JP6937206B2 - Hydraulic polymer cement composition - Google Patents
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Description
本発明は、熱水による洗浄を高頻度で行う食品工場床の下地コンクリート上に直接塗付可能であると共に、該食品工場床の下地コンクリート上に既に厚さ２〜９ｍｍ程度に形成された、ポリオール、ポリイソシアネート、セメント、骨材及び水、及び必要により希釈剤を含有してなる水硬性ポリマーセメント組成物の硬化塗膜上にさらに塗付することが出来る水硬性ポリマーセメント組成物に関し、特にはローラ刷毛で施工可能で熱水と冷水の繰り返し流下による熱衝撃性に優れる水硬性ポリマーセメント組成物に関する。 INDUSTRIAL APPLICABILITY The present invention can be directly applied onto the base concrete of a food factory floor that is frequently washed with hot water, and is already formed on the base concrete of the food factory floor to a thickness of about 2 to 9 mm. Especially with respect to the water-hard polymer cement composition which can be further applied on the cured coating of the water-hard polymer cement composition containing polyol, polyisocyanate, cement, aggregate and water, and optionally a diluent. The present invention relates to a water-hard polymer cement composition that can be applied with a roller brush and has excellent thermal impact resistance due to repeated flow of hot water and cold water.
従来、耐熱水性、耐摩耗性、耐衝撃性に優れる樹脂セメント組成物として、分子量が１０００〜３０００で両末端に水酸基を持ち、側鎖を持つポリエステルポリオールとポリフェニルポリメチルポリイソシアネート並びに水硬性セメントを含む骨材とが配合されていることを特徴とする樹脂セメント組成物が提案されている（特許文献１）。 Conventionally, as a resin cement composition having excellent heat resistance, water resistance, abrasion resistance, and impact resistance, a polyester polyol having a molecular weight of 1000 to 3000, having hydroxyl groups at both ends and having side chains, polyphenylpolymethylpolyisocyanate, and water-hardening cement. A resin cement composition characterized by being blended with an aggregate containing the above has been proposed (Patent Document 1).
また、施工現場での混合作業が行いやすく、作業性、性能、仕上がり外観にムラが生じにくく、耐熱性、耐熱水性、耐磨耗性、耐衝撃性などが要求される床などの施工に使用されるポリウレタン系セメント組成物として、少なくとも水分散型ポリオールを含むポリオールと、ポリフェニレンポリメチルポリイソ シアネートである疎水性イソシアネートと、水硬性セメントを含む骨材とから成り、コンクリートである基体上に塗布厚み４ｍｍで硬化させた組成物であって、厚み４ｍｍであって９５℃５分熱水と２０℃１０分冷水の養生を１サイクルとして２０００サイクル後の収縮応力が４．０±２．０Ｎ／ｍｍ２であり、１３００サイクル経過後に反り上がりや表層の亀裂が生じることがないことを特徴とするポリウレタン系セメント組成物が提案されている（特許文献２）。 In addition, it is easy to perform mixing work at the construction site, it is less likely to cause unevenness in workability, performance, and finished appearance, and it is used for construction of floors that require heat resistance, water resistance, abrasion resistance, impact resistance, etc. The polyurethane-based cement composition to be prepared is composed of a polyol containing at least a water-dispersible polyol, a hydrophobic isocyanate which is a polyphenylene polymethylpolyisocyanate, and an aggregate containing a water-hard cement, and is applied onto a concrete substrate. The composition is cured to a thickness of 4 mm, and the shrinkage stress after 2000 cycles is 4.0 ± 2.0 N /, with the curing of hot water at 95 ° C for 5 minutes and cold water at 20 ° C for 10 minutes as one cycle. A polyurethane-based cement composition having a thickness of 2 mm and having no warpage or cracking on the surface layer after 1300 cycles has been proposed (Patent Document 2).
しかしながら、特許文献１に記載の樹脂セメント組成物及び特許文献２のポリウレタン系セメント組成物は、食品工場等の床下地コンクリート上に直接、厚さ２〜９ｍｍ程度に塗付されて硬化し、熱水による洗浄を高頻度で行う塗り床として使用に供されるものであり、施工に当たっては鏝（木鏝や金鏝）により２〜９ｍｍの一定の厚さで塗り拡げる必要があるため、該鏝を取り扱う技能を有する限られた職人しか施工できないという課題がある。 However, the resin cement composition described in Patent Document 1 and the polyurethane cement composition of Patent Document 2 are directly applied directly on the floor base concrete of a food factory or the like to a thickness of about 2 to 9 mm to be cured, and heat is generated. It is used as a coated floor that is frequently washed with water, and it is necessary to spread it with a trowel (wooden trowel or gold trowel) to a certain thickness of 2 to 9 mm during construction. There is a problem that only a limited number of craftsmen who have the skills to handle trowels can perform the work.
また、特許文献１に記載の樹脂セメント組成物及び特許文献２のポリウレタン系セメント組成物が使用により摩耗した場合や汚れ等が生じた場合、又は該床全体を改修する際には、耐熱性、耐熱水性、耐衝撃性等が必要なため、塗膜を一度下地コンクリートに達するまで撤去し、その上で改めて２〜９ｍｍの一定厚みで樹脂セメント組成物又はポリウレタン系セメント組成物を塗付しなければならないという課題がある。 Further, when the resin cement composition described in Patent Document 1 and the polyurethane cement composition of Patent Document 2 are worn or soiled due to use, or when the entire floor is repaired, heat resistance is provided. Since heat resistance, impact resistance, etc. are required, the coating film must be removed once until it reaches the underlying concrete, and then the resin cement composition or polyurethane cement composition must be applied again with a constant thickness of 2 to 9 mm. There is a problem that it must be done.
本発明が解決しようとする課題は、誰もが取り扱うことが出来るローラ刷毛で施工可能で、下地コンクリートに直接又は、既にあるポリオール、ポリイソシアネート、セメント、骨材及び水、及び必要により希釈剤を含有してなる水硬性ポリマーセメント組成物の硬化塗膜上にさらに塗付することが出来、さらには熱水と冷水の繰り返し流下による熱衝撃性に優れ、耐摩耗性、耐衝撃性等を有する水硬性ポリマーセメント組成物を提供することにある。 The problem to be solved by the present invention is that it can be applied with a roller brush that can be handled by anyone, and a polyol, polyisocyanate, cement, aggregate and water, and if necessary, a diluent can be applied directly to the underlying concrete or existing. It can be further applied on the cured coating film of the contained hydraulic polymer cement composition, and further has excellent thermal impact resistance due to repeated flow of hot water and cold water, and has abrasion resistance, impact resistance, and the like. To provide a hydraulic polymer cement composition.
