JP2002121353A - Ethylene/vinyl acetate copolymer emulsion composition - Google Patents

Ethylene/vinyl acetate copolymer emulsion composition

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JP2002121353A
JP2002121353A JP2000312865A JP2000312865A JP2002121353A JP 2002121353 A JP2002121353 A JP 2002121353A JP 2000312865 A JP2000312865 A JP 2000312865A JP 2000312865 A JP2000312865 A JP 2000312865A JP 2002121353 A JP2002121353 A JP 2002121353A
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vinyl acetate
ethylene
copolymer emulsion
acetate copolymer
emulsion
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JP2000312865A
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JP4306943B2 (en )
Inventor
Daisuke Shinomiya
Manabu Yako
学 八箇
大輔 四宮
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Denki Kagaku Kogyo Kk
電気化学工業株式会社
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients

Abstract

PROBLEM TO BE SOLVED: To provide an ethylene/vinyl acetate copolymer emulsion composition which, when mixed with various inorganic powders and cements, reveals excellent workability and which is excellent in adherence to various kind of substrates.
SOLUTION: The copolymer emulsion composition is obtained by polymerizing a mixture of an ethylene/vinyl acetate copolymer emulsion and a vinyl acetate monomer in an amount of 1-10 mass pts. based on 100 mass pts. nonvolatile matter of the ethylene/vinyl acetate copolymer emulsion to give a modified ethylene/vinyl acetate copolymer emulsion, and incorporating an antifoaming agent into this emulsion. The copolymer emulsion composition, when mixed with various inorganic powders and cements, exhibits excellent workability and adherence.
COPYRIGHT: (C)2002,JPO

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】本発明は各種無機粉体やセメントと混合した際に、非常に良好な作業性と接着性を発現するエチレン−酢酸ビニル系共重合体エマルジョン(以下「EVAエマルジョン」という)に関するものである。 The present invention relates to when mixed with various inorganic powders and cement, ethylene express adhesion very good workability - vinyl acetate copolymer emulsion (hereinafter referred to as "EVA emulsion" ) it relates.

【0002】 [0002]

【従来の技術】EVAエマルジョンは接着剤分野や土木建材分野において広く使用され、また、塗料分野、製紙分野、繊維分野においても利用されている。 BACKGROUND ART EVA emulsion is widely used in the adhesive art and civil engineering construction materials, also the field of coating materials, papermaking art and are also used in the fiber art. これらいずれの分野においてもEVAエマルジョンの安定性や作業性は非常に重要である。 Stability and workability EVA emulsion In any of these fields is very important. EVAエマルジョンはエチレン−酢酸ビニル系共重合体(以下「EVA」という)の微小な粒子が水中に分散したものであるが、分散剤としてポリビニルアルコール(以下「PVA」という)やヒドロキシエチルセルロースといった水溶性高分子を使用している場合が多く、これら水溶性高分子の持つ接着性、 EVA emulsion is an ethylene - but in which fine particles of vinyl acetate copolymer (hereinafter referred to as "EVA") was dispersed in water, water-soluble such as polyvinyl alcohol (hereinafter referred to as "PVA") and hydroxyethylcellulose as a dispersant often using a polymer, adhesiveness possessed by the water-soluble polymer,
粘着性等の特性が、各種無機粉体やセメントと混合してなるポリマーセメントモルタルに接着性、粘着性を付与している。 Properties such as tackiness, adhesion to the polymer cement mortar formed by mixing with various inorganic powder and cement, and tackified. しかし逆にこの高い粘着性がコテでの作業性を悪くし、特にポリマーセメントモルタルがコテに付着してしまうという問題点が多々見られる。 However, this high viscosity conversely to poor workability in trowel seen many a problem that especially the polymer cement mortar adheres to the trowel.

【0003】作業性に優れたポリマーセメントモルタルを得るために、従来からポリマーエマルジョンに特定の界面活性剤を添加したり(特開昭56−12965 In order to obtain good polymer cement mortar workability, or by adding a specific surfactant conventionally polymer emulsion (JP 56-12965
3)、重合時に特定の界面活性剤を使用してポリマーエマルジョンを製造する方法(特開平6−329455) 3) a process for producing a polymer emulsion by using the specific surfactant during polymerization (JP-A-6-329455)
などが行われてきた。 Such as have been made. ところが、この様な方法で十分な作業性を得るためには界面活性剤の添加量が多く必要であり、見かけのポリマーの平均分子量が低下する。 However, in order to obtain sufficient workability such a method is required often amount of the surfactant, the average apparent molecular weight of the polymer is lowered. その為、界面活性剤を多く含有するポリマーセメントモルタルの硬化物の各種モルタル物性、特にコンクリートやスレート板、ALCパネル等の被着体への接着性や長期耐久性能が著しく低下してしまう課題が残されていた。 Therefore, various mortar properties of the cured product of the polymer cement mortar containing a large amount of surfactant, is a problem especially concrete or slate plate, adhesion and long-term durability performance to an adherend such as ALC panels significantly decreases It had been left.

【0004】 [0004]

【発明が解決しようとする課題】本発明は各種無機粉体やセメントと混合した際に、優れた作業性を発現し、且つ各種被着体との接着性に優れたエチレン−酢酸ビニル系共重合体エマルジョン組成物を提供するものである。 [SUMMARY OF THE INVENTION The present invention when mixed with various inorganic powder and cement, superior expressed workability, and various adherends and excellent ethylene adhesion - vinyl acetate copolymer there is provided a polymer emulsion composition.

【0005】 [0005]

【課題を解決するための手段】本発明者らは、かかる目的を達成すべく鋭意検討した結果、EVAエマルジョンに少量の酢酸ビニルモノマーを添加し重合させて得られる変性EVAエマルジョンに消泡剤を含有させることによって、各種無機粉体やセメントと混合した後に良好な作業性、及び接着性を示すEVAエマルジョンを製造できることを見い出したのである。 The present inventors Means for Solving the Problems] are a result of extensive studies to achieve the above object, a defoaming agent modified EVA emulsion obtained by adding the polymerization of a small amount of vinyl acetate monomer EVA emulsion by including good workability after mixing with various inorganic powder and cement, and it was found to be able to produce EVA emulsion showing adhesion.

【0006】 [0006]

【発明の実施の形態】本発明で使用されるEVAエマルジョンはエチレンと酢酸ビニル成分を必須成分とするE EVA emulsion used in the Detailed Description of the Invention The present invention is E as essential component of ethylene and vinyl acetate component
VAのエマルジョンであり、エチレンと酢酸ビニルモノマーを乳化重合したもの、あるいは市販品のいずれも使用することができる。 VA is of the emulsion, those that have been emulsion polymerization of ethylene and vinyl acetate monomer, or any commercial products can be used. EVAの組成はエチレン含有量が5〜35質量%、酢酸ビニル含有量が65〜95質量% The composition of the EVA is an ethylene content of 5 to 35 wt%, vinyl acetate content of 65 to 95 wt%
でエチレンと酢酸ビニルの合計が80質量%以上であるEVAを好適に用いることができる。 In total of ethylene and vinyl acetate it can be preferably used EVA is 80% by mass or more.

【0007】エチレンと酢酸ビニル以外に20質量%未満であればエチレン、酢酸ビニルと共重合するその他の成分を含んでいてもよい。 [0007] If it is less than ethylene and 20 wt% in addition to vinyl acetate ethylene, it may contain other components to be copolymerized with vinyl acetate. その他の成分としては例えば塩化ビニル、プロピオン酸ビニル、バーサチック酸ビニル、アクリル酸、メタアクリル酸、マレイン酸、イタコン酸、エチルアクリレート、プロピルアクリレート、ブチルアクリレート、2−エチルヘキシルアクリレート、 Other such as vinyl chloride as a component, vinyl propionate, vinyl versatate, acrylic acid, methacrylic acid, maleic acid, itaconic acid, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,
エチルメタアクリレート、プロピルメタアクリレート、 Ethyl methacrylate, propyl methacrylate,
ブチルメタアクリレート、2−エチルヘキシルメタアクリレートがあるが、これらの成分を一種類以上含有させることができる。 Butyl methacrylate, there are 2-ethylhexyl methacrylate, these components may be contained one or more. また、トリアリルシアヌレート、トリアリルイソシアヌレートを併用することができ、この場合耐アルカリを向上させる効果がある。 Further, triallyl cyanurate, can be used in combination with triallyl isocyanurate, in this case an effect of improving the alkali resistance. その添加量は1 The amount added 1
質量%以下、好ましくは0.5質量%以下である。 Mass% or less, preferably 0.5 mass% or less.

【0008】本発明ではPVAを含有するEVAエマルジョンを好適に用いることができる。 [0008] The present invention can be suitably used EVA emulsion containing PVA. PVAはEVAエマルジョンを乳化重合により製造する際に保護コロイドとして添加されてEVAエマルジョンに含有されるものであっても、あるいは乳化重合の際には全く用いず重合後にEVAエマルジョンに添加されて含有されるものであってもよい。 PVA is contained is added to EVA emulsion after being added even those contained in the EVA emulsion, or not at all used in the emulsion polymerization polymerized as a protective colloid in the production by emulsion polymerization of EVA emulsion it may be a shall.

【0009】PVAの含有量は、EVAエマルジョンの不揮発分に対して10質量%以下が好ましい。 [0009] The content of PVA is preferably 10% by mass or less with respect to the nonvolatile content of the EVA emulsion. PVAの種類には特に限定なく市販のものを用いることができる。 It can be used commercially available without particular limitation on the type of PVA. 完全ケン化PVA、部分ケン化PVAやスルホン基、カルボキシル基、アミド基等により変性されたPV Completely saponified PVA, partially saponified PVA, sulfonic group, a carboxyl group, PV modified by an amide group
Aを用いることができる。 It is possible to use the A.

【0010】本発明によればEVAエマルジョンの不揮発分100質量部に対して1〜10質量部の酢酸ビニルモノマーを混合し重合させて得られる変性EVAエマルジョンの不揮発分100質量部に対して消泡剤0.00 [0010] The present invention similar According place EVA emulsion Roh non-minute 100 mass parts Nitaishite 1 to 10 mass parts Roh vinyl acetate monomer wo mixture was polymerized to hand the resulting modified EVA emulsion Roh non-minute 100 mass parts Nitaishite anti-foaming agent 0.00
5〜1.0質量部を含有させることで、各種無機粉体やセメントと混合しても十分な作業性を発現し、且つ各種被着体との接着性に優れたEVAエマルジョンが得られる。 By incorporating 5 to 1.0 parts by mass, be mixed with various inorganic powder and cement to develop sufficient workability, EVA emulsion is obtained and excellent in adhesion to various adherends.

【0011】変性EVAエマルジョンを製造する際に、 [0011] In producing the modified EVA emulsion,
EVAエマルジョンに加えられる酢酸ビニルモノマーは、EVAエマルジョンをエチレンの圧力下で重合した後に、エチレンをパージしてEVAエマルジョンを常圧に戻した際に、EVAエマルジョンに未反応の酢酸ビニルモノマーとして残存したものであってもよい。 Vinyl acetate monomers added to the EVA emulsion, after polymerization of EVA emulsion under a pressure of ethylene, when returning the EVA emulsion to normal pressure ethylene were purged to remain as unreacted vinyl acetate monomer in the EVA emulsion it may be the one. あるいは、EVAエマルジョン製造後に残存する未反応の酢酸ビニルモノマーに更に新たに酢酸ビニルモノマーを添加してもよい。 Alternatively, it may be further added a new vinyl acetate monomer unreacted vinyl acetate monomer remaining after EVA emulsion production. 要は所定量の酢酸ビニルモノマーがEVA In short predetermined amount of vinyl acetate monomer EVA
エマルジョンに含有されてあればよい。 It is sufficient to be contained in the emulsion.

【0012】酢酸ビニルモノマーに対して少量であれば酢酸ビニルモノマーと共重合する他の単量体モノマーを併用することができる。 [0012] can be used in combination of other monomer monomer to be copolymerized with vinyl acetate monomer, if a small amount of the vinyl acetate monomer. それらの単量体としては例えば、カルボン酸のビニルエステル類、アクリル酸、アクリル酸のアルキルエステル類、メタアクリル酸のアルキルエステル類、アルキルエーテル類、アルキルアリルエーテル類、その他(メタ)アクリルアミド、(メタ)アクリロニトリル、(メタ)アリルスルホン酸塩等がある。 They include monomers such as vinyl esters of carboxylic acids, alkyl esters of acrylic acid, acrylic acid, alkyl esters of methacrylic acid, alkyl ethers, alkyl aryl ethers, etc. (meth) acrylamide, ( meth) acrylonitrile, and (meth) allylsulfonic acid salt.

【0013】EVAエマルジョンに含まれる酢酸ビニルモノマーはラジカル開始剤を添加することにより重合される。 [0013] vinyl acetate monomer contained in the EVA emulsion is polymerized by adding a radical initiator. ラジカル開始剤としてはEVAエマルジョンの重合に用いられるものは全て用いることができる。 Those used in the polymerization of EVA emulsion as the radical initiator can be used all. 例えば、過酸化水素、t−ブチルハイドロパーオキサイド等の有機過酸化物、過硫酸アンモニウム、過硫酸カリウム等の過硫酸塩を使用することができる。 For example, hydrogen peroxide, organic peroxides such as t- butyl hydroperoxide, ammonium persulfate, may be used persulfates such as potassium persulfate. また、ラジカル開始剤とナトリウムホルムアルデヒドスルホキシレート等の還元剤を併用するレドックス触媒を用いることもできる。 It is also possible to use a redox catalyst in combination with a radical initiator and sodium formaldehyde sulfoxylate or the like reducing agent. なかでも過硫酸アンモニウムや過硫酸カリウムといった過硫酸塩を好適に用いることができる。 Of these persulfates such ammonium persulfate and potassium persulfate can be preferably used.

【0014】重合方法には特に限定されず酢酸ビニルモノマーを含有したEVAエマルジョンにラジカル開始剤を添加し重合することができる。 [0014] can be added polymerization of the radical initiator to EVA emulsion containing vinyl acetate monomer is not particularly limited to the polymerization method. 重合温度は使用するラジカル開始剤の種類により異なるが40〜80℃とすることができる。 The polymerization temperature varies depending on the type of the radical initiator to be used can be a 40 to 80 ° C.. 重合はEVAエマルジョンに含有される未反応の酢酸ビニルモノマーが1質量%以下となるまで行うことが好ましい。 The polymerization is preferably carried out until the unreacted vinyl acetate monomer contained in the EVA emulsion is less than 1 wt%.

【0015】本発明で変性EVAエマルジョンに含有させる消泡剤は、一般に使用されているものであれば特に限定するものではなく、例えば必要ならば表面処理した微粉シリカをシリコーンオイルや有機変性シリコーンに分散させたシリカシリコーン系消泡剤、ステアリン酸アルミニウム、ステアリン酸カルシウム、オレイン酸カリウム及びパルミチン酸マグメシウム等の金属石鹸系消泡剤、ポリアルキレンアミド、アシレートポリアミン及びジオクタデカノイルピペラジン等のアマイド系消泡剤、 The antifoaming agent to be contained in the modified EVA emulsion in the present invention generally as long as it is used not particularly limited, the surface-treated fine silica powder in a silicone oil or an organic modified silicone, if for example necessary silica silicone anti-foaming agent is dispersed, aluminum stearate, calcium stearate, metal soap-based antifoaming agents such Magumeshiumu potassium oleate and palmitate, polyalkylene amides, acylate polyamines and amides system and di octadecanoyl piperazine anti-foaming agents,
二酸化チタンや酸化アルミニウム等をシリコーンオイルに分散させたシリコーンコンパウンド系消泡剤、オクチルアルコール、オレイルアルコール、ポリオキシアルキレングリコール等のアルコール系消泡剤、ポリプロピレングリコール脂肪族エステル、ポリオキシプロピレンポリオキシエチレン共重合体及びソルビタンモノラウレートの酸化エチレン付加物等のポリエーテル系消泡剤、ソルビタンモノ脂肪酸エステル、ソルビタントリ脂肪酸エステル、脂肪酸モノグリセリド、エチレングリコールジ脂肪酸エステル及びエチレングリコールジ脂肪酸エステル等の非イオン型消泡剤、流動パラフィンやスピンドル油等の鉱物油系消泡剤及びこれら消泡剤を乳化分散させたエマルション型消泡剤等を単独ないしは組み合わせて使用できる。 Silicone compositions based and the titanium dioxide and aluminum oxide are dispersed in a silicone oil antifoam, octyl alcohol, oleyl alcohol, alcohol-based defoaming agents such as polyoxyalkylene glycol, polypropylene glycol fatty esters, polyoxypropylene polyoxyethylene polyether-based defoaming agents such as ethylene oxide adducts of copolymers and sorbitan monolaurate, sorbitan mono fatty acid esters, sorbitan tri fatty acid esters, fatty acid monoglycerides, ethylene glycol di-fatty acid esters and non-ionic such as ethylene glycol di fatty acid esters type defoaming agent, etc. may be used singly or in combination of mineral oil-based defoaming agent and emulsion type antifoam agent was emulsified and dispersed antifoaming agent such as liquid paraffin or spindle oil.

【0016】本発明におけるEVAエマルジョン組成物に含有される消泡剤の量は、変性EVAエマルジョンの不揮発分100質量部に対して、好ましくは0.005 The amount of the defoaming agent contained in the EVA emulsion composition of the present invention is to provide a non-volatile content 100 parts by weight of the modified EVA emulsion, preferably 0.005
〜1.0質量部、特に好ましくは0.01〜0.8質量部である。 1.0 parts by weight, particularly preferably 0.01 to 0.8 parts by weight.

【0017】消泡剤の含有量が0.005質量部以下では、各種無機系粉体やセメントと混合した際の作業性の改善効果が低下し、1.0質量部以上では作業性は改善されるものの、できあがったポリマーセメントモルタルのコンクリートやスレート板、ALCパネルへの接着性が低下する傾向がある。 [0017] In 0.005 parts by weight or less content of the antifoaming agent, workability improving effect when mixed with various inorganic powders and cement is reduced, improving the workability in 1.0 part by mass or more although the concrete or slate of finished polymer cement mortar, adhesion to ALC panels tends to decrease.

【0018】また、この消泡剤の添加方法に関しては特に限定されるものではなく、EVAエマルジョンを重合する際に加えても良いし、重合が終了した後に加えても良い、更には変性EVAを重合する際に加えても良いし、変性EVAエマルジョンに加えても良い。 Further, the invention is not specifically defined, the method of adding the defoaming agent, may be added during the polymerization of EVA emulsion polymerization may be added after the completion of the further modified EVA may be added during the polymerization, it may be added to the modified EVA emulsion. 要は所定量の消泡剤が変性EVAエマルジョンに含有されてあればよい。 In short predetermined amount of the defoaming agent may, if it is contained in the modified EVA emulsion.

【0019】本発明で得られたEVAエマルジョン組成物を使用することによって、各種無機系粉体やセメントと混合して得られるポリマーセメントモルタルは、作業性が非常に優れ、且つコンクリートやスレート板、AL [0019] By using the EVA emulsion composition obtained in the present invention, polymer cement mortar obtained by mixing with various inorganic powders and cement, excellent workability, and concrete or slate plate, AL
Cパネル等の被着体との接着性に優れたものとなる。 And it is excellent in adhesion to the adherend such as a C panel.

