JPH08127691A - Poly(vinyl chloride) plastisol composition - Google Patents
Poly(vinyl chloride) plastisol compositionInfo
- Publication number
- JPH08127691A JPH08127691A JP26572594A JP26572594A JPH08127691A JP H08127691 A JPH08127691 A JP H08127691A JP 26572594 A JP26572594 A JP 26572594A JP 26572594 A JP26572594 A JP 26572594A JP H08127691 A JPH08127691 A JP H08127691A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- pts
- weight
- parts
- control agent
- 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.)
- Pending
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- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、自動車のロッカ部など
に塗布され飛石などによる塗膜の剥離や傷付きを防止す
る耐チッピング塗料や、鋼板接続部に用いられるシーリ
ング材として有用なポリ塩化ビニルプラスチゾル組成物
(以下、PVCゾル組成物という)に関する。FIELD OF THE INVENTION The present invention relates to a chipping-resistant paint applied to the rocker part of an automobile or the like to prevent the paint film from peeling off or being scratched, and a polychlorinated compound useful as a sealing material used in a steel plate connecting part. It relates to a vinyl plastisol composition (hereinafter referred to as a PVC sol composition).
【0002】[0002]
【従来の技術】自動車のロッカパネルやフロントバラン
スパネルあるいはドア下部などは、走行時に跳ね上げた
小石などが衝突しやすいため、耐チッピング性に優れた
塗料を塗装することが行われている。この耐チッピング
塗料としては、防錆性能に優れている、厚い塗膜を形成
できる、安価である、などの理由により、例えば特開平
5−43761号公報に開示されているようなPVCゾ
ル組成物が一般に用いられている。2. Description of the Related Art A rocker panel, a front balance panel or a lower portion of a door of an automobile is often coated with a paint having excellent chipping resistance because pebbles and the like that are flipped up during traveling easily collide with each other. This chipping-resistant paint is, for example, a PVC sol composition as disclosed in JP-A-5-43761 because of its excellent anticorrosion performance, ability to form a thick coating film, and low cost. Is commonly used.
【0003】このPVCゾル組成物を用いた耐チッピン
グ塗膜を形成するには、先ず鋼板表面に下塗りとしてP
VCゾル組成物が塗布され、その表面に中塗り及び上塗
り塗膜が形成される。そしてPVCゾル組成物から形成
された厚肉のPVCゾル塗膜が小石の衝突による衝撃を
緩和・吸収することで、上層の塗膜の剥離が防止され
る。In order to form a chipping-resistant coating film using this PVC sol composition, first, P is used as an undercoat on the surface of a steel sheet.
The VC sol composition is applied, and an intermediate coat and a top coat are formed on the surface thereof. Then, the thick PVC sol coating film formed from the PVC sol composition absorbs and absorbs the impact due to the collision of pebbles, so that the upper layer coating film is prevented from peeling off.
【0004】また鋼板の接合部や継ぎ目部は、通常の塗
料では被覆がなかなか困難であり、しかも境界部に水や
塵が侵入しやすく錆が発生しやすいという問題がある。
そこで、このような部分にもPVCゾル組成物からなる
シーリング材が塗布・充填され、その表面にさらに中塗
り塗膜及び上塗り塗膜が形成されている。このPVCゾ
ル組成物は、塩化ビニルの単独重合体又は塩化ビニルと
酢酸ビニル等との共重合体からなる塩化ビニル系樹脂
と、DOPなどの可塑剤を基材とし、他にポリアミドな
どの接着付与剤、炭酸カルシウムなどの充填材及び金属
石けんなどの安定剤が含まれて構成されている。また垂
れ止め性能を付与するために、脂肪酸で表面処理された
炭酸カルシウムや、超微粒子シリカ粉末などのレオロジ
ー制御剤が一般に用いられている。Further, there is a problem that it is difficult to cover the joints and joints of the steel plates with a normal paint, and moreover, water and dust easily enter the boundary and rust easily occurs.
Therefore, a sealing material made of a PVC sol composition is applied and filled in such a portion, and an intermediate coating film and a top coating film are further formed on the surface thereof. This PVC sol composition is based on a vinyl chloride resin composed of a homopolymer of vinyl chloride or a copolymer of vinyl chloride and vinyl acetate, and a plasticizer such as DOP as a base material, and also imparts adhesion such as polyamide. The agent, the filler such as calcium carbonate, and the stabilizer such as metallic soap are included. Further, in order to impart anti-sagging performance, a rheology control agent such as calcium carbonate surface-treated with fatty acid or ultrafine silica powder is generally used.
