JP2010235830A - Resin composition and processed paper or fiber product treated therewith - Google Patents

Resin composition and processed paper or fiber product treated therewith Download PDF

Info

Publication number
JP2010235830A
JP2010235830A JP2009086566A JP2009086566A JP2010235830A JP 2010235830 A JP2010235830 A JP 2010235830A JP 2009086566 A JP2009086566 A JP 2009086566A JP 2009086566 A JP2009086566 A JP 2009086566A JP 2010235830 A JP2010235830 A JP 2010235830A
Authority
JP
Japan
Prior art keywords
resin composition
meth
mass
group
monomer
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
Application number
JP2009086566A
Other languages
Japanese (ja)
Other versions
JP5669363B2 (en
Inventor
Tomofumi Otsuka
倫史 大塚
Jiro Uchida
二朗 内田
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.)
Resonac Holdings Corp
Original Assignee
Showa Highpolymer Co Ltd
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 Showa Highpolymer Co Ltd filed Critical Showa Highpolymer Co Ltd
Priority to JP2009086566A priority Critical patent/JP5669363B2/en
Priority to CN201080014691.0A priority patent/CN102369224B/en
Priority to PCT/JP2010/055369 priority patent/WO2010113796A1/en
Publication of JP2010235830A publication Critical patent/JP2010235830A/en
Application granted granted Critical
Publication of JP5669363B2 publication Critical patent/JP5669363B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which is free from any halogen-based component with a risk of generating dioxins or hydrogen halides and can impart excellent strength, bending resistance, flame resistance, and heat yellowing resistance to a processed paper or fiber product. <P>SOLUTION: The resin composition is obtained by copolymerizing an unsaturated monomer having a phosphate group or a phosphite group with a (meth)acrylic acid alkyl ester monomer and an unsaturated monomer having a carboxyl group. The resin composition also has a specific amount of phosphorus in a solid component and contains the (meth)acrylic acid alkyl ester monomer with a 1-4C alkyl chain and the unsaturated monomer having a carboxyl group, each in a specific amount. The processed paper or fiber product treated with the resin composition has excellent strength, bending resistance, flame resistance, and heat yellowing resistance. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、難燃性または防炎性を付与することができる樹脂組成物及びこれで処理された紙又は繊維加工品に関する。   The present invention relates to a resin composition capable of imparting flame retardancy or flame retardancy and a paper or fiber processed product treated with the resin composition.

各種の紙及び繊維加工品は多種多様な用途に使用され、その物性向上剤として合成樹脂が広く用いられている。近年、建築材料や自動車内装材などの用途において、使用される紙及び繊維加工品の難燃化が求められており、これに対応する合成樹脂も開発されている。   Various papers and processed textile products are used for a wide variety of applications, and synthetic resins are widely used as physical property improvers. In recent years, in applications such as building materials and automobile interior materials, it has been required to make paper and fiber processed products flame retardant, and synthetic resins corresponding to these have been developed.

一般的に合成樹脂を難燃化する方法としては、主に樹脂成分に難燃剤を添加する方法が挙げられる。例えば、赤リンやリン酸塩、三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウムなどの無機系難燃剤、ペンタブロモビフェニル、オクタブロモビフェニル、デカブロモビフェニルなどのハロゲン系難燃剤、リン酸グアニジン、トリフェニルホスフェート、スルファミン酸などの非ハロゲン系難燃剤がよく知られている。   In general, as a method for making a synthetic resin flame retardant, a method of adding a flame retardant to a resin component is mainly mentioned. For example, inorganic flame retardants such as red phosphorus, phosphate, antimony trioxide, aluminum hydroxide, magnesium hydroxide, halogen flame retardants such as pentabromobiphenyl, octabromobiphenyl, decabromobiphenyl, guanidine phosphate, Non-halogen flame retardants such as phenyl phosphate and sulfamic acid are well known.

しかし、これら難燃剤は一般的に合成樹脂との相溶性に問題があり、難燃剤成分が分離したり、沈降したりすることがある。またこれらの難燃性樹脂は加工品に難燃性や防炎性を付与するだけでなく、強度や風合いなど他の諸物性に悪影響を与えないことが必要であるが、難燃性を付与するためには一般的に多量の添加が必要であり、樹脂自身の物性を阻害する原因となっている。   However, these flame retardants generally have a problem in compatibility with synthetic resins, and the flame retardant components may be separated or settled. These flame retardant resins are not only required to impart flame retardancy and flame resistance to processed products, but also do not adversely affect other physical properties such as strength and texture. In general, a large amount of addition is necessary to inhibit the physical properties of the resin itself.

特に無機系難燃剤は樹脂の難燃化性能が乏しく、樹脂への多量の添加が必要であり、合成樹脂との比重差から沈降が生じやすい。またこれらを用いた加工品を硬くしてしまい、紙や繊維の本来の風合いを損なうといった問題も生じる。   In particular, inorganic flame retardants are poor in flame retarding performance of resins, require a large amount of resin to be added, and sedimentation is likely to occur due to a difference in specific gravity with synthetic resins. Moreover, the processed goods using these are hardened and the original texture of paper and fiber is impaired.

ハロゲン系難燃剤は難燃化性能に優れているため、添加量が少なくて済むことから、合成樹脂の物性に与える影響は少ないが、塩素や臭素といったハロゲン元素を含有しているため、これらを用いた加工品を焼却する場合にダイオキシンやハロゲン化水素といった有害物質を発生する恐れがあり、EU諸国を始めとした世界各国で規制や使用の見直しが行なわれている。   Halogen-based flame retardants have excellent flame retardancy, so the addition amount is small, so there is little effect on the physical properties of the synthetic resin, but they contain halogen elements such as chlorine and bromine. Incineration of processed products may cause harmful substances such as dioxins and hydrogen halides, and regulations and use are being reviewed in countries around the world including the EU countries.

非ハロゲン系難燃剤は、ハロゲン系難燃剤と比較して、安全性に優れているため、リン系を始めとした難燃剤が多く検討されている。しかし、リン系難燃剤の難燃化性能はハロゲン系よりも低く、比較的多量に使用しなければならないため、加工品物性を低下させてしまう。例えば、水溶性の難燃剤は潮解性が高く、見かけ上、樹脂を可塑化するため、これらを用いた加工品の強度、風合いを低下させる要因となる。また油溶性のものも樹脂の可塑化や樹脂表面へのブリードにより、強度、風合いを低下させるだけでなく、ベタツキを生じさせる要因となっている。   Since non-halogen flame retardants are superior in safety compared to halogen flame retardants, many flame retardants including phosphorus-based flame retardants have been studied. However, the flame retarding performance of the phosphorus flame retardant is lower than that of the halogen type and must be used in a relatively large amount, so that the physical properties of the processed product are deteriorated. For example, water-soluble flame retardants have high deliquescence and apparently plasticize the resin, which causes a decrease in strength and texture of processed products using them. Oil-soluble ones not only reduce strength and texture but also cause stickiness due to plasticization of the resin and bleeding on the resin surface.

これらを解決する手段として、リン酸基や亜リン酸骨格を有する不飽和単量体と、アクリル酸系不飽和単量体と、酢酸ビニル単量体とを共重合した非ハロゲン系の難燃性樹脂組成物が提案されている(例えば、特許文献1を参照)。   As a means for solving these problems, non-halogen flame retardant obtained by copolymerization of an unsaturated monomer having a phosphoric acid group or a phosphorous acid skeleton, an acrylic acid unsaturated monomer, and a vinyl acetate monomer. A functional resin composition has been proposed (see, for example, Patent Document 1).

しかしながら、特許文献1に開示される難燃性樹脂組成物を用いた加工品は、強度、剛軟性を満足するものではなく、更なる物性向上が望まれていた。   However, the processed product using the flame retardant resin composition disclosed in Patent Document 1 does not satisfy the strength and the bending resistance, and further improvement in physical properties has been desired.

また、特許文献1に開示される難燃性樹脂組成物を用いた加工品の問題を解決した非ハロゲン系の樹脂組成物も提案されているが、樹脂単独又はそれを用いた加工品が熱黄変してしまい、その意匠性を著しく低下させると共に、樹脂単独又はそれを用いた加工品が硬く、剛軟性を制御出来ないという問題点があった(例えば、特許文献2参照)。   In addition, a non-halogen resin composition that solves the problem of a processed product using the flame retardant resin composition disclosed in Patent Document 1 has also been proposed, but the resin alone or a processed product using the resin is heated. Yellowing has caused a problem that the design properties are remarkably lowered, and the resin alone or a processed product using the resin is hard and the bending resistance cannot be controlled (for example, see Patent Document 2).

特開平7−18028号公報JP-A-7-18028 特開2008−169249号公報JP 2008-169249 A

従って、本発明は、ダイオキシンやハロゲン化水素を発生する恐れのあるハロゲン系成分を含有せず、紙や繊維加工品に優れた強度や防炎性及び希望する剛軟性を付与することのできる熱黄変しない難燃性を有する樹脂組成物及びこれで処理された防炎性や自己消火性を有する紙又は繊維加工品を提供することを目的とする。   Therefore, the present invention does not contain a halogen-based component that may generate dioxin or hydrogen halide, and can provide excellent strength, flameproofness, and desired bending resistance to paper and textile processed products. An object of the present invention is to provide a resin composition having flame retardancy that does not turn yellow, and a paper or fiber processed article that is treated with the resin composition and has flame resistance and self-extinguishing properties.