【0020】 [0020]

【実施例】以下更に詳細に実施例をもって説明する。 BRIEF DESCRIPTION with more detail in Example below. (EVAエマルジョンの製造例1)攪拌機付の高圧重合缶に酢酸ビニルモノマー100質量部、PVA(電気化学工業社製)B−05とB−17を各2質量部、酢酸ソーダ0.4質量部、ロンガリット(ナトリウムホルムアルデヒドスルホキシレート、住友精化社製)0.2重量部、硫酸第一鉄・七水和物0.005質量部を90質量部の水に溶解した水溶液を攪拌下仕込み、窒素で重合缶内部を置換した後、エチレン25質量部を充填した。 (Preparation of EVA Emulsion 1) 100 parts by weight of vinyl acetate monomer in the high-pressure polymerization vessel equipped with a stirrer, PVA (manufactured by Denki Kagaku Kogyo KK) B-05 and B-17 each 2 parts by weight, sodium acetate 0.4 part by weight Rongalit (sodium formaldehyde sulfoxylate, manufactured by Sumitomo Seika Chemicals Co., Ltd.) 0.2 part by weight, stirring was charged an aqueous solution prepared by dissolving 0.005 parts by weight of ferrous sulfate heptahydrate in water 90 parts by weight, after replacing the polymerization vessel inside with nitrogen and charged with ethylene 25 weight parts. 温度を65℃とした後、5%の過硫酸カリウム水溶液を添加し重合を行った。 After a temperature of 65 ° C., it was added by polymerizing a 5% aqueous solution of potassium persulfate. 未反応の酢酸ビニルモノマー量が2 Vinyl acetate monomer content of unreacted 2
%となった時点で残存するエチレンをパージしEVAエマルジョンを得た。 % Ethylene remaining at the time of a purge to give the EVA emulsion. 生成したEVAエマルジョン中の未反応の酢酸ビニルモノマーを減圧下除去し、未反応の酢酸ビニルモノマーが0.5質量%以下のEVAエマルジョンを得た。 Unreacted vinyl acetate monomer in the resulting EVA emulsion was removed under reduced pressure, unreacted vinyl acetate monomer was obtained 0.5 mass% or less EVA emulsion. このEVAエマルジョンの不揮発分は5 A non-volatile content of the EVA emulsion 5
5.0質量%、EVA中のエチレン含量は19質量%、 5.0 wt%, an ethylene content in EVA is 19% by weight,
粘度3900mPa・s、粗粒率180ppm、セメント混和安定性6秒であった。 Viscosity 3900mPa · s, was Sotsuburitsu 180 ppm, cement stability 6 seconds.

【0021】(変性EVAエマルジョンの製造例1)同じく(EVAエマルジョンの製造例1)で得られたEV [0021] EV obtained in (modified EVA emulsion of Preparation 1) also (Preparation of EVA Emulsion 1)
Aエマルジョンに不揮発分に対して6質量%となるよう酢酸ビニルモノマーを添加した。 It was added vinyl acetate monomer such as a 6 wt% with respect to the nonvolatile content in the A emulsion. また、ナトリウムホルムアルデヒドスルホキシレート(ロンガリット)0.0 Further, sodium formaldehyde sulfoxylate (Rongalit) 0.0
01質量部、硫酸第一鉄・7水和物0.00005質量部を純水1質量部に溶解したものをし、30分間攪拌しながら、温度を55℃とした。 01 parts by weight, and those were dissolved in pure water 1 part by weight of 0.00005 parts by weight of ferrous sulfate heptahydrate, with stirring for 30 minutes, and the temperature was 55 ° C.. 5質量%の過硫酸カリウム水溶液2.64質量部を90分間に渡って添加し重合を行った。 5 wt% aqueous solution of potassium persulfate 2.64 parts by weight was added to the polymerization over 90 minutes. 残存する未反応の酢酸ビニルモノマーがEV Unreacted vinyl acetate monomer remaining EV
Aエマルジョンに対して1質量%以下となるまで重合を行い、変性EVAエマルジョンを得た。 Polymerization was conducted until 1 mass% or less with respect to the A emulsion, to obtain a modified EVA emulsion. 得られたEVA The resulting EVA
エマルジョン中の未反応の酢酸ビニルモノマーを減圧下除去し、未反応の酢酸ビニルモノマーが0.5質量%以下の変性EVAエマルジョンを得た。 Unreacted vinyl acetate monomer in the emulsion was removed under reduced pressure, unreacted vinyl acetate monomer was obtained 0.5 mass% of modified EVA emulsion.

【0022】(実施例1)同じく(変性EVAエマルジョンの製造例1)で得られたEVAエマルジョンの不揮発分100質量部に対して、消泡剤「SNデフォーマー777」(サンノプコ株式会社製、鉱物油,ポリエーテル,シリカシリコーン等の混合物)を0.1質量部添加し、良く攪拌して均一なEVAエマルジョンを得た。 [0022] (Example 1) also with respect to non-volatile matter of 100 parts by mass of EVA emulsion obtained in (modified EVA emulsion of Preparation 1), a defoaming agent "SN Defoamer 777" (San Nopco Co., mineral oil , polyether, silica silicone etc. Roh mixing things) wo 0.1 mass parts added, well stirred hand uniform name EVA emulsion wo obtain other.

【0023】(実施例2)同じく(変性EVAエマルジョンの製造例1)で得られたEVAエマルジョンの不揮発分100質量部に対して、消泡剤「クリレス P−6 [0023] (Example 2) also with respect to non-volatile matter of 100 parts by mass of EVA emulsion obtained in (Production Example of modified EVA Emulsion 1), a defoaming agent "Kuriresu P-6
66」(栗田工業株式会社製、高級アルコール系消泡剤)を0.2質量部添加し、良く攪拌して均一なEVA 66 "(Kurita Water Industries Ltd., higher alcohol type antifoaming agent) were added 0.2 part by mass, sufficiently stirred to uniform EVA
エマルジョンを得た。 To obtain an emulsion.

【0024】(実施例3)同じく(変性EVAエマルジョンの製造例1)で得られたEVAエマルジョンの不揮発分100質量部に対して、消泡剤「アデカネート B [0024] For Example 3 also nonvolatile content 100 parts by weight of the EVA emulsion obtained in (modified EVA Production Example of Emulsion 1), a defoaming agent "Adekaneto B
−925」(旭電化工業株式会社製、非イオン型消泡剤)を0.05質量部添加し、良く攪拌して均一なEV -925 "(Asahi Denka Co., Ltd., nonionic antifoaming agent) were added 0.05 part by mass, sufficiently stirred to uniform EV
Aエマルジョンを得た。 To give the A emulsion.

【0025】(比較例1)(EVAエマルジョンの製造例1)で得られたEVAエマルジョンに消泡剤を全く添加せず評価用サンプルとした。 [0025] and (Comparative Example 1) (EVA Emulsion Preparation Example 1) not at all the addition of anti-foaming agent to the EVA emulsion obtained in the evaluation sample.

【0026】(比較例2)(EVAエマルジョンの製造例1)で得られたEVAエマルジョンの不揮発分100 [0026] (Comparative Example 2) non-volatile content 100 of EVA emulsion obtained in (EVA Production Example 1 emulsion)
質量部に対して、消泡剤「SNデフォーマー777」 With respect to the mass part, anti-foaming agents "SN Defoamer 777"
(サンノプコ株式会社製、鉱物油,ポリエーテル,シリカシリコーン等の混合物)を0.1質量部添加し、良く攪拌して均一なEVAエマルジョンを得た。 (San Nopco Co., mineral oil, polyether, mixtures such as silica Silicone) was added 0.1 part by weight, to obtain a well stirred to uniform EVA emulsion.

【0027】(比較例3)(変性EVAエマルジョンの製造例1)で得られたEVAエマルジョンに、消泡剤を全く添加せず評価用サンプルとした。 [0027] EVA emulsion obtained in Comparative Example 3 (Preparation of modified EVA emulsion 1) was an evaluation sample without completely the addition of a defoaming agent.

【0028】(比較例4)同じく(変性EVAエマルジョンの製造例1)で得られたEVAエマルジョンの不揮発分100質量部に対して、消泡剤「SNデフォーマー777」(サンノプコ株式会社製、鉱物油,ポリエーテル,シリカシリコーン等の混合物)を0.003質量部添加し、良く攪拌して均一なEVAエマルジョンを得た。 [0028] (Comparative Example 4) also with respect to non-volatile matter of 100 parts by mass of EVA emulsion obtained in (modified EVA emulsion of Preparation 1), a defoaming agent "SN Defoamer 777" (San Nopco Co., mineral oil , polyethers, mixtures such as silica silicone) was added 0.003 parts by weight, to obtain a well stirred to uniform EVA emulsion.

【0029】(比較例5)同じく(変性EVAエマルジョンの製造例1)で得られたEVAエマルジョンの不揮発分100質量部に対して、消泡剤「クリレス P−6 [0029] (Comparative Example 5) also with respect to non-volatile matter of 100 parts by mass of EVA emulsion obtained in (Production Example of modified EVA Emulsion 1), a defoaming agent "Kuriresu P-6
66」(栗田工業株式会社製、高級アルコール系消泡剤)を1.5質量部添加し、良く攪拌して均一なEVA 66 "(Kurita Water Industries Ltd., higher alcohol type antifoaming agent) were added 1.5 parts by mass, thoroughly stirred to a uniform EVA
エマルジョンを得た。 To obtain an emulsion.

【0030】(セメント混和安定性)比較例1、実施例1で得られたEVAエマルジョンを用い、水48.5質量部、EVAエマルジョンを不揮発分として22.5質量部、普通ポルトランドセメント100質量部をよく混合しセメント組成物を得た。 [0030] (cement stability) Comparative Example 1, using the EVA emulsion obtained in Example 1, 48.5 parts by weight of water, 22.5 parts by weight of the EVA emulsion as nonvolatile content, ordinary portland cement 100 parts by weight They were thoroughly mixed to obtain a cement composition. それを35℃で一時間放置した後、ガラス棒で再度攪拌し流動性をみた。 After standing for one hour it at 35 ℃, and stirred again with a glass rod saw liquidity. EVAエマルジョンの安定性が悪い場合は短時間でセメント組成物は混合できないほど凝結したが、安定性のよい場合は相当時間攪拌混合することができた。 Although if the stability of the EVA emulsion is bad was condensed than can be mixed cement composition in a short time, if good stability could be equivalent time stirring and mixing. 混合可能な時間を測定しEVAエマルジョンのセメントに対する混合安定性を評価した。 The mixture possible time was measured to evaluate the mixed stability to cement EVA emulsion. 評価結果を表1に示す。 The evaluation results are shown in Table 1.

