JPS648663B2

JPS648663B2 -

Info

Publication number: JPS648663B2
Application number: JP18486481A
Authority: JP
Inventors: Toshiki Doi; Isao Matsura; Hiroshi Kondo
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 1981-11-17
Filing date: 1981-11-17
Publication date: 1989-02-14
Also published as: JPS58149936A

Description

[Detailed description of the invention]

本発明は塩化ビニル系樹脂に可塑剤をドライブ
レンドしてなる粉末組成物において塩化ビニル系
樹脂にパーフルオロアルキル基含有重合体を配合
して得られる粉体流動性および特に成形時の塗膜
均一性、離型性に優れた粉末成形用塩化ビニル系
樹脂組成物に関するものである。塩化ビニル樹脂の成形法の一つとして流動浸漬
法、静電塗装法、粉末コーテイング法、粉末回型
成形法、スラツシユ成形法などの粉末成形法があ
り、これらは粉体組成物を常温または加熱された
成形用金型面または基材面へ付着せしめ、加熱溶
融し樹脂皮膜を形成させる方法である。この粉末成形法に使用する粉末塩化ビニル系樹
脂組成物は粉体流動性および、成形時に金型面ま
たは基材面への塗膜均一性に優れたものでなけれ
ばならない。塗膜均一性とは金型または基材面に成形された
皮膜が欠肉やピンホールがなく膜厚の均一な成形
品を与える性質である。また。回転成形やスラツシユ成形などによる製
品皮膜は脱型する必要があるが、この場合金型面
からの離型性の良いことが望まれる。塩化ビニル系樹脂と可塑剤、安定剤、顔料など
を加熱用ジヤケツトの付いたブレンダーや高速回
転型ミキサー等を使つてドライブレンドして粉末
組成物をつくることはよく知られている。しかし、ドライブレンドさせるに当つて、多量
の可塑剤を配合した場合には得られる組成物は粘
着性があり、粉体流動性は低下し更には粉末同志
が凝集するという欠点が生ずるため、粉末成形時
の流動性および溶融性も十分でなく、満足した成
形品を得ることは困難である。この欠点を避けるため、可塑剤をドライブレン
ドし、冷却した後にさらに少量の微粒の塩化ビニ
ル樹脂を添加する方法や微粒の炭酸カルシウムな
どの無機充填剤を添加する方法が知られている。（ラバーダイジエストVol.14 No.８第32―40
頁およびポリ塩化ビニル―その化学と工業―
第367〜370頁 1968年）これらの方法は確かに粉体流動性の向上には有
効であるが、微粉の塩化ビニル樹脂、例えば乳化
重合塩化ビニル樹脂を添加しても可塑剤の多い場
合は粉体流動性は十分でなく、特に加熱成形時の
流動性が劣るため大型製品の成形では欠肉、ピン
ホールを生じ、塗膜均一性に欠ける。また、微粒の炭酸カルシウムなどの無機充填剤
の添加は粉体流動性が十分でなく、また溶融樹脂
の流れを抑制して、塗膜にピンホールを起させる
原因となるし、柔軟性、強度の低下をもたらし好
ましくない。一方、回転成形やスラツシユ成形により複雑な
形状の製品皮膜を形成する場合は金型面からの製
品の離型を容易にするため、事前に金型面に離型
剤を塗布するが、均一塗布は難しく、時間を要す
るし、得られた皮膜の表面に離型剤が残るため外
観、風合いが変わつてくる、離型剤自体が一般に
高価であるなどの問題点がある。また、粉末組成物に離型剤を内添する方法もあ
るが金型面塗布に比し効果が小さいため比較的多
量の添加を必要とし、経済的でないブリードが大
きいなどの問題がある。かかる現状に鑑み、本発明者は公知の粉末成形
加工に対し、粉体流動性および特に成形時の塗膜
均一性、離型性に優れた粉末組成物について鋭意
研究した結果、本発明に到達した。すなわち本発明は塩化ビニル系樹脂に可塑剤を
ドライブレンドしてなる粉末組成物において塩化
ビニル系樹脂にパーフルオロアルキル基を含有す
る重合体を配合して得られる粉末成形に適した組
成物を提供するものであり、本発明によれば粉体
流動性および特に成形時の塗膜均一性、離型性に
優れた大型で複雑形状の製品皮膜の製造にも適し
た粉末塩化ビニル系樹脂組成物が得られる。本発明に使用されるパーフルオロアルキル基を
含有する重合体はパーフルオロアルキル基含有ア
クリル酸またはメタクリル酸エステルの単独重合
体あるいは該パーフルオロアルキル基含有アクリ
ル酸またはメタクリル酸エステルとそれらのアク
リル酸またはメタクリル酸エステルと共重合可能
なビニル化合物との共重合体であり、これらの重
合体または共重合体の一種または二種以上を含む
混合物である。パーフルオロアルキル基を含有する重合体を製
造するための単量体を例示すれば、式：〔式中、Rfは炭素数３〜21のパーフルオロア
ルキル基、R₁は水素または炭素数１〜10のアル
キル基、R₂は炭素数１〜10のアルキレン基、R₃
は水素またはメチル基、ｎは１〜10の整数を表わ
す。〕などが挙げられる。またこれらと共重合可能なビニル単量体として
は The present invention focuses on powder fluidity obtained by blending a perfluoroalkyl group-containing polymer with a vinyl chloride resin in a powder composition formed by dry blending a plasticizer with a vinyl chloride resin, and in particular, coating film uniformity during molding. The present invention relates to a vinyl chloride resin composition for powder molding that has excellent properties and mold releasability. There are powder molding methods such as fluidized dipping method, electrostatic coating method, powder coating method, powder round molding method, and slush molding method as one of the molding methods for vinyl chloride resin. In this method, a resin film is formed by attaching the resin to the mold surface or base material surface and heating and melting the resin film. The powdered vinyl chloride resin composition used in this powder molding method must have excellent powder fluidity and uniformity of coating on the mold surface or substrate surface during molding. Coating film uniformity is a property of a film formed on a mold or base material surface to provide a molded product with a uniform film thickness without missing parts or pinholes. Also. Product coatings produced by rotational molding, slush molding, etc. must be removed from the mold, and in this case, it is desirable that the product has good releasability from the mold surface. It is well known that a powder composition is prepared by dry blending a vinyl chloride resin, a plasticizer, a stabilizer, a pigment, etc. using a blender equipped with a heating