そこで、本発明者らは、上記のような従来の課題を解決すべく鋭意研究、開発を遂行した結果、リン酸基又は亜リン酸基を有する不飽和単量体、(メタ)アクリル酸アルキルエステル単量体及びカルボキシル基を有する不飽和単量体を共重合して得られ、且つ固形分中に特定量のリン分、アルキル鎖の炭素数が1〜4の(メタ)アクリル酸アルキルエステル単量体及びカルボキシル基を有する不飽和単量体をそれぞれ特定量含有した樹脂組成物が、上記課題を解決できることを見出し、本発明を完成させるに至った。   Therefore, the present inventors have conducted intensive research and development to solve the conventional problems as described above, and as a result, unsaturated monomers having a phosphate group or a phosphite group, alkyl (meth) acrylates. (Meth) acrylic acid alkyl ester obtained by copolymerizing an ester monomer and an unsaturated monomer having a carboxyl group, and having a specific amount of phosphorus in the solid content and an alkyl chain having 1 to 4 carbon atoms It has been found that a resin composition containing a specific amount of each of a monomer and an unsaturated monomer having a carboxyl group can solve the above problems, and has completed the present invention.

即ち、本発明は、リン酸基又は亜リン酸基を有する不飽和単量体、アルキル鎖の炭素数が1〜4である(メタ)アクリル酸アルキルエステル単量体、並びにアクリル酸、メタクリル酸及びイタコン酸からなる群から選択される少なくとも1種のカルボキシル基を有する不飽和単量体を共重合して得られ、固形分中のリン含有量が3〜13質量%であり、前記カルボキシル基を有する不飽和単量体を全単量体に対し1〜79質量%使用し、且つアルキル鎖の炭素数が1〜4である(メタ)アクリル酸アルキルエステル単量体と前記カルボキシル基を有する不飽和単量体とを合計で全単量体に対し40質量%以上使用することを特徴とする樹脂組成物に関する。   That is, the present invention relates to an unsaturated monomer having a phosphoric acid group or a phosphorous acid group, a (meth) acrylic acid alkyl ester monomer having an alkyl chain having 1 to 4 carbon atoms, acrylic acid, and methacrylic acid. And an unsaturated monomer having at least one carboxyl group selected from the group consisting of itaconic acid and having a phosphorus content in the solid content of 3 to 13% by mass, the carboxyl group 1 to 79% by mass of an unsaturated monomer having a carboxyl group, and having a carboxyl group and a (meth) acrylic acid alkyl ester monomer having 1 to 4 carbon atoms in the alkyl chain It is related with the resin composition characterized by using 40 mass% or more of a total with an unsaturated monomer with respect to all the monomers.

リン酸基又は亜リン酸基を有する不飽和単量体は、アシッド・ホスホオキシポリオキシアルキレングリコールモノ(メタ)アクリレートであることが好ましい。   The unsaturated monomer having a phosphoric acid group or a phosphorous acid group is preferably acid phosphooxypolyoxyalkylene glycol mono (meth) acrylate.

アルキル鎖の炭素数が1〜4である(メタ)アクリル酸アルキルエステル単量体を全単量体に対し1〜79質量%使用することが好ましい。   It is preferable to use 1 to 79% by mass of a (meth) acrylic acid alkyl ester monomer having 1 to 4 carbon atoms in the alkyl chain based on the total monomers.

また、本発明は前記樹脂組成物を用いて加工された紙に関する。   Moreover, this invention relates to the paper processed using the said resin composition.

さらに、本発明は前記樹脂組成物を用いて加工された繊維加工品に関する。   Furthermore, this invention relates to the fiber processed goods processed using the said resin composition.

本発明によれば、ダイオキシンやハロゲン化水素を発生する恐れのあるハロゲン系成分を含有せず、紙や繊維加工品に優れた強度や防炎性及び希望する剛軟性を付与することのできる難燃性を有する樹脂組成物及びこれで処理された防炎性や自己消火性を有する紙又は繊維加工品を提供することができる。   According to the present invention, it does not contain a halogen-based component that may generate dioxin or hydrogen halide, and it is possible to impart excellent strength, flameproofness, and desired bending resistance to paper and textile processed products. It is possible to provide a resin composition having flammability, and a paper or fiber processed article having fire resistance and self-extinguishing properties treated with the resin composition.

以下、本発明を詳細に説明する。   Hereinafter, the present invention will be described in detail.

本発明の樹脂組成物は、リン酸基又は亜リン酸基を有する不飽和単量体、アルキル鎖の炭素数が1〜4である(メタ)アクリル酸アルキルエステル単量体、並びにアクリル酸、メタクリル酸及びイタコン酸からなる群から選択される少なくとも1種のカルボキシル基を有する不飽和単量体を共重合して得られるものである。   The resin composition of the present invention includes an unsaturated monomer having a phosphoric acid group or a phosphorous acid group, a (meth) acrylic acid alkyl ester monomer having an alkyl chain having 1 to 4 carbon atoms, and acrylic acid. It is obtained by copolymerizing an unsaturated monomer having at least one carboxyl group selected from the group consisting of methacrylic acid and itaconic acid.

本発明において用いるリン酸基又は亜リン酸基を有する不飽和単量体としては、例えば、一般式(1):   Examples of the unsaturated monomer having a phosphoric acid group or a phosphorous acid group used in the present invention include, for example, the general formula (1):

Figure 2010235830
(式中、R及びRは、それぞれ独立して水素又はアルキル基を表しており、Yは、ヒドロキシル基、アルキル基又はアルキルエステル基を表しており、Zは、水素原子、ヒドロキシル基、アルキル基又はアルキルエステル基を表し、nは1〜20の整数である)で示される化合物、この化合物の金属塩、アンモニウム塩及びアミン塩が挙げられる。
Figure 2010235830
(In the formula, R 1 and R 2 each independently represent hydrogen or an alkyl group, Y represents a hydroxyl group, an alkyl group or an alkyl ester group, Z represents a hydrogen atom, a hydroxyl group, An alkyl group or an alkyl ester group, and n is an integer of 1 to 20, and a metal salt, an ammonium salt, and an amine salt of the compound.

上記化合物の具体例としては、アシッド・ホスホオキシエチル(メタ)アクリレート、(メタ)アクロイル・オキシエチルアシッドホスフェート・モノエタノールアミン塩、アシッド・ホスホオキシポリオキシエチレングリコールモノ(メタ)アクリレート及びアシッド・ホスホオキシポリオキシプロピレングリコール(メタ)アクリレート、これらの金属塩、アンモニウム塩及びアミン塩などを挙げることができる。これらの化合物は、単独で又は二種以上の混合物として使用することができる。中でも、1分子あたりのリン含有量が高い点でアシッド・ホスホオキシポリオキシエチレングリコールモノメタクリレートが好ましい。   Specific examples of the above compounds include acid phosphooxyethyl (meth) acrylate, (meth) acryloyl oxyethyl acid phosphate monoethanolamine salt, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate and acid phospho Examples thereof include oxypolyoxypropylene glycol (meth) acrylate, metal salts thereof, ammonium salts and amine salts. These compounds can be used alone or as a mixture of two or more. Of these, acid phosphooxypolyoxyethylene glycol monomethacrylate is preferred because of its high phosphorus content per molecule.

リン酸基又は亜リン酸基を有する不飽和単量体は、全単量体に対し20質量%〜87質量%の範囲で使用することが好ましく、26質量%〜40質量%の範囲で使用することがさらに好ましい。20質量%より少なくなると本樹脂組成物やその加工品の防炎性能が低下し、87質量%より多くなると重合安定性の低下や本樹脂組成物を用いた加工品の強度や耐熱黄変性が低下する傾向にある。   The unsaturated monomer having a phosphoric acid group or a phosphorous acid group is preferably used in the range of 20% by mass to 87% by mass, and used in the range of 26% by mass to 40% by mass with respect to the total monomers. More preferably. When the amount is less than 20% by mass, the flameproofing performance of the resin composition or processed product thereof is lowered. When the amount is more than 87% by mass, the polymerization stability is deteriorated, the strength of the processed product using the resin composition or heat-resistant yellowing is reduced. It tends to decrease.

また、本発明において用いられる(メタ)アクリル酸アルキルエステル単量体は、アルキル鎖の炭素数が1〜4である。アルキル鎖の炭素数が5以上を多く使用すると、本樹脂組成物やその加工品の難燃性が低下するため、望ましくない。   The (meth) acrylic acid alkyl ester monomer used in the present invention has 1 to 4 carbon atoms in the alkyl chain. If the alkyl chain has a carbon number of 5 or more, the flame retardancy of the resin composition or processed product thereof is lowered, which is not desirable.

アルキル鎖の炭素数1〜4の(メタ)アクリル酸アルキルエステル単量体の具体例としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレートなどが挙げられ、なかでも難燃性発現の点でメチル(メタ)アクリレート、エチル(メタ)アクリレートが好ましい。これらの化合物は単独又は二種以上を組み合わせて使用することができる。前記(メタ)アクリル酸アルキルエステル単量体は、重合安定性や加工品物性に与える影響の観点から、全単量体に対し1質量%〜79質量%の範囲で使用することが好ましく、30質量%〜75質量%の範囲で使用することが更に好ましい。79質量%より多くなると本樹脂組成物やその加工品の防炎性能が低下する傾向にある。   Specific examples of (meth) acrylic acid alkyl ester monomers having 1 to 4 carbon atoms in the alkyl chain include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. Among them, methyl (meth) acrylate and ethyl (meth) acrylate are preferable in terms of flame retardancy. These compounds can be used alone or in combination of two or more. The (meth) acrylic acid alkyl ester monomer is preferably used in the range of 1% by mass to 79% by mass with respect to the total monomers from the viewpoint of influence on polymerization stability and physical properties of processed products. More preferably, it is used in the range of mass% to 75 mass%. If it exceeds 79% by mass, the flameproof performance of the present resin composition or processed product tends to be lowered.

