JP2023018554A - Aqueous coating material composition for substrate adjustment, and substrate adjustment method and coating material finishing structure using the same - Google Patents
Aqueous coating material composition for substrate adjustment, and substrate adjustment method and coating material finishing structure using the same Download PDFInfo
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- JP2023018554A JP2023018554A JP2021122765A JP2021122765A JP2023018554A JP 2023018554 A JP2023018554 A JP 2023018554A JP 2021122765 A JP2021122765 A JP 2021122765A JP 2021122765 A JP2021122765 A JP 2021122765A JP 2023018554 A JP2023018554 A JP 2023018554A
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- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000005002 finish coating Substances 0.000 description 1
- 239000011381 foam concrete Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010420 shell particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000011041 water permeability test Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、塗材仕上げ材が施工される下地の表面を調整する目的で使用する下地調整用水系塗材組成物、これを使用した下地調整工法、及び塗材仕上げ構造に関する。 TECHNICAL FIELD The present invention relates to a base preparation water-based coating composition used for the purpose of adjusting the surface of a base on which a coating finishing material is applied, a base preparation method using the same, and a coating finishing structure.
従来、建物の外壁等に施工する塗材仕上げは、下地調整材又は下塗り材、必要に応じて中塗り材、及び上塗り材を用いて仕上げられる。 BACKGROUND ART Conventionally, a coating material finish applied to an outer wall of a building or the like is finished using a substrate conditioning material or an undercoat material, and if necessary, an intermediate coating material and a top coating material.
特許文献1では、ガラス転移温度が-20℃ 以下の共重合体水分散液(A) を含む下地調整材(I)が提案されており、該下地調整材(I)の塗膜上に、共重合体のガラス転移温度が-60~0℃である共重合体水分散液(B)及び共重合体のガラス転移温度が15~50℃ である共重合体水分散液(C) を固形分質量比が(B)/(C)比で20/80~80/20の割合で含む上塗り塗料(II)を塗装することを特徴とする塗装仕上げ方法が提案されており、下地のひび割れなどに追従でき、防水性に優れることが示されている。しかしながら、特許文献1の下地調整材や上塗り塗料といった水系組成物は、塗膜形成過程において溶媒である水が蒸発することで樹脂の融着が生じるものであるが、水の蒸発速度は遅いために塗膜形成に時間を要し、速乾性がない場合があるという課題がある。また、水の蒸発速度が特に低下する低温環境においては、乾燥が不十分な塗膜を形成して塗膜形成不良が起こったり、水と樹脂の光の屈折率の違いによる塗膜の白化が生じたりする場合がある、という課題があった。 Patent Document 1 proposes a base conditioning material (I) containing a copolymer aqueous dispersion (A) having a glass transition temperature of −20° C. or lower, and on a coating film of the base conditioning material (I), An aqueous copolymer dispersion (B) having a copolymer glass transition temperature of −60 to 0° C. and an aqueous copolymer dispersion (C) having a copolymer glass transition temperature of 15 to 50° C. were solidified. A painting finishing method characterized by applying a topcoat paint (II) containing a partial mass ratio of 20/80 to 80/20 in the (B) / (C) ratio has been proposed. It is shown to be able to follow and to be excellent in waterproofness. However, water-based compositions such as the base conditioning material and the topcoat of Patent Document 1 cause fusion of the resin due to the evaporation of the solvent water during the coating film formation process, but the evaporation rate of water is slow. In addition, there is a problem that it takes time to form a coating film and there are cases where it does not dry quickly. In addition, in a low temperature environment where the evaporation rate of water is particularly low, the coating film is formed with insufficient drying, resulting in poor coating film formation, and whitening of the coating film due to the difference in the refractive index of light between water and resin. There was a problem that it may occur.
前記の課題を解決するため、特許文献2では、速乾性を有する交通用塗料に好適な保存安定性水性バインダー組成物として、(a)アニオン的に安定化されたポリマーの水性分散液と、(b)水溶性多官能性アミンポリマーと、(c)揮発性塩基中のフィロシリケートの懸濁液または分散液であって、前記フィロシリケートの濃度が、前記懸濁液または前記分散液の総重量に基づき、1重量%~18重量%である、揮発性塩基中のフィロシリケートの懸濁液または分散液と、を含む保存安定性水性組成物であって、前記揮発性塩基は、前記組成物が、実質的に全ての前記多官能性アミンポリマーが非イオン状態であるpHを有するような量で使用される、保存安定性水性組成物が提案されている。 In order to solve the above-mentioned problems, Patent Document 2 describes a storage-stable aqueous binder composition suitable for a traffic paint having a quick drying property, comprising (a) an anionically stabilized aqueous dispersion of a polymer, ( b) a water-soluble polyfunctional amine polymer; and (c) a suspension or dispersion of phyllosilicate in a volatile base, wherein the concentration of said phyllosilicate is the total weight of said suspension or said dispersion. a suspension or dispersion of a phyllosilicate in a volatile base, wherein the volatile base is from 1% to 18% by weight, based on is used in an amount such that substantially all of said polyfunctional amine polymer has a pH in the non-ionic state.
しかしながら、特許文献2の保存安定性水性組成物は、骨材を含まない場合等には水蒸気透過性がない場合があるという課題があり、これにより塗膜に膨れや剥がれが起きる場合があるという課題がある。 However, the storage-stable aqueous composition of Patent Document 2 has a problem that it may not have water vapor permeability when it does not contain aggregates, etc., and this may cause blistering and peeling of the coating film. I have a problem.
また、特許文献2の組成物は、無機系増粘剤である合成フィロシリケートを含有するため、製造時に予備混合が必要となり手間がかかるという課題があり、また均一に分散させるために長時間の高速攪拌を必要とする場合があり、結果として高コストになるという課題がある。また、合成フィロシリケートのような粘土系の材料を配合すると組成物に該材料の色味が付き、色調を調整しにくい場合や、隠蔽性と上塗り材の発色に悪影響を与える場合がある、という課題がある。 In addition, since the composition of Patent Document 2 contains a synthetic phyllosilicate that is an inorganic thickener, there is a problem that pre-mixing is required at the time of production, which is time-consuming. High-speed stirring may be required, resulting in a problem of high cost. In addition, if a clay-based material such as synthetic phyllosilicate is added to the composition, the color of the material will be added to the composition, making it difficult to adjust the color tone or adversely affecting the concealing properties and the color development of the topcoat material. I have a problem.
本発明が解決しようとする課題は、速乾性を有し、そのため低温環境での硬化性に優れ、良好な水蒸気透過性により下地に含まれる水分に起因して起こり得る塗膜の膨れや剥がれが生じることがなく、該水蒸気透過性を有するにも関わらず遮水性を併せ持ち、また下地追従性を有し、貯蔵安定性に優れ、増粘剤を配合するにあたり予備混合や長時間の高速攪拌が必要なく、またローラー刷毛による施工に適した粘度とTI値(チクソトロピックインデックス)を有する下地調整用水系塗材組成物、これを使用した下地調整工法、及び塗材仕上げ構造を提供することにある。 The problem to be solved by the present invention is that it has quick-drying properties, is therefore excellent in curability in a low-temperature environment, and has good water vapor permeability to prevent blistering and peeling of the coating film that may occur due to moisture contained in the substrate. In spite of having the water vapor permeability, it has water impermeability, also has substrate followability, is excellent in storage stability, and premixing and long-time high-speed stirring are required when blending the thickener. To provide a base preparation water-based coating material composition having a viscosity and a TI value (thixotropic index) suitable for application by a roller brush, a base preparation method using the same, and a coating finishing structure. .
上記課題を解決するために請求項1記載の発明は、ガラス転移温度が-20~10℃である架橋型アクリル樹脂系エマルジョンと、一次粒子径15~30nmのシリカ粒子を1個又は2個以上含むアクリル樹脂と乳化剤が形成する粒径60~120nmのミセルが水に分散して成るナノコンポジットエマルジョンと、水溶性カチオン化ポリマーと、沸点が100℃以下の揮発性塩基と、充填材と、有機系増粘剤と、成膜助剤と、顔料と、を含む組成物であり、
架橋型アクリル樹脂系エマルジョンの固形分とナノコンポジットエマルジョンの固形分の重量比は4~15:1であり、
前記シリカ粒子はナノコンポジットエマルジョン100重量部中10~20重量部であり、
水溶性カチオン化ポリマーの配合量は組成物全体100重量部中0.2~1.2重量部であり、
組成物全体のpHが9.5~11.5である、
ことを特徴とする下地調整用水系塗材組成物を提供する。
In order to solve the above problems, the invention according to claim 1 comprises a crosslinked acrylic resin emulsion having a glass transition temperature of −20 to 10° C. and one or more silica particles having a primary particle diameter of 15 to 30 nm. A nanocomposite emulsion in which micelles having a particle size of 60 to 120 nm formed by an acrylic resin and an emulsifier are dispersed in water, a water-soluble cationic polymer, a volatile base having a boiling point of 100 ° C. or less, a filler, an organic A composition comprising a system thickener, a film-forming aid, and a pigment,
The weight ratio of the solid content of the crosslinked acrylic resin emulsion to the solid content of the nanocomposite emulsion is 4 to 15:1,
The silica particles are 10 to 20 parts by weight in 100 parts by weight of the nanocomposite emulsion,
The amount of the water-soluble cationized polymer is 0.2 to 1.2 parts by weight in 100 parts by weight of the entire composition,
the pH of the entire composition is 9.5 to 11.5;
To provide a water-based coating material composition for base preparation characterized by:
請求項2記載の発明は、水溶性カチオン化ポリマーはポリアルキレンイミン化合物であることを特徴とする請求項1記載の下地調整用水系塗材組成物を提供する。 The invention according to claim 2 provides the water-based coating material composition for base preparation according to claim 1, wherein the water-soluble cationic polymer is a polyalkyleneimine compound.
請求項3記載の発明は、揮発性塩基はアンモニア、炭素数C1-C4の低級アルキルアミン、及びジメチルアミノメタノールの内いずれか一つ又は二つ以上の混合物から成ることを特徴とする請求項1又は請求項2記載の下地調整用水系塗材組成物を提供する。 The invention according to claim 3 is characterized in that the volatile base comprises any one or a mixture of two or more of ammonia, a C 1 -C 4 lower alkylamine, and dimethylaminomethanol. A water-based coating material composition for base preparation according to claim 1 or claim 2 is provided.
請求項4記載の発明は、有機系増粘剤は重量平均分子量(Mw)が10,000~35,000のウレタン変性ポリエーテルであることを特徴とする請求項1乃至請求項3のいずれか一つに記載の下地調整用水系塗材組成物を提供する。 The invention according to claim 4 is characterized in that the organic thickener is a urethane-modified polyether having a weight average molecular weight (Mw) of 10,000 to 35,000. In one aspect, a water-based coating material composition for base preparation is provided.
請求項5記載の発明は、組成物の粘度がBH型粘度計の2rpmにおいて60~150Pa・s/23℃であり、該BH型粘度計の2rpmにおける粘度を20rpmにおける粘度で除して求められる組成物のTI値が4~7であることを特徴とする請求項1乃至請求項4のいずれか一つに記載の下地調整用水系塗材組成物を提供する。 In the invention according to claim 5, the viscosity of the composition is 60 to 150 Pa s / 23 ° C. at 2 rpm of the BH type viscometer, and the viscosity at 2 rpm of the BH type viscometer is obtained by dividing the viscosity at 20 rpm. 5. The water-based coating material composition for base preparation according to any one of claims 1 to 4, characterized in that the composition has a TI value of 4 to 7.
請求項6記載の発明は、請求項1乃至請求項5のいずれか一つに記載の下地調整用水系塗材組成物を、塗付厚み0.15~0.5mmで下地に少なくとも2回塗付することを特徴とする下地調整工法を提供する。 In the invention according to claim 6, the water-based coating material composition for base preparation according to any one of claims 1 to 5 is applied to the base at least twice with a coating thickness of 0.15 to 0.5 mm. To provide a base preparation method characterized by attaching.
請求項7記載の発明は、請求項1乃至請求項5のいずれか一つに記載の下地調整用水系塗材組成物を塗付して形成される下地調整用水系塗材組成物層と、該下地調整用水系塗材組成物層の上に上塗り材を少なくとも1回塗付して形成される上塗り材層と、から形成されることを特徴とする塗材仕上げ構造を提供する。 The invention according to claim 7 is a base preparation water-based coating material composition layer formed by applying the base preparation water-based coating material composition according to any one of claims 1 to 5, and a topcoat material layer formed by applying a topcoat material at least once on the base conditioning water-based coating material composition layer.
