JP4574143B2 - Admixtures and joints for hydraulic materials - Google Patents
Admixtures and joints for hydraulic materials Download PDFInfo
- Publication number
- JP4574143B2 JP4574143B2 JP2003316270A JP2003316270A JP4574143B2 JP 4574143 B2 JP4574143 B2 JP 4574143B2 JP 2003316270 A JP2003316270 A JP 2003316270A JP 2003316270 A JP2003316270 A JP 2003316270A JP 4574143 B2 JP4574143 B2 JP 4574143B2
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- JP
- Japan
- Prior art keywords
- hydraulic
- emulsion
- admixture
- weight
- parts
- 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 - Fee Related
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- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 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
- 159000000001 potassium salts Chemical class 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ビニルアルコール系重合体を分散剤とし、エチレン性不飽和単量体及びジエン系単量体から選ばれる一種あるいは二種以上の不飽和単量体単位を有する重合体を分散質とするエマルジョン（Ａ）に、分子内にエチレン単位を１〜１２モル％含有するビニルアルコール系重合体（Ｂ）を配合した組成物を乾燥して得られる合成樹脂エマルジョン粉末からなる水硬性物質用混和材および打継ぎ材に関する。 The present invention uses a vinyl alcohol polymer as a dispersant, and a polymer having one or more unsaturated monomer units selected from ethylenically unsaturated monomers and diene monomers as a dispersoid. A mixture for a hydraulic substance comprising a synthetic resin emulsion powder obtained by drying a composition in which a vinyl alcohol polymer (B) containing 1 to 12 mol% of ethylene units in the molecule is blended with the emulsion (A) Material and joint material.
合成樹脂エマルジョン粉末は、合成樹脂エマルジョンを噴霧乾燥することにより製造され、合成樹脂エマルジョンに比べて粉末であることにより、取り扱いおよび輸送の点で優れている。また、使用に際しては、水を添加し、攪拌することにより容易に水中に再分散するため、セメントあるいはモルタルへの混和材、接着剤、塗料用バインダーなどの広範な用途に使用されている。なかでもモルタル等水硬性物質への混和材に関しては、粉末であることから、プレミックスが可能であり、多様な商品形態を可能にすることから、広く用いられている。しかしながら、従来、合成樹脂エマルジョンをそのまま噴霧乾燥した場合には、分散質が容易に融着し、水硬性物質に混和した際に分散しないため、多量のポリビニルアルコールを後添加し、さらにはブロッキング防止剤として無水珪酸等の無機粉末を多量に併用する必要があるのが現状であった。後添加するポリビニルアルコールとしては、粉末化後、水硬性物質に混和した際、分散することが必要であることから、従来部分けん化ＰＶＡが広く用いられてきた（特許文献１）。しかしながら、そのようにして得られたエマルジョン粉末を、例えばセメントモルタル用混和材として用いた場合、後述する比較例７〜８から明らかなように、得られるセメントモルタルの強度などが、必ずしも満足しうるものではなかった。
本発明の目的は、前述の問題点を解決し、水硬性物質への分散性に優れ、得られる水硬性物質の強度にも優れる水硬性物質用混和材を提供することにある。
また、本発明の他の目的は、接着性および耐久性に優れ、さらに機械的強度にも優れる水硬性物質用打継ぎ材を提供することにある。
An object of the present invention is to solve the above-mentioned problems, and to provide an admixture for a hydraulic substance which is excellent in dispersibility in a hydraulic substance and excellent in the strength of the obtained hydraulic substance.
Another object of the present invention is to provide a joining material for a hydraulic substance that is excellent in adhesiveness and durability and also excellent in mechanical strength.
本発明者らは、上記の実情に鑑み、鋭意検討した結果、ビニルアルコール系重合体を分散剤とし、エチレン性不飽和単量体及びジエン系単量体から選ばれる一種あるいは二種以上の不飽和単量体単位を有する重合体を分散質とするエマルジョン（Ａ）に、分子内にエチレン単位を１〜１２モル％含有するビニルアルコール系重合体（Ｂ）を配合した組成物を乾燥して得られる合成樹脂エマルジョン粉末からなる水硬性物質用混和材および打継ぎ材であって、該エマルジョン（Ａ）において、分散剤の使用量が単量体１００重量部に対して２〜３０重量部であり、かつ、エマルジョン（Ａ）の固形分１００重量部に対し、ビニルアルコール系重合体（Ｂ）を１〜５０重量部含有する水硬性物質用混和材および打継ぎ材が、上記課題を解決するものであることを見出し、本発明を完成するに至った。
As a result of intensive investigations in view of the above circumstances, the present inventors have found that one or two or more kinds of solvents selected from ethylenically unsaturated monomers and diene monomers using a vinyl alcohol polymer as a dispersant. A composition in which a vinyl alcohol polymer (B) containing 1 to 12 mol% of an ethylene unit in the molecule is blended in an emulsion (A) having a polymer having a saturated monomer unit as a dispersoid is dried. A hydraulic material admixture and joint material comprising the resulting synthetic resin emulsion powder , wherein in the emulsion (A), the dispersant is used in an amount of 2 to 30 parts by weight per 100 parts by weight of the monomer. There, and, with respect to 100 parts by weight of a solid content of the emulsion (a), the vinyl alcohol polymer (B) a hydraulic substance admixtures containing 1 to 50 parts by weight and striking joint material, to solve the above problems Also It found to be in, which resulted in the completion of the present invention.
本発明により、水硬性物質への分散性に優れ、得られる水硬性物質の強度にも優れる水硬性物質用混和材が得られる。該水硬性物質用混和材はセメントあるいはモルタル、石膏等各種の水硬性物質への混和材として好適に用いられる。また、本発明により、接着性および耐久性に優れ、さらに機械的強度にも優れる水硬性物質用打継ぎ材が得られる。 By this invention, the admixture for hydraulic substances which is excellent in the dispersibility to a hydraulic substance, and is excellent also in the intensity | strength of the obtained hydraulic substance is obtained. The admixture for hydraulic material is suitably used as an admixture for various hydraulic materials such as cement, mortar, and gypsum. Further, according to the present invention, it is possible to obtain a joining material for a hydraulic substance that is excellent in adhesiveness and durability, and further excellent in mechanical strength.
以下、まず本発明の重要な態様のひとつである水硬性物質用混和材について詳細に説明する。
本発明において、エマルジョン（Ａ）の分散質は、エチレン性不飽和単量体及びジエン系単量体から選ばれる一種あるいは二種以上の不飽和単量体単位を有する重合体からなる。エチレン性不飽和単量体としては、エチレン、プロピレン、イソブテン等のオレフィン類、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン等のハロゲン化オレフィン類、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニル、ピバリン酸ビニル等のビニルエステル類、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸ｉ−プロピル、アクリル酸ｎ−ブチル、アクリル酸ｉ−ブチル、アクリル酸ｔ−ブチル、アクリル酸２−エチルヘキシル、アクリル酸ドデシル、アクリル酸オクタデシル等のアクリル酸エステル類、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸ｉ−プロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｉ−ブチル、メタクリル酸ｔ−ブチル、メタクリル酸２−エチルヘキシル、メタクリル酸ドデシル、メタクリル酸オクタデシル等のメタクリル酸エステル類、アクリロニトリル、メタクリロニトリル等のニトリル類、酢酸アリル、塩化アリル等のアリル化合物、スチレン、α−メチルスチレン、ｐ−メチルスチレンスルホン酸およびそのナトリウム、カリウム塩等のスチレン系単量体類、トリメチル−（３−アクリルアミド−３−ジメチルプロピル）−アンモニウムクロライド、３−アクリルアミドプロピルトリメチルアンモニウムクロライド、３−メタクリルアミドプロピルトリメチルアンモニウムクロライド、Ｎ−（３−アリルオキシ−２−ヒドロキシプロピル）ジメチルアミンの４級アンモニウム塩、Ｎ−（４−アリルオキシ−３−ヒドロキシブチル）ジエチルアミンの４級アンモニウム塩、さらにはアクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、ジアセトンアクリルアミド、Ｎ−メチロールアクリルアミド、メタクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド、Ｎ−メチロールメタクリルアミド等の４級アンモニウム塩、メタクリル酸ヒドロキシプロピルトリメチルアンモニウムクロライド、アクリル酸ヒドロキシプロピルトリメチルアンモニウムクロライド、Ｎ−ビニルピロリドン等が挙げられ、またジエン系単量体としては、ブタジエン、イソプレン、クロロプレン等が挙げられる。これらの単量体は単独もしくは二種以上を組み合わせて使用される。
上記の単量体単位からなる重合体のうち、酢酸ビニル系重合体で代表されるビニルエステル系重合体、エチレン−酢酸ビニル共重合体で代表されるオレフィン−ビニルエステル共重合体などは、本発明の好ましい態様の一つである。
The hydraulic material admixture, which is one of the important aspects of the present invention, will be described in detail below.
