JPH011780A - Adhesive manufacturing method - Google Patents
Adhesive manufacturing methodInfo
- Publication number
- JPH011780A JPH011780A JP62-156453A JP15645387A JPH011780A JP H011780 A JPH011780 A JP H011780A JP 15645387 A JP15645387 A JP 15645387A JP H011780 A JPH011780 A JP H011780A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- adhesive
- weight
- peroxide
- 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.)
- Pending
Links
- 230000001070 adhesive effect Effects 0.000 title description 29
- 239000000853 adhesive Substances 0.000 title description 28
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000000178 monomer Substances 0.000 claims description 26
- -1 methacryloyl group Chemical group 0.000 claims description 15
- 150000001451 organic peroxides Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 44
- 238000000034 method Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 150000002978 peroxides Chemical class 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 239000002775 capsule Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- CVYZVNVPQRKDLW-UHFFFAOYSA-N 2,4-dinitroanisole Chemical compound COC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O CVYZVNVPQRKDLW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 235000011293 Brassica napus Nutrition 0.000 description 1
- 240000008100 Brassica rapa Species 0.000 description 1
- 235000000540 Brassica rapa subsp rapa Nutrition 0.000 description 1
- JOJZBFPJVPOWFB-UHFFFAOYSA-N C=CC(=O)OP(O)OCCO Chemical compound C=CC(=O)OP(O)OCCO JOJZBFPJVPOWFB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005822 methylenation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KHDBMTLGTSGEEG-UHFFFAOYSA-M sodium;2-methylbenzenesulfinate Chemical compound [Na+].CC1=CC=CC=C1S([O-])=O KHDBMTLGTSGEEG-UHFFFAOYSA-M 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
(イ)発明の目的
〔産業上の利用分野〕
本発明は一液型接着剤に関するものであり、特に増粘さ
れた、接着速度が大きく常温硬化盤でかつポットライフ
の長(、さらに水性状組成物となすことによって、塗工
性を付与した嫌気性接着剤に関するものである。Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention relates to a one-component adhesive, which is particularly thickened, has a high adhesion speed, is a room-temperature curing adhesive, and has a short pot life. It also relates to an anaerobic adhesive that has been given coatability by forming it into an aqueous composition.
この接着剤は、ドライタッチに仕上げることができるた
めネジのゆるみ止め用接着剤或いは積層板のフィルム型
接着剤として好適なものである。Since this adhesive can be finished to a dry touch, it is suitable as an adhesive for preventing loosening of screws or a film-type adhesive for laminated boards.
従来、急速に硬化する一液型の常温硬化型接着剤として
はアクリロイル基及び/又はメタクリロイル基を有する
単量体(以下「(メタ)アクリレート単量体」と称する
。)を主成分とする嫌気硬化性組成物が用いられてきた
。Conventionally, one-component room-temperature-curing adhesives that harden rapidly include anaerobic adhesives whose main component is a monomer having an acryloyl group and/or a methacryloyl group (hereinafter referred to as "(meth)acrylate monomer"). Curable compositions have been used.
従来の嫌気硬化性組成物は機械的に混合されん各成分か
らなり、実質的に酸素が存在する状態では油性を有し、
実質的に酸素から遮断されると粘性を制御出来ない状態
で急速に硬化する組成物である。この為、硬化以前は油
性の(メタ)アクリレート単量体、過酸化物或いは硬化
促進剤の主体をなすアミン類等の成分により、薬傷の危
険性、不安定なポットライフ性、被着剤の選択性或いは
不適当な粘性による塗工不良性などの欠点を有していた
。Conventional anaerobic curable compositions consist of components that are not mechanically mixed, and are oily in the presence of substantial oxygen;
It is a composition that hardens rapidly with uncontrollable viscosity when substantially shielded from oxygen. For this reason, before curing, components such as oil-based (meth)acrylate monomers, peroxides, or amines, which are the main curing accelerator, pose a risk of chemical damage, unstable pot life, and damage to the adhesive. However, it has drawbacks such as poor coating properties due to poor selectivity and inappropriate viscosity.