本発明の下地調整用水系塗材組成物は、速乾性を有するという効果がある。これは、架橋型アクリル樹脂系エマルジョン及びナノコンポジットエマルジョン中のアクリル樹脂ポリマーを含有してアニオンに荷電するミセル(アニオン性ミセル)と、水溶性カチオン化ポリマーが電気的相互作用により凝集し、アクリル樹脂ポリマーの融着と定着を促すことに基づくものと推測している。該速乾性は、組成物中の水分が蒸発しにくい低温環境においても作用するため、一般の水系塗材組成物を低温環境で使用した際に起こり得る塗膜の白化や塗膜形成不良を抑制するという効果がある。また、本発明の下地調整用水系塗材組成物は、夏季等の高温環境下であっても作業性良く塗付できる時間(可使時間)を十分に有し、良好な塗付作業性を有しているという効果がある。 The base preparation water-based coating material composition of the present invention has the effect of having quick-drying properties. This is because anionically charged micelles (anionic micelles) containing acrylic resin polymers in crosslinked acrylic resin emulsions and nanocomposite emulsions and water-soluble cationized polymers are aggregated by electrical interaction to form acrylic resins. It is presumed that this is based on promoting fusion and fixation of the polymer. Since the quick-drying property works even in a low-temperature environment where water in the composition does not easily evaporate, it suppresses whitening of the coating film and poor coating film formation that can occur when using a general water-based coating material composition in a low-temperature environment. has the effect of In addition, the water-based coating material composition for base preparation of the present invention has a sufficient time (pot life) that can be applied with good workability even in high temperature environments such as summer, and has good coating workability. It has the effect of having
また、本発明の下地調整用水系塗材組成物は、水系塗材組成物であるにも関わらず緻密な塗膜を形成し、尚且つナノサイズのシリカ粒子を含むため、水蒸気透過性と遮水性を併せ持つという効果がある。ナノサイズのシリカ粒子は塗膜中に分散し、目視では確認できないサイズの細孔構造を形成するため、水蒸気が透過できる多孔質な塗膜となっていると推測している。 In addition, the water-based coating material composition for base preparation of the present invention forms a dense coating film in spite of being a water-based coating material composition, and contains nano-sized silica particles. It has the effect of having water. It is speculated that the nano-sized silica particles are dispersed in the coating film and form a pore structure of a size that cannot be visually confirmed, resulting in a porous coating film that allows water vapor to permeate.
該水蒸気透過性により、下地に含まれる水分は水蒸気として本組成物によって形成される塗膜を透過し放出される、若しくは塗膜連続方向に移動するため、塗膜の一部分に局所的に水蒸気圧がかかることがなく、また、何らかの原因で下地に水分が継続的に供給され該水分が塗膜との界面に集積しても、水分を水蒸気として塗膜の外、若しくは塗膜連続方向に逃がすことができるため、塗膜の膨れや剥がれの発生が抑制される(耐膨れ性)という効果がある。 Due to the water vapor permeability, the moisture contained in the substrate is released as water vapor through the coating film formed by the composition, or moves in the continuous direction of the coating film, so that the water vapor pressure is locally applied to a part of the coating film. In addition, even if moisture is continuously supplied to the substrate for some reason and the moisture accumulates at the interface with the coating film, the moisture is released as water vapor to the outside of the coating film or in the continuous direction of the coating film. Therefore, there is an effect that the occurrence of blistering and peeling of the coating film is suppressed (blistering resistance).
また、本発明の下地調整用水系塗材組成物は、ガラス転移温度が-20~10℃である架橋型アクリル樹脂系エマルジョンを使用するため伸び物性と下地追従性に優れているという効果があり、本発明の下地調整用水系塗材組成物の上にJISA 6909の建築用仕上塗材の規定に準ずる上塗り材を塗付して塗材仕上げ構造を形成したとしても、塗膜に剥がれやひび割れが起こりにくい、という効果がある。 In addition, since the water-based coating material composition for base preparation of the present invention uses a crosslinked acrylic resin emulsion having a glass transition temperature of −20 to 10° C., it has the effect of being excellent in elongation physical properties and base conformability. , Even if a topcoat material conforming to the provisions of JISA 6909 architectural finish coating material is applied on the water-based coating material composition for base preparation of the present invention to form a coating material finish structure, the coating film will not peel off or crack. has the effect of making it difficult for
また、本発明の下地調整用水系塗材組成物は無機系増粘剤ではなく有機系増粘剤を使用するため、製造時における予備混合や長時間の高速攪拌を要さず、結果として低コストであるという効果がある。また、該有機系増粘剤により、本発明の下地調整用水系塗材組成物の粘度を60~150Pa・s/23℃、TI値を4~7とすることで、ローラー刷毛等の施工道具を使用して建物の外壁のような垂直な下地に、1回の塗布厚が0.15~0.5mmとなるように作業性良く塗付することができる効果がある。 In addition, since the water-based coating material composition for base preparation of the present invention uses an organic thickener instead of an inorganic thickener, it does not require premixing or high-speed stirring for a long time during production, resulting in a low There is an effect that it is a cost. In addition, the viscosity of the water-based coating material composition for base preparation of the present invention is adjusted to 60 to 150 Pa·s/23°C and the TI value to 4 to 7 with the organic thickener, so that construction tools such as roller brushes can be used. can be applied to a vertical substrate such as the outer wall of a building with good workability so that the thickness of one application is 0.15 to 0.5 mm.
また、請求項6記載の下地調整工法は、塗付厚み0.15~0.5mmで少なくとも2回に分けて塗付することにより、優れた水蒸気透過性と遮水性が共に十分に発揮されるだけの塗付厚みを、ダレを生じさせずに塗付作業性良く確保できるという効果がある。加えて、下地の不陸が大きく、例えば0.5mm超の不陸があっても、水蒸気透過性と遮水性を損なわずに下地の大きな不陸を調整することができる、という効果がある。 In addition, in the substrate preparation method of claim 6, both excellent water vapor permeability and water impermeability are sufficiently exhibited by applying at least two times with a coating thickness of 0.15 to 0.5 mm. There is an effect that the coating thickness of only can be secured with good coating workability without causing sagging. In addition, even if the substrate has a large unevenness, for example, an unevenness exceeding 0.5 mm, there is an effect that the large unevenness of the substrate can be adjusted without impairing the water vapor permeability and water impermeability.
請求項7記載の塗材仕上げ構造は、水蒸気透過性と下地追従性に優れる下地調整材層を有するため、膨れや剥がれが起こりにくい、という効果がある。前記のとおり、該下地調整材層は水蒸気透過性を有しており、該水蒸気透過性は塗膜の厚み方向だけでなく塗膜の連続方向にも水蒸気を透過する。そのため、塗材仕上げ構造を形成する上塗り材層が水蒸気透過性を有する場合は勿論のこと、有さない場合においても下地に含まれる水分に係る水蒸気を塗膜の連続方向に逃がすことができるため、塗材仕上げ構造の一部分に局所的に水蒸気圧がかかることがなく、また、何らかの原因で下地に水分が継続的に供給され該水分が塗膜との界面に集積しても、水分を水蒸気として塗膜の連続方向に逃がすことができるため、これらの影響によっては膨れや剥がれが起こらないという効果がある。 The coating material finishing structure according to claim 7 has the base conditioning material layer which is excellent in water vapor permeability and base conformability, so that there is an effect that swelling and peeling are less likely to occur. As described above, the base conditioning material layer has water vapor permeability, and the water vapor permeability allows water vapor to permeate not only in the thickness direction of the coating film but also in the continuous direction of the coating film. Therefore, not only when the topcoat material layer forming the coating material finish structure has water vapor permeability, but also when it does not have water vapor permeability, water vapor related to moisture contained in the base can be released in the continuous direction of the coating film. In addition, even if moisture is continuously supplied to the substrate for some reason and accumulates at the interface with the coating film, the moisture can be removed by steam. As a result, it is possible to escape in the continuous direction of the coating film, so there is an effect that swelling and peeling do not occur due to these influences.
以下、本発明について詳細に説明する。 The present invention will be described in detail below.
本発明の下地調整用水系塗材組成物は、ガラス転移温度が-20~10℃である架橋型アクリル樹脂系エマルジョンと、一次粒子径15~30nmのシリカ粒子を1個又は2個以上含むアクリル樹脂と乳化剤が形成する粒径60~120nmのミセルが水に分散して成るナノコンポジットエマルジョンと、水溶性カチオン化ポリマーと、沸点が100℃以下の揮発性塩基と、充填材と、有機系増粘剤と、成膜助剤と、顔料と、を含む組成物であり、架橋型アクリル樹脂系エマルジョンの固形分とナノコンポジットエマルジョンの固形分の重量比は4~15:1であり、前記シリカ粒子はナノコンポジットエマルジョン100重量部中10~20重量部であり、水溶性カチオン化ポリマーの配合量は組成物全体100重量部中0.2~1.2重量部であり、組成物全体のpHが9.5~11.5である、ことを特徴とする下地調整用水系塗材組成物であり、必要に応じてこれらの他に、分散剤、消泡剤、防腐剤、凍結防止剤等の添加剤を配合することができる。 The water-based coating material composition for base preparation of the present invention is a crosslinked acrylic resin emulsion having a glass transition temperature of −20 to 10° C. and an acrylic resin containing one or more silica particles having a primary particle diameter of 15 to 30 nm. A nanocomposite emulsion formed by dispersing micelles with a particle size of 60 to 120 nm formed by a resin and an emulsifier in water, a water-soluble cationic polymer, a volatile base having a boiling point of 100 ° C. or less, a filler, and an organic additive. A composition comprising a viscosity agent, a film-forming aid, and a pigment, wherein the weight ratio of the solid content of the crosslinked acrylic resin emulsion to the solid content of the nanocomposite emulsion is 4 to 15:1, and the silica The particles are 10 to 20 parts by weight in 100 parts by weight of the nanocomposite emulsion, the amount of the water-soluble cationic polymer is 0.2 to 1.2 parts by weight in 100 parts by weight of the entire composition, and the pH of the composition as a whole is is 9.5 to 11.5. of additives can be blended.
<架橋型アクリル樹脂系エマルジョン>
本発明に使用する架橋型アクリル樹脂系エマルジョンは、本発明の下地調整用水系塗材組成物を構成する主成分であって、乳化剤により乳化されてミセルを形成するアクリル樹脂が、ヒドラジン誘導体のような水溶性の架橋剤と共に水に分散されてエマルジョンを成している水系樹脂であり、伸び物性の向上や塗膜を緻密にすることで遮水性を向上させる目的で架橋型を使用する。該乳化剤としては、親水性基にカルボン酸、スルホン酸、或いはリン酸等を有し、水溶液中でアニオンに荷電するアニオン性乳化剤を使用することができ、このため本発明に使用する架橋型アクリル樹脂系エマルジョンを構成するミセルはアニオンに荷電している。
<Crosslinked acrylic resin emulsion>
The crosslinked acrylic resin emulsion used in the present invention is a main component constituting the water-based coating material composition for base preparation of the present invention, and the acrylic resin emulsified by an emulsifier to form micelles is an acrylic resin such as a hydrazine derivative. It is a water-based resin that is dispersed in water together with a water-soluble cross-linking agent to form an emulsion. As the emulsifier, it is possible to use an anionic emulsifier that has a hydrophilic group such as carboxylic acid, sulfonic acid, or phosphoric acid and is anionically charged in an aqueous solution. The micelles that make up the resin emulsion are anionically charged.
