JPS6012379B2 - Component adhesive based on polyvinyl ester - Google Patents

Component adhesive based on polyvinyl ester

Info

Publication number
JPS6012379B2
JPS6012379B2 JP48138220A JP13822073A JPS6012379B2 JP S6012379 B2 JPS6012379 B2 JP S6012379B2 JP 48138220 A JP48138220 A JP 48138220A JP 13822073 A JP13822073 A JP 13822073A JP S6012379 B2 JPS6012379 B2 JP S6012379B2
Authority
JP
Japan
Prior art keywords
weight
water
adhesive
aqueous
dispersion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
JP48138220A
Other languages
Japanese (ja)
Other versions
JPS4999342A (en
Inventor
エ−ピクト ヨアヒム
ミユ−レル ラインホルト
ホ−マンネル アルフオンス
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.)
Hoechst AG
Original Assignee
Hoechst AG
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
Priority claimed from DE19722261402 external-priority patent/DE2261402C3/en
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of JPS4999342A publication Critical patent/JPS4999342A/ja
Publication of JPS6012379B2 publication Critical patent/JPS6012379B2/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/54—Inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

【発明の詳細な説明】 本発明は、水性ポリピニルェステル分散物、尿素ーホル
ムアルデヒド樹脂および酸性金属塩より成る、良好な耐
水性および貯蔵安定性を有する一成分系接着剤に関する
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a one-component adhesive with good water resistance and storage stability, consisting of an aqueous polypinyl ester dispersion, a urea-formaldehyde resin and an acidic metal salt.

ポリビニルェステルータイプの接着剤は公知である。Polyvinyl ester type adhesives are known.

このものは、溶液として、溶融接着物としてまたは水性
重合体分散物の状態で用いられる。この分散物接着剤の
欠点は、水性分散物中に於ける乳化剤および保護コロイ
ドの如き水溶性分散物質の存在に影響されて耐水性が低
いことである。耐水性は尿素樹脂を加えることによって
改善することはできる〔イー・ラックネス（Ｅ．Ｒａｋ
ｎｅｓ）の“ホルツ・アルツ・ローーウント・ヴエルク
ストッフ（ＨｏｌｚａｌｓＲｏｈ一皿ｄＷｅｒｋｓｔｏ
ｆｆゾ、１９巻（１９６１）、第２３９〜２４刀頁）。
しかし、この様な混合物は不安定であり、最高１週間程
の限定された貯蔵安定性しか有していない。更にほとん
どの場合硬化剤も一緒に用いなければならない。ドイツ
特許出願公開第１５９４１９４号明細書からは、ポリピ
ニルアルコール含有の水性ポリビニルアセテート分散物
を、硬化剤としての酸性金属塩で処理し、その際に耐水
性で且つ遠硬化性の結合剤混合物が得られることが知ら
れている。They are used as solutions, as melt adhesives or in the form of aqueous polymer dispersions. A disadvantage of this dispersion adhesive is its low water resistance, influenced by the presence of water-soluble dispersants such as emulsifiers and protective colloids in the aqueous dispersion. Water resistance can be improved by adding urea resin [E.Rakness]
nes)'s "HolzalsRoh" plate dWerksto
ffzo, volume 19 (1961), pages 239-24).
However, such mixtures are unstable and have limited storage stability of up to one week. Furthermore, in most cases hardeners must also be used. German Patent Application No. 1,594,194 discloses that an aqueous polyvinyl acetate dispersion containing polypinyl alcohol is treated with an acidic metal salt as a hardening agent, and a water-resistant and far-curable binder mixture is known to be obtained.

しかしこの混合物は、最高４糊時間の貯蔵安定性しか有
していない。本発明者は、保護コロイドとしてポリビニ
ルアルコールを含有している水性のポリビニルェステル
分散物をベースとする一成分系接着剤において該接着剤
が、１．５〜３重量％の水溶性の低縮合度の尿素−ホル
ムアルデヒド樹脂の水溶液（樹脂舎量４０〜７の重量％
）および０．０５〜０．３重量％のアルミニウムまたは
クロムの水溶性酸性塩を含有する場合に、高い耐水性お
よび良好な貯蔵安定性を示すことを見出した。However, this mixture has a storage stability of only a maximum of 4 glue hours. The present inventor has proposed that in a one-component adhesive based on an aqueous polyvinyl ester dispersion containing polyvinyl alcohol as a protective colloid, the adhesive has a water-soluble low condensation content of 1.5 to 3% by weight. Aqueous solution of urea-formaldehyde resin (resin amount 40-7% by weight)
) and 0.05 to 0.3% by weight of a water-soluble acid salt of aluminum or chromium, it has been found that high water resistance and good storage stability are exhibited.

