JP2007262128A - Reinforced resin molding having excellent scratch resistance and high appearance - Google Patents
Reinforced resin molding having excellent scratch resistance and high appearance Download PDFInfo
- Publication number
- JP2007262128A JP2007262128A JP2006085252A JP2006085252A JP2007262128A JP 2007262128 A JP2007262128 A JP 2007262128A JP 2006085252 A JP2006085252 A JP 2006085252A JP 2006085252 A JP2006085252 A JP 2006085252A JP 2007262128 A JP2007262128 A JP 2007262128A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- resin
- reinforced thermoplastic
- high appearance
- molded article
- 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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Abstract
Description
本発明は、外観に優れ、高剛性、高表面硬度の強化樹脂製高外観成形体に関するものである。詳しくは、得られる成形品が良外観であり、機械的強度、剛性、表面硬度、寸法安定性、耐加水分解性、耐薬品性、特に耐傷付き特性に優れる強化熱可塑性樹脂成形体、及びそれを用いた自動車、住設、家電・ＯＡ部品、特に水回り建築部材に関する。 The present invention relates to a reinforced resin high appearance molded article having excellent appearance, high rigidity and high surface hardness. Specifically, the molded product obtained has a good appearance, and is a reinforced thermoplastic resin molded article having excellent mechanical strength, rigidity, surface hardness, dimensional stability, hydrolysis resistance, chemical resistance, particularly scratch resistance, and The present invention relates to automobiles, housing equipment, home appliances and OA parts, particularly water-based building materials.
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。これらの熱硬化性樹脂製品は、プレス成形、注型成型などの成型方法によって製造されている。
しかし、これらの熱硬化性樹脂製品は、初期の表面硬度は高いが、実際の使用で重要となる傷付性に問題があると言った課題を抱えていた。
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. These thermosetting resin products are manufactured by molding methods such as press molding and cast molding.
However, although these thermosetting resin products have high initial surface hardness, they have a problem that there is a problem with scratching that is important in actual use.
また熱硬化性樹脂製品は、硬化しているため、リサイクルの可能性はほとんどなく、現状で埋め立てによる廃棄処理が主な処理法である。しかも、その廃棄の際には成形品のボリュームをコンパクトにするのが困難で、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が、これらの用途では、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、耐加水分解性、耐薬品性などの厳しい性能が要求される。
In addition, since thermosetting resin products are cured, there is almost no possibility of recycling, and at present, disposal by landfill is the main treatment method. Moreover, it is difficult to make the volume of the molded product compact at the time of disposal, which causes a serious problem in terms of disposal methods.
For this reason, thermoplastic resin products are attracting attention as an alternative to thermosetting resin products, but in these applications, molded products have good appearance, mechanical strength and rigidity, as well as surface hardness and dimensions. Severe performance such as stability, hydrolysis resistance and chemical resistance is required.
一方、ガラス繊維等の充填材は、熱可塑性樹脂に配合され、広く工業的に使用されている。特にポリエステル樹脂にガラス繊維等の充填材を配合した場合には、大幅な耐熱性、機械的強度、剛性、寸法安定性等の向上が可能であり、自動車部品材料、電気電子材料、産業資材、工業材料、家庭用品など高耐熱、高強度、高剛性等の特性が要求される広い分野で好適に利用できる。 On the other hand, fillers such as glass fibers are blended in thermoplastic resins and widely used industrially. In particular, when a filler such as glass fiber is blended with polyester resin, it is possible to significantly improve heat resistance, mechanical strength, rigidity, dimensional stability, etc., such as automotive parts materials, electrical and electronic materials, industrial materials, It can be suitably used in a wide range of fields that require characteristics such as high heat resistance, high strength, and high rigidity, such as industrial materials and household products.
こういった市場の多様化に伴い、更に高度な性能、用途に応じた特殊性能、高度な品質が求められており、ポリエステル強化樹脂の耐熱性、機械的強度、剛性を更に向上させる目的で、様々な検討が行われている。
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、無機充填材、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材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）。
Along with such diversification of the market, more advanced performance, special performance according to the application, and advanced quality are required. For the purpose of further improving the heat resistance, mechanical strength and rigidity of the polyester reinforced resin, Various studies have been conducted.
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 disadvantages of polyester. An inorganic filler-containing linear polyester has been studied (see Patent Document 1).
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、特定の数平均分子量の線状高分子量クレゾールノボラックをクレシジルエーテル化したエポキシ樹脂、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）。
また、芳香族ポリエステル、特にポリエチレンテレフタレート、ポリエチレンテレフタレートとポリカーボネートからなる熱可塑性樹脂と、エポキシ基含有化合物により特定の方法で表面処理された繊維強化材からなる樹脂組成物が検討されている（特許文献３参照）。
In addition, heat resistance, mechanical properties, and composition comprising a polyester resin such as polyethylene terephthalate and polybutylene terephthalate, an epoxy resin obtained by cresidyl etherification of a linear high molecular weight cresol novolak having a specific number average molecular weight, and a fiber reinforcement Studies have been made to improve hydrolysis resistance (see Patent Document 2).
Resin compositions comprising aromatic polyesters, in particular, polyethylene terephthalate, a thermoplastic resin comprising polyethylene terephthalate and polycarbonate, and a fiber reinforcement surface-treated by a specific method using an epoxy group-containing compound have been studied (patent document) 3).
しかしながら、ポリブチレンテレフタレート樹脂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のが現状である。 However, a resin composition in which an inorganic filler is blended with a polybutylene terephthalate resin has not only a poor appearance of a molded product, but also has a large warpage deformation and low dimensional stability when molded by injection molding. There's a problem. In addition, the polyethylene terephthalate reinforced resin composition is difficult to perform normal injection molding at a mold temperature of 100 ° C. or lower, and a molded article having a good appearance cannot be obtained.
強化ポリエステルの中でも、強化ポリトリメチレンテレフタレート樹脂組成物は、機械的特性、耐候性、耐熱老化性、製品外観において特に優れ、また高濃度に充填材を添加できるという特性を持つため、成形品外観を損なうことなく、機械的特性の改良されたポリトリメチレンテレフタレート強化樹脂組成物の検討が行われてきた。（特許文献４、５参照）。
しかし、ガラス繊維による強化樹脂組成物の場合、特に高剛性を目的とし高濃度に充填材を配合した場合、ガラス繊維の表面への浮き出しや、繊維に沿った凹凸によって表面硬度や表面外観が損なわれるなど、上記の陶器代替の浴室、洗面所、トイレ、台所の洗面器、手洗器やカウンターなど水周り建築部材用途に必要とされるより高いレベルの外観と、表面硬度、寸法安定性、耐加水分解性、耐薬品性を達成するには至らず、更なる改良が必要とされている。
Among reinforced polyesters, reinforced polytrimethylene terephthalate resin composition is particularly excellent in mechanical properties, weather resistance, heat aging resistance, product appearance, and can be added with a high concentration of filler. Studies have been conducted on polytrimethylene terephthalate reinforced resin compositions having improved mechanical properties without impairing the properties. (See Patent Documents 4 and 5).
However, in the case of a reinforced resin composition made of glass fiber, especially when a filler is blended at a high concentration for the purpose of high rigidity, the surface hardness and surface appearance are impaired due to the embossment on the surface of the glass fiber and unevenness along the fiber. Such as the above-mentioned bathroom substitutes for bathrooms, toilets, toilets, kitchen basins, hand basins, counters, etc., higher level appearance and surface hardness, dimensional stability, resistance The hydrolysis and chemical resistance cannot be achieved, and further improvements are required.
本発明の目的は外観部品として用いられる住設、家電・ＯＡ部品、特に水回り建築部材である洗面カウンター、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、機械的強度、剛性、表面硬度、寸法安定性、耐加水分解性、耐薬品性に優れ、特に耐傷付特性を有する高外観強化樹脂製成形品を提供することにある。 The object of the present invention is to provide bathrooms, washrooms, toilets, kitchens such as bathrooms, bathrooms, toilet bowls, toilet counters such as bathroom counters, kitchen counters, bathtubs, wash bowls, hand wash bowls, and toilet counters, which are used as exterior parts, household appliances and OA parts. It can be used for products used in, has a very good appearance, excellent mechanical strength, rigidity, surface hardness, dimensional stability, hydrolysis resistance, chemical resistance, especially high scratch resistance The object is to provide an external appearance-reinforced resin molded product.
本発明者は、前記課題を解決するため、バーコール硬度が３０以上である表面特性を有する強化熱可塑性樹脂製高外観成形体であって、機械的強度、剛性、表面硬度、寸法安定性、耐加水分解性、耐薬品性と高度な耐傷付特性を有する表面高外観等の要求を達成することを見出し、本発明に至った。
すなわち本発明は以下に記載するとおりの強化熱可塑性樹脂製高外観成形体である。
In order to solve the above-mentioned problems, the present inventor is a reinforced thermoplastic resin high-appearance molded article having a surface characteristic having a Barcol hardness of 30 or more, which has mechanical strength, rigidity, surface hardness, dimensional stability, The present inventors have found that the requirements for high surface appearance and the like having hydrolyzability, chemical resistance and high scratch resistance are achieved, and the present invention has been achieved.
That is, the present invention is a reinforced thermoplastic resin high appearance molded body as described below.
１．バーコール硬度が３０以上である表面特性を有する強化熱可塑性樹脂製高外観成形体であって、スチールウール＃０（繊維径２５〜３５μｍ）で擦った時に実質的に大きな傷が成形品表面につかないことを特徴とする強化熱可塑性樹脂製高外観成形体。
２．スチールウール＃０（繊維径２５〜３５μｍ）で擦った後の傷の平均深さが５０μｍ以下であることを特徴とする請求項１に記載の強化熱可塑性樹脂製高外観成形体。
３．成形体表面のＪＩＳ Ｚ８７４１で定義される光沢度Ｇｓ（２０°）の値Ｘ０と成形体表面をスチールウール＃０（繊維径２５〜３５μｍ）で擦った後の光沢度Ｘ１との差（Ｘ０−Ｘ１）が２５％以内であることを特徴とする１、２に記載の強化熱可塑性樹脂製高外観成形体。
４．高外観成形体表面の少なくとも一部の光沢度が、ＪＩＳ Ｚ８７４１で定義される光沢度Ｇｓ（６０°）が８０％以上でかつＧｓ（２０°）が６０％以上であることを特徴とする１〜３に記載の強化熱可塑性樹脂製高外観成形体。
５．高外観成形体表面の表面をＪＩＳ Ｋ５６００−５−４ で定義される測定法にて鉛筆硬度がH以上であることを特徴とする１〜４に記載の強化熱可塑性樹脂製高外観成形体。
６．高外観成形体表面の少なくとも一部がマット状であることを特徴とする１〜５に記載の強化熱可塑性樹脂製高外観成形体。
７．強化熱可塑性樹脂が（Ａ１）ポリトリメチレンテレフタレート樹脂９９．９重量部〜５０重量部（Ａ２）熱可塑性樹脂０〜４９．９重量部（Ｃ）無機充填材５〜３００重量部からなる事を特徴とする１〜６に記載の強化熱可塑性樹脂製高外観成形体。
８．（Ｃ）無機充填材が、ガラス繊維であることを特徴とする１〜７に記載の強化熱可塑性樹脂製高外観成形体。
９．（Ｃ）無機充填材が、結晶性無機充填材を含むことを特徴とする１〜８に記載の強化熱可塑性樹脂製高外観成形体。
１０．結晶性無機充填材が、ウォラストナイト、タルク、マイカ、カリオン、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結晶性無機充填材である事を特徴とする９に記載の強化熱可塑性樹脂製高外観成形体。
１１．結晶性無機充填材がウォラストナイトであることを特徴とする１０に記載の強化熱可塑性樹脂製高外観成形体。
１２．（Ａ２）の熱可組成樹脂がポリカーボネート樹脂であることを特徴とする１〜１１のいずれかに記載の強化熱可塑性樹脂製高外観成形体。
１３．強化熱可塑性樹脂が（Ａ１）ポリトリメチレンテレフタレート樹脂１００重量部〜５０．１重量部（Ａ２）熱可塑性樹脂０〜４９．９重量部（Ｃ）無機充填材５〜３００重量部に対して、（Ｂ）エポキシ樹脂０．１〜２０重量部を含む事を特徴とする１〜１２に記載の強化熱可塑性樹脂製高外観成形体。
１４．表面研磨された成形体が、浴室用製品、洗面所用製品、トイレ用製品、流し台用製品の構成部材の少なくとも一部であることを特徴とする１〜１３のいずれかに記載の強化熱可塑性樹脂製高外観成形体。
１５．上記１４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、手洗いボール、トイレカウンター、キャビネット天板のいずれかであることを特徴とする強化熱可塑性樹脂製高外観成形体。
1. A high appearance molded product made of reinforced thermoplastic resin having surface characteristics with a Barcol hardness of 30 or more, and substantially large scratches do not adhere to the surface of the molded product when rubbed with steel wool # 0 (fiber diameter 25 to 35 μm). A high appearance molded article made of reinforced thermoplastic resin characterized by the above.
2. The high appearance molded article made of reinforced thermoplastic resin according to claim 1, wherein the average depth of scratches after rubbing with steel wool # 0 (fiber diameter 25 to 35 µm) is 50 µm or less.
3. Difference value X 0 and the molding surface of the gloss Gs defined in JIS Z8741 of the molding surface (20 °) and gloss X 1 after rubbing with steel wool # 0 (fiber diameter 25～35Myuemu) ( 2. The high appearance molded article made of reinforced thermoplastic resin according to 1 or 2, wherein X 0 -X 1 ) is within 25%.
4). The glossiness of at least a part of the surface of the high appearance molded article is characterized in that glossiness Gs (60 °) defined by JIS Z8741 is 80% or more and Gs (20 °) is 60% or more 1 The high appearance molded object made from the reinforced thermoplastic resin of ~ 3.
5). The high appearance molded body made of reinforced thermoplastic resin according to any one of 1 to 4, wherein the surface of the high appearance molded body has a pencil hardness of H or higher by a measurement method defined by JIS K5600-5-4.
6). The high appearance molded body made of reinforced thermoplastic resin according to 1 to 5, wherein at least a part of the surface of the high appearance molded body is mat-like.
7). That the reinforced thermoplastic resin comprises (A1) 99.9 parts by weight to 50 parts by weight of the polytrimethylene terephthalate resin (A2) 0 to 49.9 parts by weight of the thermoplastic resin (C) 5 to 300 parts by weight of the inorganic filler; The high appearance molded article made of a reinforced thermoplastic resin according to 1 to 6, which is characterized.
8). (C) The high appearance molded article made of reinforced thermoplastic resin according to 1 to 7, wherein the inorganic filler is a glass fiber.
9. (C) The high appearance molded article made of reinforced thermoplastic resin according to 1 to 8, wherein the inorganic filler includes a crystalline inorganic filler.
10. 9 wherein the crystalline inorganic filler is one or more crystalline inorganic fillers selected from the group consisting of wollastonite, talc, mica, carion, potassium titanate whisker, calcium carbonate whisker, and barium sulfate. The high appearance molded product made of the reinforced thermoplastic resin as described.
11. 11. The high appearance molded article made of reinforced thermoplastic resin according to 10, wherein the crystalline inorganic filler is wollastonite.
12 The thermo-resinable resin of (A2) is a polycarbonate resin, The reinforced thermoplastic resin high appearance molded article according to any one of 1 to 11.
13. Reinforced thermoplastic resin is (A1) 100 parts by weight to 50.1 parts by weight of polytrimethylene terephthalate resin (A2) 0 to 49.9 parts by weight of thermoplastic resin (C) 5 to 300 parts by weight of inorganic filler, (B) The high appearance molded article made of reinforced thermoplastic resin according to 1 to 12, characterized by containing 0.1 to 20 parts by weight of epoxy resin.
14 The reinforced thermoplastic resin according to any one of 1 to 13, wherein the surface-polished molded body is at least a part of constituent members of a bathroom product, a toilet product, a toilet product, and a sink product. High appearance molded product.
15. 15. A molded article made of a reinforced thermoplastic resin having a high appearance, wherein the molded article according to 14 is any one of a wash counter, a kitchen counter, a bathtub, a wash bowl, a hand wash bowl, a toilet counter, and a cabinet top plate.
本発明について、以下具体的に説明する。
本発明におけるバーコール硬度とは、ＪＩＳ Ｋ７０６０に準じて成形品表面の硬度を測定した値であり、本発明による成形品はバーコール硬度３０以上、より好ましくは３５以上、最も好ましくは４０以上である。
本発明における強化熱可塑性樹脂とは、熱可塑性樹脂の機械的強度、表面硬度等を向上させるために充填材を添加したものであり、一般的な充填材としては無機系のものが用いられる。
The present invention will be specifically described below.
The bar hardness according to the present invention is a value obtained by measuring the hardness of the surface of a molded product according to JIS K7060. The molded product according to the present invention has a barcol hardness of 30 or higher, more preferably 35 or higher, and most preferably 40 or higher.
The reinforced thermoplastic resin in the present invention is a resin to which a filler is added in order to improve the mechanical strength, surface hardness and the like of the thermoplastic resin, and an inorganic filler is used as a general filler.
本発明における耐傷付特性に優れた成形体とは、一般に家庭で水回り部品の洗浄時に磨きに用いるポリエステル系スポンジ、ポリ塩化ビニリデンスポンジ、アルミ蒸着スポンジ、研磨材付ナイロン不職布等で擦っても傷がつかない表面特性を持つものである。
本発明における成形体は、耐傷付特性に優れる物であって、繊維径２５〜３５μｍの＃０のスチールウールで擦ったときに大きな傷がつかない成形体である。本発明におけるスチールウールで擦るとは、人が掃除等で成形体表面を擦ることを想定しており、具体的には１〜３ｋｇ／ｃｍ２程度の圧力、０．５〜５ｃｍ／秒程度の速度で往復５０回擦った時の状態である。
The molded article having excellent scratch resistance in the present invention is generally rubbed with a polyester-based sponge, polyvinylidene chloride sponge, aluminum vapor-deposited sponge, nylon uncoated cloth with abrasives, etc. used for polishing at the time of washing water-related parts at home. It has surface characteristics that are not scratched.
The molded body in the present invention is a molded body that has excellent scratch resistance and does not have large scratches when rubbed with # 0 steel wool having a fiber diameter of 25 to 35 μm. The rubbing with steel wool in the present invention assumes that a person rubs the surface of the molded body by cleaning or the like. Specifically, the pressure is about 1 to 3 kg / cm 2 and about 0.5 to 5 cm / sec. This is the state when rubbed 50 times back and forth at a speed.
