JP2003026908A - Polyester resin composition - Google Patents
Polyester resin compositionInfo
- Publication number
- JP2003026908A JP2003026908A JP2001211863A JP2001211863A JP2003026908A JP 2003026908 A JP2003026908 A JP 2003026908A JP 2001211863 A JP2001211863 A JP 2001211863A JP 2001211863 A JP2001211863 A JP 2001211863A JP 2003026908 A JP2003026908 A JP 2003026908A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- weight
- polyester resin
- resin composition
- polybutylene terephthalate
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はポリエステル樹脂組
成物に関し、さらに詳しくは合成樹脂製でありながら陶
器調の重量感、質感、光沢を有し、さらに耐薬品性、耐
衝撃性に優れた成形品を得ることができるポリエステル
樹脂組成物およびその成形品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition, and more specifically to a molding which is made of a synthetic resin and has a pottery-like weight feeling, texture and luster, and further excellent chemical resistance and impact resistance. The present invention relates to a polyester resin composition and a molded product thereof that can be obtained.
【０００２】[0002]
【従来の技術】陶器調光沢を有する樹脂成形品は、食
器、洗面器具、植木鉢等の各種容器類、床材、壁材、洗
面ボウル等の住宅機器類、及びテーブルトップ、額縁、
人形等の装飾品類等の分野において広く利用されてい
る。2. Description of the Related Art A resin molded article having a pottery-like gloss is used for various containers such as tableware, washbasins, flowerpots, flooring, wall materials, washbasins and other household equipment, and table tops, frame,
It is widely used in the field of ornaments such as dolls.
【０００３】このような陶器調の光沢や重量感、質感を
有する樹脂組成物の検討がなされているが陶器に代わる
樹脂組成物は残念ながら少ない。例えば、ポリブチレン
テレフタレート樹脂、ポリエチレンテレフタレート樹脂
及び酸化亜鉛からなる組成物（特開平３−１８５０５２
号公報）の提案は光沢や耐衝撃性が劣り、ポリブチレン
テレフタレート樹脂、ポリエチレンテレフタレート樹脂
及び硫酸バリウムからなる組成物（特公平７−１３１８
２号公報）の提案は光沢及び耐衝撃性がかなり良いが、
耐衝撃性等の点において、実用上はまだ不満足な水準で
ある。また、耐衝撃性を改良する方法としてポリエステ
ル樹脂、熱可塑性エラストマー、硫酸バリウムからなる
組成物（特開平４−５０６３８２号公報）の提案がなさ
れているが、耐衝撃性は改善されるものの光沢等の表面
外観が十分ではなく、表面外観（光沢）と耐衝撃性の双
方を兼ね備えた陶器代替え材料の開発が望まれていた。Although resin compositions having such a porcelain-like luster, weight feeling and texture have been studied, unfortunately there are few resin compositions which can replace ceramics. For example, a composition comprising a polybutylene terephthalate resin, a polyethylene terephthalate resin and zinc oxide (JP-A-3-185052).
The composition of polybutylene terephthalate resin, polyethylene terephthalate resin and barium sulfate is inferior in gloss and impact resistance (Japanese Patent Publication No. 7-1318).
No. 2 gazette) has quite good gloss and impact resistance,
In terms of impact resistance, etc., it is still unsatisfactory in practical use. Further, as a method for improving impact resistance, a composition comprising a polyester resin, a thermoplastic elastomer, and barium sulfate (Japanese Patent Laid-Open No. 4-506382) has been proposed, but the impact resistance is improved but the gloss etc. However, the development of a pottery substitute material that has both surface appearance (gloss) and impact resistance has been desired.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、上述
した従来の陶器製に代わる容器組成物の欠点を解消し、
合成樹脂製でありながら優れた光沢、耐衝撃性、耐薬品
性を有し、陶器調外観を有する樹脂組成物およびその成
形品を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to overcome the above-mentioned drawbacks of container compositions that replace conventional pottery products.
(EN) It is intended to provide a resin composition which is made of a synthetic resin, has excellent gloss, impact resistance, chemical resistance, and has a pottery-like appearance, and a molded product thereof.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、組
成物全体を１００重量％として、下記（ａ）１２〜６４
重量％、下記（ｂ）６〜４８重量％および下記（ｃ）７
０〜２０重量％含有してなるポリエステル樹脂組成物お
よびそれを成形してなる、陶器調外観が要求される用途
に使用される成形品である。
（ａ）ポリブチレンテレフタレート樹脂
（ｂ）ポリブチレンテレフタレート樹脂よりも結晶化速
度の遅いポリエステル樹脂又は非晶性樹脂
（ｃ）硫酸バリウム全体を１００重量％として、粒径が
０．３μｍ以上の粒子９７〜６０重量％、０．３μｍ未
満の粒子３〜４０重量％を含有する硫酸バリウムThat is, according to the present invention, the total amount of the composition is 100% by weight, and the following (a) 12 to 64 is used.
% By weight, (b) 6 to 48% by weight below and (c) 7 below.
A polyester resin composition containing 0 to 20% by weight and a molded product obtained by molding the composition are used for applications requiring a ceramic appearance. (A) Polybutylene terephthalate resin (b) Polyester resin having a slower crystallization rate than polybutylene terephthalate resin or amorphous resin (c) Particles having a particle size of 0.3 μm or more with 100% by weight of the whole barium sulfate. ~ 60 wt%, barium sulphate containing 3-40 wt% particles less than 0.3 μm
【０００６】[0006]
【発明の実施の形態】本発明において（ａ）成分として
用いるポリブチレンテレフタレート樹脂の配合量は樹脂
組成物全体の１２〜６４重量％、好ましくは１５〜５６
重量％である。また、本発明において使用されるポリブ
チレンテレフタレート樹脂としては２５℃におけるｏ−
クロルフェノールで測定した固有粘度が０．３６〜１．
６０ｄｌ／ｇ、特に０．５２〜１．３５ｄｌ／ｇの範囲
にあることが好ましい。DETAILED DESCRIPTION OF THE INVENTION The polybutylene terephthalate resin used as the component (a) in the present invention is compounded in an amount of 12 to 64% by weight, preferably 15 to 56% by weight, based on the total resin composition.
% By weight. Further, the polybutylene terephthalate resin used in the present invention has an o-
The intrinsic viscosity measured with chlorophenol is 0.36-1.
It is preferably in the range of 60 dl / g, particularly 0.52 to 1.35 dl / g.
【０００７】本発明で用いる（ｂ）成分のうち、ポリブ
チレンテレフタレート樹脂よりも結晶化速度の遅いポリ
エステル樹脂としては、ポリエチレンテレフタレート樹
脂、ポリエチレンナフタレート樹脂、ジオール成分がエ
チレングリコール残基、シクロヘキサンジメタノール残
基及び、ジカルボン酸成分がテレフタル酸残基を構成成
分とするポリエステル共重合体が好ましい。また、非晶
性樹脂としてはポリカーボネート樹脂、ポリエーテルイ
ミド樹脂、変性ポリフェニレンエーテル樹脂が好まし
い。これら樹脂は１種以上で用いることが可能である。
なかでもポリエチレンテレフタレート樹脂を用いること
が最も好ましい。Among the components (b) used in the present invention, examples of the polyester resin having a slower crystallization rate than the polybutylene terephthalate resin include polyethylene terephthalate resin, polyethylene naphthalate resin, diol component of ethylene glycol residue, cyclohexanedimethanol. A polyester copolymer in which the residue and the dicarboxylic acid component have a terephthalic acid residue as a constituent component is preferable. Further, as the amorphous resin, a polycarbonate resin, a polyetherimide resin, or a modified polyphenylene ether resin is preferable. It is possible to use one or more of these resins.
Among them, it is most preferable to use polyethylene terephthalate resin.
【０００８】本発明における（ｂ）成分の配合量は樹脂
組成物全体の６〜４８重量％、好ましくは９〜４０重量
％である。（ｂ）成分の配合量が少なすぎると光沢が低
下し、多すぎると耐衝撃性が低下するため好ましくな
い。The amount of component (b) used in the present invention is 6 to 48% by weight, preferably 9 to 40% by weight, based on the total resin composition. If the blending amount of the component (b) is too small, the gloss is lowered, and if it is too large, the impact resistance is lowered, which is not preferable.
【０００９】なお、上述のポリエステル樹脂としてはジ
カルボン酸成分或いはグリコール成分の一部を他の共重
合成分で置き換えたものでもよい。共重合可能なジカル
ボン酸成分としては、例えばテレフタル酸、２，６−ナ
フタレンジカルボン酸、イソフタル酸、ジフェニルジカ
ルボン酸、ジフェニルエーテルジカルボン酸、ジフェノ
キシエタンジカルボン酸等の芳香族ジカルボン酸類、コ
ハク酸、アジピン酸、セバシン酸等の脂肪族ジカルボン
酸類、シクロヘキサンジカルボン酸等の脂環式ジカルボ
ン酸類が挙げられる。共重合可能なジグリコール成分と
しては、例えばエチレングリコール、プロピレングリコ
ール、１，４−ブタンジオール、ヘキサメチレングリコ
ール、１，４−シクロヘキサンジメタノール、ビスフェ
ノールＡ、ビスフェノールＳ等が挙げられる。As the above polyester resin, a part of the dicarboxylic acid component or the glycol component may be replaced with another copolymerization component. Examples of the copolymerizable dicarboxylic acid component include terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid, and other aromatic dicarboxylic acids, succinic acid, adipic acid. , Aliphatic dicarboxylic acids such as sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Examples of the copolymerizable diglycol component include ethylene glycol, propylene glycol, 1,4-butanediol, hexamethylene glycol, 1,4-cyclohexanedimethanol, bisphenol A and bisphenol S.
【００１０】本発明において（ｃ）成分として使用され
る硫酸バリウムとしては天然に産したものの粉砕物およ
び公知の合成法により得られるものを使用できる。樹脂
組成物全体に対する硫酸バリウムの配合割合は７０〜２
０重量％であるが、６５〜２５重量％であることが好ま
しい。また、本発明で用いる硫酸バリウムは、硫酸バリ
ウム全体を１００重量％としたときに、粒径０．３μｍ
以上の粒子が９７〜６０重量％、０．３μｍ未満の粒子
が３〜４０重量％である粒度分布を有するものである。
硫酸バリウムの粒子径は、電子顕微鏡写真から個々の粒
子の粒子径を求め、累積粒径グラフを作り前記粒径以上
もしくは未満の粒子の存在率を求める。電子顕微鏡写真
は４０，０００倍に拡大されたものとする。なお、硫酸
バリウムは必ずしも球状ではない。そこで、写真内に特
定の方向を定め、その方向に、写真内の各粒子を投影し
た場合の長さを粒径と呼ぶことにする。また、測定する
粒子数は４００個以上とする。本発明においては、用い
る硫酸バリウムの累積粒径グラフが、３点以上の変曲点
を持っていることが望ましく、更に望ましい変曲点数は
３点である。このように変曲点数を３点以上持つ硫酸バ
リウムを得る手法の一例として、平均粒子径の異なる２
種類以上の硫酸バリウムを混合する方法が挙げられる。
例えば硫酸バリウムとしては平均粒径が０．４〜２μｍ
の範囲にあるものと平均粒径が０．０１〜０．３μｍの
範囲にあるものを併用することが好ましく、特に平均粒
径が０．５〜１μｍの範囲にあるものと、平均粒径が
０．０２〜０．１μｍの範囲にあるものを併用すること
が好ましい。このように平均粒径の異なる２種類以上の
硫酸バリウムを混合することによって、表面外観、流動
性、耐衝撃性が改善される。The barium sulfate used as the component (c) in the present invention may be a pulverized product of a naturally occurring product or a product obtained by a known synthesis method. The compounding ratio of barium sulfate to the entire resin composition is 70 to 2
Although it is 0% by weight, it is preferably 65 to 25% by weight. The barium sulfate used in the present invention has a particle size of 0.3 μm when the total amount of barium sulfate is 100% by weight.
The above particles have a particle size distribution of 97 to 60% by weight and particles of less than 0.3 μm 3 to 40% by weight.
Regarding the particle size of barium sulfate, the particle size of individual particles is determined from an electron micrograph, and a cumulative particle size graph is prepared to determine the abundance ratio of particles having a particle size equal to or larger than the particle size. The electron micrograph shall be magnified 40,000 times. Note that barium sulfate is not necessarily spherical. Therefore, a specific direction is defined in the photograph, and the length when each particle in the photograph is projected in that direction is referred to as the particle size. The number of particles to be measured is 400 or more. In the present invention, it is desirable that the cumulative particle diameter graph of barium sulfate used has three or more inflection points, and more desirable inflection points are three points. As an example of the method for obtaining barium sulfate having three or more inflection points in this way, it is possible to
A method of mixing more than one kind of barium sulfate can be mentioned.
For example, barium sulfate has an average particle size of 0.4 to 2 μm.
It is preferable to jointly use those having an average particle size in the range of 0.01 to 0.3 μm, and particularly those having an average particle size in the range of 0.5 to 1 μm. It is preferable to use those in the range of 0.02 to 0.1 μm in combination. By mixing two or more kinds of barium sulfate having different average particle diameters in this way, the surface appearance, fluidity and impact resistance are improved.
【００１１】ほとんどの用途では、硫酸バリウムは存在
する充填材全体の１００重量％の量であるが、用途によ
っては、硫酸バリウム総含有量の５０重量％まで、好ま
しくは２０重量％までを、ガラス繊維、ガラスビーズ、
ＰＡＮ系やピッチ系の炭素繊維、ステンレススチール繊
維、アルミニウム繊維、黄銅繊維などの金属繊維、石膏
繊維、セラミック繊維、ジルコニア繊維、アルミナ繊
維、シリカ繊維、酸化チタン繊維、炭化ケイ素繊維、チ
タン酸カリウムウイスカー、チタン酸バリウムウイスカ
ー、ほう酸アルミニウムウイスカー、窒化ケイ素ウイス
カーなどの短繊維（チョップドストランド）又は／及び
長繊維（ロービング）、及びマイカ、タルク、カオリ
ン、シリカ、炭酸カルシウム、ガラスビーズ、ガラスフ
レーク、ガラスマイクロバルーン、クレー、二硫化モリ
ブデン、ワラステナイト、酸化チタン、酸化亜鉛、ポリ
リン酸カルシウム、グラファイト、合成雲母などの板片
状、粉末状又は粒状のもので置き換えることができる。In most applications, barium sulphate is present in an amount of 100% by weight of the total filler present, but in some applications up to 50%, preferably up to 20% by weight of the total barium sulphate content of glass can be obtained. Fiber, glass beads,
Metal fibers such as PAN-based and pitch-based carbon fibers, stainless steel fibers, aluminum fibers, brass fibers, gypsum fibers, ceramic fibers, zirconia fibers, alumina fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, potassium titanate whiskers , Barium titanate whiskers, aluminum borate whiskers, silicon nitride whiskers, short fibers (chopped strands) and / or long fibers (rovings), and mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flakes, glass micro It may be replaced by a flaky, powdery or granular material such as balloon, clay, molybdenum disulfide, wollastenite, titanium oxide, zinc oxide, calcium polyphosphate, graphite, synthetic mica.
【００１２】本発明のポリエステル樹脂組成物で陶器製
の代わりとなる容器を作製する場合、成形性、耐熱性に
代表される二次要求特性を満足せしめるため、本発明の
効果を損なわない範囲で他の成分を添加してもよい。例
えば、耐候剤（フェノール系、ヒンダードアミン系、ベ
ンゾフェノン系等）、離型剤及び滑剤（モンタン酸及び
その金属塩、ステアラミド等）、顔料（カーボンブラッ
ク等）、染料（ニグロシン等）、等の安定剤を添加して
もよい。In the case where the polyester resin composition of the present invention is used to produce a container as a substitute for ceramics, the secondary required characteristics represented by moldability and heat resistance are satisfied, so that the effect of the present invention is not impaired. Other ingredients may be added. For example, weathering agents (phenolic, hindered amine-based, benzophenone-based, etc.), release agents and lubricants (montanic acid and its metal salts, stearamide, etc.), pigments (carbon black, etc.), dyes (nigrosine, etc.), stabilizers, etc. May be added.
【００１３】本発明に使用されるポリエステル樹脂組成
物の混合方法は、通常用いられている溶融混練方法によ
り容易に調製することができる。混練機としては、例え
ばエクストルーダー、バンバリーミキサー、ロールニー
ダーなどを用いることができるが、なかでもエクストル
ーダーにより２５０〜２８０℃の温度範囲で溶融混練す
ることが好ましい。The polyester resin composition used in the present invention can be easily mixed by a commonly used melt-kneading method. As the kneading machine, for example, an extruder, a Banbury mixer, a roll kneader, or the like can be used, but among them, it is preferable to perform melt kneading in the temperature range of 250 to 280 ° C. by the extruder.
【００１４】本発明のポリエステル樹脂組成物は、組成
物を２５０℃で３０分間熱処理したときの加熱減量が
０．５重量％以下であることが、ガスくもりの発生が抑
制され、外観に極めて優れた成形品が得られる点で好ま
しく、特に０．３重量％以下であることが好ましい。In the polyester resin composition of the present invention, the heat loss when the composition is heat-treated at 250 ° C. for 30 minutes is 0.5% by weight or less, which suppresses the generation of gas fog and is extremely excellent in appearance. It is preferable that a molded product can be obtained, and it is particularly preferably 0.3% by weight or less.
【００１５】加熱減量は、約１００ｇの溶融混練により
得られた樹脂ペレットを予め１３０℃の温度条件下で３
時間乾燥させた後、予め乾燥させたアルミカップに１０
０ｇ±１ｇの精度で量り入れ、２５０℃で３０分ギアオ
ーブン中で処理し、重量測定により求めた値である。The weight loss on heating is obtained by preliminarily heating about 100 g of resin pellets obtained by melt-kneading under a temperature condition of 130 ° C.
After drying for 10 hours, place in a pre-dried aluminum cup for 10
It is a value obtained by weighing in with an accuracy of 0 g ± 1 g, processing in a gear oven at 250 ° C. for 30 minutes, and weighing.
【００１６】かかる組成物を得るためには、（ａ）、
（ｂ）成分として、加熱により揮発ガス発生の少ないも
のを用いて配合に供することが好ましい。To obtain such a composition, (a),
As the component (b), it is preferable to use a component that generates a small amount of volatile gas upon heating for use in the compounding.
【００１７】例えば、前記（ａ）成分として用いるポリ
ブチレンテレフタレート樹脂は、配合に供するペレット
の状態で１００℃で３０分間熱処理したときに発生する
揮発ガスの量が、水分を除いて５０ｐｐｍ以下、特に３
０ｐｐｍ以下であるものを用いることが好ましい。ポリ
ブチレンテレフタレート樹脂は、液相重合のみで得られ
たペレットを１４０〜１７０℃の窒素雰囲気下で２〜８
時間加熱乾燥することにより揮発ガスを減少させること
ができるが、ペレットを常圧・窒素雰囲気下または真空
下で１７０〜２１０℃の温度で固相重合したものが揮発
ガス抑制の面で好ましい。For example, in the polybutylene terephthalate resin used as the component (a), the amount of volatile gas generated when heat-treated at 100 ° C. for 30 minutes in the state of pellets to be compounded is 50 ppm or less, especially water, and particularly Three
It is preferable to use one having a content of 0 ppm or less. The polybutylene terephthalate resin is obtained by subjecting pellets obtained only by liquid phase polymerization to 2 to 8 in a nitrogen atmosphere at 140 to 170 ° C.
The volatile gas can be reduced by heating and drying for a period of time, but it is preferable that the pellets are subjected to solid-state polymerization at a temperature of 170 to 210 ° C. under normal pressure / nitrogen atmosphere or under vacuum from the viewpoint of suppressing volatile gas.
【００１８】前記（ｂ）成分として特に好ましく使用さ
れるポリエチレンテレフタレート樹脂の場合には、配合
に供するペレットの状態で１００℃で３０分間熱処理し
たときに発生する揮発ガスの量が、水分を除いて４０ｐ
ｐｍ以下、特に２０ｐｐｍ以下であることが成形品の外
観上好ましい。また、２５℃におけるｏ−クロルフェノ
ールで測定した固有粘度は０．３〜１．２、特に０．５
〜１．０の範囲にあることが好ましい。ポリエチレンテ
レフタレート樹脂は、液相重合のみで得られたペレット
を１４０〜１８０℃の窒素雰囲気下で２〜８時間加熱乾
燥することにより揮発ガスを減少させることができる
が、ペレットを常圧・窒素雰囲気下または真空下で１９
０〜２４０℃の温度で固相重合したものが揮発ガス抑制
の面で好ましい。In the case of the polyethylene terephthalate resin which is particularly preferably used as the component (b), the amount of the volatile gas generated when heat-treated at 100 ° C. for 30 minutes in the state of pellets to be compounded excludes moisture. 40p
pm or less, especially 20 ppm or less is preferable in terms of appearance of the molded product. Also, the intrinsic viscosity measured with o-chlorophenol at 25 ° C. is 0.3 to 1.2, especially 0.5.
It is preferably in the range of to 1.0. Polyethylene terephthalate resin can reduce volatile gas by heating and drying pellets obtained only by liquid phase polymerization in a nitrogen atmosphere at 140 to 180 ° C. for 2 to 8 hours. Under or under vacuum 19
What was solid-phase-polymerized at a temperature of 0 to 240 ° C. is preferable in terms of suppressing volatile gas.
【００１９】なお、揮発ガス発生量は、ガスクロマトグ
ラフィーを用いて測定することが可能である。すなわ
ち、試料をガスクロマトグラフィーのサンプラーに入
れ、加熱温度１００℃、加熱時間３０分、キャリアガス
（ヘリウム）を流してガスを採取する。採取したガスは
−３０℃に冷却することによりトラップし、これを３５
０℃で熱脱着してからガスクロマトグラフィーに導入す
る。揮発ガス発生量は、ガスクロマトグラムのピークを
帰属し、水分を除く各ピークを積算することにより求め
るものとする。The amount of volatile gas generated can be measured using gas chromatography. That is, the sample is placed in a gas chromatography sampler, and a gas is collected by flowing a carrier gas (helium) at a heating temperature of 100 ° C. for a heating time of 30 minutes. The collected gas is trapped by cooling it to -30 ° C,
Thermal desorption at 0 ° C. before introduction to gas chromatography. The amount of volatile gas generated shall be determined by assigning the peaks of the gas chromatogram and integrating each peak excluding water.
【００２０】かくして得られるポリエステル樹脂組成物
は、外観、耐衝撃性に優れるため、食器、洗面器具、植
木鉢等の各種容器類、床材、壁材、洗面ボウル、浴槽等
の住宅機器類、及びテーブルトップ、額縁、人形等の装
飾品類等、陶器調外観が要求される用途に極めて実用的
である。Since the polyester resin composition thus obtained has excellent appearance and impact resistance, it can be used for various containers such as tableware, washbasins and flowerpots, flooring materials, wall materials, washbasins, bathtubs and other household equipment, and It is extremely practical for applications requiring a ceramic-like appearance, such as table tops, picture frames, and ornaments such as dolls.
【００２１】[0021]
【実施例】以下に説明する実施例及び比較例における評
価は次の方法によって行った。EXAMPLES Evaluations in Examples and Comparative Examples described below were carried out by the following methods.
【００２２】［結晶化速度］ＤＳＣ（パーキン・エルマ
社製示差走査熱量計）を用い２０℃／分の昇温・降温速
度にてＴｍ（融点）、Ｔｃ（結晶化温度）を測定しＴｍ
−Ｔｃにて結晶化速度を測定した。Ｔｍ−Ｔｃの差が大
きい程結晶化速度が遅い。[Crystallization rate] Tm (melting point) and Tc (crystallization temperature) were measured using a DSC (differential scanning calorimeter manufactured by Perkin-Elma) at a temperature rising / falling rate of 20 ° C./min.
The crystallization rate was measured at -Tc. The larger the difference of Tm-Tc, the slower the crystallization rate.
【００２３】Ｔｍが観測されてもＴｃが観測されない場
合はさらに結晶化速度が遅い。When Tm is observed but Tc is not observed, the crystallization rate is slower.
【００２４】［加熱減量］加熱減量は、溶融混練により
得られた樹脂ペレット約１００ｇを予め１３０℃の温度
条件下で３時間乾燥させた後、予め乾燥させたアルミカ
ップに組成物のペレット１００ｇ±１ｇの精度で量り入
れ、２５０℃で３０分ギアオーブン中で処理し、重量測
定し、減量（重量％）を求めた。[Loss on heating] About 100 g of resin pellets obtained by melt-kneading are dried in advance at a temperature of 130 ° C. for 3 hours, and then 100 g ± 100 g of pellets of the composition are placed in a pre-dried aluminum cup. It was weighed in with an accuracy of 1 g, treated in a gear oven at 250 ° C. for 30 minutes, and weighed to determine the weight loss (% by weight).
【００２５】［光沢性］グロスメーターを使用してテス
トピース表面の光沢度（％）を測定した。光沢度が高い
ほど陶器調光沢を有することを表す。[Glossiness] The glossiness (%) of the surface of the test piece was measured using a gloss meter. The higher the glossiness, the more the porcelain gloss.
【００２６】［耐衝撃性］ＡＳＴＭ Ｄ２５６に準拠し
てノッチ付きアイゾット衝撃強度を測定した。テストピ
ースの幅は６．４ｍｍである。[Impact resistance] Notched Izod impact strength was measured according to ASTM D256. The width of the test piece is 6.4 mm.
【００２７】［耐薬品性］テストピース表面にマニュキ
ア液（大阪資生堂（株）製ヌーヴネイルカラー）及びヘ
アトニック液（大阪資生堂（株）製ブラバスヘアリキッ
ド）を塗布し、乾燥しないようシャーレ皿をかぶせて２
４時間放置して表面変化の有無を評価した。[Chemical resistance] The surface of the test piece is coated with Manukia liquid (Neuve nail color manufactured by Osaka Shiseido Co., Ltd.) and hair tonic liquid (Brass Hair Liquid manufactured by Osaka Shiseido Co., Ltd.), and a Petri dish is kept so as not to dry. Cover 2
It was left to stand for 4 hours and evaluated for surface changes.
【００２８】［硫酸バリウムの粒径］原料はそのまま、
組成物中の硫酸バリウムの粒径を測定する場合は、溶融
混練後の樹脂ペレットから樹脂を加熱焼却分離した後、
電子顕微鏡を用いて４０，０００倍に拡大し写真撮影し
た。該写真内に特定の方向を定め、その方向に各粒子を
投影した場合の長さを測定した。写真内に写り込んでい
る粒子全てを測定対象としたので測定個数は測定対象に
よって異なるが、４００個以上になるまで写真数を増や
した。全データの平均を求め、平均粒径とした。[Barium sulphate particle size]
When measuring the particle size of barium sulfate in the composition, after heating and separating the resin from the resin pellet after melt kneading,
It was magnified 40,000 times using an electron microscope and photographed. A specific direction was set in the photograph, and the length of each particle projected in that direction was measured. Since all the particles reflected in the photograph were taken as the object of measurement, the number of images measured varied depending on the object of measurement, but the number of images was increased to 400 or more. The average of all data was calculated and used as the average particle size.
【００２９】次いで、全てのデータを対数とし、粒径
０．０１μｍから２００μｍを対数化した後均等に１０
０分割し、各分割区域内の粒子個数を求めて累積粒径グ
ラフを作成した。粒度分布は、この累積粒径グラフから
求めた。Next, all the data were logarithmized, and the particle diameters of 0.01 μm to 200 μm were logarithmized and then 10
The number of particles in each divided area was determined by dividing into 0, and a cumulative particle diameter graph was created. The particle size distribution was obtained from this cumulative particle size graph.
【００３０】実施例１〜６及び比較例１，２ 下記７種類の材料を用意した。 Ａ ＰＢＴ樹脂：ポリブチレンテレフタレート（固相重合品） 固有粘度０．８の液相重合ポリマを１９０℃、常圧の条件で窒 素雰囲気下７時間固相重合を行った。Examples 1 to 6 and Comparative Examples 1 and 2 The following seven types of materials were prepared. A PBT resin: polybutylene terephthalate (solid-state polymerization product) A liquid phase polymer with an intrinsic viscosity of 0.8 is mixed at 190 ° C and atmospheric pressure. Solid phase polymerization was performed for 7 hours in an elementary atmosphere.
【００３１】 揮発ガス発生量：６．１ｐｐｍ 固有粘度 ：１．１ Ｔｍ２２３℃、Ｔｃ１８７℃、Ｔｍ−Ｔｃ：３６℃ Ｂ ＰＥＴ樹脂：ポリエチレンテレフタレート（固相重合品） 固有粘度０．６の液相重合ポリマを２２０℃、常圧の条件で窒 素雰囲気下８時間固相重合を行った。[0031] Amount of volatile gas generated: 6.1ppm Intrinsic viscosity: 1.1 Tm223 ° C, Tc187 ° C, Tm-Tc: 36 ° C B PET resin: polyethylene terephthalate (solid-state polymerization product) A liquid phase polymer with an intrinsic viscosity of 0.6 is mixed at 220 ° C and atmospheric pressure. Solid phase polymerization was carried out for 8 hours in an elementary atmosphere.
【００３２】 揮発ガス発生量：４．５ｐｐｍ 固有粘度 ：０．８ Ｔｍ２５３℃、Ｔｃ１９５℃、Ｔｍ−Ｔｃ：５８℃ Ｃ ２，６ＰＥＮ樹脂：ポリエチレンナフタレート樹脂（液相重合品） 揮発ガス発生量：１２．８ｐｐｍ 固有粘度 ：０．６ Ｔｍ２６１℃、Ｔｃ検出されず Ｄ ＰＣＴ樹脂：ポリシクロヘキサンジメチレンテレフタレート／ポリエチレン テレフタレート共重合樹脂（イーストマンコダック社製：ＤＮ００３） 揮発ガス発生量：１６．４ｐｐｍ 固有粘度 ：０．８ Ｔｍ、Ｔｃとも検出されず Ｅ ＰＣ樹脂：ポリカーボネート樹脂 （三菱エンジニアリングプラスチックス 社製：Ｈ３０００） 揮発ガス発生量：１５．５ｐｐｍ Ｔｍ、Ｔｃとも検出されず Ｆ 硫酸バリウム（堺化学工業（株）「Ｂ−５５」平均粒径＝０．６６μｍ）。 Ｇ 硫酸バリウム（堺化学工業（株）「ＢＦ−２０」平均粒径＝０．０３μｍ） 。[0032] Volatile gas generation: 4.5ppm Intrinsic viscosity: 0.8 Tm253 ° C, Tc195 ° C, Tm-Tc: 58 ° C C 2,6 PEN resin: polyethylene naphthalate resin (liquid phase polymerized product) Volatile gas generation: 12.8ppm Intrinsic viscosity: 0.6 Tm 261 ℃, Tc not detected D PCT resin: Polycyclohexane dimethylene terephthalate / polyethylene Terephthalate copolymer resin (Eastman Kodak Company: DN003) Volatile gas generation: 16.4ppm Intrinsic viscosity: 0.8 Neither Tm nor Tc detected E PC resin: Polycarbonate resin (Mitsubishi Engineering Plastics Company: H3000) Volatile gas generation: 15.5ppm Neither Tm nor Tc detected F Barium sulfate (Sakai Chemical Industry Co., Ltd. “B-55” average particle size = 0.66 μm). G Barium sulfate (Sakai Chemical Industry Co., Ltd. “BF-20” average particle size = 0.03 μm) .
【００３３】これら７種類の材料Ａ〜Ｇをそれぞれ表１
および表２に記載した配合割合でヘンシェルミキサーに
供給して混合した後、２軸ベント式押出機を使用してバ
レル設定温度は２５０℃、スクリュー回転数は２００ｒ
ｐｍの条件で溶融混練押出しながらペレタイズして樹脂
組成物を製造した。次に、樹脂組成物をあらかじめ乾燥
してから、シリンダー設定温度２６０℃、金型温度８０
℃、射出圧力３０ＭＰａの条件で日精樹脂工業製の６０
トン射出成形機を使用し試験片を成形した。これらテス
トピースの成形品光沢、耐衝撃性及び耐薬品性をそれぞ
れ測定した結果、表１及び表２の結果が得られた。Table 1 shows these seven kinds of materials A to G, respectively.
Then, the mixture was fed to the Henschel mixer at the blending ratio shown in Table 2 and mixed, and then the barrel set temperature was 250 ° C. and the screw rotation speed was 200 r using a twin-screw vent type extruder.
A resin composition was produced by pelletizing while melt-kneading and extruding under the condition of pm. Next, after drying the resin composition in advance, the cylinder temperature is set to 260 ° C. and the mold temperature is set to 80
60 manufactured by NISSEI PLASTIC INDUSTRIES under the conditions of ℃ and injection pressure of 30 MPa
The test pieces were molded using a ton injection molding machine. As a result of measuring the gloss, impact resistance and chemical resistance of the molded products of these test pieces, the results shown in Table 1 and Table 2 were obtained.
【００３４】これらの試験結果から明らかなように、本
発明のポリエステル樹脂組成物からなる成形品は、陶器
調外観を有し、従来の硫酸バリウムを配合したポリエス
テル樹脂組成物からなる成形品と比較して、陶器調光沢
性、耐衝撃性、耐薬品性がバランスよく優れていること
が分かる。As is clear from these test results, the molded product made of the polyester resin composition of the present invention has a ceramic appearance and is compared with the molded product made of the conventional polyester resin composition containing barium sulfate. It can be seen that the ceramic-like gloss, impact resistance, and chemical resistance are well balanced.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【表２】 [Table 2]
【００３７】[0037]
【発明の効果】上述したように、本発明のポリエステル
樹脂組成物は、陶器の持つ重量感、質感、光沢を有する
と共に、耐衝撃性、耐薬品性を備えた優れた成形品を得
ることができる。Industrial Applicability As described above, the polyester resin composition of the present invention can obtain an excellent molded article having impact resistance and chemical resistance as well as having the weight, texture and luster of pottery. it can.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F071 AA45 AA46 AA50 AA51 AA60 AB24 AE17 BA01 BB05 4J002 CF052 CF062 CF071 CF082 CG002 CH072 CM044 DA027 DA097 DC007 DE097 DE107 DE137 DE147 DE187 DE237 DG027 DG046 DG057 DH047 DJ007 DJ017 DJ037 DJ047 DJ057 DK007 DL007 FA047 FA107 FD016 FD017 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4F071 AA45 AA46 AA50 AA51 AA60 AB24 AE17 BA01 BB05 4J002 CF052 CF062 CF071 CF082 CG002 CH072 CM044 DA027 DA097 DC007 DE097 DE107 DE137 DE147 DE187 DE237 DG027 DG046 DG057 DH047 DJ007 DJ017 DJ037 DJ047 DJ057 DK007 DL007 FA047 FA107 FD016 FD017
Claims (5)
（ａ）１２〜６４重量％、下記（ｂ）６〜４８重量％お
よび下記（ｃ）７０〜２０重量％を含有してなるポリエ
ステル樹脂組成物。 （ａ）ポリブチレンテレフタレート樹脂 （ｂ）ポリブチレンテレフタレート樹脂よりも結晶化速
度の遅いポリエステル樹脂又は非晶性樹脂 （ｃ）硫酸バリウム全体を１００重量％として、粒径
０．３μｍ以上の粒子を９７〜６０重量％、０．３μｍ
未満の粒子を３〜４０重量％含有する硫酸バリウム1. A polyester resin containing (a) 12 to 64% by weight, (b) 6 to 48% by weight, and (c) 70 to 20% by weight based on 100% by weight of the entire composition. Composition. (A) Polybutylene terephthalate resin (b) Polyester resin or amorphous resin having a slower crystallization rate than polybutylene terephthalate resin (c) Barium sulfate is 100% by weight as a whole, and 97 particles having a particle size of 0.3 μm or more are used. ~ 60% by weight, 0.3 μm
Sulfate containing less than 3 to 40% by weight of particles
結晶化速度の遅いポリエステル樹脂又は非晶性樹脂
（ｂ）がポリエチレンテレフタレート樹脂、ポリエチレ
ンナフタレート樹脂、ジオール成分としてエチレングリ
コール残基、シクロヘキサンジメタノール残基及び、ジ
カルボン酸成分としてテレフタル酸残基を構成成分とす
るポリエステル共重合体および非晶性樹脂から選ばれる
１種以上である請求項１記載のポリエステル樹脂組成
物。2. A polyester resin or an amorphous resin (b) having a slower crystallization rate than a polybutylene terephthalate resin is a polyethylene terephthalate resin, a polyethylene naphthalate resin, an ethylene glycol residue as a diol component, a cyclohexanedimethanol residue and The polyester resin composition according to claim 1, which is one or more selected from a polyester copolymer having a terephthalic acid residue as a constituent component and a non-crystalline resin as the dicarboxylic acid component.
物の加熱減量が０．５重量％以下である請求項１または
２記載のポリエステル樹脂組成物。3. The polyester resin composition according to claim 1, wherein the weight loss upon heating of the composition when heat-treated at 250 ° C. for 30 minutes is 0.5% by weight or less.
るものである請求項１〜３のいずれかに記載のポリエス
テル樹脂組成物。4. The polyester resin composition according to any one of claims 1 to 3, which is used for applications requiring a ceramic appearance.
ステル樹脂組成物を成形してなる、陶器調外観が要求さ
れる用途に使用される成形品。5. A molded product, which is formed by molding the polyester resin composition according to any one of claims 1 to 3, and is used for applications requiring a ceramic appearance.
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|---|---|---|---|
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|---|---|---|---|
| JP2001211863A JP4910256B2 (en) | 2001-07-12 | 2001-07-12 | Polyester resin composition |
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| JP7347694B1 (en) | 2021-12-27 | 2023-09-20 | 東レ株式会社 | Thermoplastic polyester resin composition, method for producing thermoplastic polyester resin composition, and molded product |
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| US8569403B2 (en) | 2003-08-26 | 2013-10-29 | Mitsubishi Rayon Co., Ltd. | Thermoplastic resin composition for light reflector, formed article for light reflector, light reflector, and method for producing formed article for light reflector |
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| KR100964988B1 (en) | 2006-11-30 | 2010-06-21 | 주식회사 삼양사 | Polyester resin composition and molded product using the same |
| JP2010150484A (en) * | 2008-12-26 | 2010-07-08 | Wintech Polymer Ltd | Polybutylene terephthalate series resin composition and molding |
| JP2013023552A (en) * | 2011-07-20 | 2013-02-04 | Wintech Polymer Ltd | Method for producing resin pellet, and automobile interior component |
| JP7347694B1 (en) | 2021-12-27 | 2023-09-20 | 東レ株式会社 | Thermoplastic polyester resin composition, method for producing thermoplastic polyester resin composition, and molded product |
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