JP3552346B2 - Light-diffusing methacrylic resin composition and sheet-like material comprising the composition - Google Patents
Light-diffusing methacrylic resin composition and sheet-like material comprising the composition Download PDFInfo
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- calcium carbonate
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Description
【０００１】
【発明の属する技術分野】
本発明は耐熱安定性、光拡散性、隠蔽性に優れたメタクリル系樹脂組成物に関する。 さらには、光拡散性メタクリル系樹脂シート状物に関する。
【０００２】
【従来の技術】
従来より照明カバー、透過型ディスプレイ用の光拡散板、照明看板などの部材として、メタクリル系樹脂に屈折率の異なる透明性の無機系や有機系の微粒子を混在させた光拡散性樹脂材料が広く用いられている。
【０００３】
光拡散性樹脂材料としては、光透過性が高いにもかかわらず光源のイメージが見えにくい性能（隠蔽性）、広角度に光を散乱させる性能（光拡散性）が要求される。
基材となるメタクリル系樹脂に対し適度な屈折率差を有しているために隠蔽性、光拡散性が良好でありかつ、安価な材料である炭酸カルシウム粒子を光拡散剤として用いた材料についての提案がある。
特公平１−２２８６１ 号公報には平均粒径１μないし２０μの炭酸カルシウムが１０〜２００ｇ／ｍ２ の割合で分散して混入されている光拡散性アクリル系樹脂シート状物が記載されている。
特公平３−２１８８号公報にはメタクリル酸メチル重合体に対して粒子形状が実質的に六面体を有し、かつ１〜１５μの粒子径のものを８０重量％以上含む炭酸カルシウム粉体を適量配合し隠蔽性、光拡散性がより優れた光拡散性アクリル樹脂シート状物が記載されている。
【０００４】
【発明が解決しようとする課題】
上記の特公平１−２２８６１ 号公報、特公平３−２１８８号公報記載のシート状物を構成する樹脂組成物は、溶融成形することにより炭酸カルシウム粒子の崩壊が起こり隠蔽性、光拡散性共に低下する。
そこで本発明は、溶融成形加工を行っても、光拡散性及び隠蔽性が低下せず、全光線透過率も高い光拡散性メタクリル樹脂組成物を提供するものである。
【０００５】
【課題を解決するための手段】
すなわち本発明は、メタクリル系樹脂１００重量部に沈降性炭酸カルシウム０．２〜１０重量部を含有してなる光拡散性メタクリル樹脂組成物において、該沈降性炭酸カルシウムが六面体構造を有する平均粒子径１〜１５μｍの粒子であって、該沈降性炭酸カルシウム１００重量部当たり０．１〜５重量部の脂肪酸，樹脂酸，スルホン酸，脂肪酸エステル，樹脂酸エステル，スルホン酸エステル，燐酸エステル，脂肪酸塩，樹脂酸塩，スルホン酸塩から選ばれた少なくとも１種の有機物で該沈降性炭酸カルシウム粒子表面が被覆されているものであることを特徴とする光拡散性メタクリル系樹脂組成物である。
【０００６】
【発明の実施の形態】
本発明に用いるメタクリル酸メチルを主成分とするメタクリル系樹脂とは、メタクリル酸メチル単独重合体あるいはメタクリル酸メチルを５０重量％以上と、他のビニル単量体との共重合体である。
該ビニル単量体としては、例えばメタクリル酸エチル、メタクリル酸ブチル、メタクリル酸シクロヘキシル、メタクリル酸フェニル、メタクリル酸ベンジル、メタクリル酸２−エチルヘキシル、メタクリル酸２−ヒドロキシエチル等のメタクリル酸エステル類、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸シクロヘキシル、アクリル酸フェニル、アクリル酸ベンジル、アクリル酸２−エチルヘキシル、アクリル酸２−ヒドロキシエチル、等のアクリル酸エステル類、メタクリル酸、アクリル酸などの不飽和酸類、スチレン、α−メチルスチレン、アクリロニトリル、メタクリロニトリル、無水マレイン酸、フェニルマレイミド、シクロヘキシルマレイミド等である。 またこの共重合体には、無水グルタル酸単位、グルタルイミド単位をさらに含んでいても良い。
さらに前述の重合体、共重合体にジエン系ゴム、アクリル系ゴムをブレンドしたものでもよい。
【０００７】
本発明における炭酸カルシウムは、化学的に合成した沈降性炭酸カルシウムであり、その中でも実質的に六面体構造を有するものである。該沈降性炭酸カルシウムは市販されている。
【０００８】
該炭酸カルシウムの平均粒子径は１〜１５μｍ、好ましくは２〜１０μｍである。 １μｍより小さいと光拡散性と隠蔽性が悪くなり、１５μｍを越えると光拡散性が不足する他に成形品とした際に表面の平滑性が悪くなる。
【０００９】
該炭酸カルシウムの含有量は、メタクリル系樹脂１００重量部に対し０．２〜１０重量部、好ましくは１〜８重量部である。 ０．２重量部より少ないと光拡散性、隠蔽性が充分でなく、１０重量部を越えると光透過性が不足する他に成形品が脆くなる。
【００１０】
該炭酸カルシウム表面を被覆する有機物としては、脂肪酸、樹脂酸、スルホン酸、脂肪酸エステル、樹脂酸エステル、スルホン酸エステル、燐酸エステル、脂肪酸塩、樹脂酸塩スルホン酸塩等である。
【００１１】
ここでいう脂肪酸とは、カプロン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アラキン酸、ベヘン酸、リグノセリン酸などの飽和脂肪酸、ウンデシレン酸、オレイン酸、エライジン酸、セトレイン酸、エルカ酸、ブラシジン酸、ソルビン酸、リノール酸、リレノン酸、アラキドン酸、ステアロール酸などの不飽和脂肪酸を指す。
樹脂酸とは、アビエチン酸、ネオアビエチン酸、ｄ−ピマル酸、イソ−ｄ−ピマル酸、ポドカルプ酸、アガテンジカルボン酸などの脂環族樹脂酸、安息香酸、ケイ皮酸、ｐ−オキシケイ皮酸などの芳香族樹脂酸を指す。
スルホン酸とは、アルキルスルホン酸、アルキルベンゼンスルホン酸などを指す。
【００１２】
脂肪酸エステル、樹脂酸エステル、スルホン酸エステルとしては、前述の酸のメチルエステル、エチルエステル、プロピルエステル、ブチルエステル、ペンチルエステル、ヘキシルエステル、オクチルエステル、デシルエステル等である。
脂肪酸塩、樹脂酸塩、スルホン酸塩としては、前述の酸のアルカリ金属塩、アミン塩等である。
また燐酸エステルとは、燐酸、ホスホン酸、亜燐酸のアルキルまたはフェニルエステル等である。
【００１３】
これらの有機物は一般的には表面処理剤と呼ばれており、炭酸カルシウム表面を覆い粒子間の凝集を抑える働きの他に、樹脂との親和性を上げる働きもある。
さらに該粒子表面をこれらの有機物で覆うことによって、基材樹脂内での粒子同士の接触破壊を大きく抑える効果もあることが分かった。
【００１４】
これらの有機物の中でも脂肪酸、脂肪酸エステル、脂肪酸塩がメタクリル系樹脂との相性が特に良いため好ましく用いられる。
【００１５】
有機物の該炭酸カルシウム粒子への被覆量は、該炭酸カルシウム１００重量部に対して０．１〜５重量部である。 ０．１重量部以下であると表面被覆の効果が少なく、溶融成形の際崩壊され易くなる。
５重量部を越えて多いと溶融成形時に着色することがある。
【００１６】
該炭酸カルシウム表面に有機物を被覆させる手段としては、乾式法、湿式法があり、具体的には、乾式法はヘンシェルミキサー等で無機粒子を撹拌して加温状況下で有機物を投入し粒子表面に被覆する方法であり、湿式法は炭酸カルシウムの水スラリー中に有機物を投入して、炭酸カルシウムの表面に吸着・被覆させる方法である。
【００１７】
該メタクリル系樹脂に該炭酸カルシウムを含ませて組成物とするには、両者を周知の熱可塑性樹脂の混合し、組成物とする方法を用いることができる。
例えば、各成分を溶融混練する方法があり、該溶融混練は、一般的に使用されている一軸または二軸の押出機、各種のニーダー等の混練装置を用いる方法がある。 さらには、後述の成形方法を用いて一段で成形品とすることも可能である。 さらに該炭酸カルシウムを該メタクリル樹脂を構成する単量体及びその部分重合体を含むシロップに混合して、キャスト重合、連続キャスト重合させて成形品とする方法もある。
【００１８】
また、本発明の光拡散性メタクリル系樹脂組成物に、艶消し剤、染顔料、光安定剤、酸化防止剤、充填剤、離型剤、難燃剤等周知の添加剤を加えても良い。
【００１９】
さらに該光拡散性メタクリル系樹脂組成物を成形加工してシート状物とするには、押出成形、射出成形、プレス成形等の周知の方法がある。
例えば、押出成形では、一軸、二軸の押出機等で溶融混練した後、Ｔダイ、ロールユニットを介して板状に加工する方法である。
【００２０】
また該光拡散性メタクリル系樹脂組成物からなるシート状物としては、シート厚みが０．８〜５ｍｍ程度が一般的である。
該炭酸カルシウムの含有量は、該量が同一でもシート厚みによって光拡散性が異なるので、単位面積当たりの量で表すのが望ましく、結局１０〜２００ｇ／ｍ２ とするのが好ましい。
この量が少な過ぎると、光線透過率は高いものの隠蔽性と光拡散性が共に低く、この量が多過ぎると、隠蔽性と光拡散性は高いが、光線透過率が低過ぎるものとなる。
【００２１】
【発明の効果】
本発明の光拡散性メタクリル系樹脂組成物は、剪断、圧力のかかる加熱溶融成形加工、つまり押出成形や射出成形等を行っても、光拡散性、隠蔽性に優れた成形品を得ることができる。
従って該樹脂組成物は、自動車等のメーターパネル、、照明カバー、看板、透過型ディスプレイの光拡散板、発光式スイッチボタンなどの各種成形品さらには各種フィルムに好適に用いることができる。
【００２２】
【実施例】
以下実施例によって本発明を更に詳しく説明するが、本発明はこれら実施例によってなんら制限されるものではない。尚、評価方法は次の通りである。
・平均粒子径；光回折散乱粒径測定機（日機装（株）製、マイクロトラック粒度分析計 Ｍｏｄｅｌ ９２２０ ＦＲＡ）で測定し、Ｄ５０の値を平均粒子径とした。
・全光線透過率（Ｔｔ）：ＡＳＴＭ Ｄ １００３−６１に準拠してポイック積分球式ヘイズメーター（日本精密光学製ＳＥＰ−ＨＳ−３０Ｄ）により測定した。
・隠ぺい性及び光拡散性；垂直入射光による透過角０度の透過光強度（Ｉ０ ） 、垂直入射光による透過角５度の透過光強度（Ｉ５ ）、垂直入射光による透過角７０度の透過光強度（Ｉ７０） を（株）村上色彩技術研究所製、自動変角光度計ＧＰ−１Ｒ を用いて測定し、Ｉ５ ／ Ｉ０ を隠蔽性とし、Ｉ７０／ Ｉ０ を光拡散性とした。
【００２３】
実施例１〜６、比較例１〜６
メタクリル樹脂ビーズ（スミペックス−ＥＸＡ、住友化学工業（株）製）１００重量部と表１に示す種類の有機物被覆炭酸カルシウムを表２に示す割合でヘンシェルミキサーで混合した後、田辺プラスチックス機械（株）製４０ｍｍ１軸押出機を用い樹脂温度２６５℃で溶融樹脂をＴダイより押出し、ポリシングロール３本を介して幅２３ｃｍ表２に示す厚みのシートを得た。
得られたシートの物性を評価した結果を表２に示す。
【００２４】
【表１】
【表２】
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a methacrylic resin composition having excellent heat stability, light diffusing properties, and hiding properties. Furthermore, the present invention relates to a light-diffusing methacrylic resin sheet.
[0002]
[Prior art]
Conventionally, light-diffusing resin materials made of methacrylic resin mixed with transparent inorganic or organic fine particles having different refractive indices have been widely used as members for lighting covers, light diffusing plates for transmissive displays, and lighting signs. Used.
[0003]
The light-diffusing resin material is required to have a performance in which the image of the light source is hard to be seen (concealing property) despite a high light-transmitting property and a property in which light is scattered at a wide angle (light-diffusing property).
Materials that use calcium carbonate particles, which are inexpensive materials, as light diffusing agents, because they have an appropriate refractive index difference with respect to the methacrylic resin used as the base material, so that they have good concealing properties and light diffusing properties. There is a proposal.
Japanese Patent Publication No. 1-28661 discloses a light diffusing acrylic resin sheet material in which calcium carbonate having an average particle size of 1 μm to 20 μm is dispersed and mixed at a rate of 10 to 200 g / m 2 .
Japanese Patent Publication No. 3-2188 discloses that a proper amount of calcium carbonate powder having a substantially hexahedral particle shape with respect to a methyl methacrylate polymer and containing 80% by weight or more of particles having a particle size of 1 to 15 μm. A light-diffusing acrylic resin sheet having better hiding and light-diffusing properties is described.
[0004]
[Problems to be solved by the invention]
The resin composition constituting the sheet described in Japanese Patent Publication No. 1-28661 and Japanese Patent Publication No. 3-2188 causes collapse of calcium carbonate particles by melt-molding, thereby deteriorating both concealing properties and light diffusing properties. I do.
Therefore, the present invention provides a light-diffusing methacrylic resin composition which does not decrease in light-diffusing properties and hiding properties even when subjected to melt molding and has high total light transmittance.
[0005]
[Means for Solving the Problems]
That is, the present invention provides a light-diffusing methacrylic resin composition containing 0.2 to 10 parts by weight of precipitated calcium carbonate in 100 parts by weight of a methacrylic resin, wherein the precipitated calcium carbonate has an average particle size having a hexahedral structure. 0.1 to 5 parts by weight of fatty acid, resin acid, sulfonic acid, fatty acid ester, resin acid ester, sulfonic acid ester, phosphoric acid ester, fatty acid salt per 100 parts by weight of the precipitated calcium carbonate. A light diffusing methacrylic resin composition, wherein the surface of the precipitated calcium carbonate particles is coated with at least one organic substance selected from the group consisting of a resinate and a sulfonate.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The methacrylic resin containing methyl methacrylate as a main component used in the present invention is a homopolymer of methyl methacrylate or a copolymer of 50% by weight or more of methyl methacrylate and another vinyl monomer.
Examples of the vinyl monomer include methacrylates such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, and acrylic acid. Acrylates such as methyl, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, etc .; Saturated acids, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, cyclohexylmaleimide and the like. The copolymer may further contain a glutaric anhydride unit and a glutarimide unit.
Further, a blend of a diene rubber or an acrylic rubber with the above-mentioned polymer or copolymer may be used.
[0007]
The calcium carbonate in the present invention is a precipitated calcium carbonate chemically synthesized, and has substantially a hexahedral structure. The precipitated calcium carbonate is commercially available.
[0008]
The average particle size of the calcium carbonate is 1 to 15 μm, preferably 2 to 10 μm. If it is less than 1 μm, the light diffusibility and concealing properties will be poor, and if it exceeds 15 μm, the light diffusivity will be insufficient and the surface smoothness will be poor when it is formed into a molded product.
[0009]
The content of the calcium carbonate is 0.2 to 10 parts by weight, preferably 1 to 8 parts by weight based on 100 parts by weight of the methacrylic resin. When the amount is less than 0.2 parts by weight, the light diffusing property and the concealing property are not sufficient. When the amount exceeds 10 parts by weight, the light transmittance is insufficient and the molded article becomes brittle.
[0010]
Examples of the organic substance that coats the surface of the calcium carbonate include fatty acids, resin acids, sulfonic acids, fatty acid esters, resin acid esters, sulfonic acid esters, phosphoric acid esters, fatty acid salts, and resinate sulfonic acid salts.
[0011]
The fatty acids referred to here are caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachinic acid, behenic acid, saturated fatty acids such as lignoceric acid, undecylenic acid, oleic acid, elaidic acid, setrenic acid, Refers to unsaturated fatty acids such as erucic acid, brassic acid, sorbic acid, linoleic acid, rillenonic acid, arachidonic acid and stearolic acid.
The resin acids include abietic acid, neoabietic acid, alicyclic resin acids such as d-pimaric acid, iso-d-pimaric acid, podocapnic acid, and agatendicarboxylic acid, benzoic acid, cinnamic acid, and p-oxycinnamic acid Refers to aromatic resin acids such as acids.
Sulfonic acid refers to alkylsulfonic acid, alkylbenzenesulfonic acid and the like.
[0012]
Examples of the fatty acid ester, resin acid ester, and sulfonic acid ester include the above-mentioned acid methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, octyl ester, and decyl ester.
Examples of the fatty acid salts, resin salts, and sulfonates include the alkali metal salts and amine salts of the above-mentioned acids.
Phosphoric acid esters include alkyl or phenyl esters of phosphoric acid, phosphonic acid, and phosphorous acid.
[0013]
These organic substances are generally called a surface treatment agent, and have a function of covering the surface of calcium carbonate to suppress aggregation between particles and a function of increasing affinity with a resin.
Further, it was found that covering the particle surface with these organic substances also had an effect of greatly suppressing contact destruction between particles in the base resin.
[0014]
Among these organic substances, fatty acids, fatty acid esters, and fatty acid salts are preferably used because they have particularly good compatibility with methacrylic resins.
[0015]
The coating amount of the organic substance on the calcium carbonate particles is 0.1 to 5 parts by weight based on 100 parts by weight of the calcium carbonate. When the amount is less than 0.1 part by weight, the effect of the surface coating is small, and it is easily disintegrated during melt molding.
If the amount exceeds 5 parts by weight, coloring may occur during melt molding.
[0016]
Means for coating the surface of the calcium carbonate with an organic substance include a dry method and a wet method. Specifically, the dry method involves stirring inorganic particles with a Henschel mixer or the like, charging the organic substance under a heated condition, and charging the particle surface. The wet method is a method in which an organic substance is put into a water slurry of calcium carbonate to be adsorbed and coated on the surface of calcium carbonate.
[0017]
In order to form the composition by adding the calcium carbonate to the methacrylic resin, a method in which both are mixed with a known thermoplastic resin to form a composition can be used.
For example, there is a method in which each component is melt-kneaded, and the melt-kneading includes a method using a kneading device such as a generally used single-screw or twin-screw extruder or various kneaders. Furthermore, it is also possible to form a molded article in one step by using a molding method described later. Further, there is a method in which the calcium carbonate is mixed with a syrup containing the monomer constituting the methacrylic resin and a partial polymer thereof, and the mixture is subjected to cast polymerization and continuous cast polymerization to obtain a molded article.
[0018]
Further, well-known additives such as a matting agent, a dye / pigment, a light stabilizer, an antioxidant, a filler, a release agent, and a flame retardant may be added to the light-diffusing methacrylic resin composition of the present invention.
[0019]
Further, in order to form the light diffusible methacrylic resin composition into a sheet by molding, there are known methods such as extrusion molding, injection molding and press molding.
For example, extrusion molding is a method in which after melt-kneading with a single-screw or twin-screw extruder or the like, it is processed into a plate shape via a T-die and a roll unit.
[0020]
Further, as a sheet-like material made of the light-diffusing methacrylic resin composition, a sheet thickness is generally about 0.8 to 5 mm.
Since the light diffusivity differs depending on the sheet thickness even if the amount is the same, the content of the calcium carbonate is preferably represented by an amount per unit area, and is preferably 10 to 200 g / m 2 after all.
If the amount is too small, the light transmittance is high, but the concealing property and the light diffusing property are both low. If the amount is too large, the concealing property and the light diffusing property are high, but the light transmittance is too low.
[0021]
【The invention's effect】
The light-diffusible methacrylic resin composition of the present invention can obtain a molded product excellent in light-diffusing property and concealing property even when subjected to shearing, pressure-applied heat-melt molding, that is, extrusion molding or injection molding. it can.
Therefore, the resin composition can be suitably used for various molded products such as a meter panel of an automobile or the like, a lighting cover, a signboard, a light diffusion plate of a transmission type display, a light-emitting switch button, and various films.
[0022]
【Example】
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The evaluation method is as follows.
Average particle size, light diffraction scattering particle diameter measuring instrument (Nikkiso Co., Ltd., Microtrac particle size analyzer Model 9220 FRA) measured by and the average particle size values of D 50.
-Total light transmittance (Tt): Measured with a Poick integrating sphere haze meter (SEP-HS-30D manufactured by Nippon Seimitsu Kogaku) in accordance with ASTM D 1003-61.
-Opacity and light diffusivity; transmitted light intensity (I 0 ) at a transmission angle of 0 degree due to vertically incident light, transmitted light intensity (I 5 ) at a transmission angle of 5 degrees due to vertically incident light, and transmission angle of 70 degrees due to vertically incident light Of the transmitted light (I 70 ) was measured using an automatic goniophotometer GP-1R manufactured by Murakami Color Research Laboratory Co., Ltd., and I 5 / I 0 was made concealing, and I 70 / I 0 was made light. Diffusive.
[0023]
Examples 1 to 6, Comparative Examples 1 to 6
100 parts by weight of methacrylic resin beads (SUMIPEX-EXA, manufactured by Sumitomo Chemical Co., Ltd.) and an organic-coated calcium carbonate of the type shown in Table 1 were mixed at a ratio shown in Table 2 with a Henschel mixer, and then mixed with Tanabe Plastics Machine Co., Ltd. The molten resin was extruded from a T-die at a resin temperature of 265 ° C. using a 40 mm single screw extruder to obtain a sheet having a width of 23 cm and a thickness shown in Table 2 through three polishing rolls.
Table 2 shows the results of evaluating the physical properties of the obtained sheet.
[0024]
[Table 1]
[Table 2]
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18540295A JP3552346B2 (en) | 1995-07-21 | 1995-07-21 | Light-diffusing methacrylic resin composition and sheet-like material comprising the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18540295A JP3552346B2 (en) | 1995-07-21 | 1995-07-21 | Light-diffusing methacrylic resin composition and sheet-like material comprising the composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0931288A JPH0931288A (en) | 1997-02-04 |
| JP3552346B2 true JP3552346B2 (en) | 2004-08-11 |
Family
ID=16170172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18540295A Expired - Fee Related JP3552346B2 (en) | 1995-07-21 | 1995-07-21 | Light-diffusing methacrylic resin composition and sheet-like material comprising the composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3552346B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001027193A1 (en) * | 1999-10-13 | 2001-04-19 | Maruo Calcium Company Limited | Thermoplastic-resin additive for matting and thermoplastic resin composition containing the same |
| US6875800B2 (en) * | 2001-06-18 | 2005-04-05 | Ppg Industries Ohio, Inc. | Use of nanoparticulate organic pigments in paints and coatings |
| JP4494381B2 (en) * | 2005-09-30 | 2010-06-30 | 丸尾カルシウム株式会社 | Synthetic resin additive comprising heavy calcium carbonate and synthetic resin composition containing the same |
| JP6321626B2 (en) * | 2013-03-26 | 2018-05-09 | 株式会社クラレ | (Meth) acrylic resin composition and acrylic sheet |
-
1995
- 1995-07-21 JP JP18540295A patent/JP3552346B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0931288A (en) | 1997-02-04 |
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