFFAOYSA-L 0.000 description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 150000002357 guanidines Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 description 2
- GLDOAMWVDAZGLH-UHFFFAOYSA-N azane;guanidine Chemical compound N.NC(N)=N GLDOAMWVDAZGLH-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- RTQPZPWCYWVQCL-UHFFFAOYSA-N 1-[3-(2-methoxyethoxy)phenyl]piperazine Chemical compound COCCOC1=CC=CC(N2CCNCC2)=C1 RTQPZPWCYWVQCL-UHFFFAOYSA-N 0.000 description 1
- MMHVKBFOWOQNKY-UHFFFAOYSA-N 2-aminoguanidine;phosphoric acid Chemical compound NN=C(N)N.OP(O)(O)=O MMHVKBFOWOQNKY-UHFFFAOYSA-N 0.000 description 1
- LWFBRHSTNWMMGN-UHFFFAOYSA-N 4-phenylpyrrolidin-1-ium-2-carboxylic acid;chloride Chemical compound Cl.C1NC(C(=O)O)CC1C1=CC=CC=C1 LWFBRHSTNWMMGN-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- KZGLRFIQMPDBDV-UHFFFAOYSA-N boric acid;guanidine Chemical compound NC(N)=N.OB(O)O KZGLRFIQMPDBDV-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- OTNYCLQTTWHITP-UHFFFAOYSA-N guanidine;hydroxymethyl sulfamate Chemical compound NC(N)=N.NS(=O)(=O)OCO OTNYCLQTTWHITP-UHFFFAOYSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- PHUJCVAICLQULC-UHFFFAOYSA-L strontium;disulfamate Chemical compound [Sr+2].NS([O-])(=O)=O.NS([O-])(=O)=O PHUJCVAICLQULC-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Paper (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、紙などのセルロー
ス系材料用の難燃剤組成物に関する。TECHNICAL FIELD The present invention relates to a flame retardant composition for cellulosic materials such as paper.
【０００２】[0002]
【従来の技術】従来、セルロース材料用の難燃剤として
は、例えばスルファミン酸マグネシウム、スルファミン
酸カルシウムまたはスルファミン酸グアニジンを必須成
分とするものが知られている（例えば特開昭６２−１２
９３８２号公報）。また、スルファミン酸グアニジン、
メチロール化スルファミン酸グアニジンおよびスルファ
ミン酸アンモニウムからなる組成物も知られている（例
えば特開昭６０−１９９０９４号公報）。2. Description of the Related Art Conventionally, as flame retardants for cellulosic materials, those containing magnesium sulfamate, calcium sulfamate or guanidine sulfamate as an essential component are known (for example, JP-A-62-12).
9382). Also, guanidine sulfamate,
A composition comprising a methylolated guanidine sulfamate and an ammonium sulfamate is also known (for example, JP-A-60-199094).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、スル
ファミン酸マグネシウム、スルファミン酸カルシウムな
どのスルファミン酸アルカリ土類金属塩を、含浸処理し
た紙を加熱した場合、引裂強度の低下が大きい；スル
ファミン酸グアニジンを含浸処理した紙を加熱した場合
は、紙の着色が大きい；メチロール化スルファミン酸
グアニジンを含有したものは、紙の着色は少なくなる
が、含浸処理した紙からもホルマリンが遊離し、環境衛
生上好ましくない；などの欠点をそれぞれ有していた。However, when paper impregnated with an alkaline earth metal sulfamate such as magnesium sulfamate or calcium sulfamate is heated, the tear strength is greatly reduced; impregnated with guanidine sulfamate. When the treated paper is heated, the color of the paper is large; the one containing the methylolated guanidine sulfamate has less color of the paper, but formalin is released from the impregnated paper, which is not preferable for environmental hygiene. , And the like, respectively.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、上記問題
点を解決する難燃剤について鋭意検討した結果、特定の
化合物を特定量比で配合することによって、個々のもの
では発揮できない優れた効果が得られることを見いだ
し、本発明に到達した。すなわち本発明は、スルファミ
ン酸アルカリ土類金属塩（Ａ）１０〜６０重量％と、ス
ルファミン酸グアニジン（Ｂ）４０〜９０重量％との混
合物を必須成分として含有することを特徴とする難燃剤
組成物である。Means for Solving the Problems The inventors of the present invention have made earnest studies on a flame retardant which solves the above problems, and as a result, by blending a specific compound in a specific amount ratio, excellent results which cannot be exhibited by individual ones are excellent. The inventors have found that an effect can be obtained and have reached the present invention. That is, the present invention contains a mixture of an alkaline earth metal sulfamate (A) of 10 to 60% by weight and a guanidine sulfamate (B) of 40 to 90% by weight as an essential component. It is a thing.
【０００５】[0005]
【発明の実施の形態】本発明におけるスルファミン酸ア
ルカリ土類金属塩（Ａ）としては、スルファミン酸カル
シウム、スルファミン酸マグネシウム、スルファミン酸
ストロンチウム、スルファミン酸バリウムおよびこれら
の二種以上の混合物が挙げられる。これらのうち好まし
いものスルファミン酸カルシウムおよびスルファミン酸
マグネシウムであり、特に好ましいものはスルファミン
酸カルシウムである。BEST MODE FOR CARRYING OUT THE INVENTION Examples of the alkaline earth metal sulfamate (A) in the present invention include calcium sulfamate, magnesium sulfamate, strontium sulfamate, barium sulfamate and a mixture of two or more thereof. Of these, preferred are calcium sulfamate and magnesium sulfamate, and particularly preferred is calcium sulfamate.
【０００６】上記スルファミン酸アルカリ土類金属塩
（Ａ）は、例えば当モルのスルファミン酸と、アルカリ
土類金属の水酸化物、炭酸塩または酸化物とを公知の方
法で反応させることにより製造できる。該（Ａ）は、通
常ｐＨ４〜９、好ましくはｐＨ５〜８の水溶液として、
後述のスルファミン酸グアニジン（Ｂ）と混合される。The alkaline earth metal sulfamate (A) can be produced, for example, by reacting an equimolar amount of sulfamic acid with a hydroxide, carbonate or oxide of an alkaline earth metal by a known method. . The (A) is usually an aqueous solution having a pH of 4 to 9, and preferably 5 to 8,
It is mixed with guanidine sulfamate (B) described below.
【０００７】本発明におけるスルファミン酸グアニジン
（Ｂ）は、ジシアンジアミドとスルファミン酸アンモニ
ウムとを、通常１：（１〜２．０）、好ましくは１：
（１．４〜１．８）のモル比で、加熱溶融反応すること
によって製造できる。スルファミン酸アンモニウムのモ
ル比が１未満ではメラミン、アンメリンなどの水不溶物
の含有量が増大し、２．０を越えると未反応スルファミ
ン酸アンモニウムおよび副生アンモニウム化合物（イミ
ドジスルホン酸グアニジンアンモニウムなど）の量が増
大し、耐着色性が低下する。The guanidine sulfamate (B) in the present invention contains dicyandiamide and ammonium sulfamate in a proportion of usually 1: (1 to 2.0), preferably 1 :.
It can be produced by a heat melting reaction at a molar ratio of (1.4 to 1.8). When the molar ratio of ammonium sulfamate is less than 1, the content of water-insoluble substances such as melamine and ammeline increases, and when it exceeds 2.0, unreacted ammonium sulfamate and by-product ammonium compounds (guanidine ammonium imidodisulfonate, etc.) The amount increases and the coloring resistance decreases.
【０００８】溶融反応温度は通常１２０〜１９０℃、好
ましくは１４０〜１７０℃である。反応時間は、通常２
〜１０時間、好ましくは３〜５時間である。反応物はそ
のまままたは水で希釈されて上記（Ａ）と混合される。
この反応物には主生成物であるスルファミン酸グアニジ
ン（Ｂ）の他に未反応のスルファミン酸アンモニウム、
ジシアンジアミド、さらに副反応生成物（イミドジスル
ホン酸、グアニジンアンモニウム、イミドジスルホン酸
ジグアニジン、メラミン、アンメリンなど）が少量含ま
れていてもよい。これらの含有量は、通常１０％以下、
好ましくは５％以下である。The melting reaction temperature is usually 120 to 190 ° C, preferably 140 to 170 ° C. Reaction time is usually 2
-10 hours, preferably 3-5 hours. The reaction product is mixed with (A) as it is or diluted with water.
In this reaction product, in addition to the main product guanidine sulfamate (B), unreacted ammonium sulfamate,
A small amount of dicyandiamide and a side reaction product (imidodisulfonic acid, guanidine ammonium, diguanidine imidodisulfonic acid, melamine, ammeline, etc.) may be contained. The content of these is usually 10% or less,
Preferably it is 5% or less.
【０００９】本発明の難燃剤組成物における上記（Ａ）
と（Ｂ）の重量比は、通常（１０〜６０）：（４０〜９
０）、好ましくは（２０〜５０）：（５０〜８０）、特
に好ましくは（３０〜４５：５５〜７０）である。
（Ａ）の比率が１０未満では、加熱による着色が大きく
なり、６０を超えると燃焼時の残じん時間が長くなり、
また加熱による引裂強度の低下も大きくなる。The above (A) in the flame retardant composition of the present invention
The weight ratio of (B) is usually (10-60) :( 40-9)
0), preferably (20 to 50): (50 to 80), and particularly preferably (30 to 45:55 to 70).
When the ratio of (A) is less than 10, coloring due to heating becomes large, and when it exceeds 60, the residual dust time during combustion becomes long,
Further, the decrease in tear strength due to heating also increases.
【００１０】本発明の難燃剤組成物は、例えば、所定量
の（Ａ）の水溶液に、（Ｂ）または（Ｂ）の水溶液を混
合して均一溶解し、必要によりろ過精製することにより
得られる。The flame retardant composition of the present invention can be obtained by, for example, mixing a predetermined amount of the aqueous solution of (A) with the aqueous solution of (B) or (B), uniformly dissolving it, and filtering and purifying if necessary. .
【００１１】本発明の組成物には、必要に応じて他の公
知の難燃剤成分を含有させることもできる。他の公知の
難燃剤成分の具体例としては、（Ｂ）以外のグアニジン
塩系化合物［グアニジン塩（メチロール化スルファミン
酸グアニジン、リン酸グアニジン、次亜リン酸グアニジ
ン、ポリリン酸グアニジン、ホウ酸グアニジンなど）、
シアノ置換グアニジン（リン酸グアニル尿素、ポリリン
酸グアニル尿素など）、アミノ置換もしくはアミノ基含
有置換グアニジン塩（リン酸アミノグアニジンなど）な
ど］、無機酸のアンモニウム塩（硫酸アンモニウム、リ
ン酸アンモニウムなど）、ジシアンジアミド類（ジシア
ンジアミド、メチロール化ジシアンジアミド、ヘキサメ
チレンテトラミンなど）などが挙げられる。If desired, the composition of the present invention may contain other known flame retardant components. Specific examples of other known flame retardant components include guanidine salt-based compounds other than (B) [guanidine salt (guanidine methylol sulfamate, guanidine phosphate, guanidine hypophosphite, guanidine polyphosphate, guanidine borate, etc. ),
Cyano-substituted guanidine (guanylurea phosphate, guanylurea polyphosphate, etc.), amino-substituted or amino group-containing substituted guanidine salt (aminoguanidine phosphate, etc.), ammonium salt of inorganic acid (ammonium sulfate, ammonium phosphate, etc.), dicyandiamide Examples thereof include dicyandiamide, methylolated dicyandiamide, hexamethylenetetramine and the like.
【００１２】本発明の組成物は、通常水溶液の形で用い
られる。使用濃度は、使用目的、保存条件、含浸方法、
対象の基材の性質などによって異なるが、組成物の固形
分重量で通常１〜６０％、好ましくは１０〜３０％であ
る。The composition of the present invention is usually used in the form of an aqueous solution. Concentration used, purpose of use, storage conditions, impregnation method,
The solid content of the composition is usually 1 to 60%, preferably 10 to 30%, although it varies depending on the properties of the target substrate.
【００１３】本発明の組成物の使用対象セルロース系材
料としては、たとえば紙製品（障子紙、ふすま紙、壁
紙、板紙、合成紙など）、布等の繊維（木綿など）製
品、および合板、合成木材等の木質材料が挙げられる。The cellulosic materials to be used with the composition of the present invention include, for example, paper products (shoji paper, bran paper, wallpaper, paperboard, synthetic paper, etc.), fiber (cotton, etc.) products such as cloth, and plywood, synthetic. Wood-based materials such as wood can be used.
【００１４】本発明の組成物の基材（セルロース系材
料）に対する含浸量は、固形分換算で通常２〜４０重量
％、好ましくは１０〜３０重量％である。The amount of the composition of the present invention impregnated into the base material (cellulosic material) is usually 2 to 40% by weight, preferably 10 to 30% by weight in terms of solid content.
