JPH0158205B2 - - Google Patents
Info
- Publication number
- JPH0158205B2 JPH0158205B2 JP18686281A JP18686281A JPH0158205B2 JP H0158205 B2 JPH0158205 B2 JP H0158205B2 JP 18686281 A JP18686281 A JP 18686281A JP 18686281 A JP18686281 A JP 18686281A JP H0158205 B2 JPH0158205 B2 JP H0158205B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- chloroprene
- latex
- present
- weight
- 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.)
- Expired
Links
- 239000004816 latex Substances 0.000 claims description 33
- 229920000126 latex Polymers 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 31
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 25
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 21
- 229920002554 vinyl polymer Polymers 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000007870 radical polymerization initiator Substances 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000003995 emulsifying agent Substances 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- -1 sodium alkyl sulfate Chemical class 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- LIFLRQVHKGGNSG-UHFFFAOYSA-N 2,3-dichlorobuta-1,3-diene Chemical compound ClC(=C)C(Cl)=C LIFLRQVHKGGNSG-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical class C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、本質的に乳化剤を含まない、カルボ
キシル基で安定化されたポリクロロプレンラテツ
クスの製造方法に関するものである。
その特徴とするところは、ラテツクスの安定性
が良好で、かつ接着時の耐水性、木材や金属に対
する接着性などが優れたポリクロロプレンラテツ
クスを得ることにある。
クロロプレン重合体は、有機溶剤に溶かした溶
液系、あるいは水を媒体としたラテツクス系のい
ずれかの形で接着剤に広く用いられている。
しかしながら、最近、有機溶剤を用いることに
よる環境問題や火災発生の危険性のために、水性
ラテツクスの接着剤が次第に重要になつてきた。
しかしながら、通常、ラテツクスの製造には、乳
化剤あるいはそれに類する水溶性物質が使用され
る。実際、ポリクロロプレンラテツクスの製造に
は、ロジン酸の金属塩、アルキル硫酸ナトリウム
等の一般の有機乳化剤の存在でクロロプレンの重
合を行なうことにより、ラテツクスを得ることが
知られている。この通常の方法により得られたラ
テツクスを接着剤として使用する際には、皮膜中
に乳化剤が残存することになり、接着物性に種々
の悪影響を及ぼす。例えば、接着時の耐水性を極
度に低下させるというよな欠点が生じる。
本発明は、この欠点を改良したもので、本発明
