JP2021102673A - Water-based wood coating for exterior facing - Google Patents
Water-based wood coating for exterior facing Download PDFInfo
- Publication number
- JP2021102673A JP2021102673A JP2019233467A JP2019233467A JP2021102673A JP 2021102673 A JP2021102673 A JP 2021102673A JP 2019233467 A JP2019233467 A JP 2019233467A JP 2019233467 A JP2019233467 A JP 2019233467A JP 2021102673 A JP2021102673 A JP 2021102673A
- Authority
- JP
- Japan
- Prior art keywords
- water
- mass
- paint
- main component
- coating composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000002023 wood Substances 0.000 title claims abstract description 71
- 239000011248 coating agent Substances 0.000 title abstract description 71
- 238000000576 coating method Methods 0.000 title abstract description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000000843 powder Substances 0.000 claims abstract description 71
- 239000000805 composite resin Substances 0.000 claims abstract description 55
- 239000008199 coating composition Substances 0.000 claims abstract description 53
- 229910021647 smectite Inorganic materials 0.000 claims abstract description 45
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 37
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 9
- 239000003973 paint Substances 0.000 claims description 107
- 239000000203 mixture Substances 0.000 claims description 29
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000005871 repellent Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000002131 composite material Substances 0.000 abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 6
- 150000003377 silicon compounds Chemical class 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 35
- 238000002845 discoloration Methods 0.000 description 14
- 238000003860 storage Methods 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000006096 absorbing agent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 239000003755 preservative agent Substances 0.000 description 6
- -1 silane compound Chemical class 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 6
- 230000005856 abnormality Effects 0.000 description 5
- 230000008602 contraction Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- 230000003405 preventing effect Effects 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001343 alkyl silanes Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 240000005109 Cryptomeria japonica Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- KSFBTBXTZDJOHO-UHFFFAOYSA-N diaminosilicon Chemical compound N[Si]N KSFBTBXTZDJOHO-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、耐久性が良好な有機無機複合塗膜を形成することができる水性外装用木材塗料に関する。 The present invention relates to a water-based exterior wood paint capable of forming an organic-inorganic composite coating film having good durability.
公共建築物等に対し木材利用促進法が施行されるなど、建築物への木材の積極的な利用が促進されている。木材を外装として使用する場合、その耐久性を向上させるために、一般的に塗料による木材表面の被覆が行われている。 The active use of wood in buildings is being promoted, such as the enforcement of the Wood Utilization Promotion Law for public buildings. When wood is used as an exterior, the surface of the wood is generally covered with paint in order to improve its durability.
外装用木材塗料としては、紫外線や風雨等に曝されることによる変色、ひび割れ等の経年劣化に対処することが要求されるほか、木材は周囲の湿度との関係により湿気を吸ったり吐いたりすることで伸縮するために寸法が変化するので、この寸法変化に対する追従性も要求される。これは、木材の寸法変化に対する追従性が乏しいと、長い間にはひび割れやハガレが生じて被覆材としての性能を失ってしまうためである。なお、外装用木材塗料としては、塗膜を厚く形成すると木材の伸縮に追従できなくなって割れが生じるため、薄い塗膜で経年劣化に対処できるものが要望されている。 Exterior wood paints are required to deal with discoloration, cracks, and other aging deterioration caused by exposure to ultraviolet rays, wind and rain, etc., and wood absorbs and discharges moisture due to the relationship with the surrounding humidity. As a result, the dimensions change due to expansion and contraction, so followability to this dimensional change is also required. This is because if the ability to follow changes in the dimensions of wood is poor, cracks and peeling will occur over a long period of time, and the performance as a covering material will be lost. As the exterior wood paint, if the coating film is formed thick, it cannot follow the expansion and contraction of the wood and cracks occur. Therefore, there is a demand for a thin coating film that can cope with aging deterioration.
従来、塗料としては、アクリル樹脂、ウレタン樹脂、アクリルとシリコンとを反応させたシリコン樹脂等に顔料や紫外線吸収剤、防腐剤などの添加剤を配合したアクリル塗料、ウレタン塗料、シリコン塗料などの有機系塗料が多く用いられている。このような有機系塗料のうち、シリコン塗料は、耐久性はアクリル塗料やウレタン塗料よりも優れているが、基体の寸法変化に対する塗膜の追従性が乏しいため、直接木材用塗料として用いるには適していない。そのため、木材用塗料としては、外装用であっても、内装用であっても、アクリル塗料及びウレタン塗料が多く用いられている。 Conventionally, as paints, organic paints such as acrylic paints, urethane resins, acrylic paints in which additives such as pigments, ultraviolet absorbers, and preservatives are mixed with silicone resins obtained by reacting acrylic and silicon, urethane paints, silicon paints, etc. Many paints are used. Among such organic paints, silicon paints are superior in durability to acrylic paints and urethane paints, but they have poor ability to follow changes in the dimensions of the substrate, so they cannot be used directly as wood paints. Not suitable. Therefore, acrylic paints and urethane paints are often used as wood paints, whether for exteriors or interiors.
なお、シリコン塗料をその耐久性を生かして外装用木材塗料として用いる場合は、たとえば特許文献１（特開２００３−２５１２６９号公報）にも示されているように、アクリル塗料から形成された下塗り塗膜の表面にシリコン塗料から形成された上塗り塗膜を形成する方法が多く採用されている。なお、フッ素樹脂塗料も知られているが、得られる塗膜は、耐久性は最も優れているが、基体の寸法変化に対する塗膜の追従性が最も乏しいため、木材用塗料としては適していない。 When a silicon paint is used as an exterior wood paint by taking advantage of its durability, for example, as shown in Patent Document 1 (Japanese Unexamined Patent Publication No. 2003-251269), an undercoat coating formed from an acrylic paint is used. A method of forming a topcoat coating film formed of a silicon paint on the surface of a film is often adopted. Fluororesin paints are also known, but the obtained coating film has the best durability, but is not suitable as a wood paint because the coating film has the poorest followability to changes in the dimensions of the substrate. ..
一方、上述のような有機系塗料では良好な耐久性を得ることができないことから、有機無機複合塗料ないし無機系塗料の開発も行われている。例えば、特許文献２（特開２００８−２７４２４２号公報）には、特定のシラン化合物ないしその部分縮合物と、アミノ基を有するシラン化合物ないしその部分縮合物とを特定の酸の存在下で縮合反応させることにより調製された、有機無機複合塗膜を得ることができる水性塗料組成物の発明が開示されている。また、特許文献３（特開２０１２−２０１７７８号公報）には、ポリオキシアルキレン鎖を有する水溶性ないし水分散性樹脂と、特定のオルガノシラン化合物ないしその加水分解縮合物と、アルコキシシリル基の加水分解・縮合反応を促進させる硬化触媒を含む２液型ないし多成分型の水性塗料用樹脂組成物の発明が開示されている。さらに、特許文献４（特開２００１−１６３６１３号公報、）には、自己造膜性の鱗片状シリカ粒子を含む無機系塗料の発明だけでなく、鱗片状シリカ粒子をシリコン樹脂系市販塗料に配合した有機無機複合塗料（実施例１６参照）の発明も開示されている。 On the other hand, since it is not possible to obtain good durability with the above-mentioned organic paints, organic-inorganic composite paints or inorganic paints are also being developed. For example, in Patent Document 2 (Japanese Unexamined Patent Publication No. 2008-274242), a specific silane compound or a partial condensate thereof is subjected to a condensation reaction of a silane compound having an amino group or a partial condensate thereof in the presence of a specific acid. The invention of a water-based coating composition capable of obtaining an organic-inorganic composite coating film prepared by subjecting the mixture is disclosed. Further, Patent Document 3 (Japanese Unexamined Patent Publication No. 2012-201778) describes a water-soluble or water-dispersible resin having a polyoxyalkylene chain, a specific organosilane compound or a hydrolyzed condensate thereof, and water addition of an alkoxysilyl group. The invention of a two-component or multi-component resin composition for an aqueous coating material containing a curing catalyst that promotes a decomposition / condensation reaction is disclosed. Further, Patent Document 4 (Japanese Unexamined Patent Publication No. 2001-163613) not only invents an inorganic paint containing self-forming scaly silica particles, but also incorporates scaly silica particles into a silicon resin-based commercial paint. The invention of the organic-inorganic composite coating material (see Example 16) is also disclosed.
