JP4657499B2 - Plasticizer for polyester resin - Google Patents
Plasticizer for polyester resin Download PDFInfo
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- JP4657499B2 JP4657499B2 JP2001178171A JP2001178171A JP4657499B2 JP 4657499 B2 JP4657499 B2 JP 4657499B2 JP 2001178171 A JP2001178171 A JP 2001178171A JP 2001178171 A JP2001178171 A JP 2001178171A JP 4657499 B2 JP4657499 B2 JP 4657499B2
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- Prior art keywords
- polyester resin
- amorphous polyester
- plasticizer
- component
- acid
- 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.)
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Description
【０００１】
【発明の属する技術分野】
本発明は、非晶性ポリエステル樹脂用可塑剤、並びに柔軟性及び透明性に優れた非晶性ポリエステル樹脂組成物に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
明確な融点を持たない非晶性ポリエステル樹脂が、各種フィルム、シートの材料として用いられている。この非晶性ポリエステル樹脂は、通常のポリエステル樹脂に比べ加工性が良好で、カレンダー加工が可能であるが、折り曲げた時などに白化し易いという欠点を有し、透明性と柔軟性が共に満足できるものは得られていない。
【０００３】
本発明の課題は、非晶性ポリエステル樹脂の透明性を阻害させずに柔軟性を付与することができる非晶性ポリエステル樹脂用可塑剤、並びに柔軟性及び透明性に優れた非晶性ポリエステル樹脂組成物を提供することにある。
【０００４】
【課題を解決するための手段】
本発明は、芳香族スルホンアミドのＮ−アルキル化物（アルキル基の炭素数１〜２２）からなる非晶性ポリエステル樹脂用可塑剤、及びこの可塑剤と、非晶性ポリエステル樹脂とを含有する非晶性ポリエステル樹脂組成物を提供する。
【０００５】
【発明の実施の形態】
［芳香族スルホンアミドのＮ−アルキル化物］
本発明の可塑剤である芳香族スルホンアミドのＮ−アルキル化物を構成する芳香族スルホンアミドとしては、ベンゼンスルホンアミド、ナフタレンスルホンアミド等が挙げられる。また、Ｎ−アルキル化物のアルキル基の炭素数は、非晶性ポリエステル樹脂との相溶性の観点から、１〜２２、好ましくは１〜１８である。
【０００６】
芳香族スルホンアミドのＮ−アルキル化物として特に好ましいものは、一般式（Ｉ）で表されるＮ−アルキルベンゼンスルホンアミドである。
【０００７】
【化２】
（式中、Ｒは炭素数１〜２２の直鎖又は分岐鎖アルキル基を示す。）
一般式（Ｉ）において、非晶性ポリエステル樹脂との相溶性の観点から、Ｒは炭素数１〜１８の直鎖又は分岐鎖アルキル基が好ましく、炭素数２〜６のアルキル基が最も好ましい。
【０００９】
［非晶性ポリエステル樹脂］
本発明に係わる非晶性ポリエステル樹脂とは、明確な融点を持たないポリエステル樹脂であり、通常のポリエステル樹脂に比べ加工性が良好で、カレンダー加工が可能である。
【００１０】
非晶性ポリエステル樹脂の具体例としては、（Ａ）テレフタル酸又はその低級アルキルエステル（アルキル基の炭素数１〜３で、例えばテレフタル酸ジメチル等）（以下（Ａ）成分という）、（Ｂ）エチレングリコール（以下（Ｂ）成分という）、及び（Ｃ）テレフタル酸又はその低級アルキルエステル以外のジカルボン酸又はその低級アルキルエステル（アルキル基の炭素数１〜３）（以下（Ｃ）成分という）を共重合してなるポリエステル樹脂；（Ａ）成分、（Ｂ）成分、及び（Ｄ）エチレングリコール以外のグリコール成分（以下（Ｄ）成分という）を共重合してなるポリエステル樹脂；（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｄ）成分を共重合してなるポリエステル樹脂等が挙げられる。
【００１１】
上記（Ｃ）成分としては、芳香族ジカルボン酸、脂環族ジカルボン酸、脂肪族ジカルボン酸及びこれらの低級アルキルエステル等から選ばれる１種以上が挙げられ、芳香族ジカルボン酸としては、イソフタル酸、フタル酸、２，６−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸、ビス（４，４’−カルボキシフェニル）メタン、アントラセンジカルボン酸、４，４’−ジフェニルエーテルジカルボン酸等が挙げられる。脂環族ジカルボン酸としては、１，４−シクロヘキサンジカルボン酸、４，４’−ジシクロヘキシルジカルボン酸等が挙げられる。脂肪族ジカルボン酸としては、アジピン酸、セバシン酸、アゼライン酸、ダイマー酸等が挙げられる。これらの（Ｃ）成分の中では、イソフタル酸及びその低級アルキルエステルが好ましい。
【００１２】
上記（Ｄ）成分としては、１，４−シクロヘキサンジメタノール、プロピレングリコール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、デカメチレングリコール、４，４’−ジシクロヘキシルヒドロキシメタン、４，４’−ジシクロヘキシルヒドロキシプロパン、ビスフェノールＡエチレンオキサイド付加ジオール、ポリエチレンオキサイドグリコール、ポリプロピレンオキサイドグリコール等から選ばれる１種以上が挙げられる。
【００１３】
本発明に係わる非晶性ポリエステル樹脂におけるジカルボン酸成分は、好ましくは芳香族ジカルボン酸成分が６０モル％以上であり、更に好ましくは上記（Ａ）成分が６０モル％以上である。また、グリコール成分は、好ましくは上記（Ｂ）成分が６０モル％以上である。
【００１４】
本発明に係わる非晶性ポリエステル樹脂のガラス転移温度は５０〜８５℃が好ましく、６０〜８５℃が更に好ましい。
【００１５】
［非晶性ポリエステル樹脂組成物］
本発明の非晶性ポリエステル樹脂組成物は、上記のような芳香族スルホンアミドのＮ−アルキル化物からなる本発明の可塑剤と非晶性ポリエステル樹脂とを含有する。本発明の可塑剤の含有量は、非晶性ポリエステル樹脂１００重量部に対し、柔軟性、耐ブリード性及び経済性の観点から、好ましくは３〜５０重量部、更に好ましくは５〜３０重量部である。
【００１６】
本発明の組成物は、上記可塑剤以外に、滑剤等を含有することができる。滑剤としては、エチレンビス（ステアロアミド）等のアミド類、ポリエチレンワックス等の炭化水素系ワックス類、ステアリン酸等の脂肪酸類、グリセロールエステル等の脂肪酸エステル類、ステアリン酸カルシウム等の金属石鹸類、モンタン酸ワックス等のエステルワックス類等が挙げられる。滑剤の含有量は、非晶性ポリエステル樹脂１００重量部に対し、０．０５〜３重量部が好ましく、０．１〜１．５重量部が更に好ましい。
【００１７】
本発明の組成物は、加工性が良好で、例えば１６０〜１９０℃等の低温で加工することができるため、カレンダー加工も可能であり、また可塑剤の分解も起こりにくい。本発明の組成物は、フィルムやシートに成形して、各種用途に用いることができる。
【００１８】
【実施例】
実施例１〜３及び比較例１、２
非晶性ポリエステル樹脂（ＴＳＵＮＡＭＩ ＧＳ２：イーストマンケミカル社製）１００重量部、モンタン酸ワックス０．８重量部、及び表１に示す種類と量の可塑剤からなる組成物を１６５℃の６インチロールにて１５分間混練し、１９０℃のプレス成形機にて厚さ１ｍｍのテストピースを作成した。
【００１９】
得られたテストピースについて下記方法で柔軟性、透明性及び表面状態を評価した。また、このテストピースを手で１８０°折り曲げ、白化の有無を肉眼で観察した。これらの結果を表１に示す。
【００２０】
＜柔軟性の評価法＞
テストピースを３号ダンベルで打ち抜き、引張速度２００ｍｍ／ｍｉｎで引張試験を行い、１００％モジュラスで示した。
【００２１】
＜透明性の評価法＞
ヘイズメーターにてテストピースのヘイズ値を測定した。数字の小さい方が透明性が良好であることを示す。
【００２２】
＜表面状態（ブリードの有無）＞
テストピース（縦１００mm×横１００mm×厚さ１ｍｍ）を４０℃の恒温室に１週間放置し、その表面における可塑剤のブリードの有無を肉眼で観察した。
【００２３】
【表１】
【発明の効果】
本発明の可塑剤は、非晶性ポリエステル樹脂の透明性を阻害させずに柔軟性を付与することができる。また、本発明の非晶性ポリエステル樹脂組成物からなるシートやフィルムを折り曲げた時の白化を防止することもできる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a plasticizer for an amorphous polyester resin and an amorphous polyester resin composition excellent in flexibility and transparency.
[0002]
[Prior art and problems to be solved by the invention]
Amorphous polyester resins having no clear melting point are used as materials for various films and sheets. This amorphous polyester resin has better processability than ordinary polyester resins and can be calendered. However, it has the disadvantage of being easily whitened when folded, and both transparency and flexibility are satisfied. What you can do is not available.
[0003]
An object of the present invention is to provide a plasticizer for an amorphous polyester resin capable of imparting flexibility without inhibiting the transparency of the amorphous polyester resin, and an amorphous polyester resin excellent in flexibility and transparency. It is to provide a composition.
[0004]
[Means for Solving the Problems]
The present invention relates to a plasticizer for an amorphous polyester resin comprising an N-alkylated product of an aromatic sulfonamide (alkyl group having 1 to 22 carbon atoms), and a non-containing composition containing this plasticizer and an amorphous polyester resin. A crystalline polyester resin composition is provided.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
[N-alkylated products of aromatic sulfonamides]
Examples of the aromatic sulfonamide constituting the N-alkylated product of the aromatic sulfonamide that is the plasticizer of the present invention include benzenesulfonamide and naphthalenesulfonamide. In addition, the carbon number of the alkyl group of the N-alkylated product is 1 to 22, preferably 1 to 18, from the viewpoint of compatibility with the amorphous polyester resin.
[0006]
Particularly preferred as an N-alkylated product of an aromatic sulfonamide is an N-alkylbenzenesulfonamide represented by the general formula (I).
[0007]
[Chemical 2]
(In the formula, R represents a linear or branched alkyl group having 1 to 22 carbon atoms.)
In the general formula (I), R is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, and most preferably an alkyl group having 2 to 6 carbon atoms, from the viewpoint of compatibility with the amorphous polyester resin.
[0009]
[Amorphous polyester resin]
The amorphous polyester resin according to the present invention is a polyester resin having no clear melting point, has better processability than ordinary polyester resins, and can be calendered.
[0010]
Specific examples of the amorphous polyester resin include (A) terephthalic acid or a lower alkyl ester thereof (alkyl group having 1 to 3 carbon atoms such as dimethyl terephthalate) (hereinafter referred to as component (A)), (B) Ethylene glycol (hereinafter referred to as component (B)), and (C) dicarboxylic acid other than terephthalic acid or lower alkyl ester thereof or lower alkyl ester thereof (alkyl group having 1 to 3 carbon atoms) (hereinafter referred to as component (C)). Polyester resin obtained by copolymerization; (A) component, (B) component, and (D) polyester resin obtained by copolymerization of glycol components other than ethylene glycol (hereinafter referred to as (D) component); (A) component; Examples thereof include a polyester resin obtained by copolymerizing the component (B), the component (C), and the component (D).
[0011]
Examples of the component (C) include one or more selected from aromatic dicarboxylic acid, alicyclic dicarboxylic acid, aliphatic dicarboxylic acid, and lower alkyl esters thereof. As the aromatic dicarboxylic acid, isophthalic acid, Examples include phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (4,4′-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, and the like. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexane dicarboxylic acid and 4,4′-dicyclohexyl dicarboxylic acid. Examples of the aliphatic dicarboxylic acid include adipic acid, sebacic acid, azelaic acid, and dimer acid. Among these (C) components, isophthalic acid and its lower alkyl ester are preferable.
[0012]
As the component (D), 1,4-cyclohexanedimethanol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, 4,4′-dicyclohexylhydroxymethane, Examples thereof include one or more selected from 4,4′-dicyclohexylhydroxypropane, bisphenol A ethylene oxide addition diol, polyethylene oxide glycol, polypropylene oxide glycol, and the like.
[0013]
The dicarboxylic acid component in the amorphous polyester resin according to the present invention is preferably an aromatic dicarboxylic acid component of 60 mol% or more, and more preferably the above component (A) is 60 mol% or more. The glycol component is preferably 60 mol% or more of the component (B).
[0014]
The glass transition temperature of the amorphous polyester resin according to the present invention is preferably 50 to 85 ° C, more preferably 60 to 85 ° C.
[0015]
[Amorphous polyester resin composition]
The amorphous polyester resin composition of the present invention contains the plasticizer of the present invention comprising the N-alkylated product of the aromatic sulfonamide as described above and the amorphous polyester resin. The content of the plasticizer of the present invention is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the amorphous polyester resin, from the viewpoints of flexibility, bleed resistance and economy. It is.
[0016]
The composition of the present invention can contain a lubricant and the like in addition to the plasticizer. Lubricants include amides such as ethylene bis (stearamide), hydrocarbon waxes such as polyethylene wax, fatty acids such as stearic acid, fatty acid esters such as glycerol ester, metal soaps such as calcium stearate, montanic acid wax And ester waxes. The content of the lubricant is preferably 0.05 to 3 parts by weight and more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the amorphous polyester resin.
[0017]
Since the composition of the present invention has good processability and can be processed at a low temperature such as 160 to 190 ° C., it can be calendered and the plasticizer is hardly decomposed. The composition of the present invention can be formed into a film or sheet and used for various applications.
[0018]
【Example】
Examples 1 to 3 and Comparative Examples 1 and 2
A composition comprising 100 parts by weight of an amorphous polyester resin (TSUNAMI GS2: manufactured by Eastman Chemical Co., Ltd.), 0.8 parts by weight of montanic acid wax, and a plasticizer of the type and amount shown in Table 1 is a 6 inch roll at 165 ° C. Was kneaded for 15 minutes, and a test piece having a thickness of 1 mm was prepared with a press molding machine at 190 ° C.
[0019]
About the obtained test piece, the softness | flexibility, transparency, and surface state were evaluated by the following method. Further, this test piece was bent 180 ° by hand, and the presence or absence of whitening was observed with the naked eye. These results are shown in Table 1.
[0020]
<Flexibility evaluation method>
The test piece was punched with a No. 3 dumbbell, a tensile test was performed at a tensile speed of 200 mm / min, and a 100% modulus was indicated.
[0021]
<Transparency evaluation method>
The haze value of the test piece was measured with a haze meter. Smaller numbers indicate better transparency.
[0022]
<Surface condition (with or without bleeding)>
A test piece (length 100 mm × width 100 mm × thickness 1 mm) was left in a constant temperature room at 40 ° C. for 1 week, and the presence or absence of a plasticizer bleed on the surface was observed with the naked eye.
[0023]
[Table 1]
【The invention's effect】
The plasticizer of the present invention can impart flexibility without inhibiting the transparency of the amorphous polyester resin. Moreover, whitening when the sheet | seat and film which consist of an amorphous polyester resin composition of this invention are bent can also be prevented.
Claims (3)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001178171A JP4657499B2 (en) | 2001-06-13 | 2001-06-13 | Plasticizer for polyester resin |
| US10/478,847 US20060183832A1 (en) | 2001-06-13 | 2002-06-13 | Plasticizer for polyester resin |
| PCT/JP2002/005919 WO2002102897A1 (en) | 2001-06-13 | 2002-06-13 | Plasticizer for polyester resin |
| EP02736089A EP1403322A4 (en) | 2001-06-13 | 2002-06-13 | Plasticizer for polyester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001178171A JP4657499B2 (en) | 2001-06-13 | 2001-06-13 | Plasticizer for polyester resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002363390A JP2002363390A (en) | 2002-12-18 |
| JP4657499B2 true JP4657499B2 (en) | 2011-03-23 |
Family
ID=19018913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001178171A Expired - Fee Related JP4657499B2 (en) | 2001-06-13 | 2001-06-13 | Plasticizer for polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4657499B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4380808B2 (en) * | 1996-11-08 | 2009-12-09 | 東レ・デュポン株式会社 | Polyester elastomer resin composition |
| JPH11240073A (en) * | 1998-02-26 | 1999-09-07 | Toray Ind Inc | Method for producing welded resin molded article and welded resin molded article |
| JP4657411B2 (en) * | 1999-11-25 | 2011-03-23 | オカモト株式会社 | Soft polyester resin composition for calendering and film produced therefrom |
-
2001
- 2001-06-13 JP JP2001178171A patent/JP4657499B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002363390A (en) | 2002-12-18 |
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