アクリル樹脂には、アクリル酸エステル系共重合樹脂、酢酸ビニル・アクリル酸エステル系共重合樹脂、シリコン変性アクリル樹脂等を使用することができる。アクリル樹脂とするアクリル系単量体としては、メチルアクリレート、エチルアクリレート、n-プロピルアクリレート、イソプロピルアクリレート、n-ブチルアクリレート、イソブチルアクリレート、sec-ブチルアクリレート、t-ブチルアクリレート、ヘキシルアクリレート、2-エチルヘキシルアクリレート、オクチルアクリレート、ノニルアクリレート、デシルアクリレート、ドデシルアクリレート、n-アミルアクリレート、イソアミルアクリレート、ラウリルアクリレート、ステアリルアクリレート、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、ドデシル(メタ)アクリレート、n-アミル(メタ)アクリレート、イソアミル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート、メトキシエチル(メタ)アクリレート、エトキシエチル(メタ)アクリレート、メトキシプロピル(メタ)アクリレート、エトキシプロピル(メタ)アクリレート、等を使用することが出来、1種単独で使用することも、あるいは2種以上を混合して使用することもできる。他の不飽和単量体としては、スチレン、α-メチルスチレン、クロロスチレン、ビニルトルエン、メトキシスチレン等のスチレン誘導体;(メタ)アクリル酸、フマル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、及びクロトン酸等のカルボキシル基含有単量体;(メタ)アクリル酸や、クロトン酸、イタコン酸;2-ヒドロキシエチル(メタ)アクリレートや、2(3)-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチルアクリレート、アリルアルコール、多価アルコールのモノ(メタ)アクリル酸エステル等の水酸基含有単量体;(メタ)アクリルアミドや、マレインアミド等のアミド基含有単量体;2-アミノエチル(メタ)アクリレートや、ジメチルアミノエチル(メタ)アクリレート、3-アミノプロピル(メタ)アクリレート、2-ブチルアミノエチル(メタ)アクリレート、ビニルピリジン等のアミノ基含有単量体;グリシジル(メタ)アクリレートや、アリルグリシジルエーテル、2個以上のグリシジル基を有するエポキシ化合物と活性水素原子を有するエチレン性不飽和単量体との反応により得られるエポキシ基含有単量体やオリゴノマー;ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン、3-(メタ)アクリロキシプロピルトリメトキシシラン、3-(メタ)アクリロキシプロピルトリエトキシシラン、2-(メタ)アクリロキシエチルトリメトキシシラン、2-(メタ)アクリロキシエチルトリエトキシシラン、3-(メタ)アクリロキシプロピルメチルジメトキシシラン、3-(メタ)アクリロキシプロピルメチルジエトキシシラン、3-(メタ)アクリロキシプロピルメチルジプロポキシシラン、3-(メタ)アクリロキシブチルフェニルジメトキシシラン、3-(メタ)アクリロキシプロピルジメチルメトキシシラン、及び3-(メタ)アクリロキシプロピルジエチルメトキシシラン等のアルコキシシリル基含有単量体;その他、酢酸ビニル、塩化ビニル、更には、エチレン、ブタジエン、アクリロニトリル、ジアルキルフマレート等を使用することが出来、1種単独で使用することも、あるいは2種以上を混合して用いることもできる。 Examples of acrylic resins that can be used include acrylate-based copolymer resins, vinyl acetate/acrylate-based copolymer resins, and silicon-modified acrylic resins. Examples of acrylic monomers for acrylic resins include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, t-butyl acrylate, hexyl acrylate, and 2-ethylhexyl. Acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, n-amyl acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl ( meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl ( meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl ( Meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate, etc. can be used. It can be used either singly or in combination of two or more. Other unsaturated monomers include styrene derivatives such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene, methoxystyrene; (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, anhydride; Carboxyl group-containing monomers such as itaconic acid and crotonic acid; (meth)acrylic acid, crotonic acid, itaconic acid; 2-hydroxyethyl (meth)acrylate and 2(3)-hydroxypropyl (meth)acrylate, Hydroxy group-containing monomers such as 4-hydroxybutyl acrylate, allyl alcohol, mono (meth) acrylic acid esters of polyhydric alcohols; (meth) acrylamide and amide group-containing monomers such as maleamide; 2-aminoethyl ( meth) acrylate, dimethylaminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-butylaminoethyl (meth) acrylate, amino group-containing monomers such as vinylpyridine; glycidyl (meth) acrylate, Allyl glycidyl ether, epoxy group-containing monomers and oligomers obtained by reacting an epoxy compound having two or more glycidyl groups with an ethylenically unsaturated monomer having an active hydrogen atom; vinyltrimethoxysilane, vinyltriethoxy silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 2-(meth)acryloxyethyltrimethoxysilane, 2 -(meth)acryloxyethyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropylmethyldipropoxysilane, 3 -Alkoxysilyl group-containing monomers such as (meth)acryloxybutylphenyldimethoxysilane, 3-(meth)acryloxypropyldimethylmethoxysilane, and 3-(meth)acryloxypropyldimethylmethoxysilane; in addition, vinyl acetate, Vinyl chloride, and further ethylene, butadiene, acrylonitrile, dialkyl fumarate, etc. can be used, and they can be used singly or in combination of two or more.
架橋剤は、カルボニルヒドラジンであるアジピン酸ジヒドラジド、グルタル酸ジヒドラジド、イソフタル酸ジヒドラジド、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、セバシン酸ジヒドラジド、マレイン酸ジヒドラジド、フマル酸ジヒドラジド、イタコン酸ジヒドラジド等があり、又はアルキルヒドラジドであるエチレン-1,2-ジヒドラジン、プロピレン-1,3-ジヒドラジン、ブチレン-1,4-ジヒドラジド等のヒドラジン誘導体があり、これらを1種単独、あるいは2種以上を混合して使用することができる。架橋剤の配合量は、架橋型アクリル樹脂系エマルジョン100重量部中0.05~2.0重量部であることが好ましく、0.05重量部未満では伸び物性が低下する場合があり、2.0重量部超では、塗膜が緻密となり過ぎて水蒸気透過性が低下する場合がある。 Cross-linking agents include carbonyl hydrazine adipic acid dihydrazide, glutaric acid dihydrazide, isophthalic acid dihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, and itaconic acid dihydrazide. or hydrazine derivatives such as ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, and butylene-1,4-dihydrazide, which are alkyl hydrazides. can be used as The content of the cross-linking agent is preferably 0.05 to 2.0 parts by weight per 100 parts by weight of the cross-linkable acrylic resin emulsion. If it exceeds 0 parts by weight, the coating film may become too dense and the water vapor permeability may decrease.
本発明の架橋型アクリル樹脂系エマルジョンを構成するアクリル樹脂のガラス転移温度は-20~10℃であることが好ましい。ガラス転移温度が-20℃未満の場合、本発明の下地調整用水系塗材組成物の上に塗付する上塗り材によっては、該上塗り材にひび割れが生じる場合がある。これは、一般的な上塗り材のガラス転移温度は20℃程度であることが多く、本発明の下地調整用水系塗材組成物と上塗り材のガラス転移温度の差がおおよそ30~40℃を超えると、下地の動きに追従する本発明の下地調整用水系塗材組成物の動きに上塗り材が追従できず、遂には該上塗り材にひび割れが生じる場合があると考えられることに基づいている。なお、該ひび割れは、上塗り材が塗材のような数mm程度に比較的厚く塗付されるものであると生じにくい傾向にあるが、塗料のような数十μm程度に比較的薄く塗付されるものであると顕著に生じる傾向にある。一方、本発明の架橋型アクリル樹脂系エマルジョンを構成するアクリル樹脂のガラス転移温度が10℃超の場合は下地追従性が低下する場合がある。ここでいうガラス転移温度は、示差走査熱量計(Differentialscanning calorimetry、DSC)によって測定される値である。また、本発明の架橋型アクリル樹脂系エマルジョンの固形分は下地調整用水系塗材組成物100重量部中の10~30重量部が好ましく、10重量部未満では種々の塗膜強度が低下し、また30重量部超では塗付作業性が低下する。 The glass transition temperature of the acrylic resin constituting the crosslinked acrylic resin emulsion of the present invention is preferably -20 to 10°C. If the glass transition temperature is less than −20° C., cracks may occur in the topcoat material applied on top of the water-based coating material composition for base preparation of the present invention, depending on the topcoat material. This is because the glass transition temperature of common topcoat materials is often about 20 ° C., and the difference in glass transition temperature between the water-based coating material composition for base preparation of the present invention and the topcoat material exceeds about 30 to 40 ° C. This is based on the fact that the topcoat material cannot follow the movement of the water-based coating material composition for base preparation of the present invention that follows the movement of the base, and cracks may eventually occur in the topcoat material. The cracks tend not to occur when the topcoat material is applied relatively thickly to about several millimeters like the coating material, but when it is applied relatively thinly to about several tens of microns like the paint. It tends to occur remarkably when it is done. On the other hand, if the glass transition temperature of the acrylic resin constituting the crosslinked acrylic resin-based emulsion of the present invention is higher than 10° C., the followability to the base may deteriorate. The glass transition temperature referred to here is a value measured by a differential scanning calorimetry (DSC). The solid content of the crosslinkable acrylic resin emulsion of the present invention is preferably 10 to 30 parts by weight in 100 parts by weight of the water-based coating material composition for base preparation. On the other hand, if it exceeds 30 parts by weight, the coating workability is lowered.
<ナノコンポジットエマルジョン>
本発明に使用するナノコンポジットエマルジョンは、一次粒子径が15~30nmのシリカ粒子を1個又は2個以上含むアクリル樹脂が、乳化剤の作用により乳化して60~120nmのミセルを形成し、該ミセルが水に分散することで成る水系樹脂である。該乳化剤としては、親水性基にカルボン酸、スルホン酸、或いはリン酸等を有し水溶液中でアニオンに荷電するアニオン性乳化剤を使用することができ、このため本発明に使用するナノコンポジットエマルジョンを構成するミセルはアニオンに荷電している。
<Nanocomposite emulsion>
The nanocomposite emulsion used in the present invention is an acrylic resin containing one or more silica particles having a primary particle size of 15 to 30 nm, which is emulsified by the action of an emulsifier to form micelles of 60 to 120 nm. is a water-based resin that is dispersed in water. As the emulsifier, it is possible to use an anionic emulsifier which has a hydrophilic group such as carboxylic acid, sulfonic acid, or phosphoric acid and is anionically charged in an aqueous solution. The constituent micelles are anionically charged.
ナノコンポジットエマルジョンは、本発明の下地調整用水系塗材組成物に水蒸気透過性を付与する目的で含有しており、該水蒸気透過性はナノコンポジットエマルジョンに含まれるナノサイズのシリカ粒子により、水蒸気が透過できる細孔構造を形成させ、該シリカ粒子の表面に沿って水蒸気が移動することで発現されていると推測している。 The nanocomposite emulsion is contained for the purpose of imparting water vapor permeability to the water-based coating material composition for base preparation of the present invention. It is presumed that this is achieved by forming a permeable pore structure and allowing water vapor to move along the surface of the silica particles.
アクリル樹脂は段落[0026]に記載のものを使用できる。また、シリカ粒子としては、一次粒子径が15~30nmのナノサイズであればよく、粒子表面に存在するSiOH基が無修飾のもの、及びアミノ基やカルボキシル基等により表面修飾したものを使用することができ、特に限定されない。ナノサイズのシリカ粒子を含むアクリル樹脂の作製方法としては、例えば、ミニエマルション重合といって、超音波照射などの方法で該シリカ粒子を含んだサブミクロンサイズのモノマー油滴(ミニエマルション)を生成し、モノマー油滴をそのまま重合させ、サブミクロンサイズの高分子微粒子に変換させる方法がある。また、該シリカ粒子の表面にグラフト重合により高分子を成長させる方法もあり、該シリカ粒子の表面をアクリルモノマー系シランカップリング剤で修飾したものを用いてエマルション重合を行い、コア-アクリルシェル粒子におけるシェル高分子層を成長させて得るものである。これらの方法によりナノサイズのシリカ粒子を含むアクリル樹脂を調整する際には、該シリカ粒子を1個だけ含む場合もあれば2個以上含む場合もあり、アクリル樹脂と該シリカ粒子の重量比が平均して1:3~3:1となればよく、この重量比は作製方法、アクリル樹脂の種類、及び用いる添加剤等によりコントロールすることができる。また、ナノコンポジットエマルジョン100重量部中の該シリカ粒子の量は10~20重量部であることが好ましく、10重量部未満では、水蒸気透過性が得られない場合があり、20重量部超では伸び物性や遮水性が低下する場合がある。 The acrylic resin described in paragraph [0026] can be used. In addition, the silica particles may have a nano-sized primary particle diameter of 15 to 30 nm, and the SiOH groups present on the particle surface are unmodified, and those surface-modified with amino groups, carboxyl groups, etc. are used. can be used, and is not particularly limited. As a method for producing an acrylic resin containing nano-sized silica particles, for example, mini-emulsion polymerization is used to generate submicron-sized monomer oil droplets (mini-emulsion) containing the silica particles by a method such as ultrasonic irradiation. However, there is a method in which the monomer oil droplets are polymerized as they are to convert them into submicron-sized polymer fine particles. In addition, there is also a method of growing a polymer on the surface of the silica particles by graft polymerization, in which the surface of the silica particles is modified with an acrylic monomer-based silane coupling agent, emulsion polymerization is performed, and core-acrylic shell particles are obtained. obtained by growing a shell polymer layer in When preparing an acrylic resin containing nano-sized silica particles by these methods, it may contain only one silica particle or may contain two or more silica particles, and the weight ratio of the acrylic resin to the silica particles is The weight ratio should be 1:3 to 3:1 on average, and this weight ratio can be controlled by the production method, the type of acrylic resin, the additives used, and the like. In addition, the amount of the silica particles in 100 parts by weight of the nanocomposite emulsion is preferably 10 to 20 parts by weight. Physical properties and water impermeability may deteriorate.
ナノコンポジットエマルジョンの配合量は、前記の架橋型アクリル樹脂系エマルジョンの固形分とナノコンポジットエマルジョンの固形分の重量比が4~15:1となる量であることが好ましい。ナノコンポジットエマルジョンの固形分がこの範囲より少なくなると、結果としてナノサイズのシリカ粒子の含有量が少なくなり水蒸気透過性が損なわれる場合があり、またナノコンポジットエマルジョンの固形分がこの範囲より多くなると、結果として該シリカ粒子の含有量が過多となり、塗膜の緻密性が低下して遮水性を低下させる場合がある。 The amount of the nanocomposite emulsion to be blended is preferably such that the weight ratio of the solid content of the crosslinked acrylic resin emulsion to the solid content of the nanocomposite emulsion is 4 to 15:1. If the solids content of the nanocomposite emulsion is less than this range, the content of nano-sized silica particles may be reduced and the water vapor permeability may be impaired. As a result, the content of the silica particles becomes excessive, and the denseness of the coating film may be lowered, thereby lowering the water impermeability.