【００１５】基材に含浸する方法は、従来行なわれてい
る方法でよく、組成物の水溶液に基材を直接浸漬する方
法、サイズプレス法、スプレー法、ハケ塗りなどで塗布
する方法などが挙げられる。含浸処理された基材は、通
常、温度６０〜１５０℃で乾燥される。The method of impregnating the base material may be a conventional method, such as a method of directly immersing the base material in an aqueous solution of the composition, a size press method, a spray method, a method of applying by brushing, or the like. To be The impregnated substrate is usually dried at a temperature of 60 to 150 ° C.
【００１６】また、本発明の組成物は、合成サイズ剤、
デンプン等の表面処理剤、塩化ビニルなどの合成フイル
ムとの接着付与剤、ワックスエマルションなどの撥水剤
などと併用することも可能である。The composition of the present invention also comprises a synthetic sizing agent,
It is also possible to use it together with a surface treatment agent such as starch, an adhesion promoter with a synthetic film such as vinyl chloride, a water repellent such as a wax emulsion, and the like.
【００１７】[0017]
【実施例】以下、実施例により本発明をさらに詳細に説
明するが、本発明はこれに限定されるものではない。以
下において、部は重量部、％は重量％である。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In the following, parts are parts by weight, and% is% by weight.
【００１８】製造例１ 水酸化カルシウム７４部（１モル）の水分散物に、スル
ファミン酸１９４部（２モル）を、徐々に加えた。２０
〜４０℃で２時間攪拌した後ろ過して、ｐＨ６．２、固
形分３５％の透明なスルファミン酸カルシウム水溶液を
得た。Production Example 1 To an aqueous dispersion of 74 parts (1 mol) of calcium hydroxide, 194 parts (2 mol) of sulfamic acid was gradually added. 20
The mixture was stirred at -40 ° C for 2 hours and then filtered to obtain a transparent calcium sulfamate aqueous solution having a pH of 6.2 and a solid content of 35%.
【００１９】製造例２ スルファミン酸１９４部（２モル）を水に加え、予め溶
解した。これに炭酸マグネシウム８８部（１モル）を徐
々に加えた。２０〜４０℃で２時間攪拌した後ろ過し
て、ｐＨ５．７、固形分３５％の透明なスルファミン酸
マグネシウム水溶液を得た。Production Example 2 194 parts (2 mol) of sulfamic acid was added to water and dissolved in advance. 88 parts (1 mol) of magnesium carbonate was gradually added thereto. The mixture was stirred at 20 to 40 ° C. for 2 hours and then filtered to obtain a transparent aqueous magnesium sulfamate solution having a pH of 5.7 and a solid content of 35%.
【００２０】製造例３ ジシアンジアミド８４部（１モル）とスルファミン酸ア
ンモニウム１９４部（１．７モル）を混合し、溶融後１
５０〜１７０℃で３時間反応させ、未反応ジシアンジア
ミドを３．５％含むスルファミン酸グアニジンを得た。
これに水を加え、固形分３５％の水溶液を得た。Production Example 3 84 parts (1 mol) of dicyandiamide and 194 parts (1.7 mol) of ammonium sulfamate were mixed, and after mixing 1
The reaction was carried out at 50 to 170 ° C. for 3 hours to obtain guanidine sulfamate containing 3.5% of unreacted dicyandiamide.
Water was added to this to obtain an aqueous solution having a solid content of 35%.
【００２１】実施例１〜６、比較例１〜３ 製造例１のスルファミン酸カルシウム、製造例２のスル
ファミン酸マグネシウムおよび製造例３のスルファミン
酸グアニジンを用いて、表１に示す配合比により本発明
の難燃剤組成物を調製した。なお、比較例１〜３は、そ
れぞれ製造例１〜３の製造物をそのまま用いた。Examples 1 to 6 and Comparative Examples 1 to 3 Using the calcium sulfamate of Production Example 1, the magnesium sulfamate of Production Example 2 and the guanidine sulfamate of Production Example 3 according to the compounding ratios shown in Table 1, the present invention was conducted. A flame retardant composition was prepared. In Comparative Examples 1 to 3, the products of Production Examples 1 to 3 were used as they were.