では本質的に乳化剤を含まないポリクロロプレン
ラテツクスを得ることが可能であり、本発明で得
たラテツクスを接着剤として使用した場合、優れ
た耐水性が達成されるものである。
さらに、本発明で得られるラテツクスは、木材
や金属に対して優れた接着強度を発現するという
特徴を有している。
本発明のこれらの特徴は、ラテツクス粒子の表
面にポリマーと結合したカルボキシル基を有して
いることに起因している。すなわち、ビニル系単
量と親水性の不飽和酸を水中で共重合させること
により、エマルジヨン粒子表面にカルボキシル基
を持つ共重合体エマルジヨンを合成し、これを種
としてクロロプレンを重合し、その種を生長させ
ることにより達成されるものである。このように
して得られるラテツクス粒子の表面には、カルボ
キシル基が存在しており、このため乳化剤を本質
的に使用せずとも、ラテツクスの安定性は保たれ
ている。
本発明のポリクロロプレンラテツクスの製造
は、二段階に分かれて行なわれる。各段階の重合
は別々に、もしくは連続的に行なうことができ
る。
第一段階での重合は、本質的に乳化剤不含の不
飽和酸とビニル系単量体の共重合体エマルジヨン
を得ることにある。この際には、少なくとも一種
の不飽和酸とビニル系単量体を、ラジカル重合開
始剤を含む水性媒体中へ、連続的に添加しながら
重合を行なうことが重要である。これに反し、あ
らかじめ不飽和酸とビニル系単量体の全量を重合
系中に仕込んだ後、ラジカル重合開始剤を添加し
て重合を開始すると、不飽和酸は、水に溶けやす
いことから水相で単独重合し、仕込んだ不飽和酸
はほとんどホモポリマーとして水に溶けた形で水
相に存在することになり、エマルジヨン粒子表面
に存在するカルボキシル基の割合は少なくなつ
て、エマルジヨンの安定性が損なわれる。しか
し、本発明法においては、このような問題はな
く、かつ本発明の特異的なことは、本発明のよう
に不飽和酸とビニル系単量体を連続的に添加しな
がら重合することにより、不飽和酸とビニル系単
量体は共重合しやすくなるため、これまでのよう
に不飽和酸を多量に使用しなくとも、少量の不飽
和酸の使用量でもエマルジヨンの安定性を保つこ
とができるということである。この際、不飽和酸
とビニル系単量体は別個に連続添加してもよい
が、作業のしやすさや、両者の添加量比の制御等
から、混合し得るものは混合液として連続添加す
る方法によつても差し支えない。
第一段階の重合では、水に対してその0.1〜20
重量％、好ましくは0.3〜10重量％の少なくとも
一種以上の不飽和酸および水に対してその１〜80
重量％、好ましくは３〜40重量％のビニル系単量
体が用いられる。
不飽和酸の好適な例としては、アクリル酸、メ
タクリル酸、マレイン酸、フマル酸、イタコン酸
等が挙げられるが、これらは一種あるいはそれ以
上が用いられる。また、塩基で中和された塩とし
て使用してもよい。ビニル系単量体の例として
は、スチレン、メタクリル酸メチルあるいはメタ
クリル酸エチル等のメタクリル酸エステル類、ア
クリル酸メチルあるいはアクリル酸エチル等のア
クリル酸エステル類、酢酸ビニル、塩化ビニル等
が挙げられる。これらは一種あるいはそれ以上が
用いられる。
本発明において、不飽和酸とビニル系単量体を
連続的に添加する場合の添加時間は自由に選べる
が、好ましくは100分前後がよい。重合温度は特
に制限されるものでなく、使用する触媒系により
０℃から100℃以下の温度が自由に選べるが、好
ましくは50〜80℃がよい。重合時間は重合条件に
よつて変化するので、規定されるものではない
が、不飽和酸とビニル系単量体の重合が本質的に
完結するまで行なうのがよく、モノマーの添加時
間に加えて１〜３時間が適当である。
なお、第一段階の重合で必ずしも必要としない
が、重合安定性をさらに良くする目的で、通常の
乳化重合で使用されている乳化剤、例えば、アル
キル硫酸塩、アルキルベンゼンスルホン酸塩、脂
肪酸塩、ポリオキシエチレンアルキルエーテル等
を、水に対してその１〜１重量％程度の少量用い
ることは差し支えない。また、系にアルキルメル
カプタン等の連鎖移動剤を添加し、不飽和酸とビ
ニル系単量体の共重合体の分子量をコントロール
してもよい。
本発明に用いられる重合開始剤は、例えば、過
硫酸塩、アルキルハイドロパーオキサイド等ラジ
カル重合に用いられるものならいずれでもよい
が、特に過硫酸イオンを持つ過硫酸カリウム、過
硫酸アンモニウムの開始剤が極めて有効であり、
これらはさらにラテツクス粒子の安定化にも寄与
する。
また、これらは単独あるいは還元性物質、例え
ばチオ硫酸塩、チオ亜硫酸塩、有機アミン等との
併用で用いることができる。
使用される開始剤量は、不飽和酸とビニル系単
量体の共重合体エマルジヨン粒子、ひいては引き
続きクロロプレンを重合して得られるポリクロロ
プレンラテツクス粒子の粒子径、安定性に影響を
及ぼすので、ビニル系単量体に対し0.1〜30重量
％、好ましくは0.3〜20重量％の範囲がよい。
また、ここで添加された過硫酸塩は、さらに引
き続いてクロロプレンを重合する時の重合開始剤
にもなるが、条件によつてはクロロプレンの重合
時、新たに過硫酸塩等の開始剤を加えてもよい。
本発明では第二段階として、以上のようにして
生成した不飽和酸とビニル系単量体の共重合体エ
マルジヨン中で、クロロプレンの重合が続行さ
れ、ポリクロロプレンラテツクスを得る。この時
は、まず、塩基を添加することにより、共重合し
た不飽和酸を中和することが有効である。これは
中和することによつてカルボキシル基がイオン化
し、粒子表面にアニオンを持つた形となるため
に、ラテツクスの安定性をさらに増すことができ
ることによる。この際使用される塩基としては、
水酸化ナトリウム、水酸化カリウムあるいはアン
モニア水などが使用できる。また、中和後のエマ
ルジヨンのPHは７以上、好ましくは９前後がよ
い。
次に、この不飽和酸とビニル系単量体の共重合
エマルジヨンにクロロプレンを、例えば滴下しな
がら重合してポリクロロプレンラテツクスを得
る。この時、電子顕微鏡で観察すると、新たな粒
子の発生は見られず、不飽和酸とビニル系単量体
の共重合体エマルジヨン粒子を種として、この種
がクロロプレンを吸着し、重合が進むにつれて生
長してゆくことが判明した。
クロロプレンの重合においては、クロロプレン
は始めに一括して、あるいは連続的に加えられ
る。連続的に加える場合、クロロプレンの添加時
間は、自由に選べるが、モノマー油滴が重合系に
多量に現われないようにするのが望ましく、100
分以上かけて添加することが好ましい。クロロプ
レンの重合温度は、通常のクロロプレンの乳化重
合の時と同じように０〜60℃の範囲で設定でき
る。重合時間も重合条件によつて変わるが、重合
系中に加えられる全モノマーが実質的に重合し終
わるまで行なうことが有利である。あるいは適当
な重合転化率に達した時、一般に用いられる重合
停止剤を添加して重合を停止することもできる。
この場合は、常法により残存モノマーを除去して
ラテツクスとすることができる。
クロロプレンの重合においては、通常のクロロ
プレン重合体の製造で行なわれるように、クロロ
プレンにアルキルメルカプタン等の連鎖移動剤を
添加し、分子量がコントロールされる。さらにク
ロロプレンと共重合可能な他のビニル系単量体、
例えばメタクリル酸エステル、アクリロニトリ
ル、アクリルアミド、スチレン等、あるいはジエ
ン系単量体、例えばブタジエン、イソプレン、
２，３―ジクロブタジエン等、あるいは多官能性
単量体たとえばジビニルベンゼン、ジエチルグリ
コールジメタクリレート等を少量加えクロロプレ
ンと共重合することにより、ポリクロロプレンラ
テツクスの変性が可能である。このような変性
は、本発明の本質を損なわない限り特に制限され
るものではない。
本発明では、クロロプレンは第一段階で得られ
た不飽和酸とビニル系単量体の共重合体エマルジ
ヨンに対し、10〜20重量％、好ましくは50〜100
重量％の範囲で加えるのがよい。さらに本発明で
使用する不飽和酸、ビニル系単量体およびクロロ
プレンの全単量体の総量は、所望しているポリク
ロロプレンラテツクス固形分濃度によつて自由に
選べるが、系に加えられる全モノマーと系中の水
との比（全単量体／水の重量比）は、通常のエマ
ルジヨン重合で行なわれる範囲が使用可能であ
り、その比は0.1から0.7の範囲にある。
このようにして得られた本発明のポリクロロプ
レンラテツクスは、従来のポリクロロプレンラテ
ツクスと同様の多くの用途に用いることができ
る。その最も重要な用途の一つとして、接着剤と
