TWI663199B - Foamed particle for manufacturing fiber reinforced composites and foamed molded articles, fiber reinforced composites parts for automobiles - Google Patents

Foamed particle for manufacturing fiber reinforced composites and foamed molded articles, fiber reinforced composites parts for automobiles Download PDF

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TWI663199B
TWI663199B TW107127812A TW107127812A TWI663199B TW I663199 B TWI663199 B TW I663199B TW 107127812 A TW107127812 A TW 107127812A TW 107127812 A TW107127812 A TW 107127812A TW I663199 B TWI663199 B TW I663199B
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fiber
weight
dicarboxylic acid
parts
unsaturated dicarboxylic
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TW107127812A
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TW201920404A (en
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桒原佑輔
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日商積水化成品工業股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent

Abstract

本發明係關於一種纖維強化複合體製造用之發泡粒子，係由含有芳香族乙烯-(甲基)丙烯酸酯-不飽和二羧酸共聚物A及芳香族乙烯-不飽和二羧酸-不飽和二羧酸醯亞胺共聚物B之基材樹脂所構成，其中，相對於前述共聚物A與B之合計，含有1至50重量%之前述共聚物B。 The present invention relates to a foamed particle for manufacturing a fiber-reinforced composite, which is composed of aromatic ethylene- (meth) acrylate-unsaturated dicarboxylic acid copolymer A and aromatic ethylene-unsaturated dicarboxylic acid-unsaturated The saturated dicarboxylic acid fluorene imine copolymer B is composed of a base resin, and contains 1 to 50% by weight of the aforementioned copolymer B based on the total of the aforementioned copolymers A and B.

Description

纖維強化複合體製造用之發泡粒子及發泡成形體、纖維強化複合體及汽車用構件 Foamed particles and foamed moldings for manufacturing fiber-reinforced composites, fiber-reinforced composites, and automotive components

本發明係關於纖維強化複合體製造用之發泡粒子及發泡成形體、纖維強化複合體及汽車用構件。更詳細而言，本發明係關於可供給表面美觀性經提升之纖維強化複合體之發泡粒子及發泡成形體、表面美觀性經提升之纖維強化複合體及汽車用構件。 The present invention relates to foamed particles and foamed molded bodies, fiber-reinforced composites, and automotive components for fiber-reinforced composites. More specifically, the present invention relates to foamed particles and foamed molded articles that can provide a fiber-reinforced composite with improved surface aesthetics, a fiber-reinforced composite with improved surface aesthetics, and automotive components.

近年來，航空器、汽車、船舶等載運工具為了減少對地球環境的負荷而必須提升燃油經濟性(fuel economy improvement)，將構成該等載運工具之金屬材料轉換成樹脂材料以謀求大幅地輕量化之趨勢正逐漸增強。該等樹脂材料可列舉纖維強化塑膠。又，以謀求進一步的輕量化、高剛性化為目的，而有提案為積層有纖維強化塑膠及芯材之纖維強化複合體。例如就芯材而言，係檢討具有高的壓縮強度之聚苯乙烯發泡成形體(日本特開 2012-214751號公報：專利文獻1)。 In recent years, in order to reduce the load on the global environment, vehicles such as aircraft, automobiles, and ships must improve fuel economy improvement. The metal materials constituting these vehicles have been converted to resin materials in order to significantly reduce weight. The trend is gradually increasing. Examples of such resin materials include fiber-reinforced plastics. In addition, for the purpose of further reducing weight and increasing rigidity, a fiber-reinforced composite having fiber-reinforced plastic and a core material laminated thereon has been proposed. For example, in the case of core materials, a polystyrene foamed molded article having high compressive strength is reviewed (Japanese Patent Laid-Open) Publication No. 2012-214751: Patent Document 1).

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2012-214751號公報 [Patent Document 1] Japanese Patent Application Publication No. 2012-214751

然而，專利文獻1之發泡成形體為玻璃轉移溫度低之苯乙烯系樹脂所製者，故包括耐熱性之機械物性並不充分。為了提升機械物性，可考慮選擇苯乙烯系樹脂以外的樹脂。 However, since the foamed molded body of Patent Document 1 is made of a styrene resin having a low glass transition temperature, mechanical properties including heat resistance are not sufficient. In order to improve mechanical properties, a resin other than a styrene resin may be selected.

不過，關於構成纖維強化複合體之纖維強化塑膠，從提升其纖維強化面的美觀性之觀點來看，係期望使平滑性提升。 However, the fiber-reinforced plastic constituting the fiber-reinforced composite is expected to improve smoothness from the viewpoint of improving the aesthetics of the fiber-reinforced surface.

本發明之發明者為了提升纖維強化複合體的機械物性，檢討以各種樹脂作為芯材，結果意外地發現若使用含有芳香族乙烯-(甲基)丙烯酸酯-不飽和二羧酸共聚物A及芳香族乙烯-不飽和二羧酸-不飽和二羧酸醯亞胺共聚物B之基材樹脂，則可在提升機械物性的同時提升纖維強化面的平滑性，而達成本發明。 In order to improve the mechanical properties of the fiber-reinforced composite, the inventors of the present invention reviewed various resins as the core material. As a result, they unexpectedly discovered that if an aromatic ethylene- (meth) acrylate-unsaturated dicarboxylic acid copolymer A and The base resin of the aromatic ethylene-unsaturated dicarboxylic acid-unsaturated dicarboxylic acid imine copolymer B can improve the mechanical properties and the smoothness of the fiber-reinforced surface to achieve the invention.

如此，依據本發明，可提供一種纖維強化複合體製造用之發泡粒子，係由含有芳香族乙烯-(甲基)丙烯酸酯-不飽和二羧酸共聚物A及芳香族乙烯-不飽和二羧 酸-不飽和二羧酸醯亞胺共聚物B之基材樹脂所構成，其中，相對於前述共聚物A與B之合計，含有1至50重量%之前述共聚物B。 Thus, according to the present invention, it is possible to provide a foamed particle for manufacturing a fiber-reinforced composite, which comprises an aromatic ethylene- (meth) acrylate-unsaturated dicarboxylic acid copolymer A and an aromatic ethylene-unsaturated dicarboxylic acid. Carboxy The base resin of the acid-unsaturated dicarboxylic acid imine copolymer B contains 1 to 50% by weight of the aforementioned copolymer B based on the total of the aforementioned copolymers A and B.

又，依據本發明，可提供一種纖維強化複合體製造用之發泡成形體，係由含有芳香族乙烯-(甲基)丙烯酸酯-不飽和二羧酸共聚物A及芳香族乙烯-不飽和二羧酸-不飽和二羧酸醯亞胺共聚物B之基材樹脂所構成，其中，相對於前述共聚物A與B之合計，含有1至50重量%之前述共聚物B。 In addition, according to the present invention, it is possible to provide a foamed molded body for producing a fiber-reinforced composite, which comprises an aromatic ethylene- (meth) acrylate-unsaturated dicarboxylic acid copolymer A and an aromatic ethylene-unsaturation The base resin of a dicarboxylic acid-unsaturated dicarboxylic acid imine copolymer B contains 1 to 50% by weight of the aforementioned copolymer B based on the total of the aforementioned copolymers A and B.

再者，依據本發明，可提供一種纖維強化複合體，係具有發泡成形體、及積層在前述發泡成形體的表面並一體化之纖維強化塑膠層，其中，該發泡成形體係由含有芳香族乙烯-(甲基)丙烯酸酯-不飽和二羧酸共聚物A及芳香族乙烯-不飽和二羧酸-不飽和二羧酸醯亞胺共聚物B之基材樹脂所構成，且相對於前述共聚物A與B之合計，含有1至50重量%之前述共聚物B。 In addition, according to the present invention, a fiber-reinforced composite having a foamed molded body and a fiber-reinforced plastic layer laminated and integrated on the surface of the foamed molded body can be provided, wherein the foamed molding system comprises The base resin of the aromatic ethylene- (meth) acrylate-unsaturated dicarboxylic acid copolymer A and the aromatic ethylene-unsaturated dicarboxylic acid-unsaturated dicarboxylic acid imine copolymer B, and relatively The total amount of the aforementioned copolymers A and B contains the aforementioned copolymer B in an amount of 1 to 50% by weight.

又，依據本發明，可提供一種由上述纖維強化複合體所構成之汽車用構件。 Furthermore, according to the present invention, there can be provided an automobile member composed of the fiber-reinforced composite.

依據本發明，可以提供可供給表面美觀性經提升之纖維強化複合體之發泡粒子及發泡成形體、表面美觀性經提升之纖維強化複合體及汽車用構件。 According to the present invention, it is possible to provide foamed particles and foamed molded bodies capable of supplying a fiber-reinforced composite having improved surface aesthetics, a fiber-reinforced composite having improved surface aesthetics, and components for automobiles.

第1圖係實施例1之纖維強化複合體的纖維強化面之照片(a)及描線圖(b)。 Fig. 1 is a photograph (a) and a line drawing (b) of the fiber-reinforced surface of the fiber-reinforced composite of Example 1.

第2圖係實施例2之纖維強化複合體的纖維強化面之照片(a)及描線圖(b)。 FIG. 2 is a photograph (a) and a line drawing (b) of the fiber-reinforced surface of the fiber-reinforced composite of Example 2. FIG.

第3圖係實施例3之纖維強化複合體的纖維強化面之照片(a)及描線圖(b)。 Fig. 3 is a photograph (a) and a line drawing (b) of the fiber-reinforced surface of the fiber-reinforced composite of Example 3.

第4圖係比較例1之纖維強化複合體的纖維強化面之照片(a)及描線圖(b)。 FIG. 4 is a photograph (a) and a line drawing (b) of the fiber-reinforced surface of the fiber-reinforced composite of Comparative Example 1. FIG.

(發泡粒子) (Foaming particles)

發泡粒子係使用於製造在具有發泡成形體及積層在該發泡成形體的表面並一體化之纖維強化塑膠層之纖維強化複合體中之發泡成形體。 The foamed particles are used to produce a foamed molded body in a fiber-reinforced composite having a foamed molded body and a fiber-reinforced plastic layer integrated on the surface of the foamed molded body.

(1)基材樹脂 (1) Substrate resin

發泡粒子係由含有芳香族乙烯-(甲基)丙烯酸酯-不飽和二羧酸共聚物A(以下，亦簡稱為共聚物A)及芳香族乙烯-不飽和二羧酸-不飽和二羧酸醯亞胺共聚物B(以下，亦簡稱為共聚物B)之基材樹脂所構成。在基材樹脂中，共聚物A及B之合計量所佔之比率較佳係70重量%以上，更佳係85重量%以上，也可為100重量%。基材樹脂較佳係具有115至160℃之玻璃轉移溫度Tg。Tg低於115℃時，纖維強化塑膠層在使用發泡粒子所製造之發泡成形體的表面之積層一體化變得不充分，而會有纖維強化複合體的機械物性降低之情形。高於160℃時，發泡粒子之發泡性降 低，發泡粒子彼此的熱熔合一體化變得不充分，而會有纖維強化複合體的機械物性降低之情形。Tg例如為115℃、120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃、160℃。更佳的Tg係120至150℃。 The expanded particles are composed of an aromatic ethylene- (meth) acrylate-unsaturated dicarboxylic acid copolymer A (hereinafter, also simply referred to as copolymer A) and an aromatic ethylene-unsaturated dicarboxylic acid-unsaturated dicarboxylic acid. It is composed of a base resin of an acid sulfide imine copolymer B (hereinafter, also simply referred to as a copolymer B). In the base resin, the ratio of the total amount of the copolymers A and B is preferably 70% by weight or more, more preferably 85% by weight or more, and may also be 100% by weight. The base resin preferably has a glass transition temperature Tg of 115 to 160 ° C. When the Tg is lower than 115 ° C, the layer integration of the fiber-reinforced plastic layer on the surface of the foamed molded body manufactured using the foamed particles becomes insufficient, and the mechanical properties of the fiber-reinforced composite may decrease. Above 160 ° C, the foamability of foamed particles decreases Low, the thermal fusion integration of the foamed particles becomes insufficient, and the mechanical properties of the fiber-reinforced composite may decrease. Tg is, for example, 115 ° C, 120 ° C, 125 ° C, 130 ° C, 135 ° C, 140 ° C, 145 ° C, 150 ° C, 155 ° C, and 160 ° C. More preferred Tg is 120 to 150 ° C.

(i)共聚物A (i) Copolymer A

(a)芳香族乙烯 (a) Aromatic ethylene

芳香族乙烯係具備包含乙烯基之取代基的芳香族化合物。乙烯基之數目及芳香族化合物之碳數並無特別限定。具體的芳香族乙烯可列舉：苯乙烯、α-甲基苯乙烯、乙烯基甲苯、乙基苯乙烯、異丙基苯乙烯、第三丁基苯乙烯、二甲基苯乙烯、溴苯乙烯、氯苯乙烯等苯乙烯系單官能單體、二乙烯基苯、三乙烯基苯、二乙烯基甲苯、二乙烯基二甲苯、雙(乙烯基苯基)甲烷、雙(乙烯基苯基)乙烷、雙(乙烯基苯基)丙烷、雙(乙烯基苯基)丁烷、二乙烯基萘、二乙烯基蒽、二乙烯基聯苯、雙酚A的環氧乙烷加成物二(甲基)丙烯酸酯、雙酚A的環氧丙烷加成物二(甲基)丙烯酸酯等。芳香族乙烯可單獨使用或併用二種以上。其中，從取得容易性之觀點來看，較佳係苯乙烯。 The aromatic vinyl is an aromatic compound having a substituent containing a vinyl group. The number of vinyl groups and the carbon number of the aromatic compound are not particularly limited. Specific examples of the aromatic ethylene include styrene, α-methylstyrene, vinyltoluene, ethylstyrene, isopropylstyrene, third butylstyrene, dimethylstyrene, bromostyrene, Styrene-based monofunctional monomers such as chlorostyrene, divinylbenzene, trivinylbenzene, divinyltoluene, divinylxylene, bis (vinylphenyl) methane, bis (vinylphenyl) ethane Ethane, bis (vinylphenyl) propane, bis (vinylphenyl) butane, divinylnaphthalene, divinylanthracene, divinylbiphenyl, ethylene oxide adduct of bisphenol A (Meth) acrylate, propylene oxide adduct di (meth) acrylate of bisphenol A, and the like. The aromatic vinyl can be used alone or in combination of two or more. Among them, styrene is preferred from the viewpoint of availability.

(b)(甲基)丙烯酸酯 (b) (Meth) acrylate

(甲基)丙烯酸酯並無特別限定，但可列舉例如(甲基)丙烯酸烷酯。(甲基)丙烯酸烷酯中之烷基的碳數可設為1至5。具體的(甲基)丙烯酸酯可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯等。(甲基)丙烯酸酯可單獨使用或併用二種以上。從提升 纖維強化複合體的機械物性之觀點來看，較佳係(甲基)丙烯酸甲酯，更佳係甲基丙烯酸甲酯。 The (meth) acrylate is not particularly limited, and examples thereof include alkyl (meth) acrylate. The carbon number of the alkyl group in the alkyl (meth) acrylate can be set to 1 to 5. Specific (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. The (meth) acrylate may be used alone or in combination of two or more. From promotion From the viewpoint of the mechanical properties of the fiber-reinforced composite, methyl (meth) acrylate is preferred, and methyl methacrylate is more preferred.

(c)不飽和二羧酸 (c) Unsaturated dicarboxylic acid

不飽和二羧酸並無特別限定，但可列舉碳數2至6之脂肪族不飽和二羧酸。具體的不飽和二羧酸可列舉：順丁烯二酸、伊康酸、檸康酸、烏頭酸(aconitic acid)、該等的酸酐等。不飽和二羧酸可單獨使用或併用二種以上。 The unsaturated dicarboxylic acid is not particularly limited, but examples thereof include aliphatic unsaturated dicarboxylic acids having 2 to 6 carbon atoms. Specific examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, citraconic acid, aconic acid, and anhydrides thereof. Unsaturated dicarboxylic acids can be used alone or in combination of two or more.

(d)源自芳香族乙烯、(甲基)丙烯酸酯、不飽和二羧酸之單元的比例 (d) Proportion of units derived from aromatic ethylene, (meth) acrylate, unsaturated dicarboxylic acid

將源自芳香族乙烯與(甲基)丙烯酸酯與不飽和二羧酸三者之單元的合計設為100重量份時，較佳係含有30至80重量份之源自芳香族乙烯之單元、8至35重量份之源自(甲基)丙烯酸酯之單元、10至50重量份之源自不飽和二羧酸之單元。 When the total of the units derived from the aromatic ethylene, the (meth) acrylate and the unsaturated dicarboxylic acid is 100 parts by weight, it is preferred that the units contain 30 to 80 parts by weight of the units derived from the aromatic ethylene, 8 to 35 parts by weight of units derived from (meth) acrylate, and 10 to 50 parts by weight of units derived from unsaturated dicarboxylic acid.

源自芳香族乙烯之單元所佔之比例未達30重量份時，在發泡成形時發泡粒子的發泡性降低，發泡粒子彼此的熱熔合一體化變得不充分，而會有纖維強化複合體的機械物性降低之情形。該比例大於80重量份時，會有纖維強化複合體的耐熱性降低之情形。該比例例如為30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份。該比例更佳係40至75重量份，再更佳係45至70重量份。 When the proportion of the unit derived from aromatic ethylene is less than 30 parts by weight, the foamability of the foamed particles is reduced during the foam molding, and the thermal fusion integration of the foamed particles with each other becomes insufficient, and there are fibers. When the mechanical properties of the reinforced composite decrease. When the ratio is more than 80 parts by weight, the heat resistance of the fiber-reinforced composite may decrease. This ratio is, for example, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight. The ratio is more preferably 40 to 75 parts by weight, and even more preferably 45 to 70 parts by weight.

源自(甲基)丙烯酸酯之單元所佔之比例未達8重量份時，會有纖維強化複合體的機械物性降低之情 形。該比例大於35重量份時，發泡成形時發泡粒子的發泡性降低，發泡粒子彼此的熱熔合一體化變得不充分，而會有纖維強化複合體的機械物性降低之情形。該比例例如為8重量份、10重量份、12重量份、15重量份、17重量份、20重量份、22重量份、25重量份、27重量份、30重量份、33重量份、35重量份。該比例更佳係10至33重量份，再更佳係15至30重量份。 When the proportion of the unit derived from (meth) acrylate is less than 8 parts by weight, the mechanical properties of the fiber-reinforced composite may decrease. shape. When the proportion is more than 35 parts by weight, the foamability of the foamed particles is reduced during foam molding, and the thermal fusion integration of the foamed particles with each other becomes insufficient, and the mechanical properties of the fiber-reinforced composite may be reduced. The ratio is, for example, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 17 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 27 parts by weight, 30 parts by weight, 33 parts by weight, 35 parts by weight Serving. The ratio is more preferably 10 to 33 parts by weight, and even more preferably 15 to 30 parts by weight.

源自不飽和二羧酸之單元所佔之比例未達10重量份時，會有纖維強化複合體的耐熱性降低之情形。該比例大於50重量份時，發泡成形時發泡粒子的發泡性降低，發泡粒子彼此的熱熔合一體化變得不充分，而會有纖維強化複合體的機械物性降低之情形。該比例例如為10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、50重量份。該比例更佳係15至40重量份，再更佳係20至35重量份。 When the proportion of the unit derived from the unsaturated dicarboxylic acid is less than 10 parts by weight, the heat resistance of the fiber-reinforced composite may decrease. When the proportion is more than 50 parts by weight, the foamability of the foamed particles is reduced during foam molding, and the thermal fusion integration of the foamed particles with each other becomes insufficient, and the mechanical properties of the fiber-reinforced composite may be reduced. The ratio is, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, and 50 parts by weight. The ratio is more preferably 15 to 40 parts by weight, and even more preferably 20 to 35 parts by weight.

再者，單體的使用量與源自該單體之單元的含量為幾乎一致。 In addition, the amount of the monomer used is almost the same as the content of the unit derived from the monomer.

各成分比，亦即源自芳香族乙烯與(甲基)丙烯酸酯與不飽和二羧酸之單元、還有源自以下所說明的其他單體及其他樹脂之單元的比例，係可藉由1H-NMR的譜峰高度或FT-IR的面積比而規定。具體的測定方法係在實施例中說明。 The ratio of each component, that is, the ratio of the unit derived from aromatic ethylene and (meth) acrylate and unsaturated dicarboxylic acid, and the unit derived from other monomers and other resins described below, can be determined by The peak height of 1 H-NMR or the area ratio of FT-IR is specified. Specific measurement methods are described in the examples.

(ii)共聚物B (ii) Copolymer B

(a)芳香族乙烯 (a) Aromatic ethylene

芳香族乙烯並無特別限定，但可列舉上述共聚物A之(a)中例示的化合物。芳香族乙烯可單獨使用或併用二種以上。其中，從取得容易性之觀點來看，較佳係苯乙烯。 The aromatic ethylene is not particularly limited, and examples thereof include the compounds exemplified in (a) of the copolymer A described above. The aromatic vinyl can be used alone or in combination of two or more. Among them, styrene is preferred from the viewpoint of availability.

(b)不飽和二羧酸 (b) Unsaturated dicarboxylic acid

不飽和二羧酸並無特別限定，但可列舉上述共聚物A之(c)中例示的化合物。不飽和二羧酸可單獨使用或併用二種以上。從提升發泡成形體的機械物性之觀點來看，較佳係順丁烯二酸酐。 The unsaturated dicarboxylic acid is not particularly limited, and examples thereof include the compounds exemplified in (c) of the copolymer A described above. Unsaturated dicarboxylic acids can be used alone or in combination of two or more. From the viewpoint of improving the mechanical properties of the foamed molded product, maleic anhydride is preferred.

(c)不飽和二羧酸醯亞胺 (c) Unsaturated dicarboxylic acid imine

不飽和二羧酸醯亞胺並無特別限定，但可列舉：順丁烯二醯亞胺、N-甲基順丁烯二醯亞胺、N-乙基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺、N-萘基順丁烯二醯亞胺等順丁烯二醯亞胺系單體等。不飽和二羧酸醯亞胺衍生物可單獨使用或併用二種以上。從提升纖維強化複合體的耐熱性之觀點來看，較佳係N-苯基順丁烯二醯亞胺。 The unsaturated dicarboxylic acid imine imine is not particularly limited, but examples thereof include cis-butenediimide, N-methylcis-butenediimide, N-ethylcis-butenediimide, N -Maleic monomers such as cyclohexyl-cis-butene-diimide, N-phenyl-cis-butene-diimide, N-naphthyl-cis-butene-diimide, and the like. The unsaturated dicarboxylic acid sulfonium imine derivative can be used alone or in combination of two or more kinds. From the viewpoint of improving the heat resistance of the fiber-reinforced composite, N-phenylcis-butenediamidine is preferred.

(d)源自芳香族乙烯、不飽和二羧酸、不飽和二羧酸醯亞胺之單元的比例 (d) Proportion of units derived from aromatic ethylene, unsaturated dicarboxylic acid, and unsaturated imine diimide

將源自芳香族乙烯與不飽和二羧酸與不飽和二羧酸醯亞胺三者之單元的合計設為100重量份時，較佳係含有20至80重量份之源自芳香族乙烯之單元、2至30重量份之源自不飽和二羧酸之單元、20至80重量份之源自不飽和二羧酸醯亞胺之單元。 When the total of the units derived from the aromatic ethylene, the unsaturated dicarboxylic acid, and the unsaturated dicarboxylic acid / imine is set to 100 parts by weight, it is preferable to contain 20 to 80 parts by weight Unit, 2 to 30 parts by weight of an unsaturated dicarboxylic acid-derived unit, and 20 to 80 parts by weight of an unsaturated dicarboxylic acid imine-derived unit.

源自芳香族乙烯之單元所佔之比例未達20重量份時， 發泡成形時發泡粒子的發泡性降低，發泡粒子彼此的熱熔合一體化變得不充分，而會有纖維強化複合體的機械物性降低之情形。該比例大於80重量份時，會有發泡成形體的耐熱性降低之情形。該比例例如為20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份。該比例更佳係30至75重量份，再更佳係50至70重量份。 When the proportion of the unit derived from aromatic ethylene is less than 20 parts by weight, During the foam molding, the foamability of the foamed particles is reduced, and the thermal fusion integration of the foamed particles with each other becomes insufficient, and the mechanical properties of the fiber-reinforced composite may be reduced. When the ratio is more than 80 parts by weight, the heat resistance of the foamed molded article may be reduced. The ratio is, for example, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight Parts, 80 parts by weight. The ratio is more preferably 30 to 75 parts by weight, and even more preferably 50 to 70 parts by weight.

(iii)其他單體 (iii) Other monomers

共聚物A及/或B可分別為在上述3個單體以外且在不阻礙本發明特性之範圍與源自其他單體的成分之進一步的共聚物。其他單體可列舉例如：(甲基)丙烯腈、順丁烯二酸二甲酯、順丁烯二酸二乙酯、反丁烯二酸二甲酯、反丁烯二酸二乙酯、反丁烯二酸乙酯、(甲基)丙烯酸等。 Copolymers A and / or B may be further copolymers of components derived from other monomers, in addition to the three monomers described above, as long as they do not impede the characteristics of the present invention. Other monomers include, for example, (meth) acrylonitrile, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, Ethyl fumarate, (meth) acrylic acid, etc.

兩共聚物中之源自其他單體之單元所佔之比率較佳係30重量%以下，也可為0重量%。 The ratio of the units derived from other monomers in the two copolymers is preferably 30% by weight or less, and may also be 0% by weight.

(iv)共聚物A與B的含有比率 (iv) Content ratio of copolymers A and B

相對於共聚物A與B之合計，可含有1至50重量%之共聚物B。共聚物B的含量未達1重量%時，會有纖維強化複合體的表面美觀性之提升效果較低之情形。多於50重量%時，脆性變高而纖維強化複合體製作時會有發泡體挫曲之情形。共聚物B的含量例如為1重量%、5重量%、10重量%、15重量%、20重量%、25重量%、30重量%、35重量%、40重量%、45重量%、50重量%。共聚物B的 含量較佳係5至40重量%。 The copolymer B may be contained in an amount of 1 to 50% by weight based on the total of the copolymers A and B. When the content of the copolymer B is less than 1% by weight, the effect of improving the surface appearance of the fiber-reinforced composite may be low. If it is more than 50% by weight, the brittleness becomes high and the foam may be buckled during the production of the fiber-reinforced composite. The content of the copolymer B is, for example, 1% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, or 50% by weight. . Copolymer B The content is preferably 5 to 40% by weight.

(v)其他樹脂 (v) Other resins

基材樹脂中可混合其他樹脂。其他樹脂可列舉：聚乙烯、聚丙烯等聚烯烴系樹脂、聚丁二烯、苯乙烯-丁二烯共聚物、乙烯-丙烯-非共軛二烯三元共聚物等添加有二烯系的橡膠狀聚合物之橡膠改質耐衝擊性聚苯乙烯系樹脂、聚碳酸酯樹脂、聚酯樹脂、聚醯胺樹脂、聚苯醚、丙烯腈-丁二烯-苯乙烯共聚物、丙烯腈-苯乙烯共聚物、聚甲基丙烯酸甲酯等、苯乙烯-(甲基)丙烯酸共聚物、苯乙烯-(甲基)丙烯酸酯共聚物、芳香族乙烯-不飽和二羧酸-不飽和二羧酸醯亞胺共聚物等。 The base resin may be mixed with other resins. Examples of other resins include polyolefin resins such as polyethylene and polypropylene, polybutadiene, styrene-butadiene copolymers, ethylene-propylene-non-conjugated diene terpolymers, and other diene-based resins. Rubber-modified polymer impact-resistant polystyrene resin, polycarbonate resin, polyester resin, polyamide resin, polyphenylene ether, acrylonitrile-butadiene-styrene copolymer, acrylonitrile- Styrene copolymer, polymethyl methacrylate, etc., styrene- (meth) acrylic copolymer, styrene- (meth) acrylate copolymer, aromatic ethylene-unsaturated dicarboxylic acid-unsaturated dicarboxylic acid Acid sulfonium imine copolymers and the like.

上述其他樹脂之中，發泡粒子可含有聚甲基丙烯酸甲酯。藉由含有聚甲基丙烯酸甲酯，發泡粒子的熱熔合性提升，使發泡粒子彼此更堅固地熱熔合一體化，可得到具有更優異的機械物性之發泡成形體。相對於共聚物100重量份，發泡粒子中之聚甲基丙烯酸甲酯的含量較佳係10至500重量份，更佳係20至450重量份，特佳係30至400重量份。 Among the other resins, the foamed particles may contain polymethyl methacrylate. By containing polymethyl methacrylate, the thermal fusion properties of the foamed particles are improved, and the foamed particles are more strongly thermally fused and integrated with each other, so that a foamed molded body having more excellent mechanical properties can be obtained. The content of the polymethyl methacrylate in the expanded particles is preferably 10 to 500 parts by weight, more preferably 20 to 450 parts by weight, and particularly preferably 30 to 400 parts by weight with respect to 100 parts by weight of the copolymer.

發泡粒子中可含有作為加工助劑之丙烯酸系樹脂。藉由含有加工助劑，使構成發泡粒子之樹脂在發泡時之熔融張力(黏彈性)為適合發泡者，抑制發泡粒子的連續氣泡化，提升發泡粒子的發泡性，並使發泡粒子彼此的熱熔合更堅固，而可製造具有更優異的機械物性之發泡成形體。相對於共聚物100重量份，發泡粒子中之加工助 劑的含量較佳係0.5至5重量份，更佳係0.5至3重量份。 The foamed particles may contain an acrylic resin as a processing aid. By containing a processing aid, the melt tension (viscoelasticity) of the resin constituting the expanded particles is suitable for foaming, suppressing continuous foaming of the expanded particles, and improving the foamability of the expanded particles, and By making the thermal fusion of the foamed particles stronger, it is possible to produce a foamed molded body having more excellent mechanical properties. Relative to 100 parts by weight of the copolymer, the processing aid in the expanded particles The content of the agent is preferably 0.5 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight.

作為加工助劑之丙烯酸系樹脂並無特別限定，可列舉：丙烯酸系單體的均聚物或由該等之二種以上所成的共聚物；含有50重量%以上之丙烯酸系單體、且為丙烯酸系單體和能夠與該丙烯酸系單體共聚合的乙烯基單體之共聚物等。丙烯酸系單體可列舉：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯等。就能夠與丙烯酸系單體共聚合的乙烯基單體而言，可列舉：α-甲基苯乙烯、丙烯腈等。丙烯酸系樹脂的重量平均分子量較佳係150萬至600萬，更佳係200萬至450萬，特佳係250萬至400萬。丙烯酸系樹脂的重量平均分子量過低或過高都會難以將構成發泡粒子之樹脂的發泡成形時之熔融張力(黏彈性)充分地調整為適合發泡者，而會有無法提升發泡粒子的發泡性之情形。 The acrylic resin used as the processing aid is not particularly limited, and examples thereof include homopolymers of acrylic monomers or copolymers made of two or more of these, and acrylic monomers containing 50% by weight or more, and It is a copolymer of an acrylic monomer and a vinyl monomer that can be copolymerized with the acrylic monomer, and the like. Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Examples of the vinyl monomer that can be copolymerized with the acrylic monomer include α-methylstyrene, acrylonitrile, and the like. The weight average molecular weight of the acrylic resin is preferably 1.5 to 6 million, more preferably 2 to 4.5 million, and particularly preferably 2.5 to 4 million. If the weight average molecular weight of the acrylic resin is too low or too high, it may be difficult to sufficiently adjust the melt tension (viscoelasticity) of the resin constituting the expanded particles to be suitable for foaming, and there may be a failure to improve the expanded particles. Foaming situation.

(vi)添加劑 (vi) Additives

基材樹脂可視需要而在樹脂以外還含有添加劑。添加劑可列舉：塑化劑、阻燃劑、阻燃助劑、抗靜電劑、展著劑、氣泡調整劑、填充劑、著色劑、耐候劑、抗老化劑、滑劑、防霧劑、香料等。 The base resin may contain additives in addition to the resin as necessary. Examples of additives include plasticizers, flame retardants, flame retardant additives, antistatic agents, spreading agents, bubble regulators, fillers, colorants, weathering agents, anti-aging agents, slip agents, anti-fog agents, and fragrances Wait.

(2)構成 (2) Composition

發泡粒子的平均粒徑較佳係500至5000μm，更佳係1000至3000μm。平均粒徑例如為500μm、1000μm、2000μm、3000μm、4000μm、5000μm。 The average particle diameter of the expanded particles is preferably 500 to 5000 μm, and more preferably 1000 to 3000 μm. The average particle diameter is, for example, 500 μm, 1000 μm, 2000 μm, 3000 μm, 4000 μm, or 5000 μm.

發泡粒子的外形只要可製造發泡成形體則無特別限 定，可列舉例如：球狀、略球狀、圓筒形等。發泡粒子較佳係具有以0.8以上之平均的長寬比(aspect ratio)所示的外形(上限為1之真球狀)。長寬比例如為0.8、0.85、0.9、0.95、1。 The shape of the expanded particles is not particularly limited as long as it can produce a foamed molded body. Examples include: spherical, slightly spherical, and cylindrical. The expanded particles preferably have an outer shape (a true spherical shape with an upper limit of 1) represented by an average aspect ratio of 0.8 or more. The aspect ratio is, for example, 0.8, 0.85, 0.9, 0.95, or 1.

發泡粒子較佳係具有20至1.4倍之容積倍數。當容積倍數大於20倍，發泡粒子的連續氣泡率上昇，會有在發泡成形的發泡時發泡粒子的發泡性降低之情形。當小於1.4倍，則發泡粒子的氣泡變得不均勻，而會有在發泡成形時之發泡粒子的發泡性不充分之情形。容積倍數例如為20倍、18倍、14倍、12.5倍、10倍、5倍、2倍、1.6倍、1.4倍。容積倍數更佳係14至1.6倍，特佳係12.5至2倍。 The expanded particles preferably have a volume multiple of 20 to 1.4 times. When the volume multiple is more than 20 times, the continuous cell ratio of the foamed particles increases, and the foamability of the foamed particles may decrease during foaming in the foam molding. When it is less than 1.4 times, the bubbles of the expanded particles become non-uniform, and the foamability of the expanded particles may be insufficient during foam molding. The volume multiple is, for example, 20 times, 18 times, 14 times, 12.5 times, 10 times, 5 times, 2 times, 1.6 times, and 1.4 times. The volume multiple is more preferably 14 to 1.6 times, and the particularly good is 12.5 to 2 times.

發泡粒子較佳係顯示40%以下之連續氣泡率。連續氣泡率高於40%時，在發泡成形時發泡粒子的發泡壓不足，發泡粒子彼此的熱熔合一體化變得不充分，而會有纖維強化複合體的機械物性降低之情形。連續氣泡率例如為40%、35%、30%、20%、10%、5%、0%。連續氣泡率更佳係35%以下。 The expanded particles preferably have a continuous cell ratio of 40% or less. When the continuous cell ratio is higher than 40%, the foaming pressure of the foamed particles is insufficient during foam molding, and the thermal fusion integration of the foamed particles becomes insufficient, and the mechanical properties of the fiber-reinforced composite may be reduced. . The continuous cell ratio is, for example, 40%, 35%, 30%, 20%, 10%, 5%, and 0%. The continuous bubble ratio is more preferably 35% or less.

(3)製造方法 (3) Manufacturing method

發泡粒子之製造方法可列舉：使發泡劑氣相含浸於樹脂粒子而得到發泡性粒子，並使發泡性粒子發泡之方法。 Examples of the method for producing the foamed particles include a method in which a foaming agent is impregnated with resin particles in a gas phase to obtain foamable particles, and the foamable particles are foamed.

首先，樹脂粒子之製造方法可列舉下述方法：(i)將原料樹脂(基材樹脂的構成樹脂之混合物)在擠製機內熔融混煉，將混煉物在從安裝在擠製機之噴嘴模具一邊擠 出一邊切斷之後，進行冷卻而製造之方法；(ii)將原料樹脂在擠製機內熔融混煉，將混煉物從安裝在擠製機之噴嘴模具擠出後，冷卻而得到料股(strand)，將該料股每隔既定間隔予以切斷而製造之方法；(iii)將原料樹脂在擠製機內熔融混煉，將混煉物從安裝在擠製機之環狀模頭或T字模頭擠出而製造薄片，並將該薄片切斷而製造之方法；等。 First, the method for producing resin particles includes the following methods: (i) raw material resin (a mixture of constituent resins of a base resin) is melt-kneaded in an extruder, and the kneaded product is mounted on the extruder. Nozzle die extrusion A method of manufacturing after cutting out and cooling, (ii) Melting and kneading the raw resin in an extruder, extruding the kneaded product from a nozzle die installed in the extruder, and cooling to obtain a stock. (strand), a method of manufacturing the stock by cutting it at predetermined intervals; (iii) melting and kneading the raw resin in an extruder, and mixing the kneaded product from a ring die installed in the extruder Or a method of manufacturing a sheet by extruding a T-die and cutting the sheet to produce the sheet; etc.

再者，擠製機中可供給氣泡調整劑。氣泡調整劑可列舉：聚四氟乙烯粉末、經丙烯酸樹脂改質之聚四氟乙烯粉末、滑石等。相對於樹脂組成物100重量份，氣泡調整劑的量較佳係0.01至5重量份。氣泡調整劑的量未達0.01重量份時，發泡粒子的氣泡變粗大，而有所得之發泡成形體的外觀變差之情形。多於5重量份時，會有因破泡而發泡粒子的獨立氣泡率降低之情形。氣泡調整劑的量更佳係0.05至3重量份，特佳係0.1至2重量份。 Moreover, a bubble regulator can be supplied to the extruder. Examples of the bubble regulator include polytetrafluoroethylene powder, acrylic resin-modified polytetrafluoroethylene powder, and talc. The amount of the bubble regulator is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the resin composition. When the amount of the bubble regulator is less than 0.01 part by weight, bubbles of the expanded particles become coarse, and the appearance of the obtained foamed molded article may be deteriorated. When it is more than 5 parts by weight, the closed cell ratio of the foamed particles may be reduced due to foam breaking. The amount of the bubble regulator is more preferably 0.05 to 3 parts by weight, and particularly preferably 0.1 to 2 parts by weight.

其次，發泡性粒子之製造方法可列舉在可密閉之容器中使發泡劑氣相含浸於樹脂粒子之方法。發泡劑可列舉：丙烷、正丁烷、異丁烷、正戊烷、異戊烷、己烷等飽和脂肪族烴、如二甲基醚之醚類、氯甲烷、1,1,1,2-四氟乙烷、1,1-二氟乙烷、單氯二氟甲烷等氟氯碳化物、二氧化碳、氮等無機氣體。其中，較佳係二甲基醚、丙烷、正丁烷、異丁烷、二氧化碳，更佳係丙烷、正丁烷、異丁烷，特佳係正丁烷、異丁烷。再者，發泡劑可單獨使用或併用二種以上。 Next, a method for producing the expandable particles includes a method of impregnating the resin particles with the foaming agent in a gas-tight manner in a sealable container. Examples of the blowing agent include saturated aliphatic hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, and hexane, ethers such as dimethyl ether, methyl chloride, 1,1,1, Inorganic gases such as fluorochlorocarbons such as 2-tetrafluoroethane, 1,1-difluoroethane, monochlorodifluoromethane, carbon dioxide, and nitrogen. Among them, preferred are dimethyl ether, propane, n-butane, isobutane, and carbon dioxide, more preferred are propane, n-butane, isobutane, and particularly preferred are n-butane and isobutane. The foaming agent may be used alone or in combination of two or more.

