JPH09119069A - Cellulose material treated with guanidine salt or ethylenediamine salt for flame retardance and containing anti-discoloration agent - Google Patents

Cellulose material treated with guanidine salt or ethylenediamine salt for flame retardance and containing anti-discoloration agent

Info

Publication number
JPH09119069A
JPH09119069A JP20375196A JP20375196A JPH09119069A JP H09119069 A JPH09119069 A JP H09119069A JP 20375196 A JP20375196 A JP 20375196A JP 20375196 A JP20375196 A JP 20375196A JP H09119069 A JPH09119069 A JP H09119069A
Authority
JP
Japan
Prior art keywords
salt
acid
flame
cellulosic material
guanidine
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.)
Withdrawn
Application number
JP20375196A
Other languages
Japanese (ja)
Inventor
Georg Haeubl
ゲオルク・ホイブル
Scheuchenstuhl Willibald
ウイリーバルト・シヨイヒエンシユトウール
Kapeller Andreas
アンドレアース・カッペラー
Klaus Ritzberger
クラウス・リッツベルガー
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Patheon Austria GmbH and Co KG
Chemie Linz GmbH
Original Assignee
DSM Chemie Linz GmbH
Chemie Linz GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by DSM Chemie Linz GmbH, Chemie Linz GmbH filed Critical DSM Chemie Linz GmbH
Publication of JPH09119069A publication Critical patent/JPH09119069A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/34—Ignifugeants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C08K5/25—Carboxylic acid hydrazides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C08K5/31—Guanidine; Derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/332—Di- or polyamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/422—Hydrazides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/438—Sulfonamides ; Sulfamic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/467—Compounds containing quaternary nitrogen atoms derived from polyamines
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/143—Agents preventing ageing of paper, e.g. radiation absorbing substances
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Fireproofing Substances (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retarded cellulose material resistant to thermal discoloration by applying a flame-retardant composed of a guanidine salt or an ethylene diamine salt in combination with a specific discoloration preventing agent to a cellulose material. SOLUTION: The thermal discoloration preventing agent to be used in the production of the cellulose material is a 70% aqueous solution of a 2- hydroxypropionic acid of formula (R1 and R2 are each H, OH or CH2 OH), 2,2-dimethylolpropionic acid, etc., preferably 2-hydroxypropionic acid, carbohydrazide or their mixture. A cellulose material such as paper, woven cotton fabric or woven viscose rayon fabric is subjected to flame-retarding treatment with a guanidine salt or an ethylenediamine salt of sulfamic acid, sulfuric acid, phosphoric acid or boric acid, preferably sulfamic acid salt by adding 1-15wt.%, preferably 3-10wt.% (based on the flame-retardant) of the thermal discoloration preventing agent to obtain a flame-retarded material having thermal discoloration resistance.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】グアニジン塩またはエチレン
ジアミン塩で、特にスルフアミン酸グアニジンで難燃性
に仕上げ加工された、紙類および繊維製品のようなセル
ロース材料は、乾燥の場合に行なわれるような熱的処理
の際に特に変色する傾向があるので、変色防止剤の添加
が必要である。従来技術においては、すでにセルロース
のための多数の黄変防止剤ないし変色防止剤が知られて
いる。これらは、例えば、ホスフィン酸またはその塩類
またはチオアルコールのような還元剤である。しかしな
がら、これらの生成物は、グアニジン塩で難燃性に仕上
げ加工されたセルロース材料と組合された場合にはほと
んど効果を示さない。FIELD OF THE INVENTION Cellulose materials, such as papers and textiles, which have been flame-retarded with a guanidine salt or an ethylenediamine salt, in particular with a guanidine sulfamate, are thermally treated as is the case with drying. It is necessary to add a discoloration preventive agent because it tends to discolor during treatment. A large number of anti-yellowing agents or tarnish inhibitors for cellulose are already known in the prior art. These are reducing agents such as, for example, phosphinic acid or its salts or thioalcohols. However, these products show little effect when combined with cellulosic materials that are flame retarded with guanidine salts.

【０００２】[0002]

【従来の技術】エチレンジアミン化合物で難燃化加工さ
れた紙類については、変色防止剤としてヒドラジンまた
はホウ酸を使用することが記載されている〔ケミカルア
ブストラクツ(Chem. Abstr.)第１０３巻：１７９８６９
Ｋ参照〕。しかしながら、ヒドラジンは、発ガン性物質
とみなされている。スルフアミン酸グアニジンで処理さ
れたセルロース含有材料のための従来最善の変色防止剤
は、ジシアンジアミドであるが〔ケミカルアブストラク
ツ(Chem. Abstr.)第８５巻：９６０６６ｅ、１９７６年
参照〕、それは事情によっては皮膚炎を起すことがあ
る。2. Description of the Related Art For papers flame-retarded with an ethylenediamine compound, it is described that hydrazine or boric acid is used as a discoloration inhibitor [Chem. Abstr. Vol. 103]. : 179869
K]]. However, hydrazine is considered a carcinogen. The best traditional anti-tarnish agent for cellulose-containing materials treated with guanidine sulfamate is dicyandiamide [Chem. Abstr. Vol. May cause dermatitis.

