JPH03163177A - Coating composition for polycarbonate - Google Patents
Coating composition for polycarbonateInfo
- Publication number
- JPH03163177A JPH03163177A JP30367689A JP30367689A JPH03163177A JP H03163177 A JPH03163177 A JP H03163177A JP 30367689 A JP30367689 A JP 30367689A JP 30367689 A JP30367689 A JP 30367689A JP H03163177 A JPH03163177 A JP H03163177A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate
- transparency
- cyclic ether
- absorber
- 40mol
- 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
Links
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 17
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 17
- 239000008199 coating composition Substances 0.000 title claims description 5
- 239000002904 solvent Substances 0.000 claims abstract description 9
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 8
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000006096 absorbing agent Substances 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003505 polymerization initiator Substances 0.000 abstract description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012965 benzophenone Substances 0.000 abstract description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 abstract 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract 1
- 239000012964 benzotriazole Substances 0.000 abstract 1
- 230000037452 priming Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、透明性、耐久性に優れた樹脂であるポリカー
ボネートの表面に適用して各種の物性を付与することの
できる有機溶剤可溶性の含フッ素樹脂組成物に関するも
のである．
［従来技術］
ポリカーボネートは機械的強度、寸法安定性、電気絶縁
性、耐熱性、透明性等の各種物性に陸れており、電気、
電子材料の部品や機械類のハウジング、日用雑貨等に広
く使用されている．また透明であるとともに耐衝撃性が
高いため、樹脂ガラスとして建築物や自動車等の用途に
も適用されている．しかし、用途によっては、さらに特
定の物性を付与することが望まれるものである。ポリカ
ーボネートは元来耐候性，耐薬品性に関しては必ずしも
十分に優れているとはいえない。すなわちポリカーボネ
ートを屋外に使用した場合、主として太陽光中の紫外線
により劣１ヒをきたし、黄変、失透、クレイジングの発
生が認められ、強仲度持性が次第に低下することが知ら
れている。また、アルカリ、有機溶剤等の雰囲気下で使
用した場合にら失透、クレイジング等の発生が認められ
る。Detailed Description of the Invention [Industrial Field of Application] The present invention is an organic solvent-soluble compound that can be applied to the surface of polycarbonate, which is a resin with excellent transparency and durability, to impart various physical properties. This article relates to fluororesin compositions. [Prior art] Polycarbonate has excellent physical properties such as mechanical strength, dimensional stability, electrical insulation, heat resistance, and transparency, and is used for electrical,
It is widely used in electronic material parts, machinery housings, and daily miscellaneous goods. Because it is transparent and has high impact resistance, it is also used as resin glass in buildings, automobiles, and other applications. However, depending on the application, it is desired to impart further specific physical properties. Polycarbonate cannot necessarily be said to have sufficiently excellent weather resistance and chemical resistance. In other words, it is known that when polycarbonate is used outdoors, it deteriorates mainly due to ultraviolet rays in sunlight, yellowing, devitrification, and craze occur, and its strength retention gradually decreases. There is. Furthermore, when used in an atmosphere of an alkali, organic solvent, etc., devitrification, crazing, etc. are observed to occur.
このためポリカーボネート樹脂中に紫外線吸収剤を添加
することによって耐候性を改良しているが、必ずしも十
分な性能を発揮しているとは言い難い。For this reason, weather resistance has been improved by adding ultraviolet absorbers to polycarbonate resins, but it cannot be said that sufficient performance is necessarily exhibited.
また、この方広では耐薬品性ら合せて要求される用途に
は適していない．
一方、ポリカーボネートの表面を紫外線吸収剤を配合し
たアクリル、アクリルーウレタン、ウレタン系の樹脂で
コーティングすることによって耐候性および耐薬品性を
改良したポリカーボネートの製造ら一部おこなわれてい
るが、これらの被覆用樹脂そのものの耐候性が必ずしも
よくないため、満足のいく性能が得られていないのが実
情である。Also, this wide material is not suitable for applications that require chemical resistance. On the other hand, some efforts have been made to manufacture polycarbonate with improved weather resistance and chemical resistance by coating the surface of polycarbonate with acrylic, acrylic-urethane, or urethane resins containing UV absorbers; The reality is that the weather resistance of the coating resin itself is not necessarily good, so that satisfactory performance cannot be obtained.
また、これらの被覆用組或物はそのままでポリカーポネ
ート表面に適用することはできず、一般にはプライマー
で処理したのちにこれら被覆用組戊糊ｔ！−適用してい
る乙のである。また、これらの組戊糊を溶解し得る溶剤
には制限があり、溶剤は塗ｔ＋組代物のみならす、基材
となるポリカーボネートに対しても影響を与えるため好
ましいものではなかりた。また、基材のポリカーボネー
トとの密着性にも問題があり、かかる問題点のないもの
が求められていた。Also, these coating compositions cannot be applied directly to polycarbonate surfaces, and are generally treated with a primer before being applied with these coating compositions! - It is the one that is applied. In addition, there are restrictions on the solvents that can dissolve these glues, and solvents are not preferred because they affect not only the coated T+ glue but also the polycarbonate base material. Furthermore, there is a problem in the adhesion to the polycarbonate base material, and there has been a demand for something that does not have this problem.
［問題点を解決するための具体的手段］本発明昔らはか
かる従来の問題点に鑑み鋭意検討の結果本発明にＩＩ１
達したらのである。すなわち本発明は、フン化ビニリデ
ン、ヘキサフルオロアセトンおよびフルオロオレフィン
単量体を必須成分とする共重合体と紫外線吸収剤および
環状エ−テルを主戊分とずる，容剤とを含有１−でなる
ことを特徴とするポリカーボネ−１へ用被覆組成物であ
る．本発明において用いられるフルオロオレフィシとし
ては、テトラフルオ口エチレン（ＴＩ？Ｅと記す）Ｐ）
るいは１〜リフル才口エチレン（ＴｒＦＥと記一ｆ）等
か好まし＜ｆＭ用ら勿論可能である，フ・ノ化ビニリデ
ン（ＶＤＦと記す）とへキサフルオロアセトン（ＨＦＡ
とご己ず）およびフノレオロオレフィンの好ましい量的
範囲はＶＤＦが３０〜８（）モル０。、Ｈ Ｆ Ａが１
０〜４１〕モル？５、フルオロオレフィンが５〜・１０
？≦の範囲である。ＶＤＦがこの範囲未満では、塗膜の
硬度が十分ではなく、この範囲を超えると塗膜の柔軟性
に劣る．ＨＦＡがこの範囲より少ないと透明性が十分で
はなく、この範囲を超えると塗膜の硬度が低くなる。ま
たフルオロオレフィシがこの範囲未満では柔軟性に欠け
、Ｔｈｌｌ Ｍ ＊の原因となる。また、この範囲を超
えると． ．’Ｂ刑に対する溶解性が低下し、透明性ら
下がるものである。[Specific means for solving the problems] The present invention In view of the conventional problems, as a result of intensive studies, the present invention has been developed.
That's when I reached it. That is, the present invention provides a copolymer containing vinylidene fluoride, hexafluoroacetone, and a fluoroolefin monomer as essential components, and a container whose main components are an ultraviolet absorber and a cyclic ether. 1. A coating composition for polycarbonate-1, characterized in that: The fluoroolefin used in the present invention includes tetrafluoroethylene (denoted as TI?E) P)
It is preferable to use vinylidene difluoride (denoted as VDF) and hexafluoroacetone (HFA).
The preferable quantitative range of VDF is 30 to 8 moles (0 to 8 moles). , H F A is 1
0-41] moles? 5, fluoroolefin is 5 to 10
? The range is ≦. If the VDF is less than this range, the coating film will not have sufficient hardness, and if it exceeds this range, the coating film will have poor flexibility. If HFA is less than this range, transparency will not be sufficient, and if it exceeds this range, the hardness of the coating will be low. Furthermore, if the fluoroolefinicity is less than this range, flexibility will be lacking and this will cause Thll M *. Also, beyond this range. ．． 'B's solubility and transparency are reduced.
これらのモノマーからなる共重合体は、一般には重合開
始剤の存在下、溶液重合法により製造される。Copolymers made of these monomers are generally produced by solution polymerization in the presence of a polymerization initiator.
本発明の組成物は紫外線吸収７ｆｌＩを含むものであり
、ベンゾフエノン系、ペンゾトリアゾール系あるいはア
クリル系のものをその特性を失わない程度の量で適宜使
用し得る。The composition of the present invention contains ultraviolet absorbing 7flI, and benzophenone, penzotriazole, or acrylic compositions may be appropriately used in amounts that do not lose their properties.
本発明の共重合体は、ケトン、エステル、環状エーテル
、芳香族系．？７削、ハロゲン化炭化水素系溶７Ｆｌｌ
等の各種溶剤に溶解可能であるが、ポリカーボネートに
コーティングする場合、失透あるいはクレージングの発
生のない透明な被覆を得るためには、溶剤の選定が持に
１！要でありる。本発明において（ま、忍削として環状
エーテルすなわちエチレンオキシド、テトラヒドロフラ
ン、ジオキサン等を主戒分とする溶削を用いるものであ
り、少なくともこれらの環状エーテルを５０重呈％以上
含有する溶剤系を用いることが重要であり、この範囲未
満で（ｉ透明性の保持が困難である．これらの環状エー
テルの５ち危も好ましいのは基材に対する影響の少ない
テｌ・ラヒドロフランである。The copolymers of the present invention include ketones, esters, cyclic ethers, and aromatic copolymers. ? 7 milling, halogenated hydrocarbon solution 7Fll
However, when coating polycarbonate, in order to obtain a transparent coating without devitrification or crazing, the selection of the solvent is very important! It is essential. In the present invention, (well, cutting using cyclic ethers, ie, ethylene oxide, tetrahydrofuran, dioxane, etc., as the main ingredient) is used, and a solvent system containing at least 50% or more of these cyclic ethers is used. is important, and it is difficult to maintain transparency below this range. Of these cyclic ethers, the most preferred one is terahydrofuran, which has little effect on the substrate.
本発明の組戊物はブライマーなしでそのままボリカーボ
ネートに適用でき、一般におこなわれる各種の手段によ
り、コーティングをおこなうことができる。The composite of the present invention can be directly applied to polycarbonate without a primer, and can be coated by various commonly used methods.
本発明の組戊物には、目的とする耐候性、耐渠品性、透
明性を損わない範囲で安定剤、その池の添加剤を配合す
ることらできる。The composite of the present invention may contain stabilizers and other additives within a range that does not impair the desired weather resistance, drainage resistance, and transparency.
以下、本発明を実施例により具体的に説明−Ｐろ４実禮
南１〜９
オー１〜クレープに１．１．２−１−リクロＬコー１．
２．２−１−リフルオ口エタン（Ｒ−１１３）を１７献
仕込み，攪ｒ’ｌ’ ＋−ながら窒素置換後脱気し、Ｈ
ＦＡ．ＴＦＥ （またはＴｒＦＥ），ＶＤＦを第１表に
示した８′ｌ戊になるように所定量仕込みオー１〜クレ
ープ内の温度を２６℃に調整し 、 重合開始剤１と
してヘフ゜タフ４才ロフ′チリツク＋１’一才０イト′
を所定量窒素で圧入して反応温度を３０℃に保ち６時間
攪拌を続け、重合反応そ？３こなった。反応終了後，残
存ガスをパージ後メタノールを５一役人し、残存ＨＦＡ
をヘミアセクールとして安定１ヒした。オートクレープ
から重合物のＲ−１１３スラリーを抜出し遠心分離機に
より溶媒を分１１し重合物をケーキ状にして取り出し、
メタノールにより攪拌洗浄した。重合物のメタノールス
ラリーを遠心分離し、再びケーキ状にして収り出し、粉
砕機にかけたのち振動流動乾燥にて乾燥したく４０℃３
時間、８０℃５時間）．このようにして調製した共重合
体を用いて紫外線吸収剤、溶媒を第１表に示すように添
加して７１！＋？５１用組成物を調製し、厚さ５ｍｍの
ポリカーボネート板にスプレーにて塗装した。得られた
塗装板を１００℃、６０分間加熱し硬１ヒさせた。原片
と比較した透明性保持率、サンシャインウェザーメータ
ーにて２０００時間の促進耐候試験を行ない透明性保持
率を評価した．また、密着性を評価するため碁盤目試験
をおこなった。Hereinafter, the present invention will be explained in detail with reference to Examples - Pro 4 Jirei Minami 1 to 9 Oh 1 to Crepe 1.1.2-1 - Rikuro L Co 1.
2. Charge 17 hours of 2-1-refluorinated ethane (R-113), and degas after replacing with nitrogen while stirring r'l' +-.
F.A. Add TFE (or TrFE) and VDF to a predetermined amount so as to have a concentration of 8'1 as shown in Table 1. Adjust the temperature in the crepe to 26°C, and add polymerization initiator 1.
Hefty 4-year-old lof'chiritsuku+1'1-year-old 0-ite'
A predetermined amount of nitrogen was pressurized, the reaction temperature was maintained at 30°C, stirring was continued for 6 hours, and the polymerization reaction started. 3 done. After the reaction was completed, the remaining gas was purged and methanol was added to remove the remaining HFA.
He had a stable hit as a hemiasecure. The R-113 slurry of the polymer was taken out from the autoclave, the solvent was separated by centrifugation, and the polymer was taken out in the form of a cake.
It was stirred and washed with methanol. The methanol slurry of the polymer is centrifuged, collected again in the form of a cake, passed through a pulverizer, and dried at 40℃3 using a vibration fluidized dryer.
time, 80°C 5 hours). Using the copolymer thus prepared, an ultraviolet absorber and a solvent were added as shown in Table 1, and 71! +? A composition for No. 51 was prepared and applied to a polycarbonate plate with a thickness of 5 mm by spraying. The obtained coated board was heated at 100° C. for 60 minutes to harden it. The transparency retention rate was compared with the original piece, and the transparency retention rate was evaluated by conducting an accelerated weathering test for 2000 hours using a sunshine weather meter. In addition, a grid test was conducted to evaluate adhesion.
さらに１０％力性ソーダ、１０％硫酸を用いて室温にて
７日間の耐薬品性ｙ：．＠をおこなった。これらの結果
を第１表に示した。Furthermore, chemical resistance y: 7 days at room temperature using 10% hydric soda and 10% sulfuric acid. I did @. These results are shown in Table 1.
［発明の効果］
本発明の組成物は透明性に優れており、またブライマー
なしでポリカーボネーｌ・に密着性よく被覆することが
できるものであり、ポリカーボネートの透明性を損うこ
となく耐候性の向上をはかることができるものである．[Effects of the Invention] The composition of the present invention has excellent transparency and can be coated on polycarbonate with good adhesion without using a brimer, improving weather resistance without impairing the transparency of polycarbonate. It is possible to improve the
Claims (1)
オロオレフィン単量体を必須成分とする共重合体と紫外
線吸収剤および環状エーテルを主成分とする溶剤とを含
有してなることを特徴とするポリカーボネート用被覆組
成物。A coating composition for polycarbonate comprising a copolymer containing vinylidene fluoride, hexafluoroacetone, and a fluoroolefin monomer as essential components, and a solvent containing an ultraviolet absorber and a cyclic ether as a main component. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30367689A JPH03163177A (en) | 1989-11-22 | 1989-11-22 | Coating composition for polycarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30367689A JPH03163177A (en) | 1989-11-22 | 1989-11-22 | Coating composition for polycarbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03163177A true JPH03163177A (en) | 1991-07-15 |
Family
ID=17923893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30367689A Pending JPH03163177A (en) | 1989-11-22 | 1989-11-22 | Coating composition for polycarbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03163177A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0580857A1 (en) * | 1992-02-05 | 1994-02-02 | Toray Industries, Inc. | Primer and double-layer coated article |
-
1989
- 1989-11-22 JP JP30367689A patent/JPH03163177A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0580857A1 (en) * | 1992-02-05 | 1994-02-02 | Toray Industries, Inc. | Primer and double-layer coated article |
| EP0580857A4 (en) * | 1992-02-05 | 1995-06-14 | Toray Industries | Primer and double-layer coated article. |
| US5518818A (en) * | 1992-02-05 | 1996-05-21 | Toray Industries, Inc. | Primer and multilayer coated article |
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