水性ポリビニルェステル分散物としては、ビニルェステ
ルのホモ重合体または、ビニルェステル同志またはビニ
ルェステルと他のエチレン系不飽和モノマ−との共重合
体、この場合重合体中の組入れ重合されたビニルェステ
ルの割合は少なくとも５の重量％である−の重合体分散
物が適している。The aqueous polyvinyl ester dispersion may be a homopolymer of vinyl ester or a copolymer of vinyl ester itself or of vinyl ester and other ethylenically unsaturated monomers, in which case the proportion of incorporated vinyl ester in the polymer is at least A polymer dispersion of -5% by weight is suitable.

ビニルェステルとしては、１〜１８個のｃ−原子を有す
る飽和脂肪族モノカルボン酸のピニルェステル、例えば
ビニルー蟻酸ェステル、ビニルアセテート、ビニルプロ
ピオナート、ビニルイソプチラート、ビニルラウレート
等、９〜１１個のＣ−原子を有する分岐した飽和モノカ
ルポン酸のビニルェステルまたはビニルステアレートが
適しており、特にビニルアセテートが適している。ピニ
ルェステル共重合し得る、その他のエチレン系不飽和モ
ノマ−は、アクリル−またはメタアクリル酸またはこれ
らと１〜８個のＣ一原子を有する１価の飽和脂肪族アル
コールとのェステル、マレィン酸、フマル酸、ィタコン
酸またはシトラコン酸の如きＱ，８−エチレン系不飽和
ジカルボン酸と１〜８個のＣ−原子を有する１価の飽和
脂肪族フルコ−ルとのモノ−またはジ−エステル、エチ
レン系不飽和炭化水素、例えばエチレン、３〜１２個の
Ｃ−原子を有するＱーオレフィン、スチレン、ビニルト
ルェンまたはビニルキシレン、ハロゲン化不飽和脂肪族
炭化水素、例えば塩化化ビニル、弗化ビニル、ビニリデ
ンクロライドまたはビニリデンフロライド、並びにアク
リル−またはメタアクリル酸の窒素含有誘導体、例えば
アクリルニトリル、アクリルアミドまたはＮーメチロー
ルアクリルアミドである。水性ポリビニルェステル分散
物は、場合によっては、分子中に少なくとも２個のエチ
レン系二重結合を有している架橋性モノマー、例えばジ
アリルフタレート、ジアリルマレイナート、トリアリル
シアヌラレート、テトラアリルオキシエタン、ジビニル
ベンゾール、ブタンジオールー１・４ージメタアクリレ
ートまたはトリェチレングリコールージメタアクリート
等を全てのモノマーの全体量に対して１の重量％まで重
合体中に組入れ重合含有していることもできる。本発明
に従う水性ポリピニルェステル分散物は、更に、重合体
に対して１〜１５重量％、殊に４〜ｌａ重量％のポリビ
ニルアルコールを保護コロイドとして含有している。こ
のポリピニルアルコールは重合前、一中または−後に添
加することができる。開放時間、硬化時間、接着力およ
び温度安定性の如き接着剤の一定の用途技術的性質を得
る為には、種々の水性ポリビニルェステル分散物の混合
物を用いるのが、いまいま有利である。水性ポリビニル
ェステル分散物、殊にホモポリマーのポリビニルアセテ
ート分散物を用いるのが特に有利である。水性ポリビニ
ルェステル分散物の固形分量は約４０〜６の重量％であ
る。水性ポリピニルヱステル分散物の製造は、公知の方
法において水性分散液中でモノマーをラジカル重合する
ことによって行なう。Vinylesters include pinylesters of saturated aliphatic monocarboxylic acids having 1 to 18 C atoms, such as vinyl-formate, vinyl acetate, vinyl propionate, vinyl isoptylate, vinyl laurate, etc. Vinyl esters or vinyl stearates of branched saturated monocarboxylic acids having C atoms of are suitable, in particular vinyl acetate. Other ethylenically unsaturated monomers that can be copolymerized with pinylester include esters of acrylic or methacrylic acid or these with monohydric saturated aliphatic alcohols having 1 to 8 carbon atoms, maleic acid, fumaric acid, etc. acids, mono- or di-esters of Q,8-ethylenically unsaturated dicarboxylic acids such as itaconic acid or citraconic acid with monovalent saturated aliphatic flucols having 1 to 8 C-atoms, ethylenic Unsaturated hydrocarbons, such as ethylene, Q-olefins with 3 to 12 C atoms, styrene, vinyltoluene or vinylxylene, halogenated unsaturated aliphatic hydrocarbons, such as vinyl chloride, vinyl fluoride, vinylidene chloride or vinylidene. fluoride and nitrogen-containing derivatives of acrylic or methacrylic acid, such as acrylonitrile, acrylamide or N-methylolacrylamide. The aqueous polyvinyl ester dispersion may optionally contain crosslinking monomers having at least two ethylenic double bonds in the molecule, such as diallyl phthalate, diallyl maleate, triallyl cyanurate, tetraallyloxy Ethane, divinylbenzole, butanediol-1,4-dimethacrylate or triethylene glycol-dimethacrylate or the like may be incorporated and polymerized into the polymer up to 1% by weight based on the total amount of all monomers. The aqueous polypinyl ester dispersions according to the invention additionally contain from 1 to 15% by weight, in particular from 4 to 1a, % by weight, based on the polymer, of polyvinyl alcohol as a protective colloid. The polypynyl alcohol can be added before, during or after the polymerization. In order to obtain certain application properties of the adhesive, such as opening time, curing time, adhesion strength and temperature stability, it is currently advantageous to use mixtures of various aqueous polyvinyl ester dispersions. Particular preference is given to using aqueous polyvinyl ester dispersions, especially homopolymeric polyvinyl acetate dispersions. The solids content of the aqueous polyvinyl ester dispersion is about 40-6% by weight. The aqueous polypinyl ester dispersion is produced in a known manner by free-radical polymerization of the monomers in the aqueous dispersion.

水落性の低縮合度の尿素−ホルムァルデヒド樹脂は、尿
素とホルムアルデヒドとを１：１〜１：４、殊に１：２
〜１：３のモル比で縮合することによって得られ、４０
〜７の重量％の樹脂含有量の水溶液の状態に成っている
。The water-repellent urea-formaldehyde resin with a low degree of condensation contains urea and formaldehyde in a ratio of 1:1 to 1:4, especially 1:2.
obtained by condensation in a molar ratio of ~1:3, 40
It is in the form of an aqueous solution with a resin content of ~7% by weight.

この溶液は、簡単なメチロール尿素化合物、即ちモノ−
、ジー、トリ−およびテトラーメチロール尿素を主とし
て含有している。本発明に従う接着剤は、全混合物に対
して約１．５〜３重量％の低縮合度の尿素−ホルムアル
デヒド樹脂水溶液を含有している。水落性の酸性金属塩
としては、舞藷喬しながらポリビニルアルコールと反応
する如き、アルミニウムまたはクロムの塩が用いられる
。This solution consists of a simple methylol urea compound, i.e. mono-
, di-, tri-, and tetramethylol urea. The adhesive according to the invention contains about 1.5 to 3% by weight of a low degree of condensation urea-formaldehyde resin aqueous solution, based on the total mixture. As the acidic metal salt, an aluminum or chromium salt that reacts with polyvinyl alcohol is used.

アルミニウムーニトレート、クロル（ｍ）−ニトレート
が適しており、特にアルミニウムークロラィドが好まし
い。添加量は、全混合物に対して０．０５〜０．箱重量
％（固形分）あるいは１０％水溶液で０．５〜３重量％
である。更に、室温における接着剤の皮膜形成を改善す
る為には、公知の皮膜形成助剤、例えばグリコール酸プ
チルェステルまたはプチルージグリコール−アセテ−ト
を全混合物に対して約１〜３重量％添加することができ
る。Aluminum nitrate, chloro(m)-nitrate are suitable, and aluminum chloride is particularly preferred. The amount added is 0.05 to 0.05 to the total mixture. Box weight% (solid content) or 10% aqueous solution 0.5-3% by weight
It is. Furthermore, in order to improve the film formation of the adhesive at room temperature, known film-forming aids, such as glycolic acid butyl ester or putyl diglycol acetate, may be added in an amount of about 1 to 3% by weight, based on the total mixture. I can do it.

本発明による一成分系接着剤により木材や紙の接着物が
得られ、この接着物は比較的長時間湿気のある室や冷水
中に貯蔵することができ、これによって接着が弛むこと
はない。With the one-component adhesive according to the invention, wood and paper bonds are obtained which can be stored for a relatively long time in a humid room or in cold water without the bond loosening.

この様な目的に対して従来水性ポリビニルェステル分散
物は全く不適当であるか又は二成分系としてのみ適当で
あった。これは従来の水性ポリピニルェステル分散物で
は不可能であり、二成分系においてのみ適応しえたこと
である。貯蔵安定性は、接着剤のその使用能が減少する
ことないこ少なくとも１年間であり、これは公知の分散
物接着剤の貯蔵安定性に相当する。長い開放時間、短か
し、硬化時間、高い接着力および接合点の良好な温度安
定性の如き従来の好ましい分散物接着剤の有利な性質を
も保持している。更に本発明に従う接着剤は、プレス成
形層状物、発泡体、繊維、レザー、石綿およびその他の
多孔質材料等の接着にも適している。以下の実施例にて
本発明を詳細に説明する。For such purposes, aqueous polyvinyl ester dispersions have hitherto been either completely unsuitable or suitable only as two-component systems. This is not possible with conventional aqueous polypinyl ester dispersions and can only be accommodated in two-component systems. The storage stability of the adhesive is at least one year without a decrease in its usability, which corresponds to the storage stability of known dispersion adhesives. It also retains the advantageous properties of conventional preferred dispersion adhesives such as long open times, short cure times, high adhesion and good temperature stability of the bond points. Furthermore, the adhesive according to the invention is also suitable for gluing pressed layers, foams, fibres, leather, asbestos and other porous materials, etc. The present invention will be explained in detail in the following examples.

実施例 １保護コロイドとして７％のポリビニルアルコ
ールを含有するホモポリマーのポリビニルアセテ−ト５
の重量％濃度水性分散物を製造し、この水性分散物９５
．５重量部に贋梓下に低縮合度の尿素ーホルムアルデヒ
ド樹脂の５０重量％濃度水溶液１．５重量部を加える。
良好に分散させた後に、同様に濃伴しながら造膜助剤と
してのグリコール酸ブチルェステル１．５重量部および
塩化アルミニウム１０％水溶液１．５重量部を加える。
次に更に２０分間、均一化させる。蝿洋機の回転数は約
３０〜５０回転／分である。こうして得られた接着剤を
、少なくとも２独特間の熟成時間の後に以下の接着剤試
験に委ねる。Example 1 Homopolymer polyvinyl acetate 5 containing 7% polyvinyl alcohol as protective colloid
An aqueous dispersion with a weight percent concentration of 95% by weight is prepared.
．． To 5 parts by weight, 1.5 parts by weight of a 50% by weight aqueous solution of a urea-formaldehyde resin with a low degree of condensation is added.
After good dispersion, 1.5 parts by weight of glycolic acid butyl ester and 1.5 parts by weight of a 10% aluminum chloride aqueous solution as a film-forming agent are added while being concentrated in the same manner.
Then homogenize for a further 20 minutes. The rotational speed of the flywheel is about 30 to 50 revolutions/minute. The adhesive thus obtained is subjected to the following adhesive test after at least two unique aging times.

先ず、乾燥した塗腰について耐水性を試験する為に、０
．３側の一定のスリットを通してガラス坂上に接着剤を
フローコーティングする。２ぴ０の室温および５０％の
相対湿度での６日間の乾燥時間の後に、その乾燥後の塗
膜を水中に放置する。First, in order to test the water resistance of the dried coating,
．． Flow coat the adhesive onto the glass bevel through a fixed slit on the third side. After a drying time of 6 days at a room temperature of 2°C and a relative humidity of 50%, the dried coating is placed in water.

貯蔵時間は２独特間である。塗膜は白色に成ることもな
く水中に再乳化することもない。実施例例 ２ 斑．の重量部の、保護コロイドとして１０％のポリピニ
ルアルールを含有するホモポリマ−のポリビニルアセテ
ート・５の重量％濃度水性分散物、５７．５重量部の、
保護コロイドとして５％のポリビニルアルコールを有す
るホモポリマーのポリビニルアセテート・５の重量％濃
度水性分散物、１．５重量部の、低縮合度の尿素−ホル
ムアルデヒド樹脂５の重量％濃度水溶液、１．６重量部
の硝酸アルミニウム１０％水溶液および１．５重量部の
グリコール酸ブチルェステルより実施例１と同機に製造
した接着剤を、フィルム状に流す。Storage time is 2 hours. The coating does not become white and does not re-emulsify in water. Example 2 Spots. 57.5 parts by weight of a homopolymeric polyvinyl acetate 5 aqueous dispersion containing 10% polyvinyl acetate as protective colloid,
1.5 parts by weight of a 1.6% strength by weight aqueous dispersion of homopolymeric polyvinyl acetate 5 with 5% polyvinyl alcohol as protective colloid, 1.6 parts by weight of a urea-formaldehyde resin 5 with a low degree of condensation. An adhesive prepared in the same machine as in Example 1 from parts by weight of a 10% aqueous solution of aluminum nitrate and 1.5 parts by weight of butyl glycolate is poured into a film.

比較用に、５匹重量％の固形分合有愛で且つ保護コロイ
ドとして５％のポリビニルアルコールを含有している公
３句のホモポリマーポリピニルアセテート水性分散物を
同様に処理する。フィルムを造る前に、あわを取り除く
為に本発明に従う接着剤および比較用の分散物に僅かな
水を加える。周囲に囲いを有している平らなポリエチレ
ン坂上に秤量した量を流して、０．８伽の乾燥被膜厚を
有したフィルムを得る。これらのフィルムを２チ○、５
０％の相対湿度に空気調節して７日間放置する。このフ
ィルムの吸水量は、２０℃の水中に入れ、次いで１＆分
、６ひげ、１２０分、２４ぴ分および２独特間水中放置
後に重量を測定した本発明に従う接着剤のフィルムは、
次の表に示す様に比較用分散物のそれに比べて非常に水
に対して安定である。For comparison, a homopolymer polypynylacetate aqueous dispersion having a solids content of 5% by weight and containing 5% polyvinyl alcohol as a protective colloid is similarly treated. Before making the film, a little water is added to the adhesive according to the invention and to the comparative dispersion to remove bubbles. The weighed amount is poured onto a flat polyethylene ramp with a surrounding enclosure to obtain a film with a dry coating thickness of 0.8 degrees. 2 ○, 5 of these films
The air is conditioned to 0% relative humidity and left for 7 days. The water absorption of this film was determined by placing it in water at 20°C and then weighing it after standing in water for 1 min, 6 min, 120 min, 24 min and 2 min.
As shown in the following table, it is very stable in water compared to that of the comparative dispersion.

第１表 実施例 ３ 接着剤を、 ９３．の重量部の、保護コロイドとして７％のポリビニ
ルアルコールを含有するホモポリマーのポリビニルアセ
テート・５の重量％濃度水性分散物、３．の重量部の、
低縮合度の尿素−ホルムアルデヒド樹脂５の重量％濃度
溶液、２．５重量部の硝酸クロム（ｍ）・１０％水溶液
および１．５重量部のグリコール酸ブチルェステルにて
実施例１と同様に製造する。Table 1 Example 3 Adhesive, 93. 3. parts by weight of a homopolymeric polyvinyl acetate 5 aqueous dispersion containing 7% polyvinyl alcohol as protective colloid; Parts by weight of
Produced in the same manner as in Example 1 using a weight percent solution of urea-formaldehyde resin 5 with a low degree of condensation, 2.5 parts by weight of a 10% aqueous solution of chromium (m) nitrate, and 1.5 parts by weight of glycolic acid butyl ester. .

この接着剤にて並びに５の重量％の固形分合有星で且つ
保護コロイドとして５％のボリビニルアルコールを含有
している公知のホモポリマー水性ポＩＪビニルアセテー
ト分散物の状態の比較用接着剤にて結合強度について、
ＤＷ５３２５４に従ってブナ木材製の試験体を用いて試
験する。A comparative adhesive in the form of this adhesive and a known homopolymer aqueous polyvinyl acetate dispersion having a solids content of 5% by weight and containing 5% polyvinyl alcohol as a protective colloid. Regarding the bond strength,
Tests are carried out in accordance with DW 53254 using test specimens made of beech wood.

試験体は以下の如く製造した：このＤＩＮの規定に従っ
てブナの木より成る２つの接合用部材を接合する。The test specimens were produced as follows: two joining members made of beech wood were joined in accordance with the provisions of this DIN.

この接合用部村は少なくとも６００肋の長さおよび１３
０肋の中を有している。この部材の厚さは５風である。
接着剤を両方の部材に塗布する。塗布厚さは１５０夕／
仇である。次にこの両方の部材を約１の１ての圧縮圧力
にて接合する。圧縮時間は２時間である。これらの試験
体をＤＩＮ斑２Ｗに従う貯蔵シリ−ズ１、４および５に
従って耐水性を検査する。This joining part has a length of at least 600 ribs and 13
It has 0 ribs. The thickness of this member is 5 mm.
Apply adhesive to both parts. Coating thickness is 150mm/
It is an enemy. Both members are then joined together at a compressive pressure of about 1:1. Compression time is 2 hours. These test specimens are tested for water resistance according to storage series 1, 4 and 5 according to DIN marking 2W.

貯蔵シリーズ１は、２０ｑｏ、６５％の相対湿度のもと
で７日間試験体を空気調節放置することにより成ってお
り、貯蔵シリーズ４も２ぴ○、６５％の相対湿度に空調
下に７日間放置しそして次いで２蝿時間水中に放置する
ことより成っている。一方貯蔵シリーズ５は更に２０℃
、６５％の相対湿度のもとに空調下に再度７日間放置し
続けることである。貯蔵シリーズ５の後の結合強度は再
乾燥強度とも呼ぶ。次の第ロ表に得られた結果を示す。
第〇表 本発明に従う接着剤で接着した結合強度は、２４時間の
水中放電の後でも尚測定し得るが、一方比較用接着剤を
用いた試験体は水中で崩れてしまう。Storage series 1 consisted of leaving the specimen under air conditioning for 7 days at 20qo and 65% relative humidity, and storage series 4 also consisted of leaving the specimen under air conditioning for 7 days at 20qo and 65% relative humidity. and then submerged in water for 2 hours. On the other hand, storage series 5 is further 20℃
, and then left again under air conditioning at 65% relative humidity for 7 days. The bond strength after storage series 5 is also called the re-drying strength. The results obtained are shown in Table B below.
Table 0 The bond strength bonded with the adhesive according to the invention can still be measured after 24 hours of underwater discharge, whereas the test specimens with the comparative adhesive crumble in water.

本発明に従う接着剤を用いた試験体の再乾燥強度は、初
めの結合強度の値（貯蔵シリーズ１の後）にに近ずく。
実施例 ４ 第ｍ表に記した組成より成る実験Ｎｏ．１〜６の接着剤
を実施例１におけるのと同機に製造する。The redrying strength of the specimens with the adhesive according to the invention approaches the initial bond strength value (after storage series 1).
Example 4 Experiment No. 4 consisting of the composition shown in Table m. Adhesives Nos. 1 to 6 are manufactured on the same machine as in Example 1.

但し、実験Ｎｏ．４〜６の接着剤は本発明のものとの比
較の為に製造したものである。実施例１におけるのと同
機に耐水性試験を行ない、その結果を第ｍ表に示す。However, experiment no. Adhesives Nos. 4 to 6 were manufactured for comparison with those of the present invention. A water resistance test was conducted on the same machine as in Example 1, and the results are shown in Table m.

結合強度の試験は、実施例３における如く製造した試験
体を用い、ＤＩＮ球２５４に従って以下の如く行なう：
２３℃、５０％の相対湿度のもとに７日間放置した後に
、こうして接合した都村から２ｑ固の試験体を切り取る
。The bond strength test is carried out according to DIN bulb 254 as follows using test specimens prepared as in Example 3:
After standing for 7 days at 23° C. and 50% relative humidity, a 2q hard specimen was cut from the thus bonded Miyakomura.

この試験体は、１５仇帆の長さおよび２０肌の中の寸法
を有している。次に、これらの試験体を、２０×１０（
他）の試験面が現われる様に、木の柾に対して横切って
削り取る。Ｄ川５３２５４に従う引張試験で鱗断強度を
測定する。即ち、試験体が破断するまで引張り、その際
の最高の負荷力を測定する。別に、試験体を水中に放置
し、２岬時間後にその試験体を水から取り出し、その直
後に、同様に引張試験に委ねる。This specimen has a length of 15 mm and dimensions of 20 mm. Next, these test specimens were divided into 20×10 (
(etc.) Cut across the edge of the tree so that the test surface is exposed. The scale breaking strength is measured by a tensile test according to D River 53254. That is, the specimen is pulled until it breaks, and the maximum load force at that time is measured. Separately, the test specimen is left in water, and after 2 hours it is removed from the water and immediately thereafter subjected to the same tensile test.

試験体の結合強度は次式に従って算出する：試験体の船
磯顎鷺鰯蓑（Ｎ側（注） ＩＮ′協；０．１０２ｋｇ／
磯：１０．２ｋ９／柵結果を第ｍ表に示す。The bonding strength of the test specimen is calculated according to the following formula: Funaiso Jawsagi Sardine of the test specimen (N side (Note) IN'Kyo; 0.102 kg/
Iso: 10.2k9/fence The results are shown in Table M.

聡 白 糠 第ｍ表から、耐水性に関しては金属塩を含有する全ての
接着剤の塗膜が再乳化せず、良好であることが判る。From Table M of Sohiranuka, it can be seen that the coating films of all adhesives containing metal salts do not re-emulsify and are good in terms of water resistance.

また２３ｏｏでの乾燥結合強度については、いずれの塗
膜も実質的に相違していないことが判る。この試験で測
定値が多少相違しているのは、試験に用いたそれぞれの
木の強度に依存している。更に試験体を２独特間、水中
に貯蔵した後の結合強度の試験では、金属塩を加えてな
い接着剤の場合にはもはや強度を有しておらず、一方、
クロム−およびアルミニウム塩を用いた場合には非常に
良好な結果が得られている。Furthermore, it can be seen that there is no substantial difference in dry bond strength at 23oo between the coating films. The slight variations in the measurements in this test depend on the strength of the respective trees used in the test. Moreover, in tests of bond strength after the specimens had been stored in water for 2 hours, it was found that the adhesive without added metal salts no longer had any strength;
Very good results have been obtained with chromium and aluminum salts.

この効果は、従釆技術（侍公昭４４一２９５９６号）で
用いられている亜鉛塩を用いた接着剤の場合よりも格別
に優れている。以上から判る通り、クロム−およびアル
ミニウム塩を用いた本発明の接着剤は、耐水性、乾燥結
合強度および貯蔵安定性に関して、従釆技術において用
いられていた亜鉛塩の場合と同様に優れているだけでな
く、２独時間水中貯蔵後の結合強度に関しては、一応の
効果を示す亜鉛塩の場合よりも遥かに優れており、この
様な効果は従来技術からも全く予想できなかったことで
ある。This effect is exceptionally superior to that of the adhesive using zinc salt used in the adhesion technique (Samurai Ko Sho 44-129596). As can be seen, the adhesives of the invention using chromium and aluminum salts are as good in terms of water resistance, dry bond strength and storage stability as the zinc salts used in the conventional art. In addition, the bond strength after being stored in water for two hours was far superior to that of zinc salts, which showed some effect, and such an effect was completely unexpected from conventional technology. .

本発明は、特許請求の範囲に記載の接着剤に関するもの
であるが、実施の態様として以下を包含する。The present invention relates to an adhesive described in the claims, and includes the following embodiments.

‘１１ 特許請求の範囲に記載の接着剤において、分散
物の重合体成分に対して１〜１５重量％のポリビニルア
ルコールを含有する、上記接着剤。'11 The adhesive according to the claims, which contains 1 to 15% by weight of polyvinyl alcohol based on the polymer component of the dispersion.

【２１ 特許請求の範囲および上記第‘１｝項に記載の
接着剤において、ポリビニルヱステル分散物が重合体成
分に対して少なくとも５の重量％の組入れ重合されたビ
ニルェステルを含有する、上記接着剤。‘３｝ 特許請
求の範囲および上記第ｍ〜■項に記載の接着剤において
、ポリビニルェステル分散物としてポリビニルアセテー
ト分散物を用いる上記援着剤。[21] The adhesive according to claim 1 and item ``1'' above, wherein the polyvinyl ester dispersion contains at least 5% by weight of incorporated polymerized vinyl esters based on the polymer component. . '3} In the adhesive described in the claims and the above-mentioned items m to (2), the above-mentioned adhesion agent uses a polyvinyl acetate dispersion as the polyvinyl ester dispersion.

Claims (1)

【特許請求の範囲】[Claims] １ 保護コロイドとしてポリビニルアルコールを含有す
る水性ポリビニルエステル−分散物をベースとする一成
分系接着剤において、該接着剤が、尿素とホルムアルデ
ヒドとが１：１〜１：４のモル比であり且つ主としてモ
ノ−、ジ−、トリ−およびテトラ−メチロール尿素より
成る水溶性縮合度尿素−ホルムアルデヒド樹脂の水溶液
（樹脂含有量４０〜７０重量％）１．５〜３重量％およ
びアルミニウムまたはクロムの水溶性の酸性塩０．０５
〜０．３重量％を含有することを特徴とする、上記ポリ
ビニルエステルをベースとする貯蔵安定性を有する一成
分系接着剤。1. A one-component adhesive based on an aqueous polyvinyl ester dispersion containing polyvinyl alcohol as a protective colloid, in which the adhesive contains urea and formaldehyde in a molar ratio of 1:1 to 1:4 and An aqueous solution (resin content 40-70% by weight) of a water-soluble condensed degree urea-formaldehyde resin consisting of mono-, di-, tri- and tetra-methylol urea (resin content 40-70% by weight) and a water-soluble solution of aluminum or chromium. Acid salt 0.05
Storage-stable one-component adhesive based on the polyvinyl ester described above, characterized in that it contains ~0.3% by weight.
JP48138220A 1972-12-15 1973-12-13 Component adhesive based on polyvinyl ester Expired JPS6012379B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2261402.4 1972-12-15
DE19722261402 DE2261402C3 (en) 1972-12-15 Adhesive based on a dispersion of homo- or copolymers of vinyl stern

Publications (2)

Publication Number Publication Date
JPS4999342A JPS4999342A (en) 1974-09-19
JPS6012379B2 true JPS6012379B2 (en) 1985-04-01

Family

ID=5864502

Family Applications (1)

Application Number Title Priority Date Filing Date
JP48138220A Expired JPS6012379B2 (en) 1972-12-15 1973-12-13 Component adhesive based on polyvinyl ester

Country Status (14)

Country Link
JP (1) JPS6012379B2 (en)
AR (1) AR201431A1 (en)
AT (1) AT332956B (en)
AU (1) AU472865B2 (en)
BE (1) BE808732A (en)
BR (1) BR7309809D0 (en)
CA (1) CA1031887A (en)
FR (1) FR2210651B1 (en)
GB (1) GB1440337A (en)
IT (1) IT1001410B (en)
KE (1) KE2782A (en)
SE (1) SE406330B (en)
ZA (1) ZA739228B (en)
ZM (1) ZM19273A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4396739A (en) 1980-10-06 1983-08-02 National Starch And Chemical Corporation Easy-clean vinyl acetate adhesive composition
TR22877A (en) * 1982-06-09 1988-09-26 Ici Plc THE WOODEN COMPUTER AND THE FORMED UERUEN MADE OF THIS COMPUTER
DE3375387D1 (en) * 1982-06-09 1988-02-25 Ici Plc Mouldable composition and shaped product produced therefrom
JPS61271366A (en) * 1985-05-25 1986-12-01 Hohnen Oil Co Ltd Waterproof emulsion adhesive
DE4420484C2 (en) * 1994-06-11 1999-02-04 Clariant Gmbh Aqueous dispersion adhesive based on polyvinyl ester, process for its preparation and its use
DE4431343A1 (en) * 1994-09-02 1996-03-07 Hoechst Ag Heterogeneous polyvinyl ester dispersions or powder, for adhesives
DE19545608A1 (en) * 1995-12-07 1997-06-12 Hoechst Ag Dispersion powder for waterproof adhesives
DE19827475A1 (en) 1998-06-19 1999-12-23 Wacker Chemie Gmbh Fiber binding powder composition for use in the consolidation of fiber materials
DE19949332A1 (en) 1999-10-13 2001-05-23 Clariant Gmbh Low-discoloration dispersion adhesives with extended pot life
ATE289334T1 (en) 1999-12-30 2005-03-15 Henkel Kgaa POLYMER DISPERSION WITH CROSS-LINKING RESIN, PRODUCTION AND USE THEREOF
DE102007039312B4 (en) 2007-08-20 2010-06-02 Celanese Emulsions Gmbh Crosslinkable monomers and polymers and their use
DE102008048106A1 (en) 2008-09-19 2010-03-25 Henkel Ag & Co. Kgaa Aqueous dispersion adhesive based on polyvinyl acetate
EP3308916A4 (en) * 2015-06-12 2019-01-16 Grupo Garnica Plywood, S.A. Tabletop for manufacturing caravan furniture and method for producing said tabletop
CN113136154B (en) * 2020-01-20 2022-04-22 华南理工大学 Green low-toxicity high-viscosity polyoxometallate-based glass adhesive as well as preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3311581A (en) * 1964-06-22 1967-03-28 Andrew E Pink Adhesive composition comprising a polymer of a carboxylic acid ester, polyvinyl alcohol, and an aminoplast
GB1204819A (en) * 1967-11-20 1970-09-09 Borden Chemical Company Uk Ltd Improvements in or relating to adhesive compositions

Also Published As

Publication number Publication date
ZM19273A1 (en) 1974-08-22
BE808732A (en) 1974-06-17
ATA1043973A (en) 1976-02-15
DE2261402A1 (en) 1974-07-04
DE2261402B2 (en) 1976-01-15
AT332956B (en) 1976-10-25
KE2782A (en) 1977-12-09
FR2210651A1 (en) 1974-07-12
AR201431A1 (en) 1975-03-14
IT1001410B (en) 1976-04-20
AU6355873A (en) 1975-06-19
CA1031887A (en) 1978-05-23
FR2210651B1 (en) 1977-08-12
JPS4999342A (en) 1974-09-19
AU472865B2 (en) 1976-06-10
BR7309809D0 (en) 1974-09-05
SE406330B (en) 1979-02-05
GB1440337A (en) 1976-06-23
ZA739228B (en) 1974-11-27

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