JPH0364304A - New hydroxylated chlorinated ethylene-vinyl acetate copolymer and its preparation - Google Patents
New hydroxylated chlorinated ethylene-vinyl acetate copolymer and its preparationInfo
- Publication number
- JPH0364304A JPH0364304A JP20081689A JP20081689A JPH0364304A JP H0364304 A JPH0364304 A JP H0364304A JP 20081689 A JP20081689 A JP 20081689A JP 20081689 A JP20081689 A JP 20081689A JP H0364304 A JPH0364304 A JP H0364304A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl acetate
- acetate copolymer
- ethylene
- eva
- chlorinated ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005038 ethylene vinyl acetate Substances 0.000 title claims abstract description 38
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims abstract description 38
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 25
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 10
- 238000007127 saponification reaction Methods 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- 238000004581 coalescence Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000460 chlorine Substances 0.000 abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 6
- 239000000976 ink Substances 0.000 abstract description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- 239000013615 primer Substances 0.000 abstract 1
- 239000002987 primer (paints) Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000005026 oriented polypropylene Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はインク用、接着剤用、コーティング剤用、塗料
用、ポリプロピレン成型品等の種々なプライマー用又は
繊維類処理剤用等の用途に使用される水酸基含有塩素化
エチレン−酢酸ビニル系共重合体の製造法並びに該製造
法によって製造された新規な水酸基含有塩素化工ｔシン
−酢酸ビニル系共重合体に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention is applicable to various primers such as inks, adhesives, coatings, paints, polypropylene molded products, and fiber treatment agents. The present invention relates to a method for producing a hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer and a novel hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer produced by the method.
一般にエチレン−酢酸ビニル共重合体（ＥＶＡと略称）
を四塩化炭素などのそれ自メヘ素化されない有機溶媒中
に均一に溶解して塩素化すると塩素化エチレン−酢酸ビ
ニル共重合体（本発明ではＣＩ−ＥＶＡと略称）が得ら
れる。Generally ethylene-vinyl acetate copolymer (abbreviated as EVA)
A chlorinated ethylene-vinyl acetate copolymer (abbreviated as CI-EVA in the present invention) is obtained by uniformly dissolving and chlorinating the compound in an organic solvent which itself does not undergo mehelination, such as carbon tetrachloride.
ＣＩ−ＥｖＡを得る方法としてはこのほか反応速度を大
きくするために又は系全体の反応温度を低く抑えるため
に紫外線照射下で塩素化を行なう例もある。（特公昭５
Ｂ −２０９９０，特開昭４８−４７９’！。Other methods for obtaining CI-EvA include chlorination under ultraviolet irradiation in order to increase the reaction rate or to keep the reaction temperature of the entire system low. (Tokuko Showa 5
B-20990, JP-A-48-479'! .
特公昭４７−４６２０３）
上記の様にして非水系で塩素化して得られたＣ／−ＥＶ
Ａはポリマー分子中に塩素基、アセトキシ基などを含ん
だＣ／−ＥＶＡであるが、共重合体弁どのプライマー、
塗料、インキ組成物、繊維類などに広く使用されている
。(Japanese Patent Publication No. 47-46203) C/-EV obtained by chlorination in a non-aqueous system as described above
A is C/-EVA containing chlorine groups, acetoxy groups, etc. in the polymer molecule, but other primers such as copolymer valves,
Widely used in paints, ink compositions, textiles, etc.
これらの用途は何れもポリプロピレン系樹脂等の無極性
ポリマーに対する良好な付着性、優れた耐熱性、耐候性
、対薬品性に起因するものである。All of these uses are due to good adhesion to nonpolar polymers such as polypropylene resins, excellent heat resistance, weather resistance, and chemical resistance.
応性官能基を有しないため架橋反応を行なわしめること
は不可能であυ、またインク用又は塗料用などの顔料あ
るいはフィラーなどの有機系又は無機系物質に対する親
和性や分散性には自ずから限度があった。Since it does not have a reactive functional group, it is impossible to carry out a crosslinking reaction, and there is a natural limit to its affinity and dispersibility for organic or inorganic substances such as pigments or fillers for inks or paints. there were.
