JP5450346B2 - SMC and manufacturing method thereof - Google Patents
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Description
本発明は、例えば、大型医療用機器や、浴槽、浄化槽、貯水槽などの住宅設備機器の外装材などの成形品を上型及び下型を用いた加圧加熱成形加工により製造する際に用いられるシートモールディングコンパウンド（以下、「ＳＭＣ」という。）及びその製造方法に関するものである。 The present invention is used, for example, when a molded product such as a large medical device or an exterior material of a housing equipment such as a bathtub, a septic tank, or a water storage tank is manufactured by pressure hot molding using an upper mold and a lower mold. The present invention relates to a sheet molding compound (hereinafter referred to as “SMC”) and a manufacturing method thereof.
従来、この種のＳＭＣ（すなわち、シート状樹脂繊維複合成形材料）として、少なくとも主剤、架橋剤、硬化剤、内部離型剤、難燃剤及び増粘剤からなる樹脂組成物及び繊維基材を上下２枚のキャリアフィルム間に挟み込んだ状態で該樹脂組成物を該繊維基材に含浸してなる構造のものが知られている。 Conventionally, as this type of SMC (that is, a sheet-like resin fiber composite molding material), a resin composition and a fiber base material composed of at least a main agent, a crosslinking agent, a curing agent, an internal mold release agent, a flame retardant, and a thickener are moved up and down. A structure in which the fiber base material is impregnated with the resin composition in a state of being sandwiched between two carrier films is known.
しかしながら上記従来構造の場合、上記樹脂組成物を組成する架橋剤としてスチレンモノマーが用いられ、このスチレンモノマーは沸点が約１４９℃であり、ＳＭＣを用いた加圧加熱成形加工の成形温度は１３５℃〜１６０℃であり、この成形温度で成形品を加熱加圧成形したとき、スチレンモノマーが沸騰して成形品の表面が粗となって商品価値の低いＳＭＣ成形品となることがあり、スチレンモノマーを含む樹脂組成物を用いて滑らかな表面に仕上げるためには例えば１００ｋｇ／ｃｍ２程度の高圧な加工圧力が必要となり、なぜならば、スチレンモノマーは成形温度１３５℃〜１６０℃で沸騰するため、沸騰に伴う泡を封止するために上型及び下型間における成形圧力を高圧にする必要があるからであり、それだけ、成形装置の大型化及び価格の高騰化の影響でＳＭＣ成形品の製造コストを低減するための隘路となることがあり、又、従来構造の場合、繊維基材に含浸される上記樹脂組成物は液状の樹脂組成物であり、上下のキャリアフィルム間への供給手段として液体ポンプを用いなければならず、樹脂組成物に増粘剤を含むことによる経時増粘作用も相俟って樹脂組成物のハンドリング性を低下させることがあり、ひいては、ＳＭＣの生産性が低下することがあるという不都合を有している。 However, in the case of the conventional structure, a styrene monomer is used as a cross-linking agent for the resin composition, and the styrene monomer has a boiling point of about 149 ° C., and the molding temperature of the pressure heating molding process using SMC is 135 ° C. When the molded product is heated and pressure-molded at this molding temperature, the styrene monomer may boil and the surface of the molded product becomes rough, resulting in an SMC molded product having a low commercial value. For example, a high processing pressure of about 100 kg / cm 2 is required to finish a smooth surface using a resin composition containing styrene, because styrene monomer boils at a molding temperature of 135 ° C. to 160 ° C. This is because it is necessary to increase the molding pressure between the upper mold and the lower mold in order to seal the bubbles accompanying the process. In addition, in the case of a conventional structure, the resin composition impregnated in the fiber base is a liquid resin composition. The liquid pump must be used as a means for supplying the carrier film between the upper and lower carrier films, and the handling property of the resin composition is lowered due to the thickening effect with time due to the inclusion of the thickener in the resin composition. In some cases, the productivity of SMC may be reduced.
本発明はこれらの不都合を解決することを目的とするもので、本発明のうちで、請求項１記載の発明は、少なくとも主剤、架橋剤、硬化剤、内部離型剤及び難燃剤からなる樹脂組成物及び繊維基材を上下２枚のキャリアフィルム間に挟み込んだ状態で該樹脂組成物を該繊維基材に含浸してなるシートモールディングコンパウンド（以下、「ＳＭＣ」という。）であって、上記主剤としてビニルエステル樹脂を用い、かつ、上記架橋剤としてスチレンモノマーを用いず、該スチレンモノマーより沸点の高い架橋剤としてのジアリルフタレートモノマーを用い、さらに上記樹脂組成物に増粘剤を含めず、これらの樹脂組成物を６５℃乃至８５℃の加熱温度に加熱して混合し、該混合物を冷却して常温では半固形状態であって加熱温度６５℃乃至８５℃で流動状態となる樹脂組成物を形成し、その後、該半固形状の樹脂組成物を６５℃乃至８５℃の加熱温度に加熱して流動状態の該樹脂組成物を該繊維基材に含浸したのち冷却してプリプレグ状に形成してなることを特徴とするＳＭＣにある。 The present invention aims to solve these disadvantages. Among the present inventions, the invention described in claim 1 is a resin comprising at least a main agent, a crosslinking agent, a curing agent, an internal mold release agent, and a flame retardant. A sheet molding compound (hereinafter referred to as “SMC”) obtained by impregnating the fiber substrate with the resin composition in a state where the composition and the fiber substrate are sandwiched between two upper and lower carrier films. Vinyl ester resin is used as the main agent, and styrene monomer is not used as the crosslinking agent , diallyl phthalate monomer having a higher boiling point than the styrene monomer is used, and a thickener is not included in the resin composition. These resin compositions are heated and mixed at a heating temperature of 65 ° C. to 85 ° C., and the mixture is cooled to be in a semi-solid state at room temperature, and the heating temperature is 65 ° C. to 8 ° C. Forming a resin composition that is in a fluid state at ℃, and then heating the semisolid resin composition to a heating temperature of 65 ° C. to 85 ° C. to impregnate the fiber substrate with the resin composition in a fluid state Then, it is cooled and formed into a prepreg shape.
又、請求項２記載の発明は、少なくとも主剤、架橋剤、硬化剤、内部離型剤及び難燃剤からなる樹脂組成物及び繊維基材を搬送される上下２枚のキャリアフィルム間に挟み込んだ状態で該樹脂組成物を該繊維基材に含浸してＳＭＣを製造するに際し、上記主剤としてビニルエステル樹脂を用い、かつ、上記架橋剤としてスチレンモノマーを用いず、該スチレンモノマーより沸点の高い架橋剤としてのジアリルフタレートモノマーを用い、さらに上記樹脂組成物に増粘剤を含めず、これらの樹脂組成物を６５℃乃至８５℃の加熱温度に加熱して混合し、該混合物を冷却して常温では半固形状態であって加熱温度６５℃乃至８５℃で流動状態となる樹脂組成物を形成し、その後、該半固形状の樹脂組成物を６５℃乃至８５℃の加熱温度に加熱して流動状態の該樹脂組成物を該繊維基材に含浸したのち冷却してプリプレグ状に形成することを特徴とするＳＭＣの製造方法にある。 The invention described in claim 2 is a state in which a resin composition comprising at least a main agent, a crosslinking agent, a curing agent, an internal mold release agent and a flame retardant and a fiber substrate are sandwiched between two upper and lower carrier films to be conveyed. In the production of SMC by impregnating the fiber base with the resin composition, a vinyl ester resin is used as the main agent, and a styrene monomer is not used as the cross-linking agent, and a cross-linking agent having a boiling point higher than that of the styrene monomer. The above-mentioned resin composition does not contain a thickener, and these resin compositions are mixed by heating to a heating temperature of 65 ° C. to 85 ° C., and the mixture is cooled at room temperature. A resin composition which is in a semi-solid state and becomes a fluid state at a heating temperature of 65 ° C. to 85 ° C. is formed, and then the semi-solid resin composition is heated to a heating temperature of 65 ° C. to 85 ° C. There the resin composition of the dynamic state in the production method of the SMC, which comprises forming a prepreg form to cool then impregnated into the fiber substrate.
又、請求項３記載の発明は、上記繊維基材として、繊維マットを用いてなることを特徴とするものであり、又、請求項４記載の発明は、上記繊維マットはガラス繊維マットであることを特徴とするものであり、又、請求項５記載の発明にあっては、上記各加熱温度はいずれも約７５℃であることを特徴とするものである。 The invention described in claim 3 is characterized in that a fiber mat is used as the fiber base material. The invention described in claim 4 is characterized in that the fiber mat is a glass fiber mat. In addition, in the invention according to claim 5 , each of the heating temperatures is about 75 ° C.
本発明は上述の如く、請求項１又は請求項２記載の発明にあっては、少なくとも主剤、架橋剤、硬化剤、内部離型剤及び難燃剤からなる樹脂組成物及び繊維基材を搬送される上下２枚のキャリアフィルム間に挟み込んだ状態で樹脂組成物を繊維基材に含浸してＳＭＣを製造するに際し、上記主剤としてビニルエステル樹脂を用い、かつ、上記架橋剤としてスチレンモノマーを用いず、該スチレンモノマーより沸点の高い架橋剤としてのジアリルフタレートモノマーを用い、さらに上記樹脂組成物に増粘剤を含めず、これらの樹脂組成物を６５℃乃至８５℃の加熱温度に加熱して混合し、混合物を冷却して常温では半固形状態であって加熱温度６５℃乃至８５℃で流動状態となる樹脂組成物を形成して保存し、その後、ＳＭＣの製造において、この半固形状の樹脂組成物を６５℃乃至８５℃の加熱温度に加熱して流動状態の樹脂組成物を繊維基材に含浸したのち冷却してプリプレグ状のＳＭＣを形成することになり、このように、上記主剤としてビニルエステル樹脂を用い、かつ、上記架橋剤としてスチレンモノマーを用いず、該スチレンモノマーより沸点の高い架橋剤としてのジアリルフタレートモノマーを用いているから、スチレンモノマーの沸点は約１４９℃であり、ジアリルフタレートモノマーの沸点は２００℃以上であり、ＳＭＣを用いた加圧加熱成形加工の成形温度は１３５℃〜１６０℃であるところ、この成形温度で成形品を加熱加圧成形したとき、架橋剤は沸騰しないので、成形品の表面が粗となることを防ぎ、沸騰による泡を封じ込めるための高圧が必要なく、低圧での成形が可能となり、例えば、１０ｋｇ／ｃｍ２程度の低圧な加工圧力で加工することができ、ＳＭＣ成形品の品質向上及び成形装置の大型化や価格の高騰化を抑制することができ、スチレンを含有しないので環境汚染の心配を無くすこともでき、又、増粘剤を含めないので、保存期間を長くすることができ、さらに、加熱温度が６５℃乃至８５℃であるから、樹脂組成物の溶融粘度が低くなり、成形加工性を高めることができ、硬化剤の分解を抑制できて保存安定性を高めることができ、また、特に、これらの樹脂組成物を６５℃乃至８５℃の加熱温度に加熱して混合し、混合物を冷却して常温では半固形状態であって加熱温度６５℃乃至８５℃で流動状態となる樹脂組成物を形成して保存しておき、その後、ＳＭＣの製造時において、この半固形状の樹脂組成物を６５℃乃至８５℃の加熱温度に加熱して流動状態の樹脂組成物を繊維基材に含浸したのち冷却した樹脂組成物を用いるので、例えば、液状の樹脂組成物を塗工部に供給するにはポンプ搬送する必要があるが、常温では半固形状態であって加熱温度６５℃乃至８５℃で流動状態となる樹脂組成物であるから塗工部への搬送等のハンドリング性を向上することができ、かつ、難燃剤を多く含めることができ、増量化も可能となり、製作コストの低減を図ることもでき、ひいては、ＳＭＣの生産性を高めることができる。 As described above, according to the present invention, the resin composition and the fiber base material comprising at least the main agent, the crosslinking agent, the curing agent, the internal mold release agent, and the flame retardant are conveyed. When the SMC is produced by impregnating the fiber base material with the resin composition sandwiched between two upper and lower carrier films, a vinyl ester resin is used as the main agent and a styrene monomer is not used as the cross-linking agent. , Using a diallyl phthalate monomer as a cross-linking agent having a boiling point higher than that of the styrene monomer, and without adding a thickener to the resin composition, the resin composition is heated to a heating temperature of 65 ° C. to 85 ° C. and mixed. And cooling the mixture to form and store a resin composition that is in a semi-solid state at room temperature and fluidized at a heating temperature of 65 ° C. to 85 ° C. The semi-solid resin composition is heated to a heating temperature of 65 ° C. to 85 ° C. and impregnated with a fluid base resin composition, and then cooled to form a prepreg-shaped SMC. Thus, since the vinyl ester resin is used as the main agent, and the styrene monomer is not used as the cross-linking agent , but the diallyl phthalate monomer having a higher boiling point than the styrene monomer is used, the boiling point of the styrene monomer is about 149 ° C., the boiling point of diallyl phthalate monomer is 200 ° C. or higher, and the molding temperature of the pressure heating molding process using SMC is 135 ° C. to 160 ° C. The molded product is heated and pressed at this molding temperature. In this case, since the crosslinking agent does not boil, the surface of the molded product is prevented from becoming rough, and no high pressure is required to contain bubbles caused by boiling. Molding becomes possible, for example, can be processed by the low-pressure working pressure of about 10 kg / cm 2, it is possible to suppress the size and price hike of SMC molded article quality of and the molding device, Since it does not contain styrene, there is no need to worry about environmental pollution, and since no thickener is included, the storage period can be extended and the heating temperature is 65 ° C. to 85 ° C. The melt viscosity of the product is lowered, the molding processability can be improved, the decomposition of the curing agent can be suppressed, and the storage stability can be improved, and in particular, these resin compositions have a temperature of 65 ° C. to 85 ° C. Heat to the heating temperature and mix, cool the mixture and form and store a resin composition that is semi-solid at room temperature and fluidized at a heating temperature of 65 ° C to 85 ° C. At the time of manufacture Since this semi-solid resin composition is heated to a heating temperature of 65 ° C. to 85 ° C. and impregnated with a fluid resin composition into a fiber base material and then cooled, the resin composition is used. It is necessary to pump the product to supply it to the coating part, but it is a semi-solid state at normal temperature and it is in a fluid state at a heating temperature of 65 ° C to 85 ° C. The handling property such as the above can be improved, a large amount of flame retardant can be included, the amount can be increased, the production cost can be reduced, and the productivity of SMC can be increased.
又、請求項３記載の発明にあっては、上記繊維基材として、繊維マットを用いてなるから、ＳＭＣの補強性を高めることができ、又、請求項４記載の発明にあっては、上記繊維マットはガラス繊維マットであるから、一層、ＳＭＣの補強性を高めることができ、又、請求項５記載の発明にあっては、上記各加熱温度はいずれも約７５℃であるから、樹脂組成物の溶融粘度が低くなり、成形加工性を高めることができ、硬化剤の分解を抑制できて保存安定性を高めることができる。 In the invention described in claim 3 , since a fiber mat is used as the fiber base material, the reinforcing property of SMC can be enhanced. In the invention described in claim 4 , Since the fiber mat is a glass fiber mat, the reinforcing property of the SMC can be further improved. In the invention according to claim 5 , since each of the heating temperatures is about 75 ° C, The melt viscosity of the resin composition is lowered, the molding processability can be improved, the decomposition of the curing agent can be suppressed, and the storage stability can be improved.
図１乃至図４は本発明の実施の形態例を示し、図１において、１は樹脂組成物であって、主剤、架橋剤、硬化剤、内部離型剤、難燃剤及び着色剤からなり、主剤としてビニルエステル樹脂を用い、かつ、架橋剤としてスチレンモノマーを用いず、スチレンモノマーより沸点の高い架橋剤を用い、さらに上記樹脂組成物１に増粘剤を含めない組成となっている。 1 to 4 show an embodiment of the present invention. In FIG. 1, 1 is a resin composition comprising a main agent, a crosslinking agent, a curing agent, an internal mold release agent, a flame retardant, and a colorant, A vinyl ester resin is used as a main component, a styrene monomer is not used as a cross-linking agent, a cross-linking agent having a boiling point higher than that of the styrene monomer is used, and the resin composition 1 does not include a thickener.
ここに、架橋剤としてスチレンモノマーを用いない理由は、スチレンモノマーの沸点は約１４９℃であり、ＳＭＣを用いた加圧加熱成形加工の成形温度は１３５℃〜１６０℃であり、この成形温度で成形品を加熱加圧成形したとき、スチレンモノマーが沸騰し、成形品の表面が粗となって商品価値の低いＳＭＣ成形品となることがあるからであり、又、樹脂組成物１に増粘剤を含めない理由は、樹脂の硬化を進める化合物は硬化剤だけとなり、保存期間が長くなるからである。 Here, the reason for not using the styrene monomer as the cross-linking agent is that the boiling point of the styrene monomer is about 149 ° C., and the molding temperature of the pressure heating molding process using SMC is 135 ° C. to 160 ° C. This is because when the molded product is heat-pressed, the styrene monomer boils and the surface of the molded product becomes rough, resulting in an SMC molded product having a low commercial value. The reason for not including the agent is that the compound that promotes the curing of the resin is only the curing agent, and the storage period becomes longer.
しかして、この場合、上記架橋剤として、沸点が約２００℃以上のジアリルフタレートモノマー（以下「ＤＡＰモノマー」という。）を用いており、このＤＡＰモノマーを使用することにより、例えば１０ｋｇ／ｃｍ２程度の低圧な加工圧力で加工することができる。何故ならば、ＤＡＰモノマーは成形温度１３５℃〜１６０℃では沸騰しないので、沸騰に伴う泡を封止するための高圧が必要なく、単にＳＭＣを上型及び下型で押さえる程度の低圧力で良いからである。 Thus, in this case, as the cross-linking agent, boiling point of about 200 ° C. or more diallyl phthalate monomer (hereinafter referred to as "DAP monomer".) Is used to, by using this DAP monomer, for example, 10 kg / cm Processing can be performed at a processing pressure as low as about 2 . This is because the DAP monomer does not boil at a molding temperature of 135 ° C. to 160 ° C., so there is no need for a high pressure to seal the foam accompanying the boiling, and a low pressure that simply presses the SMC with the upper mold and the lower mold is sufficient. Karadea Ru.
又、その他の組成物として、上記硬化剤として各種の過酸化物など、内部離型剤としてワックス類、ステアリン酸亜鉛など、難燃剤（フィラー）として水酸化アルミニウム、炭酸カルシウムなど、着色剤として各種の顔料が用いられる。 In addition, as other compositions, various peroxides as the curing agent, waxes as internal mold release agents, zinc stearate, etc., flame retardant (filler) as aluminum hydroxide, calcium carbonate, etc. as colorants These pigments are used.
そして、これらの主剤、架橋剤、硬化剤、内部離型剤、難燃剤及び着色剤からなる樹脂組成物１を６５℃乃至８５℃の加熱温度に加熱して混合し、該混合物を冷却して常温では半固形状態であって加熱温度６５℃乃至８５℃で流動状態となるブロック状の樹脂組成物１としている。 And the resin composition 1 which consists of these main ingredients, a crosslinking agent, a hardening | curing agent, an internal mold release agent, a flame retardant, and a coloring agent is heated and mixed at the heating temperature of 65 to 85 degreeC, and this mixture is cooled. The block-shaped resin composition 1 is in a semi-solid state at room temperature and is in a fluid state at a heating temperature of 65 ° C. to 85 ° C.
ここに、上記加熱温度を６５℃乃至８５℃としているのは、６５℃以下になると樹脂組成物１の溶融粘度が高くなって成形加工し難いことになり、８５℃以上になると硬化剤の分解温度以上となって保存安定性が低下するからであり、これらの点を考慮して加熱温度を約７５℃とすることが望ましい。 Here, the heating temperature is set to 65 ° C. to 85 ° C. When the temperature is 65 ° C. or lower, the melt viscosity of the resin composition 1 becomes high and difficult to be processed, and when it is 85 ° C. or higher, the curing agent is decomposed. This is because the storage stability is lowered when the temperature is exceeded, and it is desirable that the heating temperature be about 75 ° C. in consideration of these points.
２は繊維基材であって、この場合、繊維マットが用いられ、繊維マットＲのうち、ガラス繊維を細断して接着剤によりマット状にしたガラス繊維マットが用いられている。尚、繊維マットに代えて、細断したガラス繊維を樹脂組成物１に散布することもある。又、繊維としてはガラス繊維に限らず、炭素繊維、麻、木綿等の天然繊維、ポリエステル、ポリアミド等の各種の合成繊維が用いられ、これら繊維を用いた織布、不織布なども用いられる。 Reference numeral 2 denotes a fiber base material. In this case, a fiber mat is used. Among the fiber mats R, a glass fiber mat obtained by chopping glass fibers and matting them with an adhesive is used. In addition, instead of the fiber mat, the chopped glass fiber may be sprayed on the resin composition 1. The fibers are not limited to glass fibers, and natural fibers such as carbon fibers, hemp and cotton, and various synthetic fibers such as polyester and polyamide, and woven fabrics and nonwoven fabrics using these fibers are also used.
しかして、図２の如く、上記常温では半固形状態（餅に似た状態）であって加熱温度６５℃乃至８５℃で流動状態となるブロック状の樹脂組成物１を保存しておき、ＳＭＣの製造時において、この半固形状の樹脂組成物１を６５℃乃至８５℃の加熱温度に加熱して流動状態の樹脂組成物を繊維基材２に含浸したのち冷却してプリプレグ状に形成することになる。 Thus, as shown in FIG. 2, the block-shaped resin composition 1 that is in a semi-solid state (similar to cocoon) at the normal temperature and is in a fluid state at a heating temperature of 65 ° C. to 85 ° C. is stored. At the time of manufacturing, the semi-solid resin composition 1 is heated to a heating temperature of 65 ° C. to 85 ° C. to impregnate the fiber base material 2 with the fluid resin composition, and then cooled to form a prepreg. It will be.
しかして、図３を参照して、製造過程を説明すると、Ｆ・Ｆはキャリアフィルムであって、例えば、厚さの５０μｍの片面離型処理ＰＥＴフィルムが用いられ、下側のキャリアフィルムＦは図示省略の搬送手段によりフィルム巻反Ｍより引き出されて連続搬送され、上記保存しておいた樹脂組成物１は第１塗工部Ｌのホッパーに投入され、第１塗工部Ｌ内の樹脂組成物１は第１塗工部Ｌに設けた図示省略の加熱手段により６５℃乃至８５℃、この場合、約７５℃の加熱温度で加熱され、この加熱により半固形状の樹脂組成物１は流動状態となり、この樹脂組成物１は堰板Ｓにより下側のキャリアフィルムＦ上に適宜厚さ、例えば、５００ｇ／ｍ２で塗工され、樹脂組成物１は加熱テーブルＧにより搬送状態においても約７５℃に維持され、次いで、巻反Ｎから引き出された繊維基材２を樹脂組成物１上に重ね合わせ、次いで、上側のキャリアフィルムＦをフィルム巻反Ｍより引き出して連続搬送し、上記保存しておいた樹脂組成物１は第２塗工部Ｋのホッパーに投入され、第２塗工部Ｋ内の樹脂組成物１は図示省略の加熱手段により６５℃乃至８５℃、この場合、約７５℃の加熱温度で加熱され、この加熱により半固形状の樹脂組成物１は流動状態となり、この樹脂組成物１は同じく堰板Ｓにより上側のキャリアフィルムＦ上に適宜厚さ、例えば、５００ｇ／ｍ２で塗工され、樹脂組成物１は加熱テーブルＧにより搬送状態においても約７５℃に維持され、樹脂組成物１が塗工されている下側のキャリアフィルムＦを上記繊維基材２上に重ね合わせ、次いで、数個の含浸ロールＥにより流動状態の樹脂組成物１を繊維基材２に押圧含浸し、含浸ロールＥは図示省略の加熱手段により約７５℃に加熱保持され、冷却し、図４に示す如く、上下のキャリアフィルムＦ・Ｆ間に樹脂組成物１及び繊維基材２を挟み込んだ状態のプリプレグ状のＳＭＣを製造し、巻反Ｈに巻き取って保管することになる。そして、このＳＭＣから上下のキャリアフィルムＦ・Ｆを剥離すると共に成形品に応じて適宜大きさに切断し、上型及び下型を用いて加熱加圧成形により成形品を製造することになる。 Thus, the manufacturing process will be described with reference to FIG. 3. F · F is a carrier film, for example, a single-sided release PET film having a thickness of 50 μm is used, and the lower carrier film F is The film composition M is drawn from the film roll M by a conveying means (not shown) and continuously conveyed. The stored resin composition 1 is put into a hopper of the first coating part L, and the resin in the first coating part L The composition 1 is heated at a heating temperature of 65 ° C. to 85 ° C., in this case, about 75 ° C. by heating means (not shown) provided in the first coating part L, and the semi-solid resin composition 1 is heated by this heating. The resin composition 1 is coated on the lower carrier film F by the weir plate S at an appropriate thickness, for example, 500 g / m 2 , and the resin composition 1 is heated by the heating table G even in the transported state. Maintained at about 75 ° C, then Then, the fiber base material 2 drawn out from the roll N is superposed on the resin composition 1, and then the upper carrier film F is pulled out from the film roll M and continuously conveyed. The product 1 is put into the hopper of the second coating part K, and the resin composition 1 in the second coating part K is heated at a heating temperature of 65 ° C. to 85 ° C., in this case about 75 ° C., by heating means not shown. By heating, the semi-solid resin composition 1 becomes a fluid state, and this resin composition 1 is coated on the upper carrier film F by the barrier plate S at an appropriate thickness, for example, 500 g / m 2. The resin composition 1 is maintained at about 75 ° C. even in the transported state by the heating table G, the lower carrier film F coated with the resin composition 1 is overlaid on the fiber base material 2, and then To several impregnating rolls E The fiber base material 2 is pressed and impregnated with the resin composition 1 in a fluid state, and the impregnation roll E is heated and held at about 75 ° C. by a heating means (not shown), cooled, and as shown in FIG. A prepreg-shaped SMC in which the resin composition 1 and the fiber base material 2 are sandwiched between F is manufactured, wound around a roll H and stored. Then, the upper and lower carrier films F and F are peeled off from the SMC and cut into an appropriate size according to the molded product, and a molded product is manufactured by heat and pressure molding using the upper mold and the lower mold.
この実施の形態例は上記構成であるから、少なくとも主剤、架橋剤、硬化剤、内部離型剤及び難燃剤からなる樹脂組成物１及び繊維基材２を搬送される上下２枚のキャリアフィルム間に挟み込んだ状態で樹脂組成物１を繊維基材２に含浸してＳＭＣを製造するに際し、上記主剤としてビニルエステル樹脂を用い、かつ、上記架橋剤としてスチレンモノマーを用いず、該スチレンモノマーより沸点の高い架橋剤を用い、さらに上記樹脂組成物１に増粘剤を含めず、これらの樹脂組成物１を６５℃乃至８５℃の加熱温度に加熱して混合し、混合物を冷却して常温では半固形状態であって加熱温度６５℃乃至８５℃で流動状態となる樹脂組成物を形成して保存し、その後、ＳＭＣの製造において、この半固形状の樹脂組成物を６５℃乃至８５℃の加熱温度に加熱して流動状態の樹脂組成物１を繊維基材２に含浸したのち冷却してプリプレグ状のＳＭＣを形成することになる。 Since this embodiment has the above-described configuration, it is between the upper and lower two carrier films that are conveyed with the resin composition 1 and the fiber substrate 2 composed of at least the main agent, the crosslinking agent, the curing agent, the internal mold release agent, and the flame retardant. In the production of SMC by impregnating the fiber base material 2 with the resin composition 1 in a state of being sandwiched between the vinyl ester resin and the styrene monomer as the cross-linking agent, the boiling point is higher than that of the styrene monomer. In addition, the resin composition 1 does not include a thickener, and the resin composition 1 is heated and mixed at a heating temperature of 65 ° C. to 85 ° C., and the mixture is cooled at room temperature. A resin composition that is in a semi-solid state and is fluidized at a heating temperature of 65 ° C. to 85 ° C. is formed and stored. Thereafter, in the production of SMC, this semi-solid resin composition is heated to 65 ° C. to 85 ° C. Addition By heating to a temperature of the resin composition 1 in a fluid state was cooled then impregnated into the fiber base material 2 will form a prepreg-like SMC are.
このように、上記主剤としてビニルエステル樹脂を用い、かつ、上記架橋剤としてスチレンモノマーを用いず、該スチレンモノマーより沸点の高い架橋剤を用いているから、スチレンモノマーの沸点は約１４９℃であり、ＳＭＣを用いた加圧加熱成形加工の成形温度は１３５℃〜１６０℃であるところ、この成形温度で成形品を加熱加圧成形したとき、架橋剤は沸騰しないので、成形品の表面が粗となることを防ぎ、沸騰による泡を封じ込めるための高圧が必要なく、低圧での成形が可能となり、例えば、１０ｋｇ／ｃｍ２程度の低圧な加工圧力で加工することができ、ＳＭＣ成形品の品質向上及び成形装置の大型化や価格の高騰化を抑制することができ、スチレンを含有しないので環境汚染の心配を無くすこともでき、又、増粘剤を含めないので、保存期間を長くすることができ、さらに、加熱温度が６５℃乃至８５℃であるから、樹脂組成物１の溶融粘度が低くなり、成形加工性を高めることができ、硬化剤の分解を抑制できて保存安定性を高めることができ、また、特に、これらの樹脂組成物１を６５℃乃至８５℃の加熱温度に加熱して混合し、混合物を冷却して常温では半固形状態であって加熱温度６５℃乃至８５℃で流動状態となる樹脂組成物を形成して保存しておき、その後、ＳＭＣの製造時において、この半固形状の樹脂組成物を６５℃乃至８５℃の加熱温度に加熱して流動状態の樹脂組成物１を繊維基材２に含浸したのち冷却した樹脂組成物１を用いるので、例えば、液状の樹脂組成物を塗工部に供給するにはポンプ搬送する必要があるが、常温では半固形状態であって加熱温度６５℃乃至８５℃で流動状態となる樹脂組成物１であるから塗工部への搬送等のハンドリング性を向上することができ、かつ、難燃剤を多く含めることができ、増量化も可能となり、製作コストの低減を図ることもでき、ひいては、ＳＭＣの生産性を高めることができる。 Thus, since the vinyl ester resin is used as the main agent, and the styrene monomer is not used as the cross-linking agent, and the cross-linking agent having a boiling point higher than that of the styrene monomer is used, the boiling point of the styrene monomer is about 149 ° C. The molding temperature of the pressure heating molding process using SMC is 135 ° C. to 160 ° C. When the molded product is heated and pressed at this molding temperature, the crosslinking agent does not boil, so the surface of the molded product is rough. It is possible to perform molding at low pressure, for example, at a low processing pressure of about 10 kg / cm 2 , and to improve the quality of SMC molded products. It is possible to suppress the increase in the size and cost of the molding equipment and the cost, and because it does not contain styrene, there is no need to worry about environmental pollution. Therefore, the storage period can be extended, and furthermore, since the heating temperature is 65 ° C. to 85 ° C., the melt viscosity of the resin composition 1 is lowered, the molding processability can be improved, and the curing agent is decomposed. In particular, these resin compositions 1 are heated and mixed at a heating temperature of 65 ° C. to 85 ° C., and the mixture is cooled to a semi-solid state at room temperature. A resin composition that is fluidized at a heating temperature of 65 ° C. to 85 ° C. is formed and stored, and then the semi-solid resin composition is heated at 65 ° C. to 85 ° C. during the production of SMC. Since the fiber base material 2 is impregnated with the resin composition 1 in a fluid state heated to a temperature and then cooled, the resin composition 1 is used. For example, in order to supply a liquid resin composition to the coating portion, a pump is conveyed. It is necessary, but it is semi-solid state at normal temperature Therefore, since it is a resin composition 1 that is in a fluid state at a heating temperature of 65 ° C. to 85 ° C., handling properties such as conveyance to a coating part can be improved, and a large amount of flame retardant can be included. The manufacturing cost can be reduced, and as a result, the productivity of SMC can be increased.
この場合、上記架橋剤として、ジアリルフタレートモノマーを用いてなるから、このジアリルフタレートモノマーの沸点は２００℃以上であり、加圧加熱成形加工の成形温度は１３５℃〜１６０℃であるところ、架橋剤は沸騰しないので、成形品の表面が粗となることを防ぎ、沸騰による泡を封じ込めるための高圧が必要なく、低圧での成形が可能となり、又、この場合、上記繊維基材２として、繊維マットＲを用いてなるから、ＳＭＣの補強性を高めることができ、又、この場合、上記繊維マットＲはガラス繊維マットであるから、一層、ＳＭＣの補強性を高めることができ、又、この場合、上記各加熱温度はいずれも約７５℃であるから、樹脂組成物１の溶融粘度が低くなり、成形加工性を高めることができ、硬化剤の分解を抑制できて保存安定性を高めることができる。 In this case, as the cross-linking agent, because made with diallyl phthalate monomer, where the boiling point of the diallyl phthalate monomer Ri der 200 ° C. or higher, the molding temperature of the pressurizing and heating the molding process is 135 ° C. to 160 ° C., Since the crosslinking agent does not boil, the surface of the molded product is prevented from becoming rough, high pressure is not required to contain bubbles due to boiling, and molding at low pressure is possible. Since the fiber mat R is used, the SMC reinforcement can be enhanced. In this case, since the fiber mat R is a glass fiber mat, the SMC reinforcement can be further enhanced. In this case, since each of the heating temperatures is about 75 ° C., the melt viscosity of the resin composition 1 is lowered, the moldability can be improved, and the decomposition of the curing agent can be suppressed. It is possible to improve the storage stability.
表１に示す主剤、架橋剤、硬化剤、内部離型剤及び難燃剤を約７５℃で加熱して撹拌混合冷却して、常温では半固形状態であって加熱温度約７５℃で流動状態となる樹脂組成物１を製作して保存しておき、その後、ＳＭＣの製造時において、この半固形状の樹脂組成物１を上下のキャリアフィルムＦ・Ｆ間に約７５℃の加熱温度に加熱して流動状態の樹脂組成物１を４５０ｇ／ｍ２乃至７５０ｇ／ｍ２の厚さの繊維基材２たるガラス繊維マットに含浸してＳＭＣを製造した。 The main agent, crosslinking agent, curing agent, internal mold release agent and flame retardant shown in Table 1 are heated at about 75 ° C., stirred, mixed and cooled, and are in a semi-solid state at room temperature and in a fluid state at a heating temperature of about 75 ° C. The resin composition 1 is manufactured and stored, and then the semi-solid resin composition 1 is heated to a heating temperature of about 75 ° C. between the upper and lower carrier films F and F when the SMC is manufactured. Then, the resin composition 1 in a fluid state was impregnated into a glass fiber mat as a fiber base 2 having a thickness of 450 g / m 2 to 750 g / m 2 to produce SMC.
そして、キャリアフィルムを剥離し、ＳＭＣを上型及び下型により約１６０℃、３ｋｇ／ｃｍ２、５分間の条件下で加熱加圧して成形品を製造したところ、良好な成形品を製造することができた。 Then, the carrier film is peeled off, and the SMC is heated and pressed under the conditions of about 160 ° C., 3 kg / cm 2 , 5 minutes with the upper die and the lower die to produce a good molded product. I was able to.
尚、本発明は上記実施の形態例に限られるものではなく、上記樹脂組成物１、繊維基材２の組成及び種類等は適宜変更して設計されるものである。 In addition, this invention is not restricted to the said embodiment, The composition, the kind, etc. of the said resin composition 1 and the fiber base material 2 are changed suitably, and can be designed.
以上、所期の目的を充分達成することができる。 As described above, the intended purpose can be sufficiently achieved.
Ｒ 繊維マット
Ｆ キャリアフィルム
１ 樹脂組成物
２ 繊維基材
R Fiber mat F Carrier film 1 Resin composition 2 Fiber substrate
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