しての用途が挙げられる。本発明で得られたポリ
クロロプレンラテツクスを接着剤として用いた場
合、乳化剤を本質的に含有していないことから、
水中に浸漬後も接着強度の低下は、従来の乳化剤
の存在下で得られるポリクロロプレンラテツクス
に比べ小さく、耐水性が優れている。さらに本発
明のポリクロロプレンラテツクスは、従来のポリ
クロロプレンラテツクスに比べ、木材や金属に対
して高い接剤強度を示すという点においても独特
のものである。また、従来のポリクロロプレンラ
テツクスと同様、本発明のポリクロロプレンラテ
ツクスを接着剤等に用いる際は、加硫剤、老化防
止剤、粘着付与剤等各種の配合を行なうことがで
きる。
以下に本発明をさらに一層理解しやすくするた
めに、若干の実施例により説明するが、これら実
施例のみに限定されるものではない。
本文中では特に記載しない限り、部は重量部を
表わす。
実施例１〜４および比較例１
窒素気流中でラウリル硫酸ナトリウム0.4部を
溶解した水800部を重合器に仕込み、70℃に加温
した後に過硫酸アンモニウム10部を加え、引き続
き表１に示すような所定量のスチレンとアクリル
酸の混合液を滴下し始め重合を開始した。モノマ
ー混合液の全量の滴下は100分かけて行なつた。
滴下終了後も加温を続け、重合開始後、150分経
過すると重合は実質的に終了した。
この時、実施例１〜４いずれも凝固物の発生は
実質的に見られず、エマルジヨンの安定性は優れ
ていた。
さらに引き続きクロロプレンの重合を行なつ
た。まず、前述の得られたエマルジヨンの温度を
40℃へ下げた後、28重量％のアンモニア水を添加
し、PHを8.7とした。その後、ｎ―オクチルメル
カプタン1.5部を加えたクロロプレン730部を100
分間かけて該エマルジヨン中へ滴下してクロロプ
レンの重合を行なつた。クロロプレンの滴下が終
了した後も系の温度は40℃に保ち、実質的にクロ
ロプレン全量が重合し終えるまで重合を行なつ
た。得られた結果は表１に示すように、実施例１
〜４いずれにおいても凝固物の発生は本質的にな
く、満足のゆく安定性を与えるポリクロロプレン
ラテツクスを得た。
比較例１として、実施例３と同様の処方ではあ
るが、スチレンとアクリル酸の全量をまず一括し
て重合系へ仕込んだ後、過硫酸アンモニウムを添
加して重合を開始した場合の実験を行なつたが、
第一段階において、スチレンとアクリル酸の共重
合体エマルジヨンは得られず、系全体が凝固し
た。
実施例 ５〜７
実施例３の方法において、表２に示すように過
硫酸アンモニウムあるいはラウリル硫酸ナトリウ
ムの量を変えて実施例３と同様の操作でエマルジ
ヨンの合成を行ない、次いで同様にクロロプレン
の重合を行なつた。得られたエマルジヨン、ラテ
ツクスともに凝固物の発生は見られず、安定性も
優れていた。
The present invention relates to a process for producing carboxyl-stabilized polychloroprene latexes that are essentially emulsifier-free. The characteristics of this method are to obtain a polychloroprene latex which has good latex stability, has excellent water resistance during adhesion, and has excellent adhesion to wood and metal. Chloroprene polymers are widely used in adhesives either in the form of solutions dissolved in organic solvents or as latex systems in water. Recently, however, water-based latex adhesives have become increasingly important due to the environmental concerns and fire hazards associated with the use of organic solvents.