In the present invention, the dispersoid of the emulsion (A) is composed of a polymer having one or more unsaturated monomer units selected from ethylenically unsaturated monomers and diene monomers. Examples of the ethylenically unsaturated monomer include olefins such as ethylene, propylene, and isobutene, halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, and vinylidene fluoride, vinyl formate, vinyl acetate, vinyl propionate, Vinyl esters such as vinyl versatate and vinyl pivalate, acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, acrylic acid Acrylic acid esters such as t-butyl, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n methacrylate -Butyl, meta Methacrylic acid esters such as i-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate and octadecyl methacrylate, nitriles such as acrylonitrile and methacrylonitrile, allyl such as allyl acetate and allyl chloride Compound, Styrene monomers such as styrene, α-methylstyrene, p-methylstyrenesulfonic acid and sodium and potassium salts thereof, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, 3-acrylamidopropyl Trimethylammonium chloride, 3-methacrylamidopropyltrimethylammonium chloride, quaternary ammonium salt of N- (3-allyloxy-2-hydroxypropyl) dimethylamine, N- (4-allyloxy- 3-hydroxybutyl) diethylamine quaternary ammonium salt, acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetone acrylamide, N-methylolacrylamide, methacrylamide, N-methylmethacrylamide Quaternary ammonium salts such as N-ethylmethacrylamide and N-methylolmethacrylamide, hydroxypropyltrimethylammonium methacrylate methacrylate, hydroxypropyltrimethylammonium chloride acrylate, N-vinylpyrrolidone and the like, and diene monomers Examples thereof include butadiene, isoprene, chloroprene and the like. These monomers are used alone or in combination of two or more.
Among the polymers composed of the above monomer units, vinyl ester polymers typified by vinyl acetate polymers, olefin-vinyl ester copolymers typified by ethylene-vinyl acetate copolymers, etc. This is one of the preferred embodiments of the invention.
本発明において、エマルジョン（Ａ）の分散剤にはビニルアルコール系重合体が用いられる。ビニルアルコール系重合体は、例えば、ビニルエステルを重合して得られるビニルエステル系重合体をけん化することにより製造される。該ビニルアルコール系重合体のけん化度は、特に制限されないが、７０〜９９モル％が好適であり、より好ましくは、８０〜９８モル％、さらに好ましくは８３〜９５モル％である。けん化度が７０モル％未満の場合には、ビニルアルコール系重合体本来の性質である水溶性が低下する懸念が生じる。またけん化度が９９．９モル％をこえる場合、乳化重合が不安定になる懸念がある。該ビニルアルコール系重合体の粘度平均重合度（以下重合度と略す）は、１００〜８０００の範囲が好適であり、３００〜３０００、さらには３００〜２５００がより好ましい。また、エマルジョン（Ａ）の分散剤のビニルアルコール系重合体としては、１，２−グリコール結合が１．９モル％以上のビニルアルコール系重合体が好適に用いられる。１，２−グリコール結合が１．９モル％以上の重合体の製法としては、例えば、ビニレンカーボネートを上記の１，２−グリコール結合量になるようビニルエステル系単量体と共重合する方法、またはビニルエステル系単量体を重合する際、重合温度を通常の条件より高い温度、例えば７５〜２００℃で、加圧下に重合する方法などが挙げられる。後者の方法において、重合温度は特に制限されないが通常９５〜１９０℃、好ましくは１００〜１８０℃で実施される。 In the present invention, a vinyl alcohol polymer is used as the dispersant for the emulsion (A). The vinyl alcohol polymer is produced, for example, by saponifying a vinyl ester polymer obtained by polymerizing a vinyl ester. The saponification degree of the vinyl alcohol polymer is not particularly limited, but is preferably 70 to 99 mol%, more preferably 80 to 98 mol%, and still more preferably 83 to 95 mol%. When the degree of saponification is less than 70 mol%, there is a concern that water solubility, which is the original property of the vinyl alcohol polymer, is lowered. Further, when the degree of saponification exceeds 99.9 mol%, there is a concern that emulsion polymerization becomes unstable. The viscosity average polymerization degree (hereinafter abbreviated as polymerization degree) of the vinyl alcohol polymer is preferably in the range of 100 to 8000, more preferably 300 to 3000, and even more preferably 300 to 2500. Moreover, as a vinyl alcohol polymer of the dispersing agent of emulsion (A), a vinyl alcohol polymer having a 1,2-glycol bond of 1.9 mol% or more is preferably used. As a method for producing a polymer having a 1,2-glycol bond of 1.9 mol% or more, for example, a method of copolymerizing vinylene carbonate with a vinyl ester monomer so as to have the above 1,2-glycol bond amount, Alternatively, when polymerizing a vinyl ester monomer, a method of polymerizing under pressure at a temperature higher than normal conditions, for example, 75 to 200 ° C., may be mentioned. In the latter method, the polymerization temperature is not particularly limited, but is usually 95 to 190 ° C, preferably 100 to 180 ° C.
該ビニルアルコール系重合体は、本発明の効果を損なわない範囲で共重合可能なエチレン性不飽和単量体を共重合したものでも良い。このようなエチレン性不飽和単量体としては、例えば、アクリル酸、メタクリル酸、フマル酸、（無水）マレイン酸、イタコン酸、アクリロニトリル、メタクリロニトリル、アクリルアミド、メタクリルアミド、トリメチル−（３−アクリルアミド−３−ジメチルプロピル）−アンモニウムクロリド、アクリルアミド−２−メチルプロパンスルホン酸およびそのナトリウム塩、エチルビニルエーテル、ブチルビニルエーテル、塩化ビニル、臭化ビニル、フッ化ビニル、塩化ビニリデン、フッ化ビニリデン、テトラフルオロエチレン、ビニルスルホン酸ナトリウム、アリルスルホン酸ナトリウム、Ｎ−ビニルピロリドン、 Ｎ−ビニルホルムアミド、 Ｎ−ビニルアセトアミド等のＮ−ビニルアミド類が挙げられる。また、チオール酢酸、メルカプトプロピオン酸などのチオール化合物の存在下で、酢酸ビニルなどのビニルエステル系単量体と上記エチレン性不飽和単量体とを共重合し、得られた共重合体をけん化することによって得られる末端変性物を用いることもできる。 The vinyl alcohol polymer may be a copolymer of an ethylenically unsaturated monomer that can be copolymerized within a range that does not impair the effects of the present invention. Examples of such ethylenically unsaturated monomers include acrylic acid, methacrylic acid, fumaric acid, (anhydrous) maleic acid, itaconic acid, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, trimethyl- (3-acrylamide). -3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonic acid and its sodium salt, ethyl vinyl ether, butyl vinyl ether, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene N-vinylamides such as sodium vinylsulfonate, sodium allylsulfonate, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, and the like. Also, vinyl ester monomers such as vinyl acetate and the above ethylenically unsaturated monomers are copolymerized in the presence of thiol compounds such as thiol acetic acid and mercaptopropionic acid, and the resulting copolymer is saponified. It is also possible to use a terminally modified product obtained by doing so.
本発明に用いる合成樹脂エマルジョン（Ａ）は、ビニルアルコール系重合体の存在下で、エチレン性不飽和単量体及びジエン系単量体から選ばれる１種あるいは２種以上の単量体を乳化重合することによって得られ、また合成樹脂エマルジョン粉末は合成樹脂エマルジョンを噴霧乾燥して得られる。該合成樹脂エマルジョンの製造において、乳化重合の開始剤としては、通常乳化重合に用いられる重合開始剤、すなわち過硫酸カリウム、過硫酸アンモニウム、過酸化水素、ｔ−ブチルハイドロパーオキサイド等の水溶性開始剤やアゾビスイソブチロニトリル、ベンゾイルパーオキサイド等の油溶性開始剤が単独または各種還元剤との組み合わせによるレドックス系で用いられる。これらの使用方法は特に制限はないが、初期一括で添加する方法や、連続的に重合系に添加する方法等が採用できる。 The synthetic resin emulsion (A) used in the present invention emulsifies one or more monomers selected from ethylenically unsaturated monomers and diene monomers in the presence of a vinyl alcohol polymer. The synthetic resin emulsion powder is obtained by polymerizing, and the synthetic resin emulsion powder is obtained by spray drying the synthetic resin emulsion. In the production of the synthetic resin emulsion, as an initiator for emulsion polymerization, a polymerization initiator usually used for emulsion polymerization, that is, a water-soluble initiator such as potassium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, etc. In addition, oil-soluble initiators such as azobisisobutyronitrile and benzoyl peroxide are used in redox systems alone or in combination with various reducing agents. Although there are no particular limitations on the method of using these, a method of adding in an initial batch, a method of adding continuously to a polymerization system, or the like can be employed.
本発明に用いる合成樹脂エマルジョン（Ａ）において、ビニルアルコール系重合体の使用量は特に制限されないが、通常単量体１００重量部に対して２〜３０重量部、好ましくは３〜１５重量部、さらに好ましくは３〜１０重量部である。ビニルアルコール系重合体が２重量部未満の場合、合成樹脂エマルジョンの重合安定性が低下すると共にビニルアルコール系重合体を分散剤とする合成樹脂エマルジョンの特徴である機械的安定性や化学的安定性の低下、皮膜強度の低下等が起こる懸念がある。また、ビニルアルコール系重合体が３０重量部を越える場合、重合系の粘度上昇による反応熱除去の問題や皮膜耐水性の低下等の懸念がある。
ビニルアルコール系重合体の添加方法は特に制限はなく、初期に一括して添加する方法、初期にビニルアルコール系重合体の一部を添加し、重合中に連続的に重合系へ添加する方法等がある。
また、従来公知のノニオン性、アニオン性、カチオン性、両性の界面活性剤やヒドロキシエチルセルロース等の水溶性高分子をビニルアルコール系重合体と併用してもかまわない。
In the synthetic resin emulsion (A) used in the present invention, the amount of the vinyl alcohol polymer used is not particularly limited, but is usually 2 to 30 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the monomer. More preferably, it is 3-10 weight part. When the vinyl alcohol polymer is less than 2 parts by weight, the polymerization stability of the synthetic resin emulsion is lowered, and the mechanical stability and chemical stability which are the characteristics of the synthetic resin emulsion using the vinyl alcohol polymer as a dispersant are characteristic. There is a concern that a decrease in film strength and a decrease in film strength may occur. On the other hand, when the amount of the vinyl alcohol polymer exceeds 30 parts by weight, there are concerns such as a problem of removal of reaction heat due to an increase in the viscosity of the polymerization system and a decrease in water resistance of the film.
There is no particular limitation on the method of adding the vinyl alcohol polymer, a method of adding all at once in the initial stage, a method of adding a part of the vinyl alcohol polymer in the initial stage, and continuously adding to the polymerization system during the polymerization, etc. There is.
In addition, a conventionally known nonionic, anionic, cationic or amphoteric surfactant or a water-soluble polymer such as hydroxyethyl cellulose may be used in combination with the vinyl alcohol polymer.
本発明に用いる合成樹脂エマルジョン（Ａ）を製造する際の単量体の添加方法として、初期に一括して重合系に添加する方法、初期に単量体の一部を添加し、残りを重合中に連続的に添加する方法、単量体と水と分散剤を予め乳化したものを重合系に連続的に添加する方法等、各種の方法が可能である。 As a method for adding a monomer when producing the synthetic resin emulsion (A) used in the present invention, a method of adding to the polymerization system all at once, adding a part of the monomer at the initial stage, and polymerizing the rest Various methods are possible, such as a method of continuously adding the monomer, water and a dispersant previously emulsified, and a method of continuously adding to the polymerization system.
また、本発明に用いる合成樹脂エマルジョン（Ａ）を製造する際に、連鎖移動剤を添加することもできる。連鎖移動剤としては、連鎖移動が起こるものであれば特に制限はないが、連鎖移動の効率の点でメルカプト基を有する化合物が好ましい。メルカプト基を有する化合物としては、ｎ−オクチルメルカプタン、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン等のアルキルメルカプタン、２−メルカプトエタノール、３−メルカプトプロピオン酸等が挙げられる。
連鎖移動剤の添加量は、単量体１００重量部に対して５重量部以下が好ましい。連鎖移動剤の添加量が５重量部を越える場合には、合成樹脂エマルジョンの重合安定性が低下する上、分散質を形成する重合体の分子量が著しく低下し、エマルジョン物性の低下が起こる懸念がある。
Moreover, a chain transfer agent can also be added when manufacturing the synthetic resin emulsion (A) used for this invention. The chain transfer agent is not particularly limited as long as chain transfer occurs, but a compound having a mercapto group is preferable from the viewpoint of chain transfer efficiency. Examples of the compound having a mercapto group include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan and t-dodecyl mercaptan, 2-mercaptoethanol, and 3-mercaptopropionic acid.
The addition amount of the chain transfer agent is preferably 5 parts by weight or less with respect to 100 parts by weight of the monomer. When the addition amount of the chain transfer agent exceeds 5 parts by weight, the polymerization stability of the synthetic resin emulsion is lowered, and the molecular weight of the polymer forming the dispersoid is remarkably lowered, and there is a concern that the physical properties of the emulsion may be lowered. is there.
上記エマルジョン（Ａ）に配合される、分子内にエチレン単位を１〜１２モル％含有するビニルアルコール系重合体（Ｂ）は、ビニルエステルとエチレンとの共重合体をけん化することにより得ることができる。分子内にエチレン単位を１〜１２モル％含有することは重要であり、エチレン単位の含有量は、好ましくは１．５モル％以上、さらには２モル％以上であり、また１２モル％以下が好適である。エチレン単位の含有量がこの範囲を下回ると、後述する比較例５から明らかなように、得られるセメントモルタルなどの強度が充分優れたものとはならないし、また、エチレン単位の含有量がこの範囲を上回ると、後述する比較例６から明らかなように、満足な合成樹脂粉末が得られない。また、プロピレン単位を含有させたものでは後述する比較例１０から明らかなように、モルタル物性、打ち継ぎ物性ともに良好とはいえない。 The vinyl alcohol polymer (B) containing 1 to 12 mol% of ethylene units in the molecule and blended in the emulsion (A) can be obtained by saponifying a copolymer of vinyl ester and ethylene. it can. It is important to contain 1 to 12 mol% of ethylene units in the molecule, and the content of ethylene units is preferably 1.5 mol% or more, more preferably 2 mol% or more, and 12 mol% or less. Is preferred. If the content of the ethylene unit is below this range, as will be apparent from Comparative Example 5 described later, the strength of the obtained cement mortar or the like is not sufficiently excellent, and the content of the ethylene unit is within this range. If it exceeds the range, as is apparent from Comparative Example 6 described later, a satisfactory synthetic resin powder cannot be obtained. In addition, in the case of containing propylene units, as is apparent from Comparative Example 10 described later, neither the mortar physical properties nor the joint physical properties are satisfactory.
また、分子内にエチレン単位を１〜１２モル％含有するビニルアルコール系重合体（Ｂ）としては、エチレン単位の含有量をＸモル％とするとき、１，２−グリコール結合を（１．７−Ｘ／４０）〜４モル％含有するビニルアルコール系重合体（Ｂ）も本発明の好ましい態様の一つであり、この重合体を使用することにより、水硬性物質用混和材および打継ぎ材の水硬性物質への分散性が改善される。
この重合体の製法としては、例えば、ビニレンカーボネートを上記の１，２−グリコール結合量になるようビニルエステル系単量体およびエチレンと共重合する方法、エチレンとビニルエステル系単量体を共重合する際、重合温度を通常の条件より高い温度、例えば７５〜２００℃で、加圧下に重合する方法などが挙げられる。後者の方法において、重合温度は特に制限されないが通常９５〜１９０℃、好ましくは１００〜１６０℃で実施される。
The vinyl alcohol polymer (B) containing 1 to 12 mol% of ethylene units in the molecule has 1,2-glycol bonds (1.7) when the content of ethylene units is X mol%. -X / 40) to 4 mol% of a vinyl alcohol polymer (B) is also one of the preferred embodiments of the present invention. By using this polymer, an admixture and a joining material for hydraulic substances are used. Is improved in the dispersibility in hydraulic materials.
As a method for producing this polymer, for example, a method in which vinylene carbonate is copolymerized with vinyl ester monomer and ethylene so as to have the above 1,2-glycol bond amount, and ethylene and vinyl ester monomer are copolymerized. In this case, the polymerization temperature may be higher than normal conditions, for example, 75 to 200 ° C., and polymerization may be performed under pressure. In the latter method, the polymerization temperature is not particularly limited, but is usually 95 to 190 ° C, preferably 100 to 160 ° C.
この場合、１，２−グリコール結合の含有量は、（１．７−Ｘ／４０）モル％以上であることが好ましく、より好ましくは（１．７５−Ｘ／４０）モル％以上、最適には（１．８−Ｘ／４０）モル％以上である。また、１，２−グリコール結合の含有量は４モル％以下であることが好ましく、さらに好ましくは３．５モル％以下、最適には３.２モル％以下である。ここで１，２−グリコール結合の含有量はＮＭＲスペクトルの解析から求められる。 In this case, the content of 1,2-glycol bond is preferably (1.7-X / 40) mol% or more, more preferably (1.75-X / 40) mol% or more, optimally. Is (1.8-X / 40) mol% or more. The 1,2-glycol bond content is preferably 4 mol% or less, more preferably 3.5 mol% or less, and most preferably 3.2 mol% or less. Here, the content of 1,2-glycol bonds can be determined from analysis of NMR spectra.
