JPH05163049A - Artificial marble or imitation granite having excellent transparency and its production - Google Patents

Artificial marble or imitation granite having excellent transparency and its production

Info

Publication number
JPH05163049A
JPH05163049A JP33196591A JP33196591A JPH05163049A JP H05163049 A JPH05163049 A JP H05163049A JP 33196591 A JP33196591 A JP 33196591A JP 33196591 A JP33196591 A JP 33196591A JP H05163049 A JPH05163049 A JP H05163049A
Authority
JP
Japan
Prior art keywords
resin
artificial marble
acrylonitrile
acrylic
weight
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Withdrawn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
JP33196591A
Other languages
Japanese (ja)
Inventor
Hiroyuki Hirano
弘幸 平野
Hidetoshi Innami
英敏 印南
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.)
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co 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 Asahi Chemical Industry Co Ltd filed Critical Asahi Chemical Industry Co Ltd
Priority to JP33196591A priority Critical patent/JPH05163049A/en
Publication of JPH05163049A publication Critical patent/JPH05163049A/en
Withdrawn legal-status Critical Current

Links

Abstract

PURPOSE:To provide a molded product of acrylic artificial marble or acrylic imitation granite having more transparent and deeper feeling and its producing method by bringing refractive index of a matrix resin close to refractive index of a filler to reduce irregular reflection. CONSTITUTION:(1) The objective artificial marble or imitation granite in which an inorganic filler is dispersed in a synthetic resin matrix and the synthetic resin matrix is composed of 60-90wt.% acrylic resin and 10-40wt.% AS resin and copolymerization wt. ratio of acrylonitrile and styrene in the AS resin is in the range of 2.1-9.0wt. based on 1wt. acrylonitrile. (2) The artificial marble or imitation granite is produced by a casting method, using a blend liquid obtained by blending a syrup-like polymerizable composition liquid consisting of 60-90wt.% acrylic acid ester based monomer and 10-40wt.% AS resin selected from AS resins in which copolymerization wt. ratio of acrylonitrile and styrene is in the range of 2.1-9.0 based on 1 acrylonitrile with an inorganic filler.

Description

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

【0001】[0001]

【産業上の利用分野】この発明は改良された外観をもっ
た合成樹脂を母材とした人工大理石又は模造花こう岩及
びその製造法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an artificial marble or imitation granite using a synthetic resin having an improved appearance as a base material and a method for producing the same.

【0002】[0002]

【従来の技術】大理石、及び花こう岩は従来から代表的
石材として、その装飾的外観により広く一般に用いられ
ている。しかしながら、表面の研磨に要する費用が高く
つき、また建築用等の板状加工品では、脆く割れ易いこ
とから、強度を維持するには少なくとも20mmあるいはそ
れ以上の厚さを必要とする。従って高価となり、かつ高
比重のために非常に重くなり、運搬、壁面への取付け等
に特別の注意を要した。このため、大幅に使用が制約さ
れ、例えば1m2を越えるような大きな面積の製品は実
用化が困難であった。
2. Description of the Related Art Marble and granite have hitherto been widely used as typical stone materials due to their decorative appearance. However, the cost required for polishing the surface is high, and plate-shaped products for construction use are brittle and easily cracked, so that a thickness of at least 20 mm or more is required to maintain strength. Therefore, it becomes expensive and very heavy due to the high specific gravity, and special attention is required for transportation, mounting on a wall, and the like. For this reason, the use is greatly restricted, and it is difficult to put a product having a large area exceeding 1 m 2 into practical use.

【0003】そこで、従来から、表面研磨の必要がな
く、軽量で充分な強度を有し、取り扱い、取り付けの容
易な、大理石、花こう岩調の外観の美しい素材が嘱望さ
れていた。
Therefore, conventionally, there has been a demand for a material that does not require surface polishing, is lightweight, has sufficient strength, is easy to handle and attach, and has a beautiful marble or granite appearance.

【0004】天然石を模した合成樹脂を母材とした製品
には、大理石調の成形品が注型法により製造され、人工
大理石カウンター等として実用化されている。
As a product using a synthetic resin imitating natural stone as a base material, a marble-like molded product is manufactured by a casting method and put into practical use as an artificial marble counter or the like.

【0005】前記合成樹脂母材としては、実用的に充分
な強度を有し、優美な光沢と、良好な耐候性等の優れた
性能を兼ね備えたアクリル樹脂が広く使用されている。
As the synthetic resin base material, an acrylic resin having a practically sufficient strength and having excellent luster and excellent performance such as good weather resistance is widely used.

【0006】しかし、天然大理石の研磨面に近似した深
みのある透明感を有した成形品を、アクリル樹脂を母材
として注型法で製造することは実現されていない。
[0006] However, it has not been realized to manufacture a molded product having a depth and transparency similar to the polished surface of natural marble by a casting method using an acrylic resin as a base material.

【0007】また、天然の花こう岩の研磨面に近似した
深みを有し、しかも大粒の粒子が面方向のみならず、厚
み方向にも平均して散在し、立体感に富んだ斑点状模様
を呈する成形品を注型法で製造することもまたアクリル
樹脂を母材としたものは実現していない。
Further, it has a depth close to the polished surface of natural granite, and large particles are scattered on average not only in the surface direction but also in the thickness direction. It has not been realized that an acrylic resin as a base material is also manufactured by a casting method.

【0008】[0008]

【発明が解決しようとする課題】天然大理石の深みのあ
る透明感、及び天然花こう岩の深みのある立体感に富ん
だ斑点状模様を人工的に得られない理由としては、母材
アクリル樹脂の屈折率(nDを示す、以下同じ)が1.49
であるのに対し、天然石材としての質感が得られ、また
実用上の熱、薬品等に充分安定なこと、及びコスト上の
観点から充填材として広く使用されている水酸化アルミ
ニウムの屈折率は1.57、石英は同1.54と、これら無機質
充填材の屈折率はいずれも母材アクリル樹脂より大き
く、この結果これら充填材がアクリル樹脂母材に分散さ
れた従来の人工大理石、模造花こう岩では母材樹脂と充
填材粒子の界面において光の乱反射を生じ、白濁するこ
とから外観は透明感、深み感の劣った製品に仕上がるた
めである。
The reason why it is not possible to artificially obtain the speckled pattern rich in the deep transparency of natural marble and the deep three-dimensional effect of natural granite is the base acrylic resin. refractive index of (n indicates a D, hereinafter) is 1.49
On the other hand, the refractive index of aluminum hydroxide, which is widely used as a filler from the viewpoint of being able to obtain the texture of a natural stone material, being sufficiently stable against heat and chemicals in practical use, and from the viewpoint of cost, The refractive index of these inorganic fillers is 1.57, and that of quartz is 1.54, which is higher than that of the base acrylic resin.As a result, these artificial fillers are dispersed in the acrylic resin base material. This is because irregular reflection of light occurs at the interface between the material resin and the filler particles, and the product becomes white turbid, resulting in a product having an inferior transparent appearance and a poor sense of depth.

【0009】この発明は上記事情に鑑みなされたもので
ある。その目的は、母材樹脂の屈折率を充填材の屈折率
に近づけることで、前記乱反射を軽減し、より透明感、
深み感のあるアクリル系人工大理石、あるいはアクリル
系模造花こう岩の成形品を提供することにある。
The present invention has been made in view of the above circumstances. The purpose is to bring the refractive index of the base material resin close to the refractive index of the filler to reduce the irregular reflection, and to provide a more transparent feeling.
It is to provide a molded product of acrylic artificial marble or acrylic imitation granite with a sense of depth.

【0010】アクリル樹脂母材の屈折率を大きくする方
法としては、注型に際しスチレン系単量体を共重合する
ことが一般的に知られており、こうして得られた樹脂は
スチレン系単量体の共重合比が増加するに従い屈折率は
大きくなる。しかしながら、スチレンを使用した場合、
スチレン成分の増加に伴って硬化時間が長くなり、工業
生産上はラインスピードの低下につながり、問題となる
こと、及びこうして得られた成形品は耐候性が元のアク
リル樹脂に比較して低下し、製品の使用中に黄変する等
の不都合を生ずる。
As a method for increasing the refractive index of the acrylic resin base material, it is generally known to copolymerize a styrene-based monomer during casting, and the resin thus obtained is a styrene-based monomer. The refractive index increases as the copolymerization ratio of is increased. However, when using styrene,
As the styrene content increases, the curing time becomes longer, which leads to a decrease in the line speed in industrial production, which is a problem, and the molded product thus obtained has a lower weather resistance than the original acrylic resin. , Causing inconvenience such as yellowing during use of the product.

【0011】また、α−メチルスチレンの使用はより硬
化時間が延びること、及びブロモスチレンの場合は耐候
性がさらに低下し、かつ特殊な用途にしか使用されてお
らず、単量体の入手が工業的に困難であること等から問
題であった。
Further, the use of α-methylstyrene leads to a longer curing time, and in the case of bromostyrene, the weather resistance is further deteriorated, and it is used only for a special purpose. This is a problem because it is industrially difficult.

【0012】また、透明汎用樹脂で屈折率が大きなもの
として代表的なポリスチレン(屈折率1.59)をアクリル
酸エステル系単量体に溶解し、重合硬化した場合には白
濁不透明の樹脂しか得られないことは周知であり、透明
感のある人工大理石用の母材樹脂としては適当でない。
Further, when a typical polystyrene (refractive index: 1.59), which is a transparent general-purpose resin having a large refractive index, is dissolved in an acrylic acid ester-based monomer and polymerized and cured, only a cloudy and opaque resin is obtained. This is well known and is not suitable as a base material resin for transparent artificial marble.

【0013】[0013]

【課題を解決するための手段】この発明になる人工大理
石又は模造花こう岩は、合成樹脂母材に無機質充填材が
分散してなっており、合成樹脂母材がアクリル系樹脂60
〜90重量%と、AS樹脂10〜40重量%から構成され、該
AS樹脂のアクリロニトリルとスチレンの共重合比が重
量でアクリロニトリル1に対して、2.1〜9.0の範囲から
なることを特徴とする。
In the artificial marble or imitation granite according to the present invention, an inorganic filler is dispersed in a synthetic resin base material, and the synthetic resin base material is an acrylic resin 60.
.About.90% by weight and 10 to 40% by weight of AS resin, and the copolymerization ratio of acrylonitrile and styrene of the AS resin is in the range of 2.1 to 9.0 with respect to 1 acrylonitrile by weight.

【0014】他の一つの発明になる人工大理石の製造法
は、アクリル酸エステル系の単量体にAS樹脂を溶解し
てなるシロップ状の重合性組成液に、無機質充填材を混
合した配合液を用い、注型法により人工大理石を製造す
る方法であって、シロップ状重合性組成液がアクリル酸
エステル単量体60〜90重量%にアクリロニトリルとスチ
レンの共重合比が重量でアクリロニトリル1に対して2.
1〜9.0の範囲から選ばれたAS樹脂10〜40重量%を溶解
してなることを特徴とする。
Another method of producing an artificial marble according to the present invention is a mixed liquid in which an inorganic filler is mixed with a syrup-like polymerizable composition liquid obtained by dissolving an AS resin in an acrylic ester monomer. Is a method for producing an artificial marble by a casting method, wherein the syrup-like polymerizable composition liquid is 60 to 90% by weight of an acrylic acid ester monomer, and the copolymerization ratio of acrylonitrile and styrene is 1 to acrylonitrile by weight. 2.
It is characterized by dissolving 10 to 40% by weight of AS resin selected from the range of 1 to 9.0.

【0015】また、本発明においては、無機質充填材の
一部を白色、黒色、あるいは着色有彩の粒子で置換した
配合液を用い、斑点状模様等が散在した外観を有する模
様入り人工大理石とすることもできる。
Further, in the present invention, a patterned artificial marble having an appearance in which spotted patterns and the like are scattered is used by using a mixed solution in which a part of the inorganic filler is replaced with white, black, or colored chromatic particles. You can also do it.

【0016】すなわち、特定の組成を有するAS樹脂を
アクリル酸エステル系単量体に溶解配合し、このシロッ
プ状重合性組成液を硬化し母材樹脂とした場合に、該母
材樹脂は透明性に優れ、かつアクリル酸エステル系単量
体にAS樹脂を溶解配合しないものと比べ高い屈折率を
有しており、無機質充填材の屈折率に近似することで、
該無機質充填材を充填した人工大理石、及び前述の模様
入り人工大理石としたときに、成形品の透明感が著しく
改良される。
That is, when an AS resin having a specific composition is dissolved and blended in an acrylic acid ester type monomer and the syrup-like polymerizable composition liquid is cured to form a base material resin, the base material resin is transparent. And has a high refractive index as compared with one in which the AS resin is not dissolved and blended in the acrylic ester-based monomer, and by approximating the refractive index of the inorganic filler,
When the artificial marble filled with the inorganic filler and the patterned artificial marble described above are used, the transparency of the molded product is remarkably improved.

【0017】本発明のアクリル酸エステル系単量体は、
メタクリル酸メチルを主成分とし、これに共重合しうる
不飽和単量体、例えばアクリル酸メチル、メタクリル酸
エチル、メタクリル酸2−エチルヘキシル、酢酸ビニル
などの単量体、重合速度、及び性能に実質的な影響の少
ない範囲での少量のスチレン系単量体およびジビニルベ
ンゼン、エチレングリコールジメタクリレート、ジアリ
ルフタレートなどの架橋剤、その他紫外線吸収剤などの
安定剤、また着色剤などの添加が可能である。注型法に
よって人工大理石を製造する際には作業性向上のため、
上記アクリル酸エステル系単量体に通常はアクリル樹脂
を溶解し増粘することが一般に実施されている。
The acrylic ester type monomer of the present invention is
Unsaturated monomers containing methyl methacrylate as a main component and copolymerizable therewith, for example, monomers such as methyl acrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, vinyl acetate, etc. It is possible to add a small amount of styrene-based monomer and cross-linking agent such as divinylbenzene, ethylene glycol dimethacrylate, diallyl phthalate, stabilizers such as UV absorbers, and coloring agents, etc. . To improve workability when manufacturing artificial marble by the casting method,
It is generally practiced to dissolve an acrylic resin in the acrylic acid ester-based monomer to thicken it.

【0018】本発明に使用されるAS樹脂はこの増粘作
用をも目的としており、該AS樹脂はアクリロニトリル
とスチレンを主成分とし、重量比でアクリロニトリル1
に対してスチレンが2.1〜9.0の範囲から選ばれたもの
で、この範囲を外れると上記アクリル酸エステル系単量
体に溶解し、シロップ状重合性組成液を硬化して母材樹
脂とした場合に該母材樹脂が白濁して所期の目的を達成
することができなくなる。
The AS resin used in the present invention is also intended for this thickening action. The AS resin contains acrylonitrile and styrene as main components, and the acrylonitrile 1 is used in a weight ratio.
On the other hand, styrene is selected from the range of 2.1 to 9.0, and when it is out of this range, it is dissolved in the acrylic acid ester-based monomer, and the syrup-like polymerizable composition liquid is cured to form a base material resin. In addition, the base material resin becomes cloudy, and the intended purpose cannot be achieved.

【0019】溶解するAS樹脂の割合は、アクリル酸エ
ステル系単量体に対して、10〜40重量%が好ましく、10
重量%未満では母材樹脂の改良効果が充分でなく、透明
感が不満足なものとなり、さらに注型法による製造の際
に無機質充填材の沈降により製品が不均一となることか
ら適当ではない。
The proportion of the AS resin to be dissolved is preferably 10 to 40% by weight, based on the acrylic acid ester-based monomer.
If it is less than 10% by weight, the effect of improving the base material resin is not sufficient, the transparency is unsatisfactory, and the product is not uniform due to the sedimentation of the inorganic filler during the production by the casting method.

【0020】また40部を超えた場合、シロップの粘性が
高くなり、所定量の充填材が配合困難となること、及び
注型作業時に流動性が低いことに起因する充填不足等の
製品欠陥を生ずることから問題がある。
If it exceeds 40 parts, the viscosity of the syrup becomes high and it becomes difficult to mix a predetermined amount of the filler, and product defects such as insufficient filling due to low fluidity during casting work occur. There is a problem because it arises.

【0021】本発明において、母材樹脂は25〜70重量%
の範囲である。25重量%未満では外観、及び耐衝撃強度
等の物性値が良好な成形体となり難い。また、製造に際
し、重合性組成液量の割合が低くなり、充填材等を配合
した配合液の粘度が高くなり注型法による成形がむずか
しくなる。70重量%を越すと、製造に際して微粉末の無
機質充填材粒子の沈降が顕著になり、大理石、又は花こ
う岩に近似した外観を有し、物性値が優れた成形体が得
られなくなる。母材樹脂あるいは重合性組成液は好まし
くは30〜40重量%である。
In the present invention, the base material resin is 25 to 70% by weight.
The range is. If it is less than 25% by weight, it is difficult to obtain a molded article having good appearance and physical properties such as impact strength. Further, in the production, the ratio of the amount of the polymerizable composition liquid becomes low, the viscosity of the liquid mixture containing the filler and the like becomes high, and the molding by the casting method becomes difficult. When it exceeds 70% by weight, the precipitation of finely divided inorganic filler particles becomes remarkable during the production, and a molded product having an appearance similar to marble or granite and excellent physical properties cannot be obtained. The base resin or the polymerizable composition liquid is preferably 30 to 40% by weight.

【0022】また、使用される無機質充填材としては、
母材樹脂に天然大理石、又は天然みかげ石調の質感を付
与できる、水酸化アルミニウム、石英がその代表である
が、他に例えばクリストバライト、炭酸カルシウム、水
酸化マグネシウム、珪酸カルシウム等の使用も単独又は
混合して使用することが可能である。
Further, as the inorganic filler used,
Typical examples are aluminum hydroxide and quartz, which can impart a natural marble or natural granite-like texture to the base material resin, but other examples include the use of cristobalite, calcium carbonate, magnesium hydroxide, calcium silicate, etc., either alone or mixed. It is possible to use it.

【0023】これら充填材の平均粒径は2〜70μm、より
好適には5〜50μmである。
The average particle size of these fillers is 2 to 70 μm, more preferably 5 to 50 μm.

【0024】斑点状模様を有した人工大理石又は模造花
こう岩を得るために配合する大粒径粒子の割合は配合液
総量の1〜40重量%である。1重量%未満では柄感が乏し
くなり、40重量%を越えると柄感が濃厚となり、立体感
に富んだ外観を呈する成形品が得がたくなる。不透明な
粒子を 5〜25重量%の割合で用いるのがより好適であ
る。また、粒子の粒度は0.1mm以上であり、0.1mm未満で
は、その存在感が乏しく、平均した斑点状模様を形成す
る上で 3mm以下とするのが好ましい。大粒径の粒子の色
調は、製品の外観に大きな影響がある。一般の花こう岩
調とするには白色系と黒色系とを混合して用い、その割
合をかえることで、いわゆる白みかげ、または黒みかげ
とすることができる。また、着色有彩粒子を選び混入し
て赤みかげ等の天然には稀少のものとすることもでき
る。さらにはこれ以外の色調とすることも自由にでき
る。
The proportion of large-sized particles to be mixed in order to obtain artificial marble or imitation granite having a speckled pattern is 1 to 40% by weight of the total amount of the mixed solution. If it is less than 1% by weight, the pattern feeling becomes poor, and if it exceeds 40% by weight, the pattern feeling becomes rich and it becomes difficult to obtain a molded article having a three-dimensional appearance. It is more preferred to use the opaque particles in a proportion of 5 to 25% by weight. Further, the particle size of the particles is 0.1 mm or more, and if it is less than 0.1 mm, the presence thereof is poor, and it is preferably 3 mm or less in order to form an average spot-like pattern. The color tone of large particles has a great influence on the appearance of the product. To obtain a general granite tone, a mixture of white and black is used, and by changing the ratio, so-called white or black stains can be obtained. It is also possible to select and mix colored chromatic particles to make them rare in nature such as reddish stains. Further, it is possible to freely set a color tone other than this.

【0025】大粒径の無機質粒子としては、例えば玄武
岩、鉄鉱石、花こう岩、黒鉛等の天然鉱物の粉砕粒、あ
るいは煉瓦、陶器等の人工無機物質の粉砕粒が適当な例
として挙げられ、好ましくは比重 1.7以上で不透明なも
のである。具体例を挙げれば次の通りである。
Suitable examples of the large-sized inorganic particles include crushed particles of natural minerals such as basalt, iron ore, granite and graphite, or crushed particles of artificial inorganic substances such as bricks and pottery. It is preferably opaque with a specific gravity of 1.7 or more. Specific examples are as follows.

【0026】白色粒子…陶器、貝殻、硬石膏、 黒色粒子…黒鉛、無煙炭、黒色粘板岩(那智黒石)、黒
色大理石(美濃黒石)、 黒雲母、 着色有彩粒子…煉瓦、着色陶器、着色タイル、 大粒径の有機質粒子としては、例えば各種プラスチック
の不透明又は半透明品の粉砕粒が、装飾的効果を与える
上で選択が容易で、かつ工業的にも入手し易く簡便であ
る。
White particles: pottery, shells, anhydrite, black particles: graphite, anthracite, black slate (Nachi black stone), black marble (Mino black stone), biotite, colored chromatic particles: bricks, colored pottery, colored tiles, As the large-sized organic particles, for example, crushed particles of opaque or translucent products of various plastics are easy to select in terms of providing a decorative effect, and industrially available and simple.

【0027】これらプラスチック粉砕粒は、配合液とし
た場合にアクリル酸エステル系モノマーに不溶、又は簡
単に溶解しないことが好ましく、例えばポリエチレン、
ポリエステル、架橋ポリメチルメタクリレート等の一種
またはそれらの混合物が挙げられる。
It is preferable that these crushed plastic particles are insoluble or not easily dissolved in the acrylic acid ester-based monomer when it is used as a compounding liquid. For example, polyethylene,
One or a mixture of polyester, crosslinked polymethylmethacrylate, etc. may be mentioned.

【0028】他の大粒径有機質粒子としては、木材チッ
プ、短繊維等も挙げられ、もちろん大粒径の無機質、及
び有機質粒子を混合しても差しつかえない。
Other large-sized organic particles include wood chips, short fibers and the like. Of course, large-sized inorganic and organic particles may be mixed.

【0029】注型法により成形するには、シロップ状の
重合性組成液に無機質充填材および必要があれば大粒径
粒子を混合分散せしめた配合液に重合開始剤を添加し、
減圧下で脱泡処理した後、準備した金型に注入し重合硬
化せしめる。
In order to mold by the casting method, a polymerization initiator is added to a compounded liquid in which an inorganic filler and, if necessary, large-sized particles are mixed and dispersed in a syrup-like polymerizable composition liquid,
After defoaming treatment under reduced pressure, it is poured into a prepared mold to be polymerized and cured.

【0030】重合開始剤としては、ベンゾイルパーオキ
サイド、ラウロイルパーオキサイド、ジミリスチルパー
オキシジカーボネート等の過酸化物、アゾビスイソブチ
ロニトリル、アゾビスジメチルバレロニトリル等のアゾ
化合物などのラジカル重合開始剤が一般的に用いられ
る。
As the polymerization initiator, radical polymerization initiation of peroxides such as benzoyl peroxide, lauroyl peroxide, dimyristyl peroxydicarbonate, azo compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, etc. Agents are commonly used.

【0031】また、この組成液には充填材の分散性を高
めるために分散剤を配合することも一般的に行われてい
る。
It is also common practice to add a dispersant to the composition liquid in order to enhance the dispersibility of the filler.

【0032】[0032]

【作用】この発明は以上の構成からなる。この人工大理
石、又は模造花こう岩は、アクリル酸エステル系単量体
に特定の組成から成るAS樹脂を溶解したシラップから
得られる母材樹脂に、無機質充填材が主材として含有さ
れており、両者の屈折率が近似していることから、従来
にない優れた透明感を有したアクリル系人工大理石又は
模造花こう岩を提供するものである。
The present invention is constructed as described above. This artificial marble or imitation granite contains an inorganic filler as a main material in a base material resin obtained from a syrup obtained by dissolving an AS resin having a specific composition in an acrylate monomer. Since the refractive indices of both are similar, the present invention provides an acrylic artificial marble or imitation granite having an unprecedentedly excellent transparency.

【0033】また、この人工大理石を基材として、必要
に応じ大粒径粒子が分散含有された、立体感に富んだ斑
点状模様を有する人工大理石もまた提供するものであ
る。
Further, the present invention also provides an artificial marble having a speckled pattern rich in three-dimensional effect, in which large-sized particles are dispersed and contained as needed, using the artificial marble as a base material.

【0034】さらに同時に各種用途に適する実用的耐熱
性と強度を備えており、表面研磨の必要がなく、軽量で
取り扱いに優れた人工大理石又は模造花こう岩の製造が
可能となる。
At the same time, it is possible to produce artificial marble or imitation granite which has practical heat resistance and strength suitable for various uses, does not require surface polishing, is lightweight, and is excellent in handling.

【0035】[0035]

【実施例】以下、本発明を実施例をあげて詳述する。な
お、実施例における「部」はすべて「重量部」を示す。
EXAMPLES The present invention will be described in detail below with reference to examples. In addition, all "parts" in an Example show a "weight part."

【0036】実施例1 メタクリル酸メチル85部にAS樹脂(アクリロニトリル
(以下AN)とスチレン(以下ST)の重量比が1:3
の共重合体、屈折率1.57)15部を加えて、60℃にて撹拌
溶解の後、室温まで冷却し、エチレングリコールジメタ
クリレート 1部を加えシロップ状の重合性組成液とす
る。
Example 1 Methyl methacrylate (85 parts) was mixed with AS resin (acrylonitrile (hereinafter AN) and styrene (hereinafter ST)) in a weight ratio of 1: 3.
15 parts of the copolymer of 1.57) and a refractive index of 1.57) are added and dissolved by stirring at 60 ° C, then cooled to room temperature, and 1 part of ethylene glycol dimethacrylate is added to obtain a syrup-like polymerizable composition liquid.

【0037】 (原料配合液組成) 重合性組成液 33部 水酸化アルミニウム粉(平均粒径9μm) 67部 ジミリステルパーオキシジカーボネート 0.3部 上記配合物を室温にて20分間撹拌混合し、原料配合液を
得、その粘度は10ポイズであった(B型回転粘度計によ
る)。
(Composition of Raw Material Mixing Liquid) Polymerizable composition liquid 33 parts Aluminum hydroxide powder (average particle size 9 μm) 67 parts Dimylisterperoxydicarbonate 0.3 parts The above composition was stirred and mixed at room temperature for 20 minutes to mix the raw materials. A liquid was obtained, the viscosity of which was 10 poise (by a B-type rotational viscometer).

【0038】配合液は10分間減圧下で脱泡処理を行った
後、2枚のアルマイト処理したアルミニウム板を12mmφ
の軟質塩化ビニル樹脂製のガスケットで挾みシャコ万力
で固定した金型内に注入し、65℃の温水中に2時間浸漬
して重合硬化せしめ、その後120℃の空気浴中に5時間
放置して完全硬化せしめる。金型を開き得られた板状成
形体は、透明感のある大理石調の外観を呈していた。
The mixed solution was defoamed under reduced pressure for 10 minutes, and then two alumite-treated aluminum plates were cut to 12 mmφ.
Crushed with a soft vinyl chloride resin gasket of No. 1 and poured into a mold fixed with a vise, and immersed in warm water at 65 ° C for 2 hours to polymerize and cure, then left in an air bath at 120 ° C for 5 hours. And completely cure. The plate-shaped molded product obtained by opening the mold had a marble appearance with a transparent feeling.

【0039】実施例2 AS樹脂の共重合重量比がAN:ST=1:7、屈折率
1.58であるものを用いた他は実施例1と同様に板状成形
体を得る。成形体は透明感のある大理石調の外観を呈し
ていた。
Example 2 The copolymerization weight ratio of AS resin is AN: ST = 1: 7, and the refractive index is
A plate-shaped molded body is obtained in the same manner as in Example 1 except that 1.58 is used. The molded body had a transparent, marble-like appearance.

【0040】実施例3 (原料配合液組成) 重合性組成液 30部 石英粉(平均粒径25μm) 35部 水酸化アルミニウム粉(平均粒径15μm) 15部 粘板岩(那智黒石)粉砕粒(粒度0.2〜1.5mm) 5部 白色陶器粉砕粒(粒度0.3〜2.5mm) 15部 ジミリステルパーオキシジカーボネート 0.3部 実施例1と同様にして上記組成の配合液をつくり、板状
の成形体を得る。この成形体は外観上斑点状模様が均一
に散在し、かつ表面近くの黒色、及び白色斑点が透けて
見えるいわゆる深みのある美しい模様入り大理石調であ
った。
Example 3 (Composition of raw material compounding liquid) Polymerizable composition liquid 30 parts Quartz powder (average particle size 25 μm) 35 parts Aluminum hydroxide powder (average particle size 15 μm) 15 parts Slate (Nachi Kuroishi) crushed particles (particle size 0.2 ~ 1.5 mm) 5 parts White porcelain ground particles (particle size 0.3-2.5 mm) 15 parts Dimylisterperoxydicarbonate 0.3 parts In the same manner as in Example 1, a compounded solution having the above composition is prepared to obtain a plate-shaped molded body. This molded product had a so-called deep and beautiful patterned marble tone in which the speckled pattern was scattered evenly in appearance, and black and white spots near the surface were transparent.

【0041】なお、上記実施例における平均粒径は
(株)島津製作所製の粒度分布測定装置(SA−CP2
型)を用いて測定した値であり、粒度はフルイにより、
記録範囲外の小粒子および大粒子を除いたものである。
The average particle size in the above examples is the particle size distribution measuring device (SA-CP2) manufactured by Shimadzu Corporation.
It is a value measured by using
It excludes small particles and large particles outside the recording range.

【0042】比較例1 重合性組成液を作る際に、溶解する合成樹脂としてポリ
メタクリル酸メチルを主成分とするアクリル樹脂(登録
商標デルペット80N・旭化成工業株式会社製)を用いた
他は実施例1と同様にして板状の成形体をつくる。
Comparative Example 1 Acrylic resin (registered trademark Delpet 80N, manufactured by Asahi Kasei Co., Ltd.) containing polymethylmethacrylate as a main component was used as a dissolving synthetic resin when a polymerizable composition liquid was prepared. A plate-shaped molded body is prepared in the same manner as in Example 1.

【0043】この成形体は実施例1で得られた成形体に
比較して、その外観が白濁しており、透明感が少なかっ
た。
Compared with the molded product obtained in Example 1, this molded product had a cloudy appearance and was less transparent.

【0044】比較例2 メタクリル酸メチル51部にスチレン34部とMS樹脂(登
録商標エスチレンMS600 、メタクリル酸メチルとスチ
レンの共重合体・新日鉄化学株式会社製)15部を用いた
他は実施例1と同様にして板状の成形体を得ようとした
が、65℃の温水中に4時間浸漬後も内容物が軟らかく、
良好な板状成形体を得られなかった。
Comparative Example 2 Example 1 except that 51 parts of methyl methacrylate and 34 parts of styrene and 15 parts of MS resin (registered trademark Estyrene MS600, a copolymer of methyl methacrylate and styrene, manufactured by Nippon Steel Chemical Co., Ltd.) were used. I tried to obtain a plate-shaped molded body in the same manner as in, but the contents were soft even after being immersed in warm water at 65 ° C for 4 hours,
A good plate-shaped molded product could not be obtained.

【0045】比較例3 ANとSTの共重合比を変えた各種AS樹脂を使用して
実施例1と同様にシロップ状の重合性組成液を得、この
重合性組成液を10分間減圧下で脱泡処理を行った後、内
径12mmの試験管に注入密閉し、50℃の温水中に16時間浸
漬して重合硬化せしめ、その後 120℃の空気浴中に5時
間放置して完全硬化せしめて、外観を評価した。
Comparative Example 3 A syrup-like polymerizable composition liquid was obtained in the same manner as in Example 1 by using various AS resins having different copolymerization ratios of AN and ST, and the polymerizable composition liquid was kept under reduced pressure for 10 minutes. After defoaming, inject into a test tube with an inner diameter of 12 mm, seal it, and soak it in warm water at 50 ° C for 16 hours to polymerize and cure it, then leave it in an air bath at 120 ° C for 5 hours to completely cure it. , The appearance was evaluated.

【0046】結果をまとめて表1に示す。The results are summarized in Table 1.

【0047】[0047]

【表1】 [Table 1]

【0048】[0048]

【発明の効果】この発明は以上の通りであり、この人工
大理石又は模造花こう岩は(1) 天然の大理石の研磨面に
酷似した透明感のある外観を有し、(2) 必要により天然
の花こう岩の研磨面に近似した深みのある、立体感に富
んだ斑点状模様を付すことが可能で、(3) 軽量であって
運搬、取付け等の取扱性が優れている、(4) 実用上充分
な強度を有する。
EFFECTS OF THE INVENTION The present invention is as described above. This artificial marble or imitation granite has (1) a transparent appearance that closely resembles the polished surface of natural marble, and (2) natural stone if necessary. It is possible to add a spotted pattern with a depth that is similar to the polished surface of granite, and is rich in three-dimensionality. (3) Light weight and excellent handling such as transportation and installation. ) It has practically sufficient strength.

【0049】したがって、天然の大理石、又は花こう岩
等に代わり広範囲の用途に用いることが可能となる。
Therefore, it can be used in a wide range of applications in place of natural marble or granite.

【0050】また、この人工大理石の製造法によれば原
料配合液を注型法により硬化成形するに際し、硬化時間
の遅延は無く、安定した工程によってつくることができ
る。
Further, according to this method for producing artificial marble, when the raw material-blended liquid is cured and molded by the casting method, there is no delay in the curing time, and it can be produced by a stable process.

───────────────────────────────────────────────────── 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 C08K 3/00 KJQ 7167−4J E04C 2/20 F 8504−2E // B29L 31:10 4F ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location C08K 3/00 KJQ 7167-4J E04C 2/20 F 8504-2E // B29L 31:10 4F

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 合成樹脂母材に、無機質充填材が分散さ
れてなる人工大理石であって、合成樹脂母材がアクリル
系樹脂60〜90重量%とAS樹脂10〜40重量%から構成さ
れ、該AS樹脂のアクリロニトリルとスチレンの共重合
比が重量でアクリロニトリル1に対して2.1〜9.0の範囲
からなる人工大理石又は模造花こう岩。
1. An artificial marble in which an inorganic filler is dispersed in a synthetic resin base material, wherein the synthetic resin base material comprises 60 to 90% by weight of an acrylic resin and 10 to 40% by weight of an AS resin, An artificial marble or imitation granite in which the copolymerization ratio of acrylonitrile and styrene of the AS resin is in the range of 2.1 to 9.0 based on 1 of acrylonitrile.
【請求項2】 アクリル酸エステル系の単量体60〜90重
量%と、アクリロニトリルとスチレンの共重合比が重量
でアクリロニトリル1に対して2.1〜9.0の範囲から選ば
れたAS樹脂10〜40重量%からなるシロップ状の重合性
組成液に、無機質充填材を混合した配合液を用い、注型
法により人工大理石又は模造花こう岩を製造する方法。
2. A resin containing 60 to 90% by weight of an acrylic acid ester-based monomer and 10 to 40% by weight of an AS resin selected from the range of 2.1 to 9.0 with respect to 1 acrylonitrile by a copolymerization ratio of acrylonitrile and styrene. %, A method for producing artificial marble or imitation granite by a casting method using a compounding liquid in which an inorganic filler is mixed with a syrup-like polymerizable composition liquid consisting of 10% by weight.
JP33196591A 1991-12-16 1991-12-16 Artificial marble or imitation granite having excellent transparency and its production Withdrawn JPH05163049A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP33196591A JPH05163049A (en) 1991-12-16 1991-12-16 Artificial marble or imitation granite having excellent transparency and its production

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP33196591A JPH05163049A (en) 1991-12-16 1991-12-16 Artificial marble or imitation granite having excellent transparency and its production

Publications (1)

Publication Number Publication Date
JPH05163049A true JPH05163049A (en) 1993-06-29

Family

ID=18249630

Family Applications (1)

Application Number Title Priority Date Filing Date
JP33196591A Withdrawn JPH05163049A (en) 1991-12-16 1991-12-16 Artificial marble or imitation granite having excellent transparency and its production

Country Status (1)

Country Link
JP (1) JPH05163049A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109159250A (en) * 2018-10-31 2019-01-08 广东博德精工建材有限公司 A kind of production method of the transparent jade brick with cubic texture

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109159250A (en) * 2018-10-31 2019-01-08 广东博德精工建材有限公司 A kind of production method of the transparent jade brick with cubic texture

Similar Documents

Publication Publication Date Title
JP4754579B2 (en) Artificial marble having crack pattern and manufacturing method thereof
EP0362884B1 (en) Granite-like artificial stone
JP3727658B2 (en) Acrylic sheet in which colorant and inorganic filler are uniformly distributed before and after thermoforming
AU2009327752B2 (en) Marble chips for an artificial marble, manufacturing method thereof, and artificial marble comprising same
US5756211A (en) Method of manufacturing high filler content plastics having a glitter appearance
EP0516299B1 (en) Highly filled, polymerisable compositions
AU2006346574B2 (en) Marble chip, method for preparing the same and artificial marble using the same
EP0088633B1 (en) Use of iron oxide pigments in a polymethyl methacrylate article
WO1991001353A1 (en) Resin-based artificial marble compositions
KR20040005044A (en) Artificial Marble Having Marble Chips Not Settled Down
KR100609990B1 (en) Composition for Artificial Marble Having Metal Gloss
CA2233149C (en) Thermoformable acrylic sheet having uniform distribution of color and mineral filler
JPH05163049A (en) Artificial marble or imitation granite having excellent transparency and its production
KR101685254B1 (en) Transparent artificial marble chips having stripe texture and artificial marble using the same
JPH0532720A (en) Acrylic resin premix and production of acrylic scagliolia
KR100609986B1 (en) Composition for Artificial Marble Having a Microscopic Powdery Chip
JP2550164B2 (en) Granite-like artificial stone manufacturing method
JP2813527B2 (en) Marble-like article with improved strength and method for producing the same
KR20170066938A (en) A method for manufacturing crunch chip, crunch chip manufactured by thereof and artificial marble comprising the crunch chip
KR100609987B1 (en) Translucent Artificial Marble Composition
JP2005272175A (en) Acrylic-based artificial marble excellent in transparency feeling
KR950002387B1 (en) Acrylic resin composition for artificial marble manufacture
JP3127537U (en) Acrylic artificial stone
JPH0912823A (en) Synthetic resin molding material and production of molding from the same
KR100898555B1 (en) Curable Composition Having Good Scratch-Resistance and Processability, Cured Article Thereof, and Method for Preparing the Same

Legal Events

Date Code Title Description
A300 Withdrawal of application because of no request for examination

Free format text: JAPANESE INTERMEDIATE CODE: A300

Effective date: 19990311