そのため従来のＣ／−ＥＶＡは芳香族石油ｌ！１脂など
の他のＶ！Ｊ１］！とのブレンドを行なうことによシ塗
膜硬度、スプレー性の改善などが行ｉわれでいた。Therefore, conventional C/-EVA is an aromatic oil l! 1 Other V such as fat! J1]! By blending with the paint, the hardness of the coating film and the sprayability were improved.
しかしながらこれらはすべて混合系であるため長期間紫
外線などのエネルギーにば〈露すると可塑剤等が離脱し
て塗膜が脆くなり１やかて亀裂などが生じ表面保ａｍ能
を失いがちである。However, since these are all mixed systems, if they are exposed to energy such as ultraviolet rays for a long period of time, plasticizers and the like will be removed and the coating film will become brittle, 1 and eventually crack, etc., and tend to lose its surface retaining ability.
本発明は上記の点に着目し、Ｃ／−ＥＶＡ分子内に水酸
基を含有せしめることによう他の無機材料又は有機材料
との親和性を向上させると同時に、反応性官能基を有し
、例えばイソシアネートと反応させることによってポリ
ウレタン系Ｃ／−ＥＶＡとして高分子設計上任意のデザ
インを可能ならしめるポリマー素材の開発ができるよう
になる新規な共重合分子内に水酸基を含有したＣ／−Ｅ
ＶＡ及びその製造法を提供することを目的とするもので
ある。The present invention focuses on the above points, and improves the affinity with other inorganic materials or organic materials by including a hydroxyl group in the C/-EVA molecule, and at the same time, it has reactive functional groups, such as By reacting with isocyanate, it is possible to develop a polymer material that enables arbitrary polymer design as polyurethane-based C/-EVA.C/-E containing hydroxyl groups in the new copolymer molecule.
The purpose of this invention is to provide VA and its manufacturing method.
本発明はＥＶＡなどを塩素系有機溶剤及び水の存在下で
塩素化反応と同時にケン化反応を行なわしめて水酸基含
有ｃｔ −ＥｖＡを製造する方法並びにかくして得られ
た新規な分子内に水酸基を含有するＣ／−ＥＶＡに関す
るものである。The present invention relates to a method for producing hydroxyl group-containing ct-EvA by subjecting EVA or the like to a chlorination reaction and saponification reaction in the presence of a chlorinated organic solvent and water, and a method for producing ct-EvA containing a hydroxyl group in the novel molecule thus obtained. This relates to C/-EVA.
本発明に使用されるＥＶＡはエチレンと酢酸ビニルとの
共重合体でＥＶＡ １００重量澤に対してエチレン成分
が９５〜５重量部、酢酸ビニル成分がＳ〜９５重ｔｇ６
のものであシ、これらから得られたＣ／−ＥＶＡの塩素
含有量は５〜５０重量％まで塩素化したものであう、同
時にケン化度がｏ、ｉ〜９Ｓ重量％壕でケン化したもの
である。The EVA used in the present invention is a copolymer of ethylene and vinyl acetate, and the ethylene component is 95 to 5 parts by weight and the vinyl acetate component is S to 95 parts by weight per 100 parts by weight of EVA.
The chlorine content of C/-EVA obtained from these is likely to be chlorinated to 5 to 50% by weight, and at the same time, the degree of saponification is o, i to 9S by weight. It is.