該ビニルアルコール系重合体（Ｂ）の粘度平均重合度（以下重合度と略す）は、各種の状況に応じて選定すればよく、特に制限はないが、粉末化時の作業性の観点から１００〜３０００が好適であり、好ましくは１５０〜２０００、より好ましくは２００〜１６００、さらには２００〜１０００である。一方、ビニルアルコール系重合体（Ｂ）のけん化度も特に制限されないが、７０〜９９モル％であることが好ましく、８０〜９８モル％がより好ましく、８３〜９５モル％がさらに好ましい。 The viscosity average polymerization degree (hereinafter abbreviated as polymerization degree) of the vinyl alcohol polymer (B) may be selected according to various situations, and is not particularly limited, but is 100 from the viewpoint of workability at the time of powdering. -3000 is suitable, Preferably it is 150-2000, More preferably, it is 200-1600, Furthermore, it is 200-1000. On the other hand, the saponification degree of the vinyl alcohol polymer (B) is not particularly limited, but is preferably 70 to 99 mol%, more preferably 80 to 98 mol%, and still more preferably 83 to 95 mol%.
該ビニルアルコール系重合体（Ｂ）は本発明の効果を損なわない範囲で共重合可能なエチレン性不飽和単量体を共重合したものでも良い。このようなエチレン性不飽和単量体としては、例えば、アクリル酸、メタクリル酸、フマル酸、（無水）マレイン酸、イタコン酸、アクリロニトリル、メタクリロニトリル、アクリルアミド、メタクリルアミド、トリメチル−（３−アクリルアミド−３−ジメチルプロピル）−アンモニウムクロリド、アクリルアミド−２−メチルプロパンスルホン酸およびそのナトリウム塩、エチルビニルエーテル、ブチルビニルエーテル、塩化ビニル、臭化ビニル、フッ化ビニル、塩化ビニリデン、フッ化ビニリデン、テトラフルオロエチレン、ビニルスルホン酸ナトリウム、アリルスルホン酸ナトリウム、Ｎ−ビニルピロリドン、 Ｎ−ビニルホルムアミド、 Ｎ−ビニルアセトアミド等のＮ−ビニルアミド類が挙げられ、量は特に制限されないが、通常５モル％以下のものが用いられる。また、チオール酢酸、メルカプトプロピオン酸などのチオール化合物の存在下で、酢酸ビニルなどのビニルエステル系単量体をエチレンと共重合し、得られる共重合体をけん化することによって得られる末端変性物を用いることもできる。 The vinyl alcohol polymer (B) may be a copolymer of an ethylenically unsaturated monomer that can be copolymerized within a range that does not impair the effects of the present invention. Examples of such ethylenically unsaturated monomers include acrylic acid, methacrylic acid, fumaric acid, (anhydrous) maleic acid, itaconic acid, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, trimethyl- (3-acrylamide). -3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonic acid and its sodium salt, ethyl vinyl ether, butyl vinyl ether, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene N-vinylamides such as sodium vinyl sulfonate, sodium allyl sulfonate, N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, etc. Mol% is used less. In addition, a terminal modified product obtained by copolymerizing a vinyl ester monomer such as vinyl acetate with ethylene in the presence of a thiol compound such as thiol acetic acid or mercaptopropionic acid, and saponifying the resulting copolymer. It can also be used.
合成樹脂エマルジョン（Ａ）に配合するビニルアルコール系重合体（Ｂ）の配合比は、合成樹脂エマルジョン（Ａ）の固形分１００重量部に対してビニルアルコール系重合体（Ｂ）１〜５０重量部であり、好ましくは３〜３０重量部、より好ましくは５〜２０重量部、さらには７〜２０重量部である。ビニルアルコール系重合体（Ｂ）が１重量部未満の場合、水硬性物質に混和した際の機械的安定性が不足し、水硬性物質への分散性が低下する懸念がある。また、５０重量部を越える場合、得られる水硬性物質の強度が低下する懸念がある。
The compounding ratio of the vinyl alcohol polymer (B) to be blended with the synthetic resin emulsion (A) is 1 to 50 parts by weight of the vinyl alcohol polymer (B) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (A). It is preferably 3 to 30 parts by weight, more preferably 5 to 20 parts by weight, and even more preferably 7 to 20 parts by weight. When the vinyl alcohol polymer (B) is less than 1 part by weight, there is a concern that the mechanical stability when mixed with the hydraulic substance is insufficient and the dispersibility in the hydraulic substance is lowered. Moreover, when it exceeds 50 weight part, there exists a possibility that the intensity | strength of the hydraulic substance obtained may fall.
本発明に用いる合成樹脂エマルジョン粉末は、上記の合成樹脂エマルジョン（Ａ）にビニルアルコール系重合体（Ｂ）を配合した後、乾燥、好適には噴霧乾燥して得られる。噴霧乾燥には、流体を噴霧して乾燥する通常の噴霧乾燥が使用できる。噴霧の形式により、ディスク式、ノズル式、衝撃波式などがあるが、いずれの方法でも良い。また、熱源として、熱風や加熱水蒸気等が用いられる。乾燥条件は、噴霧乾燥機の大きさや種類、合成樹脂エマルジョンの濃度、粘度、流量等によって適宜選択すればよい。乾燥温度は、１００℃〜１５０℃が適当であり、この乾燥温度の範囲内で、十分に乾燥した粉末が得られるように、他の乾燥条件を設定することが望ましい。
ビニルアルコール系重合体（Ｂ）の添加方法としては、ビニルアルコール系重合体（Ｂ）の水溶液を、エマルジョン（Ａ）に添加する方法が好適な方法であるが、ビニルアルコール系重合体（Ｂ）の粉末、フレークまたはペレットをエマルジョン（Ａ）に添加する方法も挙げられる。また、乳化重合してエマルジョン（Ａ）を製造する際、乳化重合の後半にビニルアルコール系重合体（Ｂ）を添加（一括または連続添加）する方法も挙げられる。
The synthetic resin emulsion powder used in the present invention is obtained by blending the vinyl alcohol polymer (B) with the synthetic resin emulsion (A) and then drying, preferably spray drying. For spray drying, normal spray drying in which a fluid is sprayed to dry can be used. Depending on the type of spraying, there are disc type, nozzle type, shock wave type, etc. Any method may be used. Moreover, hot air, heating steam, etc. are used as a heat source. The drying conditions may be appropriately selected depending on the size and type of the spray dryer, the concentration, viscosity, flow rate, etc. of the synthetic resin emulsion. The drying temperature is suitably from 100 ° C to 150 ° C, and it is desirable to set other drying conditions so that a sufficiently dried powder can be obtained within this drying temperature range.
As a method for adding the vinyl alcohol polymer (B), a method in which an aqueous solution of the vinyl alcohol polymer (B) is added to the emulsion (A) is a suitable method, but the vinyl alcohol polymer (B). The method of adding the powder, flakes or pellets of (1) to the emulsion (A) is also mentioned. Moreover, when manufacturing emulsion (A) by emulsion polymerization, the method of adding a vinyl alcohol polymer (B) (lump or continuous addition) to the latter half of emulsion polymerization is also mentioned.
また、本発明に用いる合成樹脂エマルジョン粉末の貯蔵安定性、水硬性物質との混和時の分散性を向上させる目的で、無機粉末（ブロッキング防止剤）を使用することが望ましい。無機粉末は、噴霧乾燥後のエマルジョン粉末に添加して均一に混合しても良いが、噴霧乾燥する際に合成樹脂エマルジョンを無機粉末の存在下に噴霧すると（同時噴霧）、均一な混合を行うことができ好適である。無機粉末は平均粒径０．１〜１００μｍの微粒子であることが好適である。無機粉末としては、微粒子の無機粉末が好ましく、炭酸カルシウム、クレー、無水珪酸、珪酸アルミニウム、ホワイトカーボン、タルク、アルミナホワイト等が使用される。これらの無機粉末のうち、無水珪酸が好適である。無機粉末（ブロッキング防止剤）の使用量は、性能上、エマルジョン粉末に対して２０重量％以下、さらには１０重量％以下が好ましい。下限値については０．１重量％以上、さらには０．２重量％以上が好ましい。 In addition, it is desirable to use an inorganic powder (antiblocking agent) for the purpose of improving the storage stability of the synthetic resin emulsion powder used in the present invention and the dispersibility when mixed with a hydraulic substance. The inorganic powder may be added to the emulsion powder after spray drying and mixed uniformly. However, when the synthetic resin emulsion is sprayed in the presence of the inorganic powder during spray drying (simultaneous spraying), uniform mixing is performed. This is preferable. The inorganic powder is preferably fine particles having an average particle size of 0.1 to 100 μm. As the inorganic powder, fine inorganic powder is preferable, and calcium carbonate, clay, anhydrous silicic acid, aluminum silicate, white carbon, talc, alumina white and the like are used. Of these inorganic powders, anhydrous silicic acid is preferred. The amount of the inorganic powder (antiblocking agent) used is preferably 20% by weight or less, more preferably 10% by weight or less based on the emulsion powder in view of performance. The lower limit is preferably 0.1% by weight or more, and more preferably 0.2% by weight or more.