【0031】 [0031]

【表1】 [Table 1]

【0032】(モルタル接着強さ)JIS A 620 [0032] (mortar adhesion strength) JIS A 620
3「セメント混和用ポリマーディスパージョンおよび再乳化形粉末樹脂」の9.6「接着強さ」の評価方法に準じ、接着強さを測定した。 3 according to the evaluation method of the 9.6 "adhesive strength" of the "cement admixture for polymer dispersions and Redispersible powder resin" was measured bond strength. なお、接着強さの品質は1. It should be noted that the quality of the adhesive strength is 1.
0MPa以上である。 It is 0MPa or more. 評価結果を表1に示す。 The evaluation results are shown in Table 1. (作業性)JIS A 6203「セメント混和用ポリマーディスパージョンおよび再乳化形粉末樹脂」の9. (Workability) JIS A 6203 of "cement admixture for polymer dispersions and Redispersible powder resin" 9.
2.3の「ポリマーセメントモルタルの練混ぜ」のa) a of "Mixing of polymer cement mortar" of 2.3)
機械練りによる方法に準じてポリマーセメントモルタルを作製し、これをJISA 5403「木毛セメント板」に規定する厚さ4mmのフレキシブル板上に塗膜厚2mmとなるように金コテで塗りつけた際、コテさばき性の優劣を下記基準で判断した。 To produce a polymer cement mortar in accordance with the method according to the milled, when smeared with gold iron so that the film thickness of 2mm to the JISA 5403 thickness prescribed in "wood wool cement board" is 4mm flexible board of, the superiority or inferiority of iron separating property was judged based on the following criteria. 評価結果を表1に示す。 The evaluation results are shown in Table 1. ○−作業性良好で、ポリマーセメントモルタルのコテへの付着が少ない。 ○ - a workability good, less attachment to trowel the polymer cement mortar. △−作業性は○と比較して若干劣り、ポリマーセメントモルタルのコテへの付着が若干ある。 △ - workability slightly worse as compared with ○, there slightly attachment to trowel the polymer cement mortar. ×−作業性が悪く、ポリマーセメントモルタルのコテへの付着が多い。 × - poor workability, is often attached to the trowel in the polymer cement mortar. (不揮発分、粘度)JIS K 6828に準じて評価した。 It was evaluated in accordance with the (non-volatile content, viscosity) JIS K 6828. 評価結果を表1に示す。 The evaluation results are shown in Table 1. 尚、表1中の粘度の値はBM型回転式粘度計を用い、30℃の30rpmの値。 The value of viscosity in Table 1 using a BM-type rotational viscometer, the value of 30rpm of 30 ° C.. (残存酢酸ビニルモノマー)JIS K 6828の5.10残存モノマーの5.10.1直接滴定法で求めた。 Determined in 5.10.1 direct titration of 5.10 residual monomer (residual vinyl acetate monomer) JIS K 6828. 結果を表1に示す。 The results are shown in Table 1.

【0033】表1に記載した様に、実施例1から3では変性EVAエマルジョンに消泡剤を添加することにより、これに骨材とセメントを混合して得られるポリマーセメントモルタルは非常に良好な作業性を発現し、更にはこれを用いたモルタル接着強さ試験でも十分な接着強さを発現した。 [0033] As set forth in Table 1, by adding a defoaming agent from Example 1 in 3, modified EVA emulsion, to which the polymer cement mortar obtained by mixing aggregates and cement is very good express workability, and further to develop sufficient adhesive strength in mortar adhesion strength test using the same.

【0034】それに対して比較例1と2では、セメント混和安定性と作業性が著しくに劣っていた。 [0034] In Comparative Examples 1 and 2 whereas cement stability and workability was inferior considerably. また、比較例3と4ではセメント混和安定性とモルタル接着強さは良好な値を示したものの、消泡剤の添加量が少なすぎたために作業性は良くなかった。 Although Comparative Examples 3 and 4 in cement admixture stability and mortar adhesive strength showed a good value, workability for the added amount of the defoaming agent is too small, it was not good. また、比較例5では消泡剤の添加量が多すぎるために、セメント混和安定性と作業性は良好であったがモルタル接着強さが大幅に低下して、JIS A 6203の品質1.0MPa未満となった。 In order amount of Comparative Example 5, a defoaming agent is too large, cement stability and workability is significantly reduced good which was but mortar bond strength, quality of JIS A 6203 1.0 MPa It was less than.

【0035】 [0035]

【発明の効果】エチレン−酢酸ビニル系共重合体エマルジョンの不揮発分100質量部に対し1〜10質量部の酢酸ビニルモノマーを混合し重合して得られる変性エチレン−酢酸ビニル系共重合体エマルジョンに、消泡剤を含有することを特徴とするエチレン−酢酸ビニル系共重合体エマルジョン組成物は、セメント混和安定性に優れ、各種無機粉体やセメントを混合して作製したポリマーセメントモルタルは良好な作業性、接着性を発現する。 EFFECT OF THE INVENTION Ethylene - vinyl acetate copolymer emulsion - non-volatile content 100 parts by mass with respect to a mixture of 1 to 10 parts by weight of vinyl acetate monomer polymerization to obtained the modified ethylene vinyl acetate copolymer emulsion , ethylene characterized in that it contains an antifoaming agent - vinyl acetate copolymer emulsion composition is excellent in cement admixture stability, polymer cement mortar was prepared by mixing various inorganic powders and cement good workability, to develop adhesion.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl. 7識別記号 FI テーマコート゛(参考) C08F 263/04 C08F 263/04 C08K 5/098 C08K 5/098 C08L 101/00 C08L 101/00 // C04B 103:56 C04B 103:56 Fターム(参考) 4G012 PB30 PC12 4J002 AE052 BE023 BN071 CH052 CP032 DE137 DE147 DJ017 EC036 EC066 EG026 EG036 EG046 EH036 EH046 EH056 EP036 FD202 FD206 GL00 HA07 4J011 KA16 KB19 KB29 PA64 PA68 PB40 PC02 PC06 4J026 AC04 BA20 DA04 DA05 DA07 DA19 DB04 DB08 DB19 DB24 FA04 GA08 GA09 ────────────────────────────────────────────────── ─── of the front page continued (51) Int.Cl. 7 identification mark FI theme Court Bu (reference) C08F 263/04 C08F 263/04 C08K 5/098 C08K 5/098 C08L 101/00 C08L 101/00 // C04B 103: 56 C04B 103: 56 F-term (reference) 4G012 PB30 PC12 4J002 AE052 BE023 BN071 CH052 CP032 DE137 DE147 DJ017 EC036 EC066 EG026 EG036 EG046 EH036 EH046 EH056 EP036 FD202 FD206 GL00 HA07 4J011 KA16 KB19 KB29 PA64 PA68 PB40 PC02 PC06 4J026 AC04 BA20 DA04 DA05 DA07 DA19 DB04 DB08 DB19 DB24 FA04 GA08 GA09

Claims (4)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】 エチレン−酢酸ビニル系共重合体エマルジョンの不揮発分100質量部に対し1〜10質量部の酢酸ビニルモノマーを混合し重合して得られる変性エチレン−酢酸ビニル系共重合体エマルジョンに、消泡剤を含有することを特徴とするエチレン−酢酸ビニル系共重合体エマルジョン組成物。 1. A ethylene - vinyl acetate copolymer emulsion - non-volatile content 100 parts by mass with respect to a mixture of 1 to 10 parts by weight of vinyl acetate monomer polymerization to obtained the modified ethylene vinyl acetate copolymer emulsion , ethylene characterized in that it contains an antifoaming agent - vinyl acetate copolymer emulsion composition.
  2. 【請求項2】 請求項1において消泡剤の含有量が、変性エチレン−酢酸ビニル系共重合体エマルジョンの不揮発分100質量部に対して0.005〜1.0質量部であることを特徴とするエチレン−酢酸ビニル系共重合体エマルジョン組成物。 The content of the defoaming agent 2. The method of claim 1, modified ethylene - characterized in that 0.005 to 1.0 parts by mass relative to the nonvolatile content 100 parts by weight of vinyl acetate copolymer emulsion to ethylene - vinyl acetate copolymer emulsion composition.
  3. 【請求項3】 請求項1または請求項2において消泡剤が、シリカシリコーン系消泡剤、金属石鹸系消泡剤、アマイド系消泡剤、シリコーンコンパウンド系消泡剤、アルコール系消泡剤、ポリエーテル系消泡剤、非イオン型消泡剤、エマルション型消泡剤、鉱物油系消泡剤から選ばれる少なくとも1種類以上の消泡剤であることを特徴とするエチレン−酢酸ビニル系共重合体エマルジョン組成物。 Defoamers 3. An apparatus according to claim 1 or claim 2, silica-silicone anti-foaming agents, metal soap-based antifoaming agents, amide-based defoaming agents, silicone compositions based defoaming agents, alcohol-based defoaming agent , polyether-based defoaming agents, nonionic defoamer, emulsion type antifoam, ethylene, characterized in that at least one or more anti-foaming agent selected from mineral oil based antifoaming agent - vinyl acetate copolymer emulsion composition.
  4. 【請求項4】 請求項3のエチレン−酢酸ビニル系共重合体エマルジョン組成物を含有してなるセメント組成物。 4. The ethylene claim 3 - cement composition comprising a vinyl acetate copolymer emulsion composition.
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