【0005】[0005]
【発明が解決しようとする課題】ところが、従来のPV
Cゾル塗膜表面に中塗り塗膜と上塗り塗膜を形成した塗
膜構成においては、中塗り塗膜と上塗り塗膜との間で層
間付着不良が発生する場合があった。そして鋭意研究し
た結果、この付着不良の原因はレオロジー制御剤として
の表面処理炭酸カルシウムに起因することが明らかとな
り、この表面処理炭酸カルシウムがPVCゾル塗膜から
移行して中塗り塗膜表面に表出することにより、上塗り
塗膜の付着不良が生じると推察された。However, the conventional PV
In the coating film structure in which the intermediate coating film and the top coating film were formed on the surface of the C sol coating film, there were cases where defective interlayer adhesion occurred between the intermediate coating film and the top coating film. As a result of diligent research, it was clarified that the cause of this adhesion failure was caused by the surface-treated calcium carbonate as a rheology control agent, and this surface-treated calcium carbonate migrated from the PVC sol coating film to the surface of the intermediate coating film. It was speculated that this would cause poor adhesion of the top coating film.
【0006】そこで本発明者らは、表面処理炭酸カルシ
ウムの添加量を低減させることを試みたが、PVCゾル
塗膜の垂れ限界膜厚が低下して厚膜化が困難となり、耐
チッピング性が低下するという問題が生じた。また表面
処理炭酸カルシウムの表面処理量を低減したり、表面処
理剤を脂肪酸系からロジン系やアルコール系に変更する
ことも試みたが、PVCゾル組成物中での分散性が低下
して粘度とレオロジー変化のばらつきが大きくなった
り、耐水性が低下するという不具合が現れた。Therefore, the present inventors tried to reduce the addition amount of the surface-treated calcium carbonate, but the sag limit film thickness of the PVC sol coating film was reduced and it became difficult to make the film thicker, and the chipping resistance was improved. There was a problem of decrease. Attempts have also been made to reduce the surface treatment amount of the surface-treated calcium carbonate and to change the surface treatment agent from a fatty acid type to a rosin type or an alcohol type, but the dispersibility in the PVC sol composition decreases and the viscosity Problems such as large variations in rheological changes and reduced water resistance have appeared.
【0007】さらにレオロジー制御剤を超微粒子シリカ
粉末などに変更することを試みたが、粘度安定性や接着
性が低下し、かつコストも高いという不具合がある。本
発明はこのような事情に鑑みてなされたものであり、表
面処理炭酸カルシウムを用いずに従来と同等のレオロジ
ー特性をもち、諸物性の低下なく層間付着性に優れたP
VCゾル組成物とすることを目的とする。Attempts have been made to change the rheology control agent to ultrafine silica powder, etc., but there are problems that the viscosity stability and adhesiveness are lowered and the cost is high. The present invention has been made in view of the above circumstances, and has the same rheological properties as conventional ones without using surface-treated calcium carbonate, and is excellent in interlayer adhesion without deterioration in various physical properties.
The purpose is to provide a VC sol composition.
【0008】[0008]
【課題を解決するための手段】上記課題を解決するため
に鋭意研究を重ねた結果、本発明者は特定のレオロジー
制御剤と特定の安定剤とを組み合わせて初めて所望の効
果が得られることを発見し、上記の課題が解決されるこ
とを見出した。すなわち本発明のPVCゾル組成物は、
塩化ビニル系樹脂と可塑剤とを主成分とし、尿素−ウレ
タン系液状レオロジー制御剤と有機亜鉛系安定剤とを含
むことを特徴とする。As a result of intensive studies to solve the above problems, the present inventors have found that the desired effect can be obtained only by combining a specific rheology control agent and a specific stabilizer. It discovered and found out that the above-mentioned subject was solved. That is, the PVC sol composition of the present invention is
It is characterized in that it contains a vinyl chloride resin and a plasticizer as main components, and contains a urea-urethane liquid rheology control agent and an organozinc stabilizer.
【0009】塩化ビニル系樹脂としては、塩化ビニルの
単独重合体、塩化ビニルと酢酸ビニル等他のビニル系単
量体との共重合体のいずれも用いることができるが、単
独重合体と共重合体とを混合して用いるのが好ましい。
単独重合体のみでは密着性などの塗膜物性が十分でない
場合があり、共重合体のみでは焼付硬化時の粘度低下が
不十分で外観品質が十分でないからである。As the vinyl chloride resin, either a vinyl chloride homopolymer or a copolymer of vinyl chloride and another vinyl monomer such as vinyl acetate can be used. It is preferable to use a mixture with the combination.
This is because the homopolymer alone may not have sufficient adhesiveness and other coating properties, and the copolymer alone may not sufficiently reduce the viscosity during bake-curing, resulting in insufficient appearance quality.
【0010】上記単独重合体と共重合体との混合比率
は、塩化ビニル系樹脂全体100重量部中に単独重合体
が30〜90重量部、共重合体が10〜70重量部の範
囲が好ましく、単独重合体が50重量部以上で共重合体
が20重量部以上の範囲が特に望ましい。上記共重合体
を構成する塩化ビニル以外の単量体としては、酢酸ビニ
ルが最も一般的でしかも好ましい単量体であるが、他に
プロピオン酸ビニル、ステアリン酸ビニル等のビニルエ
ステル類、ビニルメチルエーテル、ビニルイソブチルエ
ーテル等のビニルエーテル類、ジエチルマレエート等の
マレイン酸エステル類、ジブチルフマレート等のフマル
酸エステル類、メチルアクリレート、2−ヒドロキシエ
チルアクリレート、2−エチルヘキシルアクリレート等
のアクリル酸エステル類、メチルメタクリレート、2−
ヒドロキシエチルメタクリレート等のメタクリル酸エス
テル類、アクリロニトリル、塩化ビニリデン等が挙げら
れ、これらの1種又は2種以上を用いることができる。
これらの単量体は、一般に30重量%以下、好ましくは
20重量%以下の割合で塩化ビニルと共重合することが
できる。The mixing ratio of the above homopolymer and copolymer is preferably in the range of 30 to 90 parts by weight of the homopolymer and 10 to 70 parts by weight of the copolymer in 100 parts by weight of the entire vinyl chloride resin. The range of 50 parts by weight or more of the homopolymer and 20 parts by weight or more of the copolymer is particularly desirable. As a monomer other than vinyl chloride that constitutes the above-mentioned copolymer, vinyl acetate is the most common and preferable monomer, but other vinyl esters such as vinyl propionate and vinyl stearate, vinyl methyl, etc. Ethers, vinyl ethers such as vinyl isobutyl ether, maleates such as diethyl maleate, fumarates such as dibutyl fumarate, acrylic esters such as methyl acrylate, 2-hydroxyethyl acrylate and 2-ethylhexyl acrylate, Methyl methacrylate, 2-
Methacrylic acid esters such as hydroxyethyl methacrylate, acrylonitrile, vinylidene chloride and the like can be mentioned, and one or more of these can be used.
These monomers can be copolymerized with vinyl chloride in a proportion of generally 30% by weight or less, preferably 20% by weight or less.
【0011】塩化ビニル系樹脂とともにPVCゾル組成
物の主体をなす可塑剤としては、代表的なフタル酸ジオ
クチル(DOP)を始めとして、フタル酸ジ−2−エチ
ルヘキシル、フタル酸ジイソノニル(DINP)等のフ
タル酸エステル、セバシン酸エステル、アゼライン酸エ
ステル等のジ及びトリカルボン酸エステル、リン酸トリ
フェニル、リン酸トリクレシル等のリン酸エステル、エ
ポキシ化大豆油等のエポキシ系可塑剤等が例示される。As a plasticizer which mainly constitutes a PVC sol composition together with a vinyl chloride resin, typical examples include dioctyl phthalate (DOP), di-2-ethylhexyl phthalate, diisononyl phthalate (DINP) and the like. Examples thereof include di- and tricarboxylic acid esters such as phthalic acid ester, sebacic acid ester, and azelaic acid ester, phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, and epoxy plasticizers such as epoxidized soybean oil.
【0012】これらの可塑剤は、目的とするPVCゾル
組成物の粘度、硬化性などの物性に応じて適宜選択して
用いることができ、一般には塩化ビニル系樹脂100重
量部に対して30〜300重量部の範囲が適当である。
なお、可塑剤はその一部を減粘剤としての有機溶剤に代
えることができる。この場合有機溶剤としては、可塑剤
と同程度の高沸点の有機溶剤を用いるのが好ましい。These plasticizers can be appropriately selected and used according to the physical properties such as the viscosity and curability of the intended PVC sol composition, and generally they are 30 to 100 parts by weight of vinyl chloride resin. A range of 300 parts by weight is suitable.
A part of the plasticizer can be replaced with an organic solvent as a viscosity reducing agent. In this case, as the organic solvent, it is preferable to use an organic solvent having a boiling point as high as that of the plasticizer.
【0013】本発明のPVCゾル組成物には、尿素−ウ
レタン系の液状のレオロジー制御剤が用いられる。この
レオロジー制御剤は、尿素結合とウレタン結合をもち、
例えば商品名「BYK-LRR6237 」(BYK-Chemie GmbH 社
製)を好適に用いることができる。この尿素−ウレタン
系の液状のレオロジー制御剤は、添加量が多いほどPV
Cゾル組成物の垂れ限界膜厚が増大するが、可塑剤10
0重量部に対して7.5〜15重量部の範囲が最適であ
る。この範囲より少ないと垂れ限界膜厚が900μm以
下となり、多すぎると塗面の外観品質が低下する。A urea-urethane type liquid rheology control agent is used in the PVC sol composition of the present invention. This rheology control agent has a urea bond and a urethane bond,
For example, the trade name "BYK-LRR6237" (manufactured by BYK-Chemie GmbH) can be preferably used. This urea-urethane liquid rheology control agent is
Although the sag limit film thickness of the C sol composition increases, the plasticizer 10
The optimum range is 7.5 to 15 parts by weight with respect to 0 parts by weight. If it is less than this range, the sagging limit film thickness becomes 900 μm or less, and if it is too large, the appearance quality of the coated surface deteriorates.
【0014】本発明では、この尿素−ウレタン系の液状
のレオロジー制御剤とともに有機亜鉛系安定剤を用いる
ところに最大の特徴を有する。この有機亜鉛系安定剤
は、塩化ビニル系樹脂の熱分解を防止することを目的と
して従来より用いられている市販のものを用いることが
でき、例えば昭島科学(株)製の有機複合亜鉛系安定剤
を用いることができる。The present invention is most characterized in that an organozinc stabilizer is used together with the urea-urethane liquid rheology control agent. As this organozinc stabilizer, a commercially available one which has been conventionally used for the purpose of preventing thermal decomposition of vinyl chloride resin can be used. For example, an organic composite zinc stabilizer manufactured by Akishima Kagaku Co., Ltd. can be used. Agents can be used.
【0015】この有機亜鉛系安定剤は、可塑剤100重
量部に対して2.5〜7.5重量部の範囲が特に好まし
い。2.5重量部より少ないと垂れ限界膜厚が900μ
m以下となり、7.5重量部より多くなると塗面の外観
品質が低下する。なお、有機亜鉛系安定剤の添加量は上
記尿素−ウレタン系の液状のレオロジー制御剤の添加量
に応じて決定するのが望ましく、重量比でレオロジー制
御剤/安定剤=1/1〜2.5/1の範囲が特に好まし
い。The organozinc stabilizer is particularly preferably in the range of 2.5 to 7.5 parts by weight with respect to 100 parts by weight of the plasticizer. If the amount is less than 2.5 parts by weight, the sagging limit film thickness is 900μ
When it is less than m and more than 7.5 parts by weight, the appearance quality of the coated surface deteriorates. The amount of the organozinc stabilizer added is preferably determined according to the amount of the urea-urethane liquid rheology control agent added, and the weight ratio of the rheology control agent / stabilizer = 1/1 to 2. The range of 5/1 is particularly preferred.
【0016】本発明のPVCゾル組成物には、上記の他
に、充填材、接着性付与剤、他の安定剤、顔料、その他
の添加剤を目的に応じて適宜用いることができる。充填
材としては、炭酸カルシウム、炭酸マグネシウム、硫酸
バリウムなどのアルカリ土類金属の炭酸塩及び硫酸塩、
マイカ、シリカ、タルク、ケイソウ土、カオリン、酸化
カルシウム等が例示され、これらを単独又は複数種組み
合わせて用いることができる。またセルロース粉末、粉
末ゴム等の有機質粉末も、必要に応じて用いることがで
きる。In addition to the above, a filler, an adhesiveness-imparting agent, another stabilizer, a pigment, and other additives may be appropriately used in the PVC sol composition of the present invention depending on the purpose. As the filler, calcium carbonate, magnesium carbonate, carbonates and sulfates of alkaline earth metals such as barium sulfate,
Mica, silica, talc, diatomaceous earth, kaolin, calcium oxide and the like are exemplified, and these can be used alone or in combination of two or more kinds. In addition, organic powders such as cellulose powder and powdered rubber can be used if necessary.
【0017】この充填材の配合量は、塩化ビニル系樹脂
100重量部に対して30〜200重量部の範囲が好ま
しい。30重量部より少ないと凝集力が不十分となり、
200重量部を超えると脆くなり柔軟性や接着性が低下
する。接着性付与剤は、被塗物に対するPVCゾル塗膜
の付着性を高めるものであり、エポキシ系、アクリル
系、ポリアミド系、イソシアネート系等、従来用いられ
ている接着性付与剤を用いることができる。中でもポリ
アミド、ブロックウレタンプレポリマー、ブロックイソ
シアヌレートなどが特に好適である。The amount of the filler compounded is preferably in the range of 30 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. If it is less than 30 parts by weight, the cohesive force becomes insufficient,
If it exceeds 200 parts by weight, it becomes brittle and the flexibility and adhesiveness deteriorate. The adhesion-imparting agent enhances the adhesion of the PVC sol coating film to the article to be coated, and conventionally-used adhesion-imparting agents such as epoxy-based, acrylic-based, polyamide-based, isocyanate-based can be used. . Among them, polyamide, block urethane prepolymer, block isocyanurate and the like are particularly preferable.
【0018】他の安定剤としては、鉛、バリウム、錫、
カルシウムなどの金属の塩が従来と同様に利用できる。
その配合量は有機亜鉛系安定剤の配合量に応じて適宜決
定される。本発明のPVCゾル組成物は、エアレススプ
レー等の従来と同様の塗布手段によって任意の厚さで塗
布することができ、120〜160℃の従来と同様の焼
付温度に加熱することで塗膜とすることができる。Other stabilizers include lead, barium, tin,
Metal salts such as calcium can be used as before.
The blending amount is appropriately determined according to the blending amount of the organozinc stabilizer. The PVC sol composition of the present invention can be applied with an arbitrary thickness by a conventional coating means such as airless spray, and is heated to a conventional baking temperature of 120 to 160 ° C. to form a coating film. can do.
【0019】[0019]
【作用】尿素−ウレタン系の液状のレオロジー制御剤を
用いれば、従来の表面処理炭酸カルシウムのような中塗
り塗膜と上塗り塗膜の層間付着不良は生じないが、これ
だけでは十分な垂れ限界膜厚が得られない。また有機亜
鉛系安定剤だけでは、安定剤としての効果は有するもの
の垂れ限界膜厚を増大させる効果は全く無い。さらに、
尿素−ウレタン系の液状のレオロジー制御剤と他の安定
剤を併用しても、垂れ限界膜厚を増大させる作用は得ら
れない。When a liquid rheology control agent of urea-urethane type is used, the interlayer adhesion failure between the intermediate coating film and the top coating film as in the conventional surface-treated calcium carbonate does not occur, but this alone is sufficient for the sagging limit film. I can't get the thickness. Further, the organozinc stabilizer alone has an effect as a stabilizer, but has no effect of increasing the sag limit film thickness. further,
Even if the urea-urethane liquid rheology control agent and other stabilizer are used in combination, the effect of increasing the sag limit film thickness cannot be obtained.
【0020】しかし本発明のPVCゾル組成物では、尿
素−ウレタン系の液状のレオロジー制御剤と有機亜鉛系
安定剤を併用することにより、中塗り塗膜と上塗り塗膜
間の層間付着性が改善され、かつ垂れ限界膜厚が著しく
増大する。こうなる理由は明らかではないが、有機亜鉛
系安定剤と尿素−ウレタン系の液状のレオロジー制御剤
との間に錯体化反応のような何らかの反応が生じて、尿
素−ウレタン系の液状のレオロジー制御剤の作用が増大
するものと推察される。In the PVC sol composition of the present invention, however, the combined use of the urea-urethane type liquid rheology control agent and the organozinc stabilizer improves the interlayer adhesion between the intermediate coating film and the top coating film. And the sagging limit film thickness is significantly increased. Although the reason for this is not clear, some reaction such as a complexation reaction occurs between the organozinc stabilizer and the urea-urethane liquid rheology control agent, and the urea-urethane liquid rheology control is performed. It is speculated that the action of the agent will increase.
【0021】[0021]
【実施例】以下、実施例により具体的に説明する。なお
以下の組成のPVCゾルを基本ゾルとした。 塩化ビニルペースト用樹脂 50重量部 (PVCペースト「G−121」日本ゼオン(株)製) 塩化ビニルブレンド用樹脂 50重量部 (PVCブレンド「G−51」日本ゼオン(株)製) 可塑剤(アジピン酸系ポリエステル) 100重量部 (「PN−160」旭電化工業(株)製) 接着性付与剤(ポリアミド樹脂) 6重量部 (「ヌーリーボンド262」アクゾ(株)製、アミン価195) 減粘剤(脂肪族炭化水素系溶剤) 20重量部 (「EXXSOL D−80」エクソン(株)製) ─────────────────────────────────── 基本ゾル合計 226重量部 (実施例1)表1にも示すように、上記基本ゾル226
重量部に対して、尿素−ウレタン系の液状レオロジー制
御剤(「BYK-LRR6237 」(BYK-Chemie GmbH 社製))5
重量部と、有機複合亜鉛系安定剤(「LT−89A」昭
島化学(株)製)5重量部を混合し、減圧装置付ニーダ
を用いて30分間混合した後60分間脱泡し、実施例1
のPVCゾル組成物を得た。 (実施例2〜7)尿素−ウレタン系の液状レオロジー制
御剤(「BYK-LRR6237 」(BYK-Chemie GmbH 社製))と
有機複合亜鉛系安定剤(「LT−89A」昭島化学
(株)製)の添加量を表1に示すように種々変化させた
こと以外は実施例1と同様にして、実施例2〜7のPV
Cゾル組成物を得た。 (比較例1〜5)有機複合亜鉛系安定剤を用いず、尿素
−ウレタン系の液状レオロジー制御剤(「BYK-LRR6237
」(BYK-Chemie GmbH 社製))の添加量を表1に示す
ように種々変化させたこと以外は実施例1と同様にし
て、比較例1〜5のPVCゾル組成物を得た。 (比較例6〜8)尿素−ウレタン系の液状レオロジー制
御剤を用いず、有機複合亜鉛系安定剤(「LT−89
A」昭島化学(株)製)の添加量を表2に示すように種
々変化させたこと以外は実施例1と同様にして、比較例
6〜8のPVCゾル組成物を得た。 (比較例9〜10)基本ゾル226重量部に対して、尿
素−ウレタン系の液状レオロジー制御剤(「BYK-LRR623
7 」(BYK-Chemie GmbH 社製))10重量部と、有機亜
鉛系安定剤の代わりに鉛系安定剤(「ネオベース」堺化
学(株)製)、有機錫系安定剤(「OT−9」旭電化工
業(株)製)をそれぞれ5重量部添加したこと以外は実
施例1と同様にして、比較例9〜10のPVCゾル組成