jacket or a high-speed rotating mixer. However, if a large amount of plasticizer is added during dry blending, the resulting composition will be sticky, the powder fluidity will be reduced, and the powders will coagulate together. The fluidity and meltability during molding are also insufficient, making it difficult to obtain a satisfactory molded product. In order to avoid this drawback, methods are known in which a plasticizer is dry blended, and after cooling, a small amount of finely divided vinyl chloride resin is further added, or a finely divided inorganic filler such as calcium carbonate is added. (Rubber Digest Vol.14 No.8 32-40
Pages and polyvinyl chloride - its chemistry and industry -
(pp. 367-370, 1968) These methods are certainly effective in improving powder fluidity, but even if finely powdered vinyl chloride resin, such as emulsion polymerized vinyl chloride resin, is added, if there is a large amount of plasticizer, Powder fluidity is not sufficient, especially during hot molding, which results in underfilling and pinholes when molding large products, and lacks coating uniformity. In addition, the addition of inorganic fillers such as fine particles of calcium carbonate does not provide sufficient powder fluidity, and also inhibits the flow of molten resin, causing pinholes in the coating film, as well as improving flexibility and strength. This is undesirable because it causes a decrease in On the other hand, when forming a product film with a complex shape through rotational molding or slush molding, a release agent is applied to the mold surface in advance to make it easier to release the product from the mold surface, but it is applied evenly. It is difficult and time-consuming, and there are problems such as the mold release agent remains on the surface of the resulting film, which changes the appearance and texture, and the mold release agent itself is generally expensive. There is also a method of internally adding a mold release agent to the powder composition, but this method is less effective than applying it to the mold surface and requires a relatively large amount of addition, which poses problems such as uneconomical bleed. In view of the current situation, the present inventor has conducted extensive research on powder compositions that have excellent powder fluidity, particularly coating film uniformity during molding, and mold releasability for known powder molding processes, and as a result, has arrived at the present invention. did. That is, the present invention provides a powder composition suitable for powder molding obtained by blending a polymer containing a perfluoroalkyl group with a vinyl chloride resin in a powder composition formed by dry blending a plasticizer with a vinyl chloride resin. According to the present invention, there is provided a powdered vinyl chloride resin composition that is suitable for manufacturing large and complex-shaped product films that have excellent powder flowability, particularly coating film uniformity during molding, and mold release properties. is obtained. The perfluoroalkyl group-containing polymer used in the present invention is a homopolymer of perfluoroalkyl group-containing acrylic acid or methacrylate ester, or a perfluoroalkyl group-containing acrylic acid or methacrylate ester and their acrylic acid or It is a copolymer of a methacrylic acid ester and a copolymerizable vinyl compound, and is a mixture containing one or more of these polymers or copolymers. Examples of monomers for producing a polymer containing a perfluoroalkyl group include the formula: [In the formula, Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms, R ₃
represents hydrogen or a methyl group, and n represents an integer of 1 to 10. ] etc. In addition, vinyl monomers that can be copolymerized with these include

【式】CH₂＝CHO₂CR²、CH₂ ＝CHR³、CH₂＝CY₂、CH₂＝CHCH₂O₂CR²、
[Formula] CH ₂ = CHO ₂ CR ² , CH ₂ = CHR ³ , CH ₂ = CY ₂ , CH ₂ = CHCH ₂ O ₂ CR ² ,

【式】CH₂＝CHY、[Formula] CH ₂ = CHY,

【式】CH₂＝CR′― CONHCH₂OH、１，３―ブタジエン、２―クロ
ロブタジエン、２，３―ジクロロ―１，３―ブタ
ジエンあるいはイソプレン（R′はＨあるいはメチル、R²は１〜18個の炭
素を含有している飽和アルキル基、R³はフエニ
ルあるいはアルキル置換フエニル、R⁴は水素あ
るいは１〜６個の炭素の飽和アルキル基そしてＹ
弗素、塩素あるいは臭素である。）が挙げられる。これらのパーフルオロアルキル基含有重合体は
溶液または水分散体の形で配合するのが好まし
い。配合量は塩化ビニル樹脂100重量部に対し0.01
〜５重量部の範囲が好ましく、0.01重量部以下で
は効果なく、５重量部以上ではブリードが大き
く、粉末流動性も低下する。さらに好ましは0.05
〜２重量部の範囲である。本発明に使用されるパーフルオロアルキル基含
有重合体の配合は通常のドライブレンドにおける
初期でも、途中の段階でも、ドライブレンド終了
後冷却時でもよい。また予めポリ塩化ビニル樹脂
の重合時または重合終了後添加されたものを使用
することもできる。本発明に使われる塩化ビニル系樹脂とは、懸濁
重合法、塊状重合法および乳化重合法でつくられ
る塩化ビニル重合体および塩化ビニルと共重合し
得るエチレン、プロピレン、ビニルアセテートな
どとの共重合あるいはエチレンとビニルアセテー
トとの共重合体（EVA）とのグラフト共重合体
およびこれらの重合体、共重合体およびグラフト
共重合体の二種以上の混合物なども使用される
が、特に限定するものではない。本発明に使われる可塑剤は特に限定するもので
はなく、ジブチルフタレート、ジオクチルフタレ
ート、ジイソデシルフタレート、ジイソウンデカ
フタレートなどのフタール酸エステル、トリオク
チルトリメリテート、トリドデシルトリメリテー
トなどのトリメツト酸エステル、ジオクチルアジ
ペート、ジイソデシルアジペートなどのアジピン
酸エステル、トリクレジルホスフエート、トリオ
クチルホスフエートなどのリン酸エステル、エポ
キシ系可塑剤、液状ポリエステル系可塑剤などの
うち一種または二種以上の混合物を使うことがで
きる。本発明において配合に使用する安定剤として
は、通常公知のもので、例えばステアリン酸亜
鉛、カルシウム、バリウム、カドミウムなどの金
属石けん系安定剤、三塩基性硫酸鉛、二塩基性亜
リン酸鉛などの鉛系安定剤、錫ラウレート、錫マ
レエート、メルカプト錫系の如き錫系安定剤があ
げられる。この他必要に応じて充填剤、顔料などが配合さ
れる。本発明により、粉末成形用の流動特性および成
形時の塗膜均一性、離型性の優れた塩化ビニル系
樹脂組成物が得られ、その工業上の利用価値は大
である。具体的説明するため実施例を示すが、本発明は
これに限定されるものではない。実施例１内容積20のスーパーミキサーに通常の懸濁重
合法で得られる平均重合度1050のストレート塩化
ビニル樹脂（住友化学工業(株)製、スミリツト
SX―11F）を２Kg仕込み、一定回転速度で撹拌
しながら加温し、少量の安定剤、顔料などを含む
可塑剤（ジイソデシルフタレート）を1.4Kg加え
て120℃まで加温してドライブレンドを行なつた。
次いでパーフルオロアルキル基含有重合体の水性
分散体（固形分濃度18％住友化学工業(株)製、ス
ミフルオイル EM―11）を20ｇ添加して均一
に分散させたところ、粉体流動性の比較的優れた
粉末塩化ビニル樹脂組成物が得られた。続いて、自動車のインストルメントパネル表皮
用金型を用い270℃雰囲気で予備加熱を行い、金
型温度を150℃にした後、炉外から取出し、次い
で速やかに粉末組成物800ｇを投入し、再度加熱
炉（炉温270℃雰囲気中）で回転させながら15分
成形を行なつたところ、良好な塗膜均一性を持つ
た皮膜が得られ金型からの離型性も良好であつ
た。実施例２および比較例１および２実施例１と同様の方法でストレート塩化ビニル
樹脂1.8Kgを仕込み少量の安定剤、顔料などを含
む可塑剤を1.4Kg加えてドライブレンドを行ない
パーフルオロアルキル基含有重合体の水性分散体
（固型分濃度18％、住友化学工業(株)製、スミフル
オイル EM―11）を添加して均一に分散した
後冷却した。次いで乳化重合法で得られたペースト用樹脂
（住友化学工業(株)製、スミリツト PXNo平均
重合度1350）を0.2Kg添加し均一に分散させた。得られた粉末組成物は粉体流動性の非常に優れ
たものであつた。実施例１同様、回転成形を行なつたところ、塗
膜均一性の非常に良好な金型からの離型性も良い
成形皮膜を得た。表１に粉体物性および成形性の結果を示す。比較として、実施例１および実施例２と同様の
方法でブレンドを行つたがパーフルオロアルキル
基含有重合体を配合しない場合の結果を表１に併
記した。パーフルオロアルキル基含有重合体を添加した
ものは、粉体流動性が向上し、成形品の塗膜均一
性が良好である。更には金型からの成形品の離型性にも優れてお
り、製品面への液状成分のブリード現象もない。[Formula] CH ₂ = CR'- CONHCH ₂ OH, 1,3-butadiene, 2-chlorobutadiene, 2,3-dichloro-1,3-butadiene or isoprene (R' is H or methyl, R ² is 1- a saturated alkyl group containing 18 carbons, R ³ is phenyl or alkyl-substituted phenyl, R ⁴ is hydrogen or a saturated alkyl group of 1 to 6 carbons, and Y
Fluorine, chlorine or bromine. ). These perfluoroalkyl group-containing polymers are preferably blended in the form of a solution or an aqueous dispersion. The blending amount is 0.01 per 100 parts by weight of vinyl chloride resin.
The range of 5 parts by weight is preferable; if it is less than 0.01 parts by weight, there will be no effect, and if it is more than 5 parts by weight, bleeding will be large and the powder fluidity will also be reduced. More preferably 0.05
-2 parts by weight. The perfluoroalkyl group-containing polymer used in the present invention may be blended at the initial stage of normal dry blending, at an intermediate stage, or during cooling after completion of dry blending. Further, it is also possible to use one added in advance during or after the polymerization of the polyvinyl chloride resin. The vinyl chloride resin used in the present invention refers to vinyl chloride polymers produced by suspension polymerization, bulk polymerization, and emulsion polymerization, and copolymers with ethylene, propylene, vinyl acetate, etc. that can be copolymerized with vinyl chloride. Alternatively, graft copolymers of ethylene and vinyl acetate copolymers (EVA) and mixtures of two or more of these polymers, copolymers, and graft copolymers may also be used, but there are no particular limitations. isn't it. The plasticizer used in the present invention is not particularly limited, and includes phthalate esters such as dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, and diisoundecaphthalate, and trimethate esters such as trioctyl trimellitate and tridodecyl trimellitate. , adipic acid esters such as dioctyl adipate and diisodecyl adipate, phosphoric acid esters such as tricresyl phosphate and trioctyl phosphate, epoxy plasticizers, liquid polyester plasticizers, etc., or a mixture of two or more of them is used. be able to. The stabilizers used in the formulation in the present invention include commonly known stabilizers, such as metal soap stabilizers such as zinc stearate, calcium, barium, and cadmium, tribasic lead sulfate, dibasic lead phosphite, etc. Examples include lead-based stabilizers, tin-based stabilizers such as tin laurate, tin maleate, and mercaptotin-based stabilizers. In addition, fillers, pigments, etc. may be added as necessary. According to the present invention, a vinyl chloride resin composition with excellent flow characteristics for powder molding, coating film uniformity during molding, and mold releasability can be obtained, and its industrial utility value is great. Examples are shown for concrete explanation, but the present invention is not limited thereto. Example 1 Straight vinyl chloride resin (manufactured by Sumitomo Chemical Co., Ltd., Sumiritz) with an average degree of polymerization of 1050 obtained by a normal suspension polymerization method in a super mixer with an internal volume of 20
Add 2kg of SX-11F), heat it while stirring at a constant rotation speed, add 1.4kg of a plasticizer (diisodecyl phthalate) containing a small amount of stabilizer and pigment, and heat it to 120℃ to perform dry blending. Summer.
Next, 20 g of an aqueous dispersion of a perfluoroalkyl group-containing polymer (Sumiflu Oil EM-11, manufactured by Sumitomo Chemical Co., Ltd., solid content concentration 18%) was added and uniformly dispersed. A relatively excellent powdered vinyl chloride resin composition was obtained. Next, a mold for automobile instrument panel skin was preheated in an atmosphere of 270°C, and after the mold temperature reached 150°C, it was taken out of the furnace, and then 800g of the powder composition was immediately added and heated again. When molding was carried out for 15 minutes while rotating in a heating furnace (furnace temperature 270°C in an atmosphere), a film with good coating uniformity was obtained, and the mold releasability from the mold was also good. Example 2 and Comparative Examples 1 and 2 1.8 kg of straight vinyl chloride resin was prepared in the same manner as in Example 1, 1.4 kg of a plasticizer containing a small amount of stabilizer and pigment was added, and dry blending was performed to obtain a perfluoroalkyl group-containing product. An aqueous polymer dispersion (solid content concentration 18%, manufactured by Sumitomo Chemical Co., Ltd., Sumiflu Oil EM-11) was added and uniformly dispersed, and then cooled. Next, 0.2 kg of a paste resin (manufactured by Sumitomo Chemical Co., Ltd., Sumiritz PXNo average degree of polymerization 1350) obtained by emulsion polymerization was added and uniformly dispersed. The obtained powder composition had excellent powder flowability. As in Example 1, rotational molding was performed to obtain a molded film with very good coating uniformity and good releasability from the mold. Table 1 shows the results of powder physical properties and moldability. For comparison, Table 1 also shows the results obtained when blending was carried out in the same manner as in Examples 1 and 2, but without blending the perfluoroalkyl group-containing polymer. Those to which a perfluoroalkyl group-containing polymer is added have improved powder flowability and good coating film uniformity on molded products. Furthermore, the molded product has excellent mold releasability from the mold, and there is no bleeding phenomenon of liquid components onto the product surface.

【table】

Claims

[Claims]

1 In a powder composition formed by dry blending a plasticizer with a vinyl chloride resin, the vinyl chloride resin
Per 100 parts by weight, a homopolymer of perfluoroalkyl group-containing acrylic acid or methacrylate ester, or a vinyl copolymerizable with the perfluoroalkyl group-containing acrylic acid or methacrylate ester and these acrylic acid or methacrylate esters. A vinyl chloride resin composition for powder molding which is characterized by containing 0.01 to 5 parts by weight of a copolymer with a compound and which is excellent in powder flowability, coating film uniformity during powder molding, and mold releasability.