<水溶性カチオン化ポリマー>
本発明に使用する水溶性カチオン化ポリマーは、速乾性を付与する目的で配合しており、具体的には、架橋型アクリル樹脂系エマルジョン及びナノコンポジットエマルジョンを構成するアニオン性乳化剤の作用によってアニオンに荷電しているミセル(アニオン性ミセル)と電気的相互作用することで、一般的な水系組成物の塗膜形成過程における水の蒸発による樹脂の融着を待たずに、樹脂同士の凝集を促して塗膜形成反応を促進させる。水溶性カチオン化ポリマーは、組成物を塗付する前の状態では後述する揮発性塩基との相互作用により全てのカチオン性官能基は見かけ上は中性の状態であり、該アニオン性ミセルと電気的相互作用を起こさず、製造時や貯蔵時に組成物が凝集しないようにコントロールされている。
<Water-soluble cationized polymer>
The water-soluble cationic polymer used in the present invention is blended for the purpose of imparting quick-drying properties. By electrically interacting with charged micelles (anionic micelles), it promotes cohesion of resins without waiting for fusion of resins due to evaporation of water in the coating film formation process of general water-based compositions. promotes the film-forming reaction. In the water-soluble cationic polymer, all the cationic functional groups are apparently in a neutral state due to the interaction with the volatile base described later in the state before the composition is applied, and the anionic micelles and the electricity chemical interactions and is controlled so that the composition does not agglomerate during manufacture and storage.
本発明の水溶性カチオン化ポリマーは、カチオン性官能基を有するポリマーであれば特に限定されず、例えば、アミノ基を有するポリアルキレンイミン化合物、ポリアミド化合物、アミノスルホポリエステル化合物、ポリアリルアミン化合物、ポリビニルアミン化合物、およびこれらを変性させた塩基性含窒素ポリマー等が使用できる。好ましくはイミン化合物をイオン重合させることで得られるポリアルキレンイミン化合物であり、中でもエチレンイミンを重合させたポリエチレンイミンは分子中のカチオン性官能基の比率が大きいため特に好ましい。分子量は、ゲル浸透クロマトグラフィー(GelPermeation Chromatography、GPC)による測定で重量平均分子量(Mw)が600~200,000のものが好ましく、重量平均分子量(Mw)が大きくなると添加剤としての粘度が高くなり取り扱いづらいため、より好ましくは重量平均分子量(Mw)が600~100,000のものである。600未満では架橋型アクリル樹脂系エマルジョン及びナノコンポジットエマルジョン中のアニオン性ミセルとの凝集性が低下することにより速乾性が低下する場合があり、100,000超では冬季等の低温環境において添加剤としての粘度が高くなり取り扱いづらくなる傾向がある。 The water-soluble cationic polymer of the present invention is not particularly limited as long as it is a polymer having a cationic functional group. Compounds, basic nitrogen-containing polymers obtained by modifying these compounds, and the like can be used. A polyalkyleneimine compound obtained by ionically polymerizing an imine compound is preferred, and polyethyleneimine obtained by polymerizing ethyleneimine is particularly preferred because it has a large ratio of cationic functional groups in the molecule. The molecular weight preferably has a weight average molecular weight (Mw) of 600 to 200,000 as measured by gel permeation chromatography (GPC), and the higher the weight average molecular weight (Mw), the higher the viscosity as an additive. Since it is difficult to handle, it is more preferable that the weight average molecular weight (Mw) is 600 to 100,000. If it is less than 600, the cohesiveness with the anionic micelles in the crosslinked acrylic resin emulsion and nanocomposite emulsion may be reduced, resulting in a decrease in quick-drying properties. tends to be difficult to handle due to its high viscosity.
水溶性カチオン化ポリマーの配合量は、その種類や分子量、分子中のカチオン性官能基の比率に応じて適宜調整されるものであるが、本発明の下地調整用水系塗材組成物においては下地調整用水系塗材組成物100重量部中0.2~1.2重量部が好ましい。0.2重量部未満では速乾性が低下する場合があり、1.2重量部超では可使時間が短くなり塗付作業性に悪影響を与える場合がある。 The amount of the water-soluble cationic polymer blended is appropriately adjusted according to the type, molecular weight, and ratio of cationic functional groups in the molecule. It is preferably 0.2 to 1.2 parts by weight in 100 parts by weight of the water-based coating material composition for adjustment. If it is less than 0.2 parts by weight, the quick-drying property may deteriorate, and if it exceeds 1.2 parts by weight, the pot life may be shortened and the workability of coating may be adversely affected.
<揮発性塩基>
本発明で使用する揮発性塩基は、本発明の下地調整用水系塗材組成物が製造されて下地に塗付されるまでの間、前記の水溶性カチオン化ポリマーのカチオン性官能基と相互作用することでカチオン性官能基を見かけ上、中性の状態とし、架橋型アクリル樹脂系エマルジョン及びナノコンポジットエマルジョン中のアニオン性ミセルとの凝集を抑制し、組成物の貯蔵安定性を向上させる目的で配合する。揮発性塩基とは、標準気圧(1気圧または760mm/Hg)で大気中に容易に揮発する塩基を指し、アンモニア、モルホリン、炭素数C1-C5の低級アルキルアミン、ジメチルアミノメタノール、2-ジメチルアミノエタノール、N-メチルモルホリン、エチレンジアミン、またはそれらの混合物等が挙げられ、揮発性塩基は通常、水溶液の形態である。本発明の下地調整用水系塗材組成物においては、速乾性を十分なものとするために沸点が100℃以下の揮発性塩基を使用することがより好ましく、具体的にはアンモニア、炭素数C1-C4の低級アルキルアミン、ジメチルアミノメタノール等が挙げられる。特にアンモニアの水溶液は安価であり低コストである。
<Volatile base>
The volatile base used in the present invention interacts with the cationic functional group of the water-soluble cationic polymer during the period from the time the water-based coating material composition for base preparation of the present invention is produced until it is applied to the base. By doing so, the cationic functional group appears to be in a neutral state, suppressing aggregation with the anionic micelles in the crosslinked acrylic resin emulsion and nanocomposite emulsion, and improving the storage stability of the composition. Blend. Volatile base refers to a base that easily volatilizes into the atmosphere at standard atmospheric pressure (1 atm or 760 mm/Hg), and includes ammonia, morpholine, lower alkylamines having a carbon number of C 1 to C 5 , dimethylaminomethanol, 2- Examples include dimethylaminoethanol, N-methylmorpholine, ethylenediamine, or mixtures thereof, and the volatile base is usually in the form of an aqueous solution. In the water-based coating material composition for base preparation of the present invention, it is more preferable to use a volatile base having a boiling point of 100 ° C. or less in order to achieve sufficient quick drying, specifically ammonia, carbon number C 1 - C4 lower alkylamines, dimethylaminomethanol and the like. In particular, aqueous solutions of ammonia are inexpensive and low cost.
揮発性塩基の配合量は、本発明の下地調整用水系塗材組成物のpHが9.5~11.5となる量であることが好ましく、使用する揮発性塩基の塩基性に左右される。pHが9.5未満となる量であると貯蔵安定性が低下する場合があり、pHが11.5超となる量であると揮発性塩基が揮発するのに時間を要して速乾性が低下する場合や、揮発した塩基の臭気が激しくなり作業環境に悪影響を与える場合がある。 The amount of the volatile base to be blended is preferably such that the water-based coating composition for base preparation of the present invention has a pH of 9.5 to 11.5, and depends on the basicity of the volatile base used. . If the pH is less than 9.5, the storage stability may decrease. In some cases, the odor of the volatilized base becomes stronger, adversely affecting the working environment.
また、揮発性塩基は水に溶解させると水の凝固点を降下させるため、水を溶媒とする本発明の下地調整用水系塗材組成物においては凍結防止剤としての効果も有する。本効果は市販の凍結防止剤と併用することで相乗的に凍結防止効果を向上させる効果を有する。 In addition, since the volatile base lowers the freezing point of water when dissolved in water, it also has an antifreezing effect in the water-based base preparation coating material composition of the present invention, which uses water as a solvent. This effect has the effect of synergistically improving the antifreezing effect when used in combination with a commercially available antifreeze agent.
<充填材>
本発明の充填材は、平均粒径D50(重量による積算50%の粒径)が100μm未満のものを言い、組成物全体100重量部中5重量部以下の量で配合されて増粘剤としても扱われる合成層状シリケートは含まない。組成物の粘度や塗付性の調整を目的として配合し、重質炭酸カルシウム、クレー、カオリン、タルク、沈降性硫酸バリウム、炭酸バリウム、硅砂粉等が使用でき、中でも重質炭酸カルシウムは安価でコスト的負担を軽減させることが出来る。充填材の配合量は下地調整用水系塗材組成物全体100重量部中の25~45重量部が好ましく、より好ましくは30~40重量部であり、25重量部未満では下地の色が透けるなどの隠蔽性が不足し、45重量部超では組成物の粘度が高くなって塗付作業性が不良となる場合がある。また、30重量部未満では色調によっては隠蔽性が低下する場合があり、40重量部超では冬季等の低温環境下での塗付作業性が低下する傾向にある。
<Filling material>
The filler of the present invention has an average particle size D50 (particle size of 50% accumulated by weight) of less than 100 μm, and is blended in an amount of 5 parts by weight or less per 100 parts by weight of the entire composition as a thickener. It does not include synthetic layered silicates, which are also treated. It is blended for the purpose of adjusting the viscosity and applicability of the composition, and can be used with heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, silica sand powder, etc. Among them, heavy calcium carbonate is inexpensive. Cost burden can be reduced. The amount of the filler compounded is preferably 25 to 45 parts by weight, more preferably 30 to 40 parts by weight, based on 100 parts by weight of the entire base preparation water-based coating material composition. If the amount exceeds 45 parts by weight, the viscosity of the composition may become high, resulting in poor coating workability. On the other hand, if it is less than 30 parts by weight, the opacifying property may deteriorate depending on the color tone.
<有機系増粘剤>
本発明の有機系増粘剤は、塗付作業性の向上と、保水性を向上させ貯蔵中の組成物の凝集を防ぐことを目的として配合し、本発明の下地調整用水系塗材組成物の粘度を60~150Pa・s/23℃、TI値を4~7とするものであれば特には限定されず、水溶性セルロースエーテル、ウレタン変性ポリエーテル、ポリカルボン酸、またはこれらを混合したもの等を使用することができる。本発明の下地調整用水系塗材組成物は貯蔵安定性の観点から組成物のpHを9.5~11.5の範囲内に保つことが好ましいため、有機系増粘剤としては組成物のpHに影響を与えにくいウレタン変性ポリエーテルを使用することが好ましい。勿論、pHを低下させる等の影響を与え得るその他の有機系増粘剤を使用したとしても、前記の揮発性塩基の配合量を調整することにより、組成物のpHを9.5~11.5の範囲内に調整することができれば、いずれも問題なく使用できる。
<Organic Thickener>
The organic thickener of the present invention is blended for the purpose of improving coating workability and preventing aggregation of the composition during storage by improving water retention, and the water-based coating material composition for base preparation of the present invention. is not particularly limited as long as it has a viscosity of 60 to 150 Pa·s/23° C. and a TI value of 4 to 7, and water-soluble cellulose ether, urethane-modified polyether, polycarboxylic acid, or a mixture thereof etc. can be used. From the viewpoint of storage stability, the water-based coating material composition for base preparation of the present invention preferably maintains the pH of the composition within the range of 9.5 to 11.5. It is preferable to use a urethane-modified polyether that does not easily affect pH. Of course, even if other organic thickeners that can affect the pH such as lowering the pH are used, the pH of the composition can be adjusted from 9.5 to 11.5 by adjusting the blending amount of the volatile base. If it can be adjusted within the range of 5, both can be used without problems.
本発明の有機系増粘剤の配合量は、下地調整用水系塗材組成物100重量部中の0.1~5.0重量部が好ましく、0.1重量部未満では十分な増粘効果が得られず組成物を塗付した際にダレの原因となり、5.0重量部超では塗付作業性が低下する場合がある。また、有機系増粘剤はゲル浸透クロマトグラフィー(GelPermeation Chromatography、GPC)により測定される重量平均分子量(Mw)が10,000~35,000であることが好ましく、10,000未満であると増粘効果が不十分となる場合があり、35,000超であると過剰に増粘し塗付作業性に悪影響となる場合がある。 The amount of the organic thickener of the present invention is preferably 0.1 to 5.0 parts by weight in 100 parts by weight of the water-based coating material composition for base preparation, and if it is less than 0.1 part by weight, a sufficient thickening effect is obtained. is not obtained, causing sagging when the composition is applied. In addition, the organic thickener preferably has a weight average molecular weight (Mw) of 10,000 to 35,000 as measured by gel permeation chromatography (GPC), and is less than 10,000. The viscosity effect may be insufficient, and if it exceeds 35,000, the viscosity may be excessively increased and the coating workability may be adversely affected.
また、水系組成物に用いられる増粘剤として、ケイ酸塩、金属ケイ酸塩、モンモリロナイト、コロイド状アルミナ等の無機系増粘剤もあるが、無機系増粘剤は往々にして分散性に乏しく、水系樹脂へ混合する前に予備混合をしてミルベースを作製する必要があることや、均一に分散させるために長時間高速撹拌する必要があり手間やコストがかかる場合がある。また、そのようにして無機系増粘剤を使用したとしても、鉱物由来の泥のような着色が生じる場合があり、下地の隠蔽性や上塗り材の発色に悪影響を与える場合がある。このため、本発明においては有機系増粘剤を使用することが好ましい。 In addition, there are inorganic thickeners such as silicates, metal silicates, montmorillonite, and colloidal alumina as thickeners used in water-based compositions. In some cases, it is necessary to prepare a mill base by pre-mixing it before mixing it with the water-based resin, and it is necessary to stir at high speed for a long time to uniformly disperse it, which is laborious and costly. In addition, even if such an inorganic thickener is used, it may cause mineral-derived mud-like coloring, which may adversely affect the concealability of the undercoat and the color development of the topcoat material. Therefore, it is preferable to use an organic thickener in the present invention.
<成膜助剤>
本発明に使用する成膜助剤は、架橋型アクリル樹脂系エマルジョン及びナノコンポジットエマルジョン中のアクリル樹脂のポリマー粒子の融着を促進し、均一な皮膜を形成させることを目的で配合し、エチレングリコールジエチルエーテル、エチレングリコールモノエチルエーテルアセテート、ベンジルアルコール、ブチルセロソルブ、エステルアルコール、又はこれらの混合物等を使用することが出来る。成膜助剤の配合量は下地調整用水系塗材組成物100重量部中の0.5~10重量部が好ましく、0.5重量部未満では冬季等の低温環境での成膜が不十分となる場合があり、10重量部超では塗膜表面がベタついて汚れが付着し易くなる場合がある。
<Film deposition aid>
The film-forming aid used in the present invention is blended for the purpose of promoting the fusion of acrylic resin polymer particles in the crosslinked acrylic resin emulsion and nanocomposite emulsion and forming a uniform film, and ethylene glycol. Diethyl ether, ethylene glycol monoethyl ether acetate, benzyl alcohol, butyl cellosolve, ester alcohol, mixtures thereof, and the like can be used. The amount of the film-forming aid is preferably 0.5 to 10 parts by weight in 100 parts by weight of the water-based coating material composition for base preparation. If it exceeds 10 parts by weight, the surface of the coating film becomes sticky and dirt tends to adhere.
<顔料>
本発明で使用する顔料には、酸化チタン、酸化亜鉛、カーボンブラック、酸化第二鉄(弁柄)、クロム酸鉛、黄鉛、黄色酸化鉄等の無機系顔料等が使用できるが、中でも酸化チタンは下地の隠蔽性に優れ、白色であるため隠蔽性を付与するための主たる顔料として使用することが出来る。
<Pigment>
Pigments used in the present invention include inorganic pigments such as titanium oxide, zinc oxide, carbon black, ferric oxide (red iron oxide), lead chromate, yellow lead, and yellow iron oxide. Titanium is excellent in the hiding power of the base and can be used as a main pigment for imparting the hiding power because of its white color.
本発明の下地調整用水系塗材組成物には、上記のほかに、一般的に水系組成物に使用される消泡剤、防腐剤、分散剤、防藻防カビ剤、凍結防止剤を配合することが好ましい。 In addition to the above, the water-based coating material composition for base preparation of the present invention contains antifoaming agents, preservatives, dispersants, anti-algae and anti-mold agents, and anti-freezing agents that are generally used in water-based compositions. preferably.
本発明の下地調整用水系塗材組成物は、モルタル下地、コンクリート下地、オートクレーブ養生した軽量気泡コンクリートから成るパネル(ALCパネル)下地、窯業系サイディング下地、及び塗装下地等に塗付することができ、該塗装下地としては、アクリル樹脂系、アクリルウレタン樹脂系、ポリウレタン樹脂系、フッ素樹脂系、シリコンアクリル樹脂系、酢酸ビニル樹脂系、エポキシ樹脂系などの塗装が挙げられる。本発明の下地調整用水系塗材組成物との十分な付着性を保持するため、各下地に適した下地処理を行い清潔で乾燥した下地としておくことが望ましい。 The base preparation water-based coating composition of the present invention can be applied to mortar bases, concrete bases, panel (ALC panel) bases made of autoclave-cured lightweight cellular concrete, ceramic siding bases, paint bases, and the like. Examples of the coating substrate include acrylic resin-based, acrylic urethane resin-based, polyurethane resin-based, fluororesin-based, silicon acrylic resin-based, vinyl acetate resin-based, and epoxy resin-based coatings. In order to maintain sufficient adhesion with the water-based coating material composition for base preparation of the present invention, it is desirable to perform a base treatment suitable for each base to prepare a clean and dry base.
また、前記の下地の中には、パネルの突き付け部や目地部をシーリングした部分を有するものがあり、このような部分は特に下地の動きが激しく塗膜にひび割れが発生しやすい。これを解決するために、本発明の下地調整用水系塗材組成物を塗付する前に、不織布のような柔軟性と通気性を有する繊維シートを貼付けることで、この上に塗付される本発明の下地調整用水系塗材組成物及び塗材仕上げ構造にひび割れが発生することを抑制できる。不織布の貼付けには、例えば、本発明の下地調整用水系塗材組成物100重量部に対し繊維状骨材25~45重量部と水5~10重量部を加えて混合した組成物を使用することができる。該繊維状骨材の例としてウォラストナイト鉱石が挙げられ、繊維長100~1500μm、繊維径20~80μmのものであると繊維シートへの組成物の含浸が良好であるため好ましい。 In addition, some of the substrates have a portion where the panel abutment portion or the joint portion is sealed. In order to solve this problem, before applying the base preparation water-based coating material composition of the present invention, a flexible and breathable fiber sheet such as a non-woven fabric is attached, so that it can be coated on it. It is possible to suppress the occurrence of cracks in the base preparation water-based coating material composition and the coating material finish structure of the present invention. For attaching the nonwoven fabric, for example, a composition obtained by adding 25 to 45 parts by weight of fibrous aggregate and 5 to 10 parts by weight of water to 100 parts by weight of the water-based coating material composition for base preparation of the present invention and mixing them is used. be able to. An example of the fibrous aggregate is wollastonite ore, and a fiber length of 100 to 1500 μm and a fiber diameter of 20 to 80 μm are preferable because the composition can be well impregnated into the fiber sheet.
本発明の下地調整用水系塗材組成物の塗付にあたっては、ローラー刷毛を使用することができ、厚み0.15~0.5mmに塗付することに適している。厚み0.15~0.5mmに塗付することができるものであれば、他の塗装具等を使用してもよいのは勿論である。 A roller brush can be used to apply the water-based coating material composition for base preparation of the present invention, which is suitable for application to a thickness of 0.15 to 0.5 mm. It is needless to say that other coating tools may be used as long as they can be coated in a thickness of 0.15 to 0.5 mm.
本発明の下地調整用水系塗材組成物は、塗付作業性とダレ防止のために粘度が60~150Pa・s/23℃、TI値が4~7であるとより好ましい。粘度はBH型粘度計TVB-10(東機産業社製、商品名)を使用して回転速度2rpmで測定した際の粘度であり、TI値はJISA 6024に準拠し測定した値である。気温が高い場合には粘度が低下しダレが生じ易くなる傾向にあり、一方、気温が低い場合には粘度が高くなり塗付作業性が低下するため、下記で評価する種々の物性が著しく低下しない範囲で適当量の水を加えて粘度を調整することが出来る。これらの不具合を防止するため、気温5~35℃での使用が好ましい。 The water-based coating material composition for base preparation of the present invention more preferably has a viscosity of 60 to 150 Pa·s/23° C. and a TI value of 4 to 7 for ease of application and prevention of sagging. The viscosity is measured using a BH viscometer TVB-10 (trade name, manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 2 rpm, and the TI value is a value measured according to JISA 6024. When the temperature is high, the viscosity tends to decrease and sagging tends to occur. On the other hand, when the temperature is low, the viscosity increases and the coating workability decreases, so the various physical properties evaluated below are significantly reduced. The viscosity can be adjusted by adding an appropriate amount of water within the range that does not occur. In order to prevent these problems, it is preferable to use at an air temperature of 5 to 35°C.
また、本発明の下地調整用水系塗材組成物は1回の塗付厚みが0.15~0.5mm、且つ2回以上塗付して厚みの合計が0.3~1.0mmとなることが好ましく、0.3mm未満では遮水性が低下する場合があり、1.0mm超では水蒸気透過性が低下する場合がある。また、一度の塗付厚が0.5mm超となる場合には速乾性が低下する場合がある。また、下地が多孔質であり塗付した組成物の吸収が激しい場合には、塗付回数を増やして十分な膜厚とする必要がある。 In addition, the water-based coating material composition for base preparation of the present invention has a thickness of 0.15 to 0.5 mm per application, and a total thickness of 0.3 to 1.0 mm when applied twice or more. If the thickness is less than 0.3 mm, the water impermeability may deteriorate, and if it exceeds 1.0 mm, the water vapor permeability may deteriorate. Also, when the thickness of one application exceeds 0.5 mm, the quick-drying property may deteriorate. In addition, when the substrate is porous and the applied composition is strongly absorbed, it is necessary to increase the number of applications to obtain a sufficient film thickness.
以下、本発明の下地調整用水系塗材組成物が有する効果である速乾性、貯蔵安定性、水蒸気透過性、及び遮水性の詳細について記載する。 Hereinafter, the effects of the water-based coating material composition for base preparation of the present invention, namely quick-drying property, storage stability, water vapor permeability and water impermeability, will be described in detail.
本発明の下地調整用水系塗材組成物が有する速乾性は、架橋型アクリル樹脂系エマルジョン及びナノコンポジットエマルジョン中のアクリル樹脂ポリマーを含有するアニオン性ミセルと、水溶性カチオン化ポリマーが電気的相互作用することで発現し、該電気的相互作用状態にあるアニオン性ミセルと水溶性カチオン化ポリマーが凝集し、ポリマーの融着と定着が促されるというメカニズムと考えられる。従来の水系塗材組成物の塗膜形成過程においては水の蒸発によって樹脂の融着が生じるのに対して、本発明の下地調整用水系塗材組成物は該メカニズムによって水の蒸発を待つことなく樹脂の融着が促進されるため速乾性が得られるものと考えられる。 The quick-drying property of the water-based coating material composition for base preparation of the present invention is due to the electrical interaction between the anionic micelles containing the acrylic resin polymer in the crosslinked acrylic resin emulsion and the nanocomposite emulsion and the water-soluble cationized polymer. The mechanism is considered to be that the anionic micelles and the water-soluble cationized polymer in the state of electrical interaction are aggregated to promote fusion and fixation of the polymer. In the coating film formation process of conventional water-based coating compositions, resin fusion occurs due to evaporation of water. It is thought that the quick-drying property can be obtained because the fusion of the resin is accelerated without any heat.
なお、上記速乾性は当初本発明の下地調整用水系塗材組成物の製造時や貯蔵時にも起こり得るという課題があったが、本発明者は組成物に沸点が100℃以下の揮発性塩基を配合することでこの課題を見事に解決した。本発明の下地調整用水系塗材組成物は、架橋型アクリル樹脂系エマルジョン及びナノコンポジットエマルジョン存在下に水溶性カチオン化ポリマーを添加して作製するものであるが、該水溶性カチオン化ポリマーの添加前に予め揮発性塩基を添加して組成物全体のpHを9.5~11.5の範囲の塩基性としておくことで、水溶性カチオン化ポリマーが添加される際には揮発性塩基が水溶性カチオン化ポリマーのカチオン性官能基と相互作用し、水溶性カチオン化ポリマーを見かけ上は中性として振る舞わせるようにした。その結果、水溶性カチオン化ポリマーが架橋型アクリル樹脂系エマルジョン及びナノコンポジットエマルジョンのアニオン性ミセルと電気的に相互作用しない、つまりはこれらが製造時や貯蔵時には凝集しないように設計したものである。このように揮発性塩基を用いて組成物全体のpHをコントロールすることにより、良好な貯蔵安定性が得られたのが本発明の下地調整用水系塗材組成物である。 In addition, although there was a problem that the above-mentioned quick-drying property may occur even during the production and storage of the water-based coating material composition for base preparation of the present invention, the present inventors found that the composition contains a volatile base having a boiling point of 100 ° C. or less. This problem was successfully solved by blending The water-based coating material composition for base preparation of the present invention is prepared by adding a water-soluble cationic polymer in the presence of a crosslinked acrylic resin emulsion and a nanocomposite emulsion, and the water-soluble cationic polymer is added. By adding a volatile base in advance to make the pH of the entire composition basic in the range of 9.5 to 11.5, the volatile base becomes soluble when the water-soluble cationic polymer is added. interacting with the cationic functional groups of the water-soluble cationic polymer, causing the water-soluble cationic polymer to behave as neutral in appearance. As a result, the water-soluble cationic polymer is designed not to electrically interact with the anionic micelles of the crosslinked acrylic resin emulsion and nanocomposite emulsion, that is, they do not aggregate during manufacture or storage. By controlling the pH of the entire composition using a volatile base in this way, the water-based coating material composition for base preparation of the present invention has good storage stability.
これに対して塗膜が形成される際には、揮発性塩基が揮発し、水溶性カチオン化ポリマーのカチオン性官能基が露出して前記メカニズムによる速乾性が発揮されて塗膜形成が促進されることとなる。 On the other hand, when a coating film is formed, the volatile base volatilizes, the cationic functional groups of the water-soluble cationic polymer are exposed, and quick-drying is exhibited by the mechanism described above, promoting coating film formation. The Rukoto.
また、本発明の下地調整用水系塗材組成物の大きな特徴の一つとして、水蒸気透過性と遮水性を兼ね備える点が挙げられ、これは架橋型アクリル樹脂系エマルジョンとナノコンポジットエマルジョンの使用に起因する。架橋型アクリル樹脂系エマルジョンにより樹脂の架橋密度が増加し、緻密な塗膜が形成されて遮水性が得られる。一方で、ナノコンポジットエマルジョンに含まれるナノサイズのシリカ粒子は、塗膜中に分散するがアクリル樹脂とは化学的な結合をしないためにその周囲には極微細な隙間があり、該隙間が連続的に繋がることによって塗膜に目視では確認できないサイズの細孔構造を形成し、多孔質な塗膜とするため水蒸気が透過できると推測している。 In addition, one of the major characteristics of the water-based coating material composition for base preparation of the present invention is that it has both water vapor permeability and water impermeability, and this is due to the use of a crosslinked acrylic resin emulsion and a nanocomposite emulsion. do. The crosslinkable acrylic resin emulsion increases the crosslink density of the resin, forms a dense coating film, and provides water impermeability. On the other hand, the nano-sized silica particles contained in the nanocomposite emulsion are dispersed in the coating film but do not chemically bond with the acrylic resin, so there are very fine gaps around them, and the gaps are continuous. It is presumed that the pore structure of a size that cannot be confirmed by the naked eye is formed in the coating film by connecting to the target, and the porous coating film is made to allow water vapor to permeate.
発明者は従来のアクリル樹脂系エマルジョンにナノサイズのシリカ粒子を混合することで水蒸気透過性が付与されることを発見した。しかし、単純に既存のアクリル樹脂系エマルジョンに該シリカ粒子を配合するだけでは該シリカ粒子は塗膜表面に現れにくく、また、該シリカ粒子を塗膜全体に均一に分散することは困難であり、分散度合いによって水蒸気透過性が安定しなかった。一方で該シリカ粒子の配合量を増やして水蒸気透過性の安定化を試みるも、遮水性と塗膜強度の低下を招くという課題があった。発明者は試行錯誤と実験を繰り返すことにより、予めナノサイズのシリカ粒子をアクリル樹脂に含むナノコンポジットエマルジョンを適量使用することにより、塗膜全体に均一にナノサイズのシリカ粒子を分散させ塗膜表面にも現れることを見出し、最終的に優れた水蒸気透過性と遮水性のバランスが得られる配合に至ったものである。 The inventors discovered that water vapor permeability can be imparted by mixing nano-sized silica particles into a conventional acrylic resin emulsion. However, simply adding the silica particles to an existing acrylic resin emulsion makes it difficult for the silica particles to appear on the surface of the coating film, and it is difficult to uniformly disperse the silica particles throughout the coating film. The water vapor permeability was not stable depending on the degree of dispersion. On the other hand, although attempts were made to stabilize the water vapor permeability by increasing the amount of the silica particles, there was a problem that the water impermeability and the strength of the coating film were lowered. By repeating trial and error and experiments, the inventor found that by using an appropriate amount of a nanocomposite emulsion containing nano-sized silica particles in acrylic resin in advance, the nano-sized silica particles are uniformly dispersed throughout the coating film and the coating surface is improved. It was found that it also appeared in the water vapor permeability, and finally, a formulation was reached in which an excellent balance between water vapor permeability and water impermeability was obtained.
また、ナノサイズのシリカ粒子によって形成される細孔構造は、塗膜の厚み方向のみならず、塗膜の連続方向にも形成されており、水蒸気は塗膜の厚み方向及び連続方向に透過することができる。これは、下記の評価で示すように、本発明の下地調整用水系塗材組成物の上に水蒸気透過性を有さない上塗り材を塗付して形成した塗材仕上げ構造を、耐膨れ性の試験に供しても塗材仕上げ構造に膨れや剥がれが起こらないことから推察される。このため、本発明の下地調整用水系塗材組成物の上に、特に水蒸気透過性を有さない上塗り材を塗付したとしても、下地に含まれる水分に係る水蒸気圧によって、若しくは、何らかの原因で下地に水分が継続的に供給され該水分が塗膜との界面に集積し、水分を水蒸気として逃がすことができないことによっては膨れや剥がれが生じない塗材仕上げ構造の形成が可能である。勿論、より塗材仕上げ構造の性能を上げるために、例えば、骨材含有量を多くすることで水蒸気透過性を有するような上塗り材を塗付して塗材仕上げ構造を形成することが好ましい。 In addition, the pore structure formed by nano-sized silica particles is formed not only in the thickness direction of the coating film but also in the continuous direction of the coating film, and water vapor permeates in the thickness direction and the continuous direction of the coating film. be able to. As shown in the following evaluation, the coating material finish structure formed by coating the water-based coating material composition for base preparation of the present invention with a top coating material having no water vapor permeability was evaluated to be resistant to blistering. It is inferred from the fact that no blistering or peeling occurs in the coating material finish structure even when subjected to the test of . For this reason, even if a topcoat material that does not have water vapor permeability is applied on the water-based coating material composition for base preparation of the present invention, the water vapor pressure related to the moisture contained in the base may cause Moisture is continuously supplied to the substrate, and the moisture accumulates at the interface with the coating film, making it possible to form a coating material finish structure that does not cause blistering or peeling because the moisture cannot escape as water vapor. Of course, in order to further improve the performance of the coating material finish structure, it is preferable to form the coating material finish structure by applying a top coat material having water vapor permeability by increasing the aggregate content, for example.
本発明の塗材仕上げ構造を形成する上塗り材としては、上述するように水蒸気透過性の有無に関わらず種々の上塗り材を使用することができる。市販の上塗り材で水蒸気透過性を有するものとしては、ジョリパットフレッシュJQ-800(アクリル樹脂系エマルジョン塗料、樹脂分:10~20重量部、骨材及び充填材:40~60重量部、アイカ工業株式会社製、商品名)があり、また、水蒸気透過性を有さないものとしては、ジョリパットトップシリコーンJC-870(アクリルシリコーン樹脂エマルジョン塗料、樹脂分:60~70重量部、顔料:10~20重量部、アイカ工業株式会社製、商品名)や、アイカリノペイントシリコーンJCS-H1(2液弱溶剤シリコーン塗料、樹脂分50~60重量部、顔料:10~20重量部、アイカ工業株式会社製、商品名)等があり、本発明の塗材仕上げ構造の形成に使用できる。 Various topcoat materials can be used regardless of whether they are permeable to water vapor or not, as described above, as the topcoat material for forming the coating material finish structure of the present invention. As a commercially available topcoat material with water vapor permeability, Jolypat Fresh JQ-800 (acrylic resin emulsion paint, resin content: 10 to 20 parts by weight, aggregate and filler: 40 to 60 parts by weight, Aica Kogyo Co., Ltd. company's product name), and as a non-water vapor permeable one, Jolypat Top Silicone JC-870 (acrylic silicone resin emulsion paint, resin content: 60 to 70 parts by weight, pigment: 10 to 20 parts by weight part, manufactured by Aica Kogyo Co., Ltd., trade name) and Aika Rino Paint Silicone JCS-H1 (2-liquid weak solvent silicone paint, resin content: 50 to 60 parts by weight, pigment: 10 to 20 parts by weight, manufactured by Aica Kogyo Co., Ltd., (trade name), etc., and can be used to form the coating material finish structure of the present invention.
以下、実施例及び比較例にて具体的に説明する。 Examples and comparative examples will be described below in detail.
<実施例及び比較例>
表1及び表2の配合に従って、実施例及び比較例の下地調整用水系塗材組成物を作成した。表1及び表2において、架橋型アクリル樹脂系エマルジョンとしてアクロナールYJ2741D(固形分:56%、樹脂のガラス転移温度:-14℃、アクリルとスチレンの共重合体、架橋剤としてカルボニルヒドラジドを0.1~1.0重量%含有、BASF社製、商品名)を使用し、非架橋型アクリル樹脂系エマルジョンとしてプライマルEC-1791(固形分:55%、樹脂のガラス転移温度:-40℃、アクリルの共重合体、DOW社製、商品名)を使用し、ナノコンポジットエマルジョンとしてCol.9 1200(固形分:40%、シリカ分:15%、シリカ粒子の一次粒子径:15~30nm、ミセルの平均粒径:90nm、樹脂のガラス転移温度:2℃、アクリルの共重合体、BASF社製、商品名)を使用し、水溶性カチオン化ポリマーとしてルパゾールFG(ポリエチレンイミン、固形分:99%、重量平均分子量(Mw):800、BASF社製、商品名)を使用し、揮発性塩基として25%アンモニア水溶液(沸点:37.7℃)を使用し、充填材として重質炭酸カルシウムWA(平均粒径D50:10μm、白石カルシウム株式会社製、商品名)を使用し、有機系増粘剤Aとしてノパール700N(重量平均分子量(Mw):25,600、サンノプコ株式会社製、商品名)を、有機系増粘剤BとしてSNシックナー665T(重量平均分子量(Mw):19,800、サンノプコ株式会社製、商品名)を使用し、成膜助剤AとしてテキサノールCS-12(チッソ株式会社製、商品名)を、成膜助剤Bとしてエチレングリコールモノエチルエーテルアセテート(OXITENO社製)を使用し、顔料として酸化チタンR-820(石原産業株式会社製、商品名)を使用し、その他添加剤として水系組成物に用いる市販品の添加剤から適宜選択される、消泡剤、分散剤、防腐剤、及び凍結防止剤を添加した。尚、各実施例及び比較例における架橋型アクリル樹脂系エマルジョンの固形分又は非架橋型アクリル樹脂系エマルジョンの固形分と、ナノコンポジットエマルジョンの固形分と、の和が等しくなるように配合量を調整した。また、表1及び表2には、架橋型アクリル樹脂系エマルジョン又は非架橋型アクリル樹脂系エマルジョンの固形分とナノコンポジットエマルジョンの固形分の重量比、及び組成物のpHを示した。
<Examples and Comparative Examples>
In accordance with the formulations shown in Tables 1 and 2, base preparation water-based coating compositions of Examples and Comparative Examples were prepared. In Tables 1 and 2, Acronal YJ2741D (solid content: 56%, glass transition temperature of resin: −14° C., copolymer of acrylic and styrene, 0.1 carbonyl hydrazide as a cross-linking agent) is used as a cross-linkable acrylic resin emulsion. ~ 1.0 wt% content, manufactured by BASF, trade name), Primal EC-1791 (solid content: 55%, resin glass transition temperature: -40 ° C., acrylic resin emulsion) as a non-crosslinked acrylic resin emulsion 9 1200 as a nanocomposite emulsion (solid content: 40%, silica content: 15%, primary particle size of silica particles: 15 to 30 nm, average micelle Particle size: 90 nm, glass transition temperature of resin: 2 ° C., acrylic copolymer, manufactured by BASF, trade name), and lupasol FG (polyethyleneimine, solid content: 99%, weight) as a water-soluble cationized polymer. Average molecular weight (Mw): 800, manufactured by BASF, trade name), 25% aqueous ammonia solution (boiling point: 37.7°C) as a volatile base, and heavy calcium carbonate WA (average grain size) as a filler. Diameter D 50 : 10 μm, manufactured by Shiraishi Calcium Co., Ltd., trade name), Nopal 700N (weight average molecular weight (Mw): 25,600, manufactured by San Nopco Co., Ltd., trade name) as an organic thickener A, SN Thickener 665T (weight average molecular weight (Mw): 19,800, manufactured by San Nopco Co., Ltd., trade name) was used as the organic thickener B, and Texanol CS-12 (manufactured by Chisso Co., Ltd., (trade name), ethylene glycol monoethyl ether acetate (manufactured by OXITENO Co., Ltd.) is used as film formation aid B, titanium oxide R-820 (trade name, manufactured by Ishihara Sangyo Co., Ltd.) is used as pigment, and other additives are used. Defoamers, dispersants, preservatives, and antifreeze agents selected from commercially available additives used in water-based compositions were added. The blending amount was adjusted so that the sum of the solid content of the crosslinked acrylic resin emulsion or the solid content of the non-crosslinked acrylic resin emulsion and the solid content of the nanocomposite emulsion in each example and comparative example was equal. bottom. Tables 1 and 2 show the weight ratio of the solid content of the crosslinked acrylic resin emulsion or the non-crosslinked acrylic resin emulsion to the solid content of the nanocomposite emulsion, and the pH of the composition.