←)発明の構成
〔問題点を解決するための手段〕
本発明は、水中に乳化された(メタ)アクリレート10
0重量部、カプセル化された有機過酸化物0.2〜3重
量部及び当該有機過酸化物とレドックス系を形成する還
元剤(以下「促進剤」と称する。)a1〜2重量部とl
からなる混合物(以下「未処理混合物」と称する。)を
実質的に酸素不存在下で撹拌することを特徴とする接着
剤の製造法に関するものであり、この方法により増粘さ
れた水性状の接着剤を得ることを特徴とする。←) Structure of the invention [Means for solving the problems] The present invention provides (meth)acrylate 10 emulsified in water.
0 parts by weight, 0.2 to 3 parts by weight of the encapsulated organic peroxide, and a reducing agent (hereinafter referred to as "accelerator") that forms a redox system with the organic peroxide; 1 to 2 parts by weight;
(hereinafter referred to as "untreated mixture") in substantially the absence of oxygen, and relates to a method for producing an adhesive characterized by stirring a mixture consisting of Characterized by obtaining adhesive.
本発明における(メタ)アクリレート単量体の乳化方法
は次のとおりである。The method of emulsifying the (meth)acrylate monomer in the present invention is as follows.
水溶性状態で界面活性があり、且つ数平均分子量が五〇
00〜so、ooo程度の重合体の水溶液中に高撹拌下
で(メタ)アクリレート単量を加え、混合すると本発明
に使用され得る水中に乳化された(メタ)アクリレート
単量体を得ることが出来る。It can be used in the present invention by adding (meth)acrylate monomer under vigorous stirring to an aqueous solution of a polymer that has surface activity in a water-soluble state and has a number average molecular weight of about 5,000 to so, ooo and mixed. It is possible to obtain (meth)acrylate monomers emulsified in water.
別の方法として皮膜形成能を持ち、さらに水溶液として
界面活性及び高粘性を付与出来る重合体を使用した場合
には1段の方法で目的物を得ることが出来る。Alternatively, if a polymer is used that has a film-forming ability and can impart surface activity and high viscosity in the form of an aqueous solution, the desired product can be obtained in one step.
本発明における(メタ)アクリレート単量体の乳化にお
いて(メタ)アクリレート単量体100重量部に対して
当該重合体2〜10重量部及び純水50〜250重量部
の割合で用いることが好ましく、製造されたエマルジョ
ンは、B型粘度計により2QrpmでLO00〜30,
000cpsの粘度を示し、且つ分散された(メタ)ア
クリレート単量体の油滴の径が10〜200μであるこ
とが好しい。In the emulsification of the (meth)acrylate monomer in the present invention, it is preferable to use 2 to 10 parts by weight of the polymer and 50 to 250 parts by weight of pure water per 100 parts by weight of the (meth)acrylate monomer, The produced emulsion was measured with a B-type viscometer at 2 Qrpm with a LO of 00 to 30,
000 cps and the diameter of the dispersed (meth)acrylate monomer oil droplets is preferably 10 to 200 microns.
本発明に使用される(メタ)アクリレート単量体として
はメチル(メタ)アクリレート、エチル(メタ)アクリ
レート、瞥−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、テトラヒドロフルフリ
ル(メタ)アクリレート、2−ヒドロキシエチル(メタ
)アクリレート、アリル(メタ)アクリレート、ジメチ
ルアミノエチル(メタ)アクリレート、グリシジル(メ
タ)アクリレート、メトキシエチル(メタ)アクリレー
ト、ジ−ブトキシエチル(メタ)アクリレート、スルホ
プロピル(メタ)アクリレート、2−ヒドロキシエチル
アクリロイルホスファイト、アセトキシエチル(メタ)
アクリレート及びメチルカルピトール(メタ)アクリレ
ート等のモノ(メタ)アクリレート、或いはエチレング
リコールジ(メタ)アクリレート、トリエチレングリコ
ールジ(メタ)アクリレート、i、6プタンジオールジ
(メタ)アクリレート、多塩基酸とポリオール及び(メ
タ)ア°クリル酸より脱水縮合ポリエステル化反応によ
り得られるポリエステルジ(メタ)アクリレート、エポ
キシ化ビスフェノールAジ(メタ)アクリレート、エポ
キシ化ビスフェノールAとエチレングリコール又はジエ
チレングリコール或いはトリエチレングリコールとの縮
合体と(メタ)アクリル酸より得られるジ(メタ)アク
リレート、ジイソシアネートとグリコール及びヒドロキ
シアルキル(メタ)アクリレートより得られるポリウレ
タンジ(メタ)アクリレート等のジ(メタ)アクリレー
ト、さらにグリセリン、トリメチロールプロパン、ペン
タエリスリトール等と(メタ)アクリル酸から得られる
(メタ)アクリレート構造を2個以上含む化合物が挙げ
られる。The (meth)acrylate monomers used in the present invention include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate. , 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, methoxyethyl (meth)acrylate, di-butoxyethyl (meth)acrylate, sulfopropyl (meth)acrylate, ) Acrylate, 2-hydroxyethyl acryloyl phosphite, acetoxyethyl (meth)
Acrylates and mono(meth)acrylates such as methylcarpitol(meth)acrylate, or ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, i,6-butanediol di(meth)acrylate, polybasic acids and Polyester di(meth)acrylate obtained by dehydration condensation polyesterification reaction from polyol and (meth)acrylic acid, epoxidized bisphenol A di(meth)acrylate, epoxidized bisphenol A and ethylene glycol, diethylene glycol, or triethylene glycol. Di(meth)acrylates obtained from condensates and (meth)acrylic acid, di(meth)acrylates such as polyurethane di(meth)acrylates obtained from diisocyanates and glycols, and hydroxyalkyl(meth)acrylates, as well as glycerin and trimethylolpropane. , a compound containing two or more (meth)acrylate structures obtained from pentaerythritol, etc., and (meth)acrylic acid.
皮膜の形成能を持ち、(メタ)アクリレート単量体を乳
化し得る重合体としては、アクリル酸又はメタアクリル
酸を5重量%以上共重合体組成にもつアクリル酸エステ
ル系樹脂、酢酸ビニル共重合体或いはメチルビニルエー
テル共重合体、ポリビニルピロリドン、ケン化度が30
〜90モルチテあるポリビニルアルコール、エチルセル
ロース、メトキシヒドロキシグロピルセルロース、エチ
レン−マレイン酸無水物共重合体、水溶性ナイロン重合
体、或いはポリエチレンオキサイドとポリプロピレンオ
キサイドとのブロック共重合体、尿素−ホルマリン重合
体等の水溶性乃至水に対する膨潤度が著しい重合体が挙
げられ、又アクリル酸エステル樹脂エマルジョン、ウレ
タンエマルジョン、クロログレン重合体二iルジョン、
或いはブタジェン単独重合体乃至は共重合体エマルジョ
ンなどの乳化共重合体が挙げられる。特に此等の重合体
を混合して使用すると、本発明方法に好適な条件となる
。Examples of polymers that have film-forming ability and can emulsify (meth)acrylate monomers include acrylic acid ester resins having a copolymer composition of 5% or more of acrylic acid or methacrylic acid, and vinyl acetate copolymers. Coalescence or methyl vinyl ether copolymer, polyvinyl pyrrolidone, degree of saponification is 30
~90 molarity polyvinyl alcohol, ethyl cellulose, methoxyhydroxyglopyl cellulose, ethylene-maleic anhydride copolymer, water-soluble nylon polymer, block copolymer of polyethylene oxide and polypropylene oxide, urea-formalin polymer, etc. Examples include polymers that are water-soluble or have a remarkable degree of swelling in water;
Alternatively, emulsion copolymers such as butadiene homopolymers or copolymer emulsions may be used. In particular, when these polymers are used in combination, conditions are suitable for the method of the present invention.
粉末状又は液状の有機過酸化物はコアセルベーション法
或いは界面重合法を用いると容易にカプセル化すること
が出来る。コアセルさ−シロン法を用いる場合はゼラチ
ン−アラビアゴムで被膜を形成させる方法が挙げられる
が、耐水性を向上させる為にさらにこのコアセルベージ
讐ンのあと、尿素−ホルマリン−メラミンのプレポリマ
ーを存在させて界面重合を続けて行う、2段カプセル化
法が好しい。Powdered or liquid organic peroxides can be easily encapsulated using a coacervation method or an interfacial polymerization method. When using the Coacel silon method, a method of forming a film with gelatin and gum arabic is mentioned, but in order to improve water resistance, a prepolymer of urea-formalin-melamine is added after the Coacel coating. A two-stage encapsulation method in which interfacial polymerization is performed in succession is preferred.
微粉末状の有機過酸化物の場合は界面重合法を採用する
のが好しく、具体的には、pH7,5〜9のメチロール
化反応で得た尿素−ホルマリンのプレポリマー中に有機
過酸化物を懸濁させ次第にpHを2〜3に下げて反応温
度を65〜40℃に維持してメチレン化反応を行い、過
酸化物粉末に生成ポリマーを沈積させながらカプセル化
する方法が好適である。In the case of a finely powdered organic peroxide, it is preferable to adopt an interfacial polymerization method. Specifically, organic peroxide is added to a urea-formalin prepolymer obtained by a methylolation reaction at pH 7.5 to 9. A suitable method is to suspend the substance, gradually lower the pH to 2 to 3, maintain the reaction temperature at 65 to 40°C to carry out the methylenation reaction, and encapsulate the resulting polymer while depositing it in peroxide powder. .
本発明方法に従って当該カプセルを使用する場合、水中
に乳化された(メタ)アクリレート単量体及び促進剤と
の撹拌混合時の安定性及び接着作業時のカプセルの破壊
の必要性から、カプセルの粒径は20〜100mμが好
しく、さらにカブ9トル中に於ける過酸化物の含有量は
10〜60重量%が好しい。When using the capsules according to the method of the present invention, the granules of the capsules have to be stabilized during stirring and mixing with the (meth)acrylate monomer emulsified in water and the accelerator, and because of the necessity of breaking the capsules during the bonding operation. The diameter is preferably 20 to 100 mμ, and the content of peroxide in the turnip is preferably 10 to 60% by weight.
本発明で用いる有機過酸化物としては、ハイドロパーオ
キサイド、ケトンバーオキサイ・ド、ジアルキルパーオ
キサイド、パーオキシエステル或いはジアシルパーオキ
サイド等を使用することが出来るが、%にベンゾイルパ
ーオキサイド或いはm−)ルオイルパーオキサイドが好
しく・0
カプセル化された有機過酸化物の使用量は(メタ)アク
リレート単量体100重量部に対してα2〜3重量部が
必要である。12重量部を満さないときは、接着能が発
揮されず、他方6重量部を越える場合は適正量を越えて
異物として混入され、接着能が低下する。As the organic peroxide used in the present invention, hydroperoxide, ketone peroxide, dialkyl peroxide, peroxy ester, diacyl peroxide, etc. can be used, but benzoyl peroxide or m- ) Luoyl peroxide is preferred.0 The amount of the encapsulated organic peroxide used is α2 to 3 parts by weight per 100 parts by weight of the (meth)acrylate monomer. If the amount is less than 12 parts by weight, the adhesive ability will not be exhibited, while if it exceeds 6 parts by weight, the amount exceeds the appropriate amount and will be mixed in as foreign matter, reducing the adhesive ability.
促進剤は本発明方法に於いて(メタ)アクリレート単量
体を水中に乳化させるときK、当該単量体と同時に仕込
み、乳化液乃至水溶液として存在させることが出来る。When the (meth)acrylate monomer is emulsified in water in the method of the present invention, the accelerator can be added simultaneously with the monomer and present as an emulsion or an aqueous solution.
促進剤の具体例としては、同時に使用する有機過酸物の
種類に応じて次のものが挙げられる。Specific examples of accelerators include the following depending on the type of organic peroxide used at the same time.
有機ハイドロパーオキサイド又はパーオキシエステルに
対しては銅、コバルト、マンガンなどの有機酸繁テレン
テオ尿素、テトラメチルチオ尿素、2−メルカプトベン
ズイミダゾール、2−メルカプトエタノール、或いはチ
オリンゴ酸などのメルカプト化合物ヒドラジン、2−ヒ
ドロキシエチルヒドラジン或いはベンゾイルヒドラジン
などのヒドラジン誘導体、p−)ルエンスルフィン酸ソ
ーダ、L−アスコルビン酸、或いはトリエチレンジアミ
ンが用いられる。ジアシルパーオキサイドに対してはジ
メチルアニリン、ジメチル−p−)ルイジン、ジエチル
−p−)ルイシン、N、NジメチルーP−7ニシジン、
0−スルホ安息香酸イミド或いは前記のメルカプト化合
物がそれぞれ好しく用いられる。For organic hydroperoxides or peroxy esters, organic acids such as copper, cobalt, manganese, etc., mercapto compounds such as terenetheourea, tetramethylthiourea, 2-mercaptobenzimidazole, 2-mercaptoethanol, or thiomalic acid, hydrazine, 2 Hydrazine derivatives such as -hydroxyethylhydrazine or benzoylhydrazine, p-)sodium toluenesulfinate, L-ascorbic acid, or triethylenediamine are used. For diacyl peroxides, dimethylaniline, dimethyl-p-)luidine, diethyl-p-)luidine, N,N dimethyl-P-7nisidine,
O-sulfobenzoic acid imide or the above-mentioned mercapto compound is preferably used.
促進剤の使用量は(メタ)アクリレート単量体100重
量部に対して0.1〜2重量部が必要である。Q、1重
量部を満さないときはレドックス反応が弱く、常温以下
での接着能を有せず、他方、2重量部を越える場合、’
!、L/ドツクユ反応機構のバランスを失ない、接着能
が低下し各々不適当である。The amount of accelerator used is 0.1 to 2 parts by weight per 100 parts by weight of (meth)acrylate monomer. Q: If the amount is less than 1 part by weight, the redox reaction will be weak and it will not have adhesive ability at room temperature or below.On the other hand, if it exceeds 2 parts by weight, '
! , the balance of the L/dock reaction mechanism is lost, and the adhesion ability decreases, which are unsuitable.
未処理混合物は実質的に酸素不存在下で撹拌することに
よって増粘し、本発明の目的とする水性状の接着剤を得
ることが出来る。The untreated mixture can be thickened by stirring in the substantial absence of oxygen to obtain the aqueous adhesive that is the object of the present invention.
この際、実質的に酸素不存在下とは、(メタ)アクリレ
ート単量体のレドックス触媒系による重合反応を開始す
るに必要な酸素濃度の少ない状態をいい、気相部に窒素
又は炭酸ガスを流通させシールする方法等で得ることが
できる。In this case, "in the substantial absence of oxygen" refers to a state in which the oxygen concentration necessary to initiate the polymerization reaction of the (meth)acrylate monomer by the redox catalyst system is low, and nitrogen or carbon dioxide gas is added to the gas phase. It can be obtained by a method such as distribution and sealing.
又増粘に至る状態とは、未処理混合物に比べて粘度上昇
が確認される状態をいい、これにより各成分の混合が充
分為されると同時に過酸化物を内包するカプセルの周囲
に新たな(メタ)アクリレート単量体から生成する重合
体壁膜が形成され、本発明の目的が達成されると考えら
れる。In addition, a state leading to thickening refers to a state in which an increase in viscosity is confirmed compared to the untreated mixture, and as a result, each component is sufficiently mixed, and at the same time, a new layer is formed around the capsule containing peroxide. It is believed that a polymeric wall film formed from (meth)acrylate monomers is formed and the objectives of the present invention are achieved.
増粘の程度は未処理混合物に比べて若干増粘すれば充分
であるが10〜50チの上昇が好しい。しかしながらゲ
ル状に至り水性状態を失う迄、撹拌を続けて増粘させて
はならないことはいうまでもない。A slight increase in viscosity compared to the untreated mixture is sufficient, but an increase of 10 to 50 inches is preferred. However, it goes without saying that stirring should not be continued to increase the viscosity until it becomes gel-like and loses its aqueous state.
〔本発明方法に採用され得る他の物質〕本発明の水性状
の接着剤の性質を改良することを目的として、例えばチ
クソトロピック性を付与する為に、タルク、シリカ、ア
ルミナ或いは炭酸カルシウムを使用し、又さらに長時間
のポットライフ性を保つ為にハイドロキノン、メチルハ
イドロキノン、2,4−ジニトロアニソール或いは2.
6−ジt−ブチルp−クレゾールを用いることが出来る
。[Other substances that may be employed in the method of the present invention] Talc, silica, alumina or calcium carbonate may be used to improve the properties of the aqueous adhesive of the present invention, for example to impart thixotropic properties. In addition, in order to maintain a longer pot life, hydroquinone, methylhydroquinone, 2,4-dinitroanisole or 2.
6-di-t-butyl p-cresol can be used.
本発明において、未処理混合物を実質的に酸素が存在し
ない状態で撹拌することによって増粘する理由は、カプ
セル化された有機過酸化物の周囲に乳化された(メタ)
アクリレート単量体が吸着乃至侵透して微量の初期重合
物が生成したものと考えられる。In the present invention, the reason for thickening the green mixture by stirring it in the substantial absence of oxygen is that the (meth)
It is thought that the acrylate monomer was adsorbed or permeated to form a trace amount of an initial polymer.
これにより有機過酸物に対してち密なカプセル化が為さ
れることによりポットライフ性が増大し、さらに当該カ
プセルの壁膜が(メタ)アクリレート単量体に対して親
和性を増し接着能が増大すると考えられる。この段階で
本発明方法にとって重要な点は、過酸化物が予じめカプ
セル化されている必要があり、これにより実質的に酸素
が存在しない状態での初期の重合過程が制御され、当該
混合物の急激な増粘による凝固状に至らず若干増粘した
状態で再現性よ(、製品化し得ることが出来る。This increases the pot life by tightly encapsulating the organic peroxide, and also increases the affinity of the capsule wall for the (meth)acrylate monomer, increasing its adhesive ability. It is thought that this will increase. What is important for the process of the invention at this stage is that the peroxide must be pre-encapsulated, which controls the initial polymerization process in the substantial absence of oxygen and allows the mixture to It is possible to reproducibly produce a product in a slightly thickened state without reaching a coagulated state due to rapid viscosity increase.
本発明の方法で得られる接着剤は被着材への塗工時は水
性状態を保持しているので容易に作業が出来て、さらに
乾燥後は触媒系の主体である過酸化物がカプセル化され
ているので(メタ)アクリレート単量体は硬化反応が起
ることはなく、被着材面に油層をなし、且つ表面は予じ
め存在する重合体により、ドライブンテな皮膜を形成し
ている。The adhesive obtained by the method of the present invention maintains an aqueous state when applied to the adherend, making it easy to work with. Furthermore, after drying, the peroxide, which is the main component of the catalyst system, is encapsulated. Since the (meth)acrylate monomer does not undergo a curing reaction, it forms an oil layer on the surface of the adherend, and a dry film is formed on the surface due to the pre-existing polymer. There is.
然して、接着作業時には単に被着材面を摩擦するか又は
圧力をかけることにより、カプセルが破壊され、過酸化
物が(メタ)アクリレート単量体中に溶出し、同時に促
進剤と接触し、硬化反応を開始して、接着能が発揮され
る。However, during adhesion work, simply by rubbing or applying pressure to the surface of the adherend, the capsule is destroyed, the peroxide is eluted into the (meth)acrylate monomer, and at the same time it comes into contact with the accelerator and hardens. The reaction is initiated and adhesive ability is exhibited.
次に本発明をさらに具体的に説明する為に実施例及び比
較例を挙げる。Next, Examples and Comparative Examples will be given to further specifically explain the present invention.
実施例1
(カプセル化されたベンゾイルパーオキサイドの製造)
還流冷却器付き1Lフラスコに67重量係濃度のホルマ
リン水溶液5501尿素131y、及びトリエタノール
アミン1.71を仕込み、300rpmで70℃にて2
時間撹拌して反応させ、pH8,1及びB型粘度計に於
ける20rpmの粘度が13−3cpsである尿素−ホ
ルマリンのプレポリマーを得た。Example 1 (Production of encapsulated benzoyl peroxide) A 1 L flask equipped with a reflux condenser was charged with an aqueous formalin solution of 5501 urea with a concentration of 67% by weight, and 1.71% of triethanolamine, and heated at 70°C at 300 rpm for 2 hours.
The reaction was stirred for hours to obtain a urea-formalin prepolymer having a pH of 8.1 and a viscosity of 13-3 cps at 20 rpm in a B-type viscometer.
21ビーカーに前記のプレポリマー240gと純水52
0gを入れホモジナイザーで500Orpmの撹拌下で
、1Nの塩酸水浴液12ccの添加によりpHを2.0
にして、ベンゾイルパーオキサイドの微粉末(平均粒径
20μm)12.81を仕込み、40℃、5000rp
mで6時間撹拌を行った。さらに純水5001を仕込み
、撹拌数を低下させて、40℃、2000rpmで14
時間反応を続けて、スラリーを得て、洗浄及び乾燥した
。これは尿素−ホルマリン樹脂の皮膜の含有率が79重
量%であり、多核上の平均粒径40μmの粉末であった
。21 In a beaker, 240 g of the above prepolymer and 52 g of pure water
0g, and while stirring at 500 rpm with a homogenizer, adjust the pH to 2.0 by adding 12 cc of 1N hydrochloric acid water bath solution.
12.81 of benzoyl peroxide fine powder (average particle size 20 μm) was charged, and heated at 40°C and 5000 rpm.
Stirring was performed for 6 hours at m. Further, add pure water 5001 and reduce the stirring number to 14 at 40°C and 2000 rpm.
The reaction continued for an hour to obtain a slurry, which was washed and dried. This powder had a urea-formalin resin film content of 79% by weight and a polynuclear powder with an average particle size of 40 μm.
(未処理混合物の調整、及び本発明の目的とする接着剤
の製法)
2にビーカーに純水860g、ゴーセノールGM−14
(ケン化度86モルチのポリビニルアルコール、日本合
成化学工業■製)86Iを仕込み水溶液にしてから、ホ
モジナイザーで400Orpmの撹拌下にてN K B
、PE−200(2,2ビス(4−(メタクリロキシ・
ジェトキシ)フェニル〕プロパン、新中村化学工業■製
)1030.9.0−スルホ安息香酸イミド5.3y及
び2−メルカプトエタノール2,1gをさらに投入して
2時間撹拌を続は水性状乳化液を得た。(Preparation of untreated mixture and manufacturing method of adhesive targeted by the present invention) 2. In a beaker, add 860 g of pure water and Gohsenol GM-14.
(Polyvinyl alcohol with a degree of saponification of 86 mol, manufactured by Nippon Gosei Kagaku Kogyo ■) After preparing 86I and making it into an aqueous solution, N K B was prepared with a homogenizer under stirring at 400 Orpm.
, PE-200 (2,2bis(4-(methacryloxy)
5.3y of 0-sulfobenzoic acid imide and 2.1g of 2-mercaptoethanol were further added and stirred for 2 hours, followed by an aqueous emulsion. Obtained.
これはB型粘度計、20rpmで26℃に於ける粘度は
9100 cpsであった。(以下同一の測定法で粘度
を測定する。)
当該乳化液にこのカプセル化されたペンシイ、II/バ
ーオキサイド49.0 g<ペンソイルパーオキサイド
の含有量10.3.9)を添加して窒素を空間部に流通
させながら40℃に加温し、ホモジナイザーで200O
rpmにて、2時間撹拌を続け11000cps の粘
度の増粘された水性状の接着剤を得た。This was a B-type viscometer, and the viscosity at 26°C at 20 rpm was 9100 cps. (The viscosity is hereinafter measured using the same method.) Add this encapsulated Pencil, II/peroxide (49.0 g <pensoil peroxide content: 10.3.9) to the emulsion. Heat to 40°C while circulating nitrogen through the space, and heat to 200°C with a homogenizer.
Stirring was continued for 2 hours at rpm to obtain a thickened aqueous adhesive with a viscosity of 11,000 cps.
(水性状の接着剤のボルトネジへの塗工)8%径、長さ
40%の黄色クロメートネジのみぞ部が満されるように
当該水性状接着剤0,2Iを均一に塗布して、60℃で
30分間乾燥を行って表面がタックのない樹脂皮膜を形
成し、接着剤が塗工された接着締め付は型のネジを得た
。(Application of water-based adhesive to bolt screws) Apply the water-based adhesive 0.2I uniformly to fill the grooves of the yellow chromate screws with a diameter of 8% and a length of 40%. It was dried at ℃ for 30 minutes to form a tack-free resin film on the surface, and an adhesive-coated screw was obtained.
(接着性能他評価試験)
t 接着性試験
前記の塗工されたネジを230 kffj(cmのトル
クにて締め付け、23℃で24時間放置后の起動戻しト
ルクを測定した。(Adhesive Performance and Other Evaluation Tests) t Adhesiveness Test The coated screws described above were tightened with a torque of 230 kffj (cm), and after being left at 23° C. for 24 hours, the starting return torque was measured.
2 接着性能ポットライフ試験
前記の塗工されたネジを40℃で30日間加温を続けた
あと、250 kl!amのトルクにて締め付けて、2
3℃で24時間放置后の起動戻しトルクを測定した。2 Adhesive Performance Pot Life Test After continuing to heat the above-coated screws at 40°C for 30 days, 250 kl! Tighten to am torque, 2
After being left at 3° C. for 24 hours, the starting return torque was measured.
五 耐熱性試験
前記の塗工されたネジを230k)fizのトルクにて
締め付けて120℃で24時間加温を続け、120℃に
於ける起動戻しトルクを測定した。5. Heat Resistance Test The coated screws described above were tightened with a torque of 230k) and kept heated at 120°C for 24 hours, and the start-up return torque at 120°C was measured.
此等の試験結果を表1に記す。The results of these tests are shown in Table 1.
比較例1
実施例1に於ける未処理混合物を窒素を空間部に流通さ
せず大気に開放状態で40℃に加温し、ホモジナイザー
で200Orpmにて、2時間撹拌を続けた。Comparative Example 1 The untreated mixture in Example 1 was heated to 40° C. in a state open to the atmosphere without flowing nitrogen into the space, and continued to be stirred with a homogenizer at 200 rpm for 2 hours.
得られた試験結果を表1に記す。The test results obtained are shown in Table 1.
比較例2〜6
実施例1に於いて未処理混合物の撹拌処理時間或いはカ
プセル化していない有機過酸化物を使用し、他の条件は
実施例1と全つく同様に行った。Comparative Examples 2 to 6 All the conditions were the same as in Example 1 except that the stirring treatment time of the untreated mixture or the non-encapsulated organic peroxide was used.
得られた試験結果を表1に記す。The test results obtained are shown in Table 1.
実施例2〜8
実施例1に於いて(メタ)アクリレート単量体、カプセ
ル化された有機過酸化物或いは促進剤の種類と量或いは
、未処理混合物の処理条件を変更して、他の条件は実施
例1と全つく同様に行った。Examples 2 to 8 In Example 1, the type and amount of the (meth)acrylate monomer, encapsulated organic peroxide or accelerator, or the treatment conditions of the untreated mixture were changed to obtain other conditions. The procedure was carried out in the same manner as in Example 1.
得られた試験結果を表1に記す。The test results obtained are shown in Table 1.
/
(ハ)発明の効果
本発明の方法により得られる接着剤は、水系でありかつ
増粘されているので取扱上安全であり、塗工性に優れて
いて、且つ経時的に安定な高い接着能をも3さらに乾燥
後は、触媒系の主体である過酸化物がカプセル化されて
いるので(メタ)アクリレート単量体は硬化反応が起る
ことはな(、被着材面に油層をなし、且つ表面は予じめ
存在する重合体により、ドライタッチな皮膜を形成して
いるため、被着材の貯蔵や運送に好適なものである。/ (c) Effects of the invention The adhesive obtained by the method of the invention is water-based and thickened, so it is safe to handle, has excellent coating properties, and has high adhesive properties that are stable over time. Furthermore, after drying, the (meth)acrylate monomer does not undergo a curing reaction (no oil layer is formed on the surface of the adherend) because the peroxide, which is the main component of the catalyst system, is encapsulated. None, and the surface forms a dry-touch film due to the pre-existing polymer, making it suitable for storing and transporting adherends.
Claims (1)
クリロイル基及び/又はメタクリロイル基を有する単量
体100重量部、カプセル化された有機過酸物0.2〜
3重量部、及び当該有機過酸化物とレドックス系を形成
する還元剤0.1〜2重量部からなる混合物を実質的に
酸素の不存在下で撹拌することを特徴とする接着剤の製
造法1. 100 parts by weight of a monomer having an acryloyl group and/or methacryloyl group emulsified in water with a polymer having film-forming ability, and 0.2 to 0.2 parts by weight of an encapsulated organic peroxide.
3 parts by weight of the organic peroxide and 0.1 to 2 parts by weight of a reducing agent that forms a redox system with the organic peroxide in a substantially absence of oxygen.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62-156453A JPH011780A (en) | 1987-06-25 | Adhesive manufacturing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62-156453A JPH011780A (en) | 1987-06-25 | Adhesive manufacturing method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS641780A JPS641780A (en) | 1989-01-06 |
JPH011780A true JPH011780A (en) | 1989-01-06 |
Family
ID=
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