JPH06157842A - Polypropylene resin powder - Google Patents
Polypropylene resin powderInfo
- Publication number
- JPH06157842A JPH06157842A JP4305214A JP30521492A JPH06157842A JP H06157842 A JPH06157842 A JP H06157842A JP 4305214 A JP4305214 A JP 4305214A JP 30521492 A JP30521492 A JP 30521492A JP H06157842 A JPH06157842 A JP H06157842A
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- weight
- block copolymer
- powder
- resin powder
- block
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属製品の粉体塗装に
適したポリプロピレン系樹脂粉体に関する。更に詳しく
は、ポリプロピレン系樹脂粉体を金属製品塗装として用
いた場合、金属との密着性に優れ、表面硬度が高く、か
つ耐熱性、耐薬品性、耐ＥＳＣＲ性、耐熱水性にも優れ
る特性を有する。TECHNICAL FIELD The present invention relates to a polypropylene resin powder suitable for powder coating of metal products. More specifically, when polypropylene resin powder is used for coating metal products, it has excellent adhesion to metal, high surface hardness, and excellent heat resistance, chemical resistance, ESCR resistance, and hot water resistance. Have.
【０００２】[0002]
【従来の技術】従来、金属製品（たとえば、自転車のか
ご、水切棚、冷蔵庫棚網など）に耐腐食性、耐薬品性、
耐汚染性、装飾性などの機能を付与するために、表面に
ポリエチレン粉体を流動浸漬法、静電塗装法、ころがし
塗装法などにより塗装する方法が広く採用されてきた。
しかし、ポリエチレンは、金属との密着性が低い為に耐
久性に問題があった。2. Description of the Related Art Conventionally, metal products (for example, bicycle baskets, draining shelves, refrigerator shelving, etc.) are resistant to corrosion, chemicals,
In order to impart functions such as stain resistance and decorativeness, a method in which polyethylene powder is applied to the surface by a fluid immersion method, an electrostatic coating method, a rolling coating method, etc. has been widely adopted.
However, polyethylene has a problem in durability because it has low adhesion to metal.
【０００３】これを解決する手段として、無水マレイン
酸等で変性したポリエチレンを利用する方法が特開昭５
８−２３５８号公報、特開昭５８−１４２９４５号公
報、特開昭５９−３０８４１号公報に記載されている。
この様に金属への密着性を高め、耐久性を改善する事に
よりポリエチレン粉体はフェンス等の耐久性が要求され
る製品分野にも使用され、用途分野も拡大して来てい
る。しかし、ポリエチレン塗膜は、表面が傷付き易い、
使用可能温度が低い等の欠点を有し、改良が望まれてい
る。ポリエチレンより耐熱性に優れるポリプロピレンを
使用した組成物が特開昭６２−１９０２６５号公報、特
開平０１−２９７１７４号公報に開示されている。しか
し、いずれも塗装後のポリプロピレン塗膜の耐久性が不
十分であり、より改良された物が望まれている。As a means for solving this, a method of utilizing polyethylene modified with maleic anhydride or the like is disclosed in Japanese Patent Laid-Open No. 5-58200.
No. 8-2358, JP-A-58-142945, and JP-A-59-30841.
By thus improving the adhesion to metal and improving the durability, the polyethylene powder is used in the field of products such as fences which require durability, and the field of application is expanding. However, the surface of polyethylene coating is easily scratched,
It has drawbacks such as low usable temperature, and improvement is desired. Compositions using polypropylene, which is superior in heat resistance to polyethylene, are disclosed in JP-A-62-190265 and JP-A-01-297174. However, in all cases, the durability of the polypropylene coating film after coating is insufficient, and a further improved product is desired.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、ポリエチレ
ン塗膜と同等以上の耐腐食性、耐薬品性、耐汚染性、装
飾性の性能を有し、なおかつ、表面硬度が高く、耐熱性
に優れる塗膜を金属製品に形成しうるポリプロピレン系
樹脂粉体を提供するものである。The present invention has corrosion resistance, chemical resistance, stain resistance, and decorative properties equivalent to or higher than those of polyethylene coating films, and has high surface hardness and heat resistance. A polypropylene resin powder capable of forming an excellent coating film on a metal product.
【０００５】[0005]
【課題を解決するための手段】本発明者は、上記課題を
克服すべく鋭意研究を重ねた結果、本発明をなすに至っ
たものである。すなわち本発明は、（Ａ）ＭＦＲが５〜
２００のポリプロピレン９０〜４０重量％と（Ｂ）ビニ
ル芳香族炭化水素の含有量が６０重量％を越え、９０重
量％以下であり、少なくとも１個のビニル芳香族炭化水
素重合体ブロックＸと少なくとも１個のオレフィン化合
物重合体ブロックＹとを有し、しかもブロックＹの不飽
和度が２０％を越えないオレフィン化合物重合体ブロッ
クであるブロック共重合体にカルボン酸基またはその誘
導体を０．０５〜２０重量％結合させ変性した変性ブロ
ック共重合体、１０〜６０重量％よりなる混合物からな
るポリプロピレン系樹脂粉体に係わるものである。The inventor of the present invention has accomplished the present invention as a result of intensive studies to overcome the above problems. That is, the present invention has (A) MFR of 5 to
200 polypropylene having a content of 90 to 40% by weight and (B) vinyl aromatic hydrocarbon content exceeding 60% by weight and 90% by weight or less, and at least one vinyl aromatic hydrocarbon polymer block X and at least 1 0.05 to 20 of a carboxylic acid group or its derivative in a block copolymer which is an olefin compound polymer block in which the degree of unsaturation of the block Y does not exceed 20%. The present invention relates to a polypropylene-based resin powder composed of a mixture of a modified block copolymer modified by bonding by weight% and modified by 10 to 60% by weight.
【０００６】（Ａ）ポリプロピレン系重合体としては、
プロピレンを単独重合したホモポリマ−、プロピレンと
エチレンを共重合したランダムコポリマ−またはブロッ
クコポリマ−、プロピレン、エチレンとそれ以外の１種
以上のαーオレフィンを共重合した多元共重体合体、お
よびこれらの２種以上を組み合わせた物が挙げられる。
ポリプロピレン系重合体のＭＦＲは５〜２００である
事が必要であり、好ましくは２０〜１７５、より好まし
くは２５〜１３０の範囲が推奨される。ＭＦＲが５より
低いと溶融時の流動性が悪いため塗装品の表面が平滑に
ならない。一方、ＭＦＲが２００より高いと塗膜の引張
り強度、耐衝撃性等の物性が極端に低下するため長期使
用に耐えないものである。プロピレンとエチレンの共重
合体においては、共重合体中のエチレンが、０．１〜２
５重量％、好ましくは０．３〜１０重量％の範囲が好ま
しい。As the polypropylene-based polymer (A),
Homopolymers obtained by homopolymerizing propylene, random copolymers or block copolymers obtained by copolymerizing propylene and ethylene, propylene, multicomponent copolymers obtained by copolymerizing ethylene and one or more other α-olefins, and two kinds thereof. An example is a combination of the above.
The MFR of the polypropylene polymer is required to be 5 to 200, preferably 20 to 175, more preferably 25 to 130 is recommended. If the MFR is less than 5, the surface of the coated article will not be smooth due to poor fluidity during melting. On the other hand, when the MFR is higher than 200, the physical properties such as tensile strength and impact resistance of the coating film are extremely deteriorated, so that it cannot withstand long-term use. In a copolymer of propylene and ethylene, ethylene in the copolymer is 0.1 to 2
A range of 5% by weight, preferably 0.3 to 10% by weight is preferable.
【０００７】また、耐衝撃性、耐低温特性の面からはブ
ロックコポリマ−の使用が推奨される。多元共重合体に
使用されるαーオレフィンとしては、１−ブテン、１−
ヘキセン、１−オクテン等が挙げられるが、原料価格面
から１−ブテンが好ましい。多元共重合体中のエチレン
とαーオレフィンが、０．１〜２０重量％、好ましくは
０．３〜１０重量％の範囲が好ましく、エチレンとαー
オレフィンの比には特に制限はない。From the viewpoint of impact resistance and low temperature resistance, it is recommended to use a block copolymer. The α-olefin used in the multi-component copolymer includes 1-butene and 1-butene.
Examples include hexene and 1-octene, but 1-butene is preferable from the viewpoint of raw material price. The content of ethylene and α-olefin in the multi-component copolymer is preferably 0.1 to 20% by weight, preferably 0.3 to 10% by weight, and the ratio of ethylene and α-olefin is not particularly limited.
【０００８】（Ｂ）変性ブロック共重合体は、ビニル芳
香族炭化水素重合体ブロックＸと少なくとも１個の不飽
和度が２０％を越えないオレフィン化合物重合体ブロッ
クＹとからなるブロック共重合体（以下これを「ベ−ス
ブロック共重合体」と呼ぶ）にカルボン酸基またはその
誘導体を結合させた物である。ビニル芳香族炭化水素重
合体ブロックは、スチレン、α−メチルスチレン、ビニ
ルトルエン等の１種以上を重合させた物であり、好まし
くはスチレンが推奨される。ここで、オレフィン化合物
重合体ブロックＹとは、エチレン、プロピレン、１−ブ
テン、イソブチレン等のモノオレフィン、あるいはブタ
ジエン、イソプレン、１，３−ペンタジエン等の共役ジ
オレフィン、１，４ヘキサジエン、ノルボルネン、ノル
ボルネン誘導体等の非共役ジオレフィンのうちから選ば
れた１種以上のオレフィン化合物が重合、あるいは共重
合した物であり、しかも該ブロックの不飽和度が２０％
以下である。具体的な「ベ−スブロック共重合体」とし
ては、ビニル芳香族炭化水素と共役ジオレフィンのブロ
ック共重合体の水添物、ビニル芳香族炭化水素とモノオ
レフィンのブロック共重合体等が挙げられる。好ましく
は、ビニル芳香族炭化水素重合体ブロックと共役ジオレ
フィンを主体とする重合体ブロックとから構成されてな
るブロック共重合体の共役ジオレフィン部分の非共役度
が２０％を越えない程度まで選択的に水添された物であ
る。The modified block copolymer (B) is a block copolymer comprising a vinyl aromatic hydrocarbon polymer block X and at least one olefin compound polymer block Y whose degree of unsaturation does not exceed 20% ( Hereinafter, this is referred to as a "base block copolymer") to which a carboxylic acid group or a derivative thereof is bound. The vinyl aromatic hydrocarbon polymer block is obtained by polymerizing one or more kinds of styrene, α-methylstyrene, vinyltoluene, etc., and preferably styrene is recommended. Here, the olefin compound polymer block Y is a monoolefin such as ethylene, propylene, 1-butene or isobutylene, or a conjugated diolefin such as butadiene, isoprene or 1,3-pentadiene, 1,4 hexadiene, norbornene or norbornene. It is a product obtained by polymerizing or copolymerizing one or more olefin compounds selected from non-conjugated diolefins such as derivatives, and the degree of unsaturation of the block is 20%.
It is the following. Specific examples of "base block copolymers" include hydrogenated products of block copolymers of vinyl aromatic hydrocarbons and conjugated diolefins, block copolymers of vinyl aromatic hydrocarbons and monoolefins, and the like. To be Preferably, the degree of non-conjugation of the conjugated diolefin portion of the block copolymer composed of the vinyl aromatic hydrocarbon polymer block and the polymer block containing a conjugated diolefin as a main component is selected to an extent not exceeding 20%. It is a hydrogenated product.
【０００９】次いで、「ベ−スブロック共重合体」に不
飽和カルボン酸基またはその誘導体が付加反応により結
合されて変性ブロック共重合体が得られる。「ベ−スブ
ロック共重合体」において、ビニル芳香族炭化水素重合
体ブロックＸとオレフィン化合物重合体ブロックＹの重
量比は６０／４０〜９０／１０、好ましくは６５／３５
〜８５／１５の範囲である。また、重合体ブロックはそ
れぞれ２個以上含有する事が可能であるし、各ブロック
は同一の構造であってもよいし、構造が異なる物であっ
ても良い。分子量は数平均分子量が２００００〜５００
０００、好ましくは４００００〜４０００００の範囲で
あり、分子量分布は１．０５〜１０の範囲が推奨され
る。オレフィン化合物重合体ブロックＹに含まれる共役
ジエンに基づく二重結合は、ブロック中の不飽和度が２
０％を越えない事が必要である。ブロックＹに含まれる
不飽和度が２０％を越えると粉体の耐候性や耐熱性に悪
影響及ぼすので好ましくない。Next, an unsaturated carboxylic acid group or its derivative is bonded to the "base block copolymer" by an addition reaction to obtain a modified block copolymer. In the "base block copolymer", the weight ratio of the vinyl aromatic hydrocarbon polymer block X and the olefin compound polymer block Y is 60/40 to 90/10, preferably 65/35.
The range is from 85/15. Further, it is possible to contain two or more polymer blocks, and the blocks may have the same structure or different structures. The number average molecular weight is 20,000 to 500
000, preferably 40,000 to 400,000, and a molecular weight distribution of 1.05 to 10 is recommended. The double bond based on the conjugated diene contained in the olefin compound polymer block Y has a degree of unsaturation of 2 in the block.
It is necessary not to exceed 0%. When the degree of unsaturation contained in the block Y exceeds 20%, the weather resistance and heat resistance of the powder are adversely affected, which is not preferable.
【００１０】不飽和カルボン酸基またはその誘導体を付
加反応するにおいて使用される化合物としては、例え
ば、マレイン酸、フマル酸、イタコン酸、ハロゲン化マ
レイン酸、、ジカルボン酸の酸無水物、エステル、アミ
ド、イミドなど、アクリル酸、メタクリル酸やこれらの
モノカルボン酸エステル、アミドなどが挙げられる。こ
れらのなかで無水マレイン酸が好ましい。Examples of the compound used in the addition reaction of the unsaturated carboxylic acid group or its derivative include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, dicarboxylic acid anhydrides, esters and amides. , Imides, acrylic acid, methacrylic acid, and monocarboxylic acid esters and amides thereof. Of these, maleic anhydride is preferred.
【００１１】変性ブロック共重合体に含まれるカルボン
酸基またはその誘導体を含有する分子単位の量、即ち不
飽和カルボン酸基またはその誘導体の付加量、は「ベ−
スブロック共重合体」１００重量部当り、０．０５〜２
０重量部、好ましくは０．１〜１５重量部、更に好まし
くは０．１５〜１０重量部である。０．０５未満では密
着性の性能が全く発揮されず、一方、２０重量部を越え
てもそれ以下の量に比較して密着性の性能が向上しない
ばかりか耐熱性の低下をもたらす。The amount of the molecular unit containing the carboxylic acid group or its derivative contained in the modified block copolymer, that is, the addition amount of the unsaturated carboxylic acid group or its derivative, is "base".
"S block copolymer" per 100 parts by weight of 0.05 to 2
The amount is 0 parts by weight, preferably 0.1 to 15 parts by weight, and more preferably 0.15 to 10 parts by weight. If it is less than 0.05, the adhesion performance is not exhibited at all. On the other hand, if it exceeds 20 parts by weight, the adhesion performance is not improved and the heat resistance is lowered as compared with the amount less than 20 parts by weight.
【００１２】（Ａ）成分９０〜４０重量％と（Ｂ）成分
６０〜１０重量％を、単軸押出機、二軸押出機等により
溶融混練し均一な組成物とする。（Ａ）成分が４０重量
％より少ないと耐熱性、高表面硬度が十分に達成できな
い。一方、９０重量％より多いと、密着性と塗膜の伸び
の改善が不十分で耐久性が劣る。好ましくは、（Ａ）成
分８５〜５０重量％と（Ｂ）成分５０〜１５重量％の範
囲が使用される。溶融混練する際に顔料、又は顔料のマ
スタ−バッチを添加し着色を同時に行なうのが製造工程
を簡略化する上で有利である。更に、酸化防止剤、耐候
剤、滑剤、結晶核剤、抗菌剤、防カビ剤、帯電防止剤、
充てん剤、過酸化物等を同時に添加する方法によりポリ
プロピレン系樹脂粉体の性能を改善する事が可能であ
る。90 to 40% by weight of the component (A) and 60 to 10% by weight of the component (B) are melt-kneaded by a single-screw extruder, a twin-screw extruder or the like to obtain a uniform composition. If the amount of component (A) is less than 40% by weight, heat resistance and high surface hardness cannot be sufficiently achieved. On the other hand, if it is more than 90% by weight, the improvement of the adhesion and the elongation of the coating film is insufficient and the durability is deteriorated. Preferably, a range of 85 to 50% by weight of component (A) and 50 to 15% by weight of component (B) is used. At the time of melt-kneading, it is advantageous to add a pigment or a master-batch of pigments and perform coloring at the same time in order to simplify the manufacturing process. Furthermore, antioxidants, weathering agents, lubricants, crystal nucleating agents, antibacterial agents, antifungal agents, antistatic agents,
It is possible to improve the performance of the polypropylene resin powder by the method of simultaneously adding the filler, the peroxide and the like.
【００１３】粉体塗装に適するポリプロピレン系樹脂粉
体としては、粉体の流動性が良好である事が重要であ
る。このためには、粉体の平均粒径が１０〜５００μ、
嵩密度が０．２〜０．６ｇ／ｃｍ3 の範囲が使用され
る。粉体の好ましい粒子径は塗装方法により異なり、流
動浸漬法においては８０〜３００μ、静電塗装法におい
ては５０〜２００μ、ころがし塗装法においては８０〜
４００μが推奨される。良好な粉体の流動性を得るには
好ましくは、嵩密度が０．２５〜０．５８ｇ／ｃｍ 3 、
更に好ましくは０．３〜０．５５ｇ／ｃｍ3 が推奨され
る。Polypropylene resin powder suitable for powder coating
For the body, it is important that the powder has good fluidity.
It To this end, the average particle size of the powder is 10 to 500 μ,
Bulk density is 0.2-0.6g / cm3Range of used
It The preferred particle size of the powder depends on the coating method,
80-300μ in dynamic immersion method, electrostatic coating method
50-200μ, and in the rolling coating method 80-
400μ is recommended. To obtain good powder flowability
Preferably, the bulk density is 0.25 to 0.58 g / cm 3,
More preferably 0.3 to 0.55 g / cm3Is recommended
It
【００１４】このようなポリプロピレン系樹脂粉体を得
る方法としては、０℃以下、好ましくは−１０℃以下の
温度で各種の機械粉砕法により製造される。更に、粉砕
後粉体の融点以下の温度で高速で攪拌し粉体流動性を改
良する事も可能である。また、粉砕後に高速ミキサ−等
を使用して、カ−ボンブラック、金属粉末等を混合して
着色する方法、微粉シリカ、タルクなどの無機物を混合
して粉体性能を改良する手法の採用も可能である。As a method for obtaining such polypropylene resin powder, various mechanical grinding methods are used at a temperature of 0 ° C. or lower, preferably -10 ° C. or lower. Further, it is also possible to improve the fluidity of the powder by stirring at a temperature below the melting point of the powder after pulverization at high speed. In addition, a method of mixing carbon black, metal powder or the like for coloring by using a high speed mixer after crushing, or a method of improving powder performance by mixing an inorganic substance such as finely divided silica or talc is also adopted. It is possible.
【００１５】[0015]
【実施例】以下、実施例により本発明を更に説明するが
本発明はこれに限定される物ではない。実施例中の物性
は以下の方法で測定を行った。 １）ＭＦＲ ：ＪＩＳ Ｋ−６７５８ ２３０℃ 荷重
２．１６ｋｇ ２）平均粒径：粉体を振とう篩により篩分し粒径に対す
る積分曲線より５０重量％の粒径を平均粒径とした。 ３）引張伸び：粉体のプレス成型により２ｍｍの平板を
作成し、引張試験法（ＪＩＳ Ｋ−６７６０）にて測定
した。 ４）表面硬度：ＪＩＳ Ｋ６７６０によりショア−Ｄ硬
度を測定した。 ５）密着強度：流動浸漬法により金属試験片に塗装を行
ない、塗膜に薄刃の鋭利な刃物で試験片の素地まで達す
る平行な切れ目１１本（間隔は１ｍｍ）とこれに直角に
平行な切れ目１１本（間隔は１ｍｍ）を入れ、碁盤目
（１００個）を作り、この上にセロテ−プを貼り付け次
に剥離し、これにより剥離した塗膜の数で密着強度を表
示した。つまり、０／１００は全て剥離せず密着性が非
常に高い事を表し１００／１００は、全て剥離した事を
示し密着性がない事を示す。EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The physical properties in the examples were measured by the following methods. 1) MFR: JIS K-6758 230 ° C., load 2.16 kg 2) Average particle size: The powder was sieved with a shaking sieve, and 50% by weight of the particle size was determined as an average particle size from an integral curve with respect to the particle size. 3) Tensile elongation: A 2 mm flat plate was prepared by powder press molding and measured by a tensile test method (JIS K-6760). 4) Surface hardness: Shore-D hardness was measured according to JIS K6760. 5) Adhesion strength: A metal test piece is coated by the fluidized-bed method, and 11 parallel cuts (interval of 1 mm) and a cut parallel to this are formed on the coating film with a sharp blade of a thin blade to reach the base of the test piece. Eleven pieces (interval: 1 mm) were put in to form a grid (100 pieces), and a cello tape was attached on this and then peeled off, and the adhesion strength was indicated by the number of the peeled coating films. In other words, 0/100 means that all of them are not peeled and the adhesion is very high, and 100/100 means that all of them are peeled and that there is no adhesion.
【００１６】６）衝撃強度：デュポン衝撃試験法（ＪＩ
Ｓ Ｋ−５４００ 衝撃強度０．５ｋｇ−ｍ）にて金属
試験片の塗膜強度を測定し、塗膜にひび割れのない物を
◎、ひび割れが小さな物を○、ひび割れが大きい物を
△、塗膜が剥離した物を×で表した。 ７）防触度試験：金属試験片の塗膜に薄刃の鋭利な刃物
で試験片の素地まで達するように交差する２本の切れ目
を入れ、湿潤試験機（ＪＩＳ Ｚ−０２２８）の中に５
００時間放置した後、切り口からの錆の状態を観察し、
錆の拡大のない物を○、若干錆が拡大している物を△、
錆が拡大している物を×で表した。6) Impact strength: DuPont impact test method (JI
The coating strength of the metal test piece was measured with SK-5400 impact strength 0.5 kg-m), and those with no cracks on the coating film were marked with ◎, those with small cracks were marked with ○, and those with large cracks were marked with Δ. The peeled film was represented by x. 7) Anti-corrosion test: The coating film of the metal test piece was made into two cuts intersecting so as to reach the base material of the test piece with a sharp blade of a thin blade, and the test piece was placed in a wetness tester (JIS Z-0228) to give 5
After leaving it for 00 hours, observe the state of rust from the cut end,
○: No rust expansion, △: slightly rust expansion
The thing in which the rust has spread is shown by x.
【００１７】[0017]
【実施例１〜７】 （１）変性ブロック共重合体の製造 ｎ−ブチルリチウムを重合触媒とし、ｎ−ヘキサン溶媒
中でテトラヒドロフランをビニル含量調節剤として、ブ
タジエンとスチレンとをブロック共重合した。これをシ
クロヘキサン中でナフテン酸コバルトとトリエチルアル
ミニウムを触媒として水素圧７kg/ cm2、温度５０℃で
５時間水素添加を行ってブタジエンブロックの二重結合
部の約９０％を水素添加した後、触媒残渣を塩酸水溶液
−メタノ−ルで洗浄して除去した。この水添ブロック共
重合体１００重量部に対し３重量部の無水マレイン酸、
０．１重量部のパ−ヘキサ２５Ｂ（日本油脂社製）を均
一に混合した後、スクリュ押出機に供給しマレイン反応
を行い表１の変性ブロック共重合体を得た。 （２）ポリプロピレン系樹脂粉体の製造 表２に示すポリプロピレンと変性ブロック共重合体及び
これらの樹脂成分に対しペンタエリスリチル−テトラキ
ス〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフ
ェニル）プロピオネ−ト〕１０００ｐｐｍとテトラキス
（２，４−ジ−ｔ−ブチルフェニル）−４，４´−ビフ
ェニレンフォスフォナイト２０００ｐｐｍを混合し、３
０ｍｍφ２軸押出機を用いて２２０℃の条件で混練しペ
レットとした。このペレットを液体チッソで−２０℃以
下に冷却し機械粉砕により粉砕し、目開き２５０μのふ
るいを通過した物を取り出す事により平均粒径２００μ
のポリプロピレン粉体を得た。この粉末をプレス成形に
より２ｍｍの平板とし、引張伸びを測定した。また、表
面硬度の測定も行った。この結果は表２に示す。 （３）ポリプロピレン系樹脂粉体の塗装 ０．６ｍｍ厚みの圧延鋼板に流動浸漬法により該粉体を
塗装し、３８０μの塗膜を形成した。塗膜の物性測定結
果は表２に示す。Examples 1 to 7 (1) Production of Modified Block Copolymer butadiene and styrene were block-copolymerized with n-butyllithium as a polymerization catalyst and tetrahydrofuran as a vinyl content modifier in an n-hexane solvent. This was subjected to hydrogenation in cyclohexane at a hydrogen pressure of 7 kg / cm 2 and a temperature of 50 ° C. for 5 hours using cobalt naphthenate and triethylaluminum as a catalyst to hydrogenate about 90% of the double bond portion of the butadiene block, and then the catalyst. The residue was removed by washing with aqueous hydrochloric acid-methanol. 3 parts by weight of maleic anhydride to 100 parts by weight of this hydrogenated block copolymer,
After 0.1 part by weight of Perhexa 25B (manufactured by NOF CORPORATION) was uniformly mixed, the mixture was fed to a screw extruder to carry out a malein reaction to obtain a modified block copolymer shown in Table 1. (2) Production of polypropylene-based resin powders Polypropylene and modified block copolymers shown in Table 2 and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxy) are prepared based on these resin components. (Phenyl) propionate] 1000 ppm and tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene phosphonite 2000 ppm were mixed to obtain 3
Using a 0 mmφ twin-screw extruder, the mixture was kneaded at 220 ° C. to obtain pellets. The pellets are cooled to -20 ° C or lower with liquid nitrogen, pulverized by mechanical pulverization, and the product that has passed through a sieve having an opening of 250 µ is taken out to obtain an average particle diameter of 200 µ.
To obtain a polypropylene powder. This powder was pressed into a flat plate of 2 mm, and the tensile elongation was measured. The surface hardness was also measured. The results are shown in Table 2. (3) Coating of polypropylene resin powder The powder was coated on a rolled steel plate having a thickness of 0.6 mm by the fluidized-bed method to form a coating film of 380μ. The results of measuring the physical properties of the coating film are shown in Table 2.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【比較例３】変性ブロック共重合体として実施例１のＢ
１でブタジエン部のビニル含有量が３５％の物を使用す
る以外は実施例１と同様な条件でプロピレン粉末を製造
した。これの引張伸びは３４％、表面硬度はショア−Ｄ
７１であった。また、塗膜の性能は密着強度６５／１０
０、衝撃強度△、防触度試験×であった。Comparative Example 3 B of Example 1 as a modified block copolymer
A propylene powder was produced under the same conditions as in Example 1 except that the vinyl content of the butadiene portion in Example 1 was 35%. It has a tensile elongation of 34% and a surface hardness of Shore-D.
It was 71. In addition, the performance of the coating film has an adhesion strength of 65/10.
0, impact strength Δ, and anti-corrosion test ×.
【００２１】[0021]
【比較例４】変性ブロック共重合体として実施例１のＢ
１で無水マレイン酸を付加していない物を使用する以外
は実施例１と同様な条件でプロピレン粉末を製造した。
これの引張伸びは２４０％、表面硬度はショア−Ｄ７１
であった。また、塗膜の性能は密着強度０／１００、衝
撃強度○、防触度試験×であった。Comparative Example 4 B of Example 1 as a modified block copolymer
A propylene powder was produced under the same conditions as in Example 1 except that the product obtained in 1 was not added with maleic anhydride.
It has a tensile elongation of 240% and a surface hardness of Shore-D71.
Met. The performance of the coating film was as follows: the adhesion strength was 0/100, the impact strength was ○, and the anti-corrosion test was ×.
【００２２】[0022]
【発明の効果】本発明のポリプロピレン系樹脂粉体によ
る金属製品の塗膜はポリエチレン塗膜に比べ、表面が傷
付き難く、使用可能温度が高い等の優れた特性を有し、
その上、従来のポリプロピレン樹脂粉体を用いて塗装し
た塗膜より耐久性を大幅に改善したものである。EFFECTS OF THE INVENTION The coating film for metal products made of the polypropylene resin powder of the present invention has excellent characteristics such as less scratches on the surface and higher usable temperature than the polyethylene coating film,
In addition, the durability is greatly improved over the coating film coated with the conventional polypropylene resin powder.
Claims (1)
レン系重合体、９０〜４０重量％と（Ｂ）ビニル芳香族
炭化水素の含有量が６０重量％を越え、９０重量％以下
であり、少なくとも１個のビニル芳香族炭化水素重合体
ブロックＸと少なくとも１個のオレフィン化合物重合体
ブロックＹとを有し、しかもブロックＹの不飽和度が２
０％を越えないオレフィン化合物重合体ブロックである
ブロック共重合体にカルボン酸基またはその誘導体を
０．０５〜２０重量％結合させ変性した変性ブロック共
重合体、１０〜６０重量％よりなる混合物からなること
を特徴とするポリプロピレン系樹脂粉体。1. A polypropylene polymer having (A) MFR of 5 to 200, 90 to 40% by weight and (B) vinyl aromatic hydrocarbon content of more than 60% by weight and 90% by weight or less, It has at least one vinyl aromatic hydrocarbon polymer block X and at least one olefin compound polymer block Y, and the degree of unsaturation of the block Y is 2
A modified block copolymer obtained by binding 0.05 to 20% by weight of a carboxylic acid group or a derivative thereof to a block copolymer, which is an olefin compound polymer block not exceeding 0%, and is composed of 10 to 60% by weight. A polypropylene resin powder characterized in that
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30521492A JP3340480B2 (en) | 1992-11-16 | 1992-11-16 | Polypropylene resin powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30521492A JP3340480B2 (en) | 1992-11-16 | 1992-11-16 | Polypropylene resin powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06157842A true JPH06157842A (en) | 1994-06-07 |
| JP3340480B2 JP3340480B2 (en) | 2002-11-05 |
Family
ID=17942425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30521492A Expired - Fee Related JP3340480B2 (en) | 1992-11-16 | 1992-11-16 | Polypropylene resin powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3340480B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4898462A (en) * | 1987-02-26 | 1990-02-06 | Nippondenso Co., Ltd. | Device for detecting a transmissivity of a substance |
| EP1215238A1 (en) * | 2000-12-12 | 2002-06-19 | Sumitomo Wiring Systems, Ltd. | Fire resistant resin composition and electrical wire having a covering formed of the composition |
| US6646205B2 (en) | 2000-12-12 | 2003-11-11 | Sumitomo Wiring Systems, Ltd. | Electrical wire having a resin composition covering |
-
1992
- 1992-11-16 JP JP30521492A patent/JP3340480B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4898462A (en) * | 1987-02-26 | 1990-02-06 | Nippondenso Co., Ltd. | Device for detecting a transmissivity of a substance |
| EP1215238A1 (en) * | 2000-12-12 | 2002-06-19 | Sumitomo Wiring Systems, Ltd. | Fire resistant resin composition and electrical wire having a covering formed of the composition |
| US6646205B2 (en) | 2000-12-12 | 2003-11-11 | Sumitomo Wiring Systems, Ltd. | Electrical wire having a resin composition covering |
| US6756440B2 (en) | 2000-12-12 | 2004-06-29 | Sumitomo Wiring Systems, Ltd. | Fire resistant resin composition and electrical wire having fire resistant covering |
| US6809140B2 (en) | 2000-12-12 | 2004-10-26 | Sumitomo Wiring Systems, Ltd. | Fire resistant resin composition and electrical wire having fire resistant covering |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3340480B2 (en) | 2002-11-05 |
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