JPH1135770A - Vinyl resin emulsion - Google Patents

Vinyl resin emulsion

Info

Publication number
JPH1135770A
JPH1135770A JP20253397A JP20253397A JPH1135770A JP H1135770 A JPH1135770 A JP H1135770A JP 20253397 A JP20253397 A JP 20253397A JP 20253397 A JP20253397 A JP 20253397A JP H1135770 A JPH1135770 A JP H1135770A
Authority
JP
Japan
Prior art keywords
resin emulsion
emulsion
vinyl resin
weight
dithionite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP20253397A
Other languages
Japanese (ja)
Other versions
JP3164297B2 (en
Inventor
Masahiro Saito
昌宏 斎藤
Mitsuo Shibuya
光夫 渋谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Synthetic Chemical Industry Co Ltd
Original Assignee
Nippon Synthetic Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Synthetic Chemical Industry Co Ltd filed Critical Nippon Synthetic Chemical Industry Co Ltd
Priority to JP20253397A priority Critical patent/JP3164297B2/en
Publication of JPH1135770A publication Critical patent/JPH1135770A/en
Application granted granted Critical
Publication of JP3164297B2 publication Critical patent/JP3164297B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PROBLEM TO BE SOLVED: To obtain an emulsion excellent in long-term storage stability, adhesiveness and the water resistance of a coating film formed therefrom and useful in e.g. applications where wood is coated or impregnated therewith to catch formaldehydes in the wood by selecting an emulsion containing an acetoacetyl- containing PVA resin and a dithionite. SOLUTION: There is provided an emulsion containing acetoacetyl-containing PVA resin and desirably 0.05-4 wt.% dithionite, desirably sodium dithionite (Na2 S2 O4 ). It is more desirable that this emulsion contains desirably 0.05-2 wt.% at least one reducing agent selected among sulfites, thiosulfates, (meth)bisulfites, L-ascorbic acid and hydrazines and/or that the residual vinyl monomer content is 0.4 wt.% or below and/or that 0.01-4 wt.% alkali salt of cinnamic acid is added and/or that the pH is adjusted to 3-8.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明はビニル樹脂系エマル
ジョンに関し、更に詳しくは長期の保存安定性及び生成
塗膜の耐水性に優れたビニル樹脂系エマルジョンに関す
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl resin emulsion, and more particularly to a vinyl resin emulsion excellent in long-term storage stability and water resistance of a formed coating film.

【0002】[0002]

【従来の技術】従来より、(酢酸)ビニル樹脂系エマル
ジョンは、接着剤、塗料、繊維・織物の加工剤、紙・皮
革の加工剤、各種材料のバインダー、セメント・モルタ
ルの混和剤等の広範な用途に利用されている。中でも、
アセトアセチル化ポリビニルアルコール系樹脂を含有し
た(酢酸)ビニル樹脂系エマルジョンは、木工用接着剤
として用いた場合に各種架橋剤の併用で、耐水性のさら
なる向上が可能で、また、接着剤の切断時に刃物を傷め
ない等の利点があるため、上記の用途等に利用されてい
る。しかしながら、アセトアセチル化ポリビニルアルコ
ール系樹脂を添加した場合には、エマルジョンの安定性
が低下する(粘度の上昇、ゲルの発生等)ため、各種の
添加剤の併用が試みられている。例えば、特公昭60−
36218号公報には、亜硫酸塩、チオ硫酸塩、重亜硫
酸塩、メタ重亜硫酸等の併用が、特開平7−3102号
公報には、特定式を表される水酸基含有化合物の併用
が、特開平8−113687号公報には、水溶性有機ア
ミンと水溶性ヒドラジンとの併用が提案されており、ま
た、本出願人もケトン類、ケト酸エステル類、マロン酸
類等の併用(特公平3−50772号公報)、酸性亜硫
酸ソーダの併用(特開平7−138305号公報)、メ
ルカプタン類の併用(特開平7−138306号公報)
等を出願した。
2. Description of the Related Art Conventionally, (vinyl acetate) -based emulsions have been widely used for adhesives, paints, textile / textile processing agents, paper / leather processing agents, binders for various materials, and cement / mortar admixtures. It is used for various purposes. Among them,
(Acetic acid) vinyl resin emulsion containing acetoacetylated polyvinyl alcohol-based resin can be used as an adhesive for woodworking by using various cross-linking agents to further improve the water resistance, and to cut the adhesive. It has advantages such as not damaging the blade sometimes, and is therefore used for the above-mentioned applications. However, when an acetoacetylated polyvinyl alcohol-based resin is added, the stability of the emulsion decreases (increase in viscosity, generation of a gel, etc.), and thus various additives have been used in combination. For example,
JP-A-36218 discloses the combination use of sulfites, thiosulfates, bisulfites, metabisulfites and the like, and JP-A-7-3102 discloses the combination use of a hydroxyl group-containing compound represented by a specific formula. In Japanese Patent Application Laid-Open No. 8-113687, a combined use of a water-soluble organic amine and a water-soluble hydrazine is proposed, and the applicant of the present invention also used a combined use of ketones, keto acid esters, malonic acids, etc. JP-A-7-138305), combined use of sodium acid sulfite (JP-A-7-138305), combined use of mercaptans (JP-A-7-138306)
And so on.

【0003】[0003]

【発明が解決しようとする課題】しかし、上記の特公昭
60−36218号公報、特開平7−3102号公報、
特公平3−50772号公報、特開平7−138306
号公報に記載の添加剤の併用では、ある程度の保存安定
性は望めるものの、夏季や冬季の高温時や低温時の安定
性が十分ではなく、また長期保存後の皮膜強度や接着剤
として用いたときの接着性に劣り、まだまだ満足は行か
ず、更に特開平8−113687号公報に記載の添加剤
の併用では、ゲル化は防げるもののエマルジョンが粘度
上昇をおこして、接着剤等に用いた場合、使用時期によ
り安定した接着力を得ることができないという欠点を有
し、新なる改良が望まれるところである。
However, Japanese Patent Publication No. 60-36218 and Japanese Patent Application Laid-Open No.
JP-B-3-50772, JP-A-7-138306
In the combined use of the additives described in Japanese Patent Publication No. 1993, although a certain degree of storage stability can be expected, the stability at high and low temperatures in summer and winter is not sufficient, and it was used as a film strength or adhesive after long-term storage. Poor adhesiveness at the time, still unsatisfactory, and with the use of the additive described in JP-A-8-113687, gelling can be prevented, but the emulsion causes an increase in viscosity and is used in an adhesive or the like. However, there is a drawback that a stable adhesive force cannot be obtained depending on the time of use, and a new improvement is desired.

