JPH0987544A - Inorganic filler coated with thermoplastic resin and thermosetting resin molding material containing this filler - Google Patents

Inorganic filler coated with thermoplastic resin and thermosetting resin molding material containing this filler

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Publication number
JPH0987544A
JPH0987544A JP24331195A JP24331195A JPH0987544A JP H0987544 A JPH0987544 A JP H0987544A JP 24331195 A JP24331195 A JP 24331195A JP 24331195 A JP24331195 A JP 24331195A JP H0987544 A JPH0987544 A JP H0987544A
Authority
JP
Japan
Prior art keywords
thermoplastic resin
inorganic filler
resin
filler
molding material
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.)
Withdrawn
Application number
JP24331195A
Other languages
Japanese (ja)
Inventor
Takeshi Kuri
武 久利
Tatsuya Osako
達也 大迫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kobe Steel Ltd
Original Assignee
Kobe Steel Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kobe Steel Ltd filed Critical Kobe Steel Ltd
Priority to JP24331195A priority Critical patent/JPH0987544A/en
Publication of JPH0987544A publication Critical patent/JPH0987544A/en
Withdrawn legal-status Critical Current

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  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting resin molding material improved in molding flow without using any styrene monomer by adding a filler prepared by coating a particulate inorganic filler with a (meth)acrylic, olefinic or the like resin to a thermosetting resin molding material. SOLUTION: A filler added to a molding material based on a thermosetting resin (A) and prepared by coating a particulate inorganic filler (B) with a thermoplastic resin (C) is provided. Component B used is a known material. Component C is used as a shrinkage decreasing agent for component A and is exemplified by a (co)polymer of a (meth)acrylic acid (ester), an α-olefin resin, a styrene resin, a vinyl acetate resin or a saturated polyester resin not detrimental to the physical properties of the molding. Component B is dispersed in a solution of component C, the solvent is removed from the solution by distillation, and the residue is dried and ground to obtain a filler. A molding material, such as an unsaturated polyester resin, containing this filler can give a molding of a good appearance without causing the wear of the molding machine and is safe and applicable to tableware because of its low styrene monomer content.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、熱硬化性樹脂成形
材料に配合される粒状の無機充填材、および熱硬化性樹
脂成形材料に関し、詳細には、熱可塑性樹脂によって被
覆された粒状無機充填材、および該充填材を含有する熱
硬化性樹脂成形材料に関するものである。TECHNICAL FIELD The present invention relates to a granular inorganic filler to be blended with a thermosetting resin molding material, and a thermosetting resin molding material, and more particularly to a granular inorganic filler coated with a thermoplastic resin. And a thermosetting resin molding material containing the filler.

【０００２】[0002]

【従来の技術】現在様々なプラスチック製品が上市され
ている。中でも、不飽和ポリエステル樹脂等の熱硬化性
樹脂を主成分とする成形材料から得られるプラスチック
製品は、繊維強化型（ＦＲＰ）、非強化型にかかわら
ず、船舶・自動車分野、建築資材分野等や、工業機材、
住宅機材、タンク、雑貨等にまで広く利用されている。
これらの熱硬化性成形材料には、補強用繊維等の充填材
以外に、粒状の無機充填剤が配合されることが多い。2. Description of the Related Art Various plastic products are currently on the market. Among them, plastic products obtained from molding materials containing thermosetting resins such as unsaturated polyester resins as main components, regardless of fiber reinforced type (FRP) or unreinforced type, are used in the fields of ships and automobiles, construction materials, etc. , Industrial equipment,
Widely used for housing equipment, tanks, miscellaneous goods, etc.
In addition to fillers such as reinforcing fibers, a granular inorganic filler is often blended with these thermosetting molding materials.

【０００３】この粒状無機充填材としては、炭酸カルシ
ウム、硫酸カルシウム、水酸化アルミニウム、シリカ、
クレー、タルク等種々のものが知られており、増量作用
によるコストダウン、あるいは補強作用の他に、寸法安
定性および熱変形温度の向上を図るため、また表面硬度
を高めて成形品の耐傷つき性を改善する等の目的で配合
されている。さらに充填材の種類によっては、電気絶縁
性、導電性、難燃性、遮音性、制振性、易焼却性等の様
々な効果が期待されて配合されている。As this granular inorganic filler, calcium carbonate, calcium sulfate, aluminum hydroxide, silica,
Various types of clay, talc, etc. are known. In addition to cost reduction by increasing action or reinforcing action, in order to improve dimensional stability and heat distortion temperature, surface hardness is increased and scratch resistance of molded products is improved. It is added for the purpose of improving the sex. Further, depending on the kind of the filler, various fillers are expected to have various effects such as electric insulation, conductivity, flame retardancy, sound insulation, vibration damping, and incineration.

【０００４】しかし、充填材の配合によるデメリットも
ある。例えば、充填材の硬度が高い場合、成形材料製造
工程で用いられる混合機、混練機の内壁や撹拌羽根、あ
るいは成形機のシリンダーや金型等のステンレス鋼製等
の金属部材を損耗させるという問題である。これらの製
造ラインが損耗すると、成形材料中に金属粉が混入し
て、成形品が変色したり表面外観不良の原因となる。ま
た損耗を防ぐための窒化処理あるいはＣｒメッキ処理等
を施した耐摩耗性の製造ラインも利用されているが、耐
摩耗性は永久的に続く特性ではないので、設備コストが
高過ぎ、改善が要求されている。However, there is a disadvantage due to the blending of the filler. For example, when the hardness of the filler is high, the problem of causing wear of the mixer, the inner wall of the kneading machine, the stirring blades used in the molding material manufacturing process, or the metal member made of stainless steel such as the cylinder and the mold of the molding machine. Is. When these manufacturing lines are worn out, metal powder is mixed in the molding material, which causes discoloration of the molded product and poor surface appearance. In addition, a wear resistant production line that has been subjected to nitriding treatment or Cr plating treatment to prevent wear is also used, but since wear resistance is not a permanent property, equipment costs are too high and improvement is not possible. Is required.

【０００５】また、多量の充填材を熱硬化性樹脂成形材
料に配合すると、成形材料の粘度が急激にあるいは経時
的に上昇するという不都合がある。これは充填材の表面
や内部に成形材料中の低粘度成分が吸着されることによ
るが、成形材料の粘度が変化すると、金型内への広がり
が悪くなると共に適正な成形条件が変動して、良好な外
観や物性を有する成形品が得られない。Further, when a large amount of the filler is mixed with the thermosetting resin molding material, there is a disadvantage that the viscosity of the molding material increases rapidly or with time. This is because the low-viscosity component in the molding material is adsorbed on the surface and inside of the filler.However, if the viscosity of the molding material changes, the expansion into the mold deteriorates and appropriate molding conditions change. However, a molded product having a good appearance and physical properties cannot be obtained.

【０００６】さらに、耐酸性や耐水性が劣っている充填
材（例えば炭酸カルシウムや硫酸カルシウム等）を用い
ると、成形品を食器具として使用しているうちに、ケチ
ャップやマスタード等の着色食料品が成形品表面近傍の
充填材に吸着されることによって、食器にシミや変色が
起こるという問題も指摘されていた。Furthermore, when a filler having poor acid resistance and water resistance (eg calcium carbonate, calcium sulfate, etc.) is used, colored food products such as ketchup and mustard while the molded product is used as an eating tool. It has also been pointed out that stains and discoloration of tableware may occur due to the adsorption of the to the filler near the surface of the molded product.

【０００７】一方、ＢＭＣ等の熱硬化性樹脂成形材料の
マトリックス樹脂として汎用されている不飽和ポリエス
テル樹脂は、不飽和ポリエステルと、スチレン等のビニ
ルモノマーを主たる成分として含む液状樹脂である。し
かし近年、不飽和ポリエステル樹脂含有成形材料（以下
ＰＵ系成形材料という）の貯蔵・輸送過程や、成形工程
でのスチレンモノマーの規制が厳しくなり、スチレンモ
ノマーの揮発を極力防止することが要求されている。ま
た成形品中の残存スチレンモノマーも問題となってお
り、特に成形品を食器として用いるには、有毒かつ悪臭
のする残存スチレンモノマーを成形品から除去するため
にポストベーキング（後加熱）が必要であったが、コス
ト増大や成形品が変色してしまうという不都合があっ
た。このような観点から、ＰＵ系成形材料中のスチレン
モノマー量を低減させる試みがなされており、例えば、
スチレンに変わる高沸点モノマーの使用、不飽和ポリエ
ステルの低分子量化（低粘度化）等が提案されている。On the other hand, the unsaturated polyester resin, which is widely used as a matrix resin for thermosetting resin molding materials such as BMC, is a liquid resin containing unsaturated polyester and vinyl monomer such as styrene as main components. However, in recent years, regulations on styrene monomer in the storage / transportation process of unsaturated polyester resin-containing molding materials (hereinafter referred to as PU-based molding materials) and molding processes have become stricter, and it has been required to prevent volatilization of styrene monomers as much as possible. There is. In addition, residual styrene monomer in the molded product is also a problem, and especially when using the molded product as tableware, post-baking (post-heating) is required to remove the toxic and malodorous residual styrene monomer from the molded product. However, there were inconveniences such as increased cost and discoloration of the molded product. From such a viewpoint, attempts have been made to reduce the amount of styrene monomer in the PU-based molding material.
It has been proposed to use a high-boiling point monomer instead of styrene and to lower the molecular weight (lower the viscosity) of the unsaturated polyester.

【０００８】しかしこれらの提案では、低収縮化剤に用
いられるスチレンモノマーについて考慮されていない。
すなわちＰＵ系成形材料には、成形収縮率を下げて寸法
安定性を確保するため、ポリエチレン、ポリスチレン、
ポリメタクリル酸メチル等の熱可塑性樹脂からなる低収
縮化剤が添加されているが、これらはいずれもスチレン
モノマー溶液状態で配合されている。これらの低収縮化
剤の配合のためのスチレンモノマーは、熱可塑性樹脂の
粘度を下げ、不飽和ポリエステルと均一に混合するため
に用いられているため、ハンドリング性の点からも、そ
の量を減らすことはできなかった。However, these proposals do not consider the styrene monomer used as the low-contracting agent.
In other words, PU-based molding materials include polyethylene, polystyrene, in order to reduce molding shrinkage and ensure dimensional stability.
Although a shrinkage reducing agent made of a thermoplastic resin such as polymethylmethacrylate is added, these are all compounded in a styrene monomer solution state. The styrene monomer for blending these shrinkage reducing agents is used to reduce the viscosity of the thermoplastic resin and mix it uniformly with the unsaturated polyester, so the amount thereof is also reduced from the viewpoint of handling property. I couldn't do that.

【０００９】[0009]

【発明が解決しようとする課題】そこで本発明では、熱
硬化性樹脂成形材料における前記充填材の問題とスチレ
ンモノマーの低減化を同時に解決することを試みた。す
なわち、成形材料の粘度を変化させることなく、製造ラ
インの摩耗を起こさずに、適正な成形条件で成形を行う
ことができる充填材を提供し、また良好な低収縮性や耐
汚染性、表面硬度等の物性を保持したまま、低いスチレ
ンモノマー揮発量を示す成形品を製造することのできる
熱硬化性樹脂成形材料を提供することを課題とするもの
である。Therefore, in the present invention, an attempt was made to simultaneously solve the problem of the filler and the reduction of styrene monomer in the thermosetting resin molding material. That is, it provides a filler that can be molded under appropriate molding conditions without changing the viscosity of the molding material and without causing wear on the production line, and also has good low shrinkage, stain resistance, and surface resistance. An object of the present invention is to provide a thermosetting resin molding material capable of producing a molded product exhibiting a low volatilization amount of styrene monomer while maintaining physical properties such as hardness.

【００１０】[0010]

【課題を解決するための手段】上記課題を解決し得た本
発明の充填材は、熱硬化性樹脂を主成分とする成形材料
に配合される充填材であって、粒状無機充填材が熱可塑
性樹脂によって被覆されているところに要旨を有する。
熱可塑性樹脂被覆無機充填材に対する熱可塑性樹脂の割
合が１〜２０重量％であること、熱可塑性樹脂被覆無機
充填材の粒径が５００μｍ以下であることは、成形材料
の粘度を適正に保ち、充填材の均一な分散を可能にする
点で好ましい実施態様である。Means for Solving the Problems The filler of the present invention which has solved the above-mentioned problems is a filler to be blended with a molding material containing a thermosetting resin as a main component, wherein the granular inorganic filler is It has the gist of being covered with a plastic resin.
The ratio of the thermoplastic resin to the thermoplastic resin-coated inorganic filler is 1 to 20% by weight, and the particle size of the thermoplastic resin-coated inorganic filler is 500 μm or less means that the viscosity of the molding material is appropriately maintained, This is a preferred embodiment in that it enables a uniform dispersion of the filler.

【００１１】熱硬化性樹脂マトリックスの低収縮化を図
り、かつ得られる成形品の性能を高める点で、粒状無機
充填材を被覆する熱可塑性樹脂が、（メタ）アクリル系
樹脂、オレフィン系樹脂、スチレン系樹脂、酢酸ビニル
系樹脂、飽和ポリエステル系樹脂よりなる群から選択さ
れる１種以上の樹脂であることが推奨される。In order to reduce the shrinkage of the thermosetting resin matrix and enhance the performance of the molded article obtained, the thermoplastic resin coating the granular inorganic filler is (meth) acrylic resin, olefin resin, It is recommended to be one or more resins selected from the group consisting of styrene resins, vinyl acetate resins and saturated polyester resins.

【００１２】上記充填材は、粒状無機充填材を熱可塑性
樹脂溶液中へ分散させた後、溶媒を留去し、乾燥後、粉
砕することによって得られるものであることが好まし
い。本発明には、上記熱可塑性樹脂被覆無機充填材を含
有する熱硬化性樹脂成形材料、特に食器用成形品として
使用される該熱硬化性樹脂成形材料も含まれる。The above-mentioned filler is preferably obtained by dispersing the granular inorganic filler in the thermoplastic resin solution, distilling off the solvent, drying and pulverizing. The present invention also includes a thermosetting resin molding material containing the above thermoplastic resin-coated inorganic filler, particularly the thermosetting resin molding material used as a molded article for tableware.

【００１３】[0013]

【発明の実施の形態】本発明で用いられる粒状無機充填
材は、公知の粒状の無機充填材（以下単に無機充填材と
いう）であり、具体例としては、炭酸カルシウム、炭酸
バリウム、硫酸カルシウム、硫酸バリウム、水酸化アル
ミニウム、水酸化マグネシウム、シリカ、酸化チタン、
酸化亜鉛、カオリン、クレー、タルク、マイカ、ウオラ
ストナイト、ガラス粉末等が挙げられ、これらのうちの
１種、または２種以上を混合して使用することができ
る。熱可塑性樹脂被覆前の無機充填材の好ましい大きさ
は、０．０５〜５００μｍ未満である。０．０５μｍよ
り微細であると、熱可塑性樹脂の被覆工程で凝集し易い
ため好ましくない。また５００μｍ以上では、樹脂被覆
後の充填材が過大となって成形品の表面性状を劣化させ
ることがあるため好ましくない。BEST MODE FOR CARRYING OUT THE INVENTION The granular inorganic filler used in the present invention is a known granular inorganic filler (hereinafter simply referred to as inorganic filler), and specific examples thereof include calcium carbonate, barium carbonate, calcium sulfate, Barium sulfate, aluminum hydroxide, magnesium hydroxide, silica, titanium oxide,
Examples thereof include zinc oxide, kaolin, clay, talc, mica, wollastonite, glass powder, and the like, and one kind or a mixture of two or more kinds thereof can be used. The preferred size of the inorganic filler before coating with the thermoplastic resin is 0.05 to less than 500 μm. If it is finer than 0.05 μm, it is easy to aggregate in the step of coating the thermoplastic resin, which is not preferable. On the other hand, if it is 500 μm or more, the filler after resin coating becomes excessively large, which may deteriorate the surface properties of the molded product, which is not preferable.

【００１４】被覆される熱可塑性樹脂は、特に限定され
ないが、熱硬化性樹脂成形材料の低収縮化剤として用い
られ、成形品の物性低下を引き起こさないものとして知
られている熱可塑性樹脂が好ましい。具体的には、（メ
タ）アクリル酸、（メタ）アクリル酸のメチル、エチ
ル、ブチル、プロピル、ヘキシル、オクチル、シクロヘ
キシル、ヒドロキシエチル等のエステル類の（共）重合
体である（メタ）アクリル系樹脂；エチレン、プロピレ
ン、ブテン等のα−オレフィン類の（共）重合体である
オレフィン系樹脂；スチレン、クロロスチレン、ビニル
トルエン等の（共）重合体であるスチレン系樹脂；酢酸
ビニルの（共）重合体である酢酸ビニル系樹脂；ポリア
ミド、ポリエチレンテレフタレート、共重合ポリエステ
ル等の飽和ポリエステル系樹脂等の熱可塑性樹脂が挙げ
られる。これらは、１種または２種以上混合して使用で
きる。また、ある熱可塑性樹脂を被覆した無機充填材
と、別の熱可塑性樹脂を被覆した無機充填材を作ってか
ら、熱硬化性樹脂成形材料において複合使用することも
できる。The thermoplastic resin to be coated is not particularly limited, but a thermoplastic resin which is used as a shrinkage-reducing agent for thermosetting resin molding materials and is known not to cause deterioration of physical properties of molded articles is preferable. . Specifically, (meth) acrylic acid, which is a (co) polymer of esters of (meth) acrylic acid, methyl (meth) acrylic acid, such as methyl, ethyl, butyl, propyl, hexyl, octyl, cyclohexyl, and hydroxyethyl. Resin: olefin resin which is a (co) polymer of α-olefins such as ethylene, propylene and butene; styrene resin which is a (co) polymer of styrene, chlorostyrene, vinyltoluene, etc. ) Polymeric vinyl acetate resins; thermoplastic resins such as saturated polyester resins such as polyamide, polyethylene terephthalate and copolyester. These can be used alone or in combination of two or more. Further, an inorganic filler coated with a certain thermoplastic resin and an inorganic filler coated with another thermoplastic resin can be prepared and then used in combination in a thermosetting resin molding material.

【００１５】上記各樹脂は、それぞれの樹脂の構成モノ
マーとして例示した上記モノマーの単独重合体（例えば
ポリメタクリル酸メチル、ポリエチレン等）もしくは２
種以上のモノマーの共重合体（例えばアクリル酸−メタ
クリル酸エチル共重合体、ポリエチレン−ブチレンテレ
フタレート等）であってもよく、さらには他の樹脂の構
成モノマーとの共重合体（例えば、スチレン−メタクリ
ル酸メチル共重合体、エチレン−酢酸ビニル共重合体
等）であっても良い。さらに、例示したモノマー以外の
モノマーを若干量共重合した共重合体も本発明の熱可塑
性樹脂に含まれる。Each of the above resins is a homopolymer (for example, polymethylmethacrylate, polyethylene, etc.) of the above monomers exemplified as the constituent monomer of each resin, or 2
It may be a copolymer of one or more kinds of monomers (for example, acrylic acid-ethyl methacrylate copolymer, polyethylene-butylene terephthalate, etc.), and further, a copolymer with other resin constituting monomers (for example, styrene- Methyl methacrylate copolymer, ethylene-vinyl acetate copolymer, etc.) may be used. Further, a copolymer obtained by copolymerizing a small amount of a monomer other than the exemplified monomers is also included in the thermoplastic resin of the present invention.

【００１６】これらの熱可塑性樹脂のなかで、Ｔｇがあ
まりにも低い樹脂は、常温で粘着性を有し、無機充填剤
に被覆した後の乾燥・粉砕工程の作業性が悪化するため
好ましくない。また、粉砕後の保管時にブロッキングを
起こすという問題も生じる。さらにゴム系の樹脂は、耐
薬品性に劣るという欠点と共に、成形時の加熱によって
黄変し、白色度の高い成形品に使用できないという不具
合も有するため、本発明には好ましくない。これらの観
点から、比較的Ｔｇの高い熱可塑性樹脂の利用が推奨さ
れ、例えばポリメタクリル酸メチル等が好ましく用いら
れる。特に、成形品を食器具として用いる場合は、耐食
品汚染性に優れたポリメタクリル酸メチル等のポリメタ
クリレートが好ましい。Of these thermoplastic resins, a resin having a Tg that is too low is not preferable because it has tackiness at room temperature and deteriorates the workability of the drying and crushing process after coating with the inorganic filler. In addition, there is a problem that blocking occurs during storage after crushing. Further, the rubber-based resin is not preferable in the present invention because it has a drawback that it is inferior in chemical resistance and that it cannot be used for a molded article having high whiteness because it yellows due to heating during molding. From these viewpoints, the use of a thermoplastic resin having a relatively high Tg is recommended, and for example, polymethylmethacrylate or the like is preferably used. In particular, when the molded product is used as an eating utensil, polymethacrylate such as polymethylmethacrylate excellent in food stain resistance is preferable.

【００１７】本発明では、上記熱可塑性樹脂で粒状の無
機充填材を被覆しているので、硬度の大きい無機充填材
を使用しても、製造ラインの摩耗を起こすことはない。
また充填材が熱硬化性樹脂成形材料中の低粘度成分を吸
着することによる該成形材料の粘度上昇も起こり得ない
ので、常に適正な成形条件で成形を行うことができる。
また、成形後にケチャップやマスタード等の着色食品物
で汚染されることもない。さらに、無機充填材を被覆し
ている熱可塑性樹脂は、熱硬化性樹脂含有成形材料が熱
硬化する際に、低収縮化剤として作用するため、これら
の熱可塑性樹脂をスチレンモノマー溶液で成形材料中に
添加する必要がなく、スチレンモノマーの量を低減する
ことができる。In the present invention, since the granular inorganic filler is coated with the above-mentioned thermoplastic resin, even if the inorganic filler having a high hardness is used, the production line is not worn.
Further, since the filler absorbs the low-viscosity component in the thermosetting resin molding material, the viscosity of the molding material cannot be increased, and therefore molding can always be performed under appropriate molding conditions.
Further, it is not contaminated with colored foodstuffs such as ketchup and mustard after molding. Furthermore, since the thermoplastic resin coating the inorganic filler acts as a shrinkage reducing agent when the thermosetting resin-containing molding material is thermoset, these thermoplastic resins are molded with a styrene monomer solution. The amount of styrene monomer can be reduced without having to add it inside.

【００１８】無機充填材を熱可塑性樹脂で被覆する方法
は特に限定されないが、例えば、使用する熱可塑性樹脂
を溶解し得る溶媒を選択し、熱可塑性樹脂溶液を作製し
て無機充填材を分散させてスラリー状の懸濁液とし、溶
媒の留去後、得られる塊状物を乾燥して、粉砕する方法
が推奨される。各熱可塑性樹脂に適した良溶媒は、ＳＰ
値等を参考に選択することができる。粉砕後は、篩によ
って５００μｍ以下の熱可塑性樹脂被覆無機充填材を選
択すれば良い。該充填材の粒径が５００μｍを超える
と、熱硬化性樹脂成形材料に配合しても、均一に分散せ
ず、成形品の外観や強度特性等の低下を引き起こすため
好ましくない。The method of coating the inorganic filler with the thermoplastic resin is not particularly limited, but for example, a solvent capable of dissolving the thermoplastic resin to be used is selected, and a thermoplastic resin solution is prepared to disperse the inorganic filler. A method is recommended in which a slurry is formed into a slurry, the solvent is distilled off, and the obtained lump is dried and ground. A good solvent suitable for each thermoplastic resin is SP
It can be selected with reference to the value and the like. After crushing, a thermoplastic resin-coated inorganic filler having a size of 500 μm or less may be selected with a sieve. If the particle size of the filler exceeds 500 μm, it will not be dispersed even when blended with the thermosetting resin molding material, and the appearance and strength characteristics of the molded product will deteriorate, which is not preferable.

【００１９】無機充填材と熱可塑性樹脂の割合は、熱可
塑性樹脂被覆無機充填材に対して熱可塑性樹脂が１〜２
０重量％となる様に被覆することが好ましい。熱可塑性
樹脂の量が１重量％より少ないと、上述した熱可塑性樹
脂被覆効果が発現しない。逆に２０重量％を超えると、
樹脂を被覆する際に、熱可塑性樹脂溶液中の樹脂量を多
くしなければならないため懸濁液の粘度が上がる、溶液
中の溶媒量を増やさなければならないため溶剤留去コス
トがかかる、熱可塑性樹脂を多量配合することによって
成形品の耐熱性が悪化する、等の不都合が起こり好まし
くない。The ratio of the inorganic filler to the thermoplastic resin is such that the thermoplastic resin is 1 to 2 with respect to the thermoplastic resin-coated inorganic filler.
It is preferable that the coating is performed so as to be 0% by weight. When the amount of the thermoplastic resin is less than 1% by weight, the above-mentioned thermoplastic resin coating effect is not exhibited. On the contrary, if it exceeds 20% by weight,
When coating the resin, the amount of resin in the thermoplastic resin solution must be increased, which increases the viscosity of the suspension, and the amount of solvent in the solution must be increased, which incurs solvent evaporation costs. Addition of a large amount of the resin is not preferable because the heat resistance of the molded product is deteriorated.

【００２０】本発明の熱可塑性樹脂被覆無機充填材は、
そのままで充填材および低収縮化剤として利用でき、あ
らゆる公知の熱硬化性樹脂成形材料中に配合することが
できる。特に、スチレンモノマーの低減を可能にする、
という本発明の課題に適している成形材料としては、不
飽和ポリエステル樹脂を含有するものが挙げられる。The thermoplastic resin-coated inorganic filler of the present invention comprises:
It can be used as it is as a filler and a shrinkage-reducing agent, and can be compounded in any known thermosetting resin molding material. In particular, it enables the reduction of styrene monomer,
Examples of the molding material suitable for the subject of the present invention include those containing an unsaturated polyester resin.

【００２１】不飽和ポリエステル樹脂とは、エチレン性
不飽和多塩基酸と飽和多塩基酸からなる酸成分と多価ア
ルコール成分をエステル化反応させて得られる不飽和ポ
リエステル（不飽和を、希釈用ビニルモノマーに溶解さ
せた液状樹脂である。不飽和ポリエステルの主鎖中には
エチレン性二重結合があるため、重合開始剤の存在下で
希釈用ビニルモノマーとの間で三次元硬化反応を起こ
す。The unsaturated polyester resin is an unsaturated polyester (unsaturated vinyl for dilution is obtained by esterifying an acid component composed of an ethylenically unsaturated polybasic acid and a saturated polybasic acid, and a polyhydric alcohol component. This is a liquid resin dissolved in a monomer.Since the unsaturated polyester has an ethylenic double bond in its main chain, it undergoes a three-dimensional curing reaction with a diluting vinyl monomer in the presence of a polymerization initiator.

【００２２】不飽和ポリエステルの原料の多価アルコー
ル成分としては、エチレングリコール、プロピレングリ
コール、ジエチレングリコール、ジプロピレングリコー
ル、１，６−ヘキサンジオール、ネオペンチルグリコー
ル、水素化ビスフェノールＡ、２−メチル−１，３−プ
ロパンジオール、１，４−シクロヘキサンジメタノール
等が挙げられる。As the polyhydric alcohol component as the raw material of the unsaturated polyester, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, neopentyl glycol, hydrogenated bisphenol A, 2-methyl-1, Examples include 3-propanediol and 1,4-cyclohexanedimethanol.

【００２３】エチレン性不飽和多塩基酸としては、無水
マレイン酸、フマル酸、イタコン酸等の不飽和二塩基酸
を挙げることができ、飽和多塩基酸としては、無水フタ
ル酸、イソフタル酸、テレフタル酸、アジピン酸、テト
ラヒドロ無水フタル酸、エンドメチレンテトラヒドロ無
水フタル酸、無水メチルナジック酸等の飽和二塩基酸が
挙げられる。上記酸成分および多価アルコール成分を、
公知の反応条件でエステル化反応させることによって不
飽和ポリエステルを得ることができる。Examples of the ethylenically unsaturated polybasic acid include unsaturated dibasic acids such as maleic anhydride, fumaric acid and itaconic acid, and examples of the saturated polybasic acid include phthalic anhydride, isophthalic acid and terephthalic acid. Examples thereof include saturated dibasic acids such as acids, adipic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and methylnadic acid anhydride. The acid component and polyhydric alcohol component,
An unsaturated polyester can be obtained by carrying out an esterification reaction under known reaction conditions.

【００２４】不飽和ポリエステル樹脂とは、上記不飽和
ポリエステルを希釈用モノマーで適切な粘度に希釈した
もののことである。希釈用モノマーとしては、スチレ
ン、ビニルトルエン、ジビニルベンゼン、α−メチルス
チレン、ジアリルフタレート、トリアリルイソシアヌレ
ート、メタクリル酸メチル等の使用が推奨される。これ
らのモノマーは２種以上混合して使用してもよく、不飽
和ポリエステル１００重量部に対して２０〜２００重量
部の範囲で使用することが好ましい。The unsaturated polyester resin is a resin obtained by diluting the above unsaturated polyester with a diluting monomer to an appropriate viscosity. As the diluting monomer, use of styrene, vinyltoluene, divinylbenzene, α-methylstyrene, diallyl phthalate, triallyl isocyanurate, methyl methacrylate or the like is recommended. Two or more kinds of these monomers may be mixed and used, and it is preferably used in the range of 20 to 200 parts by weight with respect to 100 parts by weight of the unsaturated polyester.

【００２５】不飽和ポリエステル樹脂以外の熱硬化性樹
脂としては、エポキシ樹脂を（メタ）アクリル酸で変成
したエポキシ（メタ）アクリレートと上記希釈用モノマ
ーからなるビニルエステル樹脂、あるいはウレタン（メ
タ）アクリレートと上記希釈用モノマーからなる熱硬化
性樹脂（以下、単に熱硬化性樹脂というときは希釈用モ
ノマーを含めた樹脂を指す）等がある。Thermosetting resins other than unsaturated polyester resins include vinyl ester resins composed of epoxy (meth) acrylate modified with (meth) acrylic acid and the above-mentioned diluting monomer, or urethane (meth) acrylate. There is a thermosetting resin composed of the above-mentioned diluting monomer (hereinafter, simply referred to as a thermosetting resin means a resin including the diluting monomer).

【００２６】上記熱硬化性樹脂の硬化反応のための重合
開始剤としては、有機過酸化物系が好ましく、公知のベ
ンゾイルパーオキサイド、ｐ−クロロベンゾイルパーオ
キサイド、ラウロイルパーオキサイド、アセチルパーオ
キサイド、メチルエチルケトンパーオキサイド、ｔ−ブ
チルハイドロパーオキサイド、クメンハイドロパーオキ
サイド、ｔ−ブチルパーベンゾエート、ｔ−ブチルパー
オクトエート、ｔ−ブチルパーアセテート、ジクミルパ
ーオキサイド、ｔ−ブチルパーオキシイソプロピルカー
ボネート等を用いることができる。これらは、熱硬化性
樹脂に対して０．１〜５重量％使用される。必要に応じ
て、コバルト系、バナジウム系、マンガン系等の公知の
硬化促進剤を熱硬化性樹脂に対して０．０１〜５重量％
使用しても構わない。As the polymerization initiator for the curing reaction of the thermosetting resin, organic peroxides are preferable, and known benzoyl peroxide, p-chlorobenzoyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone are known. Use of peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl perbenzoate, t-butyl peroctoate, t-butyl peracetate, dicumyl peroxide, t-butyl peroxyisopropyl carbonate, etc. You can These are used in an amount of 0.1 to 5% by weight based on the thermosetting resin. If necessary, a known curing accelerator such as a cobalt-based, vanadium-based, or manganese-based compound is used in an amount of 0.01 to 5% by weight based on the thermosetting resin.
You can use it.

【００２７】本発明の熱硬化性樹脂成形材料は、少なく
とも、上記熱硬化性樹脂、重合開始剤と、熱可塑性樹脂
被覆無機充填材が含まれるものである。熱硬化性樹脂に
対する熱可塑性樹脂被覆無機充填材の使用割合は、２０
〜５００重量％が好ましい。より好ましくは５０〜３０
０重量％である。The thermosetting resin molding material of the present invention contains at least the thermosetting resin, the polymerization initiator, and the thermoplastic resin-coated inorganic filler. The use ratio of the thermoplastic resin-coated inorganic filler to the thermosetting resin is 20.
~ 500% by weight is preferred. More preferably 50-30
0% by weight.

【００２８】本発明の熱硬化性樹脂成形材料には強化用
繊維が含まれていてもよい。使用できる強化用繊維とし
ては、安価なガラス繊維の他、炭素繊維、アラミド繊
維、金属繊維、セラミック繊維等の公知の強化用繊維を
用いることもできる。繊維形態としては、不織布状ある
いは織編物状の長繊維マットや長・短のチョップドスト
ランド、ロービング等、所望の成形品に応じた形態を選
択すれば良い。なお強化用繊維は、熱硬化性樹脂に対
し、５〜３００重量％の範囲で使用することが推奨され
る。The thermosetting resin molding material of the present invention may contain reinforcing fibers. As the reinforcing fiber that can be used, not only inexpensive glass fiber but also known reinforcing fiber such as carbon fiber, aramid fiber, metal fiber, and ceramic fiber can be used. As the fiber form, a non-woven fabric or woven or knitted long fiber mat, long / short chopped strands, roving, or the like may be selected according to the desired molded product. The reinforcing fiber is recommended to be used in the range of 5 to 300% by weight based on the thermosetting resin.

【００２９】本発明の成形材料には、離型剤や他の添加
物を加えてもよい。離型剤としては、ステアリン酸、イ
ソステアリン酸、オレイン酸等の公知の高級飽和または
不飽和脂肪酸、あるいはこれらのカルシウム塩、亜鉛塩
等が挙げられ、熱硬化性樹脂の０．１〜１０重量％程度
使用される。また他の添加物の例としては、酸化マグネ
シウム、水酸化マグネシウム等の増粘剤や、酸化防止
剤、難燃剤、着色剤、顔料、滑剤、導電剤、消泡剤、濡
れ調整剤等が挙げられる。A release agent and other additives may be added to the molding material of the present invention. Examples of the release agent include known higher saturated or unsaturated fatty acids such as stearic acid, isostearic acid, and oleic acid, or calcium salts, zinc salts thereof, etc., and 0.1 to 10% by weight of the thermosetting resin. Used to a degree. Examples of other additives include thickeners such as magnesium oxide and magnesium hydroxide, antioxidants, flame retardants, colorants, pigments, lubricants, conductive agents, defoaming agents, and wetting control agents. To be

【００３０】成形材料の調製方法としては、熱可塑性樹
脂被覆無機充填材、熱硬化性樹脂、重合開始剤といった
必須成分と、上記付加成分を、ミキサー等の混合機、混
練機で撹拌混合すれば良い。その後、ＢＭＣでは、得ら
れた混練物を金型内に特定量仕込み、加熱加圧して硬化
させて成形すればよく、他の公知の成形方法を利用する
ことができる。As a method for preparing a molding material, essential components such as a thermoplastic resin-coated inorganic filler, a thermosetting resin and a polymerization initiator and the above-mentioned additional components are mixed by stirring with a mixer such as a mixer or a kneader. good. After that, in the BMC, a specific amount of the obtained kneaded product may be charged into a mold, and the mixture may be heated and pressed to be cured and molded, and other known molding methods can be used.

【００３１】[0031]

【実施例】以下実施例によって本発明をさらに詳述する
が、下記実施例は本発明を制限するものではなく、前・
後記の趣旨を逸脱しない範囲で変更実施することは全て
本発明の技術範囲に包含される。The present invention will be described in more detail with reference to the following examples, but the following examples do not limit the present invention.
Modifications and alterations that do not depart from the spirit described below are all included in the technical scope of the present invention.

【００３２】実施例１および比較例１ イソフタル酸２モル、無水マレイン酸８モルからなる酸
成分と、ネオペンチルグリコール１０モルからなる多価
アルコール成分を常法でエステル化して不飽和ポリエス
テルを得、スチレンが３５重量％になるようにこの不飽
和ポリエステルと混合し、不飽和ポリエステル樹脂１を
得た。Example 1 and Comparative Example 1 An unsaturated polyester is obtained by esterifying an acid component consisting of 2 mol of isophthalic acid and 8 mol of maleic anhydride and a polyhydric alcohol component consisting of 10 mol of neopentyl glycol by a conventional method. The unsaturated polyester resin 1 was obtained by mixing the styrene with the unsaturated polyester so that the styrene content was 35% by weight.

【００３３】ポリメタクリル酸メチルＢＲ７８（三菱レ
ーヨン社製）１９５ｇをアセトンに溶解させて１リット
ルの溶液を得た。シリカＡ−１０（Ilinois MineralsIn
c.製）３６００ｇをアセトン２リットルに分散させたス
ラリーを調製した。両者を混合し、室温で３時間撹拌を
続けた後、アセトンを減圧留去したところ、塊状物が得
られた。この塊状物をよく乾燥させた後、粉砕した。３
００μｍの篩を用いて分級し、ポリメタクリル酸メチル
被覆無機充填材を得た。この充填材は、昇温速度２０℃
／分における熱重量測定（ＴＡ社のＴＡ９５１を使用）
結果から、５．０重量％の有機物（ポリメタクリル酸メ
チル）を有していることが確認された。195 g of polymethylmethacrylate BR78 (manufactured by Mitsubishi Rayon Co., Ltd.) was dissolved in acetone to obtain a 1 liter solution. Silica A-10 (Ilinois MineralsIn
c.) 3600 g was dispersed in 2 liter of acetone to prepare a slurry. Both were mixed, and after stirring at room temperature for 3 hours, acetone was distilled off under reduced pressure to obtain a lump. This lump was thoroughly dried and then crushed. 3
Classification was carried out using a 00 μm sieve to obtain a polymethylmethacrylate-coated inorganic filler. This filling material has a heating rate of 20 ° C.
Thermogravimetric measurement at 1 / min (using TA951 manufactured by TA)
From the results, it was confirmed to have 5.0% by weight of an organic substance (polymethylmethacrylate).

【００３４】次に、表１に示した配合の熱硬化性樹脂成
形材料を、Ｌｉｔｔｌｅｆｏｒｄ社製のミキサー（内壁
およびブレードはステンレス鋼製）で混練し、ＢＭＣを
製造した。得られたＢＭＣを、金型温度１５０℃、成形
圧力７０ｋｇ／ｃｍ2 、硬化時間１分で圧縮成形し、厚
み２ｍｍ、直径１５ｃｍのプレート状成形品を得た。こ
の成形品の評価結果を表２に示した。なお、成形品から
のスチレンモノマーの揮発量は、１７０℃で３０分成形
品を加熱したときの揮発ガス（ヘッドスペースアナリシ
ス）をガスクロマトグラフィーで分析した結果である。Next, the thermosetting resin molding material having the composition shown in Table 1 was kneaded with a mixer manufactured by Littleford (inner wall and blades are made of stainless steel) to produce BMC. The obtained BMC was compression-molded at a mold temperature of 150 ° C., a molding pressure of 70 kg / cm 2 , and a curing time of 1 minute to obtain a plate-shaped molded product having a thickness of 2 mm and a diameter of 15 cm. The evaluation results of this molded product are shown in Table 2. The volatilization amount of the styrene monomer from the molded product is the result of gas chromatography analysis of the volatile gas (headspace analysis) when the molded product was heated at 170 ° C. for 30 minutes.

【００３５】[0035]

【表１】 [Table 1]

【００３６】[0036]

【表２】 [Table 2]

【００３７】表２から明らかな様に、本発明の熱可塑性
樹脂被覆無機充填材を用いた実施例１では、ミキサーの
摩耗もなく、成形品からのスチレン揮発量も極めて低い
値であった。また低収縮化剤を使用していないにもかか
わらず、良好な表面外観と表面硬度を示していた。一方
比較例１では、シリカをそのまま用いているため、ミキ
サー内の損耗によって灰色の成形品しか得られなかっ
た。また低収縮化材をスチレン溶液で加えているため、
成形後に、多量のスチレンモノマーが残存していること
が確認された。As is clear from Table 2, in Example 1 in which the thermoplastic resin-coated inorganic filler of the present invention was used, the mixer was not worn and the amount of styrene volatilized from the molded product was extremely low. In addition, despite not using the low-shrinking agent, it showed good surface appearance and surface hardness. On the other hand, in Comparative Example 1, since silica was used as it was, only a gray molded product was obtained due to wear inside the mixer. Also, because the low shrinkage material is added with the styrene solution,
After molding, it was confirmed that a large amount of styrene monomer remained.

【００３８】実施例２および比較例２ 実施例１において、シリカＡ−１０に代えて硫酸カルシ
ウムＣＡ−５（UnitedStates Gypsumn Company 製）を
用いた以外は、同様にしてポリメタクリル酸メチル被覆
無機充填材を調製した。この充填材についても熱重量測
定を行い、ポリメタクリル酸メチルが５．０重量％であ
ることを確認した。あとは、実施例１と同様にして、表
３に示した配合の熱硬化性樹脂成形材料を調製し、成形
を行って、厚み２ｍｍ、直径１５ｃｍのプレート状成形
品を得た。成形品の評価を行った結果を表４に示した。
なお耐食品汚染性は、イエローマスタードを成形品の上
に置いたまま、５０℃で３時間放置し、水洗した後の成
形品表面の汚染（着色）状態を目視で評価した。Example 2 and Comparative Example 2 In the same manner as in Example 1, except that calcium sulfate CA-5 (manufactured by United States Gypsumn Company) was used in place of silica A-10, a polymethylmethacrylate-coated inorganic filler was similarly prepared. Was prepared. Thermogravimetric measurement was also performed on this filler, and it was confirmed that polymethyl methacrylate was 5.0% by weight. After that, in the same manner as in Example 1, thermosetting resin molding materials having the formulations shown in Table 3 were prepared and molded to obtain a plate-shaped molded product having a thickness of 2 mm and a diameter of 15 cm. The results of evaluation of the molded products are shown in Table 4.
The food stain resistance was evaluated by visually observing the state of staining (coloring) on the surface of the molded product after the yellow mustard was left on the molded product for 3 hours at 50 ° C. and washed with water.

【００３９】[0039]

【表３】 [Table 3]

【００４０】[0040]

【表４】 [Table 4]

【００４１】表４から明らかな様に、本発明の熱可塑性
樹脂被覆無機充填材を用いた実施例２では、耐食品汚染
性に優れ、表面硬度、スチレン臭、揮発スチレン量、酢
酸蒸発残留物の評価結果も、食器具として実用可能なも
のであった。一方比較例２では、耐食品汚染性に劣って
おり、スチレン臭、揮発スチレン量、酢酸蒸発残留物の
結果も、食器具として実用に耐えないものであった。As is clear from Table 4, in Example 2 in which the thermoplastic resin-coated inorganic filler of the present invention was used, excellent food stain resistance, surface hardness, styrene odor, volatile styrene content, and acetic acid evaporation residue were obtained. The evaluation result of was also practical as an eating tool. On the other hand, in Comparative Example 2, the food stain resistance was inferior, and the results of the styrene odor, the amount of volatile styrene and the acetic acid evaporation residue were also unusable for practical use as an eating tool.

【００４２】[0042]

【発明の効果】本発明では、熱可塑性樹脂を用いて粒状
の無機充填材を被覆しているので、硬度の大きい無機充
填材を使用しても、製造機器を損耗させたり、金属粉の
混入によって成形品の表面外観を損なうことがなくなっ
た。また、無機充填材を被覆している熱可塑性樹脂は、
熱硬化性樹脂含有成形材料が熱硬化する際に低収縮化剤
として作用するため、これらの熱可塑性樹脂をスチレン
モノマー溶液状態で成形材料に配合する必要がなく、結
果的に、成形品の性能を良好な状態で保持したままスチ
レンモノマーの量を低減することができた。さらに、本
発明の充填材の使用によって、成形品にケチャップやマ
スタード等の着色食品物が付着しても、しみが残らない
ため、成形品を食器具として利用することも可能であ
る。According to the present invention, since the granular inorganic filler is coated with the thermoplastic resin, even if the inorganic filler having a high hardness is used, the manufacturing equipment is worn or metal powder is mixed. As a result, the surface appearance of the molded product was not impaired. Further, the thermoplastic resin coating the inorganic filler,
Since the thermosetting resin-containing molding material acts as a shrinkage reducing agent when it is thermoset, it is not necessary to mix these thermoplastic resins in the styrene monomer solution state into the molding material, and as a result, the performance of the molded product is improved. It was possible to reduce the amount of styrene monomer while maintaining the above in a good state. Furthermore, by using the filler of the present invention, even if a colored food product such as ketchup or mustard adheres to the molded product, no stain remains, so that the molded product can be used as an eating tool.

【００４３】本発明の熱可塑性樹脂被覆無機充填材は、
熱硬化性樹脂成形材料に配合することにより、充填材と
しての作用と低収縮化材としての作用を同時に発現する
非常に有用な複合充填材である。この複合充填材が配合
された熱硬化性樹脂成形材料は、繊維強化型あるいは非
強化型プラスチック成形品を製造することができ、船
舶、自動車、車両、建築資材、住宅機材、工業機材、タ
ンク・容器、雑貨、食器具等幅広い分野に適用すること
ができる。The thermoplastic resin-coated inorganic filler of the present invention comprises:
It is a very useful composite filler which, when blended with a thermosetting resin molding material, simultaneously exhibits the action as a filler and the action as a low shrinkage material. Thermosetting resin molding materials containing this composite filler can be used to manufacture fiber-reinforced or non-reinforced plastic molded products such as ships, automobiles, vehicles, building materials, housing equipment, industrial equipment, tanks, It can be applied to a wide range of fields such as containers, sundries, and eating utensils.

Claims (7)

【特許請求の範囲】[Claims] 【請求項１】 熱硬化性樹脂を主成分とする成形材料に
配合される充填材であって、粒状無機充填材が熱可塑性
樹脂によって被覆されていることを特徴とする熱可塑性
樹脂被覆無機充填材。1. A thermoplastic resin-coated inorganic filler, which is a filler mixed with a molding material containing a thermosetting resin as a main component, wherein the granular inorganic filler is coated with a thermoplastic resin. Material. 【請求項２】 熱可塑性樹脂被覆無機充填材に対する熱
可塑性樹脂の割合が１〜２０重量％である請求項１に記
載の熱可塑性樹脂被覆無機充填材。2. The thermoplastic resin-coated inorganic filler according to claim 1, wherein the ratio of the thermoplastic resin to the thermoplastic resin-coated inorganic filler is 1 to 20% by weight. 【請求項３】 熱可塑性樹脂被覆無機充填材の粒径が５
００μｍ以下である請求項１または２に記載の熱可塑性
樹脂被覆無機充填材。3. The particle size of the thermoplastic resin-coated inorganic filler is 5
The thermoplastic resin-coated inorganic filler according to claim 1 or 2, which has a diameter of 00 μm or less. 【請求項４】 熱可塑性樹脂が、（メタ）アクリル系樹
脂、オレフィン系樹脂、スチレン系樹脂、酢酸ビニル系
樹脂、飽和ポリエステル樹脂よりなる群から選択される
１種以上の樹脂である請求項１〜３のいずれかに記載の
熱可塑性樹脂被覆無機充填材。4. The thermoplastic resin is one or more resins selected from the group consisting of (meth) acrylic resins, olefin resins, styrene resins, vinyl acetate resins and saturated polyester resins. 4. The thermoplastic resin-coated inorganic filler according to any one of 3 to 3. 【請求項５】 粒状無機充填材を熱可塑性樹脂溶液中へ
分散させた後、溶媒を留去し、乾燥後、粉砕することに
よって得られる請求項１〜４のいずれかに記載の熱可塑
性樹脂被覆無機充填材。5. The thermoplastic resin according to claim 1, which is obtained by dispersing the granular inorganic filler in a thermoplastic resin solution, distilling off the solvent, drying and pulverizing. Coated inorganic filler. 【請求項６】 請求項１〜５のいずれかに記載の熱可塑
性樹脂被覆無機充填材を含有することを特徴とする熱硬
化性樹脂成形材料。6. A thermosetting resin molding material comprising the thermoplastic resin-coated inorganic filler according to any one of claims 1 to 5. 【請求項７】 食器用成形品として使用されるものであ
る請求項６に記載の熱硬化性樹脂成形材料。7. The thermosetting resin molding material according to claim 6, which is used as a molded article for tableware.
JP24331195A 1995-09-21 1995-09-21 Inorganic filler coated with thermoplastic resin and thermosetting resin molding material containing this filler Withdrawn JPH0987544A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP24331195A JPH0987544A (en) 1995-09-21 1995-09-21 Inorganic filler coated with thermoplastic resin and thermosetting resin molding material containing this filler

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP24331195A JPH0987544A (en) 1995-09-21 1995-09-21 Inorganic filler coated with thermoplastic resin and thermosetting resin molding material containing this filler

Publications (1)

Publication Number Publication Date
JPH0987544A true JPH0987544A (en) 1997-03-31

Family

ID=17101952

Family Applications (1)

Application Number Title Priority Date Filing Date
JP24331195A Withdrawn JPH0987544A (en) 1995-09-21 1995-09-21 Inorganic filler coated with thermoplastic resin and thermosetting resin molding material containing this filler

Country Status (1)

Country Link
JP (1) JPH0987544A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004156038A (en) * 2002-11-06 2004-06-03 Merck Patent Gmbh Laser marking pigment
CN108084497A (en) * 2017-12-28 2018-05-29 成都新柯力化工科技有限公司 It is a kind of for thermoplasticity inorganic filler of plastics and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004156038A (en) * 2002-11-06 2004-06-03 Merck Patent Gmbh Laser marking pigment
CN108084497A (en) * 2017-12-28 2018-05-29 成都新柯力化工科技有限公司 It is a kind of for thermoplasticity inorganic filler of plastics and preparation method thereof

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