本発明の水酸基含有（’／ＥＶＡには水酸基含有塩素化
エチレン−酢酸ビニルのほか、加水分解し得るエチレン
系ポリマー例えばエチレン−酢酸ビゝ？′
ニル−Ａｔｎ化炭素共重合物などのターポリマー更に部
分鹸化ＥＶＡも含まれる。酢酸ビニル（又は本発明に含
まれるコモノマー）の含有量を上記５〜９５重量％とし
たのは５９６未満ではポリエチレンの性質に近くなシ、
ケン化及び塩素化を行なって上水酸基の導入量が少なく
、本発明の目的を達成するのが困賭であり、逆に酢酸ビ
ニル含有量が９ｓ９６を超過するとポリ酢酸ビニルの性
質が強くなって、例えばポリプロピレン系樹脂への密着
性が劣るようになる。In addition to hydroxyl group-containing chlorinated ethylene-vinyl acetate, the hydroxyl group-containing ('/EVA) of the present invention may include terpolymers such as hydrolyzable ethylene polymers such as ethylene-vinyl acetate-Atnized carbon copolymers. Partially saponified EVA is also included.The reason why the content of vinyl acetate (or the comonomer included in the present invention) is set to 5 to 95% by weight is that if it is less than 596%, the properties are close to that of polyethylene.
It is difficult to achieve the purpose of the present invention by saponification and chlorination because the amount of introduced hydroxyl groups is small, and conversely, when the vinyl acetate content exceeds 9s96, the properties of polyvinyl acetate become stronger. For example, adhesion to polypropylene resins becomes poor.
次に実施例によって本発明を説明する。 Next, the present invention will be explained by examples.
実施例１
零発１１１Ｏ０Ｈ基含有Ｃ／−ＥＶＡは原料ＥＶＡ７５
ｇを耐塩素系溶剤例えば四塩化炭素又はパークレン又は
トリクレン等の溶剤ｓｏｏ ｌに溶解した後、水７５ｆ
ｔｍ／を加えて均−又は不均一に塩素含有量が５〜ＳＯ
＠量％になるまで塩素ガスを吹込んで塩素化した後空気
又は窒素で、残留する未反応の塩素を脱気させ％た０、
５〜５ Ｋｇ／ｃｓ”Ｇの水蒸気を吹込んで溶剤を追出
すか、又は脱溶剤装置によってベレット化するか又は塩
素系溶剤をトルエン、キシレン等の汎用溶剤と置換して
均一溶液として得られる、脱溶剤して本発明の水酸基含
有Ｃ／−ＥＶＡ １０３９が得られ、収率はＥＶＡに対
して９９１１であった。Example 1 Zero-source 111O0H group-containing C/-EVA is raw material EVA75
After dissolving g in a chlorine-resistant solvent such as carbon tetrachloride or a solvent such as perchlorene or trichlene, 75f of water is dissolved.
tm/ to uniformly or non-uniformly increase the chlorine content from 5 to SO
After chlorinating by blowing chlorine gas until the amount becomes %, degas the remaining unreacted chlorine with air or nitrogen.
A homogeneous solution can be obtained by expelling the solvent by blowing in 5 to 5 Kg/cs"G of water vapor, or by pelletizing it with a solvent removal device, or by replacing the chlorinated solvent with a general-purpose solvent such as toluene or xylene. The hydroxyl group-containing C/-EVA 1039 of the present invention was obtained by removing the solvent, and the yield was 9911 based on EVA.
上記塩素系反応は８０〜１５０℃で行ない得られるが、
好筐しくは９０〜１２０℃である。あｄ！、シに温度が
低すぎると塩素化の反応速度及びケン化の反応速度が小
さくなり、−ｔ’九反面温度を上げすぎると塩素化及び
ケン化の反応速度が大きく々シ、場合によっては一旦塩
素化されたポリマーが局部加熱によう脱塩＠を起し、黒
化するので上記適正温度範囲に保つのがよい。The above chlorine-based reaction is obtained by performing it at 80 to 150°C,
Preferably, the temperature is 90 to 120°C. Ad! However, if the temperature is too low, the chlorination reaction rate and saponification reaction rate will decrease, and if the temperature is too high, the chlorination and saponification reaction rate will increase, and in some cases, the reaction rate of chlorination and saponification will decrease. Since chlorinated polymers undergo desalination and blackening when locally heated, it is best to maintain the temperature within the above-mentioned appropriate temperature range.