また、さらに、他の(メタ)アクリル酸アルキルエステル単量体を用いてもよい。具体例としては、2−エチルヘキシル(メタ)アクリレート、アリル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、メトキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、ヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート、ヒドロキシブチルアクリレート、ポリエチレングリコールモノアクリレート、ポリプルピレングリコールモノアクリレート、ポリテトラメチレングリコールモノアクリレート、ポリエチレングリコールポリテトラメチレングリコールモノアクリレート、ポリプロピレングリコールポリテトラメチレングリコールモノアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルメタクリレート、エチレングリコールモノメタクリレート、ポリプロピレングリコールモノメタクリレート、ポリテトラメチレングリコールメタクリレート、ポリエチレングリコールポリテトラメチレングリコールモノメタクリレート、ポリプロピレングリコールポリテトラメチレングリコールモノメタクリレート、グリシジルアクリレート、グリシジルメタクリレート、メチルグリシジルアクリレート、メチルグリシジルメタクリレート、3,4−エポキシシクロヘキシルメチルアクリレート、3,4−エポキシシクロヘキシルメチルメタクリレートなどが挙げられ、単独又は二種以上を組み合わせて使用することができる。   Furthermore, other (meth) acrylic acid alkyl ester monomers may be used. Specific examples include 2-ethylhexyl (meth) acrylate, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylamino Ethyl (meth) acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polytetramethylene glycol monoacrylate, polyethylene glycol polytetramethylene glycol monoacrylate, polypropylene glycol polytetra Methylene glycol monoacrylate, hydroxyethyl methacrylate Hydroxypropyl methacrylate, hydroxybutyl methacrylate, ethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polytetramethylene glycol methacrylate, polyethylene glycol polytetramethylene glycol monomethacrylate, polypropylene glycol polytetramethylene glycol monomethacrylate, glycidyl acrylate, glycidyl methacrylate, Examples thereof include methyl glycidyl acrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexyl methyl acrylate, 3,4-epoxycyclohexyl methyl methacrylate, and the like can be used alone or in combination of two or more.

また、本発明ではアクリル酸、メタクリル酸、イタコン酸からなる群から選択される少なくとも1種のカルボキシル基を有する不飽和単量体(以下、アクリル酸等という)が必須の単量体成分として用いられ、これらは単独又は二種以上を組み合わせて使用することができる。前記アクリル酸等は、全単量体に対し1質量%〜79質量%の範囲で使用するものであり、5質量%〜50質量%の範囲で使用することが好ましい。79質量%より多いと本樹脂組成物やその加工品の防炎性能が低下する。   In the present invention, an unsaturated monomer having at least one carboxyl group selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid (hereinafter referred to as acrylic acid) is used as an essential monomer component. These can be used alone or in combination of two or more. The acrylic acid or the like is used in a range of 1% by mass to 79% by mass with respect to all monomers, and is preferably used in a range of 5% by mass to 50% by mass. When it is more than 79% by mass, the flameproof performance of the resin composition and processed product thereof is lowered.

また、さらに、他のカルボキシル基を有する不飽和単量体を用いてもよい。具体例としては、クロトン酸、フマル酸、マレイン酸、無水マレイン酸、2−メチルマレイン酸、フタル酸、テトラヒドロフタル酸、テトラヒドロフタル酸無水物、それらの金属塩、アンモニウム塩などが挙げられ、単独又は二種以上を組み合わせて使用することができる。   Furthermore, you may use the unsaturated monomer which has another carboxyl group. Specific examples include crotonic acid, fumaric acid, maleic acid, maleic anhydride, 2-methylmaleic acid, phthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, their metal salts, ammonium salts, and the like. Alternatively, two or more kinds can be used in combination.

また、アルキル鎖の炭素数が1〜4である(メタ)アクリル酸アルキルエステル単量体及び前記アクリル酸等は、本樹脂組成物やその加工品の防炎性能発現の観点から、その合計で全単量体に対し40質量%以上使用するものであり、50質量%〜80質量%使用することが好ましい。40質量%より少ないと、本樹脂組成物やその加工品の防炎性能が低下する点で望ましくない。   In addition, the (meth) acrylic acid alkyl ester monomer having 1 to 4 carbon atoms in the alkyl chain, the acrylic acid, etc. are in total from the viewpoint of the flameproof performance of the resin composition and processed product thereof. 40 mass% or more is used with respect to all monomers, and it is preferable to use 50 mass%-80 mass%. When the amount is less than 40% by mass, it is not desirable in that the flameproof performance of the resin composition or processed product thereof is lowered.

また、リン酸基又は亜リン酸基を有する不飽和単量体の重合割合は、得られる樹脂中に含まれるリン量(樹脂組成物の固形分中のリン含有量)が3〜13質量%となるように適宜決定すればよい。難燃性付与と樹脂の重合安定性、物性発現のバランスを考慮すると、リン含有量が3〜10質量%となるように重合することが好ましい。3質量%未満では樹脂自身の難燃性が低下し、13質量%超では樹脂の重合安定性が低下するため、望ましくない。   The polymerization rate of the unsaturated monomer having a phosphoric acid group or a phosphorous acid group is such that the amount of phosphorus contained in the obtained resin (phosphorus content in the solid content of the resin composition) is 3 to 13% by mass. What is necessary is just to determine suitably so that it may become. In consideration of the balance between imparting flame retardancy, resin polymerization stability, and physical properties, it is preferable to perform polymerization so that the phosphorus content is 3 to 10% by mass. If it is less than 3% by mass, the flame retardancy of the resin itself is lowered, and if it exceeds 13% by mass, the polymerization stability of the resin is lowered.

また、本発明の効果を損なわない範囲で、リン酸基又は亜リン酸基を有する不飽和単量体、(メタ)アクリル酸エステル単量体及びカルボキシル基を有する不飽和単量体以外の単量体、例えば、エテン、プロペン、ブテン、イソブテン、ペンテン、シクロペンテン、ヘキセン、シクロヘキセン、オクテン、(メタ)アクリルアミド、(メタ)アクリロニトリル、スチレン、スチレン誘導体などを単独であるいは二種以上を組み合わせて使用してもよい。   Further, as long as the effects of the present invention are not impaired, a monomer other than an unsaturated monomer having a phosphoric acid group or a phosphorous acid group, a (meth) acrylic acid ester monomer, and an unsaturated monomer having a carboxyl group. A mer such as ethene, propene, butene, isobutene, pentene, cyclopentene, hexene, cyclohexene, octene, (meth) acrylamide, (meth) acrylonitrile, styrene, styrene derivatives, etc. may be used alone or in combination of two or more. May be.

本発明の樹脂組成物は、懸濁重合法、乳化重合法、溶液重合法、塊状重合法などの公知の共重合方法を用いて製造することができる。また、連続式重合法でも回分式重合法でも製造することができる。   The resin composition of the present invention can be produced using a known copolymerization method such as a suspension polymerization method, an emulsion polymerization method, a solution polymerization method or a bulk polymerization method. Further, it can be produced by either a continuous polymerization method or a batch polymerization method.

本発明の樹脂組成物の製造に用いられる溶媒は水や通常用いられている有機溶剤を使用することができる。例えばその具体例としては、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等のアルコール類、酢酸エチル、酢酸イソプロピル、セロソルブアセテート、ブチルセロソルブアセテート等のエチレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールモノメチルエーテルアセテート、カルビトールアセテート、ブチルカルビトールアセテート等のジエチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノアルキルエーテルアセテート類等の酢酸エステル類、エチレングリコールジアルキルエーテル類、メチルカルビトール、エチルカルビトール、ブチルカルビトール等のジエチレングリコールジアルキルエーテル類、トリエチレングリコールジアルキルエーテル類、プロピレングリコールジアルキルエーテル類、ジプロピレングリコールジアルキルエーテル類、メチルエーテル、エチルエーテル、1,4−ジオキサン、テトラヒドロフラン等のエーテル類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、ベンゼン、トルエン、キシレン、ヘキサン、オクタン、デカン等の炭化水素類、石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤、乳酸メチル、乳酸エチル、乳酸ブチル等の乳酸エステル類、ジメチルホルムアミド、N−メチルピロリドン等が挙げられる。これらの水、有機溶剤は単独または2種類以上を混合し使用してもよい。   As the solvent used in the production of the resin composition of the present invention, water or a commonly used organic solvent can be used. Specific examples thereof include alcohols such as methanol, ethanol, propanol, isopropanol and butanol, ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate, diethylene glycol monomethyl ether acetate, and carbitol acetate. , Diethylene glycol monoalkyl ether acetates such as butyl carbitol acetate, propylene glycol monoalkyl ether acetates, acetate esters such as dipropylene glycol monoalkyl ether acetates, ethylene glycol dialkyl ethers, methyl carbitol, ethyl carbitol, Diethylene glycol dialkyl esters such as butyl carbitol Tells, triethylene glycol dialkyl ethers, propylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, ethers such as methyl ether, ethyl ether, 1,4-dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Ketones such as benzene, toluene, xylene, hexane, octane, decane, etc., petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, methyl lactate, ethyl lactate, butyl lactate, etc. Lactic acid esters, dimethylformamide, N-methylpyrrolidone and the like. These water and organic solvents may be used alone or in combination of two or more.

