JP4872578B2 - Artificial marble composition, artificial marble and bathtub - Google Patents
Artificial marble composition, artificial marble and bathtub Download PDFInfo
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本発明は、人工大理石用組成物、人工大理石及び浴槽に関する。 The present invention relates to a composition for artificial marble, artificial marble and a bathtub.
人工大理石は、浴槽、キッチン流し台のカウンタ、洗面台のカウンタなどに用いられているが、このような用途では汚れや異物を含んだ水に接する機会が多いため、人工大理石の表面に汚れが付着し易く、付着した汚れが落ちにくいので手入れが面倒であった。 Artificial marble is used in bathtubs, kitchen sink counters, washstand counters, etc., but in such applications there are many opportunities to come in contact with water containing dirt and foreign matter, so the surface of artificial marble is contaminated. Easy to handle and difficult to remove because the attached dirt is difficult to remove.
例えば、浴槽の内壁面、特に浴槽内の水面に接する喫水線に汚れがこびり付き易いことはしばしば経験するところである。浴槽用材料に共通する汚れの原因は、汚れ成分の組成や汚れ付着のメカニズムが複雑であるために十分な解明がなされていないが、一般的には油脂や石鹸カスによる汚れなどが挙げられる。浴槽用材料としては、さまざまなプラスチック材料や木材料などが使用されているが、汚れに対する対策がなされていない場合が多く、従来の浴槽用材料は汚れが付着し易かった。 For example, it is often the case that dirt easily adheres to the inner wall surface of a bathtub, particularly the water line in contact with the water surface in the bathtub. The cause of dirt common to bathtub materials has not been sufficiently elucidated due to the complexity of the composition of dirt components and the mechanism of dirt adhesion, but in general, dirt caused by fats and oils or soap scum is included. Various plastic materials, wood materials, and the like are used as the bathtub material, but there are many cases where measures against dirt are not taken, and the conventional bathtub materials are easily contaminated.
このような汚れが浴槽に付着すると、浴槽の美観を損ねるだけでなく衛生上からも問題がある。また、これらの汚れは容易に除去することができず、例えば浴槽の喫水線域に付着した汚れは浴槽にこびり付き容易に拭き取ることができない場合が多い。 When such dirt adheres to the bathtub, it not only impairs the beauty of the bathtub, but also has a hygienic problem. Moreover, these dirt cannot be removed easily, for example, the dirt adhering to the waterline area of the bathtub often sticks to the bathtub and cannot be easily wiped off.
これらの問題を解決するため、特開２００２−０６９３７８号公報（特許文献１）には、シリコン樹脂化合物やフッ素樹脂化合物などを使用して浴槽等の表面を撥水化する方法が開示されている。この方法では、浴槽等の表面をこれらの化合物で覆うことによってその表面自由エネルギーを低くし、防汚性を高めている。 In order to solve these problems, Japanese Patent Laid-Open No. 2002-069378 (Patent Document 1) discloses a method of making a surface of a bathtub or the like water repellent using a silicon resin compound, a fluororesin compound, or the like. . In this method, the surface free energy is lowered and the antifouling property is improved by covering the surface of a bathtub or the like with these compounds.
また、特開平１０−１６６４９５号公報（特許文献２）に開示された別な方法では、表面に光触媒粒子を含む層を形成し、光触媒作用によって物質の表面を親水化し、汚れを付着しにくくしている。 In another method disclosed in Japanese Patent Application Laid-Open No. 10-166495 (Patent Document 2), a layer containing photocatalyst particles is formed on the surface, the surface of the substance is hydrophilized by photocatalytic action, and dirt is hardly adhered. ing.
しかしながら、上記のようにシリコン樹脂化合物やフッ素樹脂化合物を用いて浴槽等の表面を撥水化する方法では、実際には十分な防汚性を得ることができず、特に浴槽の喫水線域に汚れが付着するのを防ぐことはできなかった。 However, the method of making the surface of a bathtub or the like water-repellent using a silicon resin compound or a fluororesin compound as described above cannot actually provide sufficient antifouling properties, and in particular, stains in the waterline area of the bathtub. Could not be prevented.
また、光触媒作用により物質表面を親水化する方法では、浴室内での光源の光量不足や、光触媒作用による浴槽用材料自身の劣化などから防汚効果が不十分になり易いという問題があった。 Further, the method of hydrophilizing the material surface by photocatalytic action has a problem that the antifouling effect tends to be insufficient due to insufficient light quantity of the light source in the bathroom or deterioration of the bathtub material itself due to the photocatalytic action.
本発明は、このような技術的課題に鑑みてなされたものであって、その目的とするところは、防汚性に優れた人工大理石用組成物と、当該人工大理石用組成物を重合硬化させた人工大理石と、当該人工大理石を用いた浴槽とを提供することにある。 The present invention has been made in view of such technical problems. The object of the present invention is to provide a composition for artificial marble having excellent antifouling properties and a composition for curing the artificial marble. Another object of the present invention is to provide an artificial marble and a bathtub using the artificial marble.
すなわち、本発明に係る人工大理石用組成物は、アクリルシラップ１００重量部に対して水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂を１０重量部以上含有する人工大理石用組成物であって、
(i)前記アクリル樹脂のガラス転移点温度が−５℃以上、好ましくは０℃以上であり、
(ii)重合硬化後の表面における対水接触角の値が７０°以下で、かつ、
(iii)対オレイン酸接触角の値が２０°以下であることを特徴とするものである。
That is, the composition for artificial marble according to the present invention is a composition for artificial marble containing 10 parts by weight or more of an acrylic resin composed of an acrylic monomer having a hydroxyl group or a nitrogen-containing group with respect to 100 parts by weight of acrylic syrup ,
(i) The glass transition temperature of the acrylic resin is −5 ° C. or higher, preferably 0 ° C. or higher.
(ii) The value of the contact angle with water on the surface after polymerization curing is 70 ° or less, and
(iii) The contact angle with oleic acid is 20 ° or less.
アクリル樹脂には、アクリル酸エステルの重合体とメタクリル酸エステルの重合体とがあるが、本発明の人工大理石用組成物に用いる水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂には、メタクリル酸エステルモノマーからなるアクリル樹脂が好ましい。水酸基を有するアクリルモノマー（メタクリル酸エステルモノマー）としては、例えば三菱ガス化学（株）製のＧＥ−６１０がある。また、前記窒素含有基を有するアクリルモノマー（メタクリル酸エステルモノマー）としては、例えば三菱ガス化学（株）製のＧＥ−７１０、ＧＥ−７２０がある。 Acrylic resins include acrylic acid ester polymers and methacrylic acid ester polymers, but acrylic resins composed of acrylic monomers having hydroxyl groups or nitrogen-containing groups used in the artificial marble composition of the present invention include methacrylic esters. An acrylic resin composed of an acid ester monomer is preferred. As an acrylic monomer (methacrylic acid ester monomer) having a hydroxyl group, for example, GE-610 manufactured by Mitsubishi Gas Chemical Co., Ltd. is available. Examples of the acrylic monomer having a nitrogen-containing group (methacrylic acid ester monomer) include GE-710 and GE-720 manufactured by Mitsubishi Gas Chemical Co., Ltd.
本発明の人工大理石用組成物は、アクリルシラップ１００重量部に対して水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂（以下、前記アクリル樹脂ということがある。）を１０重量部以上含有しているので、この人工大理石組成物を重合硬化させて人工大理石を作製すると、その表面における対水接触角の値が７０°以下で、かつ、対オレイン酸接触角の値が２０°以下である人工大理石成形体を得ることができる。人工大理石の対水接触角及び対オレイン酸接触角と防汚性との間には強い相関があり、対水接触角及び対オレイン酸接触角の値が小さいほど防汚性も良好となる。よって、アクリルシラップ１００重量部に対して前記アクリル樹脂を１０重量部以上含有させることにより、防汚性に優れた人工大理石を得ることができる。 The composition for artificial marble of the present invention contains 10 parts by weight or more of an acrylic resin composed of an acrylic monomer having a hydroxyl group or a nitrogen-containing group with respect to 100 parts by weight of acrylic syrup (hereinafter sometimes referred to as the acrylic resin). Therefore, when artificial marble is produced by polymerizing and curing this artificial marble composition, the value of the contact angle with water on the surface is 70 ° or less and the value of the contact angle with oleic acid is 20 ° or less. An artificial marble molded body can be obtained. There is a strong correlation between the water contact angle and the oleic acid contact angle of artificial marble and the antifouling property, and the smaller the values of the water contact angle and the oleic acid contact angle, the better the antifouling property. Therefore, the artificial marble excellent in antifouling property can be obtained by containing 10 parts by weight or more of the acrylic resin with respect to 100 parts by weight of acrylic syrup .
また、アクリルシラップ１００重量部に対して水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂を６０重量部以上混合させれば、重合硬化後の表面における対水接触角の値が５５°以下で、かつ、対オレイン酸接触角の値が１５°以下となり、人工大理石成形体の防汚性がより一層向上する。 Further, if 60 parts by weight or more of an acrylic resin composed of an acrylic monomer having a hydroxyl group or a nitrogen-containing group is mixed with 100 parts by weight of acrylic syrup , the value of the contact angle with water on the surface after polymerization curing is 55 ° or less. Moreover, the value of the contact angle with oleic acid is 15 ° or less, and the antifouling property of the artificial marble molded body is further improved.
また、水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂のガラス転移点温度が−５℃よりも低いと、人工大理石成形体の成形性が劣悪となり、防汚性もかなり低下する。これに対し、ガラス転移点温度が−５℃以上の前記アクリル樹脂を用いれば成形性が良好となり、防汚性が良好となる。さらにガラス転移点温度が０℃以上の前記アクリル樹脂を用いれば、成形性がより一層良好となる。 Moreover, when the glass transition point temperature of the acrylic resin which consists of an acrylic monomer which has a hydroxyl group or a nitrogen-containing group is lower than -5 degreeC, the moldability of an artificial marble molded object will be inferior and antifouling property will fall considerably. On the other hand, if the acrylic resin having a glass transition temperature of −5 ° C. or higher is used, the moldability is improved and the antifouling property is improved. Furthermore, if the said acrylic resin whose glass transition temperature is 0 degreeC or more is used, a moldability will become still better.
本発明の人工大理石用組成物を重合硬化させることによって人工大理石を得ることができ、人工大理石用組成物を重合硬化させ所望の形状に成形することにより所望の人工大理石成形体を得ることができる。例えば、浴槽の少なくとも表面部分（表面保護層、浴槽壁材など）、キッチン流し台のカウンタ、洗面台のカウンタ等を人工大理石によって成形することができる。 Artificial marble can be obtained by polymerizing and curing the composition for artificial marble of the present invention, and a desired artificial marble molded body can be obtained by polymerizing and curing the composition for artificial marble and molding into a desired shape. . For example, at least the surface portion of the bathtub (surface protective layer, bathtub wall material, etc.), the counter of the kitchen sink, the counter of the wash basin, etc. can be formed from artificial marble.
本発明の人工大理石用組成物によれば、汚れが付着しにくく、また汚れの落ち易い人工大理石の成形体を得ることができた。特に、浴槽に用いた場合には、浴槽内面の喫水線域における汚れを防止する効果が非常に高かった。しかも、本発明の人工大理石用組成物によれば、人工大理石成形体の成形性が悪くなることもない。さらに、本発明の人工大理石用組成物は、光触媒作用を利用していないので、光源の光量不足や、光触媒作用の劣化などにより防汚効果が低下する問題もない。 According to the composition for artificial marble of the present invention, it was possible to obtain a molded article of artificial marble which hardly adheres to dirt and easily removes dirt. In particular, when used in a bathtub, the effect of preventing dirt in the waterline area on the inner surface of the bathtub was very high. And according to the composition for artificial marble of this invention, the moldability of an artificial marble molded object does not deteriorate. Furthermore, since the composition for artificial marble of the present invention does not utilize photocatalytic action, there is no problem that the antifouling effect is lowered due to insufficient light amount of the light source or deterioration of the photocatalytic action.
以下に、本発明の好ましい実施の形態を説明するが、本発明は以下の説明に限定されるものではない。 Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following descriptions.
本発明に係る人工大理石用組成物は、人工大理石用樹脂に水酸基を有するアクリルモノマーからなるアクリル樹脂を混合したもの、あるいは人工大理石用樹脂に窒素含有基（特に、アミノ基）を有するアクリルモノマーからなるアクリル樹脂を混合したものである。ここで人工大理石用樹脂は、人工大理石製の浴槽やカウンタ等を成形するための樹脂として一般的に使用される熱硬化性樹脂や熱可塑性樹脂であればよい。人工大理石用樹脂としては、例えばメタクリル酸メチルなどのモノマーにアクリルポリマーを溶解させて得られるアクリルシラップ、不飽和ポリエステル樹脂、エポキシ樹脂などを用いることができる。 The composition for artificial marble according to the present invention is obtained by mixing an artificial marble resin with an acrylic resin made of an acrylic monomer having a hydroxyl group, or an acrylic monomer having a nitrogen-containing group (particularly an amino group) in an artificial marble resin. A mixture of acrylic resins. Here, the resin for artificial marble may be a thermosetting resin or a thermoplastic resin generally used as a resin for molding an artificial marble bathtub or counter. As the resin for artificial marble, for example, acrylic syrup obtained by dissolving an acrylic polymer in a monomer such as methyl methacrylate, an unsaturated polyester resin, an epoxy resin, or the like can be used.
水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂としては、アクリル酸エステルモノマーの重合体とメタクリル酸エステルモノマーの重合体とがあるが、本発明の人工大理石用組成物には、水酸基又は窒素含有基を有するメタクリル酸エステルモノマーからなるアクリル樹脂が望ましい。 Examples of the acrylic resin comprising an acrylic monomer having a hydroxyl group or a nitrogen-containing group include a polymer of an acrylate ester monomer and a polymer of a methacrylate ester monomer. The composition for artificial marble of the present invention includes a hydroxyl group or nitrogen. An acrylic resin composed of a methacrylic acid ester monomer having a containing group is desirable.
水酸基を有するアクリルモノマーとしては、例えば下記の化学式１で示すような構造式で表わされるメタクリル酸エステルモノマー〔例えば、三菱ガス化学（株）製ＧＥ−６１０〕があり、水酸基を有するアクリルモノマーからなるアクリル樹脂は、このようなメタクリル酸エステルモノマーを重合させたものである。
窒素含有基を有するアクリルモノマーとしては、例えば下記の化学式２で示すような構造式で表わされるメタクリル酸エステルモノマー〔例えば、三菱ガス化学（株）製ＧＥ−７１０〕や、下記の化学式３で示すような構造式で表わされるメタクリル酸エステルモノマー〔例えば、三菱ガス化学（株）製ＧＥ−７２０〕があり、窒素含有基を有するアクリルモノマーからなるアクリル樹脂は、このようなメタクリル酸エステルモノマーを重合させたものである。
本発明にかかる人工大理石用組成物の組成は、人工大理石用樹脂１００重量部に対して水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂が１０重量部以上であり、より好ましくは、６０重量部以上である。水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂の添加量の上限値としては、人工大理石用樹脂１００重量部に対して８０重量部まで防汚性の効果を確認しているが、この上限値は実験により８０重量部よりも大きな値になり得ると考えられる。 The composition of the composition for artificial marble according to the present invention is such that the acrylic resin comprising an acrylic monomer having a hydroxyl group or a nitrogen-containing group is 10 parts by weight or more with respect to 100 parts by weight of the resin for artificial marble, and more preferably 60 parts by weight. More than a part. As the upper limit of the amount of acrylic resin comprising an acrylic monomer having a hydroxyl group or a nitrogen-containing group, the antifouling effect has been confirmed up to 80 parts by weight with respect to 100 parts by weight of the resin for artificial marble. It is believed that the value can be greater than 80 parts by experiment.
よって、本発明の人工大理石用組成物では、人工大理石用樹脂が主樹脂となっていてもよく、前記アクリル樹脂が主樹脂となっていてもよい。ただし、前記アクリル樹脂を人工大理石用組成物の主樹脂として使用する場合には、その重合硬化後の強度が不足するのであれば、硬化剤や架橋剤を使用し、さらには三次元網目構造にすることにより強度を向上させることができる。また、長期的な使用の観点から耐熱性や耐水性が懸念される場合は、同様に硬化剤や架橋剤を使用して人工大理石を高密度の三次元網目構造にすることが望ましい。 Therefore, in the composition for artificial marble of the present invention, the resin for artificial marble may be the main resin, and the acrylic resin may be the main resin. However, when the acrylic resin is used as the main resin of the composition for artificial marble, if the strength after polymerization and curing is insufficient, a curing agent or a crosslinking agent is used, and further, a three-dimensional network structure is formed. By doing so, the strength can be improved. Further, when there is a concern about heat resistance or water resistance from the viewpoint of long-term use, it is desirable that the artificial marble is similarly made into a high-density three-dimensional network structure using a curing agent or a crosslinking agent.
また、本発明の人工大理石用組成物に用いる水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂のガラス転移点温度は−５℃以上であり、より好ましくは０℃以上である。前記アクリル樹脂のガラス転移点温度が−５℃よりも低いと、人工大理石の成形体強度等が著しく低下し、成形性がかなり悪くなる。また、ガラス転移点温度が−５℃よりも低い場合には、人工大理石の表面に親水性の官能基が効果的に配向しにくいため、人工大理石の表面に汚れが付着し易くなり、防汚性が悪くなる。なお、一般に使用されているアクリルモノマーからなるアクリル樹脂の範囲内では、ガラス転移点温度の上限値を見い出すことはできなかった。 Moreover, the glass transition point temperature of the acrylic resin which consists of the acrylic monomer which has a hydroxyl group or nitrogen-containing group used for the composition for artificial marble of this invention is -5 degreeC or more, More preferably, it is 0 degreeC or more. If the glass transition temperature of the acrylic resin is lower than −5 ° C., the strength of the molded article of the artificial marble is remarkably lowered and the moldability is considerably deteriorated. Further, when the glass transition temperature is lower than −5 ° C., the hydrophilic functional group is difficult to effectively orient on the surface of the artificial marble, so that the surface of the artificial marble is likely to be contaminated, and the antifouling is prevented. Sexuality gets worse. In addition, the upper limit value of the glass transition temperature could not be found within the range of acrylic resins made of commonly used acrylic monomers.
本発明の人工大理石用組成物においては、適宜用途に応じて石目調人工大理石の風合いを出すための粗粉砕物、無機充填粒子、硬化剤などを適当量添加される。石目調人工大理石の風合いを出すための粗粉砕物には、天然物シリカ、寒水石、硅石、樹脂硬化物などの粗粉砕物がある。また、人工大理石用組成物に添加する無機充填粒子としては、ガラスフリット、シリカ、アルミ粉、水酸化アルミニウムなどを使用できる。無機充填粒子の表面には、人工大理石用樹脂などとよく相溶するように適当な表面処理方法でカップリング処理することが好ましい。カップリング処理には、一般的に使用されるシラン系、チタネート系などのカップリング処理剤を使用し、乾式法、湿式法など一般的に使用される方法で処理すればよい。 In the composition for artificial marble of the present invention, an appropriate amount of a coarsely pulverized product, inorganic filler particles, a curing agent and the like for producing a texture of a stone-like artificial marble is appropriately added according to the intended use. The coarsely pulverized product for producing the texture of the stone-like artificial marble includes coarsely pulverized products such as natural product silica, cryogenic stone, meteorite, and resin cured product. Moreover, as an inorganic filling particle added to the composition for artificial marble, glass frit, silica, aluminum powder, aluminum hydroxide and the like can be used. The surface of the inorganic filler particles is preferably subjected to a coupling treatment by an appropriate surface treatment method so as to be well compatible with an artificial marble resin or the like. The coupling treatment may be performed by a commonly used method such as a dry method or a wet method using a commonly used silane or titanate coupling treatment agent.
硬化剤としては、化薬アクゾ（株）製のパーカドックス１６やトリゴノックス１２１を適当量使用し、日本ポリウレタン工業（株）製のイソシアネート硬化剤（コロネートＨＸ）なども随時適当量使用すればよい。 As the curing agent, an appropriate amount of Perkadox 16 or Trigonox 121 manufactured by Kayaku Akzo Co., Ltd. may be used, and an appropriate amount of an isocyanate curing agent (Coronate HX) manufactured by Nippon Polyurethane Industry may be used as needed.
上記のような人工大理石用組成物を用いて人工大理石の成形体を得るには、上記組成となるように調合された人工大理石用樹脂及び前記アクリル樹脂に無機充填粒子や硬化剤などを添加し、その人工大理石用組成物を均一に撹拌して無機充填粒子等を均一に分散させる。 In order to obtain a molded article of artificial marble using the composition for artificial marble as described above, inorganic filler particles and a curing agent are added to the resin for artificial marble and the acrylic resin prepared to have the above composition. Then, the artificial marble composition is uniformly stirred to uniformly disperse the inorganic filler particles and the like.
無機充填粒子を撹拌して人工大理石用樹脂や前記アクリル樹脂に均一に分散させる方法としては、ディスパーミキサー、ヘンシェルミキサー、プラネタリミキサー、ボールミキサー、ビーズミル、オムニミキサー、振動・遠心力などを利用する非メディア系の分散・撹拌装置など、一般的に用いられる分散・撹拌装置を使用し、適当な時間均一に撹拌すればよい。 As a method of stirring the inorganic filler particles and uniformly dispersing them in the resin for artificial marble and the acrylic resin, a non-dispersing mixer, Henschel mixer, planetary mixer, ball mixer, bead mill, omni mixer, vibration / centrifugal force, etc. are used. A generally used dispersing / stirring device such as a media-based dispersing / stirring device may be used and stirred uniformly for an appropriate time.
その後、人工大理石用組成物を成形型に注入して重合硬化させ、所定の製品形状に成形すれば、人工大理石の成形体、例えば人工大理石製の浴槽や浴槽壁材、キッチン流し台のカウンタ、洗面台のカウンターなどの水回り部材、給湯器外壁部材、住居用外壁部材などを製作することができる。また、この人工大理石用組成物は、他の樹脂成形品や心材の表面に塗布又は成形して表面保護層（防汚層）として用いることもできる。 After that, the artificial marble composition is injected into a mold, polymerized and cured, and molded into a predetermined product shape. Then, an artificial marble molded body, for example, an artificial marble bathtub or bathtub wall material, a kitchen sink counter, a washbasin It is possible to produce a watering member such as a table counter, a water heater outer wall member, a residential outer wall member, and the like. Moreover, this composition for artificial marble can also be used as a surface protective layer (antifouling layer) by applying or molding to the surface of another resin molded product or core material.
人工大理石用組成物の成形方法としては、注型による成型方法が最も適しているが、他の方法、例えば射出成形、圧縮成形、プレス成形などの一般的な成型方法も利用できる。また、ゲルコートなどのコーティングを利用して樹脂成形品や心材の表面に付加してもよい。注型により成形する場合には、上下金型の金型温度を適宜設定することにより、水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂を人工大理石の表面に効果的に配向させることができる。 As the molding method of the artificial marble composition, a casting molding method is most suitable, but other molding methods such as general molding methods such as injection molding, compression molding, and press molding can also be used. Moreover, you may add to the surface of a resin molded product or a core material using coatings, such as a gel coat. In the case of molding by casting, by appropriately setting the mold temperature of the upper and lower molds, an acrylic resin made of an acrylic monomer having a hydroxyl group or a nitrogen-containing group can be effectively oriented on the surface of the artificial marble. .
本発明の人工大理石用組成物においては、人工大理石用樹脂１００重量部に対して水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂が１０重量部以上となっているので、重合硬化した人工大理石又は人工大理石の成形体の表面（平滑面）に水滴を付着させたときの対水接触角の値が７０°以下となり、表面にオレイン酸を付着させたときの対オレイン酸接触角の値が２０°以下となる。さらに、人工大理石用樹脂１００重量部に対して水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂を６０重量部以上とすれば、重合硬化した人工大理石又は人工大理石の成形体の表面（平滑面）に水滴を付着させたときの対水接触角の値が５５°以下となり、表面にオレイン酸を付着させたときの対オレイン酸接触角の値が１５°以下となる。 In the composition for artificial marble of the present invention, since the acrylic resin comprising an acrylic monomer having a hydroxyl group or a nitrogen-containing group is 10 parts by weight or more with respect to 100 parts by weight of the resin for artificial marble, the polymerization-cured artificial marble Or the value of the contact angle with water when water droplets are attached to the surface (smooth surface) of the molded article of artificial marble is 70 ° or less, and the value of the contact angle with oleic acid when oleic acid is attached to the surface is It becomes 20 degrees or less. Furthermore, if the acrylic resin comprising an acrylic monomer having a hydroxyl group or a nitrogen-containing group is added to 60 parts by weight or more with respect to 100 parts by weight of the resin for artificial marble, the surface (smooth surface) of the polymerization-cured artificial marble or artificial marble molded body ) Has a water contact angle value of 55 ° or less when a water droplet is adhered, and a oleic acid contact angle value of 15 ° or less when oleic acid is adhered to the surface.
接触角とは、固体表面上に小さな液滴を乗せ、液滴を平衡状態に維持しているとき、液体表面と固体表面との成す角を指す。また、対水接触角性は、前記アクリル樹脂中の水酸基又は窒素含有基が大理石表面に配向することに起因しており、対オレイン酸接触角性は前記アクリル樹脂中のアルキル基が大理石表面に配向することに起因している。 The contact angle refers to an angle formed between the liquid surface and the solid surface when a small droplet is placed on the solid surface and the droplet is maintained in an equilibrium state. The contact angle with water is due to the orientation of the hydroxyl group or nitrogen-containing group in the acrylic resin on the marble surface, and the contact angle with oleic acid is due to the alkyl group in the acrylic resin on the marble surface. This is due to the orientation.
前記アクリル樹脂に含まれる水酸基又は窒素含有基等を重合硬化後の人工大理石表面に効果的に配向させるには、これらの官能基と人工大理石用樹脂との相互作用や立体障害などを利用できるが、それ以外にも、人工大理石用樹脂と前記アクリル樹脂との粘度の差を利用する方法、人工大理石用樹脂と前記アクリル樹脂との硬化速度の差異による方法などもある。 In order to effectively orient the hydroxyl group or nitrogen-containing group contained in the acrylic resin on the surface of the artificial marble after polymerization and curing, interaction between these functional groups and the resin for artificial marble, steric hindrance, etc. can be used. In addition, there are a method utilizing the difference in viscosity between the resin for artificial marble and the acrylic resin, and a method using a difference in curing speed between the resin for artificial marble and the acrylic resin.
人工大理石成形体の表面における対水接触角及び対オレイン酸接触角と防汚性との間には強い相関があり、対水接触角及び対オレイン酸接触角の値が小さいほど防汚性も良好となる。しかして、人工大理石用樹脂１００重量部に対して前記アクリル樹脂を１０重量部以上含有させることにより、対水接触角は７０°以下となり、対オレイン酸接触角が２０°以下となり、優れた防汚性を得ることができる。また、人工大理石用樹脂１００重量部に対して前記アクリル樹脂を６０重量部以上含有させることにより、対水接触角は５５°以下となり、対オレイン酸接触角が１５°以下となり、より一層優れた防汚性を得ることができる。 There is a strong correlation between the contact angle with water and the contact angle with oleic acid on the surface of the artificial marble molded body and the antifouling property, and the smaller the values of the contact angle with water and the contact angle with oleic acid, the more antifouling property is obtained. It becomes good. Thus, by containing 10 parts by weight or more of the acrylic resin with respect to 100 parts by weight of the resin for artificial marble, the contact angle with water becomes 70 ° or less and the contact angle with oleic acid becomes 20 ° or less. Dirty can be obtained. Further, by adding 60 parts by weight or more of the acrylic resin with respect to 100 parts by weight of the resin for artificial marble, the contact angle with water becomes 55 ° or less and the contact angle with oleic acid becomes 15 ° or less, which is even more excellent. Antifouling property can be obtained.
すなわち、このような人工大理石又は人工大理石の成形体では、親水性の官能基（水酸基、窒素含有基）や親油性の官能基（アルキル基）が人工大理石の表面に十分に配向しているので、人工大理石表面に配向した各官能基の効果により、表面に汚れがほとんど付着せず、付着したとしても容易に洗浄が可能となる。特に、浴槽の場合には、喫水線域に汚れがほとんど付着しなくなる。また、人工大理石用組成物に前記アクリル樹脂を混合していても人工大理石用樹脂（特に、アクリル系のもの）が本来兼ね備えている耐熱性と耐水性を損ねることがなく、さらに人工大理石用樹脂に対する相溶性もあり、好適な人工大理石を得ることができる。 That is, in such an artificial marble or an artificial marble molded body, hydrophilic functional groups (hydroxyl groups, nitrogen-containing groups) and lipophilic functional groups (alkyl groups) are sufficiently oriented on the surface of the artificial marble. Due to the effect of each functional group oriented on the surface of the artificial marble, the surface is hardly contaminated, and even if it adheres, it can be easily cleaned. In particular, in the case of a bathtub, dirt hardly adheres to the water line area. Further, even if the acrylic resin is mixed with the composition for artificial marble, the heat and water resistance inherent in the resin for artificial marble (especially acrylic) is not impaired, and the resin for artificial marble is further lost. Therefore, a suitable artificial marble can be obtained.
これに対し、人工大理石用樹脂１００重量部に対する前記アクリル樹脂の添加量が１０重量部よりも少ない場合には、対水接触角の値が７０°よりも大きく、対オレイン酸接触角の値が２０°よりも大きくなり、人工大理石の表面に親水性の官能基（水酸基、窒素含有基）が十分に配向しないために防汚効果が低下し、十分な防汚性能が得られない。特に、人工大理石でできた浴槽の場合、その喫水線域に汚れが付着し易くなる。また、人工大理石の成形体強度が低下し易くなり、成形体の作製も困難になる。 On the other hand, when the amount of the acrylic resin added to 100 parts by weight of the resin for artificial marble is less than 10 parts by weight, the value of the contact angle with water is greater than 70 °, and the value of the contact angle with oleic acid is Since it becomes larger than 20 ° and hydrophilic functional groups (hydroxyl groups and nitrogen-containing groups) are not sufficiently oriented on the surface of the artificial marble, the antifouling effect is lowered and sufficient antifouling performance cannot be obtained. In particular, in the case of a bathtub made of artificial marble, dirt easily adheres to the waterline area. In addition, the strength of the molded body of artificial marble is likely to decrease, making it difficult to manufacture the molded body.
水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂を用いることにより汚れの付着を防止し、また汚れの除去を容易にするメカニズムは定かではない。推測するに、前記アクリル樹脂の官能基が人工大理石表面に効果的に配向することで、人工大理石表面に分子レベルで比較的強い親油性（撥水性）と親水性とが付与され、親油性のために汚れを含んだ水が人工大理石表面に密着しにくくなって汚れが付着しにくくなると考えられる。しかも、人工大理石表面に汚れが付着した場合でも、親水性のために大理石表面と汚れとの間には多くの空隙が存在しており、この汚れと人工大理石表面との間の空隙に流動水が浸入して汚れを剥離させ、このクリーニング効果により汚れが除去され易くなると考えられる。特に、人工大理石製の浴槽の場合には、浴槽内で流動する浴槽水や喫水線域で上下する水面の影響によるセルフクリーニング効果で汚れを防止できると思われる。 By using an acrylic resin composed of an acrylic monomer having a hydroxyl group or a nitrogen-containing group, the mechanism for preventing the adhesion of dirt and facilitating the removal of the dirt is not clear. Presumably, the functional group of the acrylic resin is effectively oriented on the surface of the artificial marble, thereby imparting relatively strong lipophilicity (water repellency) and hydrophilicity at the molecular level to the artificial marble surface. For this reason, it is considered that dirt-containing water hardly adheres to the surface of the artificial marble and the dirt is difficult to adhere. In addition, even when dirt is attached to the surface of the artificial marble, there are many voids between the surface of the marble and the dirt due to the hydrophilicity, and fluid flows in the gap between the dirt and the surface of the artificial marble. Enters and peels off the dirt, which is considered to be easily removed by this cleaning effect. In particular, in the case of a bathtub made of artificial marble, it seems that contamination can be prevented by a self-cleaning effect due to the influence of the bathtub water flowing in the bathtub and the water surface moving up and down in the waterline area.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例によって何ら制限されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
まず、以下に説明するようにして本発明の実施例１〜５のサンプルと比較例１、２のサンプルとを作製した。実施例１〜５及び比較例１〜２のいずれのサンプルにおいても、人工大理石用樹脂として日本ユピカ（株）製８９００のアクリルシラップ溶液を用いた。実施例１においては、この人工大理石用樹脂１００重量部に対して前記アクリル樹脂として三菱ガス化学（株）製のメタクリル酸エステルモノマーシリーズＧＥ−６１０からなるアクリル樹脂（ガラス転移点温度５５℃）を１０重量部添加し、人工大理石用組成物のサンプルを得た。なお、このアクリルモノマーは、上記化学式１に示した構造式を有する。 First, as described below, the samples of Examples 1 to 5 and the samples of Comparative Examples 1 and 2 of the present invention were produced. In any of the samples of Examples 1 to 5 and Comparative Examples 1 and 2, 8900 acrylic syrup solution manufactured by Nippon Iupika Co., Ltd. was used as the resin for artificial marble. In Example 1, acrylic resin (glass transition temperature 55 ° C.) composed of methacrylic acid ester monomer series GE-610 manufactured by Mitsubishi Gas Chemical Co., Ltd. is used as the acrylic resin with respect to 100 parts by weight of the resin for artificial marble. 10 parts by weight was added to obtain a sample of an artificial marble composition. This acrylic monomer has the structural formula shown in Chemical Formula 1 above.
実施例２においては、上記人工大理石用樹脂１００重量部に対して前記アクリル樹脂として三菱ガス化学（株）製のメタクリル酸エステルモノマーシリーズＧＥ−６１０からなるアクリル樹脂（ガラス転移点温度５５℃）を６０重量部添加し、人工大理石用組成物のサンプルを得た。 In Example 2, an acrylic resin (glass transition temperature 55 ° C.) composed of methacrylic acid ester monomer series GE-610 manufactured by Mitsubishi Gas Chemical Co., Ltd. is used as the acrylic resin with respect to 100 parts by weight of the artificial marble resin. 60 parts by weight was added to obtain a sample of a composition for artificial marble.
実施例３においては、上記人工大理石用樹脂１００重量部に対して前記アクリル樹脂として三菱ガス化学（株）製のメタクリル酸エステルモノマーシリーズＧＥ−６１０からなるアクリル樹脂（ガラス転移点温度５５℃）を８０重量部添加し、人工大理石用組成物のサンプルを得た。 In Example 3, an acrylic resin (glass transition temperature 55 ° C.) composed of methacrylic acid ester monomer series GE-610 manufactured by Mitsubishi Gas Chemical Co., Ltd. is used as the acrylic resin with respect to 100 parts by weight of the resin for artificial marble. 80 parts by weight were added to obtain a sample of an artificial marble composition.
実施例４においては、上記人工大理石用樹脂１００重量部に対して前記アクリル樹脂として三菱ガス化学（株）製のメタクリル酸エステルモノマーシリーズＧＥ−７２０からなるアクリル樹脂（ガラス転移点温度１８℃）を６０重量部添加し、人工大理石用組成物のサンプルを得た。なお、このアクリルモノマーは、上記化学式３に示した構造式を有する。 In Example 4, an acrylic resin (glass transition temperature 18 ° C.) composed of a methacrylic acid ester monomer series GE-720 manufactured by Mitsubishi Gas Chemical Co., Ltd. is used as the acrylic resin with respect to 100 parts by weight of the artificial marble resin. 60 parts by weight was added to obtain a sample of a composition for artificial marble. This acrylic monomer has the structural formula shown in Chemical Formula 3 above.
実施例５においては、上記人工大理石用樹脂１００重量部に対して前記アクリル樹脂として三菱ガス化学（株）製のメタクリル酸エステルモノマーシリーズＧＥ−７１０（ガラス転移点温度−５℃）を６０重量部添加し、人工大理石用組成物のサンプルを得た。なお、このアクリルモノマーは、前記化学式２に示した構造式を有する。 In Example 5, 60 parts by weight of methacrylic acid ester monomer series GE-710 (glass transition temperature -5 ° C.) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the acrylic resin with respect to 100 parts by weight of the resin for artificial marble. This was added to obtain a sample of a composition for artificial marble. This acrylic monomer has the structural formula shown in Chemical Formula 2.
比較例１においては、上記人工大理石用樹脂のみによって人工大理石用組成物のサンプルを得た。比較例２においては、上記人工大理石用樹脂１００重量部に対して前記アクリル樹脂として三菱ガス化学（株）製のメタクリル酸エステルモノマーシリーズＧＥ−４１０（ガラス転移点温度−６５℃）を１０重量部添加し、人工大理石用組成物のサンプルを得た。なお、三菱ガス化学（株）製のメタクリル酸エステルモノマーシリーズＧＥ−４１０は、次の化学式４で示すような構造式を有する。すなわち、水酸基も窒素含有基も有しないアクリルモノマーである。
さらに、実施例１〜５及び比較例１、２の各サンプルには、適当量のカップリング済みの無機充填粒子として東灌マテリアル（株）製のＡＳ１０５Ｓ（カップリング処理済み硝子フリット）や適当量の硬化剤を添加した。これを分散及び撹拌することにより、無機充填粒子が均一に分散された人工大理石用組成物を得た。 Furthermore, in each sample of Examples 1 to 5 and Comparative Examples 1 and 2, AS105S (coupled glass frit) manufactured by Tokan Materials Co., Ltd. or an appropriate amount as an appropriate amount of inorganic filler particles after coupling. The curing agent was added. By dispersing and stirring this, a composition for artificial marble in which inorganic filler particles were uniformly dispersed was obtained.
ついで、各サンプルの人工大理石用組成物の樹脂溶液を注型用金型に投入し、適切な加圧下において金型温度と硬化時間を適切な値となるように調整し、縦横の寸法が各々１０ｃｍ、厚みが約５ｍｍの人工大理石成形体（試験用サンプル）を得た。 Next, the resin solution of the artificial marble composition of each sample is put into a casting mold, and the mold temperature and the curing time are adjusted to appropriate values under appropriate pressure. An artificial marble molded body (sample for test) having a thickness of 10 cm and a thickness of about 5 mm was obtained.
この後、得られた実施例１〜５及び比較例１、２の人工大理石成形体を用いて対水接触角の値、対オレイン酸接触角の値、防汚性能、成形性を評価した。この評価結果を下記の表１に示す。
対水接触角は、各サンプルの上に水滴を付着させ、Tatec社製のcontact angle meter ＣＡ−ＭＭを使用してその接触角を測定した。対水接触角は３段階にレベル分けし（対水接触角性）、対水接触角の値が５５°以下の場合には表１で「○」（親水性大）で表示し、５５°超過７０°以下の場合には表１で「○△」で表示し、７０°超過の場合には表１で「△」で表示した。 The contact angle with water was measured by using a contact angle meter CA-MM manufactured by Tatec with water droplets attached on each sample. The water contact angle is divided into three levels (water contact angle). When the water contact angle is 55 ° or less, it is displayed as “◯” (high hydrophilicity) in Table 1, 55 ° When the excess is 70 ° or less, it is indicated by “◯ △” in Table 1, and when it exceeds 70 °, it is indicated by “Δ” in Table 1.
また、対オレイン酸接触角は、各サンプルの上にオレイン酸を付着させ、Tatec社製のcontact angle meter ＣＡ−ＭＭを使用してその接触角を測定した。対オレイン酸接触角も３段階にレベル分けし（対オレイン酸接触角性）、対オレイン酸接触角の値が１５°以下の場合には表１で「○」（親油性大）で表示し、１５°超過２０°以下の場合には表１で「○△」で表示し、２０°超過の場合には表１で「△」で表示した。 The contact angle with oleic acid was measured by attaching oleic acid on each sample and using a contact angle meter CA-MM manufactured by Tatec. The contact angle for oleic acid is also divided into three levels (contact angle for oleic acid). If the contact angle for oleic acid is 15 ° or less, it is displayed as “◯” (high lipophilicity) in Table 1. In the case of exceeding 15 ° and not more than 20 °, “◯ △” is shown in Table 1, and in the case of exceeding 20 °, “△” is shown in Table 1.
人工大理石成形体の防汚性能については、４０℃の風呂に１人１０分、合計４人がジェットバス（ジャグジー）強を使用して入浴した後、各サンプルの人工大理石成形体を浴槽の喫水線付近に浸漬させ、５分間ジェットバス強で湯浴させた。そして、浴槽から取り出した人工大理石成形体の表面の光沢度を光沢度計で測定し、浸漬前後の光沢度値と目視による汚れの評価を加味して行なった。特に、光沢度値については、浸漬前の光沢度を１００％とし、浸漬後の光沢度が９０％以上の場合には防汚性能が優良であると評価し、表１では「○」で表わした。また、浸漬後の光沢度が８０％以上９０％未満の場合には防汚性能が良好であると評価し、表１では「○△」で表わした。浸漬後の光沢度が６０％以上８０％未満の場合には防汚性能が不良であると評価し、表１では「△」で表わした。 Regarding the antifouling performance of the artificial marble molded body, after bathing in a bath at 40 ° C for 10 minutes for a total of 4 people using a whirlpool (jacuzzi) strength, each artificial marble molded body of each sample was placed in the tub waterline. It was immersed in the vicinity and bathed in a hot water bath for 5 minutes. And the glossiness of the surface of the artificial marble molded body taken out from the bathtub was measured with a gloss meter, and the glossiness values before and after the immersion and visual evaluation of dirt were taken into account. In particular, regarding the gloss value, the gloss before immersion is 100%, and when the gloss after immersion is 90% or more, the antifouling performance is evaluated to be excellent. It was. Moreover, when the glossiness after immersion was 80% or more and less than 90%, it was evaluated that the antifouling performance was good. When the glossiness after immersion was 60% or more and less than 80%, it was evaluated that the antifouling performance was poor, and it was represented by “Δ” in Table 1.
人工大理石成形体の成形性については、注型用金型から人工大理石成形体を脱型する際の脱型具合（脱型の容易さ）によって３段階に分けて評価した。すなわち、容易に注型用金型から脱型できた場合には成形性が良好であると評価し、表１では「○」で表わした。脱型するのにやや時間を要した場合には成形性が許容範囲内であると評価し、表１では「△」と表わした。脱型できない場合（人工大理石成形体が注型用金型に貼り付いて脱型できない場合など）には成形性は不可（悪）と評価し、表１では「×」で表わした。 The moldability of the artificial marble molded body was evaluated in three stages according to the demolding condition (ease of demolding) when the artificial marble molded body was demolded from the casting mold. That is, when the mold was easily removed from the casting mold, it was evaluated that the moldability was good, and in Table 1, it was represented by “◯”. When it took some time to remove the mold, it was evaluated that the moldability was within an allowable range, and in Table 1, “Δ” was indicated. When it was not possible to remove the mold (such as when the artificial marble molded body was stuck to the casting mold and could not be removed), the moldability was evaluated as bad (bad).
表１の実施例１〜５と比較例１の評価結果を比較すれば、実施例１〜５では人工大理石用樹脂１００重量部に対する水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂の添加量が１０重量部以上で、かつ、前記アクリル樹脂のガラス転移点温度が−５℃以上となっているので、対水接触角が７０°以下、対オレイン酸接触角が２０°以下となり、防汚性能が良好であった。また、実施例１〜５では成形性は許容範囲内となっているが、ガラス転移点温度を０℃以上とした実施例１〜４では成形性も良好となった。 If the evaluation result of Examples 1-5 of Table 1 and the comparative example 1 are compared, in Examples 1-5, the addition amount of the acrylic resin which consists of an acrylic monomer which has a hydroxyl group or a nitrogen-containing group with respect to 100 weight part of resin for artificial marble Is 10 parts by weight or more, and the glass transition temperature of the acrylic resin is −5 ° C. or higher. Therefore, the contact angle with water is 70 ° or less, the contact angle with oleic acid is 20 ° or less, and antifouling is achieved. The performance was good. In Examples 1 to 5, the moldability was within the allowable range, but in Examples 1 to 4 in which the glass transition temperature was 0 ° C. or higher, the moldability was also good.
表１の実施例２〜５と実施例１の評価結果を比較すれば、実施例２〜５では人工大理石用樹脂１００重量部に対する水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂の添加量が６０重量部以上で、かつ、前記アクリル樹脂のガラス転移点温度が−５℃以上となっているので、対水接触角が５５°以下、対オレイン酸接触角が１５°以下となり、優秀な防汚性能が得られた。また、実施例２〜５では成形性は許容範囲内となっているが、ガラス転移点温度を０℃以上とした実施例２〜４では成形性も良好となった。 Comparing the evaluation results of Examples 2 to 5 and Table 1 in Table 1, in Examples 2 to 5, the amount of acrylic resin comprising an acrylic monomer having a hydroxyl group or a nitrogen-containing group with respect to 100 parts by weight of the resin for artificial marble Is 60 parts by weight or more, and the glass transition temperature of the acrylic resin is −5 ° C. or higher, so that the contact angle with water is 55 ° or less and the contact angle with oleic acid is 15 ° or less, which is excellent. Antifouling performance was obtained. Further, in Examples 2 to 5, the moldability was within the allowable range, but in Examples 2 to 4 in which the glass transition temperature was 0 ° C. or higher, the moldability was also good.
表１の比較例２によれば、人工大理石用樹脂１００重量部に対する水酸基又は窒素含有基を有するアクリルモノマーからなるアクリル樹脂の添加量が１０重量部以上であっても、前記アクリル樹脂のガラス転移点温度が−５℃よりも低い場合には、成形性が悪く、また防汚性も不良であった。 According to Comparative Example 2 in Table 1, the glass transition of the acrylic resin even when the amount of the acrylic resin composed of an acrylic monomer having a hydroxyl group or a nitrogen-containing group is 10 parts by weight or more with respect to 100 parts by weight of the resin for artificial marble. When the spot temperature was lower than −5 ° C., the moldability was poor and the antifouling property was poor.
なお、表１からは、対水接触角値及び対オレイン酸接触角値と防汚性能との間には、強い相関のあることも確認できる。 In addition, from Table 1, it can also confirm that there exists a strong correlation between a contact angle value with respect to water and a contact angle value with respect to oleic acid, and antifouling performance.
Claims (6)
前記アクリル樹脂のガラス転移点温度が−５℃以上であり、
重合硬化後の表面における対水接触角の値が７０°以下で、かつ、対オレイン酸接触角の値が２０°以下であることを特徴とする人工大理石用組成物。 Containing 10 parts by weight or more of an acrylic resin composed of an acrylic monomer having a hydroxyl group or a nitrogen-containing group with respect to 100 parts by weight of acrylic syrup ;
The glass transition temperature of the acrylic resin is −5 ° C. or higher,
A composition for artificial marble, which has a water contact angle value of 70 ° or less on a surface after polymerization and curing and a oleic acid contact angle value of 20 ° or less.
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