JP6848494B2 - Heat-foamable pre-coated metal plate and its manufacturing method - Google Patents
Heat-foamable pre-coated metal plate and its manufacturing method Download PDFInfo
- Publication number
- JP6848494B2 JP6848494B2 JP2017020453A JP2017020453A JP6848494B2 JP 6848494 B2 JP6848494 B2 JP 6848494B2 JP 2017020453 A JP2017020453 A JP 2017020453A JP 2017020453 A JP2017020453 A JP 2017020453A JP 6848494 B2 JP6848494 B2 JP 6848494B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- metal plate
- foamable
- resin layer
- expandable
- 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.)
- Active
Links
Landscapes
- Laminated Bodies (AREA)
Description
本発明は、加熱発泡性プレコート金属板及びその製造方法に関する。 The present invention relates to a heat-foamable precoated metal plate and a method for producing the same.
従来、金属板と熱可塑性樹脂又は熱硬化性樹脂の発泡体とを組み合わせて発泡金属板として用いることは、軽量化、低コスト化、機能性及び意匠性の付与等のために一般的に行われている。特に、熱可塑性樹脂の発泡体は一般に柔軟性、衝撃吸収性、断熱性等に優れているので、例えば、天井、ドア、計器パネル等の車両用内装材や断熱材として広く用いられている。しかし、プレス成形等で複雑な形状に加工した金属板と発泡体とを組み合わせて発泡金属板とすることは困難である。その理由は、複雑な形状に加工した金属板に発泡で剛性の高まった発泡体を接合一体化させようとしても、発泡体を金属板の成形面に確実に沿わせることができず、接合界面から剥離が生じて一体性が損なわれてしまうためである。 Conventionally, using a metal plate in combination with a foam of a thermoplastic resin or a thermosetting resin as a foamed metal plate is generally performed in order to reduce the weight, reduce the cost, and impart functionality and design. It has been. In particular, since the foam of the thermoplastic resin is generally excellent in flexibility, shock absorption, heat insulation and the like, it is widely used as an interior material for vehicles such as ceilings, doors and instrument panels and a heat insulating material. However, it is difficult to combine a metal plate processed into a complicated shape by press molding or the like with a foam to form a foamed metal plate. The reason is that even if an attempt is made to join and integrate a foam with increased rigidity by foaming on a metal plate processed into a complicated shape, the foam cannot be reliably aligned with the molded surface of the metal plate, and the joining interface cannot be met. This is because peeling occurs from the metal and the unity is impaired.
そこで、特許文献１には、熱可塑性樹脂と加熱発泡性発泡剤及び有機変性された薄片状無機質粉末を含む少なくとも１層の加熱発泡性樹脂層が金属板と積層され、積層後に成形加工してから加熱発泡させる発泡性樹脂積層金属板が開示されている。 Therefore, in Patent Document 1, at least one heat-foamable resin layer containing a thermoplastic resin, a heat-foamable foaming agent, and an organically modified flaky inorganic powder is laminated with a metal plate, and is molded after being laminated. A foamable resin laminated metal plate to be heated and foamed is disclosed.
しかしながら、特許文献１に開示された発泡性樹脂積層金属板は、加工性が十分とはいえないため、複雑な形状へ加工すると樹脂層が損傷して金属板が露出し易く、また、発泡倍率が低いという問題があった。 However, since the foamable resin laminated metal plate disclosed in Patent Document 1 is not sufficiently processable, the resin layer is easily damaged and the metal plate is easily exposed when processed into a complicated shape, and the foaming ratio is increased. There was a problem that it was low.
従って、本発明は、上記のような課題を解決するためになされたものであり、加工性に優れ且つ発泡倍率の高い加熱発泡性プレコート金属板及びその製造方法を提供することを目的とする。 Therefore, the present invention has been made to solve the above problems, and an object of the present invention is to provide a heat-foamable precoated metal plate having excellent processability and a high foaming ratio, and a method for producing the same.
本発明は、金属板の少なくとも一方の面に、熱可塑性樹脂と熱膨張性マイクロカプセルとを含む加熱発泡性樹脂層が設けられている加熱発泡性プレコート金属板であって、前記熱膨張性マイクロカプセルが、前記加熱発泡性樹脂層に対して、１５体積％以上６５体積％以下含まれることを特徴とする加熱発泡性プレコート金属板である。 The present invention is a heat-expandable precoated metal plate in which a heat-expandable resin layer containing a thermoplastic resin and a heat-expandable microcapsule is provided on at least one surface of the metal plate. The capsule is a thermosetting precoated metal plate containing 15% by volume or more and 65% by volume or less with respect to the thermosetting resin layer.
また、本発明は、金属板の少なくとも一方の面に、熱可塑性樹脂と可塑剤と熱膨張性マイクロカプセルとを含有するプラスチゾル組成物を塗布、乾燥させて加熱発泡性樹脂層を形成する工程を有する加熱発泡性プレコート金属板の製造方法であって、前記熱膨張性マイクロカプセルが、前記加熱発泡性樹脂層に対して、１５体積％以上６５体積％以下含まれることを特徴とする加熱発泡性プレコート金属板の製造方法である。 Further, in the present invention, a step of applying a plastizol composition containing a thermoplastic resin, a plasticizer and a heat-expandable microcapsule to at least one surface of a metal plate and drying it to form a heat-foamable resin layer is performed. A method for producing a heat-foamable precoated metal plate, which comprises 15% by volume or more and 65% by volume or less of the heat-expandable microcapsules with respect to the heat-foamable resin layer. This is a method for manufacturing a precoated metal plate.
本発明によれば、加工性に優れ且つ発泡倍率の高い加熱発泡性プレコート金属板及びその製造方法を提供することができる。 According to the present invention, it is possible to provide a heat-foamable precoated metal plate having excellent processability and a high foaming ratio, and a method for producing the same.