な訃塩素ガスの吹込みは徐々に行ない、吹込量は大きく
しない方が、局部加熱による脱塩酸を避けるために必要
である。It is necessary to gradually introduce chlorine gas and not to increase the amount of chlorine gas in order to avoid dehydrochlorination due to local heating.
本発明の方法によって得られた新規の水酸基含有塩素化
エチレン酢酸共重合体の特性は、主として導入された水
酸基によるものである。水の非共存下で得られたＣＩ−
ＥＶＡと上記本発明の方法によって得られた水酸基含有
Ｃ／−ＥＶＡとの特性を下記に比較する。The properties of the novel hydroxyl group-containing chlorinated ethylene acetic acid copolymer obtained by the method of the present invention are mainly due to the introduced hydroxyl groups. CI- obtained in the absence of water
The characteristics of EVA and the hydroxyl group-containing C/-EVA obtained by the method of the present invention will be compared below.
＋１１ 赤外線吸収特性（ＩＲ）
図１ ？ ３ ？ ｓ ＊ ’ Ｋ 本発明ノ水酸基含
有Ｃ／−ＥＶＡ（以下新規ポリマーという）のＩＲｆヤ
ードを、図−２゜４に従来の非水系反応によって得られ
た水酸基を含有し＆いＣ／−ＥＶＡ（単に従来（７）Ｃ
１−１，ｖＡという）のＩＲチャートを示した。+11 Infrared absorption characteristics (IR) Figure 1 ? 3? s*'K The IRf yard of the hydroxyl group-containing C/-EVA (hereinafter referred to as the new polymer) of the present invention is shown in Figure 2゜4. Simply conventional (7)C
1-1, vA) is shown.
図−１，３，５，６より本発明の新規ポリマーには３２
００〜３６００ ａｓｓ−’に何れもＯＨ基の吸収が認
められる。一方従来のＣ／−ＥＶＡの比較物質にはＯＨ
基の吸収が認められない。From Figures 1, 3, 5, and 6, the novel polymer of the present invention has 32
00 to 3600 ass-', absorption of OH groups is observed in all cases. On the other hand, the conventional C/-EVA comparison material has OH
No absorption of groups is observed.
更に表−１にＩＲ測宛試料について、本発明の新規ポリ
マーと比較物質、従来のＣ１−ＥＶＡについてその性質
を比較した。Furthermore, Table 1 compares the properties of the novel polymer of the present invention, a comparative substance, and conventional C1-EVA for IR measurement samples.
１）ケン化法によシ行った。1) The saponification method was used.
り ＭＹは光散乱法で、ＭＮは浸透圧法で求めた。MY was determined by a light scattering method, and MN was determined by an osmotic pressure method.
３）クロロホルムを移動相とし、ゲル浸透クロマトグラ
フィー（ＧＰＣ）で測定した。3) Measurement was performed by gel permeation chromatography (GPC) using chloroform as a mobile phase.
カラムは５ｈｏｄｅｘ ＧＰＣＡＣ−８０４，ｓｏ３．
８０２．５（商品名）を連結して用いた。検量線は標準
ポリスチレンの各ＭＷ＝ ２３３，０００．９２，６０
０．１９．０００．９，０００．２，１００及び８００
を用いて作製した。The column was 5hodex GPCAC-804, so3.
802.5 (trade name) was used in combination. The calibration curve is for each MW of standard polystyrene = 233,000.92,60
0.19.000.9,000.2,100 and 800
It was created using
４） ＪＩＳ Ｋ −６７３０Ｋ準シテ、塩素化ＥＶ
Ａを０．２〜０．５ｇ精秤し、キシレン１００ ｍｌに
溶解させた後、０．２Ｎ−ＮａＯＨメタノール溶液６０
ｍ１を加え、加水分解を完全に行なわしめ、水層／油層
を分液し、０．４８−ＨＣ１水溶液３０ｍ１を加え、フ
リーの酢酸分を定量する。4) JIS K-6730K quasi-cite, chlorinated EV
Precisely weigh 0.2 to 0.5 g of A, dissolve it in 100 ml of xylene, and add 60 g of 0.2N-NaOH methanol solution.
ml to complete hydrolysis, separate the aqueous and oil layers, add 30 ml of 0.48-HC1 aqueous solution, and quantify the free acetic acid content.