ラジカル重合によって樹脂組成物を得る場合、重合は開始剤の存在下にて行われる。この重合反応で使用するラジカル重合開始剤はラジカル重合を開始できるものであれば特に限定されるものではなく、通常用いられている過酸化物やアゾ化合物を使用することができる。例えばその具体例としては、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム、過酸化水素、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ジイソプロピルパーオキサイド、ジ−t−ブチルパーオキサイド、t−ブチルパーオキシベンゾエート、t−ヘキシルパーオキシベンゾエート、t−ブチルパーオキシ−2−エチルヘキサノエート、t−ヘキシルパーオキシ−2−エチルヘキサノエート、1,1−ビス(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、2,5−ジメチル−2,5−ビス(t−ブチルパーオキシ)ヘキシル−3,3−イソプロピルヒドロパーオキサイド、t−ブチルヒドロパーオキサイド、ジクミルヒドロパーオキサイド、アセチルパーオキサイド、ビス(4−t−ブチルシクロヘキシル)パーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、イソブチルパーオキサイド、3,3,5−トリメチルヘキサノイルパーオキサイド、ラウリルパーオキサイド、1,1−ビス(t−ヘキシルパーオキシ)−3,3,5−トリメチルシクロヘキサン、アゾビスイソブチロニトリル、アゾビスカルボンアミド等を挙げることができ、反応によっては適当な還元剤を使用してもよい。開始剤の使用量は、リン酸基又は亜リン酸基を有する不飽和単量体、(メタ)アクリル酸アルキルエステル単量体及びカルボキシル基を有する不飽和単量体の合計に対して0.01〜20質量%が好ましく、0.2〜10質量%が更に好ましい。   When obtaining a resin composition by radical polymerization, the polymerization is carried out in the presence of an initiator. The radical polymerization initiator used in this polymerization reaction is not particularly limited as long as radical polymerization can be initiated, and a generally used peroxide or azo compound can be used. For example, specific examples thereof include sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3 5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl hydroperoxide, acetyl peroxide Bis (4-t-butylcyclohexane Syl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-hexylperoxy) -3,3 5-Trimethylcyclohexane, azobisisobutyronitrile, azobiscarbonamide and the like can be mentioned, and an appropriate reducing agent may be used depending on the reaction. The amount of the initiator used is 0. 0 with respect to the total of the unsaturated monomer having a phosphoric acid group or phosphorous acid group, the (meth) acrylic acid alkyl ester monomer and the unsaturated monomer having a carboxyl group. 01-20 mass% is preferable and 0.2-10 mass% is still more preferable.

本発明の樹脂組成物を乳化重合法により製造する際には、界面活性剤の存在下で行われる。界面活性剤としては、一般に市販されているアニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤及び共重合性界面活性剤が使用できる。またこれらの界面活性剤は、単独または二種類以上を組み合わせて使用することができる。使用する界面活性剤量はリン酸基又は亜リン酸基を有する不飽和単量体、(メタ)アクリル酸アルキルエステル単量体及びカルボキシル基を有する不飽和単量体の合計に対して0.01〜30質量%が好ましく、0.1〜20質量%が更に好ましい。なお重合安定性の観点から、同様に水溶性(メタ)アクリル酸樹脂、水溶性(メタ)アクリル酸エステル樹脂、ポリオキシエチレンアルキルエーテル等の水溶性高分子を保護コロイドとしたり、界面活性剤と併用することもでき、その使用量は任意でよい。   When the resin composition of the present invention is produced by an emulsion polymerization method, it is carried out in the presence of a surfactant. As the surfactant, commercially available anionic surfactants, nonionic surfactants, cationic surfactants and copolymerizable surfactants can be used. These surfactants can be used alone or in combination of two or more. The amount of the surfactant used is 0. 0 with respect to the total of the unsaturated monomer having a phosphate group or phosphite group, the (meth) acrylic acid alkyl ester monomer and the unsaturated monomer having a carboxyl group. 01-30 mass% is preferable and 0.1-20 mass% is still more preferable. From the viewpoint of polymerization stability, water-soluble (meth) acrylic acid resins, water-soluble (meth) acrylic acid ester resins, polyoxyethylene alkyl ethers and other water-soluble polymers can be used as protective colloids and surfactants. They can be used in combination, and the amount used can be arbitrary.

本発明の樹脂組成物には、本発明の効果を損なわない範囲で、充填剤、防腐剤、着色剤、消泡剤、難燃剤、発泡剤、分散剤、乳化剤、連鎖移動剤、流動性調整剤、可塑剤、pH調整剤、各種油剤などの添加剤を配合してもよい。   In the resin composition of the present invention, fillers, preservatives, colorants, antifoaming agents, flame retardants, foaming agents, dispersants, emulsifiers, chain transfer agents, fluidity adjustments are within the range not impairing the effects of the present invention. You may mix | blend additives, such as an agent, a plasticizer, a pH adjuster, and various oil agents.

上述した本発明の樹脂組成物は、原液あるいは任意の割合に希釈した状態で各種紙基材や繊維基材に塗布又は含浸させた後、必要に応じて乾燥させることにより加工品を形成することができる。こうして得られる紙又は繊維加工品は、防炎性及び自己消火性に優れ、従来の難燃性樹脂を用いた加工品と比較して、強度、耐水性、風合い(剛軟性)、耐熱黄変性などの諸物性に優れる。   The above-mentioned resin composition of the present invention forms a processed product by coating or impregnating various paper base materials or fiber base materials in a stock solution or diluted to an arbitrary ratio, and then drying as necessary. Can do. The paper or fiber processed product thus obtained is excellent in flameproofing and self-extinguishing properties, and has strength, water resistance, texture (rigid / soft), and heat-resistant yellowing compared with processed products using conventional flame retardant resins. Excellent physical properties.

各種紙基材や繊維基材に対する樹脂組成物の使用量は、基材自身の難燃性にもよるが、樹脂付着量が10〜200質量%/基材となる量が適当である。また、本発明の樹脂組成物は、他の樹脂エマルジョンや溶液樹脂、エポキシ樹脂、ウレタン樹脂等の各種樹脂組成物と混合した状態で各種紙基材や繊維基材を処理してもよい。本発明の樹脂組成物と他の各種樹脂組成物との混合割合は任意でよい。   The amount of the resin composition to be used for various paper base materials and fiber base materials depends on the flame retardancy of the base material itself, but the amount of the resin adhesion amount is 10 to 200% by mass / base material is appropriate. The resin composition of the present invention may be used to treat various paper substrates and fiber substrates in a state of being mixed with various resin compositions such as other resin emulsions, solution resins, epoxy resins, and urethane resins. The mixing ratio of the resin composition of the present invention and other various resin compositions may be arbitrary.

紙基材としては、パルプを原料とした障子紙、襖紙、壁紙、板紙などやポリプロピレンなどの合成繊維を原料とした合成紙などが挙げられる。また、繊維基材としては、例えば、木綿、麻、絹、羊毛、コラーゲン繊維、アクリル繊維、レーヨン、ナイロン、ビニロン、ポリエステル、ポリプロピレン、ポリ塩化ビニル、ポリエチレン、ポリメタフェニレンイソフタルアミド、アラミド、ポリアリレート及びこれらの混紡品からなる織物、不織布、編物などが挙げられる。   Examples of the paper base include shoji paper made from pulp, paperboard, wallpaper, paperboard, and synthetic paper made from synthetic fibers such as polypropylene. Examples of the fiber base material include cotton, hemp, silk, wool, collagen fiber, acrylic fiber, rayon, nylon, vinylon, polyester, polypropylene, polyvinyl chloride, polyethylene, polymetaphenylene isophthalamide, aramid, polyarylate. And woven fabrics, non-woven fabrics, knitted fabrics, and the like made of these blends.

以下、実施例及び比較例を用いて本発明を更に説明するが、本発明は実施例及び比較例に限定されるものではない。   EXAMPLES Hereinafter, although this invention is further demonstrated using an Example and a comparative example, this invention is not limited to an Example and a comparative example.

〔実施例1〕
イオン交換水150gを1Lの五つ口セパラブルフラスコに入れ、攪拌しながら80℃まで加熱した。エチルアクリレート36g、メチルメタクリレート36g、アクリル酸18g、アシッド・ホスホオキシポリオキシエチレングリコールモノメタクリレート(共栄社化学株式会社製、ライトエステルP−1M、リン含有量15質量%)60g、ドデシルベンゼンスルホン酸ソーダ1.5g、ポリオキシエチレンアルキルエーテル7.5g、イオン交換水190gを均一に乳化した。セパラブルフラスコに過硫酸カリウム0.2gを添加し、単量体乳化物の滴下を開始することで反応を開始した。単量体乳化物は4時間掛けてセパラブルフラスコ内に添加、同時に3%過硫酸カリウム水溶液30gも4時間掛けて添加した。単量体乳化物の添加終了後、80℃で1時間攪拌し、反応を終了した。セパラブルフラスコ内を冷却し、30%水酸化ナトリウム水溶液を8g添加し、系内を中和した。得られた水性エマルジョン組成物における樹脂固形分中のリン含有量は6質量%であった。
[Example 1]
150 g of ion-exchanged water was placed in a 1 L five-necked separable flask and heated to 80 ° C. with stirring. 36 g of ethyl acrylate, 36 g of methyl methacrylate, 18 g of acrylic acid, 60 g of acid phosphooxypolyoxyethylene glycol monomethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester P-1M, phosphorus content 15% by mass), sodium dodecylbenzenesulfonate 1 0.5 g, 7.5 g of polyoxyethylene alkyl ether and 190 g of ion-exchanged water were uniformly emulsified. The reaction was started by adding 0.2 g of potassium persulfate to the separable flask and starting dropping of the monomer emulsion. The monomer emulsion was added to the separable flask over 4 hours, and at the same time, 30 g of a 3% aqueous potassium persulfate solution was added over 4 hours. After completion of the monomer emulsion addition, the reaction was terminated by stirring at 80 ° C. for 1 hour. The inside of the separable flask was cooled, and 8 g of a 30% aqueous sodium hydroxide solution was added to neutralize the system. The phosphorus content in the resin solid content in the obtained aqueous emulsion composition was 6% by mass.

〔実施例2〕
イオン交換水150gを1Lの五つ口セパラブルフラスコに入れ、攪拌しながら80℃まで加熱した。メチルメタクリレート46g、2−エチルヘキシルアクリレート15g、エチルアクリレート11g、アクリル酸18g、アシッド・ホスホオキシポリオキシエチレングリコールモノメタクリレート(共栄社化学株式会社製、ライトエステルP−1M)60g、ドデシルベンゼンスルホン酸ソーダ1.5g、ポリオキシエチレンアルキルエーテル7.5g、イオン交換水190gを均一に乳化した。セパラブルフラスコに過硫酸カリウム0.2gを添加し、単量体乳化物の滴下を開始することで反応を開始した。単量体乳化物は4時間掛けてセパラブルフラスコ内に添加、同時に3%過硫酸カリウム水溶液30gも4時間掛けて添加した。単量体乳化物の添加終了後、80℃で1時間攪拌し、反応を終了した。セパラブルフラスコ内を冷却し、30%水酸化ナトリウム水溶液を8g添加し、系内を中和した。得られた水性エマルジョン組成物における樹脂固形分中のリン含有量は6質量%であった。
[Example 2]
150 g of ion-exchanged water was placed in a 1 L five-necked separable flask and heated to 80 ° C. with stirring. 46 g of methyl methacrylate, 15 g of 2-ethylhexyl acrylate, 11 g of ethyl acrylate, 18 g of acrylic acid, 60 g of acid phosphooxypolyoxyethylene glycol monomethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester P-1M), sodium dodecylbenzenesulfonate 5 g, 7.5 g of polyoxyethylene alkyl ether and 190 g of ion-exchanged water were uniformly emulsified. The reaction was started by adding 0.2 g of potassium persulfate to the separable flask and starting dropping of the monomer emulsion. The monomer emulsion was added to the separable flask over 4 hours, and at the same time, 30 g of a 3% aqueous potassium persulfate solution was added over 4 hours. After completion of the monomer emulsion addition, the reaction was terminated by stirring at 80 ° C. for 1 hour. The inside of the separable flask was cooled, and 8 g of a 30% aqueous sodium hydroxide solution was added to neutralize the system. The phosphorus content in the resin solid content in the obtained aqueous emulsion composition was 6% by mass.

〔実施例3〕
イオン交換水150gを1Lの五つ口セパラブルフラスコに入れ、攪拌しながら80℃まで加熱した。エチルアクリレート24g、メチルメタクリレート34g、メタクリル酸2g、アシッド・ホスホオキシポリオキシエチレングリコールモノメタクリレート(共栄社化学株式会社製、ライトエステルP−1M)90g、ドデシルベンゼンスルホン酸ソーダ1.5g、ポリオキシエチレンアルキルエーテル7.5g、イオン交換水190gを均一に乳化した。セパラブルフラスコに過硫酸カリウム0.2gを添加し、単量体乳化物の滴下を開始することで反応を開始した。単量体乳化物は4時間掛けてセパラブルフラスコ内に添加、同時に3%過硫酸カリウム水溶液30gも4時間掛けて添加した。モノマー乳化物の添加終了後、80℃で1時間攪拌し、反応を終了した。セパラブルフラスコ内を冷却し、30%水酸化ナトリウム水溶液を8g添加し、系内を中和した。得られた水性エマルジョン組成物における樹脂固形分中のリン含有量は9質量%であった。
Example 3
150 g of ion-exchanged water was placed in a 1 L five-necked separable flask and heated to 80 ° C. with stirring. 24 g of ethyl acrylate, 34 g of methyl methacrylate, 2 g of methacrylic acid, 90 g of acid phosphooxypolyoxyethylene glycol monomethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester P-1M), 1.5 g of sodium dodecylbenzenesulfonate, polyoxyethylene alkyl 7.5 g of ether and 190 g of ion exchange water were uniformly emulsified. The reaction was started by adding 0.2 g of potassium persulfate to the separable flask and starting dropping of the monomer emulsion. The monomer emulsion was added to the separable flask over 4 hours, and at the same time, 30 g of a 3% aqueous potassium persulfate solution was added over 4 hours. After completion of the monomer emulsion addition, the reaction was terminated by stirring at 80 ° C. for 1 hour. The inside of the separable flask was cooled, and 8 g of a 30% aqueous sodium hydroxide solution was added to neutralize the system. The phosphorus content in the resin solid content in the obtained aqueous emulsion composition was 9% by mass.

〔実施例4〕
イオン交換水150gを1Lの五つ口セパラブルフラスコに入れ、攪拌しながら80℃まで加熱した。メチルアクリレート35g、エチルアクリレート35g、ブチルアクリレート35g、メタクリル酸5g、アシッド・ホスホオキシポリオキシエチレングリコールモノメタクリレート(共栄社化学株式会社製、ライトエステルP−1M)40g、ドデシルベンゼンスルホン酸ソーダ1.5g、ポリオキシエチレンアルキルエーテル7.5g、イオン交換水190gを均一に乳化した。セパラブルフラスコに過硫酸カリウム0.2gを添加し、単量体乳化物の滴下を開始することで反応を開始した。単量体乳化物は4時間掛けてセパラブルフラスコ内に添加、同時に3%過硫酸カリウム水溶液30gも4時間掛けて添加した。モノマー乳化物の添加終了後、80℃で1時間攪拌し、反応を終了した。セパラブルフラスコ内を冷却し、30%水酸化ナトリウム水溶液を8g添加し、系内を中和した。得られた水性エマルジョン組成物における樹脂固形分中のリン含有量は4質量%であった。
Example 4
150 g of ion-exchanged water was placed in a 1 L five-necked separable flask and heated to 80 ° C. with stirring. 35 g of methyl acrylate, 35 g of ethyl acrylate, 35 g of butyl acrylate, 5 g of methacrylic acid, 40 g of acid phosphooxypolyoxyethylene glycol monomethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester P-1M), 1.5 g of sodium dodecylbenzenesulfonate 7.5 g of polyoxyethylene alkyl ether and 190 g of ion exchange water were uniformly emulsified. The reaction was started by adding 0.2 g of potassium persulfate to the separable flask and starting dropping of the monomer emulsion. The monomer emulsion was added to the separable flask over 4 hours, and at the same time, 30 g of a 3% aqueous potassium persulfate solution was added over 4 hours. After completion of the monomer emulsion addition, the reaction was terminated by stirring at 80 ° C. for 1 hour. The inside of the separable flask was cooled, and 8 g of a 30% aqueous sodium hydroxide solution was added to neutralize the system. The phosphorus content in the resin solid content in the obtained aqueous emulsion composition was 4% by mass.

〔実施例5〕
イオン交換水300gを1Lの五つ口セパラブルフラスコに入れ、攪拌しながら80℃まで加熱した。メチルアクリレート35g、ブチルアクリレート20g、アクリル酸55g、アシッド・ホスホオキシポリオキシエチレングリコールモノメタクリレート(共栄社化学株式会社製、ライトエステルP−1M)40gを均一に混合した。セパラブルフラスコに過硫酸アンモニウム1.5gを添加し、単量体混合物の滴下を開始することで反応を開始した。単量体混合物は4時間掛けてセパラブルフラスコ内に添加、同時に2%過硫酸アンモニウム水溶液40gも4時間掛けて添加した。単量体混合物の添加終了後、80℃で1時間攪拌し、反応を終了した。セパラブルフラスコ内を冷却し、30%水酸化ナトリウム水溶液を8g添加し、系内を中和した。得られた水溶性樹脂組成物における樹脂固形分中のリン含有量は4質量%であった。
Example 5
300 g of ion-exchanged water was placed in a 1 L five-necked separable flask and heated to 80 ° C. with stirring. 35 g of methyl acrylate, 20 g of butyl acrylate, 55 g of acrylic acid, and 40 g of acid phosphooxypolyoxyethylene glycol monomethacrylate (Kyoeisha Chemical Co., Ltd., light ester P-1M) were mixed uniformly. The reaction was started by adding 1.5 g of ammonium persulfate to the separable flask and starting the dropping of the monomer mixture. The monomer mixture was added to the separable flask over 4 hours, and at the same time, 40 g of 2% aqueous ammonium persulfate solution was added over 4 hours. After completion of the monomer mixture addition, the reaction was completed by stirring at 80 ° C. for 1 hour. The inside of the separable flask was cooled, and 8 g of a 30% aqueous sodium hydroxide solution was added to neutralize the system. The phosphorus content in the resin solid content in the obtained water-soluble resin composition was 4% by mass.

