TW202416572A - Laminated body, laminated body production method, and battery case - Google Patents

Abstract

The present invention provides a molding material that is characterized by being lightweight and thin, yet exhibiting excellent flame resistance and strength, and that can be suitably used for molding purposes such as molding battery cases. A laminated body according to the present invention is characterized by comprising: a core layer (A) which is made by compressing a foam material in the thickness direction; and an outer layer (B) which is composed of fiber-reinforced plastic. The laminated body according to the present invention is useful as a molding material that is characterized by being lightweight and thin, yet exhibiting excellent flame resistance and strength, and that can be suitably used for a variety of molding purposes such as molding battery cases.

Description

積層體、積層體的製造方法及電池殼體Laminated body, method for manufacturing laminated body, and battery case

本發明是有關於一種積層體及使用其的電池殼體，所述積層體具有於為輕量且薄壁的同時耐燃性或強度亦優異的特徵，可適宜地用於多種成形品用途。The present invention relates to a laminate and a battery case using the same, wherein the laminate has the characteristics of being lightweight and thin-walled and having excellent flame resistance and strength, and can be suitably used for various molded product applications.

多數電動汽車中所使用的鋰離子電池由於有可能起火，因此對於其電池殼體而言，除強度以外，亦要求高的耐燃性或耐火性。與此同時，為了實現燃料消耗率更高且環境負荷低的汽車，謀求一種既充分維持所述性能，亦能夠實現進一步的輕量化或電池殼體自身的省空間化的成形材料。Lithium-ion batteries used in many electric vehicles have the potential to catch fire, so their battery cases are required to have high flame resistance or fire resistance in addition to strength. At the same time, in order to achieve vehicles with higher fuel efficiency and lower environmental impact, a molding material is required that can achieve further weight reduction or space saving of the battery case itself while fully maintaining the above performance.

作為重量輕且強度高的成形材料，已知有以樹脂發泡體為芯材並利用纖維強化塑膠夾住其的所謂的纖維強化塑膠（fiber reinforced plastic，FRP）夾層（sandwich）成形體（例如，參照專利文獻1）。然而，該夾層成形體中，作為芯材的樹脂發泡體通常易燃，而且為了賦予一定程度的耐燃性，需要使用具有充分厚度的樹脂發泡體，並不能用於如要求兼具高的耐燃性或耐火性與輕量性、省空間性的電池殼體般的用途。 [現有技術文獻] [專利文獻] As a lightweight and high-strength molding material, a so-called fiber reinforced plastic (FRP) sandwich molding is known, which uses a resin foam as a core material and sandwiches the resin foam with a fiber reinforced plastic (for example, refer to Patent Document 1). However, in this sandwich molding, the resin foam as the core material is generally flammable, and in order to impart a certain degree of flame resistance, a resin foam with a sufficient thickness must be used, and it cannot be used for applications such as battery cases that require both high flame resistance or fire resistance and lightness and space saving. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本專利特開2022-80629號公報[Patent Document 1] Japanese Patent Publication No. 2022-80629

[發明所欲解決之課題] 因此，本發明所欲解決的課題在於提供一種成形材料及使用其的電池殼體，所述成形材料具有於為輕量且薄壁的同時耐燃性或強度優異的特徵，可適宜地用於電池殼體等成形品用途。 [解決課題之手段] [Problem to be solved by the invention] Therefore, the problem to be solved by the present invention is to provide a molding material and a battery case using the same, wherein the molding material has the characteristics of being lightweight and thin-walled while having excellent flame resistance or strength, and can be suitably used for molding products such as battery cases. [Means for solving the problem]

本發明人進行了努力研究，結果發現：包括芯層（A）及外層（B）的積層體具有於為輕量且薄壁的同時耐燃性或強度優異的特徵，能夠用於以電池殼體為首的多種成形品用途，所述芯層（A）是將發泡體沿厚度方向壓縮而成，所述外層（B）包含纖維強化塑膠，從而完成了本發明。The inventors of the present invention have conducted diligent research and found that a laminate including a core layer (A) and an outer layer (B) has the characteristics of being lightweight and thin-walled while having excellent flame resistance or strength, and can be used for a variety of molded products including battery cases. The core layer (A) is formed by compressing a foam in the thickness direction, and the outer layer (B) contains a fiber-reinforced plastic, thereby completing the present invention.

即，本發明有關於：（I）一種積層體，包括：芯層（A），將發泡體沿厚度方向壓縮而成；及外層（B），包含纖維強化塑膠。That is, the present invention relates to: (I) a laminate comprising: a core layer (A) formed by compressing a foamed body in the thickness direction; and an outer layer (B) comprising a fiber-reinforced plastic.

本發明進而有關於：（II）如所述（I）所記載的積層體，其中，所述芯層（A）的壓縮率以厚度換算計為40%以上。The present invention further relates to: (II) the laminate as described in (I), wherein the compression ratio of the core layer (A) is 40% or more in terms of thickness.

本發明進而有關於：（III）如所述（I）或（II）所記載的積層體，其中，所述芯層（A）的發泡體單元的縱橫比為2以上。The present invention further relates to: (III) the laminate as described in (I) or (II) above, wherein the aspect ratio of the foamed unit of the core layer (A) is 2 or more.

本發明進而有關於：（IV）如所述（I）至（III）中任一項所記載的積層體，其中，所述外層（B）是對包含強化纖維（f）與基質樹脂（r）的預浸體進行加熱成形而獲得，所述基質樹脂為含有聚異氰酸酯化合物（r1）與多羥基(甲基)丙烯酸酯化合物（r2）的樹脂組成物（1）或含有聚異氰酸酯化合物（r1）、單羥基(甲基)丙烯酸酯化合物（r3）及多羥基化合物（r4）的樹脂組成物（2）。The present invention further relates to: (IV) a laminate as described in any one of items (I) to (III), wherein the outer layer (B) is obtained by heat-forming a prepreg comprising reinforcing fibers (f) and a matrix resin (r), and the matrix resin is a resin composition (1) containing a polyisocyanate compound (r1) and a polyhydroxy (meth)acrylate compound (r2) or a resin composition (2) containing a polyisocyanate compound (r1), a monohydroxy (meth)acrylate compound (r3) and a polyhydroxy compound (r4).

本發明進而有關於：（V）一種積層體的製造方法，製造如所述（I）至（IV）中任一項所記載的積層體，且所述積層體的製造方法中，對將芯層（a）與外層（b）積層而得的前驅物於壓縮所述芯層（a）的條件下進行加熱成形，所述芯層（a）包含發泡體，所述外層（b）包含含有強化纖維（f）與基質樹脂（r）的預浸體。The present invention further relates to: (V) a method for manufacturing a laminate, wherein a laminate as described in any one of items (I) to (IV) is manufactured, and in the method for manufacturing the laminate, a precursor obtained by laminating a core layer (a) and an outer layer (b) is heat-formed under the condition of compressing the core layer (a), wherein the core layer (a) includes a foamed body and the outer layer (b) includes a prepreg containing reinforcing fibers (f) and a matrix resin (r).

本發明進而有關於：（VI）一種積層體的製造方法，製造如所述（I）至（IV）中任一項所記載的積層體，且所述積層體的製造方法中，使用接著劑將所述芯層（A）與所述包含纖維強化塑膠的外層（B）接著。The present invention further relates to: (VI) a method for manufacturing a laminate, wherein the laminate is manufactured by bonding the core layer (A) to the outer layer (B) comprising a fiber-reinforced plastic using a bonding agent.

本發明進而有關於：（VII）一種積層體的製造方法，製造如所述（I）至（IV）中任一項所記載的積層體，且所述積層體的製造方法中，對將所述芯層（A）與外層（b）積層而得的前驅物進行加熱成形，所述外層（b）包含含有強化纖維（f）與基質樹脂（r）的預浸體。The present invention further relates to: (VII) a method for manufacturing a laminate, wherein the laminate as described in any one of items (I) to (IV) is manufactured, and in the method for manufacturing the laminate, a precursor obtained by laminating the core layer (A) and the outer layer (b) is heat-formed, and the outer layer (b) comprises a prepreg containing reinforcing fibers (f) and a matrix resin (r).

本發明進而有關於：（VIII）一種電池殼體，使用如所述（I）至（IV）中任一項所記載的積層體。 [發明的效果] The present invention further relates to: (VIII) a battery case using a laminate as described in any one of (I) to (IV). [Effect of the invention]

藉由本發明，可提供一種積層體及使用其的電池殼體，所述積層體具有於為輕量且薄壁的同時耐燃性或強度優異的特徵，可適宜地用於電池殼體等成形品用途。According to the present invention, a laminate having the characteristics of being lightweight and thin-walled and having excellent flame resistance and strength, and being suitably used for molded products such as battery cases, can be provided, and a battery case using the same.

以下，對本發明進行詳細說明。The present invention is described in detail below.

本發明的積層體的特徵在於包括：芯層（A），將發泡體沿厚度方向壓縮而成；及外層（B），包含纖維強化塑膠。The laminate of the present invention is characterized in that it comprises: a core layer (A) formed by compressing a foam body along the thickness direction; and an outer layer (B) comprising a fiber-reinforced plastic.

作為所述發泡體，可無特別限制地使用包含各種樹脂材料的發泡體。所述樹脂材料例如可列舉：聚胺基甲酸酯樹脂、酚樹脂、三聚氰胺樹脂、丙烯酸樹脂、聚乙烯樹脂、聚丙烯樹脂、聚氯乙烯樹脂、聚苯乙烯樹脂、苯乙烯丙烯酸樹脂、丙烯腈-丁二烯-苯乙烯（Acrylonitrile Butadiene Styrene，ABS）樹脂、聚苯醚樹脂、聚醚醯亞胺樹脂、聚甲基丙烯酸甲酯樹脂、聚甲基丙烯醯亞胺樹脂等。該些樹脂材料的發泡方法或所使用的發泡劑並無特別限定，可使用公知慣用的發泡劑及藉由發泡方法而發泡者。其中，就使所獲得的積層體的耐燃性更優異的方面而言，較佳為珠粒發泡體，更佳為聚苯乙烯樹脂的珠粒發泡體。As the foam, a foam containing various resin materials can be used without particular limitation. Examples of the resin material include polyurethane resin, phenol resin, melamine resin, acrylic resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polystyrene resin, styrene acrylic resin, acrylonitrile-butadiene-styrene (ABS) resin, polyphenylene ether resin, polyetherimide resin, polymethyl methacrylate resin, polymethacrylimide resin, etc. The foaming method of these resin materials or the foaming agent used is not particularly limited, and a known conventional foaming agent and a foamed material by a foaming method can be used. Among them, bead foam is preferred, and polystyrene resin bead foam is more preferred in terms of making the flame retardancy of the obtained laminate more excellent.

所述珠粒發泡體例如可藉由如下方法來製造：藉由向包含所述各種樹脂材料的粒子中壓入發泡氣體，並對其進行加熱而進行預發泡，獲得發泡性珠粒，對所獲得的發泡性珠粒於加熱加壓條件下進行發泡成形的方法等。就使所獲得的積層體的耐燃性與強度更優異的方面而言，所述發泡性珠粒的平均粒子徑較佳為0.5 mm～5 mm的範圍。作為所述發泡氣體，可列舉丙烷、丁烷、戊烷等，氣體的壓入量較佳為發泡珠粒的5質量%～7質量%。就使所獲得的積層體的耐燃性與強度更優異的方面而言，發泡倍率較佳為40倍～70倍。就形成輕量性、耐燃性及強度的平衡優異的積層體的方面而言，發泡體的密度較佳為0.01 g/cm ³～0.07 g/cm ³的範圍。 The bead foam can be produced, for example, by the following method: by pressurizing a foaming gas into particles containing the various resin materials, and pre-foaming them by heating, to obtain foamable beads, and foaming the obtained foamable beads under heating and pressurizing conditions. In order to make the flame retardancy and strength of the obtained laminate better, the average particle size of the foamable beads is preferably in the range of 0.5 mm to 5 mm. As the foaming gas, propane, butane, pentane, etc. can be listed, and the amount of the gas pressed is preferably 5% to 7% by mass of the foamable beads. In order to improve the flame retardancy and strength of the obtained laminate, the expansion ratio is preferably 40 to 70 times. In order to form a laminate having an excellent balance among lightness, flame retardancy and strength, the density of the foam is preferably in the range of ^0.01 to 0.07 g/cm ³ .

於所述珠粒發泡體中，藉由在作為原料的發泡性珠粒的表面塗佈功能性塗佈劑，可對所獲得的發泡體賦予所期望的性能。作為功能性塗佈劑，例如可列舉阻燃性塗佈劑、耐熱性塗佈劑等。其中，就使所獲得的積層體的耐燃性更優異的方面而言，較佳為於表面塗佈有阻燃性塗佈劑的樹脂珠粒的發泡體。所述阻燃性塗佈劑例如可列舉包含含磷原子的化合物、含鹵素原子的化合物、含氮原子的化合物、水合金屬化合物、硼酸鹽、金屬氧化物、矽酮化合物等作為阻燃劑的阻燃性塗佈劑。In the bead foam, a functional coating is applied on the surface of the foamable beads as a raw material, so that the obtained foam can be given desired performance. Examples of the functional coating include flame retardant coatings and heat resistant coatings. Among them, in terms of making the flame retardancy of the obtained laminate more excellent, a foam of resin beads coated with a flame retardant coating on the surface is preferred. Examples of the flame retardant coating agent include a phosphorus atom-containing compound, a halogen atom-containing compound, a nitrogen atom-containing compound, a hydrated metal compound, a borate, a metal oxide, a silicone compound, and the like as a flame retardant.

本發明的芯層（A）是將所述發泡體沿厚度方向壓縮而成。就使所獲得的積層體於為薄壁的同時具有充分的耐燃性的方面而言，所述芯層（A）的壓縮率以厚度換算計較佳為40%以上，更佳為60%以上，特佳為85%以上。另外，較佳為97%以下，更佳為95%以下。另外，就使所獲得的積層體於為薄壁的同時具有充分的耐燃性的方面而言，所述芯層（A）的發泡體單元的縱橫比較佳為1.7以上，更佳為2.5以上，特佳為6.7以上。另外，較佳為30以下，更佳為20以下。再者，發泡體單元的縱橫比可為利用顯微鏡觀察發泡體的剖面而測定的實測值或根據壓縮率而算出的計算值的任一者。 縱橫比=1/[1-壓縮率（%）/100] The core layer (A) of the present invention is formed by compressing the foam in the thickness direction. In order to make the obtained laminate thin-walled and have sufficient flame retardancy, the compression rate of the core layer (A) is preferably 40% or more, more preferably 60% or more, and particularly preferably 85% or more, calculated on the basis of thickness. In addition, it is preferably 97% or less, and more preferably 95% or less. In addition, in order to make the obtained laminate thin-walled and have sufficient flame retardancy, the longitudinal and transverse ratio of the foam unit of the core layer (A) is preferably 1.7 or more, more preferably 2.5 or more, and particularly preferably 6.7 or more. In addition, it is preferably 30 or less, and more preferably 20 or less. Furthermore, the aspect ratio of the foam unit can be either a measured value measured by observing the cross section of the foam using a microscope or a calculated value calculated based on the compression ratio. Aspect ratio = 1/[1-compression ratio (%)/100]

就所獲得的積層體的耐燃性、強度及輕量性的平衡優異的方面而言，所述芯層（A）的厚度較佳為0.5 mm～5 mm的範圍，更佳為1 mm～3 mm的範圍。另外，所述芯層（A）可僅以一層形成，亦可形成為多層。於芯層（A）為多層的情況下，各層可由相同種類的發泡體形成，亦可分別由種類不同的發泡體形成。即便於所述芯層（A）為多層的情況下，芯層（A）整體的厚度亦較佳為0.5 mm～5 mm的範圍，更佳為1 mm～3 mm的範圍。In terms of the excellent balance between the flame retardancy, strength and lightness of the obtained laminate, the thickness of the core layer (A) is preferably in the range of 0.5 mm to 5 mm, and more preferably in the range of 1 mm to 3 mm. In addition, the core layer (A) may be formed of only one layer or may be formed of multiple layers. In the case where the core layer (A) is multiple layers, each layer may be formed of the same type of foam or may be formed of different types of foam. Even in the case where the core layer (A) is multiple layers, the overall thickness of the core layer (A) is preferably in the range of 0.5 mm to 5 mm, and more preferably in the range of 1 mm to 3 mm.

具體而言，所述包含纖維強化塑膠的外層（B）是對包含強化纖維（f）與基質樹脂（r）的預浸體進行加熱成形而獲得。Specifically, the outer layer (B) comprising the fiber-reinforced plastic is obtained by heat-forming a prepreg comprising reinforcing fibers (f) and a matrix resin (r).

所述強化纖維（f）例如可列舉：碳纖維、玻璃纖維、碳化矽纖維、氧化鋁纖維、硼纖維、金屬纖維、聚芳醯胺纖維、維尼綸纖維、蒂托綸（tetoron）纖維等有機纖維等。該些分別可單獨使用，亦可併用兩種以上。其中，就可獲得強度更高的積層體的方面而言，較佳為碳纖維或玻璃纖維。The reinforcing fiber (f) may be, for example, carbon fiber, glass fiber, silicon carbide fiber, alumina fiber, boron fiber, metal fiber, polyarylamide fiber, vinyl fiber, tetoron fiber, and other organic fibers. These may be used alone or in combination of two or more. Of these, carbon fiber or glass fiber is preferred in terms of obtaining a laminate having a higher strength.

作為所述碳纖維，可使用聚丙烯腈系、瀝青系、嫘縈系等各種碳纖維，該些中，就可獲得強度更高的碳纖維的方面而言，較佳為聚丙烯腈系的碳纖維。As the carbon fiber, various types of carbon fibers such as polyacrylonitrile-based, asphalt-based, and rayon-based can be used. Among these, polyacrylonitrile-based carbon fibers are preferred because they can provide carbon fibers with higher strength.

作為所述強化纖維（f）的形狀，並無特別限制，可列舉：使強化纖維絲收束而得的強化纖維絲束、將強化纖維絲束沿一方向捋齊而得的單向材、織造而得的織物、裁短的強化纖維、包含裁短的強化纖維的不織布或紙等。於所述強化纖維（f）為織物的情況下，可列舉以平紋織物、斜紋織物、緞紋織物或非縐紋織物為代表的將纖維束沿一方向捋齊而得的片材、或將改變角度地進行了積層般的片材以不鬆解的方式縫合而得的縫合片材等。於使用裁短的強化纖維作為強化纖維（f）的情況下，就成形時的模具內流動性、成形品的外觀進一步提高的方面而言，較佳為使用切成長度2.5 mm～50 mm的強化纖維。其中，就形成強度更高的外層（B）的方面而言，較佳為使用單向材或織造而得的織物作為強化纖維。於將使用單向材的預浸體用作強化纖維的情況下，藉由將多片以成為類各向同性的方式，例如以纖維方向成為相互不同的0°與90°的方式依序重疊，可獲得強度更高的外層（B）。The shape of the reinforcing fiber (f) is not particularly limited, and examples thereof include: a reinforcing fiber bundle obtained by bundling reinforcing fiber filaments, a unidirectional material obtained by aligning a reinforcing fiber bundle in one direction, a woven fabric, short reinforcing fibers, a nonwoven fabric or paper containing short reinforcing fibers, and the like. When the reinforcing fiber (f) is a fabric, examples thereof include a sheet obtained by aligning fiber bundles in one direction, represented by plain weave, twill weave, satin weave or non-woven weave, or a sewed sheet obtained by sewing sheets stacked at different angles in a non-loose manner. When using a short reinforced fiber as the reinforcing fiber (f), it is preferred to use a reinforced fiber cut to a length of 2.5 mm to 50 mm in order to further improve the fluidity in the mold during molding and the appearance of the molded product. Among them, in terms of forming an outer layer (B) with higher strength, it is preferred to use a unidirectional material or a woven fabric as the reinforcing fiber. When a prepreg made of a unidirectional material is used as the reinforcing fiber, a stronger outer layer (B) can be obtained by sequentially stacking multiple sheets in a quasi-isotropic manner, for example, in a manner in which the fiber directions are 0° and 90° different from each other.

根據與所述相同的理由，所述裁短的強化纖維的長度更佳為8 mm～50 mm，特佳為10 mm～30 mm。For the same reasons as above, the length of the shortened reinforcing fiber is more preferably 8 mm to 50 mm, particularly preferably 10 mm to 30 mm.

強化纖維（f）的單位面積重量（每1 m ²纖維的重量）可無特別限制地使用多種多樣的強化纖維。另外，最佳值亦根據強化纖維（f）的不同而不同。通常而言，就強化纖維（f）的纖維寬度的均質性與基質樹脂（r）的含浸性的平衡優異的方面而言，較佳為30 g/m ²～650 g/m ²的範圍。於所述強化纖維（f）為玻璃纖維的情況下，較佳為50 g/m ²以上，更佳為100 g/m ²以上。另外，較佳為600 g/m ²以下，更佳為350 g/m ²以下。於所述強化纖維（f）為碳纖維的情況下，較佳為50 g/m ²以上，更佳為80 g/m ²以上。另外，較佳為300 g/m ²以下，更佳為200 g/m ²以下。 The weight per unit area of the reinforcing fiber (f) (weight of fiber per 1 ^m2 ) can be a variety of reinforcing fibers without particular restrictions. In addition, the optimal value also varies depending on the reinforcing fiber (f). Generally speaking, in terms of the excellent balance between the homogeneity of the fiber width of the reinforcing fiber (f) and the impregnation of the base resin (r), it is preferably in the range of 30 g/ ^m2 to 650 g/ ^m2 . When the reinforcing fiber (f) is a glass fiber, it is preferably 50 g/ ^m2 or more, and more preferably 100 g/ ^m2 or more. In addition, it is preferably 600 g/ ^m2 or less, and more preferably 350 g/ ^m2 or less. When the reinforcing fiber (f) is a carbon fiber, the weight is preferably 50 g/m ² or more, more preferably 80 g/m ² or more. In addition, the weight is preferably 300 g/m ² or less, more preferably 200 g/m ² or less.

就兼顧適宜的含浸性與高強度的觀點而言，所述裁短的強化纖維的單位面積重量較佳為250 g/m ²～1500 g/m ²，更佳為300 g/m ²～1400 g/m ²，特佳為400 g/m ²～1300 g/m ²。 From the viewpoint of achieving both appropriate impregnation and high strength, the weight per unit area of the short reinforced fiber is preferably 250 g/m ² to 1500 g/m ² , more preferably 300 g/m ² to 1400 g/m ² , and particularly preferably 400 g/m ² to 1300 g/m ² .

另外，就形成強度更高的外層（B）的方面而言，所述預浸體的強化纖維（f）的含有率較佳為40質量%以上，更佳為50質量%以上。另外，較佳為90質量%以下，更佳為80質量%以下。In order to form an outer layer (B) having higher strength, the content of the reinforcing fiber (f) in the prepreg is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less.

所述基質樹脂（r）若可含浸於所述強化纖維（f）中且所獲得的預浸體能夠藉由加熱等來成形，則可無特別限制地使用多種多樣的基質樹脂。其中，就處理的容易性等的方面而言，較佳為熱硬化性樹脂組成物。進而，就所獲得的外層（B）的強度高並且形成容易處理且向多種形狀的成形性亦優異的預浸體的方面而言，較佳為含有由異氰酸酯基與羥基所得的胺基甲酸酯化反應成分且於樹脂組成物中存在聚合性不飽和基。作為此種樹脂組成物，例如可列舉含有聚異氰酸酯化合物（r1）與多羥基(甲基)丙烯酸酯化合物（r2）的樹脂組成物（1）或含有聚異氰酸酯化合物（r1）、單羥基(甲基)丙烯酸酯化合物（r3）及多羥基化合物（r4）的樹脂組成物（2）等。The matrix resin (r) can be impregnated into the reinforcing fiber (f) and the obtained prepreg can be formed by heating or the like, and various matrix resins can be used without particular limitation. Among them, a thermosetting resin composition is preferred from the perspective of ease of handling. Furthermore, from the perspective of obtaining a prepreg having high strength of the obtained outer layer (B) and being easy to handle and having excellent moldability into various shapes, it is preferred that a urethanization reaction component obtained from an isocyanate group and a hydroxyl group be present in the resin composition. Examples of such a resin composition include a resin composition (1) containing a polyisocyanate compound (r1) and a polyhydroxy (meth)acrylate compound (r2), and a resin composition (2) containing a polyisocyanate compound (r1), a monohydroxy (meth)acrylate compound (r3), and a polyhydroxy compound (r4).

再者，於本發明中，所謂(甲基)丙烯酸酯化合物，是具有丙烯醯基與甲基丙烯醯基的其中一者或兩者的化合物，所謂(甲基)丙烯醯基，是丙烯醯基與甲基丙烯醯基的其中一者或兩者，所謂(甲基)丙烯酸，是丙烯酸與甲基丙烯酸的其中一者或兩者。Furthermore, in the present invention, the so-called (meth)acrylate compound is a compound having one or both of an acryl group and a methacryl group, the so-called (meth)acryl group is one or both of an acryl group and a methacryl group, and the so-called (meth)acrylic acid is one or both of acrylic acid and methacrylic acid.

所述聚異氰酸酯化合物（r1）例如可列舉：丁烷二異氰酸酯、五亞甲基二異氰酸酯、六亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、二聚物酸二異氰酸酯等脂肪族二異氰酸酯化合物；降冰片烷二異氰酸酯、異佛爾酮二異氰酸酯、氫化伸二甲苯基二異氰酸酯、氫化二苯基甲烷二異氰酸酯等脂環式二異氰酸酯化合物；甲苯二異氰酸酯、伸二甲苯基二異氰酸酯、四甲基伸二甲苯基二異氰酸酯、離胺酸二異氰酸酯、二苯基甲烷二異氰酸酯、1,5-萘二異氰酸酯、聚亞甲基聚苯基聚異氰酸酯等芳香族二異氰酸酯化合物；作為該些異氰酸酯化合物的改質體的異氰脲酸酯改質體、縮二脲改質體、脲甲酸酯改質體、碳二醯亞胺改質體、胺基甲酸酯亞胺改質體、利用二乙二醇、二丙二醇等多元醇改質而得的多元醇改質體等。該些可單獨使用一種，亦可併用多種。其中，就形成耐熱性優異的外層（B）的方面而言，較佳為芳香族二異氰酸酯化合物及該些的各種改質體。於併用多種作為聚異氰酸酯化合物（r1）的情況下，芳香族二異氰酸酯化合物及該些的各種改質體相對於聚異氰酸酯化合物（r）的總質量的比例較佳為50質量%以上，更佳為80質量%以上，特佳為90質量%以上。The polyisocyanate compound (r1) includes, for example, aliphatic diisocyanate compounds such as butane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, etc.; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc.; toluene diisocyanate, Aromatic diisocyanate compounds such as esters, xylene diisocyanate, tetramethylxylene diisocyanate, lysine diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate; modified isocyanurate modified products, biuret modified products, allophanate modified products, carbodiimide modified products, carbamate imine modified products, and polyol modified products obtained by modifying polyols such as diethylene glycol and dipropylene glycol, etc. These can be used alone or in combination. Among them, aromatic diisocyanate compounds and various modified products thereof are preferred in terms of forming an outer layer (B) having excellent heat resistance. When a plurality of polyisocyanate compounds (r1) are used in combination, the ratio of the aromatic diisocyanate compound and its various modified products to the total mass of the polyisocyanate compound (r) is preferably 50 mass % or more, more preferably 80 mass % or more, and particularly preferably 90 mass % or more.

所述多羥基(甲基)丙烯酸酯化合物（r2）化合物例如可列舉以環氧樹脂與(甲基)丙烯酸為反應原料的(甲基)丙烯酸酯化合物等。Examples of the polyhydroxy (meth)acrylate compound (r2) include (meth)acrylate compounds prepared by reacting epoxy resin and (meth)acrylic acid as reaction materials.

所述環氧樹脂例如可列舉：二縮水甘油基氧基苯、二縮水甘油基氧基萘、脂肪族環氧樹脂、聯苯酚型環氧樹脂、雙酚型環氧樹脂、酚醛清漆型環氧樹脂、脂環式環氧樹脂、縮水甘油基胺型環氧樹脂、雜環型環氧樹脂、縮水甘油酯型環氧樹脂、三苯酚甲烷型環氧樹脂、苯酚芳烷基型環氧樹脂或萘酚芳烷基型環氧樹脂、伸苯基醚型環氧樹脂或伸萘基醚型環氧樹脂、噁唑啶酮改質環氧樹脂、將該些溴化而得的環氧樹脂等。環氧樹脂亦可為利用伸長劑將所述具體例伸長而得的環氧樹脂。Examples of the epoxy resin include diglycidyloxybenzene, diglycidyloxynaphthalene, aliphatic epoxy resins, biphenol type epoxy resins, bisphenol type epoxy resins, novolac type epoxy resins, alicyclic epoxy resins, glycidylamine type epoxy resins, heterocyclic epoxy resins, and the like. Resins, glycidyl ester type epoxy resins, trisphenol methane type epoxy resins, phenol aralkyl type epoxy resins or naphthol aralkyl type epoxy resins, phenylene ether type epoxy resins or naphthylene ether type epoxy resins, oxazolidinone modified epoxy resins, epoxy resins obtained by brominating these, etc. The epoxy resin may be an epoxy resin obtained by extending the above-mentioned specific examples using an elongating agent.

所述脂肪族環氧樹脂例如可列舉利用表鹵醇將各種脂肪族多元醇化合物或該些的環氧烷加成物的一種或多種聚縮水甘油醚化而得者。脂肪族多元醇化合物例如可列舉：乙二醇、丙二醇、1,3-丙二醇、2-甲基丙二醇、1,2,2-三甲基-1,3-丙二醇、2,2-二甲基-3-異丙基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、3-甲基-1,3-丁二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、新戊二醇、1,6-己二醇、1,4-雙(羥基甲基)環己烷、2,2,4-三甲基-1,3-戊二醇等脂肪族二醇化合物；2,2-雙(4-羥基苯基)丙烷等脂環族二醇化合物；三羥甲基乙烷、三羥甲基丙烷、甘油、己三醇、季戊四醇、二-三羥甲基丙烷、二季戊四醇等三官能以上的脂肪族多元醇化合物等。Examples of the aliphatic epoxy resin include those obtained by etherifying various aliphatic polyol compounds or one or more polyglycidyl groups of these epoxide adducts with epihalogen alcohol. Examples of the aliphatic polyol compound include ethylene glycol, propylene glycol, 1,3-propylene glycol, 2-methylpropylene glycol, 1,2,2-trimethyl-1,3-propylene glycol, 2,2-dimethyl-3-isopropyl-1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol. , 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, 2,2,4-trimethyl-1,3-pentanediol and other aliphatic diol compounds; 2,2-bis(4-hydroxyphenyl)propane and other aliphatic cyclool compounds; trihydroxymethylethane, trihydroxymethylpropane, glycerol, hexanetriol, pentaerythritol, di-trihydroxymethylpropane, dipentaerythritol and other trifunctional or higher aliphatic polyol compounds;

所述聯苯酚型環氧樹脂例如可列舉利用表鹵醇將聯苯酚、四甲基聯苯酚等聯苯酚化合物、該些的環氧烷加成物的一種或多種聚縮水甘油醚化而得者。Examples of the biphenol type epoxy resin include those obtained by etherifying one or more polyglycidyl groups of biphenol compounds such as biphenol and tetramethylbiphenol, or alkylene oxide adducts thereof with epihalogen alcohol.

所述雙酚型環氧樹脂例如可列舉利用表鹵醇將雙酚A、四溴雙酚A、雙酚F、雙酚S、雙酚芴、雙甲酚芴等雙酚化合物、該些的環氧烷加成物的一種或多種聚縮水甘油醚化而得者。Examples of the bisphenol type epoxy resin include those obtained by etherifying one or more polyglycidyl groups of bisphenol compounds such as bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, biscresol fluorene, and alkylene oxide adducts thereof with epihalogen alcohol.

所述酚醛清漆型環氧樹脂例如可列舉利用表鹵醇將包含苯酚、二羥基苯、甲酚、二甲酚、萘酚、二羥基萘、雙酚、聯苯酚等各種酚化合物的一種或多種的酚醛清漆樹脂聚縮水甘油醚化而得者。The novolac epoxy resin may be obtained, for example, by polyglycidyl etherifying one or more novolac resins containing various phenolic compounds such as phenol, dihydroxybenzene, cresol, xylenol, naphthol, dihydroxynaphthalene, bisphenol, biphenol, etc., using epihalogen alcohol.

脂環式環氧樹脂例如除利用表鹵醇將使所述聯苯酚化合物或雙酚化合物氫化而得者或其環氧烷加成物的一種或多種聚縮水甘油醚化而得者以外，亦可列舉3,4-環氧-6-甲基環己基甲基-3,4-環氧-6-甲基環己烷羧酸酯、1-環氧乙基-3,4-環氧環己烷等。Examples of the alicyclic epoxy resin include those obtained by hydrogenating the biphenol compound or bisphenol compound or one or more polyglycidyl ethers of their alkylene oxide adducts using epihalogen alcohols, and also include 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane.

所述縮水甘油基胺型環氧樹脂例如可列舉：N,N-二縮水甘油基苯胺、三縮水甘油基胺基苯酚、四縮水甘油基二甲苯二胺、4,4'-亞甲基雙[N,N-二縮水甘油基苯胺]等。Examples of the glycidylamine epoxy resin include N,N-diglycidylaniline, triglycidylaminophenol, tetraglycidylxylenediamine, 4,4'-methylenebis[N,N-diglycidylaniline], and the like.

所述雜環型環氧樹脂例如可列舉1,3-二縮水甘油基-5,5-二甲基乙內醯脲、異氰脲酸三縮水甘油酯等。Examples of the heterocyclic epoxy resin include 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate.

所述縮水甘油酯型環氧樹脂例如可列舉：鄰苯二甲酸二縮水甘油酯、四氫鄰苯二甲酸二縮水甘油酯、對羥基苯甲酸二縮水甘油酯、二聚物酸縮水甘油酯等。Examples of the glycidyl ester type epoxy resin include diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl p-hydroxybenzoate, and diglycidyl dimer acid ester.

作為環氧樹脂的伸長劑，例如可列舉：所述各種聯苯酚化合物或其氫化物、所述各種雙酚化合物或其氫化物、二元酸化合物、含酸基的聚酯樹脂等。Examples of the epoxy resin elongating agent include the above-mentioned various biphenol compounds or hydrogenates thereof, the above-mentioned various bisphenol compounds or hydrogenates thereof, dibasic acid compounds, and acid group-containing polyester resins.

該些中，就對於所述強化纖維（f）的含浸性或所獲得的外層（B）的強度等優異的方面而言，較佳為所述雙酚型環氧樹脂。於該情況下，環氧樹脂的環氧當量較佳為150 g/當量～600 g/當量的範圍，更佳為200 g/當量～450 g/當量的範圍。Among these, the bisphenol type epoxy resin is preferred in terms of excellent impregnation into the reinforcing fiber (f) and the strength of the obtained outer layer (B). In this case, the epoxy equivalent of the epoxy resin is preferably in the range of 150 g/equivalent to 600 g/equivalent, and more preferably in the range of 200 g/equivalent to 450 g/equivalent.

環氧樹脂與(甲基)丙烯酸的反應可藉由在任意的酯化觸媒的存在下、60℃～140℃左右的溫度條件下加熱來進行。視需要亦可使用反應溶媒或添加聚合抑制劑。另外，環氧樹脂與(甲基)丙烯酸的反應比率較佳為兩者的官能基的莫耳比[羧基/環氧基]為0.6～1.1的範圍。The reaction of the epoxy resin and (meth)acrylic acid can be carried out by heating at a temperature of about 60°C to 140°C in the presence of any esterification catalyst. A reaction solvent or a polymerization inhibitor may be added as necessary. In addition, the reaction ratio of the epoxy resin and (meth)acrylic acid is preferably in a range of 0.6 to 1.1 in terms of the molar ratio [carboxyl group/epoxy group] of the functional groups of the two.

於使用所述雙酚型環氧樹脂作為環氧樹脂的情況下，所獲得的(甲基)丙烯酸酯化合物的羥價較佳為50 mg/KOH～200 mg/KOH。另外，其(甲基)丙烯醯基當量較佳為300 g/當量～600 g/當量的範圍。When the bisphenol-type epoxy resin is used as the epoxy resin, the hydroxyl valence of the obtained (meth)acrylate compound is preferably 50 mg/KOH to 200 mg/KOH. In addition, the (meth)acryl equivalent thereof is preferably in the range of 300 g/equivalent to 600 g/equivalent.

所述多羥基(甲基)丙烯酸酯化合物（r2）化合物可單獨使用一種，亦可併用多種。於併用多種作為多羥基(甲基)丙烯酸酯化合物（r2）的情況下，所述雙酚型環氧樹脂(甲基)丙烯酸酯化合物相對於多羥基(甲基)丙烯酸酯化合物（r2）化合物的總質量的比例較佳為50質量%以上，更佳為70質量%以上，特佳為80質量%以上。The polyhydroxy (meth)acrylate compound (r2) may be used alone or in combination. When a plurality of polyhydroxy (meth)acrylate compounds (r2) are used in combination, the ratio of the bisphenol type epoxy resin (meth)acrylate compound to the total mass of the polyhydroxy (meth)acrylate compound (r2) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

所述單羥基(甲基)丙烯酸酯化合物（r3）例如可列舉：(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、三羥甲基丙烷二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二-三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、於該些的分子結構中導入(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等(聚)氧伸烷基鏈而得的(聚)氧伸烷基(甲基)丙烯酸酯化合物、於該些的分子結構中導入(聚)內酯結構而得的內酯改質(甲基)丙烯酸酯化合物等。該些可單獨使用一種，亦可併用多種。Examples of the monohydroxy (meth)acrylate compound (r3) include: hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, trihydroxymethylpropane di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, di-trihydroxymethylpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (poly)oxyalkyl (meth)acrylate compounds obtained by introducing (poly)oxyethyl chains, (poly)oxypropyl chains, (poly)oxytetramethylene chains, etc., into the molecular structures of these compounds, (poly)oxyalkyl (meth)acrylate compounds obtained by introducing (poly)lactone structures into the molecular structures of these compounds, etc. These compounds may be used alone or in combination.

其中，就對於強化纖維（f）的含浸性與所獲得的外層（B）的強度的平衡優異的方面而言，較佳為單羥基單(甲基)丙烯酸酯化合物，更佳為(甲基)丙烯酸羥基乙酯。於併用多種作為所述單羥基(甲基)丙烯酸酯化合物（r3）的情況下，(甲基)丙烯酸羥基乙酯相對於單羥基(甲基)丙烯酸酯化合物（r3）化合物的總質量的比例較佳為50質量%以上，更佳為80質量%以上，特佳為90質量%以上。Among them, in terms of the excellent balance between the impregnation property of the reinforcing fiber (f) and the strength of the obtained outer layer (B), a monohydroxy mono(meth)acrylate compound is preferred, and hydroxyethyl(meth)acrylate is more preferred. When a plurality of monohydroxy(meth)acrylate compounds (r3) are used in combination, the ratio of hydroxyethyl(meth)acrylate to the total mass of the monohydroxy(meth)acrylate compound (r3) is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

所述多羥基化合物（r4）例如可列舉：二羥基苯、二羥基萘、所述各種脂肪族多元醇、聯苯酚化合物、雙酚化合物、該些的環氧烷加成物、內酯改質化合物等。該些可單獨使用一種，亦可併用多種。其中，就對於強化纖維（f）的含浸性與所獲得的外層（B）的強度的平衡優異的方面而言，較佳為雙酚化合物的環氧烷加成物。另外，環氧烷的平均加成莫耳數較佳為2莫耳～10莫耳的範圍。The polyhydroxy compound (r4) may be, for example, dihydroxybenzene, dihydroxynaphthalene, the various aliphatic polyols, biphenol compounds, bisphenol compounds, alkylene oxide adducts thereof, lactone modified compounds, etc. These may be used alone or in combination. Among them, alkylene oxide adducts of bisphenol compounds are preferred in terms of the excellent balance between the impregnation property of the reinforcing fiber (f) and the strength of the obtained outer layer (B). In addition, the average addition molar number of alkylene oxide is preferably in the range of 2 mol to 10 mol.

於併用多種作為所述多羥基化合物（r4）的情況下，雙酚化合物的環氧烷加成物相對於多羥基化合物（r4）化合物的總質量的比例較佳為50質量%以上，更佳為80質量%以上，特佳為90質量%以上。When a plurality of polyhydroxy compounds (r4) are used in combination, the ratio of the alkylene oxide adduct of the bisphenol compound to the total mass of the polyhydroxy compound (r4) is preferably 50 mass % or more, more preferably 80 mass % or more, and particularly preferably 90 mass % or more.

於所述樹脂組成物（1）中，就預浸體的處理容易度或成形性等優異的方面而言，所述聚異氰酸酯化合物（r1）所含有的異氰酸酯基與所述多羥基(甲基)丙烯酸酯化合物（r2）所含有的羥基的莫耳比（NCO/OH）較佳為0.3～1.2的範圍，更佳為0.4～1.1的範圍，特佳為0.5～1.0的範圍。In the resin composition (1), in terms of excellent handling ease and moldability of the prepreg, the molar ratio (NCO/OH) of the isocyanate group contained in the polyisocyanate compound (r1) to the hydroxyl group contained in the polyhydroxy (meth)acrylate compound (r2) is preferably in the range of 0.3 to 1.2, more preferably in the range of 0.4 to 1.1, and particularly preferably in the range of 0.5 to 1.0.

於所述樹脂組成物（2）中，就預浸體的處理容易度或成形性等優異的方面而言，所述聚異氰酸酯化合物（r1）所含有的異氰酸酯基與所述單羥基(甲基)丙烯酸酯化合物（r3）所含有的羥基及所述多羥基化合物（r4）所含有的羥基的合計的莫耳比（NCO/OH）較佳為0.7～1.3的範圍，更佳為0.8～1.1的範圍，特佳為0.8～1.0的範圍。另外，就耐熱性、硬化性進一步提高的方面而言，所述單羥基(甲基)丙烯酸酯化合物（r3）與所述多羥基化合物（r4）的莫耳比（r3/r4）較佳為40/60～80/20的範圍，更佳為50/50～70/30的範圍。In the resin composition (2), in terms of the ease of handling and formability of the prepreg, the total molar ratio (NCO/OH) of the isocyanate group contained in the polyisocyanate compound (r1) and the hydroxyl group contained in the monohydroxy (meth)acrylate compound (r3) and the hydroxyl group contained in the polyhydroxy compound (r4) is preferably in the range of 0.7 to 1.3, more preferably in the range of 0.8 to 1.1, and particularly preferably in the range of 0.8 to 1.0. In terms of further improving heat resistance and curability, the molar ratio (r3/r4) of the monohydroxy (meth)acrylate compound (r3) to the polyhydroxy compound (r4) is preferably in the range of 40/60 to 80/20, and more preferably in the range of 50/50 to 70/30.