以下、本発明を実施するための形態について説明する。
本発明の加熱発泡性プレコート金属板は、金属板の少なくとも一方の面に、熱可塑性樹脂と熱膨張性マイクロカプセルとを含む加熱発泡性樹脂層が設けられており、且つ加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルが１５体積％以上６５体積％以下含まれる。熱膨張性マイクロカプセルの含有量が１５体積％未満であると、発泡樹脂層への柔軟性、衝撃吸収性、断熱性等の付与が困難となる。一方、熱膨張性マイクロカプセルの含有量が６５体積％超であると、発泡時に発泡樹脂層が金属板から剥離する恐れがある。熱膨張性マイクロカプセルは、加熱発泡性樹脂層に対して、２０体積％以上５５体積％以下含まれることが好ましい。
Hereinafter, modes for carrying out the present invention will be described.
In the heat-foamable precoated metal plate of the present invention, a heat-foamable resin layer containing a thermoplastic resin and a heat-expandable microcapsule is provided on at least one surface of the metal plate, and the heat-foamable resin layer is formed. On the other hand, thermosetting microcapsules are contained in an amount of 15% by volume or more and 65% by volume or less. If the content of the heat-expandable microcapsules is less than 15% by volume, it becomes difficult to impart flexibility, shock absorption, heat insulating properties, etc. to the foamed resin layer. On the other hand, if the content of the heat-expandable microcapsules exceeds 65% by volume, the foamed resin layer may peel off from the metal plate during foaming. The heat-expandable microcapsules are preferably contained in an amount of 20% by volume or more and 55% by volume or less with respect to the heat-expandable resin layer.
また、本発明の加熱発泡性プレコート金属における加熱発泡性樹脂層の厚さは、各種用途において求められる発泡樹脂層（加熱発泡性樹脂層を加熱して発泡させた層）の厚さに応じて適宜設定すればよいが、塗装ラインにおける生産性が高いという点で、１００μｍ以上７００μｍ以下であることが好ましい。 The thickness of the heat-foamable resin layer in the heat-foamable precoated metal of the present invention depends on the thickness of the foamed resin layer (layer obtained by heating and foaming the heat-foamable resin layer) required for various uses. It may be set as appropriate, but it is preferably 100 μm or more and 700 μm or less in terms of high productivity in the coating line.
本発明において原板として用いられる金属板としては、特に限定されないが、例えば、冷延鋼板、ステンレス鋼板、アルミニウム板、アルミニウム合金板、銅板、銅合金板、マグネシウム板、マグネシウム合金板、溶融亜鉛系めっき鋼板、合金化溶融亜鉛めっき鋼板、電気亜鉛系めっき鋼板、蒸着亜鉛系めっき鋼板、溶融アルミニウムめっき鋼板等が挙げられる。亜鉛系めっきには、Ｚｎ−Ａｌ、Ｚｎ−Ｍｇ、Ｚｎ−Ｎｉ、Ｚｎ−Ａｌ−Ｍｇ等がある。 The metal plate used as the original plate in the present invention is not particularly limited, but for example, a cold-rolled steel plate, a stainless steel plate, an aluminum plate, an aluminum alloy plate, a copper plate, a copper alloy plate, a magnesium plate, a magnesium alloy plate, and a hot-dip galvanized sheet. Examples thereof include steel sheets, alloyed hot-dip galvanized steel sheets, electrozinc-based plated steel sheets, vapor-deposited galvanized steel sheets, and hot-dip aluminum-plated steel sheets. Zinc-based plating includes Zn-Al, Zn-Mg, Zn-Ni, Zn-Al-Mg and the like.
本発明において用いられる熱可塑性樹脂としては、アクリル系樹脂、塩化ビニル系樹脂、塩化ビニルと酢酸ビニルとを共重合した樹脂等が挙げられる。これらの中でも、より低温造膜性に優れるという点で、アクリル系樹脂が好ましい。 Examples of the thermoplastic resin used in the present invention include acrylic resins, vinyl chloride resins, and resins obtained by copolymerizing vinyl chloride and vinyl acetate. Among these, acrylic resins are preferable because they are more excellent in low-temperature film forming property.
本発明において用いられる熱膨張性マイクロカプセルとしては、ガス化する液体とその液体を包み込むカプセル壁とから構成され、加熱により液体がガス化すると同時にカプセル壁が軟化することによって膨張するものであればよい。このような熱膨張性マイクロカプセルは、市販されており、例えば、積水化学工業株式会社製の「アドバンセル（登録商標）」シリーズ、松本油脂製薬株式会社製の「マツモトマイクロスフェアー(登録商標)」シリーズ、日本フィライト株式会社製の「エクスパンセル(登録商標)」シリーズ、株式会社クレハ製の「クレハマイクロスフェアー(登録商標)」シリーズ等が挙げられる。これらは単独で用いてもよいし、又は２種類以上を組み合わせて用いてもよい。これらの中でも、加熱発泡性樹脂層を形成する際に用いるプラスチゾル組成物の保管安定性に優れるという点で、低沸点炭化水素をアクリルニトリルコポリマーで包み込んだ熱膨張性マイクロカプセルである積水化学工業株式会社製の「アドバンセル（登録商標）」シリーズが好ましい。また、熱膨張性マイクロカプセルの平均粒径は、加熱発泡性プレコート金属板の加工部における発泡能力が優れるという点で、１５μｍ以上３０μｍ以下であることが好ましい。 The heat-expandable microcapsules used in the present invention are composed of a liquid to be gasified and a capsule wall that encloses the liquid, as long as the liquid is gasified by heating and at the same time the capsule wall is softened to expand. Good. Such heat-expandable microcapsules are commercially available, for example, "Advancel (registered trademark)" series manufactured by Sekisui Chemical Industry Co., Ltd. and "Matsumoto Microsphere (registered trademark)" manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd. Series, "Expansel (registered trademark)" series manufactured by Nippon Phillite Co., Ltd., "Kureha Microsphere (registered trademark)" series manufactured by Kureha Corporation, and the like. These may be used alone or in combination of two or more. Among these, Sekisui Chemical Co., Ltd., which is a heat-expandable microcapsule in which a low-boiling hydrocarbon is wrapped in an acrylonitrile copolymer, is excellent in storage stability of the plastisol composition used when forming a heat-foamable resin layer. The company-made "Advancel (registered trademark)" series is preferable. Further, the average particle size of the heat-expandable microcapsules is preferably 15 μm or more and 30 μm or less in that the foaming ability in the processed portion of the heat-foamable precoated metal plate is excellent.
本発明の加熱発泡性プレコート金属における金属板と加熱発泡性樹脂層との間には、金属板への加熱発泡性樹脂層の密着性を高めるために、プライマー層を設けることが好ましい。プライマー層は、塗装金属板に一般に使用されているウレタン系プライマー、エポキシ系プライマー、ポリエステル系プライマー、アクリル系プライマー等を金属板に塗布、乾燥することによって形成することができる。プライマー層の厚さは、特に限定されるものではないが、通常、４μｍ以上７μｍ以下の範囲である。 It is preferable to provide a primer layer between the metal plate and the heat-foamable resin layer in the heat-foamable precoated metal of the present invention in order to enhance the adhesion of the heat-foamable resin layer to the metal plate. The primer layer can be formed by applying a urethane-based primer, an epoxy-based primer, a polyester-based primer, an acrylic-based primer, or the like, which are generally used for a coated metal plate, to the metal plate and drying it. The thickness of the primer layer is not particularly limited, but is usually in the range of 4 μm or more and 7 μm or less.
本発明の加熱発泡性プレコート金属板は、金属板の少なくとも一方の面に、熱可塑性樹脂と可塑剤と熱膨張性マイクロカプセルとを含有するプラスチゾル組成物を塗布、乾燥させて加熱発泡性樹脂層を形成することにより製造することができる。プラスチゾル組成物の塗布方法は、特に限定されるものではないが、ロールコート法、フローコート法、カーテンフロー法、スプレー法等が挙げられる。また、プラスチゾル組成物の塗膜の乾燥条件（温度及び時間）は、熱膨張性マイクロカプセルが発泡しない範囲で適宜設定すればよい。 In the heat-foamable precoated metal plate of the present invention, a plastisol composition containing a thermoplastic resin, a plasticizer, and heat-expandable microcapsules is applied to at least one surface of the metal plate, dried, and the heat-foamable resin layer is formed. Can be manufactured by forming. The method for applying the plastisol composition is not particularly limited, and examples thereof include a roll coating method, a flow coating method, a curtain flow method, and a spray method. Further, the drying conditions (temperature and time) of the coating film of the plastisol composition may be appropriately set within a range in which the heat-expandable microcapsules do not foam.
プラスチゾル組成物は、例えば、プラネタリーミキサー等の混合分散機を用いて、熱可塑性樹脂粉体及び熱膨張性マイクロカプセルを可塑剤に分散させることにより調製することができる。このようなプラスチゾル組成物を用いることで、加熱発泡性樹脂層が、加熱による熱可塑性樹脂粉体の膨潤、ゲル化及び溶融のプロセスを経て形成されることとなる。ここで用いる熱可塑性樹脂粉体の平均粒径は０．１μｍ以上５μｍ以下であることが好ましい。 The plastisol composition can be prepared by dispersing the thermoplastic resin powder and the heat-expandable microcapsules in a plasticizer using, for example, a mixing / dispersing machine such as a planetary mixer. By using such a plastisol composition, a thermosetting resin layer is formed through a process of swelling, gelling, and melting of the thermoplastic resin powder by heating. The average particle size of the thermoplastic resin powder used here is preferably 0.1 μm or more and 5 μm or less.
プラスチゾル組成物の組成は、形成される加熱発泡性樹脂層に含まれる熱膨張性マイクロカプセルが１５体積％以上６５体積％以下となるように調節すればよい。 The composition of the plastisol composition may be adjusted so that the amount of the heat-expandable microcapsules contained in the formed heat-foamable resin layer is 15% by volume or more and 65% by volume or less.
プラスチゾル組成物において用いられる可塑剤としては、トリキシレニルホスフェート、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリ−２−エチルヘキシルホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、クレジルフェニルホスフェート等のリン酸エステル系可塑剤、ジメチルフタレート、ジエチルフタレート、ジブチルフタレート、ジヘプチルフタレート、ジ−２−エチルヘキシルフタレート、ジオクチルフタレート、ジイソノニルフタレート、ジイソデシルフタレート、ブチルベンジルフタレート等のフタル酸エステル系可塑剤、ジメチルアジペート、ジブチルアジペート、ジイソブチルアジペート、ジヘキシルアジペート、ジ−２−エチルヘキシルアジペート、ジイソノニルアジペート、ジブチルジグリコールアジペート等のアジピン酸エステル系可塑剤、トリ−２−エチルヘキシルトリメリテート等のトリメリット酸エステル系可塑剤、ジメチルセバケート、ジブチルセバケート、ジ−２−エチルヘキシルセバケート等のセバチン酸エステル系可塑剤、ポリ−１，３−ブタンジオールアジペート等の脂肪族系ポリエステル可塑剤、ジエチレングリコールジベンゾエート、ジブチレングリコールジベンゾエート等の安息香酸系可塑剤、エポキシ化大豆油等のエポキシ化エステル系可塑剤、アルキルスルホン酸フェニルエステル等のアルキルスルホン酸フェニルエステル系可塑剤、脂環式二塩基酸エステル系可塑剤、ポリプロピレングリコール、ポリブチレングリコール等のポリエーテル系可塑剤、クエン酸アセチルトリブチル等のクエン酸系可塑剤が挙げられる。これらは単独で用いてもよいし、又は２種類以上を組み合わせて用いてもよい。これらの中でも、特に良好な加工性を付与できるという点で、トリキシレニルホスフェートが好ましい。 The plasticizers used in the plastizol composition include trixylenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresylphenyl phosphate. Phthalate-based plasticizers such as dimethylphthalate, diethylphthalate, dibutylphthalate, diheptylphthalate, di-2-ethylhexylphthalate, dioctylphthalate, diisononylphthalate, diisodecylphthalate, phthalate-based plasticizers such as butylbenzylphthalate, etc. Adipate-based plasticizers such as dimethyl adipate, dibutyl adipate, diisobutyl adipate, dihexyl adipate, di-2-ethylhexyl adipate, diisononyl adipate, dibutyl diglycol adipate, trimellitic acid esters such as tri-2-ethylhexyl trimerite Plasticizers, dimethyl sevacates, dibutyl sevacates, di-2-ethylhexyl sevacates and other sebatic acid ester-based plasticizers, poly-1,3-butanediol adipate and other aliphatic polyester plasticizers, diethylene glycol dibenzoate, di An benzoic acid-based plasticizer such as butylene glycol dibenzoate, an epoxidized ester-based plasticizer such as epoxidized soybean oil, an alkyl sulfonic acid phenyl ester-based plastic agent such as alkyl sulfonic acid phenyl ester, and an alicyclic dibasic acid ester-based plastic Examples thereof include agents, phthalate-based plasticizers such as polypropylene glycol and polybutylene glycol, and citrate-based plasticizers such as acetyltributyl citrate. These may be used alone or in combination of two or more. Among these, trixylenyl phosphate is preferable because it can impart particularly good processability.
プラスチゾル組成物は、ミネラルスピリット等の希釈剤、酸化チタン、カーボンブラック等の顔料、消泡剤、防黴剤、レベリング剤等を本発明の効果を阻害しない範囲で含有してもよい。 The plastisol composition may contain a diluent such as mineral spirit, a pigment such as titanium oxide and carbon black, an antifoaming agent, a fungicide, a leveling agent and the like as long as the effects of the present invention are not impaired.
上述したように、金属板への加熱発泡性樹脂層の密着性を高めるために、金属板と加熱発泡性樹脂層との間にプライマー層を設けることが好ましい。プライマー層は、塗装金属板に一般に使用されているプライマーを金属板に塗布、乾燥することによって形成することができる。プライマーの塗布方法は、特に限定されるものではないが、ロールコート法、フローコート法、カーテンフロー法、スプレー法等が挙げられる。プライマーの塗膜の乾燥条件（温度及び時間）は、塗装金属板製造における標準的な条件が採用され、通常、２６０〜３００℃で１〜２分間である。 As described above, in order to enhance the adhesion of the heat-foamable resin layer to the metal plate, it is preferable to provide a primer layer between the metal plate and the heat-foamable resin layer. The primer layer can be formed by applying a primer generally used for a coated metal plate to the metal plate and drying it. The method of applying the primer is not particularly limited, and examples thereof include a roll coating method, a flow coating method, a curtain flow method, and a spray method. The drying conditions (temperature and time) of the coating film of the primer are standard conditions in the production of a coated metal plate, and are usually 260 to 300 ° C. for 1 to 2 minutes.
なお、実施例１０〜１２は、参考例とする。
＜実施例１＞
板厚０．６ｍｍの亜鉛系めっき鋼板にウレタン系プライマー（日本ペイント株式会社製、塩ビゾルウレタンプライマー）をバーコーターで塗布した後、２８０℃、１分間加熱して厚さ５μｍのプライマー層を形成した。
次に、アクリル系樹脂粉体（三菱レイヨン株式会社製、ダイヤナール（登録商標）ＬＰ−３２０２、最小粒径１μｍ以下）１０質量部、トリキシレニルホスフェート（大八化学工業株式会社製、ＴＸＰ）１０質量部、熱膨張性マイクロカプセル（積水化学工業株式会社製、アドバンセル（登録商標）ＥＨＭ３０２、平均粒径２０μｍ）３質量部及び希釈剤（キシダ化学株式会社製、ミネラルスピリット）６質量部を、プラネタリーミキサーを用いて混合してプラスチゾル組成物を調製した。このプラスチゾル組成物をバーコーターでプライマー層上に塗布した後、加熱炉で１８０℃、３０秒間加熱して厚さ１００μｍの加熱発泡性樹脂層を形成し、実施例１の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは２０体積％含まれていた。
In addition, Examples 10 to 12 are reference examples.
<Example 1>
A urethane-based primer (manufactured by Nippon Paint Co., Ltd., PVC sol urethane primer) is applied to a galvanized steel sheet with a thickness of 0.6 mm with a bar coater, and then heated at 280 ° C. for 1 minute to form a primer layer with a thickness of 5 μm. did.
Next, 10 parts by mass of acrylic resin powder (manufactured by Mitsubishi Rayon Co., Ltd., Dianal (registered trademark) LP-3202, minimum particle size of 1 μm or less), trixylenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., TXP) 10 parts by mass, 3 parts by mass of heat-expandable microcapsules (manufactured by Sekisui Chemical Industry Co., Ltd., Advancel (registered trademark) EHM302, average particle size 20 μm) and 6 parts by mass of diluent (manufactured by Kishida Chemical Co., Ltd., Mineral Spirit) , A planetary mixer was used to mix to prepare a plastic composition. After applying this plastisol composition on the primer layer with a bar coater, it is heated in a heating furnace at 180 ° C. for 30 seconds to form a heat-foamable resin layer having a thickness of 100 μm, and the heat-foamable precoated metal plate of Example 1 is formed. Got The heat-expandable microcapsules were contained in an amount of 20% by volume based on the formed heat-expandable resin layer.
＜実施例２＞
プラスチゾル組成物の塗布量を変えて加熱発泡性樹脂層の厚さを３５０μｍとしたこと以外は実施例１と同様にして実施例２の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは２０体積％含まれていた。
<Example 2>
A heat-foamable precoated metal plate of Example 2 was obtained in the same manner as in Example 1 except that the thickness of the heat-foamable resin layer was set to 350 μm by changing the coating amount of the plastisol composition. The heat-expandable microcapsules were contained in an amount of 20% by volume based on the formed heat-expandable resin layer.
＜実施例３＞
プラスチゾル組成物の塗布量を変えて加熱発泡性樹脂層の厚さを５４０μｍとしたこと以外は実施例１と同様にして実施例３の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは２０体積％含まれていた。
<Example 3>
A heat-foamable precoated metal plate of Example 3 was obtained in the same manner as in Example 1 except that the thickness of the heat-foamable resin layer was set to 540 μm by changing the coating amount of the plastisol composition. The heat-expandable microcapsules were contained in an amount of 20% by volume based on the formed heat-expandable resin layer.
＜実施例４＞
プラスチゾル組成物の組成をアクリル系樹脂粉体（三菱レイヨン株式会社製、ダイヤナール（登録商標）ＬＰ−３２０２、最小粒径１μｍ以下）１０質量部、トリキシレニルホスフェート（大八化学工業株式会社製、ＴＸＰ）１０質量部、熱膨張性マイクロカプセル（積水化学工業株式会社製、アドバンセル（登録商標）ＥＨＭ３０２、平均粒径２０μｍ）５質量部及び希釈剤（キシダ化学株式会社製、ミネラルスピリット）６質量部に変更し、加熱発泡性樹脂層の厚さを１１０μｍとしたこと以外は実施例１と同様にして実施例４の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは４７体積％含まれていた。
<Example 4>
The composition of the plastizol composition is 10 parts by mass of acrylic resin powder (manufactured by Mitsubishi Rayon Co., Ltd., Dianal (registered trademark) LP-3202, minimum particle size of 1 μm or less), trixylenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.). , TXP) 10 parts by mass, heat-expandable microcapsules (manufactured by Sekisui Chemical Industry Co., Ltd., Advancel (registered trademark) EHM302, average particle size 20 μm) 5 parts by mass and diluent (manufactured by Kishida Chemical Co., Ltd., Mineral Spirit) 6 A heat-foamable precoated metal plate of Example 4 was obtained in the same manner as in Example 1 except that the thickness was changed to 110 μm and the thickness of the heat-foamable resin layer was changed to 110 μm. 47% by volume of the heat-expandable microcapsules were contained in the formed heat-expandable resin layer.
＜実施例５＞
プラスチゾル組成物の塗布量を変えて加熱発泡性樹脂層の厚さを３１０μｍとしたこと以外は実施例４と同様にして実施例５の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは４７体積％含まれていた。
<Example 5>
A heat-foamable precoated metal plate of Example 5 was obtained in the same manner as in Example 4 except that the thickness of the heat-foamable resin layer was set to 310 μm by changing the coating amount of the plastisol composition. 47% by volume of the heat-expandable microcapsules were contained in the formed heat-expandable resin layer.
＜実施例６＞
プラスチゾル組成物の塗布量を変えて加熱発泡性樹脂層の厚さを５２０μｍとしたこと以外は実施例４と同様にして実施例６の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは４７体積％含まれていた。
<Example 6>
A heat-foamable precoated metal plate of Example 6 was obtained in the same manner as in Example 4 except that the thickness of the heat-foamable resin layer was set to 520 μm by changing the coating amount of the plastisol composition. 47% by volume of the heat-expandable microcapsules were contained in the formed heat-expandable resin layer.
＜実施例７＞
プラスチゾル組成物の組成をアクリル系樹脂粉体（三菱レイヨン株式会社製、ダイヤナール（登録商標）ＬＰ−３２０２、最小粒径１μｍ以下）１０質量部、トリキシレニルホスフェート（大八化学工業株式会社製、ＴＸＰ）１０質量部、熱膨張性マイクロカプセル（積水化学工業株式会社製、アドバンセル（登録商標）ＥＨＭ３０２、平均粒径２０μｍ）７質量部及び希釈剤（キシダ化学株式会社製、ミネラルスピリット）６質量部に変更し、加熱発泡性樹脂層の厚さを１１０μｍとしたこと以外は実施例１と同様にして実施例７の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは６３体積％含まれていた。
<Example 7>
The composition of the plastizol composition is 10 parts by mass of acrylic resin powder (manufactured by Mitsubishi Rayon Co., Ltd., Dianal (registered trademark) LP-3202, minimum particle size of 1 μm or less), trixylenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.). , TXP) 10 parts by mass, heat-expandable microcapsules (manufactured by Sekisui Chemical Industry Co., Ltd., Advancel (registered trademark) EHM302, average particle size 20 μm) 7 parts by mass and diluent (manufactured by Kishida Chemical Co., Ltd., Mineral Spirit) 6 A heat-foamable precoated metal plate of Example 7 was obtained in the same manner as in Example 1 except that the thickness was changed to 110 μm and the thickness of the heat-foamable resin layer was changed to 110 μm. The heat-expandable microcapsules were contained in an amount of 63% by volume based on the formed heat-expandable resin layer.
＜実施例８＞
プラスチゾル組成物の塗布量を変えて加熱発泡性樹脂層の厚さを３１０μｍとしたこと以外は実施例７と同様にして実施例８の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは６３体積％含まれていた。
<Example 8>
A heat-foamable precoated metal plate of Example 8 was obtained in the same manner as in Example 7 except that the thickness of the heat-foamable resin layer was set to 310 μm by changing the coating amount of the plastisol composition. The heat-expandable microcapsules were contained in an amount of 63% by volume based on the formed heat-expandable resin layer.
＜実施例９＞
プラスチゾル組成物の塗布量を変えて加熱発泡性樹脂層の厚さを５４０μｍとしたこと以外は実施例７と同様にして実施例９の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは６３体積％含まれていた。
<Example 9>
A heat-foamable precoated metal plate of Example 9 was obtained in the same manner as in Example 7 except that the thickness of the heat-foamable resin layer was set to 540 μm by changing the coating amount of the plastisol composition. The heat-expandable microcapsules were contained in an amount of 63% by volume based on the formed heat-expandable resin layer.
＜実施例１０＞
プラスチゾル組成物の組成を塩化ビニル系樹脂粉体（株式会社カネカ製、ペーストＰＶＣ ＰＣＨ−７２、平均粒径５μｍ以下）１０質量部、トリキシレニルホスフェート（大八化学工業株式会社製、ＴＸＰ）１０質量部、熱膨張性マイクロカプセル（積水化学工業株式会社製、アドバンセル（登録商標）ＥＨＭ３０２、平均粒径２０μｍ）５質量部及び希釈剤（キシダ化学株式会社製、ミネラルスピリット）６質量部に変更し、加熱発泡性樹脂層の厚さを１３０μｍとしたこと以外は実施例１と同様にして実施例１０の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは４７体積％含まれていた。
<Example 10>
The composition of the plastisol composition is 10 parts by mass of vinyl chloride resin powder (manufactured by Kaneka Co., Ltd., paste PVC PCH-72, average particle size of 5 μm or less), trixylenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., TXP) 10. Changed to 5 parts by mass, thermally expandable microcapsules (manufactured by Sekisui Chemical Industry Co., Ltd., Advancel (registered trademark) EHM302, average particle size 20 μm) and 6 parts by mass of diluent (manufactured by Kishida Chemical Co., Ltd., Mineral Spirit). A heat-foamable precoated metal plate of Example 10 was obtained in the same manner as in Example 1 except that the thickness of the heat-foamable resin layer was 130 μm. 47% by volume of the heat-expandable microcapsules were contained in the formed heat-expandable resin layer.
＜実施例１１＞
プラスチゾル組成物の塗布量を変えて加熱発泡性樹脂層の厚さを３１５μｍとしたこと以外は実施例１０と同様にして実施例１１の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは４７体積％含まれていた。
<Example 11>
A heat-foamable precoated metal plate of Example 11 was obtained in the same manner as in Example 10 except that the thickness of the heat-foamable resin layer was set to 315 μm by changing the coating amount of the plastisol composition. 47% by volume of the heat-expandable microcapsules were contained in the formed heat-expandable resin layer.
＜実施例１２＞
プラスチゾル組成物の塗布量を変えて加熱発泡性樹脂層の厚さを５５０μｍとしたこと以外は実施例１０と同様にして実施例１２の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは４７体積％含まれていた。
<Example 12>
A heat-foamable precoated metal plate of Example 12 was obtained in the same manner as in Example 10 except that the thickness of the heat-foamable resin layer was set to 550 μm by changing the coating amount of the plastisol composition. 47% by volume of the heat-expandable microcapsules were contained in the formed heat-expandable resin layer.
＜実施例１３＞
ウレタン系プライマーの代わりにポリエステル系プライマー（斉藤塗料株式会社製、ＰＵ５００プライマーＮｏ．２２）を用い、プラスチゾル組成物の組成をアクリル系樹脂粉体（三菱レイヨン株式会社製、ダイヤナール（登録商標）ＬＰ−３２０２、最小粒径１μｍ以下）１０質量部、トリキシレニルホスフェート（大八化学工業株式会社製、ＴＸＰ）１０質量部、熱膨張性マイクロカプセル（積水化学工業株式会社製、アドバンセル（登録商標）ＥＨＭ３０２、平均粒径２０μｍ）５質量部及び希釈剤（キシダ化学株式会社製、ミネラルスピリット）６質量部に変更し、加熱発泡性樹脂層の厚さを５４０μｍとしたこと以外は実施例１と同様にして実施例１３の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは４７体積％含まれていた。
<Example 13>
A polyester-based primer (manufactured by Saito Paint Co., Ltd., PU500 Primer No. 22) was used instead of the urethane-based primer, and the composition of the plastisol composition was adjusted to an acrylic resin powder (manufactured by Mitsubishi Rayon Co., Ltd., Dianal (registered trademark) LP -3202, minimum particle size 1 μm or less) 10 parts by mass, trixylenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., TXP) 10 parts by mass, heat-expandable microcapsules (manufactured by Sekisui Chemical Industry Co., Ltd., Advancel (registered trademark) ) EHM302, average particle size 20 μm) 5 parts by mass and diluent (manufactured by Kishida Chemical Industry Co., Ltd., Mineral Spirit) 6 parts by mass, and the thickness of the heat-foamable resin layer was changed to 540 μm. In the same manner, a heat-foamable precoated metal plate of Example 13 was obtained. 47% by volume of the heat-expandable microcapsules were contained in the formed heat-expandable resin layer.
＜実施例１４＞
ポリエステル系プライマーの代わりにエポキシ系プライマー（日本ペイント株式会社製、ニッペ ファインパーフェクトシーラー）を用い、加熱発泡性樹脂層の厚さを５３０μｍとしたこと以外は実施例１３と同様にして実施例１４の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは４７体積％含まれていた。
<Example 14>
Example 14 was the same as in Example 13 except that an epoxy primer (Nippe Fine Perfect Sealer manufactured by Nippon Paint Co., Ltd.) was used instead of the polyester primer and the thickness of the thermosetting resin layer was set to 530 μm. A thermosetting precoated metal plate was obtained. 47% by volume of the heat-expandable microcapsules were contained in the formed heat-expandable resin layer.
＜実施例１５＞
ポリエステル系プライマーの代わりにアクリル系プライマー（株式会社トウベ製、ナイトボンド３９）を用い、加熱発泡性樹脂層の厚さを５４５μｍとしたこと以外は実施例１３と同様にして実施例１５の加熱発泡性プレコート金属板を得た。形成された加熱発泡性樹脂層に対して、熱膨張性マイクロカプセルは４７体積％含まれていた。
<Example 15>
Acrylic primer (Nightbond 39, manufactured by Toube Co., Ltd.) was used instead of the polyester primer, and the thermosetting resin layer of Example 15 was heated and foamed in the same manner as in Example 13 except that the thickness of the thermosetting resin layer was 545 μm. A pre-coated metal plate was obtained. 47% by volume of the heat-expandable microcapsules were contained in the formed heat-expandable resin layer.