上記特許文献２に開示されている水性塗料組成物によれば、硬度が高く、耐溶剤性及び耐摩耗性に優れた有機無機複合塗膜が得られるとともに、保存安定性に優れた水性塗料組成物が得られるが、得られる有機無機複合塗膜が基体の寸法変化に対する塗膜の追従性が乏しいため、直接木材用塗料として用いるには適していない。また、上記特許文献３に開示されている水性塗料用樹脂組成物の発明によれば、耐久性及び耐汚染性に優れた塗膜が得られる水性塗料が得られるが、従来のシリコン塗料の場合と同様に基体の寸法変化に対する塗膜の追従性が乏しいため、直接木材用塗料として用いるには適していない。 According to the water-based coating composition disclosed in Patent Document 2, an organic-inorganic composite coating film having high hardness and excellent solvent resistance and abrasion resistance can be obtained, and the water-based coating composition has excellent storage stability. Although a product can be obtained, the obtained organic-inorganic composite coating film is not suitable for direct use as a paint for wood because the coating film has poor followability to changes in the dimensions of the substrate. Further, according to the invention of the resin composition for water-based paint disclosed in Patent Document 3, a water-based paint capable of obtaining a coating film having excellent durability and stain resistance can be obtained, but in the case of a conventional silicon paint Similarly, it is not suitable for direct use as a paint for wood because the coating film has poor followability to changes in the dimensions of the substrate.
さらに、上記特許文献４に開示されている有機無機複合塗料の発明によれば、自己造膜性を有する鱗片状シリカ粒子がシリコン樹脂系市販塗料中に配合されているため、鱗片状シリカ粒子からなる無機塗膜とシリコン塗料による有機塗膜との両者の利点を兼ね備えた有機無機複合塗膜が得られるが、シリカリッチであって鉛筆硬度Ｈと硬いので、基体の寸法変化に対する塗膜の追従性が劣り、木材用塗料として用いるには適していなかった。 Further, according to the invention of the organic-inorganic composite paint disclosed in Patent Document 4, since the scaly silica particles having self-forming property are blended in the silicon resin-based commercially available paint, the scaly silica particles are used. An organic-inorganic composite coating film having the advantages of both an inorganic coating film and an organic coating film made of a silicon paint can be obtained. However, since it is silica-rich and has a pencil hardness of H, it follows the dimensional change of the substrate. It was inferior in properties and was not suitable for use as a wood paint.
本発明は、特に上記特許文献４に開示されている有機無機複合塗料において、鱗片状シリカ粒子やスメクタイト粉末等の無機粒子とシリコン塗料を構成するシリコン樹脂との間の結合強度を大きくし、基体の寸法変化に対する塗膜の追従性を改善することにより、耐候性、耐汚染性、耐水性等の耐久性が良好な水性外装用木材塗料が得られることを見出し、完成するに至ったのである。 In particular, in the organic-inorganic composite coating material disclosed in Patent Document 4, the present invention increases the bond strength between inorganic particles such as scaly silica particles and smectite powder and a silicon resin constituting the silicon coating material, and increases the bonding strength of the substrate. By improving the followability of the coating film to dimensional changes, it was found that a water-based exterior wood paint with good durability such as weather resistance, stain resistance, and water resistance could be obtained, and it was completed. ..
すなわち、本発明は、水性ポリシロキサン−アクリル複合樹脂と、鱗片状シリカ粉末及びスメクタイト粉末とを含む塗料主剤と、加水分解性シリコン化合物を含む硬化剤とからなる、耐久性が良好な有機無機複合塗膜を形成することができる水性外装用木材塗料を提供することを目的とする。 That is, the present invention is an organic-inorganic composite having good durability, which comprises a water-based polysiloxane-acrylic composite resin, a paint main agent containing scaly silica powder and smectite powder, and a curing agent containing a hydrolyzable silicon compound. It is an object of the present invention to provide a water-based exterior wood paint capable of forming a coating film.
本発明の水性外装用木材塗料は、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物と、加水分解性シリコン化合物を主成分とする前記水性塗料組成物の硬化剤とからなる水性外装用木材塗料であって、前記水性塗料組成物は鱗片状シリカ粉末及びポリカルボジイミドを吸着させたスメクタイト粉末を含むことを特徴とする。 The water-based exterior wood paint of the present invention is composed of a water-based paint composition containing a reactive water-based polysiloxane-acrylic composite resin as a main component and a curing agent of the water-based paint composition containing a hydrolyzable silicon compound as a main component. A water-based exterior wood paint, wherein the water-based paint composition contains a scaly silica powder and a smectite powder on which polycarbodiimide is adsorbed.
反応型水性ポリシロキサン−アクリル複合樹脂は、架橋剤としてのエポキシ基を有する加水分解性シリコン化合物とアクリル樹脂とから形成されたものであり、既に各種のものが市販されている。また、反応型水性ポリシロキサン−アクリル複合樹脂の硬化剤は、加水分解性シリコン化合物からなるものであり、ポリシロキサン−アクリル複合化合物１分子に対して１分子の割合で結合し、以下の反応式（Ｉ）に示したように、架橋化合物を形成して硬化する。 The reactive aqueous polysiloxane-acrylic composite resin is formed from a hydrolyzable silicone compound having an epoxy group as a cross-linking agent and an acrylic resin, and various types are already on the market. The curing agent for the reactive aqueous polysiloxane-acrylic composite resin is composed of a hydrolyzable silicon compound, and is bonded at a ratio of 1 molecule to 1 molecule of the polysiloxane-acrylic composite compound, and has the following reaction formula. As shown in (I), a crosslinked compound is formed and cured.
反応型水性ポリシロキサン−アクリル複合樹脂としては、例えば、株式会社カネカ製のゼムラックＷ３１０８Ｆ、ゼムラックＷ３１５３ＣＦ（何れも商品名）、ＤＩＣ株式会社製のボンコートＳＡ−６３６０（商品名）、ジャパンコーティングレジン株式会社製のモビニールＬＤＭ７５３２(商品名）等、市販の反応型水性ポリシロキサン−アクリル複合樹脂から適宜に選択して使用することができる。また、加水分解性シリコン化合物を主成分とする前記水性塗料組成物の硬化剤としては、アミノシラン、アミノシラン／アルキルシラン加水分解物、ジアミノシラン加水分解物、アミノシラン／アルキルシラン加水分解物、エポキシシラン加水分解物等を使用することができ、それぞれ市販品としては、例えばＤｙｎａｓｙｌａｎ ＨＹＤＲＯＳＩＬ １１５１、２６２７、２７７６、２９０９、２９２６（何れも商品名、エボニック製）等を使用することができる。 Examples of the reactive aqueous polysiloxane-acrylic composite resin include Zemlac W3108F manufactured by Kaneka Co., Ltd., Zemrack W3153CF (trade name), Boncoat SA-6360 (trade name) manufactured by DIC Corporation, and Japan Coating Resin Co., Ltd. It can be appropriately selected and used from commercially available reactive aqueous polysiloxane-acrylic composite resins such as MOVIN LDM7532 (trade name) manufactured by the company. Examples of the curing agent for the aqueous coating composition containing a hydrolyzable silicon compound as a main component include aminosilane, aminosilane / alkylsilane hydrolyzate, diaminosilane hydrolyzate, aminosilane / alkylsilane hydrolyzate, and epoxysilane hydrolyzate. Decomposed products and the like can be used, and as commercially available products, for example, Dynasilan HYDROSIL 1151, 2627, 2776, 2909, 2926 (all trade names, manufactured by Epoxy) and the like can be used.
また、本発明の水性外装用木材塗料においては、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中に鱗片状シリカ粉末及びポリカルボジイミドを吸着させたスメクタイト粉末の両者を同時に含むことは必須の構成要件である。スメクタイトは、モンモリロナイト、サポナイト、スチーブンサイト、ヘクライト等の層状ケイ酸塩からなり、金属イオン（アルミニウムイオン、ナトリウムイオン、カルシウムイオン等）とケイ酸とが結合して形成されたシートが層状に形成された粘土鉱物であって、膨潤性を有している。このスメクタイトへのアミン化合物のインターカーレーション現象はよく知られており、ポリカルボジイミドもスメクタイトのような層状ケイ酸塩に強く吸着される。 Further, in the water-based exterior wood paint of the present invention, both the scaly silica powder and the smectite powder in which polycarbodiimide is adsorbed in the water-based paint composition containing the reactive water-based polysiloxane-acrylic composite resin as the main component are simultaneously used. Including is an essential component. Smectite is composed of layered silicates such as montmorillonite, saponite, stephensite, and hexrite, and a sheet formed by combining metal ions (aluminum ion, sodium ion, calcium ion, etc.) and silicic acid is formed in layers. It is a clay mineral and has swelling properties. The intercaration phenomenon of amine compounds with smectite is well known, and polycarbodiimide is also strongly adsorbed on layered silicates such as smectite.