物を得た。 (比較例11〜12)基本ゾル226重量部に対して、
尿素−ウレタン系の液状レオロジー制御剤の代わりに脂
肪酸表面処理炭酸カルシウム(「CC−R」白石カルシ
ウム(株)製)を表2に示す添加量で添加し、安定剤を
用いなかったこと以外は実施例1と同様にして、比較例
11〜12のPVCゾル組成物を得た。 (比較例13〜15)基本ゾル226重量部に対して、
尿素−ウレタン系の液状レオロジー制御剤の代わりに脂
肪酸表面処理炭酸カルシウム(「CC−R」白石カルシ
ウム(株)製)を75重量部用い、有機複合亜鉛系安定
剤(「LT−89A」昭島化学(株)製)を表2に示す
添加量で添加したこと以外は実施例1と同様にして、比
較例13〜15のPVCゾル組成物を得た。 (比較例16〜18)基本ゾル226重量部に対して、
尿素−ウレタン系の液状レオロジー制御剤の代わりに超
微粒子シリカ(「アエロジル#380」日本アエロジル
(株)製)を表2に示す添加量で添加し、安定剤を用い
なかったこと以外は実施例1と同様にして、比較例16
〜18のPVCゾル組成物を得た。 (比較例19〜21)基本ゾル226重量部に対して、
尿素−ウレタン系の液状レオロジー制御剤の代わりに超
微粒子シリカ(「アエロジル#380」日本アエロジル
(株)製)を10重量部用い、有機複合亜鉛系安定剤
(「LT−89A」昭島化学(株)製)を表2に示す添
加量で添加したこと以外は実施例1と同様にして、比較
例16〜18のPVCゾル組成物を得た。 (試験)上記の各実施例及び各比較例のPVCゾル組成
物について、垂れ限界膜厚、上塗り塗膜付着性及び塗面
状態を試験し、結果を表1及び表2に示す。試験条件は
以下のとおりである。 <垂れ限界膜厚>100×300mmの電着塗装板を用
意し、各PVCゾル組成物を膜厚が0〜2000μmに
徐々に変化するように、それぞれアプリケータで断面く
さび状に塗布し、直ちに垂直に立てて25℃で30分間
保持した。塗膜はこの時水平方向に膜厚が傾斜した状態
である。この後120℃×30分の焼付けを行い、垂れ
が発生している最大膜厚部分の膜厚を測定して垂れ限界
膜厚とした。 <上塗り塗膜付着性>70×150mmの電着塗装板に
それぞれのPVCゾル組成物をエアレススプレーにて膜
厚600μmに塗布し、110℃×10分のプレヒート
を行う。次に室温まで冷却後、アルキド−メラミン系中
塗り塗料(「TP−37」関西ペイント(株)製)を1
5μmの厚さにPVCゾル塗膜上にエアスプレーで塗布
し、10分間セッティング後140℃×30分間焼付け
た。そして室温まで冷却後、アクリル−メラミン系上塗
り塗料(「NEO♯6000」関西ペイント(株)製)
を中塗り塗膜表面にエアスプレーで25±5μmの膜厚
に塗布し、10分間セッティング後140℃×30分間
焼付けた。EXAMPLES The present invention will be specifically described below with reference to examples. A PVC sol having the following composition was used as a basic sol. Resin for vinyl chloride paste 50 parts by weight (PVC paste "G-121" manufactured by Nippon Zeon Co., Ltd.) Resin for vinyl chloride blend 50 parts by weight (PVC blend "G-51" manufactured by Nippon Zeon Co., Ltd.) Plasticizer (adipine Acid-based polyester) 100 parts by weight ("PN-160" manufactured by Asahi Denka Kogyo Co., Ltd.) Adhesiveness imparting agent (polyamide resin) 6 parts by weight ("Nuri Bond 262" manufactured by Akzo Co., Ltd., amine value 195) Agent (aliphatic hydrocarbon solvent) 20 parts by weight (“EXXSOL D-80” manufactured by Exxon Corporation) ───────────────────────── Total 226 parts by weight of basic sol (Example 1) As shown in Table 1, the above basic sol 226
5 parts by weight of urea-urethane liquid rheology control agent ("BYK-LRR6237" (BYK-Chemie GmbH))
Part by weight and 5 parts by weight of an organic composite zinc stabilizer (“LT-89A” manufactured by Akishima Chemical Co., Ltd.) were mixed and mixed for 30 minutes using a kneader with a pressure reducing device, followed by defoaming for 60 minutes. 1
A PVC sol composition of was obtained. (Examples 2 to 7) Urea-urethane type liquid rheology control agent ("BYK-LRR6237" (manufactured by BYK-Chemie GmbH)) and organic composite zinc stabilizer ("LT-89A" manufactured by Akishima Chemical Co., Ltd.) ) PVs of Examples 2 to 7 in the same manner as in Example 1 except that the addition amount of) was changed variously as shown in Table 1.
A C sol composition was obtained. (Comparative Examples 1 to 5) Urea-urethane type liquid rheology control agent (“BYK-LRR6237
The PVC sol compositions of Comparative Examples 1 to 5 were obtained in the same manner as in Example 1 except that the addition amount of "(BYK-Chemie GmbH)" was changed as shown in Table 1. (Comparative Examples 6 to 8) The organic composite zinc-based stabilizer ("LT-89
A ”PVC sol compositions of Comparative Examples 6 to 8 were obtained in the same manner as in Example 1 except that the addition amount of“ A ”manufactured by Akishima Chemical Co., Ltd. was changed variously as shown in Table 2. (Comparative Examples 9 to 10) With respect to 226 parts by weight of the basic sol, a urea-urethane liquid rheology control agent (“BYK-LRR623
7 "(manufactured by BYK-Chemie GmbH), lead-based stabilizers (" Neobase "manufactured by Sakai Chemical Co., Ltd.), organotin-based stabilizers (" OT-9 "instead of organozinc-based stabilizers). The PVC sol compositions of Comparative Examples 9 to 10 were obtained in the same manner as in Example 1 except that 5 parts by weight of Asahi Denka Kogyo Co., Ltd. was added. (Comparative Examples 11 to 12) Based on 226 parts by weight of the basic sol,
Instead of the urea-urethane type liquid rheology control agent, fatty acid surface-treated calcium carbonate (“CC-R” manufactured by Shiraishi Calcium Co., Ltd.) was added at the addition amount shown in Table 2 and no stabilizer was used. In the same manner as in Example 1, PVC sol compositions of Comparative Examples 11 to 12 were obtained. (Comparative Examples 13 to 15) Based on 226 parts by weight of the basic sol,
75 parts by weight of fatty acid surface-treated calcium carbonate (“CC-R” manufactured by Shiraishi Calcium Co., Ltd.) was used in place of the urea-urethane liquid rheology control agent, and an organic composite zinc-based stabilizer (“LT-89A” Akishima Kagaku) was used. PVC sol compositions of Comparative Examples 13 to 15 were obtained in the same manner as in Example 1 except that the amount added in Table 2 was used. (Comparative Examples 16 to 18) Based on 226 parts by weight of the basic sol,
Ultrafine particle silica (“Aerosil # 380” manufactured by Nippon Aerosil Co., Ltd.) was added in the amount shown in Table 2 instead of the urea-urethane liquid rheology control agent, and no stabilizer was used. Comparative Example 16
~ 18 PVC sol compositions were obtained. (Comparative Examples 19 to 21) Based on 226 parts by weight of the basic sol,
10 parts by weight of ultrafine particle silica (“Aerosil # 380” manufactured by Nippon Aerosil Co., Ltd.) was used in place of the urea-urethane liquid rheology control agent, and an organic composite zinc stabilizer (“LT-89A” Akishima Chemical Co., Ltd.) was used. Comparative Examples 16 to 18 were obtained in the same manner as in Example 1 except that (a) was added in the amount shown in Table 2. (Test) With respect to the PVC sol composition of each of the above Examples and Comparative Examples, the sag limit film thickness, the adhesion of the top coating film and the state of the coated surface were tested, and the results are shown in Tables 1 and 2. The test conditions are as follows. <Dripping limit film thickness> Prepare an electrodeposition coated plate of 100 × 300 mm, apply each PVC sol composition in a wedge-shaped cross section with an applicator so that the film thickness gradually changes to 0 to 2000 μm, and immediately It was placed vertically and kept at 25 ° C. for 30 minutes. At this time, the coating film is in a state in which the film thickness is inclined in the horizontal direction. After that, baking was performed at 120 ° C. for 30 minutes, and the film thickness at the maximum film thickness portion where the sagging occurred was measured to be the sagging limit film thickness. <Adhesion of Topcoat Film> Each PVC sol composition is applied to a 70 × 150 mm electrodeposition coated plate by airless spraying to a film thickness of 600 μm, and preheated at 110 ° C. for 10 minutes. Next, after cooling to room temperature, 1 piece of alkyd-melamine intermediate coating composition (“TP-37” manufactured by Kansai Paint Co., Ltd.)
A 5 μm-thick PVC sol coating film was applied with an air spray, set for 10 minutes, and then baked at 140 ° C. for 30 minutes. After cooling to room temperature, acrylic-melamine topcoat paint (“NEO # 6000” manufactured by Kansai Paint Co., Ltd.)
Was coated on the surface of the intermediate coating film by air spraying to a film thickness of 25 ± 5 μm, set for 10 minutes, and then baked at 140 ° C. for 30 minutes.
【0022】それぞれの塗板を温度20℃・湿度60%
の標準状態の環境に24時間放置し、その後JISK5
400に規定された碁盤目(2×2mm)を刻み、セロ
ファンテープ剥離試験を行って上塗り塗膜の付着性を評
価した。結果は分母に刻んだ枡目の数を、分子に上塗り
塗膜が付着して残った数を示す。 <塗面状態>エアー比40:のエアレスポンプとエアレ
スノズルチップ「163−519」 (日本グレー(株)製)を用い、ガン元圧力10MP
a、ガン距離300mm、ガン速度300mm/se
c、温度35℃の条件で、それぞれのPVCゾル組成物
を塗布し、塗面の状態(凹凸とテールの有無)を目視で
評価した。結果は比較例11の従来品を○とした場合に
それより優れているものを◎、それよりやや劣るものを
△、著しく劣るものを×とした。Each coated plate has a temperature of 20 ° C. and a humidity of 60%
Left in standard environment for 24 hours, then JISK5
A grid pattern (2 × 2 mm) defined by 400 was carved, and a cellophane tape peeling test was performed to evaluate the adhesion of the top coat film. The results show the number of squares cut in the denominator and the number of remaining topcoat coatings attached to the numerator. <Coating state> Using an airless pump with an air ratio of 40: and an airless nozzle tip "163-519" (manufactured by Nippon Gray Co., Ltd.), a gun source pressure of 10MP
a, gun distance 300 mm, gun speed 300 mm / se
Each of the PVC sol compositions was applied under the conditions of c and a temperature of 35 ° C., and the state of the coated surface (presence or absence of unevenness and tail) was visually evaluated. In the results, when the conventional product of Comparative Example 11 was evaluated as ◯, ◎ was superior to that, Δ was slightly inferior to that, and x was significantly inferior.
【0023】[0023]
【表1】 [Table 1]
【0024】[0024]
【表2】 [Table 2]
【0025】(評価)比較例1〜5の結果より、尿素−
ウレタン系レオロジー制御剤を単独で用いると、上塗り
塗膜付着性は良好であるものの、垂れ限界膜厚の増大効
果が小さく多量に添加する必要があることがわかる。ま
た比較例6〜9の結果より、有機亜鉛系安定剤単独では
垂れ限界膜厚を向上させる作用はないことも明らかであ
る。しかし実施例では、尿素−ウレタン系レオロジー制
御剤が少量でも垂れ限界膜厚が著しく向上しており、ま
た塗面も良好であって、これは尿素−ウレタン系レオロ
ジー制御剤と有機亜鉛系安定剤とを併用したことによる
相乗効果であることが明らかである。(Evaluation) From the results of Comparative Examples 1 to 5, urea-
It can be seen that when the urethane rheology control agent is used alone, the adhesion of the top coat film is good, but the effect of increasing the sag limit film thickness is small and it is necessary to add a large amount. It is also clear from the results of Comparative Examples 6 to 9 that the organozinc stabilizer alone does not have the effect of improving the sag limit film thickness. However, in the examples, even with a small amount of the urea-urethane type rheology control agent, the sag limit film thickness is remarkably improved, and the coating surface is also good. This is because the urea-urethane type rheology control agent and the organozinc stabilizer are used. It is clear that the combined use of and is a synergistic effect.
【0026】また比較例9〜10の結果より、尿素−ウ
レタン系レオロジー制御剤と他の安定剤を組み合わせて
も、実施例のような相乗効果はみられない。さらに各比
較例の比較より、表面処理炭酸カルシウムが上塗り塗膜
付着性を阻害していることがわかり、また尿素−ウレタ
ン系以外の他のレオロジー制御剤と有機亜鉛系安定剤を
組み合わせても、垂れ限界膜厚の向上はみられず、かえ
って塗面状態が悪化するような弊害が生じていることも
わかる。Further, from the results of Comparative Examples 9 to 10, even if the urea-urethane type rheology control agent and other stabilizers were combined, the synergistic effect as in the Examples was not observed. Furthermore, by comparing the respective comparative examples, it was found that the surface-treated calcium carbonate inhibits the adhesion of the top coating film, and even if a combination of a rheology control agent other than urea-urethane and an organozinc stabilizer was used, It can be seen that the sagging limit film thickness is not improved, and rather the adverse effect that the coated surface state is deteriorated is occurring.
【0027】[0027]
【発明の効果】すなわち本発明のポリ塩化ビニルプラス
チゾル組成物によれば、従来と同等の流動特性が維持さ
れ、大きな垂れ限界膜厚と良好な塗面状態を両立できる
とともに、上塗り塗膜の付着不良の発生を確実に防止す
ることができる。According to the polyvinyl chloride plastisol composition of the present invention, the same flow characteristics as the conventional one can be maintained, a large sag limit film thickness and a good coating state can be achieved, and the adhesion of the top coating film can be achieved. It is possible to reliably prevent the occurrence of defects.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 (C09D 127/06 175:00) ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location (C09D 127/06 175: 00)
Claims (1)
し、尿素−ウレタン系液状レオロジー制御剤と有機亜鉛
系安定剤とを含むことを特徴とするポリ塩化ビニルプラ
スチゾル組成物。1. A polyvinyl chloride plastisol composition comprising a vinyl chloride resin and a plasticizer as main components, and a urea-urethane liquid rheology control agent and an organic zinc stabilizer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26572594A JPH08127691A (en) | 1994-10-28 | 1994-10-28 | Poly(vinyl chloride) plastisol composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26572594A JPH08127691A (en) | 1994-10-28 | 1994-10-28 | Poly(vinyl chloride) plastisol composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH08127691A true JPH08127691A (en) | 1996-05-21 |
Family
ID=17421141
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP26572594A Pending JPH08127691A (en) | 1994-10-28 | 1994-10-28 | Poly(vinyl chloride) plastisol composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH08127691A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001342316A (en) * | 2000-06-02 | 2001-12-14 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride paste resin composition and disposable glove |
-
1994
- 1994-10-28 JP JP26572594A patent/JPH08127691A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001342316A (en) * | 2000-06-02 | 2001-12-14 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride paste resin composition and disposable glove |
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