JP2001062857A - Manufacture of thermosettable resin molded body having silica surface layer - Google Patents
Manufacture of thermosettable resin molded body having silica surface layerInfo
- Publication number
- JP2001062857A JP2001062857A JP23724399A JP23724399A JP2001062857A JP 2001062857 A JP2001062857 A JP 2001062857A JP 23724399 A JP23724399 A JP 23724399A JP 23724399 A JP23724399 A JP 23724399A JP 2001062857 A JP2001062857 A JP 2001062857A
- Authority
- JP
- Japan
- Prior art keywords
- mold
- solution
- polysilazane
- silica
- molding material
- 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.)
- Pending
Links
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、住宅内装材、浴室
用基材、洗面台基材等に使用される表面の耐磨耗性に優
れた熱硬化性樹脂成形体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thermosetting resin molded article having excellent abrasion resistance on the surface used for a housing interior material, a bathroom substrate, a washbasin substrate and the like.
【0002】[0002]
【従来の技術】従来、住宅内装材、浴室用基材、洗面台
基材等に使用される繊維強化プラスチック(以下、FR
Pという)製品を大量生産する場合に、原料として、シ
ート・モールディング・コンパウンド(以下、SMCと
いう)、又はバルク・モールディング・コンパウンド
(以下、BMCという)等の熱硬化性成形材料を用いた
プレス成形法又は射出成形法が広く工業的に行われてい
る。2. Description of the Related Art Conventionally, fiber reinforced plastics (hereinafter referred to as FRs) used for housing interior materials, bathroom base materials, wash basin base materials, and the like.
Press molding using a thermosetting molding material such as a sheet molding compound (hereinafter, referred to as SMC) or a bulk molding compound (hereinafter, referred to as BMC) as a raw material when mass-producing a product (hereinafter referred to as P). The method or the injection molding method is widely industrially performed.
【0003】しかし、このようなSMCあるいはBMC
のプレス成形法又は射出成形法により得られた成形品
は、その表面硬度や耐磨耗性が充分でなく、表面に傷が
入りやすく、傷により表面に光沢ムラが発生する、等の
欠点を有する。However, such SMC or BMC
Molded products obtained by press molding or injection molding have disadvantages such as insufficient surface hardness and abrasion resistance, easily scratching the surface, and uneven gloss due to scratching. Have.
【0004】そこで、表面硬度及び耐磨耗性を強化向上
させ、傷等を入りにくくする様々の方法がとられてい
る。例えば、上記熱硬化性成形材料に、マイカ粉やガラ
スフレ−ク等の粒状添加剤をを添加する方法がある。こ
の方法で表面硬度を向上させるには、粒状添加剤を多量
に添加する必要があり、粒状添加剤を多量に添加すると
熱硬化性成形材料の粘度が上昇して、成形時の熱硬化性
成形材料に含まれる強化繊維(通常はガラス繊維)への
樹脂の含浸性が低下する。含浸性が低下すると、浴槽の
ような温水に曝される用途では外観不良が発生しやすく
なる、という問題がある。[0004] Therefore, various methods have been adopted to enhance and improve the surface hardness and abrasion resistance so as not to cause scratches or the like. For example, there is a method of adding a granular additive such as mica powder or glass flake to the thermosetting molding material. In order to improve the surface hardness by this method, it is necessary to add a large amount of a granular additive, and when a large amount of the granular additive is added, the viscosity of the thermosetting molding material increases, and the thermosetting molding at the time of molding is performed. The impregnating property of the resin into the reinforcing fibers (usually glass fibers) contained in the material is reduced. When the impregnation property is reduced, there is a problem that appearance defects are likely to occur in applications such as bathtubs that are exposed to warm water.
【0005】この問題を解決するため、特開平10−1
80972号公報では、ゲルコ−ト用樹脂にガラスビ−
ズを分散混合し、これを表面層として成形型に塗布し硬
化又は半硬化させ、次いで基材層を積層する方法が提案
されているが、SMCあるいはBMCを熱硬化性成形材
料として用いる成形法にゲルコ−トを行う方法を取り入
れることは、生産性を大幅に悪化させる問題が生じ、ま
た、表面硬度を充分向上させるだけのガラスビ−ズ量を
混合させるには困難が伴うといった問題が残されてい
る。In order to solve this problem, Japanese Patent Laid-Open Publication No. 10-1
No. 80972 discloses that a glass bead is used for a resin for gel coating.
A method of dispersing and mixing the particles, applying the resultant to a mold as a surface layer, curing or semi-curing, and then laminating a substrate layer has been proposed, but a molding method using SMC or BMC as a thermosetting molding material has been proposed. Incorporating a method of applying a gel coat to the method causes a problem that productivity is greatly deteriorated, and a problem that it is difficult to mix a glass bead amount sufficient to sufficiently improve the surface hardness remains. ing.
【0006】高い耐磨耗性のシリカ膜を得られることで
知られるポリシラザンは、プラスチックとの密着性が良
くない。このため、特開平9−39161号公報では、
プラスチック層との中間に接着剤層を設ける提案がなさ
れているが、SMCあるいはBMCを熱硬化性成形材料
として用いるFRP成形において接着剤層を設けるの
は、工程を複雑にしコストアップをきたすという問題が
ある。[0006] Polysilazane, which is known to provide a silica film having high abrasion resistance, has poor adhesion to plastic. For this reason, in Japanese Patent Application Laid-Open No. 9-39161,
It has been proposed to provide an adhesive layer in the middle of the plastic layer. However, providing an adhesive layer in FRP molding using SMC or BMC as a thermosetting molding material complicates the process and increases the cost. There is.
【0007】[0007]
【発明が解決しようとする課題】本発明は、上記の如
き、従来のFRP成形体の問題点に着目してなされたも
のであり、表面硬度及び耐磨耗性が大きく、従って、表
面に傷が入りにくく、傷により表面に光沢ムラが発生し
たり、光沢度が低下したりしない、シリカ表面層を有す
る熱硬化性樹脂成形体の製造方法を提供することを目的
とする。SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the conventional FRP molded article as described above, and has a large surface hardness and abrasion resistance. It is an object of the present invention to provide a method for producing a thermosetting resin molded article having a silica surface layer, which hardly causes cracks, does not cause uneven gloss on the surface due to scratches, and does not reduce glossiness.
【0008】[0008]
【課題を解決するための手段】本発明は、予め加熱した
成形型の表面にポリシラザン溶液を塗布した後、この成
形型内に熱硬化性樹脂成形材料を投入し、該成形型を閉
め、上記熱硬化性樹脂成形材料を加熱圧縮硬化させるこ
とを特徴とするシリカ表面層を有する熱硬化性樹脂成形
体の製造方法である。According to the present invention, after a polysilazane solution is applied to the surface of a preheated mold, a thermosetting resin molding material is charged into the mold, and the mold is closed. A method for producing a thermosetting resin molded article having a silica surface layer, wherein the thermosetting resin molding material is heat-compressed and cured.
【0009】本発明のポリシラザンとは、−SiH2 N
H−を基本ユニットとする有機溶剤に可溶な無機ポリマ
−であり、140℃〜150℃で1〜3分間大気中で加
熱すると、水分や酸素と反応してシリカに転化し、高純
度で緻密なシリカ膜を形成するものである。そしてこの
シリカ膜は、高い耐磨耗性、耐薬品性を有するものであ
る。The polysilazane of the present invention is -SiH 2 N
H- is an inorganic polymer that is soluble in an organic solvent having a basic unit. When heated at 140 ° C. to 150 ° C. for 1 to 3 minutes in the air, it reacts with moisture and oxygen to be converted into silica, and has high purity. It forms a dense silica film. The silica film has high abrasion resistance and chemical resistance.
【0010】ポリシラザン溶液から溶剤を揮散させる方
法によると、比較的厚肉のシリカ膜を形成させることが
容易であり、最大2.0μmの厚みの膜が得られる。
2.0μmを超えるとクラックが発生しやすくなり、
0.1μm未満では、膜の耐久性が不十分となる。ポリ
シラザン溶液に用いられる有機溶剤としては、例えば、
キシレン、ジブチルエ−テル、シクロヘキサン等が挙げ
られる。According to the method of evaporating the solvent from the polysilazane solution, it is easy to form a relatively thick silica film, and a film having a maximum thickness of 2.0 μm can be obtained.
If it exceeds 2.0 μm, cracks are likely to occur,
When the thickness is less than 0.1 μm, the durability of the film becomes insufficient. Examples of the organic solvent used in the polysilazane solution include, for example,
Xylene, dibutyl ether, cyclohexane and the like can be mentioned.
【0011】本発明で熱硬化性樹脂成形材料を加熱圧縮
硬化させる成形方法としては、プレス成形又は射出成形
が用いられる。そして、成形型に用いられる材質として
は、加えられる温度、圧力に耐える材質であれば特に限
定されないが、例えば、鉄鋼、アルミニウム、ニッケル
電鋳等が挙げられる。プレス成形の場合には、通常、5
〜120kg/cm2 の成形圧力で圧縮成形される。In the present invention, press molding or injection molding is used as a molding method for heat-compressing and curing the thermosetting resin molding material. The material used for the molding die is not particularly limited as long as it can withstand the applied temperature and pressure, and examples thereof include steel, aluminum, and nickel electroforming. In the case of press molding, usually 5
It is compression molded at a molding pressure of up to 120 kg / cm 2 .
【0012】上記成形型の予め加熱する温度としては、
通常、90〜160℃が好ましい。本発明では、加熱さ
れた成形型の表面にポリシラザン溶液が塗布されるが、
熱硬化性樹脂成形材料を圧縮成形して得られる成形体
(製品)の耐磨耗性を必要とする表面、例えば、浴槽で
あれば浴槽の内面及び周縁部表面に対応する成形型の表
面に塗布される。The temperature at which the mold is pre-heated is
Usually, 90 to 160 ° C. is preferable. In the present invention, the polysilazane solution is applied to the surface of the heated mold,
A surface of a molded article (product) obtained by compression molding of a thermosetting resin molding material, which requires abrasion resistance, for example, in the case of a bathtub, the surface of a mold corresponding to the inner surface of the bathtub and the surface of the peripheral portion. Applied.
【0013】上記ポリシラザン溶液の塗布方法として
は、特に限定されるものではないが、スプレ−による方
法が好適である。成形型の表面にポリシラザン溶液を塗
布した後、熱硬化性樹脂成形材料をプレス成形又は射出
成形を行うまでの時間としては、塗布したポリシラザン
溶液層から溶剤がほぼ揮散し、シリカへの転化がある程
度進行するまでの時間が好ましい。成形型の温度に応じ
て、最適な溶剤及び反応速度を持つポリシラザンが選択
される。The method of applying the polysilazane solution is not particularly limited, but a spray method is preferred. After applying the polysilazane solution to the surface of the mold, the time until the thermosetting resin molding material is subjected to press molding or injection molding is such that the solvent is substantially volatilized from the applied polysilazane solution layer, and conversion to silica is performed to some extent. Time to progress is preferred. Depending on the temperature of the mold, a polysilazane having an optimum solvent and reaction rate is selected.
【0014】さらに、ポリシラザンのシリカへの転化を
完全なものにするために、成形して得られた成形体を、
湿熱環境下で処理するのが好ましい。湿熱環境下の条件
としては、例えば、95℃、80%RHで2〜4時間が
好適である。Further, in order to complete the conversion of polysilazane to silica, a molded product obtained by molding is
The treatment is preferably performed in a moist heat environment. As a condition in a moist heat environment, for example, 95 ° C. and 80% RH for 2 to 4 hours is preferable.
【0015】本発明で用いられる熱硬化性樹脂成形材料
としては、従来公知のSMC及びBMCの調製方法、調
製装置により、熱硬化性樹脂、低収縮化剤、補強繊維と
してのガラス繊維、無機充填材、硬化剤、離型剤、増粘
剤、さらに必要に応じて顔料、禁止剤を加えた組成物を
熟成して増粘し、SMC又はBMCとしたものを用いる
のが好適である。As the thermosetting resin molding material used in the present invention, a thermosetting resin, a low-shrinking agent, a glass fiber as a reinforcing fiber, an inorganic filler, and the like can be prepared by a conventionally known method and apparatus for preparing SMC and BMC. It is preferable to use a composition obtained by adding a material, a curing agent, a release agent, a thickener, and further, if necessary, a pigment and an inhibitor to the composition to ripen and thicken it to form SMC or BMC.
【0016】上記熱硬化性樹脂としては、FRP工業に
おいて一般的に用いられる樹脂であり、例えば、不飽和
ポリエステル樹脂、ビニルエステル樹脂、エポキシ樹
脂、ジアリルフタレ−ト樹脂等が挙げられる。中でも、
不飽和ポリエステル樹脂が、価格、増粘性、成形性が良
好であり、好ましい。The thermosetting resin is a resin generally used in the FRP industry, for example, unsaturated polyester resin, vinyl ester resin, epoxy resin, diallyl phthalate resin and the like. Among them,
Unsaturated polyester resins are preferred because of their good price, viscosity and moldability.
【0017】(作用)本発明のシリカ表面層を有する熱
硬化性樹脂成形体の製造方法は、予め加熱した成形型の
表面にポリシラザン溶液を塗布した後、この成形型内に
熱硬化性樹脂成形材料を投入し、該成形型を閉め、上記
熱硬化性樹脂成形材料を加熱圧縮硬化させる方法である
ので、ポリシラザンがシリカへの転化の途中に熱硬化性
樹脂成形材料を成形するため、シリカ膜と成形体との密
着性が良好となる。そして、得られるシリカ表面層を有
する熱硬化性樹脂成形体は、表面硬度及び耐磨耗性が大
きく、従って、表面に傷が入りにくく、傷により表面に
光沢ムラが発生したり、光沢度が低下したりしない。さ
らに、表面は化学的耐久性に優れているため、長期間美
麗な表面が保たれる。(Function) In the method for producing a thermosetting resin molded article having a silica surface layer according to the present invention, a polysilazane solution is applied to the surface of a preheated molding die, and then the thermosetting resin molding is formed in the molding die. Since the material is charged, the molding die is closed, and the thermosetting resin molding material is heated and compression-cured, the polysilazane is formed into a thermosetting resin molding material during the conversion to silica. And the molded body have good adhesion. The resulting thermosetting resin molded product having a silica surface layer has a high surface hardness and abrasion resistance, and therefore is hardly scratched on the surface. Do not drop. Furthermore, since the surface is excellent in chemical durability, a beautiful surface is maintained for a long time.
【0018】[0018]
【発明の実施の形態】(実施例1) (SMCの調製)イソ系不飽和ポリエステル樹脂のスチ
レン溶液80重量部と、ポリスチレンのスチレン溶液2
0重量部に、平均粒径2μmの炭酸カルシウム140重
量部、酸化マグネシウム1重量部、タ−シャリ−ブチル
パ−オキシベンゾエ−ト1重量部、パラベンゾキノン
0.03重量部、ステアリン酸亜鉛5重量部を混合した
樹脂ペ−ストに、長さ1インチのチョップドストランド
ガラス繊維を含浸し、40℃で1日熟成してSMCとし
た。このSMC中のガラス繊維の含有量は25重量%で
あった。(Example 1) (Preparation of SMC) 80 parts by weight of a styrene solution of an iso-unsaturated polyester resin and a styrene solution of polystyrene 2
0 parts by weight, 140 parts by weight of calcium carbonate having an average particle size of 2 μm, 1 part by weight of magnesium oxide, 1 part by weight of tert-butyl peroxybenzoate, 0.03 part by weight of parabenzoquinone, and 5 parts by weight of zinc stearate. The mixed resin paste was impregnated with a 1-inch long chopped strand glass fiber and aged at 40 ° C. for 1 day to obtain SMC. The glass fiber content in this SMC was 25% by weight.
【0019】(シリカ膜の形成とSMCの成形)150
℃に加熱した浴槽を成形するための成形型のコア−型の
表面(得られる浴槽の内面に対応する面)に、ポリシラ
ザンの20重量%キシレン溶液をスプレ−にて吹きつけ
塗布をした。得られるシリカ膜の厚さが0.8μmとな
るようにスプレ−する回数を調整した。スプレ−終了後
1分間反応させた後、上記SMCを上記成形型内に投入
して型を閉め、100kg/cm2 の圧力で4分間プレ
ス成形した。得られた成形体(浴槽)を95℃、80%
RHの条件下に3時間処理を行い、ポリシラザンのシリ
カ転化を完全化した。(Formation of Silica Film and Molding of SMC) 150
A 20% by weight xylene solution of polysilazane was sprayed onto the surface of a core (a surface corresponding to the inner surface of the resulting bathtub) of a forming die for forming a bathtub heated to a temperature of 0 ° C. The number of spraying was adjusted so that the thickness of the obtained silica film was 0.8 μm. After reacting for 1 minute after the spraying was completed, the SMC was put into the mold, the mold was closed, and press-molded at a pressure of 100 kg / cm 2 for 4 minutes. The obtained molded body (bath) was heated at 95 ° C. and 80%
Treatment was performed for 3 hours under RH conditions to complete the conversion of polysilazane to silica.
【0020】(耐久性評価)先ず上記浴槽の表面光沢を
測定した。次いでこの浴槽に水を溜め、加熱ヒ−タ−に
より80℃として1000時間保持して温水試験を行
い、表面光沢を測定した。その後、塩化ビニリデン製の
樹脂たわしを用い、荷重5kgを加えながら表面を1万
回擦り磨耗させる磨耗試験を施し、表面光沢を測定し
た。その結果は表1に示す。(Evaluation of Durability) First, the surface gloss of the bath was measured. Then, water was pooled in the bath, and kept at 80 ° C. for 1000 hours with a heating heater to perform a warm water test to measure the surface gloss. Thereafter, using a resin scourer made of vinylidene chloride, an abrasion test of rubbing the surface 10,000 times while applying a load of 5 kg was performed to measure the surface gloss. The results are shown in Table 1.
【0021】[0021]
【表1】 [Table 1]
【0022】(比較例1)ポリシラザン溶液のスプレ−
による吹きつけ塗布をしなかった以外は実施例1と同様
にして浴槽の成形体を得た。そして、実施例1と同様
に、初期、温水試験後、及び磨耗試験後の表面光沢を測
定した。結果は表1に示す。(Comparative Example 1) Spraying of polysilazane solution
A molded body of a bathtub was obtained in the same manner as in Example 1 except that spray coating was not performed. Then, in the same manner as in Example 1, the surface gloss was measured at the initial stage, after the warm water test, and after the abrasion test. The results are shown in Table 1.
【0023】(比較例2)比較例1で得られた成形体の
表面に、実施例1で用いたと同一のポリシラザン溶液
を、得られるシリカ膜の厚さが0.8μmとなるように
スプレ−する回数を調整してスプレ−にて吹きつけ塗布
をし、150℃で3分間加熱した後、95℃、80%R
Hの条件下に3時間処理を行った。そして、実施例1と
同様に、初期の表面光沢、温水試験後、及び磨耗を施し
た後の表面光沢を測定した。結果は表1に示す。(Comparative Example 2) The same polysilazane solution as used in Example 1 was sprayed on the surface of the molded article obtained in Comparative Example 1 so that the obtained silica film had a thickness of 0.8 μm. The number of times of spraying is adjusted, spray coating is performed by spraying, and after heating at 150 ° C. for 3 minutes, 95 ° C., 80% R
The treatment was performed for 3 hours under the condition of H. Then, as in Example 1, the initial surface gloss, the surface gloss after the warm water test, and the surface gloss after abrasion were measured. The results are shown in Table 1.
【0024】表1から判る通り、シリカ表面層を有する
実施例1の成形体は、温水試験後も、その後に施した磨
耗試験後も、初期の表面光沢からの低下は僅少であり、
表面の美麗さを保持していた。一方、シリカ表面層を有
しない比較例1の成形体は、温水試験でも、磨耗試験後
でも、表面光沢を失った。また、成形体に後工程でシリ
カ表面層を形成させた比較例2の成形体は、温水試験後
の表面光沢は初期の光沢をほぼ維持していたが、シリカ
と成形体との密着性が不十分のため、磨耗試験後は表面
光沢を失った。As can be seen from Table 1, the molded article of Example 1 having the silica surface layer showed a slight decrease in the initial surface gloss both after the warm water test and after the abrasion test performed thereafter.
The surface was beautiful. On the other hand, the molded article of Comparative Example 1 having no silica surface layer lost its surface gloss both in the warm water test and after the abrasion test. The molded article of Comparative Example 2 in which a silica surface layer was formed in a post-process on the molded article had almost the initial surface gloss after the warm water test, but the adhesion between silica and the molded article was poor. Due to the lack, the surface gloss was lost after the abrasion test.
【0025】[0025]
【発明の効果】本発明のシリカ表面層を有する熱硬化性
樹脂成形体の製造方法の構成は上述の通りであり、本発
明によれば、シリカ膜と成形体との密着性が良好な成形
体が得られる。そのため、成形体表面の表面硬度及び耐
磨耗性が大きく、表面に傷が入りにくく、傷により表面
に光沢ムラが発生したり、光沢度が低下したりしない成
形体となる。The structure of the method for producing a thermosetting resin molded article having a silica surface layer according to the present invention is as described above. According to the present invention, a molding having good adhesion between the silica film and the molded article is provided. The body is obtained. Therefore, the surface of the molded body has high surface hardness and abrasion resistance, and the surface is hardly scratched, and the scratches do not cause uneven gloss on the surface or reduce the glossiness.
Claims (1)
ン溶液を塗布した後、この成形型内に熱硬化性樹脂成形
材料を投入し、該成形型を閉め、上記熱硬化性樹脂成形
材料を加熱圧縮硬化させることを特徴とするシリカ表面
層を有する熱硬化性樹脂成形体の製造方法。After applying a polysilazane solution to the surface of a preheated mold, a thermosetting resin molding material is charged into the mold, the mold is closed, and the thermosetting resin molding material is heated. A method for producing a thermosetting resin molded article having a silica surface layer, which is compression-cured.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23724399A JP2001062857A (en) | 1999-08-24 | 1999-08-24 | Manufacture of thermosettable resin molded body having silica surface layer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23724399A JP2001062857A (en) | 1999-08-24 | 1999-08-24 | Manufacture of thermosettable resin molded body having silica surface layer |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2001062857A true JP2001062857A (en) | 2001-03-13 |
Family
ID=17012529
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP23724399A Pending JP2001062857A (en) | 1999-08-24 | 1999-08-24 | Manufacture of thermosettable resin molded body having silica surface layer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2001062857A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014512986A (en) * | 2011-06-13 | 2014-05-29 | エルジー・ハウシス・リミテッド | Display panel bezel manufacturing method using mold casting and display panel bezel manufactured through the method |
-
1999
- 1999-08-24 JP JP23724399A patent/JP2001062857A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014512986A (en) * | 2011-06-13 | 2014-05-29 | エルジー・ハウシス・リミテッド | Display panel bezel manufacturing method using mold casting and display panel bezel manufactured through the method |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1162377A (en) | Process for the manufacture of objects from thermosetting resin | |
JPS6030256B2 (en) | Manufacturing method for plastic molded parts | |
JP2002060608A (en) | Thermosetting resin composition for vehicle body outer panel | |
US8475890B2 (en) | Colored material coated transparent chip for artificial stone, method of preparing same, and artificial stone including same | |
JP2001062857A (en) | Manufacture of thermosettable resin molded body having silica surface layer | |
CN1092019A (en) | High-strength compounded glass fibre reinforced plastic and preparation method thereof | |
JP3161538B2 (en) | Method for producing molded article having gel coat layer | |
US3579477A (en) | Polyester coating and molding composition | |
JPH0716850A (en) | Production of artificial stone decorative panel | |
JP3265731B2 (en) | Method for producing fiber reinforced plastics and molded article thereof | |
JP2017193599A (en) | Sheet molding compound, method for producing the same, and molded article | |
CN111113956A (en) | Processing method of decorative composite board | |
CN110670795A (en) | Stone-plastic curtain wall board and preparation method thereof | |
JPH07242456A (en) | Production of antifungal artificial marble product | |
JPH0376331B2 (en) | ||
JP3331195B2 (en) | Laminated molded product, bathtub and method for producing laminated molded product | |
JPH02251442A (en) | Flame resistant phenol resin frp formed object | |
JPH0564839A (en) | Metallic tone coloring method for plastic molded body | |
JPS62259837A (en) | Fiber reinforced plastic product and manufacture thereof | |
JPS5887196A (en) | Matte-finishing thin film type parting agent for use in molding of fiber-reinforced thermosetting resin article | |
JPH0546910Y2 (en) | ||
JPH0826805A (en) | Manufacture of artificial marble article having antimicrobial activity | |
JPH0416314A (en) | Manufacture of fiber reinforced thermoplastic resin formed body | |
JPH054204B2 (en) | ||
JPH0873251A (en) | Production of antibacterial artificial marble product |