〔実施例6〕
アルキレングリコールモノアルキルエーテル300gを1Lの五つ口セパラブルフラスコに入れ、攪拌しながら80℃まで加熱した。メチルアクリレート50g、アクリル酸50g、アシッド・ホスホオキシポリオキシエチレングリコールモノメタクリレート(共栄社化学株式会社製、ライトエステルP−1M)40gを均一に混合した。セパラブルフラスコにN,N−アゾイソブチルニトリル1.5gを添加し、単量体混合物の滴下を開始することで反応を開始した。単量体混合物は4時間掛けてセパラブルフラスコ内に添加、同時に2%N,N−アゾイソブチルニトリル溶液(アルキレングリコールモノアルキルエーテルに溶解)40gも4時間掛けて添加した。単量体混合物の添加終了後、80℃で1時間攪拌し、反応を終了した。セパラブルフラスコ内を冷却し、モノアルキルアミンを19g添加し、系内を中和した。得られた溶剤系樹脂組成物における樹脂固形分中のリン含有量は4質量%であった。
Example 6
300 g of alkylene glycol monoalkyl ether was placed in a 1 L five-necked separable flask and heated to 80 ° C. with stirring. 50 g of methyl acrylate, 50 g of acrylic acid, and 40 g of acid phosphooxypolyoxyethylene glycol monomethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester P-1M) were uniformly mixed. The reaction was started by adding 1.5 g of N, N-azoisobutylnitrile to the separable flask and starting dropping of the monomer mixture. The monomer mixture was added to the separable flask over 4 hours, and 40 g of 2% N, N-azoisobutylnitrile solution (dissolved in alkylene glycol monoalkyl ether) was also added over 4 hours. After completion of the monomer mixture addition, the reaction was completed by stirring at 80 ° C. for 1 hour. The inside of the separable flask was cooled, and 19 g of monoalkylamine was added to neutralize the system. The phosphorus content in the resin solid content in the obtained solvent-based resin composition was 4% by mass.

〔比較例1〕
イオン交換水150gを1Lの五つ口セパラブルフラスコに入れ、攪拌しながら80℃まで加熱した。エチルアクリレート36g、メチルメタクリレート54g、アシッド・ホスホオキシポリオキシエチレングリコールモノメタクリレート(共栄社化学株式会社製、ライトエステルP−1M)60g、ポリビニルアルコール(株式会社クラレ製、PVA205(鹸化度86.5〜89.0%、平均重合度500))15g、イオン交換水190gを均一に乳化した。セパラブルフラスコに過硫酸カリウム0.2gを添加し、単量体乳化物の滴下を開始することで反応を開始した。単量体乳化物は4時間掛けてセパラブルフラスコ内に添加、同時に3%過硫酸カリウム水溶液30gも4時間掛けて添加した。単量体乳化物の添加終了後、80℃で1時間攪拌し、反応を終了した。セパラブルフラスコ内を冷却し、30%水酸化ナトリウム水溶液を8g添加し、系内を中和した。得られた水性エマルジョン組成物における樹脂固形分中のリン含有量は6質量%であった。
[Comparative Example 1]
150 g of ion-exchanged water was placed in a 1 L five-necked separable flask and heated to 80 ° C. with stirring. 36 g of ethyl acrylate, 54 g of methyl methacrylate, 60 g of acid phosphooxypolyoxyethylene glycol monomethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester P-1M), polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA205 (degree of saponification 86.5-89) 0.0%, average polymerization degree 500)) 15 g and ion-exchanged water 190 g were uniformly emulsified. The reaction was started by adding 0.2 g of potassium persulfate to the separable flask and starting dropping of the monomer emulsion. The monomer emulsion was added to the separable flask over 4 hours, and at the same time, 30 g of a 3% aqueous potassium persulfate solution was added over 4 hours. After completion of the monomer emulsion addition, the reaction was terminated by stirring at 80 ° C. for 1 hour. The inside of the separable flask was cooled, and 8 g of a 30% aqueous sodium hydroxide solution was added to neutralize the system. The phosphorus content in the resin solid content in the obtained aqueous emulsion composition was 6% by mass.

〔比較例2〕
イオン交換水150gを1Lの五つ口セパラブルフラスコに入れ、攪拌しながら80℃まで加熱した。エチルアクリレート55g、メチルメタクリレート83g、アシッド・ホスホオキシポリオキシエチレングリコールモノメタクリレート(共栄社化学株式会社製、ライトエステルP−1M)12g、ドデシルベンゼンスルホン酸ソーダ1.5g、ポリオキシエチレンアルキルエーテル7.5g、イオン交換水190gを均一に乳化した。セパラブルフラスコに過硫酸カリウム0.2gを添加し、単量体乳化物の滴下を開始することで反応を開始した。単量体乳化物は4時間掛けてセパラブルフラスコ内に添加、同時に3%過硫酸カリウム水溶液30gも4時間掛けて添加した。単量体乳化物の添加終了後、80℃で1時間攪拌し、反応を終了した。セパラブルフラスコ内を冷却し、30%水酸化ナトリウム水溶液を8g添加し、系内を中和した。得られた水性エマルジョン組成物における樹脂固形分中のリン含有量は1.2質量%であった。
[Comparative Example 2]
150 g of ion-exchanged water was placed in a 1 L five-necked separable flask and heated to 80 ° C. with stirring. 55 g of ethyl acrylate, 83 g of methyl methacrylate, 12 g of acid phosphooxypolyoxyethylene glycol monomethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester P-1M), 1.5 g of sodium dodecylbenzenesulfonate, 7.5 g of polyoxyethylene alkyl ether In addition, 190 g of ion-exchanged water was uniformly emulsified. The reaction was started by adding 0.2 g of potassium persulfate to the separable flask and starting dropping of the monomer emulsion. The monomer emulsion was added to the separable flask over 4 hours, and at the same time, 30 g of a 3% aqueous potassium persulfate solution was added over 4 hours. After completion of the monomer emulsion addition, the reaction was terminated by stirring at 80 ° C. for 1 hour. The inside of the separable flask was cooled, and 8 g of a 30% aqueous sodium hydroxide solution was added to neutralize the system. The phosphorus content in the resin solid content in the obtained aqueous emulsion composition was 1.2% by mass.

〔比較例3〕
イオン交換水150gを1Lの五つ口セパラブルフラスコに入れ、攪拌しながら80℃まで加熱した。エチルアクリレート20g、2−エチルヘキシルアクリレート54g、アクリル酸16g、アシッド・ホスホオキシポリオキシエチレングリコールモノメタクリレート(共栄社化学株式会社製、ライトエステルP−1M)60g、ドデシルベンゼンスルホン酸ソーダ1.5g、ポリオキシエチレンアルキルエーテル7.5g、イオン交換水190gを均一に乳化した。セパラブルフラスコに過硫酸カリウム0.2gを添加し、単量体乳化物の滴下を開始することで反応を開始した。単量体乳化物は4時間掛けてセパラブルフラスコ内に添加、同時に3%過硫酸カリウム水溶液30gも4時間掛けて添加した。単量体乳化物の添加終了後、80℃で1時間攪拌し、反応を終了した。セパラブルフラスコ内を冷却し、30%水酸化ナトリウム水溶液を8g添加し、系内を中和した。得られた水性エマルジョン組成物における樹脂固形分中のリン含有量は6質量%であった。
[Comparative Example 3]
150 g of ion-exchanged water was placed in a 1 L five-necked separable flask and heated to 80 ° C. with stirring. 20 g of ethyl acrylate, 54 g of 2-ethylhexyl acrylate, 16 g of acrylic acid, 60 g of acid phosphooxypolyoxyethylene glycol monomethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester P-1M), 1.5 g of sodium dodecylbenzenesulfonate, polyoxy 7.5 g of ethylene alkyl ether and 190 g of ion exchange water were uniformly emulsified. The reaction was started by adding 0.2 g of potassium persulfate to the separable flask and starting dropping of the monomer emulsion. The monomer emulsion was added to the separable flask over 4 hours, and at the same time, 30 g of a 3% aqueous potassium persulfate solution was added over 4 hours. After completion of the monomer emulsion addition, the reaction was terminated by stirring at 80 ° C. for 1 hour. The inside of the separable flask was cooled, and 8 g of a 30% aqueous sodium hydroxide solution was added to neutralize the system. The phosphorus content in the resin solid content in the obtained aqueous emulsion composition was 6% by mass.