【００２２】試験例１ 実施例１〜６および比較例１〜３の難燃剤組成物水溶液
を固形分２０％になるよう希釈した。その希釈液に紙を
浸漬し、難燃剤組成物量が紙に対し固形分で２０％にな
るようにゴムロールで絞り、１００〜１０５℃に温度調
整したドラムドライヤーで乾燥した。その紙を下記の方
法で評価した。その結果を表２に示す。 難燃性 ：ＪＩＳ Ｚ−２１５０「薄い材料の防炎性
試験」（４５°メッケルバーナー法）に準じ、炭化長
（ｃｍ）、残じん（秒）を測定した。小さい数値程優れ
る。 引裂強度 ：２００℃×５分間オーブン中で加熱処理
後、ＪＩＳ Ｐ−８１１６「紙の引裂強さ試験方法」に
準じ測定した。大きい数値程優れる。 着色防止性：含浸処理した紙を２００℃×５分間オーブ
ン中で加熱し、ハンター白色度を測定した。大きい数値
程優れる。Test Example 1 The aqueous flame retardant composition solutions of Examples 1 to 6 and Comparative Examples 1 to 3 were diluted to a solid content of 20%. Paper was dipped in the diluted solution, squeezed with a rubber roll so that the amount of the flame retardant composition was 20% of the solid content relative to the paper, and dried with a drum dryer whose temperature was adjusted to 100 to 105 ° C. The paper was evaluated by the following method. Table 2 shows the results. Flame retardancy: Carbonization length (cm) and residual dust (seconds) were measured according to JIS Z-2150 "Flameproofness test for thin materials" (45 ° Meckel burner method). The smaller the value, the better. Tear strength: After heat treatment in an oven at 200 ° C. for 5 minutes, the tear strength was measured according to JIS P-8116 “Paper tear strength test method”. The larger the number, the better. Anti-coloring property: The impregnated paper was heated in an oven at 200 ° C for 5 minutes to measure Hunter whiteness. The larger the number, the better.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【発明の効果】本発明の難燃剤組成物を含浸して得た紙
は、難燃性、引裂強度および着色防止性がいずれも良好
であり、従来のスルファミン酸グアニジン、スルファミ
ン酸カルシウムまたはスルファミン酸マグネシウム単独
使用に比べ、バランスよい品質を有する優れた難燃紙を
製造することができる。特に残じんに優れ、スルファミ
ン酸アルカリ土類金属塩単独では製造できなかったＪＩ
Ｓ規定防炎２級合格の難燃材料を得ることができる。上
記効果を奏することから本発明の組成物は、各種セルロ
ース系材料（紙類、布類、木質材料など）の難燃剤とし
て極めて有用である。また、合成繊維、樹脂フィルム等
の防燃加工にも用いることができる。The paper obtained by impregnating the flame retardant composition of the present invention has good flame retardancy, tear strength, and anti-coloring property, and has a conventional guanidine sulfamate, calcium sulfamate or sulfamic acid. It is possible to produce an excellent flame-retardant paper having a well-balanced quality as compared with the case of using magnesium alone. JI which was particularly excellent in residual dust and could not be produced by alkaline earth metal sulfamate salt alone
It is possible to obtain a flame-retardant material that passes the S standard flameproofing class 2. The composition of the present invention having the above-mentioned effects is extremely useful as a flame retardant for various cellulosic materials (papers, cloths, wood materials, etc.). It can also be used for flameproofing of synthetic fibers and resin films.
Claims (2)
（Ａ）１０〜６０重量％と、スルファミン酸グアニジン
（Ｂ）４０〜９０重量％との混合物を必須成分として含
有することを特徴とするセルロース材料用難燃剤組成
物。1. A cellulosic material comprising a mixture of 10 to 60% by weight of an alkaline earth metal sulfamate (A) and 40 to 90% by weight of guanidine sulfamate (B) as an essential component. Flame retardant composition.
カルシウムである請求項１記載の組成物。2. The alkaline earth metal constituting (A) is
The composition of claim 1 which is calcium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03276696A JP3761954B2 (en) | 1996-01-26 | 1996-01-26 | Flame retardant composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03276696A JP3761954B2 (en) | 1996-01-26 | 1996-01-26 | Flame retardant composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09202882A true JPH09202882A (en) | 1997-08-05 |
| JP3761954B2 JP3761954B2 (en) | 2006-03-29 |
Family
ID=12367975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03276696A Expired - Fee Related JP3761954B2 (en) | 1996-01-26 | 1996-01-26 | Flame retardant composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3761954B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010229312A (en) * | 2009-03-27 | 2010-10-14 | Fuji Xerox Co Ltd | Resin composition and resin-molded article |
-
1996
- 1996-01-26 JP JP03276696A patent/JP3761954B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010229312A (en) * | 2009-03-27 | 2010-10-14 | Fuji Xerox Co Ltd | Resin composition and resin-molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3761954B2 (en) | 2006-03-29 |
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