をトルエン溶液として再溶解させた状態からキャストフ
ィルムとしたものを用いた。A cast film was prepared by re-dissolving it as a toluene solution.
（り水酸基価
表−１よシ明かなように比較物質（従来のＣ／−ＥＶＡ
）は何れも水酸基価が０なのに対して、本発明の新規ポ
リマーは２０〜ｒｚ ＫＯＨｍｆｌｇの水酸基価を有す
ることがわかる。(As is clear from Hydroxyl Value Table-1, comparative materials (conventional C/-EVA)
) has a hydroxyl value of 0, whereas the novel polymer of the present invention has a hydroxyl value of 20 to rz KOHmflg.
（３） 核磁気共鳴（プロトンＮＭＲ）本発明の新規
ポリマー（表−１物質属４）についてのＮＭＲｆで一ト
を図−７に示した本発明の新規ポリマー 表−１の戚１
〜３のＮＭＲチャートは各ピークの面積比が異なるのみ
で基本的には図−７と大差はない。なお溶媒はＣＤＣｌ
３を、また内部標準としてはベンゼンを使用した。(3) Nuclear magnetic resonance (proton NMR) NMRf of the novel polymer of the present invention (Table 1 Substance Group 4) is shown in Figure 7. New polymer of the present invention Relative 1 of Table 1
The NMR charts of ~3 differ only in the area ratio of each peak, and are basically not much different from Figure 7. Note that the solvent is CDCl
3 and benzene was used as an internal standard.
（４）対溶剤、溶解特性
本発明の新規ポリマー１，２（表−１）を相当する比較
物質（従来のＣ１−ＥＶＡ ） ＋１）、＋２＋ ト対
比する形で溶剤のＳ 値（品、Ω）を用いて整理した結
果を表−２、表−３及び図８〜１１に示した。(4) Solvent resistance and solubility characteristics The novel polymers 1 and 2 (Table 1) of the present invention are compared with the corresponding comparative substance (conventional C1-EVA) +1), +2+. ) The results are shown in Table 2, Table 3, and Figures 8 to 11.
（測定方法）
ｓ ｏ ｍｆｌのポリマー（乾燥）とｔ、ｏＩＩの溶媒
をアンプル中に封入し一晩膨潤させた後、１３０℃のオ
イルバス中で１時間放置し、以後ｉｏｏ℃になってから
１時間、更に２５℃でｘＷＦＰ間、かつ冷凍機を使用し
て１０℃で１時間それぞ上記図−８〜図−１０よシ木発
明の新規ポリマーは比較物質（従来の０ｆ−ＥＶＡ）に
比較して Ｇの溶解領域がやや高い方に存在することが
わかる。(Measurement method) The polymer (dry) of s o mfl and the solvent of t and oII were sealed in an ampoule and allowed to swell overnight, then left in an oil bath at 130°C for 1 hour, and after the temperature reached ioo°C. 1 hour, then xWFP at 25℃ and 1 hour at 10℃ using a refrigerator, respectively, as shown in Figures 8 to 10 above. By comparison, it can be seen that the solubility region of G exists on the slightly higher side.
これはポリマー中に導入されたＯＨの効果によるもので
ある。図−８，９，１０，１１共に、ポリマー／溶媒＝
６（重置）／１０Ｇ（重ｆｆ１）とした。This is due to the effect of OH introduced into the polymer. Figure-8, 9, 10, 11, polymer/solvent =
6 (overlapping)/10G (overlapping ff1).