なお、ポリカルボジイミドを吸着させたスメクタイト粉末は、例えば水中に適量のポリカルボジイミド及びスメクタイト粉末を添加して撹拌・混合し、数分〜数十分間静置し、濾過及び乾燥することにより調製することができる。ポリカルボジイミド及びスメクタイト粉末のそれぞれの添加量は、臨界的限度は明確ではないが、質量比で１：０．１〜０．５とすることが好ましい。ポリカルボジイミドの添加量がスメクタイト粉末の添加量の０．１倍よりも少ないとポリカルボジイミドを吸着させたことの効果が良好に現れず、また、０．５倍よりも多すぎても吸着されなかったポリカルボジイミドが無駄となるので、不経済となる。 The smectite powder on which polycarbodiimide is adsorbed is prepared by, for example, adding an appropriate amount of polycarbodiimide and smectite powder to water, stirring and mixing, allowing the mixture to stand for several minutes to several tens of minutes, filtering and drying. be able to. The amount of each of the polycarbodiimide and smectite powder added is preferably 1: 0.1 to 0.5 in terms of mass ratio, although the critical limit is not clear. If the amount of polycarbodiimide added is less than 0.1 times the amount of smectite powder added, the effect of adsorbing polycarbodiimide does not appear well, and if it is more than 0.5 times, it is not adsorbed. It is uneconomical because the polycarbodiimide is wasted.
このポリカルボジイミドは、下記反応式（Ｉ）に示したように、ポリシロキサン−アクリル複合樹脂中に含まれる官能基（カルボキシル基）と反応してＮ−アシルウレア化合物を形成するので、ポリカルボジイミドを吸着させたスメクタイト粉末は、ポリシロキサン−アクリル複合樹脂に強固に結合して複合化され、塗膜中に安定的に存在できるようになる。 As shown in the reaction formula (I) below, this polycarbodiimide reacts with a functional group (carboxyl group) contained in the polysiloxane-acrylic composite resin to form an N-acylurea compound, and thus adsorbs the polycarbodiimide. The resulting smectite powder is firmly bonded to the polysiloxane-acrylic composite resin and compounded so that it can be stably present in the coating film.
また、鱗片状シリカは、耐水性、耐熱性に優れ、自己造膜性を有しているが、膨潤性は小さい。そのため、塗膜中に鱗片状シリカ粉末のみを含んでいる場合には、伸縮性が少ない強固な塗膜が得られるが、外装用木材塗料としては木材の伸縮に対して追従性が劣るために適さなくなる。また、塗膜中にポリカルボジイミドを吸着させたスメクタイト粉末のみを含む場合には、伸縮性が良好で木材の伸縮に対して良好に追従できる塗膜が得られるが、鱗片状シリカ粉末を用いた場合よりも耐水性、耐候性及び耐汚染性に劣るようになる。また、鱗片状シリカ粉末及びスメクタイト粉末の粒度は、それぞれ塗料用として市販されているものを適宜に選択して使用すればよい。 In addition, scaly silica is excellent in water resistance and heat resistance, and has self-forming property, but has low swelling property. Therefore, when the coating film contains only scaly silica powder, a strong coating film with low elasticity can be obtained, but the exterior wood paint is inferior in followability to the expansion and contraction of wood. It becomes unsuitable. Further, when the coating film contains only smectite powder having polycarbodiimide adsorbed, a coating film having good elasticity and capable of following the expansion and contraction of wood can be obtained, but scaly silica powder was used. It becomes inferior in water resistance, weather resistance and stain resistance than in the case. Further, as the particle size of the scaly silica powder and the smectite powder, those commercially available for paints may be appropriately selected and used.
本発明の水性外装用木材塗料においては、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中にポリカルボジイミドを吸着させたスメクタイト粉末及び鱗片状シリカ粉末の両者を同時に含んでいるため、スメクタイト粉末及び鱗片状シリカ粉末添加の両者の添加の利点を生かした上で、両者の欠点を互いに補うことができ、耐久性が良好な有機無機複合塗膜を形成することができる外装用木材塗料が得られる。なお、本発明の水性外装用木材塗料におけるポリカルボジイミドを吸着させたスメクタイト粉末及び鱗片状シリカ粉末の両者の機能としては、それぞれの塗膜形成作用というよりは木材内部の空隙に入り込んで木材と塗膜との間のアンカー機能を強化する補強材として作用を奏しているものと推定される。 The water-based exterior wood paint of the present invention simultaneously contains both smectite powder and scaly silica powder in which polycarbodiimide is adsorbed in a water-based paint composition containing a reactive water-based polysiloxane-acrylic composite resin as a main component. Therefore, while taking advantage of the addition of both smectite powder and scaly silica powder, the drawbacks of both can be compensated for each other, and an organic-inorganic composite coating film having good durability can be formed. Wood paint for use is obtained. The functions of both the smectite powder adsorbed with polycarbodiimide and the scaly silica powder in the water-based exterior wood paint of the present invention are to enter the voids inside the wood and coat the wood rather than the respective coating film forming actions. It is presumed that it acts as a reinforcing material to strengthen the anchor function with the membrane.
そのため、本発明の水性外装用木材塗料によれば、ポリカルボジイミドを吸着させたスメクタイト粉末及び鱗片状シリカ粉末が強固に塗膜中に複合化されているので、木材の伸縮に伴う寸法変化に追従して塗膜が伸縮しても良好に追従できる耐久性が良好な有機無機複合塗膜が得られる。しかも、スメクタイト粉末及び鱗片状シリカ粉末は、ともに無機材料であるため、良好な耐久性を得ることができるようになる。なお、ポリカルボジイミドのカルボジイミド等量は３００〜６００のものであることが好ましい。また、鱗片状シリカ粉末としては、例えば市販のサンラブリー(登録商標名、ＡＧＣＳＩテック株式会社）を使用することができる。 Therefore, according to the water-based exterior wood paint of the present invention, the smectite powder and the scaly silica powder adsorbed with polycarbodiimide are firmly composited in the coating film, so that the dimensional change due to the expansion and contraction of the wood can be followed. As a result, an organic-inorganic composite coating film having good durability that can follow well even if the coating film expands and contracts can be obtained. Moreover, since both smectite powder and scaly silica powder are inorganic materials, good durability can be obtained. The equivalent amount of carbodiimide of polycarbodiimide is preferably 300 to 600. Further, as the scaly silica powder, for example, a commercially available Sun Lovely (registered trademark name, AGCSI Tech Co., Ltd.) can be used.
なお、本発明の水性外装用木材塗料においては、使用直前に、水性塗料組成物中に含まれる反応型水性ポリシロキサン−アクリル複合樹脂のモル比と硬化剤中に含まれる加水分解性シリコン化合物のモル比が１：１となるように混合して使用すれば、良好な塗膜が得られる。 In the water-based exterior wood paint of the present invention, immediately before use, the molar ratio of the reactive water-based polysiloxane-acrylic composite resin contained in the water-based paint composition and the hydrolyzable silicone compound contained in the curing agent. A good coating film can be obtained by mixing and using the mixture so that the molar ratio is 1: 1.
さらに、本発明の水性外装用木材塗料においては、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中に、水性外装用木材塗料に慣用的に使用されている造膜助剤、紫外線吸収剤、光安定剤、防腐剤等を適宜に添加してもよい。 Further, in the water-based exterior wood paint of the present invention, a film-forming aid commonly used in water-based exterior wood paints in a water-based paint composition containing a reactive water-based polysiloxane-acrylic composite resin as a main component. Agents, UV absorbers, light stabilizers, preservatives and the like may be added as appropriate.
本発明の反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物は、水中にポリマー粒子が分散したものであるので、ＭＦＴ（最低造膜温度）が存在する。ＭＦＴは塗装後ポリマー粒子同士が融着する最低の温度である。乾燥時に塗膜の温度がＭＦＴを下回ると、ポリマー粒子同士が融着せず、造膜不良となってひび割れが発生する。本発明の水性外装用木材塗料中に造膜助剤（成膜助剤と称されることもある）を添加すると、ポリマー粒子同士が融着しやすくなり、ＭＦＴを下げることができる。ポリシロキサン―アクリル複合樹脂のＭＦＴは５〜１０℃程度であるが、本発明の水性外装用木材塗料においては、これらの造膜助剤を添加することによってＭＦＴを０℃以下まで下げることができ、冬季でも現場塗装が可能な状態とすることができる。 The aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin of the present invention as a main component has polymer particles dispersed in water, and therefore has an MFT (minimum film forming temperature). MFT is the lowest temperature at which polymer particles fuse with each other after painting. If the temperature of the coating film falls below the MFT during drying, the polymer particles do not fuse with each other, resulting in poor film formation and cracking. When a film-forming auxiliary (sometimes referred to as a film-forming auxiliary) is added to the water-based exterior wood paint of the present invention, the polymer particles are easily fused to each other, and the MFT can be lowered. The MFT of the polysiloxane-acrylic composite resin is about 5 to 10 ° C., but in the water-based exterior wood paint of the present invention, the MFT can be lowered to 0 ° C. or lower by adding these film-forming aids. , It is possible to make it possible to paint on-site even in winter.
この造膜助剤としては、例えば花王株式会社製のスマックＭＰ−４０、スマックＭＰ−７０(何れも商品名）、安藤パラケミー株式会社製のダワノールＰＮＰ(商品名）等を使用することができるほか、ブチルセロセルブ、ブチルカルビトール、グリコールジアセテート等も使用することができる。 As the film-forming auxiliary, for example, Smack MP-40 and Smack MP-70 manufactured by Kao Corporation (trade names), Dawanol PNP manufactured by Ando Parachemie Co., Ltd. (trade name), and the like can be used. , Butyl cellocerve, butyl carbitol, glycol diacetate and the like can also be used.
また、紫外線吸収剤としては、有機系紫外線吸収剤及び無機系紫外線吸収剤の少なくとも１種を使用することができる。有機系紫外線吸収剤としては、トリアジン系の紫外線吸収剤であるチヌビン４００（商品名、ＢＡＳＦ製）、ベンゾトリアソール系の紫外線吸収剤であるアデカスタブＬＡ３１、アデカスタブＬＡ３２、アデカスタブＬＡ３６（何れも商品名、株式会社ＡＤＥＫＡ製）、ＨＯＳＴＡＶＩＮ３３１５ＤＩＳＰ、ＨＯＳＴＡＶＩＮ３３２６ＤＩＳＰ(何れも商品名、クラリアントケミカルズ株式会社製）等を使用することができる。さらに、無機系紫外線吸収剤としては、酸化チタン、酸化亜鉛、酸化セリウム等を使用することができる。本発明の水性外装用木材塗料においては、有機系紫外線吸収剤及び無機系紫外線吸収剤を併用することが好ましい。 Further, as the ultraviolet absorber, at least one of an organic ultraviolet absorber and an inorganic ultraviolet absorber can be used. Examples of the organic UV absorber include triazine-based UV absorber Tinubin 400 (trade name, manufactured by BASF), benzotriazol-based UV absorber Adecastab LA31, Adecastab LA32, and Adecastab LA36 (trade names, all of which are trade names). ADEKA Corporation), HOSTAVIN3315DISP, HOSTAVIN3326DISP (all trade names, manufactured by Clariant Chemicals Co., Ltd.) and the like can be used. Further, as the inorganic ultraviolet absorber, titanium oxide, zinc oxide, cerium oxide and the like can be used. In the water-based exterior wood paint of the present invention, it is preferable to use an organic ultraviolet absorber and an inorganic ultraviolet absorber in combination.
また、光安定剤は、ヒンダードアミン系光安定剤（ＨＡＬＳ）が汎用的に用いられており、高分子の光劣化を抑制し、特に表面の劣化防止に優れている添加剤である。この光安定剤としては、ＢＡＳＦ製のチヌビン（商品名）、アデカスタブＬＡ７２、アデカスタブＬＡ８２（何れも商品名、株式会社ＡＤＥＫＡ製）、ＨＯＳＴＡＶＩＮ３０５１−２ＤＩＳＰ、ＨＯＳＴＡＶＩＮ３０７０ＤＩＳＰ(何れも商品名、クラリアントケミカルズ株式会社製）等を使用することができる。 Further, as the light stabilizer, a hindered amine-based light stabilizer (HALS) is generally used, and it is an additive that suppresses photodegradation of a polymer and is particularly excellent in preventing surface deterioration. Examples of this light stabilizer include BASF's tinubin (trade name), ADEKA STAB LA72, ADEKA STAB LA82 (all product names, manufactured by ADEKA Corporation), HOSTAVIN3051-2DISP, and HOSTAVIN3070DISP (all product names, manufactured by Clariant Chemicals Co., Ltd.). Etc. can be used.
なお、防腐剤としては、木部用防腐剤として周知のものうち、水溶性のものであれば適宜のものを選択して使用することができ、例えば第４級アンモニウム化合物、銅・第四級アンモニウム化合物、銅・アゾール化合物等を使用することができる。 As the preservative, among the well-known preservatives for wood parts, any water-soluble preservative can be selected and used. For example, a quaternary ammonium compound, copper / quaternary. Ammonium compounds, copper / azole compounds and the like can be used.
また、本発明の水性外装用木材塗料においては、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中のポリカルボジイミドを吸着させたスメクタイトの含有割合は、水性塗料組成物１００質量部に対して０．５質量部以上３質量部以下が好ましい。ポリカルボジイミドを吸着させたスメクタイトの含有割合が水性塗料組成物１００質量部に対して０．５質量部未満であると、ガスや水に対して優れたバリア性を持った塗膜が得られず、同じく３質量部を越えると塗料の粘度が高くなって作業性が悪くなる。より好ましいポリカルボジイミドを吸着させたスメクタイトの含有割合は、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物１００質量部に対して１質量部以上２．５質量部以下である。 Further, in the water-based exterior wood paint of the present invention, the content ratio of smectite adsorbed with polycarbodiimide in the water-based paint composition containing a reactive water-based polysiloxane-acrylic composite resin as a main component is the water-based paint composition 100. It is preferably 0.5 parts by mass or more and 3 parts by mass or less with respect to parts by mass. If the content of smectite adsorbed with polycarbodiimide is less than 0.5 parts by mass with respect to 100 parts by mass of the aqueous coating composition, a coating film having an excellent barrier property against gas and water cannot be obtained. Similarly, if it exceeds 3 parts by mass, the viscosity of the paint becomes high and the workability deteriorates. The content ratio of smectite on which a more preferable polycarbodiimide is adsorbed is 1 part by mass or more and 2.5 parts by mass or less with respect to 100 parts by mass of the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as a main component. ..
また、本発明の水性外装用木材塗料においては、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中の鱗片状シリカ粉末の含有割合は、水性塗料組成物１００質量部に対して０．５質量部以上５質量部以下が好ましい。鱗片状シリカ粉末の含有割合が水性塗料組成物１００質量部に対して０．５質量部未満であると、良好な木部のひび割れ防止補強効果が得られず、同じく５質量部を越えると塗膜の外観が損なわれる。より好まししい反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中の鱗片状シリカ粉末の含有割合は、水性塗料組成物１００質量部に対して０．５質量部以上４質量部以下である。なお、鱗片状シリカ粉末としては、臨界的限度は必ずしも明確ではないが、平均粒径が０．５μｍ以上３．０μｍ以下のものが好ましい。 Further, in the water-based exterior wood paint of the present invention, the content ratio of the scaly silica powder in the water-based paint composition containing the reactive water-based polysiloxane-acrylic composite resin as a main component is 100 parts by mass of the water-based paint composition. On the other hand, it is preferably 0.5 parts by mass or more and 5 parts by mass or less. If the content of the scaly silica powder is less than 0.5 parts by mass with respect to 100 parts by mass of the aqueous coating composition, a good crack-preventing and reinforcing effect on the wood part cannot be obtained, and if it exceeds 5 parts by mass, the coating is applied. The appearance of the film is impaired. More preferably, the content ratio of the scaly silica powder in the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as a main component is 0.5 parts by mass or more with respect to 100 parts by mass of the aqueous coating composition. It is less than a part by mass. The scaly silica powder preferably has an average particle size of 0.5 μm or more and 3.0 μm or less, although the critical limit is not always clear.
また、本発明の水性外装用木材塗料においては、塗膜構造中にシラノール基が含まれているため、このシラノール基に起因する塗膜表面の親水化が起こる。一般的な建築外装用塗料であれば、このシラノール基の存在によって、雨水によるセルフクリーニング機能が発現し、耐汚染性に優れた塗膜が形成されるが、木部用塗料として使用した場合、木の内部に水分が浸透しやすくなり、腐朽菌の増殖につながって木の劣化が促進されてしまう。本発明の水性外装用木材塗料においては、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中に撥水性添加剤を添加することにより、塗膜の表面に撥水性が付与され、木部用に使用した場合でも木の内部に水分が浸透し難くなるので、木の劣化が抑制される。 Further, in the water-based exterior wood paint of the present invention, since a silanol group is contained in the coating film structure, the coating film surface becomes hydrophilic due to the silanol group. In general building exterior paints, the presence of this silanol group causes a self-cleaning function with rainwater to form a coating film with excellent stain resistance, but when used as a wood paint, Moisture easily permeates the inside of the tree, leading to the growth of rotting fungi and promoting the deterioration of the tree. In the water-based exterior wood paint of the present invention, water repellency is imparted to the surface of the coating film by adding a water-repellent additive to the water-based paint composition containing a reactive water-based polysiloxane-acrylic composite resin as a main component. Therefore, even when it is used for wood, it becomes difficult for water to permeate inside the wood, so that deterioration of the wood is suppressed.
この撥水性添加剤としては、フッ素／アクリル系コポリマーであるモディバーＦ２６６（商品名、日油株式会社製）、シコーン／アクリルコポリマーであるモディバーＦＳ７７０（日油株式会社製）、フッ素樹脂であるメガファックＦ−５５２（商品名、ＤＩＣ株式会社製）等を使用することができるほか、一般的なシリコーンオイルも使用することができる。 Examples of this water-repellent additive include Modiver F266 (trade name, manufactured by Nichiyu Co., Ltd.), which is a fluorine / acrylic copolymer, Modiver FS770 (manufactured by Nichiyu Co., Ltd.), which is a cicorn / acrylic copolymer, and Megafuck, which is a fluororesin. In addition to being able to use F-552 (trade name, manufactured by DIC Co., Ltd.), general silicone oil can also be used.
以上述べたように、本発明の水性外装用木材塗料によれば、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中に鱗片状シリカ粉末及びポリカルボジイミドを吸着させたスメクタイト粉末の両者が同時に含まれているため、耐候性、耐汚染性、耐水性等の耐久性が良好な有機無機複合塗膜を形成することができる外装用木材塗料が得られる。 As described above, according to the water-based exterior wood paint of the present invention, smectite in which scaly silica powder and polycarbodiimide are adsorbed in a water-based paint composition containing a reactive water-based polysiloxane-acrylic composite resin as a main component. Since both powders are contained at the same time, an exterior wood paint capable of forming an organic-inorganic composite coating film having good durability such as weather resistance, stain resistance, and water resistance can be obtained.
以下、本発明に係る水性外装用木材塗料について、各種実験例を用いて詳細に説明する。ただし、以下に示す各種実験例は、本発明の技術思想を具体化するための例を示すものであって、本発明をこれらの実験例に示したものに特定することを意図するものではない。本発明は特許請求の範囲に含まれるその他の実施形態のものにも等しく適用し得るものである。 Hereinafter, the water-based exterior wood paint according to the present invention will be described in detail with reference to various experimental examples. However, the various experimental examples shown below show examples for embodying the technical idea of the present invention, and are not intended to specify the present invention as those shown in these experimental examples. .. The present invention is equally applicable to other embodiments included in the claims.
［ポリカルボジイミドを吸着させたスメクタイト粉末の調製］
最初に本発明のポリカルボジイミドを吸着させたスメクタイト粉末の調製工程について説明する。まず、水に所定量のスメクタイト粉末を分散させるとともに、市販のポリカルボジイミド（カルボジライトＶ-１０（商品名）、日清紡ケミカル社）を質量比でスメクタイト粉末の１／１０となるように添加し、５分間良く撹拌した後に濾過及び乾燥して、各種実験例で使用するポリカルボジイミドを吸着させたスメクタイト粉末を得た。
[Preparation of smectite powder adsorbed with polycarbodiimide]
First, the step of preparing the smectite powder adsorbed with the polycarbodiimide of the present invention will be described. First, a predetermined amount of smectite powder is dispersed in water, and commercially available polycarbodiimide (carbodilite V-10 (trade name), Nisshinbo Chemical Co., Ltd.) is added so as to be 1/10 of the smectite powder by mass ratio. After stirring well for 1 minute, it was filtered and dried to obtain a smectite powder adsorbed with polycarbodiimide used in various experimental examples.
［実験例１］
実験例１の水性外装用木材塗料における反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物としては、反応形ポリシロキサン−アクリル複合樹脂（ゼムラックＷ３１０８Ｆ(商品名)、株式会社カネカ）２５質量部、鱗片状シリカ粉末（サンラブリー(登録商標名、ＡＧＣＳＩテック株式会社）３質量部、ポリカルボジイミドを吸着させたスメクタイト粉末を２質量部、造膜助剤（ダワノールＰＮＰ(商品名)、安藤パラケミー株式会社）を５質量部、撥水性添加剤（モディバーＦ２６６（商品名、日油株式会社製））、無機系紫外線吸収材（酸化チタン）２質量部、有機系紫外線吸収剤（チヌビン４００（商品名、ＢＡＳＦ製））２質量部、光安定剤（チヌビン（商品名）、ＢＡＳＦ社）２質量部、防腐剤２質量部、イソプロピルアルコール１０質量部、残部水からなる透明のものを用いた。
[Experimental Example 1]
As the water-based paint composition containing the reactive water-based polysiloxane-acrylic composite resin as the main component in the water-based exterior wood paint of Experimental Example 1, the reactive polysiloxane-acrylic composite resin (Zemrack W3108F (trade name), Kaneka Co., Ltd.) ) 25 parts by mass, scaly silica powder (3 parts by mass of Sun Lovely (registered brand name, AGCSI Tech Co., Ltd.), 2 parts by mass of smectite powder adsorbed with polycarbodiimide, film-forming aid (Dawanol PNP (trade name)) , Ando Parachemy Co., Ltd.), 5 parts by mass, water-repellent additive (Modiver F266 (trade name, manufactured by Nichiyu Co., Ltd.)), inorganic UV absorber (titanium oxide), 2 parts by mass, organic UV absorber (Chinubin) 400 (trade name, manufactured by BASF)) 2 parts by mass, light stabilizer (Chinubin (trade name), BASF) 2 parts by mass, preservative 2 parts by mass, isopropyl alcohol 10 parts by mass, remaining transparent Using.
この実験例１の水性塗料組成物について、密閉状態で３ヶ月間静置する貯蔵安定性試験を行った。結果は、ゲル化や分離等が生じなかったものを「○」と判定し、ゲル化や分離等が生じたものを「×」と判定し、下記表１に示した。 The aqueous coating composition of Experimental Example 1 was subjected to a storage stability test in which it was allowed to stand in a sealed state for 3 months. As a result, those without gelation or separation were judged as "○", and those with gelation or separation were judged as "x" and are shown in Table 1 below.
また、実験例１の水性外装用木材塗料における反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物に対する加水分解性シリコン化合物を主成分とする硬化剤としては、加水分解性シリコン化合物（Ｄｙｎａｓｙｌａｎ ＨＹＤＲＯＳＩＬ １１５１（商品名）、エボニック製）４０質量部、プロピレングリコール６０質量部からなるものを用いた。 Further, as a curing agent containing a hydrolyzable silicone compound as a main component for a water-based paint composition containing a reactive water-based polysiloxane-acrylic composite resin as a main component in the water-based exterior wood paint of Experimental Example 1, hydrolyzable silicone is used. A compound (Dynamiclan HYDROSIL 1151 (trade name), manufactured by Ebonic) consisting of 40 parts by mass and 60 parts by mass of propylene glycol was used.
上記のように調製された反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物と、同じく上記のようにして調製された加水分解性シリコン化合物を主成分とする硬化剤とを、それぞれ質量比で１：０．１となるように混合し、実験例１の水性外装用木材塗料を得た。 An aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin prepared as described above as a main component and a curing agent containing a hydrolyzable silicone compound as a main component also prepared as described above. , Each was mixed so as to have a mass ratio of 1: 0.1 to obtain a water-based exterior wood paint of Experimental Example 1.
この実験例１の水性外装用木材塗料を用い、被塗装物としてスギ材（無節）の７０×１５０×１０ｍｍのものを２枚用意し、直ちにスプレー法により、予め定めた条件で、所定厚さに塗布し、実験例１の被検試料を得た。このスプレー塗装を行った際の塗装作業性について、２枚とも塗布ムラや外観不良が生じなかったものを「○」と判定し、２枚中１枚でも塗布ムラや外観不良が生じたものを「×」と判定した。結果を下記表１に纏めて示した。 Using the water-based exterior wood paint of Experimental Example 1, two sheets of Sugi material (no knot) of 70 x 150 x 10 mm were prepared as objects to be coated, and immediately sprayed by a spray method to a predetermined thickness under predetermined conditions. Then, it was applied to obtain a test sample of Experimental Example 1. Regarding the coating workability when this spray coating was performed, those in which no coating unevenness or poor appearance occurred in both sheets were judged as "○", and those in which even one of the two sheets had coating unevenness or poor appearance was judged as "○". It was judged as "x". The results are summarized in Table 1 below.
さらに、スプレー塗装した２枚の被検試料について、室温下で十分に乾燥させ、ＪＩＳ Ｋ ５６００−７−７のサイクルＡに準じて促進耐候性試験を行い、変色やひび割れの有無を調査した。評価は、５００時間、１０００時間、１５００時間及び２０００時間で実施した。「耐候性（変色試験）」結果及び（耐候性(ひび割れ）」結果は、いずれも２０００時間まで異常がなかったものを「○」と判定し、１０００時間まで異常がなかったが２０００時間で異常があったものを「△」と判定し、１０００時間及び２０００時間の両方で異常が認められたものを「×」と判定した。結果を下記表１に纏めて示した。 Further, the two spray-coated samples were sufficiently dried at room temperature, and an accelerated weather resistance test was conducted according to cycle A of JIS K 5600-7-7 to investigate the presence or absence of discoloration and cracks. The evaluation was carried out at 500 hours, 1000 hours, 1500 hours and 2000 hours. The "weather resistance (discoloration test)" result and the (weather resistance (crack)" result were judged as "○" if there was no abnormality up to 2000 hours, and there was no abnormality up to 1000 hours, but there was an abnormality in 2000 hours. Those with an abnormality were judged to be "Δ", and those in which an abnormality was observed in both 1000 hours and 2000 hours were judged to be "x". The results are summarized in Table 1 below.
［実験例２］
鱗片状シリカ粉末及びポリカルボジイミド吸着スメクタイト粉末と、撥水性添加剤とを添加しなかった以外は実験例１の水性塗料組成物の場合と同様にして、実験例２の反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物を調製し、その他の条件は全て実験例１の場合と同様にして実験例２の被検試料を作成した。そして、実験例１の場合と同様の各種試験を行ない、結果を纏めて下記表１に示した。
[Experimental Example 2]
Reactive aqueous polysiloxane-acrylic of Experimental Example 2 in the same manner as in the case of the aqueous coating composition of Experimental Example 1 except that the scaly silica powder, the polycarbodiimide-adsorbed smectite powder, and the water-repellent additive were not added. An aqueous coating composition containing a composite resin as a main component was prepared, and a test sample of Experimental Example 2 was prepared in the same manner as in Experimental Example 1 under all other conditions. Then, various tests similar to those in Experimental Example 1 were performed, and the results are summarized in Table 1 below.
［実験例３］
鱗片状シリカ粉末のみを添加しなかった以外は実験例１の水性塗料組成物の場合と同様にして、実験例３の反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物を調製し、その他の条件は全て実験例１の場合と同様にして実験例３の被検試料を作成した。そして、実験例１の場合と同様の各種試験を行い、結果を纏めて下記表１に示した。
[Experimental Example 3]
Similar to the case of the aqueous coating composition of Experimental Example 1 except that only the scaly silica powder was not added, the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin of Experimental Example 3 as a main component was prepared. The test sample of Experimental Example 3 was prepared in the same manner as in Experimental Example 1 under all other conditions. Then, various tests similar to those in Experimental Example 1 were performed, and the results are summarized in Table 1 below.
［実験例４］
鱗片状シリカ粉末の添加料を実験例１場合（４質量部）よりも多い６質量部とした以外は実験例１の水性塗料組成物の場合と同様にして、実験例４の反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物を調製し、その他の条件は全て実験例１の場合と同様にして実験例４の被検試料を作成した。そして、実験例１の場合と同様の各種試験を行い、結果を纏めて下記表１に示した。
[Experimental Example 4]
Reactive aqueous poly of Experimental Example 4 in the same manner as in the case of the aqueous coating composition of Experimental Example 1 except that the additive of the scaly silica powder was 6 parts by mass, which was larger than that of Experimental Example 1 (4 parts by mass). An aqueous coating composition containing a siloxane-acrylic composite resin as a main component was prepared, and a test sample of Experimental Example 4 was prepared in the same manner as in Experimental Example 1 under all other conditions. Then, various tests similar to those in Experimental Example 1 were performed, and the results are summarized in Table 1 below.
［実験例５］
ポリカルボジイミド吸着スメクタイト粉末を添加しなかった以外は実験例１の水性塗料組成物の場合と同様にして、実験例５の反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物を調製し、その他の条件は全て実験例１の場合と同様にして実験例５の被検試料を作成した。そして、実験例１の場合と同様の各種試験を行い、結果を纏めて下記表１に示した。
[Experimental Example 5]
The aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin of Experimental Example 5 as a main component was prepared in the same manner as in the case of the aqueous coating composition of Experimental Example 1 except that the polycarbodiimide-adsorbed smectite powder was not added. The test sample of Experimental Example 5 was prepared in the same manner as in Experimental Example 1 under all other conditions. Then, various tests similar to those in Experimental Example 1 were performed, and the results are summarized in Table 1 below.
［実験例６］
ポリカルボジイミド吸着スメクタイト粉末の添加料を実験例１場合（２質量部）よりも多い４質量部とした以外は実験例１の水性塗料組成物の場合と同様にして、実験例６の反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物を調製し、その他の条件は全て実験例１の場合と同様にして実験例６の被検試料を作成した。そして、実験例１の場合と同様の各種試験を行い、結果を纏めて下記表１に示した。
[Experimental Example 6]
The reactive water-based solution of Experimental Example 6 was the same as in the case of the aqueous coating composition of Experimental Example 1 except that the additive of the polycarbodiimide-adsorbed smectite powder was 4 parts by mass, which was larger than that of Experimental Example 1 (2 parts by mass). An aqueous coating composition containing a polysiloxane-acrylic composite resin as a main component was prepared, and a test sample of Experimental Example 6 was prepared in the same manner as in Experimental Example 1 under all other conditions. Then, various tests similar to those in Experimental Example 1 were performed, and the results are summarized in Table 1 below.
［実験例７］
撥水性添加剤を添加しなかった以外は実験例１の水性塗料組成物の場合と同様にして、実験例７の反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物を調製し、その他の条件は全て実験例１の場合と同様にして実験例７の被検試料を作成した。そして、実験例１の場合と同様の各種試験を行い、結果を纏めて下記表１に示した。
[Experimental Example 7]
An aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin of Experimental Example 7 as a main component was prepared in the same manner as in the case of the aqueous coating composition of Experimental Example 1 except that no water repellent additive was added. However, the test sample of Experimental Example 7 was prepared in the same manner as in Experimental Example 1 under all other conditions. Then, various tests similar to those in Experimental Example 1 were performed, and the results are summarized in Table 1 below.
さらに、実験例１〜３及び５の被検試料について耐候性試験を行った際の、５００時間、１０００時間、２０００時間及び２５００時間経過時の表面状態を撮影した写真を図１に示した。 Further, FIG. 1 shows photographs of the surface conditions of the test samples of Experimental Examples 1 to 3 and 5 after the lapse of 500 hours, 1000 hours, 2000 hours and 2500 hours when the weather resistance test was performed.
表１及び図１に示した結果から以下のことがわかる。すなわち、実験例１の被検試料では、貯蔵安定性及び塗装作業性は良好であり、耐候性試験結果は変色及びビ割れともに認められず、２５００時間経過時でも良好な結果が得られていた。それに対し、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中に鱗片状シリカ、ポリカルボジイミド吸着スメクタイト粉末及び撥水性添加剤を含有していない実験例２の被検試料では、貯蔵安定性及び塗装作業性は良好であったが、耐候性試験結果は、１０００時間経過時で既に変色及びひび割れが生じていた。また、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中に鱗片状シリカ粉末のみ含有していない実験例３の被検試料では、貯蔵安定性及び塗装作業性は良好であったが、耐候性試験結果は、１０００時間経過時は変色はあまり認められなかったひび割れが生じており、２０００時間経過時にはひび割れだけでなく明確に変色も生じていた。 The following can be seen from the results shown in Table 1 and FIG. That is, in the test sample of Experimental Example 1, storage stability and coating workability were good, and neither discoloration nor cracking was observed in the weather resistance test results, and good results were obtained even after 2500 hours had passed. .. On the other hand, in the test sample of Experimental Example 2 which does not contain scaly silica, polycarbodiimide-adsorbed smectite powder and water-repellent additive in the water-based coating composition containing the reactive water-based polysiloxane-acrylic composite resin as the main component. Although the storage stability and coating workability were good, the weather resistance test result showed that discoloration and cracks had already occurred after 1000 hours. Further, in the test sample of Experimental Example 3 in which only the scaly silica powder was not contained in the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as the main component, the storage stability and the coating workability were good. However, the weather resistance test result showed that after 1000 hours, there were cracks in which discoloration was not so much observed, and after 2000 hours, not only cracks but also clear discoloration occurred.
一方、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中の鱗片状シリカ粉末の添加量を、実験例１の３質量部よりも増大させて６質量部とした実験例４の被検試料では、貯蔵安定性は良好であり、耐候性試験結果も２０００時間経過時にひび割れ及び変色は実質的に認められなかったが、塗装作業時に塗装ムラが生じて外観不良となっていた。また、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中にポリカルボジイミド吸着スメクタイト粉末のみ含有していない実験例５の被検試料では、貯蔵安定性及び塗装作業性は良好であったが、耐候性試験結果は、１０００時間経過時でヒビ割れは実質的に生じていなかったが既に変色が生じており、２０００時間経過時では完全にひび割れも生じていた。 On the other hand, in the experimental example, the amount of the scaly silica powder added to the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as a main component was increased from 3 parts by mass of Experimental Example 1 to 6 parts by mass. In the test sample of No. 4, the storage stability was good, and the weather resistance test result showed that cracks and discoloration were not substantially observed after 2000 hours, but coating unevenness occurred during the coating operation and the appearance was poor. It was. Further, in the test sample of Experimental Example 5 in which only the polycarbodiimide-adsorbed smectite powder is not contained in the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as the main component, the storage stability and the coating workability are good. However, the weather resistance test result showed that cracks were not substantially generated after 1000 hours, but discoloration had already occurred, and cracks were completely generated after 2000 hours.
また、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中のポリカルボジイミドを吸着させたスメクタイト粉末の添加量を、実験例１の２質量部よりも増大させて４質量部とした実験例６の被検試料では、貯蔵安定性及び塗装作業性が不良であり、実質的に塗装不可となっていた。さらに、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中に撥水性添加剤の身を含有していない実験例７の被検試料では、貯蔵安定性及び塗装作業性は良好であり、耐候性試験結果は、１０００時間経過時は変色及びひび割れは実質的に認められなかったが、２０００時間経過時には変色及びひび割れともに明確に生じていた。 Further, the amount of smectite powder adsorbed with polycarbodiimide in the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as a main component was increased from 2 parts by mass of Experimental Example 1 to 4 parts by mass. In the test sample of Experimental Example 6, the storage stability and the coating workability were poor, and coating was substantially impossible. Further, in the test sample of Experimental Example 7 in which the body of the water-repellent additive was not contained in the water-based coating composition containing the reactive water-based polysiloxane-acrylic composite resin as the main component, the storage stability and the coating workability were improved. It was good, and the weather resistance test result showed that discoloration and cracks were not substantially observed after 1000 hours, but discoloration and cracks were clearly observed after 2000 hours.
したがって、実験例１〜３及び５の結果を対比すると、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中への鱗片状シリカ粉末ないしポリカルボジイミドを吸着させたスメクタイト粉末の添加の有無は、加水分解性シリコン化合物を主成分とする前記水性塗料組成物の硬化剤を混合して水性外装用木材塗料を調製した際の貯蔵安定性及び塗装作業性に実質的な影響は与えないが、耐候性劣るようになることがわかる。 Therefore, comparing the results of Experimental Examples 1 to 3 and 5, a smectite powder having scaly silica powder or polycarbodiimide adsorbed in an aqueous coating composition containing a reactive aqueous polysiloxane-acrylic composite resin as a main component. The presence or absence of the addition has a substantial effect on the storage stability and coating workability when a water-based exterior wood paint is prepared by mixing the curing agent of the water-based paint composition containing a hydrolyzable silicone compound as a main component. It is not given, but it is found that the weather resistance becomes inferior.
また、実験例１及び３の結果を対比すると、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中に鱗片状シリカ粉末を含有していないと、加水分解性シリコン化合物を主成分とする前記水性塗料組成物の硬化剤を混合して水性外装用木材塗料を調製した際の貯蔵安定性及び塗装作業性に実質的な影響は生じないが、耐候性に影響を与え、変色はあまり生じないがひび割れが多くなる。また、実験例１及び５の結果を対比すると、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中にポリカルボジイミドを吸着させたスメクタイト粉末を含有していないと、水性塗料組成物の硬化剤を混合して水性外装用木材塗料を調製した際の貯蔵安定性及び塗装作業性に実質的な影響は生じないが、耐候性に影響を与え、ひび割れはあまり生じないが変色が多くなる。 Further, comparing the results of Experimental Examples 1 and 3, if the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as a main component does not contain the scaly silica powder, the hydrolyzable silicone compound is obtained. When a water-based exterior wood paint is prepared by mixing the curing agent of the water-based paint composition as a main component, there is no substantial effect on storage stability and coating workability, but it affects weather resistance. There is not much discoloration, but there are many cracks. In addition, comparing the results of Experimental Examples 1 and 5, if the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as the main component does not contain smectite powder having polycarbodiimide adsorbed, the aqueous coating material must be contained. There is no substantial effect on storage stability and coating workability when a water-based exterior wood paint is prepared by mixing a curing agent of the composition, but it affects weather resistance and does not cause much cracking but discoloration. Will increase.
そのため、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物と加水分解性シリコン化合物を主成分とする前記水性塗料組成物の硬化剤とからなる水性外装用木材塗料においては、ポリカルボジイミドを吸着させたスメクタイト粉末及び鱗片状シリカ粉末の両者を同時に含ませることにより、スメクタイト粉末及び鱗片状シリカ粉末添加の両者の添加の利点を生かした上で、それぞれの欠点を互いに補うことができ、耐久性が良好な有機無機複合塗膜を形成することができる外装用木材塗料が得られることがわかる。 Therefore, in a water-based exterior wood paint composed of a water-based paint composition containing a reactive water-based polysiloxane-acrylic composite resin as a main component and a curing agent of the water-based paint composition containing a hydrolyzable silicon compound as a main component, By simultaneously containing both the smectite powder and the scaly silica powder adsorbed with polycarbodiimide, it is possible to take advantage of the addition of both the smectite powder and the scaly silica powder and to compensate for each other's shortcomings. It can be seen that an exterior wood paint capable of forming an organic-inorganic composite coating film having good durability can be obtained.
さらに、実験例１及び４の結果を対比すると、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中の鱗片状シリカ粉末の添加量が多くなると塗装作業性が劣るようになることがわかり、その添加量の上限は水性塗料組成物全体に対して５質量部以下が好ましいと予測される。なお、その添加量の下限は、水性塗料組成物全体に対して０．５質量部未満であると良好な木部のひび割れ防止補強効果が得られなくなるので、より好ましい水性塗料組成物中の鱗片状シリカ粉末の含有割合は、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物１００質量部に対して０．５質量部以上４質量部以下であると認められる。なお、鱗片状シリカ粉末の平均粒径は、臨界的限度は必ずしも明確ではないが、０．５μｍ以上３．０μｍ以下のものが好ましい。 Further, comparing the results of Experimental Examples 1 and 4, the coating workability is deteriorated when the amount of the scaly silica powder added to the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as a main component is large. It is predicted that the upper limit of the addition amount is preferably 5 parts by mass or less with respect to the entire water-based coating composition. If the lower limit of the addition amount is less than 0.5 parts by mass with respect to the entire water-based coating composition, a good crack-preventing and reinforcing effect on the wood portion cannot be obtained. Therefore, scales in the more preferable water-based coating composition It is recognized that the content ratio of the state silica powder is 0.5 parts by mass or more and 4 parts by mass or less with respect to 100 parts by mass of the water-based coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as a main component. Although the critical limit of the average particle size of the scaly silica powder is not always clear, it is preferably 0.5 μm or more and 3.0 μm or less.
さらに、実験例１及び６の結果を対比すると、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中のポリカルボジイミドを吸着させたスメクタイトの含有割合が多くなると貯蔵安定性だけでなく塗装作業性が劣るようになり、実質的に塗装不可となるので、その添加量は水性塗料組成物全体に対して３質量部以下が好ましいと予測される。なお、その添加量の下限は、水性塗料組成物全体に対して０．５質量部未満であるとガスや水に対し優れたバリア性を持った塗膜が得られなくなるので、より好ましいポリカルボジイミドを吸着させたスメクタイトの含有割合は、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物１００質量部に対して１質量部以上２．５質量部以下であると認められる。 Furthermore, comparing the results of Experimental Examples 1 and 6, when the content ratio of smectite adsorbed with polycarbodiimide in the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as the main component increases, only the storage stability is achieved. However, the coating workability becomes inferior and coating becomes practically impossible. Therefore, it is predicted that the addition amount thereof is preferably 3 parts by mass or less with respect to the entire water-based coating composition. If the lower limit of the addition amount is less than 0.5 parts by mass with respect to the entire aqueous coating composition, a coating film having an excellent barrier property against gas and water cannot be obtained, which is more preferable polycarbodiimide. It is recognized that the content ratio of smectite adsorbed is 1 part by mass or more and 2.5 parts by mass or less with respect to 100 parts by mass of the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as a main component.
さらに、実験例１及び７の結果を対比すると、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中への撥水性添加剤の添加の有無は、耐候性に影響を与え、撥水性添加剤を添加すると長期耐候性が良好となることがわかる。このことは、反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中へ撥水性添加剤をすると、塗膜の表面に撥水性が付与されるため、木部用に使用した場合でも長期的に木の内部に水分が浸透し難くなるので、木の劣化が抑制され、耐久性が良好となることを意味している。 Furthermore, comparing the results of Experimental Examples 1 and 7, the presence or absence of the addition of the water-repellent additive in the water-based coating composition containing the reactive water-based polysiloxane-acrylic composite resin as the main component affects the weather resistance. , It can be seen that the long-term weather resistance is improved by adding the water-repellent additive. This is because when a water-repellent additive is added to a water-based paint composition containing a reactive water-based polysiloxane-acrylic composite resin as a main component, water repellency is imparted to the surface of the coating film, so that this was used for wood. Even in this case, it is difficult for water to permeate the inside of the tree for a long period of time, which means that deterioration of the tree is suppressed and the durability is improved.
［実験例８〜１０］
実験例８〜１０においては、実験例１の反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物中に、市販のクリーム色顔料（実験例８）、ピニー色顔料（実験例９）及びウォルナット色顔料（実験例１０）を微量添加し、実験例１の場合と同様にして被検試料を作成した。そして、実験例８〜１０の被検試料について耐候性試験を行った際の、５００時間、１０００時間、２０００時間及び２５００時間経過時の表面状態の写真を、実験例１のものとともに、図２に示した。図２に示した結果から、実験例１の反応型水性ポリシロキサン−アクリル複合樹脂を主成分とする水性塗料組成物と同様の組成を有していれば、顔料添加の有無によらず、貯蔵安定性及び塗装作業性は当然のこと、耐候性も変色及びヒビ割れの何れにおいても良好な効果が得られ、耐久性が良好な水性外装用木材塗料となることが確認された。
[Experimental Examples 8 to 10]
In Experimental Examples 8 to 10, commercially available cream-colored pigments (Experimental Example 8) and piny-colored pigments (Experimental Examples) were added to the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin of Experimental Example 1 as a main component. 9) and Walnut color pigment (Experimental Example 10) were added in a small amount to prepare a test sample in the same manner as in Experimental Example 1. Then, photographs of the surface state after 500 hours, 1000 hours, 2000 hours, and 2500 hours when the weather resistance test was performed on the test samples of Experimental Examples 8 to 10 are taken together with those of Experimental Example 1 in FIG. It was shown to. From the results shown in FIG. 2, as long as it has the same composition as the aqueous coating composition containing the reactive aqueous polysiloxane-acrylic composite resin as the main component of Experimental Example 1, it can be stored regardless of the presence or absence of pigment addition. It was confirmed that not only stability and coating workability but also weather resistance and good effects were obtained in both discoloration and cracking, and the wood paint for water-based exterior had good durability.
Claims (4)
前記水性塗料組成物は、鱗片状シリカ粉末及びポリカルボジイミドを吸着させたスメクタイト粉末を含むことを特徴とする、水性外装用木材塗料。 A water-based exterior wood paint containing a water-based paint composition containing a reactive water-based polysiloxane-acrylic composite resin as a main component and a curing agent of the water-based paint composition containing a hydrolyzable silicone compound as a main component.
The water-based paint composition is a water-based exterior wood paint, which comprises a scaly silica powder and a smectite powder on which polycarbodiimide is adsorbed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019233467A JP7410710B2 (en) | 2019-12-24 | 2019-12-24 | Water-based exterior wood paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019233467A JP7410710B2 (en) | 2019-12-24 | 2019-12-24 | Water-based exterior wood paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021102673A true JP2021102673A (en) | 2021-07-15 |
| JP7410710B2 JP7410710B2 (en) | 2024-01-10 |
Family
ID=76754795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019233467A Active JP7410710B2 (en) | 2019-12-24 | 2019-12-24 | Water-based exterior wood paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7410710B2 (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053769A (en) * | 2000-05-29 | 2002-02-19 | Mitsui Kinzoku Toryo Kagaku Kk | Pigment for corrosion preventive coating composition and corrosion preventive coating composition therewith |
| JP2002080834A (en) * | 2000-09-11 | 2002-03-22 | Dokai Chemical Industries Co Ltd | Cured film having high water resistance |
| JP2003064298A (en) * | 2001-08-24 | 2003-03-05 | Asahi Glass Co Ltd | Coatings for building material and coated building component |
| JP2005048035A (en) * | 2003-07-31 | 2005-02-24 | Fimatec Ltd | Magnesium hydroxide-based flame retardant and resin composition containing the same |
| WO2006137432A1 (en) * | 2005-06-21 | 2006-12-28 | Nisshinbo Industries, Inc. | Filler for substrate and composition for use as material for inorganic/organic composite substrate formation |
| JP2008127424A (en) * | 2006-11-17 | 2008-06-05 | Agc Coat-Tech Co Ltd | Coating composition, coating, coating kit, and coated article |
| JP2008156434A (en) * | 2006-12-22 | 2008-07-10 | Kaneka Corp | 2 pot type aqueous coating composition |
| JP2012201778A (en) * | 2011-03-25 | 2012-10-22 | Kaneka Corp | Resin composition for water-based coating and coating provided by compounding the resin composition for water-based coating |
| JP2020125402A (en) * | 2019-02-05 | 2020-08-20 | 株式会社Ｄｅｓｉｇｎ京都 | Thixotropic agent |
-
2019
- 2019-12-24 JP JP2019233467A patent/JP7410710B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053769A (en) * | 2000-05-29 | 2002-02-19 | Mitsui Kinzoku Toryo Kagaku Kk | Pigment for corrosion preventive coating composition and corrosion preventive coating composition therewith |
| JP2002080834A (en) * | 2000-09-11 | 2002-03-22 | Dokai Chemical Industries Co Ltd | Cured film having high water resistance |
| JP2003064298A (en) * | 2001-08-24 | 2003-03-05 | Asahi Glass Co Ltd | Coatings for building material and coated building component |
| JP2005048035A (en) * | 2003-07-31 | 2005-02-24 | Fimatec Ltd | Magnesium hydroxide-based flame retardant and resin composition containing the same |
| WO2006137432A1 (en) * | 2005-06-21 | 2006-12-28 | Nisshinbo Industries, Inc. | Filler for substrate and composition for use as material for inorganic/organic composite substrate formation |
| JP2008127424A (en) * | 2006-11-17 | 2008-06-05 | Agc Coat-Tech Co Ltd | Coating composition, coating, coating kit, and coated article |
| JP2008156434A (en) * | 2006-12-22 | 2008-07-10 | Kaneka Corp | 2 pot type aqueous coating composition |
| JP2012201778A (en) * | 2011-03-25 | 2012-10-22 | Kaneka Corp | Resin composition for water-based coating and coating provided by compounding the resin composition for water-based coating |
| JP2020125402A (en) * | 2019-02-05 | 2020-08-20 | 株式会社Ｄｅｓｉｇｎ京都 | Thixotropic agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7410710B2 (en) | 2024-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101744500B1 (en) | Composition of high elastic putty for crack repair containing inorganic filler surface modified with silane coupling agent and construction method thereof | |
| KR100982451B1 (en) | Anti-corrosion ceramic coating material containing nano-sized flakes | |
| KR101512965B1 (en) | Eco-Friendly Surface Protectant and Eco-Friendly Surface Method of Surface Protection Using Thereof | |
| KR101868073B1 (en) | Eco-friendly surface protection composition with enhanced functions and durability and method for protecting surface of concrete structure therewith | |
| CN113755036B (en) | Modified graphene oxide, water-based anticorrosive paint and preparation method thereof | |
| KR101934694B1 (en) | Coating composition for surface protection of concrete structure with excellent weather resistance and strain resistance containing silicone modified hybrid ceramic resin and, Method for waterproof and anti-corrosion of concrete structure using the same | |
| KR102110301B1 (en) | Composition of eco-friendly composite ceramic coating agent for steel structure and, its manufacturing method | |
| UA58487C2 (en) | Epoxy polysiloxane composition for coatings (variants), a method for preparing thereof (variants) | |
| KR101715825B1 (en) | Non-solvent high-anticorrosive paint and silane containing high-anticorrosive paint and painting method of double-coated ultraweatheralbility steel structure using the high-anticorrosive paint | |
| KR101724527B1 (en) | Hybrid coating composition, preparation method thereof and coating method on the surface of the concrete or steel material for non-combustibility and preventing neutralization/salt damage using the same | |
| US4495247A (en) | Primer coating composition of a fluorocarbon polymer and an amino alkyl alkoxy silane | |
| KR100942027B1 (en) | Aqueous painting composition and coating method for steel corrosion.concrete blocks neutralization prevention water proof using the same | |
| KR101702118B1 (en) | Environment-friendly heavy duty steel paint composition and heavy duty steel coating method of steel material structure using the same | |
| KR101876888B1 (en) | Steel coating composition having excellent corrosion resistance and durability and method for coating steel structure using the same | |
| KR20160105060A (en) | A inorganic nonflammable coating composition having the increased water resistant and fouling resistant qualities and a process for the preparation thereof | |
| JP4842599B2 (en) | Water-based paint for architectural civil engineering | |
| KR101722753B1 (en) | Ceramic coating composition with strengthened durability and method for eco-friendly protecting and strengthening surface of concrete or metal structure | |
| KR20180107915A (en) | An eco-friendly and water-soluble hybrid multipurpose primer compositions and an organic-inorganic floor coating using the same | |
| US7037966B2 (en) | Stain resistant coating | |
| KR20170094028A (en) | Adhesives for sticking architectural finishing materials and manufacturing method thereof | |
| KR101614399B1 (en) | Coating Composition for Iron and Concrete Construction and Constructing Methods Using Thereof | |
| KR102060601B1 (en) | Water proof painting composition for concrete structure and painting method | |
| JP2000210616A (en) | Formation of moisture permeable coating film | |
| JP7410710B2 (en) | Water-based exterior wood paint | |
| KR102067736B1 (en) | Repair-reinforcement method for concrete structure using base coating material containing functional-aqueous epoxy, polymer mortar containing aramid fibers and surface protectant containing nano-size silver |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20210409 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210929 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220722 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20220916 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20220916 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20230407 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230516 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230615 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230926 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20231027 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20231212 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20231222 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7410710 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |