JPH05319886A - Composition for artificial stone - Google Patents
Composition for artificial stoneInfo
- Publication number
- JPH05319886A JPH05319886A JP15152392A JP15152392A JPH05319886A JP H05319886 A JPH05319886 A JP H05319886A JP 15152392 A JP15152392 A JP 15152392A JP 15152392 A JP15152392 A JP 15152392A JP H05319886 A JPH05319886 A JP H05319886A
- Authority
- JP
- Japan
- Prior art keywords
- water
- composition
- artificial stone
- resin
- metakaolin
- 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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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、天然石の質感を有する
人造石材を製造するための組成物に関する。この人造石
材用組成物は、労働環境上好ましくない有機溶媒を使用
することなく、水を用いて混練するだけで天然石の質感
を保有した硬化体となるという特性をもっている。FIELD OF THE INVENTION The present invention relates to a composition for producing an artificial stone material having a texture of natural stone. This composition for an artificial stone material has a characteristic that it becomes a hardened body having the texture of natural stone simply by kneading with water without using an organic solvent which is unfavorable in the working environment.
【０００２】[0002]
【従来の技術】建材に対する要求の多様化に伴い、各種
の天然石材のみならず、人造石材が近年広範に使用され
つつある。中でも、有機系樹脂を使用した人造石材はそ
の形状の多様化の容易さもあって、種々の組成のものが
開発されている。これらの人造石材は、天然石を粉砕し
た石粉を有機系樹脂で練り固めたものが主体である。こ
のような人造石材の製造においては、成形時のハンドリ
ングその他の特性を改善するために、何らかの有機系溶
媒を使用するのが一般的である。しかしながら、これら
の有機系溶媒には、人体に好ましくないものが多く、労
働環境上有機溶媒を使用しないものが望まれていた。有
機系溶媒を使用しなくても実用上故障のないハンドリン
グ特性が得られる樹脂として水溶性の樹脂があるが、こ
れを単に天然石を粉砕した石粉と混ぜ、成形・固化した
ものは強度が低く、人造石材として実用に供し得ないも
のであった。2. Description of the Related Art With the diversification of requirements for building materials, not only various natural stone materials but also artificial stone materials have been widely used in recent years. Among them, artificial stone materials using organic resins have been developed with various compositions because the shapes thereof are easy to diversify. These artificial stone materials are mainly composed of stone powder obtained by crushing natural stone and kneaded with an organic resin. In manufacturing such an artificial stone material, it is common to use some sort of organic solvent in order to improve handling and other characteristics during molding. However, many of these organic solvents are not suitable for the human body, and there has been a demand for a solvent that does not use an organic solvent in the work environment. There is a water-soluble resin as a resin that can get handling characteristics practically without using an organic solvent, but this is simply mixed with stone powder obtained by crushing natural stone, the one that is molded and solidified has low strength, It could not be put to practical use as an artificial stone material.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、水溶
性有機樹脂を用いて水と混練して硬化させることによ
り、有機系溶媒を使用して石粉と樹脂との混合物を硬化
させた場合に匹敵する強度が得られ、しかも、天然石の
質感が得られる人造石用材料を提供するにある。The object of the present invention is to cure a mixture of stone powder and resin by using an organic solvent by kneading and curing with water using a water-soluble organic resin. The purpose of the present invention is to provide a material for an artificial stone, which is capable of obtaining a strength comparable to that of the above-mentioned material and which can also obtain the texture of natural stone.
【０００４】[0004]
【課題を解決するための手段】上記の目的は、メタカオ
リンとクエン酸と水溶性メラミン樹脂または水溶性フェ
ノール樹脂の少なくとも一種とからなることを特徴とす
る人造石材用組成物によって達成される。The above object is achieved by a composition for an artificial stone material comprising metakaolin, citric acid, and at least one of a water-soluble melamine resin and a water-soluble phenol resin.
【０００５】本発明に使用するメタカオリンとしては、
天然のカオリナイトを約５００℃以上、特に６００℃〜
８００℃で加熱して脱水酸基化することにより得られる
ものが製造コストの面からは好適であるが、硬化体の白
色度を向上させる場合には、人工的に合成される人工カ
オリンを使用しても良い。本発明の人造石材用組成物に
おいては、メタカオリンを使用することが必須であり、
加熱による脱水酸基化の工程を経由しない単なるカオリ
ナイトを使用した場合には、メタカオリンを使用した場
合に比較して、常温下での硬化時間が長くなると同時
に、硬化体自体の強度も低くなり好ましくない。As the metakaolin used in the present invention,
Natural kaolinite is about 500 ℃ or more, especially 600 ℃ ~
What is obtained by heating at 800 ° C. to dehydroxylate is preferable from the viewpoint of manufacturing cost, but when improving the whiteness of the cured product, artificially synthesized artificial kaolin is used. May be. In the composition for artificial stone material of the present invention, it is essential to use metakaolin,
In the case of using mere kaolinite which does not go through the step of dehydroxylation by heating, the curing time at room temperature is longer than that in the case of using metakaolin, and at the same time, the strength of the cured product itself is low, which is preferable. Absent.
【０００６】本発明においては水溶性樹脂として水溶性
メラミン樹脂および水溶性フェノール樹脂の中から選ば
れた少くとも一種を用いる。水溶性メラミン樹脂はメラ
ミンとホルムアルデヒドまたは低級脂肪族アルデヒドと
の縮合により得られる樹脂であり、また、水溶性フェノ
ール樹脂はフエールとホルムアルデヒドまたは低級脂肪
族アルデヒドとを縮合させて得られる樹脂である。In the present invention, at least one selected from water-soluble melamine resin and water-soluble phenol resin is used as the water-soluble resin. The water-soluble melamine resin is a resin obtained by condensing melamine with formaldehyde or a lower aliphatic aldehyde, and the water-soluble phenolic resin is a resin obtained by condensing phenyl with formaldehyde or a lower aliphatic aldehyde.
【０００７】メタカオリンと水溶性樹脂との配合比率
は、メタカオリン１００重量部に対して、水溶性樹脂固
形分を１重量部から４０重量部、好ましくは、１０重量
部から２０重量部である。水溶性固形分の配合比率が１
重量部より少ないと、実用的な流動性を得るための混練
水量を多くせざるを得ず、結果として、常温での硬化時
間が長くなると同時に、硬化体自体の曲げ強度も低くな
り好ましくない。この配合量が４０重量部を越えると、
メタカオリン粒子相互の間隔が不必要に大きくなり、そ
の間を樹脂が占めることになり、結果として、圧縮強度
が低くなり、好ましくない。The mixing ratio of metakaolin and water-soluble resin is 1 to 40 parts by weight, preferably 10 to 20 parts by weight, of the solid content of the water-soluble resin to 100 parts by weight of metakaolin. Mixing ratio of water-soluble solids is 1
If the amount is less than the amount by weight, the amount of kneading water for obtaining practical fluidity is inevitably increased, and as a result, the curing time at room temperature becomes longer and at the same time, the bending strength of the cured product itself becomes low, which is not preferable. If this amount exceeds 40 parts by weight,
The interval between the metakaolin particles becomes unnecessarily large, and the resin occupies the space between them, resulting in low compressive strength, which is not preferable.
【０００８】本発明の人造石材用組成物においては、水
溶性樹脂に硬化剤としてクエン酸を併用する。クエン酸
の併用によって人造石材用組成物から高い圧縮強度を有
する硬化体が得られる。クエン酸を用いることによっ
て、水溶性メラミン樹脂および水溶性フェノール樹脂の
硬化剤として知られている他の多くの硬化剤を用いた場
合と比較して、より強度の高い硬化体が得られる。クエ
ン酸の配合比率は、水溶性樹脂固形分１００重量部に対
して３０〜１００重量部、好ましくは、４５〜５５重量
部である。このクエン酸の配合量が１００重量部を越え
たり、または、３０重量部より少なくなると圧縮強度が
弱くなり、実用性に欠け好ましくない。In the artificial stone material composition of the present invention, citric acid is used in combination with the water-soluble resin as a curing agent. By using citric acid in combination, a cured product having high compressive strength can be obtained from the composition for artificial stone material. By using citric acid, a cured product having higher strength can be obtained as compared with the case where many other curing agents known as curing agents for water-soluble melamine resin and water-soluble phenol resin are used. The mixing ratio of citric acid is 30 to 100 parts by weight, preferably 45 to 55 parts by weight, based on 100 parts by weight of the water-soluble resin solid content. If the blending amount of citric acid exceeds 100 parts by weight or is less than 30 parts by weight, the compressive strength becomes weak, which is unpractical and not preferable.
【０００９】本発明の人造石材用組成物は、適量の水を
加えて混練し、適当な型枠に流し込み、硬化させること
により天然石の質感を有する人造石材となる。人工石材
用組成物と混練する水の量は、硬化体の強度を考慮すれ
ば型枠への流し込みなどのハンドリング上の許容範囲内
において、なるべく少ないほうが好ましいが、実用上
は、人工石材用組成物１００重量部に対して３０〜５０
重量部、好ましくは４０重量部である。The artificial stone material composition of the present invention is kneaded by adding an appropriate amount of water, poured into an appropriate mold, and hardened to obtain an artificial stone material having a texture of natural stone. The amount of water to be kneaded with the composition for artificial stone material is preferably as small as possible within the allowable range of handling such as pouring into a mold in consideration of the strength of the hardened body, but in practice, the composition for artificial stone material is preferable. 30 to 50 per 100 parts by weight
It is 40 parts by weight, preferably 40 parts by weight.
【００１０】本発明の人造石材用組成物は、例えば、各
成分を粉体で混合し、水を加えて混練するか、または、
あらかじめ前記組成物の一部を水に溶解させ、これを残
部と混練して用いることができる。混練物を適当な型枠
に流し込み、常温または必要に応じて約５０〜６０℃の
養生条件下で硬化させることにより目的とする人造石材
が得られる。The artificial stone material composition of the present invention is prepared, for example, by mixing the respective components in powder form and adding water to knead them, or
It is possible to dissolve a part of the composition in water in advance and knead it with the rest to use. The target artificial stone material is obtained by pouring the kneaded product into an appropriate mold and curing at room temperature or, if necessary, under curing conditions of about 50 to 60 ° C.
【００１１】本発明の人造石材組成物には、所望なら
ば、骨材として花崗岩のような天然石材を混合すること
ができる。但し、本発明の組成物から得られる人造石材
は不透明なので、型枠に流し込んで製作したままの製品
では、骨材の審美性は十分に活性されない。さらに、本
発明の人造石材用組成物には仮焼長石粉を混合すること
ができ、その添加量を変えることによって強度低下をも
たらすことなくクリーム色に着色することができる。そ
して、その濃度の異なるものを交互に積層して大理石調
の人造石材を得ることができる。If desired, the artificial stone composition of the present invention may be mixed with a natural stone material such as granite as an aggregate. However, since the artificial stone material obtained from the composition of the present invention is opaque, the aesthetic property of the aggregate is not sufficiently activated in the product as cast and produced. Further, the composition for artificial stone material of the present invention can be mixed with calcined feldspar powder, and by changing the addition amount thereof, it can be colored in cream color without lowering the strength. And, the artificial stone material having a marble tone can be obtained by alternately laminating materials having different concentrations.
【００１２】[0012]
【作用】本発明の人造石材組成物においては、水溶性メ
ラミン樹脂または水溶性フェノール樹脂の水酸基とクエ
ン酸のカルボキシル基とがエステル化反応を起こし、さ
らに、クエン酸は、表面活性が高められたメタカオリン
中のＡｌ3+とキレート化反応を起こすため、本発明の組
成物から得られる石材は、単なるファンデルワールス結
合による混合物と比較して大きな強度を発現する。In the artificial stone material composition of the present invention, the hydroxyl group of the water-soluble melamine resin or the water-soluble phenol resin and the carboxyl group of citric acid undergo an esterification reaction, and further, the surface activity of citric acid is increased. Due to the chelation reaction with Al 3+ in metakaolin, the stone obtained from the composition of the present invention develops a greater strength compared to a mixture with only van der Waals bonds.
【００１３】[0013]
【実施例】次に実施例によって本発明を更に具体的に説
明するが、本発明はその要旨を越えない限り、以下の実
施例に制約されるものではない。実施例１ 人造石試料を下記のように調製した。すなわち、陶磁器
用の天然カオリナイトを電気炉を使い８００℃で３時間
仮焼し、調製用のメタカオリンを得た。このメタカオリ
ン１００重量部に対して、市販の水溶性メラミン樹脂
（ヘキストジャパン（株）製「マドリット ９０９」と
無水クエン酸と水とを表１に示す割合で、配合し、２０
℃において混練した。混練水の配合量は固型組成物に基
づき４０重量％とした。混練物は型枠内に入れ、６０℃
にセットされた乾燥炉内で１日養成して、直径６ｍｍ、
高さ１２ｍｍの円柱供試体を得た。この供試体について
圧縮強度を測定した。圧縮試験機のヘッドスピードは２
インチ／分とした。測定結果は表１に示す。EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. Example 1 An artificial stone sample was prepared as follows. That is, natural kaolinite for ceramics was calcined in an electric furnace at 800 ° C. for 3 hours to obtain metakaolin for preparation. To 100 parts by weight of this metakaolin, a commercially available water-soluble melamine resin (“Madrit 909” manufactured by Hoechst Japan KK), anhydrous citric acid and water were mixed at a ratio shown in Table 1, and 20
Kneading was carried out at ℃. The blending amount of kneading water was 40% by weight based on the solid composition. Put the kneaded product in the mold, 60 ℃
1 day in a drying oven set to a diameter of 6 mm,
A cylindrical specimen having a height of 12 mm was obtained. The compressive strength of this sample was measured. Head speed of compression tester is 2
Inches / minute. The measurement results are shown in Table 1.
【００１４】[0014]
【表１】 [Table 1]
【００１５】比較例１ 比較のために、メタカオリンに代えて天然のカオリナイ
トを用いた他は実施例１と全く同様にして供試体を作成
し、圧縮強度を測定した。結果を表２に示す。 Comparative Example 1 For comparison, a specimen was prepared in the same manner as in Example 1 except that natural kaolinite was used in place of metakaolin, and the compressive strength was measured. The results are shown in Table 2.
【００１６】[0016]
【表２】 [Table 2]
【００１７】比較例２ メチロールメラミンの硬化剤として広く市販され、用い
られているスルホン酸基を含有する有機系硬化剤を、ク
エン酸に代替して用いた他は実施例１と同様にして供試
体を作成し、圧縮強度を測定した。結果を表３に示す。 Comparative Example 2 The same procedure as in Example 1 was carried out except that citric acid was used in place of the organic curing agent containing a sulfonic acid group widely used as a curing agent for methylolmelamine. A sample was prepared and the compressive strength was measured. The results are shown in Table 3.
【００１８】[0018]
【表３】 [Table 3]
【００１９】上記実施例から明らかなように、本発明に
係わる人造石材用組成物は、労働環境上好ましくない有
機溶媒を用いることなく、単に水と混練するだけで、人
造石材として実用に耐えられる強度が得られる。この場
合、カオリンを脱水酸基化したメタカオリンを使用する
ことが必要で、比較例１にみられるように、単なる乾燥
カオリンを使用した場合には、強度の高い硬化体は望め
ない。As is clear from the above examples, the composition for artificial stone material according to the present invention can be practically used as an artificial stone material by simply kneading with water without using an organic solvent which is not preferable in the working environment. Strength is obtained. In this case, it is necessary to use metakaolin in which kaolin is dehydroxylated, and as seen in Comparative Example 1, when simply dry kaolin is used, a cured product having high strength cannot be expected.
【００２０】これは、カオリンの脱水酸基化の過程でカ
オリンの結晶構造が崩れ、その結果、硬化体の強度の増
加につながる何らかの反応が生起しているものと推測さ
れる。また、この反応の生起にはクエン酸が大きく寄与
すると考えられる。発明者らの実験では、水溶性メラミ
ン樹脂および水溶性フェノール樹脂の硬化剤として知ら
れている他の多くのもの（比較例２に記載のスルホン酸
基含有硬化剤を含め、）を用いた場合には、クエン酸を
用いたときに得られる程度の高い強度をもつ硬化体は得
られなかった。It is presumed that the crystal structure of kaolin collapses in the process of dehydroxylation of kaolin, and as a result, some reaction that causes an increase in the strength of the cured product occurs. In addition, it is considered that citric acid greatly contributes to the occurrence of this reaction. In the experiments conducted by the inventors, when many other known curing agents for water-soluble melamine resins and water-soluble phenolic resins (including the sulfonic acid group-containing curing agent described in Comparative Example 2) were used. However, a cured product having a strength as high as that obtained by using citric acid could not be obtained.
【００２１】実施例１による硬化体の質感は、メタカオ
リンとメラミン樹脂との相互作用により、研磨をしなく
ても艶のあるもので、天然石を研磨したものと類似して
いた。なお、水溶性のフェノール樹脂を用いた実験で
も、同様な結果が得られたが、硬化体がフェノール樹脂
特有の黄色味を帯びており、着色の自由度から言えば、
水溶性フェノール樹脂よりも水溶性メラミン樹脂のほう
が好ましい。The texture of the cured product of Example 1 was glossy without polishing due to the interaction between metakaolin and melamine resin, and was similar to that of natural stone. Similar results were obtained in experiments using a water-soluble phenolic resin, but the cured product has a yellowish color peculiar to the phenolic resin, and from the degree of freedom of coloring,
Water-soluble melamine resins are preferred over water-soluble phenolic resins.
【００２２】[0022]
【発明の効果】本発明の人造石材用組成物によれば、労
働環境上好ましくない有機溶媒を用いることなく、単
に、水と混練するだけで、従来の有機系溶媒と硬化性樹
脂を用いて得られる人造石材に匹敵する強度と、天然石
の質感を有する人造石材を簡易に得ることができる。According to the composition for an artificial stone material of the present invention, a conventional organic solvent and a curable resin are used by simply kneading with water without using an organic solvent which is not preferable in a working environment. It is possible to easily obtain an artificial stone material having a strength comparable to that of the obtained artificial stone material and a texture of natural stone.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０４Ｂ 14:10） Ｚ 2102−4Ｇ Front page continuation (51) Int.Cl. 5 Identification code Office reference number FI technical display area C04B 14:10) Z 2102-4G
Claims (2)
ン樹脂または水溶性フェノール樹脂の少なくとも一種と
からなることを特徴とする人造石材用組成物。1. A composition for an artificial stone material comprising metakaolin, citric acid, and at least one of a water-soluble melamine resin and a water-soluble phenol resin.
オリナイトを加熱することにより脱水酸基化したもので
ある請求項１に記載の人造石材用組成物。2. The composition for an artificial stone material according to claim 1, wherein the metakaolin is dehydroxylated by heating natural or artificial kaolinite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15152392A JP3123814B2 (en) | 1992-05-19 | 1992-05-19 | Composition for artificial stone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15152392A JP3123814B2 (en) | 1992-05-19 | 1992-05-19 | Composition for artificial stone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05319886A true JPH05319886A (en) | 1993-12-03 |
| JP3123814B2 JP3123814B2 (en) | 2001-01-15 |
Family
ID=15520382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15152392A Expired - Fee Related JP3123814B2 (en) | 1992-05-19 | 1992-05-19 | Composition for artificial stone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3123814B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009120469A (en) * | 2007-10-22 | 2009-06-04 | Hitoshi Murakami | Method for effective use of metakaolin in paper sludge ash and coal ash and device for manufacturing the same |
| CN113480234A (en) * | 2021-07-16 | 2021-10-08 | 湖北联弘新材料科技股份有限公司 | Production and manufacturing process of novel artificial stone |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100971494B1 (en) | 2008-05-23 | 2010-07-21 | 포항공과대학교 산학협력단 | Area-variable capacitive sensor having a mechanical guide |
-
1992
- 1992-05-19 JP JP15152392A patent/JP3123814B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009120469A (en) * | 2007-10-22 | 2009-06-04 | Hitoshi Murakami | Method for effective use of metakaolin in paper sludge ash and coal ash and device for manufacturing the same |
| CN113480234A (en) * | 2021-07-16 | 2021-10-08 | 湖北联弘新材料科技股份有限公司 | Production and manufacturing process of novel artificial stone |
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| JP3123814B2 (en) | 2001-01-15 |
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