JP2021172806A - Water-based melamine resin coating for shielding infrared rays and ultraviolet rays and preparation method therefor - Google Patents

Water-based melamine resin coating for shielding infrared rays and ultraviolet rays and preparation method therefor Download PDF

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JP2021172806A
JP2021172806A JP2020178661A JP2020178661A JP2021172806A JP 2021172806 A JP2021172806 A JP 2021172806A JP 2020178661 A JP2020178661 A JP 2020178661A JP 2020178661 A JP2020178661 A JP 2020178661A JP 2021172806 A JP2021172806 A JP 2021172806A
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張家暘
Jiayang Zhang
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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Abstract

To provide a water-based melamine resin coating for shielding infrared rays and ultraviolet rays and a preparation method therefor.SOLUTION: A water-based melamine resin coating for shielding infrared rays and ultraviolet rays has: 30 pts. of PEEK modified MOF, 1 pt. of SAC-100, 30 pts. of an acrylic resin emulsion, 3 pts. of carbon aerogel, 5 pts. of silicon carbide, 5 pts. of nano bamboo fibers, 1 pt. of montmorillonite, 1 pt. of modified graphene, 5 pts. of rutile type nano titanium dioxide, 1 pt. of a thickening agent, 1 pt. of water-based defoamer and 10 pts. of water.SELECTED DRAWING: None

Description

本発明は建築塗料技術分野に属し、具体的には赤外線と紫外線を遮蔽する水性メラミン樹脂塗料及びその製造方法に関する。 The present invention belongs to the field of architectural paint technology, and specifically relates to an aqueous melamine resin paint that shields infrared rays and ultraviolet rays, and a method for producing the same.

水性メラミン樹脂塗料は、家、ホテル等の内装に広く使用されている内壁用塗料である。水性メラミン樹脂塗料は一般的に、溶剤型メラミン樹脂塗料と水性エマルジョンメラミン樹脂塗料に分けられる。溶剤型メラミン樹脂塗料は硬化中に、有毒な揮発性溶剤を放出し、労働者や住戸の身体の健康を脅かし、環境保護の要求に適合しないため、応用において制限される。一方、化学工業、冶金、熱間加工などの特殊な分野では、１５０℃を超える発熱体が赤外放射を発生することにより、塗料の断熱性能が急激に低下し、熱伝導率が急激に上昇し、塗料がより速く割れて剥げ、生産過程の安全性に影響を及ぼすため、耐赤外線性と耐紫外線性の良い、環境に優しいメラミン樹脂塗料を調製する必要があるが、現在では、それに関する研究報告が少ない。
ＣＮ１０５１９９５１５Ａには、ＰＰプライマーと、中層水性メラミン樹脂塗料と、表層ＵＶ塗料とから構成されるメラミン樹脂塗料及びその塗装方法が開示され、従来の塗料におけるプライマーが割れやすい問題と、中層が相対的に硬度が低い問題と、耐候性、耐老化性、層間付着力が劣る問題とを解決した。しかし、このメラミン樹脂塗料は、コストが高く、塗装が面倒であり、抗赤外放射性が普通であり、適用範囲が制限されている。
ＣＮ１０８２１９６６６Ｂには、改質ポリイミド樹脂溶液と、方解石と、二酸化チタンと、ベントナイトと、断熱エアロゲル粒子とを含む、耐赤外線、静菌、耐候性の水性メラミン樹脂塗料及びその製造方法が開示されているが、改質ポリイミド樹脂溶液の調製過程でホルムアルデヒドが使用され、ホルムアルデヒドは常温で気体であり、発がん性物質であり、人体や環境に毒があるため、この耐赤外線、静菌、耐候性の水性メラミン樹脂塗料の製造方法を採用して製造した水性メラミン樹脂塗料は安全性の問題が存在する。
ＣＮ１０９３８５１６３Ａには、赤外線と紫外線を全部遮蔽するＰＥＥＫ改質アクリル酸水性透明断熱塗料が開示され、この水性透明断熱塗料は、ＰＥＥＫ改質水性アクリル樹脂、ナノ透明断熱剤、ナノ光触媒、透明ナノカラーペーストなどの材料からなり、優れた耐放射線性を有するが、ナノ透明断熱剤に添加されるＷＯ３は、皮膚に刺激性を有し、人体安全に不利であり、また、製造工程が複雑であり、１０００ｈの耐湿熱、耐劣化性能試験のみを行い、耐候性が不足している。 The water-based melamine resin paint is a paint for interior walls that is widely used in the interior of houses, hotels, and the like. Water-based melamine resin paints are generally divided into solvent-based melamine resin paints and water-based emulsion melamine resin paints. Solvent-type melamine resin paints are limited in application because they release toxic volatile solvents during curing, threaten the physical health of workers and dwelling units, and do not meet environmental protection requirements. On the other hand, in special fields such as the chemical industry, metallurgy, and hot working, the heat insulating performance of the paint drops sharply and the thermal conductivity rises sharply due to the generation of infrared radiation by the heating element exceeding 150 ° C. However, because the paint cracks and peels off faster and affects the safety of the production process, it is necessary to prepare an environmentally friendly melamine resin paint with good infrared resistance and ultraviolet resistance, but nowadays, it is related to that. There are few research reports.
CN105199515A discloses a melamine resin paint composed of a PP primer, a middle layer water-based melamine resin paint, and a surface layer UV paint, and a coating method thereof. The problem of low hardness and the problem of poor weather resistance, aging resistance, and interlayer adhesion have been solved. However, this melamine resin paint is expensive, cumbersome to paint, usually has anti-infrared radioactivity, and its scope of application is limited.
CN108219666B discloses an infrared-resistant, bacteriostatic, and weather-resistant water-based melamine resin coating material containing a modified polyimide resin solution, a calcified stone, titanium dioxide, bentonite, and adiabatic aerogel particles, and a method for producing the same. However, formaldehyde is used in the process of preparing the modified polyimide resin solution, and formaldehyde is a gas at room temperature, is a carcinogenic substance, and is toxic to the human body and the environment. The water-based melamine resin paint produced by adopting the method for producing the melamine resin paint has a safety problem.
CN109385163A discloses a PEEK-modified acrylic acid water-based transparent heat insulating paint that shields all infrared rays and ultraviolet rays, and the water-based transparent heat insulating paint includes a PEEK-modified water-based acrylic resin, a nanotransparent heat insulating agent, a nanophotocatalyst, and a transparent nanocolor paste. WO3, which is made of such materials and has excellent radiation resistance, is irritating to the skin, is disadvantageous to human safety, and the manufacturing process is complicated. Only 1000h of moisture resistance and deterioration resistance performance test is performed, and the weather resistance is insufficient.