【0004】[0004]

【課題を解決するための手段】そこで、上記の事情に鑑
みて、本発明者が鋭意研究した結果、アセトアセチル基
含有ポリビニルアルコール系樹脂を含有し、かつビニル
モノマーの含有量が0.4重量%以下であるとき、更に
pHを3〜8とするとき、夏季や冬季の高温時や低温時
においても十分な安定性を発揮し、また長期保存後の皮
膜強度や接着剤として用いたときの接着力等の維持が可
能なエマルジョンが得られることを見いだし、本発明を
完成するに至った。
In view of the above circumstances, the present inventor has conducted intensive studies, and as a result, it has been found that a polyvinyl alcohol resin containing an acetoacetyl group is contained and a vinyl monomer content is 0.4 wt. % Or less, and when the pH is 3 to 8, it exhibits sufficient stability even at high or low temperatures in summer or winter, and when used as a film strength or adhesive after long-term storage. The inventors have found that an emulsion capable of maintaining the adhesive force or the like can be obtained, and have completed the present invention.

【0005】[0005]

【発明の実施の形態】以下、本発明を詳細に説明する。
本発明に用いるアセトアセチル化ポリビニルアルコール
系樹脂(以下、AA化PVAと略記することがある)
は、ポリビニルアルコール系樹脂(以下、PVAと略記
することがある)とジケテンとを公知の方法で反応して
得ることができ、例えばPVAを酢酸溶媒中に分散させ
ておき、これにジケテンを添加する方法、PVAをジメ
チルホルムアミド、またはジオキサンなどの溶媒にあら
かじめ溶解しておき、これにジケテンを添加する方法で
ある。またPVAにジケテンガスまたは液状ジケテンを
直接接触させてAA化PVAを得る方法やPVAのアル
コール溶剤のケン化スラリーに硫酸などの酸触媒を加え
てアセト酢酸エステルをエステル交換させて、AA化P
VAを得る方法等も採り得る。
DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
Acetoacetylated polyvinyl alcohol resin used in the present invention (hereinafter sometimes abbreviated as AA-PVA)
Can be obtained by reacting a polyvinyl alcohol-based resin (hereinafter sometimes abbreviated as PVA) with diketene by a known method. For example, PVA is dispersed in an acetic acid solvent, and diketene is added thereto. In this method, PVA is previously dissolved in a solvent such as dimethylformamide or dioxane, and diketene is added thereto. A method for obtaining AA-PVA by directly contacting PVA with diketene gas or liquid diketene, or adding an acid catalyst such as sulfuric acid to a saponified slurry of an alcoholic solvent for PVA to transesterify acetoacetate to obtain AA-P
A method of obtaining VA can be employed.

【0006】かかるAA化PVAの平均重合度は特に制
限はないが、200〜3000が好ましく、更には40
0〜2600が好ましく、かかる平均重合度が200未
満では後述する乳化剤としての保護コロイド力が得難
く、乳化重合時の安定性に欠け、逆に3000を越える
と乳化剤として使用した場合に得られるエマルジョン粘
度が上昇して好ましくない。又、AA化PVAの原料P
VAの平均ケン化度は68〜100モル%が好ましく、
更には80〜100モル%の範囲が好ましく、かかる平
均ケン化度が68モル%未満では得られるAA化PVA
が水不溶性となって好ましくない。更に、AA化PVA
のアセトアセチル基の含有量(AA化度)は0.05〜
15モル%が好ましく、更には1〜10モル%の範囲が
好ましく、かかるAA化度が0.05モル%未満ではエ
マルジョンを塗膜にしたときの耐水性が低下する傾向に
あり、逆に15モル%を越えると、エマルジョン粘度が
高すぎたり、保存安定性が低下する傾向にあり好ましく
ない。
The average degree of polymerization of the AA-PVA is not particularly limited, but is preferably from 200 to 3,000, more preferably from 40 to 3,000.
If the average degree of polymerization is less than 200, it is difficult to obtain a protective colloid as an emulsifier described later, and the emulsion has poor stability during emulsion polymerization. Conversely, if it exceeds 3,000, an emulsion obtained when used as an emulsifier The viscosity increases, which is not preferable. Also, a raw material P for AA-PVA
The average degree of saponification of VA is preferably 68 to 100 mol%,
Further, it is preferably in the range of 80 to 100 mol%, and the AA-PVA obtained when the average saponification degree is less than 68 mol% is obtained.
Is not preferred because it becomes insoluble in water. Furthermore, AA-PVA
Acetoacetyl group content (AA degree) of 0.05 to
When the AA degree is less than 0.05 mol%, the water resistance when the emulsion is formed into a coating film tends to decrease. If it exceeds mol%, the emulsion viscosity is too high and the storage stability tends to decrease, which is not preferred.

【0007】また、本発明においては、かかるAA化P
VAを単独で用いるのみならず、他のPVAを併用する
ことも可能で、更にはケン化度等が異なる2種以上のA
A化PVAを用いることも可能である。かかるAA化P
VAの含有量は、本発明のビニル樹脂系エマルジョンの
全体に対し、0.1〜30重量%(更には1〜10重量
%)の範囲から選択することが好ましく、かかる含有量
が0.1重量%未満ではエマルジョンを塗膜にしたとき
の耐水性が低下し、逆に30重量%を越えるとエマルジ
ョン粘度が高すぎたり、保存安定性が低下して好ましく
ない。
In the present invention, the AA-P
It is possible to use not only VA alone, but also other PVAs, and furthermore, two or more kinds of A having different degrees of saponification and the like.
It is also possible to use A-PVA. Such AA-P
The content of VA is preferably selected from the range of 0.1 to 30% by weight (more preferably 1 to 10% by weight) based on the whole of the vinyl resin emulsion of the present invention. When the amount is less than 30% by weight, the water resistance of the emulsion when formed into a coating film is reduced. On the other hand, when the amount is more than 30% by weight, the emulsion viscosity is too high and the storage stability is undesirably reduced.

【0008】上記の如きAA化PVAが含有される本発
明の酢酸ビニル樹脂系エマルジョンは、通常ビニル化合
物を乳化重合して得られるもので、かかるビニル化合物
としては、酢酸ビニル、プロピオン酸ビニル、(メタ)
アクリル酸エステル、塩化ビニル、塩化ビニリデン、
(メタ)アクリロニトリル、スチレン、エチレン、プロ
ピレン、アセトアセチル基含有アクリルモノマーなどが
挙げられ、これらの単独重合あるいは共重合あるいはブ
タジエン系等のジエン系モノマーとの共重合である。な
かんずく酢酸ビニル単独あるいは酢酸ビニルを主体とし
た共重合が好適である。乳化重合触媒としてはラジカル
発生剤、なかんずく水溶性触媒が好適なものとして用い
られ、例えば過酸化水素等の過酸化物、酒石酸、ギ酸、
シュウ酸等の還元剤、2,2−アゾビス(2−アミジノ
プロパン)二酸塩等の水溶性アゾビス、過硫酸アンモニ
ウム、過硫酸カリウム等の1種またはこれらの2種以上
が用いられ、好適には過硫酸アンモニウム、過硫酸カリ
ウム等の過硫酸系の触媒が用いられる。
The vinyl acetate resin emulsion of the present invention containing the AA-PVA as described above is usually obtained by emulsion polymerization of a vinyl compound. Examples of such a vinyl compound include vinyl acetate, vinyl propionate, and ( Meta)
Acrylic acid ester, vinyl chloride, vinylidene chloride,
Examples thereof include (meth) acrylonitrile, styrene, ethylene, propylene, and an acetoacetyl group-containing acrylic monomer. These are homopolymerization or copolymerization, or copolymerization with a diene monomer such as butadiene. In particular, vinyl acetate alone or a copolymer mainly composed of vinyl acetate is preferred. As the emulsion polymerization catalyst, a radical generator, in particular, a water-soluble catalyst is preferably used.For example, peroxides such as hydrogen peroxide, tartaric acid, formic acid,
One or more of a reducing agent such as oxalic acid, a water-soluble azobis such as 2,2-azobis (2-amidinopropane) diacid salt, ammonium persulfate, potassium persulfate and the like, or two or more thereof are preferably used. A persulfate-based catalyst such as ammonium persulfate or potassium persulfate is used.