〔比較例4〕(アクリル樹脂+リン系難燃剤)
イオン交換水150gを1Lの五つ口セパラブルフラスコに入れ、攪拌しながら80℃まで加熱した。エチルアクリレート60g、メチルメタクリレート90g、ドデシルベンゼンスルホン酸ソーダ1.5g、ポリオキシエチレンアルキルエーテル7.5g、イオン交換水190gを均一に乳化した。セパラブルフラスコに過硫酸カリウム0.2gを添加し、単量体乳化物の滴下を開始することで反応を開始した。単量体乳化物は4時間掛けてセパラブルフラスコ内に添加、同時に3%過硫酸カリウム水溶液30gも4時間掛けて添加した。単量体乳化物の添加終了後、80℃で1時間攪拌し、反応を終了した(得られた水性エマルジョン組成物における樹脂固形分中のリン含有量は0質量%であった)。得られた水性エマルジョン組成物における樹脂固形分中のリン含有量が9質量%となるように、リン酸グアニジン系難燃剤を水性エマルジョン組成物に添加、均一に混合した。
[Comparative Example 4] (Acrylic resin + phosphorus flame retardant)
150 g of ion-exchanged water was placed in a 1 L five-necked separable flask and heated to 80 ° C. with stirring. 60 g of ethyl acrylate, 90 g of methyl methacrylate, 1.5 g of sodium dodecylbenzenesulfonate, 7.5 g of polyoxyethylene alkyl ether, and 190 g of ion-exchanged water were uniformly emulsified. The reaction was started by adding 0.2 g of potassium persulfate to the separable flask and starting dropping of the monomer emulsion. The monomer emulsion was added to the separable flask over 4 hours, and at the same time, 30 g of a 3% aqueous potassium persulfate solution was added over 4 hours. After completion of the addition of the monomer emulsion, the reaction was terminated by stirring at 80 ° C. for 1 hour (the phosphorus content in the resin solid content in the obtained aqueous emulsion composition was 0% by mass). The guanidine phosphate flame retardant was added to the aqueous emulsion composition and mixed uniformly so that the phosphorus content in the resin solid content in the obtained aqueous emulsion composition was 9% by mass.

実施例1〜6及び比較例1〜4で得られた樹脂組成物を用いて、加工品の物性評価を行なった。加工品の作製及び評価は下記の方法に従って行った。結果を表1に示した。   Using the resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 4, the physical properties of the processed products were evaluated. Fabrication and evaluation of processed products were performed according to the following methods. The results are shown in Table 1.

(加工品の作製−1)
実施例1〜6及び比較例1〜4で得られた樹脂組成物をイオン交換水で15%に希釈し、加工浴液とした。なお、実施例6の溶剤系樹脂組成物のみ、反応溶媒として使用したアルキレングリコールモノアルキルエーテルで15%に希釈し、加工浴液とした。この加工浴液に、基材であるろ紙(No.2、東洋濾紙株式会社製)を含浸させ、樹脂付着量が約15質量%/基材となるように二本マングルで絞った後、熱風式乾燥機にて110℃で10分間乾燥させた。
(Preparation of processed product-1)
The resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were diluted to 15% with ion-exchanged water to obtain a processing bath solution. Only the solvent-based resin composition of Example 6 was diluted to 15% with alkylene glycol monoalkyl ether used as a reaction solvent to obtain a processing bath solution. The processing bath liquid is impregnated with filter paper as a base material (No. 2, manufactured by Toyo Roshi Kaisha, Ltd.), squeezed with two mangles so that the resin adhesion amount is about 15 mass% / base material, It was made to dry at 110 degreeC for 10 minute (s) with a type dryer.

(加工品の作製−2)
実施例1〜6及び比較例1〜4で得られた樹脂組成物をイオン交換水で15%に希釈し、加工浴液とした。なお、実施例6の溶剤系樹脂組成物のみ、反応溶媒として使用したアルキレングリコールモノアルキルエーテルで15%に希釈し、加工浴液とした。この加工浴液に、基材であるT/Cブロード(#40、株式会社谷頭商店製)を含浸させ、樹脂付着量が約15質量%/基材となるように二本マングルで絞った後、ピンテンターにて110℃で5分間乾燥させた。
(Fabrication of processed products-2)
The resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were diluted to 15% with ion-exchanged water to obtain a processing bath solution. Only the solvent-based resin composition of Example 6 was diluted to 15% with alkylene glycol monoalkyl ether used as a reaction solvent to obtain a processing bath solution. After this processing bath liquid is impregnated with T / C broad (# 40, manufactured by Tanigami Shoten Co., Ltd.) as a base material, and after squeezing with two mangles so that the resin adhesion amount is about 15% by mass / base material Then, it was dried at 110 ° C. for 5 minutes with a pin tenter.

(加工品の評価)
加工品の燃焼性、常態強度、湿潤強度及び剛軟性、耐熱黄変性について評価した。なお、常態強度及び湿潤強度の評価には(加工品の作製−1)で得られた加工品を用い、燃焼性及び剛軟性、耐熱黄変性については(加工品の作製−2)で得られた加工品を用いた。
(Evaluation of processed products)
The processed products were evaluated for combustibility, normal strength, wet strength and bending resistance, and heat yellowing. For the evaluation of normal strength and wet strength, the processed product obtained in (Preparation of processed product-1) was used, and the combustibility, stiffness, and heat yellowing were obtained in (Preparation of processed product-2). The processed product was used.

(1)燃焼性
加工品作製後、23℃、65%RHの条件下に12時間以上静置した試験体をJIS L1091 A−1法(45°ミクロバーナー法)に準拠し、燃焼性試験を行なった。なお、この試験における区分は、1から3になるに従って燃焼性が低いことを意味している。
(1) Flammability After preparing a processed product, a test body that was allowed to stand for 12 hours or more under conditions of 23 ° C. and 65% RH was subjected to a flammability test in accordance with JIS L1091 A-1 method (45 ° micro burner method). I did it. In addition, the division in this test means that combustibility is low as it becomes 1 to 3.

(2)常態強度
加工品作製後、23℃、65%RHの条件下に12時間以上静置した試験体を25×100mmに裁断し、AUTOGRAPH(AG−2000A、株式会社島津製作所製)を用いて、200mm/分の速度で引っ張り強度測定を行なった。この時のチャック間距離は50mmとした。
(2) Normal strength After fabrication of a processed product, a specimen that was allowed to stand for 12 hours or more at 23 ° C. and 65% RH was cut into 25 × 100 mm, and AUTOGRAPH (AG-2000A, manufactured by Shimadzu Corporation) was used. The tensile strength was measured at a speed of 200 mm / min. The distance between chucks at this time was 50 mm.

(3)湿潤強度
加工品作製後、23℃、65%RHの条件下に12時間以上静置した試験体を25×100mmに裁断し、イオン交換水に10分間浸漬した後、常態強度と同様の方法で強度測定を行なった。
(3) Wet strength After the processed product was prepared, the specimen that had been allowed to stand for 12 hours or more at 23 ° C. and 65% RH was cut into 25 × 100 mm, immersed in ion-exchanged water for 10 minutes, and then the normal strength. The strength was measured by this method.

(4)剛軟性
加工品作製後、23℃、65%RHの条件下に12時間以上静置した試験体を150×150mmに裁断し、JIS L 1096 一般織物試験方法に記載される8.19.5 E法(ハンドルオメータ法)に準拠し、測定を行なった。なお、剛軟性(g)は繊維の硬さ、柔らかさを表しており、数値が高いほど加工品の風合いは硬いことを示す。
(4) Rigid softness After preparing the processed product, a test body that was allowed to stand for 12 hours or more under conditions of 23 ° C. and 65% RH was cut into 150 × 150 mm and described in JIS L 1096 General Textile Test Method 8.19. .5 Measurement was performed in accordance with the E method (handle ohmmeter method). The bending resistance (g) represents the hardness and softness of the fiber. The higher the value, the harder the texture of the processed product.

(5)耐熱黄変性
加工品作製後、23℃、65%RHの条件下に12時間以上静置した試験体を100×100mmに裁断し、150℃で10分間加熱した。その後、さらに加工品を23℃、65%RHの条件下に12時間以上静置し、SMカラーコンピューター(SM−5−CH、スガ試験機株式会社製)を用いてΔb値の測定を行った。なお、Δb値は黄変度合を表しており、数値が高いほど加工品の黄変度合が強いことを示す。
(5) Heat-resistant yellowing After preparation of the processed product, a test specimen that was allowed to stand for 12 hours or more under conditions of 23 ° C. and 65% RH was cut into 100 × 100 mm and heated at 150 ° C. for 10 minutes. Thereafter, the processed product was further allowed to stand for 12 hours or more at 23 ° C. and 65% RH, and the Δb value was measured using an SM color computer (SM-5-CH, manufactured by Suga Test Instruments Co., Ltd.). . The Δb value represents the degree of yellowing, and the higher the value, the stronger the degree of yellowing of the processed product.

Figure 2010235830
Figure 2010235830

Figure 2010235830
Figure 2010235830

表1から分かるように、実施例1〜6で得られた樹脂組成物で処理された加工品は、防炎性、常態強度、湿潤強度及び剛軟性、耐熱黄変性に優れていた。これに対し、比較例1〜4で得られた樹脂組成物で基材を処理しても、防炎性、常態強度、湿潤強度及び剛軟性の全てが優れる加工品は得られなかった。   As can be seen from Table 1, the processed products treated with the resin compositions obtained in Examples 1 to 6 were excellent in flame resistance, normal strength, wet strength and stiffness, and heat-resistant yellowing. On the other hand, even if the substrate was treated with the resin compositions obtained in Comparative Examples 1 to 4, a processed product excellent in all of flame resistance, normal strength, wet strength, and bending resistance was not obtained.