【０００３】[0003]

【発明が解決しようとする課題】従って、本発明の解決
すべき課題は、グアニジン塩またはエチレンジアミン塩
で難燃性に加工されたセルロース材料に適した、上記の
欠点を有しない変色防止剤を見出すことであった。意外
にもこの課題は、プロピオン酸または２- 位においてヒ
ドロキシル基で置換されたプロピオン酸またはカルボヒ
ドラジドを添加することによって解決することができ
た。The problem to be solved by the invention is therefore to find a discoloration inhibitor which is suitable for cellulosic materials which have been flame-retarded with guanidine salts or ethylenediamine salts and which do not have the abovementioned disadvantages. Was that. Surprisingly this problem could be solved by adding propionic acid or propionic acid or carbohydrazide substituted with a hydroxyl group at the 2-position.

【０００４】[0004]

【課題を解決するための手段】従って、本発明の対象
は、熱による変色に対して保護された、難燃化加工され
たセルロース材料において、この材料がグアニジン塩ま
たはエチレンジアミン塩を難燃剤としてそして式The object of the present invention is therefore to provide a flame-retarded cellulosic material protected against thermal discoloration, which material comprises a guanidine salt or an ethylenediamine salt as a flame retardant and formula

【０００５】[0005]

【化３】 Embedded image

【０００６】（上式中、Ｒ1 およびＲ2 は互いに無関係
にＨ、ＯＨまたは -ＣＨ2-ＯＨを意味する）で表される
化合物またはその塩またはカルボヒドラジドあるいはこ
れらの混合物を変色防止剤として含有することを特徴と
する上記セルロース材料である。これらの材料は、難燃
化するためにグアニジン塩またはエチレンジアミン塩を
含有する。適当な塩は、例えば、スルフアミン酸塩、硫
酸塩、リン酸塩およびホウ酸塩である。スルフアミン酸
塩および硫酸塩が難燃剤として好ましく、スルフアミン
酸塩が特に好ましく使用される。その際、使用される難
燃剤の量は、セルロース材料の用途、難燃剤の種類その
他によって変えることができ、そして好ましくはセルロ
ース材料に対して約１ないし５０重量％、特に好ましく
は約５ないし２５重量％である。(Wherein R 1 and R 2 independently of each other represent H, OH or —CH 2 —OH) or a salt thereof or carbohydrazide or a mixture thereof as an anti-tarnish agent. The above-mentioned cellulose material is characterized by containing. These materials contain a guanidine salt or an ethylenediamine salt for flame retarding. Suitable salts are, for example, sulfamate, sulphate, phosphate and borate. Sulfaminates and sulphates are preferred as flame retardants and sulphamates are particularly preferred. The amount of flame retardant used may vary depending on the use of the cellulosic material, the type of flame retardant, etc., and is preferably about 1 to 50% by weight, particularly preferably about 5 to 25% by weight with respect to the cellulosic material. % By weight.

【０００７】本発明による材料は、更に、式The material according to the invention further has the formula

【０００８】[0008]

【化４】 Embedded image

【０００９】（上式中、Ｒ1 およびＲ2 は互いに無関係
にＨ、ＯＨまたは -ＣＨ2-ＯＨを意味する）で表される
変色防止剤を含有する。式Ｉで表される好ましい化合物
は、２- ヒドロキシプロピオン酸、２，２- ジメチロー
ルプロピオン酸およびプロピオン酸である。特に好まし
い化合物は、２- ヒドロキシプロピオン酸（乳酸）であ
る。その際、乳酸は、右旋性および左旋性乳酸としてな
らびにラセミ化合物として使用されうる。式Ｉの化合物
は、また塩として例えばアルカリ金属塩、アルカリ土類
金属塩またはグアニジン塩として使用されうる。また、
式Ｉの化合物は、第四アンモニウム化合物として、また
は第一、第二または第三級有機アミンの塩としても使用
されうる。式Ｉの化合物の代りに、カルボヒドラジドも
また変色防止剤として使用されうる。更に、式Ｉの化合
物とカルボヒドラジドとの混合物もまた変色防止剤とし
て使用されうる。(In the above formula, R 1 and R 2 are, independently of each other, H, OH or --CH 2 --OH) and contain a discoloration inhibitor. Preferred compounds of formula I are 2-hydroxypropionic acid, 2,2-dimethylolpropionic acid and propionic acid. A particularly preferred compound is 2-hydroxypropionic acid (lactic acid). Lactic acid can then be used as dextrorotatory and levorotatory lactic acid and as a racemate. The compounds of formula I can also be used as salts, for example as alkali metal salts, alkaline earth metal salts or guanidine salts. Also,
The compounds of formula I can also be used as quaternary ammonium compounds or as salts of primary, secondary or tertiary organic amines. Instead of the compound of formula I, carbohydrazides can also be used as tarnish inhibitors. In addition, mixtures of compounds of formula I with carbohydrazides can also be used as tarnish inhibitors.

