JP2006282933A - Thermoplastic reinforced resin composition - Google Patents
Thermoplastic reinforced resin composition Download PDFInfo
- Publication number
- JP2006282933A JP2006282933A JP2005107461A JP2005107461A JP2006282933A JP 2006282933 A JP2006282933 A JP 2006282933A JP 2005107461 A JP2005107461 A JP 2005107461A JP 2005107461 A JP2005107461 A JP 2005107461A JP 2006282933 A JP2006282933 A JP 2006282933A
- Authority
- JP
- Japan
- Prior art keywords
- component
- resin composition
- reinforced resin
- thermoplastic
- thermoplastic reinforced
- 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
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- 239000011342 resin composition Substances 0.000 title claims abstract description 55
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 36
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 36
- -1 polytrimethylene terephthalate Polymers 0.000 claims abstract description 74
- 239000011256 inorganic filler Substances 0.000 claims abstract description 43
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 43
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims abstract description 30
- 239000004611 light stabiliser Substances 0.000 claims abstract description 19
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- 239000003822 epoxy resin Substances 0.000 claims description 23
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
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- 229910052618 mica group Inorganic materials 0.000 claims description 9
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
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- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
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- 239000000843 powder Substances 0.000 description 3
- 150000003902 salicylic acid esters Chemical class 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical class CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
本発明は、耐光性、外観に優れ、高剛性、高表面硬度の熱可塑性強化樹脂組成物、及びそれを含んでなる成形体に関する。詳しくは、得られる成形品が良外観であり、耐光性、機械的強度、剛性、表面硬度、寸法安定性に優れるポリトリメチレンテレフタレート強化樹脂組成物、及びそれを用いた洗面カウンター、キッチンカウンター、浴槽、洗面ボール、手洗ボール、トイレカウンターなど浴室、洗面所、トイレ、台所で使用される製品に関する。 The present invention relates to a thermoplastic reinforced resin composition having excellent light resistance and appearance, high rigidity, and high surface hardness, and a molded body comprising the same. Specifically, the molded product obtained has a good appearance, light resistance, mechanical strength, rigidity, surface hardness, dimensional stability, polytrimethylene terephthalate reinforced resin composition, and a wash counter, kitchen counter using the same The present invention relates to products used in bathrooms, washrooms, toilets, and kitchens such as bathtubs, wash-basins, hand-wash balls, and toilet counters.
浴室、洗面所、トイレ、台所の洗面ボール、手洗ボールやカウンターなど水周り建築部材には重くて脆い陶器に代わり、不飽和ポリエステルやアクリル系の熱硬化性樹脂にガラス繊維などを配合した繊維補強熱硬化性樹脂が多く使用されてきた。
しかし、熱硬化性樹脂製品は、リサイクルの可能性はほとんどなく、その廃棄処理は現状では埋め立てが主な処理法となっている。しかも、その廃棄の際には成形品を減容するのが困難で、廃棄処理法の点で大きな問題を生じている。
このため、熱硬化性樹脂製品に代わる、熱可塑性樹脂製品が注目されつつある。必要な特性としては、成形品が良外観であり、機械的強度、剛性に優れることはもとより、表面硬度、寸法安定性、耐光性などの厳しい性能が要求される。
Fiber reinforcement with glass fiber in unsaturated polyester or acrylic thermosetting resin instead of heavy and brittle ceramics for water-related building materials such as bathrooms, washrooms, toilets, kitchen washbasins, hand-washing balls and counters Many thermosetting resins have been used.
However, thermosetting resin products have little possibility of recycling, and the disposal method is currently the main disposal method by landfill. Moreover, it is difficult to reduce the volume of the molded product at the time of disposal, which causes a big problem in terms of the disposal method.
For this reason, thermoplastic resin products replacing the thermosetting resin products are attracting attention. Necessary properties are that the molded product has a good appearance, excellent mechanical strength and rigidity, as well as severe performance such as surface hardness, dimensional stability, and light resistance.
熱可塑性樹脂組成物の機械的強度、剛性を改良する手法としては、ガラス繊維を配合する方法が知られている。
例えば、ポリブチレンテレフタレート、ポリブチレンテレフタレートとポリエチレンテレフタレートの混合物などのポリエステル樹脂とエポキシ化合物、無機充填剤、触媒化合物からなる組成物によってポリエステルの欠点である加水分解安定性、溶融粘度安定性を改良した無機充填剤含有線状ポリエステルの検討が行われている（特許文献１参照）。
また、ポリエチレンテレフタレート、ポリブチレンテレフタレートなどポリエステル樹脂と、特定エポキシ樹脂、繊維強化材を配合した組成物により耐熱性、機械的特性、耐加水分解性を改良する検討が行われている（特許文献２参照）。
As a method for improving the mechanical strength and rigidity of the thermoplastic resin composition, a method of blending glass fibers is known.
For example, a polyester resin such as polybutylene terephthalate, a mixture of polybutylene terephthalate and polyethylene terephthalate, and an epoxy compound, an inorganic filler, and a catalyst compound improve the hydrolytic stability and melt viscosity stability, which are the disadvantages of polyester. An inorganic filler-containing linear polyester has been studied (see Patent Document 1).
In addition, studies are being made to improve heat resistance, mechanical properties, and hydrolysis resistance by a composition comprising a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, a specific epoxy resin, and a fiber reinforcing material (Patent Document 2). reference).
また、機械的強度と耐熱性を改良するために、芳香族ポリエステル、特に、ポリブチレンテレフタレートとポリカーボネートからなる樹脂組成物に無機充填材を配合させることも検討されている（特許文献３参照）。
しかし、ポリブチレンテレフタレートに無機充填材を配合した樹脂組成物は、成形品外観が不良であるばかりか、射出成形により成形した場合に、成形品のそり変形が大きく、寸法安定性が低いという問題がある。また、ポリエチレンテレフタレート強化樹脂組成物は金型温度１００℃以下の通常の射出成形が困難であり、よい外観の成形品を得ることはできない。
In addition, in order to improve mechanical strength and heat resistance, it has been studied to add an inorganic filler to a resin composition composed of aromatic polyester, in particular, polybutylene terephthalate and polycarbonate (see Patent Document 3).
However, the resin composition in which an inorganic filler is blended with polybutylene terephthalate has not only a poor appearance of the molded product, but also has a problem that when molded by injection molding, warpage deformation of the molded product is large and dimensional stability is low. There is. In addition, the polyethylene terephthalate reinforced resin composition is difficult to perform normal injection molding at a mold temperature of 100 ° C. or less, and a molded article having a good appearance cannot be obtained.
特に高剛性を目的とし高濃度に無機充填材を配合した場合、無機充填材の表面への浮き出しや、充填材に沿った凹凸によって表面硬度や表面外観が著しく損なわれる。また、無機充填材の表面特性や物性を改良するための表面処理剤によって、耐光性を損ない、初期耐光変色（黄変）をおこし、上記用途に必要な耐光性を達成することができない。
従来のポリエステル強化樹脂組成物では上記の水周り建築部材用途に必要とされる高剛性、機械的強度、表面硬度、寸法安定性などと、良外観、耐光性の要求を同時に達成することはできず、これらを満足する熱可塑性強化樹脂組成物の開発が必要とされている。
The conventional polyester reinforced resin composition can achieve the high rigidity, mechanical strength, surface hardness, dimensional stability, and other requirements for good appearance and light resistance required for the above-mentioned water-based building materials. However, it is necessary to develop a thermoplastic reinforced resin composition that satisfies these requirements.
本発明の目的は洗面カウンター、キッチンカウンター、浴槽、洗面ボール、手洗ボール、トイレカウンターなど浴室、洗面所、トイレ、台所で使用される製品に使用することができる、外観が極めて良好であり、耐光性、機械的強度、剛性、表面硬度、寸法安定性に優れるポリトリメチレンテレフタレート強化樹脂組成物、及びそれを用いた成形品を提供することにある。 The object of the present invention can be used for products used in bathrooms, washrooms, toilets, kitchens such as washbasins, kitchen counters, bathtubs, washbasins, hand-washing balls, toilet counters, etc. An object of the present invention is to provide a polytrimethylene terephthalate reinforced resin composition having excellent properties, mechanical strength, rigidity, surface hardness, and dimensional stability, and a molded article using the same.
本発明者は、前記課題を解決するため、（Ａ）ポリトリメチレンテレフタレート、（Ｂ）熱可塑性樹脂組成物、（Ｃ）光安定剤および（Ｄ）無機充填材からなる熱可塑性強化樹脂組成物によって、外観、耐光性、機械的強度、剛性、表面硬度、寸法安定性の要求を達成することを見出し、本発明に至った。
すなわち本発明は、
（１）（Ａ）ポリトリメチレンテレフタレート、（Ｂ）熱可塑性樹脂組成物、（Ｃ）光安定剤および（Ｄ）無機充填材を含む熱可塑性強化樹脂組成物であって、下記ｉ）からｉｉｉ）の条件を満たすことを特徴とする熱可塑性強化樹脂組成物、
ｉ）（Ａ）成分と（Ｂ）成分の重量比が１／９９〜１００／０の範囲である、
ｉｉ）（Ａ）成分と（Ｂ）成分の合計１００重量部に対し、（Ｃ）光安定剤が０．０１〜５重量部である、
ｉｉｉ）（Ａ）成分と（Ｂ）成分の合計１００重量部に対し、（Ｄ）無機充填材が５〜３００重量部である。
（２）（Ａ）成分と（Ｂ）成分の重量比が、５０／５０〜９９／１である上記（１）記載の熱可塑性強化樹脂組成物、
（３）（Ｂ）成分が、ポリカーボネートであることを特徴とする上記１又は２記載の熱可塑性樹脂組成物、
（４）（Ｃ）成分が、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物、トリアジン系化合物、ベンゾエート系化合物、安息香酸エステル系化合物、サリチル酸エステル系化合物、マロン酸エステル系化合物、有機ニッケル化合物、シアノアクリレート系化合物、オキシアニリド系化合物およびヒンダードアミン系化合物の群から選ばれる一種以上の光安定剤からなる上記（１）〜（３）のいずれかに記載の熱可塑性強化樹脂組成物、
（５）（Ｃ）成分の少なくとも１つが、２５０〜３２０ｎｍに吸収波長ピークを有する紫外線吸収剤である請求項４記載の熱可塑性強化樹脂組成物、
（６）（Ｄ）成分が、ガラス繊維（Ｄ１）である上記（１）〜（５）のいずれかに記載の熱可塑性強化樹脂組成物、
（７）（Ｄ）成分が、ウォラストナイト、タルク、マイカ、カオリン、チタン酸カリウムウィスカー、炭酸カルシウムウィスカーおよび硫酸バリウムの群から選ばれる一種以上の無機充填材（Ｄ２）である上記（１）〜（５）のいずれかに記載の熱可塑性強化樹脂組成物、
（８）（Ｄ）成分が、ガラス繊維（Ｄ１）とウォラストナイト、タルク、マイカ、カオリン、チタン酸カリウムウィスカー、炭酸カルシウムウィスカー、硫酸バリウムの群から選ばれる一種以上の無機充填材（Ｄ２）からなる上記（１）〜（５）のいずれかに記載の熱可塑性強化樹脂組成物、
（９）（Ｄ１）成分と（Ｄ２）成分の重量比が、（Ｄ１）＜（Ｄ２）である上記（８）に記載の熱可塑性強化樹脂組成物、
（１０）熱可塑性強化樹脂組成物が、更に（Ａ）成分と（Ｂ）成分の合計１００重量部に対し（Ｅ）エポキシ樹脂を０．１〜２０重量部含む上記（１）〜（９）のいずれかに記載の熱可塑性強化樹脂組成物、
（１１）（Ａ）ポリトリメチレンテレフタレートを溶融した後に、（Ｄ）無機充填材を添加することにより製造される上記（１）〜（１０）のいずれかに記載の熱可塑性強化樹脂組成物、
（１２）上記（１）〜（１１）のいずれかに記載の熱可塑性強化樹脂組成物からなる成形体、
（１３）上記（１２）に記載の成形体を構造部材の少なくとも一部に含む、浴室用製品、洗面所用製品、トイレ用製品、又は流し台用製品である成形体、
（１４）上記（１３）に記載の成形体が、洗面カウンター、キッチンカウンター、浴槽、洗面ボール、手洗ボール、トイレカウンター、キャビネット天板である成形体、
（１５）上記（１２）〜（１４）のいずれかに記載の成形体の表面硬度が、バーコル硬度３０以上である成形体、
である。
In order to solve the above problems, the present inventor has (A) polytrimethylene terephthalate, (B) a thermoplastic resin composition, (C) a light stabilizer and (D) a thermoplastic reinforced resin composition comprising an inorganic filler. Thus, the inventors have found that the requirements for appearance, light resistance, mechanical strength, rigidity, surface hardness, and dimensional stability can be achieved, and the present invention has been achieved.
That is, the present invention
(1) A thermoplastic reinforced resin composition comprising (A) polytrimethylene terephthalate, (B) a thermoplastic resin composition, (C) a light stabilizer and (D) an inorganic filler, the following i) to iii A thermoplastic reinforced resin composition characterized by satisfying the condition of
i) The weight ratio of the component (A) to the component (B) is in the range of 1/99 to 100/0.
ii) (C) Light stabilizer is 0.01-5 weight part with respect to a total of 100 weight part of (A) component and (B) component,
iii) The inorganic filler is 5 to 300 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B).
(2) The thermoplastic reinforced resin composition according to the above (1), wherein the weight ratio of the component (A) and the component (B) is 50/50 to 99/1,
(3) The thermoplastic resin composition as described in 1 or 2 above, wherein the component (B) is polycarbonate,
(4) Component (C) is a benzotriazole compound, a benzophenone compound, a triazine compound, a benzoate compound, a benzoate compound, a salicylate compound, a malonate compound, an organic nickel compound, or a cyanoacrylate compound. The thermoplastic reinforced resin composition according to any one of the above (1) to (3), which comprises one or more light stabilizers selected from the group of compounds, oxyanilide compounds and hindered amine compounds,
(5) The thermoplastic reinforced resin composition according to claim 4, wherein at least one of the components (C) is an ultraviolet absorber having an absorption wavelength peak at 250 to 320 nm.
(6) The thermoplastic reinforced resin composition according to any one of (1) to (5), wherein the component (D) is glass fiber (D1),
(7) The above (1), wherein the component (D) is one or more inorganic fillers (D2) selected from the group of wollastonite, talc, mica, kaolin, potassium titanate whisker, calcium carbonate whisker and barium sulfate. The thermoplastic reinforced resin composition according to any one of to (5),
(8) One or more inorganic fillers (D2) in which component (D) is selected from the group consisting of glass fiber (D1) and wollastonite, talc, mica, kaolin, potassium titanate whisker, calcium carbonate whisker, and barium sulfate. The thermoplastic reinforced resin composition according to any one of (1) to (5), comprising:
(9) The thermoplastic reinforced resin composition according to (8), wherein the weight ratio of the component (D1) and the component (D2) is (D1) <(D2),
(10) The above-mentioned (1) to (9), wherein the thermoplastic reinforced resin composition further comprises 0.1 to 20 parts by weight of (E) epoxy resin with respect to 100 parts by weight of the total of component (A) and component (B). The thermoplastic reinforced resin composition according to any one of
(11) The thermoplastic reinforced resin composition according to any one of the above (1) to (10), which is produced by adding (D) an inorganic filler after melting (A) polytrimethylene terephthalate,
(12) A molded article comprising the thermoplastic reinforced resin composition according to any one of (1) to (11) above,
(13) A molded product that is a bathroom product, a toilet product, a toilet product, or a sink product, comprising the molded product according to (12) in at least a part of the structural member,
(14) The molded product according to (13) above is a wash counter, kitchen counter, bathtub, wash bowl, hand wash ball, toilet counter, cabinet top plate,
(15) A molded body having a surface hardness of 30 or more in Barcol hardness, according to any one of (12) to (14) above,
It is.
本発明について、以下具体的に説明する。
本発明における（Ａ）ポリトリメチレンテレフタレート（以下、ＰＴＴと略称することがある。）とは、酸成分としてテレフタル酸を用い、グリコール成分としてトリメチレングリコールを用いたポリエステルポリマーを示している。ここで、トリメチレングリコールとは、１，３−プロパンジオールである。
このほかに、本発明の目的を損なわない範囲で、酸成分として、テレフタル酸以外の芳香族ジカルボン酸、例えばフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、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、ジフェニルメタンジカルボン酸、ジフェニルケトンジカルボン酸、ジフェニルスルフォンジカルボン酸等；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；シクロヘキサンジカルボン酸等の脂環族ジカルボン酸；ε−オキシカプロン酸、ヒドロキシ安息香酸、ヒドロキシエトキシ安息香酸等のオキシジカルボン酸を用い、グリコール成分として、エチレングリコール、テトラメチレングリコール、ペンタメチレングリコール、ヘキサメチレングリコール、オクタメチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノール、キシリレングリコール、ジエチレングリコール、ポリオキシアルキレングリコール、ハイドロキノン等を一部用いて共重合することができる。
The present invention will be specifically described below.
In the present invention, (A) polytrimethylene terephthalate (hereinafter sometimes abbreviated as PTT) refers to a polyester polymer using terephthalic acid as the acid component and trimethylene glycol as the glycol component. Here, trimethylene glycol is 1,3-propanediol.
In addition, as long as the object of the present invention is not impaired, an aromatic dicarboxylic acid other than terephthalic acid, for example, phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, Diphenoxyethane dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenyl ketone dicarboxylic acid, diphenyl sulfone dicarboxylic acid, etc .; aliphatic dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; ε-oxy Using oxydicarboxylic acid such as caproic acid, hydroxybenzoic acid, hydroxyethoxybenzoic acid, etc., as glycol components, ethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, Kuta glycol, neopentyl glycol, cyclohexanedimethanol, xylylene glycol, diethylene glycol, polyoxyalkylene glycol, may be copolymerized with some hydroquinone.
共重合する場合の共重合成分の量は、本発明の目的を損なわない範囲であれば特に制限はないが、通常、全酸成分の２０モル％以下、あるいは全グリコール成分の２０モル％以下であることが好ましい。
また、上述のポリエステル成分に分岐成分、例えばトリカルバリル酸、トリメシン酸、トリメリット酸等の、三官能または四官能のエステル形成能を持つ酸、またはグリセリン、トリメチロールプロパン、ペンタエリトリット等の三官能または四官能のエステル形成能を持つアルコールを共重合してもよく、その場合、これらの分岐成分の量は全酸成分、または全グリコール成分の１．０モル％以下、好ましくは、０．５モル％以下、さらに好ましくは、０．３モル％以下である。更に、ＰＴＴはこれら共重合成分を２種類以上組み合わせて使用しても構わない。
The amount of the copolymer component in the copolymerization is not particularly limited as long as it does not impair the object of the present invention, but is usually 20 mol% or less of the total acid component or 20 mol% or less of the total glycol component. Preferably there is.
In addition, the above-described polyester component may be added to a branched component, for example, an acid having trifunctional or tetrafunctional ester-forming ability such as tricarballylic acid, trimesic acid, trimellitic acid, or glycerin, trimethylolpropane, pentaerythritol, etc. Alcohols having a functional or tetrafunctional ester-forming ability may be copolymerized, and in this case, the amount of these branching components is 1.0 mol% or less of the total acid component or the total glycol component, preferably 0.8. It is 5 mol% or less, More preferably, it is 0.3 mol% or less. Further, PTT may be used in combination of two or more of these copolymer components.
本発明に用いられるＰＴＴの製造方法は、特に限定されるものではないが、例えば、特開昭５１−１４０９９２号公報、特開平５−２６２８６２号公報、特開平８−３１１１７７号公報等に記載されている方法に従って得ることができる。
例えば、テレフタル酸またはそのエステル形成性誘導体（例えばジメチルエステル、モノメチルエステル等の低級アルキルエステル）とトリメチレングリコールまたはそのエステル形成性誘導体とを、触媒の存在下、好適な温度・時間で加熱反応させ、更に得られるテレフタル酸のグリコールエステルを触媒の存在下、好適な温度・時間で所望の重合度まで重縮合反応させる方法が挙げられる。
The method for producing the PTT used in the present invention is not particularly limited. For example, it is described in JP-A-51-140992, JP-A-5-262862, JP-A-8-311177, and the like. Can be obtained according to the method.
For example, terephthalic acid or an ester-forming derivative thereof (for example, a lower alkyl ester such as dimethyl ester or monomethyl ester) is reacted with trimethylene glycol or an ester-forming derivative thereof at a suitable temperature and time in the presence of a catalyst. Further, there is a method in which the glycol ester of terephthalic acid obtained is subjected to a polycondensation reaction to a desired degree of polymerization at a suitable temperature and time in the presence of a catalyst.
重合方法についても、特に限定されず、溶融重合、界面重合、溶液重合、塊状重合、固相重合、及びこれらを組み合わせた方法を利用することができる。
本発明に用いられるＰＴＴの極限粘度［η］は０．６０ｄｌ／ｇ〜１．５０ｄｌ／ｇであることが組成物の機械特性、成形性、特に靭性面から好ましく、［η］が０．６８ｄｌ／ｇ〜１．４０ｄｌ／ｇであることがより好ましい。さらに組成物の成形性、耐薬品性の観点から［η］が０．７５ｄｌ／ｇ〜１．３０ｄｌ／ｇであることが最も好ましい。
ＰＴＴの極限粘度［η］については、オストワルド粘度計を用い、３５℃、ｏ-クロロフェノール中にＰＴＴを含む樹脂組成物を、溶質（ＰＴＴ樹脂成分）／溶液＝１．００ｇ／ｄｌになるように溶解させ、不溶分（無機充填材等）をフィルターで除去した後、不溶分除去後の溶液を用いて比粘度ηｓｐを測定し、下記式により求めることができる。
［η］＝０．７１３×ηｓｐ／Ｃ＋０．１０８６
Ｃ＝１．００ｇ／ｄｌ
The polymerization method is not particularly limited, and melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, and a combination thereof can be used.
The intrinsic viscosity [η] of the PTT used in the present invention is preferably 0.60 dl / g to 1.50 dl / g from the viewpoint of mechanical properties and moldability, particularly toughness of the composition, and [η] is 0.68 dl. / G to 1.40 dl / g is more preferable. Furthermore, from the viewpoint of moldability and chemical resistance of the composition, [η] is most preferably 0.75 dl / g to 1.30 dl / g.
With respect to the intrinsic viscosity [η] of PTT, an Ostwald viscometer was used, and a resin composition containing PTT in o-chlorophenol at 35 ° C. was dissolved (PTT resin component) /solution=1.00 g / dl. Insoluble matter (inorganic filler, etc.) is removed with a filter, the specific viscosity ηsp is measured using the solution after the insoluble matter is removed, and can be determined by the following formula.
[Η] = 0.713 × ηsp / C + 0.1086
C = 1.00 g / dl
本発明のポリトリメチレンテレフタレートには、必要に応じて、各種の添化剤、例えば、熱安定剤、消泡剤、整色剤、難燃剤、酸化防止剤、結晶核剤、蛍光増白剤、艶消し剤等を共重合又は混合してもよい。
次に、本発の（Ｂ）熱可塑性樹脂について説明する。熱可塑性樹脂とは加熱すると流動性を示し、これを利用して成形加工できる合成樹脂のことである。
熱可塑性樹脂の具体例としては、例えば、ポリカーボネート、ポリトリメチレンテレフタレート以外のポリエステル、ポリアミド、ポリフェニレンスルフィド、ポリオキシメチレン、ポリフェニレンエーテル、エチレン／プロピレン／非共役ジエン樹脂、エチレン／アクリル酸エチル樹脂、エチレン／メタクリル酸グリシジル樹脂、エチレン／酢酸ビニル／メタクリル酸グリシジル樹脂、エチレン／酢酸ビニル／メタクリル酸グリシジル樹脂、エチレン／プロピレン−ｇ−無水マレイン酸樹脂、スチレン系樹脂又はこれら熱可塑性樹脂の２種以上の混合物が挙げられる。
In the polytrimethylene terephthalate of the present invention, various additives, for example, a heat stabilizer, an antifoaming agent, a color adjuster, a flame retardant, an antioxidant, a crystal nucleating agent, and a fluorescent brightening agent are used as necessary. A matting agent or the like may be copolymerized or mixed.
Next, the original (B) thermoplastic resin will be described. A thermoplastic resin is a synthetic resin that exhibits fluidity when heated and can be molded using this.
Specific examples of the thermoplastic resin include polycarbonate, polyester other than polytrimethylene terephthalate, polyamide, polyphenylene sulfide, polyoxymethylene, polyphenylene ether, ethylene / propylene / non-conjugated diene resin, ethylene / ethyl acrylate resin, ethylene / Glycidyl methacrylate resin, ethylene / vinyl acetate / glycidyl methacrylate resin, ethylene / vinyl acetate / glycidyl methacrylate resin, ethylene / propylene-g-maleic anhydride resin, styrenic resin or two or more of these thermoplastic resins A mixture is mentioned.
中でも、ポリカーボネート、ポリトリメチレンテレフタレート以外のポリエステルが好ましく、特に機械的特性の観点からポリカーボネートが最も好ましい。
本発明に好ましく用いられるポリカーボネート（以下ＰＣと省略することもある）は、下記式（１）で表される繰り返し単位からなる主鎖を有するものである。
−(Ｏ−Ａｒ−Ｏ−ＣＯ)− （１）
（式中、Ａｒは、二価の芳香族残基であり、例えば、フェニレン、ナフチレン、ビフェニレン、ピリジレンや、下記式（２）で表される基が挙げられる。）
−Ａｒ１−Ｙ−Ａｒ２− （２）
（式中、Ａｒ１及びＡｒ２はそれぞれアリーレン基であり、例えば、フェニレン、ナフチレン、ビフェニレン、ピリジレン等の基を表す。Ｙはアルキレン基または置換アルキレン基である。）
また、下記式（３）で示される二価の芳香族残基を共重合体成分として含有している場合も含む。
−Ａｒ１−Ｚ−Ａｒ２− （３）
（式中Ａｒ１、Ａｒ２は式（２）と同じ。Ｚは単なる結合または−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ２−、−ＣＯ２−、−ＣＯＮＲ１−等の二価の基である。ただし、Ｒ１は、それぞれ独立に水素原子、炭素数１〜６の低級アルキル基、炭素数５〜１０のシクロアルキル基または炭素数６〜３０のアリール基である。）
これら二価の芳香族残基の具体例としては下記式（４）で表されるもの等が挙げられる。
Of these, polyesters other than polycarbonate and polytrimethylene terephthalate are preferable, and polycarbonate is most preferable from the viewpoint of mechanical properties.
The polycarbonate preferably used in the present invention (hereinafter sometimes abbreviated as PC) has a main chain composed of a repeating unit represented by the following formula (1).
-(O-Ar-O-CO)-(1)
(In the formula, Ar is a divalent aromatic residue, and examples thereof include phenylene, naphthylene, biphenylene, pyridylene, and groups represented by the following formula (2).)
—Ar 1 —Y—Ar 2 — (2)
(In the formula, Ar 1 and Ar 2 are each an arylene group, for example, a group such as phenylene, naphthylene, biphenylene, pyridylene, etc. Y is an alkylene group or a substituted alkylene group.)
Moreover, the case where the bivalent aromatic residue shown by following formula (3) is contained as a copolymer component is also included.
—Ar 1 —Z—Ar 2 — (3)
(In the formula, Ar 1 and Ar 2 are the same as those in the formula (2). Z represents a simple bond or two such as —O—, —CO—, —S—, —SO 2 —, —CO 2 —, —CONR 1 —, etc. R 1 is independently a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms.)
Specific examples of these divalent aromatic residues include those represented by the following formula (4).
（式中、Ｒ７及びＲ８は、それぞれ独立に、水素、ハロゲン、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、炭素数５〜１０のシクロアルキル基または炭素数６〜３０のアリール基である。ｍ及びｎは１〜４の整数で、ｍが２〜４の場合には各Ｒ７はそれぞれ同一でも異なるものであってもよいし、ｎが２〜４の場合は各Ｒ８はそれぞれ同一でも異なるものであっても良い。）
これら二価の芳香族残基の中でも、下記式（５）で表される基が好ましい一例である。
(Wherein R 7 and R 8 are each independently hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 carbon atoms. M and n are integers of 1 to 4, and when m is 2 to 4, each R 7 may be the same or different, and n is 2 to 4. In this case, each R 8 may be the same or different.)
Among these divalent aromatic residues, a group represented by the following formula (5) is a preferred example.
特に、上記の式（５）で表される基をＡｒとする繰り返し単位を８５モル％以上（ポリカーボネート中の全モノマー単位を基準として）含むポリカーボネートが特に好ましい。
また、本発明に用いることができるポリカーボネートは、三価以上の芳香族残基を共重合成分として含有している場合も含む。
ポリマー末端の分子構造は特に限定されないが、フェノール性水酸基、アリールカーボネート基、アルキルカーボネート基から選ばれた１種以上の末端基を結合することができる。これらの中で、フェノール性水酸基、フェニルカーボネート基、ｐ−ｔ−ブチルフェニルカーボネート基、ｐ−クミルフェニルカーボネート等が末端構造として好ましい。フェノール性水酸基末端の全末端基数に対する割合は、特に限定されないが、よりすぐれた色調や機械的物性を得る観点からは、フェノール性水酸基末端の割合が全末端基数の２０％以上であることが好ましく、２０〜８０％の範囲にあることが更に好ましい。フェノール性水酸基末端の割合が全末端基数の８０％を超えると、組成物の溶融時の熱安定性が若干低下する傾向にある。フェノール性水酸基末端の割合は、一般にＮＭＲを用いて測定する方法（ＮＭＲ法）や、チタンを用いて測定する方法（チタン法）や、ＵＶもしくはＩＲを用いて測定する方法（ＵＶ法もしくはＩＲ法）で求めることができる。
Particularly preferred is a polycarbonate containing 85 mol% or more (based on all monomer units in the polycarbonate) of a repeating unit having Ar as the group represented by the above formula (5).
Moreover, the polycarbonate which can be used for this invention includes the case where the trivalent or more aromatic residue is contained as a copolymerization component.
Although the molecular structure of the polymer terminal is not particularly limited, one or more terminal groups selected from a phenolic hydroxyl group, an aryl carbonate group, and an alkyl carbonate group can be bonded. Among these, a phenolic hydroxyl group, a phenyl carbonate group, a pt-butylphenyl carbonate group, p-cumylphenyl carbonate and the like are preferable as a terminal structure. The ratio of the number of phenolic hydroxyl groups to the total number of terminal groups is not particularly limited, but from the viewpoint of obtaining better color tone and mechanical properties, the ratio of phenolic hydroxyl groups is preferably 20% or more of the total number of terminal groups. More preferably, it is in the range of 20 to 80%. When the proportion of phenolic hydroxyl groups exceeds 80% of the total number of terminal groups, the thermal stability during melting of the composition tends to be slightly reduced. The ratio of phenolic hydroxyl terminal is generally measured using NMR (NMR method), measured using titanium (titanium method), or measured using UV or IR (UV method or IR method). ).
本発明に使用されるポリカーボネートの重量平均分子量（Ｍｗ）は、一般に耐衝撃性の観点から５０００以上、また熱可塑性樹脂組成物の溶融流動性の観点から２０００００以下の範囲にあることが好ましく、より好ましくは１００００〜６００００であり、さらに好ましくは１５０００〜４００００であり、特に好ましくは１８０００〜３００００である。
重量平均分子量（Ｍｗ）の測定は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）を用いて行い、測定条件は以下の通りである。すなわち、テトラヒドロフランを溶媒とし、ポリスチレンゲルを使用し、標準単分散ポリスチレンの構成曲線から下式による換算分子量較正曲線を用いて求められる。
ＭＰＣ＝０．３５９１ＭＰＳ １．０３８８
（式中、ＭＰＣはポリカーボネートの重量平均分子量、ＭＰＳはポリスチレンの重量平均分子量である。）
In general, the weight average molecular weight (Mw) of the polycarbonate used in the present invention is preferably 5000 or more from the viewpoint of impact resistance, and preferably 200,000 or less from the viewpoint of the melt fluidity of the thermoplastic resin composition. Preferably it is 10,000-60000, More preferably, it is 15000-40000, Most preferably, it is 18000-30000.
The weight average molecular weight (Mw) is measured using gel permeation chromatography (GPC), and the measurement conditions are as follows. That is, it is obtained using a converted molecular weight calibration curve according to the following formula from a standard monodisperse polystyrene composition curve using tetrahydrofuran as a solvent and polystyrene gel.
M PC = 0.3591 M PS 1.0388
(In the formula, MPC is the weight average molecular weight of polycarbonate, and MPS is the weight average molecular weight of polystyrene.)
本発明で用いられるポリカーボネート樹脂は、公知の方法で製造したものを使用することができる。例えば、芳香族ジヒドロキシ化合物とカーボネート前駆体と反応せしめる公知の方法で製造することができる。具体的には、芳香族ジヒドロキシ化合物とカーボネート前駆体（例えばホスゲン）を水酸化ナトリウム水溶液及び塩化メチレン溶媒の存在下に反応させる界面重合法（例えばホスゲン法）、芳香族ジヒドロキシ化合物と炭酸ジエステル（例えばジフェニルカーボネート）などを反応させるエステル交換法（溶融法）、ホスゲン法または溶融法で得られた結晶化カーボネートプレポリマーを固相重合する方法〔特開平１−１５８０３３号公報（米国特許第４，９４８，８７１号明細書に対応）、特開平１−２７１４２６号公報、特開平３−６８６２７号公報（米国特許第５，２０４，３７７号明細書に対応）〕等の方法により製造されたものが用いられる。 What was manufactured by the well-known method can be used for the polycarbonate resin used by this invention. For example, it can be produced by a known method in which an aromatic dihydroxy compound and a carbonate precursor are reacted. Specifically, an interfacial polymerization method (for example, phosgene method) in which an aromatic dihydroxy compound and a carbonate precursor (for example, phosgene) are reacted in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent, an aromatic dihydroxy compound and a carbonic acid diester (for example, A method of solid-phase polymerization of a crystallized carbonate prepolymer obtained by a transesterification method (melting method), a phosgene method or a melting method in which diphenyl carbonate) is reacted [Japanese Patent Laid-Open No. 1-158033 (US Pat. No. 4,948) , 871), JP-A-1-271426, JP-A-3-68627 (corresponding to US Pat. No. 5,204,377)] and the like are used. It is done.
好ましいポリカーボネート樹脂としては、２価フェノール（芳香族ジヒドロキシ化合物）と炭酸ジエステルとからエステル交換法にて製造された実質的に塩素原子を含まないポリカーボネート樹脂があげられる。本発明では異なる構造や分子量の２種以上の異なるポリカーボネートを組み合わせて使用することも可能である。
ポリエステル樹脂としては、ポリトリメチレンテレフタレート以外のポリエステル樹脂であれば特に制限はなく、公知のポリエステル樹脂又はそれらの２種以上の混合物を用いることができる。
ポリアミド樹脂としては特に制限はなく公知のポリアミド樹脂あるいはそれらの２種以上の混合物を用いることができる。特に好適なポリアミド樹脂としては、ポリカプロラクタム（ナイロン６）、ポリヘキサメチレンアジパミド（ナイロン６６）、ポリヘキサメチレンドデカミド（ナイロン６１２）、ポリヘキサメチレンイソフタルアミド（ナイロン６Ｉ）又はこれらのうち少なくとも２種の異なったポリアミドを含むポリアミド共重合体である。
A preferable polycarbonate resin is a polycarbonate resin containing substantially no chlorine atom and produced by a transesterification method from a dihydric phenol (aromatic dihydroxy compound) and a carbonic acid diester. In the present invention, two or more different polycarbonates having different structures and molecular weights can be used in combination.
The polyester resin is not particularly limited as long as it is a polyester resin other than polytrimethylene terephthalate, and a known polyester resin or a mixture of two or more thereof can be used.
There is no restriction | limiting in particular as a polyamide resin, A well-known polyamide resin or those 2 or more types of mixtures can be used. Particularly suitable polyamide resins include polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene dodecamide (nylon 612), polyhexamethylene isophthalamide (nylon 6I) or at least of these A polyamide copolymer containing two different polyamides.
スチレン系樹脂としては、ポリスチレン、ゴム変性ポリスチレン、ＡＳ樹脂、ＡＢＳ樹脂あるいはそれらの混合物などが挙げられる。
（Ａ）ポリトリメチレンテレフタレートと（Ｂ）熱可塑性樹脂の重量比は、（Ａ）／（Ｂ）が１／９９〜１００／０の範囲である。剛性と表面硬度の観点から（Ａ）／（Ｂ）が５０／５０〜９９／１の範囲がより好ましく、（Ａ）／（Ｂ）が７０／３０〜９９／１の範囲が更に好ましく、（Ｂ）成分がポリカーボネートで且つ（Ａ）／（Ｂ）が８０／２０〜９９／１の範囲が最も好ましい。
Examples of the styrene resin include polystyrene, rubber-modified polystyrene, AS resin, ABS resin, or a mixture thereof.
As for the weight ratio of (A) polytrimethylene terephthalate and (B) thermoplastic resin, (A) / (B) is in the range of 1/99 to 100/0. From the viewpoint of rigidity and surface hardness, (A) / (B) is more preferably in the range of 50/50 to 99/1, (A) / (B) is more preferably in the range of 70/30 to 99/1, ( Most preferably, the component B) is polycarbonate and (A) / (B) is in the range of 80/20 to 99/1.
本発明の（Ｃ）成分としては、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物、トリアジン系化合物、ベンゾエート系化合物、安息香酸エステル系化合物、サリチル酸エステル系化合物、マロン酸エステル系化合物、有機ニッケル化合物、シアノアクリレート系化合物、オキシアニリド系化合物、ヒンダードアミン系化合物の群から選ばれる一種以上の光安定剤を用いることができる。具体的には、２−（２’−ヒドロキシ−５’−メチルフェニル）−ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−ベンゾトリアゾール−２’−イル）−４，６−ビス（１−メチル−１−フェニルエチル）−フェノール、２−（２‘−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）−５−クロロベンゾトリアゾールなどのベンゾトリアゾール系化合物、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−オクトキシベンゾフェノン、２−ヒドロキシ−４−メチルベンゾフェノン、２−ヒロドキシ−４−ｔ−ブトキシベンゾフェノンなどのベンゾフェノン系化合物が挙げられる。 また、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−［（ヘキシル）オキシ］−フェノールなどのトリアジン化合物、２，４−ジ−ｔ−ブチルフェニル−３，５−ジ−ｔ−ブチル−４−ヒドロキシベンゾエートなどのベンゾエート系化合物、安息香酸エステル系化合物、フェニルサリシレート、４−ｔ−ブチルフェニルサリシレートなどのサリチル酸エステル系化合物、マロン酸エステル系化合物、［２、２’−チオビス（４−ｔ−オクチルフェノレート）−２−エチルヘキシルアミンニッケル（ＩＩ）などの有機ニッケル化合物、エチル−２−シアノ−３，３−ジフェニルアクリレートなどのシアノアクリレート系化合物、オキシアニリド系化合物、４−アセトキシ−２，２，６，６−テトラメチルピペリジン、ビス（２，２，６，６−テトラメチル−４−ピペリジル）−セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドリキシフェニル］メチル］ブチルマロネートなどのヒンダードアミン系化合物が挙げられる。 Component (C) of the present invention includes benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, benzoate compounds, salicylate compounds, malonic ester compounds, organonickel compounds, cyanoacrylates. One or more kinds of light stabilizers selected from the group consisting of a series compound, an oxyanilide type compound, and a hindered amine series compound can be used. Specifically, 2- (2′-hydroxy-5′-methylphenyl) -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-benzotriazol-2'-yl) -4,6-bis (1-methyl-1-phenylethyl) -phenol, 2- (2'-hydroxy-3 ', 5'-di-t- Benzotriazole compounds such as (butylphenyl) -5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methylbenzophenone, 2-hydroxy-4-t- Examples include benzophenone compounds such as butoxybenzophenone. Further, triazine compounds such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4-di-t-butylphenyl- Benzoate compounds such as 3,5-di-t-butyl-4-hydroxybenzoate, benzoate compounds, phenyl salicylates, salicylate compounds such as 4-t-butylphenyl salicylate, malonic acid esters, [ Organic nickel compounds such as 2,2′-thiobis (4-t-octylphenolate) -2-ethylhexylamine nickel (II), cyanoacrylate compounds such as ethyl-2-cyano-3,3-diphenylacrylate, oxy Anilide compounds, 4-acetoxy-2,2,6,6-tetramethylpiperidine, (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1- And hindered amine compounds such as dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate.
上記の化合物のうち、特に２５０〜３２０ｎｍに吸収波長ピークを有する紫外線吸収剤が好ましく用いられる。更には２５０〜３２０ｎｍに最大吸収波長ピークを有する紫外線吸収剤をより好ましく用いることができる。光安定剤の吸収波長はクロロホルム、シクロヘキサンなど適切な溶剤に光安定剤を溶解し、紫外可視分光光度計により測定することができる。
更に上記のベンゾトリアゾール系化合物、ベンゾフェノン系化合物、トリアジン系化合物、ベンゾエート系化合物、安息香酸エステル系化合物、サリチル酸エステル系化合物、マロン酸エステル系化合物などの紫外線吸収剤とヒンダードアミン系化合物を併用して用いることが好ましく、２５０〜３２０ｎｍに吸収波長ピークを有する紫外線吸収剤とヒンダードアミン系化合物を併用して用いることが最も好ましい。
Among the above compounds, an ultraviolet absorber having an absorption wavelength peak at 250 to 320 nm is particularly preferably used. Furthermore, an ultraviolet absorber having a maximum absorption wavelength peak at 250 to 320 nm can be used more preferably. The absorption wavelength of the light stabilizer can be measured by dissolving the light stabilizer in an appropriate solvent such as chloroform or cyclohexane and using an ultraviolet-visible spectrophotometer.
Further, UV absorbers such as the above benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, benzoate compounds, salicylate compounds, malonic ester compounds, and hindered amine compounds are used in combination. It is preferable to use an ultraviolet absorber having an absorption wavelength peak at 250 to 320 nm and a hindered amine compound in combination.
（Ｃ）成分の光安定剤の好ましい配合量は、機械的特性、着色や乾燥、成形時の光安定剤のブリードの観点から（Ａ）成分と（Ｂ）成分の合計１００重量部に対し、（Ｃ）成分が０．０１〜５重量部が好ましい。さらに好ましくは０．１〜３重量部である。
次に本発明で用いることのできる（Ｄ）無機充填材について説明する。
本発明における無機充填材としては、目的に応じて繊維状、粉粒状、板状の無機充填材からなる群から選ばれる一種以上の無機充填材を用いることができる。
繊維状無機充填材としては、ガラス繊維、アスベスト繊維、カーボン繊維、シリカ繊維、シリカ・アルミナ繊維、ジルコニア繊維、窒化硼素繊維、窒化硅素繊維、硼素繊維、チタン酸カリウムウィスカー、ウォラストナイト、さらにステンレス、アルミニウム、チタン、銅、真鍮等の金属の繊維状物などの無機質繊維状物質があげられる。
(C) The preferable compounding quantity of the light stabilizer of a component is with respect to a total of 100 weight part of (A) component and (B) component from a viewpoint of the bleeding of the light stabilizer at the time of mechanical characteristics, coloring, drying, and shaping | molding, Component (C) is preferably 0.01 to 5 parts by weight. More preferably, it is 0.1-3 weight part.
Next, (D) inorganic filler that can be used in the present invention will be described.
As the inorganic filler in the present invention, one or more inorganic fillers selected from the group consisting of fibrous, granular, and plate-like inorganic fillers can be used depending on the purpose.
Examples of fibrous inorganic fillers include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate whisker, wollastonite, and stainless steel. Inorganic fibrous materials such as metallic fibrous materials such as aluminum, titanium, copper, and brass.
粉粒状無機充填剤としてはカーボンブラック、シリカ、石英粉末、ガラスビーズ、ガラス粉、硅酸カルシウム、硅酸アルミニウム、カオリン、クレー、硅藻土のごとき硅酸塩、酸化鉄、酸化チタン、酸化亜鉛、アルミナのごとき金属の酸化物、炭酸カルシウム、炭酸マグネシウムのごとき金属の炭酸塩、硫酸カルシウム、硫酸バリウムのごとき金属の硫酸塩、その他、炭化硅素、窒化硅素、窒化硼素、各種金属粉末が挙げられる。
また、板状無機充填剤としてはタルク、マイカ、ガラスフレーク、各種の金属箔等が挙げられる。
本発明の無機充填剤としては、（Ｄ１）ガラス繊維、（Ｄ２）ウォラストナイト、タルク、マイカ、カオリン、チタン酸カリウムウィスカー、炭酸カルシウムウィスカー、硫酸バリウムからなる群から選ばれた一種以上の無機充填材が好ましく、更に、機械的強度と表面外観、剛性、表面硬度、寸法安定性などのバランスの観点から、（Ｄ１）成分と（Ｄ２）成分を併用して用いることが好ましい。更に、（Ｄ１）成分と（Ｄ２）成分の重量比が（Ｄ１）＜（Ｄ２）であることが最も好ましい。
As granular inorganic fillers, carbon black, silica, quartz powder, glass beads, glass powder, calcium oxalate, aluminum oxalate, kaolin, clay, oxalate such as diatomaceous earth, iron oxide, titanium oxide, zinc oxide Metal oxides such as alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, and other types, including silicon carbide, silicon nitride, boron nitride, and various metal powders. .
Examples of the plate-like inorganic filler include talc, mica, glass flakes, and various metal foils.
The inorganic filler of the present invention includes (D1) glass fiber, (D2) one or more inorganic substances selected from the group consisting of wollastonite, talc, mica, kaolin, potassium titanate whisker, calcium carbonate whisker, and barium sulfate. A filler is preferable, and it is preferable to use the component (D1) and the component (D2) in combination from the viewpoint of balance between mechanical strength and surface appearance, rigidity, surface hardness, dimensional stability, and the like. Further, the weight ratio of the component (D1) and the component (D2) is most preferably (D1) <(D2).
また、本発明に用いられる繊維状無機充填材の平均繊維長（Ｌ）、平均繊維径（Ｄ）、アスペクト比（Ｌ／Ｄ）については特に限定されないが、機械的特性の点から、平均繊維長が５０μｍ以上、平均繊維径は５μｍ以上、アスペクト比は１０以上であることが好ましい。さらに、ウォラストナイトは、平均繊維径が３〜３０μｍ、平均繊維長が１０〜５００μｍ、アスペクト比が３〜１００のものが好ましく用いられる。その他、タルク、マイカ、カオリン、炭酸カルシウム、チタン酸カリウムウィスカーは平均粒径が０．１〜１００μｍのものが最も好ましく用いられる。
（Ｄ）無機充填材の配合量は機械的強度、剛性、表面硬度の改良効果と、成形品表面の光沢低下など外観への影響の観点から、（Ａ）ポリトリメチレンテレフタレート、（Ｂ）ポリカーボネートの合計１００重量部に対し、（Ｄ）無機充填材５〜３００重量部、より好ましくは２５〜２５０重量部である。
（Ｄ１）ガラス繊維と（Ｄ２）ウォラストナイト、タルク、マイカ、カオリン、チタン酸カリウムウィスカー、炭酸カルシウムウィスカー、硫酸バリウムからなる群から選ばれた一種以上の無機充填材を併用して用いた場合のより好ましい配合量は（Ａ）成分と（Ｂ）成分の合計１００重量部に対し、（Ｄ１）２〜１００重量部、（Ｄ２）３〜２００重量部である。
Further, the average fiber length (L), average fiber diameter (D), and aspect ratio (L / D) of the fibrous inorganic filler used in the present invention are not particularly limited, but from the viewpoint of mechanical properties, the average fiber It is preferable that the length is 50 μm or more, the average fiber diameter is 5 μm or more, and the aspect ratio is 10 or more. Further, wollastonite having an average fiber diameter of 3 to 30 μm, an average fiber length of 10 to 500 μm, and an aspect ratio of 3 to 100 is preferably used. In addition, talc, mica, kaolin, calcium carbonate, and potassium titanate whiskers having an average particle diameter of 0.1 to 100 μm are most preferably used.
(D) The blending amount of the inorganic filler is (A) polytrimethylene terephthalate, (B) polycarbonate from the viewpoint of the effect of improving the mechanical strength, rigidity, surface hardness, and the appearance of the molded article, such as the gloss reduction. (D) 5 to 300 parts by weight, more preferably 25 to 250 parts by weight of the inorganic filler.
When (D1) glass fiber and (D2) one or more inorganic fillers selected from the group consisting of wollastonite, talc, mica, kaolin, potassium titanate whisker, calcium carbonate whisker, and barium sulfate are used in combination The more preferable blending amount is (D1) 2 to 100 parts by weight and (D2) 3 to 200 parts by weight with respect to 100 parts by weight as a total of the components (A) and (B).
本発明の無機充填材は公知のカップリング剤やフィルム形成剤を用いて表面処理した無機充填材が好ましく用いられる。
カップリング剤としては、シラン系カップリング剤、チタン系カップリング剤を挙げることができる。特にγ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、β−（１，１−エポキシシクロヘキシル）エチルトリメトキシシラン等のアミノシラン及びエポキシシランが好ましく用いられる。
またフィルム形成剤としては、ウレタン系ポリマー、アクリル酸系ポリマー、無水マレイン酸とエチレン、スチレン、α−メチルスチレン、ブタジエン、イソプレン、クロロプレン、２，３ジクロロブタジエン、１，３−ペンタジエン、シクロオクタジエン等の不飽和単量体とのコポリマー、エポキシ系ポリマー、ポリエステル系ポリマー、ポリエーテル系ポリマー等の重合体を挙げることが出来る。中でも、エポキシ系ポリマー、ウレタン系ポリマー、アクリル酸系ポリマー、ブタジエン無水マレイン酸コポリマー、エチレン無水マレイン酸コポリマー、スチレン無水マレイン酸コポリマー、及びこれらの混合物が特に好ましく用いられる。
As the inorganic filler of the present invention, an inorganic filler surface-treated with a known coupling agent or film forming agent is preferably used.
Examples of the coupling agent include a silane coupling agent and a titanium coupling agent. Especially γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (1,1-epoxycyclohexyl) ethyltrimethoxysilane Amino silane and epoxy silane such as these are preferably used.
Film forming agents include urethane polymers, acrylic polymers, maleic anhydride and ethylene, styrene, α-methylstyrene, butadiene, isoprene, chloroprene, 2,3 dichlorobutadiene, 1,3-pentadiene, cyclooctadiene. And polymers such as copolymers with unsaturated monomers such as epoxy polymers, polyester polymers, and polyether polymers. Among these, epoxy polymers, urethane polymers, acrylic acid polymers, butadiene maleic anhydride copolymers, ethylene maleic anhydride copolymers, styrene maleic anhydride copolymers, and mixtures thereof are particularly preferably used.
また、本発明においては機械的強度と滞留安定性の観点から、（Ｅ）エポキシ樹脂を好ましく用いることができる。
（Ｅ）エポキシ樹脂とは、分子中にエポキシ基（オキシラン環）を２個以上持つ熱硬化性の化合物を示す。具体的には、ビルフェノールＡとエピクロルヒドリンとの縮合反応により製造されるいわゆるビスフェノールＡ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、レゾルシン型エポキシ樹脂、フェノールノボラックや線状高分子量クレゾールノボラックをグリシジル化した多官能エポキシであるノボラック型エポキシ樹脂、脂肪族エポキシ樹脂、脂環型エポキシ樹脂、ポリグリシジルアミン型エポキシなどが挙げられる。
In the present invention, (E) an epoxy resin can be preferably used from the viewpoint of mechanical strength and residence stability.
(E) Epoxy resin refers to a thermosetting compound having two or more epoxy groups (oxirane rings) in the molecule. Specifically, the so-called bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, resorcin type epoxy resin, phenol novolac and linear high molecular weight cresol produced by the condensation reaction of bilphenol A and epichlorohydrin. Examples thereof include novolak type epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, polyglycidylamine type epoxies, etc., which are polyfunctional epoxies obtained by glycidylation of novolak.
本発明で用いられるエポキシ樹脂としては、耐薬品と樹脂への分散の観点からエポキシ当量１５０〜２８０（／ｅｑ．）のノボラック型エポキシ樹脂、またはエポキシ当量６００〜３０００（／ｅｑ．）のビスフェノールＡ型エポキシ樹脂が好ましく用いられる。より好ましくはエポキシ当量１８０〜２５０（／ｅｑ．）で分子量１０００〜６０００のノボラック型エポキシ樹脂、又はエポキシ当量６００〜３０００（／ｅｑ．）で分子量１２００〜６０００のビスフェノールＡ型エポキシ樹脂である。
（Ｅ）エポキシ樹脂の好ましい配合量は、（Ａ）ポリトリメチレンテレフタレート、（Ｂ）ポリカーボネートの合計１００重量部に対し、（Ｅ）エポキシ樹脂が０．１〜２０重量部であり、より好ましくは０．３〜１０重量部である。
As an epoxy resin used in the present invention, a novolak type epoxy resin having an epoxy equivalent of 150 to 280 (/ eq.) Or a bisphenol A having an epoxy equivalent of 600 to 3000 (/ eq.) From the viewpoint of chemical resistance and dispersion in the resin. A type epoxy resin is preferably used. More preferably, it is a novolak type epoxy resin having an epoxy equivalent of 180 to 250 (/ eq.) And a molecular weight of 1000 to 6000, or a bisphenol A type epoxy resin having an epoxy equivalent of 600 to 3000 (/ eq.) And a molecular weight of 1200 to 6000.
(E) The preferable compounding quantity of an epoxy resin is 0.1-20 weight part of (E) epoxy resin with respect to a total of 100 weight part of (A) polytrimethylene terephthalate and (B) polycarbonate, More preferably 0.3 to 10 parts by weight.
また、本発明においては、無機充填材や添加剤によって引き起こされる機械的物性低下防止の観点からリン酸金属塩、ピロリン酸金属塩、リン酸アンモニウム、オキソ酸などのｐＨ調整剤を好ましく用いることができる。
本発明の熱可塑性強化樹脂組成物は、ポリトリメチレンテレフタレート、熱可塑性樹脂、光安定剤、及び／またはエポキシ樹脂と無機充填材、その他の添加剤等を、適切にデザインされたスクリューを有する押出し機を用いて溶融混練して得ることができるが、特に、（Ａ）ポリトリメチレンテレフタレートを溶融した後に（Ｄ）無機充填材を添加する製造方法が、機械的強度と無機充填材の添加により起こる樹脂組成物の分子量低下を抑制する点で好ましい。（Ｂ）熱可塑性樹脂、（Ｃ）光安定剤は（Ａ）成分と混合して始めに溶融することもできるし、必要に応じて分割、または全量を後段に添加したり、（Ｃ）成分とその他の添加剤をマスターバッチ化して使用することもできる。また、必要に応じて（Ｄ）無機充填材を多段に分割して添加することができる。
In the present invention, it is preferable to use a pH adjuster such as a metal phosphate, metal pyrophosphate, ammonium phosphate or oxo acid from the viewpoint of preventing deterioration of mechanical properties caused by inorganic fillers and additives. it can.
The thermoplastic reinforced resin composition of the present invention is formed by extruding polytrimethylene terephthalate, a thermoplastic resin, a light stabilizer, and / or an epoxy resin and an inorganic filler, other additives, and the like with an appropriately designed screw. Although it can be obtained by melt-kneading using a machine, in particular, (A) after the polytrimethylene terephthalate is melted, (D) an inorganic filler is added by mechanical strength and addition of an inorganic filler. It is preferable at the point which suppresses the molecular weight fall of the resin composition which occurs. The (B) thermoplastic resin and (C) light stabilizer can be mixed with the component (A) and melted at the beginning, or can be divided or added in the subsequent stage as necessary, or the component (C) And other additives can be used as a master batch. Moreover, (D) inorganic filler can be divided | segmented and added in multiple steps as needed.
本発明の熱可塑性強化樹脂組成物には、上記のポリトリメチレンテレフタレート、熱可塑性樹脂、光安定剤、エポキシ樹脂、無機充填材に加え、各種用途及び目的に応じて、その他の成分を適宜配合することができる。
例えば、本発明の組成物に、結晶核剤を更に配合することができる。結晶核剤としては有機物、無機物のいずれも使用することができる。
また、本発明の樹脂組成物に、成形性改良剤を更に配合することができる。成形性改良剤としては、リン酸エステル類、亜リン酸エステル類、高級脂肪酸類、高級脂肪酸金属塩類、高級脂肪酸エステル類、高級脂肪酸アミド化合物類、ポリアルキレングリコールあるいはその末端変性物類、低分子量ポリエチレンあるいは酸化低分子量ポリエチレン類、置換ベンジリデンソルビトール類、ポリシロキサン類、カプロラクトン類が挙げられるが、特に好ましいのは、高級脂肪酸類、高級脂肪酸金属塩類、高級脂肪酸エステル類である。
In addition to the above polytrimethylene terephthalate, thermoplastic resin, light stabilizer, epoxy resin, and inorganic filler, other components are appropriately blended in the thermoplastic reinforced resin composition of the present invention depending on various uses and purposes. can do.
For example, a crystal nucleating agent can be further blended in the composition of the present invention. As the crystal nucleating agent, both organic and inorganic substances can be used.
Moreover, a moldability improving agent can further be mix | blended with the resin composition of this invention. Formability improvers include phosphate esters, phosphites, higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amide compounds, polyalkylene glycols or terminal modified products thereof, low molecular weight Although polyethylene or oxidized low molecular weight polyethylenes, substituted benzylidene sorbitols, polysiloxanes, and caprolactones can be mentioned, higher fatty acids, higher fatty acid metal salts, and higher fatty acid esters are particularly preferable.
また、本発明の樹脂組成物には、本発明の目的を損なわない範囲で、通常使用される難燃剤、紫外線吸収剤、耐熱安定剤、酸化防止剤、可塑剤、着色剤、整色剤、帯電防止剤、蛍光増白剤、つや消し剤、衝撃強度改良剤等の添加剤を配合することもできる。
本発明のポリトリメチレンテレフタレート強化樹脂組成物は、外観が極めて良好であり、耐光性、機械的強度、剛性、表面硬度、寸法安定性に優れるため、洗面カウンター、キッチンカウンター、浴槽、洗面ボール（洗面器）、手洗ボール（手洗器）、各種流し、トイレカウンター、キャビネット天板など浴室、洗面所、トイレ、台所で使用される製品の構成部材の少なくとも一部に使用することができる。特に、成形体の表面硬度が、バーコル硬度３０、鉛筆硬度２Ｈ以上、より好ましくはバーコル硬度４０以上、鉛筆高度３Ｈ以上の本発明組成物からなる成形体はこの用途に最適に用いることができる。
In addition, the resin composition of the present invention includes flame retardants, ultraviolet absorbers, heat stabilizers, antioxidants, plasticizers, colorants, color adjusters, and the like, as long as the object of the present invention is not impaired. Additives such as an antistatic agent, a fluorescent brightening agent, a matting agent, and an impact strength improving agent can also be blended.
The polytrimethylene terephthalate reinforced resin composition of the present invention has a very good appearance and is excellent in light resistance, mechanical strength, rigidity, surface hardness, and dimensional stability. Therefore, a wash counter, kitchen counter, bathtub, wash bowl ( It can be used for at least some of the components of products used in bathrooms, washrooms, toilets, kitchens, such as basins), hand-washing balls (wash basins), various sinks, toilet counters, cabinet tops. In particular, a molded article made of the composition of the present invention having a surface hardness of a Barcol hardness of 30, a pencil hardness of 2H or higher, more preferably a Barcol hardness of 40 or higher, and a pencil height of 3H or higher can be optimally used for this application.
本発明を実施例に基づいて説明する。実施例及び比較例で用いた樹脂を以下に記す。
（Ａ）ＰＴＴ樹脂：ポリトリメチレンテレフタレート［η］＝１．０
ＰＢＴ樹脂：ポリブチレンテレフタレート ウィンテック社製 ジュラネックス２００２
（Ｂ）ＰＣ樹脂：ポリカーボネート 三菱エンジニアリングプラスチックス社製、ユーピロンＳ−２０００
（Ｃ）光安定剤
ＬＡ−１：ベンゾトリアゾール系化合物、２−（２−ヒロドキシ−ベンゾトリアゾール−２−イル）−４，６−ビス（１−メチル−１−フェニルメチル）フェノール：最大吸収波長３０２ｎｍ、３４８ｎｍ
ＬＡ−２：トリアジン系化合物、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）５−［（ヘキシル）オキシ］−フェノール：最大吸収波長２８８ｎｍ、３２５ｎｍ
ＬＡ−３：マロン酸エステル系化合物、（ｐ−メトキシベンジリデン）マロン酸ジメチルエステル：最大吸収波長３０８ｎｍ
ＬＡ−４：ヒンダードアミン系化合物：ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート
The present invention will be described based on examples. The resins used in Examples and Comparative Examples are described below.
(A) PTT resin: polytrimethylene terephthalate [η] = 1.0
PBT resin: Polybutylene terephthalate Wintech's Juranex 2002
(B) PC resin: Polycarbonate Mitsubishi Engineering Plastics, Iupilon S-2000
(C) Light stabilizer LA-1: Benzotriazole-based compound, 2- (2-hydroxy-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylmethyl) phenol: maximum absorption wavelength 302nm, 348nm
LA-2: Triazine compound, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) 5-[(hexyl) oxy] -phenol: maximum absorption wavelength 288 nm, 325 nm
LA-3: Malonic acid ester compound, (p-methoxybenzylidene) malonic acid dimethyl ester: Maximum absorption wavelength 308 nm
LA-4: hindered amine compound: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate
（Ｄ１）ガラス繊維
日本電気硝子社製 ０３Ｔ−１８７／ＰＬ（エポキシ集束処理、繊維径１３μｍ）
（Ｄ２）無機充填材
ＭＦ−１：ウォラストナイト ＮＩＣＯ社製 ＮＹＧＬＯＳＳ８エポキシ処理
ＭＦ−２：マイカ レプコ社製 Ｍ−４００
ＭＦ−３：硫酸バリウム 堺化学工業社製 ＢＭＨ−６０
（Ｅ）エポキシ樹脂
ＥＰ：旭化成エポキシ（株）製、ビスフェノールＡ型エポキシ樹脂 ＡＥＲ ＥＣＮ６０９７、エポキシ当量約２０００（／ｅｑ．）
（Ｆ）ｐＨ調整剤
ＰＨ：リン酸一水素Ｎａ、太平科学産業製
(D1) Glass fiber 03T-187 / PL manufactured by Nippon Electric Glass Co., Ltd. (epoxy focusing treatment, fiber diameter 13 μm)
(D2) Inorganic filler MF-1: Wollastonite manufactured by NICO NYGLOSS8 epoxy treatment MF-2: manufactured by Mica Repco M-400
MF-3: Barium sulfate BMH-60 manufactured by Sakai Chemical Industry Co., Ltd.
(E) Epoxy resin EP: Asahi Kasei Epoxy Co., Ltd., bisphenol A type epoxy resin AER ECN6097, epoxy equivalent of about 2000 (/ eq.)
(F) pH adjuster PH: Na monohydrogen phosphate, manufactured by Taihei Kagaku Sangyo
評価方法は以下の通り。
（１）樹脂成形品の作成
日精樹脂（株）製ＰＳ４０Ｅ、射出成形機を用いて、シリンダー温度２６０℃、金型温度９０℃に設定し、射出２０秒、冷却２０秒の条件で射出成形を行い樹脂試験片を作成した。
（２）曲げ弾性率（ＧＰａ）
ＡＳＴＭ Ｄ７９０に準じて行った。
（３）外観
堀場製ハンディ光沢計ＩＧ３２０を用いて、ＪＩＳ−Ｋ７１５０に準じてダンベル試験片のＧｓ２０°を測定した。光沢が４５％以上を○、４５％未満を×とした。
（４）表面硬度
ＪＩＳ Ｋ７０６０に準じ成形品表面のバーコル硬度を測定した。バーコル硬度が３５以上を○、３５未満を×とした。
（５）耐光性
熱可塑性樹脂組成物に、含有量１．５重量％となるように酸化チタンをマスターバッチ法により添加し、日精樹脂（株）製ＰＳ４０Ｅ、射出成形機を用いて、シリンダー温度２６０℃、金型温度９０℃で白色平板６０×８０×３ｍｍを成形した。この平板成形品をウェザーメーター（スガ試験機製サンシャイン・スーパーロングライフ。ウェザーメーター ＷＥＬ−ＳＵＮ−ＨＣＨ−Ｂ型）を用いて、ブラックパネル温度６３℃、降雨なしの条件にて３００時間、照射試験を実施した。試験前後の色差（ΔＥ）を日本電色社製色差計ＮＤ−３００Ａを用いて測定した。
The evaluation method is as follows.
(1) Preparation of resin molded product Using NISSEI Plastics Co., Ltd. PS40E and an injection molding machine, set the cylinder temperature to 260 ° C and the mold temperature to 90 ° C, and perform injection molding under conditions of 20 seconds for injection and 20 seconds for cooling. A resin test piece was prepared.
(2) Flexural modulus (GPa)
This was performed according to ASTM D790.
(3) Appearance Using a Horiba handy gloss meter IG320, Gs20 ° of the dumbbell test piece was measured according to JIS-K7150. A glossiness of 45% or more was evaluated as ◯, and a glossiness of less than 45% was evaluated as ×.
(4) Surface hardness According to JIS K7060, the Barcol hardness on the surface of the molded product was measured. Barcol hardness of 35 or more was evaluated as ○, and less than 35 was evaluated as ×.
(5) Light resistance Titanium oxide was added to the thermoplastic resin composition by a master batch method so as to have a content of 1.5% by weight, and cylinder temperature was measured using PS40E manufactured by Nissei Resin Co., Ltd. and an injection molding machine. A white flat plate 60 × 80 × 3 mm was molded at 260 ° C. and a mold temperature of 90 ° C. This flat plate molded product was subjected to an irradiation test using a weather meter (Sunshine Super Long Life manufactured by Suga Test Instruments Co., Ltd., Weather Meter WEL-SUN-HCH-B type) at a black panel temperature of 63 ° C. and no rain for 300 hours. Carried out. The color difference (ΔE) before and after the test was measured using a color difference meter ND-300A manufactured by Nippon Denshoku.
［実施例１〜７、比較例１〜４］
ＰＴＴ樹脂、ＰＢＴ樹脂、ＰＣ樹脂、光安定剤、エポキシ樹脂、ｐＨ調整剤を表１に示した配合比で混合し、二軸押出機（東芝機械（株）製：ＴＥＭ５８）を用いてスクリュー回転数１５０ｒｐｍ、シリンダー温度２６０℃、押出速度１５０ｋｇ／ｈｒ、減圧度０．０４ＭＰａの条件で溶融混練し、サイドフィーダーから無機充填材を表１に示した配合比で添加した。ストランド状に排出された組成物は、水冷後カッティングしペレットとした。該ペレットを除湿型乾燥機で１２０℃にて５時間乾燥した後、日精樹脂（株）製ＰＳ４０Ｅ射出成形機を用いて、シリンダー温度２６０℃、金型温度９０℃に設定し、射出成形を行い試験片を作成、評価を行った。結果を表１に示した。
[Examples 1-7, Comparative Examples 1-4]
PTT resin, PBT resin, PC resin, light stabilizer, epoxy resin, and pH adjuster are mixed at the mixing ratio shown in Table 1, and screw rotation is performed using a twin screw extruder (Toshiba Machine Co., Ltd .: TEM58). The mixture was melt-kneaded under the conditions of several 150 rpm, cylinder temperature 260 ° C., extrusion rate 150 kg / hr, and degree of vacuum 0.04 MPa, and inorganic fillers were added from the side feeder at the compounding ratio shown in Table 1. The composition discharged in the form of a strand was cut into water and pelletized by cutting. After drying the pellets at 120 ° C. for 5 hours with a dehumidifying dryer, the cylinder temperature is set to 260 ° C. and the mold temperature is set to 90 ° C. using a PS40E injection molding machine manufactured by Nissei Resin Co., Ltd. A test piece was prepared and evaluated. The results are shown in Table 1.
［実施例８］
実施例３で作成したペットを除湿型乾燥機で１２０℃にて５時間乾燥した後、（株）日本製鋼所製Ｊ６５０ＥＬＩＩＩ−３１００Ｈ射出成形機を用いて、シリンダー温度２７０℃、金型温度９５℃に設定し、図１に示す手洗器（Ａ＝４００ｍｍ、Ｂ＝３２０ｍｍ、洗面部深さ１２５ｍｍ、洗面台よりの立ち上がり部高さ６０ｍｍ、排水口φ＝３０ｍｍ、取付孔φ＝１０ｍｍ）を成形した。得られた成形品の洗面部表面のバーコル硬度は４２、鉛筆硬度４Ｈ、成形品上部平面部のＧｓ２０°は４９％であった。
[Example 8]
After the pet created in Example 3 was dried at 120 ° C. for 5 hours with a dehumidifying dryer, the cylinder temperature was 270 ° C. and the mold temperature was 95 ° C. using a J650ELIII-3100H injection molding machine manufactured by Japan Steel Works. 1 was formed (A = 400 mm, B = 320 mm, depth of the wash surface 125 mm, height of the rising portion from the wash basin 60 mm, drain port φ = 30 mm, mounting hole φ = 10 mm). . The obtained molded article had a Barcol hardness of 42 on the surface of the wash surface, a pencil hardness of 4H, and a Gs20 ° of the upper plane of the molded article was 49%.
本発明の熱可塑性強化樹脂組成物は、得られる成形品が良外観であり、耐光性、機械的強度、剛性、表面硬度、寸法安定性に優れる。かかる樹脂組成物からなる洗面カウンター、キッチンカウンター、浴槽、洗面ボール、手洗ボール、トイレカウンター、キャビネット天板などの製品は優れた性能を持ち、浴室、洗面所、トイレ、台所で使用される、陶器製、熱硬化性樹脂製品を代替することが可能であり、また成形原料の一部にリワークしてサイクルして使用するなどリサイクルして使用することが可能である。 In the thermoplastic reinforced resin composition of the present invention, the obtained molded product has a good appearance and is excellent in light resistance, mechanical strength, rigidity, surface hardness, and dimensional stability. Products such as wash counters, kitchen counters, bathtubs, wash bowls, hand wash balls, toilet counters, cabinet tops made of such resin compositions have excellent performance and are used in bathrooms, washrooms, toilets, kitchens, pottery It is possible to replace the manufactured and thermosetting resin product, and it is possible to recycle and use it by reworking a part of the molding raw material and using it in a cycle.
Claims (15)
ｉ）（Ａ）成分と（Ｂ）成分の重量比が、１／９９〜１００／０の範囲である、
ｉｉ）（Ａ）成分と（Ｂ）成分の合計１００重量部に対し、（Ｃ）光安定剤が０．０１〜５重量部である、
ｉｉｉ）（Ａ）成分と（Ｂ）成分の合計１００重量部に対し、（Ｄ）無機充填材が５〜３００重量部である。 (A) a polytrimethylene terephthalate, (B) a thermoplastic resin composition, (C) a thermoplastic reinforcing resin composition containing a light stabilizer and (D) an inorganic filler, the following conditions i) to iii) A thermoplastic reinforced resin composition characterized by satisfying:
i) The weight ratio of the component (A) and the component (B) is in the range of 1/99 to 100/0.
ii) (C) Light stabilizer is 0.01-5 weight part with respect to a total of 100 weight part of (A) component and (B) component,
iii) The inorganic filler is 5 to 300 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B).
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