中国特許出願公開第１０５１９９５１５号明細書Chinese Patent Application Publication No. 105199515 中国特許出願公開第１０８２１９６６６号明細書Chinese Patent Application Publication No. 1082196666 中国特許出願公開第１０９３８５１６３号明細書Chinese Patent Application Publication No. 1093851163

本発明は、上記の技術的課題を解決するために、赤外線と紫外線を遮蔽する水性メラミン樹脂塗料及びその製造方法を提供することを目的とする。 An object of the present invention is to provide an aqueous melamine resin coating material that shields infrared rays and ultraviolet rays and a method for producing the same, in order to solve the above technical problems.

赤外線と紫外線を遮蔽する水性メラミン樹脂塗料であって、３０‐３５部のＰＥＥＫ改質ＭＯＦ、１‐５部の架橋剤、３０‐５０部のアクリル樹脂乳液、３‐４部のカーボンエアロゲル、５‐１０部の炭化ケイ素、５‐１０部のナノ竹繊維、１‐５部のモンモリロナイト、１‐５部の改質グラフェン、５‐６部のルチル型ナノ二酸化チタン、１‐２部の増粘剤、１‐５部の水性消泡剤、及び１０‐２０部の水からなる。 A water-based melamine resin paint that shields infrared rays and ultraviolet rays, 30-35 parts of PEEK-modified MOF, 1-5 parts of cross-linking agent, 30-50 parts of acrylic resin emulsion, 3-4 parts of carbon airgel, 5 -10 parts silicon carbide, 5-10 parts nanobamboo fiber, 1-5 parts montmorillonite, 1-5 parts modified graphene, 5-6 parts rutile nanotitanium dioxide, 1-2 parts thickening The agent consists of 1-5 parts of aqueous defoaming agent and 10-20 parts of water.

前記架橋剤はＳＡＣ‐１００であり、
前記増粘剤は炭素を１０‐１８個含有する脂肪族アルコールである。 The cross-linking agent is SAC-100.
The thickener is an aliphatic alcohol containing 10-18 carbons.

前記ＰＥＥＫ改質ＭＯＦの製造方法は、重合反応器に、ジフルオロベンゾフェノン：ハイドロキノン：ＭＯＦ＝１：１：１のモル比で添加し、ジフルオロベンゾフェノン量の２倍のフェニルスルホンを加え、窒素ガスを流して１８０℃まで加熱昇温し、ハイドロキノン量の２倍の無水炭酸カリウムを加え、２００℃まで昇温して１時間保温した後、３００℃まで昇温して２．７５時間保温し、反応物を反応器から放出し、結晶を冷却した後ポリマーを粉砕し、アセトンで洗浄し、乾燥して前記ＰＥＥＫ改質ＭＯＦを得る。 In the method for producing PEEK-modified MOF, a molar ratio of difluorobenzophenone: hydroquinone: MOF = 1: 1: 1 is added to a polymerization reactor, phenylsulfone twice the amount of difluorobenzophenone is added, and nitrogen gas is allowed to flow. Heat and raise to 180 ° C, add anhydrous potassium carbonate twice the amount of hydroquinone, raise to 200 ° C and keep warm for 1 hour, then raise to 300 ° C and keep warm for 2.75 hours, and the reaction product. Is released from the reactor, the crystals are cooled, the polymer is ground, washed with acetone and dried to give the PEEK modified MOF.

前記改質グラフェンの製造方法は、反応フラスコにルチル型ナノ二酸化チタンを加え、硝酸で溶解し、常温で撹拌しながら酸化グラフェンを加え、２日間撹拌し、濾過、洗浄、乾燥して改質グラフェンを得る。 In the method for producing modified graphene, rutile-type nanotitanium dioxide is added to a reaction flask, dissolved in nitric acid, graphene oxide is added while stirring at room temperature, and the mixture is stirred for 2 days, filtered, washed, and dried to modify graphene. To get.

前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料の製造方法であって、以下のステップ一とステップ二とステップ三を含み、
前記ステップ一（改質アクリル樹脂乳液の調製）は、上記配合比率で、アクリル樹脂乳液及びＰＥＥＫ改質ＭＯＦを水に加え、撹拌しながらＳＡＣ‐１００を加え、６０℃で３６ｈ撹拌し、混合原料Ａを得、
前記ステップ二（原料ミックス）は、上記配合比率で、前記ステップ一で得られた混合原料Ａ、カーボンエアロゲル、炭化ケイ素、ナノ竹繊維、モンモリロナイト、改質グラフェン、ルチル型ナノ二酸化チタン、及び増粘剤を混合し、５０℃に昇温し、４５０ｒ／ｍｉｎで１５分間撹拌し、混合原料を得、
前記ステップ三（泡消し）は、混合原料を室温まで冷却した後、水性消泡剤を加え、表面に粒子状物質がなくなるまで、均一に撹拌分散し、前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料を得る。 A method for producing a water-based melamine resin paint that shields infrared rays and ultraviolet rays, which comprises the following steps 1, 2, and 3.
In step 1 (preparation of modified acrylic resin emulsion), the acrylic resin emulsion and PEEK modified MOF are added to water at the above blending ratio, SAC-100 is added with stirring, and the mixture is stirred at 60 ° C. for 36 hours to prepare a mixed raw material. Get A
In step 2 (raw material mix), the mixed raw material A, carbon airgel, silicon carbide, nanobamboo fiber, montmorillonite, modified graphene, rutile-type nanotitanium dioxide, and thickening obtained in step 1 were obtained in the above blending ratio. The agent was mixed, the temperature was raised to 50 ° C., and the mixture was stirred at 450 r / min for 15 minutes to obtain a mixed raw material.
In step 3 (foam elimination), after cooling the mixed raw material to room temperature, an aqueous defoaming agent is added, and the mixture is uniformly stirred and dispersed until there are no particulate matter on the surface, and the aqueous melamine resin that shields infrared rays and ultraviolet rays. Get the paint.

ＰＥＥＫ改質ＭＯＦにおけるＰＥＥＫは、優れた耐放射線性を有し、赤外線を吸収することができるとともに、赤外線の作用により発生したフリーラジカルを消去することができ、塗料を安定化する役割を果たし、ルチル型ナノ二酸化チタンは、紫外線と赤外線を吸収する作用を有し、改質グラフェンとともに光触媒として利用され、塗料に吸着した油汚れを光触媒酸化により二酸化炭素と水とに分解し、セルフクリーニングの効果を奏する。カーボンエアロゲルは、超強の吸着力を有し、環境中の有毒有害物質を吸収することができ、ルチル型ナノ二酸化チタンが二酸化炭素と水とに分解されるため、塗料がエコである。炭化ケイ素は、耐摩耗性および化学的安定性に優れ、塗料の安定性および耐摩耗性を向上させることができる。添加されるモンモリロナイトは、塗料の懸濁性と分散性を向上させることができ、ナノ竹繊維は、塗料に優れた接着性と靭性を付与することができる。さらに、ＭＯＦの構造特性を利用して、より多くの二酸化チタン、改質グラフェン、エアロゲル等の成分を収容し、遮蔽とセルフクリーニングの効果を高めることができる。 PEEK in the PEEK modified MOF has excellent radiation resistance, can absorb infrared rays, and can eliminate free radicals generated by the action of infrared rays, and plays a role of stabilizing the paint. Rutyl-type nanotitanium dioxide has the function of absorbing ultraviolet rays and infrared rays, and is used as a photocatalyst together with modified graphene. Oil stains adsorbed on paint are decomposed into carbon dioxide and water by photocatalytic oxidation, and the effect of self-cleaning. Play. Carbon airgel has an ultra-strong adsorptive power, can absorb toxic and harmful substances in the environment, and rutile-type nanotitanium dioxide is decomposed into carbon dioxide and water, so the paint is eco-friendly. Silicon carbide is excellent in abrasion resistance and chemical stability, and can improve the stability and abrasion resistance of the coating material. The added montmorillonite can improve the suspendability and dispersibility of the paint, and the nanobamboo fiber can impart excellent adhesiveness and toughness to the paint. Furthermore, by utilizing the structural properties of MOF, more components such as titanium dioxide, modified graphene, and airgel can be contained, and the effect of shielding and self-cleaning can be enhanced.

本発明は、人体に無毒な物質を原料とし、健康問題を引き起こさないうえに、赤外線や紫外線に対して良好な吸収作用を有し、輻射防止効果が高く、塗料と壁体とが良好な接着性を有し、外観が簡潔で、使用寿命が長い。 The present invention uses a substance that is non-toxic to the human body as a raw material, does not cause health problems, has a good absorption effect on infrared rays and ultraviolet rays, has a high radiation prevention effect, and has good adhesion between the paint and the wall body. It has the property, the appearance is simple, and the service life is long.

以下に実施例により本発明の技術案を明確で完全に説明し、明らかに、説明された実施例は本発明の一部の実施例に過ぎず、全ての実施例ではない。本発明の実施例に基づいて、当業者が創造的な労力をしない前提で得られる全ての他の実施例は、本発明の保護する範囲に属する。 The technical proposal of the present invention is clearly and completely described below by examples, and the clearly described examples are only a part of the examples of the present invention, not all the examples. Based on the examples of the present invention, all other examples obtained on the premise that those skilled in the art do not make creative efforts belong to the scope of protection of the present invention.

実施例１
赤外線と紫外線を遮蔽する水性メラミン樹脂塗料であって、３０部のＰＥＥＫ改質ＭＯＦ、１部のＳＡＣ‐１００、３０部のアクリル樹脂乳液、３部のカーボンエアロゲル、５部の炭化ケイ素、５部のナノ竹繊維、１部のモンモリロナイト、１部の改質グラフェン、５部のルチル型ナノ二酸化チタン、１部の増粘剤、１部の水性消泡剤、及び１０部の水からなり、
前記増粘剤は炭素を１０−１８個含有する脂肪族アルコールであり、
前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料の製造方法であって、以下のステップ一とステップ二とステップ三を含み、
前記ステップ一（改質アクリル樹脂乳液の調製）は、上記配合比率で、アクリル樹脂乳液及びＰＥＥＫ改質ＭＯＦを水に加え、撹拌しながらＳＡＣ‐１００を加え、６０℃で３６ｈ撹拌し、混合原料Ａを得、
前記ステップ二（原料ミックス）は、上記配合比率で、前記ステップ一で得られた混合原料Ａ、カーボンエアロゲル、炭化ケイ素、ナノ竹繊維、モンモリロナイト、改質グラフェン、ルチル型ナノ二酸化チタン、及び増粘剤を混合し、５０℃に昇温し、４５０ｒ／ｍｉｎで１５分間撹拌し、混合原料を得、
前記ステップ三（泡消し）は、混合原料を室温まで冷却した後、水性消泡剤を加え、表面に粒子状物質がなくなるまで、均一に撹拌分散し、前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料を得る。
なお、前記改質グラフェンは、予め、以下の方法により調製することができ、
反応フラスコにルチル型ナノ二酸化チタンを加え、硝酸で溶解し、常温で撹拌しながら酸化グラフェンを加え、２日間撹拌し、濾過、洗浄、乾燥して改質グラフェンを得る。 Example 1
A water-based melamine resin paint that shields infrared rays and ultraviolet rays. 30 parts of PEEK modified MOF, 1 part of SAC-100, 30 parts of acrylic resin emulsion, 3 parts of carbon airgel, 5 parts of silicon carbide, 5 parts. Nano-bamboo fiber, 1 part montmorillonite, 1 part modified graphene, 5 parts rutile-type nanotitanium dioxide, 1 part thickener, 1 part water-based defoaming agent, and 10 parts water.
The thickener is an aliphatic alcohol containing 10-18 carbons.
A method for producing a water-based melamine resin paint that shields infrared rays and ultraviolet rays, which comprises the following steps 1, 2, and 3.
In step 1 (preparation of modified acrylic resin emulsion), the acrylic resin emulsion and PEEK modified MOF are added to water at the above blending ratio, SAC-100 is added with stirring, and the mixture is stirred at 60 ° C. for 36 hours to prepare a mixed raw material. Get A
In step 2 (raw material mix), the mixed raw material A, carbon airgel, silicon carbide, nanobamboo fiber, montmorillonite, modified graphene, rutile-type nanotitanium dioxide, and thickening obtained in step 1 were obtained in the above blending ratio. The agent was mixed, the temperature was raised to 50 ° C., and the mixture was stirred at 450 r / min for 15 minutes to obtain a mixed raw material.
In step 3 (foam elimination), after cooling the mixed raw material to room temperature, an aqueous defoaming agent is added, and the mixture is uniformly stirred and dispersed until there are no particulate matter on the surface, and the aqueous melamine resin that shields infrared rays and ultraviolet rays. Get the paint.
The modified graphene can be prepared in advance by the following method.
Rutile-type nanotitanium dioxide is added to the reaction flask, dissolved in nitric acid, graphene oxide is added while stirring at room temperature, and the mixture is stirred for 2 days, filtered, washed, and dried to obtain modified graphene.

実施例２
赤外線と紫外線を遮蔽する水性メラミン樹脂塗料であって、３１部のＰＥＥＫ改質ＭＯＦ、２部のＳＡＣ‐１００、３１部のアクリル樹脂乳液、３．２部のカーボンエアロゲル、６部の炭化ケイ素、６部のナノ竹繊維、２部のモンモリロナイト、２部の改質グラフェン、５．２部のルチル型ナノ二酸化チタン、１．２部の増粘剤、２部の水性消泡剤、及び１２部の水からなり、
前記増粘剤は炭素を１０−１８個含有する脂肪族アルコールであり、
前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料の製造方法であって、以下のステップ一とステップ二とステップ三を含み、
前記ステップ一（改質アクリル樹脂乳液の調製）は、上記配合比率で、アクリル樹脂乳液及びＰＥＥＫ改質ＭＯＦを水に加え、撹拌しながらＳＡＣ‐１００を加え、６０℃で３６ｈ撹拌し、混合原料Ａを得、
前記ステップ二（原料ミックス）は、上記配合比率で、前記ステップ一で得られた混合原料Ａ、カーボンエアロゲル、炭化ケイ素、ナノ竹繊維、モンモリロナイト、改質グラフェン、ルチル型ナノ二酸化チタン、及び増粘剤を混合し、５０℃に昇温し、４５０ｒ／ｍｉｎで１５分間撹拌し、混合原料を得、
前記ステップ三（泡消し）は、混合原料を室温まで冷却した後、水性消泡剤を加え、表面に粒子状物質がなくなるまで、均一に撹拌分散し、前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料を得る。 Example 2
A water-based melamine resin paint that shields infrared rays and ultraviolet rays, 31 parts of PEEK-modified MOF, 2 parts of SAC-100, 31 parts of acrylic resin emulsion, 3.2 parts of carbon airgel, 6 parts of silicon carbide, 6 parts nanobamboo fiber, 2 parts montmorillonite, 2 parts modified graphene, 5.2 parts rutile-type nanotitanium dioxide, 1.2 parts thickener, 2 parts water-based defoaming agent, and 12 parts. Consists of water
The thickener is an aliphatic alcohol containing 10-18 carbons.
A method for producing a water-based melamine resin paint that shields infrared rays and ultraviolet rays, which comprises the following steps 1, 2, and 3.
In step 1 (preparation of modified acrylic resin emulsion), the acrylic resin emulsion and PEEK modified MOF are added to water at the above blending ratio, SAC-100 is added with stirring, and the mixture is stirred at 60 ° C. for 36 hours to prepare a mixed raw material. Get A
In step 2 (raw material mix), the mixed raw material A, carbon airgel, silicon carbide, nanobamboo fiber, montmorillonite, modified graphene, rutile-type nanotitanium dioxide, and thickening obtained in step 1 were obtained in the above blending ratio. The agent was mixed, the temperature was raised to 50 ° C., and the mixture was stirred at 450 r / min for 15 minutes to obtain a mixed raw material.
In step 3 (foam elimination), after cooling the mixed raw material to room temperature, an aqueous defoaming agent is added, and the mixture is uniformly stirred and dispersed until there are no particulate matter on the surface, and the aqueous melamine resin that shields infrared rays and ultraviolet rays. Get the paint.

実施例３
赤外線と紫外線を遮蔽する水性メラミン樹脂塗料であって、３２部のＰＥＥＫ改質ＭＯＦ、３部のＳＡＣ‐１００、３２部のアクリル樹脂乳液、３．４部のカーボンエアロゲル、７部の炭化ケイ素、７部のナノ竹繊維、３部のモンモリロナイト、３部の改質グラフェン、５．４部のルチル型ナノ二酸化チタン、１．４部の増粘剤、３部の水性消泡剤、及び１４部の水１４からなり、
前記増粘剤は炭素を１０−１８個含有する脂肪族アルコールであり、
前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料の製造方法であって、以下のステップ一とステップ二とステップ三を含み、
前記ステップ一（改質アクリル樹脂乳液の調製）は、上記配合比率で、アクリル樹脂乳液及びＰＥＥＫ改質ＭＯＦを水に加え、撹拌しながらＳＡＣ‐１００を加え、６０℃で３６ｈ撹拌し、混合原料Ａを得、
前記ステップ二（原料ミックス）は、上記配合比率で、前記ステップ一で得られた混合原料Ａ、カーボンエアロゲル、炭化ケイ素、ナノ竹繊維、モンモリロナイト、改質グラフェン、ルチル型ナノ二酸化チタン、及び増粘剤を混合し、５０℃に昇温し、４５０ｒ／ｍｉｎで１５分間撹拌し、混合原料を得、
前記ステップ三（泡消し）は、混合原料を室温まで冷却した後、水性消泡剤を加え、表面に粒子状物質がなくなるまで、均一に撹拌分散し、前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料を得る。 Example 3
A water-based melamine resin paint that shields infrared rays and ultraviolet rays, 32 parts of PEEK modified MOF, 3 parts of SAC-100, 32 parts of acrylic resin emulsion, 3.4 parts of carbon airgel, 7 parts of silicon carbide, 7 parts nanobamboo fiber, 3 parts montmorillonite, 3 parts modified graphene, 5.4 parts rutyl-type nanotitanium dioxide, 1.4 parts thickener, 3 parts aqueous defoamer, and 14 parts Consists of water 14
The thickener is an aliphatic alcohol containing 10-18 carbons.
A method for producing a water-based melamine resin paint that shields infrared rays and ultraviolet rays, which comprises the following steps 1, 2, and 3.
In step 1 (preparation of modified acrylic resin emulsion), the acrylic resin emulsion and PEEK modified MOF are added to water at the above blending ratio, SAC-100 is added with stirring, and the mixture is stirred at 60 ° C. for 36 hours to prepare a mixed raw material. Get A
In step 2 (raw material mix), the mixed raw material A, carbon airgel, silicon carbide, nanobamboo fiber, montmorillonite, modified graphene, rutile-type nanotitanium dioxide, and thickening obtained in step 1 were obtained in the above blending ratio. The agent was mixed, the temperature was raised to 50 ° C., and the mixture was stirred at 450 r / min for 15 minutes to obtain a mixed raw material.
In step 3 (foam elimination), after cooling the mixed raw material to room temperature, an aqueous defoaming agent is added, and the mixture is uniformly stirred and dispersed until there are no particulate matter on the surface, and the aqueous melamine resin that shields infrared rays and ultraviolet rays. Get the paint.

実施例４
赤外線と紫外線を遮蔽する水性メラミン樹脂塗料であって、３４部のＰＥＥＫ改質ＭＯＦ、４部のＳＡＣ‐１００、３４部のアクリル樹脂乳液、３．６部のカーボンエアロゲル、８部の炭化ケイ素、８部のナノ竹繊維、４部のモンモリロナイト、４部の改質グラフェン、５．６部のルチル型ナノ二酸化チタン、１．６部の増粘剤、４部の水性消泡剤、及び１６部の水からなり、
前記増粘剤は炭素を１０−１８個含有する脂肪族アルコールであり、
前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料の製造方法であって、以下のステップ一とステップ二とステップ三を含み、
前記ステップ一（改質アクリル樹脂乳液の調製）は、上記配合比率で、アクリル樹脂乳液及びＰＥＥＫ改質ＭＯＦを水に加え、撹拌しながらＳＡＣ‐１００を加え、６０℃で３６ｈ撹拌し、混合原料Ａを得、
前記ステップ二（原料ミックス）は、上記配合比率で、前記ステップ一で得られた混合原料Ａ、カーボンエアロゲル、炭化ケイ素、ナノ竹繊維、モンモリロナイト、改質グラフェン、ルチル型ナノ二酸化チタン、及び増粘剤を混合し、５０℃に昇温し、４５０ｒ／ｍｉｎで１５分間撹拌し、混合原料を得、
前記ステップ三（泡消し）は、混合原料を室温まで冷却した後、水性消泡剤を加え、表面に粒子状物質がなくなるまで、均一に撹拌分散し、前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料を得る。 Example 4
A water-based melamine resin paint that shields infrared rays and ultraviolet rays, 34 parts of PEEK modified MOF, 4 parts of SAC-100, 34 parts of acrylic resin emulsion, 3.6 parts of carbon airgel, 8 parts of silicon carbide, 8 parts nanobamboo fiber, 4 parts montmorillonite, 4 parts modified graphene, 5.6 parts rutile-type nanotitanium dioxide, 1.6 parts thickener, 4 parts water-based defoaming agent, and 16 parts. Consists of water
The thickener is an aliphatic alcohol containing 10-18 carbons.
A method for producing a water-based melamine resin paint that shields infrared rays and ultraviolet rays, which comprises the following steps 1, 2, and 3.
In step 1 (preparation of modified acrylic resin emulsion), the acrylic resin emulsion and PEEK modified MOF are added to water at the above blending ratio, SAC-100 is added with stirring, and the mixture is stirred at 60 ° C. for 36 hours to prepare a mixed raw material. Get A
In step 2 (raw material mix), the mixed raw material A, carbon airgel, silicon carbide, nanobamboo fiber, montmorillonite, modified graphene, rutile-type nanotitanium dioxide, and thickening obtained in step 1 were obtained in the above blending ratio. The agent was mixed, the temperature was raised to 50 ° C., and the mixture was stirred at 450 r / min for 15 minutes to obtain a mixed raw material.
In step 3 (foam elimination), after cooling the mixed raw material to room temperature, an aqueous defoaming agent is added, and the mixture is uniformly stirred and dispersed until there are no particulate matter on the surface, and the aqueous melamine resin that shields infrared rays and ultraviolet rays. Get the paint.

実施例５
赤外線と紫外線を遮蔽する水性メラミン樹脂塗料であって、３５部のＰＥＥＫ改質ＭＯＦ、５部のＳＡＣ‐１００、３５部のアクリル樹脂乳液、４部のカーボンエアロゲル、１０部の炭化ケイ素、１０部のナノ竹繊維、５部のモンモリロナイト、５部の改質グラフェン、６部のルチル型ナノ二酸化チタン、２部の増粘剤、５部の水性消泡剤、及び２０部の水からなり、
前記増粘剤は炭素を１０−１８個含有する脂肪族アルコールであり、
前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料の製造方法であって、以下のステップ一とステップ二とステップ三を含み、
前記ステップ一（改質アクリル樹脂乳液の調製）は、上記配合比率で、アクリル樹脂乳液及びＰＥＥＫ改質ＭＯＦを水に加え、撹拌しながらＳＡＣ‐１００を加え、６０℃で３６ｈ撹拌し、混合原料Ａを得、
前記ステップ二（原料ミックス）は、上記配合比率で、前記ステップ一で得られた混合原料Ａ、カーボンエアロゲル、炭化ケイ素、ナノ竹繊維、モンモリロナイト、改質グラフェン、ルチル型ナノ二酸化チタン、及び増粘剤を混合し、５０℃に昇温し、４５０ｒ／ｍｉｎで１５分間撹拌し、混合原料を得、
前記ステップ三（泡消し）は、混合原料を室温まで冷却した後、水性消泡剤を加え、表面に粒子状物質がなくなるまで、均一に撹拌分散し、前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料を得る。 Example 5
A water-based melamine resin paint that shields infrared rays and ultraviolet rays, 35 parts of PEEK modified MOF, 5 parts of SAC-100, 35 parts of acrylic resin emulsion, 4 parts of carbon airgel, 10 parts of silicon carbide, 10 parts. Nano-bamboo fiber, 5 parts of montmorillonite, 5 parts of modified graphene, 6 parts of rutile-type nanotitanium dioxide, 2 parts of thickener, 5 parts of aqueous defoaming agent, and 20 parts of water.
The thickener is an aliphatic alcohol containing 10-18 carbons.
A method for producing a water-based melamine resin paint that shields infrared rays and ultraviolet rays, which comprises the following steps 1, 2, and 3.
In step 1 (preparation of modified acrylic resin emulsion), the acrylic resin emulsion and PEEK modified MOF are added to water at the above blending ratio, SAC-100 is added with stirring, and the mixture is stirred at 60 ° C. for 36 hours to prepare a mixed raw material. Get A
In step 2 (raw material mix), the mixed raw material A, carbon airgel, silicon carbide, nanobamboo fiber, montmorillonite, modified graphene, rutile-type nanotitanium dioxide, and thickening obtained in step 1 were obtained in the above blending ratio. The agent was mixed, the temperature was raised to 50 ° C., and the mixture was stirred at 450 r / min for 15 minutes to obtain a mixed raw material.
In step 3 (foam elimination), after cooling the mixed raw material to room temperature, an aqueous defoaming agent is added, and the mixture is uniformly stirred and dispersed until there are no particulate matter on the surface, and the aqueous melamine resin that shields infrared rays and ultraviolet rays. Get the paint.

比較例１
ＣＮ１０８２１９６６６Ｂにおける実施例１で製造された水性メラミン樹脂塗料を参照する。 Comparative Example 1
Refer to the water-based melamine resin paint produced in Example 1 in CN108219666B.

比較例２
ＣＮ１０９３８５１６Ａにおける実施例１で製造された水性透明断熱塗料を参照する。 Comparative Example 2
Refer to the water-based transparent heat insulating paint produced in Example 1 in CN10938516A.

比較例３
比較例３は、実施例１に比べ、ＰＥＥＫ改質ＭＯＦを含まない点で異なっている。 Comparative Example 3
Comparative Example 3 is different from Example 1 in that it does not contain PEEK-modified MOF.

試験例
実施例１〜５で得られた赤外線と紫外線を遮蔽する水性メラミン樹脂塗料と比較例１〜３とを、関連基準に従い性能試験を行った結果を表１に示す。

Figure 2021172806
Test Example Table 1 shows the results of performance tests of the water-based melamine resin coating material obtained in Examples 1 to 5 and Comparative Examples 1 to 3 that shield infrared rays and ultraviolet rays according to the related criteria.
Figure 2021172806

実施例と比較例の実験データから見ると、本発明の赤外線と紫外線を遮蔽する水性メラミン樹脂塗料は、塗料の耐候性と耐紫外線性と耐赤外線性との効果を顕著に向上させた。 From the experimental data of Examples and Comparative Examples, the water-based melamine resin coating material that shields infrared rays and ultraviolet rays of the present invention has significantly improved the effects of the coating material on weather resistance, ultraviolet ray resistance, and infrared ray resistance.

Claims (5)

赤外線と紫外線を遮蔽する水性メラミン樹脂塗料であって、３０‐３５部のＰＥＥＫ改質ＭＯＦ、１‐５部の架橋剤、３０‐５０部のアクリル樹脂乳液、３‐４部のカーボンエアロゲル、５‐１０部の炭化ケイ素、５‐１０部のナノ竹繊維、１‐５部のモンモリロナイト、１‐５部の改質グラフェン、５‐６部のルチル型ナノ二酸化チタン、１‐２部の増粘剤、１‐５部の水性消泡剤、及び１０‐２０部の水からなる、
ことを特徴とする赤外線と紫外線を遮蔽する水性メラミン樹脂塗料。 A water-based melamine resin paint that shields infrared rays and ultraviolet rays, 30-35 parts of PEEK-modified MOF, 1-5 parts of cross-linking agent, 30-50 parts of acrylic resin emulsion, 3-4 parts of carbon airgel, 5 -10 parts silicon carbide, 5-10 parts nanobamboo fiber, 1-5 parts montmorillonite, 1-5 parts modified graphene, 5-6 parts rutile nanotitanium dioxide, 1-2 parts thickening The agent consists of 1-5 parts of aqueous defoaming agent and 10-20 parts of water.
A water-based melamine resin paint that shields infrared rays and ultraviolet rays. 前記架橋剤はＳＡＣ‐１００であり、
前記増粘剤は炭素を１０‐１８個含有する脂肪族アルコールである、
ことを特徴とする請求項１に記載の赤外線と紫外線を遮蔽する水性メラミン樹脂塗料。 The cross-linking agent is SAC-100.
The thickener is an aliphatic alcohol containing 10-18 carbons.
The water-based melamine resin coating material according to claim 1, wherein the water-based melamine resin coating material shields infrared rays and ultraviolet rays. 前記改質グラフェンの製造方法は、反応フラスコにルチル型ナノ二酸化チタンを加え、硝酸で溶解し、常温で撹拌しながら酸化グラフェンを加え、２日間撹拌し、濾過、洗浄、乾燥して改質グラフェンを得る、
ことを特徴とする請求項１に記載の赤外線と紫外線を遮蔽する水性メラミン樹脂塗料。 In the method for producing modified graphene, rutile-type nanotitanium dioxide is added to a reaction flask, dissolved in nitric acid, graphene oxide is added while stirring at room temperature, and the mixture is stirred for 2 days, filtered, washed, and dried to modify graphene. Get,
The water-based melamine resin coating material according to claim 1, wherein the water-based melamine resin coating material shields infrared rays and ultraviolet rays. 前記ＰＥＥＫ改質ＭＯＦの製造方法は、重合反応器に、ジフルオロベンゾフェノン：ハイドロキノン：ＭＯＦ＝１：１：１のモル比で添加し、ジフルオロベンゾフェノン量の２倍のフェニルスルホンを加え、窒素ガスを流して１８０℃まで加熱昇温し、ハイドロキノン量の２倍の無水炭酸カリウムを加え、２００℃まで昇温して１時間保温した後、３００℃まで昇温して２．７５時間保温し、反応物を反応器から放出し、結晶を冷却した後ポリマーを粉砕し、アセトンで洗浄し、乾燥して前記ＰＥＥＫ改質ＭＯＦを得る、
ことを特徴とする請求項１に記載の赤外線と紫外線を遮蔽する水性メラミン樹脂塗料。 In the method for producing PEEK-modified MOF, a molar ratio of difluorobenzophenone: hydroquinone: MOF = 1: 1: 1 is added to a polymerization reactor, phenylsulfone twice the amount of difluorobenzophenone is added, and nitrogen gas is allowed to flow. Heat and raise to 180 ° C, add anhydrous potassium carbonate twice the amount of hydroquinone, raise to 200 ° C and keep warm for 1 hour, then raise to 300 ° C and keep warm for 2.75 hours, and the reaction product. Is released from the reactor, the crystals are cooled, the polymer is ground, washed with acetone and dried to give the PEEK modified MOF.
The water-based melamine resin coating material according to claim 1, wherein the water-based melamine resin coating material shields infrared rays and ultraviolet rays. 前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料の製造方法であって、ステップ一とステップ二とステップ三を含み、
前記ステップ一（改質アクリル樹脂乳液の調製）は、上記配合比率で、アクリル樹脂乳液及びＰＥＥＫ改質ＭＯＦを水に加え、撹拌しながらＳＡＣ‐１００を加え、６０℃で３６ｈ撹拌し、混合原料Ａを得、
前記ステップ二（原料ミックス）は、上記配合比率で、前記ステップ一で得られた混合原料Ａ、カーボンエアロゲル、炭化ケイ素、ナノ竹繊維、モンモリロナイト、改質グラフェン、ルチル型ナノ二酸化チタン、及び増粘剤を混合し、５０℃に昇温し、４５０ｒ／ｍｉｎで１５分間撹拌し、混合原料を得、
前記ステップ三（泡消し）は、混合原料を室温まで冷却した後、水性消泡剤を加え、表面に粒子状物質がなくなるまで、均一に撹拌分散し、前記赤外線と紫外線を遮蔽する水性メラミン樹脂塗料を得る、
ことを特徴とする請求項１に記載の赤外線と紫外線を遮蔽する水性メラミン樹脂塗料の製造方法。 A method for producing a water-based melamine resin paint that shields infrared rays and ultraviolet rays, including step 1, step 2, and step 3.
In step 1 (preparation of modified acrylic resin emulsion), the acrylic resin emulsion and PEEK modified MOF are added to water at the above blending ratio, SAC-100 is added with stirring, and the mixture is stirred at 60 ° C. for 36 hours to prepare a mixed raw material. Get A
In step 2 (raw material mix), the mixed raw material A, carbon airgel, silicon carbide, nanobamboo fiber, montmorillonite, modified graphene, rutile-type nanotitanium dioxide, and thickening obtained in step 1 were obtained in the above blending ratio. The agent was mixed, the temperature was raised to 50 ° C., and the mixture was stirred at 450 r / min for 15 minutes to obtain a mixed raw material.
In step 3 (foam elimination), after cooling the mixed raw material to room temperature, an aqueous defoaming agent is added, and the mixture is uniformly stirred and dispersed until there are no particulate matter on the surface, and the aqueous melamine resin that shields infrared rays and ultraviolet rays. Get the paint,
The method for producing an aqueous melamine resin paint that shields infrared rays and ultraviolet rays according to claim 1.
JP2020178661A 2020-04-27 2020-10-26 Water-based melamine resin coating for shielding infrared rays and ultraviolet rays and preparation method therefor Pending JP2021172806A (en)

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CN115368771A (en) * 2022-09-22 2022-11-22 浙江和谐光催化科技有限公司 Preparation process of environment-friendly rheological additive material with photocatalysis cleaning function
CN115652617A (en) * 2022-11-15 2023-01-31 苏州联胜化学有限公司 Anti-infrared anti-pilling agent and preparation method thereof

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