【００１０】一方、変色防止剤の量は、使用された化合
物、セルロース材料の用途および処理の種類その他に応
じて変えることができる。好ましくは、変色防止剤は、
グアニジン塩またはエチレンジアミン塩の量に対して約
１ないし１５重量％の量で使用され、特に好ましくは約
３ないし１０重量％の量で使用される。本発明に従って
加工されたセルロース材料は、難燃剤および変色防止剤
に加えて、更に、それぞれの使用目的にとって通例の、
例えば殺菌剤、スライム防止剤、顔料、染色、繊維加工
剤、例えば防皺剤を含有しうる。On the other hand, the amount of the anti-tarnish agent can be varied depending on the compound used, the use of the cellulosic material, the type of treatment and the like. Preferably, the anti-tarnish agent is
It is used in an amount of about 1 to 15% by weight, based on the amount of guanidine salt or ethylenediamine salt, particularly preferably in an amount of about 3 to 10% by weight. The cellulosic material processed according to the invention, in addition to flame retardants and tarnish inhibitors, is furthermore customary for the respective purpose of use,
It may contain, for example, bactericides, antislime agents, pigments, dyes, textile finishing agents, such as anti-wrinkling agents.

【００１１】セルロース材料を難燃剤および変色防止剤
を用いて加工するために、グアニジン塩またはエチレン
ジアミン塩および変色防止剤の水溶液、好ましくはグア
ニジン塩またはエチレンジアミン塩に関して７０重量％
までの溶液が調製される。その際、上記の溶液のｐＨ値
は、セルロース材料ができうる限り損なわれないように
調整される。約４ないし８．５のｐＨ値が好ましい。そ
のために、例えばまず相当する量のグアニジン塩または
エチレンジアミン塩が水に溶解され、そして次に式Ｉの
化合物が、場合によっては塩として、および／またはカ
ルボヒドラジッドが、変色防止剤の所望の濃度に達する
まで徐々に添加される。To process cellulosic materials with flame retardants and tarnish inhibitors, an aqueous solution of guanidine salt or ethylenediamine salt and tarnish inhibitor, preferably 70% by weight with respect to guanidine salt or ethylenediamine salt.
Solutions are prepared. At that time, the pH value of the solution is adjusted so as not to damage the cellulosic material as much as possible. A pH value of about 4 to 8.5 is preferred. For that purpose, for example, first the corresponding amount of the guanidine salt or the ethylenediamine salt is dissolved in water, and then the compound of formula I, optionally as a salt and / or carbohydrazide, is added to the desired concentration of the tarnish inhibitor. Is gradually added until reaching.

【００１２】しかしながら、またまず例えば炭酸グアニ
ジンまたはエチレンジアミンとスルフアミン酸または硫
酸またはリンと水溶液中で、場合によっては泡止め剤の
添加のもとに反応せしめることによって、難燃剤が調製
され、そのようにして得られた反応溶液を難燃剤を単離
することなく対応する量の変色防止剤に添加することも
できる。However, it is also possible to prepare the flame retardant by first reacting it with, for example, guanidine carbonate or ethylenediamine and sulfamic acid or sulfuric acid or phosphorus in aqueous solution, optionally with the addition of antifoam agents, and The reaction solution obtained in this way can also be added to the corresponding amount of tarnish inhibitor without isolating the flame retardant.

【００１３】場合によっては、ｐＨ値は、例えば炭酸グ
アニジンまたはアルカリ金属またはアルカリ土類金属の
水酸化物の添加により、あるいは酸、例えば乳酸、塩
酸、酢酸、スルフアミン酸またはギ酸その他の添加によ
って後刻調整されうる。次に、この溶液を適当なセルロ
ース材料に塗布するか、または適当なセルロース材料を
溶液に含浸せしめる。塗布または含浸は、材料の種類に
応じて、例えば、浸漬、噴霧、加圧ローリング、空気ブ
ラストまたは接着剤プレッシング(Leimpressen) によっ
て、あるいはドクターブレード塗布法またはパジング法
によって実施される。その際、加工された材料が、その
後の乾燥後に前記の重量％の難燃剤および／または変色
防止剤を乾燥物質として含有するような量の溶液が使用
される。その他の加工は、それぞれ使用された材料にと
って通例の加工法によって行われる。In some cases, the pH value is adjusted later by addition of, for example, guanidine carbonate or hydroxides of alkali metals or alkaline earth metals, or by addition of acids such as lactic acid, hydrochloric acid, acetic acid, sulfamic acid or formic acid and the like. Can be done. The solution is then applied to a suitable cellulosic material or the solution is impregnated with a suitable cellulosic material. Application or impregnation is carried out depending on the type of material, for example by dipping, spraying, pressure rolling, air blasting or adhesive pressing (Leimpressen) or by doctor blade application or padding. A solution is used in such an amount that the processed material, after subsequent drying, contains the abovementioned weight% of flame retardant and / or tarnish inhibitor as dry substance. The other processing is carried out by the processing methods customary for the material used.

【００１４】グアニジン塩および／またはエチレンジア
ミン塩を用いて難燃化されたセルロース材料は、式Ｉで
表される変色防止剤またはカルボヒドラジッドを添加す
ることによって、熱処理による乾燥の際に現れる変色を
著しく減少することができる。更に、特に変色防止剤と
して乳酸を使用することによって、乳酸の殺生物作用に
基いて変色と共にカビ類の発生もまた減少しまたは防止
されるという利点もまた得られる。The cellulosic material flame-retarded with the guanidine salt and / or the ethylenediamine salt is treated with the anti-tarnish agent of the formula I or carbohydrazide so that the discoloration which appears upon drying by heat treatment is It can be significantly reduced. In addition, the use of lactic acid, in particular as an anti-tarnish agent, also has the advantage that the development of fungi with discoloration is also reduced or prevented due to the biocidal action of lactic acid.

【００１５】式Ｉの変色防止剤の効果の検査は、ＤＩＮ
５０３３によるランゲ (Dr. Lange)の色彩計を用いる測
定によってより、ならびに比較標準に基づく光学的評価
によって行われる。A test of the effect of the tarnish inhibitors of the formula I is DIN
By measurement with a 5033 Lange colorimeter, as well as by optical evaluation based on comparative standards.

【００１６】[0016]

【実施例】【Example】

例１： スルフアミン酸グアニジンおよび乳酸からの水溶液の調
製 炭酸グアニジン（ヘミーリンツ社製）４３２．６ｇおよ
び蒸留水７０６．９ｇから調製された炭酸グアニジン水
溶液を６０℃に加熱し、その上にアミド硫酸〔アルブラ
イトアンドウイルソン社(Albright & Wilson) 製〕４６
６．２ｇを攪拌下に、泡立ちが生じないように少量づつ
に分けて注加した。次いで、この溶液を黒色帯状濾紙上
で濾過し、そして以後の試験において使用した。 例２：スルフアミン酸グアニジン５０重量％および
（＋）乳酸〔ヤンセンヘミー社(Jannsen Chemie)製〕
２．５重量％から例１と類似方法で水溶液を調製した。
この溶液のｐＨ値は、約５．５であった。次に、２枚の
黒色帯状濾紙を溶液に浸漬して、濾紙に難燃剤の乾燥物
質約１５重量％を含有せしめた。これらの濾紙を１００
℃において１０分間予備乾燥し、そしてその後で２００
℃において１０分間の温度処理にかけた。まず比較標準
を用いて光学的に変色を測定した。その際、濾紙は、２
の評点を得た。比較として３つの規準が用いられた。 評点５：変色防止剤が添加されていない難燃剤としての
スルフアミン酸グアニジン１５重量％を含有する黒色帯
状濾紙 評点３：スルフアミン酸グアニジンの量に関して５重量
％のジシアンジアミドをを添加された難燃剤としてスル
フアミン酸グアニジン１５重量％を含有する黒色帯状濾
紙 評点１：スルフアミン酸グアニジンを含有しない黒色帯
状濾紙 規準体は、同様にして１００℃において予備乾燥し、そ
して２００℃において１０分間熱処理することによって
調製された。Example 1 Preparation of Aqueous Solution from Guanidine Sulfamate and Lactic Acid An aqueous guanidine carbonate solution prepared from 432.6 g of guanidine carbonate (manufactured by Chemie Linz) and 706.9 g of distilled water was heated to 60 ° C., and amide sulfate [alcohol] Made by Bright & Wilson] 46
With stirring, 6.2 g was added in small portions so as to prevent foaming. The solution was then filtered on black strip filter paper and used in subsequent tests. Example 2: 50% by weight of guanidine sulfamate and (+) lactic acid [manufactured by Jannsen Chemie]
An aqueous solution was prepared from 2.5% by weight in a similar manner to Example 1.
The pH value of this solution was about 5.5. Two black strips of filter paper were then dipped into the solution so that the filter paper contained about 15% by weight dry matter of flame retardant. 100 of these filter papers
Pre-dry at 10 ° C for 10 minutes and then 200
It was subjected to a temperature treatment at 0 ° C for 10 minutes. First, the color change was measured optically using a comparative standard. At that time, filter paper is 2
Got the score of. Three criteria were used for comparison. Rating 5: Black strip filter paper containing 15% by weight of guanidine sulfamate as flame retardant without addition of tarnish inhibitor Rating 3: Sulfamine as flame retardant with addition of 5% by weight of dicyandiamide with respect to the amount of guanidine sulfamate Black strip filter paper containing 15% by weight of guanidine acid Rating 1: Black strip filter paper not containing guanidine sulfamate A reference standard was similarly prepared by predrying at 100 ° C and heat treatment at 200 ° C for 10 minutes. .

【００１７】更に、濾紙は、ＤＩＮ５０３３に従ってラ
ンゲ(Dr. Lange) による色彩計を用いて測定された。測
定は、標準光源Ｄ６５／１０o を用いて実施された。測
定値は、ｄ／８°であった。色度値(Normfarbwerte)
Ｘ，Ｙ，Ｚ，ＣＩＥ三刺戟値（ＣＩＥ- Lab-Werte)Ｌ*,
ａ* ，ｂ* 、色度座標(Normfarbwerte-Anteile) ｘ，
ｙ，Ｙおよびハンター(Hunter)による色値（Farbwert)
Ｌ，ａ，ｂが測定された。Furthermore, the filter papers were measured according to DIN 5033 using a colorimeter from Dr. Lange. The measurements were carried out with a standard light source D65 / 10 ° . The measured value was d / 8 °. Chromaticity value (Normfarbwerte)
X, Y, Z, CIE Tristimulus Value (CIE-Lab-Werte) L * ,
a * , b * , chromaticity coordinates (Normfarbwerte-Anteile) x,
Color values (Farbwert) by y, Y and Hunter
L, a, b were measured.

【００１８】結果は、表１および２に要約されている。
更に、例２と類似方法で、難燃剤および変色防止剤の溶
液を用いて黒色帯状濾紙が処理され、その際、変色防止
剤、濃度またはｐＨ値が変えられた。結果は、同様に表
１および２から明らかである。対照としてジシアンジア
ミドで処理された濾紙が使用された。The results are summarized in Tables 1 and 2.
Further, in a manner similar to Example 2, black strip filter paper was treated with a solution of flame retardant and tarnish inhibitor, the tarnish inhibitor, concentration or pH value being varied. The results are likewise apparent from Tables 1 and 2. Filter paper treated with dicyandiamide was used as a control.

【００１９】下記の略語が使用された： ＦＨ 難燃剤、乾燥物質としての重量％、 ＶＩ 変色防止剤、ＦＨに対する重量％、 ｏｐｔ．Ｂ． 光学的評価 ＧｕＳｕ スルフアミン酸グアニジン ＤＭＰＳ ジメチロールプロピオン酸 ＭＳ 乳酸 ＣＨ カルボヒドラジド表１ ： 例 ＦＨ／（重量％） ＶＩ／（重量％） ｐＨ ｏｐｔ．Ｂ． ２ ＧｕＳｕ／１５．１ ＭＳ／５ ５．５ ２− ３ ＧｕＳｕ／１６．６ ＭＳ／５ ４．０ ２− ４ ＧｕＳｕ／１７．０ ＭＳ／５ ７．０ ３＋ ５ ＧｕＳｕ／１３．６ ＭＳ／５ ８．０ ３＋ ６ ＧｕＳｕ／１４．９ ＭＳ／２ ５．５ ３＋ ７ ＧｕＳｕ／１６．１ ＭＳ／１０ ５．５ ３ ８ ＧｕＳｕ／１５．２ ＤＭＰＳ／５ ８．４ ３＋ ９ ＧｕＳｕ／１４．７ ＣＨ／５ ７．９ ２＋* １０ ＧｕＳｕ／１５．１ ＭＳ／５ｕ．ＣＨ／３ ６．９ ２ １１ ＧｕＳｕ／１５．２ ジシアンジアミド／５ ８．０ ３ １２ ＧｕＳｕ／１７．５ ジシアンジアミド／５ ５．５ ２ １３ ＧｕＳｕ／１６．０７ ＶＩを含有せず ５．５ ５* 濾紙の周縁は、暗色に変色した。表２ ： 例 色度値 三刺激値 色度座標 ハンターによる色値 X Y Z L* a* b * x y Y L a b 2 54.25 55.03 37.85 79.04 5.4 22.66 0.369 0.37 55.03 74.16 5.11 17.88 3 53.65 54.37 37.85 78.67 5.47 21.95 0.368 0.37 54.37 73.73 5.17 17.36 4 42.44 42.33 27.69 71.08 7.06 22.86 0.377 0.38 42.33 65.04 6.43 17.03 5 44.66 44.73 29.44 72.71 6.64 23.02 0.376 0.38 44.73 66.87 6.09 17.34 6 34.57 34.50 23.79 65.28 6.56 19.26 0.372 0.37 34.50 58.68 5.76 14.08 7 40.48 40.23 25.79 69.63 7.40 23.31 0.380 0.38 40.23 63.43 6.69 17.12 11 53.21 54.00 39.21 78.45 5.26 19.90 0.363 0.37 54.00 73.47 4.96 15.93 12 53.82 54.70 39.53 78.86 5.10 20.21 0.363 0.37 54.70 73.95 4.82 16.90 13 22.84 22.20 14.63 54.18 8.38 18.21 0.383 0.37 22.20 47.08 6.91 12.19The following abbreviations have been used: FH flame retardant, wt% as dry substance, VI tarnish inhibitor, wt% relative to FH, opt. B. Optical evaluation GuSu Guanidine sulfamate DMPS Dimethylolpropionic acid MS Lactate CH Carbohydrazide Table 1 : Example FH / (wt%) VI / (wt%) pH opt. B. 2 GuSu / 15.1 MS / 5 5.5 2-3 GuSu / 16.6 MS / 5 4.0 2-4 GuSu / 17.0 MS / 5 7.0 3+ 5 GuSu / 13.6 MS / 5 8.0 3+ 6 GuSu / 14.9 MS / 2 5.5 3+ 7 GuSu / 16.1 MS / 10 10 5.5 3 8 GuSu / 15.2 DMPS / 5 8.4 3+ 9 GuSu / 14.7 CH / 5 7.9 2 + * 10 GuSu / 15.1 MS / 5u. CH / 3 6.9 2 11 GuSu / 15.2 dicyandiamide / 5 8.0 3 12 GuSu / 17.5 dicyandiamide / 5 5.5 2 13 GuSu / 16.07 VI-free 5.5 5.5 * filter paper The perimeter of was discolored dark. Table 2 : Example Chromaticity value Tristimulus value Chromaticity coordinate Color value by hunter XYZL * a * b * xy YL ab 2 54.25 55.03 37.85 79.04 5.4 22.66 0.369 0.37 55.03 74.16 5.11 17.88 3 53.65 54.37 37.85 78.67 5.47 21.95 0.368 0.37 54.37 73.73 5.17 17.36 4 42.44 42.33 27.69 71.08 7.06 22.86 0.377 0.38 42.33 65.04 6.43 17.03 5 44.66 44.73 29.44 72.71 6.64 23.02 0.376 0.38 44.73 66.87 6.09 17.34 6 34.57 34.50 23.79 37.80.48.40 7.80.40.50. 40.23 63.43 6.69 17.12 11 53.21 54.00 39.21 78.45 5.26 19.90 0.363 0.37 54.00 73.47 4.96 15.93 12 53.82 54.70 39.53 78.86 5.10 20.21 0.363 0.37 54.70 73.95 4.82 16.90 13 22.84 22.20 14.63 54.18 8.38 18.21 0.383 0.37 22.20 14.63 54.18 8.38 18.21 0.383 0.37 22.20

フロントページの続き (72)発明者 ウイリーバルト・シヨイヒエンシユトウー ル オーストリア国、4271 ザンクト・オスウ アルト、ノイドルフ、22 (72)発明者 アンドレアース・カッペラー オーストリア国、4264 グリユンバッハ、 シユラーク、57 (72)発明者 クラウス・リッツベルガー オーストリア国、4074 アルコーフエン、 エーデルウアイッスストラーセ、13Front Page Continuation (72) Inventor Willie Bart Schijochiensshutur, Austria, 4271 St. Oswald, Neudorf, 22 (72) Inventor Andreas Kappeler, Austria, 4264 Griyunbach, Schilark, 57 (72) ) Inventor Klaus Ritzberger Austria, 4074 Alcohuen, Edelweissstraße, 13

Claims (8)

【特許請求の範囲】[Claims] 【請求項１】 熱による変色に対し保護された、難燃化
処理されたセルロ−ス材料において、この材料が難燃剤
としてグアニジン塩またはエチレンジアミン塩を、そし
て変色防止剤として式 【化１】 （上式中、Ｒ1 およびＲ2 は互いに無関係にＨ、ＯＨま
たは -ＣＨ2-ＯＨを意味する）で表される化合物または
その塩またはカルボヒドラジドあるいはそれらの混合物
を含有することを特徴とする上記セルロース材料。1. A flame-retardant cellulosic material protected against thermal discoloration, which material comprises a guanidine salt or an ethylenediamine salt as a flame retardant and a formula of the formula: ## STR1 ## (Wherein R 1 and R 2 independently of each other mean H, OH or —CH 2 —OH) or a salt thereof or carbohydrazide or a mixture thereof. The above cellulose material. 【請求項２】 セルロース材料が紙類または木綿織物ま
たはビスコース織物である請求項１に記載のセルロース
材料。2. The cellulosic material according to claim 1, wherein the cellulosic material is paper or cotton fabric or viscose fabric. 【請求項３】 セルロース材料が紙類である請求項２に
よるセルロース材料。3. Cellulosic material according to claim 2, wherein the cellulosic material is paper. 【請求項４】 グアニジン塩またはエチレンジアミン塩
がスルフアミン酸塩、硫酸塩、リン酸塩またはホウ酸塩
である請求項１に記載のセルロース材料。4. The cellulosic material according to claim 1, wherein the guanidine salt or the ethylenediamine salt is a sulfamate, a sulfate, a phosphate or a borate. 【請求項５】 グアニジン塩またはエチレンジアミン塩
がスルフアミン酸塩である請求項１に記載のセルロース
材料。5. The cellulosic material according to claim 1, wherein the guanidine salt or the ethylenediamine salt is a sulfamate. 【請求項６】 変色防止剤として２- ヒドロキシプロピ
オン酸、２，２- ジメチロールプロピオン酸またはプロ
ピオン酸またはカルボヒドラジドあるいはそれらの混合
物が使用される請求項１に記載のセルロース材料。6. Cellulosic material according to claim 1, wherein 2-hydroxypropionic acid, 2,2-dimethylolpropionic acid or propionic acid or carbohydrazide or mixtures thereof are used as tarnish inhibitors. 【請求項７】 変色防止剤として２- ヒドロキシプロピ
オン酸またはカルボヒドラジドあるいはそれらの混合物
が使用される請求項１に記載のセルロース材料。7. The cellulosic material according to claim 1, wherein 2-hydroxypropionic acid or carbohydrazide or a mixture thereof is used as a discoloration inhibitor. 【請求項８】 グアニジン塩またはエチレンジアミン塩
および式Ｉ 【化２】 （上式中、Ｒ1 およびＲ2 は互いに無関係にＨ、ＯＨま
たは -ＣＨ2-ＯＨを意味する）で表される化合物または
その塩またはカルボヒドラジドあるいはそれらの混合物
の７０％までの水溶液を変色防止剤としてセルロース材
料の仕上げ加工のために使用する方法。8. A guanidine salt or an ethylenediamine salt and a compound of formula I (In the above formula, R 1 and R 2 independently of each other represent H, OH or —CH 2 —OH) and discolor an aqueous solution of up to 70% of a salt thereof or a carbohydrazide or a mixture thereof. The method used for finishing of cellulosic material as an inhibitor.
JP20375196A 1995-08-03 1996-08-01 Cellulose material treated with guanidine salt or ethylenediamine salt for flame retardance and containing anti-discoloration agent Withdrawn JPH09119069A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT1325/95 1995-08-03
AT132595A AT402518B (en) 1995-08-03 1995-08-03 FLAME-RETARDED CELLULOSE MATERIALS WITH GUANIDINE OR ETHYLENE DIAMINE SALT, CONTAINING A DISCOLORATION INHIBITOR

Publications (1)

Publication Number Publication Date
JPH09119069A true JPH09119069A (en) 1997-05-06

Family

ID=3511463

Family Applications (1)

Application Number Title Priority Date Filing Date
JP20375196A Withdrawn JPH09119069A (en) 1995-08-03 1996-08-01 Cellulose material treated with guanidine salt or ethylenediamine salt for flame retardance and containing anti-discoloration agent

Country Status (3)

Country Link
JP (1) JPH09119069A (en)
AT (1) AT402518B (en)
DE (1) DE19631381A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009008239A1 (en) * 2007-06-20 2009-01-15 Nankyo Efnica Co., Ltd. Polyfunctional composition having flame retardancy, antifogging property and the like
WO2009096444A1 (en) * 2008-01-30 2009-08-06 Kurashiki Boseki Kabushiki Kaisha Flame retardant processing method, and cellulosic fiber material imparted with flame retardancy
JP2012140716A (en) * 2010-12-28 2012-07-26 Seiren Co Ltd Processing method for cellulose fiber-containing fabric, and processed fabric containing cellulose fiber

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007028997A1 (en) * 2007-06-23 2008-12-24 Cht R. Beitlich Gmbh Method for yellowing inhibition

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009008239A1 (en) * 2007-06-20 2009-01-15 Nankyo Efnica Co., Ltd. Polyfunctional composition having flame retardancy, antifogging property and the like
US8076385B2 (en) 2007-06-20 2011-12-13 Nankyo Efnica Co., Ltd. Use of flame retardant aqueous liquid composition in making flame retardant polyurethane foam article
WO2009096444A1 (en) * 2008-01-30 2009-08-06 Kurashiki Boseki Kabushiki Kaisha Flame retardant processing method, and cellulosic fiber material imparted with flame retardancy
JP5396283B2 (en) * 2008-01-30 2014-01-22 倉敷紡績株式会社 Flame retardant processing method and flame retardant cellulose fiber material
JP2012140716A (en) * 2010-12-28 2012-07-26 Seiren Co Ltd Processing method for cellulose fiber-containing fabric, and processed fabric containing cellulose fiber

Also Published As

Publication number Publication date
AT402518B (en) 1997-06-25
DE19631381A1 (en) 1997-02-06
ATA132595A (en) 1996-10-15

Similar Documents

Publication Publication Date Title
DE763862C (en) Process for finishing textile goods
DE1794330A1 (en) Use of bis-s-triazinyl-amino-stilbene-2,2'-disulfonic acids for the optical brightening of cellulose textile materials in acidic crosslinking baths
DE2210087B2 (en) Imidazolinium salts and fabric softeners containing them
DE1293720B (en) Process for improving the properties of polymers bearing active hydrogen atoms in the form of textile goods
US3900327A (en) Flame retardant cellulosic materials
DE1930307C3 (en) Cationic derivatives of 4,4'Biss-triazinylamino-stilbene ^^ - disulfonic acid, process for their preparation and use from optical brightening agents
EP0057668B1 (en) Salts of phosphonic acids, their manufacture and their use for flame-proofing organic fibers
JPH09119069A (en) Cellulose material treated with guanidine salt or ethylenediamine salt for flame retardance and containing anti-discoloration agent
US4107373A (en) Flame retardant cellulosic materials
EP0616071A1 (en) Process for the treatment of fibrous materials with triazin derivatives
DE2455685A1 (en) WATER-SOLUBLE CONDENSATION PRODUCTS MADE FROM A POLY (ALPHA-HYDROXYALKYL) PHOSPHORUS COMPOUND AND A NITROGEN COMPOUND
DE19920784A1 (en) Stilbene brightener
US2483008A (en) Proofing proteinaceous fibers against biological attack
DE10038100A1 (en) Flameproofing cellulose fibers comprises swelling the fibers under alkaline conditions and then treating them with a 4,6-dichloro-1,3,5-triazin-2-ylamine
EP2402416A1 (en) Flame retardant compound for cotton wool items
DE3041580C2 (en) Water-soluble, oligomeric condensation product of glyoxal and cyclic urea and its use for the production of crease-resistant textiles
US5707404A (en) Formaldehyde free method for imparting permanent press properties to cotton and cotton blends
JPS6357550B2 (en)
DE2301531A1 (en) 4,4'-DIAMINOSTILBE-2,2'-DISULPHONIC ACID DERIVATIVES AND THEIR USES
CH671491B5 (en)
CA1058356A (en) Flame retardant cellulosic materials
JPS61179289A (en) Auxiliary flame retarder for cellulose material
JP3761954B2 (en) Flame retardant composition
EP0469387A1 (en) Compositions containing phosphonic compounds and organic di- or trivalent acids, used as flame retardants
DE2903928A1 (en) METHOD FOR FLAME RETARDING ORGANIC FIBER MATERIAL WITH PHOSPHONIC ACID SALTS

Legal Events

Date Code Title Description
A300 Withdrawal of application because of no request for examination

Free format text: JAPANESE INTERMEDIATE CODE: A300

Effective date: 20031007