投入容器的發泡劑量過少時，會有無法將發泡粒子發泡至所期望的發泡倍率之情形。發泡劑量過多時，發泡劑會作為塑化劑而發揮作用，故基材樹脂的黏彈性過度降低而發泡性降低，會有無法得到良好的發泡粒子之情形。因此，相對於原料樹脂100重量份，發泡劑量較佳係0.1至5重量份，更佳係0.2至4重量份，特佳係0.3至3重量份。 When the amount of the foaming agent put into the container is too small, the foamed particles may not be foamed to a desired expansion ratio. When the foaming amount is too large, the foaming agent functions as a plasticizer, so the viscoelasticity of the base resin is excessively lowered, and the foamability is lowered, and good foamed particles may not be obtained. Therefore, the foaming amount is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, and particularly preferably 0.3 to 3 parts by weight, with respect to 100 parts by weight of the raw resin.

再者，發泡粒子之製造方法可列舉：在可密閉之容器中藉由如水蒸氣等加熱介質而進行加熱之方法。加熱條件可列舉例如：0.3至0.5MPa之錶壓、120至159℃之溫度、10至180秒之時間。 The method for producing the foamed particles includes a method of heating in a hermetically sealed container with a heating medium such as water vapor. Examples of heating conditions include a gauge pressure of 0.3 to 0.5 MPa, a temperature of 120 to 159 ° C, and a time of 10 to 180 seconds.

發泡粒子的粒徑可藉由變更安裝在擠製機的前端之多噴嘴模具的徑等而變動。 The particle diameter of the foamed particles can be changed by changing the diameter of a multi-nozzle die installed at the front end of the extruder, or the like.

(發泡成形體) (Foam molding)

(1)基材樹脂 (1) Substrate resin

發泡成形體係由含有共聚物A及B之基材樹脂所構成，相對於共聚物A與B之合計，含有1至50重量%之共聚物B。共聚物B的含量例如為1重量%、5重量%、10重量%、15重量%、20重量%、25重量%、30重量%、35重量%、40重量%、45重量%、50重量%。構成發泡成形體之基材樹脂係與上述發泡粒子之基材樹脂相同。 The foam molding system is composed of a base resin containing copolymers A and B, and contains 1 to 50% by weight of copolymer B relative to the total of copolymers A and B. The content of the copolymer B is, for example, 1% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, or 50% by weight. . The base resin constituting the foamed molded body is the same as the base resin of the foamed particles.

(2)物性 (2) Physical properties

構成發泡成形體之經熔合的發泡粒子的平均粒徑較佳係600至6000μm，更佳係1200至3600μm。平均粒徑例如 為600μm、1200μm、2000μm、3000μm、3600μm、6000μm。 The average particle diameter of the fused expanded particles constituting the expanded molded article is preferably 600 to 6000 μm, and more preferably 1200 to 3600 μm. Average particle size e.g. It is 600 μm, 1200 μm, 2000 μm, 3000 μm, 3600 μm, and 6000 μm.

就經熔合的發泡粒子之外形而言，只要可維持發泡成形體則無特別限定。 The outer shape of the fused foamed particles is not particularly limited as long as the foamed molded body can be maintained.

發泡成形體較佳係具有20至1.4倍之倍數。倍數大於20倍時，會有機械物性不充分之情形。小於1.4倍時，重量會增加，故會有發泡的優點變小之情形。容積倍數例如為20倍、18倍、14倍、12.5倍、10倍、5倍、2倍、1.6倍、1.4倍。倍數更佳係14至1.6倍，特佳係12.5至2倍。 The foamed molded body preferably has a multiple of 20 to 1.4 times. When the multiple is more than 20 times, mechanical properties may be insufficient. If it is less than 1.4 times, the weight will increase, so the advantage of foaming may become small. The volume multiple is, for example, 20 times, 18 times, 14 times, 12.5 times, 10 times, 5 times, 2 times, 1.6 times, and 1.4 times. The better multiple is 14 to 1.6 times, and the better multiple is 12.5 to 2 times.

發泡成形體較佳係顯示40%以下之連續氣泡率。連續氣泡率高於40%時，會有纖維強化複合體的機械物性降低之情形。連續氣泡率例如為40%、35%、30%、20%、10%、5%、0%。連續氣泡率更佳係35%以下。 The foamed molded product preferably has a continuous cell ratio of 40% or less. When the continuous cell ratio is higher than 40%, the mechanical properties of the fiber-reinforced composite may decrease. The continuous cell ratio is, for example, 40%, 35%, 30%, 20%, 10%, 5%, and 0%. The continuous bubble ratio is more preferably 35% or less.

發泡成形體在120℃之加熱尺寸變化率較佳係-1至1%。發泡成形體藉由使其加熱尺寸變化率為-1至1%，也可適合使用於在高溫環境下之用途。加熱尺寸變化率例如為-1%、-0.07%、-0.05%、0%、0.05%、0.07%、1%。 The heating dimensional change rate of the foamed molded body at 120 ° C is preferably -1 to 1%. The foamed molded body can also be suitably used in applications in a high-temperature environment by making the heating dimensional change rate -1 to 1%. The heating dimensional change rate is, for example, -1%, -0.07%, -0.05%, 0%, 0.05%, 0.07%, or 1%.

發泡成形體的每單位密度之彎曲彈性模數較佳係600MPa/(g/cm3)以上。彎曲彈性模數過小時，會有發泡成形體因為在發泡成形體的表面積層如纖維強化塑膠等表皮材並一體化時所施加的壓力而變形之情形。彎曲彈性模數例如為600、800、1000、1200、1400(省略單位)。 The flexural modulus of elasticity per unit density of the foamed molded product is preferably 600 MPa / (g / cm 3 ) or more. When the bending elastic modulus is too small, the foamed molded body may be deformed due to the pressure applied when the surface area layer of the foamed molded body such as fiber-reinforced plastic is integrated. The bending elastic modulus is, for example, 600, 800, 1000, 1200, or 1400 (units are omitted).

(3)製造方法 (3) Manufacturing method

發泡成形體之製造方法可列舉：將發泡粒子填充於模 具的模槽(cavity)內，並將加熱介質供給至模槽內，將發泡粒子加熱並使其再發泡，並使經再發泡之發泡粒子彼此因該等之發泡壓力而互相熱熔合一體化，藉此得到發泡成形體之方法。加熱介質可列舉例如：水蒸氣、熱風、溫水等，較佳係水蒸氣。 Examples of the method for producing a foamed molded article include: filling a mold with foamed particles In the mold cavity (cavity), the heating medium is supplied into the mold cavity, the foamed particles are heated and refoamed, and the refoamed foamed particles are caused by the foaming pressure of each other. A method for obtaining a foamed molded body by thermal fusion bonding with each other. Examples of the heating medium include water vapor, hot air, and warm water. Water vapor is preferred.

(纖維強化複合體) (Fiber-reinforced composite)

纖維強化複合體係具有發泡成形體、及積層在該發泡成形體的表面並一體化之纖維強化塑膠層。發泡成形體係由含有共聚物A及B之基材樹脂所構成，相對於共聚物A與B之合計，含有1至50重量%之共聚物B。構成發泡成形體之基材樹脂係與上述發泡粒子之基材樹脂相同。 The fiber-reinforced composite system includes a foamed molded body and a fiber-reinforced plastic layer laminated on the surface of the foamed molded body and integrated. The foam molding system is composed of a base resin containing copolymers A and B, and contains 1 to 50% by weight of copolymer B relative to the total of copolymers A and B. The base resin constituting the foamed molded body is the same as the base resin of the foamed particles.

發泡成形體為發泡片時，無須在發泡成形體的兩面積層纖維強化塑膠並一體化，而只要在發泡成形體的兩面中之至少一面積層纖維強化塑膠並一體化即可。纖維強化塑膠的積層係因應強化複合體的用途來決定即可。其中，若考量到強化複合體的表面硬度、機械強度，較佳係在發泡成形體之在厚度方向之兩面分別積層纖維強化塑膠並一體化。 When the foamed molded body is a foamed sheet, it is not necessary to integrate and integrate fiber-reinforced plastic on two areas of the foamed molded body, but only to integrate and integrate fiber-reinforced plastic on at least one area of both sides of the foamed molded body. The lamination of the fiber-reinforced plastic may be determined according to the use of the reinforcing composite. Among them, if the surface hardness and mechanical strength of the reinforced composite are taken into consideration, it is preferable that the fiber reinforced plastic is laminated and integrated on both sides in the thickness direction of the foamed molded body.

構成纖維強化塑膠之強化纖維可列舉：玻璃纖維、碳纖維、碳化矽纖維、氧化鋁纖維、契拉諾(音譯；Tyranno)纖維、玄武岩纖維、陶瓷纖維等無機纖維；不鏽鋼纖維、鋼纖維等金屬纖維；芳綸(aramid)纖維、聚乙烯纖維、聚對伸苯基苯并唑(PBO)纖維等有機纖維；硼纖維。強化纖維可單獨使用一種或併用二種以上。其中，較 佳係碳纖維、玻璃纖維及芳綸纖維，更佳係碳纖維。該等強化纖維即使為輕量，仍然具有優異的機械物性。 The reinforcing fibers constituting the fiber-reinforced plastic include glass fibers, carbon fibers, silicon carbide fibers, alumina fibers, Tyranno fibers, basalt fibers, ceramic fibers, and other inorganic fibers; stainless steel fibers, and metal fibers such as steel fibers ; Aramid fiber, polyethylene fiber, polyparaphenylene benzo Organic fibers such as azole (PBO) fibers; boron fibers. The reinforcing fibers may be used singly or in combination of two or more kinds. Among them, preferred are carbon fibers, glass fibers, and aramid fibers, and more preferred are carbon fibers. Even if these reinforcing fibers are lightweight, they have excellent mechanical properties.

強化纖維較佳係使用來作為已加工成為所期望的形狀之強化纖維基材。強化纖維基材可列舉：使用強化纖維而成之梭織物、針織物、不織布、及將使強化纖維在一方向併線所成之纖維束(股)以紗綑紮(縫合)而成之面料等。梭織物的織法可列舉：平紋梭織(plain woven)、斜紋梭織(twill woven)、緞紋梭織(satin woven)等。又，紗可列舉聚醯胺樹脂紗、聚酯樹脂紗等合成樹脂紗及如玻璃纖維紗等縫合紗。 The reinforcing fiber is preferably used as a reinforcing fiber substrate processed into a desired shape. Examples of the reinforcing fiber base material include woven fabrics, knitted fabrics, and non-woven fabrics made of reinforcing fibers, and fabrics made by bundling (stitching) fiber bundles (strands) formed by reinforcing fibers in one direction. . Examples of the weaving method of the woven fabric include plain woven, twill woven, and satin woven. Examples of the yarn include synthetic resin yarns such as polyamide resin yarns and polyester resin yarns, and stitching yarns such as glass fiber yarns.

強化纖維基材可使用未積層的僅一片之強化纖維基材，也可使用將複數片強化纖維基材積層所成之積層強化纖維基材。將複數片強化纖維基材積層而成之積層強化纖維基材可使用：(1)準備複數片單一種的強化纖維基材，並將該等強化纖維基材積層而成之積層強化纖維基材；(2)準備複數種強化纖維基材，並將該等強化纖維基材積層而成之積層強化纖維基材；以及(3)準備複數片將使強化纖維在一方向併線所成之纖維束(股)以紗綑紮(縫合)而成之強化纖維基材，將該等強化纖維基材以使纖維束的纖維方向互相朝向不同方向之方式予以重疊，並將重疊的強化纖維基材彼此以紗一體化(縫合)而成之積層強化纖維基材等。 As the reinforcing fiber substrate, only one unreinforced reinforcing fiber substrate may be used, or a laminated reinforcing fiber substrate formed by laminating a plurality of reinforcing fiber substrates may be used. A laminated reinforcing fiber substrate obtained by laminating a plurality of reinforcing fiber substrates can be used: (1) a laminated reinforcing fiber substrate prepared by laminating a plurality of single types of reinforcing fiber substrates and laminating these reinforcing fiber substrates; (2) a laminated reinforcing fiber substrate prepared by preparing a plurality of types of reinforcing fiber substrates and laminating the reinforcing fiber substrates; and (3) preparing a plurality of fibers formed by aligning reinforcing fibers in one direction Bundles (strands) are reinforced fiber substrates formed by bundling (stitching) yarns, and the reinforcing fiber substrates are superimposed so that the fiber directions of the fiber bundles face each other in different directions, and the overlapping reinforcing fiber substrates are overlapped with each other Laminated reinforced fiber base material formed by yarn integration (sewing).

纖維強化塑膠係使強化纖維含浸合成樹脂而成者。其係藉由所含浸的合成樹脂而使強化纖維彼此黏結一體化。 Fiber-reinforced plastics are made by impregnating synthetic fibers with synthetic resin. It is based on the impregnated synthetic resin to bond and reinforce the reinforcing fibers to each other.

使強化纖維含浸合成樹脂之方法並無特別限定，可列舉例如：(1)將強化纖維浸漬於合成樹脂中之方法、(2)將合成樹脂塗佈於強化纖維之方法等。 The method of impregnating the reinforcing fiber with the synthetic resin is not particularly limited, and examples thereof include (1) a method of immersing the reinforcing fiber in the synthetic resin, (2) a method of applying the synthetic resin to the reinforcing fiber, and the like.

就使強化纖維含浸之合成樹脂而言，可使用熱塑性樹脂或熱硬化性樹脂中之任一者，較佳係使用熱硬化性樹脂。使強化纖維含浸之熱硬化性樹脂並無特別限定，可列舉：環氧樹脂、不飽和聚酯樹脂、酚樹脂、三聚氰胺樹脂、聚胺酯(polyurethane)樹脂、矽氧樹脂、順丁烯二醯亞胺樹脂、乙烯基酯樹脂、氰酸酯樹脂、將順丁烯二醯亞胺樹脂與氰酸酯樹脂預聚合而成之樹脂等，就耐熱性、衝擊吸收性或耐藥品性優異而言，較佳係環氧樹脂、乙烯基酯樹脂。熱硬化性樹脂可含有硬化劑、硬化促進劑等添加劑。再者，熱硬化性樹脂可單獨使用或併用二種以上。 As the synthetic resin impregnated with the reinforcing fibers, any of a thermoplastic resin and a thermosetting resin can be used, and a thermosetting resin is preferably used. The thermosetting resin impregnated with the reinforcing fiber is not particularly limited, and examples thereof include epoxy resin, unsaturated polyester resin, phenol resin, melamine resin, polyurethane resin, silicone resin, and maleimide Resins, vinyl ester resins, cyanate resins, and resins obtained by pre-polymerizing a maleimide resin and a cyanate resin, etc., are superior in heat resistance, shock absorption, and chemical resistance. Best epoxy resin, vinyl ester resin. The thermosetting resin may contain additives such as a hardener and a hardening accelerator. The thermosetting resin may be used alone or in combination of two or more.

又，使強化纖維含浸之熱塑性樹脂並無特別限定，可列舉：烯烴系樹脂、聚酯系樹脂、熱塑性環氧樹脂、醯胺系樹脂、熱塑性聚胺酯樹脂、硫醚系樹脂、丙烯酸系樹脂等，就與發泡成形體的接著性或構成纖維強化塑膠之強化纖維彼此的接著性優異而言，較佳係聚酯系樹脂、熱塑性環氧樹脂。再者，熱塑性樹脂可單獨使用或併用二種以上。 The thermoplastic resin impregnated with the reinforcing fibers is not particularly limited, and examples thereof include olefin resins, polyester resins, thermoplastic epoxy resins, ammonium resins, thermoplastic polyurethane resins, thioether resins, and acrylic resins. A polyester resin and a thermoplastic epoxy resin are preferred because they have excellent adhesion to the foamed molded article or the adhesion between the reinforcing fibers constituting the fiber-reinforced plastic. The thermoplastic resin may be used alone or in combination of two or more.

熱塑性環氧樹脂可列舉：屬於環氧化合物彼此的聚合物或共聚物且具有直鏈結構之聚合物、或屬於環氧化合物與能夠與該環氧化合物聚合的單體之共聚物且具有直鏈結構之共聚物。具體而言，熱塑性環氧樹脂可列舉例如：雙 酚A型環氧樹脂、雙酚茀型環氧樹脂、甲酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、環狀脂肪族型環氧樹脂、長鏈脂肪族型環氧樹脂、環氧丙基酯型環氧樹脂、環氧丙基胺型環氧樹脂等，較佳係雙酚A型環氧樹脂、雙酚茀型環氧樹脂。再者，熱塑性環氧樹脂可單獨使用或併用二種以上。 Examples of the thermoplastic epoxy resin include a polymer having a linear structure, which is a polymer or copolymer of epoxy compounds, or a copolymer having an epoxy compound and a monomer capable of polymerizing with the epoxy compound, and has a linear chain. Copolymer of structure. Specific examples of the thermoplastic epoxy resin include: Phenol A epoxy resin, bisphenol fluorene epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, cyclic aliphatic epoxy resin, long chain aliphatic epoxy resin, Epoxypropyl ester epoxy resin, epoxypropylamine epoxy resin and the like are preferably bisphenol A epoxy resin and bisphenol amidine epoxy resin. The thermoplastic epoxy resin may be used alone or in combination of two or more.

熱塑性聚胺酯樹脂可列舉使二醇與二異氰酸酯聚合而得之具有直鏈結構之聚合物。二醇可列舉例如：乙二醇、二乙二醇、丙二醇、二丙二醇、1,3-丁烷二醇、1,4-丁烷二醇等。二醇可單獨使用或併用二種以上。二異氰酸酯可列舉例如：芳香族二異氰酸酯、脂肪族二異氰酸酯、脂環式二異氰酸酯。二異氰酸酯可單獨使用或併用二種以上。再者，熱塑性聚胺酯樹脂可單獨使用或併用二種以上。 Examples of the thermoplastic polyurethane resin include polymers having a linear structure obtained by polymerizing a diol and a diisocyanate. Examples of the diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, and 1,4-butanediol. The diol may be used alone or in combination of two or more. Examples of the diisocyanate include aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate. Diisocyanates can be used alone or in combination of two or more. The thermoplastic polyurethane resin may be used alone or in combination of two or more.

纖維強化塑膠中之合成樹脂的含量較佳係20至70重量%。含量未達20重量%時，強化纖維彼此的黏結性、纖維強化塑膠與發泡成形體的接著性變得不充分，會有無法充分地提升纖維強化塑膠的機械物性、纖維強化複合體的機械強度之情形。多於70重量%時，纖維強化塑膠的機械物性降低，會有無法充分地提升纖維強化複合體的機械強度之情形。含量更佳係30至60重量%。 The content of the synthetic resin in the fiber-reinforced plastic is preferably 20 to 70% by weight. When the content is less than 20% by weight, the adhesion of the reinforcing fibers to each other, the adhesion between the fiber-reinforced plastic and the foamed molded body become insufficient, and there is a possibility that the mechanical properties of the fiber-reinforced plastic and the fiber-reinforced composite cannot be sufficiently improved. Case of intensity. When it exceeds 70% by weight, the mechanical properties of the fiber-reinforced plastic are lowered, and the mechanical strength of the fiber-reinforced composite may not be sufficiently improved. The content is more preferably 30 to 60% by weight.

纖維強化塑膠的厚度較佳係0.02至2mm，更佳係0.05至1mm。厚度在此範圍內之纖維強化塑膠，即使為輕量，仍然有優異的機械物性。 The thickness of the fiber-reinforced plastic is preferably 0.02 to 2 mm, and more preferably 0.05 to 1 mm. Fiber-reinforced plastics with a thickness within this range have excellent mechanical properties even if they are lightweight.

纖維強化塑膠的單位面積重量較佳係50至4000g/m2，更佳係100至1000g/m2。單位面積重量在此範圍內之纖維強化塑膠，即使為輕量，仍然有優異的機械物性。 The weight per unit area of the fiber-reinforced plastic is preferably 50 to 4000 g / m 2 , and more preferably 100 to 1000 g / m 2 . Fiber-reinforced plastics having a weight per unit area within this range have excellent mechanical properties even if they are lightweight.

其次，說明強化複合體之製造方法。在發泡成形體的表面積層纖維強化塑膠並一體化而製造強化複合體之方法並無特別限定，可列舉例如：(1)在發泡成形體的表面經由接著劑而積層纖維強化塑膠並一體化之方法；(2)在發泡成形體的表面積層使強化纖維含浸熱塑性樹脂而成之纖維強化塑膠形成材，將強化纖維中所含浸之熱塑性樹脂作為黏合劑，將纖維強化塑膠形成材作為纖維強化塑膠積層在發泡成形體的表面並一體化之方法；(3)在發泡成形體的表面積層使強化纖維含浸有未硬化熱硬化性樹脂而成之纖維強化塑膠形成材，將強化纖維中所含浸之熱硬化性樹脂作為黏合劑，將使熱硬化性樹脂硬化而形成之纖維強化塑膠積層在發泡成形體的表面並一體化之方法；(4)在發泡成形體的表面配設被加熱而呈軟化狀態的纖維強化塑膠，藉由使纖維強化塑膠壓附在發泡成形體的表面以視需要而使纖維強化塑膠沿著發泡成形體的表面變形同時在發泡成形體的表面積層並一體化之方法；以及(5)纖維強化塑膠的成形中一般應用之方法等。 Next, a method for manufacturing a reinforced composite will be described. The method of manufacturing a reinforced composite by integrating fiber-reinforced plastic on the surface area of the foamed molded product is not particularly limited, and examples include: (1) fiber-reinforced plastic is laminated and integrated on the surface of the foamed molded product through an adhesive; (2) A fiber-reinforced plastic forming material obtained by impregnating reinforcing fibers with a thermoplastic resin on a surface area layer of a foamed molded body, using the thermoplastic resin impregnated in the reinforcing fibers as a binder, and using the fiber-reinforced plastic forming material as a binder A method of integrating fiber-reinforced plastic on the surface of a foamed molded body and integrating it; (3) A fiber-reinforced plastic forming material in which a reinforcing fiber is impregnated with an unhardened thermosetting resin on a surface area layer of the foamed molded body to strengthen A method in which a fiber-reinforced plastic laminate formed by hardening a thermosetting resin as an adhesive is used as an adhesive on the surface of a foamed molded body; (4) on the surface of a foamed molded body A fiber-reinforced plastic that is heated and softened is arranged, and the fiber is reinforced by pressing the fiber-reinforced plastic on the surface of the foamed molded body as required. Plastic molded foam along the surface modification simultaneously molded foamed layer and the surface area of the integrated process; and (5) a method of molding in general use fiber-reinforced plastic.

就可用於纖維強化塑膠的成形之方法而言，可列舉例如：高壓釜法、手積層法(hand lay-up method)、噴佈法(spray up method)、PCM(預浸料模壓成型，Prepreg Compression Molding)法、RTM(樹脂轉注成 形，Resin Transfer Molding)法、VaRTM(真空輔助樹脂轉注成形，Vacuum assisted Resin Transfer Molding)法等。 As for the method that can be used for the molding of fiber-reinforced plastic, for example, an autoclave method, a hand lay-up method, a spray up method, and PCM (prepreg compression molding, Prepreg) Compression Molding) method, RTM (resin transfer into Shape, Resin Transfer Molding) method, VaRTM (Vacuum assisted Resin Transfer Molding) method, etc.

如此所得之纖維強化複合體係耐熱性、機械強度及輕量性優異，且具有美觀性經提升之纖維強化面。因此，可用於汽車、航空器、鐵路列車、船舶等運輸機器領域、家電領域、情報終端領域、家具領域等廣範用途。在此，美觀性經提升之纖維強化面可藉由其表面平滑率來評估。表面平滑率較佳係10%以下。表面平滑率例如為0%、1%、3%、5%、7%、10%。 The fiber-reinforced composite system thus obtained is excellent in heat resistance, mechanical strength, and lightweight, and has a fiber-reinforced surface with improved aesthetics. Therefore, it can be used in a wide range of applications such as transportation equipment fields such as automobiles, aircrafts, railway trains, and ships, home appliances fields, information terminal fields, and furniture fields. Here, the fiber-reinforced surface with improved aesthetics can be evaluated by its surface smoothness. The surface smoothness is preferably 10% or less. The surface smoothing rate is, for example, 0%, 1%, 3%, 5%, 7%, or 10%.

例如，纖維強化複合體可適合用來作為包括運輸機器的構件及構成運輸機器的本體之構造構件之運輸機器構成用構件(尤其汽車用構件)、風車葉片、機械手臂、頭盔(helmet)用緩衝材、農產箱、保溫保冷容器等運輸容器、產業用直昇機的旋葉(rotor blade)、構件梱包材。 For example, the fiber-reinforced composite can be suitably used as a transport machine component (especially a car component), a windmill blade, a robot arm, and a helmet cushion including a transport machine component and a structural member constituting the body of the transport machine. Materials, agricultural containers, transport containers such as thermal insulation and cold storage containers, rotor blades for industrial helicopters, and component packaging materials.

依據本發明，可提供由本發明之纖維強化複合體所構成之汽車用構件，該汽車用構件可列舉例如：地板(floor panel)、車頂(roof)、引擎罩蓋(hood)、擋泥板(fender)、下護蓋(undercover)、輪圈(wheel)、方向盤(steering wheel)、外殼(container)(殼體)、蓋板(hood panel)、懸吊臂(suspension arm)、保險桿(bumper)、遮陽板(sun visor)、後車箱蓋(trunk lid)、行李箱(luggage box)、座椅、車門、整流罩(cowl)等構件。 According to the present invention, it is possible to provide an automobile component composed of the fiber-reinforced composite of the present invention. Examples of the automobile component include a floor panel, a roof, a hood, and a fender. (fender), undercover, wheel, steering wheel, container (housing), hood panel, suspension arm, bumper ( components such as bumpers, sun visors, trunk lids, luggage boxes, seats, doors, cowls, etc.

[實施例] [Example]

以下雖係列舉實施例來更詳細說明本發 明，但不受限於本實施例。首先，說明實施例及比較例之評估方法。 The following series of examples illustrate the present invention in more detail. It is not limited to this embodiment. First, the evaluation methods of Examples and Comparative Examples will be described.

(玻璃轉移溫度) (Glass transition temperature)

玻璃轉移溫度係由JIS K7121：1987「塑膠的轉移溫度測定方法」所記載之方法測定。但是，關於採樣方法/溫度條件係如以下方式進行。 The glass transition temperature is measured by the method described in JIS K7121: 1987 "Method for Measuring the Transition Temperature of Plastics". However, the sampling method and temperature conditions are performed as follows.

使用示差掃描熱量計裝置DSC6220型(SII NanoTechnology公司製)，在鋁製測定容器的底部以無縫隙之方式填充約6mg之試料。將試料在氮氣流量20mL/分鐘下以20℃/分鐘之昇溫速度從30℃昇溫到220℃。保持10分鐘後迅速地取出試料，在25±10℃之環境下放冷後，由以20℃/分鐘之昇溫速度從30℃昇溫到220℃時所得之DSC曲線計算出玻璃轉移溫度(起始點)。此時係使用氧化鋁作為基準物質。此玻璃轉移起始溫度係依規準(9.3「玻璃轉移溫度的求法」)來求取。 A differential scanning calorimeter device DSC6220 (manufactured by SII NanoTechnology Co., Ltd.) was used to fill a gap of approximately 6 mg of a sample in a seamless manner at the bottom of an aluminum measurement container. The sample was heated from 30 ° C to 220 ° C at a temperature increase rate of 20 ° C / minute under a nitrogen flow rate of 20mL / minute. After holding for 10 minutes, the sample was quickly taken out, and after being left to cool in an environment of 25 ± 10 ° C, the glass transition temperature (starting point) was calculated from the DSC curve obtained when the temperature was raised from 30 ° C to 220 ° C at a heating rate of 20 ° C / minute. ). In this case, alumina was used as a reference substance. This glass transition initiation temperature is determined in accordance with the standard (9.3 "How to Determine the Glass Transition Temperature").

(容積密度及容積倍數) (Bulk density and volume multiple)

容積密度係依據JIS K6911：1995年「熱硬化性塑膠一般試驗方法」而測定。亦即，使用依據JIS K6911之表觀密度測定器來測定，並基於下述式來測定容積密度。 Bulk density is measured in accordance with JIS K6911: 1995 "General Test Method for Thermosetting Plastics". That is, it measured using the apparent density measuring device based on JIS K6911, and measured the bulk density based on the following formula.

發泡粒子的容積密度(g/cm3)=[放入有試料之量筒的重量(g)-量筒的重量(g)]/[量筒的容量(cm3)] Bulk density of foamed particles (g / cm 3 ) = [Weight of a graduated cylinder (g)-Weight of a graduated cylinder (g)] / [Capacity of a graduated cylinder (cm 3 )]

容積倍數係將容積密度的倒數乘以樹脂的密度而得之值。 The volume multiple is a value obtained by multiplying the inverse of the bulk density by the density of the resin.

(密度及倍數) (Density and multiples)

以使有效數字成為3位以上之方式分別測定從發泡成形體裁切出之試驗片(例如75×300×30mm)的重量(a)與體積(b)，由式(a)/(b)求取發泡成形體的密度(g/cm3)。 The weight (a) and the volume (b) of a test piece (for example, 75 × 300 × 30mm) cut out from the foamed molded body are measured so that the effective number becomes three or more. The density (g / cm 3 ) of the foamed molded body was determined.

倍數係將密度的倒數乘以樹脂的密度而得之值。 The multiple is a value obtained by multiplying the inverse of the density by the density of the resin.

(FT-IR) (FT-IR)

依下述要領來測定基材樹脂的吸光度比(D1780/D698、D1720/D698)。 The absorbance ratio (D1780 / D698, D1720 / D698) of the base resin was measured in the following manner.

針對隨機選擇的10個各樹脂粒子，藉由紅外線分光分析ATR測定法進行表面分析而得到紅外線吸收光譜。在此分析中，得到從試料表面算起至數μm(約2μm)為止的深度之範圍之紅外線吸收光譜。由各紅外線吸收光譜計算出吸光度比(D1780/D698、D1720/D698)，將所算出的吸光度比之算術平均作為吸光度比。 For 10 randomly selected resin particles, surface analysis was performed by an infrared spectroscopic analysis ATR measurement method to obtain an infrared absorption spectrum. In this analysis, an infrared absorption spectrum was obtained in a range from the sample surface to a depth of several μm (about 2 μm). The absorbance ratios (D1780 / D698, D1720 / D698) were calculated from each infrared absorption spectrum, and the arithmetic mean of the calculated absorbance ratios was taken as the absorbance ratio.

關於吸光度D1780、D1720及D698，係將Thermo SCIENTIFIC公司製「Smart-iTR」作為ATR附件而連接到Thermo SCIENTIFIC公司以商品名「傅立葉轉換紅外線分光光度計Nicolet iS10」販售之測定裝置並進行測定。以下述條件進行紅外線分光分析ATR測定。 The absorbances D1780, D1720, and D698 were measured using a "Smart-iTR" manufactured by Thermo SCIENTIFIC Corporation as an ATR accessory and connected to a measurement device sold under the trade name "Fourier Transform Infrared Spectrophotometer Nicolet iS10". An infrared spectroscopic analysis ATR measurement was performed under the following conditions.

<測定條件> <Measurement conditions>

˙測定裝置：傅立葉轉換紅外線分光光度計Nicolet iS10(Thermo SCIENTIFIC公司製)及單次反射型水平狀ATR Smart-iTR(Thermo SCIENTIFIC公司製) ˙Measuring device: Fourier transform infrared spectrophotometer Nicolet iS10 (manufactured by Thermo SCIENTIFIC) and single reflection horizontal ATR Smart-iTR (manufactured by Thermo SCIENTIFIC)

˙ATR晶體：Diamond with ZnSe lens，角度=42° ˙ATR crystal: Diamond with ZnSe lens, angle = 42 °

˙測定法：單次ATR法 ˙Determination method: single ATR method

˙測定波數區域：4000cm-1至650cm-1 ˙Measured wave number area: 4000cm -1 to 650cm -1

˙測定深度之波數相依性：未修正 ˙Wave number dependence of measured depth: uncorrected

˙檢測器：氘化硫酸三甘胺酸(DTGS)檢測器及KBr分光器(KBr beamsplitter) Tritium Detectors: Deuterated Triglycine Sulfate (DTGS) Detector and KBr Beamsplitter

˙解析能力：4cm-1 ˙Analysis ability: 4cm -1

˙累計次數：16次(背景測定時亦相同) ˙ Cumulative number of times: 16 times (the same applies to background measurement)

ATR法中，由於測定所得之紅外線吸收光譜的強度會因為試料與高折射率結晶的密著程度而有所改變，故係施加由ATR附件之「Smart-iTR」所能施加之最大荷重而使密著程度幾乎均勻並進行測定。 In the ATR method, the intensity of the infrared absorption spectrum obtained by the measurement will change due to the closeness of the sample to the high refractive index crystal. Therefore, the maximum load that can be applied by the "Smart-iTR" attached to the ATR is applied. The degree of adhesion was almost uniform and was measured.

以上述條件所得之紅外線吸收光譜係如以下方式進行譜峰處理，而求取各自的D1780、D1720及D698。 The infrared absorption spectrum obtained under the above conditions is subjected to peak processing in the following manner, and the respective D1780, D1720, and D698 are obtained.

由紅外線吸收光譜所得之在1780cm-1之吸光度D1780係作為對應於源自順丁烯二酸酐中之2個羰基的C=O所致之反對稱伸縮振動(antisymmetric stretching vibration)的吸收光譜之吸光度。 The absorbance at 1780 cm -1 obtained from the infrared absorption spectrum D1780 is the absorbance of the absorption spectrum corresponding to the antisymmetric stretching vibration caused by C = O derived from two carbonyl groups in maleic anhydride. .

在此吸光度的測定中，即使在1780cm-1有其他吸收光譜重疊時仍不實施譜峰分離。吸光度D1780係意指將連結1920cm-1與1620cm-1的直線作為基線之在1810cm-1與1745cm-1之間的最大吸光度。 In this absorbance measurement, even when other absorption spectra overlap at 1780 cm -1 , peak separation is not performed. It is intended to refer to link absorbance D1780 1920cm maximum absorbance between 1810 cm -1 and 1745 cm -1 and 1620 cm -1 in a straight line as a baseline of -1.

又，在1720cm-1之吸光度D1720係作為對應於源自甲基丙烯酸甲酯中所含之羰基C=O所致之反對稱伸縮振動的吸收光譜之吸光度。 In addition, the absorbance D1720 at 1720 cm -1 is the absorbance corresponding to the absorption spectrum derived from the antisymmetric stretching vibration caused by the carbonyl group C = O contained in methyl methacrylate.

在此吸光度的測定中，即使在1720cm-1有其他吸收光譜重疊時仍不實施譜峰分離。吸光度D1720係意指將連結1920cm-1與1620cm-1的直線作為基線之在1745cm-1與1690cm-1之間的最大吸光度。 In this absorbance measurement, even when other absorption spectra overlap at 1720 cm -1 , peak separation is not performed. D1720 is intended to refer to link absorbance maximum absorbance at 1920cm -1 and 1690cm between 1745 cm -1 and 1620 cm -1 in a straight line as a baseline of -1.

在698cm-1之吸光度D698係作為對應於源自苯乙烯中之1取代苯環中之C-H的面外彎曲振動的吸收光譜之吸光度。 The absorbance D698 at 698 cm -1 is the absorbance corresponding to the absorption spectrum derived from out-of-plane bending vibration of CH in the 1-substituted benzene ring in styrene.

在此吸光度的測定中，即使在698cm-1有其他吸收光譜重疊時仍不實施譜峰分離。吸光度D698係意指將連結1510cm-1與810cm-1的直線作為基線之在720cm-1與660cm-1之間的最大吸光度。 In this absorbance measurement, even when other absorption spectra overlap at 698 cm -1 , peak separation is not performed. Absorbance D698 is intended to refer to link 1510cm maximum absorbance between 660 cm -1 and 720cm -1 and 810 cm -1 in a straight line as a baseline of -1.

基於後述檢量線，由吸光度比(D1780/D698、D1720/D698)計算出苯乙烯、甲基丙烯酸甲酯、順丁烯二酸酐比率(質量%)。再者，譜峰處理方法係使用與前述樹脂粒子相同的方法。 Based on the calibration curve described later, the ratio (mass%) of styrene, methyl methacrylate, and maleic anhydride was calculated from the absorbance ratios (D1780 / D698, D1720 / D698). The peak processing method is the same as that of the resin particles.

就由吸光度比求取苯乙烯與甲基丙烯酸甲酯之組成比率之方法而言，係製作將苯乙烯樹脂與甲基丙烯酸甲酯樹脂均勻地混合為既定組成比率而成之複數種標準試料。 The method for determining the composition ratio of styrene and methyl methacrylate from the absorbance ratio is to prepare a plurality of standard samples in which a styrene resin and a methyl methacrylate resin are uniformly mixed into a predetermined composition ratio.

具體而言，將分別以0/100、20/80、40/60、50/50及60/40之重量比稱量的甲基丙烯酸甲酯與苯乙烯而得之單體放入10ml之旋蓋瓶中，於其中添加相對於單體100重量份為10重量份之2,2’-偶氮雙(2,4-二甲基戊腈)並使單體溶解。將所得之混合液移入2ml試料管( 7mm×122mm×190mm)中，進行氮氣沖洗後封管。其次，將其放入已設定 為65℃之水浴中，加熱10小時而使聚合完成，將從安瓿取出的聚合物作為標準試料。 Specifically, a monomer obtained by weighing methyl methacrylate and styrene in a weight ratio of 0/100, 20/80, 40/60, 50/50, and 60/40, respectively, was put into a 10 ml spin. In a capped bottle, 2,2'-azobis (2,4-dimethylvaleronitrile) was added thereto in an amount of 10 parts by weight based on 100 parts by weight of the monomer, and the monomer was dissolved. Transfer the resulting mixture to a 2 ml sample tube ( 7mm × 122mm × 190mm), the tube was sealed after nitrogen flushing. Next, this was placed in a water bath set at 65 ° C. and heated for 10 hours to complete the polymerization. The polymer taken out from the ampoule was used as a standard sample.

針對各標準試料藉由紅外線分光分析ATR法而得到紅外線吸收光譜後，計算出吸光度比(D1780/D698)。然後，以縱軸為組成比率(標準試料中之苯乙烯樹脂比率=質量%)並以橫軸為吸光度比(D1780/D698)而繪製檢量線。基於該檢量線來求取苯乙烯樹脂與甲基丙烯酸甲酯樹脂之組成比率。 For each standard sample, an infrared absorption spectrum was obtained by an infrared spectroscopic analysis ATR method, and an absorbance ratio (D1780 / D698) was calculated. Then, the calibration line was drawn with the vertical axis as the composition ratio (the styrene resin ratio in the standard sample = mass%) and the horizontal axis as the absorbance ratio (D1780 / D698). Based on this calibration curve, the composition ratio of the styrene resin and the methyl methacrylate resin was obtained.

又，使用苯乙烯與順丁烯二酸酐之1/1共聚物(商品名SMA1000(P)CRAY VALLEY公司製)及苯乙烯與順丁烯二酸酐之3/1共聚物(SMA3000(P)CRAY VALLEY公司製)作為苯乙烯樹脂與順丁烯二酸酐樹脂之標準試料。 A 1/1 copolymer of styrene and maleic anhydride (trade name SMA1000 (P) CRAY VALLEY) and a 3/1 copolymer of styrene and maleic anhydride (SMA3000 (P) CRAY) were used. (Made by Valley Co., Ltd.) as standard samples for styrene resin and maleic anhydride resin.

針對各標準試料藉由紅外線分光分析ATR法而得到紅外線吸收光譜後，計算出吸光度比(D1720/D698)。然後，以縱軸為組成比率(標準試料中之苯乙烯樹脂比率=質量%)並以橫軸為吸光度比(D1720/D698)而繪製檢量線。基於該檢量線來求取苯乙烯樹脂與順丁烯二酸酐樹脂之組成比率。 For each standard sample, an infrared absorption spectrum was obtained by an infrared spectroscopic analysis ATR method, and an absorbance ratio (D1720 / D698) was calculated. Then, the calibration line was drawn with the vertical axis as the composition ratio (the styrene resin ratio in the standard sample = mass%) and the horizontal axis as the absorbance ratio (D1720 / D698). Based on the calibration curve, the composition ratio of the styrene resin and the maleic anhydride resin was determined.

由檢量線求取苯乙烯與甲基丙烯酸甲酯及苯乙烯與順丁烯二酸酐之組成比率。依下述順序由各自之組成比率求取樹脂中之苯乙烯、甲基丙烯酸甲酯、順丁烯二酸酐之三成分的組成比率。 The composition ratios of styrene and methyl methacrylate and styrene and maleic anhydride were obtained from the calibration curve. The composition ratio of the three components of styrene, methyl methacrylate, and maleic anhydride in the resin was determined from the respective composition ratios in the following order.

在此，將各標準試料的比率設定如下。 Here, the ratio of each standard sample is set as follows.

甲基丙烯酸甲酯：苯乙烯=A：B [1] Methyl methacrylate: styrene = A: B [1]

苯乙烯：順丁烯二酸酐=C：D [2] Styrene: maleic anhydride = C: D [2]

因苯乙烯為共通項目，故將[2]之苯乙烯比率C與[1]之苯乙烯比率B合併。 Since styrene is a common item, the styrene ratio C of [2] and the styrene ratio B of [1] are combined.

由[2]推導 Derived from [2]

苯乙烯：順丁烯二酸酐 =C：D =C×(B/C)：D×(B/C) =B：D×(B/C) [3] Styrene: maleic anhydride = C: D = C × (B / C): D × (B / C) = B: D × (B / C) [3]

由[3]推導，因為苯乙烯的比率會與[1]相等，故由[1]、[3]推導甲基丙烯酸甲酯、苯乙烯、順丁烯二酸酐的存在比如下。 Derived from [3], because the ratio of styrene will be equal to [1], the existence of methyl methacrylate, styrene, and maleic anhydride is derived from [1] and [3] as follows.

甲基丙烯酸甲酯：苯乙烯：順丁烯二酸酐 =A：B：D×(B/C) [4] Methyl methacrylate: styrene: maleic anhydride = A: B: D × (B / C) [4]

由[4]的存在比，推導各成分的比率如下。 From the existence ratio of [4], the ratio of each component is derived as follows.

甲基丙烯酸甲酯={A/[A+B+D×(B/C)]}×100 Methyl methacrylate = {A / [A + B + D × (B / C)]} × 100

苯乙烯={B/[A+B+D×(B/C)]}×100 Styrene = {B / [A + B + D × (B / C)]} × 100

順丁烯二酸酐={D×(B/C)/[A+B+D×(B/C)]}×100 Maleic anhydride = (D × (B / C) / [A + B + D × (B / C)]) × 100

(纖維強化複合體的表面平滑率) (Surface smoothness of fiber-reinforced composite)

使用數位顯微鏡(KEYENCE公司製「VHX-1000」，透鏡：VH-Z 20R)拍攝纖維強化複合體的纖維強化面之20倍放大照片。將所得之放大照片印刷在A4尺寸的紙面。於所得之紙面選擇25cm×20cm之任意區域。在該任意區域中，以目視在未與平板模具接觸之區域及與平板模具接觸 之區域的境界描繪出線而得到描線圖。使用描線圖計算出全區域中的未接觸之區域所佔之比率。將該比率作為表面平滑率。表面平滑率小時，纖維強化塑膠形成材中之塑膠成分的脫落少，其結果係與平板模具接觸之區域多，判斷為纖維強化面之美觀性高。 A digital microscope ("VHX-1000" manufactured by KEYENCE Corporation, lens: VH-Z 20R) was used to take a 20-times magnified photo of the fiber-reinforced surface of the fiber-reinforced composite. The resulting enlarged photograph was printed on A4 size paper. An arbitrary area of 25 cm × 20 cm was selected on the obtained paper surface. In this arbitrary area, visually observe the area not in contact with the flat mold and the flat mold The realm of the area is drawn with a line to obtain a line drawing. Use the line chart to calculate the ratio of untouched areas in the entire area. This ratio is used as the surface smoothness. When the surface smoothness is small, the plastic components in the fiber-reinforced plastic forming material fall off, and as a result, there are more areas in contact with the flat mold, and it is judged that the fiber-reinforced surface has high aesthetics.

(實施例1) (Example 1)

(樹脂粒子製造步驟) (Resin particle manufacturing step)

將含有80重量份之苯乙烯-甲基丙烯酸甲酯-順丁烯二酸酐共聚物A(電氣化學工業公司製，商品名「DENKA RESISFY R-310」，苯乙烯：62重量份，甲基丙烯酸甲酯：12重量份，順丁烯二酸酐：26重量份，密度1.15g/cm3)及20重量份之苯乙烯-順丁烯二酸酐-N-苯基順丁烯二醯亞胺共聚物B(電氣化學工業公司製，商品名「DENKA IP MS-NIP」，苯乙烯：57重量份，順丁烯二酸酐：5重量份，N-苯基順丁烯二醯亞胺：38重量份，密度1.18g/cm3，玻璃轉移溫度Tg186℃)之樹脂組成物供給至口徑為30mm的二軸擠製機，並在260℃熔融混煉。繼而，從安裝在二軸擠製機的前端之多噴嘴模具[呈圓狀地配置有12個直徑1.0mm的噴嘴者]之各噴嘴擠出樹脂組成物。將所擠出的樹脂立即在冷卻水槽進行冷卻。然後，將經冷卻的股狀樹脂充分地除水之後，使用製粒機切斷成小粒狀而製造樹脂粒子。所得之樹脂粒子之粒子長度L為1.3至1.8mm，粒徑D為1.0至1.2mm。 Containing 80 parts by weight of styrene-methyl methacrylate-maleic anhydride copolymer A (manufactured by Denki Chemical Industries, trade name "DENKA RESISFY R-310", styrene: 62 parts by weight, methacrylic acid Methyl ester: 12 parts by weight, maleic anhydride: 26 parts by weight, density 1.15 g / cm 3 ) and 20 parts by weight of styrene-maleic anhydride-N-phenylmaleimide diimide copolymer Product B (manufactured by Denki Kogyo Co., Ltd. under the trade name "DENKA IP MS-NIP", styrene: 57 parts by weight, maleic anhydride: 5 parts by weight, N-phenyl maleimide diimide: 38 parts by weight Resin composition having a density of 1.18 g / cm 3 and a glass transition temperature Tg of 186 ° C.) was supplied to a biaxial extruder with a caliber of 30 mm, and melt-kneaded at 260 ° C. Then, the resin composition was extruded from each nozzle of a multi-nozzle die [one having 12 nozzles with a diameter of 1.0 mm arranged in a circle] attached to the front end of the biaxial extruder. The extruded resin was immediately cooled in a cooling water tank. Then, the cooled strand-shaped resin was sufficiently dewatered, and then cut into small pellets using a pelletizer to produce resin particles. The obtained resin particles had a particle length L of 1.3 to 1.8 mm and a particle diameter D of 1.0 to 1.2 mm.

(含浸步驟) (Impregnation step)

將上述樹脂粒子100重量份密閉於壓力容器中，將壓力容器內以二氧化碳氣體取代後，將二氧化碳氣體壓入直到含浸壓力0.5MPa為止。在20℃環境下靜置，經過含浸時間24小時後，花費5分鐘將壓力容器內徐緩地除壓。如此地使樹脂粒子含浸二氧化碳氣體而得到發泡性粒子。 100 parts by weight of the resin particles were sealed in a pressure vessel, and the inside of the pressure vessel was replaced with carbon dioxide gas, and then the carbon dioxide gas was pushed in until the impregnation pressure was 0.5 MPa. It was left to stand in a 20 ° C environment, and after 24 hours of impregnation time, it took 5 minutes to gradually depressurize the pressure vessel. In this manner, the resin particles are impregnated with carbon dioxide gas to obtain foamable particles.

(發泡步驟) (Foaming step)

在上述含浸步驟中之除壓後，立即從壓力容器取出發泡性粒子，之後添加碳酸鈣0.08重量份並混合。其後，使用水蒸氣以發泡溫度146℃攪拌150秒，同時在高壓發泡槽藉由水蒸氣使上述含浸物發泡。發泡後，從高壓發泡槽取出粒子，以氯化氫水溶液去除碳酸鈣之後，以氣流乾燥機進行乾燥，得到發泡粒子。發泡粒子的容積倍數為10倍。 Immediately after removing the pressure in the impregnation step, the foamable particles were taken out from the pressure vessel, and then 0.08 parts by weight of calcium carbonate was added and mixed. After that, the steam was stirred at a foaming temperature of 146 ° C. for 150 seconds using water vapor, and the impregnated matter was foamed with water vapor in a high-pressure foaming tank. After foaming, the particles were taken out from the high-pressure foaming tank, and calcium carbonate was removed with an aqueous hydrogen chloride solution, followed by drying with an air dryer to obtain foamed particles. The volume multiple of the expanded particles is 10 times.

(成形步驟) (Forming step)

將所得之發泡粒子在室溫(23℃)放置1天之後，密閉於壓力容器中。將壓力容器內以二氧化碳氣體取代之後，將二氧化碳氣體壓入直到含浸壓力(錶壓)0.4MPa為止。在20℃環境下靜置，實施加壓熟化8小時。取出後，填充於30mm×300mm×400mm之成形用模具，以0.45MPa的水蒸氣加熱60秒，然後，冷卻到發泡成形體的最高面壓力降低至0.01MPa為止，藉此得到厚度30mm×長300mm×寬400mm之發泡成形體。發泡成形體的倍數為10倍。 After the obtained foamed particles were left at room temperature (23 ° C) for one day, they were sealed in a pressure vessel. After replacing the inside of the pressure vessel with carbon dioxide gas, the carbon dioxide gas was pressurized until the impregnation pressure (gauge pressure) was 0.4 MPa. It was left to stand in a 20 ° C environment, and was subjected to pressure aging for 8 hours. After taking out, it was filled in a 30 mm × 300 mm × 400 mm forming mold, heated with 0.45 MPa of water vapor for 60 seconds, and then cooled until the maximum surface pressure of the foamed molded body was reduced to 0.01 MPa, thereby obtaining a thickness of 30 mm × long 300mm × 400mm wide foam molding. The multiple of the foamed molded product was 10 times.

(纖維強化步驟) (Fiber strengthening step)

準備4片纖維強化塑膠形成材(厚度0.23mm，單位面 積重量：200g/m2，三菱麗陽公司製之「Pyrofil Prepreg TR3523-395GMP」)，該纖維強化塑膠形成材係在由包含碳纖維之斜紋梭織之梭織物所成的強化纖維基材含浸40重量%之未硬化環氧樹脂(玻璃轉移溫度128℃)者。 Prepare 4 pieces of fiber-reinforced plastic forming material (0.23mm thickness, unit area weight: 200g / m 2 , “Pyrofil Prepreg TR3523-395GMP” manufactured by Mitsubishi Rayon Corporation). The fiber-reinforced plastic forming material is made of carbon fiber-based twill A reinforced fiber substrate made of a woven woven fabric is impregnated with 40% by weight of an unhardened epoxy resin (glass transition temperature: 128 ° C).

將2片纖維強化塑膠形成材以使強化纖維基材之經紗長度方向彼此的交差角度呈90°之方式重疊。然後，將2片纖維強化塑膠形成材重疊的部分裁切出長300mm×寬400mm之平面長方形狀，而製作積層纖維強化塑膠形成材。以同樣的要領製作另一片積層纖維強化塑膠形成材。 Two pieces of the fiber-reinforced plastic forming material are overlapped so that the intersection angle of the warp yarn length directions of the reinforcing fiber base material is 90 °. Then, the overlapping portion of the two fiber-reinforced plastic forming materials was cut into a flat rectangular shape having a length of 300 mm × width of 400 mm to produce a laminated fiber-reinforced plastic forming material. In the same way, another laminated fiber-reinforced plastic forming material was produced.

將積層纖維強化塑膠形成材分別積層於發泡成形體之在厚度方向直交的兩面，製作厚度約31mm之積層體。 The laminated fiber-reinforced plastic forming material was laminated on both sides of the foamed molded body orthogonal to each other in the thickness direction to produce a laminated body having a thickness of approximately 31 mm.

繼而，將上述積層體配設於平板模具間，將配置有厚度30mm的間隔件之平板模具合模，藉此壓製成形，使纖維強化塑膠熱接著於發泡成形體而製作纖維強化複合體。 Next, the laminated body is arranged between flat molds, and the flat mold with a spacer having a thickness of 30 mm is clamped, thereby press-molding, and the fiber-reinforced plastic is heated and then foamed to form a fiber-reinforced composite.

再者，壓製成形時，係以使積層體成為135℃之方式保持8分鐘，藉此使纖維強化樹塑膠所含有之樹脂硬化。藉由該硬化，以經硬化的環氧樹脂將纖維強化塑膠之纖維彼此黏結、固定，而將纖維強化塑膠積層在發泡成形體的兩面並一體化，製造纖維強化複合體。 In addition, during the press molding, the laminated body was kept at 135 ° C. for 8 minutes to harden the resin contained in the fiber-reinforced tree plastic. By this hardening, the fibers of the fiber-reinforced plastic are bonded and fixed to each other with a hardened epoxy resin, and the fiber-reinforced plastic is laminated and integrated on both sides of the foamed molded body to produce a fiber-reinforced composite.

將纖維強化複合體冷卻至30℃以下後，將平板模具打開並取出厚度30mm的纖維強化複合體。 After the fiber-reinforced composite was cooled to 30 ° C or lower, the flat mold was opened and the fiber-reinforced composite having a thickness of 30 mm was taken out.

(實施例2) (Example 2)

除了在樹脂粒子製造步驟中係將苯乙烯-甲基丙烯酸甲酯-順丁烯二酸酐共聚物A設為85重量份，並將苯乙烯 -順丁烯二酸酐-N-苯基順丁烯二醯亞胺共聚物B設為15重量份，以及在成形步驟中係以0.43MPa之水蒸氣加熱60秒以外，以與實施例1同樣的方式得到發泡粒子、發泡成形體、纖維強化複合體。 Except that the styrene-methyl methacrylate-maleic anhydride copolymer A was set to 85 parts by weight in the resin particle manufacturing step, and the styrene -Maleic anhydride-N-phenyl maleimide diimine copolymer B was set to 15 parts by weight, and was heated with 0.43 MPa of water vapor for 60 seconds in the forming step, and was the same as in Example 1. In this way, foamed particles, foamed molded bodies, and fiber-reinforced composites were obtained.

(實施例3) (Example 3)

除了在樹脂粒子製造步驟中係將苯乙烯-甲基丙烯酸甲酯-順丁烯二酸酐共聚物A設為90重量份，並將苯乙烯-順丁烯二酸酐-N-苯基順丁烯二醯亞胺共聚物B設為10重量份，在發泡步驟中係使用水蒸氣以發泡溫度143℃攪拌150秒，同時在高壓發泡槽使其發泡，以及在成形步驟中係以0.40MPa之水蒸氣加熱60秒以外，以與實施例1同樣的方式得到發泡粒子、發泡成形體、纖維強化複合體。 In the resin particle manufacturing step, the styrene-methyl methacrylate-maleic anhydride copolymer A was set to 90 parts by weight, and the styrene-maleic anhydride-N-phenylmaleic acid was used. The difluorene imine copolymer B was set to 10 parts by weight. In the foaming step, water vapor was used to stir at a foaming temperature of 143 ° C for 150 seconds. At the same time, it was foamed in a high-pressure foaming tank. Except that water vapor of 0.40 MPa was heated for 60 seconds, foamed particles, foamed molded bodies, and fiber-reinforced composites were obtained in the same manner as in Example 1.

(比較例1) (Comparative example 1)

除了在樹脂粒子製造步驟中係不使用苯乙烯-順丁烯二酸酐-N-苯基順丁烯二醯亞胺共聚物，在發泡步驟中係使用水蒸氣以發泡溫度142℃攪拌150秒，同時在高壓發泡槽使其發泡，以及在成形步驟中係以0.38MPa之水蒸氣加熱60秒以外，以與實施例1同樣的方式得到發泡粒子、發泡成形體、纖維強化複合體。 Except that the styrene-maleic anhydride-N-phenyl maleimide diimide copolymer was not used in the resin particle manufacturing step, the foaming step was performed by using water vapor at a foaming temperature of 142 ° C and stirring at 150 ° C. In the same manner as in Example 1, foamed particles, foamed molded bodies, and fiber reinforcement were obtained in the same manner as in Example 1 except that foaming was performed in a high-pressure foaming tank at the same time, and heating was performed with 0.38 MPa of water vapor for 60 seconds in the molding step Complex.

將實施例1至3及比較例1之基材樹脂的內容、發泡粒子的容積倍數、發泡成形體的倍數、纖維強化複合體的表面平滑率彙整並表示於表1。又，將實施例1至3及比較例1之纖維強化複合體的纖維強化面之照片及對應的描線圖表示於第1圖至第4圖。該等圖中，(a)為照 片，(b)為描線圖。 Table 1 shows the contents of the base resins of Examples 1 to 3 and Comparative Example 1, the volume multiples of the foamed particles, the multiples of the foamed molded body, and the surface smoothness of the fiber-reinforced composite. In addition, photographs and corresponding line drawings of the fiber-reinforced surfaces of the fiber-reinforced composites of Examples 1 to 3 and Comparative Example 1 are shown in FIGS. 1 to 4. In these figures, (a) is a photo (B) is a line drawing.

A：共聚物A A: Copolymer A

B：共聚物B B: copolymer B

ST：苯乙烯 ST: styrene

MAM：甲基丙烯酸甲酯 MAM: methyl methacrylate

MAH：順丁烯二酸酐 MAH: maleic anhydride

NPM：N-苯基順丁烯二醯亞胺 NPM: N-phenyl-cis-butene difluorene imine

從表1可知實施例1至3之發泡粒子可供給表面美觀性經提升之纖維強化複合體。又，從第1圖至 第4圖可確認實施例1至3之纖維強化複合體的表面為美觀。 It can be seen from Table 1 that the foamed particles of Examples 1 to 3 can provide a fiber-reinforced composite with improved surface aesthetics. From Figure 1 to Fig. 4 confirms that the surfaces of the fiber-reinforced composites of Examples 1 to 3 are beautiful.

Claims (9)

一種纖維強化複合體製造用之發泡粒子，係由含有芳香族乙烯-(甲基)丙烯酸酯-不飽和二羧酸共聚物A及芳香族乙烯-不飽和二羧酸-不飽和二羧酸醯亞胺共聚物B之基材樹脂所構成，其中，相對於前述共聚物A與B之合計，含有1至50重量%之前述共聚物B。A foamed particle for manufacturing a fiber-reinforced composite, comprising an aromatic ethylene- (meth) acrylate-unsaturated dicarboxylic acid copolymer A and an aromatic ethylene-unsaturated dicarboxylic acid-unsaturated dicarboxylic acid The fluorene imine copolymer B is composed of a base resin, and contains the copolymer B in an amount of 1 to 50% by weight based on the total of the copolymers A and B. 如申請專利範圍第1項所述之纖維強化複合體製造用之發泡粒子，其中，前述基材樹脂具有115至160℃之玻璃轉移溫度Tg。The foamed particles for manufacturing a fiber-reinforced composite body according to item 1 of the scope of the patent application, wherein the base resin has a glass transition temperature Tg of 115 to 160 ° C. 如申請專利範圍第1項所述之纖維強化複合體製造用之發泡粒子，其中，前述芳香族乙烯係選自苯乙烯、α-甲基苯乙烯、乙烯基甲苯、乙基苯乙烯、異丙基苯乙烯、第三丁基苯乙烯、二甲基苯乙烯、溴苯乙烯、氯苯乙烯、二乙烯基苯、三乙烯基苯、二乙烯基甲苯、二乙烯基二甲苯、雙(乙烯基苯基)甲烷、雙(乙烯基苯基)乙烷、雙(乙烯基苯基)丙烷、雙(乙烯基苯基)丁烷、二乙烯基萘、二乙烯基蒽、二乙烯基聯苯、雙酚A的環氧乙烷加成物二(甲基)丙烯酸酯及雙酚A的環氧丙烷加成物二(甲基)丙烯酸酯，前述(甲基)丙烯酸酯係選自(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯及(甲基)丙烯酸丁酯，前述不飽和二羧酸係選自順丁烯二酸、伊康酸、檸康酸、烏頭酸及該等的酸酐，前述不飽和二羧酸醯亞胺係選自順丁烯二醯亞胺、N-甲基順丁烯二醯亞胺、N-乙基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺及N-萘基順丁烯二醯亞胺。The foamed particles for producing a fiber-reinforced composite body according to item 1 of the scope of the patent application, wherein the aromatic vinyl is selected from styrene, α-methylstyrene, vinyl toluene, ethylstyrene, and isopropyl Propylstyrene, third butylstyrene, dimethylstyrene, bromostyrene, chlorostyrene, divinylbenzene, trivinylbenzene, divinyltoluene, divinylxylene, bis (ethylene Phenyl) methane, bis (vinylphenyl) ethane, bis (vinylphenyl) propane, bis (vinylphenyl) butane, divinylnaphthalene, divinylanthracene, divinylbiphenyl 2, ethylene oxide adduct di (meth) acrylate of bisphenol A and propylene oxide adduct di (meth) acrylate of bisphenol A, the (meth) acrylate is selected from (formaldehyde) Methyl) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate, the unsaturated dicarboxylic acid is selected from maleic acid, itaconic acid, and lemon Conic acid, aconitic acid, and anhydrides thereof, and the aforementioned unsaturated dicarboxylic acid sulfonium imine is selected from the group consisting of cis butylene diimide, N-methylcis butylene diimide, and N -Ethylcis-butenediimide, N-cyclohexyl-cis-butenediimide, N-phenyl-cis-butenedi-imide, and N-naphthyl-cis-butenediimide. 如申請專利範圍第1項所述之纖維強化複合體製造用之發泡粒子，其中，將源自芳香族乙烯與(甲基)丙烯酸酯與不飽和二羧酸三者之單元的合計設為100重量份時，前述共聚物A含有30至80重量份之源自芳香族乙烯之單元、8至35重量份之源自(甲基)丙烯酸酯之單元、10至50重量份之源自不飽和二羧酸之單元，將源自芳香族乙烯與不飽和二羧酸與不飽和二羧酸醯亞胺三者之單元的合計設為100重量份時，前述共聚物B含有20至80重量份之源自芳香族乙烯之單元、2至30重量份之源自不飽和二羧酸之單元、20至80重量份之源自不飽和二羧酸醯亞胺之單元。The foamed particles for producing a fiber-reinforced composite as described in the first patent application scope, wherein a total of units derived from three of aromatic ethylene, (meth) acrylate and unsaturated dicarboxylic acid is set as At 100 parts by weight, the aforementioned copolymer A contains 30 to 80 parts by weight of units derived from aromatic ethylene, 8 to 35 parts by weight of units derived from (meth) acrylate, and 10 to 50 parts by weight of When the unit of the saturated dicarboxylic acid is 100 parts by weight based on the total of the units derived from the aromatic ethylene, the unsaturated dicarboxylic acid, and the unsaturated dicarboxylic acid and imine, the copolymer B contains 20 to 80 weight. Parts of units derived from aromatic ethylene, 2 to 30 parts by weight of units derived from unsaturated dicarboxylic acid, and 20 to 80 parts by weight of units derived from unsaturated dicarboxylic acid imine. 一種纖維強化複合體製造用之發泡成形體，係由含有芳香族乙烯-(甲基)丙烯酸酯-不飽和二羧酸共聚物A及芳香族乙烯-不飽和二羧酸-不飽和二羧酸醯亞胺共聚物B之基材樹脂所構成，其中，相對於前述共聚物A與B之合計，含有1至50重量%之前述共聚物B。A foamed molded body for manufacturing a fiber-reinforced composite, comprising an aromatic ethylene- (meth) acrylate-unsaturated dicarboxylic acid copolymer A and an aromatic ethylene-unsaturated dicarboxylic acid-unsaturated dicarboxylic acid The base resin of the acid fluorene imine copolymer B is composed of the copolymer B in an amount of 1 to 50% by weight based on the total of the copolymers A and B. 一種纖維強化複合體，係具有發泡成形體、及積層在前述發泡成形體的表面並一體化之纖維強化塑膠層，其中，該發泡成形體係由含有芳香族乙烯-(甲基)丙烯酸酯-不飽和二羧酸共聚物A及芳香族乙烯-不飽和二羧酸-不飽和二羧酸醯亞胺共聚物B之基材樹脂所構成，且相對於前述共聚物A與B之合計，含有1至50重量%之前述共聚物B。A fiber-reinforced composite is provided with a foamed molded body and a fiber-reinforced plastic layer laminated and integrated on the surface of the foamed molded body, wherein the foamed molding system consists of aromatic ethylene- (meth) acrylic acid It is composed of a base resin of an ester-unsaturated dicarboxylic acid copolymer A and an aromatic ethylene-unsaturated dicarboxylic acid-unsaturated dicarboxylic acid imine copolymer B, and is relative to the total of the aforementioned copolymers A and B. Contains 1 to 50% by weight of the aforementioned copolymer B. 如申請專利範圍第6項所述之纖維強化複合體，其中，前述纖維強化複合體係用於風車葉片、機械手臂或汽車用構件。The fiber-reinforced composite according to item 6 of the patent application scope, wherein the fiber-reinforced composite system is used for a windmill blade, a robot arm, or an automobile component. 如申請專利範圍第6項所述之纖維強化複合體，其中，前述纖維強化複合體具有10%以下之表面平滑率。The fiber-reinforced composite according to item 6 of the scope of patent application, wherein the fiber-reinforced composite has a surface smoothness of 10% or less. 一種汽車用構件，係由申請專利範圍第6項所述之纖維強化複合體所構成者。An automobile component is composed of a fiber-reinforced composite as described in item 6 of the scope of patent application.
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