本発明の水硬性物質用混和材は、水中に再分散させた後、２０℃で製膜した皮膜の水中への溶出が少ない場合、特に該皮膜を２０℃水中に２４時間浸漬したときの溶出率が７％以下である場合に、水硬性物質に混和した際、得られる水硬性物質の強度がより改善されることから好ましい。より好ましい溶出率は６％以下である。 The admixture for hydraulic substances of the present invention is dissolved when the film formed at 20 ° C. after re-dispersion in water has little elution into water, particularly when the film is immersed in water at 20 ° C. for 24 hours. When the ratio is 7% or less, it is preferable because the strength of the obtained hydraulic substance is further improved when mixed with the hydraulic substance. A more preferable elution rate is 6% or less.
本発明の水硬性物質用混和材は合成樹脂エマルジョン粉末（平均粒径１〜１０００μｍ、好適には２〜５００μｍ）をそのまま用いることができるが、必要に応じ、本発明の効果を損なわない範囲で、従来公知の各種エマルジョン、エマルジョン粉末を添加して用いることもできる。
水硬性物質としては、例えばポルトランドセメント、アルミナセメント、スラグセメント、フライアッシュセメントなどの水硬セメント、あるいは石膏、プラスターなどのセメント以外の水硬性材料が挙げられる。
As the admixture for hydraulic substance of the present invention, a synthetic resin emulsion powder (average particle diameter of 1 to 1000 μm, preferably 2 to 500 μm) can be used as it is, but as long as the effect of the present invention is not impaired, if necessary. Various conventionally known emulsions and emulsion powders can be added and used.
Examples of the hydraulic substance include hydraulic cements such as Portland cement, alumina cement, slag cement and fly ash cement, and hydraulic materials other than cement such as gypsum and plaster.
上記の水硬性物質用混和材を、例えば、セメント、骨材および水からなるセメントモルタルに配合して使用する場合、水硬性物質用混和材の配合量は、セメントに対し５〜２０重量％が好適である。ここで、骨材としては、川砂、砕砂、色砂、けい砂などの細骨材、川砂利、砕石などの粗骨材が挙げられる。
また、本発明の他の態様として、上記水硬性物質用混和材と同一の組成物を、水硬性物質用打継ぎ材として使用することも挙げられる。打継ぎ材として使用する場合は、上記水硬性物質用混和材と同一の組成物を水で適宜再乳化し、打継ぎ材（プライマー処理材）としてコンクリートなどの水硬性物質基板に塗り付け、その後で、セメントモルタルなどの水硬性物質を塗り付けることにより施工が行われる。上記のように本発明の打継ぎ材を使用することにより、優れた接着性および耐久性、さらには優れた機械的強度などを付与することができる。
When the above-mentioned admixture for a hydraulic substance is used by blending it in a cement mortar composed of cement, aggregate and water, for example, the blending quantity of the admixture for hydraulic substance is 5 to 20% by weight with respect to the cement. Is preferred. Here, examples of the aggregate include fine aggregates such as river sand, crushed sand, colored sand and silica sand, and coarse aggregates such as river gravel and crushed stone.
Moreover, using the same composition as the said admixture for hydraulic substances as a joining material for hydraulic substances is also mentioned as another aspect of this invention. When used as a joining material, the same composition as the admixture for hydraulic material is re-emulsified with water as appropriate, and applied to a hydraulic material substrate such as concrete as a joining material (primer treatment material). Then, the construction is performed by applying a hydraulic substance such as cement mortar. As described above, by using the joint material of the present invention, it is possible to impart excellent adhesion and durability, and excellent mechanical strength.
水硬性物質用混和材および打継ぎ材の分散性をより向上させるために、各種の添加剤を加えることもできる。添加剤は、噴霧乾燥前に合成樹脂エマルジョンに添加して噴霧乾燥すると均一に混合されるため好ましい。水溶性添加剤の使用量は特に制限はなく、エマルジョンの耐水性等の物性に悪影響を与えない程度に適宜コントロールされる。このような添加剤としては、ヒドロキシエチルセルロース、メチルセルロース、でんぷん誘導体、ポリビニルピロリドン、ポリエチレンオキサイド等の他、水溶性アルキッド樹脂、水溶性フェノール樹脂、水溶性尿素樹脂、水溶性メラミン樹脂、水溶性ナフタレンスルホン酸樹脂、水溶性アミノ樹脂、水溶性ポリアミド樹脂、水溶性アクリル樹脂、水溶性ポリカルボン酸樹脂、水溶性ポリエステル樹脂、水溶性ポリウレタン樹脂、水溶性ポリオール樹脂、水溶性エポキシ樹脂等が挙げられる。 In order to further improve the dispersibility of the admixture for hydraulic substance and the joining material, various additives can be added. The additive is preferable because it is uniformly mixed when added to the synthetic resin emulsion before spray drying and spray dried. The amount of the water-soluble additive used is not particularly limited, and is appropriately controlled to such an extent that it does not adversely affect physical properties such as water resistance of the emulsion. Examples of such additives include hydroxyethyl cellulose, methyl cellulose, starch derivatives, polyvinyl pyrrolidone, polyethylene oxide, etc., water-soluble alkyd resins, water-soluble phenol resins, water-soluble urea resins, water-soluble melamine resins, water-soluble naphthalene sulfonic acids. Examples include resins, water-soluble amino resins, water-soluble polyamide resins, water-soluble acrylic resins, water-soluble polycarboxylic acid resins, water-soluble polyester resins, water-soluble polyurethane resins, water-soluble polyol resins, and water-soluble epoxy resins.
本発明の水硬性物質用混和材および打継ぎ材には、ＡＥ剤、減水剤、流動化剤、保水剤、増粘剤、防水剤、消泡剤等が適宜使用される。 AE agent, water reducing agent, fluidizing agent, water retention agent, thickening agent, waterproofing agent, antifoaming agent and the like are appropriately used for the admixture and jointing material for hydraulic substances of the present invention.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらによって何等限定されるものではない。なお、実施例中、「部」および「％」はいずれも重量基準を意味する。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” and “%” mean weight basis.
実施例
エマルジョン製造例１
窒素吹き込み口、温度計、撹拌機を備えた耐圧オートクレーブにＰＶＡ−２１７（（株）クラレ製、重合度１７００、けん化度８８モル％）の９．５％水溶液８０部を仕込み、６０℃に昇温してから、窒素置換を行った。酢酸ビニル８０部を仕込んだ後、エチレンを４．９ＭＰａまで加圧し、０．５％過酸化水素水溶液２ｇおよび２％ロンガリット水溶液０．３ｇを圧入し、重合を開始した。残存酢酸ビニル濃度が１０％となったところで、エチレン放出し、エチレン圧力２．０ＭＰａとし、３％過酸化水素水溶液０．３ｇを圧入し重合を完結させた。重合中に凝集などがなく、重合安定性に優れており、固形分濃度５５％、エチレン含量１８重量％のエチレン−酢酸ビニル共重合体エマルジョン（Ｅｍ−１）が得られた。
Example Emulsion Production Example 1
A pressure-resistant autoclave equipped with a nitrogen inlet, a thermometer, and a stirrer was charged with 80 parts of a 9.5% aqueous solution of PVA-217 (manufactured by Kuraray Co., Ltd., polymerization degree 1700, saponification degree 88 mol%) and the temperature was raised to 60 ° C. After warming, nitrogen substitution was performed. After charging 80 parts of vinyl acetate, ethylene was pressurized to 4.9 MPa, and 2 g of 0.5% hydrogen peroxide aqueous solution and 0.3 g of 2% Rongalite aqueous solution were injected to initiate polymerization. When the residual vinyl acetate concentration reached 10%, ethylene was released, the ethylene pressure was set to 2.0 MPa, and 0.3 g of 3% hydrogen peroxide aqueous solution was injected to complete the polymerization. There was no aggregation during the polymerization and the polymerization stability was excellent, and an ethylene-vinyl acetate copolymer emulsion (Em-1) having a solid content concentration of 55% and an ethylene content of 18% by weight was obtained.
エマルジョン製造例２
還流冷却器、滴下ロート、温度計、窒素吹込口、撹拌機を備えたガラス製容器に、末端にメルカプト基を有するＰＶＡ（重合度５５０、鹸化度８８．３モル％、メルカプト基含量３．３×１０−５当量／ｇ）５部とイオン交換水９０部を仕込み、９５℃で完全溶解させた。次いで、希硫酸によりｐＨ＝４とした後、１５０ｒｐｍで撹拌しながらメチルメタクリレート１０部、ｎ−ブチルアクリレート１０部、ｎ−ドデシルメルカプタン０．１部を添加し、窒素置換後７０℃まで昇温した。１％過硫酸カリウム５部を添加し重合を開始し、さらに２時間かけてメチルメタクリレート４０部、ｎ−ブチルアクリレート４０部、ｎ−ドデシルメルカプタン０．４部を混合したものを連続的に添加した。重合開始３時間後、転化率９９．５％となり重合を終了した。固形分濃度５２．０％の安定なメチルメタクリレート／ｎ−ブチルアクリレート共重合体エマルジョン（Ｅｍ−２）を得た。
Emulsion production example 2
In a glass container equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet, and a stirrer, PVA having a mercapto group at the end (polymerization degree 550, saponification degree 88.3 mol%, mercapto group content 3.3) × 10 −5 equivalent / g) 5 parts and 90 parts of ion-exchanged water were charged and completely dissolved at 95 ° C. Next, after adjusting the pH to 4 with dilute sulfuric acid, 10 parts of methyl methacrylate, 10 parts of n-butyl acrylate and 0.1 part of n-dodecyl mercaptan were added while stirring at 150 rpm, and the temperature was raised to 70 ° C. after nitrogen substitution. . Polymerization was started by adding 5 parts of 1% potassium persulfate, and a mixture of 40 parts of methyl methacrylate, 40 parts of n-butyl acrylate and 0.4 part of n-dodecyl mercaptan was continuously added over 2 hours. . Three hours after the start of the polymerization, the conversion was 99.5% and the polymerization was terminated. A stable methyl methacrylate / n-butyl acrylate copolymer emulsion (Em-2) having a solid content concentration of 52.0% was obtained.
エマルジョン製造例３
エマルジョン製造例２において、末端にメルカプト基を有するＰＶＡ（重合度５５０、鹸化度８８．３モル％、メルカプト基含量３．３×１０−５当量／ｇ）の代わりに、末端にメルカプト基を有するＰＶＡ（エチレン含量０．５モル％、重合度５５０、鹸化度８８．３モル％、メルカプト基含量３．３×１０−５当量／ｇ）を使用した以外は、エマルジョン製造例２と同様にしてエマルジョン（Ｅｍ−３）を得た。
Emulsion production example 3
In emulsion production example 2, instead of PVA having a mercapto group at the terminal (polymerization degree 550, saponification degree 88.3 mol%, mercapto group content 3.3 × 10 −5 equivalent / g), it has a mercapto group at the terminal Except for using PVA (ethylene content 0.5 mol%, polymerization degree 550, saponification degree 88.3 mol%, mercapto group content 3.3 × 10 −5 eq / g), the same procedure as in Emulsion Production Example 2 was used. An emulsion (Em-3) was obtained.
エマルジョン製造例１で得たエチレン−酢酸ビニル共重合体エマルジョン（Ａ）（Ｅｍ−１）固形分１００部とエチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１、エチレン単位含有量５モル％、重合度５００、けん化度９５モル％）の５％水溶液２００部を混合したものと、エマルジョンの固形分に対して２％の無水珪酸微粉末（平均粒径２μｍ）とを別々に１２０℃の熱風中に同時噴霧して乾燥し、平均粒径２０μｍの水硬性物質用混和材および打継ぎ材を得た。 100 parts of ethylene-vinyl acetate copolymer emulsion (A) (Em-1) solid content obtained in Emulsion Production Example 1 and ethylene-modified PVA (B) (PVA-1, ethylene unit content 5 mol%, polymerization degree 500) , Saponification degree 95 mol%) 200% 5% aqueous solution mixed with 2% silicic anhydride fine powder (average particle size 2 μm) separately in hot air at 120 ° C. The mixture was sprayed and dried to obtain a hydraulic material admixture and joint material having an average particle diameter of 20 μm.
（水硬性物質用混和材の性能評価）
セメントモルタル用混和材としての性能
セメントモルタルの物性試験
１）モルタル組成：
水硬性物質用混和材／セメント重量比＝０．１０
砂／セメント重量比＝３．０、水／セメント重量比＝０．６
２）スランプ値 ：ＪＩＳ Ａ−１１７３に準じて測定
（セメントモルタルへの分散性を示す指標）
３）曲げ強度 ：ＪＩＳ Ａ−６２０３に準じて測定
４）圧縮強度 ：ＪＩＳ Ａ−６２０３に準じて測定
(Performance evaluation of admixtures for hydraulic materials)
Performance as an admixture for cement mortar Properties test of cement mortar 1) Mortar composition:
Hydraulic material admixture / cement weight ratio = 0.10
Sand / cement weight ratio = 3.0, water / cement weight ratio = 0.6
2) Slump value: Measured according to JIS A-1173
(Indicator of dispersibility in cement mortar)
3) Bending strength: measured according to JIS A-6203 4) Compressive strength: measured according to JIS A-6203
また、水硬性物質用混和材１００部にイオン交換水１００部を添加して、攪拌機により十分攪拌し、以下の物性を評価した。結果を表１〜２に示す。
・耐水性（皮膜の水中溶出率）：再分散したエマルジョンを２０℃下で製膜し、皮膜を得た（膜厚１００μｍ）。該皮膜を２０℃水中に２４時間浸漬し、以下の式により溶出率を算出した。
溶出率(％)＝｛１−（浸漬後の皮膜絶乾重量）／（浸漬前の皮膜絶乾重量）｝×１００
＊浸漬前の皮膜絶乾重量；浸漬前の皮膜重量（含水）−（浸漬前の皮膜重量（含
水）× 皮膜含水率(％)／１００）
＊浸漬後の皮膜絶乾重量；浸漬後の皮膜を１０５℃で絶乾した重量。
Moreover, 100 parts of ion-exchanged water was added to 100 parts of the admixture for hydraulic substance, and the mixture was sufficiently stirred with a stirrer to evaluate the following physical properties. The results are shown in Tables 1-2.
Water resistance (elution rate of film in water): The redispersed emulsion was formed at 20 ° C. to obtain a film (film thickness 100 μm). The film was immersed in 20 ° C. water for 24 hours, and the elution rate was calculated by the following formula.
Elution rate (%) = {1− (absolute dry weight after immersion) / (absolute dry weight before immersion)} × 100
* Absolute dry weight before immersion; film weight before immersion (moisture content)-(film weight before immersion (water content) x film moisture content (%) / 100)
* Absolute dry weight after immersion: Weight obtained by absolute drying of the immersed film at 105 ° C.
（水硬性物質用打継ぎ材の性能評価）
セメントモルタル用打継ぎ材としての性能
上記で得た水硬性物質用混和材をそのまま打継ぎ材として用い以下の試験を行った。
接着強度試験
１）試験用基板
試験に用いるコンクリート基板としては、建築における標準的な調合である、ポルトランドセメント３００部、けい砂８００部、粗骨材（バラス）１０００部、水１８０部を練り混ぜた後、合板型枠で３００ｍｍ×３００ｍｍ×厚さ５０ｍｍの大きさに打設して、試験室｛温度２０℃、相対湿度（ＲＨ）６５％｝中で２８日間養生したものを用いた。
(Performance evaluation of joint material for hydraulic materials)
Performance as a cement mortar joint material The following test was conducted using the hydraulic material admixture obtained above as a joint material.
Adhesive strength test 1) Test substrate As a concrete substrate used for the test, 300 parts of Portland cement, 800 parts of silica sand, 1000 parts of coarse aggregate (ballast) and 180 parts of water, which are standard blends in architecture, are mixed. Then, it was cast in a size of 300 mm × 300 mm × thickness 50 mm with a plywood mold and cured for 28 days in a test room {temperature 20 ° C., relative humidity (RH) 65%}.
２）塗り付けモルタル
試験に用いる塗り付けモルタルの調合は、重量比でセメント１、骨材（標準砂）２とし、フロー値が１７０±５となるように水−セメント比を調整して、ＪＩＳ Ｒ５２０１の９．４の規定に準拠して練り混ぜた。
なお、セメントとしては、ＪＩＳ Ｒ５２１０（ポルトランドセメント）に規定される普通ポルトランドセメントを、骨材としては、ＪＩＳ Ｒ５２１０の９．２に規定される豊浦標準砂を用いた。
2) Coated mortar The composition of the coated mortar used in the test is cement 1 and aggregate (standard sand) 2 by weight ratio, and the water-cement ratio is adjusted so that the flow value becomes 170 ± 5. It knead | mixed according to prescription | regulation of 9.4 of R5201.
In addition, the normal Portland cement prescribed | regulated to JISR5210 (Portland cement) was used as a cement, and the Toyoura standard sand prescribed | regulated to 9.2 of JISR5210 was used as an aggregate.
３）試験体の作製方法
上記打継ぎ材を、上記１）の試験用基板の表面に刷毛で均一に塗り付け、２４時間、温度２０℃、６５％ＲＨの雰囲気下に放置した。なお、打継ぎ材の塗布量は、固形分として５０ｇ／ｍ２とした。次に、上記２）のモルタルを厚さ６ｍｍになるように金ゴテで塗り付けて、４８時間、２０℃、８０％ＲＨ以上の雰囲気下で養生後、さらに試験室中で２６日間養生して試験体とした。
3) Method for preparing test body The joint material was uniformly applied to the surface of the test substrate of 1) with a brush, and left in an atmosphere of a temperature of 20 ° C. and 65% RH for 24 hours. The application amount of the joining material was 50 g / m 2 as a solid content. Next, apply the mortar of 2) above with a gold trowel so that the thickness is 6 mm, and after curing in an atmosphere of 20 ° C. and 80% RH or more for 48 hours, further curing in the test room for 26 days. A test body was obtained.
４）標準状態の接着強度試験
上記３）で作成した試験体のモルタル面を、寸法４０ｍｍ×９０ｍｍに基板に達するまで切り込んだ後、ＪＩＳ Ａ６９１６の５．６に規定する試験方法に準じて接着強度試験を行い、５箇所の測定値の平均値を求めた。
4) Bond strength test in standard state After the mortar surface of the specimen prepared in 3) above was cut into a size of 40 mm × 90 mm until reaching the substrate, the bond strength was measured according to the test method specified in 5.6 of JIS A6916. The test was performed and the average value of the measured values at five locations was obtained.
５）冷熱繰り返し抵抗性試験（耐久性試験）
上記３）で作成した試験体の表面温度が７０℃になるように、１０５分間赤外線ランプを照射し、その後１５分間散水することを１サイクルとして３００サイクル継続した。但し、水温は１５±５℃とし、試験体１体当たりの散水量は毎分６リットルとした。３００サイクル終了後、試験体を標準状態に２４時間放置し、上記４）と同様に試験を行った。
5) Cold and hot resistance test (durability test)
Irradiation with an infrared lamp for 105 minutes and subsequent watering for 15 minutes were continued for 300 cycles so that the surface temperature of the test specimen prepared in 3) was 70 ° C. However, the water temperature was 15 ± 5 ° C., and the amount of water sprayed per specimen was 6 liters per minute. After 300 cycles, the specimen was left in the standard state for 24 hours, and the test was conducted in the same manner as in 4) above.
６）凍結融解抵抗性試験（耐久性試験）
上記３）で作成した試験体を、２０±３℃の水中に１５時間浸漬し、−２０±３℃の恒温槽中に３時間浸漬後、７０±３℃の恒温槽中に６時間浸漬することを１サイクルとして５０サイクル継続した。５０サイクル終了後、試験体を標準状態に２４時間放置し、上記４）と同様に試験を行った。
得られた水硬性物質用混和剤および打継ぎ材の物性を表１〜２に示す。
6) Freeze-thaw resistance test (durability test)
The specimen prepared in 3) above is immersed in 20 ± 3 ° C. water for 15 hours, immersed in a −20 ± 3 ° C. constant temperature bath for 3 hours, and then immersed in a 70 ± 3 ° C. constant temperature bath for 6 hours. This was regarded as one cycle and continued for 50 cycles. After 50 cycles, the specimen was left in the standard state for 24 hours, and the test was conducted in the same manner as in 4) above.
The physical properties of the obtained admixture for hydraulic substance and the joining material are shown in Tables 1-2.
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−２、エチレン単位含有量１０モル％、重合度５００、けん化度９８モル％）を用いる以外は、実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。 In Example 1, instead of ethylene-modified PVA (B) (PVA-1), ethylene-modified PVA (B) (PVA-2, ethylene unit content 10 mol%, polymerization degree 500, saponification degree 98 mol%) was used. Except for using, the admixture for hydraulic substance and the joining material were obtained in the same manner as in Example 1. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−３、エチレン単位含有量５モル％、重合度５００、けん化度８８モル％）を用いる以外は、実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。 In Example 1, instead of ethylene-modified PVA (B) (PVA-1), ethylene-modified PVA (B) (PVA-3, ethylene unit content 5 mol%, polymerization degree 500, saponification degree 88 mol%) was used. Except for using, the admixture for hydraulic substance and the joining material were obtained in the same manner as in Example 1. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
比較例１
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、無変性ＰＶＡ（Ｂ）（ＰＶＡ−４、（株）クラレ製ＰＶＡ−１０５、重合度５００、けん化度９８．５モル％）を用いる以外は実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。
Comparative Example 1
In Example 1, instead of ethylene-modified PVA (B) (PVA-1), unmodified PVA (B) (PVA-4, Kuraray Co., Ltd. PVA-105, polymerization degree 500, saponification degree 98.5 mol) %) Was used in the same manner as in Example 1 to obtain a hydraulic material admixture and joint material. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
比較例２
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、無変性ＰＶＡ（Ｂ）（ＰＶＡ−５、（株）クラレ製ＰＶＡ−２０５、重合度５００、けん化度８８モル％）を用いる以外は実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られたエマルジョン粉末の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。
Comparative Example 2
In Example 1, instead of ethylene-modified PVA (B) (PVA-1), unmodified PVA (B) (PVA-5, PVA-205 manufactured by Kuraray Co., Ltd., polymerization degree 500, saponification degree 88 mol%) A hydraulic material admixture and joint material were obtained in the same manner as in Example 1 except that was used. The physical properties of the obtained emulsion powder were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
比較例３
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）を用いなかった以外は、実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。
Comparative Example 3
In Example 1, an admixture for hydraulic material and a joint material were obtained in the same manner as in Example 1 except that ethylene-modified PVA (B) (PVA-1) was not used. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−６、エチレン単位含有量５モル％、重合度１３００、けん化度９３モル％）を用いる以外は実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。 In Example 1, instead of ethylene-modified PVA (B) (PVA-1), ethylene-modified PVA (B) (PVA-6, ethylene unit content 5 mol%, polymerization degree 1300, saponification degree 93 mol%) was used. A hydraulic material admixture and joint material were obtained in the same manner as in Example 1 except for using. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
比較例４
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、無変性ＰＶＡ（Ｂ）（ＰＶＡ−７、（株）クラレ製ＰＶＡ−６１３、重合度１３００、けん化度９５モル％）を用いる以外は実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。
Comparative Example 4
In Example 1, instead of ethylene-modified PVA (B) (PVA-1), unmodified PVA (B) (PVA-7, PVA-613 manufactured by Kuraray Co., Ltd., polymerization degree 1300, saponification degree 95 mol%) A hydraulic material admixture and joint material were obtained in the same manner as in Example 1 except that was used. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の５％水溶液を１００部とした以外は実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。 In Example 1, a hydraulic material admixture and joint material were obtained in the same manner as in Example 1 except that 100 parts of a 5% aqueous solution of ethylene-modified PVA (B) (PVA-1) was used. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の５％水溶液を３００部とした以外は、実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。 In Example 1, an admixture for hydraulic substance and a joint material were obtained in the same manner as in Example 1 except that 300 parts of a 5% aqueous solution of ethylene-modified PVA (B) (PVA-1) was used. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の５％水溶液を４０部とした以外は、実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。 In Example 1, an admixture for hydraulic material and a joint material were obtained in the same manner as in Example 1 except that 40 parts of a 5% aqueous solution of ethylene-modified PVA (B) (PVA-1) was used. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の５％水溶液を５００部とした以外は、実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。 In Example 1, an admixture for hydraulic substance and a joining material were obtained in the same manner as in Example 1 except that 500 parts of a 5% aqueous solution of ethylene-modified PVA (B) (PVA-1) was used. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−８、エチレン単位含有量２．５モル％、重合度５００、けん化度８８モル％）を用いる以外は、実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。 In Example 1, instead of ethylene-modified PVA (B) (PVA-1), ethylene-modified PVA (B) (PVA-8, ethylene unit content 2.5 mol%, polymerization degree 500, saponification degree 88 mol%) ) Was used in the same manner as in Example 1 to obtain a hydraulic material admixture and joint material. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−９、エチレン単位含有量１．５モル％、重合度５００、けん化度８８モル％）を用いる以外は、実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。 In Example 1, instead of ethylene-modified PVA (B) (PVA-1), ethylene-modified PVA (B) (PVA-9, ethylene unit content 1.5 mol%, polymerization degree 500, saponification degree 88 mol%) ) Was used in the same manner as in Example 1 to obtain a hydraulic material admixture and joint material. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
比較例５
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１０、エチレン単位含有量０．５モル％、重合度５００、けん化度９５モル％）を用いる以外は、実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。
Comparative Example 5
In Example 1, instead of ethylene-modified PVA (B) (PVA-1), ethylene-modified PVA (B) (PVA-10, ethylene unit content 0.5 mol%, polymerization degree 500, saponification degree 95 mol%) ) Was used in the same manner as in Example 1 to obtain a hydraulic material admixture and joint material. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
比較例６
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１１、エチレン単位含有量２５モル％、重合度５００、けん化度９５モル％）を用いる以外は、実施例１と同様にしてエマルジョンの粉末化を試みた。しかし、該ＰＶＡは水溶液にした際、激しく白濁し、完溶せず試験を中止した。
Comparative Example 6
In Example 1, instead of ethylene-modified PVA (B) (PVA-1), ethylene-modified PVA (B) (PVA-11, ethylene unit content 25 mol%, polymerization degree 500, saponification degree 95 mol%) was used. The emulsion was pulverized in the same manner as in Example 1 except that it was used. However, when the PVA was made into an aqueous solution, it became cloudy vigorously and was not completely dissolved, so the test was stopped.
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、高温重合により得たエチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１２、エチレン単位含有量３モル％、１，２−グリコール結合量１．９モル％、重合度１３００、けん化度９３モル％）を用いる以外は実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。 In Example 1, instead of ethylene-modified PVA (B) (PVA-1), ethylene-modified PVA (B) obtained by high temperature polymerization (PVA-12, ethylene unit content 3 mol%, 1,2-glycol bond) The admixture for hydraulic material and the joining material were obtained in the same manner as in Example 1 except that the amount was 1.9 mol%, the polymerization degree was 1300, and the saponification degree was 93 mol%. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、高温重合により得たエチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１３、エチレン単位含有量５モル％、１，２−グリコール結合量２．２モル％、重合度５００、けん化度８８モル％）を用いる以外は、実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。 In Example 1, instead of ethylene-modified PVA (B) (PVA-1), ethylene-modified PVA (B) obtained by high-temperature polymerization (PVA-13, ethylene unit content 5 mol%, 1,2-glycol bond) An admixture for hydraulic material and a joint material were obtained in the same manner as in Example 1 except that the amount was 2.2 mol%, the degree of polymerization was 500, and the degree of saponification was 88 mol%. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
実施例１において、Ｅｍ−１の代わりに、エマルジョン製造例２で調製したメチルメタクリレート／ｎ−ブチルアクリレート共重合体エマルジョン（Ａ）（Ｅｍ−２）を用いた以外は、実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。 In Example 1, instead of Em-1, the same procedure as in Example 1 was used except that the methyl methacrylate / n-butyl acrylate copolymer emulsion (A) (Em-2) prepared in Emulsion Production Example 2 was used. As a result, an admixture for hydraulic material and a joining material were obtained. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
比較例７
実施例１３において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、無変性ＰＶＡ（Ｂ）（ＰＶＡ−５）を用いた以外は、実施例１と同様にして水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。
Comparative Example 7
In Example 13, an admixture for hydraulic material was used in the same manner as in Example 1 except that unmodified PVA (B) (PVA-5) was used instead of ethylene-modified PVA (B) (PVA-1). And got the joint material. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
比較例８
比較例１において、Ｅｍ−１の代わりに、Ｅｍ−３を使用した以外は、比較例１と同様にして、水硬性物質用混和材および打継ぎ材を得た。得られた水硬性物質用混和材および打継ぎ材の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。
Comparative Example 8
In Comparative Example 1, an admixture for hydraulic material and a joint material were obtained in the same manner as in Comparative Example 1, except that Em-3 was used instead of Em-1. The physical properties of the obtained hydraulic material admixture and joint material were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
比較例９
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１４、エチレン単位含有量１５モル％、重合度１３００、けん化度９３モル％）を用いる以外は実施例１と同様にしてエマルジョンの粉末化を試みた。しかし、該ＰＶＡは水溶液にした際、白濁し、完溶しなかった。白濁液をエマルジョンに配合し、実施例１と同様にして得られたエマルジョン粉末の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。
Comparative Example 9
In Example 1, instead of ethylene-modified PVA (B) (PVA-1), ethylene-modified PVA (B) (PVA-14, ethylene unit content 15 mol%, polymerization degree 1300, saponification degree 93 mol%) was used. The emulsion was pulverized in the same manner as in Example 1 except that it was used. However, when the PVA was made into an aqueous solution, it became cloudy and was not completely dissolved. The cloudy liquid was blended into the emulsion, and the physical properties of the emulsion powder obtained in the same manner as in Example 1 were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
比較例１０
実施例１において、エチレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１）の代わりに、プロピレン変性ＰＶＡ（Ｂ）（ＰＶＡ−１５、プロピレン単位含有量５モル％、重合度１３００、けん化度９３モル％）を用いる以外は実施例１と同様にしてエマルジョンの粉末化を試みた。得られたエマルジョン粉末の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。
Comparative Example 10
In Example 1, instead of ethylene-modified PVA (B) (PVA-1), propylene-modified PVA (B) (PVA-15, propylene unit content 5 mol%, polymerization degree 1300, saponification degree 93 mol%) was used. The emulsion was pulverized in the same manner as in Example 1 except that it was used. The physical properties of the obtained emulsion powder were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
エマルジョン製造例１において、（株）クラレ製「ＰＶＡ２１７」の代わりに、高温重合により得たＰＶＡ（１，２−グリコール結合量２．２モル％、重合度１７００、けん化度８８モル％）を使用した以外はエマルジョン製造例１と同様の方法で、固形分濃度５５％、エチレン含量１８重量％のエチレン−酢酸ビニル共重合体エマルジョン（Ｅｍ−４）を得た。
次に、実施例１において、エチレン−酢酸ビニル共重合体エマルジョン（Ａ）（Ｅｍ−１）の代わりに、Ｅｍ−４を使用した以外は、実施例１と同様の方法でエマルジョン粉末を得た。得られたエマルジョン粉末の物性を実施例１と同様にして評価した。結果を併せて表１〜２に示す。
In emulsion production example 1, instead of “PVA217” manufactured by Kuraray Co., Ltd., PVA obtained by high-temperature polymerization (1,2-glycol bond amount 2.2 mol%, polymerization degree 1700, saponification degree 88 mol%) was used. Except that, an ethylene-vinyl acetate copolymer emulsion (Em-4) having a solid content of 55% and an ethylene content of 18% by weight was obtained in the same manner as in Emulsion Production Example 1.
Next, an emulsion powder was obtained in the same manner as in Example 1, except that Em-4 was used instead of the ethylene-vinyl acetate copolymer emulsion (A) (Em-1). . The physical properties of the obtained emulsion powder were evaluated in the same manner as in Example 1. The results are also shown in Tables 1 and 2.
本発明により、水硬性物質への分散性に優れ、得られる水硬性物質の強度にも優れる水硬性物質用混和材が得られる。該水硬性物質用混和材はセメントあるいはモルタル、石膏等各種の水硬性物質への混和材として好適に用いられる。また、本発明により、接着性および耐久性に優れ、さらに機械的強度にも優れる水硬性物質用打継ぎ材が得られる。
By this invention, the admixture for hydraulic substances which is excellent in the dispersibility to a hydraulic substance, and is excellent also in the intensity | strength of the obtained hydraulic substance is obtained. The admixture for hydraulic material is suitably used as an admixture for various hydraulic materials such as cement, mortar, and gypsum. Further, according to the present invention, it is possible to obtain a joining material for a hydraulic substance that is excellent in adhesiveness and durability, and further excellent in mechanical strength.
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| JP2012166985A (en) * | 2011-02-14 | 2012-09-06 | Kajima Corp | Fiber-reinforced cement paste for jointing, and construction joint method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1121380A (en) * | 1997-06-30 | 1999-01-26 | Kuraray Co Ltd | Aqueous emulsion |
| JPH11263849A (en) * | 1998-03-18 | 1999-09-28 | Kuraray Co Ltd | Preparation of synthetic resin emulsion powder |
| JP2000211955A (en) * | 1999-01-22 | 2000-08-02 | Kuraray Co Ltd | Cement admixture |
| JP2001234018A (en) * | 2000-02-21 | 2001-08-28 | Kuraray Co Ltd | Dispersant for emulsion polymerization and aqueous emulsion |
| JP2001342260A (en) * | 2000-06-02 | 2001-12-11 | Kuraray Co Ltd | Synthetic resin emulsion powder |
| JP2004131720A (en) * | 2002-09-17 | 2004-04-30 | Kuraray Co Ltd | Powder from synthetic resin emulsion and use of the same |
| JP2004211059A (en) * | 2002-12-16 | 2004-07-29 | Kuraray Co Ltd | Synthetic resin powder and admixture or construction joint material for hydraulic material |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1121380A (en) * | 1997-06-30 | 1999-01-26 | Kuraray Co Ltd | Aqueous emulsion |
| JPH11263849A (en) * | 1998-03-18 | 1999-09-28 | Kuraray Co Ltd | Preparation of synthetic resin emulsion powder |
| JP2000211955A (en) * | 1999-01-22 | 2000-08-02 | Kuraray Co Ltd | Cement admixture |
| JP2001234018A (en) * | 2000-02-21 | 2001-08-28 | Kuraray Co Ltd | Dispersant for emulsion polymerization and aqueous emulsion |
| JP2001342260A (en) * | 2000-06-02 | 2001-12-11 | Kuraray Co Ltd | Synthetic resin emulsion powder |
| JP2004131720A (en) * | 2002-09-17 | 2004-04-30 | Kuraray Co Ltd | Powder from synthetic resin emulsion and use of the same |
| JP2004211059A (en) * | 2002-12-16 | 2004-07-29 | Kuraray Co Ltd | Synthetic resin powder and admixture or construction joint material for hydraulic material |
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