<作製方法>
実施例及び比較例の下地調整用水系塗材組成物の作製方法であるが、まず、特定の容器へ架橋型アクリル樹脂系エマルジョン又は非架橋型アクリル樹脂系エマルジョン、ナノコンポジットエマルジョン、充填材、成膜助剤、顔料、及びその他添加剤を量り取り、5分程度混合して均一にした後、揮発性塩基を添加し1分程度混合して均一に分散させた。次に、有機系増粘剤を添加して混合し、水溶性カチオン化ポリマーを添加し5分程度混合して均一に分散させることで実施例及び比較例の下地調整用水系塗材組成物を作製した。最後にpH測定器を用いて組成物のpHを測定した。作製した下地調整用水系塗材組成物は、揮発性塩基が揮発することを防ぐため密閉容器に移し、評価に供するまで23℃、50%RHの環境下で保管した。
<Production method>
Regarding the method for producing the water-based coating material composition for base preparation of Examples and Comparative Examples, first, a crosslinked acrylic resin emulsion or a non-crosslinked acrylic resin emulsion, a nanocomposite emulsion, a filler, and a composition are poured into a specific container. A film auxiliary agent, a pigment, and other additives were weighed out and mixed for about 5 minutes to homogenize them. Then, a volatile base was added and mixed for about 1 minute to disperse them uniformly. Next, an organic thickener is added and mixed, and a water-soluble cationized polymer is added and mixed for about 5 minutes to uniformly disperse, thereby preparing the base preparation water-based coating compositions of Examples and Comparative Examples. made. Finally, the pH of the composition was measured using a pH meter. The prepared water-based coating material composition for base preparation was transferred to a sealed container to prevent volatilization of the volatile base, and stored under an environment of 23° C. and 50% RH until evaluation.
<下地調整用水系塗材組成物の評価方法>
上記の実施例及び比較例の下地調整用水系塗材組成物について、以下の評価を行った。尚、特に記載のない限り、試験体の作製、養生、評価試験は23℃、50%RHの環境下にて行った。
<Evaluation method for base preparation water-based coating composition>
The water-based coating compositions for base preparation of the above examples and comparative examples were evaluated as follows. Unless otherwise specified, the preparation, curing, and evaluation test of test specimens were conducted in an environment of 23° C. and 50% RH.
<速乾性/硬化性>
実施例又は比較例の下地調整用水系塗材組成物をガラス板へローラー刷毛を使用して塗付量0.4kg/m2で塗付し、1.5時間経過後に目視及び指触にて乾燥状況を観察した。乾燥し白化がなく滑らかな塗膜を形成しているものを〇と、表面のみ乾燥し塗膜内部が未硬化(所謂皮バリ状態)のものを△と、乾燥していないもの、白化しているもの、及び硬化不良を起こしているものを×と評価した。
<Quick-drying/hardening>
The water-based coating material composition for base preparation of Example or Comparative Example was applied to a glass plate using a roller brush at a coating amount of 0.4 kg/m 2 , and visually and by touch after 1.5 hours. Observe the drying condition. ◯ indicates that the coating is dried and forms a smooth coating without whitening, and △ indicates that only the surface is dry and the inside of the coating is uncured (so-called skin burrs). Those with poor curing were evaluated as x.
35℃、5℃、及び-5℃においても上記同様に試験を実施し、同様に評価した。 Tests were also conducted at 35°C, 5°C and -5°C in the same manner as above and evaluated in the same manner.
<塗付作業性>
水平と垂直になるよう立てかけたJIS A5422規定の窯業系サイディングを下地とし、実施例及び比較例の下地調整用水系塗材組成物をローラー刷毛にて塗付量0.4kg/m2で塗付し、塗付作業性を確認した。塗付した際にダレが生じずはね返りがないものを〇と、ダレは生じないが組成物の凝集・硬化の進行により塗付作業性が悪い、又ははね返りがあるものを△と、ダレが生じた、はね返りが激しい、又は塗付作業中に組成物が硬化し塗付できなくなったものを×と評価した。尚、該はね返りとは、塗付するためにローラー刷毛を転動した際、組成物が周囲や作業者に飛散することである。
<Coating workability>
A ceramic siding defined by JIS A5422, which is set vertically and horizontally, is used as a base, and the water-based coating material composition for base preparation of Examples and Comparative Examples is applied with a roller brush at a coating amount of 0.4 kg / m 2 . and confirmed the coating workability. ○ indicates that there is no dripping and no rebound when applied. In addition, when the rebound was severe, or when the composition hardened during the application work and could not be applied, it was evaluated as x. The rebound means that the composition scatters around or to the operator when a roller brush is rolled for application.
35℃、5℃、及び-5℃においても上記同様に塗付作業性を確認し、同様に評価した。 At 35°C, 5°C, and -5°C, the coating workability was confirmed and evaluated in the same manner as described above.
<粘度/TI値>
実施例及び比較例の下地調整用水系塗材組成物について、BH型粘度計TVB-10(東機産業社製、商品名)を使用し回転速度2rpmでの粘度と回転速度20rpmでの粘度を測定した。TI値(チキソトロピックインデックス)をJISA 6024に準拠して求めることとし、2rpmでの粘度を20rpmでの粘度で除して求めた。2rpmでの粘度が60~150Pa・sであるものを〇と、それ以外のものを×と評価し、TI値が4~7であるものを〇と、それ以外のものを×と評価した。
<Viscosity/TI value>
For the water-based coating material compositions for base preparation of Examples and Comparative Examples, a BH type viscometer TVB-10 (manufactured by Toki Sangyo Co., Ltd., trade name) was used to measure the viscosity at a rotation speed of 2 rpm and the viscosity at a rotation speed of 20 rpm. It was measured. The TI value (thixotropic index) was determined according to JISA 6024 by dividing the viscosity at 2 rpm by the viscosity at 20 rpm. Those with a viscosity of 60 to 150 Pa s at 2 rpm were evaluated as ◯, and those with other values were evaluated as x.
<伸び物性>
実施例及び比較例の下地調整用水系塗材組成物をローラー刷毛にて厚さ0.5mmに塗付して1時間養生して乾燥させ、同様の下地調整用水系塗材組成物を厚さ0.5mmに塗付して合計厚み1.0mmとし、1週間養生して塗膜のシートを作製し、JISK 6251に規定するダンベル状3号形に打ち抜いて試験体とした。該試験体をJIS A 6021に規定する引張性能試験に供して破断時の伸び率を測定し、破断時の伸び率が230%以上のものを〇と、230%未満のものを×と評価した。
<Elongation properties>
The water-based coating material compositions for base preparation of Examples and Comparative Examples were applied to a thickness of 0.5 mm with a roller brush and cured for 1 hour to dry. It was applied to a thickness of 0.5 mm to give a total thickness of 1.0 mm, cured for 1 week to prepare a sheet of the coating film, and punched out into a dumbbell-shaped No. 3 shape specified in JISK 6251 to obtain a test specimen. The specimen was subjected to a tensile performance test specified in JIS A 6021, and the elongation at break was measured. .
<水蒸気透過性>
円形のろ紙(直径150mm、厚さ0.2mm、Whatman社製、グレード41)の片面へ実施例及び比較例の下地調整用水系塗材組成物を塗付量0.4kg/m2でローラー刷毛にて塗付し1時間養生して乾燥させた後、同様の下地調整用水系塗材組成物を塗付量0.4kg/m2でローラー刷毛にて塗付し1週間養生して試験体とした。高さ75mm、直径140mmの円柱状のアルミ合金製のカップに水を400mL入れ、カップ上部に塗付面が上になるよう試験体を設置し、試験体とカップの隙間から水蒸気が逃げることを防ぐために試験体の端部をシーリング処理し、3日間静置した。静置後、容器全体の重量を測定し、その値を試験前の値とし、さらに7日間静置した後、容器全体の重量を測定して試験後の値とした。試験前と試験後の容器全体の重量の減少量を試験日数で除した値を透湿度(g/日)として、透湿度(g/日)が0.6以上のものを水蒸気透過性に優れるとして〇と、透湿度が0.6未満のものを水蒸気透過性が不十分として×と評価した。
<Water vapor permeability>
On one side of a circular filter paper (diameter 150 mm, thickness 0.2 mm, Whatman, grade 41), the water-based coating material composition for base preparation of Examples and Comparative Examples was applied with a roller brush at a coating amount of 0.4 kg / m 2 . After coating with and drying for 1 hour, the same water-based coating material composition for base preparation was applied with a roller brush at a coating amount of 0.4 kg / m 2 and cured for 1 week. and Pour 400 mL of water into a cylindrical aluminum alloy cup with a height of 75 mm and a diameter of 140 mm. In order to prevent this, the ends of the specimen were sealed and allowed to stand for 3 days. After standing still, the weight of the entire container was measured, and the value was taken as the value before the test. Moisture permeability (g/day) is the value obtained by dividing the weight loss of the entire container before and after the test by the number of test days. A sample having a water vapor permeability of less than 0.6 was evaluated as having insufficient water vapor permeability and was rated as having a poor water vapor permeability.
<遮水性>
JIS A 5430規定のフレキシブルボード(400×200mm、厚さ4mm)に対し、実施例及び比較例の下地調整用水系塗材組成物を塗付量0.4kg/m2となるようにローラー刷毛にて塗付して1時間養生して乾燥させた後、同様の下地調整用水系塗材組成物を塗付量0.4kg/m2となるようにローラー刷毛にて塗付し、14日間養生して試験体とした。作製した試験体を使いJIS A6909の透水試験B法の透水量を測定した。該試験法における透水量が0.5mL以下のものは遮水性を有すると評価し〇と、透水量が0.5mL超のものは遮水性を有さないとして×と評価した。
<Water barrier>
For a flexible board (400 × 200 mm, thickness 4 mm) specified in JIS A 5430, apply the water-based coating material composition for base preparation of Examples and Comparative Examples to a coating amount of 0.4 kg / m 2 with a roller brush. After applying it to the surface and drying it for 1 hour, the same water-based coating composition for base preparation was applied with a roller brush so that the coating amount was 0.4 kg / m 2 and cured for 14 days. and used as a test specimen. Using the prepared specimen, the water permeability of the water permeability test B method of JIS A6909 was measured. In the test method, those with a water permeability of 0.5 mL or less were evaluated as having water impermeability, and those with a water permeability of more than 0.5 mL were evaluated as having no water impermeability, and were evaluated as x.
<耐膨れ性>
JIS A 6909に準拠した方法で試験体を作製して試験を行った。JISR 5201規定のモルタル(70×70mm、厚さ20mm)に実施例又は比較例の下地調整用水系塗材組成物を塗付量0.4kg/m2でローラー刷毛にて塗付し、1時間養生し乾燥させた後、同様の下地調整用水系塗材組成物を塗付量0.4kg/m2でローラー刷毛にて塗付して乾燥させた。その後、モルタルの四側面をパテ状エポキシ樹脂にて止水処理をし、14日間養生して試験体とした。該試験体を、「23℃、18時間水浸漬→-20℃、3時間→50℃、3時間」のサイクルに10サイクル供し、塗膜表面の膨れの有無を目視にて観察した。膨れが発生しないものを〇と、小さな膨れが発生したものを△と、それ以外のものを×と評価した。
<Swelling resistance>
A test specimen was prepared by a method conforming to JIS A 6909 and tested. JISR 5201 specified mortar (70 × 70 mm, thickness 20 mm) was coated with a water-based coating material composition for base preparation of Examples or Comparative Examples at a coating amount of 0.4 kg / m 2 with a roller brush, and was left for 1 hour. After curing and drying, the same water-based coating material composition for base preparation was applied with a roller brush at a coating amount of 0.4 kg/m 2 and dried. After that, the four sides of the mortar were waterproofed with putty-like epoxy resin, and cured for 14 days to obtain a test specimen. The specimen was subjected to 10 cycles of "immersion in water at 23° C. for 18 hours→−20° C. for 3 hours→50° C. for 3 hours" for 10 cycles, and the presence or absence of swelling on the surface of the coating film was visually observed. A case where no swelling occurred was evaluated as ◯, a case where small swelling occurred was evaluated as Δ, and other cases were evaluated as x.
<貯蔵安定性>
実施例及び比較例の下地調整用水系塗材組成物の粘度をBH型粘度計TVB-10(商品名、東機産業社製)にて測定し、容量500mLの密閉容器に入れ50℃雰囲気下にて60日間静置した後に再度粘度を測定し、試験前後の粘度を比較した。また、外観を目視にて観察した。著しい粘度の変化、組成物の分離、及び凝集のないものを〇と、軽微な粘度の変化または小さな凝集物を確認したものを△と、著しい粘度の変化、組成物の分離、及び凝集のうちいずれかの異状があるものを×と評価した。
<Storage stability>
The viscosity of the water-based coating material composition for base preparation of Examples and Comparative Examples was measured with a BH type viscometer TVB-10 (trade name, manufactured by Toki Sangyo Co., Ltd.), and placed in a sealed container with a capacity of 500 mL under a 50 ° C. atmosphere. After standing still for 60 days, the viscosity was measured again, and the viscosities before and after the test were compared. Moreover, the appearance was visually observed. 〇 for those without significant viscosity change, composition separation, and aggregation, △ for those with slight viscosity change or small aggregates, and significant viscosity change, composition separation, and aggregation Those with any abnormality were evaluated as x.
5℃においても上記同様に60日間静置し、試験前後の粘度の比較と外観の観察を行い、同様に評価した。 At 5° C., the samples were allowed to stand for 60 days in the same manner as above, and the viscosities before and after the test were compared and the appearance was observed, and evaluated in the same manner.
<下地調整用水系塗材組成物の評価結果>
表3及び表4に下地調整用水系塗材組成物の評価結果を示す。尚、組成物の凝集や硬化等により評価に供せなかったものは「-」と示す。
<Evaluation results of base preparation water-based coating composition>
Tables 3 and 4 show the evaluation results of the base preparation water-based coating composition. Those that could not be evaluated due to agglomeration, hardening, etc. of the composition are indicated with "-".
<塗材仕上げ構造の評価>
表5に塗材仕上げ構造の構成と、その評価結果を示す。表5に示すように、下地調整用水系塗材組成物として、実施例2、実施例3、比較例3、及び比較例4を使用し、上塗り材として、水蒸気透過性を有する上塗り剤であるジョリパットフレッシュJQ-800(アクリル樹脂系エマルジョン塗料、樹脂分:10~20重量%、骨材及び充填材:40~60重量%、アイカ工業株式会社製、商品名)を上塗り材Aとして、水蒸気透過性を有さない上塗り材であるジョリパットトップシリコーンJC-870(アクリルシリコーン樹脂エマルジョン塗料、樹脂分:60~70重量%、顔料:10~20重量%、アイカ工業株式会社製、商品名)を上塗り材Bとして使用し、実施例I乃至実施例IV、及び比較例I乃至比較例IVの塗材仕上げ構造を形成して以下の評価を行った。尚、特に記載のない限り、試験体の作製、養生、評価試験は23℃、50%RHの環境下にて行った。
<Evaluation of coating material finish structure>
Table 5 shows the composition of the coating material finishing structure and the evaluation results thereof. As shown in Table 5, Examples 2, 3, Comparative Example 3, and Comparative Example 4 were used as water-based coating compositions for base preparation, and topcoats having water vapor permeability were used as topcoats. Jolypat Fresh JQ-800 (acrylic resin emulsion paint, resin content: 10 to 20% by weight, aggregate and filler: 40 to 60% by weight, manufactured by Aica Kogyo Co., Ltd., trade name) as topcoat material A, water vapor permeation Jolypat Top Silicone JC-870 (acrylic silicone resin emulsion paint, resin content: 60-70% by weight, pigment: 10-20% by weight, manufactured by Aica Kogyo Co., Ltd., trade name), which is a topcoat material that does not have properties. Using this material as Material B, coating material finish structures of Examples I to IV and Comparative Examples I to IV were formed and evaluated as follows. Unless otherwise specified, the preparation, curing, and evaluation test of test specimens were conducted in an environment of 23° C. and 50% RH.
<水蒸気透過性>
円形のろ紙(直径150mm、厚さ0.2mm、Whatman社製、グレード41)の片面へ表5の実施例及び比較例の下地調整用水系塗材組成物を塗付量0.4kg/m2でローラー刷毛にて塗付し1時間養生して乾燥させた後、同様の下地調整用水系塗材組成物を塗付量0.4kg/m2でローラー刷毛にて塗付して乾燥させて下地調整用水系塗材組成物層を形成した。その上に上塗り剤Aを塗布量0.35kg/m2、又は上塗り材Bを塗布量0.15kg/m2でローラー刷毛にて塗付し5時間以上乾燥させた後、再度上塗り剤Aを塗布量0.35kg/m2、又は上塗り材Bを塗布量0.15kg/m2でローラー刷毛にて塗付して乾燥させ、1週間養生して試験体とした。高さ75mm、直径140mmの円柱状のアルミ合金製のカップに水を400mL入れ、カップ上部に塗付面が上になるよう試験体を設置し、試験体とカップの隙間から水蒸気が逃げることを防ぐために試験体の端部をシーリング処理し、3日間静置した。静置後、容器全体の重量を測定し、その値を試験前の値とし、さらに7日間静置した後、容器全体の重量を測定して試験後の値とした。試験前と試験後の容器全体の重量の減少量を試験日数で除した値を透湿度(g/日)として、透湿度(g/日)が0.6以上のものを水蒸気透過性に優れるとして〇と、0.6未満のものを水蒸気透過性が不十分として×と評価した。
<Water vapor permeability>
A circular filter paper (diameter 150 mm, thickness 0.2 mm, Whatman, grade 41) was applied to one side of the base preparation water-based coating composition of Examples and Comparative Examples in Table 5 in an amount of 0.4 kg/m 2 . After applying with a roller brush and curing for 1 hour to dry, the same water-based coating material composition for base preparation is applied with a roller brush at an application amount of 0.4 kg / m 2 and dried. A water-based coating material composition layer for base preparation was formed. On top of that, topcoat agent A is applied in an amount of 0.35 kg/m 2 or topcoat material B is applied in an amount of 0.15 kg/m 2 with a roller brush, dried for 5 hours or more, and then topcoat agent A is applied again. A coating amount of 0.35 kg/m 2 or topcoat material B was applied with a roller brush at a coating amount of 0.15 kg/m 2 , dried, and cured for 1 week to obtain a test specimen. Pour 400 mL of water into a cylindrical aluminum alloy cup with a height of 75 mm and a diameter of 140 mm. In order to prevent this, the ends of the specimen were sealed and allowed to stand for 3 days. After standing still, the weight of the entire container was measured, and the value was taken as the value before the test. Moisture permeability (g/day) is the value obtained by dividing the weight loss of the entire container before and after the test by the number of test days. and those with a value of less than 0.6 were evaluated as having insufficient water vapor permeability and were evaluated as x.
<耐膨れ性>
JIS A 6909に準拠した方法で試験体を作製し、試験を行った。JISR 5201規定のモルタル(70×70×20mm)に実施例及び比較例の下地調整用水系塗材組成物を塗付量0.4kg/m2でローラー刷毛にて塗付し、1時間養生し乾燥させた後、同様の下地調整用水系塗材組成物を塗付量0.4kg/m2でローラー刷毛にて塗付して乾燥させて下地調整用水系塗材組成物層を形成した。その上に上塗り剤Aを塗布量0.35kg/m2、又は上塗り材Bを塗布量0.15kg/m2でローラー刷毛にて塗付し5時間以上乾燥させた後、再度上塗り剤Aを塗布量0.35kg/m2、又は上塗り材Bを塗布量0.15kg/m2でローラー刷毛にて塗付して乾燥させた。乾燥後、モルタルの四側面をパテ状エポキシ樹脂にて止水処理をし、14日間養生して試験体とした。当該試験体を、「23℃、18時間水浸漬→-20℃、3時間→50℃、3時間」のサイクルに10サイクル供し、塗膜表面の状態を目視にて観察した。膨れが発生しないものを〇と、小さな膨れが発生したものを△と、それ以外のものを×と評価した。
<Swelling resistance>
A test specimen was prepared by a method conforming to JIS A 6909 and tested. The base preparation water-based coating composition of Examples and Comparative Examples was applied to JISR 5201 mortar (70 × 70 × 20 mm) at a coating amount of 0.4 kg / m 2 with a roller brush, and cured for 1 hour. After drying, the same water-based coating material composition for base preparation was applied with a roller brush at a coating amount of 0.4 kg/m 2 and dried to form a water-based coating material composition layer for base preparation. On top of that, topcoat agent A is applied in an amount of 0.35 kg/m 2 or topcoat material B is applied in an amount of 0.15 kg/m 2 with a roller brush, dried for 5 hours or more, and then topcoat agent A is applied again. A coating amount of 0.35 kg/m 2 or topcoat material B was applied with a coating amount of 0.15 kg/m 2 with a roller brush and dried. After drying, the four sides of the mortar were waterproofed with a putty-like epoxy resin, and cured for 14 days to obtain a test specimen. The specimen was subjected to 10 cycles of "immersion in water at 23° C. for 18 hours→−20° C. for 3 hours→50° C. for 3 hours" for 10 cycles, and the state of the coating film surface was visually observed. A case where no swelling occurred was evaluated as ◯, a case where small swelling occurred was evaluated as Δ, and other cases were evaluated as x.
<ゼロスパン引張伸び>
下地としてJISA 5430規定のフレキシブルボード(100×100mm、厚さ10mm)を使用し、当該下地2枚の木口同士を突き付け、その裏面を養生テープで仮止めする。下地表面に実施例及び比較例の下地調整用水系塗材組成物を塗付量0.4kg/m2でローラー刷毛にて塗付して1時間養生して乾燥させた後、同様の下地調整用水系塗材組成物を塗付量0.4kg/m2でローラー刷毛にて塗付し、4時間以上乾燥させて下地調整用水系塗材組成物層を形成した。その上に上塗り剤Aを塗布量0.35kg/m2、又は上塗り材Bを塗布量0.15kg/m2でローラー刷毛にて塗付し5時間以上乾燥させた後、再度上塗り剤Aを塗布量0.35kg/m2、又は上塗り材Bを塗布量0.15kg/m2でローラー刷毛にて塗付し14日間養生して試験体とした。試験体裏面の仮止めの養生テープをはがし、万能試験機(インストロン社製)にて、試験体の両端を2mm/分で引張り、突きつけ部の塗膜にピンホールが発生した時の距離が0.5mm以上のものを○と、0.5mm未満のものを×と評価した。
<Zero span tensile elongation>
A flexible board (100×100 mm, thickness 10 mm) specified in JISA 5430 is used as a substrate, and the edges of the two substrates are pressed against each other, and the back surface is temporarily fixed with a curing tape. After applying the water-based coating material composition for base preparation of Examples and Comparative Examples to the surface of the base with a roller brush at a coating amount of 0.4 kg / m 2 and drying for 1 hour, the same base preparation was performed. The water-based coating material composition for industrial use was applied with a roller brush in an application amount of 0.4 kg/m 2 and dried for 4 hours or longer to form a water-based coating material composition layer for base preparation. On top of that, topcoat agent A is applied in an amount of 0.35 kg/m 2 or topcoat material B is applied in an amount of 0.15 kg/m 2 with a roller brush, dried for 5 hours or more, and then topcoat agent A is applied again. A coating amount of 0.35 kg/m 2 or topcoat material B was applied with a roller brush at a coating amount of 0.15 kg/m 2 and cured for 14 days to obtain a test specimen. Peel off the temporary curing tape on the back of the specimen, pull both ends of the specimen at 2 mm / min with a universal testing machine (manufactured by Instron), and the distance when a pinhole occurs in the coating film at the thrust part is Those having a thickness of 0.5 mm or more were evaluated as ◯, and those having a thickness of less than 0.5 mm were evaluated as x.
Claims (7)
架橋型アクリル樹脂系エマルジョンの固形分とナノコンポジットエマルジョンの固形分の重量比は4~15:1であり、
前記シリカ粒子はナノコンポジットエマルジョン100重量部中10~20重量部であり、
水溶性カチオン化ポリマーの配合量は組成物全体100重量部中0.2~1.2重量部であり、
組成物全体のpHが9.5~11.5である、
ことを特徴とする下地調整用水系塗材組成物。 A micelle with a particle size of 60 to 120 nm formed by a crosslinked acrylic resin emulsion having a glass transition temperature of −20 to 10° C., an acrylic resin containing one or more silica particles having a primary particle size of 15 to 30 nm, and an emulsifier. is dispersed in water, a water-soluble cationic polymer, a volatile base having a boiling point of 100 ° C. or less, a filler, an organic thickener, a film formation aid, a pigment, A composition comprising
The weight ratio of the solid content of the crosslinked acrylic resin emulsion to the solid content of the nanocomposite emulsion is 4 to 15:1,
The silica particles are 10 to 20 parts by weight in 100 parts by weight of the nanocomposite emulsion,
The amount of the water-soluble cationized polymer is 0.2 to 1.2 parts by weight in 100 parts by weight of the entire composition,
the pH of the entire composition is 9.5 to 11.5;
A water-based coating material composition for preparing a base, characterized by:
A base preparation water-based coating composition layer formed by applying the base preparation water-based coating composition according to any one of claims 1 to 5, and the base preparation water-based coating composition. and a topcoat material layer formed by applying the topcoat material at least once onto the material layer.
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