JP2012001590A - Thermoplastic resin composition having modified surface characteristic - Google Patents
Thermoplastic resin composition having modified surface characteristic Download PDFInfo
- Publication number
- JP2012001590A JP2012001590A JP2010136107A JP2010136107A JP2012001590A JP 2012001590 A JP2012001590 A JP 2012001590A JP 2010136107 A JP2010136107 A JP 2010136107A JP 2010136107 A JP2010136107 A JP 2010136107A JP 2012001590 A JP2012001590 A JP 2012001590A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- thermoplastic resin
- resin composition
- fluorine
- copolymer
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
【課題】本発明は、熱可塑性樹脂の離型性、潤滑性、摩耗性等の表面特性を改質するとともにベタツキや白化が見られない樹脂組成物を提供することを目的とする。
【解決手段】パーフルオロアルキルアクリレートとポリエチレングリコールモノ（メタ）クリレートとポリエチレングリコールジ（メタ）クリレートとの共重合体を含有する熱可塑性樹脂組成物。
【選択図】なしAn object of the present invention is to provide a resin composition in which surface properties such as releasability, lubricity, and abrasion of a thermoplastic resin are improved and no stickiness or whitening is observed.
A thermoplastic resin composition comprising a copolymer of perfluoroalkyl acrylate, polyethylene glycol mono (meth) acrylate and polyethylene glycol di (meth) acrylate.
[Selection figure] None
Description
本発明は、疎水性であるパーフルオロ炭化水素基と親水性であるポリオキシエチレン基を同時に有する含フッ素化合物を含有する表面改質された樹脂組成物に関するものである。 The present invention relates to a surface-modified resin composition containing a fluorine-containing compound having simultaneously a perfluorohydrocarbon group that is hydrophobic and a polyoxyethylene group that is hydrophilic.
従来、熱可塑性樹脂の離型性、潤滑性、摩耗性等の表面特性を改質する目的でパーフルオロアルキル基を有する化合物や珪素原子を有する化合物を樹脂の表面改質剤として用いることは公知である。これらの改質剤は樹脂表面に塗布したり、樹脂中に添加する方法で用いられている。
このようなパーフルオロアルキル基を有する含フッ素化合物としては、アルコール類、カルボン酸類、カルボン酸塩類、エステル類、アミド類等の低分子型化合物や、パーフルオロアルキル基を有する重合性モノマーが重合したオリゴマー型やポリマー型が公知である。また、共重合しうる他のモノマーとの共重合体も公知である。具体的には、パーフルオロアルキル基を含有するエステルあるいはアクリレート類のオリゴマー化合物を熱可塑性樹脂に添加配合した樹脂組成物が知られている（例えば、特許文献１、２参照）。このような樹脂組成物において、パーフルオロアルキル基を有する含フッ素化合物はフッ素原子の持つ低表面張力により樹脂組成物内部から表面へ移行し、表面部分に偏在することで樹脂の表面改質の機能を発揮すると言われている。
Conventionally, it is known that a compound having a perfluoroalkyl group or a compound having a silicon atom is used as a resin surface modifier for the purpose of modifying the surface properties of thermoplastic resins such as releasability, lubricity, and abrasion. It is. These modifiers are used by applying to the resin surface or adding to the resin.
As such fluorine-containing compounds having a perfluoroalkyl group, low molecular weight compounds such as alcohols, carboxylic acids, carboxylates, esters, amides, and polymerizable monomers having a perfluoroalkyl group were polymerized. The oligomer type and polymer type are known. Copolymers with other monomers that can be copolymerized are also known. Specifically, a resin composition in which an ester compound or an acrylate oligomer compound containing a perfluoroalkyl group is added to a thermoplastic resin is known (see, for example, Patent Documents 1 and 2). In such a resin composition, the fluorine-containing compound having a perfluoroalkyl group moves from the inside of the resin composition to the surface due to the low surface tension of fluorine atoms, and is unevenly distributed on the surface portion, thereby functioning to modify the surface of the resin. It is said to demonstrate.
これら従来公知の樹脂組成物においては、充分なレベルの表面改質性能を発揮するには多量のフッ素化合物を樹脂に配合する必要があった。このため、樹脂自身の機械的物性や熱的物性の低下や、表面への含フッ素化合物の過剰な移行によるベタツキや白化など表面特性の低下が生ずる場合もある。また、樹脂によっては多量の含フッ素化合物を配合しても充分な効果が得られないという問題点もあった。さらに、含フッ素化合物が比較的高価であることから、経済的観点からも不利であった。 In these conventionally known resin compositions, it was necessary to add a large amount of fluorine compound to the resin in order to exhibit a sufficient level of surface modification performance. For this reason, the mechanical properties and thermal properties of the resin itself may be deteriorated, and surface characteristics may be deteriorated such as stickiness and whitening due to excessive migration of the fluorine-containing compound to the surface. Further, depending on the resin, there is a problem that a sufficient effect cannot be obtained even if a large amount of fluorine-containing compound is added. Furthermore, since the fluorine-containing compound is relatively expensive, it is disadvantageous from an economic viewpoint.
本発明は、熱可塑性樹脂の離型性、潤滑性、摩耗性等の表面特性を改質するとともにベタツキや白化が見られない樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a resin composition in which surface properties such as releasability, lubricity, and wearability of a thermoplastic resin are improved and no stickiness or whitening is observed.
本発明者らは、上記課題を解決するために鋭意検討した結果、疎水性であるパーフルオロ炭化水素基と親水性であるポリオキシエチレン基を同時に有する含フッ素化合物を含有する樹脂組成物が表面特性の改質に効果があることを見出し本発明を完成した。
即ち、本発明。以下の構成からなる。
１．下記単量体（a）、単量体（ｂ）、および単量体（ｃ）を共重合した含フッ素化合物を含有する熱可塑性樹脂組成物。
Ｒ1、R2：水素原子またはメチル基。
ｎ：0〜６の整数。
Ｒｆ：炭素数１〜１８のパーフルオロアルキル基。
Ｘ：−ＣＨ2−ＣＨ2−０−、−ＣＨ2−ＣＨ（ＣＨ3）−０−、またはこれらの組合せ。
ｐ：１〜２０の整数。
２．単量体（a）の割合が１〜８０質量％、単量体（ｂ）の割合が1〜８０質量％、単量体（ｃ）の割合が1〜５０質量％であることを特徴とする前記１に記載の熱可塑性樹脂組成物。
３．共重合した含フッ素化合物の含有量が０．０１〜１０質量％である前記1または２いずれかに記載の熱可塑性樹脂組成物。
As a result of intensive investigations to solve the above problems, the present inventors have found that a resin composition containing a fluorine-containing compound having a hydrophobic perfluorohydrocarbon group and a hydrophilic polyoxyethylene group simultaneously has a surface. The present invention has been completed by finding that it has an effect on property modification.
That is, the present invention. It consists of the following composition.
1. The thermoplastic resin composition containing the fluorine-containing compound which copolymerized the following monomer (a), monomer (b), and monomer (c).
R1, R2: hydrogen atom or methyl group.
n: An integer from 0 to 6.
Rf: a perfluoroalkyl group having 1 to 18 carbon atoms.
X: -CH 2 -CH 2 -0 - , - CH 2 -CH (CH 3) -0- , or a combination thereof.
p: an integer of 1-20.
2. The ratio of the monomer (a) is 1 to 80% by mass, the ratio of the monomer (b) is 1 to 80% by mass, and the ratio of the monomer (c) is 1 to 50% by mass. 2. The thermoplastic resin composition as described in 1 above.
3. 3. The thermoplastic resin composition as described in 1 or 2 above, wherein the content of the copolymerized fluorine-containing compound is 0.01 to 10% by mass.
本発明のパーフルオロ炭化水素基と親水性であるポリオキシエチレン基を同時に有する含フッ素化合物を含有する樹脂組成物は、樹脂成型品の離型性、潤滑性、摩耗性等の表面特性を改質する効果がある。 The resin composition containing a fluorine-containing compound having both a perfluorohydrocarbon group and a hydrophilic polyoxyethylene group according to the present invention improves the surface properties such as releasability, lubricity, and wearability of the resin molded product. There is a quality effect.
本発明で用いられる単量体（ａ）は、以下の（式１）で示される化合物が挙げられる。
Ｒ1：水素原子またはメチル基。
ｎ：０〜６の整数。
Ｒｆ：炭素数１〜１８のパーフルオロアルキル基。
（式１）において、ｎ＝０〜６が好ましく、ｎ＝２が特に好ましい。Ｒｆとしては、炭素数１〜１８のパーフルオロアルキル基が好ましく、炭素数１〜６のパーフルオロアルキル基が特に好ましい。パーフルオロアルキル基は直鎖状および分岐状のどちらでも構わない。
Examples of the monomer (a) used in the present invention include compounds represented by the following (formula 1).
R1: hydrogen atom or methyl group.
n: An integer of 0-6.
Rf: a perfluoroalkyl group having 1 to 18 carbon atoms.
In (Formula 1), n = 0 to 6 is preferable, and n = 2 is particularly preferable. As Rf, a C1-C18 perfluoroalkyl group is preferable and a C1-C6 perfluoroalkyl group is especially preferable. The perfluoroalkyl group may be linear or branched.
単量体（ａ）の具体例としては、
ＣＨ2＝ＣＨＣＯＯＣＦ3
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ3
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ3
ＣＨ2＝ＣＨＣＯＯＣ2Ｈ4Ｃ2Ｆ5
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣ2Ｈ4Ｃ2Ｆ5
ＣＨ2＝ＣＨＣＯＯＣ2Ｈ4Ｃ4Ｆ9
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣ2Ｈ4Ｃ4Ｆ9
ＣＨ2＝ＣＨＣＯＯＣ2Ｈ4Ｃ6Ｆ13
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣ2Ｈ4Ｃ6Ｆ13
ＣＨ2＝ＣＨＣＯＯＣ2Ｈ4Ｃ8Ｆ17
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣ2Ｈ4Ｃ8Ｆ17
ＣＨ2＝ＣＨＣＯＯＣ2Ｈ4（ＣＦ2）6ＣＦ（ＣＦ3）2
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣ2Ｈ4（ＣＦ2）6ＣＦ（ＣＦ3）2
等の直鎖または分岐状のパーフルオロアルキル基を有する（メタ）アクリル酸エステルが挙げられる。これらは、１種のみを単独で、または２種以上を組み合わせて用いることが出来る。
これらのパーフルオロアルキル基を有する（メタ）アクリル酸エステルは共栄社化学社（「ライトエステル」、「ライトアクリレート」シリーズ）等から市販されている。また、市販されているフッ素含有化合物を原料として既知の方法で合成することも出来る。
As a specific example of the monomer (a),
CH 2 = CHCOOCF 3
CH 2 = CHCOOCH 2 CF 3
CH 2 = C (CH 3) COOCH 2 CF 3
CH 2 = CHCOOC 2 H 4 C 2 F 5
CH 2 = C (CH 3) COOC 2 H 4 C 2 F 5
CH 2 = CHCOOC 2 H 4 C 4 F 9
CH 2 = C (CH 3) COOC 2 H 4 C 4 F 9
CH 2 = CHCOOC 2 H 4 C 6 F 13
CH 2 = C (CH 3) COOC 2 H 4 C 6 F 13
CH 2 = CHCOOC 2 H 4 C 8 F 17
CH 2 = C (CH 3) COOC 2 H 4 C 8 F 17
CH 2 = CHCOOC 2 H 4 ( CF 2) 6 CF (CF 3) 2
CH 2 = C (CH 3) COOC 2 H 4 (CF 2) 6 CF (CF 3) 2
(Meth) acrylic acid ester having a linear or branched perfluoroalkyl group such as These can be used alone or in combination of two or more.
These (meth) acrylic acid esters having a perfluoroalkyl group are commercially available from Kyoeisha Chemical Co., Ltd. ("light ester", "light acrylate" series). It can also be synthesized by a known method using a commercially available fluorine-containing compound as a raw material.
本発明で用いられる単量体（ｂ）は、以下の（式２）で示される化合物が挙げられる。
Ｒ1：水素原子またはメチル基。
X：−ＣＨ2−ＣＨ2−０−、−ＣＨ2−ＣＨ（ＣＨ3）−０−、またはこれらの組合せ。
ｐ：１〜２０の整数。
（式２）において、Xは−ＣＨ2−ＣＨ2−０−、−ＣＨ2−ＣＨ（ＣＨ3）−０−、またはこれらの組合せが好ましい。ｐ＝１〜２０が好ましい。
Examples of the monomer (b) used in the present invention include compounds represented by the following (formula 2).
R1: hydrogen atom or methyl group.
X: -CH 2 -CH 2 -0 - , - CH 2 -CH (CH 3) -0- , or a combination thereof.
p: an integer of 1-20.
In (Formula 2), X is preferably —CH 2 —CH 2 —0—, —CH 2 —CH (CH 3 ) —0—, or a combination thereof. p = 1-20 is preferable.
単量体（ｂ）の具体例としては、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2ＯＨ
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2ＯＨ
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ（ＣＨ3）ＯＨ
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ（ＣＨ3）ＯＨ
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＯＨ
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＯＨ
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ（ＣＨ3）ＯＣＨ2ＣＨ（ＣＨ3）ＯＨ
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ（ＣＨ3）ＯＣＨ2ＣＨ（ＣＨ3）ＯＨ
ＣＨ2＝ＣＨＣＯＯ（ＣＨ2ＣＨ2Ｏ）8Ｈ
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2ＣＨ2Ｏ）8Ｈ
ＣＨ2＝ＣＨＣＯＯ（ＣＨ2ＣＨ（ＣＨ3）Ｏ）8Ｈ
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2ＣＨ（ＣＨ3）Ｏ）8Ｈ
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ（ＣＨ3）ＯＨ
等が挙げられる。これらは、１種のみを単独で、または２種以上を組み合わせて用いることが出来る。
As a specific example of the monomer (b),
CH 2 = CHCOOCH 2 CH 2 OH
CH 2 = C (CH 3) COOCH 2 CH 2 OH
CH 2 = CHCOOCH 2 CH (CH 3 ) OH
CH 2 = C (CH 3) COOCH 2 CH (CH 3) OH
CH 2 = CHCOOCH 2 CH 2 OCH 2 CH 2 OH
CH 2 = C (CH 3) COOCH 2 CH 2 OCH 2 CH 2 OH
CH 2 = CHCOOCH 2 CH (CH 3) OCH 2 CH (CH 3) OH
CH 2 = C (CH 3) COOCH 2 CH (CH 3) OCH 2 CH (CH 3) OH
CH 2 = CHCOO (CH 2 CH 2 O) 8 H
CH 2 = C (CH 3) COO (CH 2 CH 2 O) 8 H
CH 2 = CHCOO (CH 2 CH (CH 3) O) 8 H
CH 2 = C (CH 3) COO (CH 2 CH (CH 3) O) 8 H
CH 2 = CHCOOCH 2 CH 2 OCH 2 CH (CH 3) OH
Etc. These can be used alone or in combination of two or more.
本発明で用いられる単量体（ｃ）は、以下の（式３）で示される化合物が挙げられる。
Ｒ1、R2：水素原子またはメチル基。
X：−ＣＨ2−ＣＨ2−０−、−ＣＨ2−ＣＨ（ＣＨ3）−０−、またはこれらの組合せ。
ｐ：１〜２０の整数。
単量体（ｃ）において、Xは−ＣＨ2−ＣＨ2−０−、−ＣＨ2−ＣＨ（ＣＨ3）−０−、またはこれらの組合せが好ましい。ｐ＝１〜２０が好ましい。
単量体（ｃ）の具体例としては、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ（ＣＨ3）ＯＣＯＣＨ＝ＣＨ2
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ（ＣＨ3）ＯＣＯＣ（ＣＨ3）＝ＣＨ2
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ（ＣＨ3）ＯＣＨ2ＣＨ（ＣＨ3）ＯＣＯＣＨ＝ＣＨ2
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ（ＣＨ3）ＯＣＨ2ＣＨ（ＣＨ3）ＯＣＯＣ（ＣＨ3）＝ＣＨ2
ＣＨ2＝ＣＨＣＯＯ（ＣＨ2ＣＨ2Ｏ）8ＣＯＣＨ＝ＣＨ2
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2ＣＨ2Ｏ）8ＣＯＣ（ＣＨ3）＝ＣＨ2
ＣＨ2＝ＣＨＣＯＯ（ＣＨ2ＣＨ（ＣＨ3）Ｏ）8ＣＯＣＨ＝ＣＨ2
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2ＣＨ（ＣＨ3）Ｏ）8ＣＯＣ（ＣＨ3）＝ＣＨ2
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ（ＣＨ3）ＯＣＯＣＨ＝ＣＨ2
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ（ＣＨ3）ＯＣＯＣ（ＣＨ3）＝ＣＨ2
等が挙げられる。これらは、１種のみを単独で、または２種以上を組み合わせて用いることが出来る。
Examples of the monomer (c) used in the present invention include compounds represented by the following (formula 3).