Claims (5)

リン酸基又は亜リン酸基を有する不飽和単量体、アルキル鎖の炭素数が1〜4である(メタ)アクリル酸アルキルエステル単量体、並びにアクリル酸、メタクリル酸及びイタコン酸からなる群から選択される少なくとも1種のカルボキシル基を有する不飽和単量体を共重合して得られ、固形分中のリン含有量が3〜13質量%であり、前記カルボキシル基を有する不飽和単量体を全単量体に対し1〜79質量%使用し、且つアルキル鎖の炭素数が1〜4である(メタ)アクリル酸アルキルエステル単量体と前記カルボキシル基を有する不飽和単量体とを合計で全単量体に対し40質量%以上使用することを特徴とする樹脂組成物。 Group consisting of unsaturated monomer having phosphoric acid group or phosphorous acid group, (meth) acrylic acid alkyl ester monomer having 1 to 4 carbon atoms in alkyl chain, and acrylic acid, methacrylic acid and itaconic acid Obtained by copolymerizing an unsaturated monomer having at least one carboxyl group selected from the group consisting of 3 to 13% by mass of phosphorus in the solid content, and an unsaturated monomer having the carboxyl group (Meth) acrylic acid alkyl ester monomer having 1 to 79% by mass of the polymer based on the total monomers and having 1 to 4 carbon atoms in the alkyl chain, and an unsaturated monomer having the carboxyl group, In a total of 40% by mass or more based on the total amount of monomers. リン酸基又は亜リン酸基を有する不飽和単量体が、アシッド・ホスホオキシポリオキシアルキレングリコールモノ(メタ)アクリレートであることを特徴とする、請求項1に記載の樹脂組成物。 2. The resin composition according to claim 1, wherein the unsaturated monomer having a phosphoric acid group or a phosphorous acid group is acid phosphooxypolyoxyalkylene glycol mono (meth) acrylate. アルキル鎖の炭素数が1〜4である(メタ)アクリル酸アルキルエステル単量体を全単量体に対し1〜79質量%使用することを特徴とする、請求項1又は2のいずれかに記載の樹脂組成物。 The alkyl (meth) acrylic acid alkyl ester monomer having 1 to 4 carbon atoms in the alkyl chain is used in an amount of 1 to 79% by mass based on the total amount of monomers. The resin composition as described. 請求項1、2又は3のいずれかに記載の樹脂組成物を用いて加工された紙。 A paper processed using the resin composition according to claim 1. 請求項1、2又は3のいずれかに記載の樹脂組成物を用いて加工された繊維加工品。 A fiber processed product processed using the resin composition according to claim 1.
JP2009086566A 2009-03-31 2009-03-31 Resin composition and paper or fiber processed product treated with the same Active JP5669363B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2009086566A JP5669363B2 (en) 2009-03-31 2009-03-31 Resin composition and paper or fiber processed product treated with the same
CN201080014691.0A CN102369224B (en) 2009-03-31 2010-03-26 Resin combination and with its paper processed or fiber process product
PCT/JP2010/055369 WO2010113796A1 (en) 2009-03-31 2010-03-26 Resin composition and processed paper or fiber product treated therewith

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2009086566A JP5669363B2 (en) 2009-03-31 2009-03-31 Resin composition and paper or fiber processed product treated with the same

Publications (2)

Publication Number Publication Date
JP2010235830A true JP2010235830A (en) 2010-10-21
JP5669363B2 JP5669363B2 (en) 2015-02-12

Family

ID=42828087

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2009086566A Active JP5669363B2 (en) 2009-03-31 2009-03-31 Resin composition and paper or fiber processed product treated with the same

Country Status (3)

Country Link
JP (1) JP5669363B2 (en)
CN (1) CN102369224B (en)
WO (1) WO2010113796A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014532782A (en) * 2011-10-31 2014-12-08 ルブリゾル アドバンスド マテリアルズ, インコーポレイテッド Non-halogen flame retardant polymer
US10174140B2 (en) 2013-05-28 2019-01-08 Lubrizol Advanced Materials, Inc. Non-halogen flame retardant polymers
KR20200020806A (en) 2017-06-27 2020-02-26 쇼와 덴코 가부시키가이샤 Copolymers, Resin Compositions, Processing Agents and Processed Products

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8399451B2 (en) 2009-08-07 2013-03-19 Bristol-Myers Squibb Company Heterocyclic compounds
KR102104913B1 (en) 2011-10-31 2020-04-27 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 Non-halogen flame retardant as coatings for fibrous filter media
CN103101228A (en) * 2012-11-14 2013-05-15 合肥朗胜新材料有限公司 Manufacturing method of modified nano-carbon honeycomb paperboards
TW201420614A (en) * 2012-11-20 2014-06-01 Ind Tech Res Inst Halogen-free retardant acrylic resin and molded article
WO2017183535A1 (en) * 2016-04-18 2017-10-26 昭和電工株式会社 Fiber treatment agent, method for producing processed fiber article, and processed fiber article

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62184018A (en) * 1986-02-08 1987-08-12 Toyobo Co Ltd Flame-retarding curable resin composition
JP2000029234A (en) * 1998-07-13 2000-01-28 Konica Corp Light-transmitting base body for electrophotographic photoreceptor, its production and electrophotographic photoreceptor, image forming method and image forming device using that
JP2003137915A (en) * 2001-11-05 2003-05-14 Sumitomo Chem Co Ltd Methyl methacrylate-based resin

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4917196B2 (en) * 1999-09-24 2012-04-18 Jsr株式会社 Resin composition and cured product thereof
JP4251017B2 (en) * 2003-05-26 2009-04-08 住友化学株式会社 Method for producing methacrylic resin particle composition
US8877852B2 (en) * 2006-12-15 2014-11-04 Rohm And Haas Company Phosphorous-containing organic polymer and compositions and processes including same
JP4354999B2 (en) * 2007-01-09 2009-10-28 昭和高分子株式会社 Aqueous emulsion composition and processed paper or fiber processed with the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62184018A (en) * 1986-02-08 1987-08-12 Toyobo Co Ltd Flame-retarding curable resin composition
JP2000029234A (en) * 1998-07-13 2000-01-28 Konica Corp Light-transmitting base body for electrophotographic photoreceptor, its production and electrophotographic photoreceptor, image forming method and image forming device using that
JP2003137915A (en) * 2001-11-05 2003-05-14 Sumitomo Chem Co Ltd Methyl methacrylate-based resin

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014532782A (en) * 2011-10-31 2014-12-08 ルブリゾル アドバンスド マテリアルズ, インコーポレイテッド Non-halogen flame retardant polymer
KR102064933B1 (en) * 2011-10-31 2020-01-10 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 Non-halogen flame retardant polymers
US10174140B2 (en) 2013-05-28 2019-01-08 Lubrizol Advanced Materials, Inc. Non-halogen flame retardant polymers
KR20200020806A (en) 2017-06-27 2020-02-26 쇼와 덴코 가부시키가이샤 Copolymers, Resin Compositions, Processing Agents and Processed Products
CN110869401A (en) * 2017-06-27 2020-03-06 昭和电工株式会社 Copolymer, resin composition, treating agent, and processed product
CN110869401B (en) * 2017-06-27 2022-07-12 昭和电工株式会社 Copolymer, resin composition, treating agent, and processed product

Also Published As

Publication number Publication date
WO2010113796A1 (en) 2010-10-07
CN102369224A (en) 2012-03-07
CN102369224B (en) 2015-11-25
JP5669363B2 (en) 2015-02-12

Similar Documents

Publication Publication Date Title
JP5669363B2 (en) Resin composition and paper or fiber processed product treated with the same
US9139677B2 (en) Composite polymer emulsion
CN110869401B (en) Copolymer, resin composition, treating agent, and processed product
JP4851346B2 (en) Brominated polymers and flame retardant products containing them
JP2005054020A (en) Water and oil repellant
JP4354999B2 (en) Aqueous emulsion composition and processed paper or fiber processed with the same
JP7012007B2 (en) Fiber treatment agents, manufacturing methods for processed fiber products, and processed fiber products
JP5211425B2 (en) Method for producing aqueous resin dispersion for processing fiber
EP3176187B1 (en) Formaldehyde-free thermally curable polymers
KR100855598B1 (en) Aqueous emulsion comprising ethylene-vinylester copolymer
TWI763799B (en) Formaldehyde-free curable composition
JP2009270247A (en) Composition for coating paper/fiber product, coating film, and paper/fiber product
JP5201781B2 (en) Coating composition for vehicle interior material and vehicle interior material
US20190375867A1 (en) Formaldehyde-free thermally curable polymers
JP4051970B2 (en) Aqueous emulsion containing ethylene / vinyl ester copolymer
WO2021253405A1 (en) Formaldehyde-free aqueous curable composition
JP5596967B2 (en) Paper or textile processed product treated with thermosetting oil-in-water emulsion
JP2013049858A (en) Coating composition for vehicular interior material, and vehicular interior material
JP5991191B2 (en) Acrylic aqueous resin emulsion composition
JP5667772B2 (en) Resin emulsion for glass fiber treatment
JPH0328212A (en) Water-base resin composition
WO2019115392A1 (en) Soil release formulations for textile applications
JP2007186624A (en) Emulsifying agent for emulsion polymerization, method for producing polymer emulsion and polymer emulsion

Legal Events

Date Code Title Description
A711 Notification of change in applicant

Free format text: JAPANESE INTERMEDIATE CODE: A712

Effective date: 20100730

A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20111201

RD02 Notification of acceptance of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7422

Effective date: 20131204

RD04 Notification of resignation of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7424

Effective date: 20131204

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20131224

A601 Written request for extension of time

Free format text: JAPANESE INTERMEDIATE CODE: A601

Effective date: 20140224

A602 Written permission of extension of time

Free format text: JAPANESE INTERMEDIATE CODE: A602

Effective date: 20140227

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20140312

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A821

Effective date: 20140312

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20140924

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20141119

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20141209

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20141216

R150 Certificate of patent or registration of utility model

Ref document number: 5669363

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313111

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350