＜比較例１＞
熱可塑性飽和ポリエステル樹脂の水分散体（高松油脂株式会社製、ペスレジンＡ−６４５ＧＨ、固形分３０質量％）１０質量部、熱分解型発泡剤（三協化成株式会社製、セルマイク（登録商標）Ｃ−１、アゾジカルボンアミド（ＡＤＣＡ）、平均粒径１０μｍ）２．７質量部及び有機変性無機質粉末（株式会社ホージュン製、エスベン（登録商標）ＮＸ、有機変性ベントナイト）２．４質量部を、プラネタリーミキサーを用いて混合してポリエステル樹脂組成物を調製した。このポリエステル樹脂組成物をバーコーターで板厚０．６ｍｍの亜鉛系めっき鋼板に塗布した後、加熱炉で２２０℃、４０秒間加熱して厚さ１００μｍの加熱発泡性樹脂層を形成し、比較例１の加熱発泡性プレコート金属板を得た。
<Comparative example 1>
10 parts by mass of an aqueous dispersion of thermoplastic saturated polyester resin (manufactured by Takamatsu Oil & Fat Co., Ltd., pesresin A-645GH, solid content 30% by mass), pyrolytic foaming agent (manufactured by Sankyo Kasei Co., Ltd., Cellmic (registered trademark) C) -1, Azodicarbonamide (ADCA), average particle size 10 μm) 2.7 parts by mass and organically modified inorganic powder (manufactured by Hojun Co., Ltd., Esben® NX, organically modified bentonite) 2.4 parts by mass, planeta A polyester resin composition was prepared by mixing using a Lee mixer. This polyester resin composition is applied to a galvanized steel sheet having a thickness of 0.6 mm with a bar coater, and then heated in a heating furnace at 220 ° C. for 40 seconds to form a heat-foamable resin layer having a thickness of 100 μm. A heat-foamable precoated metal plate of No. 1 was obtained.
＜比較例２＞
ポリエステル樹脂組成物の組成を熱可塑性飽和ポリエステル樹脂の水分散体（高松油脂株式会社製、ペスレジンＡ−６４５ＧＨ、固形分３０質量％）１０質量部及び熱分解型発泡剤（三協化成株式会社製、セルマイク（登録商標）Ｃ−１、アゾジカルボンアミド（ＡＤＣＡ）、平均粒径１０μｍ）２．７質量部に変更し、加熱発泡性樹脂層の厚さを３５０μｍとしたこと以外は比較例１と同様にして比較例２の加熱発泡性プレコート金属板を得た。
<Comparative example 2>
The composition of the polyester resin composition is 10 parts by mass of an aqueous dispersion of thermoplastic saturated polyester resin (manufactured by Takamatsu Oil & Fat Co., Ltd., pesresin A-645GH, solid content 30% by mass) and a pyrolytic foaming agent (manufactured by Sankyo Kasei Co., Ltd.). , Cellmic (registered trademark) C-1, azodicarbonamide (ADCA), average particle size 10 μm) 2.7 parts by mass, and the thickness of the heat-foamable resin layer was 350 μm. In the same manner, a heat-foamable precoated metal plate of Comparative Example 2 was obtained.
＜加工性の評価＞
作製した加熱発泡性プレコート金属板から５０ｍｍ×５０ｍｍの試験片を切り出し、加熱発泡性樹脂層が外側となるように、１８０°折り曲げ加工を施した（０ｔ曲げ、２Ｔ曲げ又は４Ｔ曲げ）。加熱発泡性樹脂層の状態を目視で観察し、下地の露出が認められない場合を「○」と評価し、下地の露出が認められた場合を「×」と評価した。結果を表１に示す。
<Evaluation of workability>
A 50 mm × 50 mm test piece was cut out from the prepared heat-foamable precoated metal plate and subjected to 180 ° bending (0t bending, 2T bending or 4T bending) so that the heat-foamable resin layer was on the outside. The state of the heat-foamable resin layer was visually observed, and the case where the base was not exposed was evaluated as “◯”, and the case where the base was exposed was evaluated as “x”. The results are shown in Table 1.
＜発泡倍率の評価＞
作製した加熱発泡性プレコート金属板から５０ｍｍ×５０ｍｍの試験片を切り出し、加熱炉で１６０℃、１５分間加熱して樹脂層を発泡させた。得られた金属板における発泡樹脂層の厚さを無作為に選択した５箇所以上で測定することによって発泡樹脂層の平均厚さ（ｔ１）を求め、この発泡樹脂層の平均厚さ（ｔ１）と発泡前の樹脂層の厚さ（ｔ０）とを用いて下記式により発泡倍率を求めた。
発泡倍率＝（ｔ１／ｔ０）
<Evaluation of foaming ratio>
A 50 mm × 50 mm test piece was cut out from the prepared heat-foamable precoated metal plate, and heated in a heating furnace at 160 ° C. for 15 minutes to foam the resin layer. The average thickness of the foamed resin layer (t 1 ) was obtained by measuring the thickness of the foamed resin layer in the obtained metal plate at five or more randomly selected points, and the average thickness of the foamed resin layer (t 1) was obtained. Using 1 ) and the thickness of the resin layer before foaming (t 0 ), the foaming ratio was calculated by the following formula.
Foaming ratio = (t 1 / t 0 )
表１の結果より、実施例１〜１５の加熱発泡性プレコート金属板は、加工性に優れている上に、発泡倍率が４．５２〜９．３５と高いことが分かる。一方、比較例１及び２の加熱発泡性プレコート金属板は、０Ｔ曲げで下地の露出が認められ、加工性が劣ることが分かる。更に、比較例１及び２の加熱発泡性プレコート金属板は、発泡倍率が４．３０と低いことが分かる。 From the results in Table 1, it can be seen that the heat-foamable precoated metal plates of Examples 1 to 15 are excellent in processability and have a high foaming ratio of 4.52 to 9.35. On the other hand, it can be seen that the heat-foamable precoated metal plates of Comparative Examples 1 and 2 are inferior in processability because the base is exposed by bending at 0 T. Further, it can be seen that the heat-foamable precoated metal plates of Comparative Examples 1 and 2 have a low foaming ratio of 4.30.
Claims (5)
前記熱膨張性マイクロカプセルが、前記加熱発泡性樹脂層に対して、１５体積％以上６５体積％以下含まれ、
前記加熱発泡性樹脂層の厚さが１００μｍ以上７００μｍ以下であることを特徴とする加熱発泡性プレコート金属板。 A heat-foamable precoated metal plate in which a heat-foamable resin layer containing an acrylic thermoplastic resin and heat-expandable microcapsules is provided on at least one surface of the metal plate.
The heat-expandable microcapsules are contained in an amount of 15% by volume or more and 65% by volume or less with respect to the heat-expandable resin layer.
A heat-foamable precoated metal plate characterized in that the thickness of the heat-foamable resin layer is 100 μm or more and 700 μm or less.
前記熱膨張性マイクロカプセルが、前記加熱発泡性樹脂層に対して、１５体積％以上６５体積％以下含まれ、
前記加熱発泡性樹脂層の厚さが１００μｍ以上７００μｍ以下であることを特徴とする加熱発泡性プレコート金属板の製造方法。 A heat-foamable material having a step of applying a plastisol composition containing an acrylic thermoplastic resin , a plasticizer, and heat-expandable microcapsules to at least one surface of a metal plate and drying the plastisol composition to form a heat-foamable resin layer. It is a method of manufacturing a precoated metal plate.
The heat-expandable microcapsules are contained in an amount of 15% by volume or more and 65% by volume or less with respect to the heat-expandable resin layer.
A method for producing a heat-foamable precoated metal plate, wherein the heat-foamable resin layer has a thickness of 100 μm or more and 700 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017020453A JP6848494B2 (en) | 2017-02-07 | 2017-02-07 | Heat-foamable pre-coated metal plate and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017020453A JP6848494B2 (en) | 2017-02-07 | 2017-02-07 | Heat-foamable pre-coated metal plate and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018126900A JP2018126900A (en) | 2018-08-16 |
| JP6848494B2 true JP6848494B2 (en) | 2021-03-24 |
Family
ID=63173530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017020453A Active JP6848494B2 (en) | 2017-02-07 | 2017-02-07 | Heat-foamable pre-coated metal plate and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6848494B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022014498A1 (en) | 2020-07-15 | 2022-01-20 | 日本製鉄株式会社 | Pre-coated metal sheet, burn prevention cover, and method for manufacturing pre-coated metal sheet |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0931371A (en) * | 1995-07-21 | 1997-02-04 | Nippon Paint Co Ltd | Coating material composition and manufacture of coated board and decorative coated board |
| JPH11156290A (en) * | 1997-11-28 | 1999-06-15 | Nippon Paint Co Ltd | Formation of precoating film including foaming agent-containing base coating film and having designability |
| JP5965101B2 (en) * | 2010-12-27 | 2016-08-03 | サンスター技研株式会社 | Paste heating foam filler |
| JP5995891B2 (en) * | 2014-03-12 | 2016-09-21 | アイシン化工株式会社 | Vinyl chloride plastisol composition |
-
2017
- 2017-02-07 JP JP2017020453A patent/JP6848494B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018126900A (en) | 2018-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20060160932A1 (en) | Heat activated sealants and foamed materials | |
| KR101456730B1 (en) | Use of cyclohexane polycarbonic acid esters for the production of coating materials for the coil coating method and the production of coated coils | |
| DE4421012A1 (en) | Acoustically effective plastisols | |
| WO2009107463A1 (en) | Vinyl chloride resin composition for powder molding, vinyl chloride resin molded body, laminate, automobile interior material, and method for producing vinyl chloride resin composition for powder molding | |
| DE102005052130A1 (en) | Sprayable acoustics | |
| WO2007018394A9 (en) | Highly elastic polyvinyl chloride composition and products prepared using the same | |
| CA2164696A1 (en) | Acoustically active plastisols | |
| EP2918647A1 (en) | Vinyl chloride plastisol composition | |
| JP6848494B2 (en) | Heat-foamable pre-coated metal plate and its manufacturing method | |
| EP2016123A1 (en) | Rigid polyvinyl chloride polymer compositions having improved impact properties | |
| WO2012090565A1 (en) | Paste-like thermally expandable filler | |
| EP3696225B1 (en) | Plastisol composition suitable for sealing of metal parts | |
| WO2003002645A1 (en) | Adhesion promoter for plastisols | |
| CN103741546B (en) | A kind of corn particle effect wallpaper and production technology thereof | |
| WO2015174372A1 (en) | Acrylic polymer, method for producing same, and plastisol composition including said acrylic polymer | |
| WO2017170160A1 (en) | Spray coating sol, vinyl chloride resin molded body with spray coating layer, manufacturing method for said molded body, and laminate | |
| JPH10279878A (en) | Matte polyvinyl chloride sol coating composition and matte coated metal sheet | |
| JP2017205962A (en) | Jet-black tone decorative film, decorative molded product, and method for producing jet-black tone decorative film | |
| JP2000169756A (en) | Undercoating agent for noise prevention | |
| JP2021143213A (en) | Mastic adhesive | |
| JP2506020B2 (en) | Resin composition for powder molding | |
| JP2019099933A (en) | Foamed wallpaper | |
| CN109776998A (en) | The PVC hard plastic sheet and its processing method of anti-static and abrasion-resistant | |
| JP2020029541A (en) | Vinyl chloride plastisol composition | |
| JPH01110549A (en) | Fomable plastisol composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200122 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20200901 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20201023 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20201110 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20201222 |
|
| 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: 20210202 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210215 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6848494 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |