JPH08225705A - Material for compression molding and resin molding using the same - Google Patents
Material for compression molding and resin molding using the sameInfo
- Publication number
- JPH08225705A JPH08225705A JP7293172A JP29317295A JPH08225705A JP H08225705 A JPH08225705 A JP H08225705A JP 7293172 A JP7293172 A JP 7293172A JP 29317295 A JP29317295 A JP 29317295A JP H08225705 A JPH08225705 A JP H08225705A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- acrylic
- compression molding
- particles
- acrylic resin
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/06—Acrylates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/54—Substitutes for natural stone, artistic materials or the like
- C04B2111/542—Artificial natural stone
- C04B2111/545—Artificial marble
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アクリル樹脂系の圧縮
成形用成形材料及びそれを硬化させた樹脂成形物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic resin-based molding material for compression molding and a resin molding obtained by curing the same.
【０００２】[0002]
【従来の技術】無機系充填剤を含んだアクリル樹脂は、
深みのある外観と高級な感触が特徴であり人工大理石と
してキッチン天板、各種カウンタートップ、洗面化粧
台、浴室回り、床材、壁材などに広く使用されている。Acrylic resins containing inorganic fillers are
It has a deep appearance and a high-class feel, and is widely used as an artificial marble for kitchen top plates, various countertops, vanities, bathroom areas, flooring and wall materials.
【０００３】これらの製品を製造する手段としては、メ
タクリル酸メチルを主成分とするアクリル系シラップに
水酸化アルミニウムと、重合開始剤を混合した混合物を
型材に注入し、加熱重合させるキャスト法（特公昭５０
−２２５８６号公報）、押出機中でアクリル系シラップ
と水酸化アルミニウム、ポリメチルメタクリレート粉末
を混合、溶融し賦形加工する方法（特開平１−１４１３
８号公報）が一般的であった。As a means for producing these products, a casting method (special method) in which a mixture of aluminum syrup containing methyl methacrylate as a main component and aluminum hydroxide and a polymerization initiator is poured into a mold material and heated and polymerized is used. Kosho 50
No. 22586), a method of mixing acrylic syrup, aluminum hydroxide, and polymethylmethacrylate powder in an extruder, melting and shaping (Japanese Patent Application Laid-Open No. 1-1413).
No. 8) was common.
【０００４】最近、特開平５−３２７２０号公報に見ら
れるように新しくアクリル樹脂を圧縮成形により賦形加
工する方法が提案されている。アクリル系樹脂を圧縮成
形する場合には、一般にプリミックスと呼ばれるパテ状
の成形材料を調製した後、圧縮成形する方法が採用され
ている。Recently, as disclosed in Japanese Unexamined Patent Publication No. 5-32720, a new method of shaping an acrylic resin by compression molding has been proposed. In the case of compression molding an acrylic resin, a method of preparing a putty-shaped molding material generally called a premix and then performing compression molding is adopted.
【０００５】アクリル樹脂に無機充填剤を含有させた人
工大理石は、一般的にはメタクリル酸メチルを主体とす
る不飽和単量体に重合体を溶解含有させたシラップに無
機粉末を分散含有せしめてスラリーとなし、これを型に
沿わせて重合硬化するキャスト法により製造されてい
る。An artificial marble containing an acrylic resin containing an inorganic filler is generally prepared by dispersing an inorganic powder in a syrup prepared by dissolving a polymer in an unsaturated monomer mainly containing methyl methacrylate. It is manufactured by a casting method in which a slurry is formed and is polymerized and hardened along a mold.
【０００６】メタクリル酸メチルを主体とする不飽和単
量体は、沸点が低いため、重合時のモノマーの揮散や、
揮発による空孔の発生を防止するため、重合硬化に際し
ては重合温度を沸点以下である６０〜８０℃の比較的低
温にて行う必要がある。したがって、重合温度が低いた
めに硬化が遅く、成形に長時間を要し、生産性が劣ると
いう問題点があった。Unsaturated monomers mainly composed of methyl methacrylate have a low boiling point, so that the evaporation of the monomers during polymerization,
In order to prevent the generation of voids due to volatilization, it is necessary to carry out the polymerization and curing at a relatively low temperature of 60 to 80 ° C., which is the boiling point or less. Therefore, since the polymerization temperature is low, the curing is slow, the molding requires a long time, and the productivity is poor.
【０００７】一方、熱硬化性樹脂が主成分である不飽和
ポリエステル系人工大理石は、アクリル系人工大理石と
同様なキャスト法と圧縮成形法による方法で製造され
る。熱硬化性樹脂を圧縮成形する際には、前もって液状
の熱硬化性樹脂（特に不飽和ポリエステル）に、補強
剤、充填剤、硬化剤、着色剤などを練り合わせてパテ状
の成形材料を調製する。On the other hand, the unsaturated polyester artificial marble containing a thermosetting resin as a main component is manufactured by the same casting method and compression molding method as the acrylic artificial marble. When the thermosetting resin is compression-molded, a putty-like molding material is prepared by previously kneading a liquid thermosetting resin (particularly unsaturated polyester) with a reinforcing agent, a filler, a curing agent, a coloring agent and the like. .
【０００８】一般に、このパテ状の成形材料をプリミッ
クスと呼んでいる。熱硬化性樹脂の成形においては品質
の安定したプリミックスを作ることが重要であり、その
ための各種の工夫がなされている。プリミックスを用い
た圧縮成形の成形速度は、一般に成形品の肉厚１ｍｍに
つき１分以内の割合で短時間に加熱圧縮成形できるとさ
れている。Generally, this putty-like molding material is called a premix. In molding a thermosetting resin, it is important to make a premix with stable quality, and various measures have been taken for that purpose. The molding speed of compression molding using the premix is generally said to be such that heat compression molding can be performed in a short time at a rate of 1 minute or less per 1 mm of the wall thickness of the molded product.
【０００９】圧縮成形法は、キャスト法に比べ生産性が
高く、経済性も優れている。アクリル系人工大理石を生
産性良く、しかも種々の形態の製品が製造できる圧縮成
形にて得る方法も報告されており、メタクリル酸メチル
を主体とする不飽和単量体と無機粉末の高粘度混合物す
なわちプリミックスを加圧下、高温下で重合硬化する方
法が特開平５−３２７２０号公報などに報告されてい
る。The compression molding method has higher productivity and is more economical than the casting method. A method for obtaining an acrylic artificial marble with good productivity, and also by compression molding capable of producing products in various forms, has been reported, that is, a high-viscosity mixture of an unsaturated monomer mainly composed of methyl methacrylate and an inorganic powder, that is, A method of polymerizing and curing the premix under pressure and at a high temperature is reported in JP-A-5-32720.
【００１０】この方法では、メタクリル酸メチルを主体
とする不飽和単量体に不溶で膨潤度が３〜１５倍である
樹脂微粒子を含有させてプリミックスを得ているが、膨
潤度が３〜１５倍と大きいため、十分にしかも均一に膨
潤させるためには長時間を要することと、樹脂粒子の膨
潤度が大きいため得られる成形品の光沢や透明性などの
意匠効果が低下することは避けられなかった。また特開
平５−３１０８３８号公報ではアクリル系シラップに高
分子物質微小粒子を静置溶解することにより高粘度アク
リルシラップを製造する方法が開示されているが、溶解
するのに半日以上の長時間を要する。According to this method, a premix is obtained by containing fine resin particles insoluble in an unsaturated monomer mainly containing methyl methacrylate and having a swelling degree of 3 to 15 times. Since it is as large as 15 times, it takes a long time to swell sufficiently and uniformly, and it is possible to avoid deterioration of design effects such as gloss and transparency of the obtained molded product due to the large degree of swelling of resin particles. I couldn't do it. Further, Japanese Patent Application Laid-Open No. 5-310838 discloses a method for producing a high-viscosity acrylic syrup by statically dissolving polymeric substance fine particles in an acrylic syrup, but it takes a long time of half a day or more for dissolution. It costs.
【００１１】メタクリル樹脂系の不飽和単量体（モノマ
ー）を用いた圧縮成形においても、プリミックスの調製
が最も重要な要点の一つである。アクリル系プリミック
スは、不飽和ポリエステルのように簡単には増粘できな
いので、粘度の高いプリミックス調製のための各種の工
夫がされており、例えば特公昭６４−１１６５２号公報
にはカルボキシル基を有するビニルモノマーを、部分的
に共重合させたアクリル系シラップに、増粘剤としてＭ
ｇＯやＭｇ（ＯＨ）2 などのアルカリ土類金属酸化物や
水酸化物を添加してプリミックスを調製する方法が提案
されている。また、特公平１−４６５３０号公報にはヒ
ドロキシル基を有するビニルモノマーを部分的に共重合
させたアクリル系シラップに、ポリイソシアネート化合
物とアルミニウムアルコラートを添加することにより増
粘したプリミックスを調製する方法が提案されている。Preparation of a premix is also one of the most important points in compression molding using a methacrylic resin-based unsaturated monomer. Since acrylic premixes cannot be easily thickened like unsaturated polyesters, various measures have been taken to prepare highly viscous premixes. For example, Japanese Patent Publication No. 64-11652 discloses a carboxylic group. Acrylic syrup obtained by partially copolymerizing the vinyl monomer with M is used as a thickener.
A method for preparing a premix by adding an alkaline earth metal oxide or hydroxide such as gO or Mg (OH) 2 has been proposed. Further, JP-B-1-46530 discloses a method for preparing a thickened premix by adding a polyisocyanate compound and an aluminum alcoholate to an acrylic syrup obtained by partially copolymerizing a vinyl monomer having a hydroxyl group. Is proposed.
【００１２】さらに、特開平５−１２４８４４号公報に
は水酸基を含有したポリメチルメタアクリレート共重合
体を含んだアクリル系シラップに充填剤とポリイソシア
ネートを加えて粘度の高いプリミックスを調製した後、
加熱下で圧縮成形により人工大理石を製造することが提
案されている。Further, in JP-A-5-124844, after adding a filler and polyisocyanate to an acrylic syrup containing a polymethylmethacrylate copolymer having a hydroxyl group to prepare a highly viscous premix,
It has been proposed to produce artificial marble by compression molding under heating.
【００１３】[0013]
【発明が解決しようとする課題】アクリル樹脂系プリミ
ックスを調製する場合には、特開昭６１−１７１７１３
号公報や特開平２−１６０６４８号公報に見られるよう
に、ポリメチルメタクリレート系の樹脂粉末をシラップ
に添加し溶解させることにより粘度を高める方法が一般
的である。しかし、以上の方法では高粘度のプリミック
スを調製する場合に、均一撹拌が難しいためプリミック
スの温度調節が困難となり、異常重合などが発生し易く
なるため重合率や重合度などの品質管理が難しい点があ
る。また無機材料粉末を高濃度に充填することによりプ
リミックスを調製する方法も一般的であるが、得られる
成形品は透明性が劣る点が問題である。SUMMARY OF THE INVENTION When preparing an acrylic resin-based premix, there is disclosed in JP-A-61-171713.
As disclosed in Japanese Patent Application Laid-Open No. 2-160648 and Japanese Patent Application Laid-Open No. 2-160648, a method of increasing viscosity by adding a polymethylmethacrylate resin powder to a syrup and dissolving it is common. However, in the case of preparing a high-viscosity premix by the above method, it is difficult to control the temperature of the premix because uniform stirring is difficult, and abnormal polymerization or the like is likely to occur, so quality control such as polymerization rate or degree of polymerization can be performed. There are difficulties. Further, a method of preparing a premix by filling an inorganic material powder at a high concentration is also common, but a problem is that the obtained molded product is inferior in transparency.
【００１４】以上、説明したように、従来のプリミック
スを調製する圧縮成形法では、粘度が高いプリミックス
を均一に混合撹拌する事が難しく、そのため圧縮成形に
より得られる製品の品質にムラが生じやすいという問題
点があった。As described above, in the conventional compression molding method for preparing a premix, it is difficult to uniformly mix and stir a high-viscosity premix, and therefore the quality of the product obtained by compression molding becomes uneven. There was a problem that it was easy.
【００１５】[0015]
【課題を解決するための手段】本発明の要旨は、メタク
リル酸メチルを主成分とするアクリル系シラップ（ａ）
６０〜１０重量％、水酸化アルミニウム（ｂ）５０〜８
５重量％、メタクリル酸メチルを主成分としアクリル系
シラップに溶解する重量平均分子量２０〜８０万、平均
粒径１ｍｍ以下のアクリル樹脂微粒子（ｃ）６０〜１重
量％及び重合開始剤からなり、アクリル樹脂微粒子
（ｃ）の一部が溶解し残部が未溶解状態にあることを特
徴とする圧縮成形用材料にある。The gist of the present invention is to provide an acrylic syrup (a) containing methyl methacrylate as a main component.
60 to 10% by weight, aluminum hydroxide (b) 50 to 8
5% by weight, 60 to 1% by weight of acrylic resin fine particles (c) having a weight average molecular weight of 200 to 800,000 having a methyl methacrylate as a main component and dissolved in an acrylic syrup and an average particle diameter of 1 mm or less, and a polymerization initiator, and acryl. The compression molding material is characterized in that a part of the resin fine particles (c) is dissolved and the rest is in an undissolved state.
【００１６】また本発明の要旨は、メタクリル酸メチル
を主成分とするアクリル系シラップ（ａ）６０〜１０重
量％、水酸化アルミニウム（ｂ）、メタクリル酸メチル
を主成分としアクリル系シラップに溶解する平均分子量
２０〜８０万、平均粒径１ｍｍ以下のアクリル樹脂微粒
子（ｃ）６０〜１重量％、水酸化アルミニウムを５０重
量％以上含有したアクリル系人工大理石粉砕粒子（ｄ）
１〜８０重量％及び重合開始剤からなり、アクリル樹脂
微粒子（ｃ）の一部が溶解し残部が未溶解の状態にあ
り、且つ全組成中の水酸化アルミニウムの合計量が５０
〜８５重量％になるような量に（ｂ）の水酸化アルミニ
ウムが配合されてなることを特徴とする圧縮成形用材料
にある。Further, the gist of the present invention is to dissolve 60 to 10% by weight of acrylic syrup (a) containing methyl methacrylate as a main component, aluminum hydroxide (b), and acrylic syrup containing methyl methacrylate as main components. Acrylic artificial marble ground particles (d) containing acrylic resin fine particles (c) having an average molecular weight of 200,000 to 800,000 and an average particle size of 1 mm or less (c) of 60 to 1% by weight and aluminum hydroxide of 50% by weight or more.
1 to 80% by weight and a polymerization initiator, a part of the acrylic resin fine particles (c) is dissolved and the rest is undissolved, and the total amount of aluminum hydroxide in the entire composition is 50.
The material for compression molding is characterized in that the aluminum hydroxide of (b) is blended in an amount such that the amount becomes to 85% by weight.
【００１７】更に本発明の要旨は、これらの圧縮成形用
材料を加圧下に賦形して重合硬化させて得られた樹脂成
形物にある。Further, the gist of the present invention resides in a resin molded product obtained by shaping these compression molding materials under pressure and polymerizing and curing them.
【００１８】本発明の成形材料は、アクリル系シラップ
にアクリル樹脂微粒子（ｃ）の一部が溶解し残部が溶解
していない半溶解の状態に調製されていることを特徴と
する。即ち、高粘度のプリミックスを調製するに際して
ポリメチルメタクリレート樹脂微粒子を増粘剤として用
いる点に特徴があり、これによりプリミクッスの調製が
容易になる。また本発明の成形材料は、アクリル樹脂微
粒子（ｃ）と水酸化アルミニウムを５０重量％以上含有
したアクリル系人工大理石粉砕粒子（ｄ）とを併用する
点に特徴がある。The molding material of the present invention is characterized in that it is prepared in a semi-dissolved state in which a part of the acrylic resin fine particles (c) is dissolved and the rest is not dissolved in the acrylic syrup. That is, it is characterized in that fine particles of polymethylmethacrylate resin are used as a thickener when preparing a high-viscosity premix, which facilitates preparation of the premix. Further, the molding material of the present invention is characterized in that the acrylic resin fine particles (c) and the crushed acrylic artificial marble particles (d) containing 50% by weight or more of aluminum hydroxide are used together.
【００１９】以下本発明を詳細に説明する。本発明に用
いるメタクリル酸メチルを主成分とするアクリル系シラ
ップ（ａ）としては、メタクリル酸メチル単量体単独、
又はメタクリル酸メチル単量体に酢酸ビニル、スチレ
ン、メチルアクリレート、エチルメタクリレート、ブチ
ルメタアクリレート、シクロヘキシルメタアクリレート
などのα，β不飽和化合物を混合したメタクリル酸メチ
ルを主成分とする単量体混合物もしくはこれらの部分重
合体、又はメタクリル酸メチルにポリメチルメタクリレ
ート又は上記単量体混合物の共重合体を溶解させたもの
が挙げられる。アクリル系シラップ（ａ）の使用量は１
０〜６０重量％、好ましくは１５〜５０重量％である。The present invention will be described in detail below. As the acrylic syrup (a) containing methyl methacrylate as a main component used in the present invention, a methyl methacrylate monomer alone,
Alternatively, a methyl methacrylate-based monomer mixture obtained by mixing an α, β unsaturated compound such as vinyl acetate, styrene, methyl acrylate, ethyl methacrylate, butyl methacrylate, or cyclohexyl methacrylate with a methyl methacrylate monomer, or These partial polymers or those obtained by dissolving polymethyl methacrylate or a copolymer of the above-mentioned monomer mixture in methyl methacrylate can be mentioned. The amount of acrylic syrup (a) used is 1
It is 0 to 60% by weight, preferably 15 to 50% by weight.
【００２０】アクリル系シラップ（ａ）は、アクリル系
シラップの総重量に対して１５重量％以下の範囲で架橋
剤を含有しても良い。用いられる架橋剤としてはエチレ
ングリコールジメタクリレート、１，３−プロピレング
リコールジメタクリレート、ジビニルベンゼン、トリア
リルシアヌレート、ネオペンチルグリコールジメタクリ
レートなどを挙げることができる。The acrylic syrup (a) may contain a crosslinking agent in the range of 15% by weight or less based on the total weight of the acrylic syrup. Examples of the cross-linking agent used include ethylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, divinylbenzene, triallyl cyanurate and neopentyl glycol dimethacrylate.
【００２１】本発明は、無機充填剤として水酸化アルミ
ニウム（ｂ）を用いる。炭酸カルシウム、水酸化マグネ
シウム、シリカ、ガラスなどを少量併用してもよい。水
酸化アルミニウム（ｂ）の使用量は圧縮成形用材料の総
重量に対して５０〜８５重量％である。The present invention uses aluminum hydroxide (b) as an inorganic filler. A small amount of calcium carbonate, magnesium hydroxide, silica, glass or the like may be used together. The amount of aluminum hydroxide (b) used is 50 to 85% by weight based on the total weight of the compression molding material.
【００２２】一般に市販されているアクリル樹脂微粒子
は、アクリル系シラップには時間をかければ溶解するが
完全に溶解するまでに長時間を要する。溶解を早めるた
めに一般にはニーダーなどで混練・溶解や、ヘンシェル
ミキサーなどを用いた撹拌が行われるが、溶解が進むに
従って粘度が高くなるため十分な撹拌混合が困難であ
り、また、撹拌熱により異常重合が起こる危険性も高ま
る。Generally, the commercially available acrylic resin fine particles dissolve in the acrylic syrup over time, but it takes a long time to completely dissolve it. In order to accelerate the dissolution, kneading and dissolution are generally performed with a kneader or the like, and stirring using a Henschel mixer or the like is performed, but it is difficult to perform sufficient stirring and mixing because the viscosity increases as the dissolution progresses, and due to the heat of stirring. The risk of abnormal polymerization also increases.
【００２３】本発明に用いられるアクリル系樹脂微粒子
（ｃ）としては、メタクリル酸メチルの単独重合体やメ
タクリル酸メチルと酢酸ビニル、スチレン、メチルアク
リレート、エチルメタアクリレートなどの単量体との共
重合体が適用できる。好ましくは重量平均分子量が２０
万〜８０万のポリメチルメタアクリレートである。重量
平均分子量が２０万未満の場合には適切な粘度を得るた
めに必要となる樹脂微粒子量が多くなり、対応するアク
リル系シラップ量も多くなる結果、圧縮成形時における
重合収縮が大きくなり製品品質を損なう。また重量平均
分子量が８０万を超えるとメタクリル酸メチルへの溶解
速度が遅くなり生産性が低下する。また樹脂微粒子の粒
径は大きすぎると成形時にピンホ−ルやフィッシュアイ
生じさせ成形品の品質を損なうため１ｍｍ以下であるこ
とが好ましく５００μｍ以下であることがより好まし
い。The acrylic resin fine particles (c) used in the present invention include a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and a monomer such as vinyl acetate, styrene, methyl acrylate or ethyl methacrylate. Coalescence can be applied. Preferably the weight average molecular weight is 20
10,000 to 800,000 polymethylmethacrylate. When the weight average molecular weight is less than 200,000, the amount of fine resin particles required to obtain an appropriate viscosity is large, and the corresponding amount of acrylic syrup is also large, resulting in large polymerization shrinkage during compression molding and product quality. Spoil. On the other hand, if the weight average molecular weight exceeds 800,000, the dissolution rate in methyl methacrylate will be slow and productivity will be reduced. On the other hand, if the particle size of the resin fine particles is too large, pinholes or fish eyes are generated during molding, which impairs the quality of the molded product, and is preferably 1 mm or less, more preferably 500 μm or less.
【００２４】本発明で使用するアクリル樹脂微粒子
（ｃ）は、アクリル系シラップ（ａ）に完全溶解させる
必要はなく、混合することによる部分的な溶解で成形材
料として十分な性能を有するだけでなく、驚くことに溶
けていないアクリル樹脂微粒子が骨材として働き、不飽
和ポリエステル樹脂の圧縮成形にアクリル樹脂を収縮防
止剤として添加しているごとく、本発明においても未溶
解アクリル樹脂粒子の存在により収縮が低く抑えられ、
著しく寸法安定性などの物性が改善される。従って本発
明の圧縮形成用材料中においてアクリル樹脂微粒子は一
部が溶解し、残部は未溶解の状態にあることが必要であ
る。The acrylic resin fine particles (c) used in the present invention do not need to be completely dissolved in the acrylic syrup (a), and not only has sufficient performance as a molding material due to partial dissolution by mixing. Surprisingly, as undissolved acrylic resin fine particles act as an aggregate, and acrylic resin is added as an anti-shrink agent in compression molding of unsaturated polyester resin, shrinkage also occurs in the present invention due to the presence of undissolved acrylic resin particles. Is kept low,
Physical properties such as dimensional stability are remarkably improved. Therefore, in the compression-forming material of the present invention, it is necessary that the acrylic resin fine particles are partially dissolved and the rest are undissolved.
【００２５】本発明において、圧縮成形用材料を圧縮成
形して得られる樹脂成形物が、石目調等の模様がなく白
以外の色で薄く着色された様なモノトーン系の色調の場
合には、アクリル樹脂微粒子の粒径が大きめであると、
樹脂成形物の色調と異なった色調としてアクリル樹脂微
粒子が見え、意匠性を低下させることがある。このよう
な場合にはアクリル樹脂微粒子としては粒径１５０μｍ
以上のものが１０％以下であることが好ましい。In the present invention, in the case where the resin molded product obtained by compression molding the compression molding material has a monotone color tone such that there is no pattern such as stone tone and is lightly colored with a color other than white. If the particle size of the acrylic resin particles is large,
Acrylic resin fine particles can be seen as a color tone different from the color tone of the resin molded product, which may deteriorate the design. In such a case, the particle size of the acrylic resin particles is 150 μm.
It is preferable that the above is 10% or less.
【００２６】また、製品の意匠効果を高めるためやボイ
ドを減少させるために本発明の圧縮成形用材料に、更に
無機充填剤を５０重量％以上含有したアクリル人工大理
石粉砕粒子（ｄ）を添加しても良い。適用できる樹脂と
しては、アクリル系シラップに溶解しないものであれば
どのような樹脂でも良いが、意匠効果から不飽和ポリエ
ステル系人工大理石、または水酸化アルミニウムを充填
剤としたアクリル系人工大理石を粉砕した粒子が好まし
く、特に後者がよい。なお、粉砕粒子中の樹脂成分がア
クリル系シラップにより膨潤することは差し支えない。
人工大理石粉砕粒子の使用量は１〜８０重量％であり、
好ましくは４０〜７０重量％である。人工大理石粉砕粒
子を使用する際には、（ｂ）成分としての水酸化アルミ
ニウムの量は、（ｄ）成分に含まれる無機充填剤の量を
含めて圧縮成形用材料中５０〜８５重量％となるような
量を配合する必要がある。このような粉砕粒子として
は、粉砕粒子の平均粒径が０．１〜１０ｍｍであって、
粉砕粒子中のアクリル系樹脂が架橋樹脂であり、粉砕粒
子のメタクリル酸メチルに対する膨潤度が２．０以下で
あるものが好ましい。粉砕粒子の粒径が小さすぎると模
様のメリハリが無く、また、粒径が大きすぎると成形品
にクラックが発生したり、模様の輪郭が乱れる。粉砕粒
子の膨潤度が大きすぎると模様の輪郭がぼやけてメリハ
リがなくなり、また流れ状の汚れが発生する。Further, in order to enhance the design effect of the product and to reduce voids, acrylic artificial marble ground particles (d) containing 50% by weight or more of an inorganic filler are added to the compression molding material of the present invention. May be. Applicable resin may be any resin as long as it does not dissolve in acrylic syrup, but unsaturated polyester artificial marble or acrylic artificial marble containing aluminum hydroxide as a filler is crushed from the design effect. Particles are preferred, especially the latter. The resin component in the crushed particles may swell with the acrylic syrup.
The amount of crushed artificial marble particles used is 1 to 80% by weight,
It is preferably 40 to 70% by weight. When using the artificial marble ground particles, the amount of aluminum hydroxide as the component (b) is 50 to 85% by weight in the compression molding material, including the amount of the inorganic filler contained in the component (d). It is necessary to blend such an amount. As such crushed particles, the average particle size of the crushed particles is 0.1 to 10 mm,
It is preferable that the acrylic resin in the crushed particles is a crosslinked resin and the swelling degree of the crushed particles with respect to methyl methacrylate is 2.0 or less. If the particle size of the crushed particles is too small, the pattern will not be sharp, and if the particle size is too large, cracks will occur in the molded product or the contour of the pattern will be disturbed. If the degree of swelling of the crushed particles is too large, the contour of the pattern is blurred and the sharpness is lost, and flow-like dirt is generated.
【００２７】本発明に用いられる重合開始剤は、一般に
アクリル系モノマーに対して用いられる重合開始剤であ
る。例えば過酸化物系開始剤であるジ−３−メトキシブ
チルパーオキシジ−カーボネート、ジイソプロピルパー
オキシジカーボネート、ジシクロヘキシルパーオキシジ
カーボネート、ジセカンダリーブチルパーオキシジカー
ボネート、ジノルマルプロピルパーオキシジカーボネー
ト、２，４，４−トリメチルペンチルパーオキシフェノ
キシアセテート、イソブチルパーオキサイド、メチルエ
チルケトンパーオキサイド、ラウロイルパーオキサイ
ド、メチルイソブチルケトンパーオキサイド、シクロヘ
キサノンパーオキサイド、メチルシクロヘキサノンケト
ンパーオキサイド、ジクミルパーオキサイド、ターシャ
リ−ブチルパーオキシアセテートなど、アゾ系開始剤と
してはアゾビスイソブチロニトリル、１，１−アゾビス
−１−シクロヘキサンカーボニトリル、２−カーバモイ
ルアゾイソブチロニトリル、２，２’−アゾビス−２，
４，４−トリメチルペンタンなどが単独もしくは２種以
上を併用して使用できる。重合開始剤の使用量は（ａ）
と（ｃ）の総重量１００部に対して０．１〜５重量部で
ある。The polymerization initiator used in the present invention is a polymerization initiator generally used for acrylic monomers. For example, peroxide initiators such as di-3-methoxybutylperoxydicarbonate, diisopropylperoxydicarbonate, dicyclohexylperoxydicarbonate, disecondary butylperoxydicarbonate, dinormalpropylperoxydicarbonate, 2 , 4,4-Trimethylpentylperoxyphenoxyacetate, isobutyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone ketone peroxide, dicumyl peroxide, tertiary-butyl peroxide As an azo-based initiator such as acetate, azobisisobutyronitrile, 1,1-azobis-1-cyclohexanecarbene Bonitoriru, 2- Kaaba Moyle azoisobutyronitrile, 2,2'-azobis -2,
4,4-Trimethylpentane and the like can be used alone or in combination of two or more kinds. The amount of the polymerization initiator used is (a)
0.1 to 5 parts by weight based on 100 parts by weight of (c).
【００２８】本発明の圧縮成形用材料を調製するに当
り、水酸化アルミニウム（ｂ）、アクリル樹脂微粒子
（ｃ）及び重合開始剤をアクリル系シラップ（ａ）に混
合する順序は重要ではない。しかし、望ましくはアクリ
ル系シラップ（ａ）に所定量の重合開始剤を最初に均一
に混合し、次いで水酸化アルミニウム（ｂ）又は更に人
工大理石粒子（ｄ）を添加、混合し、最後にアクリル樹
脂微粒子（ｃ）を添加することが望ましい。アクリル樹
脂微粒子（ｃ）の混合・撹拌はミキサーやニーダーなど
を用いて１時間以内簡単に行い、アクリル樹脂微粒子の
一部が溶解し残りの部分が未溶解の状態にあるように調
製する。In preparing the compression molding material of the present invention, the order of mixing the aluminum hydroxide (b), the acrylic resin fine particles (c) and the polymerization initiator with the acrylic syrup (a) is not important. However, it is desirable to first uniformly mix a predetermined amount of a polymerization initiator with acrylic syrup (a), then add and mix aluminum hydroxide (b) or artificial marble particles (d), and finally add acrylic resin. It is desirable to add the fine particles (c). The mixing and stirring of the acrylic resin fine particles (c) are easily performed within 1 hour using a mixer or a kneader, and the acrylic resin fine particles are prepared so that a part of the acrylic resin fine particles is dissolved and the rest is in an undissolved state.
【００２９】本発明の圧縮成形用材料は、アクリル系シ
ラップが少ない組成の場合には混合物がフレーク状であ
り、シラップが多い場合には餅状のあるプリミックスと
なる。The composition for compression molding of the present invention is a flake-like premix when the composition has a small amount of acrylic syrup, and becomes a dough-like premix when there is a large amount of syrup.
【００３０】本発明圧縮成形用材料としてのプリミック
スの粘度も重要である。粘度はＲｈｅｏｍｅｔｒｉｃｓ
（レオメトリックス）社製ＲＤＡ−７００型粘度計（Ｒ
ｈｅｏｍｅｔｒｉｃｓ Ｄｙｎａｍｉｃ Ａｎａｌｙｚ
ｅｒ）にて測定（本明細書を通じ同じ）した粘度が１
０，０００〜１，５００，０００ポイズの範囲が適当で
ある。なお、好ましい粘度範囲は１００，０００〜１，
０００，０００ポイズである。The viscosity of the premix as the compression molding material of the present invention is also important. Viscosity is Rheometrics
(Rheometrics) RDA-700 viscometer (R
hemometrics Dynamic Analytics
er) (viscosity throughout this specification) has a viscosity of 1
A range of 10,000 to 1,500,000 poise is suitable. The preferred viscosity range is 100,000-1,
It is, 000,000 poise.
【００３１】本発明の圧縮成形用材料は、圧縮成形、射
出成形、トランスファー成形が可能である。圧縮成形条
件としては、圧力が１０〜５００ｋｇ／ｃｍ2 、好まし
くは５０〜１５０ｋｇ／ｃｍ2 、加熱温度は８０〜１２
０℃で重合硬化させる。好ましくは９０〜１１０℃、圧
縮時間は２〜１０分、好ましくは３〜７分である。The compression molding material of the present invention can be subjected to compression molding, injection molding and transfer molding. The compression molding conditions include a pressure of 10 to 500 kg / cm 2 , preferably 50 to 150 kg / cm 2 , and a heating temperature of 80 to 12.
Polymerize and cure at 0 ° C. The temperature is preferably 90 to 110 ° C., and the compression time is 2 to 10 minutes, preferably 3 to 7 minutes.
【００３２】本発明の圧縮成形用材料には必要に応じて
補強剤、離型剤、顔料、安定剤、重合調節剤、有機充填
剤などを加えてあってもよい。If desired, the compression molding material of the present invention may contain a reinforcing agent, a release agent, a pigment, a stabilizer, a polymerization regulator, an organic filler and the like.
【００３３】[0033]
【実施例】以下実施例により具体的に説明する。実施例
において、アクリル系人工大理石粉砕粒子の膨潤度は、
１０００ｍｌメスシリンダ内に粉砕粒子を２００ｍｌ入
れ２５℃の大量のＭＭＡ中に１時間浸漬して膨潤させた
後の粒子の体積Ｖと元の粒子の体積Ｖ0のとの比Ｖ／Ｖ0
で求めた。Embodiments will be specifically described below with reference to embodiments. In the examples, the degree of swelling of the acrylic artificial marble ground particles is
The ratio V / V 0 of the volume V 0's and the volume V and the original particles of the particles after the grinding particles was swollen by immersion for 1 hour in a large amount of MMA in 200ml insertion 25 ° C. in a 1000ml measuring cylinder
I asked for.
【００３４】［実施例１］常温に設定されたヘンシェル
ミキサーを用いてポリメチルメタルリレート（平均分子
量６万）２０重量部を溶解した粘度５０センチポイズの
メチルメタクリレートシラップ２７．１重量％、架橋剤
としてエチレングリコールジメタクリレート０．４重量
％、水酸化アルミニウム（日本軽金属（株）製）６２．
５重量％、重合開始剤としてはラウロイルパーオキサイ
ド１．５重量％の割合で投入し、撹拌混合した。ついで
アクリル樹脂微粒子（重量平均分子量２８００００、粒
子径２６０μｍ）（三菱レイヨン（株）製、商品名ＢＲ
−８５）８．５重量％を添加し３分間混合した後３０分
間放置した。このようにして得られた高粘度アクリル樹
脂プリミックスの２０℃における粘度をＲＤＡ−７００
型粘度計で測定したところ２５万ポイズであった。[Example 1] 27.1% by weight of methyl methacrylate syrup having a viscosity of 50 centipoise dissolved in 20 parts by weight of polymethylmetallate (average molecular weight 60,000) using a Henschel mixer set at room temperature, as a crosslinking agent 0.4% by weight of ethylene glycol dimethacrylate, aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd.) 62.
5% by weight and a polymerization initiator of 1.5% by weight of lauroyl peroxide were added, and the mixture was stirred and mixed. Then, acrylic resin fine particles (weight average molecular weight 280000, particle diameter 260 μm) (trade name BR, manufactured by Mitsubishi Rayon Co., Ltd.)
-85) 8.5 wt% was added and mixed for 3 minutes, and then left for 30 minutes. The viscosity of the high-viscosity acrylic resin premix thus obtained at 20 ° C. was measured by RDA-700.
It was 250,000 poise as measured by a viscometer.
【００３５】次いで、３００トン・プレス（川崎油工
（株）製）にてクロム鍍金面を有するシャンプーボウル
の成型用金型を用いて、金型温度を１００℃にして上記
プリミックスを面圧８０ｋｇ／ｃｍ2 ，真空引き６５０
ｍｍＨｇの条件下３００秒加圧重合して肉厚１３ｍｍの
アクリル人工大理石のシャンプーボウルを成形した。得
られたシャンプーボウルは製品表面の外観は良好で、透
明感に優れ、金型面を忠実に転写した美しい光沢面を有
していた。Then, using a 300-ton press (manufactured by Kawasaki Yuko Co., Ltd.), using a mold for molding a shampoo bowl having a chrome-plated surface, the mold temperature was set to 100 ° C., and the surface pressure of the premix was 80 kg. / Cm 2 , vacuum 650
It was pressure-polymerized for 300 seconds under the condition of mmHg to form a shampoo bowl made of acrylic artificial marble having a thickness of 13 mm. The resulting shampoo bowl had a good appearance on the product surface, was excellent in transparency, and had a beautiful glossy surface faithfully transferred to the mold surface.
【００３６】［実施例２］実施例１で得た高粘度アクリ
ル樹脂プリミックスを、２００トン射出成形機（（株）
日本製鋼所製）にてクロム鍍金面を有する自動車ヘッド
ランプ反射鏡成形用金型を用いて、金型温度１００℃、
射出圧６０ｋｇ／ｃｍ2 、型締め圧１００トンの条件
下、真空を６５０ｍｍＨｇに引きながら１８０秒間加圧
重合して肉厚３ｍｍのアクリル人工大理石自動車ヘッド
ランプ反射鏡を成形した。得られた成形品は外観が良好
で、透明感に優れ、金型面を忠実に転写した美しい光沢
面を有していた。Example 2 The high-viscosity acrylic resin premix obtained in Example 1 was mixed with a 200-ton injection molding machine (produced by Co., Ltd.).
(Manufactured by Japan Steel Works), using a mold for molding an automobile headlamp reflecting mirror having a chrome-plated surface, mold temperature 100 ° C.,
Under the conditions of an injection pressure of 60 kg / cm 2 and a mold clamping pressure of 100 tons, pressure polymerization was performed for 180 seconds while drawing a vacuum of 650 mmHg to mold a 3 mm thick acrylic artificial marble automobile headlamp reflector. The obtained molded product had a good appearance, was excellent in transparency, and had a beautiful glossy surface faithfully transferring the mold surface.
【００３７】［実施例３］実施例１で得た高粘度アクリ
ル樹脂プリミックスを、１００トン・トランスファー成
形機（東邦プレス製作所社製）にてクロム鍍金面を有す
る事務機器（コインカウンター）成形用金型を用いて、
金型温度１００℃、射出圧３０ｋｇ／ｃｍ2 、型締め圧
１００トンにて１８０秒間加圧重合して肉厚５ｍｍのア
クリル人工大理石コインカウンターを成形した。得られ
た製品は外観が良好で、透明感に優れ、表面も金型面を
忠実に転写した美しい光沢面を有していた。[Example 3] The high-viscosity acrylic resin premix obtained in Example 1 was molded with a 100-ton transfer molding machine (manufactured by Toho Press Mfg. Co., Ltd.) for office equipment (coin counter) having a chrome-plated surface. Using the mold
A 5 mm thick acrylic artificial marble coin counter was formed by pressure polymerization for 180 seconds at a mold temperature of 100 ° C., an injection pressure of 30 kg / cm 2 , and a mold clamping pressure of 100 tons. The obtained product had a good appearance, was excellent in transparency, and had a beautiful glossy surface on which the mold surface was faithfully transferred.
【００３８】［実施例４］常温に設定されたヘンシェル
ミキサーを用いてポリメチルメタルリレート（平均分子
量６万）２０重量部を溶解した粘度５０センチポイズの
メチルメタクリレートシラップ（ａ）２０重量％、水酸
化アルミニウム（日本軽金属（株）社製）５重量％、ア
クリル樹脂微粒子（ｃ）（三菱レイヨン（株）製商品名
ＢＲ−８５）５重量％、人工大理石粒子として水酸化ア
ルミニウムを６５重量％含有する「デュポンコーリア
ン」（エムアールシー・デユポン（株）製、商標）を粉
砕して得られた数平均粒径が５ｍｍの粒子７０重量％
と、重合開始剤としてラウロイルパーオキサイドを
（ａ）と（ｃ）の混合物総重量１００部にたいし１．５
重量％の割合で混合し１０分間撹拌しプリミックスを調
製した。[Example 4] Using a Henschel mixer set at room temperature, 20 parts by weight of polymethylmetallate (average molecular weight 60,000) dissolved in 20 parts by weight of methyl methacrylate syrup (a) having a viscosity of 50 centipoise, hydroxylated 5% by weight of aluminum (manufactured by Nippon Light Metal Co., Ltd.), 5% by weight of acrylic resin fine particles (c) (trade name BR-85 manufactured by Mitsubishi Rayon Co., Ltd.), and 65% by weight of aluminum hydroxide as artificial marble particles. 70% by weight of particles having a number average particle diameter of 5 mm obtained by crushing "Dupont Corian" (trademark, manufactured by MRC Deyupon Co., Ltd.)
And lauroyl peroxide as a polymerization initiator with respect to 100 parts by weight of the total mixture of (a) and (c).
A premix was prepared by mixing in a weight% ratio and stirring for 10 minutes.
【００３９】得られたプリミックスを２０分放置したの
ち粘度を測定したところ３０万ポイズであった。このプ
リミックスを実施例１と同様な成形条件でシャンプーボ
ウルを成形した。得られた成形製品は全組成中の水酸化
アルミニウム５０．５重量％で、添加した人工大理石粒
子の意匠効果が明瞭な外観を持っており、金型面を忠実
に転写した美しい光沢面を有していた。The premix thus obtained was allowed to stand for 20 minutes and then its viscosity was measured and found to be 300,000 poise. A shampoo bowl was molded from this premix under the same molding conditions as in Example 1. The obtained molded product was 50.5% by weight of aluminum hydroxide in the total composition and had an appearance in which the design effect of the added artificial marble particles was clear, and had a beautiful glossy surface faithfully transferred to the mold surface. Was.
【００４０】［実施例５］常温に設定されたヘンシェル
ミキサーを用いてメチルメタクリレート部分重合体を２
０重量％溶解した粘度５０センチポイズのメチルメタク
リレートシラップ２７．１重量％、架橋剤としてエチレ
ングリコールジメタクリレート０．４重量％、水酸化ア
ルミニウム６２．５重量％、重合開始剤としてラウロイ
ルパーオキサイド１．５重量％の割合で投入し、５分間
撹拌混合した。Example 5 Using a Henschel mixer set at room temperature, 2 parts of the methyl methacrylate partial polymer was prepared.
0% by weight dissolved methyl methacrylate syrup having a viscosity of 50 centipoise 27.1% by weight, ethylene glycol dimethacrylate as a crosslinking agent 0.4% by weight, aluminum hydroxide 62.5% by weight, lauroyl peroxide 1.5 as a polymerization initiator The mixture was added at a weight percentage and stirred and mixed for 5 minutes.
【００４１】ついでアクリル樹脂微粒子（平均粒子径７
０μｍ、重量平均分子量６４００００）（三菱レイヨン
（株）製、商品名：アクリコンＡＣＰ−３）８．５重量
％を３分間で混合した後、３０分間放置した。このよう
にして得られた高粘度アクリル樹脂プリミックスの２０
℃における粘度をＲＤＡ−７００型粘度計で測定したと
ころ３０万ポイズであった。以下実施例１と同様にして
シャンプーボールを成形した。得られた人工大理石シャ
ンプーボウルは、表面外観は良好で、透明感に優れ金型
面を忠実に転写した美しい光沢面を有していた。Next, fine particles of acrylic resin (average particle size 7
8.5 μ% of 0 μm, weight average molecular weight of 640000 (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrycon ACP-3) was mixed for 3 minutes and then left for 30 minutes. 20 of the high viscosity acrylic resin premix thus obtained
The viscosity at 0 ° C. was measured with an RDA-700 type viscometer and it was 300,000 poise. Thereafter, a shampoo ball was molded in the same manner as in Example 1. The obtained artificial marble shampoo bowl had a good surface appearance, was excellent in transparency, and had a beautiful glossy surface faithfully transferring the mold surface.
【００４２】［実施例６］常温に設定されたヘンシェル
ミキサーを用いてポリメチルメタルリレート（平均分子
量６万）２０重量部を溶解した粘度５０センチポイズの
メチルメタクリレートシラップ１７．０重量％、架橋材
としてエチレングリコールジメタクリレ−ト１．２重量
％、水酸化アルミニウム（日本軽金属（株）製）６３．
３重量％、重合開始剤としてラウロイルパーオキサイド
１．５重量％、アクリル樹脂微粒子（三菱レイヨン
（株）製、商品名アクリコンＡＣＰ−３）３．４重量％
の割合で投入し撹拌混合した。ついでアクリル樹脂微粒
子（商品名アクリコンＡＣＰ−３）１３．６重量％を追
加して加え３分間撹拌混合した後３０分間放置した。Example 6 Using a Henschel mixer set at room temperature, 20 parts by weight of polymethylmetallate (average molecular weight 60,000) was dissolved, and 17.0% by weight of methyl methacrylate syrup having a viscosity of 50 centipoise was used as a crosslinking agent. 1.2% by weight of ethylene glycol dimethacrylate, aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd.) 63.
3% by weight, lauroyl peroxide as a polymerization initiator 1.5% by weight, fine particles of acrylic resin (Mitsubishi Rayon Co., Ltd., trade name Acrycon ACP-3) 3.4% by weight
And the mixture was stirred and mixed. Then, 13.6% by weight of acrylic resin fine particles (trade name: Acrycon ACP-3) was added, and the mixture was stirred and mixed for 3 minutes and then left for 30 minutes.
【００４３】このようにして得られた高粘度アクリル樹
脂プリミックスの２０℃における粘度をＲＤＡ−７００
型粘度計で測定したところ２０万ポイズであった。以
下、実施例１と同様にしてシャンプーボールを成形し
た。得られた人工大理石シャンプーボールは、表面外観
は良好で、透明感に優れ、金型面を忠実に転写した美し
い光沢面を有していた。The viscosity of the high-viscosity acrylic resin premix thus obtained at 20 ° C. was measured by RDA-700.
It was 200,000 poise when measured by a viscometer. Thereafter, a shampoo ball was molded in the same manner as in Example 1. The obtained artificial marble shampoo ball had a good surface appearance, was excellent in transparency, and had a beautiful glossy surface faithfully transferred to the mold surface.
【００４４】［実施例７］シラップ、架橋剤及び重合開
始剤として実施例１と同様のものを同量用い、内部離型
剤としてエアロゾ−ルＯＴ−１００（三井サイアミナッ
ド（株）製）０．１重量％、重合禁止剤としてハイドロ
キノンモノメチルエ−テル０．０１重量％を添加した混
合物を、ミキサ−（井上製作所（株）製）中で１０分間
十分に攪拌した。次いで、この混合物、水酸化アルミニ
ウム（日本軽金属（株）製）５２．５重量％、黒色、茶
色及び白色粒子の混合物であるアクリル系人工大理石粒
子（平均粒径５ｍｍ、膨潤度１．７、樹脂成分含有量３
５重量％、水酸化アルミニウム含有量６５重量％）１
０．０重量％を常温に設定されたＭＴＩミキサ−（月島
機械（株）製）に投入して、直ちに６分間混合した。更
に実施例１と同様のアクリル樹脂微粒子を８．５重量％
添加して２分間混合し、４８時間放置した。得られたプ
リミックスの粘度は３０万ポイズであった。[Example 7] The same amount of syrup, cross-linking agent and polymerization initiator as in Example 1 was used, and the internal release agent was Aerosol OT-100 (manufactured by Mitsui Ciaminad Co., Ltd.). A mixture containing 1% by weight and 0.01% by weight of hydroquinone monomethyl ether as a polymerization inhibitor was sufficiently stirred in a mixer (manufactured by Inoue Seisakusho Co., Ltd.) for 10 minutes. Then, this mixture, 52.5% by weight of aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd.), acrylic artificial marble particles (average particle size 5 mm, swelling degree 1.7, resin) which is a mixture of black, brown and white particles. Ingredient content 3
5% by weight, aluminum hydroxide content 65% by weight) 1
0.0 wt% was put into an MTI mixer (manufactured by Tsukishima Kikai Co., Ltd.) set at room temperature and immediately mixed for 6 minutes. Further, 8.5% by weight of the same acrylic resin fine particles as in Example 1 was added.
Add and mix for 2 minutes and leave for 48 hours. The viscosity of the obtained premix was 300,000 poise.
【００４５】このプリミックスを用いて実施例１と同様
にしてシャンプ−ボウルを成形した。得られたシャンプ
−ボウルは表面を研削しなくても天然石に近い石目調の
外観を呈しており、透明感、寸法安定性に優れ、金型面
を忠実に転写した美しい光沢面を有していた。また、こ
のシャンプ−ボウルを切断して断面を目視観察したとこ
ろボイドは観察されなかった。Using this premix, a shampoo bowl was molded in the same manner as in Example 1. The obtained shamp-bowl has a stone-like appearance similar to natural stone without grinding the surface, has excellent transparency and dimensional stability, and has a beautiful glossy surface that faithfully transfers the mold surface. Was there. Further, when the shampoo bowl was cut and the cross section was visually observed, no void was observed.
【００４６】［実施例８］アクリル系人工大理石粒子の
平均粒径が３ｍｍであること以外は実施例７と同様の条
件でプリミックスを調製し、シャンプ−ボウルを成形し
たところ同様の結果が得られた。[Example 8] A premix was prepared under the same conditions as in Example 7 except that the average particle size of the acrylic artificial marble particles was 3 mm, and a shampoo-bowl was molded. Similar results were obtained. Was given.
【００４７】［実施例９］実施例７と同様にして得たプ
リミックスを用いて、実施例３と同様にしてコインカウ
ンタ−を成形した。得られたコインカウンタ−は表面を
研削しなくても天然石に近い石目調の外観を呈してお
り、透明感、寸法安定性に優れ、金型面を忠実に転写し
た美しい光沢面を有していた。また、内部にボイドは観
察されなかった。[Example 9] Using the premix obtained in the same manner as in Example 7, a coin counter was molded in the same manner as in Example 3. The coin counter obtained has a stone-grained appearance similar to natural stone without grinding the surface, has excellent transparency and dimensional stability, and has a beautiful glossy surface that faithfully transfers the mold surface. Was there. Further, no void was observed inside.
【００４８】［比較例１］常温に設定されたヘンシェル
ミキサーを用いてメチルメタクリレート部分重合体を２
０重量％を溶解した粘度５０センチポイズのメチルメタ
クリレートシラップ２７．１重量％、架橋剤としてエチ
レングリコールジメタクリレート０．４重量％、アクリ
ル樹脂微粒子（三菱レイヨン（株）製、商品名アクリコ
ンＡＣＰ−３）８．５重量％、重合開始剤としてラウロ
イルパーオキサイド１．５重量％、水酸化アルミニウム
（日本軽金属（株）製）６２．５重量％の割合で投入、
撹拌混合しアクリル樹脂微粒子を完全溶解しようとした
が、撹拌中に重合してしまい、目的とする成形用材料を
得ることができなかった。[Comparative Example 1] A methyl methacrylate partial polymer was mixed with a Henschel mixer set at room temperature.
27.1% by weight of methyl methacrylate syrup having a viscosity of 50 centipoise in which 0% by weight is dissolved, 0.4% by weight of ethylene glycol dimethacrylate as a cross-linking agent, acrylic resin fine particles (Mitsubishi Rayon Co., Ltd., trade name Acrycon ACP-3) 8.5% by weight, lauroyl peroxide as a polymerization initiator 1.5% by weight, aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd.) 62.5% by weight,
Although it was attempted to completely dissolve the acrylic resin fine particles by stirring and mixing, polymerization was performed during stirring, and the intended molding material could not be obtained.
【００４９】[0049]
【発明の効果】本発明の圧縮成形用材料は、アクリル樹
脂微粒子（ｃ）が成形時に骨材として作用するため、成
形時の収縮が小さく優れた成形品が得られる。また、ア
クリル樹脂微粒子（ｃ）は、成形用材料中で完全に溶解
させる必要がないためプリミックスの調製も短時間で済
み効率的である。特に、膨潤度が２．０以下の架橋型の
アクリル系人工大理石粒子を併用した場合は、成形時の
粘度コントロ−ルが容易であって、成形時の流れ斑が顕
著に改善される。また、成形時の重合収縮の抑制効果が
大きく、更に、成形品の内部ボイドが著しく減少すると
いう優れた効果が発現する。In the compression molding material of the present invention, since the acrylic resin fine particles (c) act as an aggregate during molding, an excellent molded product with a small shrinkage during molding can be obtained. Further, since it is not necessary to completely dissolve the acrylic resin fine particles (c) in the molding material, the premix can be prepared in a short time and is efficient. In particular, when the cross-linked acrylic artificial marble particles having a swelling degree of 2.0 or less are used together, the viscosity control during molding is easy and the flow unevenness during molding is remarkably improved. In addition, the effect of suppressing polymerization shrinkage during molding is large, and further, the excellent effect that the internal voids of the molded product are significantly reduced is exhibited.
───────────────────────────────────────────────────── 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 26/06 20:00 14:36 16:04） Ｂ２９Ｋ 33:04 103:04 Ｃ０４Ｂ 111:54 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display area // (C04B 26/06 20:00 14:36 16:04) B29K 33:04 103: 04 C04B 111: 54
Claims (4)
リル系シラップ（ａ）６０〜１０重量％、水酸化アルミ
ニウム（ｂ）５０〜８５重量％、メタクリル酸メチルを
主成分としアクリル系シラップに溶解する重量平均分子
量２０〜８０万、平均粒径１ｍｍ以下のアクリル樹脂微
粒子（ｃ）６０〜１重量％及び重合開始剤からなり、ア
クリル樹脂微粒子（ｃ）の一部が溶解し残部が未溶解状
態にあることを特徴とする圧縮成形用材料。1. Acrylic syrup (a) containing methyl methacrylate as a main component 60 to 10% by weight, aluminum hydroxide (b) 50 to 85% by weight, and methyl methacrylate as a main component and dissolving in acrylic syrup. It is composed of 60 to 1% by weight of acrylic resin fine particles (c) having a weight average molecular weight of 200,000 to 800,000 and an average particle diameter of 1 mm or less, and a polymerization initiator. A part of the acrylic resin fine particles (c) is dissolved and the rest is in an undissolved state. A material for compression molding which is characterized by being present.
リル系シラップ（ａ）６０〜１０重量％、水酸化アルミ
ニウム（ｂ）、メタクリル酸メチルを主成分としアクリ
ル系シラップに溶解する平均分子量２０〜８０万、平均
粒径１ｍｍ以下のアクリル樹脂微粒子（ｃ）６０〜１重
量％、水酸化アルミニウムを５０重量％以上含有したア
クリル系人工大理石粉砕粒子（ｄ）１〜８０重量％及び
重合開始剤からなり、アクリル樹脂微粒子（ｃ）の一部
が溶解し残部が未溶解の状態にあり、且つ全組成中の水
酸化アルミニウムの合計量が５０〜８５重量％になるよ
うな量に（ｂ）の水酸化アルミニウムが配合されてなる
ことを特徴とする圧縮成形用材料。2. Acrylic syrup (a) containing methyl methacrylate as a main component in an amount of 60 to 10% by weight, aluminum hydroxide (b) and methyl methacrylate as a main component and having an average molecular weight of 20 to 80 dissolved in the acrylic syrup. It comprises 60 to 1% by weight of acrylic resin fine particles (c) having an average particle size of 1 mm or less, 1 to 80% by weight of crushed acrylic artificial marble particles (d) containing 50% by weight or more of aluminum hydroxide, and a polymerization initiator. A part of the acrylic resin fine particles (c) is dissolved and the rest is undissolved, and the amount of the water of (b) is such that the total amount of aluminum hydroxide in the entire composition is 50 to 85% by weight. A material for compression molding, which is characterized by containing aluminum oxide.
粉砕粒子（ｄ）の平均粒径が０．１〜１０ｍｍであっ
て、粉砕粒子（ｄ）中のアクリル系樹脂が架橋樹脂であ
り、粉砕粒子（ｄ）のメタクリル酸メチルに対する膨潤
度が２．０以下であることを特徴とする圧縮成形用材
料。3. The crushed particles according to claim 2, wherein the crushed acrylic artificial marble particles (d) have an average particle size of 0.1 to 10 mm, and the acrylic resin in the crushed particles (d) is a crosslinked resin. A material for compression molding, wherein the degree of swelling of (d) with respect to methyl methacrylate is 2.0 or less.
材料を加圧下に賦形して重合硬化させて得られた樹脂成
形物。4. A resin molded product obtained by shaping the material for compression molding according to claim 1, 2 or 3 under pressure and polymerizing and curing it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29317295A JP3482287B2 (en) | 1994-11-11 | 1995-11-10 | Compression molding material and resin molding using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-341188 | 1994-11-11 | ||
| JP34118894 | 1994-11-11 | ||
| JP29317295A JP3482287B2 (en) | 1994-11-11 | 1995-11-10 | Compression molding material and resin molding using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08225705A true JPH08225705A (en) | 1996-09-03 |
| JP3482287B2 JP3482287B2 (en) | 2003-12-22 |
Family
ID=26559301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29317295A Expired - Lifetime JP3482287B2 (en) | 1994-11-11 | 1995-11-10 | Compression molding material and resin molding using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3482287B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997040098A1 (en) * | 1996-04-19 | 1997-10-30 | Mitsubishi Rayon Co., Ltd. | Acrylic resin composition, acrylic premixes, process for producing acrylic artificial marble, and thickener |
| WO1998046679A1 (en) * | 1997-04-14 | 1998-10-22 | Mitsubishi Rayon Co., Ltd. | (meth)acrylic premix, (meth)acrylic smc or bmc, and process for producing (meth)acrylic artificial marble |
| WO1998051743A1 (en) * | 1997-05-14 | 1998-11-19 | Mitsubishi Rayon Co., Ltd. | (meth)acrylic resin composition for thermoset injection molding, process for the preparation of the composition, and process for the production of moldings of (meth)acrylic resins |
| EP0786479A3 (en) * | 1996-01-23 | 1999-12-22 | E.I. Du Pont De Nemours And Company | Compression molding method, mix and product |
| US6316548B1 (en) | 1997-04-14 | 2001-11-13 | Mitsubishi Rayon Co., Ltd. | (Meth)acrylic premix, (meth)acrylic SMC or BMC, and process producing (meth)acrylic artificial marble |
| JP2002362954A (en) * | 2001-06-07 | 2002-12-18 | Takagi Kogyo Kk | Acrylic reinforced artificial marble and method for manufacturing the same |
| US6974784B1 (en) | 1999-03-16 | 2005-12-13 | Dainippon Ink And Chemicals, Inc. | Sheet-form photocurable material |
| GB2436106A (en) * | 2006-01-21 | 2007-09-19 | Advanced Composites Group Ltd | Resinous materials |
| JP2010018450A (en) * | 2008-07-08 | 2010-01-28 | Du Pont-Mrc Co Ltd | Method for producing artificial marble having excellent design |
-
1995
- 1995-11-10 JP JP29317295A patent/JP3482287B2/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0786479A3 (en) * | 1996-01-23 | 1999-12-22 | E.I. Du Pont De Nemours And Company | Compression molding method, mix and product |
| WO1997040098A1 (en) * | 1996-04-19 | 1997-10-30 | Mitsubishi Rayon Co., Ltd. | Acrylic resin composition, acrylic premixes, process for producing acrylic artificial marble, and thickener |
| US6323259B1 (en) | 1996-04-19 | 2001-11-27 | Mitsubishi Rayon Co., Ltd. | Acrylic resin composition, acrylic premix, process for producing acrylic artificial marble and thickening agent |
| WO1998046679A1 (en) * | 1997-04-14 | 1998-10-22 | Mitsubishi Rayon Co., Ltd. | (meth)acrylic premix, (meth)acrylic smc or bmc, and process for producing (meth)acrylic artificial marble |
| US6316548B1 (en) | 1997-04-14 | 2001-11-13 | Mitsubishi Rayon Co., Ltd. | (Meth)acrylic premix, (meth)acrylic SMC or BMC, and process producing (meth)acrylic artificial marble |
| WO1998051743A1 (en) * | 1997-05-14 | 1998-11-19 | Mitsubishi Rayon Co., Ltd. | (meth)acrylic resin composition for thermoset injection molding, process for the preparation of the composition, and process for the production of moldings of (meth)acrylic resins |
| US6974784B1 (en) | 1999-03-16 | 2005-12-13 | Dainippon Ink And Chemicals, Inc. | Sheet-form photocurable material |
| JP2002362954A (en) * | 2001-06-07 | 2002-12-18 | Takagi Kogyo Kk | Acrylic reinforced artificial marble and method for manufacturing the same |
| GB2436106A (en) * | 2006-01-21 | 2007-09-19 | Advanced Composites Group Ltd | Resinous materials |
| GB2436106B (en) * | 2006-01-21 | 2011-10-19 | Advanced Composites Group Ltd | Resinous materials, articles made therewith and methods of producing same |
| JP2010018450A (en) * | 2008-07-08 | 2010-01-28 | Du Pont-Mrc Co Ltd | Method for producing artificial marble having excellent design |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3482287B2 (en) | 2003-12-22 |
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