定量的な評価としては、スチールウール（＃０）で擦ったときの成形体表面に大きな傷が形成されないこと、具体的には５０μｍ以上の傷が殆どつかない耐傷付特性を有する成形体である。また別の定量的評価としては、スチールウールで擦る前の表面光沢度Ｇｓ（２０°）の値がＸ０、スチールウールで擦った後の表面光沢度Ｇｓ（２０°）の値がＸ１のとき、本発明の成形体は、表面光沢度（Ｇｓ２０°）の差（Ｘ０−Ｘ１）が、２５％以内である傷付きにくい成形体である。一般に、表面硬度、例えばバーコール硬度が高い樹脂成形体は、熱可塑性の注型アクリル板、キャストアクリル板や熱硬化性のＢＭＣ成形体などあるが、スチールウールのような硬い素材による傷付き性に関してはかなり悪く、＃０のスチールウールによる擦りによって表面に深い傷が多数発生して曇ってしまう。具体例として成形品が曇るとは、成形品表面に蛍光灯を映した場合、蛍光灯の輪郭が肉眼で見えない程度まで成形品が傷によって曇る程度の事を示す。 As a quantitative evaluation, it is a molded body having a scratch-resistant characteristic in which large scratches are not formed on the surface of the molded body when rubbed with steel wool (# 0), specifically, scratches of 50 μm or more are hardly formed. . As another quantitative evaluation, when the value of the surface glossiness Gs (20 °) before rubbing with steel wool is X0 and the value of the surface glossiness Gs (20 °) after rubbing with steel wool is X1, The molded body of the present invention is a molded body that is less likely to be scratched and has a difference in surface glossiness (Gs of 20 °) (X0−X1) of 25% or less. In general, resin moldings with high surface hardness, for example, Barcol hardness, are thermoplastic cast acrylic plates, cast acrylic plates, thermosetting BMC moldings, etc., but with respect to scratching by hard materials such as steel wool Is quite bad, and many deep scratches occur on the surface due to rubbing with # 0 steel wool, resulting in cloudiness. As a specific example, the fogging of the molded product indicates that when the fluorescent lamp is projected on the surface of the molded product, the molded product is clouded by scratches to the extent that the outline of the fluorescent lamp cannot be seen with the naked eye.
本発明における表面研磨前にスチールウール＃０（繊維径２５〜３５μｍ）で表面を擦った時のＪＩＳ Ｚ８７４１で定義される光沢度Ｇｓ（２０°）であるＸ１の絶対値としては、５０％以上となるものが好ましく、更に好ましくは６０％以上である。また、傷つけ前の光沢度Ｇｓ（２０°）であるＸ０の絶対値としては、６０％以上が好ましく更に好ましくは９０％以上である。
また、Ｘ０が、ＪＩＳ Ｚ８７４１で定義される光沢度Ｇｓ（６０°）の場合は、８０％以上、更に好ましくは ９０％以上、最も好ましくは９５％以上である。
The absolute value of X1, which is the glossiness Gs (20 °) defined by JIS Z8741 when the surface is rubbed with steel wool # 0 (fiber diameter 25 to 35 μm) before surface polishing in the present invention, is 50% or more. Is preferable, and more preferably 60% or more. Further, the absolute value of X0, which is the glossiness Gs (20 °) before being damaged, is preferably 60% or more, and more preferably 90% or more.
When X0 is the glossiness Gs (60 °) defined by JIS Z8741, it is 80% or more, more preferably 90% or more, and most preferably 95% or more.
本発明の成形体表面の硬度を表す別の尺度として、ＪＩＳ Ｋ５６００−５−４に準じた鉛筆硬度を測定した時に、鉛筆硬度がＨ以上が好ましく、より好ましくは２Ｈである。
本発明における成形体表面は、鏡面状態に限定されるものではなく、成形体表面に凹凸を付けたマット状、あるいはシボ形状の成形であっても、傷がつきにくい特性を生かした高外観成形体であっても良い。
As another scale representing the hardness of the surface of the molded article of the present invention, when measuring the pencil hardness according to JIS K5600-5-4, the pencil hardness is preferably H or more, more preferably 2H.
The surface of the molded body in the present invention is not limited to a mirror surface state, and is a high appearance molding that takes advantage of the characteristic that it is difficult to get scratched even if the surface of the molded body is formed into a matt or wrinkled shape. It may be the body.
本発明で好ましい樹脂である（Ａ１）ポリトリメチレンテレフタレート樹脂（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しては、１，３−プロパンジオール、１，２−プロパンジオール、１，１−プロパンジオール、２，２−プロパンジオール、あるいはこれらの混合物の中から選ばれるが、安定性の観点から１，３−プロパンジオールが特に好ましい。
(A1) Polytrimethylene terephthalate resin (hereinafter sometimes abbreviated as PTT) which is a preferred resin in the present invention is a polyester polymer using terephthalic acid as an acid component and trimethylene glycol as a glycol component. Show.
Here, the trimethylene glycol is selected from 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, or a mixture thereof. From this viewpoint, 1,3-propanediol is particularly preferable.
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。
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。
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 and the like; 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.
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.
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。 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。
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。
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 resulting terephthalic acid glycol ester is subjected to a polycondensation reaction in a presence of a catalyst at a suitable temperature and time to a desired degree of polymerization.
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.
本発明におけるポリトリメチレンテレフタレート強化樹脂組成物は、その極限粘度［η］が０．６０６ｄｌ／ｇ以上であることが機械特性、特に靭性面から好ましく、［η］が０．６８６ｄｌ／ｇ以上であることがより好ましく、さらに成形性、特にバリ特性から［η］が０．７５６ｄｌ／ｇ以上であることが最も好ましい。 The intrinsic viscosity [η] of the polytrimethylene terephthalate reinforced resin composition in the present invention is preferably 0.606 dl / g or more from the viewpoint of mechanical properties, particularly toughness, and [η] is 0.686 dl / g or more. It is more preferable that [η] is 0.756 dl / g or more from the viewpoint of moldability, particularly burr characteristics.
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、紫外線吸収剤、赤外線吸収剤、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。 In the polytrimethylene terephthalate of the present invention, various additives, for example, heat stabilizer, antifoaming agent, color adjuster, flame retardant, antioxidant, ultraviolet absorber, infrared absorber, Crystal nucleating agents, optical brighteners, matting agents, and the like may be copolymerized or mixed.
次に、本発明に用いることのできる（Ａ２）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、ポリカーボネート樹脂、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、ポリアミド樹脂、ポリフェニレンスルフィド樹脂、ポリオキシメチレン樹脂、ポリフェニレンエーテル樹脂、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、スチレン系樹脂あるい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。
Next, (A2) thermoplastic resin that can be used in the present invention 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, for example, polycarbonate resins, polyester resins other than polytrimethylene terephthalate, polyamide resins, polyphenylene sulfide resins, polyoxymethylene resins, polyphenylene ether resins, ethylene / propylene / nonconjugated diene resins, 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 these thermoplastics The mixture of 2 or more types of resin is mentioned.
中でも、ポリカーボネート樹脂、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樹脂が最も好ましい。
ポリカーボネート樹脂は二価フェノールとカーボネート前駆体から溶融法または溶液法によって製造される。即ち、塩化メチレン等の溶剤中で公知の酸受容体、分子量調整剤の存在下、二価フェノールとホスゲンのようなカーボネート前駆体との反応、または二価フェノールとジフェニルカルボネートのようなカルボネート前駆体とのエステル交換反応等によって製造することができる。ここで好ましい二価フェノールとしてはビスフェノール類が挙げられ、特に２，２−ビス（４−ヒドロキシフェニル）プロパン、即ちビスフェノールＡが好ましい。また、ビスフェノールＡの一部または全部を二価フェノールで置換したものであってもよい。
Of these, polyester resins other than polycarbonate resin and polytrimethylene terephthalate are preferable, and polycarbonate resin is most preferable from the viewpoint of mechanical properties.
The polycarbonate resin is produced from a dihydric phenol and a carbonate precursor by a melting method or a solution method. That is, in the presence of a known acid acceptor or molecular weight regulator in a solvent such as methylene chloride, a reaction between a dihydric phenol and a carbonate precursor such as phosgene, or a carbonate precursor such as a dihydric phenol and diphenyl carbonate. It can be produced by transesterification with a body. Preferred dihydric phenols here include bisphenols, and 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A is particularly preferred. Further, a part or all of bisphenol A may be substituted with dihydric phenol.
ビスフェノールＡ以外の二価フェノールとしては、例えばハイドロキノン、４，４−ジヒドロキシジフェニル、ビス（４−ヒドロキシフェニル）アルカン、ビス（４−ヒドロキシフェニル）シクロアルカン、ビス（４−ヒドロキシフェニル）スルフィド、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）スルホキシド、ビス（４−ヒドロキシフェニル）エーテルのような化合物を挙げることができる。これらの二価フェノールは、二価フェノールのホモポリマーまたは二種以上のコポリマーであってもよい。
また、カーボネート前駆体としては、カルボニルハライド、カルボニルエステル等が挙げられるが、ホスゲン、ジフェニルカーボネート、及びこれらの混合物が好ましく用いられる。また、本発明に用いられるポリカーボネート樹脂の重量平均分子量（ＭＷ）は、５０００から２０００００の範囲が好ましく、より好ましくは１５０００〜４００００である。
Examples of dihydric phenols other than bisphenol A include hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) sulfide, bis ( Examples include compounds such as 4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, and bis (4-hydroxyphenyl) ether. These dihydric phenols may be homopolymers of dihydric phenols or two or more copolymers.
Examples of the carbonate precursor include carbonyl halides and carbonyl esters, and phosgene, diphenyl carbonate, and mixtures thereof are preferably used. In addition, the weight average molecular weight (MW) of the polycarbonate resin used in the present invention is preferably in the range of 5000 to 200000, more preferably 15000 to 40000.
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。その中でも、特にポリエチレンテレフタレート樹脂とポリブチレンテレフタレート樹脂は、ポリトリメチレンテレフタレートの結晶化速度を著しく上昇させる効果があり、該組成物の高温強度は著しく向上する。 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. Among them, polyethylene terephthalate resin and polybutylene terephthalate resin have the effect of remarkably increasing the crystallization rate of polytrimethylene terephthalate, and the high temperature strength of the composition is remarkably improved.
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）あるい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。
スチレン系樹脂としては、ポリスチレン樹脂、ゴム変性ポリスチレン樹脂、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。
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.
Examples of the styrene resin include polystyrene resin, rubber-modified polystyrene resin, AS resin, ABS resin, or a mixture thereof.
本発明の（Ｂ）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。 The (B) epoxy resin of the present invention 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、またはエポキシ当量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。エポキシ当量、分子量が小さ過ぎると十分な耐薬品性が得られず、大き過ぎると十分な樹脂への分散性が得られず均一な組成物が得にくい。 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. If the epoxy equivalent and molecular weight are too small, sufficient chemical resistance cannot be obtained, and if it is too large, sufficient dispersibility in the resin cannot be obtained and a uniform composition is difficult to obtain.
（Ａ１）ポリトリメチレンテレフタレートと（Ａ２）熱可組性樹脂の配合量は、外観と表面硬度の観点から（Ａ１）ポリトリメチレンテレフタレート樹脂９９．９〜５０重量部、（Ａ２）熱可塑性樹脂０〜４９．９重量部であり、（Ａ２）熱可塑性樹脂の配合量は（Ａ１）ポリトリメチレンテレフタレート樹脂の配合量を超えない。より好ましくはポリトリメチレンテレフタレート９９．５〜７０重量部、（Ａ２）熱可塑性樹脂０〜２９．５重量部である。
（Ｂ）エポキシ樹脂の配合量は、機械的特性、表面硬度、耐薬品性と流動性低下防止の観点から、０．１〜２０重量％であり、より好ましくは０．３〜１０重量％である。
The blending amount of (A1) polytrimethylene terephthalate and (A2) heat-settable resin is (A1) 99.9 to 50 parts by weight of polytrimethylene terephthalate resin from the viewpoint of appearance and surface hardness, and (A2) thermoplastic resin. It is 0-49.9 weight part, and the compounding quantity of (A2) thermoplastic resin does not exceed the compounding quantity of (A1) polytrimethylene terephthalate resin. More preferably, it is 99.5 to 70 parts by weight of polytrimethylene terephthalate, and (A2) 0 to 29.5 parts by weight of the thermoplastic resin.
(B) The compounding quantity of an epoxy resin is 0.1 to 20 weight% from a viewpoint of mechanical characteristics, surface hardness, chemical resistance, and fluidity | liquidity fall prevention, More preferably, it is 0.3 to 10 weight% is there.
次に本発明の（Ｃ）無機充填材について説明する。
本発明に用いられる（Ｃ）無機充填材は目的に応じて繊維状、粉粒状、板状の無機充填材が用いられる。
本発明における（Ｃ）無機充填材の総添加量は、熱可塑性樹脂の総量１００重量部に対して、５〜３００重量部の範囲で本発明の効果が得られる。更に好ましくは２５〜１５０重量部、最も好ましくは、５０〜１２０重量部である。無機充填材の種類にもよるが、充填量が少ないと充分な耐傷付き性が得られなくなり、また多すぎると成形体表面の高外観が得られにくくなる。即ち、上記の観点から成形品表面の外観、特に光沢度Ｘ０が、ＪＩＳ Ｚ８７４１で定義される光沢度Ｇｓ（６０°）において、９０％以上、最も好ましくは９５％以上となり、かつ耐傷付き性に優れる無機充填材の好ましい量も見出した。
Next, (C) the inorganic filler of the present invention will be described.
As the (C) inorganic filler used in the present invention, a fibrous, powdery, or plate-like inorganic filler is used depending on the purpose.
The total amount of (C) inorganic filler added in the present invention is in the range of 5 to 300 parts by weight with respect to 100 parts by weight of the total amount of the thermoplastic resin. More preferably, it is 25-150 weight part, Most preferably, it is 50-120 weight part. Although depending on the kind of the inorganic filler, if the filling amount is small, sufficient scratch resistance cannot be obtained, and if it is too large, it is difficult to obtain a high appearance on the surface of the molded body. That is, from the above viewpoint, the appearance of the surface of the molded article, in particular, the glossiness X0 is 90% or more, most preferably 95% or more in the glossiness Gs (60 °) defined by JIS Z8741, and the scratch resistance is improved. A preferred amount of excellent inorganic filler was also found.
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。特に代表的な繊維状無機充填材はガラス繊維およびカーボン繊維である。なおポリアミド、フッ素樹脂、アクリル樹脂などの高融点有機質繊維状物質も使用することができる。 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. Particularly typical fibrous inorganic fillers are glass fiber and carbon fiber. High melting point organic fibrous materials such as polyamide, fluororesin, and acrylic resin can also be used.
一方、粉粒状無機充填材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。
又、板状無機充填材としてはタルク、マイカ、ガラスフレーク、各種の金属箔等が挙げられる。
On the other hand, powdered inorganic fillers include silicates such as carbon black, silica, quartz powder, glass beads, glass powder, calcium oxalate, aluminum oxalate, kaolin, clay, diatomaceous earth, iron oxide, titanium oxide. Metal oxides such as zinc oxide and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, silicon carbide, silicon nitride, boron nitride, various metal powders Is mentioned.
Examples of the plate-like inorganic filler include talc, mica, glass flakes, various metal foils and the like.
本発明における結晶性無機充填材とは、非結晶性の充填材、例えばガラス繊維、ガラスフレーク、ガラスビーズを除く、結晶性の無機充填材であり、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。結晶性無機充填材を用いることにより非晶性無機充填材では達成できなかった高度な表面外観と剛性、表面硬度の成形品を得ることができる。
繊維状の結晶性無機充填材としては、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、炭酸カルシウムウィスカー、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等の無機質繊維状物質が挙げられる。
The crystalline inorganic filler in the present invention is a crystalline inorganic filler excluding non-crystalline fillers such as glass fibers, glass flakes, and glass beads, and is fibrous, granular, or plate depending on the purpose. One or more inorganic fillers selected from the group consisting of shaped inorganic fillers can be used. By using the crystalline inorganic filler, it is possible to obtain a molded product having a high surface appearance, rigidity, and surface hardness that cannot be achieved by the amorphous inorganic filler.
Examples of fibrous crystalline inorganic fillers include carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate whisker, calcium carbonate whisker, wollastonite, Examples thereof include inorganic fibrous materials such as metallic fibrous materials such as stainless steel, aluminum, titanium, copper, and brass.
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。また炭素繊維は、平均繊維長が１００〜７５０μｍ、数平均繊維径が３〜３０μｍ、アスペクト比が１０〜１００であるものが好ましく用いられる。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。 The average fiber length (L), average fiber diameter (D), and aspect ratio (L / D) of the fibrous inorganic filler are not particularly limited, but from the viewpoint of mechanical properties, the average fiber length is 50 μm or more, and the average fiber The diameter is preferably 5 μm or more, and the aspect ratio is preferably 10 or more. Carbon fibers having an average fiber length of 100 to 750 μm, a number average fiber diameter of 3 to 30 μm, and an aspect ratio of 10 to 100 are preferably used. 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.
粉粒状の結晶性無機充填材としてはカーボンブラック、シリカ、石英粉末、硅酸カルシウム、硅酸アルミニウム、カオリン、クレー、硅藻土等の硅酸塩、酸化鉄、酸化チタン、酸化亜鉛、アルミナ等の金属の酸化物、炭酸カルシウム、炭酸マグネシウム等の金属の炭酸塩、硫酸カルシウム、硫酸バリウム等の金属の硫酸塩、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。
又、板状の結晶性無機充填材としてはタルク、マイカ、各種の金属箔等が挙げられる。なお、タルク、マイカ、カオリン、炭酸カルシウム、チタン酸カリウムは平均粒径が０．１〜１００μｍのものが好ましく用いられる。
Examples of granular crystalline inorganic fillers include carbon black, silica, quartz powder, calcium oxalate, aluminum oxalate, kaolin, clay, oxalate such as diatomaceous earth, iron oxide, titanium oxide, zinc oxide, alumina, etc. Metal oxides such as, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, silicon carbide, silicon nitride, boron nitride and various metal powders.
Examples of the plate-like crystalline inorganic filler include talc, mica, and various metal foils. In addition, talc, mica, kaolin, calcium carbonate, and potassium titanate having an average particle diameter of 0.1 to 100 μm are preferably used.
本発明の無機充填材としては、外観、機械的強度の点から、ウォラストナイト、タルク、マイカ、カオリン、炭酸カルシウム，炭素繊維（ＣＦ）、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結晶性無機充填材が好ましい。最も好ましくはウォラストナイトである。 Examples of the inorganic filler of the present invention include wollastonite, talc, mica, kaolin, calcium carbonate, carbon fiber (CF), potassium titanate whisker, calcium carbonate whisker, and barium sulfate in terms of appearance and mechanical strength. One or more crystalline inorganic fillers selected from are preferred. Most preferred is wollastonite.
Ｃ１）結晶性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、（Ａ１）ポリトリメチレンテレフタレート樹脂、（Ａ２）熱可塑性樹脂、（Ｂ）エポキシ樹脂の合計１００重量部に対して、（Ｃ１）結晶性無機充填材５〜３００重量部、より好ましくは２５〜２５０重量部である。 C1) The compounding amount of the crystalline inorganic filler is (A1) a polytrimethylene terephthalate resin, (A2) from the viewpoint of improving the mechanical strength, rigidity and surface hardness, and affecting the appearance such as gloss reduction of the molded product surface. (C1) 5 to 300 parts by weight, more preferably 25 to 250 parts by weight of the crystalline inorganic filler with respect to 100 parts by weight of the total of the thermoplastic resin and (B) epoxy resin.
また、本発明においては、（Ｃ１）結晶性無機充填材に併用して、（Ｃ２）ガラス繊維を用いることができる。
（Ｃ２）ガラス繊維は（Ｃ１）結晶性無機充填材の配合量を超えない範囲で用いることで、ガラス繊維単独で用いた場合の外観不足を補い、優れた表面外観を得ると共に機械的強度を改良することができる。
In the present invention, (C2) glass fibers can be used in combination with (C1) crystalline inorganic filler.
(C2) The glass fiber is used in a range not exceeding the blending amount of the (C1) crystalline inorganic filler to compensate for the lack of appearance when used alone and to obtain an excellent surface appearance and mechanical strength. It can be improved.
本発明においては、ポリトリメチレンテレフタレート樹脂組成物中の無機充填材表面にグラフトした樹脂を特定の割合で存在させることが好ましい。
ここで、無機充填材表面にグラフトした樹脂とは、強化ポリトリメチレンテレフタレート樹脂組成物を、ポリエステル樹脂の溶媒に浸し、ポリトリメチレンテレフタレートを溶出させ無機充填材を析出させた時、溶媒中に溶出せず無機充填材表面に残るポリトリメチレンテレフタレートを主成分とする有機物層のことをいい、赤外吸収スペクトル、熱分解ガスクロマトグラフ分析からポリトリメチレンテレフタレートの存在が確認できるものをいう。
In the present invention, the resin grafted on the surface of the inorganic filler in the polytrimethylene terephthalate resin composition is preferably present in a specific ratio.
Here, the resin grafted on the surface of the inorganic filler means that the reinforced polytrimethylene terephthalate resin composition is immersed in a polyester resin solvent to elute the polytrimethylene terephthalate and precipitate the inorganic filler. This refers to an organic substance layer composed mainly of polytrimethylene terephthalate that does not elute and remains on the surface of the inorganic filler. It can be confirmed from the infrared absorption spectrum and pyrolysis gas chromatographic analysis.
具体的には下記の方法によって得ることができる。まず、強化ポリトリメチレンテレフタレート樹脂組成物中の無機充填材と無機充填材にグラフトしていない樹脂とを分離するためにＨＦＩＰ（ヘキサフルオロイソプロパノール）溶媒と混合する。次に、ポリトリメチレンテレフタレートを主体とする樹脂が溶解したＨＦＩＰ溶液部分を除去し、残った無機充填材部分を、ポリトリメチレンテレフタレートが溶出しなくなるまで数回ＨＦＩＰ溶媒で洗浄した後、ＨＦＩＰを除去するためにエタノールで数回洗浄し、エタノールを乾燥して除去する。この様にして、樹脂組成物中から有機物層がグラフトした無機充填材を取り出す。この無機充填材にグラフトした有機物層を、グラフトした樹脂という。なお、この有機物層を、赤外吸収スペクトル（ＩＲ）、熱分解ガスクロマトグラフ／マススペクトル（ＰｙＧＣ／ＭＳ）等を用いて分析することで、有機物層の主成分がポリトリメチレンテレフタレートであることを確認できる。 Specifically, it can be obtained by the following method. First, in order to separate the inorganic filler in the reinforced polytrimethylene terephthalate resin composition and the resin not grafted on the inorganic filler, it is mixed with an HFIP (hexafluoroisopropanol) solvent. Next, the HFIP solution part in which the resin mainly composed of polytrimethylene terephthalate is dissolved is removed, and the remaining inorganic filler part is washed with HFIP solvent several times until the polytrimethylene terephthalate does not elute, and then the HFIP is removed. Wash with ethanol several times to remove, and remove ethanol by drying. In this manner, the inorganic filler grafted with the organic layer is taken out from the resin composition. The organic layer grafted on the inorganic filler is referred to as grafted resin. By analyzing this organic material layer using infrared absorption spectrum (IR), pyrolysis gas chromatograph / mass spectrum (PyGC / MS), etc., it is confirmed that the main component of the organic material layer is polytrimethylene terephthalate. I can confirm.
また、無機充填材表面にグラフトした樹脂の量は、上記の様にして得られた樹脂がグラフトした無機充填材を用い、ＪＩＳＲ３４２０（強熱減量、Ｉｇ．Ｌｏｓｓ）に従って、次式から求めることができる。
グラフトした樹脂量（重量部）＝［（Ｗ０−Ｗ１）／Ｗ１］×１００
Ｗ０：焼成前の樹脂がグラフトした無機充填材の重量
Ｗ１：焼成後の無機充填材の重量
（結晶性樹脂と併用してガラス繊維を用いた場合、両者を合わせた無機充填材の表面にグラフトした樹脂の量として求めることができる。）
The amount of the resin grafted on the surface of the inorganic filler can be obtained from the following formula according to JISR3420 (ignition loss, Ig. Loss) using the inorganic filler grafted with the resin obtained as described above. it can.
Grafted resin amount (parts by weight) = [(W 0 −W 1 ) / W 1 ] × 100
W 0 : Weight of inorganic filler grafted with resin before firing W 1 : Weight of inorganic filler after firing (when glass fiber is used in combination with crystalline resin, surface of inorganic filler combined with both) It can be determined as the amount of resin grafted on the
この無機充填材表面にグラフトした樹脂の量（結晶性樹脂と併用してガラス繊維を用いた場合、両者を合わせた無機充填材の表面にグラフトした樹脂の量）は、無機充填材１００重量部あたり０．０１〜５重量部、好ましくは０．０２〜３重量部、最も好ましくは０．０５〜２重量部である。０．０１重量部未満では得られる組成物の機械的強度が充分とはいえない。また、５重量部を越えると、溶融流動性が低下し射出成形時の圧力が高くなる。
本発明において、ポリトリメチレンテレフタレート樹脂組成物中の無機充填材表面にグラフトした樹脂を特定の割合で存在させるために、（Ｃ）結晶性無機充填材及び併用することができる（Ｃ２）ガラス繊維は、表面処理を施したものが好ましく用いられる。
The amount of resin grafted on the surface of the inorganic filler (when glass fiber is used in combination with the crystalline resin, the amount of resin grafted on the surface of the inorganic filler combined with both) is 100 parts by weight of the inorganic filler. 0.01-5 parts by weight, preferably 0.02-3 parts by weight, most preferably 0.05-2 parts by weight. If it is less than 0.01 part by weight, the mechanical strength of the resulting composition is not sufficient. On the other hand, if it exceeds 5 parts by weight, the melt fluidity is lowered and the pressure during injection molding is increased.
In the present invention, in order to make the resin grafted on the surface of the inorganic filler in the polytrimethylene terephthalate resin composition exist in a specific ratio, (C) a crystalline inorganic filler and (C2) glass fiber can be used in combination. Those subjected to surface treatment are preferably used.
無機充填材の表面処理としては特に制限はなく、カップリング剤やフィルム形成剤を用いて行えばよい。
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経済性に優れ、取り扱い易いため、好ましく用いられる。
The surface treatment of the inorganic filler is not particularly limited, and may be performed using a coupling agent or a film forming agent.
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 Aminosilanes and epoxysilanes such as these are preferably used because they are economical and easy to handle.
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、経済性と機械的強度が優れるという観点から、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。 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, from the viewpoint of excellent economic efficiency and mechanical strength, an epoxy polymer, a urethane polymer, an acrylic acid polymer, a butadiene maleic anhydride copolymer, an ethylene maleic anhydride copolymer, a styrene maleic anhydride copolymer, and a mixture thereof are used. Particularly preferably used.
このようなカップリング剤及びフィルム形成剤を用いて、無機充填材の表面処理を行うには、公知の方法によればよい。例えば、上記カップリング剤及び／又はフィルム形成剤及び有機溶媒からなる溶液又は懸濁液をいわゆるサイジング剤として表面に塗布するサイジング処理、ヘンシェルミキサー、スーパーミキサー、レーディミキサー、Ｖ型ブレンダー等を用いてカップリング剤及び／又はフィルム形成剤を塗布する乾式混合、スプレーによりカップリング剤及び／又はフィルム形成剤を塗布するスプレー法、さらには、インテグラルブレンド法、ドライコンセントレート法を挙げることができる。また、これらの方法を組み合わせた方法、例えばカップリング剤とフィルム形成剤の一部をサイジング処理により塗布した後、残りのフィルム形成剤をスプレーする方法等も挙げることができる。この中でも、経済性に優れるという観点から、サイジング処理、乾式混合、スプレー法及びこれらを組合せた方法が好ましく用いられる。 In order to perform the surface treatment of the inorganic filler using such a coupling agent and a film forming agent, a known method may be used. For example, a sizing treatment, a Henschel mixer, a super mixer, a ready mixer, a V-type blender, or the like that applies a solution or suspension composed of the above coupling agent and / or film forming agent and an organic solvent to the surface as a so-called sizing agent is used. Examples thereof include dry mixing for applying the coupling agent and / or film forming agent, spraying method for applying the coupling agent and / or film forming agent by spraying, and integral blending method and dry concentrate method. . In addition, a method combining these methods, for example, a method of spraying the remaining film forming agent after applying a part of the coupling agent and the film forming agent by sizing treatment, and the like can also be mentioned. Among these, from the viewpoint of being excellent in economic efficiency, a sizing treatment, a dry mixing method, a spray method, and a method combining these are preferably used.
また、本発明においては、樹脂組成物より無機充填材及び無機充填材にグラフトした樹脂を除いた、無機充填材にグラフトしていない樹脂中のエポキシ樹脂の量が特定の量であることが好ましい。無機充填材にグラフトしていない樹脂は前出の樹脂がグラフトした無機充填材の分離作業において、ポリトリメチレンテレフタレートを主体とする樹脂が溶解したＨＦＩＰ溶液部分として、分離することができる。
この有機物を、核磁気共鳴（ＮＭＲ）、熱分解ガスクロマトグラフ／マススペクトル（ＰｙＧＣ／ＭＳ）等を用いて定量分析することで、無機充填材にグラフトしていない樹脂中のエポキシ樹脂の量を求めることができる。
Moreover, in this invention, it is preferable that the quantity of the epoxy resin in resin which is not grafted to an inorganic filler except the resin grafted on the inorganic filler and the inorganic filler from the resin composition is a specific quantity. . The resin not grafted to the inorganic filler can be separated as a HFIP solution portion in which the resin mainly composed of polytrimethylene terephthalate is dissolved in the separation work of the inorganic filler grafted with the above-mentioned resin.
This organic matter is quantitatively analyzed using nuclear magnetic resonance (NMR), pyrolysis gas chromatograph / mass spectrum (PyGC / MS), etc., to determine the amount of epoxy resin in the resin not grafted to the inorganic filler. be able to.
無機充填材にグラフトしていない樹脂中の好ましいエポキシ樹脂の量は０．１〜２０重量％、より好ましくは０．３〜１０重量％である。無機充填材にグラフトしていない樹脂中に、０．１重量％以上のエポキシ樹脂が存在することで、機械的強度、剛性、表面硬度を高めると共に、耐薬品性、耐加水分解性をめざましく改善するとともに、無機充填材の配合によって引き起こされる樹脂組成物の分子量低下を防ぐことができる。２０重量％を越えると、溶融流動性が低下し射出成形時の圧力が高くなる。 A preferable amount of the epoxy resin in the resin not grafted on the inorganic filler is 0.1 to 20% by weight, more preferably 0.3 to 10% by weight. The presence of 0.1% by weight or more of epoxy resin in the resin that is not grafted on the inorganic filler increases mechanical strength, rigidity, and surface hardness, and dramatically improves chemical resistance and hydrolysis resistance. In addition, a decrease in the molecular weight of the resin composition caused by the blending of the inorganic filler can be prevented. If it exceeds 20% by weight, the melt fluidity is lowered and the pressure during injection molding is increased.
本発明の強化ポリトリメチレンテレフタレート樹脂組成物は、ポリトリメチレンテレフタレート、熱可塑性樹脂、結晶性無機充填材、及び必要に応じて加えられるガラス繊維や、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、（Ａ１）ポリトリメチレンテレフタレート樹脂（Ａ２）熱可塑性樹（Ｂ）エポキシ樹脂を溶融混錬した後に（Ｃ１）結晶性無機充填材を添加する
製造方法が、樹脂にエポキシ樹脂を効果的に分散させ、無機充填材表面のグラフトした樹脂量を制御し、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。
The reinforced polytrimethylene terephthalate resin composition of the present invention is appropriately designed with polytrimethylene terephthalate, thermoplastic resin, crystalline inorganic filler, and glass fiber added as necessary, other additives, and the like. In particular, (A1) polytrimethylene terephthalate resin (A2) thermoplastic tree (B) after melt-kneading epoxy resin (C1) crystal The production method of adding an inorganic filler effectively disperses the epoxy resin in the resin, controls the amount of grafted resin on the surface of the inorganic filler, and suppresses the decrease in the molecular weight of the resin composition caused by the addition of the inorganic filler. This is preferable.
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には、上記のポリトリメチレンテレフタレート樹脂、熱可塑性樹脂、エポキシ樹脂、結晶性無機充填材、ガラス繊維に加え、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。
In addition to the polytrimethylene terephthalate resin, thermoplastic resin, epoxy resin, crystalline inorganic filler, and glass fiber, the polytrimethylene terephthalate reinforced resin composition of the present invention can be used in accordance with various applications and purposes. Components can be appropriately blended.
For example, a crystal nucleating agent can be further blended in the composition of the present invention. As the crystal nucleating agent, either an organic substance or an inorganic substance can be used.
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。 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。
本発明における表面研磨する前に成形体表面に傷を有していた事を特徴とする表面が研磨された強化熱可塑性樹脂製高外観成形体とは、表面に傷がついた成形品を補修して高外観成形体を作成することを意味する。
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.
In the present invention, the surface of the reinforced thermoplastic resin having a polished surface characterized by having scratches on the surface of the molded body before the surface polishing is to repair a molded product having a scratched surface. This means that a molded article with a high appearance is produced.
本発明の表面研磨された高外観強化樹脂製成形品、特にポリトリメチレンテレフタレート強化樹脂組成物を用いた成形体は、外観が極めて良好であり、機械的強度、剛性、表面硬度、寸法安定性、耐加水分解性、耐薬品性に優れるため、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、バーコール硬度３０、鉛筆硬度２Ｈ以上、ＪＩＳ Ｚ８７４１で定義される光沢度Ｇｓ（２０°）が好ましくは６０％以上、より好ましくはバーコール硬度３５以上、鉛筆高度２Ｈ以上、ＪＩＳ Ｚ８７４１で定義される光沢度Ｇｓ（２０°）が９０％以上の成形体はこの用途に最適に用いることができる。
更に本発明の成形体は、無塗装でもかなりの高外観が得られるが、更に機能付与や意匠性を付与するために塗装や、メッキを行っても良い。薄肉塗装やメッキなどでは下地の形状がより外観に影響することがあり、本発明の成形体の特徴である高光沢面が得られる。
The surface-polished high appearance reinforced resin molded product of the present invention, in particular, the molded body using the polytrimethylene terephthalate reinforced resin composition has a very good appearance, mechanical strength, rigidity, surface hardness, dimensional stability. Because of its excellent resistance to hydrolysis and chemicals, it has a bathroom counter, kitchen counter, bathtub, wash bowl (basin), hand wash bowl (wash basin), various sinks, toilet counters, cabinet tops, bathrooms, toilets, It can be used for at least some of the components of products used in toilets and kitchens. In particular, the surface hardness of the molded body is a Barcol hardness of 30 and a pencil hardness of 2H or higher, and the glossiness Gs (20 °) defined by JIS Z8741 is preferably 60% or higher, more preferably a Barcol hardness of 35 or higher and a pencil height of 2H or higher. A molded product having a glossiness Gs (20 °) defined by JIS Z8741 of 90% or more can be optimally used for this application.
Furthermore, although the molded article of the present invention can have a considerably high appearance even without coating, it may be coated or plated in order to impart functions or design properties. In the case of thin-wall coating or plating, the shape of the base may affect the appearance more, and the high gloss surface that is a feature of the molded article of the present invention can be obtained.
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、熱可塑性樹脂
（Ａ１）ＰＴＴ樹脂
ポリトリメチレンテレフタレート樹脂［η］＝１．０ｄｌ／ｇ
（Ａ２）熱可塑性樹脂
ＰＢＴ樹脂：ポリブチレンテレフタレート樹脂 ポリプラスチックス（株）製 ジュラネックス２００２
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（株）製 ユーピロンＳ２０００
The present invention will be described based on examples. The resins used in Examples and Comparative Examples are described below.
(A) PTT resin, thermoplastic resin (A1) PTT resin Polytrimethylene terephthalate resin [η] = 1.0 dl / g
(A2) Thermoplastic resin PBT resin: Polybutylene terephthalate resin DURANEX 2002 manufactured by Polyplastics Co., Ltd.
Polycarbonate resin: Iupilon S2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.
（Ｂ）エポキシ樹脂
（Ｂ１）エポキシ樹脂−１：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．）
（Ｂ２）エポキシ樹脂−２：旭化成エポキシ（株）製、オルソクレゾールノボラック型エポキシ樹脂 ＡＥＲ ＥＣＮ１２９９、エポキシ当量約２３０（／ｅｑ．）
(B) Epoxy resin (B1) Epoxy resin-1: Asahi Kasei Epoxy Corporation, bisphenol A type epoxy resin AER ECN6097, epoxy equivalent of about 2000 (/ eq.)
(B2) Epoxy resin-2: manufactured by Asahi Kasei Epoxy Corporation, orthocresol novolac type epoxy resin AER ECN1299, epoxy equivalent of about 230 (/ eq.)
（Ｃ）無機充填材
（Ｃ１）結晶性無機充填材
ＭＦ−１：ウォラストナイト ＮＩＣＯ社製 ＮＹＧＬＯＳＳ８ エポキシシラン処理
ＭＦ−２：ウォラストナイト ＮＩＣＯ社製 ＮＹＧＬＯＳＳ８ アミノシラン処理
ＭＦ−３：マイカ レプコ社製 Ｍ−４００
ＭＦ−４：硫酸バリウム 堺化学工業社製 ＢＭＨ−６０
（Ｃ２）ガラス繊維
日本電気硝子社製 ０３Ｔ−１８７／ＰＬ
(C) Inorganic filler (C1) Crystalline inorganic filler MF-1: Wollastonite manufactured by NICO NYGLOSS8 epoxy silane treatment MF-2: Wollastonite manufactured by NICO NYGLOSS8 aminosilane treatment MF-3: Made by Mica Repco M -400
MF-4: Barium sulfate BMH-60 manufactured by Sakai Chemical Industry Co., Ltd.
(C2) Glass fiber 03T-187 / PL manufactured by Nippon Electric Glass Co., Ltd.
評価方法は以下の通り。
（１）曲げ弾性率（ＧＰａ）
ＡＳＴＭ Ｄ７９０に準じて行った。
（２）表面硬度
ＪＩＳ Ｋ７０６０に準じ成形品表面のバーコール硬度を測定した。
（３）耐薬品性
成形品を排水パイプ洗浄剤原液に室温にて２週間浸漬し、取り出し後水で洗浄し乾燥して形品の重量変化を測定した。
使用洗浄剤：ジョンソン株式会社（製）パイプユニッシュプラス（水酸化ナトリウム３％、次亜塩素酸塩、界面活性剤アルキルアミンオキシド）
（４）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°とＧｓ６０°を測定した。
The evaluation method is as follows.
(1) Flexural modulus (GPa)
This was performed according to ASTM D790.
(2) Surface hardness According to JIS K7060, the Barcol hardness of the surface of the molded product was measured.
(3) Chemical resistance The molded product was immersed in a stock solution for cleaning wastewater pipes at room temperature for 2 weeks, taken out, washed with water and dried, and the change in weight of the molded product was measured.
Cleaning agent used: Johnson Co., Ltd. (Pipe unish plus) (3% sodium hydroxide, hypochlorite, surfactant alkylamine oxide)
(4) Appearance Using a Horiba handy gloss meter IG320, Gs20 ° and Gs60 ° of the dumbbell test piece were measured according to JIS-K7150.
［実施例１〜３、比較例１〜４］
樹脂、エポキシ樹脂を表１に示した配合比で混合し、二軸押出機（東芝機械（株）製：ＴＥＭ５８）を用いて溶融混練し、サイドフィーダーから結晶性無機充填材とガラス繊維の少なくとも一つを表１に示した配合比で添加した。押出条件はスクリュー回転数１５０ｒｐｍ、シリンダー温度２６０℃、押出速度１５０ｋｇ／ｈｒ、減圧度０．０４ＭＰａ、先端ノズル付近の樹脂温度は２８０℃であった。先端ノズルから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を用いて、シリンダー温度２６０℃、金型温度９５℃に設定し、射出成形を行い試験片を作成した。この試験片を用いて評価を行った。結果を表1に示した。
[Examples 1 to 3, Comparative Examples 1 to 4]
A resin and an epoxy resin are mixed at a blending ratio shown in Table 1, and melt-kneaded using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM58). From the side feeder, at least a crystalline inorganic filler and glass fiber are mixed. One was added at the compounding ratio shown in Table 1. The extrusion conditions were a screw rotation speed of 150 rpm, a cylinder temperature of 260 ° C., an extrusion speed of 150 kg / hr, a degree of vacuum of 0.04 MPa, and the resin temperature near the tip nozzle was 280 ° C. The composition discharged in a strand form from the tip nozzle was cut with water and then cut into pellets. The pellets were dried at 120 ° C. for 5 hours with a dehumidifying dryer, and then the cylinder temperature was set to 260 ° C. and the mold temperature was set to 95 ° C. using a Nissei Resin Co., Ltd. PS40E. Created. Evaluation was performed using this test piece. The results are shown in Table 1.
成形品の表面光沢度と耐傷付き性の評価は、下記のように行った。
（Ａ）傷つけ前の成形品表面の光沢度Ｘ０測定
（Ｂ）成形品表面を種々の研磨材を用いて傷つけた後の外観を判定し、必要に応じて光沢度Ｘ１を測定した。
傷付け試験方法としては、表２に示す種々研磨材を用いて成形品表面を手で往復５０回こすり、その後ティッシュペーパーで表面についた研磨材の粉をふき取った部分。研磨材で擦ったときの圧力は、１〜３ｋｇｆ／ｃｍ２、速度は約１ｃｍ／秒であった。
これらの組成を表１に示す。
The surface glossiness and scratch resistance of the molded product were evaluated as follows.
(A) Measurement of glossiness X0 of the surface of the molded product before scratching (B) The appearance after the surface of the molded product was scratched with various abrasives was determined, and the glossiness X1 was measured as necessary.
As a scratch test method, the surface of the molded product was rubbed 50 times back and forth by hand using various abrasives shown in Table 2, and then the abrasive powder on the surface was wiped off with tissue paper. The pressure when rubbed with the abrasive was 1 to 3 kgf / cm 2 , and the speed was about 1 cm / sec.
These compositions are shown in Table 1.
［比較例５〜７］
比較例５〜７について下記に説明する。
比較例５は、ガラス繊維のような強化材が入っていない非強化型ＰＭＭＡ樹脂のキャスト法により成形されたキャスト板（三菱レイヨン製「アクリルサンデー」）より９０×５０ｍｍの平板を切り出して評価した。
比較例６は、熱硬化型の不飽和ポリエステル樹脂を主成分としたＢＭＣ（ｂｕｌｋ ｍｏｌｄｉｎｇ ｃｏｍｐｏｕｎｄ）材料を用いたＢＭＣ成形品より８０×５０ｍｍの試験片を切り出して評価した。
比較例４は、ガラス繊維３０重量％充填したＰＢＴ強化樹脂成形品（９０×５０ｍｍ平板）である。
表１に示すように本発明の成形体は、外観特性に優れ、特に傷がつきにくい成形体である。更に実施例１〜７に示したように、成形体の表面が硬いために、スチールウール（＃０）のような非常に硬い素材でこすっても表面に大きな傷はつかなかった。これに対して、比較例１、５〜７の成形体は、スチールウール（＃０）のような非常に硬い素材でこすると、深い傷が多数ついて表面が曇ってしまった。
[Comparative Examples 5 to 7]
Comparative Examples 5 to 7 will be described below.
Comparative Example 5 was evaluated by cutting out a 90 × 50 mm flat plate from a cast plate (“Acrylic Sunday” manufactured by Mitsubishi Rayon) formed by a casting method of non-reinforced PMMA resin that does not contain a reinforcing material such as glass fiber. .
In Comparative Example 6, an 80 × 50 mm test piece was cut out from a BMC molded product using a BMC (bulk molding compound) material mainly composed of a thermosetting unsaturated polyester resin.
Comparative Example 4 is a PBT reinforced resin molded product (90 × 50 mm flat plate) filled with 30% by weight of glass fiber.
As shown in Table 1, the molded product of the present invention is a molded product that has excellent appearance characteristics and is not easily damaged. Further, as shown in Examples 1 to 7, since the surface of the molded body was hard, even if it was rubbed with a very hard material such as steel wool (# 0), the surface was not damaged greatly. On the other hand, when the molded bodies of Comparative Examples 1 and 5 to 7 were rubbed with a very hard material such as steel wool (# 0), the surface was clouded with many deep scratches.
表２には、成形品表面の光沢度を測定した結果を示す。また、参考値として、ＪＩＳ Ｋ５６００−５−４ 「塗膜の機械的性質−引っかき硬度（鉛筆法）」に記載の方法に準じて成形品表面の鉛筆硬度も測定した。 Table 2 shows the results of measuring the glossiness of the molded product surface. Further, as a reference value, the pencil hardness of the surface of the molded product was also measured according to the method described in JIS K5600-5-4 “Mechanical properties of coating film—scratch hardness (pencil method)”.
実施例８〜１０は、表１に記載の組成物を実施例１と同様に、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を用いて、シリンダー温度２６０℃、金型温度９５℃に設定し、射出成形を行い試験片（９０ｍｍ×５０ｍｍ、厚み２．５ｍｍ）の試験片を作成した。 In Examples 8 to 10, after the pellets were dried with a dehumidifying dryer at 120 ° C. for 5 hours in the same manner as in Example 1, using PS40E manufactured by Nissei Resin Co., Ltd. The cylinder temperature was set to 260 ° C. and the mold temperature was set to 95 ° C., and injection molding was performed to prepare a test piece (90 mm × 50 mm, thickness 2.5 mm).
比較例５〜７について下記に説明する。
比較例５は、ガラス繊維のような強化材が入っていない非強化型ＰＭＭＡ樹脂のキャスト法により成形されたキャスト板（三菱レイヨン製「アクリルサンデー」）より９０×５０ｍｍの平板を切り出して評価した。
比較例６は、熱硬化型の不飽和ポリエステル樹脂を主成分としたＢＭＣ（ｂｕｌｋ ｍｏｌｄｉｎｇ ｃｏｍｐｏｕｎｄ）材料を用いたＢＭＣ成形品より８０×５０ｍｍの試験片を切り出して評価した。
比較例７は、ガラス繊維３０重量％充填したＰＢＴ強化樹脂成形品（９０×５０ｍｍ平板）である。
Comparative Examples 5 to 7 will be described below.
Comparative Example 5 was evaluated by cutting out a 90 × 50 mm flat plate from a cast plate (“Acrylic Sunday” manufactured by Mitsubishi Rayon) formed by a casting method of non-reinforced PMMA resin that does not contain a reinforcing material such as glass fiber. .
In Comparative Example 6, an 80 × 50 mm test piece was cut out from a BMC molded product using a BMC (bulk molding compound) material mainly composed of a thermosetting unsaturated polyester resin.
Comparative Example 7 is a PBT reinforced resin molded product (90 × 50 mm flat plate) filled with 30% by weight of glass fiber.
評価法は、下記のように耐傷付き性、補修性の評価と同様に実施し、以下の２ヶ所の光沢度を測定して評価した。
（Ａ）成形品表面
（B）成形品表面をスチールウール（＃０）にて手で往復５０回こすり、その後ティッシュペーパーで表面についたスチールウールの粉をふき取った部分。スチールウールで擦ったときの圧力は、１〜３ｋｇｆ／ｃｍ２、速度は約１ｃｍ／秒であった。
本発明の成形体である実施例８は、表面硬度を測定した所、鉛筆硬度２Ｈで、比較例５（ＰＭＭＡキャスト板）の４Ｈ、比較例６（ＢＭＣ成形品）の３Ｈよりも低いにも関わらず、（B）傷つけ後の光沢度はＧｓ（２０°）で７０％、Ｇｓ（６０°）で８８％と比較例５の１６％（Ｇｓ２０°測定値）、５０％（Ｇｓ６０°測定値）、比較例６の１７％（Ｇｓ２０°測定値）、５３％（Ｇｓ６０°測定値）、比較例７の３％（Ｇｓ２０°測定値）、２１％（Ｇｓ６０°測定値）、に比べて大きく耐傷付性に優れることがわかる。また目視判定での外観は、実施例８の成形品表面は、（B）傷つけ後に細かな傷が僅かに見えるのに対して、比較例５、６、７の成形品では、（B）傷つけ後の表面は白く曇っていた。
The evaluation method was carried out in the same manner as the evaluation of scratch resistance and repairability as described below, and the glossiness at the following two locations was measured and evaluated.
(A) Molded product surface (B) The surface of the molded product was rubbed 50 times by hand with steel wool (# 0), and then the steel wool powder adhered to the surface with tissue paper was wiped off. The pressure when rubbing with steel wool was 1 to 3 kgf / cm 2 , and the speed was about 1 cm / sec.
In Example 8 which is a molded body of the present invention, the surface hardness was measured. The pencil hardness was 2H, which was lower than 4H of Comparative Example 5 (PMMA cast plate) and 3H of Comparative Example 6 (BMC molded product). Regardless, (B) the gloss after damage is 70% for Gs (20 °), 88% for Gs (60 °), 16% of Comparative Example 5 (measured value of Gs20 °), 50% (measured value of Gs60 °). ), 17% (Gs20 ° measured value), 53% (Gs60 ° measured value) of Comparative Example 6, 3% (Gs20 ° measured value), 21% (Gs60 ° measured value) of Comparative Example 7 It can be seen that it has excellent scratch resistance. Further, the appearance by visual judgment is that the surface of the molded product of Example 8 (B) is slightly scratched after being scratched, whereas the molded products of Comparative Examples 5, 6, and 7 are (B) damaged. The later surface was white and cloudy.
表２では、研磨材としてスチールウール（＃０）を用いて評価したが、それに加えて更に種々の研磨材を用いて耐傷付き特性の評価を実施した。評価結果を表３に示す。実施例８、９の成形体は、光沢度Ｇｓ（６０°）が９０％以上と外観に優れた成形体である。更に実施例８、９の成形体は、比較例４、５、６に比べて耐傷付き特性に優れていた。 In Table 2, evaluation was made using steel wool (# 0) as an abrasive, but in addition to this, evaluation of scratch resistance was conducted using various abrasives. The evaluation results are shown in Table 3. The molded bodies of Examples 8 and 9 are molded bodies having a glossiness Gs (60 °) of 90% or more and an excellent appearance. Furthermore, the molded bodies of Examples 8 and 9 were superior in scratch resistance properties as compared to Comparative Examples 4, 5, and 6.
実施例８、実施例９、比較例５、比較例６、比較例７の成形体の表面をキーエンス製レーザー顕微鏡「VK ９５１０ 」を用いて成形体表面観察を行った。図１〜図５に観察結果を示す。図中Ａは、成形体の反射光量像であり、測定条件は対物レンズの倍率５倍、測定ピッチ５μｍである。図中Ｂ−１は、（B）成形品表面をスチールウール（＃０）で擦った後の成形品表面の反射光量像であり、図中Ｂ−２は、スチールウール（＃０）で擦った方向に対して垂直方向の表面形状プロフィールの結果である。この結果より、傷の深さを観察した。 The surface of the molded body of Example 8, Example 9, Comparative Example 5, Comparative Example 6, and Comparative Example 7 was observed using a Keyence laser microscope “VK 9510”. The observation results are shown in FIGS. In the figure, A is a reflected light amount image of the molded body, and the measurement conditions are an objective lens magnification of 5 times and a measurement pitch of 5 μm. B-1 in the figure is an image of the amount of reflected light on the surface of the molded article after (B) the surface of the molded article is rubbed with steel wool (# 0), and B-2 in the figure is rubbed with steel wool (# 0). FIG. 6 is a result of a surface shape profile perpendicular to the direction. From this result, the depth of the wound was observed.
図１（実施例８）、図２（実施例９）の結果より、本発明の成形体は、スチールウール（＃０）で擦った傷は、５０μｍ以下の小さなものであった。これに対して、図３（比較例５）に示すように、鉛筆硬度が４Ｈのアクリル板は、スチールウール（＃０）で擦ると表面に多くの傷が付き、傷の深さも５０μｍ以上の傷が多く観察された。図４（比較例６）、図５（比較例７）の結果でも、成形品表面に深い傷が多数観察された。 From the results shown in FIG. 1 (Example 8) and FIG. 2 (Example 9), in the molded article of the present invention, scratches rubbed with steel wool (# 0) were as small as 50 μm or less. In contrast, as shown in FIG. 3 (Comparative Example 5), the acrylic plate having a pencil hardness of 4H has many scratches on the surface when rubbed with steel wool (# 0), and the depth of the scratch is 50 μm or more. Many scratches were observed. Even in the results of FIG. 4 (Comparative Example 6) and FIG. 5 (Comparative Example 7), many deep scratches were observed on the surface of the molded product.
本発明の表面が研磨されたバーコール硬度３０以上である表面特性を有する事を特徴とする成形品は、良外観であり、機械的強度、剛性、表面硬度、寸法安定性、耐加水分解性、耐薬品性に優れる。特に耐傷付き特性に優れ、更に細かな傷がついても容易に研磨によって補修が可能となる。本発明による洗面カウンター、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、またリサイクルして使用することが可能である。 The molded product characterized in that the surface of the present invention has a surface property of polished Barcol hardness of 30 or more has a good appearance, mechanical strength, rigidity, surface hardness, dimensional stability, hydrolysis resistance, Excellent chemical resistance. In particular, it has excellent scratch resistance and can be easily repaired by polishing even if there are finer scratches. Products such as wash counter, kitchen counter, bathtub, wash bowl, hand wash bowl, toilet counter, cabinet top, etc. according to the present invention have excellent performance, are used in bathrooms, washrooms, toilets, kitchens, made of ceramics, heat It is possible to replace the curable resin product, and it can be recycled and used.
Ａ 成形体表面の反射光量像
Ｂ−１ スチールウール（＃０）研磨後の反射光量像
Ｂ−２ スチールウールで擦った方向と垂直な方向の成形品表面形状プロフィール結果
A Reflected light quantity image on the surface of the molded body B-1 Reflected light quantity image after steel wool (# 0) polishing B-2 Molded product surface shape profile result in the direction perpendicular to the direction rubbed with steel wool
Claims (15)
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| JP2006085252A JP2007262128A (en) | 2006-03-27 | 2006-03-27 | Reinforced resin molding having excellent scratch resistance and high appearance |
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| JP2006085252A JP2007262128A (en) | 2006-03-27 | 2006-03-27 | Reinforced resin molding having excellent scratch resistance and high appearance |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5742221B2 (en) * | 2009-08-20 | 2015-07-01 | 三菱レイヨン株式会社 | Method for producing thermoplastic resin composition, molded body and light-emitting body |
| JP2020075458A (en) * | 2018-11-09 | 2020-05-21 | 旭化成株式会社 | Molded article |
-
2006
- 2006-03-27 JP JP2006085252A patent/JP2007262128A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5742221B2 (en) * | 2009-08-20 | 2015-07-01 | 三菱レイヨン株式会社 | Method for producing thermoplastic resin composition, molded body and light-emitting body |
| JP2020075458A (en) * | 2018-11-09 | 2020-05-21 | 旭化成株式会社 | Molded article |
| JP7100565B2 (en) | 2018-11-09 | 2022-07-13 | 旭化成株式会社 | Mold |
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