上記課題を解決するために請求項１記載の発明は、ポリオール、ポリイソシアネート、希釈剤、セメント、骨材及び水を含有してなる水硬性ポリマーセメント組成物であって、ポリオールはヒマシ油系ポリオールとビスフェノールＡ骨格を有する４官能ポリオールとから成り、ヒマシ油系ポリオールはヒマシ油系２官能ポリオールとヒマシ油系３官能ポリオールとからなりヒマシ油系２官能ポリオールは組成物全体１００重量部中の１〜３重量部で、水酸基当量が１５０〜３２０であり、ヒマシ油系３官能ポリオールは組成物全体１００重量部中の４〜１０重量部で、水酸基当量が２５０〜４５０であり、ビスフェノールＡ骨格を有する４官能ポリオールは組成物全体１００重量部中の０．５〜３重量部で、水酸基当量が２５０〜４５０であり、ポリイソシアネートはポリメチルポリフェニルポリイソシアネートであり、組成物全体１００重量部中の２０〜４０重量部であり、水酸基１個に対するＮＣＯ基の数が６．０〜７．０であり、骨材は球状有機微粒子と水酸化アルミニウムと硅砂とから成り、球状有機微粒子はアクリル微粒子であり、組成物全体１００重量部中の１０〜１５重量部であり、水酸化アルミニウムは組成物全体１００重量部中の１〜４重量部であり、硅砂は組成物全体１００重量部中の０．５〜２重量部であり、セメントは組成物全体１００重量部中の２５〜３５重量部であり、希釈剤はアルキルスルホン酸エステル化合物を含むことを特徴とする水硬性ポリマーセメント組成物を提供する。
In order to solve the above problems, the invention according to claim 1 is a water-hard polymer cement composition containing a polyol, a polyisocyanate, a diluent, a cement, an aggregate and water, and the polyol is a castor oil-based polyol. 1 and consists of a tetrafunctional polyol having a bisphenol a skeleton, a castor oil-based polyol castor oil-based bifunctional polyol and castor oil-based 3 consists of a functional polyol castor oil-based bifunctional polyol total composition of 100 parts by weight The hydroxyl group equivalent is 150 to 320 in ~ 3 parts by weight , and the castor oil-based trifunctional polyol has 4 to 10 parts by weight in 100 parts by weight of the entire composition, has a hydroxyl group equivalent of 250 to 450, and has a bisphenol A skeleton. The tetrafunctional polyol has 0.5 to 3 parts by weight in 100 parts by weight of the entire composition, the hydroxyl group equivalent is 250 to 450, and the polyisocyanate is polymethylpolyphenylpolyisocyanate, and the polyisocyanate is polymethylpolyphenylpolyisocyanate in 100 parts by weight of the entire composition. The number of NCO groups per hydroxyl group is 6.0 to 7.0, the aggregate is composed of spherical organic fine particles, aluminum hydroxide and silica sand, and the spherical organic fine particles are acrylic fine particles. It is 10 to 15 parts by weight in 100 parts by weight of the whole composition, aluminum hydroxide is 1 to 4 parts by weight in 100 parts by weight of the whole composition, and silica sand is 0 in 100 parts by weight of the whole composition. Provided is a water-hard polymer cement composition characterized in that it is 5 to 2 parts by weight, the cement is 25 to 35 parts by weight in 100 parts by weight of the entire composition, and the diluent contains an alkylsulfonic acid ester compound. do.
また、請求項２記載の発明は、さらにベンズイミダゾール系化合物から成る防かび剤を含むことを特徴とする請求項１記載の水硬性ポリマーセメント組成物を提供する。 The invention according to claim 2 further provides the hydraulic polymer cement composition according to claim 1, further comprising a fungicide composed of a benzimidazole compound.
本発明の水硬性ポリマーセメント組成物は、熱水と冷水の繰り返し流下による熱衝撃性に優れ、耐摩耗性を有すると共に、重量物が落下しても剥離しないような耐衝撃性を有するという効果がある。また、まだ固まらない状態で下地コンクリート又は既にあるポリオール、ポリイソシアネート、セメント、骨材及び水、及び必要により希釈剤を含有してなる水硬性ポリマーセメント組成物の硬化塗膜上に塗付することが出来る時間が十分に有り、その際の作業性も低粘度であることから良好であり、ローラ刷毛で容易に施工できる効果がある。 The hydraulic polymer cement composition of the present invention has an effect of being excellent in thermal shock resistance due to repeated flow of hot water and cold water, having abrasion resistance, and having impact resistance so as not to peel off even if a heavy object is dropped. There is. Also, it should be applied on the cured coating of the base concrete or the hydraulic polymer cement composition containing existing polyol, polyisocyanate, cement, aggregate and water, and if necessary, a diluent in a state where it has not hardened yet. It is good because there is enough time to do it and the workability at that time is low viscosity, and there is an effect that it can be easily applied with a roller brush.
特に請求項２記載の発明は、食品工場床で行われているような熱水による洗浄が行われても、防かび性を長期に亘って保持する効果があり、食品工場床としての用途に優れるという効果がある。 In particular, the invention according to claim 2 has an effect of maintaining antifungal properties for a long period of time even if it is washed with hot water as is performed on a food factory floor, and is used as a food factory floor. It has the effect of being excellent.
以下本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の水硬性ポリマーセメント組成物は、ポリオール、ポリイソシアネート、希釈剤、セメント、骨材及び水を含有してなる水硬性ポリマーセメント組成物であって、ポリオールはヒマシ油系ポリオールとビスフェノールＡ骨格を有する４官能ポリオールとから成り、ヒマシ油系ポリオールはヒマシ油系２官能ポリオールとヒマシ油系３官能ポリオールとからなりヒマシ油系２官能ポリオールは組成物全体１００重量部中の１〜３重量部で、水酸基当量が１５０〜３２０であり、ヒマシ油系３官能ポリオールは組成物全体１００重量部中の４〜１０重量部で、水酸基当量が２５０〜４５０であり、ビスフェノールＡ骨格を有する４官能ポリオールは組成物全体１００重量部中の０．５〜３重量部で、水酸基当量が２５０〜４５０であり、ポリイソシアネートはポリメチルポリフェニルポリイソシアネートであり、組成物全体１００重量部中の２０〜４０重量部であり、水酸基１個に対するＮＣＯ基の数が６．０〜７．０であり、骨材は球状有機微粒子と水酸化アルミニウムと硅砂とから成り、球状有機微粒子はアクリル微粒子であり、組成物全体１００重量部中の１０〜１５重量部であり、水酸化アルミニウムは組成物全体１００重量部中の１〜４重量部であり、硅砂は組成物全体１００重量部中の０．５〜２重量部であり、セメントは組成物全体１００重量部中の２５〜３５重量部であり、希釈剤はアルキルスルホン酸エステル化合物を含むことを特徴とする水硬性ポリマーセメント組成物であり、必要に応じてこれらの他に、顔料、分散剤、消泡剤等の添加剤が配合することができる。
The water-hard polymer cement composition of the present invention is a water-hard polymer cement composition containing a polyol, a polyisocyanate, a diluent, cement, aggregate and water, and the polyol is a castor oil-based polyol and a bisphenol A skeleton. The persimmon oil-based polyol is composed of a persimmon oil-based bifunctional polyol and a persimmon oil-based trifunctional polyol, and the persimmon oil-based bifunctional polyol is 1 to 3 parts by weight in 100 parts by weight of the entire composition. The hydroxyl group equivalent is 150 to 320, the castor oil-based trifunctional polyol is 4 to 10 parts by weight in 100 parts by weight of the entire composition, the hydroxyl group equivalent is 250 to 450, and the tetrafunctional polyol has a bisphenol A skeleton. Is 0.5 to 3 parts by weight in 100 parts by weight of the entire composition, the hydroxyl group equivalent is 250 to 450, and the polyisocyanate is polymethylpolyphenylpolyisocyanate, which is 20 to 40 parts by weight of 100 parts by weight of the entire composition. It is a part by weight, the number of NCO groups per hydroxyl group is 6.0 to 7.0, the aggregate is composed of spherical organic fine particles, aluminum hydroxide and silica sand, and the spherical organic fine particles are acrylic fine particles, and the composition is 10 to 15 parts by weight of 100 parts by weight of the whole composition, aluminum hydroxide is 1 to 4 parts by weight of 100 parts by weight of the whole composition, and silica sand is 0.5 to 2 parts by weight of 100 parts by weight of the whole composition. By weight, the cement is 25-35 parts by weight of the total 100 parts by weight of the composition, and the diluent is a water-hard polymer cement composition comprising an alkylsulfonic acid ester compound, as required. In addition to these, additives such as pigments, dispersants, and antifoaming agents can be blended.
本発明の水硬性ポリマーセメント組成物に使用されるポリオールは、ヒマシ油系ポリオールとビスフェノールＡ骨格を有する４官能ポリオールとから成り、ヒマシ油系ポリオールはヒマシ油系２官能ポリオールとヒマシ油系３官能ポリオールとから成る。 The polyol used in the water-hard polymer cement composition of the present invention is composed of a castor oil-based polyol and a tetrafunctional polyol having a bisphenol A skeleton, and the castor oil-based polyol is a castor oil-based bifunctional polyol and a castor oil-based trifunctional polyol. Consists of polyol.