R1, R2: hydrogen atom or methyl group.
X: -CH 2 -CH 2 -0 - , - CH 2 -CH (CH 3) -0- , or a combination thereof.
p: an integer of 1-20.
In the monomer (c), X is -CH 2 -CH 2 -0 -, - CH 2 -CH (CH 3) -0-, or a combination thereof are preferred. p = 1-20 is preferable.
Specific examples of the monomer (c) include CH 2 ═CHCOOCH 2 CH 2 OCOCH═CH 2.
CH 2 = C (CH 3) COOCH 2 CH 2 OCOC (CH 3) = CH 2
CH 2 = CHCOOCH 2 CH (CH 3) OCOCH = CH 2
CH 2 = C (CH 3) COOCH 2 CH (CH 3) OCOC (CH 3) = CH 2
CH 2 = CHCOOCH 2 CH 2 OCH 2 CH 2 OCOCH = CH 2
CH 2 = C (CH 3) COOCH 2 CH 2 OCH 2 CH 2 OCOC (CH 3) = CH 2
CH 2 = CHCOOCH 2 CH (CH 3) OCH 2 CH (CH 3) OCOCH = CH 2
CH 2 = C (CH 3) COOCH 2 CH (CH 3) OCH 2 CH (CH 3) OCOC (CH 3) = CH 2
CH 2 = CHCOO (CH 2 CH 2 O) 8 COCH = CH 2
CH 2 = C (CH 3) COO (CH 2 CH 2 O) 8 COC (CH 3) = CH 2
CH 2 = CHCOO (CH 2 CH (CH 3 ) O) 8 COCH = CH 2
CH 2 = C (CH 3) COO (CH 2 CH (CH 3) O) 8 COC (CH 3) = CH 2
CH 2 = CHCOOCH 2 CH 2 OCH 2 CH (CH 3) OCOCH = CH 2
CH 2 = CHCOOCH 2 CH 2 OCH 2 CH (CH 3) OCOC (CH 3) = CH 2
Etc. These can be used alone or in combination of two or more.
本発明に用いられる共重合体化合物には、これら単量体（a）（b）（c）3種の必須単量体のほかに、これらと共重合し得る単量体を、本発明に用いられる共重合した含フッ素化合物に対して質量比の５０質量％を超えない範囲で共重合することも出来る。 The copolymer compound used in the present invention includes, in addition to these three essential monomers (a), (b), and (c), monomers that can be copolymerized with these monomers in the present invention. Copolymerization can also be performed within a range not exceeding 50% by mass of the mass ratio of the copolymerized fluorine-containing compound used.
上記、単量体（a）（b）（c）と共重合し得る単量体としては、例えば、メチレン、酢酸ビニル、塩化ビニル、フッ化ビニル、ハロゲン化ビニル、スチレン、メチルスチレン、（メタ）アクリル酸とそのエステル、(メタ)アクリルアミド系単量体、(メタ)アリル単量体等が挙げられる。上記他の単量体の共重合化合物における比率は０〜４０質量％が好ましい。 Examples of the monomer that can be copolymerized with the monomers (a), (b), and (c) include methylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl halide, styrene, methylstyrene, (meta ) Acrylic acid and its esters, (meth) acrylamide monomers, (meth) allyl monomers and the like. The ratio of the other monomer in the copolymer compound is preferably 0 to 40% by mass.
一般に熱可塑性樹脂への配合において含フッ素化合物中のフッ素含有量を高くしすぎると樹脂への溶解度が極端に低下する。そのため使用する樹脂に応じてこれらの材料の比率を調整する必要がある。 Generally, when the fluorine content in the fluorine-containing compound is too high in the blending with a thermoplastic resin, the solubility in the resin is extremely lowered. Therefore, it is necessary to adjust the ratio of these materials according to the resin used.
本発明に用いられる含フッ素化合物の分子量は、目的とする表面改質特性の改質効果および熱可塑性樹脂の種類により異なるが、１０００〜２００００が好ましい。分子量の調節は、市販の重合連鎖移動剤（チオール、メルカプタン、α―メチルスチレン、四塩化炭素等）により容易に行うことができる。 The molecular weight of the fluorine-containing compound used in the present invention varies depending on the modification effect of the target surface modification characteristics and the type of the thermoplastic resin, but is preferably 1000 to 20000. The molecular weight can be easily adjusted with a commercially available polymerization chain transfer agent (thiol, mercaptan, α-methylstyrene, carbon tetrachloride, etc.).
本発明に用いられる含フッ素化合物の熱可塑性樹脂に対する配合量は、対象とする樹脂、表面特性の改質の目的により適宜選択されるが、おおよそ０．０１〜１０質量％である。特に、オレフィン系樹脂等の非極性樹脂に離型性を目的として配合する場合には成形用樹脂に対して１質量％未満の非常に少ない添加量で効果が期待できる。
本発明に関わる含フッ素化合物を配合した熱可塑性樹脂は、用途は特に限定しないが、離型性、潤滑性、耐摩耗性等の優れた表面を形成する。
Although the compounding quantity with respect to the thermoplastic resin of the fluorine-containing compound used for this invention is suitably selected by the objective of modification | reformation of target resin and surface characteristics, it is about 0.01-10 mass%. In particular, when blended with a nonpolar resin such as an olefin resin for the purpose of releasability, the effect can be expected with a very small addition amount of less than 1% by mass with respect to the molding resin.
The use of the thermoplastic resin in which the fluorine-containing compound according to the present invention is blended is not particularly limited, but forms a surface excellent in releasability, lubricity, wear resistance and the like.
本発明の疎水性であるパーフルオロ炭化水素基と親水性であるポリオキシエチレン基を同時に有する含フッ素化合物と熱可塑性樹脂を溶融ブレンドする方法としては、例えば、一軸押出機、二軸押出機、オープンロール、ニーダー、ミキサー等いずれも用いることが出来る。実際の配合方法としては、直接成形用樹脂に添加して混練する方法、または予めマスターバッチを作製しておき、次いでマスターバッチを成形用樹脂に添加して均一に混合する方法が挙げられる。 Examples of the method for melt blending a fluorine-containing compound having a perfluorohydrocarbon group that is hydrophobic and a polyoxyethylene group that is hydrophilic and a thermoplastic resin of the present invention include, for example, a single screw extruder, a twin screw extruder, Any of open roll, kneader, mixer and the like can be used. Examples of the actual blending method include a method of directly adding to the molding resin and kneading, or a method of preparing a master batch in advance and then adding the master batch to the molding resin and mixing uniformly.
本発明に用いられる熱可塑性樹脂としてはポリオレフィン、ポリ塩化ビニル、ポリスチレン、アクリル樹脂、ポリエステル、ポリカーボネート、ポリアミド等の一般的な熱可塑性樹脂を挙げることが出来るが、本発明は特にポリオレフィンの表面特性の改質のために有効である。 Examples of the thermoplastic resin used in the present invention include general thermoplastic resins such as polyolefin, polyvinyl chloride, polystyrene, acrylic resin, polyester, polycarbonate, and polyamide. Effective for reforming.
ポリオレフィンとしては、ポリエチレン、ポリプロピレン、エチレン−プロピレンランダム共重合体、エチレン−プロピレンブロック共重合体、エチレンまたはプロピレンとα−オレフィンとの共重合体、ポリブタジエン、ポリイソプレン、エチレン−アクリル酸エステル共重合体、エチレン−酢ビ共重合体、塩素化ポリエチレン、塩素化ポリプロピレン、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、ブタジエン−スチレン−アクリロニトリル共重合体等が挙げられるが、これらに限定されるものではない。 Polyolefins include polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene or a copolymer of propylene and α-olefin, polybutadiene, polyisoprene, and ethylene-acrylic acid ester copolymer. , Ethylene-vinyl acetate copolymer, chlorinated polyethylene, chlorinated polypropylene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-styrene-acrylonitrile copolymer, and the like. It is not a thing.
こうして得られた熱可塑性樹脂組成物を押出成形、射出成形、圧縮成形、フィルム化等公知の方法により成形することにより表面特性の改質された成形体を得ることが出来る。表面特性の改質の効果を充分に発揮させるためには、成形後更に加熱処理することで配合された該含フッ素化合物は表面への移行促進がなされる。
加熱処理は、例えば成形体を加熱オーブン中に所定時間放置することにより行われるが、その温度は５０〜１３０℃である。
By molding the thermoplastic resin composition thus obtained by a known method such as extrusion molding, injection molding, compression molding, or film formation, a molded body with improved surface characteristics can be obtained. In order to sufficiently exhibit the effect of modifying the surface characteristics, the fluorine-containing compound added by further heat treatment after molding promotes the transition to the surface.
The heat treatment is performed, for example, by leaving the molded body in a heating oven for a predetermined time, and the temperature is 50 to 130 ° C.
また、本発明の熱可塑性樹脂組成物には、該含フッ素化合物と同時にフィラー、顔料、帯電防止剤、滑剤、防曇剤等の添加剤を効果の損なわない範囲で加えることが可能である。 In addition, the thermoplastic resin composition of the present invention can contain additives such as fillers, pigments, antistatic agents, lubricants, antifogging agents and the like in addition to the fluorine-containing compounds as long as the effects are not impaired.
以下、実施例を示し、本発明を具体的に説明するが、本発明はこれら実施例により制限されるものではない。
以下の合成手法にて、共重合体を得た。
EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not restrict | limited by these Examples.
A copolymer was obtained by the following synthesis method.
[共重合体１]
５００ｍｌの四つ口フラスコにパーフルオロアルキルアクリレート{ＣＨ2＝ＣＨＣＯＯＣ2Ｈ4Ｃ6Ｆ13}を２５ｇ、ポリエチレングリコールモノアクリレート{ＣＨ2＝ＣＨＣＯＯ（ＣＨ2ＣＨ2Ｏ）8Ｈ}５０ｇ、ポリエチレングリコールジメタクリレート{ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2ＣＨ2Ｏ）8ＣＯＣ（ＣＨ3）＝ＣＨ2}を２５ｇ、溶媒（トリフルオロトルエン）を１００ｇ、重合開始剤{２，２‘−アゾビス（２，４−ジメチルバレロニトリル）}を１ｇ、連鎖移動剤（ラウリルメルカプタン）を３．８ｇ加え、窒素気流下、攪拌しながら６０℃で5時間重合させた。
その後、大量のメタノールに投入し、沈殿物を濾別後減圧乾燥させて目的の化合物を得た。収量は、９５ｇであった。
[Copolymer 1]
In a 500 ml four-necked flask, 25 g of perfluoroalkyl acrylate {CH 2 ═CHCOOC 2 H 4 C 6 F 13 }, polyethylene glycol monoacrylate {CH 2 ═CHCOO (CH 2 CH 2 O) 8 H} 50 g, polyethylene glycol 25 g of dimethacrylate {CH 2 ═C (CH 3 ) COO (CH 2 CH 2 O) 8 COC (CH 3 ) ═CH 2 }, 100 g of solvent (trifluorotoluene), polymerization initiator {2, 2′- 1 g of azobis (2,4-dimethylvaleronitrile)} and 3.8 g of a chain transfer agent (lauryl mercaptan) were added, and polymerization was performed at 60 ° C. for 5 hours with stirring under a nitrogen stream.
Thereafter, it was poured into a large amount of methanol, and the precipitate was filtered off and dried under reduced pressure to obtain the desired compound. Yield was 95 g.
[共重合体２]
使用する単量体原料を、パーフルオロアルキルアクリレート{ＣＨ2＝ＣＨＣＯＯＣ2Ｈ4Ｃ6Ｆ13}を５０ｇ、ポリエチレングリコールモノアクリレート{ＣＨ2＝ＣＨＣＯＯ（ＣＨ2ＣＨ2Ｏ）8Ｈ}４０ｇ、ポリエチレングリコールジメタクリレート{ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2ＣＨ2Ｏ）8ＣＯＣ（ＣＨ3）＝ＣＨ2}を１０ｇとした以外は、共重合体１の合成例と同様に重合させ目的の化合物を得た。収量は９４ｇであった。
[Copolymer 2]
As the monomer raw material to be used, 50 g of perfluoroalkyl acrylate {CH 2 ═CHCOOC 2 H 4 C 6 F 13 }, polyethylene glycol monoacrylate {CH 2 ═CHCOO (CH 2 CH 2 O) 8 H} 40 g, polyethylene Glycol dimethacrylate {CH 2 ═C (CH 3 ) COO (CH 2 CH 2 O) 8 COC (CH 3 ) ═CH 2 } was polymerized in the same manner as in the synthesis example of copolymer 1 except that 10 g was used. To give a compound. The yield was 94g.
[共重合体３]
使用する単量体原料を、パーフルオロアルキルアクリレート{ＣＨ2＝ＣＨＣＯＯＣ2Ｈ4Ｃ6Ｆ13}を５０ｇ、ポリエチレングリコールモノアクリレート{ＣＨ2＝ＣＨＣＯＯ（ＣＨ2ＣＨ2Ｏ）8Ｈ}４９ｇ、ポリエチレングリコールジメタクリレート{ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2ＣＨ2Ｏ）8ＣＯＣ（ＣＨ3）＝ＣＨ2}を１ｇとした以外は、重合体１の合成例と同様に重合させ目的の化合物を得た。収量は９５ｇであった。
[Copolymer 3]
The monomer raw material used is 50 g of perfluoroalkyl acrylate {CH 2 ═CHCOOC 2 H 4 C 6 F 13 }, polyethylene glycol monoacrylate {CH 2 ═CHCOO (CH 2 CH 2 O) 8 H} 49 g, polyethylene Glycol dimethacrylate {CH 2 ═C (CH 3 ) COO (CH 2 CH 2 O) 8 COC (CH 3 ) ═CH 2 } was polymerized in the same manner as in the synthesis example of polymer 1 except that 1 g was used. A compound was obtained. The yield was 95g.
[共重合体４]
使用する単量体原料を、パーフルオロアルキルアクリレート｛ＣＨ2＝ＣＨＣＯＯＣ2Ｈ4Ｃ6Ｆ13｝を１０ｇ、ポリエチレングリコールモノアクリレート{ＣＨ2＝ＣＨＣＯＯ（ＣＨ2ＣＨ2Ｏ）8Ｈ}８０ｇ、ポリエチレングリコールジメタクリレート{ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2ＣＨ2Ｏ）8ＣＯＣ（ＣＨ3）＝ＣＨ2}を１０ｇとした以外は、重合体１の合成例と同様に重合させ目的の化合物を得た。収量は９５ｇであった。
[Copolymer 4]
As the monomer raw material to be used, 10 g of perfluoroalkyl acrylate {CH 2 ═CHCOOC 2 H 4 C 6 F 13 }, 80 g of polyethylene glycol monoacrylate {CH 2 ═CHCOO (CH 2 CH 2 O) 8 H}, polyethylene Glycol dimethacrylate {CH 2 ═C (CH 3 ) COO (CH 2 CH 2 O) 8 COC (CH 3 ) ═CH 2 } was polymerized in the same manner as in the synthesis example of polymer 1 except that 10 g was used. A compound was obtained. The yield was 95g.
[共重合体５]
使用する単量体原料を、パーフルオロアルキルアクリレート｛ＣＨ2＝ＣＨＣＯＯＣ2Ｈ4Ｃ6Ｆ13｝を８０ｇ、ポリエチレングリコールモノアクリレート{ＣＨ2＝ＣＨＣＯＯ（ＣＨ2ＣＨ2Ｏ）8Ｈ}１０ｇ、ポリエチレングリコールジメタクリレート{ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2ＣＨ2Ｏ）8ＣＯＣ（ＣＨ3）＝ＣＨ2}を１０ｇとした以外は、重合体１の合成例と同様に重合させ目的の化合物を得た。収量は９４ｇであった。
[Copolymer 5]
As the monomer raw material to be used, 80 g of perfluoroalkyl acrylate {CH 2 ═CHCOOC 2 H 4 C 6 F 13 }, polyethylene glycol monoacrylate {CH 2 ═CHCOO (CH 2 CH 2 O) 8 H} 10 g, polyethylene Glycol dimethacrylate {CH 2 ═C (CH 3 ) COO (CH 2 CH 2 O) 8 COC (CH 3 ) ═CH 2 } was polymerized in the same manner as in the synthesis example of polymer 1 except that 10 g was used. A compound was obtained. The yield was 94g.
[共重合体６]
使用する単量体原料を、パーフルオロアルキルアクリレート｛ＣＨ2＝ＣＨＣＯＯＣ2Ｈ4Ｃ6Ｆ13｝を５０ｇ、ポリエチレングリコールモアタクリレート{ＣＨ2＝ＣＨＣＯＯ（ＣＨ2ＣＨ2Ｏ）8Ｈ}５０ｇとした以外は、合成例１と同様に目的の化合物を得た。収量は９４ｇであった。
[Copolymer 6]
The monomer raw material used, the perfluoroalkyl acrylate {CH 2 = CHCOOC 2 H 4 C 6 F 13} 50g, polyethylene glycol mower Takuri rate {CH 2 = CHCOO (CH 2 CH 2 O) 8 H} and 50g The target compound was obtained in the same manner as in Synthesis Example 1 except that. The yield was 94g.
[共重合体７]
使用する単量体原料を、パーフルオロアルキルアクリレート｛ＣＨ2＝ＣＨＣＯＯＣ2Ｈ4Ｃ6Ｆ13｝を１００ｇとした以外は、重合体１の合成例と同様に重合させ目的の化合物を得た。収量は９６ｇであった。
[Copolymer 7]
The target compound was obtained by polymerizing in the same manner as in Synthesis Example of Polymer 1 except that the monomer raw material used was 100 g of perfluoroalkyl acrylate {CH 2 ═CHCOOC 2 H 4 C 6 F 13 }. The yield was 96g.
[共重合体８]
使用する単量体原料を、ポリエチレングリコールモノアクリレート{ＣＨ2＝ＣＨＣＯＯ（ＣＨ2ＣＨ2Ｏ）8Ｈ}５０ｇ、ポリエチレングリコールジメタクリレート{ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2ＣＨ2Ｏ）8ＣＯＣ（ＣＨ3）＝ＣＨ2}を５０ｇとした以外は、重合体１の合成例と同様に重合させ目的の化合物を得た。収量は９６ｇであった。
[Copolymer 8]
The monomer raw materials to be used are polyethylene glycol monoacrylate {CH 2 ═CHCOO (CH 2 CH 2 O) 8 H} 50 g, polyethylene glycol dimethacrylate {CH 2 ═C (CH 3 ) COO (CH 2 CH 2 O) Polymerization was carried out in the same manner as in Synthesis Example of Polymer 1 except that 50 g of 8 COC (CH 3 ) ═CH 2 } was changed to obtain the target compound. The yield was 96g.
[離型試験方法]
表１に示した比率で上記共重合体を配合したポリプロピレン樹脂（プライムポリマー社製 プライムポリプロＪ−１０５Ｇ ホモポリマー、ＭＩ＝９）を二軸押出機（サーモプラスチックス工業社製 ＴＰ−２０−Ｔ）にて混練、ストランド状に押出した後ストランドカッターにてカッティングして試験用コンパウンドを得た。次いで、離型力を測定できるカップ離型力測定器付き金型を備えた射出成形機（東芝機械社製 ＩＳ５５ＥＰＮ）にて、成形したカップ（内径８０ｍｍ×高さ５０ｍｍ）を金型から引き離す時の離型力（ｋｇ）を測定した。結果を表１に示す。
射出成形条件 シリンダー温度：
Ｃ１ Ｃ２ Ｃ３ ヘッド 金型
１９０℃ ２２０℃ ２４０℃ ２４０℃ ４０℃
スクリュー回転数：８０ｒｐｍ
射出圧：８００ｋｇ／ｃｍ2
[Release test method]
Polypropylene resin (Prime Polypro J-105G homopolymer, MI = 9, manufactured by Prime Polymer Co., Ltd.) blended with the above copolymer at the ratio shown in Table 1 was twin-screw extruder (TP-20-T manufactured by Thermo Plastics Co., Ltd.) ) And extruded into a strand shape, and then cut with a strand cutter to obtain a test compound. Next, when the molded cup (inner diameter 80 mm × height 50 mm) is pulled away from the mold with an injection molding machine (IS55EPN manufactured by Toshiba Machine Co., Ltd.) equipped with a mold with a cup mold release force measuring device that can measure the mold release force. The mold release force (kg) was measured. The results are shown in Table 1.
Injection molding conditions Cylinder temperature:
C1 C2 C3 Head Mold
190 ° C 220 ° C 240 ° C 240 ° C 40 ° C
Screw rotation speed: 80rpm
Injection pressure: 800kg / cm2
＜評価基準＞
＊離型力の数値の小さい方が、金型から成形品を剥がしやすく離型性に優れる。
＊成形品の表面観察：射出成形したカップの表面を肉眼で観察し、添加した共重合体が表面へ滲み出してベタツキがあるかを評価した。結果を表１に示す。
<Evaluation criteria>
* The smaller the value of the release force, the easier it is to peel off the molded product from the mold and the better the release property.
* Surface observation of molded product: The surface of the injection-molded cup was observed with the naked eye, and it was evaluated whether the added copolymer oozed out to the surface and was sticky. The results are shown in Table 1.
本発明品は、特定の単量体を共重合した含フッ素化合物を熱可塑性樹脂に配合した組成物であり、この組成物を成形するとき成形時の離型性能に優れる成形体を得ることが出来る。更に、表面潤滑性や耐磨耗性を必要とする成形品に利用することが出来る。 The product of the present invention is a composition in which a fluorine-containing compound copolymerized with a specific monomer is blended in a thermoplastic resin, and when this composition is molded, a molded product having excellent mold release performance can be obtained. I can do it. Furthermore, it can be used for molded products that require surface lubricity and wear resistance.
Claims (3)
Ｒ1、R2：水素原子またはメチル基。
ｎ：0〜６の整数。
Ｒｆ：炭素数１〜１８のパーフルオロアルキル基。
Ｘ：−ＣＨ2−ＣＨ2−０−、−ＣＨ2−ＣＨ（ＣＨ3）−０−、またはこれらの組合せ。
ｐ：１〜２０の整数。 The thermoplastic resin composition containing the fluorine-containing compound which copolymerized the following monomer (a), monomer (b), and monomer (c).
R1, R2: hydrogen atom or methyl group.
n: An integer from 0 to 6.
Rf: a perfluoroalkyl group having 1 to 18 carbon atoms.
X: -CH 2 -CH 2 -0 - , - CH 2 -CH (CH 3) -0- , or a combination thereof.
p: an integer of 1-20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010136107A JP5399981B2 (en) | 2010-06-15 | 2010-06-15 | Thermoplastic resin composition with modified surface properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010136107A JP5399981B2 (en) | 2010-06-15 | 2010-06-15 | Thermoplastic resin composition with modified surface properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012001590A true JP2012001590A (en) | 2012-01-05 |
| JP5399981B2 JP5399981B2 (en) | 2014-01-29 |
Family
ID=45533944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010136107A Expired - Fee Related JP5399981B2 (en) | 2010-06-15 | 2010-06-15 | Thermoplastic resin composition with modified surface properties |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5399981B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200010331A (en) | 2017-06-30 | 2020-01-30 | 후지필름 가부시키가이샤 | Composition, Optical Film, Polarizing Plate, Display Device, and Manufacturing Method of Composition |
| EP3889231A4 (en) * | 2018-11-30 | 2022-08-17 | Daikin Industries, Ltd. | ANTI-FOG COATING COMPOSITION |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5155391A (en) * | 1974-09-17 | 1976-05-15 | Nat Res Dev | HIDOROGER UKEISEI HORIMAA |
| JPS57211119A (en) * | 1981-06-23 | 1982-12-24 | Hoya Corp | Contamination resistant soft contact lens |
| JPS61103912A (en) * | 1984-10-25 | 1986-05-22 | Nitto Electric Ind Co Ltd | Aqueous emulsion of resin |
| WO2009057716A1 (en) * | 2007-11-01 | 2009-05-07 | Asahi Glass Company, Limited | Fluorinated copolymer, water-proof and oil-proof agent composition, and their production methods |
| JP2009108296A (en) * | 2007-10-11 | 2009-05-21 | Yunimatekku Kk | Water and oil repellent |
| WO2009123051A1 (en) * | 2008-03-31 | 2009-10-08 | ダイキン工業株式会社 | Fluorine-containing copolymer, paper processing agent, and coating film-forming agent for cosmetic preparation |
-
2010
- 2010-06-15 JP JP2010136107A patent/JP5399981B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5155391A (en) * | 1974-09-17 | 1976-05-15 | Nat Res Dev | HIDOROGER UKEISEI HORIMAA |
| JPS57211119A (en) * | 1981-06-23 | 1982-12-24 | Hoya Corp | Contamination resistant soft contact lens |
| JPS61103912A (en) * | 1984-10-25 | 1986-05-22 | Nitto Electric Ind Co Ltd | Aqueous emulsion of resin |
| JP2009108296A (en) * | 2007-10-11 | 2009-05-21 | Yunimatekku Kk | Water and oil repellent |
| WO2009057716A1 (en) * | 2007-11-01 | 2009-05-07 | Asahi Glass Company, Limited | Fluorinated copolymer, water-proof and oil-proof agent composition, and their production methods |
| WO2009123051A1 (en) * | 2008-03-31 | 2009-10-08 | ダイキン工業株式会社 | Fluorine-containing copolymer, paper processing agent, and coating film-forming agent for cosmetic preparation |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200010331A (en) | 2017-06-30 | 2020-01-30 | 후지필름 가부시키가이샤 | Composition, Optical Film, Polarizing Plate, Display Device, and Manufacturing Method of Composition |
| US11613596B2 (en) | 2017-06-30 | 2023-03-28 | Fujifilm Corporation | Composition, optical film, polarizing plate, display device, and method for producing composition |
| EP3889231A4 (en) * | 2018-11-30 | 2022-08-17 | Daikin Industries, Ltd. | ANTI-FOG COATING COMPOSITION |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5399981B2 (en) | 2014-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101544232B1 (en) | Powdery processing aid for polyolefin-based resins, method of producing the same, resin composition and molded article | |
| CN105745239B (en) | Polymer, method for producing the same, and molded article | |
| TW201229066A (en) | Water-soluble or water-disintegrable copolymer | |
| JP5554566B2 (en) | Dendritic polymer and method for producing the same | |
| AU653085B2 (en) | Copolymers and their use as lubricants and release agents for processing thermoplastics | |
| JP5668474B2 (en) | Additive for thermoplastic resin and method for producing the same, thermoplastic resin composition and molded article | |
| JP5399981B2 (en) | Thermoplastic resin composition with modified surface properties | |
| JP5206093B2 (en) | Granular additive composition | |
| JPS6365702B2 (en) | ||
| JP2001518950A (en) | Transparent, impact-resistant, thermoplastic molding composition | |
| TWI481651B (en) | (meth) acrylate-styrene based copolymer composition and the molding product thereof | |
| JPH05209129A (en) | Releasing agent for molded article of synthetic resin in mold and method for providing releasability to molded article of synthetic resin in mold | |
| JPH09143326A (en) | Polyvinyl chloride resin composition | |
| WO2000042104A1 (en) | Modifier for methacrylic resin | |
| EP0459587A2 (en) | Polyketone polymer compositions | |
| JP3105366B2 (en) | Method for imparting release property to molded article of thermoplastic polyester resin using mold release agent for molding in synthetic resin mold and thermoplastic polyester resin composition | |
| JP2009067930A (en) | Vinyl chloride-based sheet | |
| JP4752141B2 (en) | Resin composition | |
| CA2033158A1 (en) | Compositions containing ethylene copolymers | |
| JPH0250137B2 (en) | ||
| CN115702175A (en) | Fluorine-containing copolymer, thermoplastic resin composition, molded article, and method for producing molded article | |
| JP3549665B2 (en) | Vinyl chloride resin composition | |
| JP2016216580A (en) | Vinyl chloride resin composition and molded article | |
| JP2014001370A (en) | Processing aid for polyolefin resin, polyolefin resin composition and molded article | |
| JP2013023540A (en) | Resin powder composition for slush molding |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120328 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130529 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130611 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130808 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131022 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131024 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5399981 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313532 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |