JP2011089068A - Unsaturated polyester resin molded article - Google Patents
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本発明は、不飽和ポリエステル樹脂成形品に関する。 The present invention relates to an unsaturated polyester resin molded article.
繊維強化プラスチック（以下、ＦＲＰという）は、ガラス繊維等の補強繊維を樹脂で固めた材料であり、機械的強度、耐薬品性、耐熱性、電気的性質に優れた複合材料として様々な分野で利用されている。ＦＲＰの成形方法としては、様々あるが、中でもシートモールディングコンパウンド（以下、ＳＭＣという）を用いた加圧加熱成形法は、簡便なことから幅広く利用されている。 Fiber reinforced plastic (hereinafter referred to as FRP) is a material in which reinforcing fibers such as glass fibers are solidified with resin, and is used in various fields as a composite material having excellent mechanical strength, chemical resistance, heat resistance, and electrical properties. It's being used. There are various FRP molding methods. Among them, a pressure heating molding method using a sheet molding compound (hereinafter referred to as SMC) is widely used because of its simplicity.
ＳＭＣは、重合性単量体、充填剤、低収縮剤等を混合した不飽和ポリエステル樹脂組成物（コンパウンド）をドクターブレードでフィルムに塗布し、その上にガラス繊維ロービングを切断、散布し、もう片側を同じく不飽和ポリエステル樹脂組成物を塗布したフィルムで挟み、ロールで含浸、脱泡し、厚さ１〜５ｍｍ程度のシート状に加工した熱硬化性成形材料である。加工されたＳＭＣは３５〜５０℃で数日養生させ、充分増粘させたものを成形に使用する。成形は金型を用いた圧縮成形により、高温・高圧で行われることが多く、所望の形状に成形することが可能である。従来、この方法により成形した成形品（例えば、特許文献１−３参照）は、浴槽や洗面化粧台、キッチンのカウンター等の住宅設備機器として用いられるため、強度と外観に優れた成形品が望まれている。 SMC is to apply an unsaturated polyester resin composition (compound) mixed with a polymerizable monomer, filler, low shrinkage agent, etc. to a film with a doctor blade, and then cut and spray glass fiber rovings on it. It is a thermosetting molding material in which one side is similarly sandwiched between films coated with an unsaturated polyester resin composition, impregnated with a roll, defoamed, and processed into a sheet shape having a thickness of about 1 to 5 mm. The processed SMC is cured at 35 to 50 ° C. for several days and sufficiently thickened for use in molding. Molding is often performed at high temperature and high pressure by compression molding using a mold, and can be molded into a desired shape. Conventionally, molded products formed by this method (see, for example, Patent Documents 1-3) are used as housing equipment such as bathtubs, vanity tables, kitchen counters, etc., and thus molded products with excellent strength and appearance are desired. It is rare.
成形品の強度は、補強繊維であるガラス繊維にかかる部分が大きく、従来、高強度化にはガラス繊維の含有量を増加する方法がとられていた。しかし、ガラス含有量が多いとガラス繊維の含浸が悪く、成形品の外観が悪化するなどの不具合が発生する。また、ガラス繊維を多く含有した場合、圧縮成形法ではガラス繊維を分散させることが難しい。 The strength of the molded article is large in the portion of the glass fiber that is the reinforcing fiber, and conventionally, a method of increasing the glass fiber content has been taken to increase the strength. However, when the glass content is large, impregnation of the glass fiber is poor and problems such as deterioration of the appearance of the molded product occur. Moreover, when a lot of glass fibers are contained, it is difficult to disperse the glass fibers by the compression molding method.
本発明は、以上の通りの事情に鑑みてなされたものであり、ガラス繊維の含有量を増加することなしに高強度化が可能であり、かつ、良好な外観を有する不飽和ポリエステル樹脂成形品を提供することを課題としている。 The present invention has been made in view of the circumstances as described above, and can be increased in strength without increasing the glass fiber content, and an unsaturated polyester resin molded article having a good appearance. It is an issue to provide.
本発明は以下のことを特徴としている。 The present invention is characterized by the following.
第１に、本発明の不飽和ポリエステル樹脂成形品は、不飽和ポリエステル樹脂、重合性単量体、充填剤及びガラス繊維とともに低収縮剤を含有する不飽和ポリエステル樹脂組成物の成形品であって、その中に含まれる空孔径が０．１〜５μｍであり、その空孔の総体積が１ｍ３辺り０．０１〜０．０４ｍ３であることを特徴とする。 First, the unsaturated polyester resin molded article of the present invention is a molded article of an unsaturated polyester resin composition containing a low shrinkage agent together with an unsaturated polyester resin, a polymerizable monomer, a filler and glass fibers. , hole diameter contained therein is 0.1 to 5 [mu] m, the total volume of the pores is characterized by a 1 m 3 around 0.01~0.04m 3.
第２に、上記第１の発明において、低収縮剤が、次式（１） Second, in the first invention, the low shrinkage agent is represented by the following formula (1):
（式中、ｍは１〜３の数値であり、ｎは３〜３００の数値であり、Ｒは炭素数４〜１２のアルキル基である）で表されるアルコール変性スチレン−フマル酸共重合体であることを特徴とする。 (Wherein m is a numerical value of 1 to 3, n is a numerical value of 3 to 300, and R is an alkyl group having 4 to 12 carbon atoms) It is characterized by being.
第３に、上記第１または第２の発明において、低収縮剤の含有量が、不飽和ポリエステル樹脂組成物中２〜１０質量％の範囲であることを特徴とする。 3rdly, in said 1st or 2nd invention, content of a low shrinkage agent is the range of 2-10 mass% in unsaturated polyester resin composition, It is characterized by the above-mentioned.
第４に、上記第１ないし第３の発明において、ガラス繊維の含有量が、不飽和ポリエステル樹脂組成物中５〜３０質量％の範囲であることを特徴とする。 4thly, in said 1st thru | or 3rd invention, content of glass fiber is the range of 5-30 mass% in unsaturated polyester resin composition, It is characterized by the above-mentioned.
第５に、上記第１ないし第４の発明において、充填剤の平均粒径が１〜３０μｍであり、かつ、充填剤の含有量が、不飽和ポリエステル樹脂組成物中３０〜６０質量％の範囲であることを特徴とする。 Fifth, in the first to fourth inventions described above, the average particle diameter of the filler is 1 to 30 μm, and the content of the filler is in the range of 30 to 60 mass% in the unsaturated polyester resin composition. It is characterized by being.
第６に、上記第１ないし第５の発明において、シートモールディングコンパウンドの加圧加熱成形品であることを特徴とする。 Sixth, in the first to fifth inventions, the invention is characterized in that it is a pressure molding product of a sheet molding compound.
本発明によれば、不飽和ポリエステル樹脂成形品中に微小な空孔が内包されているので、不飽和ポリエステル樹脂成形品に付与された外力は、成形品内部において微小な空孔によりその応力が分散する。このため、応力集中に伴う空孔を起点とする亀裂等の発生が生じにくい等、変形、撓みに対して優れた高強度の不飽和ポリエステル樹脂成形品が得られる。また、高強度化のためにガラス繊維を大量に配合する必要が無く、ガラス繊維の含有量を低減できる。その結果、ガラス繊維の含浸不良による成形品の外観の悪化等の不具合の発生を抑制でき、良好な外観の不飽和ポリエステル樹脂成形品を得ることができる。 According to the present invention, since the fine pores are included in the unsaturated polyester resin molded product, the external force applied to the unsaturated polyester resin molded product is stressed by the fine pores inside the molded product. scatter. For this reason, it is possible to obtain a high-strength unsaturated polyester resin molded article that is excellent in deformation and flexure, such that cracks and the like starting from holes due to stress concentration are less likely to occur. Moreover, it is not necessary to mix | blend a glass fiber in large quantities for high intensity | strength, and content of glass fiber can be reduced. As a result, it is possible to suppress the occurrence of defects such as deterioration of the appearance of the molded product due to poor impregnation of glass fibers, and it is possible to obtain an unsaturated polyester resin molded product having a good appearance.
以下、本発明を実施するための最良の形態を挙げて、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to the best mode for carrying out the present invention.
本発明の不飽和ポリエステル樹脂成形品は、重合性単量体、充填剤及びガラス繊維とともに低収縮剤を含有する不飽和ポリエステル樹脂組成物の成形品であり、その成形品中に微小な空孔が多数形成されている。 The unsaturated polyester resin molded product of the present invention is a molded product of an unsaturated polyester resin composition containing a low shrinkage agent together with a polymerizable monomer, a filler and glass fiber, and there are minute voids in the molded product. Many are formed.
不飽和ポリエステル樹脂成形品中の微小な空孔は、不飽和ポリエステル樹脂組成物に配合した低収縮剤成分によって生じるものであり、形態としては、空孔径が平均で０．１〜５μｍである。空孔径が５μｍより大きいと応力分散が充分でなく、強度向上効果が小さくなり、空孔径が０．１μ未満であると応力を吸収できず、強度向上を望めない。空孔の総体積は、不飽和ポリエステル樹脂成形品１ｍ３辺り０．０１〜０．０４ｍ３である。この範囲の成形品は、良好な外観を有し、原料である不飽和ポリエステル樹脂組成物の成形性は高い。空孔の総体積が不飽和ポリエステル樹脂成形品１ｍ３辺り０．０１ｍ３より小さいと、不飽和ポリエステル樹脂組成物の低収縮効果が小さく、クラックや反り等の問題が生じて成形性が悪くなり、成形品は外観が悪化したものとなる。０．０４ｍ３を超えると、不飽和ポリエステル樹脂組成物の低収縮効果が大きすぎるために成形性が劣り、成形品は外観が悪化したものとなる。なお、不飽和ポリエステル樹脂成形品１ｍ３辺りの空孔の総体積は、不飽和ポリエステル樹脂成形品の密度等から算出される。具体的には、下記式による。 The fine pores in the unsaturated polyester resin molded product are produced by the low shrinkage agent component blended in the unsaturated polyester resin composition, and the pore diameter is 0.1 to 5 μm on average as the form. When the pore diameter is larger than 5 μm, the stress dispersion is not sufficient and the effect of improving the strength is reduced, and when the pore diameter is less than 0.1 μm, the stress cannot be absorbed and the strength improvement cannot be expected. The total volume of the pores is an unsaturated polyester resin molded article 1 m 3 around 0.01~0.04m 3. The molded product in this range has a good appearance, and the unsaturated polyester resin composition as a raw material has high moldability. Pore total volume and is smaller than an unsaturated polyester resin molded article 1 m 3 around 0.01 m 3 of a low shrinkage effect is small in the unsaturated polyester resin composition, the moldability caused problems such as cracking and warping becomes worse The molded product has a deteriorated appearance. If it exceeds 0.04 m 3 , the low shrinkage effect of the unsaturated polyester resin composition is too great, so that the moldability is inferior and the appearance of the molded product is deteriorated. The total volume of holes around 1 m 3 of the unsaturated polyester resin molded product is calculated from the density of the unsaturated polyester resin molded product. Specifically, according to the following formula.
ここで、成形品1kg辺りの空孔の総体積（m3 空孔/kg）は、次式により算出される。 Here, the total volume (m 3 holes / kg) of holes per 1 kg of the molded product is calculated by the following equation.
不飽和ポリエステル樹脂組成物において使用される不飽和ポリエステル樹脂は、脂肪族不飽和ポリカルボン酸、脂肪族飽和ポリカルボン酸、芳香族ポリカルボン酸等の不飽和、飽和のポリカルボン酸とジオール、トリオール、テトラオール等の有機ポリオールとの縮合反応によって得られる熱硬化性樹脂である。これにビニルモノマー等の不飽和単量体が溶解されていてもよい。 The unsaturated polyester resin used in the unsaturated polyester resin composition includes unsaturated, saturated polycarboxylic acid and diol, triol such as aliphatic unsaturated polycarboxylic acid, aliphatic saturated polycarboxylic acid, and aromatic polycarboxylic acid. It is a thermosetting resin obtained by a condensation reaction with an organic polyol such as tetraol. An unsaturated monomer such as a vinyl monomer may be dissolved therein.
脂肪族不飽和ポリカルボン酸としては、（無水）マレイン酸、フマル酸等が例示され、脂肪族飽和ポリカルボン酸としてはセパシン酸、（無水）コハク酸、アジピン酸等が例示され、芳香族ポリカルボン酸としては、（無水）フタル酸、イソフタル酸、テレフタル酸等が例示される。有機ポリオールは、脂肪族ポリオールと芳香族ポリオールに分けられる。脂肪族ポリオールとしては、エチレングリコール、プロピレングリコール、ジプロピレングリコール、ブチレングリコール、トリエチレングリコール、ネオペンチルグリコール、ヘキサメチレングリコール、トリメチレングリコール、グリセリン、水素化ビスフェノールＡ等が例示される。芳香族ポリオールとしては、ビスフェノールＡ、ビスフェノールＳ等が例示される。これらのポリカルボン酸、有機ポリオールは、２種以上混合して用いても構わない。 Examples of the aliphatic unsaturated polycarboxylic acid include (anhydrous) maleic acid and fumaric acid. Examples of the aliphatic saturated polycarboxylic acid include sepacic acid, (anhydrous) succinic acid and adipic acid. Examples of the carboxylic acid include (anhydrous) phthalic acid, isophthalic acid, terephthalic acid and the like. Organic polyols are divided into aliphatic polyols and aromatic polyols. Examples of the aliphatic polyol include ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, triethylene glycol, neopentyl glycol, hexamethylene glycol, trimethylene glycol, glycerin, hydrogenated bisphenol A, and the like. Examples of the aromatic polyol include bisphenol A and bisphenol S. These polycarboxylic acids and organic polyols may be used in combination of two or more.
不飽和ポリエステル樹脂組成物に配合される重合性単量体は、本発明の効果を損なわない範囲で通常不飽和ポリエステル樹脂組成物に使用されるものであれば、特に種類を問わない。例えば、スチレン、ビニルトルエン、酢酸ビニル、ジアリルフタレート、トリアリルシアヌレート、アクリル酸エステル、メタクリル酸エステル、メタクリル酸メチル、メタクリル酸エチル等を単独使用または併用でき、樹脂と架橋可能な不飽和単量体が例示される。 The polymerizable monomer blended in the unsaturated polyester resin composition is not particularly limited as long as it is normally used in the unsaturated polyester resin composition within a range not impairing the effects of the present invention. For example, styrene, vinyl toluene, vinyl acetate, diallyl phthalate, triallyl cyanurate, acrylic acid ester, methacrylic acid ester, methyl methacrylate, ethyl methacrylate, etc. can be used alone or in combination, and unsaturated monomer capable of crosslinking with resin The body is illustrated.
不飽和ポリエステル樹脂組成物に配合される低収縮剤としては、特に限定されるものではないが、例えば、前記式（１）で表されるアルコール変性スチレン−フマル酸共重合体を挙げることができる。このものは、不飽和ポリエステル樹脂成形品中に微少な空孔を均一に分散させることができるので好ましい。低収縮剤としては、従来より、ポリスチレン、ポリメタクリル酸メチル、セルロース・アセテート・ブチレート、ポリカプロラクタン、ポリ酢酸ビニル、ポリエチレン、ポリ塩化ビニル等があるが、上記のような微小な空孔を均一に分散させることは技術的に難しい。例えば、最も汎用されているポリスチレンは、不飽和ポリエステル樹脂と相溶性が悪く、硬化中に急激に分離するため、空孔の大きさは、平均で数十μｍとなり、さらに、空孔は硬化物の表面近くに偏在する傾向がある。前記式（１）で表されるアルコール変性スチレン−フマル酸共重合体の製造方法は、本出願人が特開２００８−２０８１８６号公報で報告している。具体的には、下記式（４）に示すように、スチレン−フマル酸共重合体にＲ−ＯＨで表される１価のアルコールを反応させることにより、スチレン−フマル酸共重合体の末端カルボン酸基がエステル化（疎水化）されて得られる。 Although it does not specifically limit as a low shrinkage agent mix | blended with an unsaturated polyester resin composition, For example, the alcohol modified styrene-fumaric acid copolymer represented by the said Formula (1) can be mentioned. . This is preferable because minute pores can be uniformly dispersed in the unsaturated polyester resin molded article. Conventionally, low shrinkage agents include polystyrene, polymethyl methacrylate, cellulose acetate butyrate, polycaprolactan, polyvinyl acetate, polyethylene, polyvinyl chloride, and the like. It is technically difficult to disperse uniformly. For example, the most widely used polystyrene is poorly compatible with unsaturated polyester resins and rapidly separates during curing, so the average pore size is several tens of μm. There is a tendency to be unevenly distributed near the surface. The manufacturing method of the alcohol-modified styrene-fumaric acid copolymer represented by the formula (1) has been reported by the present applicant in Japanese Patent Application Laid-Open No. 2008-208186. Specifically, as shown in the following formula (4), by reacting the styrene-fumaric acid copolymer with a monovalent alcohol represented by R—OH, the terminal carboxylic acid of the styrene-fumaric acid copolymer is reacted. An acid group is obtained by esterification (hydrophobization).
ここで、式中のｍは１〜３の数値であり、ｎは３〜３００の数値であり、両末端は一般に水素である。また、アルコールは炭素数が４〜１２であり、符号Ｒは直鎖または分岐のアルキル基である。式（４）の出発物質であるスチレン−フマル酸共重合体は、不飽和ポリエステルとその架橋部としてスチレンを含んでなる熱硬化性樹脂を亜臨界水分解して得られる。 Here, m in the formula is a numerical value of 1 to 3, n is a numerical value of 3 to 300, and both ends are generally hydrogen. The alcohol has 4 to 12 carbon atoms, and the symbol R is a linear or branched alkyl group. The styrene-fumaric acid copolymer which is a starting material of the formula (4) is obtained by subcritical water decomposition of an unsaturated polyester and a thermosetting resin containing styrene as a cross-linked portion thereof.
上述した通り、不飽和ポリエステル樹脂成形品中の空孔は、低収縮剤成分によって生じるものであり、前記式（１）中、Ｒの炭素数が４よりも少ないアルコール変性スチレン−フマル酸共重合体を低収縮剤として用いると分散性が悪くなり、成形性が悪化する傾向がある。前記式（１）中、Ｒの炭素数が１２よりも多いアルコール変性スチレン−フマル酸共重合体を低収縮剤として用いると、重合性単量体であるスチレンとの相溶性が高いため、扱いづらい。なお、分散剤等を用いて相溶性、分散性を向上させることも可能である。 As described above, the voids in the unsaturated polyester resin molded article are generated by the low shrinkage agent component, and in the formula (1), the alcohol-modified styrene-fumaric acid copolymer having R less than 4 carbon atoms. When the coalescence is used as a low shrinkage agent, the dispersibility is deteriorated and the moldability tends to be deteriorated. In the above formula (1), when an alcohol-modified styrene-fumaric acid copolymer having more than 12 carbon atoms in R is used as a low shrinkage agent, the compatibility with styrene, which is a polymerizable monomer, is high. It ’s hard. It is also possible to improve the compatibility and dispersibility using a dispersant or the like.
低収縮剤の含有量としては、不飽和ポリエステル樹脂組成物中、２〜１０質量％の範囲であることが望ましい。かかる範囲よりも少なくなると、不飽和ポリエステル樹脂組成物の低収縮効果が充分でなく、成形性が悪化する場合がある。上記の範囲より多くなると、過剰に添加することとなり、不飽和ポリエステル樹脂組成物やそのシートモールディングコンパウンドのべたつき、外観の悪化が発生する傾向にある。 The content of the low shrinkage agent is desirably in the range of 2 to 10% by mass in the unsaturated polyester resin composition. If the amount is less than this range, the low shrinkage effect of the unsaturated polyester resin composition is not sufficient, and the moldability may deteriorate. If it exceeds the above range, it will be added excessively, and there is a tendency for the unsaturated polyester resin composition and its sheet molding compound to become sticky and the appearance to deteriorate.
本発明において、使用されるガラス繊維としては、一般的には繊維径０．０１〜５ｍｍ程度のものが用いられ、不飽和ポリエステル樹脂組成物中、５〜３０質量％の割合で含有していることが好ましい。ガラス繊維の含有量が、かかる範囲よりも少なくなると、不飽和ポリエステル樹脂成形品は、強度が充分でない箇所が生じる場合がある。上記の範囲より多くなると、成形性、光沢等の外観が悪化する傾向がある。 In the present invention, the glass fiber used generally has a fiber diameter of about 0.01 to 5 mm, and is contained at a ratio of 5 to 30% by mass in the unsaturated polyester resin composition. It is preferable. If the glass fiber content is less than this range, the unsaturated polyester resin molded product may have a portion with insufficient strength. When it exceeds the above range, appearance such as moldability and gloss tends to deteriorate.
充填剤としては、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、硫酸バリウム、硫酸カルシウム、水酸化アルミニウム、シリカ、クレー、タルク、ガラス粉、ガラスバルーン、木粉、ＦＲＰ成形品の粉砕物等が挙げられる。成形性、コスト及び成形品の強度等の観点から、炭酸カルシウム、水酸化アルミニウムがより好ましい。充填剤の平均粒径は、１〜３０μｍの範囲であることが好ましい。充填剤の平均粒径が、かかる範囲よりも小さくなると、不飽和ポリエステル樹脂組成物の粘度が高くなり、ガラス繊維への含浸が悪くなり、成形品特性が悪化する。上記の範囲より大きくなると光沢等の外観が悪化する。これらの充填剤の含有量は、不飽和ポリエステル樹脂組成物中、３０〜６０質量％の範囲であることが好ましい。かかる範囲よりも少なくなると、不飽和ポリエステル樹脂組成物の粘度が低いために増粘が難しく、増粘後の粘度も低いために成形しづらく、外観が悪くなる。上記の範囲より多くなると、不飽和ポリエステル樹脂組成物の粘度が高くなり、繊維への含浸が悪くなり、成形品特性が悪化する。 Examples of the filler include calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, aluminum hydroxide, silica, clay, talc, glass powder, glass balloon, wood powder, and pulverized FRP molded product. From the viewpoints of moldability, cost, strength of the molded product, etc., calcium carbonate and aluminum hydroxide are more preferable. The average particle size of the filler is preferably in the range of 1 to 30 μm. When the average particle size of the filler is smaller than the above range, the viscosity of the unsaturated polyester resin composition is increased, the impregnation into the glass fiber is deteriorated, and the molded product characteristics are deteriorated. When it exceeds the above range, the appearance such as gloss deteriorates. The content of these fillers is preferably in the range of 30 to 60% by mass in the unsaturated polyester resin composition. If it is less than this range, it is difficult to thicken the unsaturated polyester resin composition because the viscosity is low, and it is difficult to mold because the viscosity after thickening is low, resulting in poor appearance. If it exceeds the above range, the viscosity of the unsaturated polyester resin composition becomes high, the impregnation of the fibers becomes worse, and the molded product characteristics deteriorate.
上記不飽和ポリエステル樹脂組成物には、硬化剤、離型剤、増粘剤をはじめ、各種の硬化禁止剤や着色剤等が含有されていてもよい。 The unsaturated polyester resin composition may contain a curing agent, a release agent, a thickener, various curing inhibitors, colorants, and the like.
硬化剤としては、ケトンパーオキサイド類、パーオキシジカーボネート類、ハイドロパーオキサイド類、ジアシルパーオキサイド類、パーオキシケタール類、ジアルキルパーオキ サイド類、パーオキシエステル類、アルキルパーエステル類等が挙げられる。離型剤としては、ステアリン酸亜鉛、ステアリン酸カルシウム等が挙げられ、増粘剤としては、酸化マグネシウム、水酸化マグネシウム、酸化カリウム、水酸化カリウム等が挙げられる。 Examples of the curing agent include ketone peroxides, peroxydicarbonates, hydroperoxides, diacyl peroxides, peroxyketals, dialkyl peroxides, peroxyesters, alkylperesters, and the like. . Examples of the mold release agent include zinc stearate and calcium stearate, and examples of the thickener include magnesium oxide, magnesium hydroxide, potassium oxide, potassium hydroxide and the like.
本発明の不飽和ポリエステル樹脂成形品は、例えば、ＳＭＣの形態にされた不飽和ポリエステル樹脂組成物が加圧加熱成形されて作製される。ＳＭＣは、公知のＳＭＣ製造装置を用いて製造される。例えば、重合性単量体、充填剤、低収縮剤等を混合した不飽和ポリエステル樹脂組成物をドクターブレードでフィルムに塗布し、その上にガラス繊維ロービングを２０〜３０ｍｍ程度の長さに切断、散布する。もう片側を同じく不飽和ポリエステル樹脂組成物を塗布したフィルムで挟み、ロールで含浸、脱泡し、厚さ１〜５ｍｍ程度のシート状に加工してＳＭＣを作製する。目的とする成形品を製造するに際しては、従来と同様な手法を採用することが可能である。例えば、目的とする成形品形状を与える上下分離可能な金型を準備して、この金型に、上記のＳＭＣを必要な量だけ注入した後、加熱加圧し、その後、金型を開き、目的とする成形品を取り出すこととなる。なお、成形温度、成形圧力等は、目的とする成形品の形状等に合わせて適宜に選択することができる。 The unsaturated polyester resin molded article of the present invention is produced, for example, by pressurizing and heating an unsaturated polyester resin composition in the form of SMC. The SMC is manufactured using a known SMC manufacturing apparatus. For example, an unsaturated polyester resin composition mixed with a polymerizable monomer, a filler, a low shrinkage agent and the like is applied to a film with a doctor blade, and a glass fiber roving is cut into a length of about 20 to 30 mm thereon. Scatter. The other side is similarly sandwiched between films coated with the unsaturated polyester resin composition, impregnated with a roll, defoamed, and processed into a sheet of about 1 to 5 mm thickness to produce SMC. When manufacturing the target molded article, it is possible to adopt the same technique as in the past. For example, a mold capable of separating the upper and lower sides to give the desired molded product shape is prepared, and the above-mentioned SMC is injected into this mold in a necessary amount, and then heated and pressurized, and then the mold is opened, The molded product is taken out. The molding temperature, molding pressure and the like can be appropriately selected according to the shape of the target molded product.
このようにして得られた不飽和ポリエステル樹脂成形品には、微小な空孔が内包され、それらが均一に分散されている。これらの微小な空孔により応力が分散されるので、前記不飽和ポリエステル樹脂成形品は高い機械的強度を有し、同程度の強度を有する従来品に比べてガラス繊維の含有量を少なくすることができる。また、表面が平滑で光沢のある良好な外観を実現することができる。 The unsaturated polyester resin molded product thus obtained contains fine pores and is uniformly dispersed therein. Since the stress is dispersed by these minute pores, the unsaturated polyester resin molded product has a high mechanical strength, and the glass fiber content is reduced as compared with the conventional product having the same strength. Can do. In addition, a good appearance with a smooth surface and gloss can be realized.
以下、本発明を実施例によりさらに詳しく説明する。
＜実施例１＞
不飽和ポリエステル樹脂８０質量部、低収縮剤としてオクチル化スチレン−フマル酸共重合体２０質量部、硬化剤としてｔ−アミルパーオキシイソピルカーボネート１質量部、硬化禁止剤組成物としてｐ−ベンゾキノンを樹脂で５質量％濃度に希釈したもの２質量部、離型剤としてステアリン酸７質量部、充填剤として炭酸カルシウム（平均粒径４μｍ）１６０質量部、増粘剤として酸化マグネシウム１質量部、トナー１０質量部をよく混合し、ＳＭＣ用コンパウンドを得た。なお、不飽和ポリエステル樹脂は、溶媒としてのスチレンモノマーを４０質量％含有する樹脂溶液であり、昭和高分子製Ｍ−６４０ＬＳを用いた。オクチル化スチレン−フマル酸共重合体は、前記式（４）において、スチレン−フマル酸共重合体にオクタノールを反応させて得たアルコール変性スチレン−フマル酸共重合体であり、Ｒは炭素数８のアルキル基である。
Hereinafter, the present invention will be described in more detail with reference to examples.
<Example 1>
80 parts by mass of an unsaturated polyester resin, 20 parts by mass of an octylated styrene-fumaric acid copolymer as a low shrinkage agent, 1 part by mass of t-amylperoxyisopropyl carbonate as a curing agent, and p-benzoquinone as a curing inhibitor composition 2 parts by weight diluted with a resin to a concentration of 5% by weight, 7 parts by weight of stearic acid as a release agent, 160 parts by weight of calcium carbonate (average particle size 4 μm) as a filler, 1 part by weight of magnesium oxide as a thickener, toner 10 parts by mass was mixed well to obtain a compound for SMC. The unsaturated polyester resin is a resin solution containing 40% by mass of a styrene monomer as a solvent, and M-640LS made by Showa High Polymer was used. The octylated styrene-fumaric acid copolymer is an alcohol-modified styrene-fumaric acid copolymer obtained by reacting a styrene-fumaric acid copolymer with octanol in the formula (4), and R is a carbon number of 8 It is an alkyl group.
次に、このように調整したＳＭＣ用コンパウンドをドクターブレードでフィルムに塗布し、ガラス繊維６０質量部を散布し、もう片側を同じく樹脂コンパウンドを塗布したフィルムで挟み、ロールで押さえることにより、ガラス繊維にＳＭＣ用コンパウンドを含浸させ、その後、４０℃で２４時間熟成処理を行い、ＳＭＣを得た。なお、ガラス繊維は、１インチにカットしたガラスロービングを用いた。 Next, the SMC compound adjusted as described above is applied to the film with a doctor blade, 60 parts by mass of glass fiber is dispersed, the other side is sandwiched between films with the same resin compound applied, and the glass fiber is pressed by a roll. Was impregnated with a compound for SMC, and then aged for 24 hours at 40 ° C. to obtain SMC. In addition, the glass fiber used the glass roving cut into 1 inch.
以上のようにして作製したＳＭＣを下記条件にて成形し、目的とする成形品を得、成形品の性能を評価した。その得られた結果を、表１に示す。
（成形条件）
ＳＭＣ重量：９００ｇ、金型サイズ：３００×３００ｍｍ（成形品板厚６ｍｍ）
成形温度：金型意匠面１４５℃、裏面１３５℃
成形圧力：７ＭＰａ
成形時間：４分
（性能評価）
上記のようにして得た成形品の空孔径、成形品１ｍ３辺りの空孔の総体積、曲げ強度、成形性、光沢を測定、評価し、また外観を観察した。
（１）空孔径
成形品断面を走査型電子顕微鏡（ＳＥＭ）で観察し、平均空孔径を算出した。
（２）成形品１ｍ３辺りの空孔の総体積
ピクノメーターを用いて成形品の密度(kg/m3)を測定し、前記式（２）（３）から成形品1m3辺りの空孔の総体積（m3 空孔/ m3 成形品）を算出した。
（３）曲げ強度
成形品の曲げ強度は、ＪＩＳＫ７１７１プラスチック 曲げ試験の試験方法で測定した。
（４）成形性
成形品の長さと基準長さ（３００ｍｍ）から算出し、成形収縮率を算出した。
成形収縮率が、０．２０％以下のものを「○」、０．２０以上のものを「×」とした。
（５）光沢
成形品表面を光沢計にて、測定角度２０°で測定し、光沢を測定した。
８０以上のものを「○」、６０〜７９のものを「△」、６０未満のものを「×」とした。
（６）外観
成形品の外観を目視で観察し、ガラス目などの成形欠陥が全く観察されず、外観のよいものを「○」、欠陥が観察されるものを「×」とした。
＜実施例２〜９、参考例１〜８＞
表１に示すように、低収縮剤の種類及び部数、アルコール炭素数及び部数、充填剤である炭酸カルシウムの平均粒径及び部数、ガラス繊維の部数を変えて、実施例１と同様にＳＭＣを作製した。実施例４のみさらに分散剤を加えた。なお、低収縮剤であるブチル化スチレン−フマル酸共重合体及びラウリル化スチレン−フマル酸共重合体は、オクチル化スチレン−フマル酸共重合体と同様、スチレン−フマル酸共重合体にそれぞれブタノール（炭素数４）、ラウリルアルコール（炭素数１２）を反応させて得たアルコール変性スチレン−フマル酸共重合体である。分散剤としてはＢＹＫ製のＬＰＷ２０７６３を用いた。
＜比較例１〜３＞
表１に示すように、低収縮剤をポリスチレン樹脂に代え、さらにガラス繊維の部数を変えた以外は実施例１と同様にＳＭＣを作製した。
The SMC produced as described above was molded under the following conditions to obtain a target molded product, and the performance of the molded product was evaluated. The obtained results are shown in Table 1.
(Molding condition)
SMC weight: 900 g, mold size: 300 x 300 mm (molded product thickness 6 mm)
Molding temperature: mold design surface 145 ° C, back surface 135 ° C
Molding pressure: 7MPa
Molding time: 4 minutes (performance evaluation)
The pore diameter of the molded product obtained as described above, the total volume of pores around 1 m 3 of the molded product, bending strength, moldability, and gloss were measured and evaluated, and the appearance was observed.
(1) Pore Diameter The cross section of the molded product was observed with a scanning electron microscope (SEM), and the average hole diameter was calculated.
(2) Total volume of holes around 1m 3 of molded product Measure the density (kg / m 3 ) of the molded product using a pycnometer. From the above formulas (2) and (3), the holes around 1m 3 of molded product The total volume (m 3 holes / m 3 molded product ) was calculated.
(3) Bending strength The bending strength of the molded product was measured by the test method of JISK7171 plastic bending test.
(4) Moldability The mold shrinkage was calculated from the length of the molded product and the reference length (300 mm).
A mold shrinkage of 0.20% or less was rated as “◯”, and a mold shrinkage of 0.20 or more as “x”.
(5) Gloss The surface of the molded product was measured with a gloss meter at a measurement angle of 20 °, and gloss was measured.
80 or more were designated as “◯”, 60-79 as “Δ”, and less than 60 as “x”.
(6) Appearance The appearance of the molded product was visually observed, and no molding defects such as glass eyes were observed, and those with good appearance were “◯” and those with defects observed were “x”.
<Examples 2-9, Reference Examples 1-8>
As shown in Table 1, by changing the type and number of low shrinkage agents, the number and the number of alcohol carbons, the average particle size and the number of parts of calcium carbonate as a filler, and the number of parts of glass fiber, SMC was obtained in the same manner as in Example 1. Produced. In Example 4 only, a dispersant was further added. In addition, butylated styrene-fumaric acid copolymer and laurylated styrene-fumaric acid copolymer, which are low shrinkage agents, are similar to octylated styrene-fumaric acid copolymer, butanol and styrene-fumaric acid copolymer, respectively. It is an alcohol-modified styrene-fumaric acid copolymer obtained by reacting (carbon number 4) and lauryl alcohol (carbon number 12). As a dispersing agent, LPK20766 manufactured by BYK was used.
<Comparative Examples 1-3>
As shown in Table 1, SMCs were produced in the same manner as in Example 1 except that the low shrinkage agent was replaced with polystyrene resin and the number of parts of glass fiber was changed.
得られたＳＭＣは４０℃で２４時間熟成処理を行い、このＳＭＣを成形することにより、成形品を得、実施例１と同様に評価を行い、その結果を表１に示した。 The obtained SMC was subjected to aging treatment at 40 ° C. for 24 hours. By molding this SMC, a molded product was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 1.
表１の結果より、実施例１〜９は全て、従来のガラス繊維配合比率と比べ、高強度で外観の良好な成形品を提供できることが示された。 From the results in Table 1, it was shown that all Examples 1 to 9 can provide molded products having high strength and good appearance as compared with the conventional glass fiber blending ratio.
品質としては寸法精度が高く、光沢、外観が共に良好であった。実施例４では、分散剤を配合することにより、空孔をさらに微小化することが示された。 As for quality, dimensional accuracy was high, and gloss and appearance were both good. In Example 4, it was shown that pores were further miniaturized by adding a dispersant.
これに対し、参考例１は、ガラス繊維の含有量が少ないために、部位による強度バラツキが大きく、品質の悪いものであった。参考例２は、ガラス繊維の含有量が多いために、光沢が低下し、ガラス目などの外観が悪化した。 On the other hand, in Reference Example 1, since the glass fiber content was small, the strength variation due to the site was large and the quality was poor. In Reference Example 2, since the glass fiber content was large, the gloss was lowered and the appearance such as glass eyes was deteriorated.
参考例３は、充填剤の平均粒径が小さいために、樹脂成分を多く吸油し、得られるコンパウンドの粘度が高くなった。そのために繊維への含浸ができず、ＳＭＣにすることができなかった。参考例４は、充填剤の平均粒径が大きいために、光沢が低下した。 In Reference Example 3, since the average particle size of the filler was small, a large amount of the resin component was absorbed, and the viscosity of the resulting compound was increased. For this reason, the fiber could not be impregnated and could not be made into SMC. In Reference Example 4, the gloss was lowered because the average particle size of the filler was large.
参考例５は、充填剤の含有量が少ないために、得られるコンパウンドの粘度が低く、増粘が充分に進まず、ＳＭＣにすることができなかった。参考例６は、充填剤の含有量が多いために、得られるコンパウンドの粘度が高くなり、繊維への含浸が悪いために、ＳＭＣにすることができなかった。 In Reference Example 5, since the content of the filler was small, the viscosity of the obtained compound was low, the thickening did not proceed sufficiently, and SMC could not be obtained. In Reference Example 6, since the content of the filler was high, the viscosity of the obtained compound was high, and the impregnation into the fiber was poor, so that SMC could not be obtained.
参考例７は、低収縮剤の含有量が少ないために、低収縮効果が充分でなく、寸法精度が悪く、成形性の低いものであった。参考例８は、低収縮剤の含有量が多いために、光沢が低下した。 In Reference Example 7, since the content of the low shrinkage agent was small, the low shrinkage effect was not sufficient, the dimensional accuracy was poor, and the moldability was low. In Reference Example 8, the gloss decreased due to the high content of the low shrinkage agent.
比較例１と比較例２は、成形性、光沢、外観が良好であるが、曲げ強度はガラス繊維の含有量が同じである実施例１〜４と実施例５と比べ、低いものであった。 Comparative Example 1 and Comparative Example 2 have good moldability, gloss, and appearance, but the bending strength was lower than those of Examples 1 to 4 and Example 5 in which the glass fiber content was the same. .
比較例３は、実施例１〜４と同等の曲げ強度になるように、ガラス繊維含有量を多くしたものであるが、光沢が低下し、ガラス目などの外観が悪化した。また、曲げ強度はガラス繊維の含有量が同じである実施例６と比べ、低いものであった。 Although the comparative example 3 increased glass fiber content so that it might become the bending strength equivalent to Examples 1-4, glossiness fell and external appearances, such as a glass eye, deteriorated. Moreover, bending strength was low compared with Example 6 with the same glass fiber content.
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| JP2009029917A (en) * | 2007-07-26 | 2009-02-12 | Panasonic Electric Works Co Ltd | Low shrinkage material for plastic, plastic molded article using the same, method for producing low shrinkage material for plastic, and method for recovering and reusing plastic |
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| JP2015183025A (en) * | 2014-03-20 | 2015-10-22 | Dic株式会社 | Molding material for hot compression molding and molded part thereof |
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