ビスフェノールＡ骨格を有する４官能ポリオールは、ビスフェノールＡ骨格を有するポリエポキシ化合物に活性水素化合物を反応させて得られるエポキシ開環ポリオールであり、水酸基当量は２５０〜４５０が好ましい。水酸基当量が２５０未満では水系ポリウレタン組成物としての硬化が速くなって作業性が不良となり、４５０超では水系ポリウレタン組成物として硬化後の強度が不十分となる。ビスフェノールＡ骨格を有する４官能ポリオールの配合量は組成物全体１００重量部中の０．５〜３重量部が好ましく、０．５重量部未満では組成物の硬化物の強度が低下する場合があり３重量部超では組成物をローラ刷毛で塗付する際の作業性が低下する場合がある。 The tetrafunctional polyol having a bisphenol A skeleton is an epoxy ring-opening polyol obtained by reacting a polyepoxy compound having a bisphenol A skeleton with an active hydrogen compound, and the hydroxyl equivalent is preferably 250 to 450. If the hydroxyl group equivalent is less than 250, the water-based polyurethane composition cures faster and the workability becomes poor, and if it exceeds 450, the water-based polyurethane composition becomes insufficient in strength after curing. The blending amount of the tetrafunctional polyol having a bisphenol A skeleton is preferably 0.5 to 3 parts by weight in 100 parts by weight of the entire composition, and if it is less than 0.5 parts by weight, the strength of the cured product of the composition may decrease. If it exceeds 3 parts by weight, the workability when applying the composition with a roller brush may decrease.
ヒマシ油系２官能ポリオールは、ヒマシ油を加工して得られた２官能ポリオールであり、その水酸基当量は１５０〜３２０が好ましい。１５０未満では、硬化が早くなって作業性が不良となる場合があり、３２０超では水硬性ポリマーセメント組成物として硬化後の強度が不十分となる場合がある。ヒマシ油系２官能ポリオールの配合量は組成物全体１００重量部中の１〜３重量部が好ましく、１重量部未満では組成物の硬化物の強度が低下し３重量部超では組成物をローラ刷毛で塗付する際の作業性が低下する。 The castor oil-based bifunctional polyol is a bifunctional polyol obtained by processing castor oil, and its hydroxyl group equivalent is preferably 150 to 320. If it is less than 150, curing may be accelerated and workability may be poor, and if it is more than 320, the strength of the hydraulic polymer cement composition after curing may be insufficient. The blending amount of the castor oil-based bifunctional polyol is preferably 1 to 3 parts by weight in 100 parts by weight of the entire composition, and if it is less than 1 part by weight, the strength of the cured product of the composition decreases, and if it exceeds 3 parts by weight, the composition is rolled. Workability when applying with a brush is reduced.
本発明の水硬性ポリマーセメント組成物に使用されるヒマシ油系３官能ポリオールには、ヒマシ油又はその誘導体を使用することができ、水酸基数が３のポリオールである。本発明に使用するヒマシ油系３官能ポリオールの水酸基当量は、２５０〜４５０が好ましく、２５０未満では水系ポリウレタン組成物としての硬化が速くなって作業性が不良となり、４５０超では水硬性ポリマーセメント組成物として硬化後の強度が不十分となる。ヒマシ油系３官能ポリオールの配合量は組成物全体１００重量部中の４〜１０重量部が好ましく、４重量部未満では組成物の硬化物の強度が低下し１０重量部超では組成物をローラ刷毛で塗付する際の作業性が低下する。 Castor oil or a derivative thereof can be used as the castor oil-based trifunctional polyol used in the water-hard polymer cement composition of the present invention, and is a polyol having 3 hydroxyl groups. The hydroxyl group equivalent of the castor oil-based trifunctional polyol used in the present invention is preferably 250 to 450. If it is less than 250, the water-based polyurethane composition cures faster and workability becomes poor, and if it exceeds 450, the water-hard polymer cement composition. As a product, the strength after curing becomes insufficient. The blending amount of the castor oil-based trifunctional polyol is preferably 4 to 10 parts by weight in 100 parts by weight of the entire composition, and if it is less than 4 parts by weight, the strength of the cured product of the composition decreases, and if it exceeds 10 parts by weight, the composition is rolled. Workability when applying with a brush is reduced.
本発明の水硬性ポリマーセメント組成物に使用するポリイソシアネートは、作業性が良好となり、また低温での速硬化性さらには硬化後の強度が高いことより、４，４´−ジフェニルメタンジイソシアネートからなるポリメリックＭＤＩ（ポリメチルポリフェニルポリイソシアネート）を使用することが好ましく、ＮＣＯ当量は１００〜１５０が好ましい。ＮＣＯ当量が１００未満では硬化物が発泡による膨れが生じる等で仕上がりが不良となり、ＮＣＯ当量が１５０超では硬化後の強度が不十分となる。もちろん、他の脂肪族ポリイソシアネートや芳香族ポリイソシアネートや脂環式ポリイソシアネート等も使用することもでき、また併用することも可能である。ポリイソシアネートの配合量は組成物全体１００重量部中の２０〜４０重量部が好ましく、２０重量部未満では組成物の硬化物の強度が低下し４０重量部超では硬化物が発泡による膨れが生じる等で仕上がりが不良となる。 The polyisocyanate used in the water-hardening polymer cement composition of the present invention has good workability, quick-curing property at low temperature, and high strength after curing. Therefore, the polyisocyanate is composed of 4,4'-diphenylmethane diisocyanate. It is preferable to use MDI (polymethylpolyphenyl polyisocyanate), and the NCO equivalent is preferably 100 to 150. If the NCO equivalent is less than 100, the cured product will swell due to foaming and the finish will be poor, and if the NCO equivalent is more than 150, the strength after curing will be insufficient. Of course, other aliphatic polyisocyanates, aromatic polyisocyanates, alicyclic polyisocyanates and the like can also be used, and can also be used in combination. The blending amount of the polyisocyanate is preferably 20 to 40 parts by weight in 100 parts by weight of the entire composition, and if it is less than 20 parts by weight, the strength of the cured product of the composition decreases, and if it exceeds 40 parts by weight, the cured product swells due to foaming. The finish will be poor due to such factors.
ポリオールの水酸基一個に対するイソシアネート基の数は、６．０〜７．０が好ましく、６．０未満では耐熱衝撃性が低下し、７．０超では可使時間が短くなって塗付作業性が不良となる。 The number of isocyanate groups per hydroxyl group of the polyol is preferably 6.0 to 7.0, and if it is less than 6.0, the thermal impact resistance is lowered, and if it is more than 7.0, the pot life is shortened and the coating workability is improved. It becomes defective.
本発明の水硬性ポリマーセメント組成物に使用する希釈剤はアルキルスルホン酸エステル化合物を含み、組成物を低粘度としてローラ刷毛にて下地コンクリート又は既存の塗膜上に容易に塗付可能にしている。アルキルスルホン酸エステル化合物は非フタル酸系の可塑剤であり、市販品としてメザモール（商品名、１００％アルキルスルホン酸エステル化合物、バイエル社製）がある。アルキルスルホン酸エステル化合物の配合量は組成物全体１００重量部中の４〜１０重量部が好ましく、４重量部未満では組成物をローラ刷毛で塗付する際の作業性が低下し、１０重量部超では組成物の硬化物の強度が低下する。 The diluent used in the water-hard polymer cement composition of the present invention contains an alkyl sulfonic acid ester compound, and the composition has a low viscosity so that it can be easily applied to the underlying concrete or an existing coating film by a roller brush. .. The alkyl sulfonic acid ester compound is a non-phthalic acid-based plasticizer, and there is Mezamol (trade name, 100% alkyl sulfonic acid ester compound, manufactured by Bayer) as a commercially available product. The blending amount of the alkyl sulfonic acid ester compound is preferably 4 to 10 parts by weight out of 100 parts by weight of the entire composition, and if it is less than 4 parts by weight, the workability when applying the composition with a roller brush is lowered and 10 parts by weight is used. If it is super, the strength of the cured product of the composition decreases.
本発明の水硬性ポリマーセメント組成物に使用するベンズイミダゾール系化合物から成る防かび剤は、熱に対する安定性とｐＨに対する安定性が高いため、熱水洗浄が行われ、組成物としてセメントを含有する本水硬性ポリマーセメント組成物に適する防かび剤として使用される。市販品として１０％水懸濁液としてコートサイドＤ２（商品名、日本エンバイロケミカルズ株式会社製）がある。ベンズイミダゾール系化合物から成る防かび剤の配合量は、組成物全体１００重量部に対して０．６〜４．０重量部が好ましい。０．６重量部未満では防かび効果が不十分であり、４．０重量部超ではコスト高と成る。 The fungicide composed of a benzimidazole compound used in the hydraulic polymer cement composition of the present invention is highly stable against heat and pH, so that it is washed with hot water and contains cement as the composition. It is used as a fungicide suitable for this hydraulic polymer cement composition. As a commercially available product, there is Coatside D2 (trade name, manufactured by Japan Enviro Chemicals Co., Ltd.) as a 10% aqueous suspension. The amount of the fungicide containing the benzimidazole compound is preferably 0.6 to 4.0 parts by weight with respect to 100 parts by weight of the entire composition. If it is less than 0.6 parts by weight, the antifungal effect is insufficient, and if it exceeds 4.0 parts by weight, the cost is high.
本発明の水硬性ポリマーセメント組成物に使用するセメントは、本発明の水系ポリウレタン組成物が床下地コンクリートに塗布し美観を付与することを目的としているため、特定の色調が付与できるように、主として白色ポルトランドセメントを使用することが好ましい。他に普通ポルトランドセメント、アルミナセメント、高炉セメント、早強ポルトランドセメントを併用することができる。セメントの配合量は組成物全体１００重量部中の２５〜３５重量部である。２５重量部未満では組成物の硬化物の強度が低下し、３５重量部超では組成物をローラ刷毛で塗付する際の作業性が低下する。 Since the cement used in the hydraulic polymer cement composition of the present invention is intended to be applied to the floor base concrete to give an aesthetic appearance by the water-based polyurethane composition of the present invention, it is mainly used so that a specific color tone can be imparted. It is preferable to use white Portland cement. In addition, ordinary Portland cement, alumina cement, blast furnace cement, and early-strength Portland cement can be used in combination. The blending amount of cement is 25 to 35 parts by weight in 100 parts by weight of the entire composition. If it is less than 25 parts by weight, the strength of the cured product of the composition is lowered, and if it is more than 35 parts by weight, the workability when the composition is applied with a roller brush is lowered.
本発明の水硬性ポリマーセメント組成物に使用する骨材には、本組成物をローラ刷毛で塗付できるようにすることを目的として、球状有機微粒子と水酸化アルミニウムと硅砂から成る。骨材のかさ比重は０．５〜１．０が好ましく、０．５未満ではローラ刷毛塗布作業が不良となり、１．０超では塗膜平滑性が不良となる。 The aggregate used in the hydraulic polymer cement composition of the present invention is composed of spherical organic fine particles, aluminum hydroxide and silica sand for the purpose of allowing the composition to be applied with a roller brush. The bulk specific gravity of the aggregate is preferably 0.5 to 1.0, and if it is less than 0.5, the roller brush application work becomes poor, and if it exceeds 1.0, the coating film smoothness becomes poor.
本発明の水硬性ポリマーセメント組成物に使用する骨材としての球状有機微粒子には、アクリル微粒子、スチレン微粒子、ナイロン微粒子、ウレタン微粒子等を使用することができ、特には塗膜の強靭性及びコストの面でアクリル微粒子が好ましい。球状有機微粒子の粒子径は１０μｍ〜３０μｍが好ましく、１０μｍ未満では光沢ムラによる仕上がり不良となり、３０μｍ超では塗膜平滑性が不良となる。球状有機微粒子を配合することにより表面仕上がり性と耐熱衝撃性が良好となる。球状有機微粒子の配合部数は組成物全体１００重量部中１０〜１５重量部が好ましく、１０重量部未満では塗膜平滑性が不良となり、１５重量部超では耐熱衝撃性が低下する。 Acrylic fine particles, styrene fine particles, nylon fine particles, urethane fine particles and the like can be used as the spherical organic fine particles as the aggregate used in the water-hard polymer cement composition of the present invention, and in particular, the toughness and cost of the coating film. Acrylic fine particles are preferable in terms of. The particle size of the spherical organic fine particles is preferably 10 μm to 30 μm, and if it is less than 10 μm, the finish is poor due to uneven gloss, and if it exceeds 30 μm, the coating film smoothness is poor. By blending spherical organic fine particles, surface finish and thermal impact resistance are improved. The number of parts of the spherical organic fine particles to be blended is preferably 10 to 15 parts by weight out of 100 parts by weight of the entire composition, and if it is less than 10 parts by weight, the coating film smoothness is poor, and if it exceeds 15 parts by weight, the thermal shock resistance is lowered.
本発明の水硬性ポリマーセメント組成物に使用する骨材としての水酸化アルミニウムは、耐熱衝撃性を確保し且つ組成物のローラ刷毛作業性を良好とすることを目的として配合する。また水酸化アルミニウムの平均粒子径Ｄ５０は５μｍ〜３０μｍが好ましく、５μｍ未満ではローラ刷毛作業性が低下し、３０μｍ超では塗膜平滑性が不良となる。ここで言う平均粒子径Ｄ５０とは、重量による積算分率が５０％の粒子径を言う。水酸化アルミニウムの配合部数は組成物全体１００重量部中１〜４重量部が好ましく１重量部未満では耐熱衝撃性が低下すると共に下地の隠蔽性が不良となる。４重量部超ではローラ刷毛作業性が低下する。 Aluminum hydroxide as an aggregate used in the water-hard polymer cement composition of the present invention is blended for the purpose of ensuring heat impact resistance and improving the roller brush workability of the composition. The average particle diameter D 50 of aluminum hydroxide is preferably 5 m to 30 m, is less than 5μm and lowered roller brush workability, coating smoothness becomes poor at 30μm greater. The average particle size D 50 referred to here means a particle size in which the integrated fraction by weight is 50%. The number of parts of the aluminum hydroxide compounded is preferably 1 to 4 parts by weight out of 100 parts by weight of the entire composition, and if it is less than 1 part by weight, the heat impact resistance is lowered and the hiding property of the base is poor. If it exceeds 4 parts by weight, the roller brush workability is lowered.
本発明の水硬性ポリマーセメント組成物に使用する骨材としての硅砂は、塗膜平滑性を良好とすることを目的として配合する。硅砂の粒子径は０．０５ｍｍ〜０．２ｍｍが好ましく、０．０５ｍｍ未満ではセメント粒子の凝集が生じ、０．２ｍｍ超では塗膜平滑性が不十分となる。硅砂の配合部数は組成物全体１００重量部中１〜４重量部が好ましく１重量部未満では耐熱衝撃性が低下すると共にセメント粒子が凝集し、４重量部超ではローラ刷毛作業性が低下する。 The silica sand as an aggregate used in the hydraulic polymer cement composition of the present invention is blended for the purpose of improving the smoothness of the coating film. The particle size of silica sand is preferably 0.05 mm to 0.2 mm, and if it is less than 0.05 mm, cement particles agglomerate, and if it exceeds 0.2 mm, the smoothness of the coating film becomes insufficient. The number of parts of silica sand blended is preferably 1 to 4 parts by weight out of 100 parts by weight of the entire composition, and if it is less than 1 part by weight, the heat impact resistance is lowered and cement particles are aggregated, and if it exceeds 4 parts by weight, the roller brushing workability is lowered.
本発明の水硬性ポリマーセメント組成物はローラ刷毛にて、下地コンクリート又は下地コンクリート上に既に厚さ２〜９ｍｍ程度に形成された、ポリオール、ポリイソシアネート、セメント、骨材及び水、及び必要により希釈剤を含有してなる水硬性ポリマーセメント組成物の硬化塗膜上にさらに塗付する。ローラ刷毛は、毛丈１０〜１５ｍｍが好ましく、塗付厚みは０．１〜０．２ｍｍ、塗付量は０．２〜０．４ｋｇ／ｍ２が好ましい。このような施工性（ローラ刷毛作業性）を得るため、本発明の水硬性ポリマーセメント組成物は、骨材に上記球状有機微粒子と水酸化アルミニウムと硅砂を使用する。 The hydraulic polymer cement composition of the present invention is diluted with polyol, polyisocyanate, cement, aggregate and water already formed on the base concrete or the base concrete to a thickness of about 2 to 9 mm by a roller brush, and if necessary. It is further applied onto the cured coating of the hydraulic polymer cement composition containing the agent. The roller brush preferably has a hair length of 10 to 15 mm, a coating thickness of 0.1 to 0.2 mm, and a coating amount of 0.2 to 0.4 kg / m 2 . In order to obtain such workability (roller brush workability), the water-hard polymer cement composition of the present invention uses the above-mentioned spherical organic fine particles, aluminum hydroxide and silica sand as an aggregate.
以下、実施例及び比較例にて具体的に説明する。 Hereinafter, a specific description will be given with reference to Examples and Comparative Examples.
＜実施例及び比較例＞
水酸基当量が１６０のヒマシ油系２官能ポリオール８重量部と水酸基当量が３５０のヒマシ油系３官能ポリオール２０重量部と水酸基当量が３５０のビスフェノールＡ骨格を有する４官能ポリオール４重量部とアルキルスルホン酸エステル化合物としてメザモールを２２重量部とフタル酸ジオクチルを６重量部とイオン交換水２０重量部と着色トナー２０重量部（水１０重量部、顔料１０重量部）から成るポリオールと希釈剤と水を含む主剤１００重量部と、ポリイソシアネートとしてポリメリックＭＤＩ（ポリメチルポリフェニルポリイソシアネート）であるルプラネートＭＢ−５Ｓ（商品名、ＢＡＳＦ ＩＮＯＡＣポリウレタン株式会社製、ＮＣＯ重量％：３１．４〜３２．６％）を硬化剤１００重量部とし、セメントとして白色ポルトランドセメント（太平洋セメント社製）を使用し、骨材として球状有機微粒子としてガンツパールＧＭ２００１（ポリアクリル酸エステル樹脂の球状微粒子、粒径２０μｍ、アイカ工業社製）を使用し、同水酸化アルミニウムとして、ハイジライトＨ−３２（平均粒子径Ｄ５０：８μｍ、昭和電工社製）を使用し、同硅砂として粒径０．０５〜０．２ｍｍの東北硅砂８号を使用し、セメントと骨材の合計部数を１５０重量部として表１の配合にて、主剤部：硬化剤部：骨材部を１００重量部：１００重量部：１５０重量部で均一に混合したものを実施例１及び比較例１乃至比比較例６の水硬性ポリマーセメント組成物とした。実施例１及び比較例１乃至比較例６の水酸基１個当たりのＮＣＯ基数は６．５である。
<Examples and Comparative Examples>
8 parts by weight of castor oil-based bifunctional polyol having a hydroxyl group equivalent of 160, 20 parts by weight of castor oil-based trifunctional polyol having a hydroxyl group equivalent of 350, 4 parts by weight of a tetrafunctional polyol having a bisphenol A skeleton having a hydroxyl group equivalent of 350, and alkyl sulfonic acid. As an ester compound, it contains a polyol consisting of 22 parts by weight of mezamol, 6 parts by weight of dioctyl phthalate, 20 parts by weight of ion-exchanged water and 20 parts by weight of colored toner (10 parts by weight of water, 10 parts by weight of pigment), a diluent and water. 100 parts by weight of the main agent and Luplanate MB-5S (trade name, manufactured by BASF INOC Polyurethane Co., Ltd., NCO weight%: 31.4 to 32.6%) which is a polymeric MDI (polymethylpolyphenyl polyisocyanate) as a polyisocyanate. 100 parts by weight of hardener, white Portland cement (manufactured by Pacific Cement Co., Ltd.) as cement, and Ganzpearl GM2001 (spherical fine particles of polyacrylic acid ester resin, particle size 20 μm, manufactured by Aika Kogyo Co., Ltd.) as spherical organic fine particles as aggregate. ) Is used, and Heidilite H-32 (average particle size D 50 : 8 μm, manufactured by Showa Denko Co., Ltd.) is used as the same aluminum hydroxide, and Tohoku silica sand 8 having a particle size of 0.05 to 0.2 mm is used as the same silica sand. Using No., the total number of parts of cement and aggregate is 150 parts by weight, and in the formulation shown in Table 1, the main agent part: hardener part: aggregate part is uniformly mixed in 100 parts by weight: 100 parts by weight: 150 parts by weight. Was used as the water-hard polymer cement composition of Example 1 and Comparative Examples 1 to 6. The number of NCO groups per hydroxyl group in Example 1 and Comparative Examples 1 to 6 is 6.5.
実施例１の主剤９７重量部にベンズイミダゾール系化合物から成る防かび剤としてコートサイドＤ２（１０％水懸濁液）３重量部を混合して全体として１００重量部として実施例２の主剤１００重量部とし、硬化剤と、骨材部は実施例１と同じとし、主剤：硬化剤：骨材部を１００重量部：１００重量部：１５０重量部で均一に混合したものを実施例１の水硬性ポリマーセメント組成物とした。実施例２の水酸基１個当たりのＮＣＯ基数は６．７である。 3 parts by weight of coat side D2 (10% aqueous suspension) was mixed with 97 parts by weight of the main agent of Example 1 as a fungicide composed of a benzimidazole compound to make 100 parts by weight of the main agent of Example 2 as a whole. The hardener and the aggregate part are the same as in Example 1, and the water of Example 1 is obtained by uniformly mixing the main agent: hardener: aggregate part in 100 parts by weight: 100 parts by weight: 150 parts by weight. A rigid polymer cement composition was used. The number of NCO groups per hydroxyl group in Example 2 is 6.7.
水酸基当量が１６０の水酸基当量が３５０のヒマシ油系３官能ポリオール２８重量部と水酸基当量が３５０のビスフェノールＡ骨格を有する４官能ポリオール６重量部とアルキルスルホン酸エステル化合物としてメザモールを２５重量部とイオン交換水２１重量部と着色トナー２０重量部（水１０重量部、顔料１０重量部）から成るポリオールと希釈剤と水を含む主剤１００重量部と、ポリイソシアネートとしてポリメリックＭＤＩ（ポリメチルポリフェニルポリイソシアネート）であるルプラネートＭＢ−５Ｓ（商品名、ＢＡＳＦ ＩＮＯＡＣポリウレタン株式会社製、ＮＣＯ重量％：３１．４〜３２．６％）を硬化剤１００重量部とし、セメント及び骨材を実施例１と同様のものを使用し、セメントと骨材の合計部数を１５０重量部として表１の配合にて、主剤部：硬化剤部：骨材部を１００重量部：１００重量部：１５０重量部で均一に混合したものを比較例７の水硬性ポリマーセメント組成物とした。比較例７の水酸基１個当たりのＮＣＯ基数は７．９である。 28 parts by weight of castor oil-based trifunctional polyol having a hydroxyl group equivalent of 160 and a hydroxyl group equivalent of 350, 6 parts by weight of a tetrafunctional polyol having a bisphenol A skeleton having a hydroxyl group equivalent of 350, and 25 parts by weight of mezamol as an alkylsulfonic acid ester compound. Polyol consisting of 21 parts by weight of exchanged water and 20 parts by weight of colored toner (10 parts by weight of water, 10 parts by weight of pigment), 100 parts by weight of a main agent containing a diluent and water, and polymeric MDI (polymethylpolyphenylpolyisocyanate) as polyisocyanate. ) Luplanate MB-5S (trade name, manufactured by BASF INOC Polyurethane Co., Ltd., NCO weight%: 31.4 to 32.6%) as 100 parts by weight of the curing agent, and cement and aggregate were the same as in Example 1. In the formulation shown in Table 1, the total number of parts of cement and aggregate is 150 parts by weight, and the main agent part: hardener part: aggregate part is uniformly mixed in 100 parts by weight: 100 parts by weight: 150 parts by weight. Was used as the water-hard polymer cement composition of Comparative Example 7. The number of NCO groups per hydroxyl group in Comparative Example 7 is 7.9.
水酸基当量が１６０のヒマシ油系２官能ポリオール１３重量部と水酸基当量が３５０のヒマシ油系３官能ポリオール１５重量部と水酸基当量が３５０のビスフェノールＡ骨格を有する４官能ポリオール４重量部とアルキルスルホン酸エステル化合物としてメザモールを２０重量部とフタル酸ジオクチルを９重量部とイオン交換水１９重量部と着色トナー２０重量部（水１０重量部、顔料１０重量部）から成るポリオールと希釈剤と水を含む主剤１００重量部と、ポリイソシアネートとしてポリメリックＭＤＩ（ポリメチルポリフェニルポリイソシアネート）であるルプラネートＭＢ−５Ｓ（商品名、ＢＡＳＦ ＩＮＯＡＣポリウレタン株式会社製、ＮＣＯ重量％：３１．４〜３２．６％）を硬化剤１００重量部とし、セメント及び骨材を実施例１と同様のものを使用し、セメントと骨材の合計部数を１５０重量部として表１の配合にて、主剤部：硬化剤部：骨材部を１００重量部：１００重量部：１５０重量部で均一に混合したものを比較例７の水硬性ポリマーセメント組成物とした。比較例８の水酸基１個当たりのＮＣＯ基数は５．７である。 13 parts by weight of castor oil-based bifunctional polyol having a hydroxyl group equivalent of 160, 15 parts by weight of castor oil-based trifunctional polyol having a hydroxyl group equivalent of 350, 4 parts by weight of a tetrafunctional polyol having a bisphenol A skeleton having a hydroxyl group equivalent of 350, and alkyl sulfonic acid. As an ester compound, it contains a polyol consisting of 20 parts by weight of mezamol, 9 parts by weight of dioctyl phthalate, 19 parts by weight of ion-exchanged water and 20 parts by weight of colored toner (10 parts by weight of water, 10 parts by weight of pigment), a diluent and water. 100 parts by weight of the main agent and ruplanate MB-5S (trade name, manufactured by BASF INOC Polyurethane Co., Ltd., NCO weight%: 31.4 to 32.6%) which is a polymeric MDI (polymethylpolyphenyl polyisocyanate) as a polyisocyanate. The hardener is 100 parts by weight, the same cement and aggregate as in Example 1 are used, and the total number of parts of the cement and aggregate is 150 parts by weight. A mixture of 100 parts by weight: 100 parts by weight: 150 parts by weight of the material was used as the water-hard polymer cement composition of Comparative Example 7. The number of NCO groups per hydroxyl group in Comparative Example 8 is 5.7.
＜評価項目及び評価方法＞ <Evaluation items and evaluation methods>
＜骨材のかさ比重＞
実施例及び比較例の骨材（球状有機微粒子と水酸化アルミニウムと硅砂を均一に混合したもの）をＪＩＳＡ６９０４ 付属書３ 粉末物性の測定 ５．かさ比重、に準拠してかさ比重を測定した。
<Bulk specific gravity of aggregate>
4. Measurement of powder physical properties of the aggregates of Examples and Comparative Examples (a uniform mixture of spherical organic fine particles, aluminum hydroxide, and silica sand) Annex 3 of JIS A6904. The bulk specific density was measured according to the bulk specific density.
＜粘度及び揺変値＞
２３℃下において実施例及び比較例の水硬性ポリマーセメント組成物の混合物（混合直後）について、ＢＭ型粘度計（ローターＮｏ４、回転数６０ｒｐｍ）にて粘度（Ｐａ・ｓ）を測定した。２．０Ｐａ・ｓ未満を○とし、２．０Ｐａ・ｓ以上を×と評価した。また、同ＢＭ型粘度計にてローターＮｏ４、６ｒｐｍの粘度を測定し、６ｒｐｍ時の粘度を６０ｒｐｍ時の粘度で除した値を揺変値とした。揺変値は１．０以上１．５未満を○と評価し、これ以外を×と評価した。
<Viscosity and fluctuation value>
The viscosity (Pa · s) of the mixture (immediately after mixing) of the hydraulic polymer cement compositions of Examples and Comparative Examples at 23 ° C. was measured with a BM type viscometer (rotor No. 4, rotation speed 60 rpm). Less than 2.0 Pa · s was evaluated as ◯, and 2.0 Pa · s or more was evaluated as ×. Further, the viscosities of rotors No. 4 and 6 rpm were measured with the same BM type viscometer, and the value obtained by dividing the viscosity at 6 rpm by the viscosity at 60 rpm was taken as the fluctuation value. The fluctuation value of 1.0 or more and less than 1.5 was evaluated as ◯, and the other values were evaluated as x.
＜耐摩耗性＞
２３℃下にて７日養生後の実施例及び比較例の水硬性ポリマーセメント組成物の硬化物について、ＪＩＳＫ ７２０４（プラスチック−摩耗輪による摩耗試験方法）に準拠し、摩耗輪（ＣＳ−１７）、荷重９．８Ｎ、１０００回転の摩耗量を測定した。１００ｍｇ未満であれば耐摩耗性を有すると評価した。
<Abrasion resistance>
The cured product of the hydraulic polymer cement composition of Examples and Comparative Examples after curing at 23 ° C. for 7 days is based on JIS K 7204 (Plastic-wear test method using wear wheel), and wear wheel (CS-17). , The amount of wear was measured at a load of 9.8 N and 1000 rotations. If it was less than 100 mg, it was evaluated as having wear resistance.
＜圧縮強さ＞
２３℃下にて７日養生後の実施例及び比較例の水硬性ポリマーセメント組成物の硬化物について、ＪＩＳＫ６９１１の規定に準じて圧縮強さ（Ｎ/ｍｍ２）を測定した。試験体の大きさは１３ｍｍ×１３ｍｍ×２５ｍｍとした。圧縮強さが４０Ｎ/ｍｍ２超であれば十分な強度を有すると評価した。
<Compressive strength>
The compressive strength (N / mm 2 ) of the cured product of the hydraulic polymer cement composition of Examples and Comparative Examples after curing at 23 ° C. for 7 days was measured according to the provisions of JIS K6911. The size of the test piece was 13 mm × 13 mm × 25 mm. When the compressive strength was more than 40 N / mm 2 , it was evaluated as having sufficient strength.
＜耐熱性＞
２３℃にて７日養生後にさらに８５℃熱水に７日間浸漬し、２３℃に徐冷した実施例及び比較例の水硬性ポリマーセメント組成物の硬化物について、ＪＩＳＫ６９１１の規定に準じて圧縮強さ（Ｎ/ｍｍ２）を測定した。試験体の大きさは１３ｍｍ×１３ｍｍ×２５ｍｍとした。得られた圧縮強さの値を上記２３℃７日養生後の圧縮強さにて除し保持率（％）を求めた。保持率９０％超であれば耐熱性を有すると評価した。
<Heat resistance>
After curing at 23 ° C. for 7 days, the cured product of the hydraulic polymer cement composition of Examples and Comparative Examples, which was further immersed in hot water at 85 ° C. for 7 days and slowly cooled to 23 ° C., was compressed according to the provisions of JIS K6911. (N / mm 2 ) was measured. The size of the test piece was 13 mm × 13 mm × 25 mm. The obtained compressive strength value was divided by the compressive strength after curing at 23 ° C. for 7 days to determine the retention rate (%). If the retention rate was more than 90%, it was evaluated as having heat resistance.
＜耐衝撃性＞
２３℃下でＪＩＳＡ５３７１の３００ｍｍ×３００ｍｍ×厚さ６０ｍｍの乾燥したコンクリート平板（ケット水分計ＨＩ−５２０コンクリートレンジにて表示値５％以下）の表面に、均一に混合した実施例、比較例の水硬性ポリマーセメント組成物を厚さ約０．２ｍｍにローラ刷毛（ウーローラー毛丈１０〜１５ｍｍ、大塚刷毛社製）にて塗付して７日間養生し、中央部に高さ１ｍから１ｋｇの鋼球を７回落下させ、塗膜に割れ、剥がれ等の異常のないものを○、割れ、剥がれ等の異常が生じたものを×と評価した。
<Impact resistance>
Water of Examples and Comparative Examples uniformly mixed on the surface of a dry concrete flat plate (display value 5% or less in a Ket Moisture Analyzer HI-520 concrete range) of JIS A5371 at 23 ° C. of 300 mm × 300 mm × thickness 60 mm. A hard polymer cement composition is applied to a thickness of about 0.2 mm with a roller brush (Wool roller hair length 10 to 15 mm, manufactured by Otsuka Brush Co., Ltd.) and cured for 7 days. The ball was dropped 7 times, and those having no abnormality such as cracking or peeling in the coating film were evaluated as ◯, and those having abnormalities such as cracking or peeling were evaluated as x.
また、２３℃下でＪＩＳＡ５３７１の３００ｍｍ×３００ｍｍ×厚さ６０ｍｍの乾燥したコンクリート平板（ケット水分計ＨＩ−５２０コンクリートレンジにて表示値５％以下）の表面に、均一に混合したポリオール、ポリイソシアネート、セメント、骨材及び水から成る下地用水硬性ポリマーセメント組成物 アイカピュールＪＪ−５００（商品名、アイカ工業株式会社製、骨材含有率：７５重量％、セメント含有率：７．５重量％）を厚さ約６ｍｍに塗付し７日間養生硬化後、均一に混合した実施例、比較例の水硬性ポリマーセメント組成物を厚さ約０．２ｍｍにローラ刷毛（ウーローラー毛丈１０〜１５ｍｍ、大塚刷毛社製）にて塗付して７日間養生し、中央部に高さ１ｍから１ｋｇの鋼球を３０回落下させ、塗膜に割れ、剥がれ等の異常のないものを○、割れ、剥がれ等の異常が生じたものを×と評価した。 Further, a polyol, polyisocyanate, which are uniformly mixed on the surface of a dried concrete flat plate of JIS A5371 having a thickness of 300 mm × 300 mm × thickness 60 mm (display value of 5% or less in a Ket moisture meter HI-520 concrete range) at 23 ° C. Water-hard polymer cement composition for groundwork consisting of cement, aggregate and water Aikapur JJ-500 (trade name, manufactured by Aika Kogyo Co., Ltd., aggregate content: 75% by weight, cement content: 7.5% by weight) The water-hard polymer cement composition of Examples and Comparative Examples, which was applied to a thickness of about 6 mm, cured for 7 days, and then uniformly mixed, was roller-brushed to a thickness of about 0.2 mm (Wool roller hair length 10 to 15 mm, Otsuka). Apply with (Brush Co., Ltd.) and cure for 7 days, drop a steel ball with a height of 1 m to 1 kg 30 times in the center, and if there is no abnormality such as cracking or peeling in the coating film, ○, cracking, peeling Those with abnormalities such as these were evaluated as x.
＜耐熱衝撃性＞
ＪＩＳＡ５３７１の３００ｍｍ×３００ｍｍ×厚さ６０ｍｍの乾燥したコンクリート平板（ケット水分計ＨＩ−５２０コンクリートレンジにて５％以下）を４分の１にカットして１５０ｍｍ×１５０ｍｍ×厚さ６０ｍｍの試験板とし、該試験板の表面に均一に混合した実施例、比較例の水硬性ポリマーセメント組成物を厚さ約０．２ｍｍにローラ刷毛（ウーローラー毛丈１０〜１５ｍｍ、大塚刷毛社製）にて塗付して７日間養生する。その後試験体中央部に９５℃熱水を５分流下させ次に２０℃の冷水を１０分流下させることを１サイクルとして１２００サイクル繰り返し、塗膜に剥がれ、浮き等異常が生じないものを○、異常が生じたものを×と評価した。
<Heat-resistant impact resistance>
A dry concrete flat plate of JIS A5371 of 300 mm x 300 mm x 60 mm in thickness (5% or less in the Ket Moisture Analyzer HI-520 concrete range) was cut into quarters to make a test plate of 150 mm x 150 mm x 60 mm in thickness. The hydraulic polymer cement composition of Examples and Comparative Examples uniformly mixed on the surface of the test plate was applied to a thickness of about 0.2 mm with a roller brush (Wool roller hair length 10 to 15 mm, manufactured by Otsuka Brush Co., Ltd.). Then cure for 7 days. After that, the hot water at 95 ° C. was allowed to flow down to the center of the test piece for 5 minutes, and then the cold water at 20 ° C. was allowed to flow down for 10 minutes, which was repeated for 1200 cycles. Those with abnormalities were evaluated as x.
また、ＪＩＳＡ５３７１の３００ｍｍ×３００ｍｍ×厚さ６０ｍｍの乾燥したコンクリート平板（ケット水分計ＨＩ−５２０コンクリートレンジにて５％以下）を４分の１にカットして１５０ｍｍ×１５０ｍｍ×厚さ６０ｍｍの試験板とし、該の試験板の表面であって４面の木口より５ｍｍ内側に深さ１０ｍｍ幅１０ｍｍの目地部を設ける。２３℃下において該目地部に、均一に混合したポリオール、ポリイソシアネート、セメント、骨材及び水から成る下地用水硬性ポリマーセメント組成物 アイカピュールＪＪ−５００（商品名、アイカ工業株式会社製、骨材含有率：７５重量％、セメント含有率：７．５重量％）を充填しながら、厚さ約６ｍｍに塗付し７日間養生硬化後、均一に混合した実施例、比較例の水硬性ポリマーセメント組成物を厚さ約０．２ｍｍにローラ刷毛（ウーローラー毛丈１０〜１５ｍｍ、大塚刷毛社製）にて塗付して７日間養生する。その後試験体中央部に９５℃熱水を５分流下させ次に２０℃の冷水を１０分流下させることを１サイクルとして１５００サイクル繰り返し、塗膜に剥がれ、浮き等異常が生じないものを○、異常が生じたものを×と評価した。 In addition, a dry concrete flat plate of JIS A5371 of 300 mm x 300 mm x 60 mm in thickness (5% or less in a Ket moisture meter HI-520 concrete range) is cut into quarters and a test plate of 150 mm x 150 mm x 60 mm in thickness. Then, a joint portion having a depth of 10 mm and a width of 10 mm is provided on the surface of the test plate 5 mm inward from the end of the four surfaces. Water-hard polymer cement composition for groundwork composed of polyol, polyisocyanate, cement, aggregate and water uniformly mixed in the joint at 23 ° C. Aikapur JJ-500 (trade name, manufactured by Aika Kogyo Co., Ltd., aggregate) Water-hard polymer cement of Examples and Comparative Examples, which was coated with a thickness of about 6 mm while being filled with (content rate: 75% by weight, cement content: 7.5% by weight), cured and cured for 7 days, and then uniformly mixed. The composition is applied to a thickness of about 0.2 mm with a roller brush (Wool roller hair length 10 to 15 mm, manufactured by Otsuka Brush Co., Ltd.) and cured for 7 days. After that, the hot water at 95 ° C. was allowed to flow down to the center of the test piece for 5 minutes, and then the cold water at 20 ° C. was allowed to flow down for 10 minutes, which was repeated for 1500 cycles. Those with abnormalities were evaluated as x.
＜付着性＞
２３℃下でＪＩＳＡ５３７１の３００ｍｍ×３００ｍｍ×厚さ６０ｍｍの乾燥したコンクリート平板（ケット水分計ＨＩ−５２０コンクリートレンジにて５％以下）の表面に、均一に混合した実施例、比較例の水硬性ポリマーセメント組成物を厚さ約０．２ｍｍにローラ刷毛（ウーローラー毛丈１０〜１５ｍｍ、大塚刷毛社製）にて塗付して７日間養生し、建研式接着力試験器により、４０×４０ｍｍ部分の水硬性ポリマーセメント組成物とコンクリート平板との付着強度（Ｎ／ｍｍ２）を測定した。破壊状態は下地コンクリート１００％凝集破壊を○と、それ以外を×と評価した。
<Adhesiveness>
The hydraulic polymers of Examples and Comparative Examples were uniformly mixed on the surface of a dry concrete flat plate (5% or less in a Ket Moisture Analyzer HI-520 concrete range) of JIS A5371 300 mm × 300 mm × thickness 60 mm at 23 ° C. The cement composition is applied to a thickness of about 0.2 mm with a roller brush (Wool roller hair length 10 to 15 mm, manufactured by Otsuka Brush Co., Ltd.) and cured for 7 days. The adhesive strength (N / mm 2 ) between the hydraulic polymer cement composition of the portion and the concrete flat plate was measured. As for the fracture state, 100% cohesive fracture of the base concrete was evaluated as ◯, and the others were evaluated as x.
＜ローラ刷毛作業性＞
５℃、２３℃、及び３０℃にて実施例及び比較例の水硬性ポリマーセメント組成物の混合物（混合直後）を、ローラ刷毛（ウーローラー毛丈１０〜１５ｍｍ、大塚刷毛社製）にてＪＩＳＡ５３７１の３００ｍｍ×３００ｍｍ×厚さ６０ｍｍの乾燥したコンクリート平板（ケット水分計ＨＩ−５２０コンクリートレンジにて５％以下）上に厚さ約０．２ｍｍに塗付し、全ての温度下において該ローラ刷毛にてスムーズに塗り拡げることができるものを○、そうでないものを×と評価した。
<Roller brush workability>
Mixtures (immediately after mixing) of the hydraulic polymer cement compositions of Examples and Comparative Examples at 5 ° C., 23 ° C., and 30 ° C. with a roller brush (Wool roller hair length 10 to 15 mm, manufactured by Otsuka Brush Co., Ltd.), JIS A5371 On a dry concrete flat plate (5% or less in a Ket Moisture Analyzer HI-520 concrete range) of 300 mm x 300 mm x 60 mm thickness, apply it to a thickness of about 0.2 mm, and apply it to the roller brush under all temperatures. Those that can be spread smoothly are evaluated as ○, and those that are not are evaluated as ×.
＜塗膜平滑性＞
５℃、２３℃、及び３０℃にて実施例及び比較例の水硬性ポリマーセメント組成物の混合物（混合直後）を、ローラ刷毛（ウーローラー毛丈１０〜１５ｍｍ、大塚刷毛社製）にてＪＩＳＡ５３７１の３００ｍｍ×３００ｍｍ×厚さ６０ｍｍの乾燥したコンクリート平板（ケット水分計ＨＩ−５２０コンクリートレンジにて５％以下）上に厚さ約０．２ｍｍに塗付し、全ての温度下において均一な塗膜となるものを○と、そうでないものを×と評価した。
<Smoothness of coating film>
Mixtures (immediately after mixing) of the hydraulic polymer cement compositions of Examples and Comparative Examples at 5 ° C., 23 ° C., and 30 ° C. with a roller brush (Wool roller hair length 10 to 15 mm, manufactured by Otsuka Brush Co., Ltd.), JIS A5371 300 mm x 300 mm x 60 mm thick dry concrete flat plate (5% or less in a Ket Moisture Analyzer HI-520 concrete range), coated to a thickness of about 0.2 mm, and a uniform coating film under all temperatures. Those that became ○ were evaluated as ○, and those that did not were evaluated as ×.
＜下地隠蔽性＞
５℃、２３℃、及び３０℃にて実施例及び比較例の水硬性ポリマーセメント組成物の混合物（混合直後）を、ローラ刷毛（ウーローラー毛丈１０〜１５ｍｍ、大塚刷毛社製）にてＪＩＳＡ５３７１の３００ｍｍ×３００ｍｍ×厚さ６０ｍｍの乾燥したコンクリート平板（ケット水分計ＨＩ−５２０コンクリートレンジにて５％以下）上に厚さ約０．２ｍｍに塗付し、全ての温度下において下地の透けがないものを○と、部分的に下地の透けがあうものを△と、それ以外を×と評価した。
<Background concealment>
Mixtures (immediately after mixing) of the hydraulic polymer cement compositions of Examples and Comparative Examples at 5 ° C., 23 ° C., and 30 ° C. with a roller brush (Wool roller hair length 10 to 15 mm, manufactured by Otsuka Brush Co., Ltd.), JIS A5371 300 mm x 300 mm x 60 mm thick dry concrete flat plate (5% or less with Kett Moisture Analyzer HI-520 concrete range), coated to a thickness of about 0.2 mm, and the base is transparent under all temperatures. Those that did not exist were evaluated as ◯, those that partially showed through the base were evaluated as Δ, and those that did not were evaluated as ×.
＜可使時間＞
２３℃にて実施例及び比較例の水硬性ポリマーセメント組成物の混合物（混合直後）を、ローラ刷毛（ウーローラー毛丈１０〜１５ｍｍ、大塚刷毛社製）にてＪＩＳＡ５３７１の３００ｍｍ×３００ｍｍ×厚さ６０ｍｍの乾燥したコンクリート平板（ケット水分計ＨＩ−５２０コンクリートレンジにて５％以下）上に厚さ約０．２ｍｍに塗付し、該ローラ刷毛にてスムーズに塗り拡げることができる時間を測定した。１５分以上を○、そうでないものを×と評価した。
<Available time>
A mixture (immediately after mixing) of the hydraulic polymer cement compositions of Examples and Comparative Examples at 23 ° C. was applied with a roller brush (wool roller hair length 10 to 15 mm, manufactured by Otsuka Brush Co., Ltd.) to a thickness of 300 mm × 300 mm × thickness of JIS A5371. It was applied to a thickness of about 0.2 mm on a 60 mm dry concrete flat plate (5% or less with a Ket Moisture Analyzer HI-520 concrete range), and the time during which it could be spread smoothly with the roller brush was measured. .. Those that took 15 minutes or more were evaluated as ◯, and those that did not were evaluated as x.
＜防カビ性＞
２３℃下にて７日養生後の実施例、比較例の水硬性ポリマーセメント組成物の硬化物について、９５℃熱水を５分流下させ次に２０℃の冷水を１０分流下させることを１サイクルとした熱衝撃を１００回と２５０回加え、その後の試験体について、ＪＩＳ Ｚ ２９１１ かび抵抗性試験方法（プラスチック製品の試験（方法Ａ：乾式法）に準じ、シャーレ中の試験体（５ｃｍ×５ｃｍ）上に試験かび混合胞子を付着乾燥させた磁器素焼き板を置き、ガラス板を載せ蓋をする。２６±２℃で４週間培養し、菌糸の発育の様子を観察し、以下によって評価した。Ａ法培地は無機塩寒天培地であり、試験菌はＡｓｐｅｒｇｉｌｌｕｓ ｎｉｇｅｒ、Ｐｅｎｉｃｉｌｌｉｕｍ ｐｉｎｏｐｈｉｌｕｍ、Ｐａｅｃｉｌｏｍｙｃｅｓ ｖａｒｉｏｔｉｉ、Ｔｒｉｃｈｏｄｅｒｍａ ｖｉｒｅｎｓ、及びＣｈａｅｔｏｍｉｕｍ ｇｌｏｂｏｓｕｍである。
０：肉眼及び顕微鏡下でかびの発育は認められない。
１：肉眼でかびの発育が認められ、顕微鏡下では明らかに確認できる。
２：肉眼でかびの発育が認められ、発育部分の面積は試料の全面積の２５％未満。
３：肉眼でかびの発育が認められ、発育部分の面積は試料の全面積の２５％以上〜５０％未満。
４：菌糸はよく発育し、発育部分の面積は全面積の５０％以上。
５：菌糸の発育は激しく、試料全面を覆っている。
<Mold resistance>
For the cured product of the water-hard polymer cement composition of Examples and Comparative Examples after curing at 23 ° C. for 7 days, hot water at 95 ° C. was allowed to flow down for 5 minutes, and then cold water at 20 ° C. was allowed to flow down for 10 minutes. Cycled thermal shock was applied 100 times and 250 times, and the subsequent test piece was subjected to the JIS Z 2911 mold resistance test method (plastic product test (method A: dry method)), and the test piece in a petri dish (5 cm ×). Place a porcelain unglazed plate on which test mold and mixed spores were attached and dried, place a glass plate on it, and cover it. Incubate at 26 ± 2 ° C. for 4 weeks, observe the growth of mycelia, and evaluate by the following. The method A medium is an inorganic salt agar medium, and the test bacteria are Aspergillus niger, Penicillium pinophylum, Paecilomyces variotii, Trichoderma virens, and Chaetomium globosum.
0: No mold growth is observed with the naked eye or under a microscope.
1: Mold growth is observed with the naked eye and can be clearly confirmed under a microscope.
2: Mold growth is observed with the naked eye, and the area of the growth part is less than 25% of the total area of the sample.
3: Mold growth is observed with the naked eye, and the area of the growth part is 25% or more and less than 50% of the total area of the sample.
4: Mycelium grows well, and the area of the growing part is 50% or more of the total area.
5: Mycelium grows violently and covers the entire surface of the sample.
＜評価結果＞
評価結果を表２に示す。
<Evaluation result>
The evaluation results are shown in Table 2.
Claims (2)
The hydraulic polymer cement composition according to claim 1, further comprising a fungicide composed of a benzimidazole compound.
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