JP2002038023A - Synthetic resin material containing natural stone and its molding method - Google Patents
Synthetic resin material containing natural stone and its molding methodInfo
- Publication number
- JP2002038023A JP2002038023A JP2000221365A JP2000221365A JP2002038023A JP 2002038023 A JP2002038023 A JP 2002038023A JP 2000221365 A JP2000221365 A JP 2000221365A JP 2000221365 A JP2000221365 A JP 2000221365A JP 2002038023 A JP2002038023 A JP 2002038023A
- Authority
- JP
- Japan
- Prior art keywords
- synthetic resin
- natural stone
- mold
- resin material
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- Compositions Of Macromolecular Compounds (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、台所のシステムキ
ッチンや洗面（化粧）台などの天板（ワークトップ）、
浴室内の棚類や壁面材、浴槽、建物内部の一般的な壁材
などに広く適用できる合成樹脂材であって、とくに天然
石の粉末が混入された合成樹脂材と、その成形方法とに
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a worktop, such as a kitchen system kitchen or a washbasin (make-up) stand.
The present invention relates to a synthetic resin material that can be widely applied to shelves and wall materials in a bathroom, a bathtub, a general wall material inside a building, and more particularly to a synthetic resin material mixed with natural stone powder and a molding method thereof.
【０００２】[0002]
【従来の技術】例えば、前述の天板や浴槽の類は、いわ
ゆるエポキシ樹脂などを用いた注型成形や、ＦＲＰのハ
ンドレーアップ成形により製造している。問題は、各種
の天然石の特性を有効利用するために、選ばれた天然石
の粉末を合成樹脂材料に分散混入する場合である。天然
石の粉末を混入するのは、成形品の外表面の模様を石目
状に現出させる装飾目的であったり、選ばれた天然石が
持つマイナスイオンの発生性能や遠赤外線の放射性能な
どの機能を利用するためである。2. Description of the Related Art For example, the above-mentioned top plate and bathtub are manufactured by cast molding using a so-called epoxy resin or by hand lay-up molding of FRP. The problem is the case where the powder of the selected natural stone is dispersed and mixed into the synthetic resin material in order to effectively utilize the characteristics of various natural stones. The mixing of natural stone powder is used for decorative purposes to make the outer surface of the molded product look like a grain, and the selected natural stone has negative ion generation performance and far infrared radiation performance. It is for utilizing.
【０００３】[0003]
【発明が解決しようとする課題】ところが、例えばマイ
ナスイオンを発生させるのに有利なトルマリンは、汎用
のフィラー類とは異なり、著しく高価であり、樹脂成形
品の厚み方向にわたって均一状態でトルマリンの粉末を
混在させると製品価格が高騰する。これが製品化を困難
なものにしていた。However, for example, tourmaline which is advantageous for generating negative ions, unlike general-purpose fillers, is extremely expensive, and has a uniform state of tourmaline powder in the thickness direction of the resin molded product. If mixed, the product price will rise. This made commercialization difficult.
【０００４】本発明者は、天然石粉末入りの合成樹脂成
形品を得るに際し、合成樹脂溶液と天然石粉末との間に
比重差があることに着目し、この比重差を利用して吹き
付け塗装法で成形したらどうなるか、更に天然石の粉末
と合成樹脂材料との間の界面エネルギーに大きな差を付
与すればどうなるか、このテーマに基づいて試作検討し
たところ、天然石粉末の使用量を可及的に抑えて安価に
成形できるとともに、天然石の効能が有効に発揮される
ことを確認し、本発明を完成するに至った。The inventor of the present invention paid attention to the difference in specific gravity between the synthetic resin solution and the natural stone powder when obtaining a synthetic resin molded product containing natural stone powder. Based on this theme, we examined what would happen if it was molded, and what would happen if there was a large difference in the interfacial energy between the natural stone powder and the synthetic resin material. It was confirmed that the natural stone could be effectively used, and that the present invention was completed.
【０００５】すなわち本発明の目的は、製品の外表面と
なる表層部に天然石の粉末を浮き上がった状態で集中的
に偏在（析出）させることにより、天然石の使用量が少
なくて安価に仕上がる合成樹脂材と、その成形方法を提
供することにある。[0005] That is, an object of the present invention is to provide a low-cost synthetic resin which uses a small amount of natural stone by intensively dispersing (precipitating) the natural stone powder in a floating state on the surface layer serving as the outer surface of the product. An object of the present invention is to provide a material and a molding method thereof.
【０００６】[0006]
【課題を解決するための手段】請求項１に係る本発明の
天然石入り合成樹脂材は、図１に示すごとく表層部に天
然石の粉末が集中的に偏在していることを特徴とする。According to the first aspect of the present invention, there is provided a synthetic resin material containing natural stones, wherein natural stone powder is concentrated and unevenly distributed on a surface layer as shown in FIG.
【０００７】請求項２に係る本発明の天然石入り合成樹
脂材は、天然石の粉末が混入された合成樹脂溶液を金型
の表面に吹き付けることにより、表層部に天然石の粉末
が集中的に偏在していることを特徴とする。この場合の
合成樹脂材は、吹き付けを利用した一種の注型用では仕
上がっていることを意味する。In the synthetic resin material containing natural stone according to the second aspect of the present invention, the synthetic resin solution mixed with the natural stone powder is sprayed onto the surface of the mold, whereby the natural stone powder is concentrated and concentrated on the surface layer. It is characterized by having. In this case, the synthetic resin material is finished by a kind of casting using spraying.
【０００８】請求項３に係る本発明の天然石入り合成樹
脂材は、外表面に疎水化処理剤が吸着された天然石の粉
末を合成樹脂材料に混合して金型で成形することによ
り、表層部に天然石の粉末が集中的に偏していることを
特徴とする。The synthetic resin material containing natural stone of the present invention according to claim 3 is obtained by mixing a natural stone powder having a hydrophobizing agent adsorbed on the outer surface thereof with a synthetic resin material and molding the mixture with a mold to form a surface layer portion. It is characterized in that natural stone powder is concentrated and concentrated.
【０００９】請求項５に係る本発明方法は、図２に示す
ごとく天然石の粉末が混入された合成樹脂溶液を金型２
に吹き付けることにより、合成樹脂溶液よりも比重の大
きい天然石の粉末４が金型２に面する表面側に偏在する
状態で、硬化させた天然石入り合成樹脂材の成形方法で
ある。この場合は、比較的厚みが薄い成形品を得るに適
っている。成形品に厚みを要し、とくに強度アップを図
る必要があれば、得られた成形品に他の部材に重ねて接
着等の適当な手段で接合すればよい。According to a fifth aspect of the present invention, as shown in FIG. 2, a synthetic resin solution mixed with natural stone powder is placed in a mold 2.
Is a method of molding a synthetic resin material containing natural stone which is hardened in a state where natural stone powder 4 having a higher specific gravity than the synthetic resin solution is unevenly distributed on the surface side facing the mold 2. This case is suitable for obtaining a molded product having a relatively small thickness. If the molded article needs to have a thickness, and if it is particularly necessary to increase the strength, the molded article may be overlaid on another member and joined by appropriate means such as adhesion.
【００１０】かかる他の部材の接合を省略する場合とし
て、請求項６記載の本発明に係る天然石入りの合成樹脂
材の成形方法は、天然石の粉末が混入された合成樹脂溶
液を金型２に吹き付けることにより、合成樹脂溶液より
も比重の大きい天然石の粉末４が金型２に面する表面側
に偏在する中間成形品３をつくり、この中間成形品３を
半硬化状態にしたのち、図４に示すごとく中間成形品３
の裏面側に、相溶性を有する液状合成樹脂材料７からな
るバックアップ層９を積層し、中間成形品３とバックア
ップ層９とを硬化させて一体に成形するようにしたもの
である。According to a sixth aspect of the present invention, there is provided a method for molding a synthetic resin material containing natural stone, in which a synthetic resin solution mixed with natural stone powder is poured into a mold 2. By spraying, an intermediate molded product 3 in which natural stone powder 4 having a higher specific gravity than the synthetic resin solution is unevenly distributed on the surface side facing the mold 2 is formed, and after the intermediate molded product 3 is semi-cured, FIG. Intermediate molded product 3 as shown in
A back-up layer 9 made of a liquid synthetic resin material 7 having compatibility is laminated on the back side of the substrate, and the intermediate molded article 3 and the back-up layer 9 are cured to be integrally molded.
【００１１】本発明を実施するために用いる天然石とし
ては、医王石、竜王石、トルマリン、角閃石などを含む
火成岩、光明石、麦飯石、黒曜石を挙げることができ
る。天然石の粉末は、平均粒径が0.１〜5.０mmであり、
吹き付け用の合成樹脂溶液の樹脂成分に対する混入量が
１〜７０重量％、好ましくは５〜７０重量％になるよう
に設定することができる。Examples of the natural stones used for carrying out the present invention include igneous rocks including Ioite, Ryuoite, tourmaline, amphibolite, etc., komashiite, barite and obsidian. Natural stone powder has an average particle size of 0.1 to 5.0 mm,
The mixing amount of the synthetic resin solution for spraying with respect to the resin component can be set to 1 to 70% by weight, preferably 5 to 70% by weight.
【００１２】請求項９に係る本発明は、エポキシ樹脂又
はポリエステル樹脂からなる合成樹脂溶液にトルマリン
の粉末が混入された注型用樹脂液Ａを調整し、この注型
用樹脂液Ａを金型２に吹き付けることにより、合成樹脂
溶液よりも比重の大きいトルマリンの粉末４が金型２に
面する表面側に偏在する状態で、硬化させた天然石入り
合成樹脂材の成形方法である。すなわち、吹き付けを利
用した注型方法である。According to a ninth aspect of the present invention, there is provided a resin solution for casting A in which tourmaline powder is mixed in a synthetic resin solution comprising an epoxy resin or a polyester resin, and the resin solution for casting A is formed into a mold. 2 is a method for molding a synthetic resin material containing natural stone, which is cured in a state where tourmaline powder 4 having a larger specific gravity than the synthetic resin solution is unevenly distributed on the surface side facing the mold 2. That is, it is a casting method using spraying.
【００１３】請求項１０に係る本発明の成形方法は、エ
ポキシ樹脂又はポリエステル樹脂からなる合成樹脂溶液
の樹脂成分に対してトルマリンの粉末が１〜４０重量％
の割合で混入された注型用樹脂液Ａを調整し、この注型
用樹脂液Ａを金型２に吹き付けることにより、合成樹脂
溶液よりも比重の大きいトルマリンの粉末４が前記金型
２に面する表面側に偏在する中間成形品３をつくる工程
と、中間成形品３を金型２ごと加熱処理して裏面側に薄
い皮膜６が形成された半硬化状態にする工程と、中間成
形品３の前記皮膜６を有する裏面側に、中間成形品３と
相溶性を有する液状合成樹脂材料７を重ねてバックアッ
プ層９を積層する工程と、前記金型２ごと加熱処理する
ことにより、中間成形品３およびバックアップ層９を硬
化させて一体化する工程とを経て、天然石入り合成樹脂
材を成形する。この場合、中間成形品３とバックアップ
層９とは、接着強度を確保するために同一の合成樹脂材
料であることがより好ましい。According to a tenth aspect of the present invention, there is provided the molding method, wherein the amount of the tourmaline powder is 1 to 40% by weight based on the resin component of the synthetic resin solution comprising the epoxy resin or the polyester resin.
The casting resin solution A mixed in the ratio of 1 is adjusted, and the casting resin solution A is sprayed on the mold 2 so that the tourmaline powder 4 having a higher specific gravity than the synthetic resin solution is added to the mold 2. A step of forming an intermediate molded product 3 unevenly distributed on the facing front side, a step of heating the intermediate molded product 3 together with the mold 2 to a semi-cured state in which a thin film 6 is formed on the back side, 3, a step of laminating a liquid synthetic resin material 7 having compatibility with the intermediate molded product 3 on the back surface side having the film 6 and laminating a backup layer 9; Through a step of curing and integrating the article 3 and the backup layer 9 to form a synthetic resin material containing natural stones. In this case, the intermediate molded product 3 and the backup layer 9 are more preferably made of the same synthetic resin material in order to secure the adhesive strength.
【００１４】[0014]
【作用】金型２に天然石粉末入りの合成樹脂溶液を吹き
付けるのは、注型用樹脂液Ａを金型表面に衝突させたと
き、合成樹脂溶液よりも比重の大きい天然石粉末４を金
型の表面側に集中的に偏在させるためである。これにて
金型２上の中間成形品３は、製品化したとき外面側とな
る表層部５に天然石粉末４が集中して偏在したものとな
る。この中間成形品３は、加熱するなどして硬化処理す
ることにより、そのまま製品化することができる。ここ
での偏在とは、析出ないし密度勾配というも同義語であ
る。The reason why the synthetic resin solution containing natural stone powder is sprayed onto the mold 2 is that when the casting resin solution A collides with the surface of the mold, the natural stone powder 4 having a specific gravity greater than that of the synthetic resin solution is applied to the mold. This is for the purpose of concentrated distribution on the surface side. As a result, the intermediate molded product 3 on the mold 2 has the natural stone powder 4 concentrated and unevenly distributed on the surface layer portion 5 on the outer surface side when commercialized. This intermediate molded product 3 can be directly commercialized by being subjected to a curing treatment by heating or the like. The uneven distribution here is synonymous with precipitation or density gradient.
【００１５】合成樹脂成形品の表層部に天然石粉末を集
中的に偏在させる別の手段としては、炭化水素系あるい
はふっ化物系などの有機物系疎水化処理剤を用いる。か
かる疎水化処理剤としては、天然石粉末への吸着性に優
れるシラン系、テタネート系、アルミニウム系などのカ
ップリング剤、あるいはオルガノシラザンなどが挙げら
れる。すなわち、上記の疎水化処理剤の溶液中に天然石
粉末を混合分散して、天然石粉末の外表面に疎水化処理
剤を化学的に吸着させ、以て天然石粉末の表面エネルギ
ーを低下させる。しかるときは、合成樹脂材料に疎水化
処理済みの天然石粉末を混合して金型内に入れて成形す
るとき、天然石粉末と合成樹脂材料との間の界面エネル
ギーに大きな差が生じるため、合成樹脂材料の硬化前に
天然石粉末が合成樹脂材料中で浮き上がり、硬化後の合
成樹脂成形品をみたとき、その表層部にのみ天然石粉末
が集中的に偏在したものとなる。As another means for concentrating the natural stone powder on the surface layer of the synthetic resin molded article, an organic-based hydrophobizing agent such as a hydrocarbon-based or fluoride-based agent is used. Examples of such a hydrophobizing agent include a silane-based, tetanate-based, or aluminum-based coupling agent having excellent adsorptivity to natural stone powder, or an organosilazane. That is, natural stone powder is mixed and dispersed in the above-mentioned solution of the hydrophobizing agent, and the hydrophobizing agent is chemically adsorbed on the outer surface of the natural stone powder, thereby lowering the surface energy of the natural stone powder. In such a case, when the synthetic resin material is mixed with a natural stone powder having been subjected to a hydrophobic treatment and then molded in a mold, a large difference occurs in the interfacial energy between the natural stone powder and the synthetic resin material. Before the material is hardened, the natural stone powder floats up in the synthetic resin material, and when the synthetic resin molded product after hardening is viewed, the natural stone powder is concentrated and concentrated only on the surface layer.
【００１６】中間成形品３の厚み不足を補って補強を図
ったり、裏面側の形を所望通りに仕上げるために、中間
成形品３を硬化処理したのち、中間成形品３の裏面にバ
ックアップ層９を積層して一体化することができる。こ
のときのバックアップ層９は、中間成形品３とは異材質
の合成樹脂材、木質材、金属材などを接着する等の手段
で一体化することができる。After the intermediate molded product 3 has been subjected to a hardening treatment in order to compensate for the lack of thickness of the intermediate molded product 3 and to finish the shape on the back side as desired, a backup layer 9 is formed on the rear surface of the intermediate molded product 3. Can be laminated and integrated. At this time, the backup layer 9 can be integrated by means such as bonding a synthetic resin material, a wooden material, a metal material, or the like, which is different from the intermediate molded product 3.
【００１７】但し、本発明方法を用いてシステムキッチ
ンの天板やシステムバスの棚板、それに浴槽を得る場合
は、吹き付け用の合成樹脂溶液にエポキシ樹脂やポリエ
ステル樹脂を用い、中間成形品３を金型２ごと半硬化状
態に処理して中間成形品３の裏面側に薄い皮膜６を形成
したのち、中間成形品３の前記皮膜６上に相溶性を有す
る、好ましくは同一の液状合成樹脂材料７を流し込み、
中間成形品３の裏面にバックアップ層９を一体に積層形
成したものとする。中間成形品３に薄い皮膜６を形成す
るのは、中間成形品３とバックアップ層９との一体化を
図りながらも、バックアップ層９を構成する液状合成樹
脂材料７を溶融下で中間成形品３の裏面上に注ぎ込んだ
とき、中間成形品３が形崩れをして天然石粉末４の偏在
を損なうことがないようにするためである。この限りに
おいて、中間成形品３はいったん硬化させておき、その
うえにバックアップ層９を構成する液状合成樹脂材料７
を流し込んでよく、この場合にも相互に相溶性を有する
液状合成樹脂材料７を用いるときは、かなりの接合強度
を期待できる。However, when a top plate of a system kitchen, a shelf plate of a system bath, and a bathtub are obtained by using the method of the present invention, an epoxy resin or a polyester resin is used for a synthetic resin solution for spraying, and the intermediate molded product 3 is used. After processing the mold 2 in a semi-cured state to form a thin film 6 on the back surface side of the intermediate molded product 3, the liquid synthetic resin material having compatibility on the film 6 of the intermediate molded product 3, preferably the same liquid synthetic resin material Pour 7,
It is assumed that the backup layer 9 is integrally formed on the back surface of the intermediate molded product 3. The reason why the thin film 6 is formed on the intermediate molded product 3 is that the liquid synthetic resin material 7 constituting the backup layer 9 is melted while the intermediate molded product 3 and the backup layer 9 are integrated. The reason is that the intermediate molded product 3 does not lose its shape when poured onto the back surface of the natural stone powder 4 and impairs the uneven distribution of the natural stone powder 4. To this extent, the intermediate molded product 3 is once cured, and then the liquid synthetic resin material 7 constituting the backup layer 9
In this case, when liquid synthetic resin materials 7 having compatibility with each other are used, considerable joining strength can be expected.
【００１８】吹き付け用の合成樹脂溶液とは、代表例で
ある二液反応硬化型のエポキシ樹脂の場合、エポキシ樹
脂の主剤とその硬化剤とを含む概念であり、別に硬化促
進剤や消泡剤などが常法通り必要に応じて混合分散され
る。The synthetic resin solution for spraying is a concept including, in the case of a typical example of a two-pack reaction curing type epoxy resin, a main agent of the epoxy resin and a curing agent thereof. And the like are mixed and dispersed as necessary in a usual manner.
【００１９】天然石としては、マイナスイオン発生の観
点からみると、空気１cc中のマイナスイオン個数をみた
とき、ひとつの測定データによれば、医王石で４５０
０、龍王石で３４００、トルマリンで２５００、長野県
八ケ岳山麓の角閃石で１８００、岡山県阿部鉱山の光明
石で１０００、岐阜県の麦飯石で８００、黒曜石で８０
０とされている。因みに、同一の測定条件下における空
気１cc中のマイナスイオンの個数を身近にみると、滝の
中で１５００、森林の中で８００であり、先の天然石が
マイナスイオンの発生体として有効であることが判る。
そしてマイナスイオンは、空気や水の浄化作用、抗菌作
用を有し、人体にも有利に作用することが知られてい
る。このうち光明石は、湯船の中に入れると有効なもの
として医薬部外品承認を受けており（承認番号：（４３
Ｄ）第２５１号）、本発明者が確認したところによれ
ば、約４０℃前後において遠赤外線が有効に発生する。
その他、遠赤外線を放射する天然石は、他にもいくつか
公知であり、それらは例えば浴槽に用いたとき有利とな
る。本発明での天然石とは、遠赤外線の放射性能を有効
利用する場合などには焼成したセラミックスの類も含む
概念である。As a natural stone, from the viewpoint of generation of negative ions, when the number of negative ions in 1 cc of air is measured, according to one measurement data, Io stone is 450
0, 3400 for Ryuoishi, 2500 for tourmaline, 1800 for amphibolite at the foot of Mt. Yatsugatake, Nagano Prefecture, 1000 for Komitsuishi at Abe Mine, Okayama Prefecture, 800 for Barley Stone in Gifu Prefecture, and 80 for Obsidian
It is set to 0. Incidentally, the number of negative ions in 1 cc of air under the same measurement conditions is close to 1500 in a waterfall and 800 in a forest, indicating that the natural stone is effective as a negative ion generator. I understand.
It is known that negative ions have a purifying action of air and water and an antibacterial action, and also have an advantageous effect on the human body. Among them, Mitsuaki has received quasi-drug approval as being effective when placed in a bathtub (approval number: (43
D) No. 251), the inventors have confirmed that far infrared rays are effectively generated at about 40 ° C.
In addition, some other natural stones emitting far-infrared rays are known, and they are advantageous, for example, when used in bathtubs. The natural stone in the present invention is a concept including fired ceramics when the radiation performance of far-infrared rays is effectively used.
【００２０】マイナスイオン効果に関して、測定データ
とは別に本発明者が確認したところによれば、トルマリ
ンが最も用いて好適であった。その場合の前記注型用樹
脂液Ａは、これを構成する合成樹脂材料にエポキシ樹脂
を用いることが望まれる。エポキシ樹脂は、電気絶縁性
が高く、これにトルマリン粉末を入れたとき、マイナス
イオンの相殺がないからであろうと推認される。注型用
樹脂液がエポキシ樹脂であれポリエステル樹脂であれ、
これらの樹脂成分に対するトルマリン粉末の混入量は１
重量％を下回るとマイナスイオンの発生効能が十二分に
発揮されず、４０重量％を越えると粉末どうしが近付き
過ぎてマイナスイオンどうしの相殺が生じるからか却っ
て効果が出ず、かつ製品外表面に大理石様の石目模様が
現出しなくなるので、１〜４０重量％、更に好ましくは
５〜３０重量％に設定することが望まれる。Regarding the negative ion effect, according to what the present inventors confirmed separately from the measurement data, tourmaline was most preferably used. In such a case, it is desired that the casting resin liquid A uses an epoxy resin as a synthetic resin material constituting the same. It is presumed that the epoxy resin has a high electrical insulation property, and when tourmaline powder is added to the epoxy resin, there is no cancellation of negative ions. Whether the casting resin liquid is an epoxy resin or a polyester resin,
The amount of tourmaline powder mixed into these resin components is 1
If the content is less than 40% by weight, the effect of generating negative ions is not sufficiently exhibited. If the content is more than 40% by weight, the powders are too close to each other and the negative ions are canceled each other. Therefore, it is desired to set the content to 1 to 40% by weight, more preferably 5 to 30% by weight, since a marble-like grain pattern does not appear.
【００２１】本発明では、人工の大理石紋様など石目模
様を現出させることをも狙っているが、そのためにのみ
天然石の粉末を混入することも含む。その限りにおい
て、とくに天然石の種類は問わない。但し、石目模様の
現出を考慮すると、トルマリンを含む天然石粉末は、平
均粒径が0.１〜5.０mmのものを用いる。平均粒径が0.１
mmを下回ると、天然石粉末の混入量が多くなって行くに
従い天然石粉末が着色顔料のようになって点在状の石目
模様が現出せず、一方で平均粒径が5.０mmを上回ると吹
付ガンによる吹き付けに支障を来すからである。また、
注型用樹脂液の樹脂成分に対する天然石粉末の混入量
は、１〜７０重量％（トルマリンのマイナスイオンの発
生効能を利用する場合は先にみたとおり１〜３５重量
％）に設定する。１重量％を下回ると天然石の本来の存
在意義が発揮されず、７０重量％を越えると、先にみた
とおり石目模様が出ず、粘度が高くなり過ぎて混合攪拌
が困難になるとともに、吹き付けおよび注型の作業性が
困難になるからである。In the present invention, the aim is to make a grain pattern such as an artificial marble pattern appear, but for that purpose, it is also possible to mix natural stone powder. As long as that is the case, the type of natural stone is not particularly limited. However, considering the appearance of the stone pattern, natural stone powder containing tourmaline having an average particle size of 0.1 to 5.0 mm is used. Average particle size is 0.1
If the average particle size exceeds 5.0 mm, the natural stone powder becomes a colored pigment and does not show a dotted pattern as the amount of the natural stone powder increases increases. This is because spraying with the spray gun is hindered. Also,
The mixing amount of the natural stone powder with respect to the resin component of the resin solution for casting is set at 1 to 70% by weight (when using the negative ion generation effect of tourmaline, 1 to 35% by weight as described above). If the amount is less than 1% by weight, the natural significance of natural stone is not exhibited. If the amount is more than 70% by weight, the stone pattern does not appear as described above, and the viscosity becomes too high, so that mixing and stirring becomes difficult and spraying is performed. This is because the workability of casting becomes difficult.
