JPH0784045B2 - Painted parts - Google Patents
Painted partsInfo
- Publication number
- JPH0784045B2 JPH0784045B2 JP30910288A JP30910288A JPH0784045B2 JP H0784045 B2 JPH0784045 B2 JP H0784045B2 JP 30910288 A JP30910288 A JP 30910288A JP 30910288 A JP30910288 A JP 30910288A JP H0784045 B2 JPH0784045 B2 JP H0784045B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- compound
- carboxylic acid
- unsaturated carboxylic
- vinyl
- 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.)
- Expired - Fee Related
Links
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、樹脂成形品に塗装を施してなる塗装部品に関
する。さらに詳しくは、特定の樹脂組成物からなる成形
品にウレタン樹脂系塗料を塗装してなる密着強度に優れ
た塗装部品に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a coated part obtained by coating a resin molded product. More specifically, the present invention relates to a coated part having excellent adhesion strength, which is formed by coating a urethane resin-based paint on a molded product made of a specific resin composition.
＜従来技術＞ 軽量化、防錆性の面より各種樹脂成形品が車両分野、弱
電分野、雑貨分野、電子・電気分野などで用いられてい
る。特にABS樹脂、AES樹脂、AAS樹脂などのゴム強化芳
香族ビニル系樹脂組成物は、耐衝撃性と加工性のバラン
ス、耐熱性、耐薬品性等に優れることよりそれらの分野
において多用されている。<Prior Art> Various resin molded products are used in the fields of vehicles, light electrical appliances, sundries, electronic / electrical fields, etc. in terms of weight reduction and rust prevention. In particular, ABS resin, AES resin, rubber-reinforced aromatic vinyl resin composition such as AAS resin is widely used in those fields because of its excellent balance of impact resistance and processability, heat resistance, chemical resistance, etc. .
通常、これら樹脂組成物は装飾あるいは耐候性向上を目
的として塗装される。Usually, these resin compositions are painted for the purpose of decoration or improvement of weather resistance.
塗料としては、ウレタン樹脂系塗料、アクリル樹脂系塗
料、塩ビ樹脂系塗料、フタル酸樹脂系塗料等々が用いら
れているが、塗料中の溶剤（シンナー）によってストレ
スクラックが発生する場合があるため、樹脂中のアクリ
ロニトリル量を増大させたり、耐溶剤性に優れた他のポ
リマーを配合するなど樹脂組成面からの改良が行われて
きた。As paints, urethane resin paints, acrylic resin paints, vinyl chloride resin paints, phthalic acid resin paints, etc. are used, but stress cracks may occur due to the solvent (thinner) in the paint, Improvements have been made in terms of resin composition, such as increasing the amount of acrylonitrile in the resin and compounding another polymer having excellent solvent resistance.
一方、塗膜との密着力強化を目的とする場合には、塗装
工程面で溶剤処理、界面活性剤処理等の前処理及びプラ
イマー塗装の実施、あるいは塗料面でシンナー組成の変
更等が行なわれているが、工程面、コスト面でこれらの
対応が不可能な場合がある。On the other hand, for the purpose of strengthening the adhesion with the coating film, pretreatment such as solvent treatment and surfactant treatment and primer coating are performed on the coating process side, or the thinner composition is changed on the coating side. However, there are cases where it is not possible to deal with them in terms of process and cost.
＜発明が解決しようとする問題点＞ 本発明者らは、従来の塗装部品における密着力不足を解
決すべく樹脂成形品を構成する樹脂組成ならびに塗料と
の組み合わせについて鋭意研究した。<Problems to be Solved by the Invention> The inventors of the present invention have earnestly studied a combination of a resin composition and a paint constituting a resin molded article in order to solve the lack of adhesion in conventional coated parts.
＜問題点を解決するための手段＞ 本発明者らの研究において、不飽和カルボン酸を微量導
入（共重合）してなる特定組成の樹脂組成物からなる成
形品に対し、塗料としてウレタン樹脂系塗料を塗装して
なる塗装部品が優れた密着力を有していることが見い出
され、本発明に到達した。<Means for Solving Problems> In the study conducted by the present inventors, a urethane resin-based resin was used as a coating for a molded article made of a resin composition having a specific composition obtained by introducing (copolymerizing) a small amount of an unsaturated carboxylic acid. It has been found that a coated part formed by coating with a paint has excellent adhesion, and has reached the present invention.
