JP2006188552A - Viscous resin composition - Google Patents
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本発明は、コンクリート構造物の保護，防食，耐震若しくは剥落防止等を目的とした土木建築工事において、プライマー処理後の乾燥及び湿潤コンクリート面に塗布される粘稠性樹脂組成物に関するものである。 The present invention relates to a viscous resin composition applied to a dried and wet concrete surface after primer treatment in civil engineering and construction work for the purpose of protecting a concrete structure, preventing corrosion, preventing earthquakes, or preventing peeling.
低温環境下において、粘性が増大し塗布作業性を低下させると共に、反応性が著しく低下することにより施工を妨げるエポキシ樹脂に代わり、低温速硬化性を有する不飽和ポリエステル樹脂及びビニルエステル樹脂等のラジカル重合性樹脂が土木建築工事用材料として用いられてきている。 Radicals such as unsaturated polyester resins and vinyl ester resins with low-temperature fast-curing properties in place of epoxy resins that interfere with construction due to increased viscosity and reduced coating workability in a low-temperature environment. Polymerizable resins have been used as civil engineering and construction materials.
例えば、ラジカル重合性樹脂に揺変性付与剤及び充填剤を配合した粘稠性樹脂組成物は、コンクリート構造物に連続繊維シートを貼り付けて構造部材の耐力を向上させる接着工法の不陸修正材として使用されてきた。 For example, a viscous resin composition in which a thixotropic agent and a filler are blended with a radical polymerizable resin is a non-land surface correction material for an adhesion method in which a continuous fiber sheet is attached to a concrete structure to improve the strength of the structural member. Has been used as.
しかしながら、多軸組布を貼り付けてコンクリート片の剥落を防止する接着工法において、施工期間の短縮化を図るため、粘稠性樹脂組成物を不陸修正材のみならず多軸組布を貼り付ける含浸接着樹脂として用いる場合、作業性を重視した低粘稠性樹脂組成物は粘着性が弱く多軸組布の貼り付け時、特にコーナー部で多軸組布の跳ねを押えきれない問題を生じていた。一方、多軸組布の跳ねを押えるため粘性を増大させると硬い性状となりコテ塗り作業性の悪化を招いていた。 However, in the bonding method that affixes multiaxial fabrics to prevent concrete pieces from peeling off, in order to shorten the construction period, the viscous resin composition is applied not only with non-land surface correction materials but also with multiaxial fabrics. When used as an impregnating adhesive resin, the low-viscosity resin composition that emphasizes workability is weak in tackiness, and it is difficult to suppress the splashing of the multiaxial assembly fabric, especially at the corner. It was happening. On the other hand, if the viscosity is increased to suppress the splash of the multi-axis assembly fabric, it becomes hard and the workability of the trowel coating is deteriorated.
これは、従来から用いられている熱硬化性樹脂組成物の揺変性付与剤であるコロイダルシリカ，繊維状鉱物及び微粉末鉱物を、液伸びの良さと液垂れ難さとを両立させて配合調整することが困難であるためである。 This is a combination adjustment of colloidal silica, fibrous minerals and fine powder minerals, which are thixotropic agents for thermosetting resin compositions that have been used in the past, with both good liquid elongation and difficulty in dripping. This is because it is difficult.
更に、上述のコロイダルシリカは高価であることから製品のコストが高くなる問題があり、また、コロイダルシリカは常温硬化系で用いる硬化促進剤の第３アミン及びナフテン酸コバルトを添加すると、樹脂組成物の粘稠性を低下させる問題もあった。 Furthermore, since the above-mentioned colloidal silica is expensive, there is a problem that the cost of the product is increased. When the colloidal silica is added with a tertiary amine and a cobalt naphthenate as a curing accelerator used in a room temperature curing system, the resin composition There was also a problem of lowering the viscosity.
更に、上述の繊維状鉱物及び微粉末鉱物は粘稠性樹脂組成物製造時に粘性の撹拌時間依存性があるために、一定粘性の品質確保が困難であった。 Furthermore, since the above-mentioned fibrous mineral and fine powder mineral have viscosity stirring time dependency at the time of producing the viscous resin composition, it has been difficult to ensure the quality of constant viscosity.
本発明は、従来の揺変性付与剤による上述の問題点を解決するもので、液伸びの良さと液垂れ難さとを両立させることができ、しかも低コストな粘稠性樹脂組成物を提供するものである。 The present invention solves the above-mentioned problems caused by conventional thixotropic agents, and provides a viscous resin composition that can achieve both good liquid elongation and difficulty in dripping, and that is low in cost. Is.
本発明の要旨を説明する。 The gist of the present invention will be described.
熱硬化性樹脂組成物（Ａ），脂肪酸表面処理炭酸カルシウム（Ｂ）及び充填剤（Ｃ）から構成され、前記熱硬化性樹脂組成物（Ａ）は不飽和ポリエステル樹脂及びビニルエステル樹脂より選択される１種類以上の樹脂とラジカル重合性不飽和単量体とを含有することを特徴とする粘稠性樹脂組成物に係るものである。 It is composed of a thermosetting resin composition (A), a fatty acid surface-treated calcium carbonate (B), and a filler (C), and the thermosetting resin composition (A) is selected from unsaturated polyester resins and vinyl ester resins. The present invention relates to a viscous resin composition comprising at least one kind of resin and a radically polymerizable unsaturated monomer.
また、請求項１記載の粘稠性樹脂組成物において、この粘稠性樹脂組成物は、不飽和ポリエステル樹脂及びビニルエステル樹脂より選択される１種類以上の樹脂が２０〜１００重量％、ラジカル重合性不飽和単量体が０〜８０重量％である熱硬化性樹脂組成物（Ａ）が採用され、更に、この熱硬化性樹脂組成物（Ａ）が１００重量部、脂肪酸表面処理炭酸カルシウム（Ｂ）が２０〜２００重量部及び充填剤（Ｃ）が０〜２００重量部配合されていることを特徴とする粘稠性樹脂組成物に係るものである。 The viscous resin composition according to claim 1, wherein the viscous resin composition comprises 20 to 100% by weight of one or more resins selected from unsaturated polyester resins and vinyl ester resins, and radical polymerization. The thermosetting resin composition (A) in which the amount of the unsaturated unsaturated monomer is 0 to 80% by weight is employed. Further, the thermosetting resin composition (A) is 100 parts by weight, and the fatty acid surface-treated calcium carbonate ( 20) to 200 parts by weight of B) and 0 to 200 parts by weight of filler (C) are blended. The present invention relates to a viscous resin composition.
また、請求項１，２のいずれか１項に記載の粘稠性樹脂組成物において、この粘稠性樹脂組成物は、ブルックフィールド形回転粘度計において、２０℃環境下，分速２０回転時の粘度が２０Ｐａ・ｓ〜８０Ｐａ・ｓであるとともに、２０℃環境下，分速２回転時の粘度を２０℃環境下，分速１０回転時の粘度で除した値が３．８〜６．０であることを特徴とする粘稠性樹脂組成物に係るものである。 The viscous resin composition according to any one of claims 1 and 2, wherein the viscous resin composition is a Brookfield rotary viscometer in a 20 ° C environment and at a speed of 20 revolutions per minute. The viscosity is 20 Pa · s to 80 Pa · s, and the value obtained by dividing the viscosity at 20 ° C. under 2 revolutions per minute by the viscosity at 20 ° C. under 10 revolutions per minute under 20 ° C. environment is 3.8-6. The present invention relates to a viscous resin composition characterized by being zero.
また、請求項１〜３いずれか１項に記載の粘稠性樹脂組成物において、この粘稠性樹脂組成物はコンクリートの不陸修正材として用いられるものであることを特徴とする粘稠性樹脂組成物に係るものである。 Moreover, the viscous resin composition of any one of Claims 1-3 WHEREIN: This viscous resin composition is used as an unevenness correction material of concrete, The viscous property characterized by the above-mentioned. It relates to a resin composition.
また、請求項１〜３いずれか１項に記載の粘稠性樹脂組成物において、この粘稠性樹脂組成物は多軸組布等の繊維シートを貼り付けるコンクリート剥落防止用接着剤として用いられるものであることを特徴とする粘稠性樹脂組成物に係るものである。 Moreover, the viscous resin composition of any one of Claims 1-3 WHEREIN: This viscous resin composition is used as an adhesive agent for concrete peeling prevention which affixes fiber sheets, such as a multiaxial assembly cloth. The present invention relates to a viscous resin composition characterized by being a thing.
本発明は上述のように構成したから、液伸びの良さと液垂れ難さとを両立させることができ、しかも製品コストを低減し得る粘稠性樹脂組成物となる。 Since this invention was comprised as mentioned above, it becomes a viscous resin composition which can make the liquid elongation good and the liquid dripping difficult, and can reduce product cost.
本発明の熱硬化性樹脂組成物（Ａ）に含有される不飽和ポリエステル樹脂及びビニルエステル樹脂は公知の方法により製造されるものである。 The unsaturated polyester resin and vinyl ester resin contained in the thermosetting resin composition (A) of the present invention are produced by a known method.
不飽和ポリエステル樹脂は、無水マレイン酸、フマル酸、イタコン酸等の不飽和多塩基酸と、無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロ無水フタル酸等の芳香族あるいは脂環式等の多塩基酸と、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、ネオペンチルグリコール等のグリコール類と、その他の成分を原料に合成された不飽和ポリエステルを、架橋剤を兼ねるモノマーに溶解させたものである。 Unsaturated polyester resins include unsaturated polybasic acids such as maleic anhydride, fumaric acid and itaconic acid, and aromatic or alicyclic polybasic such as phthalic anhydride, isophthalic acid, terephthalic acid and tetrahydrophthalic anhydride. An acid, glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and neopentyl glycol, and unsaturated polyester synthesized from other ingredients are dissolved in a monomer that also serves as a crosslinking agent. .
ビニルエステル樹脂は、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、（メタ）アクリル酸エステル及びその他の成分を原料に合成されたエポキシアクリレートを、架橋剤を兼ねるモノマーに溶解させたものである。 The vinyl ester resin is obtained by dissolving epoxy acrylate synthesized using bisphenol A type epoxy resin, bisphenol F type epoxy resin, (meth) acrylic acid ester and other components as raw materials in a monomer that also serves as a crosslinking agent.
不飽和ポリエステル樹脂及びビニルエステル樹脂には、貯蔵安定性付与の為、p-ベンゾキノン、ナフトキノン、ハイドロキノン、p-t-ブチルカテコール、ジ-t-ブチル・パラクレゾール、ハイドロキノンモノメチルエーテル、ナフテン酸銅、フェニル-β-ナフチルアミン等の重合禁止剤が添加される。 For unsaturated polyester resin and vinyl ester resin, p-benzoquinone, naphthoquinone, hydroquinone, pt-butylcatechol, di-t-butyl paracresol, hydroquinone monomethyl ether, copper naphthenate, phenyl- A polymerization inhibitor such as β-naphthylamine is added.
熱硬化性樹脂組成物（Ａ）に含有されるラジカル重合性不飽和単量体は、活性基としてビニル基を有するエチレン性不飽和単量体、１個の（メタ）アクリロイル基を有する単官能（メタ）アクリレート及び活性基として２個以上の（メタ）アクリロイル基を有する多官能（メタ）アクリレートである。 The radical polymerizable unsaturated monomer contained in the thermosetting resin composition (A) is an ethylenically unsaturated monomer having a vinyl group as an active group and a monofunctional having one (meth) acryloyl group. It is a polyfunctional (meth) acrylate having (meth) acrylate and two or more (meth) acryloyl groups as active groups.
例えばビニル基を有するエチレン性不飽和単量体として、スチレン、ビニルトルエン、α―メチルスチレン等が挙げられる。 Examples of the ethylenically unsaturated monomer having a vinyl group include styrene, vinyl toluene, α-methyl styrene and the like.
単官能（メタ）アクリレートとして、（メタ）アクリル酸、メチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート等が挙げられる。 Examples of the monofunctional (meth) acrylate include (meth) acrylic acid, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
多官能（メタ）アクリレートとして、ポリエチレングリコールジ（メタ）アクリレート、１,４−ブタンジオールジ（メタ）アクリレート、１,６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリストールテトラ（メタ）アクリレート等が挙げられる。 Polyfunctional (meth) acrylates include polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tri Examples include methylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate.
これらラジカル重合性不飽和単量体は、1種または2種以上併用して用いることが出来る。 These radically polymerizable unsaturated monomers can be used alone or in combination of two or more.
本発明の粘稠性樹脂組成物を構成する脂肪酸表面処理炭酸カルシウム（Ｂ）とは、不飽和高級脂肪酸、不飽和高級脂肪酸金属塩、不飽和高級脂肪酸エステル、飽和高級脂肪酸、飽和高級脂肪酸金属塩、及び飽和高級脂肪酸エステルのいずれかで表面処理されている軽質炭酸カルシウム微粉末である。 The fatty acid surface-treated calcium carbonate (B) constituting the viscous resin composition of the present invention is an unsaturated higher fatty acid, an unsaturated higher fatty acid metal salt, an unsaturated higher fatty acid ester, a saturated higher fatty acid, or a saturated higher fatty acid metal salt. , And a light calcium carbonate fine powder surface-treated with any of saturated higher fatty acid esters.
不飽和高級脂肪酸としては、オレイン酸、リノール酸等が挙げられる。 Examples of unsaturated higher fatty acids include oleic acid and linoleic acid.
不飽和高級脂肪酸金属塩としては、オレイン酸ナトリウム、オレイン酸カリウム、リノール酸ナトリウム、リノール酸カリウム等が挙げられる。 Examples of unsaturated higher fatty acid metal salts include sodium oleate, potassium oleate, sodium linoleate, and potassium linoleate.
不飽和高級脂肪酸エステルとしては、オレイン酸のグリセリンエステル、リノール酸のグリセリンエステル等が挙げられる。 Examples of the unsaturated higher fatty acid ester include glycerin ester of oleic acid and glycerin ester of linoleic acid.
飽和高級脂肪酸としては、パルミチン酸、ステアリン酸等が挙げられる。 Examples of saturated higher fatty acids include palmitic acid and stearic acid.
飽和高級脂肪酸金属塩としては、パルミチン酸ナトリウム、パルミチン酸カリウム、ステアリン酸ナトリウム、ステアリン酸カリウム等が挙げられる。 Examples of the saturated higher fatty acid metal salt include sodium palmitate, potassium palmitate, sodium stearate, potassium stearate and the like.
飽和高級脂肪酸エステルとしては、パルミチン酸のグリセリンエステル、ステアリン酸のグリセリンエステル等が挙げられる。 Examples of the saturated higher fatty acid ester include glycerin ester of palmitic acid and glycerin ester of stearic acid.
本発明の粘稠性樹脂組成物を構成する充填剤（Ｃ）とは、無機質フィラー若しくは有機質フィラー又は両者の混合物である。 The filler (C) constituting the viscous resin composition of the present invention is an inorganic filler, an organic filler, or a mixture of both.
無機質フィラーとしては、水酸化アルミニウム、重質炭酸カルシウム、硫酸バリウム、酸化チタン、ガラス紛、シリカ紛、タルク、クレー、珪砂等が挙げられる。 Examples of the inorganic filler include aluminum hydroxide, heavy calcium carbonate, barium sulfate, titanium oxide, glass powder, silica powder, talc, clay, and silica sand.
有機質フィラーとしては、フェノール樹脂紛、エポキシ樹脂紛、アクリル樹脂紛等が挙げられる。 Examples of the organic filler include phenol resin powder, epoxy resin powder, and acrylic resin powder.
これら充填剤は、１種または２種以上併用して用いることができる。 These fillers can be used alone or in combination of two or more.
更に本発明では、補助的に揺変性を付与してもよく、揺変性付与剤として乾式シリカ、湿式シリカ等のコロイダルシリカ、セピオライト系鉱物、クリスタライト系鉱物等が挙げられる。 Further, in the present invention, thixotropic properties may be supplementarily provided, and examples of the thixotropic properties include colloidal silica such as dry silica and wet silica, sepiolite minerals, crystallite minerals, and the like.
本発明の粘稠性樹脂組成物には、本発明の目的を損なわない範囲で、公知である可塑剤、空気乾燥剤、酸化防止剤、重合禁止剤等の添加剤を使用することが出来る。 In the viscous resin composition of the present invention, known additives such as a plasticizer, an air drying agent, an antioxidant, and a polymerization inhibitor can be used as long as the object of the present invention is not impaired.
本発明の粘稠性樹脂組成物は常温硬化型であり、硬化に際しては有機過酸化物と促進剤のレドックス系硬化剤を添加する。尚、望ましい使用温度範囲は−１０〜３０℃である。 The viscous resin composition of the present invention is a room temperature curing type, and an organic peroxide and an accelerator redox curing agent are added upon curing. In addition, a desirable use temperature range is -10-30 degreeC.