１６１ メルトフローレー） （ＭＦＲ）本発明のＯ
Ｈ含有Ｃ１−ＥＶＡのメルトフローレー）（ＭＦＲ）を
ＡＳＴＭ−Ｄ−１２３８−５７Ｔに基いて測定した。測
定結果を表−１に示した。161 Melt Flow Ray) (MFR) O of the present invention
The melt flow rate (MFR) of H-containing C1-EVA was measured based on ASTM-D-1238-57T. The measurement results are shown in Table-1.
メルトフローレートがｘＪｉ＋／１ｏ分以下になると有
機溶剤に対する溶解性が悪くなｉ、５００Ｊ９／１０分
以上になると分子量が小さくなシすぎ接着剤やコーティ
ング剤としての実用に耐えなくなる。When the melt flow rate is less than xJi+/10 minutes, the solubility in organic solvents becomes poor, and when it is more than 500J9/10 minutes, the molecular weight is too small to be used as an adhesive or coating agent.
１！−ｚ 各温度にかける新規ポリマーの対溶剤溶解
性９：分散成分溶解性パラメーター
５：ＦＭ性力成分溶解性パラメーター
５＝水素結合力成分溶解性パラメーターｆｄ：分散力成
分溶解性パラメーター
ｌ：￥′ｐ ：極性力成分溶解性パラメーターｆｈ＝水
素結合力成分溶解性パラメーター表−３各湯度にお・け
る新規ポリマーの対溶剤溶解比〔発明の効果〕
本発明の効果を纒めると次の通りである。1! -z Solvent solubility of the new polymer applied to each temperature 9: Dispersion component solubility parameter 5: FM force component solubility parameter 5 = Hydrogen bond force component solubility parameter fd: Dispersion force component solubility parameter l: ¥' p: Polar force component solubility parameter fh=Hydrogen bond force component solubility parameter Table-3 Solubility ratio of the new polymer to solvent at each hot water temperature [Effects of the invention] The effects of the present invention are summarized as follows. That's right.
（１）本発明の新規ｔｏｎＯＨ基含有、１−ＥＶＡはそ
の含有するＯＨ基に起因する良好な耐溶解性を生かして
例えば自動車バンパーのプライマーなどの自動車塗料、
ＯＨ基含有による無機質顔料との良好な親和性に起因す
る優れた発色性を持つインキ組成物、機料、各種のプラ
イマーや繊維処理用などに広く利用することができる。(1) The novel tonOH group-containing 1-EVA of the present invention takes advantage of its good dissolution resistance due to the OH group it contains, and is used in automobile paints, such as primers for automobile bumpers, etc.
It can be widely used in ink compositions, materials, various primers, fiber treatments, etc., which have excellent color development properties due to good affinity with inorganic pigments due to the OH group content.
（１１） 接着特性 表−４に本発明の新規ポリマ−・の接着特性を示した。(11) Adhesive properties Table 4 shows the adhesive properties of the new polymer of the present invention.
表−４より本発明の新規ポリマーは対ＯＰＰ密着性、０
ＰＰ１０ＰＰ剥離強度について何れも比較物質として使
用した従来のＣＩ！ −ＥＶＡを土建る性能を有するこ
とがわかる。From Table 4, the novel polymer of the present invention has an adhesion to OPP of 0.
Conventional CI used as a comparison material for PP10PP peel strength! - It can be seen that it has the performance of building EVA.
表−４に接着特性結果を示した。Table 4 shows the adhesive properties results.
表−４新規ポリマー１，２の接着特性
（方法）
対ＯＰＰ密着性：２軸延伸ポリプロピレンフィルム（ｏ
ｐｐ）（厚さｓａｐ ； ＴＯＹＯＢＯ問製）上にポリ
マーのトルエン溶液を塗布して８０℃の温風で３０分間
強制乾燥した後、１晩風乾した塗膜に対し、巾０．５備
の井げたに切目を作シ、ニチバン■製セロハンテープで
５回はがして、そのはがれた回数目を表示する。このテ
ストを井げた５つに対して行い、その平均値を取る。Table 4 Adhesive properties of new polymers 1 and 2 (method) Adhesion to OPP: Biaxially oriented polypropylene film (O
pp) (thickness sap; manufactured by TOYOBO) was coated with a toluene solution of the polymer, forced to dry with hot air at 80°C for 30 minutes, and then air-dried overnight. Make a cut on the tape and peel it off 5 times using cellophane tape manufactured by Nichiban ■, and indicate the number of times it was peeled off. Perform this test on five successful cases and take the average value.
剥離強度：上記の乾燥室膜フィルムに対し、１３０℃、
Ｉ Ｋｇ／ｒｙｍ” Ｇで１秒間ヒ−）シールした後、
１時間室温で養生したものを、巾０．９のに切断し１ａ
当ジの剥離強度を求め７’ｈ。Peel strength: 130℃,
After sealing with G for 1 second,
Cured at room temperature for 1 hour, then cut into 0.9-inch pieces.
Determine the peel strength of the area for 7'h.
図−１、図−３、図−５、図−６は本発明の新規ポリマ
ーのＩＲチャート、図−２、図−４は従来のＣＩ！−Ｅ
ＶＡのＩＲチャート、図−７は本発明の新規ポリマーの
ＮＭＲチャートの図、図−８、図−１０ｉｉ本本発の新
規ポリマーの溶解性を示す０ １０〜１００℃で溶解
の ２５〜１００℃で溶解
０１００℃で溶解
命 ２５ＮＺｏｏ℃で不溶Figures 1, 3, 5, and 6 are IR charts of the new polymer of the present invention, and Figures 2 and 4 are conventional CI! -E
VA's IR chart, Figure 7 is an NMR chart of the novel polymer of the present invention, Figure 8, Figure 10ii shows the solubility of the novel polymer of this invention. Melts at 0100°C Insoluble at 25NZoo°C
Claims (1)
下で塩素化反応と同時に鹸化反応を行なわしめることを
特徴とする水酸基含有塩素化エチレン−酢酸ビニル系共
重合体の製造法。 ２、請求項１記載の製造法によって得られた新規な水酸
基含有塩素化エチレン−酢酸ビニル系共重合体。 ３、インク用、接着剤用、コーティング剤用、塗料用、
ポリプロピレン成型品等のプライマー用、繊維類処理剤
用に使用する請求項２記載の新規な水酸基含有塩素化エ
チレン−酢酸ビニル系共重合体。[Claims] 1. Hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer, characterized in that the vinyl acetate copolymer is subjected to a chlorination reaction and a saponification reaction simultaneously in the presence of a chlorinated organic solvent and water. Coalescence manufacturing method. 2. A novel hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer obtained by the production method according to claim 1. 3. For ink, adhesives, coatings, paints,
The novel hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer according to claim 2, which is used as a primer for polypropylene molded products and as a treatment agent for fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20081689A JPH07119256B2 (en) | 1989-08-01 | 1989-08-01 | Method for producing hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20081689A JPH07119256B2 (en) | 1989-08-01 | 1989-08-01 | Method for producing hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0364304A true JPH0364304A (en) | 1991-03-19 |
| JPH07119256B2 JPH07119256B2 (en) | 1995-12-20 |
Family
ID=16430675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20081689A Expired - Fee Related JPH07119256B2 (en) | 1989-08-01 | 1989-08-01 | Method for producing hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07119256B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343348C (en) * | 2005-12-07 | 2007-10-17 | 江苏常铝铝业股份有限公司 | Hot sealing coating for calorifier aluminum foil, and its preparation method and coating method |
-
1989
- 1989-08-01 JP JP20081689A patent/JPH07119256B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343348C (en) * | 2005-12-07 | 2007-10-17 | 江苏常铝铝业股份有限公司 | Hot sealing coating for calorifier aluminum foil, and its preparation method and coating method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07119256B2 (en) | 1995-12-20 |
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