JPH0717426B2 - Resin composition for artificial marble - Google Patents
Resin composition for artificial marbleInfo
- Publication number
- JPH0717426B2 JPH0717426B2 JP2294916A JP29491690A JPH0717426B2 JP H0717426 B2 JPH0717426 B2 JP H0717426B2 JP 2294916 A JP2294916 A JP 2294916A JP 29491690 A JP29491690 A JP 29491690A JP H0717426 B2 JPH0717426 B2 JP H0717426B2
- Authority
- JP
- Japan
- Prior art keywords
- glass powder
- weight
- artificial marble
- particle size
- acid
- 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.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、人造大理石用樹脂組成物に関し、詳しくは、
透明性及び表面平滑性にすぐれると共に、表面硬度にも
すぐれる人造大理石用不飽和ポリエステル樹脂組成物に
関する。The present invention relates to a resin composition for artificial marble, and more specifically,
The present invention relates to an unsaturated polyester resin composition for artificial marble, which has excellent transparency and surface smoothness and also has excellent surface hardness.
（従来の技術） 従来、種々の充填材を不飽ポリエステル樹脂に配合し、
硬化させてなる成形品は、人造大理石として、浴槽、洗
面カウンター、キツチンカウンター、テーブル等に広く
用いられている。これらは、シートモールデイングコン
パウンド（以下、SMCと略する。）やバルクモールデイ
ングコンパウンド（以下、BMCと略する。）等を用いる
プレス成形によつて製造されている。(Prior Art) Conventionally, various fillers have been blended with the saturable polyester resin,
Molded products obtained by curing are widely used as artificial marble in bathtubs, wash counters, kittin counters, tables and the like. These are manufactured by press molding using a sheet molding compound (hereinafter abbreviated as SMC) or a bulk molding compound (hereinafter abbreviated as BMC).
しかし、このように不飽和ポリエステル樹脂を基材樹脂
とする人造大理石は、アクリル樹脂、エポキシ樹脂、フ
エノール樹脂等を基材樹脂とするものに比べて表面硬度
が低いために表面に疵が付きやすい。However, artificial marble using an unsaturated polyester resin as a base resin has a lower surface hardness than those using an acrylic resin, an epoxy resin, a phenol resin, etc. as a base resin. .
また、従来、充填材として、水酸化アルミニウムは、透
明性、難燃性、価格、白色度等にバランスよくすぐれて
おり、広く用いられているが、得られる成形品は、表面
硬度が不十分であつて、この点からも、成形品の表面に
疵が付きやすい。Further, conventionally, aluminum hydroxide as a filler has excellent balance in transparency, flame retardancy, price, whiteness, etc., and is widely used, but the obtained molded product has insufficient surface hardness. Even from this point, the surface of the molded product is likely to be flawed.
そこで、成形品の表面硬度を高めるために、従来、高硬
度のガラス粉末を充填材として樹脂組成物に配合する方
法が広く採用されている。この方法によれば、成形品の
表面硬度を高めることができるが、前述したSMCやBMCに
て成形するときは、近年、人造大理石に求められるに至
つている透明感や表面平滑性等に代表される高級感を有
する製品を得ることは困難である。Therefore, in order to increase the surface hardness of the molded product, conventionally, a method of incorporating a glass powder having high hardness into a resin composition as a filler has been widely adopted. According to this method, it is possible to increase the surface hardness of the molded product, but when molding with the above-mentioned SMC or BMC, it is typical for the transparency and surface smoothness that have recently been demanded for artificial marble. It is difficult to obtain a product having a high-grade feeling.
他方、得られる成形品に表面平滑性を与えるためには、
従来、金型を高温にしてプレス成形したり、或いは粒径
の小さい充填材を用いる等の方法が採用されている。し
かし、この方法によれば、得られる成形品は透明感をも
たない。On the other hand, in order to impart surface smoothness to the obtained molded product,
Heretofore, methods such as press-molding a mold at a high temperature or using a filler having a small particle size have been adopted. However, according to this method, the obtained molded article does not have a transparent feeling.
このように、従来の方法によれば、透明感と表面平滑性
を共に有すると共に、表面硬度にもすぐれる人造大理石
を得ることは困難である。As described above, according to the conventional method, it is difficult to obtain artificial marble having both transparency and surface smoothness and excellent surface hardness.
（発明が解決しようとする課題） 本発明は、従来の人造大理石の製造における上記した問
題を解決するためになされたものであつて、充填材とし
てガラス粉末を用いて、そのすぐれた表面硬度を保持し
つつ、透明性及び表面平滑性にすぐれる人造大理石を得
ることができる人造大理石用不飽和ポリエステル樹脂組
成物を提供することを目的とする。(Problems to be Solved by the Invention) The present invention has been made in order to solve the above-mentioned problems in the production of conventional artificial marble, in which glass powder is used as a filler, and its excellent surface hardness is obtained. It is an object of the present invention to provide an unsaturated polyester resin composition for artificial marble, which is capable of obtaining an artificial marble excellent in transparency and surface smoothness while holding it.
（課題を解決するための手段） 本発明による人造大理石用樹脂組成物は、不飽和ポリエ
ステル樹脂100重量部に対して、平均粒径10μｍ以下の
ガラス粉末と平均粒径30〜40μｍのガラス粉末と平均粒
径60〜80μｍのガラス粉末とを合計量にて150〜400重量
部を含有し、且つ、上記ガラス粉末の配合割合は、平均
粒径30〜40μｍのガラス粉末75〜92重量％と平均粒径60
〜80μｍのガラス粉末25〜８重量％とかなるガラス粉末
５〜30重量％に対して、平均粒径10μｍ以下のガラス粉
末95〜70重量％であることを特徴とする。(Means for Solving the Problems) The resin composition for artificial marble according to the present invention comprises a glass powder having an average particle size of 10 μm or less and a glass powder having an average particle size of 30 to 40 μm with respect to 100 parts by weight of an unsaturated polyester resin. The total amount of glass powder having an average particle diameter of 60 to 80 μm is contained in an amount of 150 to 400 parts by weight, and the mixing ratio of the glass powder is 75 to 92% by weight of the glass powder having an average particle diameter of 30 to 40 μm. Particle size 60
It is characterized in that 95 to 70% by weight of glass powder having an average particle size of 10 μm or less is used with respect to 5 to 30% by weight of glass powder such as 25 to 8% by weight of glass powder of ˜80 μm.
不飽和ポリエステル樹脂は、通常、不飽和ポリエステル
50〜80重量％と重合性単量体50〜20重量％とからなる。
不飽和ポリエステルが50重量％よりも少ないときは、十
分な強度をもつ人造大理石を得ることができず、他方、
80重量％を越えるときは、樹脂組成物の成形性及び作業
性が悪化する。The unsaturated polyester resin is usually an unsaturated polyester
It comprises 50 to 80% by weight and 50 to 20% by weight of the polymerizable monomer.
When the unsaturated polyester is less than 50% by weight, it is not possible to obtain artificial marble with sufficient strength, while
When it exceeds 80% by weight, the moldability and workability of the resin composition deteriorate.
不飽和ポリエステル樹脂は、一般に、α，β−不飽和二
塩基酸及び／又はその酸無水物である酸成分と多価アル
コール成分とを反応させることによつて得ることができ
る。The unsaturated polyester resin can be generally obtained by reacting an acid component which is an α, β-unsaturated dibasic acid and / or its acid anhydride with a polyhydric alcohol component.
α，β−不飽和二塩基酸としては、例えば、マレイン
酸、フマル酸、イタコン酸、シトラコン酸、クロルマレ
イン酸等を挙げることができ、これらは２種以上を併用
してもよい。多価アルコールとしては、例えば、エチレ
ングリコール、ジエチレングリコール、プロピレングリ
コール、ジプロピレングリコール、1,3−ブタンジオー
ル、ネオペンチルグリコール、1,6−ヘキサンジオー
ル、トリエチレングリコール、水素添加ビスフエノール
Ａ、イソペンチルグリコール、グリセリン、トリメチロ
ールプロパン、ジシクロペンタジエン等を挙げることが
できる。これらも２種以上を併用してもよい。Examples of the α, β-unsaturated dibasic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and chloromaleic acid. These may be used in combination of two or more. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, triethylene glycol, hydrogenated bisphenol A and isopentyl. Examples thereof include glycol, glycerin, trimethylolpropane, dicyclopentadiene and the like. These may also be used in combination of two or more.
不飽和ポリエステル樹脂の製造において、酸成分とし
て、必要に応じて、飽和二塩基酸及び／又はその酸無水
物を併用してもよい。このような飽和二塩基酸として
は、例えば、フタル酸、イソフタル酸、テレフタル酸、
トリメリツト酸、コハク酸、アゼライン酸、アジピン
酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ク
ロレンデイツク酸、テトラクロロフタル酸、テトラブロ
モフタル酸等を挙げることができる。In the production of the unsaturated polyester resin, a saturated dibasic acid and / or its acid anhydride may be used in combination as the acid component, if necessary. Examples of such a saturated dibasic acid include phthalic acid, isophthalic acid, terephthalic acid,
Examples thereof include trimellitic acid, succinic acid, azelaic acid, adipic acid, tetrahydrophthalic acid, hexahydrophthalic acid, chlorendic acid, tetrachlorophthalic acid and tetrabromophthalic acid.
他方、重合性単量体としては、スチレン、ビニルトルエ
ン、ジビニルベンゼン、α−メチルスチレン、クロルス
チレン、ジクロルスチレン、酢酸ビニル、ジアリルフタ
レート、ジアリルイソフタレート、ジアリルテレフタレ
ート等、不飽和ポリエステル樹脂と架橋可能なビニル単
量体、ジビニル単量体、ビニルオリゴマー等を挙げるこ
とができる。通常、スチレンが好ましく用いられる。On the other hand, as the polymerizable monomer, styrene, vinyltoluene, divinylbenzene, α-methylstyrene, chlorostyrene, dichlorostyrene, vinyl acetate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, etc., cross-linked with an unsaturated polyester resin. Possible vinyl monomers, divinyl monomers, vinyl oligomers and the like can be mentioned. Usually, styrene is preferably used.
本発明による人造大理石用樹脂組成物においては、無機
質充填材として、不飽和ポリエステル樹脂100重量部に
対して、平均粒径10μｍ以下、好ましくは３μｍ以上の
ガラス粉末と平均粒径30〜40μｍのガラス粉末と平均粒
径60〜80μｍのガラス粉末とが合計量にて150〜400重量
部の範囲で用いられる。ガラス粉末の合計量が150重量
部未満の場合は、樹脂組成物の粘度が低すぎて成形性が
悪くなり、400重量部を越えると、ガラス粉末の分散性
が不十分となつて、樹脂組成物が塊状となり、成形性が
悪くなる。In the resin composition for artificial marble according to the present invention, as an inorganic filler, a glass powder having an average particle size of 10 μm or less, preferably 3 μm or more, and a glass having an average particle size of 30 to 40 μm are used with respect to 100 parts by weight of the unsaturated polyester resin. The powder and glass powder having an average particle size of 60 to 80 μm are used in a total amount of 150 to 400 parts by weight. When the total amount of the glass powder is less than 150 parts by weight, the viscosity of the resin composition is too low and the moldability becomes poor, and when it exceeds 400 parts by weight, the dispersibility of the glass powder becomes insufficient and the resin composition The product becomes lumpy and the moldability deteriorates.
ここに、本発明によれば、上記ガラス粉末の配合割合
は、平均粒径30〜40μｍのガラス粉末75〜92重量％と平
均粒径60〜80μｍのガラス粉末25〜８重量％とからなる
ガラス粉末５〜30重量％に対して、平均粒径10μｍ以下
のガラス粉末95〜70重量％であり、このように平均粒径
の異なるガラス粉末を上記所定の割合で樹脂組成物に用
いることによつて、すぐれた表面硬度を確保しつつ、透
明性及び表面平滑性にすぐれる人造大理石を得ることが
できる。Here, according to the present invention, the compounding ratio of the glass powder is a glass consisting of 75 to 92% by weight of glass powder having an average particle size of 30 to 40 μm and 25 to 8% by weight of glass powder having an average particle size of 60 to 80 μm. 95 to 70% by weight of glass powder having an average particle size of 10 μm or less is used with respect to 5 to 30% by weight of the powder, and thus glass powder having different average particle sizes is used in the resin composition in the above-mentioned predetermined ratio. Thus, it is possible to obtain an artificial marble having excellent transparency and surface smoothness while ensuring excellent surface hardness.
平均粒径30〜40μｍのガラス粉末と平均粒径60〜80μｍ
のガラス粉末との合計量がガラス粉末全体の30重量％を
越えるときは、得られる成形品の表面平滑性が悪くな
り、他方、平均粒径10μｍ以下のガラス粉末がガラス粉
末全体の95重量％を越えるときは、得られる成形品が透
明性に乏しくなる。Glass powder with an average particle size of 30-40 μm and average particle size of 60-80 μm
When the total amount of the glass powder and the glass powder exceeds 30% by weight of the total glass powder, the surface smoothness of the obtained molded product becomes poor, while the glass powder having an average particle size of 10 μm or less is 95% by weight of the total glass powder. When it exceeds, the resulting molded article becomes poor in transparency.
本発明による人造大理石用不飽和ポリエステル樹脂は、
通常、硬化剤を含有し、更に、必要に応じて、補強材、
低収縮材、硬化促進剤、内部離型剤、増粘剤、着色剤等
を含有する。The unsaturated polyester resin for artificial marble according to the present invention,
Usually, it contains a curing agent, and if necessary, a reinforcing material,
It contains a low shrinkage material, a curing accelerator, an internal release agent, a thickener, a coloring agent and the like.
硬化剤としては、例えば、ｔ−ブチルパーベンゾエー
ト、ベンゾイルパーオキサイド、メチルエチルケトンパ
ーオキサイド、ジクミルパーオキサイド、ｔ−ブチルパ
ーオキシ−２−エチルヘキサノエート、1,1−ジ−ｔ−
ブチルパーオキシシクロヘキサン、ｔ−ブチルパーオキ
シイソプロピルカーボネート等の有機過酸化物が用いら
れる。Examples of the curing agent include t-butyl perbenzoate, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl peroxy-2-ethylhexanoate, 1,1-di-t-.
Organic peroxides such as butylperoxycyclohexane and t-butylperoxyisopropyl carbonate are used.
補強材としては、ガラス繊維、ポリエステル繊維、フエ
ノール繊維、ポリビニルアルコール繊維、炭素繊維等を
挙げることができるが、通常、ガラス繊維が好ましく用
いられる。Examples of the reinforcing material include glass fiber, polyester fiber, phenol fiber, polyvinyl alcohol fiber, carbon fiber and the like, but glass fiber is usually preferably used.
また、低収縮材としては、例えば、ポリエチレン、ポリ
スチレン、ポリメタクリル酸メチル、ポリ塩化ビニル、
ポリ酢酸ビニル、ポリカプロラクタム、飽和ポリエステ
ル等の熱可塑性樹脂、ポリブタジエンゴム、ポリスチレ
ン−アクリロニトリル共重合体等が用いられる。Further, as the low shrinkage material, for example, polyethylene, polystyrene, polymethyl methacrylate, polyvinyl chloride,
Thermoplastic resins such as polyvinyl acetate, polycaprolactam and saturated polyester, polybutadiene rubber, polystyrene-acrylonitrile copolymer and the like are used.
硬化促進剤としては、有機酸の金属塩、特に、コバルト
塩、例えば、ナフテン酸コバルト、オクチル酸コバル
ト、アセチルアセトンコバルト等が用いられる。As the curing accelerator, a metal salt of an organic acid, particularly a cobalt salt, for example, cobalt naphthenate, cobalt octylate, acetylacetone cobalt or the like is used.
内部離型剤としては、ステアリン酸、ステアリン酸亜鉛
等の高級脂肪酸や高級脂肪酸塩、アルキルリン酸エステ
ル等が用いられる。As the internal release agent, higher fatty acids such as stearic acid and zinc stearate, higher fatty acid salts, alkyl phosphates and the like are used.
増粘剤は、不飽和ポリエステルが有する水酸基、カルボ
キシル基やエステル基等と化学的に結合し、線状又は一
部交叉結合を生ぜしめて、分子量を増大させ、不飽和ポ
リエステル樹脂を増粘させるものであつて、例えば、ト
ルエンジイソシアネートのようなジイソシアネート類、
アルミニウムイソプロポキシド、チタンテトラブトキシ
ドのような金属アルコキシド、酸化マグネシウム、酸化
カルシウム、酸化ブリリウムのような二価金属の酸化
物、水酸化カルシウムのような二価金属の水酸化物等が
用いられる。The thickener chemically binds to a hydroxyl group, a carboxyl group, an ester group or the like of the unsaturated polyester to form a linear or partially cross-linked bond, which increases the molecular weight and thickens the unsaturated polyester resin. Where, for example, diisocyanates such as toluene diisocyanate,
A metal alkoxide such as aluminum isopropoxide and titanium tetrabutoxide, an oxide of a divalent metal such as magnesium oxide, calcium oxide and bryllium oxide, a hydroxide of a divalent metal such as calcium hydroxide and the like are used.
本発明による人造大理石用樹脂組成物は、通常、上述し
たような不飽和ポリエステル樹脂と充填材とを混練し、
更にこれに上述したような硬化剤、その他必要に応じ
て、補強材、低収縮材、硬化促進剤、内部離型剤、増粘
剤、着色剤等を混合することによつて得ることができ
る。The artificial marble resin composition according to the present invention is usually obtained by kneading the unsaturated polyester resin and the filler as described above,
Further, it can be obtained by mixing with the above-mentioned curing agent and, if necessary, a reinforcing material, a low shrinkage material, a curing accelerator, an internal release agent, a thickener, a coloring agent and the like. .
本発明による人造大理石用樹脂組成物は、通常、成形温
度120〜160℃、成形圧力70〜140kg/cm2でプレス成形す
ることによつて、人造大理石を得ることができる。The artificial marble resin composition according to the present invention can usually be produced by press molding at a molding temperature of 120 to 160 ° C. and a molding pressure of 70 to 140 kg / cm 2 to obtain artificial marble.
（実施例） 以下に実施例を挙げて本発明を説明する。(Example) Hereinafter, the present invention will be described with reference to examples.
実施例１〜４ 充填材として平均粒径５μｍと35μｍと75μｍのガラス
粉末をそれぞれ所定割合で用いて、第１表に示す組成を
有するBMCを調製し、成形温度130℃、成形圧力100kgf/c
m2、成形時間７分の条件で成形し、厚さ6mmの平板を得
た。この成形品についての特性を第１表に示す。Examples 1 to 4 BMCs having the compositions shown in Table 1 were prepared by using glass powders having an average particle diameter of 5 μm, 35 μm and 75 μm as a filler at predetermined ratios, and a molding temperature of 130 ° C. and a molding pressure of 100 kgf / c.
Molding was performed under the conditions of m 2 and molding time of 7 minutes to obtain a flat plate having a thickness of 6 mm. The characteristics of this molded product are shown in Table 1.
比較例１〜３ 充填材として平均粒径５μｍと35μｍと75μｍのガラス
粉末のいずれか一種を用い、又はこれらを本発明による
条件を満たさない割合で用いて、第１表に示す組成を有
するBMCを調製し、実施例１と同じ条件で成形し、厚さ6
mmの平板を得た。この成形品についての特性を第１表に
示す。Comparative Examples 1 to 3 BMCs having the composition shown in Table 1 were prepared by using any one of glass powders having an average particle size of 5 μm, 35 μm and 75 μm as a filler, or by using them in a proportion not satisfying the conditions according to the present invention. Was prepared and molded under the same conditions as in Example 1 to give a thickness of 6
A flat plate of mm was obtained. The characteristics of this molded product are shown in Table 1.
第１表に示す結果から明らかなように、本発明の樹脂組
成物によれば、透明性及び表面平滑性にすぐれるのみな
らず、表面硬度にもすぐれる成形品を得ることができ
る。As is clear from the results shown in Table 1, according to the resin composition of the present invention, it is possible to obtain a molded article which is excellent not only in transparency and surface smoothness but also in surface hardness.
（発明の効果） 本発明による人造大理石用樹脂組成物は、以上のよう
に、不飽和ポリエステル樹脂と共に、平均粒径の異なる
ガラス粉末を所定の割合で含むので、すぐれた表面硬度
を確保しつつ、透明性と表面平 滑性にすぐれる人造大理石を得ることができる。 (Effect of the Invention) As described above, the artificial marble resin composition of the present invention contains glass powders having different average particle diameters in a predetermined ratio together with the unsaturated polyester resin, so that an excellent surface hardness is ensured. It is possible to obtain artificial marble with excellent transparency and surface smoothness.
従つて、このような樹脂組成物は、例えば、浴槽、洗面
カウンター、キツチンカウンター、テーブル等の製造に
好適である。Therefore, such a resin composition is suitable for manufacturing, for example, a bathtub, a washbasin counter, a kittin counter, a table, or the like.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０４Ｂ 14:22） 111:54 111:80 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display area C04B 14:22) 111: 54 111: 80
Claims (1)
て、平均粒径10μｍ以下のガラス粉末と平均粒径30〜40
μｍのガラス粉末と平均粒径60〜80μｍのガラス粉末と
を合計量にて150〜400重量部を含有し、且つ、上記ガラ
ス粉末の配合割合は、平均粒径30〜40μｍのガラス粉末
75〜92重量％と平均粒径60〜80μｍのガラス粉末25〜８
重量％とからなるガラス粉末５〜30重量％に対して、平
均粒径10μｍ以下のガラス粉末95〜70重量％であること
を特徴とする人造大理石用樹脂組成物。1. A glass powder having an average particle size of 10 μm or less and an average particle size of 30 to 40 relative to 100 parts by weight of an unsaturated polyester resin.
Glass powder having a mean particle size of 30 to 40 μm, containing a total amount of 150 to 400 parts by weight of a glass powder having a mean particle size of 60 to 80 μm and a glass powder having a mean particle size of 30 to 40 μm.
Glass powder with 75-92% by weight and average particle size of 60-80 μm 25-8
The resin composition for artificial marble is characterized in that 95% to 70% by weight of glass powder having an average particle diameter of 10 μm or less is used with respect to 5% to 30% by weight of glass powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2294916A JPH0717426B2 (en) | 1990-10-30 | 1990-10-30 | Resin composition for artificial marble |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2294916A JPH0717426B2 (en) | 1990-10-30 | 1990-10-30 | Resin composition for artificial marble |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04170351A JPH04170351A (en) | 1992-06-18 |
| JPH0717426B2 true JPH0717426B2 (en) | 1995-03-01 |
Family
ID=17813913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2294916A Expired - Lifetime JPH0717426B2 (en) | 1990-10-30 | 1990-10-30 | Resin composition for artificial marble |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717426B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100396834B1 (en) * | 1996-12-19 | 2004-02-14 | 주식회사 효성 | Thermosetting unsaturated polyester resin composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6469311A (en) * | 1987-09-11 | 1989-03-15 | Ferro Enamels Japan | Unsaturated polyester resin press-molded article with improved transparency and manufacture thereof |
| JPH0618999B2 (en) * | 1988-12-07 | 1994-03-16 | 日本フェロー株式会社 | Bright resin molding materials and molded products |
| JPH02233571A (en) * | 1989-03-03 | 1990-09-17 | Toto Ltd | Stone-textured artificial stone |
-
1990
- 1990-10-30 JP JP2294916A patent/JPH0717426B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04170351A (en) | 1992-06-18 |
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