【0009】またノニオン界面活性剤、アニオン界面活
性剤等の各種界面活性剤もAA化PVAと併用しうる。
さらに他の乳化剤、例えばセルロース誘導体(カルボキ
シメチルセルロース、ヒドロキシエチルセルロース、メ
チルセルロースなど)、ポリビニルアルコール類、ポリ
アクリル酸誘導体、(無水)マレイン酸−ビニルエーテ
ル共重合体、(無水)マレイン酸−酢酸ビニル共重合
体、酢酸ビニル−(メタ)アリルスルホン酸(塩)共重
合体ケン化物なども適宜併用できる。
Various surfactants such as nonionic surfactants and anionic surfactants can be used in combination with AA-PVA.
Still other emulsifiers such as cellulose derivatives (carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, etc.), polyvinyl alcohols, polyacrylic acid derivatives, maleic anhydride-vinyl ether copolymer, maleic anhydride-vinyl acetate copolymer And a saponified product of vinyl acetate- (meth) allylsulfonic acid (salt) copolymer and the like can also be appropriately used.

【0010】本発明においては、上記の如きAA化PV
Aが含有されるビニル樹脂系エマルジョンに更に亜ジチ
オン酸塩を含有させることを最大の特徴とするもので、
かかる亜ジチオン酸塩としては亜ジチオン酸ナトリウム
(Na224)、亜ジチオン酸カリウム(K2
24)、亜ジチオン酸アンモニウム([(NH)422
4)、が例示でき、これに限定されるものではない
が、亜ジチオン酸ナトリウム(Na224)が好適に
用いられる。
In the present invention, the AA-PV as described above is used.
The greatest feature is that the dithionite is further contained in the vinyl resin emulsion containing A.
Examples of the dithionite include sodium dithionite (Na 2 S 2 O 4 ) and potassium dithionite (K 2 S)
2 O 4 ), ammonium dithionite ([(NH) 4 ] 2 S 2
O 4 ) can be given as an example, but not limited thereto. Sodium dithionite (Na 2 S 2 O 4 ) is preferably used.

【0011】かかる亜ジチオン酸塩の含有量は、ビニル
系エマルジョン中に0.05〜4重量%であることが好
ましく、更には0.05〜2重量%で、かかる含有量が
0.05重量%未満では、エマルジョンの保存安定性が
低下し、逆に4重量%を越えるとエマルジョンの耐水性
が若干低下したり、硫黄臭が強くなる傾向にあり好まし
くない。また、かかる亜ジチオン酸塩の添加方法につい
ては特に限定されず、重合中、重合後等いつでもよい
が、より良好な皮膜の耐水性を得るためには重合後が好
ましく、添加に際しては固形状のままでもよいが、水溶
液として添加する方が好ましい。
The content of such a dithionite is preferably 0.05 to 4% by weight, more preferably 0.05 to 2% by weight in the vinyl emulsion, and the content is 0.05% by weight. If it is less than 4% by weight, the storage stability of the emulsion will be reduced. Conversely, if it exceeds 4% by weight, the water resistance of the emulsion will be slightly reduced and the sulfur smell will be undesirably increased. The method for adding the dithionite is not particularly limited, and may be any time during polymerization, such as after polymerization, but is preferably performed after polymerization in order to obtain better water resistance of the film. Although it may be as it is, it is preferable to add it as an aqueous solution.

【0012】本発明では、更に、亜硫酸塩、チオ硫酸
塩、重亜硫酸塩、メタ重亜硫酸塩、L−アスコルビン
酸、ヒドラジン類等の還元剤を含有させることも好まし
く、かかる還元剤として具体的には亜硫酸ナトリウム、
亜硫酸カリウム、亜硫酸アンモニウム、チオ硫酸ナトリ
ウム、チオ硫酸カリウム、チオ硫酸アンモニウム、重亜
硫酸ナトリウム、重亜硫酸アンモニウム、メタ重亜硫酸
ナトリウム、メタ重亜硫酸カリウム、L−アスコルビン
酸、硫酸ヒドラジン、塩酸ヒドラジン、炭酸ヒドラジ
ン、置換ヒドラジン、リン酸ヒドラジン、メチルヒドラ
ジン等を挙げることができ、好適には重亜硫酸ナトリウ
ムが用いられ、その含有量は0.05〜2重量%(更に
は0.1〜1重量%)であることが好ましく、かかる含
有量が0.05重量%未満ではエマルジョンの保存安定
性の向上があまり期待できず、逆に2重量%を越えると
皮膜の耐水性や接着力が低下して好ましくない。これら
の還元剤の添加も、重合中または重合後のいずれでもよ
いが、重合後が好ましく、添加にあたっては固体状のま
までもよいが、水溶液として添加することが好ましい。
In the present invention, it is preferable to further include a reducing agent such as a sulfite, a thiosulfate, a bisulfite, a metabisulfite, L-ascorbic acid, and hydrazines. Is sodium sulfite,
Potassium sulfite, ammonium sulfite, sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, sodium bisulfite, ammonium bisulfite, sodium metabisulfite, potassium metabisulfite, L-ascorbic acid, hydrazine sulfate, hydrazine hydrochloride, hydrazine carbonate, substitution Hydrazine, hydrazine phosphate, methyl hydrazine and the like can be mentioned. Preferably, sodium bisulfite is used, and its content is 0.05 to 2% by weight (further 0.1 to 1% by weight). When the content is less than 0.05% by weight, the storage stability of the emulsion cannot be expected to be much improved. On the contrary, when the content exceeds 2% by weight, the water resistance and adhesive strength of the film are undesirably reduced. The addition of these reducing agents may be during or after the polymerization, but is preferably performed after the polymerization. The addition may be performed in a solid state, but is preferably performed as an aqueous solution.

【0013】かくして、アセトアセチル基含有ポリビニ
ルアルコール系樹脂及び亜ジチオン酸塩を含有した本発
明の(酢酸)ビニル樹脂系エマルジョンが得られるわけ
であるが、本発明においては、かかるエマルジョン中の
ビニルモノマーの残存量を0.4重量%以下、更には
0.3重量%以下、特に0.2重量%以下にしたり、か
かるエマルジョンのpHを3〜8、更には4〜7にする
ことも好ましい。かかるエマルジョン中のビニルモノマ
ーの残存量を0.4重量%以下にコントロールする方法
としては、特に限定されないが、例えば、上記の如き
(酢酸)ビニル化合物の乳化重合時に、イソプロピルア
ルコールを共存させておき、更に重合触媒の滴下終了後
にブチルアルコールを添加する方法、AA化PVAを
含有した(酢酸)ビニル樹脂系エマルジョン中の残留
(酢酸)ビニルモノマーをケイ酸のアルカリ金属塩を添
加する方法、乳化重合時の重合温度を上げる方法等が
挙げられるが、やが、工業的に有用で、かかる方法
について、更に詳しく説明する。
Thus, the (acetic acid) vinyl resin-based emulsion of the present invention containing the acetoacetyl group-containing polyvinyl alcohol-based resin and the dithionite is obtained. In the present invention, the vinyl monomer in the emulsion is used. It is also preferable to keep the residual amount of 0.4% by weight or less, more preferably 0.3% by weight or less, particularly 0.2% by weight or less, and the pH of such an emulsion at 3-8, more preferably 4-7. The method for controlling the residual amount of the vinyl monomer in the emulsion to 0.4% by weight or less is not particularly limited. For example, during the emulsion polymerization of the (acetic acid) vinyl compound as described above, isopropyl alcohol is allowed to coexist. A method of adding butyl alcohol after the addition of the polymerization catalyst, a method of adding an alkali metal salt of silicic acid to a residual (acetic acid) vinyl monomer in a (acetic acid) vinyl resin emulsion containing AA-PVA, Although a method of raising the polymerization temperature at the time is mentioned, the method is industrially useful, and such a method will be described in more detail.

【0014】の方法におけるイソプロピルアルコール
の共存量は該ビニル化合物100重量部に対して、0.
2〜2重量部(更には0.5〜1.5重量部)が好まし
く、かかる添加量が0.2重量部未満では、該モノマー
量の低減効果が十分でなく、逆に添加量が2重量部を越
えるとエマルジョンの粘度安定性が低下して好ましくな
い。また、重合触媒の滴下終了後に添加するブチルアル
コールの添加量は該ビニル化合物100重量部に対し
て、0.05〜0.3重量部(更には0.1〜0.2重
量部)が好ましく、かかる添加量が0.05重量部未満
では、該モノマー量の低減効果が十分でなく、逆に添加
量が0.3重量部を越えても残存モノマーの低減に寄与
しない。
In the above method, the coexistence amount of isopropyl alcohol is 0.1 to 100 parts by weight of the vinyl compound.
The amount is preferably from 2 to 2 parts by weight (more preferably from 0.5 to 1.5 parts by weight). If the amount is less than 0.2 part by weight, the effect of reducing the amount of the monomer is not sufficient. Exceeding the weight part is not preferred because the viscosity stability of the emulsion decreases. Further, the addition amount of butyl alcohol to be added after the completion of the dropwise addition of the polymerization catalyst is preferably 0.05 to 0.3 parts by weight (more preferably 0.1 to 0.2 parts by weight) based on 100 parts by weight of the vinyl compound. If the amount is less than 0.05 part by weight, the effect of reducing the amount of the monomer is not sufficient, and if the amount exceeds 0.3 part by weight, it does not contribute to the reduction of the residual monomer.

【0015】の方法においては、ケイ酸ナトリウム
(メタケイ酸ナトリウム、オルトケイ酸ナトリウム、二
ケイ酸ナトリウム、四ケイ酸ナトリウム等)、ケイ酸カ
リウム(メタケイ酸カリウム、二ケイ酸水素カリウム
等)、ケイ酸リチウム(メタケイ酸リチウム、オルトケ
イ酸リチウム等)、及びこれらの水化物を挙げることが
でき、好適にはケイ酸ナトリウムやケイ酸カリウム等の
ケイ酸のアルカリ金属塩を用いて、その含有(添加)量
を0.01〜4重量%(更には0.02〜2重量%)に
すればよく、かかる含有量が0.01重量%未満では残
存モノマーの低減効果に乏しく、逆に4重量%を越える
とエマルジョンの安定性や皮膜強度が低下して好ましく
ない。また、かかるエマルジョンのpHのコントロール
方法についても特に限定されず、例えば各種の有機・無
機酸の金属塩やアミン類等を添加して調整すればよく、
より具体的には、酢酸ナトリウム、リン酸ナトリウム、
炭酸ナトリウム、酢酸アルミニウム、酢酸マグネシム等
を該エマルジョン中に0.01〜5重量%(対エマルジ
ョン)程度添加する(添加時期は重合中または重合後の
いずれでもよく、特に限定されないが、重合率が90%
以上の時点で添加することが好ましい)ことでコントロ
ールすることができる。
In the above method, sodium silicate (sodium metasilicate, sodium orthosilicate, sodium disilicate, sodium tetrasilicate, etc.), potassium silicate (potassium metasilicate, potassium hydrogen disilicate, etc.), silicate Lithium (lithium metasilicate, lithium orthosilicate, etc.) and hydrates thereof can be mentioned. Preferably, the content (addition) of an alkali metal salt of silicic acid such as sodium silicate or potassium silicate is used. The content may be set to 0.01 to 4% by weight (further 0.02 to 2% by weight). When the content is less than 0.01% by weight, the effect of reducing the residual monomer is poor. Exceeding this is undesirable because the stability of the emulsion and the strength of the film decrease. The method of controlling the pH of the emulsion is not particularly limited, and may be adjusted by adding, for example, various organic or inorganic acid metal salts or amines.
More specifically, sodium acetate, sodium phosphate,
Sodium carbonate, aluminum acetate, magnesium acetate and the like are added to the emulsion in an amount of about 0.01 to 5% by weight (based on the emulsion) (the timing of addition may be either during or after polymerization, and is not particularly limited. 90%
It is preferable to add at the above time).

【0016】また、上記の重合においては、その他通常
の乳化重合で用いられる種々の添加剤が使用でき、本発
明においては、特にポリエチレングリコール、メルカプ
タン類(アルキルメルカプタン、芳香族メルカプタ
ン)、スルフィド類(ジブチルジスルフィド、ジアセチ
ルジスルフィド、ジエチルジチオグリコート)、窒素含
有化合物(メチルシアノアセテート、ニトロメタン、ベ
ンジルシアナイド)等の連鎖移動剤を用いることで、エ
マルジョンの安定性に対して有用で、その添加量はビニ
ルモノマーに対して0.01〜5重量%が好ましく、更
には0.02〜2重量%が好ましく、かかる添加量が
0.01重量%未満ではエマルジョンの保存安定性が得
られにくく、逆に5重量%を越えるとエマルジョンの皮
膜の耐水性が低下して好ましくない。
In the above-mentioned polymerization, various additives used in ordinary emulsion polymerization can be used. In the present invention, polyethylene glycol, mercaptans (alkyl mercaptan, aromatic mercaptan), sulfides ( Use of a chain transfer agent such as dibutyl disulfide, diacetyl disulfide, diethyl dithioglycate) or a nitrogen-containing compound (methyl cyanoacetate, nitromethane, benzyl cyanide) is useful for the stability of the emulsion. The amount is preferably 0.01 to 5% by weight, more preferably 0.02 to 2% by weight, based on the vinyl monomer. When the amount is less than 0.01% by weight, the storage stability of the emulsion is hardly obtained. If it exceeds 5% by weight, the water resistance of the emulsion film is lowered, which is preferable. Not properly.

【0017】また、最低造膜温度等の調整のため、ジブ
チルフタレート、ジオクチルフタレート、ブチルカルビ
トール等の可塑剤を添加してもよく、更にはエマルジョ
ンの皮膜のさらなる耐水性向上のためにアジポイルジヒ
ドラジド、シュウ酸ジヒドラジド、マロン酸ジヒドラジ
ド、コハク酸ジヒドラジド、アジピン酸ジヒドラジド等
の水溶性脂肪族ジヒドラジド類を添加したり、また、フ
ェノール樹脂初期縮合物やレゾルシノール系初期縮合物
を混合することにより変性酢酸ビニルエマルジョンとし
て取り扱うことも可能である。上記の如くAA化PVA
を乳化剤として、(酢酸)ビニル系化合物の重合時に共
存させてAA化PVA含有の(酢酸)ビニル樹脂系エマ
ルジョンを得ることは勿論、(酢酸)ビニル樹脂系エマ
ルジョンにAA化PVAを後添加して本発明の(酢酸)
ビニル樹脂系エマルジョンとすることも勿論可能であ
る。
A plasticizer such as dibutyl phthalate, dioctyl phthalate, or butyl carbitol may be added for adjusting the minimum film forming temperature and the like, and adipoi for improving the water resistance of the emulsion film. Modified by adding a water-soluble aliphatic dihydrazide such as rudihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, or by mixing a phenolic resin initial condensate or resorcinol initial condensate. It can be handled as a vinyl acetate emulsion. AA-PVA as described above
Is used as an emulsifier to obtain an (AA) PVA-containing (Acetate) vinyl resin emulsion by coexisting during the polymerization of the (Acetate) vinyl compound. (Acetic acid) of the present invention
Of course, a vinyl resin emulsion can be used.

【0018】かくして、得られた本発明の(酢酸)ビニ
ル樹脂系エマルジョンは紙、木材、プラスチックス、繊
維、壁紙などの接着剤、バインダー、コーティング剤、
塗料として用いられ、特に木工接着や紙の接着の高速機
械化、更に耐水性に優れているので、合板や耐水段ボー
ル等の接着用途等に有用であり、また、木材等に塗工或
いは含浸させて木材中のホルムアルデヒド類を補足する
用途(接着剤、塗料、コーティング剤等)に用いること
も有用である。
The thus-obtained (acetic acid) vinyl resin emulsion of the present invention can be used for adhesives, binders, coating agents for paper, wood, plastics, fibers, wallpaper, etc.
It is used as a paint, especially for high-speed mechanization of woodworking and paper bonding, and is also excellent in water resistance, so it is useful for bonding applications such as plywood and water-resistant corrugated cardboard. It is also useful to use for supplementing formaldehydes in wood (adhesives, paints, coatings, etc.).

【0019】[0019]

【実施例】次に実施例によって本発明をより具体的に説
明する。尚、例中「部」、「%」とあるのは、特に断り
のない限り重量基準を表す。 実施例1 酢酸ビニルモノマー10.8部と平均重合度1400,
平均ケン化度99モル%,AA化度5.5モル%のAA
化PVAの10%水溶液120部、0.6%酢酸ナトリ
ウム水溶液10部、水37部、0.96%過硫酸アンモ
ニウム水溶液5部を撹拌機、還流冷却器、滴下ロート、
温度計を備えたセパラブルフラスコに仕込み、撹拌しな
がらフラスコ内の温度を70℃にして1時間初期重合を
行った。次いで、更に酢酸ビニルモノマー97.2部を
3時間かけて滴下すると共に、0.96%過硫酸アンモ
ニウム水溶液5部添加し、更に1時間おきに同量の0.
96%過硫酸アンモニウム水溶液を3回添加した。酢酸
ビニルモノマー滴下終了1時間後に1%ハイドロキノン
水溶液1部を添加して重合を終了させた。最後に40%
亜ジチオン酸ナトリウム水溶液2部を添加して本発明の
酢酸ビニル樹脂エマルジョンを得た。得られた酢酸ビニ
ル樹脂エマルジョンの残存酢酸ビニルモノマー量は0.
4%で、重合率98.9%、pH2.5、粘度2700
0mPa・s(BH型回転粘度計、ローター回転数10
rpm、25℃)であった。上記の酢酸ビニル樹脂エマ
ルジョンを用いて、下記の如く放置安定性及生成塗膜の
耐水性の評価を行った。
Next, the present invention will be described more specifically with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified. Example 1 10.8 parts of a vinyl acetate monomer and an average degree of polymerization of 1400,
AA having an average saponification degree of 99 mol% and an AA degree of 5.5 mol%
120 parts of a 10% aqueous PVA solution, 10 parts of a 0.6% aqueous sodium acetate solution, 37 parts of water, and 5 parts of a 0.96% aqueous ammonium persulfate solution were stirred with a stirrer, a reflux condenser, a dropping funnel,
The mixture was charged into a separable flask equipped with a thermometer, and the temperature in the flask was increased to 70 ° C. with stirring to perform initial polymerization for 1 hour. Next, 97.2 parts of vinyl acetate monomer was added dropwise over 3 hours, and 5 parts of a 0.96% ammonium persulfate aqueous solution was added.
A 96% aqueous solution of ammonium persulfate was added three times. One hour after the completion of the addition of the vinyl acetate monomer, 1 part of a 1% aqueous solution of hydroquinone was added to terminate the polymerization. Finally 40%
Two parts of an aqueous solution of sodium dithionite were added to obtain a vinyl acetate resin emulsion of the present invention. The amount of residual vinyl acetate monomer in the obtained vinyl acetate resin emulsion was 0.1.
48.9% polymerization rate 98.9%, pH 2.5, viscosity 2700
0 mPa · s (BH type rotational viscometer, rotor speed 10
rpm, 25 ° C.). Using the above-mentioned vinyl acetate resin emulsion, the stability of standing and the water resistance of the resulting coating film were evaluated as follows.

【0020】(放置安定性)得られた酢酸ビニル樹脂エ
マルジョンを450mlのマヨネーズビンに密封して、
70℃で7日放置後と室温で1年放置後の粘度を測定し
て、放置前の粘度(上記と同方法)の何倍(放置後の粘
度/放置前の粘度)になったかを調べた。尚、粘度の測
定はすべて25℃で行った。 (耐水性)上記の室温で1年放置後の酢酸ビニル樹脂エ
マルジョンをガラス板上に塗工して、40℃で3分間乾
熱処理後、24時間風乾して、約100μmの塗膜を調
整し、かかる塗膜を90℃の熱水に3時間浸漬させて、
塗膜の溶出残分測定した。 (低温安定性)得られた酢酸ビニル樹脂エマルジョンを
450mlのマヨネーズビンに密封して、0℃の恒温器
に3時間放置して、取り出し直後の粘度を測定し、この
エマルジョンを更に0℃の恒温器に1ケ月放置して、同
様に粘度を測定して、1ケ月放置前の粘度の何倍(1ケ
月放置後の粘度/3時間放置後の粘度)になったかを調
べた。
(Stability on standing) The obtained vinyl acetate resin emulsion was sealed in a 450 ml mayonnaise bottle,
The viscosities after standing at 70 ° C. for 7 days and after standing at room temperature for one year are measured to determine how many times the viscosity before standing (the same method as above) (viscosity after standing / viscosity before standing). Was. In addition, the measurement of the viscosity was all performed at 25 degreeC. (Water resistance) The above-mentioned vinyl acetate resin emulsion left for one year at room temperature is coated on a glass plate, dried and heat-treated at 40 ° C. for 3 minutes, and air-dried for 24 hours to prepare a coating film of about 100 μm. Immersing the coating film in hot water of 90 ° C. for 3 hours,
The elution residue of the coating film was measured. (Low-temperature stability) The obtained vinyl acetate resin emulsion was sealed in a 450 ml mayonnaise bottle, left in a thermostat at 0 ° C. for 3 hours, the viscosity immediately after being taken out was measured, and the emulsion was further thermostated at 0 ° C. The container was left for one month, and the viscosity was measured in the same manner to determine how many times the viscosity before standing for one month (viscosity after standing for one month / viscosity after standing for three hours).

【0021】実施例2 実施例1において、更に40%亜硫酸水素ナトリウム水
溶液2部を添加した以外は同様に行って、残存酢酸ビニ
ルモノマー量0.4%、重合率98.9%、pH2.
5、粘度26000mPa・s(同上)の酢酸ビニル樹
脂エマルジョンを得て、同様に評価を行った。
Example 2 The procedure of Example 1 was repeated except that 2 parts of a 40% aqueous solution of sodium bisulfite was further added. The amount of the remaining vinyl acetate monomer was 0.4%, the conversion was 98.9%, and the pH was 2.0.
5. A vinyl acetate resin emulsion having a viscosity of 26000 mPa · s (same as above) was obtained and similarly evaluated.

【0022】実施例3 実施例1において、更に亜ジチオン酸ナトリウム水溶液
と同時に10%ケイ酸ナトリウム水溶液を5部添加した
以外は同様に行って、残存酢酸ビニルモノマー量0.3
%、重合率99.1%、pH5.0、粘度25000m
Pa・s(同上)の酢酸ビニル樹脂エマルジョンを得
て、同様に評価を行った。
Example 3 The procedure of Example 1 was repeated except that 5 parts of a 10% aqueous sodium silicate solution was added simultaneously with the aqueous sodium dithionite solution.
%, Polymerization rate 99.1%, pH 5.0, viscosity 25000 m
A vinyl acetate resin emulsion having a Pa · s (same as above) was obtained and similarly evaluated.

【0023】実施例4 実施例1において、40%亜ジチオン酸ナトリウム水溶
液の配合量を10部とした以外は同様に行って、残存酢
酸ビニルモノマー量0.4%、重合率98.8%、pH
3.0、粘度25000mPa・s(同上)の酢酸ビニ
ル樹脂エマルジョンを得て、同様に評価を行った。
Example 4 The procedure of Example 1 was repeated except that the amount of the 40% aqueous solution of sodium dithionite was changed to 10 parts. The amount of the remaining vinyl acetate monomer was 0.4%, the polymerization rate was 98.8%, pH
A vinyl acetate resin emulsion having a viscosity of 3.0 and a viscosity of 25,000 mPa · s (same as above) was obtained and evaluated in the same manner.

【0024】実施例5 実施例1において、更に亜ジチオン酸ナトリウム水溶液
と同時に15%酢酸ナトリウム水溶液1部添加した以外
は同様に行って、残存酢酸ビニルモノマー量0.4%、
重合率98.9%、pH4.5、粘度26000mPa
・s(同上)の酢酸ビニル樹脂エマルジョンを得て、同
様に評価を行った。
Example 5 The procedure of Example 1 was repeated, except that 1 part of a 15% aqueous sodium acetate solution was added simultaneously with the aqueous sodium dithionite solution.
Polymerization rate 98.9%, pH 4.5, viscosity 26000 mPa
-A vinyl acetate resin emulsion of s (same as above) was obtained and similarly evaluated.

【0025】実施例6 予め酢酸ビニルモノマー108部とイソプロピルアルコ
ール2部からなる混合液を用意しておき、かかる混合液
11部、平均重合度1400,平均ケン化度99モル
%,AA化度5.5モル%のAA化PVAの10%水溶
液120部、0.6%酢酸ナトリウム水溶液10部、水
37部、0.96%過硫酸アンモニウム水溶液5部を撹
拌機、還流冷却器、滴下ロート、温度計を備えたセパラ
ブルフラスコに仕込み、撹拌しながらフラスコ内の温度
を70℃にして1時間初期重合を行った。次いで、残り
の混合液99部を3時間かけて滴下すると共に、0.9
6%過硫酸アンモニウム水溶液5部を添加し、更に1時
間おきに同量の0.96%過硫酸アンモニウム水溶液を
3回添加した。酢酸ビニルモノマー滴下終了と同時に、
ブチルアルコール0.3部を添加し、1時間後に1%ハ
イドロキノン水溶液1部を添加して重合を終了させた。
最後に40%亜ジチオン酸ナトリウム水溶液2部、15
%酢酸ナトリウム水溶液1部を添加して酢酸ビニル樹脂
エマルジョンを得た。得られた酢酸ビニル樹脂エマルジ
ョンの残存酢酸ビニルモノマー量は0.2%で、重合率
99.4%、pH4.2、粘度25000mPa・s
(同上)であった。
Example 6 A mixed solution composed of 108 parts of vinyl acetate monomer and 2 parts of isopropyl alcohol was prepared in advance, 11 parts of the mixed solution, average degree of polymerization was 1400, average degree of saponification was 99 mol%, and degree of AA was 5 120 parts of a 10% aqueous solution of 0.5 mol% AA-PVA, 120 parts of a 0.6% aqueous sodium acetate solution, 37 parts of water, and 5 parts of a 0.96% aqueous ammonium persulfate solution were stirred with a stirrer, a reflux condenser, a dropping funnel, and a temperature. The mixture was charged into a separable flask equipped with a meter, and the temperature in the flask was set to 70 ° C. with stirring to carry out initial polymerization for 1 hour. Next, 99 parts of the remaining liquid mixture was added dropwise over 3 hours,
5 parts of a 6% ammonium persulfate aqueous solution was added, and the same amount of a 0.96% ammonium persulfate aqueous solution was further added three times every hour. At the same time as vinyl acetate monomer dropping,
0.3 parts of butyl alcohol was added, and one hour later, 1 part of a 1% aqueous solution of hydroquinone was added to terminate the polymerization.
Finally, 2 parts of a 40% aqueous sodium dithionite solution, 15 parts
1% aqueous sodium acetate solution was added to obtain a vinyl acetate resin emulsion. The obtained vinyl acetate resin emulsion had a residual vinyl acetate monomer content of 0.2%, a polymerization rate of 99.4%, a pH of 4.2, and a viscosity of 25,000 mPa · s.
(Id.)

【0026】実施例7 実施例6と同様に重合を始め、ブチルアルコール0.3
部添加時に、15%酢酸ナトリウム水溶液1部を添加し
(このときの重合率は96%、pHは4.7であっ
た)、更に1時間後に重合を終了させ、次いで、40%
亜ジチオン酸ナトリウム水溶液2部を添加して、残存酢
酸ビニルモノマー量は0.2%で、重合率99.4%、
pH4.1、粘度23000mPa・s(同上)を得
て、同様に評価を行った。
Example 7 Polymerization was started in the same manner as in Example 6, and butyl alcohol 0.3
At the time of addition, 1 part of a 15% aqueous solution of sodium acetate was added (at this time, the polymerization rate was 96%, and the pH was 4.7). After one hour, the polymerization was terminated.
By adding 2 parts of an aqueous solution of sodium dithionite, the amount of the residual vinyl acetate monomer was 0.2%, the polymerization rate was 99.4%,
A pH of 4.1 and a viscosity of 23,000 mPa · s (same as above) were obtained and evaluated in the same manner.

【0027】実施例8 実施例6において、酢酸ナトリウム水溶液の代わりに3
0%炭酸ナトリウム水溶液を10部とした以外は同様に
重合を行って、残存酢酸ビニルモノマー量0.2%、重
合率99.4%、pH6.7、粘度24000mPa・
s(同上)の酢酸ビニル樹脂エマルジョンを得て、同様
に評価を行った。
Example 8 The procedure of Example 6 was repeated, except that the aqueous sodium acetate solution was replaced with 3
Polymerization was carried out in the same manner except that 10 parts of a 0% aqueous sodium carbonate solution was used. The amount of the remaining vinyl acetate monomer was 0.2%, the polymerization rate was 99.4%, the pH was 6.7, and the viscosity was 24,000 mPa · s.
s (same as above) was obtained and similarly evaluated.

【0028】実施例9 実施例6において、最後に40%亜ジチオン酸ナトリウ
ム水溶液1部と40%亜硫酸水素ナトリウム水溶液1部
を添加した以外は同様に行って、残存酢酸ビニルモノマ
ー量0.2%、重合率99.4%、pH4.3、粘度2
3000mPa・s(同上)の酢酸ビニル樹脂エマルジ
ョンを得て、同様に評価を行った。
Example 9 The procedure of Example 6 was repeated except that, finally, 1 part of a 40% aqueous sodium dithionite solution and 1 part of a 40% aqueous sodium bisulfite solution were added. , Polymerization rate 99.4%, pH 4.3, viscosity 2
A 3000 mPa · s (same as above) vinyl acetate resin emulsion was obtained and evaluated in the same manner.

【0029】比較例1 実施例1において、亜ジチオン酸ナトリウム水溶液を無
添加とした以外は同様に行って、残存酢酸ビニルモノマ
ー量0.4%、重合率98.9%、pH2.5、粘度2
7000mPa・s(同上)の酢酸ビニル樹脂エマルジ
ョンを得て、同様に評価を行った。
Comparative Example 1 The procedure of Example 1 was repeated except that the aqueous solution of sodium dithionite was not added. The amount of the remaining vinyl acetate monomer was 0.4%, the conversion was 98.9%, the pH was 2.5, and the viscosity was 2
A 7000 mPa · s (same as above) vinyl acetate resin emulsion was obtained and similarly evaluated.

【0030】比較例2 実施例1において、亜ジチオン酸ナトリウム水溶液に変
えて40%亜硫酸水素ナトリウム水溶液2部を添加した
以外は同様に行って、残存酢酸ビニルモノマー量0.4
%、重合率98.9%、pH2.6、粘度27000m
Pa・s(同上)の酢酸ビニル樹脂エマルジョンを得
て、同様に評価を行った。実施例及び比較例の評価結果
を表1に示す。
Comparative Example 2 The procedure of Example 1 was repeated, except that the aqueous sodium bisulfite solution was replaced by 2 parts of a 40% aqueous sodium bisulfite solution.
%, Polymerization rate 98.9%, pH 2.6, viscosity 27000 m
A vinyl acetate resin emulsion having a Pa · s (same as above) was obtained and similarly evaluated. Table 1 shows the evaluation results of the examples and the comparative examples.

【0031】[0031]

【表1】 放置安定性 耐水性 低温安定性 70℃×7日 室温×1年 (%) 実施例1 2.4 2.5 98.3 1.4 〃 2 2.4 2.5 96.5 1.6 〃 3 1.1 1.1 97.2 1.2 〃 4 2.3 2.4 98.5 1.3 〃 5 2.2 2.4 98.7 1.3 〃 6 1.0 1.0 98.1 1.0 〃 7 1.0 1.0 97.5 1.1 〃 8 1.0 1.0 97.8 1.2 〃 9 1.1 1.2 96.5 1.2 比較例1 ゲル化 ゲル化 測定不能 3.5 〃 2 4.5 ゲル化 測定不能 3.2 [Table 1] Storage stability Water resistance Low temperature stability 70 ° C x 7 days Room temperature x 1 year (%) Example 1 2.4 2.5 98.3 1.4 22.4 2.5 96.5 1.6 〃 3 1.1 1.1 97.2 1.2 〃 4 2.3 2.4 98.5 1.3 5 5 2.2 2.4 98.7 1.3 6 6 1.0 1.0 98.1 1.0 7 7 1.0 1.0 97.5 1.1 8 8 1.0 1.0 97.8 1.2 〃 9 1.1 1.2 96.5 1. 2 Comparative Example 1 Gelation Gelation not possible 3.5 測定 2 4.5 Gelation not possible 3.2

【0032】[0032]

【発明の効果】本発明の(酢酸)ビニル樹脂系エマルジ
ョンは、アセトアセチル基含有ポリビニルアルコール系
樹脂及び亜ジチオン酸塩を含有しているため、放置(保
存)安定性や生成塗膜の耐水性等に優れ、特に耐水/耐
熱水性を必要とされる木工用接着剤や紙管用接着剤等の
用途に有用である。
Since the (acetic acid) vinyl resin emulsion of the present invention contains an acetoacetyl group-containing polyvinyl alcohol resin and a dithionite salt, the emulsion has a standing (preservation) stability and a water resistance of the resulting coating film. It is particularly useful for applications such as woodworking adhesives and paper tube adhesives that require water / hot water resistance.

─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───

【手続補正書】[Procedure amendment]

【提出日】平成9年8月22日[Submission date] August 22, 1997

【手続補正1】[Procedure amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0004[Correction target item name] 0004

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【0004】[0004]

【課題を解決するための手段】そこで、上記の事情に鑑
みて、本発明者が鋭意研究した結果、アセトアセチル基
含有ポリビニルアルコール系樹脂及び亜ジチオン酸塩を
含有するビニル樹脂系エマルジョンが、夏季や冬季の高
温時や低温時においても十分な安定性を発揮し、また長
期保存後の皮膜強度や接着剤として用いたときの接着力
等の維持が可能なエマルジョンが得られることを見いだ
し、本発明を完成するに至った。
In view of the above circumstances, the present inventors have conducted intensive studies and as a result, have found that an acetoacetyl group-containing polyvinyl alcohol-based resin and a dithionite salt have been produced.
Contained vinyl resin emulsion exhibits sufficient stability even at high and low temperatures in summer and winter, and can maintain film strength after long-term storage and adhesive strength when used as an adhesive It was found that an emulsion was obtained, and the present invention was completed.

Claims (11)

【特許請求の範囲】[Claims] 【請求項1】 アセトアセチル基含有ポリビニルアルコ
ール系樹脂及び亜ジチオン酸塩を含有することを特徴と
するビニル樹脂系エマルジョン。
1. A vinyl resin emulsion comprising an acetoacetyl group-containing polyvinyl alcohol resin and a dithionite.
【請求項2】 亜ジチオン酸塩が亜ジチオン酸ナトリウ
ム(Na224)であることを特徴とする請求項1記
載のビニル樹脂系エマルジョン。
2. The vinyl resin emulsion according to claim 1, wherein the dithionite is sodium dithionite (Na 2 S 2 O 4 ).
【請求項3】 亜ジチオン酸塩の含有量が0.05〜4
重量%であることを特徴とする請求項1または2記載の
ビニル樹脂系エマルジョン。
3. The content of dithionite is 0.05-4.
3. The vinyl resin emulsion according to claim 1, wherein the content of the emulsion is 3% by weight.
【請求項4】 更に、亜硫酸塩、チオ硫酸塩、重亜硫酸
塩、メタ重亜硫酸塩、L−アスコルビン酸、ヒドラジン
類から選ばれる少なくとも1種の還元剤を含有すること
を特徴とする請求項1〜3いずれか記載のビニル樹脂系
エマルジョン。
4. The method according to claim 1, further comprising at least one reducing agent selected from the group consisting of sulfites, thiosulfates, bisulfites, metabisulfites, L-ascorbic acid and hydrazines. 4. The vinyl resin emulsion according to any one of claims 1 to 3.
【請求項5】 還元剤の含有量が0.05〜2重量%で
あることを特徴とする請求項4記載のビニル樹脂系エマ
ルジョン。
5. The vinyl resin emulsion according to claim 4, wherein the content of the reducing agent is 0.05 to 2% by weight.
【請求項6】 ビニルモノマーの残存量が0.4重量%
以下であることを特徴とする請求項1〜5いずれか記載
のビニル樹脂系エマルジョン。
6. The residual amount of the vinyl monomer is 0.4% by weight.
The vinyl resin emulsion according to any one of claims 1 to 5, wherein:
【請求項7】 イソプロピルアルコールの存在下にビニ
ルモノマーを滴下重合し、重合触媒の滴下終了後にブチ
ルアルコールを添加してなることを特徴とする請求項1
〜6記載のビニル樹脂系エマルジョン。
7. The method according to claim 1, wherein a vinyl monomer is dropped and polymerized in the presence of isopropyl alcohol, and butyl alcohol is added after dropping the polymerization catalyst.
A vinyl resin emulsion according to any one of claims 1 to 6.
【請求項8】 更に、ケイ酸のアルカリ塩を含有するこ
とを特徴とする請求項1〜6いずれか記載のビニル樹脂
系エマルジョン。
8. The vinyl resin emulsion according to claim 1, further comprising an alkali salt of silicic acid.
【請求項9】 ケイ酸のアルカリ塩の含有量が0.01
〜4重量%であることを特徴とする請求項8記載のビニ
ル樹脂系エマルジョン。
9. The content of an alkali salt of silicic acid is 0.01
The vinyl resin emulsion according to claim 8, wherein the amount is from 4 to 4% by weight.
【請求項10】 pHが3〜8であることを特徴とする
請求項1〜9いずれか記載のビニル樹脂系エマルジョ
ン。
10. The vinyl resin emulsion according to claim 1, wherein the pH is 3 to 8.
【請求項11】 木材に塗工或いは含浸させて木材中の
ホルムアルデヒド類を捕捉する用途に用いることを特徴
とする請求項1〜10いずれか記載のビニル樹脂系エマ
ルジョン。
11. The vinyl resin emulsion according to claim 1, which is used for coating or impregnating wood to capture formaldehyde in the wood.
JP20253397A 1997-07-11 1997-07-11 Vinyl acetate resin emulsion Expired - Fee Related JP3164297B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP20253397A JP3164297B2 (en) 1997-07-11 1997-07-11 Vinyl acetate resin emulsion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP20253397A JP3164297B2 (en) 1997-07-11 1997-07-11 Vinyl acetate resin emulsion

Publications (2)

Publication Number Publication Date
JPH1135770A true JPH1135770A (en) 1999-02-09
JP3164297B2 JP3164297B2 (en) 2001-05-08

Family

ID=16459083

Family Applications (1)

Application Number Title Priority Date Filing Date
JP20253397A Expired - Fee Related JP3164297B2 (en) 1997-07-11 1997-07-11 Vinyl acetate resin emulsion

Country Status (1)

Country Link
JP (1) JP3164297B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009280754A (en) * 2008-05-26 2009-12-03 Nippon Synthetic Chem Ind Co Ltd:The Resin composition, coat layer and inkjet recording medium

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009280754A (en) * 2008-05-26 2009-12-03 Nippon Synthetic Chem Ind Co Ltd:The Resin composition, coat layer and inkjet recording medium

Also Published As

Publication number Publication date
JP3164297B2 (en) 2001-05-08

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