有機過酸化物と促進剤の組合せとしては、特に限定されるものでないが、以下の組合せが例示される。第１の組合せとして、メチルエチルケトンパーオキサイド、アセチルアセトンパーオキサイド、アセト酢酸メチルパーオキサイド等のケトンパーオキサイドとナフテン酸コバルト、オクテン酸コバルト等のコバルトの有機酸塩、第２の組合せとして、ベンゾイルパーオキサイド等のアシルパーオキサイドとＮ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジメチル−ｐ−トルイジン等の芳香族第３アミン、第３の組合せとして、ハイドロパーオキサイドとバナジウム塩等がある。 Although it does not specifically limit as a combination of an organic peroxide and a promoter, The following combinations are illustrated. As a first combination, ketone peroxide such as methyl ethyl ketone peroxide, acetylacetone peroxide, methyl acetoacetate peroxide and an organic acid salt of cobalt such as cobalt naphthenate and cobalt octenoate, as a second combination, benzoyl peroxide and the like As a third combination of an aromatic peroxide such as N, N-dimethylaniline and N, N-dimethyl-p-toluidine, a third combination includes hydroperoxide and vanadium salt.
上記組合せの他、特に限定されるものではないが、硬化速度調整のために添加剤を加えることが出来る。 Other than the above combinations, although not particularly limited, an additive can be added to adjust the curing rate.
第１の組合せの添加剤として、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジメチル−ｐ−トルイジン等の芳香族第３アミン、第２の組合せの添加剤として、ナフテン酸コバルト、オクテン酸コバルト等のコバルトの有機酸塩が例示できる。 As an additive in the first combination, an aromatic tertiary amine such as N, N-dimethylaniline and N, N-dimethyl-p-toluidine, and as an additive in the second combination, cobalt naphthenate, cobalt octenoate, etc. The organic acid salt of cobalt can be illustrated.
有機過酸化物取扱い時の安全性と水分存在下における硬化性を考慮すると、純度５０重量％以下のペースト状若しくはサスペンション状のベンゾイルパーオキサイドとＮ，Ｎ−ジメチルアニリン若しくはＮ，Ｎ−ジメチル−ｐ−トルイジンの芳香族第３アミンの組合せが望ましい。 Considering safety when handling organic peroxides and curability in the presence of moisture, paste or suspension benzoyl peroxide having a purity of 50% by weight or less and N, N-dimethylaniline or N, N-dimethyl-p -A combination of toluidine aromatic tertiary amines is desirable.
本発明において、熱硬化性樹脂組成物（Ａ）１００重量部のうち、不飽和ポリエステル樹脂及びビニルエステル樹脂より選択される１種類以上の樹脂は２０〜１００重量％とすることが望ましく、また、ラジカル重合性不飽和単量体は０〜８０重量％とすることが望ましい。尚、脂肪酸表面処理炭酸カルシウム（Ｂ）は２０〜２００重量部，充填剤（Ｃ）は０〜２００重量部とすることが望ましい。 In the present invention, among 100 parts by weight of the thermosetting resin composition (A), one or more kinds of resins selected from unsaturated polyester resins and vinyl ester resins are preferably 20 to 100% by weight, The radical polymerizable unsaturated monomer is preferably 0 to 80% by weight. The fatty acid surface-treated calcium carbonate (B) is preferably 20 to 200 parts by weight, and the filler (C) is preferably 0 to 200 parts by weight.
前記不飽和ポリエステル樹脂及びビニルエステル樹脂より選択される１種類以上の樹脂は２０重量％未満であると脆性の発現及び耐水性の低下等のため好ましくない。 When the content of one or more resins selected from the unsaturated polyester resin and vinyl ester resin is less than 20% by weight, it is not preferable because of the occurrence of brittleness and a decrease in water resistance.
また、前記不飽和ポリエステル樹脂及びビニルエステル樹脂は、粘度が高く、粘りを生じるために接着剤、塗料として用いる際の作業性が悪い場合があるが、低粘度の単量体であるラジカル重合性不飽和単量体を配合することで、樹脂粘度を下げることができる。 In addition, the unsaturated polyester resin and vinyl ester resin are high in viscosity and may cause poor viscosity and workability when used as an adhesive or paint. By blending an unsaturated monomer, the resin viscosity can be lowered.
更に、前記不飽和ポリエステル樹脂及びビニルエステル樹脂は、加熱硬化に対し、常温硬化では反応温度が低いがために硬化物の架橋ネットワーク形成に違いが生じ、例えば脆さ等の物性低下が起こる場合があるため、問題点を解決するような分子骨格を有するラジカル重合性単量体を配合することで、靭性を付与したり、架橋密度を調整したりすることにより、物性を向上させることができる。 Furthermore, since the unsaturated polyester resin and vinyl ester resin have a low reaction temperature at room temperature curing compared to heat curing, a difference occurs in the formation of a crosslinked network of the cured product, and physical properties such as brittleness may be deteriorated. Therefore, by adding a radical polymerizable monomer having a molecular skeleton that solves the problem, physical properties can be improved by imparting toughness or adjusting the crosslinking density.
加えて、不飽和ポリエステル樹脂及びビニルエステル樹脂そのものでは目的とするコンクリート及び既に硬化した塗膜上への強固な接着性が得られない為、被着体との反応性官能基を有するラジカル重合性単量体を配合することにより、接着性を向上させることができる。この際、前記ラジカル重合性不飽和単量体は、８０重量％を越えると脆性の発現，耐水性の低下及び高コスト等のため好ましくない。 In addition, the unsaturated polyester resin and vinyl ester resin itself do not provide strong adhesion to the target concrete and the already cured coating film, so that the radical polymerizability has a reactive functional group with the adherend. Adhesiveness can be improved by mix | blending a monomer. In this case, if the radical polymerizable unsaturated monomer exceeds 80% by weight, it is not preferable because of the occurrence of brittleness, a decrease in water resistance and high cost.
また、前記脂肪酸表面処理炭酸カルシウムは２０重量部未満であると液垂れが生じるため好ましくなく、また、２００重量部を越えると液伸びが困難となるため好ましくない。 Further, if the fatty acid surface-treated calcium carbonate is less than 20 parts by weight, it is not preferable because dripping occurs, and if it exceeds 200 parts by weight, it is not preferable because it becomes difficult to extend the liquid.
また、前記充填剤は２００重量部を超えると液伸びが困難となるため好ましくない。 Further, when the amount of the filler exceeds 200 parts by weight, the liquid elongation becomes difficult, which is not preferable.
次に、本発明の特性を確認した評価試験について説明する。 Next, an evaluation test for confirming the characteristics of the present invention will be described.
本発明の粘稠性樹脂組成物の塗布作業性は、２０℃環境下分速２０回転時の粘度と、５℃環境下ローラー塗布作業性により評価した。 The coating workability of the viscous resin composition of the present invention was evaluated based on the viscosity at 20 revolutions per minute in a 20 ° C environment and the roller coating workability in a 5 ° C environment.
粘度測定は、トキメック社製の粘度計であるブルックフィールド形回転粘度計のＢ形を用いた。作業性に関わるコテ塗り時の重さが回転粘度計のトルクと相関することを考慮し、最大回転数である２０回転時の粘度で評価した。 Viscosity was measured by using a Brookfield type rotational viscometer B type, which is a viscometer manufactured by Tokimec. Considering that the weight at the time of ironing relating to workability correlates with the torque of the rotational viscometer, the viscosity at the time of 20 rotations, which is the maximum rotation speed, was evaluated.
ローラー塗布作業性評価は、粘性が増大する低温の５℃環境下、マスチックローラーを用いて、１ｍ２の垂直面に対しローラーを回転させて１ｍｍの厚さで塗布を行った時のローラー回転性、ローラーにかかる重さ、液垂れにより評価を行った。 Roller application workability evaluation is performed by rotating a roller with respect to a vertical surface of 1 m 2 using a mastic roller in a low temperature 5 ° C. environment where the viscosity increases, and applying the roller with a thickness of 1 mm. Evaluation was made based on the weight applied to the roller and dripping.
その結果、２０℃環境下における２０回転時の粘度が２０ｐａ・ｓ〜８０ｐａ・ｓの範囲にある場合、５℃環境下におけるマスチックローラーが適度な負荷で回転することが確認でき、よって、塗布作業性が良好となる。 As a result, when the viscosity at 20 revolutions in a 20 ° C. environment is in the range of 20 pa · s to 80 pa · s, it can be confirmed that the mastic roller in the 5 ° C. environment rotates with an appropriate load. Property is improved.
本発明の粘稠性樹脂組成物の垂れ難さは、スランプ、３５ｍｍ三角目地充填性及び粘度比（２ｒｐｍ／１０ｒｐｍ）により評価した。 The difficulty of dripping of the viscous resin composition of the present invention was evaluated by slump, 35 mm triangular joint filling property, and viscosity ratio (2 rpm / 10 rpm).
スランプ試験は、ＪＩＳ Ａ １４３９建築用シーリング材の試験方法に準拠し、２０℃環境下、幅２０ｍｍ長さ１５０ｍｍ高さ１０ｍｍの溝へ樹脂組成物を充填後、垂直に立て、溝下端より垂れ下がった先端までの距離を測定した。 The slump test conforms to the test method of JIS A 1439 sealing material for building, and in a 20 ° C environment, after filling a resin composition into a groove having a width of 20 mm, a length of 150 mm and a height of 10 mm, it stands vertically and hangs down from the lower end of the groove. The distance to the tip was measured.
３５ｍｍ三角目地充填性評価は、２０℃環境下、厚さ５ｍｍの４０ｍｍ等辺山形鋼を上向きに設置し、内のり部３５ｍｍ角への樹脂組成物の三角目地充填性を評価した。 In the evaluation of 35 mm triangular joint filling property, in a 20 ° C. environment, a 40 mm equilateral angle steel with a thickness of 5 mm was installed upward, and the triangular joint filling property of the resin composition to the inner 35 mm square was evaluated.
粘度比（２ｒｐｍ／１０ｒｐｍ）は、樹脂組成物の垂れが粘度計の低回転トルクと中回転トルクの応答性即ち分速２回転と分速２０回転の間より狭い範囲である分速２回転と分速１０回転の間におけるチキソトロピーに相関することを考慮し、ブルックフィールド形回転粘度計のＢ形を用いて測定した分速２回転時の粘度を分速１０回転時の粘度で除した値とした。 The viscosity ratio (2 rpm / 10 rpm) is such that the sag of the resin composition is a responsiveness of low and medium rotational torques of the viscometer, that is, a range of 2 rotations per minute that is narrower than a range between 2 rotations per minute and 20 rotations per minute. Considering the correlation with thixotropy during 10 revolutions per minute, the value obtained by dividing the viscosity at 2 revolutions per minute measured using the Brookfield type rotational viscometer B type by the viscosity at 10 revolutions per minute did.
その結果、粘度比（２ｒｐｍ／１０ｒｐｍ）が３．８〜６．０の範囲にある場合、スランプ５０ｍｍ以内で且つ３５ｍｍ三角目地充填性評価において硬化時まで垂れずに完全に充填される。 As a result, when the viscosity ratio (2 rpm / 10 rpm) is in the range of 3.8 to 6.0, the slump is completely filled within 50 mm and without dripping until curing in the 35 mm triangular joint filling evaluation.
以上より、本発明の粘稠性樹脂組成物は、ブルックフィールド形回転粘度計のＢ形を用い、２０℃環境下、分速２０回転時の粘度が２０Ｐａ・ｓ〜８０Ｐａ・ｓであること且つ粘度比（２ｒｐｍ／１０ｒｐｍ）が３．８〜６．０であることが好適である。 As described above, the viscous resin composition of the present invention uses a Brookfield type rotational viscometer type B, and has a viscosity of 20 Pa · s to 80 Pa · s at 20 rpm in a 20 ° C. environment. The viscosity ratio (2 rpm / 10 rpm) is preferably 3.8 to 6.0.
分速２０回転時の粘度が２０Ｐａ・ｓ未満及び粘度比（２ｒｐｍ／１０ｒｐｍ）が３．８未満では、コンクリート垂直面及び天井面への塗布時に液垂れを生じ、分速２０回転時の粘度が８０Ｐａ・ｓを超え、粘度比（２ｒｐｍ／１０ｒｐｍ）が６．０を超える場合には、５℃環境下におけるローラー塗布作業が困難となる。 If the viscosity at 20 revolutions per minute is less than 20 Pa · s and the viscosity ratio (2 rpm / 10 rpm) is less than 3.8, liquid dripping occurs when applied to the concrete vertical surface and ceiling surface, and the viscosity at 20 revolutions per minute is When the viscosity exceeds 80 Pa · s and the viscosity ratio (2 rpm / 10 rpm) exceeds 6.0, it is difficult to perform the roller coating operation in a 5 ° C. environment.
従って、本発明は、液伸びの良さと液垂れ難さとを両立する粘稠性樹脂組成物となる。 Accordingly, the present invention provides a viscous resin composition that achieves both good liquid elongation and difficulty in dripping.
以下、従来例（比較例）を示して本実施例の特性を説明するが、本発明はこれらの例に限定されるものではない。尚、従来例と本実施例の各性能は以下の項目について記載した方法により比較を行った。 Hereinafter, the characteristics of this example will be described with reference to conventional examples (comparative examples), but the present invention is not limited to these examples. In addition, each performance of a prior art example and a present Example compared by the method described about the following items.
（１）塗布作業性評価
塗布作業性の評価項目は、２０℃環境下分速２０回転時の粘度と、５℃環境下ローラー塗布作業性の２項目とした。
(1) Evaluation of coating workability The evaluation items for coating workability were two items: viscosity at 20 rotations per minute under 20 ° C environment and roller coating workability under 5 ° C environment.
粘度は、トキメック社製の粘度計であるブルックフィールド形回転粘度計のＢ形を用いて測定した。作業性に関わるコテ塗り時の重さが回転粘度計のトルクと相関することを考慮し、最大回転数である２０回転時の粘度で評価した。 The viscosity was measured using a Brookfield type rotational viscometer B type, which is a viscometer manufactured by Tokimec. Considering that the weight at the time of ironing relating to workability correlates with the torque of the rotational viscometer, the viscosity at the time of 20 rotations, which is the maximum rotation speed, was evaluated.
ローラー塗布作業性評価は、粘性が増大する低温の５℃環境下、マスチックローラーを用いて、１ｍ２の垂直面に対しローラーを回転させて１ｍｍの厚さで塗布を行った時のローラー回転性、ローラーにかかる重さ、液垂れより、評価を行い、良好であった場合に○、不具合が生じた場合に×と判定した。 Roller application workability evaluation is performed by rotating a roller with respect to a vertical surface of 1 m 2 using a mastic roller in a low temperature 5 ° C. environment where the viscosity increases, and applying the roller with a thickness of 1 mm. Evaluation was made based on the weight applied to the roller and dripping, and it was judged as “good” when it was good, and “poor” when trouble occurred.
（２）液垂れ難さ評価
液垂れ難さの評価項目は、スランプ試験、３５ｍｍ三角目地充填性評価及び粘度比（２ｒｐｍ／１０ｒｐｍ）の３項目とした。
(2) Evaluation of difficulty of dripping The evaluation items of difficulty of dripping were three items: slump test, 35 mm triangular joint filling evaluation and viscosity ratio (2 rpm / 10 rpm).
スランプ試験は、ＪＩＳ Ａ １４３９建築用シーリング材の試験方法に準拠し、２０℃環境下、幅２０ｍｍ長さ１５０ｍｍ高さ１０ｍｍの溝へ樹脂組成物を充填後、垂直に立て、溝下端より垂れ下がった先端までの距離を測定した。 The slump test conforms to the test method of JIS A 1439 sealing material for building, and in a 20 ° C environment, after filling a resin composition into a groove having a width of 20 mm, a length of 150 mm and a height of 10 mm, it stands vertically and hangs down from the lower end of the groove. The distance to the tip was measured.
３５ｍｍ三角目地充填性評価は、２０℃環境下、厚さ５ｍｍの４０ｍｍ等辺山形鋼を上向きに設置し、内のり部３５ｍｍ角への樹脂組成物の三角目地充填性を評価した。硬化時まで垂れずに完全に充填されていた場合に○、充填不可能であった場合若しくは硬化前に垂れが生じた場合に×と判定した。 In the evaluation of 35 mm triangular joint filling property, in a 20 ° C. environment, a 40 mm equilateral angle steel with a thickness of 5 mm was installed upward, and the triangular joint filling property of the resin composition to the inner 35 mm square was evaluated. It was judged as ◯ when it was completely filled without dripping until the time of curing, and when it was impossible to fill or when dripping occurred before curing.
粘度比（２ｒｐｍ／１０ｒｐｍ）は、樹脂組成物の垂れが粘度計の低回転トルクと中回転トルクの応答性即ち分速２回転と分速２０回転の間より狭い範囲である分速２回転と分速１０回転の間におけるチキソトロピーに相関することを考慮し、ブルックフィールド形回転粘度計のＢ形を用いて測定した分速２回転時の粘度を分速１０回転時の粘度で除した値とした。 The viscosity ratio (2 rpm / 10 rpm) is such that the sag of the resin composition is a responsiveness of low and medium rotational torques of the viscometer, that is, a range of 2 rotations per minute that is narrower than a range between 2 rotations per minute and 20 rotations per minute. Considering the correlation with thixotropy during 10 revolutions per minute, the value obtained by dividing the viscosity at 2 revolutions per minute measured using the Brookfield type rotational viscometer B type by the viscosity at 10 revolutions per minute did.
（３）粘度の第３アミン添加依存性評価
粘度の第３アミン添加依存性の評価は、分速１０回転時の粘度の３級アミン添加前数値と添加後数値の変化率とした。
(3) Evaluation of dependency of viscosity on addition of tertiary amine Evaluation of dependency of viscosity on addition of tertiary amine was based on the rate of change between the value before addition of tertiary amine and the value after addition of viscosity at 10 revolutions per minute.
（４）粘度の攪拌時間依存性評価
粘度の攪拌時間依存性の評価は、分速１０回転時の粘度の攪拌時間１０分経過時測定値と２０分経過時測定値の変化率とした。
(4) Viscosity stirring time dependency evaluation Viscosity stirring time dependency evaluation was based on the rate of change between the measured value of the viscosity when the stirring time was 10 minutes and the measured value when the viscosity was 20 minutes, at 10 revolutions per minute.
（実施例１）
実施例１は、２Ｌポリプロピレン製容器に、ビニルエステル樹脂（商品名：ネオポール８２６０、日本ユピカ製）１０００ｇ及び脂肪酸表面処理炭酸カルシウム４００ｇを配合し、高トルク型攪拌機を用いて１０分間攪拌混合し、完全分散した粘稠性樹脂組成物を得た。当該樹脂組成物１００重量部に促進剤であるＮ，Ｎ−ジメチルアニリンを０．１１重量部及び硬化剤である４０重量％ベンゾイルパーオキサイドを１．１重量部添加し、攪拌混合後、各評価試験を実施した（表１）。
Example 1
Example 1 blends 1000 g of vinyl ester resin (trade name: Neopol 8260, made by Nippon Iupika) and 400 g of fatty acid surface-treated calcium carbonate in a 2 L polypropylene container, and stirs and mixes for 10 minutes using a high torque stirrer. A completely dispersed viscous resin composition was obtained. To 100 parts by weight of the resin composition, 0.11 part by weight of N, N-dimethylaniline as an accelerator and 1.1 parts by weight of 40% by weight benzoyl peroxide as a curing agent were added, stirred and mixed, and then evaluated. The test was conducted (Table 1).
（実施例２〜５）
実施例２は、ビニルエステル樹脂１０００ｇ，脂肪酸表面処理炭酸カルシウム５００ｇ，Ｎ，Ｎ−ジメチルアニリン０．１０重量部及び４０重量％ベンゾイルパーオキサイドを１．０重量部添加した。
(Examples 2 to 5)
In Example 2, 1000 g of vinyl ester resin, 500 g of fatty acid surface-treated calcium carbonate, 0.10 parts by weight of N, N-dimethylaniline and 1.0 part by weight of 40% by weight benzoyl peroxide were added.
また、実施例３は、ビニルエステル樹脂１０００ｇ，脂肪酸表面処理炭酸カルシウム７００ｇ，Ｎ，Ｎ−ジメチルアニリン０．０９重量部及び４０重量％ベンゾイルパーオキサイドを０．９重量部添加した。 In Example 3, 1000 g of vinyl ester resin, 700 g of fatty acid surface-treated calcium carbonate, 0.09 part by weight of N, N-dimethylaniline and 0.9 part by weight of 40% by weight benzoyl peroxide were added.
また、実施例４は、ビニルエステル樹脂１０００ｇ，脂肪酸表面処理炭酸カルシウムと重質炭酸カルシウムとを夫々５００ｇつづ，Ｎ，Ｎ−ジメチルアニリン０．０７重量部及び４０重量％ベンゾイルパーオキサイドを０．７重量部添加した。 In Example 4, 1000 g of vinyl ester resin, 500 g each of fatty acid surface-treated calcium carbonate and heavy calcium carbonate, 0.07 part by weight of N, N-dimethylaniline and 0.7% of 40% by weight of benzoyl peroxide were used. Part by weight was added.
また、実施例５は、ビニルエステル樹脂１０００ｇ，脂肪酸表面処理炭酸カルシウム８００ｇ，Ｎ，Ｎ−ジメチルアニリン０．０８重量部及び４０重量％ベンゾイルパーオキサイドを０．８重量部添加した。 In Example 5, 1000 g of vinyl ester resin, 800 g of fatty acid surface-treated calcium carbonate, 0.08 part by weight of N, N-dimethylaniline and 0.8 part by weight of 40% by weight benzoyl peroxide were added.
上記実施例２〜５についても、実施例１と同様の操作及び各評価試験を実施した（表１）。 For Examples 2 to 5, the same operations as in Example 1 and the evaluation tests were performed (Table 1).
尚、上記実施例１〜５のビニルエステル樹脂とは、ビスフェノールＡ型エポキシ樹脂とメタクリル酸を反応させて得たエポキシアクリレートをスチレン単量体に溶解し、エポキシアクリレートが５５重量％、スチレンが４５重量％であるビニルエステル樹脂（商品名：ネオポール８２６０、日本ユピカ製）である。 The vinyl ester resins of Examples 1 to 5 described above are obtained by dissolving epoxy acrylate obtained by reacting bisphenol A type epoxy resin and methacrylic acid in a styrene monomer, epoxy acrylate being 55% by weight, and styrene being 45%. It is a vinyl ester resin (trade name: Neopol 8260, manufactured by Nippon Iupika) that is wt%.
また、上記実施例１〜５における、粘稠性樹脂組成物１００部に対する４０重量％ベンゾイルパーオキサイド及びＮ，Ｎ−ジメチルアニリンの配合部数は、２０℃環境下における１６０ｇスケールの硬化時間が各組成物６０分となるよう調整し決定されたものである。 In addition, in Examples 1 to 5 above, the number of blending parts of 40 wt% benzoyl peroxide and N, N-dimethylaniline with respect to 100 parts of the viscous resin composition is as follows. It has been determined by adjusting to 60 minutes.
上記各評価試験の結果を示した表１から、実施例１における、２０℃環境下、塗布作業性を示す分速２０回転時の粘度は３３Ｐａ・ｓであった。また、垂れ難さを示す粘度比（２ｒｐｍ／１０ｒｐｍ）は３．８であった。 From Table 1 showing the results of the above-described evaluation tests, the viscosity at 20 revolutions per minute showing the coating workability in a 20 ° C. environment in Example 1 was 33 Pa · s. Moreover, the viscosity ratio (2 rpm / 10 rpm) showing difficulty in dripping was 3.8.
尚、５℃環境下におけるローラー塗布作業性は、適度な負荷でローラーの回転が認められたことより良好であった。更に、スランプは４５ｍｍで、３５ｍｍ三角目地に対しては硬化時まで垂れずに充填された。加えて、第３アミン添加による分速１０回転時粘度の変化率は３．０％であった。 In addition, the roller coating workability in a 5 ° C. environment was better than the fact that the rotation of the roller was recognized with an appropriate load. Furthermore, the slump was 45 mm, and the 35 mm triangular joint was filled without dripping until curing. In addition, the rate of change in viscosity at 10 revolutions per minute due to the addition of the tertiary amine was 3.0%.
また、実施例２〜５における、２０℃環境下、塗布作業性を示す分速２０回転時の粘度は、実施例２で５４Ｐａ・ｓ、実施例３で７７Ｐａ・ｓ、実施例４で６８Ｐａ・ｓ、実施例５で８０Ｐａ・ｓであった。 In addition, in Examples 2 to 5, the viscosity at the time of 20 revolutions per minute indicating the coating workability in a 20 ° C. environment is 54 Pa · s in Example 2, 77 Pa · s in Example 3, and 68 Pa · s in Example 4. s, 80 Pa · s in Example 5.
また、垂れ難さを示す粘度比（２ｒｐｍ／１０ｒｐｍ）は、実施例２で４．５、実施例３で４．０、実施例４で４．３、実施例５で６．０であった。 Moreover, the viscosity ratio (2 rpm / 10 rpm) indicating the difficulty of dripping was 4.5 in Example 2, 4.0 in Example 3, 4.3 in Example 4, and 6.0 in Example 5. .
尚、５℃環境下におけるローラー塗布作業性は、実施例２、３、４、５共に適度な負荷でローラーの回転が認められたことより良好であった。更に、スランプは実施例２で１６ｍｍ、実施例３で０ｍｍ、実施例４で２ｍｍ、実施例５で０ｍｍとなり、３５ｍｍ三角目地に対しては実施例２、３、４、５共に硬化時まで垂れずに充填された。加えて、第３アミン添加による分速１０回転時粘度の変化率は、実施例２で−１．９％、実施例３で３．９％、実施例４で０％、実施例５で０％であった。更に、実施例２において、攪拌時間１０分間延長による分速１０回転時の粘度の変化率は２．１％であった。 The roller coating workability in a 5 ° C. environment was better than that in Examples 2, 3, 4, and 5 in which the rotation of the roller was recognized with an appropriate load. Further, the slump is 16 mm in Example 2, 0 mm in Example 3, 2 mm in Example 4, and 0 mm in Example 5. Both the Examples 2, 3, 4 and 5 hang down to the 35 mm triangular joint until curing. Without filling. In addition, the rate of change in viscosity at 10 revolutions per minute due to the addition of the tertiary amine was -1.9% in Example 2, 3.9% in Example 3, 0% in Example 4, and 0 in Example 5. %Met. Furthermore, in Example 2, the rate of change in viscosity at 10 revolutions per minute by extending the stirring time by 10 minutes was 2.1%.
（比較例１，２）
比較例１，２として、２Ｌポリプロピレン製容器に、ビニルエステル樹脂（商品名：ネオポール８２６０、日本ユピカ製）１０００ｇに対し、親水性乾式シリカ（商品名：レオロシールＱＳ２０Ｌ、トクヤマ製）５０ｇ（比較例１）または疎水性乾式シリカ（商品名：レオロシールＰＭ２０Ｌ、トクヤマ製）５０ｇ（比較例２）を配合し、高トルク型攪拌機を用いて１０分間攪拌混合し、完全分散した粘稠性樹脂組成物を得た。当該樹脂組成物１００重量部に促進剤であるＮ，Ｎ−ジメチルアニリンを０．１４重量部及び硬化剤である４０重量％ベンゾイルパーオキサイドを１．４重量部添加し、攪拌混合後、実施例１〜４と同様の操作及び各評価試験を実施した（表２）。
(Comparative Examples 1 and 2)
As Comparative Examples 1 and 2, in a 2 L polypropylene container, 50 g of hydrophilic dry silica (trade name: Leoroseal QS20L, manufactured by Tokuyama) with respect to 1000 g of vinyl ester resin (trade name: Neopole 8260, manufactured by Nippon Iupika) ) Or hydrophobic dry silica (trade name: Leolosil PM20L, manufactured by Tokuyama) 50 g (Comparative Example 2) was mixed and stirred for 10 minutes using a high torque stirrer to obtain a completely dispersed viscous resin composition. It was. After adding 0.14 parts by weight of N, N-dimethylaniline as an accelerator and 1.4 parts by weight of 40% by weight of benzoyl peroxide as a curing agent to 100 parts by weight of the resin composition, stirring and mixing, Example The same operation as 1-4 and each evaluation test were implemented (Table 2).
（比較例３〜６）
比較例３〜６として、２Ｌポリプロピレン製容器に、ビニルエステル樹脂（商品名：ネオポール８２６０、日本ユピカ製）１０００ｇに対し、クリスタライト系鉱物（商品名：アタゲル♯４０、東新化成製）を３００ｇ（比較例３），３５０ｇ（比較例４），４００ｇ（比較例５）及び４５０ｇ（比較例６）となるように夫々配合し、高トルク型攪拌機を用いて10分間攪拌混合し、完全分散した粘稠性樹脂組成物を得た。当該樹脂組成物１００重量部に促進剤であるＮ，Ｎ−ジメチルアニリンを０．１１重量部(比較例３〜５）若しくは０．１０重量部（比較例６）、硬化剤である４０重量％ベンゾイルパーオキサイドを１．１重量部(比較例３〜５）若しくは１．０重量部（比較例６）添加し、攪拌混合後、実施例１〜５及び比較例１，２と同様の各評価試験を実施した（表２）。
(Comparative Examples 3-6)
As Comparative Examples 3 to 6, 300 g of crystallite mineral (trade name: Atagel # 40, manufactured by Toshin Kasei Co., Ltd.) with respect to 1000 g of vinyl ester resin (trade name: Neopole 8260, manufactured by Nippon Iupika) in a 2 L polypropylene container (Comparative Example 3), 350 g (Comparative Example 4), 400 g (Comparative Example 5) and 450 g (Comparative Example 6) were blended, respectively, and stirred and mixed for 10 minutes using a high torque stirrer, and completely dispersed. A viscous resin composition was obtained. 0.11 part by weight (Comparative Examples 3 to 5) or 0.10 part by weight (Comparative Example 6) of N, N-dimethylaniline as an accelerator in 100 parts by weight of the resin composition, 40% by weight as a curing agent 1.1 parts by weight (Comparative Examples 3 to 5) or 1.0 part by weight (Comparative Example 6) of benzoyl peroxide was added, and after stirring and mixing, the same evaluations as in Examples 1 to 5 and Comparative Examples 1 and 2 were made. The test was conducted (Table 2).
尚、上記比較例１〜６のビニルエステル樹脂とは、ビスフェノールＡ型エポキシ樹脂とメタクリル酸を反応させて得たエポキシアクリレートをスチレン単量体に溶解し、エポキシアクリレートが５５重量％、スチレンが４５重量％であるビニルエステル樹脂（商品名：ネオポール８２６０、日本ユピカ製）である。 The vinyl ester resins of Comparative Examples 1 to 6 are obtained by dissolving an epoxy acrylate obtained by reacting a bisphenol A type epoxy resin and methacrylic acid in a styrene monomer. The epoxy acrylate is 55% by weight and the styrene is 45%. It is a vinyl ester resin (trade name: Neopol 8260, manufactured by Nippon Iupika) that is wt%.
また、上記実施例１〜６における、粘稠性樹脂組成物１００部に対する４０重量％ベンゾイルパーオキサイド及びＮ，Ｎ−ジメチルアニリンの配合部数は、２０℃環境下における１６０ｇスケールの硬化時間が各組成物６０分となるよう調整し決定されたものである。 In addition, in Examples 1 to 6, the number of blending parts of 40% by weight of benzoyl peroxide and N, N-dimethylaniline with respect to 100 parts of the viscous resin composition is as follows. It has been determined by adjusting to 60 minutes.
上記表２の各評価試験の結果から、比較例１，２における、２０℃環境下、塗布作業性を示す分速２０回転時の粘度は、比較例１で３Ｐａ・ｓ比較例２で３５Ｐａ・ｓであった。 From the results of the evaluation tests shown in Table 2 above, the viscosity at 20 revolutions per minute indicating the coating workability in the Comparative Examples 1 and 2 in the environment of 20 ° C. s.
また、垂れ難さを示す粘度比（２ｒｐｍ／１０ｒｐｍ）は、比較例１で１．５、比較例２で３．５であった。 Moreover, the viscosity ratio (2 rpm / 10 rpm) indicating the difficulty of dripping was 1.5 in Comparative Example 1 and 3.5 in Comparative Example 2.
尚、５℃環境下におけるローラー塗布作業性は、比較例１においては液垂れを生じたことより悪く、一方比較例２においては適度な負荷でローラーの回転が認められたことより良好であった。更に、スランプは比較例１，２共に５０ｍｍ以上となり、３５ｍｍ三角目地に対しては比較例１，２共に充填不可能であった。加えて、第３アミン添加による分速１０回転時粘度の変化率は、比較例２で−１３．３％であった。更に、比較例２において、攪拌時間１０分間延長による分速１０回転時の粘度の変化率は１３．３％であった。 In addition, the roller coating workability in an environment of 5 ° C. was worse than that causing dripping in Comparative Example 1, whereas it was better in Comparative Example 2 that the rotation of the roller was recognized with an appropriate load. . Further, the slump was 50 mm or more in both Comparative Examples 1 and 2, and both Comparative Examples 1 and 2 could not be filled into a 35 mm triangular joint. In addition, the rate of change in viscosity at the time of 10 rotations per minute due to the addition of the tertiary amine was -13.3% in Comparative Example 2. Furthermore, in Comparative Example 2, the rate of change in viscosity at the time of 10 revolutions per minute by extending the stirring time by 10 minutes was 13.3%.
また、比較例３〜６における、２０℃環境下、塗布作業性を示す分速２０回転時の粘度は、比較例３で４Ｐａ・ｓ、比較例４で２４Ｐａ・ｓ、比較例５で６０Ｐａ・ｓ、比較例６では抵抗が大きいためメーターが振り切れ測定不能であった。 Further, in Comparative Examples 3 to 6, the viscosity at 20 rotations per minute showing the coating workability in a 20 ° C. environment is 4 Pa · s in Comparative Example 3, 24 Pa · s in Comparative Example 4, and 60 Pa · in Comparative Example 5. s In Comparative Example 6, since the resistance was large, the meter could not be measured by shaking.
また、垂れ難さを示す粘度比（２ｒｐｍ／１０ｒｐｍ）は、比較例３で２．３、比較例４で６．４、比較例５で７．８であった。 Moreover, the viscosity ratio (2 rpm / 10 rpm) indicating difficulty of dripping was 2.3 in Comparative Example 3, 6.4 in Comparative Example 4, and 7.8 in Comparative Example 5.
尚、５℃環境下におけるローラー塗布作業性は、比較例３においては液垂れを生じたことより悪く、一方比較例４，５においては適度な負荷でローラーの回転が認められたことより良好であり、比較例６においては粘性が強くローラーの回転が不可能であった。更に、スランプは比較例３，４，５共に５０ｍｍ以上となり、比較例６では０ｍｍであった。３５ｍｍ三角目地に対しては比較例３，４，５共に充填不可能であったが、比較例６においては硬化時まで垂れずに充填された。加えて、第3アミン添加による分速１０回転時粘度の変化率は、比較例４で−１２．５％、比較例５で１２．５％であった。更に、比較例４において、攪拌時間１０分間延長による分速１０回転時の粘度の変化率は−８０．０％、比較例５で−３０．０％であった。 In addition, the roller coating workability in a 5 ° C. environment is worse than that in which Comparative Example 3 caused liquid dripping, whereas in Comparative Examples 4 and 5, it was better that the rotation of the roller was recognized with an appropriate load. In Comparative Example 6, the viscosity was strong and the roller could not be rotated. Further, the slump was 50 mm or more in Comparative Examples 3, 4 and 5, and 0 mm in Comparative Example 6. In Comparative Examples 3, 4 and 5, it was impossible to fill the 35 mm triangular joint, but in Comparative Example 6, it was filled without dripping until curing. In addition, the rate of change in viscosity at 10 revolutions per minute due to the addition of the tertiary amine was -12.5% in Comparative Example 4 and 12.5% in Comparative Example 5. Furthermore, in Comparative Example 4, the rate of change in viscosity at 10 revolutions per minute by extending the stirring time for 10 minutes was -80.0%, and in Comparative Example 5 was -30.0%.
以上、上記表１及び表２の各評価試験の結果より、塗布作業性を示すローラー塗布作業性評価及び液垂れ難さを示す３５ｍｍ三角目地充填性評価において、双方とも判定が○である例は実施例１〜５の場合のみである。即ち、揺変性付与剤として、脂肪酸表面処理炭酸カルシウム若しくは脂肪酸表面処理炭酸カルシウムと重質炭酸カルシウムを用いた実施例１〜５は、親水性若しくは疎水性の乾式シリカやクリスタライト系鉱物を用いた比較例１〜６と比較して、液伸びの良さと液垂れ難さの点で優れるとともに、液伸びの良さと液垂れ難さとが両立する結果となった。 As described above, from the results of the evaluation tests in Tables 1 and 2 above, in the roller coating workability evaluation indicating the coating workability and the 35 mm triangular joint filling property evaluation indicating the difficulty of dripping, an example in which both are judged as ◯ This is only the case with Examples 1-5. That is, Examples 1 to 5 using fatty acid surface-treated calcium carbonate or fatty acid surface-treated calcium carbonate and heavy calcium carbonate as thixotropic agents used hydrophilic or hydrophobic dry silica or crystallite minerals. As compared with Comparative Examples 1 to 6, the liquid elongation was excellent and the liquid was difficult to drip, and the liquid elongation was good and the liquid was difficult to drip.
尚、ブルックフィールド形回転粘度計のＢ形による測定では、この実施例１〜５の粘稠性樹脂組成物は、分速２０回転時の粘度が２０Ｐａ・ｓ〜８０Ｐａ・ｓの範囲内であり且つ粘度比（２ｒｐｍ／１０ｒｐｍ）が３．８〜６．０の範囲内にあることが判明した。 In addition, in the measurement by B type of Brookfield type rotational viscometer, the viscous resin compositions of Examples 1 to 5 have a viscosity in the range of 20 Pa · s to 80 Pa · s at 20 revolutions per minute. The viscosity ratio (2 rpm / 10 rpm) was found to be in the range of 3.8 to 6.0.
よって、揺変性付与剤として脂肪酸表面処理炭酸カルシウム若しくは脂肪酸表面処理炭酸カルシウムと重質炭酸カルシウムを用いた粘稠性樹脂組成物において、ブルックフィールド形回転粘度計のＢ形による分速２０回転時の粘度が２０Ｐａ・ｓ〜８０Ｐａ・ｓの範囲内であり且つ粘度比（２ｒｐｍ／１０ｒｐｍ）が３．８〜６．０の範囲内にある場合に、液伸びの良さと液垂れ難さが両立した粘稠性樹脂組成物となるといえる。これに対し、比較例１〜６では上記性能を全て満たす樹脂組成物は得られない結果となった。 Therefore, in a viscous resin composition using fatty acid surface-treated calcium carbonate or fatty acid surface-treated calcium carbonate and heavy calcium carbonate as a thixotropic agent, the Brookfield-type rotational viscometer at the time of 20 revolutions per minute with the B shape When the viscosity is in the range of 20 Pa · s to 80 Pa · s and the viscosity ratio (2 rpm / 10 rpm) is in the range of 3.8 to 6.0, both good elongation and difficulty in dripping are compatible. It can be said that it becomes a viscous resin composition. On the other hand, in Comparative Examples 1-6, the result which cannot obtain the resin composition which satisfy | fills all the said performance was brought.
また、第３アミン添加による１０回転時の粘度の変化率は、実施例１〜５で絶対値４％未満の結果に対し、比較例１〜６では絶対値１０％以上の結果であったことから、実施例１〜５の樹脂組成物は第３アミン添加による粘度変化の影響を受け難いことが明らかとなった。 Moreover, the change rate of the viscosity at the time of 10 rotation by addition of a tertiary amine was a result of absolute value 10% or more in Comparative Examples 1-6, compared with the result of less than 4% absolute value in Examples 1-5. From these results, it was revealed that the resin compositions of Examples 1 to 5 were hardly affected by the viscosity change due to the addition of the tertiary amine.
更に、攪拌時間延長による１０回転時の粘度の変化率は、実施例２で２．１％の結果に対し、比較例２では１３．３％、比較例４では−８０．０％、比較例５では−３０．０％の結果であったことから、実施例２の樹脂組成物は攪拌時間延長による粘度変化の影響を受け難いことが明らかとなった。 Further, the rate of change in viscosity at 10 revolutions due to the extension of the stirring time was 13.3% in Comparative Example 2, -80.0% in Comparative Example 4 compared to 2.1% in Example 2, and Comparative Example 5, the result was −30.0%, and thus it was revealed that the resin composition of Example 2 was not easily affected by the viscosity change due to the extension of the stirring time.
以上、本実施例は、従来用いられていた熱硬化性樹脂組成物の揺変性付与剤であるコロイダルシリカ，繊維状鉱物及び微粉末鉱物の代わりに脂肪酸表面処理炭酸カルシウム若しくは脂肪酸表面処理炭酸カルシウムと重質炭酸カルシウムを用いることにより、液伸びの良さと液垂れ難さとを両立することができる。 As described above, in this example, fatty acid surface-treated calcium carbonate or fatty acid surface-treated calcium carbonate is used instead of colloidal silica, a fibrous mineral, and a fine powder mineral that are conventionally used thixotropic agents for thermosetting resin compositions. By using heavy calcium carbonate, both good liquid elongation and difficulty in dripping can be achieved.
また、高価なコロイダルシリカに代わり安価な脂肪酸表面処理炭酸カルシウムを用いることにより、製品コストを抑制できるとともに、常温硬化系で用いる硬化促進剤の第３アミン及びナフテン酸コバルトを添加しても、組成物の粘稠性が低下することがない。 Further, by using inexpensive fatty acid surface-treated calcium carbonate instead of expensive colloidal silica, the product cost can be suppressed, and even if a tertiary amine and cobalt naphthenate, which are curing accelerators used in a room temperature curing system, are added, the composition The viscosity of the object is not lowered.
また、本実施例の粘稠性樹脂組成物に用いる脂肪酸表面処理炭酸カルシウムは、粘稠性樹脂組成物製造時に粘性の撹拌時間依存性がないことから、一定粘性の品質を確保することができる。 In addition, the fatty acid surface-treated calcium carbonate used in the viscous resin composition of the present example does not depend on the viscosity stirring time during the production of the viscous resin composition, so that a certain viscosity quality can be ensured. .
また、本実施例の粘稠性樹脂組成物は、塗布作業性と液垂れ難さの相反する性能を両立させることにより、コンクリートの不陸修正材及び多軸組布等の繊維シートを貼り付けるコンクリート剥落防止用接着剤として、優れた施工性を発揮することが出来る。
In addition, the viscous resin composition of the present example attaches a fiber sheet such as a concrete unevenness correcting material and a multiaxial assembly fabric by reconciling the performance of coating workability and the difficulty of dripping. As a concrete peeling prevention adhesive, it can exhibit excellent workability.
Claims (5)
The viscous resin composition of any one of Claims 1-3 WHEREIN: This viscous resin composition is used as an adhesive agent for concrete peeling prevention which affixes fiber sheets, such as a multiaxial assembly cloth. There is a viscous resin composition.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011084380A1 (en) * | 2009-12-17 | 2011-07-14 | 3M Innovative Properties Company | Nanocalcite and vinyl ester composites |
| US20120214948A1 (en) * | 2009-10-21 | 2012-08-23 | Condo Peter D | Solventless functionalization, milling, and compounding process with reactive diluents |
| JP2013032675A (en) * | 2011-07-01 | 2013-02-14 | Takenaka Komuten Co Ltd | Exterior method |
| US8448885B2 (en) | 2008-06-12 | 2013-05-28 | 3M Innovative Properties Company | Methods of compounding nanoparticles with a resin |
| US9221970B2 (en) | 2008-12-19 | 2015-12-29 | 3M Innovative Properties Company | Nanocalcite composites |
| US10035909B2 (en) | 2009-12-17 | 2018-07-31 | 3M Innovative Properties Company | High magnesium surface concentration nanocalcite composites |
| ES2942461A1 (en) * | 2021-12-01 | 2023-06-01 | Clades Composites S L | COMPOSITE CONSTRUCTION MATERIAL COMPRISING A THERMOSTABLE RESIN AND SURFACE-TREATED FILLERS (Machine-translation by Google Translate, not legally binding) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0260958A (en) * | 1988-08-29 | 1990-03-01 | Asahi Fiber Glass Co Ltd | Filler for thickened resin composition and production of molding material |
| JPH08199061A (en) * | 1995-01-26 | 1996-08-06 | Dainippon Ink & Chem Inc | One-component thixotropic polyurethane composition and coating material, sealant, and adhesive |
| JPH11268912A (en) * | 1998-03-24 | 1999-10-05 | Maruo Calcium Co Ltd | Inorganic dispersing agent, stabilizer for suspension polymerization, polymeric particle, unsaturated polyester resin composition, and toner composition |
| JP2000086316A (en) * | 1998-09-17 | 2000-03-28 | Mitsubishi Rayon Co Ltd | Unevenness-adjusting material |
| JP2001089505A (en) * | 1999-09-21 | 2001-04-03 | Maruo Calcium Co Ltd | Inorganic dispersant, stabilizer for suspension polymerization, polymer particle and unsaturated polyester resin composition |
| JP2001288371A (en) * | 2000-04-07 | 2001-10-16 | Ishizuka Glass Co Ltd | Antimicrobial resin material containing inorganic filler and method for producing the same |
| JP2003307034A (en) * | 2002-04-18 | 2003-10-31 | Konishi Co Ltd | Separation preventive method for concrete piece |
| JP2004181934A (en) * | 2002-10-10 | 2004-07-02 | Showa Highpolymer Co Ltd | Method for frp lining |
-
2004
- 2004-12-28 JP JP2004381689A patent/JP2006188552A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0260958A (en) * | 1988-08-29 | 1990-03-01 | Asahi Fiber Glass Co Ltd | Filler for thickened resin composition and production of molding material |
| JPH08199061A (en) * | 1995-01-26 | 1996-08-06 | Dainippon Ink & Chem Inc | One-component thixotropic polyurethane composition and coating material, sealant, and adhesive |
| JPH11268912A (en) * | 1998-03-24 | 1999-10-05 | Maruo Calcium Co Ltd | Inorganic dispersing agent, stabilizer for suspension polymerization, polymeric particle, unsaturated polyester resin composition, and toner composition |
| JP2000086316A (en) * | 1998-09-17 | 2000-03-28 | Mitsubishi Rayon Co Ltd | Unevenness-adjusting material |
| JP2001089505A (en) * | 1999-09-21 | 2001-04-03 | Maruo Calcium Co Ltd | Inorganic dispersant, stabilizer for suspension polymerization, polymer particle and unsaturated polyester resin composition |
| JP2001288371A (en) * | 2000-04-07 | 2001-10-16 | Ishizuka Glass Co Ltd | Antimicrobial resin material containing inorganic filler and method for producing the same |
| JP2003307034A (en) * | 2002-04-18 | 2003-10-31 | Konishi Co Ltd | Separation preventive method for concrete piece |
| JP2004181934A (en) * | 2002-10-10 | 2004-07-02 | Showa Highpolymer Co Ltd | Method for frp lining |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8448885B2 (en) | 2008-06-12 | 2013-05-28 | 3M Innovative Properties Company | Methods of compounding nanoparticles with a resin |
| US9221970B2 (en) | 2008-12-19 | 2015-12-29 | 3M Innovative Properties Company | Nanocalcite composites |
| US9783681B2 (en) | 2009-10-21 | 2017-10-10 | 3M Innovative Properties Company | Solventless functionalization, milling, and compounding process with reactive diluents |
| US20120214948A1 (en) * | 2009-10-21 | 2012-08-23 | Condo Peter D | Solventless functionalization, milling, and compounding process with reactive diluents |
| US20120244338A1 (en) * | 2009-12-17 | 2012-09-27 | Schultz William J | Nanocalcite and vinyl ester composites |
| JP2013514437A (en) * | 2009-12-17 | 2013-04-25 | スリーエム イノベイティブ プロパティズ カンパニー | Nanocalcite and vinyl ester composites |
| WO2011084380A1 (en) * | 2009-12-17 | 2011-07-14 | 3M Innovative Properties Company | Nanocalcite and vinyl ester composites |
| CN102639623A (en) * | 2009-12-17 | 2012-08-15 | 3M创新有限公司 | Nanocalcite and vinyl ester composites |
| US10023726B2 (en) | 2009-12-17 | 2018-07-17 | 3M Innovative Properties Company | Nanocalcite and vinyl ester composites |
| US10035909B2 (en) | 2009-12-17 | 2018-07-31 | 3M Innovative Properties Company | High magnesium surface concentration nanocalcite composites |
| JP2013032675A (en) * | 2011-07-01 | 2013-02-14 | Takenaka Komuten Co Ltd | Exterior method |
| ES2942461A1 (en) * | 2021-12-01 | 2023-06-01 | Clades Composites S L | COMPOSITE CONSTRUCTION MATERIAL COMPRISING A THERMOSTABLE RESIN AND SURFACE-TREATED FILLERS (Machine-translation by Google Translate, not legally binding) |
| WO2023099800A1 (en) * | 2021-12-01 | 2023-06-08 | Clades Composites, S.L. | Composite construction material comprising a thermosetting resin and surface-treated loads |
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