However, emulsifiers or similar water-soluble substances are usually used in latex production. In fact, it is known that polychloroprene latex can be produced by polymerizing chloroprene in the presence of common organic emulsifiers such as metal salts of rosin acid and sodium alkyl sulfate. When the latex obtained by this conventional method is used as an adhesive, the emulsifier remains in the film, which has various adverse effects on the physical properties of the adhesive. For example, there is a drawback that water resistance during adhesion is extremely reduced. The present invention improves this drawback. According to the present invention, it is possible to obtain a polychloroprene latex that essentially does not contain an emulsifier, and when the latex obtained according to the present invention is used as an adhesive, it has excellent properties. Water resistance is achieved. Furthermore, the latex obtained by the present invention is characterized by exhibiting excellent adhesive strength to wood and metal. These features of the present invention are due to the presence of carboxyl groups bonded to polymers on the surface of the latex particles. That is, by copolymerizing a vinyl monomer and a hydrophilic unsaturated acid in water, a copolymer emulsion having carboxyl groups on the surface of the emulsion particles is synthesized, and this is used as a seed to polymerize chloroprene. This is achieved by growing. Carboxyl groups are present on the surface of the latex particles thus obtained, and therefore the stability of the latex is maintained even without the use of an emulsifier. The production of the polychloroprene latex of the present invention is carried out in two stages. Each stage of polymerization can be carried out separately or sequentially. The first stage of polymerization consists in obtaining an essentially emulsifier-free copolymer emulsion of unsaturated acid and vinyl monomer. At this time, it is important to carry out the polymerization while continuously adding at least one unsaturated acid and a vinyl monomer to an aqueous medium containing a radical polymerization initiator. On the other hand, if the entire amount of the unsaturated acid and vinyl monomer is charged into the polymerization system in advance and then a radical polymerization initiator is added to start polymerization, the unsaturated acid is easily dissolved in water, so Most of the charged unsaturated acid is homopolymerized in the phase and exists in the aqueous phase in the form of a homopolymer dissolved in water, and the proportion of carboxyl groups present on the surface of the emulsion particles decreases, improving the stability of the emulsion. is damaged. However, the method of the present invention does not have such problems, and the unique feature of the present invention is that, as in the present invention, polymerization is carried out while continuously adding an unsaturated acid and a vinyl monomer. Since unsaturated acids and vinyl monomers copolymerize easily, emulsion stability can be maintained even with small amounts of unsaturated acids, instead of using large amounts of unsaturated acids as in the past. This means that it can be done. At this time, the unsaturated acid and the vinyl monomer may be added separately and continuously, but for ease of work and controlling the ratio of the amounts added, if they can be mixed, they are added continuously as a mixed solution. There is no problem depending on the method. In the first stage of polymerization, its 0.1 to 20
% by weight, preferably 0.3-10% by weight of at least one unsaturated acid and 1-80% by weight of at least one unsaturated acid and water
% by weight, preferably 3 to 40% by weight of vinyl monomer is used. Suitable examples of unsaturated acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc., and one or more of these may be used. It may also be used as a salt neutralized with a base. Examples of vinyl monomers include styrene, methacrylic esters such as methyl methacrylate or ethyl methacrylate, acrylic esters such as methyl acrylate or ethyl acrylate, vinyl acetate, and vinyl chloride. One or more of these may be used. In the present invention, the addition time when continuously adding the unsaturated acid and the vinyl monomer can be freely selected, but is preferably about 100 minutes. The polymerization temperature is not particularly limited and can be freely selected from 0°C to 100°C depending on the catalyst system used, but preferably 50 to 80°C. The polymerization time varies depending on the polymerization conditions and is not specified, but it is best to carry out the polymerization until the polymerization of the unsaturated acid and the vinyl monomer is essentially completed, in addition to the monomer addition time. 1 to 3 hours is appropriate. Although not necessarily required in the first stage of polymerization, emulsifiers used in normal emulsion polymerization, such as alkyl sulfates, alkylbenzenesulfonates, fatty acid salts, and polyesters, may be added to improve polymerization stability. There is no problem in using oxyethylene alkyl ether or the like in a small amount of about 1 to 1% by weight based on water. Furthermore, a chain transfer agent such as an alkyl mercaptan may be added to the system to control the molecular weight of the copolymer of an unsaturated acid and a vinyl monomer. The polymerization initiator used in the present invention may be any initiator used in radical polymerization, such as persulfates and alkyl hydroperoxides, but particularly potassium persulfate and ammonium persulfate initiators having persulfate ions are particularly preferred. valid and