【００２２】なお、吹き付け用の合成樹脂溶液には、ト
ルマリンなどの天然石粉末のほかに、色目を調整するた
めのポリチップや色付きの天然砂などを混入でき、更に
硬化促進剤や、成形品の機械的強度（とくに曲げ強度）
を維持し得る限りにおいて増量材として水酸化アルミニ
ウム粉末、炭酸カルシウム、ガラスクリットなどを混入
できる。これらの混入物の量によって、先の天然石粉末
の混入量が適宜調整される。The synthetic resin solution for spraying may contain, in addition to natural stone powder such as tourmaline, poly chips for adjusting the color tone and colored natural sand, etc., and may further contain a hardening accelerator and a machine for molding molded articles. Strength (especially bending strength)
Aluminum hydroxide powder, calcium carbonate, glass krit and the like can be mixed as extenders as long as the above can be maintained. The amount of the natural stone powder to be mixed is appropriately adjusted depending on the amounts of these contaminants.
【００２３】本発明者の知見によれば、マイナスイオン
の発生、遠赤外線の放射に関し、異なる天然石どうしを
混ぜて用いると、それぞれの効果が相乗的に発揮され、
とくにトルマリンと光明石との併用が有効であった。According to the knowledge of the present inventor, regarding the generation of negative ions and the emission of far infrared rays, when different natural stones are mixed and used, the respective effects are synergistically exhibited,
In particular, the combination of tourmaline and Koumashi was effective.
【００２４】[0024]
【発明の実施の形態】（実施例１） 二液反応硬化型の
エポキシ樹脂（比重1.２ｇ／cm3 ）の主剤１００重量部
とその硬化剤９５重量部とを加えた低粘度の合成樹脂溶
液に対して、平均粒径が1.５mmのトルマリン（比重3.１
ｇ／cm3 ）の黒色粉末を３２重量部混入した注型用樹脂
液Ａを調整した。更に注型用樹脂液Ａには、色目を整え
るために茶色の中国砂２８重量部と、白砂（パール４
号）２８重量部と、ピンク色のガーネットの粉末２８重
量部と、桃色水晶粉２８重量部と、珪石（砂）１００重
量部とを均一に混合分散させた。なお、中国砂、白砂、
ガーネット粉末、珪石の比重はそれぞれ2.６ｇ／cm3 で
ある。次に、図２に示すごとく注型用樹脂液Ａを吹付ガ
ン１で圧縮空気とともに略垂直状に立て掛けた金型２に
向けて吹き付けた。これにて、トルマリン粉末入り注型
用樹脂液Ａを金型２に吹き付けたとき、合成樹脂溶液よ
りもトルマリン粉末などの比重が大きいため、金型２上
の塗工層は金型２に面する表面側にトルマリン粉末など
が集中的に偏在した。DESCRIPTION OF THE PREFERRED EMBODIMENTS (Example 1) A low-viscosity synthetic resin obtained by adding 100 parts by weight of a main component of a two-component reaction-curable epoxy resin (specific gravity: 1.2 g / cm 3 ) and 95 parts by weight of a curing agent thereof. Tourmaline with an average particle size of 1.5 mm (specific gravity 3.1
g / cm 3 ) of the black resin powder 32 was mixed to prepare a casting resin liquid A. Further, the resin liquid A for casting contains 28 parts by weight of brown Chinese sand and white sand (pearl 4) for coloring.
No. 28), 28 parts by weight of pink garnet powder, 28 parts by weight of pink quartz powder, and 100 parts by weight of silica (sand) were uniformly mixed and dispersed. In addition, Chinese sand, white sand,
The specific gravity of garnet powder and silica stone is 2.6 g / cm 3 respectively. Next, as shown in FIG. 2, the resin liquid A for casting was sprayed by the spray gun 1 together with the compressed air toward the mold 2 which was set up substantially vertically. With this, when the casting resin liquid A containing tourmaline powder is sprayed on the mold 2, the specific gravity of the tourmaline powder and the like is larger than that of the synthetic resin solution, so that the coating layer on the mold 2 faces the mold 2. The tourmaline powder and the like were concentrated and unevenly distributed on the surface side.
【００２５】次に、塗工層を有する金型２ごとオーブン
に入れ、１４０〜１５０℃で約５分間加熱処理して半硬
化させ、図３の中間成形品３を得た。図３において中間
成形品３は、金型２に面する表面側（図の下側）にトル
マリン粉末４が集中した表層部５を有し、裏面側（図の
上側）に1.０mm厚の薄い皮膜６が形成された。Next, the mold 2 having the coating layer was put in an oven, and was heat-treated at 140 to 150 ° C. for about 5 minutes to be semi-cured to obtain an intermediate molded product 3 shown in FIG. In FIG. 3, the intermediate molded product 3 has a surface layer portion 5 on which the tourmaline powder 4 is concentrated on the front side (lower side in the figure) facing the mold 2, and has a 1.0 mm thick rear side (upper side in the figure). A thin film 6 was formed.
【００２６】続いて、図４に示すごとく金型２上の中間
成形品３をこれの裏面側が上向き状態になるようにセッ
トして、同じ二液反応硬化型のエポキシ樹脂の主剤１０
０重量部とその硬化剤９５重量部とを加えた低粘度の合
成樹脂溶液に、増量材としての水酸化アルミニウム（比
重2.５６ｇ／cm3 ）を４００重量部混入して液状合成樹
脂材料７を調整し、これを中間成形品３の皮膜６上に注
ぎ込み、その液状合成樹脂材料７を中間成形品３上にお
いてローラなど展延して所定の厚みのバックアップ層９
を積層した。Subsequently, as shown in FIG. 4, the intermediate molded product 3 on the mold 2 is set so that the back side thereof faces upward, and the same two-component reaction-curable epoxy resin base material 10 is used.
To a low-viscosity synthetic resin solution containing 0 parts by weight and 95 parts by weight of a curing agent, 400 parts by weight of aluminum hydroxide (specific gravity 2.56 g / cm 3 ) was mixed as an extender to form a liquid synthetic resin material 7. Is poured onto the film 6 of the intermediate molded product 3, and the liquid synthetic resin material 7 is spread on the intermediate molded product 3 by a roller or the like to form a backup layer 9 having a predetermined thickness.
Were laminated.
【００２７】最後に金型２ごとオーブンに入れ、１４０
〜１５０℃で中間成形品３およびバックアップ層９を９
０分間加熱して硬化させたのち、成形品１０を金型２か
ら取り外した。図１はその成形品１０の断面図であり、
中間成形品３とバックアップ層９とが溶融下で境界なく
接合し、２mm厚の中間成形品３の裏面に、６mm厚のバッ
クアップ層９が不離一体に積層形成された成形品１０を
得た。この成形品１０を目視観察したところ、前記皮膜
６の介在で液状合成樹脂材料７を中間形成品３上に注ぎ
込む際の形崩れがよく防止されており、従って成形品１
０の表層部５にのみトルマリン粉末４などが集中的に偏
在（析出）したものが得られた。成形品１０の外表面
は、全体的にベージュ色を帯びた下地に黒色、茶色、白
色およびピンク色などが点在した大理石模様を呈し、乳
白色のバックアップ層９が表層部５にて完全に隠ぺいさ
れたものとなった。Finally, the mold 2 is put into an oven and
At 150 ° C., the intermediate molded product 3 and the backup layer 9
After heating and curing for 0 minutes, the molded article 10 was removed from the mold 2. FIG. 1 is a sectional view of the molded product 10,
The intermediate molded product 3 and the backup layer 9 were joined without any boundary under melting, and a molded product 10 in which a 6 mm thick backup layer 9 was integrally formed on the back surface of the 2 mm thick intermediate molded product 3 in a non-separable manner. When the molded article 10 was visually observed, the shape of the liquid synthetic resin material 7 when the liquid synthetic resin material 7 was poured onto the intermediate molded article 3 was well prevented by the presence of the coating film 6.
No. 0, the tourmaline powder 4 and the like were concentratedly distributed (precipitated) only on the surface layer portion 5. The outer surface of the molded article 10 has a marble pattern in which black, brown, white, pink, etc. are scattered on a beige base as a whole, and a milky white backup layer 9 is completely hidden in the surface layer portion 5. It was done.
【００２８】（実施例２） 先の注型用樹脂液Ａにおい
て、エポキシ樹脂主剤１００重量部とその硬化剤９０重
量部とからなる合成樹脂溶液に、平均粒径が0.３５mmの
トルマリン粉末を１９重量部、茶色の中国砂１９重量
部、白砂（パール４号）１９重量部、桃色水晶粉１９重
量部、比重で2.５６ｇ／cm3 の水酸化アルミニウム２０
０重量部を混入し、ガーネットの粉末を除いたそれ以外
は、実施例１と同様にして成形品１０をつくった。この
場合の成形品１０の外表面は、全体的にグレー色を帯び
た下地に黒色、茶色およびピンク色の点が密集した大理
石模様を呈し、バックアップ層９の色が完璧に隠ぺいさ
れたものが得られた。(Example 2) Tourmaline powder having an average particle diameter of 0.35 mm was added to a synthetic resin solution comprising 100 parts by weight of an epoxy resin base and 90 parts by weight of a curing agent thereof in the resin solution A for casting. 19 parts by weight, 19 parts by weight of brown Chinese sand, 19 parts by weight of white sand (Pearl No. 4), 19 parts by weight of pink quartz powder, aluminum hydroxide 20 having a specific gravity of 2.56 g / cm 3
A molded product 10 was prepared in the same manner as in Example 1 except that 0 parts by weight were mixed and the garnet powder was removed. In this case, the outer surface of the molded article 10 has a marble pattern in which black, brown, and pink dots are densely formed on a gray base, and the color of the backup layer 9 is completely hidden. Obtained.
【００２９】（実施例３） 先の注型用樹脂液Ａおよび
バックアップ層９用の液状合成樹脂材料７をエポキシ樹
脂に代えてポリエステル樹脂（比重1.２ｇ／cm3 ）と
し、オーブンで中間成形品３を５０〜１００℃で５分間
加熱し、中間成形品３にバックアップ層９を重ねた後の
オーブンでの最終加熱を１００〜１２０℃で６０分間と
した以外は、実施例１と同様にして成形品１０をつくっ
た。この場合の目視による外観形態は、実質的にみて実
施例１と同様であった。Example 3 A polyester resin (specific gravity: 1.2 g / cm 3 ) was used in place of the epoxy resin in place of the resin liquid A for casting and the liquid synthetic resin material 7 for the backup layer 9, and intermediate molding was performed in an oven. The same procedure as in Example 1 was performed except that the article 3 was heated at 50 to 100 ° C. for 5 minutes, and the final heating in the oven after the backup layer 9 was overlaid on the intermediate molded article 3 was performed at 100 to 120 ° C. for 60 minutes. Thus, a molded product 10 was produced. The visual appearance in this case was substantially the same as in Example 1.
【００３０】（実施例４） トルマリンを火成岩のうち
角閃石（比重3.１ｇ／cm3 ）の粉末（粒径1.５mm）とし
た以外は、実施例１と同様にして成形品１０をつくっ
た。この場合の目視による外観形態は、実質的にみて実
施例１と同様であった。Example 4 A molded product 10 was prepared in the same manner as in Example 1, except that tourmaline was used as powder (particle diameter: 1.5 mm) of amphibolite (specific gravity: 3.1 g / cm 3 ) of igneous rock. Was. The visual appearance in this case was substantially the same as in Example 1.
【００３１】（実施例５） 実施例１において、注型用
樹脂液Ａに平均粒径が0.５mmのトルマリンの粉末と平均
粒径が0.５mmの光明石（比重2.６ｇ／cm3 ）の粉末とを
半分ずつの割合で合計２０重量部混入した以外は、実施
例１と同様にした。この場合の目視による外観形態は、
実質的にみて実施例１と同様であった。(Example 5) In Example 1, tourmaline powder having an average particle size of 0.5 mm and luminous aragonite having an average particle size of 0.5 mm (specific gravity 2.6 g / cm 3) were added to the resin solution A for casting. ) Was mixed in the same manner as in Example 1 except that a total of 20 parts by weight of the powder was mixed in half. In this case, the visual appearance is
Substantially the same as in Example 1.
【００３２】（実施例６） トルマリンの粉末（平均粒
径1.５mm）を５重量部、疎水化処理剤（Ｃ18Ｈ37Ｓｉ
（ＮＨ）３／２）を0.１重量部、溶剤（トルエン）を５
重量部それぞれ１００時間、混合して分散混合物を得
た。この分散混合物を二液反応硬化型のエポキシ樹脂溶
液に混合分散して金型内に入れて注型成形し、厚さ２mm
の成形品を得た。よって得た成形品は、断面構造および
目視による外観形態とも図１に示す実施例１の中間成形
品３と実質的に同一であった。Example 6 5 parts by weight of tourmaline powder (average particle size: 1.5 mm) was treated with a hydrophobizing agent (C 18 H 37 Si).
0.1 parts by weight of (NH) 3/2) and 5 parts by weight of a solvent (toluene).
Each part by weight was mixed for 100 hours to obtain a dispersion mixture. This dispersion mixture is mixed and dispersed in a two-component reaction-curing type epoxy resin solution, placed in a mold and cast and molded to a thickness of 2 mm.
Was obtained. Thus, the obtained molded product was substantially the same in cross-sectional structure and visual appearance as the intermediate molded product 3 of Example 1 shown in FIG.
【００３３】よって試作した実施例１〜６の各成形品１
０によるときは、とくに実施例４の場合にマイナスイオ
ンの発生に有効であった。また、これら各実施例の成形
品１０は、外表面から見たとき、トルマリン粉末４を含
む天然石粉末が点在して石目模様（人工大理石模様）を
現出したものとなった。Each of the molded articles 1 of Examples 1 to 6 thus experimentally produced
When it was 0, it was particularly effective in the case of Example 4 for generating negative ions. In addition, when viewed from the outer surface, the molded product 10 of each of the examples had natural stone powders including the tourmaline powder 4 interspersed and appeared as a stone pattern (artificial marble pattern).
【００３４】図示例では単純な平板状の成形品１０を得
る場合について説明したが、金型２の表面形状は目的の
製品に応じて凹凸ないし湾曲状を呈したものとすれば、
これが成形品１０の外表面の形状になる。また、金型２
上のバックアップ層９の裏面側となる外面に別の金型を
先の金型２と合わせて最終的な加熱処理を行い、成形品
１０の裏面の形状も任意に設定し得ることは言うまでも
ない。In the illustrated example, the case where a simple flat molded product 10 is obtained has been described. However, if the surface shape of the mold 2 is uneven or curved depending on the target product,
This becomes the shape of the outer surface of the molded article 10. Also, mold 2
It goes without saying that the final surface of the molded product 10 can be arbitrarily set by performing a final heat treatment by combining another mold with the former mold 2 on the outer surface on the back surface side of the upper backup layer 9. .
【００３５】[0035]
【発明の効果】以上みたとおり本発明によれば、樹脂成
形品の表面に天然石の粉末を集中的に偏在させることが
できるので、マイナスイオンの発生、遠赤外線の放射な
ど、使用する天然石の機能特性を有効に発揮させなが
ら、その使用量を極力抑えることができる。従って、従
来高価とされていた特殊機能を持つ天然石入りの合成樹
脂成形品でも安価に生産できる。とくに本発明方法によ
れば、中間成形品にバックアップ層が共に液状合成樹脂
材料の積層で一体に成形されていると、バックアップ層
で全体の強度不足などを補うことができる利点を有す
る。As described above, according to the present invention, the natural stone powder can be concentrated and unevenly distributed on the surface of the resin molded product. The use amount can be suppressed as much as possible while exhibiting the characteristics effectively. Accordingly, a synthetic resin molded product containing a natural stone having a special function, which has been conventionally regarded as expensive, can be produced at low cost. In particular, according to the method of the present invention, when both the backup layer and the intermediate molded article are integrally formed by laminating a liquid synthetic resin material, there is an advantage that the backup layer can compensate for the lack of overall strength.
【図１】成形品の断面図FIG. 1 is a sectional view of a molded product.
【図２】注型用樹脂液の吹き付けの要領を説明する概略
斜視図FIG. 2 is a schematic perspective view illustrating a point of spraying a casting resin liquid.
【図３】中間成形品の断面図FIG. 3 is a sectional view of an intermediate molded product.
【図４】中間成形品にバックアップ層を積層する要領を
示す概略斜視図FIG. 4 is a schematic perspective view showing a procedure for laminating a backup layer on an intermediate molded product.
Ａ 注型用樹脂液 １ 吹付ガン ２ 金型 ３ 中間成形品 ４ 天然石の粉末 ５ 表層部 ６ 皮膜 ７ 液状合成樹脂材料 ９ バックアップ層 １０ 成形品 A Casting resin liquid 1 Spray gun 2 Mold 3 Intermediate molded product 4 Natural stone powder 5 Surface layer 6 Coating 7 Liquid synthetic resin material 9 Backup layer 10 Molded product
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 67/00 Ｃ０８Ｌ 67/00 // Ｂ２９Ｋ 63:00 Ｂ２９Ｋ 63:00 67:00 67:00 105:16 105:16 Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) C08L 67/00 C08L 67/00 // B29K 63:00 B29K 63:00 67:00 67:00 105: 16 105: 16
Claims (11)
ていることを特徴とする天然石入り合成樹脂材。1. A synthetic resin material containing natural stone, wherein natural stone powder is concentrated and unevenly distributed on the surface layer.
を金型の表面に吹き付けることにより、表層部に天然石
の粉末が集中的に偏在していることを特徴とする天然石
入り合成樹脂材。2. A synthetic resin material containing natural stone, characterized in that natural stone powder is concentrated and unevenly distributed on the surface layer by spraying a synthetic resin solution mixed with natural stone powder on the surface of a mold.
石の粉末を合成樹脂材料に混合して金型で成形すること
により、表層部に天然石の粉末が集中的に偏在している
ことを特徴とする天然石入り合成樹脂材。3. Mixing a natural stone powder having a hydrophobizing agent adsorbed on the outer surface thereof with a synthetic resin material and molding the mixture with a mold, whereby the natural stone powder is concentrated and unevenly distributed on the surface layer. Synthetic resin material containing natural stone.
ン、角閃石などを含む火成岩、光明石、麦飯石、黒曜石
から選ばれる少なくともひとつである請求項１又は２又
は３記載の天然石入り合成樹脂材。4. The synthetic resin containing a natural stone according to claim 1, wherein the natural stone is at least one selected from igneous rocks including Ioite, Ryuoishi, tourmaline, amphibolite, glowstone, barite, and obsidian. Wood.
を金型に吹き付けることにより、合成樹脂溶液よりも比
重の大きい天然石の粉末が金型に面する表面側に偏在す
る状態で、硬化させたことを特徴とする天然石入り合成
樹脂材の成形方法。5. A synthetic resin solution mixed with natural stone powder is sprayed onto a mold, whereby natural stone powder having a specific gravity greater than that of the synthetic resin solution is hardened in a state unevenly distributed on the surface side facing the mold. A method of molding a synthetic resin material containing natural stone.
を金型に吹き付けることにより、合成樹脂溶液よりも比
重の大きい天然石の粉末が金型に面する表面側に偏在す
る中間成形品をつくり、 この中間成形品を半硬化状態にしたのち、中間成形品の
裏面側に、相溶性を有する液状の合成樹脂材料からなる
バックアップ層を積層し、 中間成形品とバックアップ層とを硬化させて一体に成形
したことを特徴とする天然石入り合成樹脂材の成形方
法。6. A synthetic resin solution mixed with natural stone powder is sprayed onto a mold to form an intermediate molded article in which natural stone powder having a specific gravity greater than that of the synthetic resin solution is unevenly distributed on the surface side facing the mold. After the intermediate molded product is in a semi-cured state, a backup layer made of a compatible liquid synthetic resin material is laminated on the back side of the intermediate molded product, and the intermediate molded product and the backup layer are cured and integrated. A method for molding a synthetic resin material containing natural stone, characterized by being molded into a shape.
ン、角閃石などを含む火成岩、光明石、麦飯石、黒曜石
から選ばれる少なくともひとつである請求項５又は６記
載の天然石入り合成樹脂材の成形方法。7. The natural stone-containing synthetic resin material according to claim 5 or 6, wherein the natural stone is at least one selected from igneous rocks including Io stone, Ryuo stone, tourmaline, amphibolite, etc .; Molding method.
mmであり、 合成樹脂溶液の樹脂成分に対する天然石の粉末の混入量
が、１〜７０重量％である請求項５又は６又は７記載の
天然石入り合成樹脂材の成形方法。8. The natural stone powder has an average particle size of 0.1 to 5.0.
The method for molding a natural stone-containing synthetic resin material according to claim 5, wherein the amount of the natural stone powder mixed with the resin component of the synthetic resin solution is 1 to 70% by weight.
なる合成樹脂溶液にトルマリンの粉末が混入された注型
用樹脂液を金型に吹き付けることにより、合成樹脂溶液
よりも比重の大きいトルマリンの粉末が金型に面する表
面側に偏在する状態で、硬化させたことを特徴とする天
然石入り合成樹脂材の成形方法。9. A molding resin solution in which tourmaline powder is mixed into a synthetic resin solution made of an epoxy resin or a polyester resin is sprayed on a mold, so that the tourmaline powder having a higher specific gravity than the synthetic resin solution is molded. A method of molding a natural stone-containing synthetic resin material, wherein the synthetic resin material is cured in a state of being unevenly distributed on the surface side facing the surface.
らなる合成樹脂溶液の樹脂成分に対してトルマリンの粉
末が１〜４０重量％の割合で混入された注型用樹脂液を
調整し、この注型用樹脂液を金型に吹き付けることによ
り、合成樹脂溶液よりも比重の大きいトルマリンの粉末
が金型に面する表面側に偏在する中間成形品をつくる工
程と、 中間成形品を前記金型ごと加熱処理して裏面側に薄い皮
膜が形成された半硬化状態にする工程と、 中間成形品の前記皮膜を有する裏面側に、中間成形品と
相溶性を有する液状の合成樹脂材料を重ねてバックアッ
プ層を積層する工程と、 前記金型ごと加熱処理することにより、中間成形品およ
びバックアップ層を硬化させて一体化する工程とからな
ることを特徴とする天然石入り合成樹脂材の成形方法。10. A resin solution for casting in which tourmaline powder is mixed at a ratio of 1 to 40% by weight with respect to a resin component of a synthetic resin solution composed of an epoxy resin or a polyester resin. A step of forming an intermediate molded article in which tourmaline powder having a higher specific gravity than the synthetic resin solution is unevenly distributed on the surface side facing the mold by spraying the liquid onto the mold; and heating the intermediate molded article together with the mold. To a semi-cured state in which a thin film is formed on the back surface side, and laminating a backup layer by overlaying a liquid synthetic resin material compatible with the intermediate molded product on the back surface side of the intermediate molded product having the film. And a step of curing and integrating the intermediate molded product and the backup layer by performing a heat treatment together with the mold, thereby forming a natural stone-containing synthetic resin material.
〜5.０mmである請求項９又は１０記載の天然石入り合成
樹脂材の成形方法。11. The tourmaline powder has an average particle size of 0.1.
The method for molding a synthetic resin material containing natural stone according to claim 9 or 10, wherein the thickness is from 5.0 to 5.0 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000221365A JP2002038023A (en) | 2000-07-21 | 2000-07-21 | Synthetic resin material containing natural stone and its molding method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000221365A JP2002038023A (en) | 2000-07-21 | 2000-07-21 | Synthetic resin material containing natural stone and its molding method |
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| Publication Number | Publication Date |
|---|---|
| JP2002038023A true JP2002038023A (en) | 2002-02-06 |
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ID=18715785
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000221365A Pending JP2002038023A (en) | 2000-07-21 | 2000-07-21 | Synthetic resin material containing natural stone and its molding method |
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| Country | Link |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010000168A (en) * | 2008-06-19 | 2010-01-07 | Sugiura Kinzoku Kk | Button, accessory, and manufacturing method thereof |
| JP4610663B1 (en) * | 2009-07-06 | 2011-01-12 | 株式会社日進産業 | Rail for railroad and method of painting railroad rail |
| WO2021184136A1 (en) * | 2020-03-20 | 2021-09-23 | Ortega Sazo Felipe Alejandro | A method and composition for forming a negative ion-generating plate based on tourmaline, zeolite, quartz and igneous rock for installation in air filters that allows harmful emissions to be reduced and increases fuel performance |
| CN114349395A (en) * | 2021-12-31 | 2022-04-15 | 贺州续宝矿业投资有限公司 | Functional artificial stone and preparation method thereof |
-
2000
- 2000-07-21 JP JP2000221365A patent/JP2002038023A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010000168A (en) * | 2008-06-19 | 2010-01-07 | Sugiura Kinzoku Kk | Button, accessory, and manufacturing method thereof |
| JP4581007B2 (en) * | 2008-06-19 | 2010-11-17 | 杉浦金属株式会社 | Buttons, ornaments and methods for producing them |
| JP4610663B1 (en) * | 2009-07-06 | 2011-01-12 | 株式会社日進産業 | Rail for railroad and method of painting railroad rail |
| JP2011012505A (en) * | 2009-07-06 | 2011-01-20 | Nisshin Sangyo:Kk | Railway rail and coating method for the same |
| WO2021184136A1 (en) * | 2020-03-20 | 2021-09-23 | Ortega Sazo Felipe Alejandro | A method and composition for forming a negative ion-generating plate based on tourmaline, zeolite, quartz and igneous rock for installation in air filters that allows harmful emissions to be reduced and increases fuel performance |
| CN114349395A (en) * | 2021-12-31 | 2022-04-15 | 贺州续宝矿业投资有限公司 | Functional artificial stone and preparation method thereof |
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