すなわち、本発明は、不飽和カルボン酸を共重合してな
るゴム強化芳香族ビニル系樹脂組成物であって、不飽和
カルボン酸含有量が0.05〜2.0重量％である組成物から
なる樹脂成形品にウレタン樹脂系塗料を塗装してなる良
好な密着強度を有する塗装部品を提供するものである。That is, the present invention is a rubber-reinforced aromatic vinyl-based resin composition obtained by copolymerizing an unsaturated carboxylic acid, the resin molded product comprising an unsaturated carboxylic acid content of 0.05 to 2.0 wt% A coated part having good adhesion strength, which is obtained by coating a urethane resin-based paint on the above.
以下、本発明について詳細に説明する。Hereinafter, the present invention will be described in detail.
不飽和カルボン酸を共重合してなるゴム強化芳香族ビニ
ル系樹脂組成物とは、ゴムの存在下に不飽和カルボン
酸、芳香族ビニル化合物およびシアン化ビニル化合物な
らびに必要に応じてそれらと共重合可能な他のビニル化
合物を重合してなる重合体（Ｇ−１）を必須とするか、
又はゴムの存在下に芳香族ビニル化合物およびシアン化
ビニル化合物ならびに必要に応じてそれらと共重合可能
な他のビニル化合物を重合してなる重合体（Ｇ−２）と
不飽和カルボン酸ならびに芳香族ビニル化合物およびシ
アン化ビニル化合物ならびに必要に応じてそれらと共重
合可能な他のビニル化合物を重合してなる共重合体（Ｒ
−１）とを必須とする組成物である。The rubber-reinforced aromatic vinyl-based resin composition obtained by copolymerizing an unsaturated carboxylic acid means an unsaturated carboxylic acid, an aromatic vinyl compound and a vinyl cyanide compound in the presence of rubber, and a copolymer with them, if necessary. A polymer (G-1) obtained by polymerizing another possible vinyl compound is essential,
Or a polymer (G-2) obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound in the presence of rubber, and optionally another vinyl compound copolymerizable therewith, an unsaturated carboxylic acid, and an aromatic compound. A copolymer obtained by polymerizing a vinyl compound, a vinyl cyanide compound and, if necessary, another vinyl compound copolymerizable therewith (R
-1) and the essential composition.
より具体的に述べると、上述の不飽和カルボン酸変性
重合体（Ｇ−１）、（Ｇ−１）と未変性重合体（Ｇ−
２）の混合物、（Ｇ−２）と不飽和カルボン酸変性共
重合体（Ｒ−１）との混合物、（Ｇ−１）と不飽和カ
ルボン酸変性共重合体（Ｒ−１）との混合物、（Ｇ−
１）と芳香族ビニル化合物およびシアン化ビニル化合物
ならびに必要に応じてそれらと共重合可能な他のビニル
化合物を重合してなる共重合体（Ｒ−２）との混合物、
（Ｇ−１）、（Ｇ−２）と（Ｒ−１）との混合物、
（Ｇ−１）、（Ｇ−２）と（Ｒ−２）との混合物、
（Ｇ−１）、（Ｒ−１）と（Ｒ−２）との混合物、
（Ｇ−２）、（Ｒ−１）と（Ｒ−２）との混合物、
（Ｇ−１）、（Ｇ−２）、（Ｒ−１）と（Ｒ−２）との
混合物のいずれかである。More specifically, the unsaturated carboxylic acid modified polymers (G-1) and (G-1) and the unmodified polymer (G-
2) mixture, (G-2) mixture with unsaturated carboxylic acid modified copolymer (R-1), (G-1) mixture with unsaturated carboxylic acid modified copolymer (R-1) , (G-
A mixture of 1) with an aromatic vinyl compound, a vinyl cyanide compound and, if necessary, a copolymer (R-2) obtained by polymerizing another vinyl compound copolymerizable therewith;
(G-1), a mixture of (G-2) and (R-1),
(G-1), a mixture of (G-2) and (R-2),
(G-1), a mixture of (R-1) and (R-2),
(G-2), a mixture of (R-1) and (R-2),
It is any of (G-1), (G-2), and a mixture of (R-1) and (R-2).
組成物の物性バランスならびに工業的な生産性の面よ
り、上述のもしくはの混合物であることが好まし
い。From the viewpoint of the balance of physical properties of the composition and industrial productivity, a mixture of the above or or is preferable.
かかるゴム強化芳香族ビニル系樹脂組成物における共重
合してなる不飽和カルボン酸量は、0.05〜2.0重量％で
ある。The amount of unsaturated carboxylic acid formed by copolymerization in the rubber-reinforced aromatic vinyl resin composition is 0.05 to 2.0% by weight.
0.05重量％未満では密着力の改善が充分でなく、又2.0
重量％を越すと物性バランス（衝撃強度、加工性）の低
下、成形品外観が損われる。If it is less than 0.05% by weight, the adhesive strength is not sufficiently improved, and it is 2.0
If it exceeds the weight%, the balance of physical properties (impact strength, workability) is deteriorated and the appearance of the molded product is impaired.
密着力、物性バランス、外観の面より0.07〜1.0重量％
が好ましい。0.07 to 1.0% by weight from the aspect of adhesion, physical property balance, and appearance
Is preferred.
なお、ゴム強化芳香族ビニル系樹脂組成物においては、
不飽和カルボン酸成分以外の成分に対しては特に制限は
ないが、組成物又は塗装部品の物性面（耐衝撃性、加工
性、耐熱性、塗料中のシンナーに対する抵抗性等々）よ
り、組成物中のゴム５〜40重量％、特に10〜30重量％、
芳香族ビニル化合物20〜70重量％、特に30〜60重量％、
シアン化ビニル化合物５〜50重量％、特に10〜40重量
％、他のビニル化合物０〜30重量％、特に０〜20重量％
が好ましい。In the rubber-reinforced aromatic vinyl resin composition,
There is no particular limitation on the components other than the unsaturated carboxylic acid component, but the composition or the coated part has physical properties (impact resistance, processability, heat resistance, resistance to thinner in the paint, etc.) 5-40% by weight of rubber, especially 10-30% by weight,
Aromatic vinyl compound 20-70% by weight, especially 30-60% by weight,
Vinyl cyanide compound 5 to 50% by weight, especially 10 to 40% by weight, other vinyl compound 0 to 30% by weight, especially 0 to 20% by weight
Is preferred.
不飽和カルボン酸としては、アクリル酸、メタクリル
酸、マレイン酸、フマル酸、イタコン酸などが例示さ
れ、単独又は二種以上混合して使用できる。これらの中
で特にメタクリル酸が好ましい。Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and the like, which may be used alone or in combination of two or more. Of these, methacrylic acid is particularly preferable.
ゴムとしては、ポリブタジエン、ブタジエン−スチレン
共重合体、ブタジエン−アクリロニトリル共重合体等の
ジエン系ゴム状重合体およびエチレン−プロピレン共重
合体、エチレン−プロピレン−非共役ジエン共重合体、
アクリル系ゴム状重合体、塩素化ポリエチレン等の非ジ
エン系ゴム状重合体が例示され、単独又は二種以上混合
して使用することができる。As the rubber, polybutadiene, butadiene-styrene copolymer, diene rubber polymer such as butadiene-acrylonitrile copolymer and ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer,
Acrylic rubbery polymers and non-diene rubbery polymers such as chlorinated polyethylene are exemplified, and they can be used alone or in combination of two or more.
これらのゴムは乳化重合、溶液重合、塊状重合、懸濁重
合等により製造される。These rubbers are produced by emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like.
なお、乳化重合により製造する場合におけるゴムの粒子
径およびゲル含有率については特に制限はないが、粒子
径0.1〜１μｍおよびゲル含有率０〜95％であることが
好ましい。There are no particular restrictions on the particle size and gel content of the rubber when it is produced by emulsion polymerization, but a particle size of 0.1 to 1 μm and a gel content of 0 to 95% are preferred.
芳香族ビニル化合物としては、スチレン、α−メチルス
チレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ
−メチルスチレン、ｔ−ブチルスチレン、α−メチルビ
ニルトルエン、ジメチルスチレン、クロルスチレン、ジ
クロルスチレン、ブロムスチレン、ジブロムスチレン、
ビニルナフタレン等が例示され、単独又は二種以上混合
して用いることができる。As the aromatic vinyl compound, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p
-Methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene,
Examples thereof include vinylnaphthalene, which may be used alone or in combination of two or more.
シアン化ビニル化合物としては、アクリロニトリル、メ
タクリロニトリル、エタクリロニトリル、フマロニトリ
ル等が例示され、単独又は二種以上混合して用いること
ができる。Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, and fumaronitrile, and they can be used alone or in combination of two or more.
芳香族ビニル化合物およびシアン化ビニル化合物と共重
合可能な他のビニル化合物としては、メチルアクリレー
ト、エチルアクリレート、ブチルアクリレート、２−エ
チルヘキシルアクリレート、メチルメタクリレート、エ
チルメタクリレート、プロピルメタクリレート、２−エ
チルヘキシルメタクリレート等の不飽和カルボン酸アル
キルエステル、マレイミド、Ｎ−フェニルマレイミド、
Ｎ−メチルマレイミド、Ｎ−シクロヘキシルマレイミド
等のマレイミド化合物が例示され単独又は二種以上混合
して用いることができる。Other vinyl compounds copolymerizable with the aromatic vinyl compound and the vinyl cyanide compound include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate and the like. Unsaturated carboxylic acid alkyl ester, maleimide, N-phenylmaleimide,
Maleimide compounds such as N-methylmaleimide and N-cyclohexylmaleimide are exemplified, and they can be used alone or in combination of two or more.
本発明における不飽和カルボン酸を共重合してなるゴム
強化芳香族ビニル系樹脂組成物には、従来より公知の安
定剤、離型剤、染顔料、充填剤、難燃剤、帯電防止剤等
の添加剤を配合することも可能である。The rubber-reinforced aromatic vinyl-based resin composition obtained by copolymerizing the unsaturated carboxylic acid in the present invention includes a conventionally known stabilizer, release agent, dye / pigment, filler, flame retardant, antistatic agent, etc. It is also possible to add additives.
塗装前の成形品は、上述のゴム強化芳香族ビニル系樹脂
組成物を用いて従来より公知の成形方法、すなわち射出
成形法、押出成形法、ブロー成形法、真空成形法、発泡
成形法、冷間塑性加工法などによって得ることができ
る。もちろん成形品の形状、寸法等には何ら制限はな
い。The molded product before coating is a conventionally known molding method using the above-mentioned rubber-reinforced aromatic vinyl resin composition, that is, an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, a foam molding method, and a cold molding method. It can be obtained by the inter-plastic working method. Of course, there is no restriction on the shape and size of the molded product.
以下に示す実施例及び比較例に基づき本発明を更に具体
的に説明するが、本発明はその要旨を変えない限り、こ
れら実施例によって制限されるものではない。The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to these examples unless the gist thereof is changed.
実施例及び比較例 表−１に示すグラフト重合体と共重合体とからなる各種
組成物を得た後、それら組成物の物性ならびにそれら組
成物に基づき得られた成形品と塗装部品の外観及び密着
性を評価した。結果を表−４に示す。Examples and Comparative Examples After obtaining various compositions consisting of the graft polymer and the copolymer shown in Table-1, the physical properties of these compositions and the appearance of molded articles and coated parts obtained based on these compositions and The adhesion was evaluated. The results are shown in Table-4.
グラフト重合体 平均粒子径0.4μ、ゲル80％のポリブタジエンゴムラテ
ックス、スチレン、アクリロニトリルおよびメタクリル
酸を用いて、公知の乳化重合によって表−２に示す組成
のグラフト重合体を得た。Graft Polymer A polybutadiene rubber latex having an average particle size of 0.4 μm and a gel of 80%, styrene, acrylonitrile and methacrylic acid were used to obtain a graft polymer having a composition shown in Table 2 by known emulsion polymerization.
共重合体 スチレン、アクリロニトリルおよびメタクリル酸を用い
て公知の乳化重合によって、表−３に示す組成の共重合
体を得た。Copolymer A copolymer having the composition shown in Table 3 was obtained by known emulsion polymerization using styrene, acrylonitrile and methacrylic acid.
試験方法 1.塗料 主剤（日本油脂株式会社製ハイウレタン＃5100ブラッ
ク）、硬化剤（日本油脂株式会社製ハイウレタンHL硬化
剤）およびシンナー（日本油脂株式会社製ハイウレタン
SSSシンナー）を用い、以下の調合比率にて塗料を調合
した。Test method 1. Paint Main ingredient (Nippon Oil & Fat Co., Ltd. Hi Urethane # 5100 Black), Hardener (Nippon Oil and Fat Co., Ltd. Hi Urethane HL Hardener) and thinner (Nippon Oil and Fat Co., Ltd.
Using SSS thinner), paints were prepared at the following mixing ratios.
調合比率（重合比率）：主剤／硬化剤／シンナー＝50/9
/25〜30（フォードカップNo.4粘度13〜14sec） 2.塗装方法 東芝機械株式会社製IS−90B射出成形機により、90×150
×3mm tの平板プレートを成形し、スプレーガンを用い
て所定の膜厚に塗装を行なった。Mixing ratio (polymerization ratio): Main agent / hardening agent / thinner = 50/9
/ 25-30 (Ford Cup No.4 viscosity 13-14sec) 2. Painting method 90 × 150 with IS-90B injection molding machine manufactured by Toshiba Machine Co., Ltd.
A flat plate of × 3 mm t was molded and coated with a predetermined thickness using a spray gun.
塗装した成形品はセッティング（室温にて10分）後、65
℃オーブン中にて30分間の焼付けを実施した。After setting (10 minutes at room temperature) the painted molded product, 65
Baking was performed for 30 minutes in an oven.
3.密着性の評価 上記塗装プレートを室温にて24時間放置後、下記Ａ法お
よびＢ法により密着性を評価した。3. Evaluation of Adhesion After the coated plate was left at room temperature for 24 hours, the adhesion was evaluated by the following method A and method B.
Ａ法：片刃カミソリの切刃を塗面に対して約30度に保持
し、素地に達する1mmのごばん目100個（10×10）を作
り、24mm幅のセロハン粘着テープをごばん目上に完全に
密着させ、直ちにテープの一端を有効面に直角に保ち瞬
間的に引き離し、はがれの有無を判定した。Method A: Hold the cutting edge of a single-edged razor at about 30 degrees to the coated surface and make 100 1 mm (10 x 10) 1 mm squares that reach the base, and use 24 mm wide cellophane adhesive tape Then, the tape was immediately kept at a right angle to the effective surface, and immediately separated to determine whether or not there was peeling.
Ｂ法：カッターナイフにて90度クロスカットを入れ、ク
ロス部塗膜をめくり上げ、剥がれた塗膜の一端を手で持
ち上げ、剥がれの有無を判定した。Method B: A 90 degree cross cut was made with a cutter knife, the coating film on the cloth portion was turned up, and one end of the peeled coating film was lifted by hand to determine the presence or absence of peeling.
＜判定基準＞ 4.特性 得られた樹脂組成物の特性を以下の方法により測定し、
その結果を別表−１に示した。<Judgment criteria> 4. Characteristics The characteristics of the obtained resin composition are measured by the following methods,
The results are shown in Appendix-1.
衝撃強度:1/4″ｔノッチ付アイゾット、23℃測定 加工性：高化式フロー、210℃×30kg/cm2 外観：塗装評価用プレートにて塗装前後の外観を目視
判定 ＜判定基準＞ ＜発明の効果＞ 本発明の塗装部品は、従来の塗装部品に比べ優れた外観
ならびに密着性を有する。Impact strength: 1/4 "t notched Izod, 23 ℃ measurement Workability: High-performance flow, 210 ℃ × 30kg / cm 2 Appearance: Visual evaluation before and after coating with a coating evaluation plate <Judgment criteria> <Effects of the Invention> The coated part of the present invention has excellent appearance and adhesion as compared with conventional coated parts.
Claims (1)
ビニル化合物およびシアン化ビニル化合物ならびに必要
に応じてそれらと共重合可能な他のビニル化合物を重合
してなる重合体（Ｇ−１）を必須とするか、又はゴムの
存在下に芳香族ビニル化合物およびシアン化ビニル化合
物ならびに必要に応じてそれらと共重合可能な他のビニ
ル化合物を重合してなる重合体（Ｇ−２）と不飽和カル
ボン酸、芳香族ビニル化合物およびシアン化ビニル化合
物ならびに必要に応じてそれらと共重合可能な他のビニ
ル化合物を重合してなる共重合体（Ｒ−１）とを必須と
するゴム強化芳香族ビニル系樹脂組成物であって、不飽
和カルボン酸含有量が0.05〜2.0重量％である組成物か
らなる樹脂成形品にウレタン樹脂系塗料を塗装してなる
塗装部品。1. A polymer (G-1) obtained by polymerizing an unsaturated carboxylic acid, an aromatic vinyl compound and a vinyl cyanide compound in the presence of rubber, and optionally another vinyl compound copolymerizable therewith. ), Or a polymer (G-2) obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound in the presence of rubber, and optionally another vinyl compound copolymerizable therewith. Rubber-reinforced fragrance essentially comprising an unsaturated carboxylic acid, an aromatic vinyl compound and a vinyl cyanide compound, and optionally a copolymer (R-1) obtained by polymerizing another vinyl compound copolymerizable therewith. A coated part obtained by coating a urethane resin-based paint on a resin molded product made of a vinyl group resin composition having an unsaturated carboxylic acid content of 0.05 to 2.0% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30910288A JPH0784045B2 (en) | 1988-12-06 | 1988-12-06 | Painted parts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30910288A JPH0784045B2 (en) | 1988-12-06 | 1988-12-06 | Painted parts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02153738A JPH02153738A (en) | 1990-06-13 |
| JPH0784045B2 true JPH0784045B2 (en) | 1995-09-13 |
Family
ID=17988912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30910288A Expired - Fee Related JPH0784045B2 (en) | 1988-12-06 | 1988-12-06 | Painted parts |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0784045B2 (en) |
-
1988
- 1988-12-06 JP JP30910288A patent/JPH0784045B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02153738A (en) | 1990-06-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |