JP3235579B2 - Natural stone-like artificial marble and method for producing the same - Google Patents
Natural stone-like artificial marble and method for producing the sameInfo
- Publication number
- JP3235579B2 JP3235579B2 JP37582198A JP37582198A JP3235579B2 JP 3235579 B2 JP3235579 B2 JP 3235579B2 JP 37582198 A JP37582198 A JP 37582198A JP 37582198 A JP37582198 A JP 37582198A JP 3235579 B2 JP3235579 B2 JP 3235579B2
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- natural
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、熱硬化性樹脂と天
然砕石等を用いて成形された天然石風人工大理石及びそ
の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a natural stone-like artificial marble formed by using a thermosetting resin and natural crushed stone, and a method for producing the same.
【０００２】[0002]
【従来の技術】天然の大理石は、床材や壁材に用いられ
ているが、天然石では強度が弱く、薄物や大型品が得ら
れないのみならず、同じ模様のものが得られないので、
天然石風人工大理石を天然石の代わりに用いることが行
われている。天然石風人工大理石は天然石の砕石、石粉
を樹脂類と共に成形した成形材を表面研磨し、天然石風
にした人工大理石である。2. Description of the Related Art Natural marble is used for flooring and wall materials. However, natural stone has low strength, so that not only thin and large products cannot be obtained, but also those having the same pattern cannot be obtained.
It has been practiced to use natural stone-like artificial marble instead of natural stone. The natural stone-like artificial marble is an artificial marble in which the surface of a molded material obtained by molding crushed natural stone and stone powder together with resins is polished to give a natural stone style.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記砕
石を用いた成形材は、天然の質感を出すために、粒子径
を大きくしたものが使用されるため、その成形材の成形
に用いる組成物の流動性が悪く、成形が難しい。また、
成形時にクラック、ワレあるいはそりが発生し、良好な
成形品が得られないという問題がある。そこで、従来
は、微粉末の石粉を使用するか、あるいは粒子径の小さ
い砕石を少量添加する方法、あるいは注型法のように常
温にて型の中に樹脂と砕石を流し込んで成形した後、表
面を研磨することによって天然石の質感を出す方法が採
られている。しかし、この場合には強度の点で問題があ
った。本発明の目的は、天然石の質感を失わず、しかも
強度が大きく、成形性の優れた天然石風人工大理石及び
その製造方法を提供することにある。However, since a molding material using the above crushed stone has a large particle diameter in order to give a natural texture, a composition used for molding the molding material is used. Poor fluidity and difficult to mold. Also,
There is a problem that cracks, cracks or warpage occur during molding, and good molded products cannot be obtained. Therefore, conventionally, a method of using a fine powder of stone powder, or a method of adding a small amount of crushed stone having a small particle size, or after casting a resin and crushed stone into a mold at room temperature as in a casting method, and then molding. A method has been adopted in which a natural stone texture is obtained by polishing the surface. However, in this case, there was a problem in strength. An object of the present invention is to provide a natural stone-like artificial marble having high strength and excellent formability without losing the texture of natural stone, and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明は、上記課題を解
決するために、熱硬化性樹脂１００重量部と、微粉末充
填剤３０〜３００重量部と、平均粒径が１０ｍｍ以上２
０ｍｍ以下の天然砕石４００〜８００重量部を含有する
樹脂コンパウンドに対して硬化触媒と、低収縮剤、２５
ｍｍ以下の繊維状強化材及び増粘剤の群からなる添加助
剤の少なくとも２５ｍｍ以下の繊維状強化材及び低収縮
剤３重量部より多く５０重量部以下を含有した組成物か
ら得られる天然石風人工大理石を提供するものである。
この際、樹脂コンパウンドは熱硬化性樹脂１００重量部
と、微粉末充填剤３０〜３００重量部と、天然砕石４０
０〜８００重量部の割合でそれぞれの成分を含有し、添
加助剤として含有される各成分は低収縮剤３重量部より
多く５０重量部以下、繊維状強化材１００重量部以下、
増粘剤５重量部以下の割合であることが好ましい。ま
た、本発明は、上記組成物を増粘させた後、型内に投入
し、１１０〜１７０℃で加圧成形し、更に成形品の表面
を研磨することを特徴とする天然石風人工大理石の製造
方法を提供するものである。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a thermosetting resin of 100 parts by weight, a fine powder filler of 30 to 300 parts by weight, and an average particle size of 10 mm or more.
For a resin compound containing 400 to 800 parts by weight of natural crushed stone of 0 mm or less, a curing catalyst, a low shrinkage agent, 25
mm or less of the auxiliary agent consisting of a group of fibrous reinforcements and thickeners of at least 25 mm or less and low shrinkage
It is intended to provide a natural stone-like artificial marble obtained from a composition containing more than 3 parts by weight and not more than 50 parts by weight of an agent .
At this time, the resin compound was composed of 100 parts by weight of a thermosetting resin, 30 to 300 parts by weight of a fine powder filler, and 40 parts of natural crushed stone.
Each component is contained at a ratio of 0 to 800 parts by weight, and each component contained as an additive aid is from 3 parts by weight of a low shrinkage agent.
Many 50 parts by weight or less, fibrous reinforcing material 100 parts by weight or less,
It is preferable that the ratio is 5 parts by weight or less. Further, the present invention provides a natural stone-like artificial marble characterized in that after thickening the above composition, it is put into a mold, pressure-molded at 110 to 170 ° C, and further polished the surface of the molded article. It is intended to provide a manufacturing method.
【０００５】次に本発明を詳細に説明する。本発明で使
用する熱硬化性樹脂としては、不飽和ポリエステル樹
脂、エポキシ樹脂、尿素樹脂、メラミン樹脂、ジアリル
フタレート樹脂等が挙げられる。不飽和ポリエステル樹
脂としては、α，β−不飽和二塩基酸又はその酸無水物
と、芳香族飽和二塩基酸又はその酸無水物と、グリコー
ル類の重縮合によって製造され、場合によっては酸成分
として脂肪族或いは脂環族飽和二塩基酸を併用して製造
された不飽和ポリエステル３０〜８０重量部を、α，β
−不飽和単量体７０〜２０重量部に溶解して得られるも
のが挙げられるが、そのほかに不飽和ポリエステルの末
端をビニル変性したもの、及びエポキシ樹脂骨格の末端
をビニル変性したビニルエステル等も挙げられる。上記
のα，β−不飽和二塩基酸又はその酸無水物としては、
マレイン酸、無水マレイン酸、フマル酸、イタコン酸、
シトラコン酸、クロルマレイン酸及びこれらのエステル
等があり、芳香族飽和二塩基酸又はその酸無水物として
は、フタル酸、無水フタル酸、イソフタル酸、テレフタ
ル酸、ニトロフタル酸、ジフエン酸、テトラヒドロ無水
フタル酸、エンドメチレンテトラヒドロ無水フタル酸、
ハロゲン化無水フタル酸及びこれらのエステル等があ
り、脂肪族或いは脂環族飽和二塩基酸としては、シュウ
酸、マロン酸、コハク酸、アジピン酸、セバシン酸、ア
ゼライン酸、グルタル酸、ヘキサヒドロ無水フタル酸及
びこれらのエステル等があり、それぞれ単独或いは併用
して使用される。Next, the present invention will be described in detail. Examples of the thermosetting resin used in the present invention include unsaturated polyester resins, epoxy resins, urea resins, melamine resins, diallyl phthalate resins, and the like. The unsaturated polyester resin is produced by polycondensation of an α, β-unsaturated dibasic acid or an acid anhydride thereof, an aromatic saturated dibasic acid or an acid anhydride thereof, and glycols. 30 to 80 parts by weight of an unsaturated polyester produced in combination with an aliphatic or alicyclic saturated dibasic acid as α, β
Examples thereof include those obtained by dissolving 70 to 20 parts by weight of an unsaturated monomer, but also those obtained by modifying the terminal of an unsaturated polyester with vinyl, and the vinyl ester obtained by modifying the end of an epoxy resin skeleton with vinyl. No. As the above α, β-unsaturated dibasic acid or its acid anhydride,
Maleic acid, maleic anhydride, fumaric acid, itaconic acid,
There are citraconic acid, chlormaleic acid and esters thereof, and as the aromatic saturated dibasic acid or its anhydride, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, diphenic acid, tetrahydrophthalic anhydride Acid, endomethylenetetrahydrophthalic anhydride,
There are halogenated phthalic anhydride and esters thereof, and aliphatic or alicyclic saturated dibasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, and hexahydrophthalic anhydride. There are acids and esters thereof, and these are used alone or in combination.
【０００６】グリコール類としては、エチレングリコー
ル、プロピレングリコール、ジエチレングリコール、ジ
プロピレングリコール、１，３−ブタンジオール、１，
４−ブタンジオール、２−メチルプロパン−１，３−ジ
オール、ネオペンチルグリコール、トリエチレングリコ
ール、テトラエチレングリコール、１，５−ペンタンジ
オール、１，６−ヘキサンジオール、ビスフェノール
Ａ、水素化ビスフェノールＡ、エチレングリコールカー
ボネート、２，２−ジ−（４−ヒドロキシプロポキシジ
フェニル）プロパン等が挙げられ、単独或いは併用して
使用されるが、そのほかにエチレンオキサイド、プロピ
レンオキサイド等の酸化物も同様に使用できる。また、
グリコール類と酸成分の一部としてポリエチレンテレフ
タレート等の重縮合物も使用できる。また、上記α，β
−不飽和単量体としては、スチレン、ビニルトルエン、
α−メチルスチレン、クロルスチレン、ジクロルスチレ
ン、ビニルナフタレン、エチルビニルエーテル、メチル
ビニルケトン、メチルアクリレート、エチルアクリレー
ト、メチルメタクリレート、アクリロニトリル、メタク
リロニトリル等のビニル化合物及びジアリルフタレー
ト、ジアリルフマレート、ジアリルサクシネート、トリ
アリルシアヌレート等のアリル化合物などの不飽和ポリ
エステルやビニルエステル樹脂と架橋可能なビニルモノ
マー或いはビニルオリゴマー等が挙げられ、単独或いは
併用して用いられるが、一般的にはスチレンが使用され
る。The glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol,
4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, Ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane and the like can be mentioned, and these are used alone or in combination. In addition, oxides such as ethylene oxide and propylene oxide can also be used. Also,
Polycondensates such as polyethylene terephthalate can also be used as part of the glycols and acid components. In addition, the above α, β
-Unsaturated monomers include styrene, vinyl toluene,
vinyl compounds such as α-methylstyrene, chlorostyrene, dichlorostyrene, vinyl naphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, and diallyl phthalate, diallyl fumarate, diallyl succinate And unsaturated polyesters such as allyl compounds such as triallyl cyanurate and vinyl monomers or vinyl oligomers crosslinkable with vinyl ester resins. These are used alone or in combination, but styrene is generally used. You.
【０００７】本発明に用いられる微粉末充填剤として
は、炭酸カルシウム粉、クレー、アルミナ粉、珪石粉、
タルク、硫酸バリウム、シリカパウダー、ガラス粉、ガ
ラスビーズ、マイカ、砕石粉、水酸化アルミニウム、セ
ルロース系の充填剤が挙げられ、なかでも硬化時半透明
性を与えるのでガラス粉、水酸化アルミニウム、硫酸バ
リウムなどが好ましい。充填剤は不飽和ポリエステル樹
脂１００重量部に対して通常３０〜３００重量部の割合
で用いることができる。微粉末の粒径としては６０μｍ
以下のものが好ましい。天然砕石としては、火成岩、変
成岩、水成岩（堆積岩）の砕石が使用される。火成岩に
は火山岩、深成岩（御影石）があり、一般的には安山岩
と呼ばれる小松石、鉄平石などがある。また、深成岩に
は一般的には花崗岩と呼ばれる白御影、桜御影、赤御
影、ハンレイ岩と呼ばれる黒御影、閃緑岩などの御影石
類がある。変成岩には蛇紋岩、結晶質石灰岩、石灰岩な
どの大理石類がある。水成岩（堆積岩）には、石灰岩、
砂岩と呼ばれるインド砂岩、多胡石、粘板岩と呼ばれる
玄晶石、仙台石、凝灰岩と呼ばれる大谷石、福光石など
があり、使用される。また、陶器、磁器、ガラス、ステ
ッドガラスなどの砕石も併用して用いられる。また、砕
石は単独又はこれを２種以上組合わせて使用することも
できる。天然砕石は、不飽和ポリエステル樹脂１００重
量部対して通常５０〜８００重量部の割合で用いること
ができる。好ましくは平均粒径１〜２０ｍｍ位の範囲の
天然砕石が用いられる。The fine powder filler used in the present invention includes calcium carbonate powder, clay, alumina powder, silica powder,
Examples include talc, barium sulfate, silica powder, glass powder, glass beads, mica, crushed stone powder, aluminum hydroxide, and a cellulose-based filler. Barium is preferred. The filler can be used usually in a proportion of 30 to 300 parts by weight based on 100 parts by weight of the unsaturated polyester resin. The particle size of the fine powder is 60 μm
The following are preferred. As natural crushed stone, crushed rock of igneous rock, metamorphic rock, aquatic rock (sedimentary rock) is used. Igneous rocks include volcanic rocks and plutonic rocks (granite), such as andesite, commonly known as komatsu stone and iron flat stone. In addition, plutonic rocks include granites such as White Mikage, Sakura Mikage and Red Mage, which are generally called granite, Black Mage, which is called gabbro, and diorite. Metamorphic rocks include marbles such as serpentine, crystalline limestone, and limestone. Aquatic rocks (sedimentary rocks) include limestone,
There are Indian sandstone called sandstone, tagolite, slate, bryolite, Sendai stone, Oya stone called tuff, and fukutsuite. In addition, crushed stones such as pottery, porcelain, glass, and stationary glass are also used in combination. Also, crushed stones can be used alone or in combination of two or more. Natural crushed stone can be used usually in a proportion of 50 to 800 parts by weight based on 100 parts by weight of the unsaturated polyester resin. Preferably, natural crushed stone having an average particle size of about 1 to 20 mm is used.