These also contribute to the stabilization of the latex particles. Further, these can be used alone or in combination with reducing substances such as thiosulfates, thiosulfites, organic amines, etc. The amount of initiator used affects the particle size and stability of the copolymer emulsion particles of an unsaturated acid and a vinyl monomer, as well as the polychloroprene latex particles obtained by subsequent polymerization of chloroprene. The amount is preferably 0.1 to 30% by weight, preferably 0.3 to 20% by weight based on the vinyl monomer. Additionally, the persulfate added here also serves as a polymerization initiator for the subsequent polymerization of chloroprene, but depending on the conditions, a new initiator such as persulfate may be added during the polymerization of chloroprene. It's okay. In the second step of the present invention, polymerization of chloroprene is continued in the copolymer emulsion of unsaturated acid and vinyl monomer produced as described above to obtain a polychloroprene latex. At this time, it is effective to first neutralize the copolymerized unsaturated acid by adding a base. This is because the carboxyl groups are ionized by neutralization and the particles have anions on their surfaces, which further increases the stability of the latex. The base used in this case is
Sodium hydroxide, potassium hydroxide or aqueous ammonia can be used. Further, the pH of the emulsion after neutralization is preferably 7 or more, preferably around 9. Next, chloroprene is polymerized, for example, while being added dropwise, to the copolymerized emulsion of the unsaturated acid and the vinyl monomer to obtain a polychloroprene latex. At this time, when observed with an electron microscope, no new particles were observed to be generated, and as the seeds of the copolymer emulsion particles of unsaturated acid and vinyl monomer were used as seeds, these seeds adsorbed chloroprene, and as the polymerization progressed, It turned out that it was growing. In the polymerization of chloroprene, chloroprene can be added either all at once or continuously. When adding chloroprene continuously, the addition time of chloroprene can be freely selected, but it is desirable to prevent a large amount of monomer oil droplets from appearing in the polymerization system.
It is preferable to add over a period of at least 1 minute. The polymerization temperature of chloroprene can be set in the range of 0 to 60°C, as in the case of ordinary emulsion polymerization of chloroprene. The polymerization time also varies depending on the polymerization conditions, but it is advantageous to carry out the polymerization until substantially all the monomers added to the polymerization system have been polymerized. Alternatively, when a suitable polymerization conversion rate is reached, a commonly used polymerization terminator can be added to terminate the polymerization.
In this case, the remaining monomer can be removed by a conventional method to obtain a latex. In the polymerization of chloroprene, the molecular weight is controlled by adding a chain transfer agent such as an alkyl mercaptan to chloroprene, as is done in the production of ordinary chloroprene polymers. Furthermore, other vinyl monomers copolymerizable with chloroprene,
For example, methacrylic acid ester, acrylonitrile, acrylamide, styrene, etc., or diene monomers such as butadiene, isoprene,
Polychloroprene latex can be modified by adding a small amount of 2,3-dichlorobutadiene or a polyfunctional monomer such as divinylbenzene or diethyl glycol dimethacrylate and copolymerizing it with chloroprene. Such modification is not particularly limited as long as it does not impair the essence of the present invention. In the present invention, chloroprene is used in an amount of 10 to 20% by weight, preferably 50 to 100% by weight, based on the copolymer emulsion of unsaturated acid and vinyl monomer obtained in the first step.
It is preferable to add it in a range of % by weight. Furthermore, the total amount of unsaturated acids, vinyl monomers, and chloroprene monomers used in the present invention can be freely selected depending on the desired solid content concentration of the polychloroprene latex; The ratio of monomer to water in the system (total monomer/water weight ratio) can be within the range used in normal emulsion polymerization, and the ratio is in the range of 0.1 to 0.7. The polychloroprene latex of the present invention thus obtained can be used in many of the same applications as conventional polychloroprene latex. One of its most important uses is as an adhesive. When the polychloroprene latex obtained in the present invention is used as an adhesive, since it essentially does not contain an emulsifier,
Even after immersion in water, the decrease in adhesive strength is smaller than that of polychloroprene latexes obtained in the presence of conventional emulsifiers, and they have excellent water resistance. Furthermore, the polychloroprene latex of the present invention is unique in that it exhibits higher adhesive strength to wood and metal than conventional polychloroprene latexes. Furthermore, like conventional polychloroprene latexes, when the polychloroprene latex of the present invention is used in adhesives, etc., various types of vulcanizing agents, anti-aging agents, tackifiers, etc. can be added. In order to make the present invention even easier to understand, the present invention will be explained below using some examples, but the present invention is not limited to these examples. In the text, unless otherwise specified, parts represent parts by weight. Examples 1 to 4 and Comparative Example 1 800 parts of water in which 0.4 parts of sodium lauryl sulfate was dissolved in a nitrogen stream was charged into a polymerization vessel, heated to 70°C, 10 parts of ammonium persulfate was added, and then the mixture was heated as shown in Table 1. A predetermined amount of a mixed solution of styrene and acrylic acid was added dropwise to initiate polymerization. The entire amount of the monomer mixture was added dropwise over 100 minutes.
Heating was continued even after the dropwise addition was completed, and the polymerization was substantially completed 150 minutes after the start of the polymerization. At this time, in all of Examples 1 to 4, substantially no coagulum was observed, and the stability of the emulsion was excellent. Furthermore, polymerization of chloroprene was subsequently carried out. First, the temperature of the emulsion obtained above is
After lowering the temperature to 40°C, 28% by weight aqueous ammonia was added to adjust the pH to 8.7. Then, add 730 parts of chloroprene to 100 parts of n-octyl mercaptan.
The mixture was added dropwise into the emulsion over a period of minutes to polymerize chloroprene. Even after the dropwise addition of chloroprene was completed, the temperature of the system was maintained at 40°C, and polymerization was continued until substantially all of the chloroprene had been polymerized. The obtained results are shown in Table 1, as shown in Example 1.
In all cases 4 to 4, essentially no coagulum was generated, and polychloroprene latexes with satisfactory stability were obtained. As Comparative Example 1, an experiment was conducted in which the recipe was the same as in Example 3, but the entire amount of styrene and acrylic acid was first charged into the polymerization system at once, and then ammonium persulfate was added to start polymerization. However,
In the first stage, no styrene and acrylic acid copolymer emulsion was obtained and the entire system solidified. Examples 5 to 7 Emulsions were synthesized in the same manner as in Example 3 using the method of Example 3, changing the amount of ammonium persulfate or sodium lauryl sulfate as shown in Table 2, and then polymerizing chloroprene in the same manner. I did it. No coagulum was observed in both the emulsion and latex obtained, and the stability was excellent.
【表】【table】
【表】
参考例 １
実施例５で得られたラテツクスを９号帆布の幅
25mmの２枚の片にそれぞれ３回塗布し、オープン
タイム５分の後、互いに貼り合せプレスし、室温
で７日間熟成させた。この接着した試験片をヘツ
ド速度200mm／分でインストロン引張り試験機に
より剥離し、剥離強度を測定した。さらに耐水性
を調べるため、同様にして作製した試験片を30℃
の水中に24時間浸漬後、直ちに剥離強度を求め、
水に浸漬後の剥離強度低下率を求めた。
比較のために、乳化剤の存在下で製造されてい
る市販のポリクロロプレンラテツクス（東洋曹達
工業(株)製LA−502）を用いて同様に試験を行な
い、得られた典型的な結果を対照例１として示
す。表３から明らかなように、市販品に比べ本発
明品は、水に浸漬後の剥離強度低下率が小さく、
耐水性は優れていた。[Table] Reference example 1 The latex obtained in Example 5 was added to the width of No. 9 canvas.
Two 25 mm pieces were coated three times each, pressed together after an open time of 5 minutes, and aged for 7 days at room temperature. This adhered test piece was peeled off using an Instron tensile tester at a head speed of 200 mm/min, and the peel strength was measured. In order to further investigate water resistance, test pieces prepared in the same manner were heated to 30°C.
After immersing in water for 24 hours, immediately determine the peel strength.
The peel strength reduction rate after immersion in water was determined. For comparison, a similar test was conducted using a commercially available polychloroprene latex (LA-502 manufactured by Toyo Soda Kogyo Co., Ltd.) manufactured in the presence of an emulsifier, and the typical results obtained were compared. This is shown as Example 1. As is clear from Table 3, compared to commercially available products, the product of the present invention has a smaller rate of decrease in peel strength after being immersed in water.
Water resistance was excellent.
【表】
参考例 ２
実施例５で得られたラテツクスを幅25mmの木材
（ブナ材）、鉄あるいはアルミニウムの２枚の片の
それぞれ25mm×25mmの面積に１回塗布し、直ちに
貼り合せプレスし、室温で７日間熟成した。この
接着した試験片をヘツド速度50mm／分でインスト
ロン引張り試験機により引張り剪断強度を求め
た。さらに耐水性の評価のため、参考例１と同様
に30℃の水中に24時間浸漬後、直ちに剪断強度を
測定し、剪断強度低下率を求めた。
比較のために、参考例１と同様の市販のラテツ
クスを用いて同様に試験を行ない、得られた典型
的な結果を対照例２として示す。
表４から明らかなように、市販品に比べ本発明
品は木材や金属に対する剪断強度が大きく、また
水に浸漬後の剪断強度低下率も小さく、耐水性も
優れていた。[Table] Reference Example 2 The latex obtained in Example 5 was applied once to an area of 25 mm x 25 mm on each of two pieces of wood (beech), iron, or aluminum with a width of 25 mm, and immediately pressed together. , aged for 7 days at room temperature. The tensile shear strength of this bonded test piece was determined using an Instron tensile tester at a head speed of 50 mm/min. Furthermore, in order to evaluate water resistance, the shear strength was immediately measured after being immersed in water at 30° C. for 24 hours in the same manner as in Reference Example 1, and the shear strength reduction rate was determined. For comparison, a similar test was conducted using the same commercially available latex as in Reference Example 1, and the typical results obtained are shown as Control Example 2. As is clear from Table 4, the products of the present invention had greater shear strength against wood and metal than commercially available products, had a smaller rate of decline in shear strength after being immersed in water, and had excellent water resistance.
Claims (1)
の水量の0.1〜20重量％の少なくとも一種の不飽
和酸と１〜80重量％のビニル系単量体を連続的に
添加しながら重合することにより得られるエマル
ジヨン中に、その10〜120重量％のクロロプレン
を添加しクロロプレンの重合を行なうことを特徴
とするカルボキシル基で安定化されたポリクロロ
プレンラテツクスの製造方法。1. By polymerizing while continuously adding 0.1 to 20% by weight of at least one unsaturated acid and 1 to 80% by weight of a vinyl monomer to an aqueous medium containing a radical polymerization initiator. A method for producing polychloroprene latex stabilized with carboxyl groups, which comprises adding 10 to 120% by weight of chloroprene to the resulting emulsion to polymerize chloroprene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18686281A JPS5889602A (en) | 1981-11-24 | 1981-11-24 | Preparation of polychloroprene latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18686281A JPS5889602A (en) | 1981-11-24 | 1981-11-24 | Preparation of polychloroprene latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5889602A JPS5889602A (en) | 1983-05-28 |
| JPH0158205B2 true JPH0158205B2 (en) | 1989-12-11 |
Family
ID=16195956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18686281A Granted JPS5889602A (en) | 1981-11-24 | 1981-11-24 | Preparation of polychloroprene latex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5889602A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61111304A (en) * | 1984-11-06 | 1986-05-29 | Tokuyama Soda Co Ltd | Production of polymer particle |
| ITMI20041194A1 (en) * | 2004-06-15 | 2004-09-15 | Polimeri Europa Spa | PROCEDURE FOR THE PREPARATION OF POLYCHLOROPRENE-BASED LACTICS AND THEIR USE AS ADHESIVES |
| JP2007039654A (en) * | 2005-07-08 | 2007-02-15 | Tosoh Corp | Chloroprene-based block copolymer and method for producing the same |
| US20090036608A1 (en) * | 2005-07-08 | 2009-02-05 | Tosoh Corporation | Chloroprene-based block copolymer, soapless polychloroprene-based latex, and processes for producing the same |
| US8118969B2 (en) | 2006-11-30 | 2012-02-21 | Illinois Tool Works Inc. | Water-based polychloroprene adhesive |
| WO2020189456A1 (en) * | 2019-03-15 | 2020-09-24 | デンカ株式会社 | Rubber latex and water-based adhesive composition |
-
1981
- 1981-11-24 JP JP18686281A patent/JPS5889602A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5889602A (en) | 1983-05-28 |
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