JP2001089519A - Epoxy-modified polyethylene resin and its production - Google Patents
Epoxy-modified polyethylene resin and its productionInfo
- Publication number
- JP2001089519A JP2001089519A JP26622699A JP26622699A JP2001089519A JP 2001089519 A JP2001089519 A JP 2001089519A JP 26622699 A JP26622699 A JP 26622699A JP 26622699 A JP26622699 A JP 26622699A JP 2001089519 A JP2001089519 A JP 2001089519A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy
- polyethylene resin
- modified polyethylene
- component
- equivalent
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、バインダー樹脂、
接着剤などに用いられるエポキシ変性ポリエチレン系樹
脂及びその製造法に関する。The present invention relates to a binder resin,
The present invention relates to an epoxy-modified polyethylene resin used for an adhesive or the like and a method for producing the same.
【０００２】[0002]
【従来の技術】ポリエチレン樹脂は、結晶性熱可塑性樹
脂であり、機械的強度、加工性、電気絶縁性、防湿性、
耐水性、耐寒性、耐薬品性等に優れることから、絶縁材
料、各種容器、管、パッキング、工業用装置の内張り、
被覆用及び包装用フィルム、工業用繊維などに広く用い
られている。しかしながら、適当な溶剤がなく、他材料
との相溶性、接着性に劣るため、塗料用、バッテリー用
など各種用途のバインダー樹脂、接着剤などへの適用が
困難であるという問題があった。2. Description of the Related Art Polyethylene resin is a crystalline thermoplastic resin, and has mechanical strength, workability, electrical insulation, moisture resistance,
Since it has excellent water resistance, cold resistance, chemical resistance, etc., it is used for insulating materials, various containers, pipes, packing, lining of industrial equipment,
Widely used for coating and packaging films, industrial fibers and the like. However, since there is no suitable solvent and the compatibility with other materials and the adhesiveness are poor, there has been a problem that it is difficult to apply the composition to binder resins and adhesives for various uses such as paints and batteries.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、含窒
素系溶剤への分散安定性に優れ、かつ、他材料との相溶
性、接着性の良好なエポキシ変性ポリエチレン系樹脂を
提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide an epoxy-modified polyethylene resin which is excellent in dispersion stability in a nitrogen-containing solvent, and has good compatibility and adhesion with other materials. It is in.
【０００４】本発明の他の目的は、より含窒素系溶剤へ
の分散安定性に優れたエポキシ変性ポリエチレン系樹脂
を提供することにある。[0004] Another object of the present invention is to provide an epoxy-modified polyethylene resin having more excellent dispersion stability in a nitrogen-containing solvent.
【０００５】本発明の他の目的は、より他材料との相溶
性、接着性の良好なエポキシ変性ポリエチレン系樹脂を
提供することにある。[0005] Another object of the present invention is to provide an epoxy-modified polyethylene resin having better compatibility and adhesion with other materials.
【０００６】本発明の他の目的は、含窒素系溶剤への分
散安定性に優れ、かつ、他材料との相溶性、接着性の良
好なエポキシ変性ポリエチレン系樹脂の製造法を提供す
ることにある。Another object of the present invention is to provide a method for producing an epoxy-modified polyethylene resin which has excellent dispersion stability in a nitrogen-containing solvent, and has good compatibility and adhesion with other materials. is there.
【０００７】本発明の他の目的は、より含窒素系溶剤へ
の分散安定性に優れたエポキシ変性ポリエチレン系樹脂
の製造法を提供することにある。It is another object of the present invention to provide a method for producing an epoxy-modified polyethylene resin having more excellent dispersion stability in a nitrogen-containing solvent.
【０００８】本発明の他の目的は、より他材料との相溶
性、接着性の良好なエポキシ変性ポリエチレン系樹脂の
製造法を提供することにある。Another object of the present invention is to provide a method for producing an epoxy-modified polyethylene resin having better compatibility and adhesion with other materials.
【０００９】[0009]
【課題を解決するための手段】本発明は、少なくとも、
一般式（Ι）Means for Solving the Problems The present invention provides at least:
General formula (Ι)
【００１０】[0010]
【化３】 で表されるユニットと一般式（ΙΙ）Embedded image And the general formula (ΙΙ)
【００１１】[0011]
【化４】 （式中、Ｒ1は水素又はメチル基を示し、Ｒ2はモノエポ
キシ化合物残基を表す一価の有機基を示す）で表される
ユニットを有するエポキシ変性ポリエチレン系樹脂に関
する。Embedded image (Wherein, R 1 represents hydrogen or a methyl group, and R 2 represents a monovalent organic group representing a monoepoxy compound residue).
【００１２】また、本発明は、Ｒ1がメチル基である上
記エポキシ変性ポリエチレン系樹脂に関する。The present invention also relates to the above epoxy-modified polyethylene resin, wherein R 1 is a methyl group.
【００１３】また、本発明は、Ｒ2が芳香環を有するモ
ノエポキシ化合物残基である上記エポキシ変性ポリエチ
レン系樹脂に関する。The present invention also relates to the above epoxy-modified polyethylene resin, wherein R 2 is a monoepoxy compound residue having an aromatic ring.
【００１４】また、本発明は、（Ａ）カルボキシル基を
有するポリエチレン系樹脂と（Ｂ）モノエポキシ化合物
とを、（Ａ）成分中のカルボキシル基１当量に対して、
（Ｂ）成分中のエポキシ基が１当量以下となるような割
合で反応させることを特徴とするエポキシ変性ポリエチ
レン系樹脂の製造法に関する。Further, the present invention relates to a method in which (A) a polyethylene resin having a carboxyl group and (B) a monoepoxy compound are added to one equivalent of the carboxyl group in the component (A).
The present invention relates to a method for producing an epoxy-modified polyethylene resin, wherein the reaction is carried out at such a ratio that the epoxy group in the component (B) becomes 1 equivalent or less.
【００１５】また、本発明は、（Ａ）成分が、エチレン
−メタクリル酸共重合体である上記エポキシ変性ポリエ
チレン系樹脂の製造法に関する。The present invention also relates to a method for producing the above epoxy-modified polyethylene resin, wherein the component (A) is an ethylene-methacrylic acid copolymer.
【００１６】また、本発明は、（Ｂ）成分が、芳香環を
有するモノエポキシ化合物である上記エポキシ変性ポリ
エチレン系樹脂の製造法に関する。The present invention also relates to a method for producing the above epoxy-modified polyethylene resin, wherein the component (B) is a monoepoxy compound having an aromatic ring.
【００１７】[0017]
【発明の実施の形態】本発明のエポキシ変性ポリエチレ
ン系樹脂は、少なくとも、一般式（Ι）BEST MODE FOR CARRYING OUT THE INVENTION The epoxy-modified polyethylene resin of the present invention has at least the general formula (一般)
【００１８】[0018]
【化５】 で表されるユニットと一般式（ΙΙ）Embedded image And the general formula (ΙΙ)
【００１９】[0019]
【化６】 （式中、Ｒ1は水素又はメチル基を示し、Ｒ2はモノエポ
キシ化合物残基を表す一価の有機基を示す）で表される
ユニットを有するものであり、含窒素系溶剤への分散安
定性向上等の点で一般式（ΙΙ）におけるＲ1がメチル
基であるものが好ましく、また、他材料との相溶性、接
着性向上等の点で一般式（ΙΙ）におけるＲ2が芳香環
を有するモノエポキシ化合物残基であるものが好まし
い。Embedded image (Wherein, R 1 represents hydrogen or a methyl group, R 2 represents a monovalent organic group representing a monoepoxy compound residue), and is dispersed in a nitrogen-containing solvent. Preferably, R 1 in the general formula (あ る) is a methyl group from the viewpoint of improving stability, and R 2 in the general formula (ΙΙ) is aromatic from the viewpoint of improving compatibility with other materials and adhesion. Those which are monoepoxy compound residues having a ring are preferred.
【００２０】本発明のエポキシ変性ポリエチレン系樹脂
は、下記一般式（ＩＩＩ）で表されるユニットを含有し
ていてもよい。一般式（ＩＩＩ）で表されるユニットび
含有割合は、（ＩＩＩ）／［（Ｉ）＋（ＩＩ）］＝５／
９５〜０／１００（モル％）が好ましい。The epoxy-modified polyethylene resin of the present invention may contain a unit represented by the following general formula (III). The content of the unit represented by the general formula (III) is (III) / [(I) + (II)] = 5 /
95-0 / 100 (mol%) is preferable.
【００２１】[0021]
【化７】 （式中、Ｒ1は水素又はメチル基を示す） また、本発明のエポキシ変性ポリエチレン系樹脂中の一
般式（Ｉ）で表されるユニット及び一般式（ＩＩ）で表
されるユニットの好ましい含有割合は、（ＩＩ）／
（Ｉ）＝１／９９〜１５／８５（モル％）が好ましく、
（ＩＩ）／（Ｉ）＝３／９７〜９／９１（モル％）がよ
り好ましい。Embedded image (In the formula, R 1 represents hydrogen or a methyl group.) Further, the epoxy-modified polyethylene resin of the present invention preferably contains a unit represented by the general formula (I) and a unit represented by the general formula (II) The ratio is (II) /
(I) = 1/99 to 15/85 (mole%) is preferable,
(II) / (I) = 3/97 to 9/91 (mol%) is more preferable.
【００２２】本発明のエポキシ変性ポリエチレン系樹脂
は、メルトフローレート（ＪＩＳＫ ６７６０）が１０
〜１００ｇ／１０ｍｉｎであるものが好ましく、２０〜
６０ｇ／１０ｍｉｎであるものがより好ましい。The epoxy-modified polyethylene resin of the present invention has a melt flow rate (JIS K 6760) of 10
１００100 g / 10 min, preferably 20 to 100 g / 10 min.
More preferably, it is 60 g / 10 min.
【００２３】上記エポキシ変性ポリエチレン系樹脂は、
例えば、（Ａ）カルボキシル基を有するポリエチレン系
樹脂と（Ｂ）モノエポキシ化合物とを、（Ａ）成分中の
カルボキシル基１当量に対して、（Ｂ）成分中のエポキ
シ基が１当量以下となるような割合で反応させて製造さ
れる。The epoxy-modified polyethylene resin is
For example, when the (A) polyethylene resin having a carboxyl group and the (B) monoepoxy compound are used, the epoxy group in the component (B) is 1 equivalent or less per 1 equivalent of the carboxyl group in the component (A). It is produced by reacting at such a ratio.
【００２４】本発明に用いる（Ａ）カルボキシル基を有
するポリエチレン系樹脂としては、特に制限はなく、例
えば、エチレン−アクリル酸共重合体、エチレン−メタ
クリル酸共重合体などが挙げられる。これらのうちでは
含窒素系溶剤への分散安定性向上等の点でエチレン−メ
タクリル酸共重合体が好ましい。これらの（Ａ）成分
は、単独で又は二種類以上組合せて用いられる。The (A) polyethylene resin having a carboxyl group used in the present invention is not particularly limited, and examples thereof include an ethylene-acrylic acid copolymer and an ethylene-methacrylic acid copolymer. Among these, an ethylene-methacrylic acid copolymer is preferred from the viewpoint of improving the dispersion stability in a nitrogen-containing solvent. These components (A) are used alone or in combination of two or more.
【００２５】エチレン（メタ）アクリル酸共重合体は、
（メタ）アクリル酸ユニット／エチレンユニット＝１／
９９〜１５／８５（モル％）のものが好ましく、（メ
タ）アクリル酸ユニット／エチレンユニット＝３／９７
〜９／９１（モル％）のものがより好ましい。分子量
は、メルトフローレート（ＪＩＳ Ｋ ６７６０）が１
０〜１００ｇ／１０ｍｉｎであるものが好ましく、２０
〜６０ｇ／１０ｍｉｎであるものがより好ましい。The ethylene (meth) acrylic acid copolymer is
(Meth) acrylic acid unit / ethylene unit = 1 /
It is preferably from 99 to 15/85 (mol%), and (meth) acrylic acid unit / ethylene unit = 3/97
~ 9/91 (mol%) is more preferable. The molecular weight is such that the melt flow rate (JIS K 6760) is 1
It is preferably from 0 to 100 g / 10 min.
What is 60 g / 10min is more preferable.
【００２６】本発明に用いる（Ｂ）モノエポキシ化合物
としては、特に制限はなく、例えば、フェニルグリシジ
ルエーテル、ｐ−ｔ−ブチルフェニルグリシジルエーテ
ル、ｓ−ブチルフェニルグリシジルエーテル、グリシジ
ルフタルイミド、ジブロモフェニルグリシジルエーテ
ル、メチルジブロモフェニルグリシジルエーテル、クレ
ジルグリシジルエーテル、スチレンオキサイド等の芳香
環を有するモノエポキシ化合物、２−エチルヘキシルグ
リシジルエーテル、グリシジルメタクリレート、メチル
グリシジルエーテル、アリルグリシジルエーテル、ブチ
ルグリシジルエーテル、デシルグリシジルエーテル、ス
テアリルグリシジルエーテル、グリシドール、３，４−
エポキシシクロヘキシルメチルメタクリレート、シクロ
ヘキセンオキサイド、シクロヘキセンビニルモノオキサ
イド、ジペンテンモノオキサイド、プロピレンオキサイ
ド、ブチレンオキサイド、２、３−エポキシ−トランス
−デカリン、イソホロンオキサイド等の脂肪鎖のみから
なるモノエポキシ化合物などが挙げられる。これらのう
ちでは他材料との相溶性、接着性向上等の点で芳香環を
有するモノエポキシ化合物が好ましい。これらの（Ｂ）
成分は、単独で又は二種類以上組合せて用いられる。The monoepoxy compound (B) used in the present invention is not particularly limited. For example, phenylglycidyl ether, pt-butylphenylglycidyl ether, s-butylphenylglycidylether, glycidylphthalimide, dibromophenylglycidylether , Monoepoxy compounds having an aromatic ring such as methyldibromophenyl glycidyl ether, cresyl glycidyl ether, styrene oxide, 2-ethylhexyl glycidyl ether, glycidyl methacrylate, methyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, stearyl Glycidyl ether, glycidol, 3,4-
Monoepoxy compounds consisting only of a fatty chain, such as epoxycyclohexylmethyl methacrylate, cyclohexene oxide, cyclohexene vinyl monooxide, dipentene monooxide, propylene oxide, butylene oxide, 2,3-epoxy-trans-decalin, and isophorone oxide. Among these, a monoepoxy compound having an aromatic ring is preferable in terms of compatibility with other materials and improvement in adhesion. These (B)
The components are used alone or in combination of two or more.
【００２７】本発明のエポキシ変性ポリエチレン系樹脂
を製造するための（Ａ）成分と（Ｂ）成分との配合割合
（（Ａ）成分中のカルボキシル基／（Ｂ）成分中のエポ
キシ基）は、等量比で１／１以下とすることが好まし
く、１当量／０．５０当量〜１当量／０．９９当量とす
ることがより好ましく、１当量／０．７０当量〜１当量
／０．９７当量とすることが特に好ましく、１当量／
０．８５当量〜１当量／０．９５当量とすることが極め
て好ましい。この配合割合が等量比で１未満／１以上で
あると、（Ｂ）成分が未反応物として多量に残留しやす
くなる傾向がある。The proportion of the components (A) and (B) (the carboxyl group in the component (A) / the epoxy group in the component (B)) for producing the epoxy-modified polyethylene resin of the present invention is as follows: The equivalent ratio is preferably 1/1 or less, more preferably 1 equivalent / 0.50 equivalent to 1 equivalent / 0.99 equivalent, and more preferably 1 equivalent / 0.70 equivalent to 1 equivalent / 0.97. It is particularly preferable that the equivalent amount be 1 equivalent /
It is extremely preferable to set 0.85 equivalent to 1 equivalent / 0.95 equivalent. If the blending ratio is less than 1/1 or more in an equivalent ratio, the component (B) tends to remain in a large amount as an unreacted substance.
【００２８】（Ａ）成分と（Ｂ）成分の反応は、有機溶
媒中で行うことができる。この有機溶媒としては、特に
制限はなく、例えば、Ｎ−メチル−２−ピロリドン、
Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホル
ムアミド等のアミド系溶媒、Ｎ，Ｎ−ジメチルエチレン
ウレア、Ｎ，Ｎ−ジメチルプロピレンウレア、テトラメ
チル尿素等の尿素系溶媒、γ−ブチロラクトン、γ−カ
プロラクトン等のラクトン系溶媒、プロピレンカーボネ
ート等のカーボネート系溶媒、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系
溶媒、酢酸エチル、酢酸ｎ−ブチル、ブチルセロソルブ
アセテート、ブチルカルビトールアセテート、エチルセ
ロソルブアセテート、エチルカルビトールアセテート等
のエステル系溶媒、ジグライム、トリグライム、テトラ
グライム等のグライム系溶媒、トルエン、キシレン、シ
クロヘキサン等の炭化水素系溶媒、スルホラン等のスル
ホン系溶媒などが挙げられる。これらのうちでは高溶解
性、高反応促進性、本発明のエポキシ変性ポリエチレン
系樹脂が常温で溶媒に微粒子状に均一かつ安定に分散し
た分散液の状態で得られる等の点で含窒素系のアミド系
溶媒、尿素系溶媒が好ましく、中でも（Ａ）成分と
（Ｂ）成分の反応を阻害しやすい活性水素をもたない等
の点で、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチ
ルアセトアミド、Ｎ，Ｎ−ジメチルエチレンウレア、
Ｎ，Ｎ−ジメチルプロピレンウレア、テトラメチル尿素
がより好ましく、この中では、Ｎ−メチル−２−ピロリ
ドンが特に好ましい。The reaction between the components (A) and (B) can be performed in an organic solvent. The organic solvent is not particularly limited and includes, for example, N-methyl-2-pyrrolidone,
Amide solvents such as N, N-dimethylacetamide and N, N-dimethylformamide; urea solvents such as N, N-dimethylethyleneurea, N, N-dimethylpropyleneurea and tetramethylurea; γ-butyrolactone; Lactone solvents such as caprolactone, carbonate solvents such as propylene carbonate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl acetate, n-butyl acetate, butyl cellosolve acetate, butyl carbitol acetate, ethyl cellosolve acetate, ethyl carbine Examples include ester solvents such as tall acetate, glyme solvents such as diglyme, triglyme and tetraglyme, hydrocarbon solvents such as toluene, xylene and cyclohexane, and sulfone solvents such as sulfolane. I can do it. Among them, nitrogen-containing ones having high solubility, high reaction accelerating property, and the point that the epoxy-modified polyethylene-based resin of the present invention can be obtained in the form of a dispersion liquid which is uniformly and stably dispersed in a solvent at room temperature in the form of fine particles. Amide-based solvents and urea-based solvents are preferred. Among them, N-methyl-2-pyrrolidone, N, N-dimethyl is preferred because it does not have active hydrogen which easily inhibits the reaction between the components (A) and (B). Acetamide, N, N-dimethylethylene urea,
N, N-dimethylpropylene urea and tetramethyl urea are more preferred, of which N-methyl-2-pyrrolidone is particularly preferred.
【００２９】有機溶媒の使用量は、（Ａ）成分と（Ｂ）
成分との総量１００重量部に対して、５０〜１０，００
０重量部とすることが好ましく、２００〜５，０００重
量部とすることがより好ましく、３００〜３，０００重
量部とすることが特に好ましい。この使用量が５０重量
部未満では溶解性が乏しく、反応系の不均一化や高粘度
化を起こしやすい傾向があり、１０，０００重量部を超
えると反応が進みにくく、反応が完結しにくい傾向があ
る。これらの有機溶媒は、単独で又は二種類以上組合せ
て用いることができる。The amount of the organic solvent used depends on the amount of the component (A) and the amount of the component (B).
50 to 10,000 based on 100 parts by weight of the total amount of the components
It is preferably 0 parts by weight, more preferably 200 to 5,000 parts by weight, and particularly preferably 300 to 3,000 parts by weight. If the amount is less than 50 parts by weight, the solubility is poor and the reaction system tends to be non-uniform and the viscosity tends to be increased. If the amount exceeds 10,000 parts by weight, the reaction does not easily proceed and the reaction tends to be difficult to complete. There is. These organic solvents can be used alone or in combination of two or more.
【００３０】（Ａ）成分と（Ｂ）成分の反応温度は、４
０〜２５０℃とすることが好ましく、８０〜２００℃と
することがより好ましく、１２０〜１８０℃とすること
が特に好ましい。この反応温度が４０℃未満では反応が
進みにくく、反応が完結しにくい傾向があり、反応温度
が２５０℃を超えると、副反応により系がゲル化するこ
ともあり、反応が制御しにくい傾向がある。The reaction temperature of the component (A) and the component (B) is 4
The temperature is preferably from 0 to 250 ° C, more preferably from 80 to 200 ° C, particularly preferably from 120 to 180 ° C. If the reaction temperature is lower than 40 ° C., the reaction does not easily proceed and the reaction tends to be difficult to complete. If the reaction temperature exceeds 250 ° C., the system may gel due to side reactions, and the reaction tends to be difficult to control. is there.
【００３１】本発明のエポキシ変性ポリエチレン系樹脂
の製造においては、必要に応じて触媒を用いることがで
きる。触媒としては、特に制限はなく、例えば、トリエ
チルアミン、トリエチレンジアミン、Ｎ，Ｎ−ジメチル
アニリン、Ｎ，Ｎ−ジエチルアニリン、Ｎ，Ｎ−ジメチ
ルベンジルアミン、Ｎ−メチルモルフォリン、Ｎ−エチ
ルモルフォリン、Ｎ，Ｎ′−ジメチルピペラジン、ピリ
ジン、ピコリン、１，８−ジアザビシクロ［５，４，
０］ウンデセン−７等の三級アミン、２−メチルイミダ
ゾール、２−エチルイミダゾール、２−エチル−４−メ
チルイミダゾール、２−メチル−４−メチルイミダゾー
ル、１−シアノエチル−２−メチルイミダゾール、１−
シアノエチル−２−フェニルイミダゾール、２−フェニ
ル−４−メチル−５−ヒドロキシメチルイミダゾール、
２−フェニル−４，５−ジヒドロキシメチルイミダゾー
ル、１−アジン−２−メチルイミダゾール等のイミダゾ
ール化合物、ジブチルチンジラウレート、１，３−ジア
セトキシテトラブチルジスタノキサン等の有機スズ化合
物、臭化テトラエチルアンモニウム、臭化テトラブチル
アンモニウム、塩化ベンジルトリエチルアンモニウム、
塩化トリオクチルメチルアンモニウム、臭化セチルトリ
メチルアンモニウム、ヨウ化テトラブチルアンモニウ
ム、ヨウ化ドデシルトリメチルアンモニウム、ベンジル
ジメチルテトラデシルアンモニウムアセテート、塩化テ
トラフェニルホスホニウム、塩化トリフェニルメチルホ
スホニウム、臭化テトラメチルホスホニウム等の四級オ
ニウム塩、３−メチル−１−フェニル−２−ホスフォレ
ン−１−オキシド等の有機リン化合物、安息香酸ナトリ
ウム、安息香酸カリウム等の有機酸アルカリ金属塩、塩
化亜鉛、塩化鉄、塩化リチウム、臭化リチウム等の無機
塩、オクタカルボニル二コバルト（コバルトカルボニ
ル）等の金属カルボニル化合物、テトラブトキシチタン
等の金属エーテル化合物などが挙げられる。これらの触
媒は、単独でまたは二種以上組合せて用いることができ
る。これらの触媒の使用量は、反応系の固形分に対して
０．０１〜１０重量％程度である。In the production of the epoxy-modified polyethylene resin of the present invention, a catalyst can be used if necessary. The catalyst is not particularly limited and includes, for example, triethylamine, triethylenediamine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N, N'-dimethylpiperazine, pyridine, picoline, 1,8-diazabicyclo [5,4
0] tertiary amines such as undecene-7, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-
Cyanoethyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole,
Imidazole compounds such as 2-phenyl-4,5-dihydroxymethylimidazole and 1-azine-2-methylimidazole; organic tin compounds such as dibutyltin dilaurate and 1,3-diacetoxytetrabutyldistannoxane; tetraethylammonium bromide , Tetrabutylammonium bromide, benzyltriethylammonium chloride,
Tetraoctylmethylammonium chloride, cetyltrimethylammonium bromide, tetrabutylammonium iodide, dodecyltrimethylammonium iodide, benzyldimethyltetradecylammonium acetate, tetraphenylphosphonium chloride, triphenylmethylphosphonium chloride, tetramethylphosphonium bromide, etc. Organic onium salts such as quaternary onium salts, 3-methyl-1-phenyl-2-phospholene-1-oxide, alkali metal salts of organic acids such as sodium benzoate and potassium benzoate, zinc chloride, iron chloride, lithium chloride, odor Inorganic salts such as lithium chloride; metal carbonyl compounds such as octacarbonyldicobalt (cobaltcarbonyl); and metal ether compounds such as tetrabutoxytitanium. These catalysts can be used alone or in combination of two or more. The use amount of these catalysts is about 0.01 to 10% by weight based on the solid content of the reaction system.
【００３２】本発明のエポキシ変性ポリエチレン系樹脂
の製造法では、本発明のエポキシ変性ポリエチレン系樹
脂が、通常、有機溶媒に微粒子状に均一かつ安定に分散
した分散液の状態で得られる。この樹脂分散液（樹脂製
造後の反応液）は、使用した有機溶媒を取り除くことな
く、そのまま塗料用、バッテリー用など各種用途のバイ
ンダ樹脂、接着剤などに利用できる。また、この樹脂分
散液には、必要に応じて製造に使用した有機溶媒以外の
有機溶媒、硬化剤、熱可塑性樹脂等を配合することもで
きる。In the process for producing the epoxy-modified polyethylene resin of the present invention, the epoxy-modified polyethylene resin of the present invention is usually obtained in the form of a dispersion liquid which is uniformly and stably dispersed in fine particles in an organic solvent. This resin dispersion (reaction liquid after resin production) can be used as it is for binder resins and adhesives for various uses such as for paints and batteries without removing the used organic solvent. In addition, an organic solvent other than the organic solvent used in the production, a curing agent, a thermoplastic resin, and the like can be added to the resin dispersion as needed.
【００３３】[0033]
【実施例】以下、実施例により本発明を説明するが、本
発明はこれに限定されるものではない。The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【００３４】実施例１ 撹拌機、温度計、冷却管及び窒素ガス導入管を装備した
０．５リットルのセパラブルフラスコ内に、窒素雰囲気
下、（Ａ）成分として一般式（ΙΙΙ）Example 1 In a 0.5-liter separable flask equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen gas introducing pipe, under a nitrogen atmosphere, the general formula (Ａ)
【００３５】[0035]
【化８】 で表されるエチレン−メタクリル酸共重合体（アルドリ
ッチカタログ１９９８−１９９９、コード番号４２６６
３−６）１９．３５１ｇ（０．６２０モル）及び有機溶
媒としてＮ−メチル−２−ピロリドン２７０．０ｇ（関
東化学（株）製、脱水グレード）を仕込み、１５０℃に
昇温後、同温度で１時間保温して均一溶液を調製した。Embedded image Ethylene-methacrylic acid copolymer represented by the following formula (Aldrich Catalog 1998-1999, code number 4266)
3-6) 19.351 g (0.620 mol) and 270.0 g of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd., dehydration grade) as an organic solvent were charged, and the temperature was raised to 150 ° C. For 1 hour to prepare a homogeneous solution.
【００３６】次いで、１５０℃保温下の上記溶液に、
（Ｂ）成分としてフェニルグリシジルエーテル（和光純
薬工業（株）製、試薬一級グレード）４．６５５ｇ
（０．０３１モル）及びＮ−メチル−２−ピロリドン
６．１ｇを添加し、同温度で２時間保温して（Ａ）成分
と（Ｂ）成分の反応を完結させた。反応液の冷却過程で
樹脂の結晶化により樹脂が反応液中に微粒子状に析出
し、常温まで冷却すると、一般式（ΙＶ）Next, the above solution kept at a temperature of 150 ° C.
4.655 g of phenylglycidyl ether (first grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) as the component (B)
(0.031 mol) and 6.1 g of N-methyl-2-pyrrolidone were added, and the mixture was kept at the same temperature for 2 hours to complete the reaction between the components (A) and (B). During the cooling of the reaction solution, the resin precipitates in the reaction solution in the form of fine particles due to crystallization of the resin.
【００３７】[0037]
【化９】 で表される本発明のエポキシ変性ポリエチレン系樹脂が
最終的にＮ−メチル−２−ピロリドンに微粒子状に均一
に分散した分散液の状態で得られた。このエポキシ変性
ポリエチレン系樹脂のメルトフローレート（ＪＩＳ Ｋ
６７６０）は２３ｇ／１０ｍｉｎであった。Embedded image Was finally obtained in the form of a dispersion liquid in which the epoxy-modified polyethylene resin of the present invention represented by the formula (1) was uniformly dispersed in N-methyl-2-pyrrolidone in the form of fine particles. The melt flow rate of this epoxy-modified polyethylene resin (JIS K
6760) was 23 g / 10 min.
【００３８】実施例２ （Ｂ）成分としてグリシジルフタルイミド（ナガセ化成
工業（株）製、商品名デナコールＥＸ−７３１、エポキ
シ当量２２５）６．９７５ｇ（０．０３１モル）を用い
る以外は実施例１と同様な操作で、一般式（Ｖ）Example 2 The procedure of Example 1 was repeated except that 6.975 g (0.031 mol) of glycidyl phthalimide (Denacol EX-731, trade name: 225, epoxy equivalent, manufactured by Nagase Kasei Kogyo KK) was used as the component (B). By the same operation, the general formula (V)
【００３９】[0039]
【化１０】 で表される本発明のエポキシ変性ポリエチレン系樹脂を
Ｎ−メチル−２−ピロリドンに微粒子状に均一に分散し
た分散液の状態で得た。このエポキシ変性ポリエチレン
系樹脂のメルトフローレート（ＪＩＳ Ｋ ６７６０）
は２２ｇ／１０ｍｉｎであった。Embedded image Was obtained in the form of a dispersion liquid in which the epoxy-modified polyethylene resin of the present invention represented by the formula (1) was uniformly dispersed in N-methyl-2-pyrrolidone in the form of fine particles. Melt flow rate of this epoxy-modified polyethylene resin (JIS K 6760)
Was 22 g / 10 min.
【００４０】実施例３ （Ｂ）成分としてｐ−ｔ−ブチルフェニルグリシジルエ
ーテル（ナガセ化成工業（株）製、商品名デナコールＥ
Ｘ−１４６、エポキシ当量２２６）７．００６ｇ（０．
０３１モル）を用いる以外は実施例１と同様な操作で、
一般式（ＶΙ）Example 3 As a component (B), pt-butylphenylglycidyl ether (Denacol E, trade name, manufactured by Nagase Kasei Kogyo Co., Ltd.)
X-146, epoxy equivalent 226) 7.006 g (0.
031 mol) in the same manner as in Example 1, except that
General formula (VΙ)
【００４１】[0041]
【化１１】 で表される本発明のエポキシ変性ポリエチレン系樹脂を
Ｎ−メチル−２−ピロリドンに微粒子状に均一に分散し
た分散液の状態で得た。このエポキシ変性ポリエチレン
系樹脂のメルトフローレート（ＪＩＳ Ｋ ６７６０）
は２４ｇ／１０ｍｉｎであった。Embedded image Was obtained in the form of a dispersion liquid in which the epoxy-modified polyethylene resin of the present invention represented by the formula (1) was uniformly dispersed in N-methyl-2-pyrrolidone in the form of fine particles. Melt flow rate of this epoxy-modified polyethylene resin (JIS K 6760)
Was 24 g / 10 min.
【００４２】比較例１ 実施例１において調製した１５０℃保温下の（Ａ）成分
の均一溶液を、（Ｂ）成分と反応させずにそのまま冷却
した。系の冷却過程で（Ａ）成分の結晶化により（Ａ）
成分が系中に微粒子状に析出し、常温まで冷却すると、
結晶化の進行により凝集・沈降した（Ａ）成分が最終的
にＮ−メチル−２−ピロリドンに不溶な塊状物の状態で
得られ、含窒素系溶剤（Ｎ−メチル−２−ピロリドン）
には分散不能であった。Comparative Example 1 The homogeneous solution of the component (A) prepared in Example 1 while keeping the temperature at 150 ° C. was cooled without reacting with the component (B). During the cooling of the system, (A)
The components precipitate in the form of fine particles in the system, and when cooled to room temperature,
The component (A) that has aggregated and precipitated due to the progress of crystallization is finally obtained in the form of a mass insoluble in N-methyl-2-pyrrolidone, and is contained in a nitrogen-containing solvent (N-methyl-2-pyrrolidone).
Could not be dispersed.
【００４３】実施例１〜３で得たエポキシ変性ポリエチ
レン系樹脂（本発明品）のＮ−メチル−２−ピロリドン
分散液を２０ｃｃサイズのスクリュー管容器に半分程入
れて２３℃で７２時間静置した後、容器内の底部の分散
液をスパチユラでかき混ぜ、本発明品の含窒素系溶剤
（Ｎ−メチル−２−ピロリドン）への分散安定性を調べ
た。含窒素系溶剤への分散安定性は、スパチユラによる
触診で樹脂の凝集・沈降が全く認められない場合を良
好、樹脂の凝集・沈降が認められる場合を不良と判定し
た。About half of the N-methyl-2-pyrrolidone dispersion of the epoxy-modified polyethylene resin (product of the present invention) obtained in Examples 1 to 3 was placed in a 20 cc screw tube vessel and allowed to stand at 23 ° C. for 72 hours. After that, the dispersion at the bottom in the container was stirred with a spatula, and the dispersion stability of the product of the present invention in a nitrogen-containing solvent (N-methyl-2-pyrrolidone) was examined. The dispersion stability in a nitrogen-containing solvent was determined to be good when no agglomeration or sedimentation of the resin was observed by palpation with a spatula, and poor when agglutination or sedimentation of the resin was observed.
【００４４】また、実施例１〜３で得た本発明品のＮ−
メチル−２−ピロリドン分散液に代表的な結晶性熱可塑
性樹脂であるポリフッ化ビニリデン（略称ＰＶＤＦ、呉
羽化学工業（株）製、商品名ＫＦポリマ＃１１２０、バ
ッテリー用バインダ樹脂グレード、ＮＶ１２％Ｎ−メチ
ル−２−ピロリドン溶液）を両者が樹脂分換算で等重量
比となるように配合し、ブレンド液を調製した。In addition, N- of the product of the present invention obtained in Examples 1 to 3
Polyvinylidene fluoride (abbreviation: PVDF, manufactured by Kureha Chemical Industry Co., Ltd., trade name: KF polymer # 1120, binder resin grade for battery, NV12% N-), which is a crystalline thermoplastic resin representative of methyl-2-pyrrolidone dispersion Methyl-2-pyrrolidone solution) was blended so that the two had an equal weight ratio in terms of resin content to prepare a blended liquid.
【００４５】次いで、各ブレンド液を、乾燥膜厚が約２
０μｍとなるように、軟質ガラス板上に均一に流延した
後、８０℃で１時間常圧乾燥し、得られた塗膜の外観を
観察して、他材料（ＰＶＤＦ）との相溶性を調べた。他
材料との相溶性は、肉眼で塗膜表面にはじき、むら、し
わ等の外観不良がほとんど観察されない場合を良好、外
観不良が顕著に観察される場合を不良と判定した。Next, each of the blended liquids was dried to a dry film thickness of about 2
After casting uniformly on a soft glass plate so as to have a thickness of 0 μm, the film was dried under normal pressure at 80 ° C. for 1 hour, and the appearance of the obtained coating film was observed to confirm compatibility with another material (PVDF). Examined. Compatibility with other materials was judged as good when the appearance defects such as repelling, unevenness and wrinkles were hardly observed with the naked eye, and as poor when the appearance defects were remarkably observed.
【００４６】また、実施例１〜３で得た本発明品のＮ−
メチル−２−ピロリドン分散液を、乾燥膜厚が約２０μ
ｍとなるように、銅板（（株）ニラコ製、商品名ＣＵ−
１１３４６８、０．５ｍｍ厚）上に均一に流延した後、
８０℃で１時間常圧乾燥し、次いで、１５０℃で３時間
減圧乾燥させて片面銅板付き樹脂塗膜を得た。この塗膜
について、まず、ＪＩＳ Ｄ ０２０２に準じ、碁盤目
試験を行い、初期の銅板との接着維持率（１００個の１
ｍｍ角クロスカットパターンのうちセロテープ剥離試験
で剥離しなかった碁盤目の維持率）を調べた。次いで、
碁盤目試験後の樹脂塗膜を薬品（１Ｍ−六フッ化リン酸
リチウム含有エチレンカーボネート／ジメチルカーボネ
ート＝１／２（容積比）混合液、キシダ化学（製）、バ
ッテリー用電解液グレード）に浸漬し、これを５０℃の
恒温槽中に７２時間密閉保管した後、薬品中から取り出
した樹脂塗膜について、肉眼で数えた薬品浸漬後の銅板
との接着維持率を調べた。接着性は、初期の銅板との接
着維持率、薬品浸漬後の銅板との接着維持率が共に１０
０％である場合を良好、初期の銅板との接着維持率、薬
品浸漬後の銅板との接着維持率のいずれか一方でも１０
０％未満である場合を不良と判定した。In addition, N- of the product of the present invention obtained in Examples 1 to 3
The methyl-2-pyrrolidone dispersion was dried to a thickness of about 20 μm.
m, copper plate (manufactured by Nilaco Co., Ltd., trade name CU-
(11468, 0.5 mm thick)
After drying at 80 ° C. for 1 hour under normal pressure, and then drying at 150 ° C. for 3 hours under reduced pressure, a resin coating film with a copper plate on one side was obtained. First, a cross-cut test was performed on this coating film in accordance with JIS D0202, and the initial adhesion maintenance ratio with the copper plate (100 1
The cross-cut pattern of the mm-square pattern was checked for the percentage of crosscuts that were not peeled off in the cellophane tape peeling test. Then
The resin coating film after the grid test is immersed in a chemical (1M-lithium hexafluorophosphate-containing ethylene carbonate / dimethyl carbonate = 1/2 (volume ratio) mixed solution, Kishida Chemical Co., Ltd., battery electrolyte grade) Then, this was sealed and stored in a thermostat at 50 ° C. for 72 hours, and then, the resin coating film taken out of the chemical was examined with the naked eye for the adhesion retention ratio with the copper plate after the chemical immersion. The adhesiveness was as follows: both the initial adhesion retention rate with the copper plate and the adhesion retention rate with the copper plate after chemical immersion were 10
0% is good, and either one of the initial adhesion maintenance ratio with the copper plate and the adhesion maintenance ratio with the copper plate after chemical immersion is 10%.
When it was less than 0%, it was determined to be defective.
【００４７】これらの結果をまとめて表１に示す。The results are summarized in Table 1.
【００４８】[0048]
【表１】 以上の結果から、本発明のエポキシ変性ポリエチレン系
樹脂は、他材料との相溶性、接着性に優れ、かつ、比較
用樹脂では得られない優れた含窒素系溶剤への分散安定
性を有していることが分かる。[Table 1] From the above results, the epoxy-modified polyethylene resin of the present invention has excellent compatibility with other materials, excellent adhesiveness, and has excellent dispersion stability in nitrogen-containing solvents that cannot be obtained with the comparative resin. You can see that it is.
【００４９】[0049]
【発明の効果】本発明のエポキシ変性ポリエチレン系樹
脂は、含窒素系溶剤への分散安定性に優れ、かつ、他材
料との相溶性、接着性が良好である。The epoxy-modified polyethylene resin of the present invention has excellent dispersion stability in a nitrogen-containing solvent, and has good compatibility and adhesion with other materials.
【００５０】本発明のエポキシ変性ポリエチレン系樹脂
の製造法は、含窒素系溶剤への分散安定性に優れ、か
つ、他材料との相溶性、接着性の良好なエポキシ変性ポ
リエチレン系樹脂を製造できる。According to the method for producing an epoxy-modified polyethylene resin of the present invention, an epoxy-modified polyethylene resin having excellent dispersion stability in a nitrogen-containing solvent and having good compatibility and adhesion with other materials can be produced. .
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中澤 哲 茨城県日立市東町四丁目13番１号 日立化 成工業株式会社総合研究所内 (72)発明者 栗原 美穂 茨城県日立市東町四丁目13番１号 日立化 成工業株式会社総合研究所内 Ｆターム(参考） 4J100 AA02P AJ02Q BA02H BA03H BB03H BC04H BC12H BC43H BC66H CA04 CA31 DA43 HA61 HA62 HB29 HC27 HC39 HC43 HC45 HC63 HC75 HC85 HC88 HE14 HE32 JA01 JA03 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Satoshi Nakazawa 4-3-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside Hitachi Chemical Co., Ltd. (72) Inventor Miho Kurihara 4--13 Higashicho, Hitachi City, Ibaraki Prefecture No. 1 F term in Hitachi Chemical Co., Ltd. Research Laboratory 4J100 AA02P AJ02Q BA02H BA03H BB03H BC04H BC12H BC43H BC66H CA04 CA31 DA43 HA61 HA62 HB29 HC27 HC39 HC43 HC45 HC63 HC75 HC85 HC88 HE14 HE32 JA01 JA03
Claims (6)
キシ化合物残基を表す一価の有機基を示す）で表される
ユニットを有するエポキシ変性ポリエチレン系樹脂。At least a compound represented by the general formula (Ι): And a unit represented by the general formula (ΙΙ) (Wherein, R 1 represents hydrogen or a methyl group, and R 2 represents a monovalent organic group representing a monoepoxy compound residue).
ポキシ変性ポリエチレン系樹脂。2. The epoxy-modified polyethylene resin according to claim 1, wherein R 1 is a methyl group.
物残基である請求項１又は２記載のエポキシ変性ポリエ
チレン系樹脂。3. The epoxy-modified polyethylene resin according to claim 1, wherein R 2 is a residue of a monoepoxy compound having an aromatic ring.
レン系樹脂と（Ｂ）モノエポキシ化合物とを、（Ａ）成
分中のカルボキシル基１当量に対して、（Ｂ）成分中の
エポキシ基が１当量以下となるような割合で反応させる
ことを特徴とするエポキシ変性ポリエチレン系樹脂の製
造法。4. A method according to claim 1, wherein (A) a polyethylene resin having a carboxyl group and (B) a monoepoxy compound, wherein one equivalent of the carboxyl group in the component (A) has one equivalent of the epoxy group in the component (B). A method for producing an epoxy-modified polyethylene-based resin, characterized by reacting at the following ratio.
共重合体である請求項４記載のエポキシ変性ポリエチレ
ン系樹脂の製造法。5. The method according to claim 4, wherein the component (A) is an ethylene-methacrylic acid copolymer.
キシ化合物である請求項４又は５記載のエポキシ変性ポ
リエチレン系樹脂の製造法。6. The process for producing an epoxy-modified polyethylene resin according to claim 4, wherein the component (B) is a monoepoxy compound having an aromatic ring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26622699A JP2001089519A (en) | 1999-09-20 | 1999-09-20 | Epoxy-modified polyethylene resin and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26622699A JP2001089519A (en) | 1999-09-20 | 1999-09-20 | Epoxy-modified polyethylene resin and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001089519A true JP2001089519A (en) | 2001-04-03 |
Family
ID=17428030
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26622699A Pending JP2001089519A (en) | 1999-09-20 | 1999-09-20 | Epoxy-modified polyethylene resin and its production |
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| Country | Link |
|---|---|
| JP (1) | JP2001089519A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011096837A (en) * | 2009-10-29 | 2011-05-12 | Kaneka Corp | Back sheet for solar cell, and solar cell module |
| JP2011139022A (en) * | 2009-12-02 | 2011-07-14 | Kaneka Corp | Back sheet for solar cell and solar cell module |
| WO2017204312A1 (en) * | 2016-05-25 | 2017-11-30 | 日本ポリエチレン株式会社 | Olefin copolymer and method for preparing same |
-
1999
- 1999-09-20 JP JP26622699A patent/JP2001089519A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011096837A (en) * | 2009-10-29 | 2011-05-12 | Kaneka Corp | Back sheet for solar cell, and solar cell module |
| JP2011139022A (en) * | 2009-12-02 | 2011-07-14 | Kaneka Corp | Back sheet for solar cell and solar cell module |
| WO2017204312A1 (en) * | 2016-05-25 | 2017-11-30 | 日本ポリエチレン株式会社 | Olefin copolymer and method for preparing same |
| JP2017214561A (en) * | 2016-05-25 | 2017-12-07 | 日本ポリエチレン株式会社 | Olefin copolymer and method for producing the same |
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