【０００８】また、本発明で使用される低収縮剤として
は、熱可塑性樹脂が使用でき、その具体例としては、メ
チルメタクリレート、エチルメタクリレート、ブチルメ
タクリレート、メチルアクリレート、エチルアクリレー
トなどのアクリル酸又はメタクリル酸の低級アルキルエ
ステル類、スチレン、塩化ビニル、酢酸ビニルなどの単
量体の単独重合体又は共重合体類、前記ビニル単量体の
少なくとも１種と、ラウリルメタクリレート、イソビニ
ルメタクリレート、アクリルアミド、メタクリルアミ
ド、ヒドロキシルアルキルアクリレート又はメタクリレ
ート、アクリニトリル、メタクリルロニトリル、アクリ
ル酸、メタクリル酸、セチルステアリルメタクリレート
よりなる単量体の少なくとも１種の共重合体などのほ
か、セルロースアセテートブチレート及びセルロースア
セテートプロピオネート、ポリエチレン、ポリプロピレ
ン、飽和ポリエステル等を挙げることができる。その添
加量は熱硬化性樹脂１００重量部に対して３重量部より
多く５０重量部以下が好ましく、３重量部より多く３５
重量部以下が特に好ましい。As the low-shrinkage agent used in the present invention, a thermoplastic resin can be used. Specific examples thereof include acrylic acid or methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, and ethyl acrylate. Lower alkyl esters of acids, homopolymers or copolymers of monomers such as styrene, vinyl chloride and vinyl acetate, at least one of the above vinyl monomers, lauryl methacrylate, isovinyl methacrylate, acrylamide, methacryl In addition to amide, hydroxylalkyl acrylate or methacrylate, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, cetylstearyl methacrylate, at least one copolymer of monomers, and cellulose acetate Tobuchireto and cellulose acetate propionate, polyethylene, polypropylene, saturated polyester. The addition amount is from 3 parts by weight to 100 parts by weight of the thermosetting resin.
Most preferably less than 50 parts by weight, more than 3 parts by weight 35
Particularly preferred is not more than parts by weight.
【０００９】増粘剤は不飽和ポリエステルの有する水酸
基、カルボキシル基やエステル結合等と化学的に結合し
て線状又は一部交叉結合を生じせ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性質を有する
もので、例えばトルエンジイソシアネートの如きジイソ
シアネート類、アルミニウムイソプロポキシド、チタン
テトラブトキシの如き金属アルコキシド類、酸化マグネ
シウム、酸化カルシウム、酸化ベリリウムの如き２価金
属の酸化物、水酸化カルシウムの如き２金属の水酸化物
等を挙げることができる。増粘剤の使用量は不飽和ポリ
エステル樹脂１００重量部に対して通常０．２〜５重量
部、好ましくは０．５〜４重量部の割合である。そして
必要ならば水の如き極性の強い物質を増粘助剤として少
量使用することができる。The thickener is chemically bonded to a hydroxyl group, a carboxyl group, an ester bond, or the like of the unsaturated polyester to form a linear or partial cross-link, thereby increasing the molecular weight and thickening the unsaturated polyester resin. For example, diisocyanates such as toluene diisocyanate, metal alkoxides such as aluminum isopropoxide and titanium tetrabutoxy, oxides of divalent metals such as magnesium oxide, calcium oxide and beryllium oxide, and calcium hydroxide And bimetallic hydroxides. The amount of the thickener used is usually 0.2 to 5 parts by weight, preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the unsaturated polyester resin. If necessary, a small amount of a highly polar substance such as water can be used as a thickening aid.
【００１０】本発明で使用される繊維強化材としては、
一般にはガラス繊維が挙げられるが、その他のビニロ
ン、ポリエステル、フェノール等の有機繊維、アスベス
ト、カーボンファイバーなども挙げられる。繊維強化材
の繊維長さは２５ｍｍ以下のものが用いられるが、好ま
しくは３〜１８ｍｍであり、その添加量はポリエステル
樹脂１００重量部に対して０〜１００重量部となる範
囲、好ましくは０〜６０重量部である。硬化触媒として
は、不飽和ポリエステル樹脂、ビニルエステル樹脂等に
作用するもので、例えばアゾイソブチロニトリルのよう
なアゾ化合物、ターシャリーブチルパーベンゾエート、
ターシャリーパーオクトエート、ペ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
ーオキサイド等の有機過酸化物等を挙げることができ、
不飽和ポリエステル樹脂１００重量部に対して通常０．
３〜３重量部の範囲で用いることができる。本発明にお
いては硬化促進剤も使用でき、これには有機酸の金属塩
類特にコバルト塩、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使用され
る。また、内部離型剤も使用でき、これにはステアリン
酸、ステアリン酸亜鉛等の如き高級脂肪酸や高級脂肪酸
エステル、アルキルリン酸エステル等の公知のものを挙
げることができ、熱硬化性樹脂１００重量部に対して通
常０．５〜５重量部の割合で用いることができる。ま
た、着色剤も用いることができ、有機及び無機の染料、
顔料が使用でき、なかでも耐熱性、透明性に優れ、かつ
熱硬化性樹脂の硬化を著しく妨害することのないものが
好ましい。本発明の天然石風人工大理石を製造するに
は、上記の各成分を混練し、その混練物を例えばシート
状にプリフォームし、増粘させた後、常温で熟成させ、
ついで例えば１００〜１７０℃に加熱された平板用金型
に充填し、加圧して硬化させる。本発明の天然石風人工
大理石は、カウンター、テーブルトップ、床、壁、ビル
内装、下箱天板、洗面台などの材料に用いることができ
る。[0010] The fiber reinforcing material used in the present invention includes:
Generally, glass fibers are mentioned, but other organic fibers such as vinylon, polyester, and phenol, asbestos, carbon fibers, and the like are also mentioned. The fiber length of the fiber reinforcing material is 25 mm or less, but is preferably 3 to 18 mm, and the amount added is in the range of 0 to 100 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of the polyester resin. 60 parts by weight. As the curing catalyst, those which act on unsaturated polyester resins, vinyl ester resins, etc., for example, azo compounds such as azoisobutyronitrile, tertiary butyl perbenzoate,
Tertiary peroctoate, benzoyl peroxide, methyl ethyl ketone peroxide, organic peroxides such as dicumyl peroxide, and the like,
Usually, 0.1 parts by weight per 100 parts by weight of the unsaturated polyester resin.
It can be used in the range of 3 to 3 parts by weight. In the present invention, a curing accelerator can also be used, and examples thereof include metal salts of organic acids, particularly, cobalt salts such as cobalt naphthenate, cobalt octylate, and acetylacetone cobalt. In addition, an internal release agent can also be used, and examples thereof include known fatty acids such as stearic acid and zinc stearate, higher fatty acid esters, and alkyl phosphate esters. It can be used usually in a proportion of 0.5 to 5 parts by weight to parts. In addition, coloring agents can also be used, and organic and inorganic dyes,
Pigments which can be used, and which are excellent in heat resistance and transparency and which do not significantly hinder the curing of the thermosetting resin, are preferred. In order to produce the natural stone-like artificial marble of the present invention, the above components are kneaded, and the kneaded material is preformed into, for example, a sheet, thickened, and then aged at room temperature.
Then, for example, it is filled in a flat plate mold heated to 100 to 170 ° C. and cured by applying pressure. The natural stone-like artificial marble of the present invention can be used for materials such as counters, table tops, floors, walls, building interiors, lower box tops, and sinks.
【００１１】[0011]
【実施例】次に本発明の実施例を説明する。Next, embodiments of the present invention will be described.
【００１２】参考例１ Reference Example 1
【００１３】不飽和ポリエステル樹脂としてポリライト
ＰＳ−２６６（大日本インキ化学工業（株）製）１００
重量部、低収縮剤としてポリライトＰＢ−９５６（大日
本インキ化学工業（株）製）３０部、水酸化アルミニウ
ムとしてＢＷ−１５３（日本軽金属（株）製）２００重
量部、平均１０ｍｍの白御影石と呼ばれる天然砕石５０
０重量部、触媒としてｔ−ブチルパーベンゾエート１．
０重量部を混練させる。この混合物をシート状にプリフ
ォームし、常温で２４時間熟成させた後、１４５℃に加
熱された平板用金型に充填させ、成形圧力８０Ｋｇ／ｃ
ｍ2 の条件下で１５分硬化させた。これにより、厚さ１
５ｍｍでクラックやそりの無い成形品を得た。この成形
品を研磨機で表面を０．５〜１．０ｍｍ研磨した。この
製品は強度も十分で御影石風であった。Polylite PS-266 (manufactured by Dainippon Ink and Chemicals, Inc.) 100 as an unsaturated polyester resin
Parts by weight, 30 parts of Polylite PB-956 (manufactured by Dainippon Ink and Chemicals, Inc.) as a low-shrinking agent, 200 parts by weight of BW-153 (manufactured by Nippon Light Metal Co., Ltd.) as aluminum hydroxide, and white granite having an average of 10 mm 50 natural crushed stones
0 parts by weight, t-butyl perbenzoate as catalyst 1.
0 parts by weight are kneaded. This mixture was preformed into a sheet, aged at room temperature for 24 hours, filled in a flat plate mold heated to 145 ° C., and formed at a molding pressure of 80 kg / c.
Cured for 15 minutes under m 2 conditions. Thereby, the thickness 1
A molded product of 5 mm without cracks or warpage was obtained. The surface of this molded product was polished by 0.5 to 1.0 mm with a polishing machine. This product had sufficient strength and was granite-like.
【００１４】参考例２ Reference Example 2
【００１５】上記ポリライトＰＳ−２６６ １００重量
部、上記水酸化アルミニウムＢＷ−１５３ ２００重量
部、平均粒径１０ｍｍの白御影石と呼ばれる天然砕石５
００重量部、ｔ−ブチルパーベンゾエート１．０重量
部、酸化マグネシウム １重量部、１３ｍｍガラスチョ
ップ４０重量部を実施例１と同様な方法で混練し、熟成
及び成形し、得られた成形品を研磨した。得られた製品
はクラックやそりが無く、強度も十分で白御影大理石風
であった。Natural crushed stone 5 called white granite having 100 parts by weight of the polylite PS-266, 200 parts by weight of the aluminum hydroxide BW-153, and an average particle diameter of 10 mm.
00 parts by weight, t-butyl perbenzoate 1.0 part by weight, magnesium oxide 1 part by weight, 13 mm glass chop 40 parts by weight were kneaded in the same manner as in Example 1, aged and molded, and the obtained molded product was Polished. The obtained product was free from cracks and warpage, had sufficient strength, and was white marble-like.
【００１６】参考例３ Reference Example 3
【００１７】上記ポリライトＰＳ−２６６ １００重量
部、上記水酸化アルミニウムＢＷ−１５３ ２００重量
部、平均粒径１０ｍｍの白御影石と呼ばれる天然砕石５
００重量部、ｔ−ブチルパーベンゾエート１．０重量
部、酸化マグネシウム １重量部を実施例１と同様な方
法で混練し、熟成及び成形し、得られた成形品を研磨し
た。得られた製品はクラックヤそりが無く、強度も十分
で白御影大理石風であった。100 parts by weight of the polylite PS-266, 200 parts by weight of the aluminum hydroxide BW-153, and natural crushed stone 5 called white granite having an average particle diameter of 10 mm.
00 parts by weight, t-butyl perbenzoate 1.0 part by weight, and magnesium oxide 1 part by weight were kneaded in the same manner as in Example 1, aged and molded, and the obtained molded product was polished. The resulting product had no cracky warpage, had sufficient strength, and was white-gray marble-like.
【００１８】参考例４ Reference Example 4
【００１９】エボキシ樹脂としてエポン８２８（シェル
油化工業（株）製）１００重量部、硬化剤としてジフェ
ニルジアミノメタン１８．５重量部、上記水酸化アルミ
ニウムＢＷ−１５３ ２００重量部、平均粒径１３ｍｍ
の黒御影石５００重量部、酸化マグネシウム３．０重量
部及び１３ｍｍ長さのガラスチョップ４５重量部を混練
し、この混練物をシート状にプリフォームした後、５０
℃、２４時間熟成し、成形温度１５５℃、成形圧力９０
Ｋｇ／ｃｍ2 、硬化時間２０分で成形した。成形品はク
ラックやそりがなく、またこれを研磨した結果、黒色で
天然の黒御影石に近いものが得られた。100 parts by weight of Epon 828 (manufactured by Shell Yuka Kogyo KK) as an ethoxy resin, 18.5 parts by weight of diphenyldiaminomethane as a curing agent, 200 parts by weight of the above aluminum hydroxide BW-153, and an average particle diameter of 13 mm
500 parts by weight of black granite, 3.0 parts by weight of magnesium oxide and 45 parts by weight of a 13 mm long glass chop are kneaded, and the kneaded material is preformed into a sheet, and then kneaded.
Aging for 24 hours, molding temperature 155 ° C, molding pressure 90
Molding was performed with a curing time of 20 minutes at Kg / cm 2 . The molded product was free of cracks and warpage, and as a result of polishing, a black product close to natural black granite was obtained.
【００２０】実施例１ Embodiment 1
【００２１】上記ポリライトＰＳ−２６６ １００重量
部、上記ポリライトＰＢ−９５６３０部、上記水酸化ア
ルミニウムＢＷ−１５３ ２００重量部、平均粒径１０
ｍｍの白御影石と呼ばれる天然砕石５００重量部、ｔ−
ブチルパーベンゾエート１．０重量部、酸化マグネシウ
ム１．０重量部、１３ｍｍガラスチョップ４０重量部を
実施例１と同様な方法で混練し、熟成した後、成形し
た。得られた成形品はクラックやそりがなく、これを研
磨した結果、得られた製品は白御影石風であった。100 parts by weight of the polylite PS-266, 100 parts by weight of the polylite PB-95630 parts, 200 parts by weight of the aluminum hydroxide BW-153, and an average particle diameter of 10
500 parts by weight of natural crushed stone called white granite of mm, t-
1.0 part by weight of butyl perbenzoate, 1.0 part by weight of magnesium oxide, and 40 parts by weight of 13 mm glass chop were kneaded in the same manner as in Example 1, aged, and then molded. The obtained molded product was free from cracks and warpage, and as a result of polishing, the obtained product was white granite-like.
【００２２】比較例１ 上記ポリライトＰＳ−２６６ １００重量部、上記水酸
化アルミニウムＢＷ−１５３ ２００重量部、平均粒径
１０ｍｍの白御影石と呼ばれる天然砕石５００重量部、
ｔ−ブチルパーベンゾエート１．０重量部を混練させ、
この混練物をシート状にプリフォームし、常温で２４時
間熟成させた後、１４５℃に加熱された平板用金型に充
填させ、成形圧力８０Ｋｇ／ｃｍ2 の条件下で１５分硬
化させ、厚み２０ｍｍの板を成形したが、成形品中央部
に無数のクラックが発生するとともに、巣が数個所に発
生し、充填不良を起こした。この成形品を研磨機で０．
５〜１．０ｍｍ研磨したが外観は良好であった。Comparative Example 1 100 parts by weight of the polylite PS-266, 200 parts by weight of the aluminum hydroxide BW-153, 500 parts by weight of natural crushed stone called white granite having an average particle diameter of 10 mm,
kneading 1.0 part by weight of t-butyl perbenzoate;
The kneaded material was preformed into a sheet, aged at room temperature for 24 hours, filled in a flat plate mold heated to 145 ° C., cured at a molding pressure of 80 kg / cm 2 for 15 minutes, and cured. Although a 20 mm plate was formed, countless cracks were generated at the center of the formed product, and burrs were formed at several places, resulting in defective filling. This molded product is polished with a grinder.
Polished 5 to 1.0 mm, but good appearance.
【００２３】比較例２ 上記ポリライトＰＳ−２６６ １００重量部、ｔ−ブチ
ルパーベンゾエート１．０重量部、上記水酸化アルミニ
ウムＢＷ−１５３ ２００重量部、平均粒径０．５ｍｍ
の白御影石の石粉５００重量部、を比較例１と同様な方
法で混練し、熟成した後成形したが、成形品はクラック
や巣のない成形品が得られた。この成形品を研磨した結
果、外観は良好であったが、自然石らしくない製品であ
った。Comparative Example 2 100 parts by weight of the polylite PS-266, 1.0 part by weight of t-butyl perbenzoate, 200 parts by weight of the aluminum hydroxide BW-153, and an average particle size of 0.5 mm
Was mixed and kneaded in the same manner as in Comparative Example 1, and aged. The molded product was a molded product without cracks or nests. As a result of polishing this molded product, the appearance was good, but the product was not like natural stone.
【００２４】比較例３ 上記ポリライトＰＳ−２６６ １００重量部、上記ポリ
ライトＰＢ−９５６３重量部、上記水酸化アルミニウム
ＢＷ−１５３ ２００重量部、平均粒径２５ｍｍの白御
影石と呼ばれる天然砕石５００重量部、ｔ−ブチルパー
ベンゾエート１．０重量部、酸化マグネシウム１．０重
量部、３３ｍｍガラスチョップ４０重量部を実施例１と
同様な方法で混練し、熟成した後、成形した。得られた
成形品は流動性が悪く、成形品に欠けが生じ、良品が得
られなかった。この成形品を研磨したが質感は良好であ
った。上記実施例及び比較例の成形品について評価した
結果を表に示す。Comparative Example 3 100 parts by weight of the polylite PS-266, 200 parts by weight of the aluminum hydroxide BW-153, 500 parts by weight of natural crushed stone called white granite having an average particle diameter of 25 mm, t 1.0 part by weight of butyl perbenzoate, 1.0 part by weight of magnesium oxide, and 40 parts by weight of a 33 mm glass chop were kneaded in the same manner as in Example 1, aged, and then molded. The obtained molded article had poor fluidity, chipped the molded article, and could not obtain a good product. The molded product was polished, but the texture was good. The results of evaluating the molded products of the above Examples and Comparative Examples are shown in the table.
【００２５】[0025]
【表１】 [Table 1]
【００２６】なお、表中、材料反発硬さはＪＩＳ ６３
０１、成形収縮率、曲げ強度、シャルビー衝撃値はＪＩ
Ｓ ６９１１に依った。また、流動性はサイズ６００×
１２００ｍｍ、厚さ２０ｍｍ成形品のショートショット
欠けの有無、クラックは上記成形品における割れの有
無、質感は御影石の質感の良否である。In the table, the material rebound hardness is JIS 63
01, molding shrinkage, flexural strength, Charby impact value is JI
Depends on S6911. The fluidity is 600 ×
The presence or absence of short shot chipping of a molded product having a thickness of 1200 mm and a thickness of 20 mm, the presence of cracks indicates the presence or absence of cracks in the molded product, and the texture is the quality of the granite.
【００２７】[0027]
【発明の効果】本発明によれば、平均粒径が１０ｍｍ以
上２０ｍｍ以下の天然砕石４００〜８００重量部を使用
するとともに、硬化触媒と、添加剤として少なくとも２
５ｍｍ以下の繊維状強化材及び低収縮剤を３重量部より
多く５０重量部以下使用したので、天然の大理石と同様
な艶と模様柄、色調等の質感を有するのみならず、天然
石では得られない強度のある材料が得られ、従来得られ
なかった薄型成形品を提供することができる。According to the present invention, the average particle size is 10 mm or less.
Use 400-800 parts by weight of natural crushed stone of 20mm or less
And a curing catalyst and at least 2
5mm or less fibrous reinforcement and low shrinkage agent from 3 parts by weight
Since it is used in less than 50 parts by weight, not only does it have the same luster, pattern, color tone, and other textures as natural marble, but it is also possible to obtain materials with strength that cannot be obtained with natural stone, and thin molding that could not be obtained conventionally Goods can be provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０４Ｂ 16:06 Ｃ０４Ｂ 16:06 Ｅ 22:06 22:06 Ｚ 24:24） 24:24） Ａ 111:54 111:54 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI C04B 16:06 C04B 16:06 E 22:06 22:06 Z 24:24) 24:24) A 111: 54 111: 54
Claims (3)
填剤３０〜３００重量部と、平均粒径が１０ｍｍ以上２
０ｍｍ以下の天然砕石４００〜８００重量部を含有する
樹脂コンパウンドに対して硬化触媒と、低収縮剤、２５
ｍｍ以下の繊維状強化材及び増粘剤の群からなる添加助
剤の少なくとも２５ｍｍ以下の繊維状強化材及び低収縮
剤３重量部より多く５０重量部以下を含有した組成物か
ら得られる天然石風人工大理石。1. 100 parts by weight of a thermosetting resin, 30 to 300 parts by weight of a fine powder filler, and an average particle diameter of 10 mm or more.
For a resin compound containing 400 to 800 parts by weight of natural crushed stone of 0 mm or less, a curing catalyst, a low shrinkage agent, 25
mm or less of the auxiliary agent consisting of a group of fibrous reinforcements and thickeners of at least 25 mm or less and low shrinkage
A natural stone-like artificial marble obtained from a composition containing more than 3 parts by weight and not more than 50 parts by weight of an agent .
重量部と、微粉末充填剤３０〜３００重量部と、天然砕
石４００〜８００重量部の割合でそれぞれの成分を含有
し、添加助剤として含有される各成分は低収縮剤３重量
部より多く５０重量部以下、繊維状強化材１００重量部
以下、増粘剤５重量部以下の割合である請求項１記載の
天然石風人工大理石。2. The resin compound is a thermosetting resin 100.
And parts, and the fine powder filler 30 to 300 parts by weight, and containing the respective components in the ratio of natural crushed stone 400-800 parts by weight, each component is 3 weight low shrinkage agent contained as an additive aid
The natural stone-like artificial marble according to claim 1, wherein the proportion is more than 50 parts by weight, 100 parts by weight or less of the fibrous reinforcing material, and 5 parts by weight or less of the thickener.
に投入し、１１０〜１７０℃で加圧成形し、更に成形品
の表面を研磨することを特徴とする天然石風人工大理石
の製造方法。3. A natural stone-like artificial material characterized in that the composition according to claim 1 is thickened, then put into a mold, pressed at 110 to 170 ° C., and further polished on the surface of the molded product. Marble manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37582198A JP3235579B2 (en) | 1998-12-18 | 1998-12-18 | Natural stone-like artificial marble and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37582198A JP3235579B2 (en) | 1998-12-18 | 1998-12-18 | Natural stone-like artificial marble and method for producing the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1287521A Division JP3052143B2 (en) | 1989-11-06 | 1989-11-06 | Natural stone-like artificial marble and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11263655A JPH11263655A (en) | 1999-09-28 |
| JP3235579B2 true JP3235579B2 (en) | 2001-12-04 |
Family
ID=18506116
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101147395B1 (en) * | 2009-11-13 | 2012-05-22 | 한국생산기술연구원 | Method of manufacturing polymer composite material using natural stone |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102243646B1 (en) * | 2020-10-23 | 2021-04-23 | 주식회사 주안 | Ultra high strength fiber reinforced plastics using natural fiber and preparing method thereof |
-
1998
- 1998-12-18 JP JP37582198A patent/JP3235579B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101147395B1 (en) * | 2009-11-13 | 2012-05-22 | 한국생산기술연구원 | Method of manufacturing polymer composite material using natural stone |
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| Publication number | Publication date |
|---|---|
| JPH11263655A (en) | 1999-09-28 |
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