JPH051230A - O / W type emulsion and manufacturing method thereof - Google Patents
O / W type emulsion and manufacturing method thereofInfo
- Publication number
- JPH051230A JPH051230A JP17877391A JP17877391A JPH051230A JP H051230 A JPH051230 A JP H051230A JP 17877391 A JP17877391 A JP 17877391A JP 17877391 A JP17877391 A JP 17877391A JP H051230 A JPH051230 A JP H051230A
- Authority
- JP
- Japan
- Prior art keywords
- water
- emulsion
- soluble resin
- hydrophilic group
- highly reactive
- 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
- 239000000839 emulsion Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000004945 emulsification Methods 0.000 title description 2
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000012071 phase Substances 0.000 claims abstract description 7
- 239000008346 aqueous phase Substances 0.000 claims abstract description 3
- 229920000877 Melamine resin Polymers 0.000 abstract description 23
- 239000004640 Melamine resin Substances 0.000 abstract description 23
- 239000003973 paint Substances 0.000 abstract description 16
- 238000003860 storage Methods 0.000 abstract description 10
- 230000009257 reactivity Effects 0.000 abstract description 3
- 238000013035 low temperature curing Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- -1 hydroxyalkyl ester Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Colloid Chemistry (AREA)
Abstract
(57)【要約】
【構成】 メラミン樹脂等の高反応性架橋剤と親水性基
含有量の互いに異なる少なくとも２種の水溶性樹脂とを
混合し、この混合物を水相に投入してエマルション化を
行うことをにより、上記高反応性架橋剤核の周囲に親水
性基含有量の少ない水溶性樹脂層が形成され、その周囲
に親水性基含有量の多い水溶性樹脂層が形成された粒子
を分散相とするＯ／Ｗ型エマルションを得る。
【請求項２】
【効果】 本発明のＯ／Ｗ型エマルションは、エマルシ
ョン粒子が複層化しているため低温硬化性メラミン樹脂
等の高反応性架橋剤の反応性が制御され、貯蔵安定性が
良好で貯蔵中にゲル化するような不都合が可及的に防止
される。このＯ／Ｗ型エマルションは塗料とした場合、
低温硬化が可能である。(57) [Summary] [Structure] A highly reactive cross-linking agent such as a melamine resin and at least two water-soluble resins having different hydrophilic group contents are mixed, and the mixture is put into an aqueous phase to form an emulsion. By carrying out, a water-soluble resin layer having a low hydrophilic group content is formed around the highly reactive crosslinking agent nucleus, and a water-soluble resin layer having a high hydrophilic group content is formed around the water-soluble resin layer. To obtain an O / W type emulsion having as a dispersed phase. 2. The O / W type emulsion of the present invention has a multiplicity of emulsion particles so that the reactivity of a highly reactive crosslinking agent such as a low temperature curable melamine resin is controlled and the storage stability is improved. The disadvantages of being good and gelling during storage are prevented as much as possible. When this O / W emulsion is used as a paint,
Low temperature curing is possible.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塗料等として好適なＯ
／Ｗ型エマルション及びその製造方法に関する。FIELD OF THE INVENTION The present invention is suitable for paints and the like.
/ W type emulsion and its manufacturing method.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
メラミン樹脂系塗料として、メラミン樹脂を核とし、そ
の周りにアクリル酸モノマーを含む種々のモノマーを共
重合させて得られた水溶性樹脂層を形成した粒子を分散
相とするＯ／Ｗ型エマルション塗料が知られている。2. Description of the Related Art Conventionally, the problems to be solved by the invention
As a melamine resin-based paint, an O / W emulsion paint having a melamine resin as a core and particles having a water-soluble resin layer formed by copolymerizing various monomers including an acrylic acid monomer around the core as a dispersed phase It has been known.
【０００３】しかしながら、最近において、低温硬化性
の塗料が要望されるようになり、上記メラミン樹脂系塗
料においても、メラミン樹脂として従来の１８０℃以上
で硬化するものに代え、１２０〜１５０℃程度で硬化す
るものを使用することにより、低温硬化を可能にするこ
とが望まれるようになったが、上述したＯ／Ｗ型エマル
ションタイプのメラミン樹脂系塗料に低温硬化性のメラ
ミン樹脂を使用すると、貯蔵安定性が低下し、貯蔵中に
しばしばゲル化が生じる場合があった。However, recently, a low temperature curable coating material has been demanded, and even in the above melamine resin-based coating material, instead of the conventional melamine resin which is cured at 180 ° C. or higher, it is about 120 to 150 ° C. It has been desired to enable low temperature curing by using a curable material. However, when a low temperature curable melamine resin is used in the above-mentioned O / W emulsion type melamine resin coating composition, Stability was reduced and gelation often occurred during storage.
【０００４】本発明は、上記事情を改善するためになさ
れたもので、貯蔵安定性に優れ、塗料として用いた場合
に低温硬化可能な塗膜を形成し得るＯ／Ｗ型エマルショ
ン及びその製造方法を提供することを目的とする。The present invention has been made in order to improve the above circumstances, and is an O / W type emulsion having excellent storage stability and capable of forming a low temperature curable coating film when used as a paint, and a method for producing the same. The purpose is to provide.
【０００５】[0005]
【課題を解決するための手段及び作用】本発明者は、上
記目的を達成するため鋭意検討を行った結果、低温硬化
性のメラミン樹脂等の高反応性架橋剤と親水性基含有量
の互いに異なる少なくとも２種の水溶性樹脂とを混合
し、この混合物を水相に投入してエマルション化を行う
ことにより、高反応性架橋剤核の周囲に親水性基含有量
の少ない水溶性樹脂層が形成され、その周囲に親水性基
含有量の多い水溶性樹脂層が形成された粒子を分散相と
するＯ／Ｗ型エマルションが簡単かつ確実に得られると
共に、このＯ／Ｗ型エマルションは貯蔵安定性に優れて
いることを知見した。Means and Actions for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventor has found that a highly reactive crosslinking agent such as a low temperature curable melamine resin and a hydrophilic group content are By mixing at least two different water-soluble resins and adding the mixture to the aqueous phase for emulsification, a water-soluble resin layer having a low hydrophilic group content is formed around the highly reactive crosslinking agent nucleus. An O / W emulsion is formed that has a water-soluble resin layer with a large amount of hydrophilic groups formed around it as a dispersed phase and can be easily and reliably obtained, and this O / W emulsion is stable in storage. It was found that it has excellent properties.
【０００６】即ち、例えば高反応性架橋剤として低温硬
化性メラミン樹脂を用い、該メラミン樹脂に対し硬化触
媒として良好に作用する共重合可能なカルボン酸やスル
ホン酸をメラミン樹脂と直接接触する水溶性樹脂の被覆
層に導入したような場合、本発明者の知見では、架橋剤
と硬化触媒とが近接し、貯蔵安定性が低下する。しか
し、メラミン樹脂核に対し親水性基含有量の少ない水溶
性樹脂層で被覆し、更にこれを親水性基含有量の多い水
溶性樹脂層で被覆した場合、メラミン樹脂に対し硬化触
媒能の高いアクリル酸を導入、修飾しても、メラミン樹
脂核との間に低反応層が形成介在されているため、その
貯蔵安定性が向上するものであること、またこの場合、
該エマルションを塗料として使用し、塗装した場合にお
いて、このようにメラミン樹脂核を覆って多層の水溶性
樹脂層が形成されていても、メラミン樹脂の硬化性が阻
害されることがなく、低温で容易に硬化し得ることを知
見し、本発明をなすに至ったものである。That is, for example, a low-temperature curable melamine resin is used as a highly reactive crosslinking agent, and a copolymerizable carboxylic acid or sulfonic acid that works well as a curing catalyst for the melamine resin is directly contacted with the melamine resin. In the case of introduction into a resin coating layer, the present inventors have found that the crosslinking agent and the curing catalyst are in close proximity to each other and storage stability decreases. However, when the melamine resin core is coated with a water-soluble resin layer having a low hydrophilic group content, and further it is coated with a water-soluble resin layer having a high hydrophilic group content, the curing catalyst ability for the melamine resin is high. Even if acrylic acid is introduced or modified, since a low reaction layer is formed between the melamine resin core and the core, the storage stability thereof is improved, and in this case,
When the emulsion is used as a paint and is applied, even if a multi-layered water-soluble resin layer is formed so as to cover the melamine resin core, the curability of the melamine resin is not impaired, and at low temperature. The present invention has been completed by finding that it can be easily cured.
【０００７】以下、本発明につき更に詳しく説明する
と、本発明に係るＯ／Ｗ型エマルションは、高反応性架
橋剤核の周囲に親水性基含有量の少ない第１の水溶性樹
脂層が形成され、その周囲に親水性基含有量の多い第２
の水溶性樹脂層が形成された粒子を分散相とするもので
ある。The present invention will be described in more detail below. In the O / W type emulsion according to the present invention, the first water-soluble resin layer having a small hydrophilic group content is formed around the core of the highly reactive crosslinking agent. , Second with a high content of hydrophilic groups around it
The particles on which the water-soluble resin layer is formed are used as the dispersed phase.
【０００８】ここで、高反応性架橋剤核としては、エマ
ルションの使用目的により適宜選定され、例えば１５０
℃以下、特に１２０〜１５０℃の温度で反応、硬化する
低温硬化性メラミン樹脂などを挙げることができる。Here, the highly reactive crosslinking agent nucleus is appropriately selected according to the purpose of use of the emulsion, for example, 150
A low temperature curable melamine resin that reacts and cures at a temperature of not higher than 0 ° C., particularly at a temperature of 120 to 150 ° C. can be mentioned.
【０００９】また、上記第１及び第２水溶性樹脂層の親
水性基としては、カルボキシル基、水酸基、スルフォン
基等を挙げることができ、特に水酸基とカルボキシル基
又はスルフォン基とを含んでいることが好ましい。上記
第１及び第２水溶性樹脂層中の親水性基含有量は、本発
明のＯ／Ｗ型エマルションを塗料として用いる場合、３
０重量％以下、特に２０重量％以下であることが好まし
く、また、第１及び第２水溶性樹脂層間の親水性基含有
量の差は３〜５重量％、特に３．５〜４．５重量％であ
ることが好ましい。更に、第１及び第２水溶性樹脂層
は、いずれも数平均分子量が１０００〜３００００、特
に１０００〜２００００であることが好ましい。The hydrophilic groups of the first and second water-soluble resin layers may include a carboxyl group, a hydroxyl group, a sulfone group, and the like, and particularly include a hydroxyl group and a carboxyl group or a sulfone group. Is preferred. The hydrophilic group content in the first and second water-soluble resin layers is 3 when the O / W emulsion of the present invention is used as a coating material.
It is preferably 0% by weight or less, particularly preferably 20% by weight or less, and the difference in hydrophilic group content between the first and second water-soluble resin layers is 3 to 5% by weight, particularly 3.5 to 4.5. It is preferably in the weight%. Furthermore, the number average molecular weight of each of the first and second water-soluble resin layers is preferably 1,000 to 30,000, and particularly preferably 1,000 to 20,000.
【００１０】上記第１及び第２水溶性樹脂層を形成する
水溶性樹脂は、エマルションの使用目的に応じた種々の
重合性モノマーより共重合によって形成することができ
る。例えば、塗料目的であれば、アクリル酸、メタクリ
ル酸、アクリル酸やメタクリル酸のアルキルエステル，
ヒドロキシアルキルエステル、スチレンなどを上記親水
基含有量となるように選定して使用し、公知の重合開始
剤を用いて溶液重合法等の適宜な重合法により形成する
ことができる。この場合、エマルション粒子の核を低温
硬化性メラミン樹脂とすると、貯蔵安定性の点からメラ
ミン樹脂に対する硬化触媒能の高いアクリル酸などはメ
ラミン樹脂核に直接接触しないようにすることがよく、
かつ親水性基含有量の多い第２水溶性樹脂層に高い硬化
触媒能を修飾し、しかも親水性基含有量の少ない第１水
溶性樹脂層を低反応性とするため、第１水溶性樹脂には
アクリル酸を導入せず、メタクリル酸等の弱酸を導入す
る一方、第２水溶性樹脂にはアクリル酸等の強酸を導入
することが推奨される。The water-soluble resin forming the first and second water-soluble resin layers can be formed by copolymerizing various polymerizable monomers depending on the purpose of use of the emulsion. For example, for paint purposes, acrylic acid, methacrylic acid, alkyl esters of acrylic acid and methacrylic acid,
A hydroxyalkyl ester, styrene or the like may be selected and used so as to have the above-mentioned hydrophilic group content, and can be formed by an appropriate polymerization method such as a solution polymerization method using a known polymerization initiator. In this case, when the core of the emulsion particles is a low temperature curable melamine resin, acrylic acid, which has a high curing catalytic ability for the melamine resin from the viewpoint of storage stability, may be prevented from directly contacting the melamine resin core,
In addition, since the second water-soluble resin layer having a high hydrophilic group content is modified with a high curing catalyst ability and the first water-soluble resin layer having a low hydrophilic group content is made to have low reactivity, It is recommended that a weak acid such as methacrylic acid is introduced into the second water-soluble resin, while a strong acid such as acrylic acid is introduced into the second water-soluble resin.
【００１１】なお、第１水溶性樹脂の酸価は５〜３０ｍ
ｇ−ＫＯＨ／ｇ、特に１５〜２０ｍｇ−ＫＯＨ／ｇ、第
２水溶性樹脂の酸価は１５〜８０ｍｇ−ＫＯＨ／ｇ、特
に２０〜７０ｍｇ−ＫＯＨ／ｇ、両者の差は３〜４０ｍ
ｇ−ＫＯＨ／ｇ、特に５〜２０ｍｇ−ＫＯＨ／ｇである
ことが好ましい。また、第１水溶性樹脂の水酸基価は５
〜３０ｍｇ−ＫＯＨ／ｇ、特に１０〜２０ｍｇ−ＫＯＨ
／ｇ、第２水溶性樹脂の水酸基価は２０〜８０ｍｇ−Ｋ
ＯＨ／ｇ、特に２０〜５０ｍｇ−ＫＯＨ／ｇ、両者の差
は１０〜５０ｍｇ−ＫＯＨ／ｇ、特に１０〜４０ｍｇ−
ＫＯＨ／ｇであることが好ましい。なおまた、塗料、特
に電着塗料としての用途には、水溶性樹脂はアニオン性
質を持つことが好適である。The acid value of the first water-soluble resin is 5 to 30 m.
g-KOH / g, particularly 15 to 20 mg-KOH / g, the acid value of the second water-soluble resin is 15 to 80 mg-KOH / g, especially 20 to 70 mg-KOH / g, and the difference between the two is 3 to 40 m.
It is preferably g-KOH / g, particularly 5 to 20 mg-KOH / g. The hydroxyl value of the first water-soluble resin is 5
~ 30 mg-KOH / g, especially 10-20 mg-KOH
/ G, the hydroxyl value of the second water-soluble resin is 20 to 80 mg-K
OH / g, especially 20-50 mg-KOH / g, the difference between them is 10-50 mg-KOH / g, especially 10-40 mg-
It is preferably KOH / g. In addition, it is preferable that the water-soluble resin has an anionic property for use as a paint, especially as an electrodeposition paint.
【００１２】また、本発明のＯ／Ｗ型エマルションにお
いて、エマルション粒子（分散粒子）の粒径は種々選定
されるが、塗料とした場合は低温硬化性や硬化後の外観
の点から２００ｎｍ以下であることが好ましい。Further, in the O / W type emulsion of the present invention, various particle diameters of emulsion particles (dispersion particles) are selected, but when it is used as a paint, it is 200 nm or less in view of low temperature curability and appearance after curing. Preferably there is.
【００１３】本発明のＯ／Ｗ型エマルションを製造する
方法としては、高反応性架橋剤と上述した親水性基含有
量の互いに異なる少なくとも２種の水溶性樹脂とを混合
し、この混合物を水相に投入してエマルション化を行う
方法が採用される。As a method for producing the O / W type emulsion of the present invention, a highly reactive cross-linking agent and at least two water-soluble resins having different hydrophilic group contents described above are mixed, and the mixture is mixed with water. A method of emulsifying by adding to the phase is adopted.
【００１４】この場合、まず水溶性樹脂同士をホットブ
レンド等の方法で混合した後、高反応性架橋剤を加え、
これにアルカリ、アミン等の中和剤を加えて水溶性樹脂
混合物の中和度を３０〜８０％程度に調整し、水相に転
送し、エマルション化する方法が好適で、予め樹脂混合
物を中和剤で中和し、水中に該樹脂混合物を投入するこ
とにより、エマルション粒子の粒径制御及び複層化が効
果的に行われ、本発明のエマルションを簡単かつ確実に
調製することができる。In this case, first, the water-soluble resins are mixed with each other by a method such as hot blending, and then a highly reactive crosslinking agent is added,
It is preferable to add a neutralizing agent such as an alkali or amine to this to adjust the neutralization degree of the water-soluble resin mixture to about 30 to 80%, transfer it to the water phase, and emulsify it. By neutralizing with a solvating agent and introducing the resin mixture into water, the particle size control of emulsion particles and the formation of a multilayer are effectively performed, and the emulsion of the present invention can be prepared easily and reliably.
【００１５】本発明のＯ／Ｗ型エマルションは、特に塗
料として好適に用いられ、この場合バーコーティング型
の塗料として好適であるばかりでなく、電着塗料として
も好適である。The O / W type emulsion of the present invention is particularly preferably used as a paint, and in this case, it is suitable not only as a bar coating type paint but also as an electrodeposition paint.
【００１６】[0016]
【実施例】以下、実施例と比較例を示し、本発明を具体
的に説明するが、本発明は下記の実施例に制限されるも
のではない。EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.
【００１７】〔実施例，比較例〕撹拌機、窒素ガス導入
管、冷却管及び滴下ロートを備えた２リットルの反応容
器に表１に示すモノマー成分を仕込み、９０℃で３時間
反応させて、互いに親水性基含有量の異なる水溶性樹脂
Ａ及びＢを製造した。[Examples and Comparative Examples] The monomer components shown in Table 1 were charged in a 2 liter reaction vessel equipped with a stirrer, a nitrogen gas introducing tube, a cooling tube and a dropping funnel, and reacted at 90 ° C. for 3 hours. Water-soluble resins A and B having different hydrophilic group contents were produced.
【００１８】[0018]
【表１】 [Table 1]
【００１９】次に、ディスパーにより表２に示す割合で
水溶性樹脂Ａ，Ｂを９０℃で２時間混合し、５０℃に冷
却した後、メラミン樹脂を加え、ジメチルエーテルアミ
ン（ＤＭＥＡ）を中和剤として添加した後、これを固形
分２５％になるように脱イオン水中に混合し、エマルシ
ョン化を行って、Ｏ／Ｗ型エマルションの塗料を得た。Next, water-soluble resins A and B were mixed with a disperser at a ratio shown in Table 2 at 90 ° C. for 2 hours, cooled to 50 ° C., melamine resin was added, and dimethyl ether amine (DMEA) was added as a neutralizing agent. As a solid content of 25%, the mixture was mixed in deionized water to form an emulsion, and an O / W emulsion coating material was obtained.
【００２０】この塗料をアプリケーターでアルミニウム
板に１５μｍ塗装し、所定温度で３０分間焼付け、塗料
の硬化温度を調べた。なお、硬化性の評価は、アセトン
／メタノール＝１／１の混合溶剤を用いて塗膜をラビン
グ試験し、下記基準で評価した。結果を表２に示す。
◎：異常なし
○：若干傷が生じる
△：白化する
×：剥離する。This paint was applied on an aluminum plate by an applicator to a thickness of 15 μm and baked at a predetermined temperature for 30 minutes to examine the hardening temperature of the paint. The curability was evaluated by rubbing the coating film with a mixed solvent of acetone / methanol = 1/1 and evaluated according to the following criteria. The results are shown in Table 2. ⊚: No abnormality ○: Slightly scratched Δ: Whitening ×: Peeling off
【００２１】また、上記塗料を室温で１か月保存した後
の状態を調べ、貯蔵安定性を評価した。結果を表２に併
記する。Further, the storage stability was evaluated by examining the condition of the above coating composition after storing it at room temperature for one month. The results are also shown in Table 2.
【００２２】[0022]
【表２】 [Table 2]
【００２３】[0023]
【発明の効果】本発明のＯ／Ｗ型エマルションは、エマ
ルション粒子が複層化しているため低温硬化性メラミン
樹脂等の高反応性架橋剤の反応性が制御され、貯蔵安定
性が良好で貯蔵中にゲル化するような不都合が可及的に
防止される。このＯ／Ｗ型エマルションは塗料とした場
合、低温硬化が可能である。更に、本発明の製造方法に
よれば、かかるＯ／Ｗ型エマルションを容易かつ確実に
調製し得る。EFFECTS OF THE INVENTION The O / W type emulsion of the present invention has a multiplicity of emulsion particles, so that the reactivity of a highly reactive crosslinking agent such as a low temperature curable melamine resin is controlled and the storage stability is good. Inconvenience such as gelation is prevented as much as possible. This O / W emulsion can be cured at a low temperature when used as a paint. Furthermore, according to the production method of the present invention, such an O / W emulsion can be easily and reliably prepared.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 土家 和代 大阪府枚方市出口１丁目５番１号 上村工 業株式会社中央研究所内 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Kazuyo Tsuchiya Uemura-ko, 1-5-1, Exit Hirakata, Osaka Central Research Institute
Claims (2)
量の少ない水溶性樹脂層が形成され、その周囲に親水性
基含有量の多い水溶性樹脂層が形成された粒子を分散相
とするＯ／Ｗ型エマルション。1. A particle in which a water-soluble resin layer having a small hydrophilic group content is formed around a highly reactive cross-linking agent nucleus and a water-soluble resin layer having a large hydrophilic group content is formed around the core. O / W type emulsion as a phase.
に異なる少なくとも２種の水溶性樹脂とを混合し、この
混合物を水相に投入してエマルション化を行うことを特
徴とする請求項１に記載のＯ／Ｗ型エマルションを製造
する方法。2. A highly reactive crosslinking agent and at least two kinds of water-soluble resins having different hydrophilic group contents from each other are mixed, and the mixture is added to an aqueous phase to emulsify. Item 2. A method for producing an O / W emulsion according to Item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3178773A JPH08888B2 (en) | 1991-06-24 | 1991-06-24 | O / W emulsion and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3178773A JPH08888B2 (en) | 1991-06-24 | 1991-06-24 | O / W emulsion and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH051230A true JPH051230A (en) | 1993-01-08 |
| JPH08888B2 JPH08888B2 (en) | 1996-01-10 |
Family
ID=16054378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3178773A Expired - Fee Related JPH08888B2 (en) | 1991-06-24 | 1991-06-24 | O / W emulsion and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08888B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5251426A (en) * | 1975-10-23 | 1977-04-25 | Kansai Paint Co Ltd | Watr-based coating composition |
| JPS54123141A (en) * | 1978-03-17 | 1979-09-25 | Toyo Ink Mfg Co Ltd | Thermosetting water-based coating compositon |
| JPS61145265A (en) * | 1984-12-19 | 1986-07-02 | Honny Chem Ind Co Ltd | Resin composition for matted ectrodeposition coating |
| JPS63156871A (en) * | 1986-12-22 | 1988-06-29 | Daicel Chem Ind Ltd | Colored paving material |
| JPH03133916A (en) * | 1989-10-18 | 1991-06-07 | Kao Corp | Water-based manicure |
-
1991
- 1991-06-24 JP JP3178773A patent/JPH08888B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5251426A (en) * | 1975-10-23 | 1977-04-25 | Kansai Paint Co Ltd | Watr-based coating composition |
| JPS54123141A (en) * | 1978-03-17 | 1979-09-25 | Toyo Ink Mfg Co Ltd | Thermosetting water-based coating compositon |
| JPS61145265A (en) * | 1984-12-19 | 1986-07-02 | Honny Chem Ind Co Ltd | Resin composition for matted ectrodeposition coating |
| JPS63156871A (en) * | 1986-12-22 | 1988-06-29 | Daicel Chem Ind Ltd | Colored paving material |
| JPH03133916A (en) * | 1989-10-18 | 1991-06-07 | Kao Corp | Water-based manicure |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08888B2 (en) | 1996-01-10 |
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