所述樹脂組成物（1）、樹脂組成物（2）亦可含有所述多羥基(甲基)丙烯酸酯化合物（r2）或所述單羥基(甲基)丙烯酸酯化合物（r3）以外的其他含聚合性不飽和基的化合物。作為其具體例，例如可列舉：(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、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異十三烷基酯、(甲基)丙烯酸正硬脂酯、乙二醇(甲基)丙烯酸酯烷基醚、丙二醇(甲基)丙烯酸酯烷基醚等脂肪族單(甲基)丙烯酸酯化合物；(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、單(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸二環戊烯基氧基乙酯、甲基丙烯酸二環戊烷基酯等脂環式單(甲基)丙烯酸酯化合物；(甲基)丙烯酸縮水甘油酯、丙烯酸四氫糠酯等含雜環的單(甲基)丙烯酸酯化合物；(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苯基苄酯、(甲基)丙烯酸苯氧酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯氧基乙氧基乙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸苯氧基苄酯、(甲基)丙烯酸苄基苄酯、(甲基)丙烯酸苯基苯氧基乙酯等含芳香環的單(甲基)丙烯酸酯化合物；於所述各種單(甲基)丙烯酸酯單體的分子結構中導入(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等聚氧伸烷基鏈而得的(聚)氧伸烷基改質單(甲基)丙烯酸酯化合物；於所述各種單(甲基)丙烯酸酯化合物的分子結構中導入(聚)內酯結構而得的內酯改質單(甲基)丙烯酸酯化合物；乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯等脂肪族二(甲基)丙烯酸酯化合物；1,4-環己烷二甲醇二(甲基)丙烯酸酯、降冰片烷二(甲基)丙烯酸酯、降冰片烷二甲醇二(甲基)丙烯酸酯、二(甲基)丙烯酸二環戊烷基酯、三環癸烷二甲醇二(甲基)丙烯酸酯等脂環式二(甲基)丙烯酸酯化合物；聯苯酚二(甲基)丙烯酸酯、雙酚二(甲基)丙烯酸酯等含芳香環的二(甲基)丙烯酸酯化合物；於所述各種二(甲基)丙烯酸酯化合物的分子結構中導入(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等(聚)氧伸烷基鏈而得的聚氧伸烷基改質二(甲基)丙烯酸酯化合物；於所述各種二(甲基)丙烯酸酯化合物的分子結構中導入(聚)內酯結構而得的內酯改質二(甲基)丙烯酸酯化合物；三羥甲基丙烷三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯等脂肪族三(甲基)丙烯酸酯化合物；於所述脂肪族三(甲基)丙烯酸酯化合物的分子結構中導入(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等(聚)氧伸烷基鏈而得的(聚)氧伸烷基改質三(甲基)丙烯酸酯化合物；於所述脂肪族三(甲基)丙烯酸酯化合物的分子結構中導入(聚)內酯結構而得的內酯改質三(甲基)丙烯酸酯化合物；季戊四醇四(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等四官能以上的脂肪族聚(甲基)丙烯酸酯化合物；於所述脂肪族聚(甲基)丙烯酸酯化合物的分子結構中導入(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等(聚)氧伸烷基鏈而得的四官能以上的(聚)氧伸烷基改質聚(甲基)丙烯酸酯化合物；於所述脂肪族聚(甲基)丙烯酸酯化合物的分子結構中導入(聚)內酯結構而得的四官能以上的內酯改質聚(甲基)丙烯酸酯化合物等。該些可單獨使用一種，亦可併用多種。The resin composition (1) and the resin composition (2) may also contain other polymerizable unsaturated group-containing compounds other than the polyhydroxy (meth)acrylate compound (r2) or the monohydroxy (meth)acrylate compound (r3). Specific examples thereof include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isotridecyl (meth)acrylate, stearyl (meth)acrylate, ethylene glycol (meth)acrylate alkyl ether, propylene glycol (meth)acrylate, aliphatic mono(meth)acrylate compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, adamantyl mono(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, dicyclopentyl methacrylate, etc.; heterocyclic mono(meth)acrylate compounds such as glycidyl(meth)acrylate and tetrahydrofurfuryl acrylate; benzyl(meth)acrylate, phenyl(meth)acrylate, phenyl(meth)acrylate, etc. Mono(meth)acrylate compounds containing aromatic rings, such as benzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc.; (poly)oxyethyl chain, (poly)oxypropyl chain, (poly)oxytetramethylene chain are introduced into the molecular structure of the various mono(meth)acrylate monomers. (Poly)oxyalkylene modified mono(meth)acrylate compounds obtained by forming polyoxyalkylene chains such as alkylene chains; lactone modified mono(meth)acrylate compounds obtained by introducing a (poly)lactone structure into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate; 1,4 - alicyclic di(meth)acrylate compounds such as cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate; di(meth)acrylate compounds containing aromatic rings such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; introducing (poly)ethylene oxide into the molecular structure of the above di(meth)acrylate compounds The present invention relates to a polyoxyalkylene-modified di(meth)acrylate compound obtained by introducing a (poly)lactone structure into the molecular structure of the above-mentioned various di(meth)acrylate compounds; an aliphatic tri(meth)acrylate compound such as trihydroxymethylpropane tri(meth)acrylate and glycerol tri(meth)acrylate; and a polyoxyalkylene-modified di(meth)acrylate compound obtained by introducing a (poly)lactone structure into the molecular structure of the above-mentioned various di(meth)acrylate compounds. A (poly)oxyalkylene modified tri(meth)acrylate compound obtained by introducing a (poly)oxyethylene chain, a (poly)oxypropylene chain, a (poly)oxytetramethylene chain or the like into the molecular structure; a lactone modified tri(meth)acrylate compound obtained by introducing a (poly)lactone structure into the molecular structure of the aliphatic tri(meth)acrylate compound; a tetrafunctional tri(meth)acrylate compound such as pentaerythritol tetra(meth)acrylate, di-trihydroxymethylpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate or the like; aliphatic poly(meth)acrylate compounds having a functional group of 1 or more; (poly)oxyalkylene modified poly(meth)acrylate compounds having a functional group of 4 or more obtained by introducing (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. into the molecular structure of the aliphatic poly(meth)acrylate compounds; (poly)oxylactone modified poly(meth)acrylate compounds having a functional group of 4 or more obtained by introducing (poly)lactone structures into the molecular structure of the aliphatic poly(meth)acrylate compounds, etc. These may be used alone or in combination of a plurality of them.

其中，就對於強化纖維（f）的含浸性與所獲得的外層（B）的強度的平衡優異的方面而言，較佳為分子量為150～600的範圍的二官能以上的(甲基)丙烯酸酯化合物。於併用多種作為所述其他含聚合性不飽和基的化合物的情況下，分子量為150～600的範圍的二官能以上的(甲基)丙烯酸酯化合物相對於其他含聚合性不飽和基的化合物的總質量的比例較佳為50質量%以上，更佳為80質量%以上，特佳為90質量%以上。Among them, from the viewpoint of excellent balance between impregnation into the reinforcing fiber (f) and strength of the obtained outer layer (B), a difunctional or higher (meth)acrylate compound having a molecular weight in the range of 150 to 600 is preferred. When a plurality of other polymerizable unsaturated group-containing compounds are used in combination, the ratio of the difunctional or higher (meth)acrylate compound having a molecular weight in the range of 150 to 600 to the total mass of the other polymerizable unsaturated group-containing compounds is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

於在所述樹脂組成物（1）中使用其他含聚合性不飽和基的化合物的情況下，關於其調配量，就對於強化纖維（f）的含浸性與所獲得的外層（B）的強度的平衡優異的方面而言，相對於聚異氰酸酯化合物（r1）與多羥基(甲基)丙烯酸酯化合物（r2）的合計質量，較佳為40質量%以下，較佳為30質量%以下。另外，於在所述樹脂組成物（2）中使用其他含聚合性不飽和基的化合物的情況下，關於其調配量，相對於聚異氰酸酯化合物（r1）、單羥基(甲基)丙烯酸酯化合物（r3）、多羥基化合物（r4）的合計質量，較佳為40質量%以下，更佳為30質量%以下。When other polymerizable unsaturated group-containing compounds are used in the resin composition (1), the amount thereof is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total mass of the polyisocyanate compound (r1) and the polyhydroxy (meth)acrylate compound (r2), in terms of an excellent balance between the impregnation property of the reinforcing fiber (f) and the strength of the obtained outer layer (B). When other polymerizable unsaturated group-containing compounds are used in the resin composition (2), the amount thereof is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total mass of the polyisocyanate compound (r1), the monohydroxy (meth)acrylate compound (r3), and the polyhydroxy compound (r4).

所述樹脂組成物（1）、樹脂組成物（2）亦可含有聚合起始劑。該聚合起始劑可無特別限制地使用通常的聚合起始劑，特佳為有機過氧化物。作為有機過氧化物，例如可列舉：二醯基過氧化物化合物、過氧化酯化合物、氫過氧化物化合物、酮過氧化物化合物、烷基過酸酯化合物、過碳酸酯化合物、過氧化縮酮等。該些可單獨使用一種，亦可併用多種。其中，就可縮短成形時間的方面而言，較佳為用於獲得10小時半衰期的溫度為60℃以上的聚合起始劑。另外，於藉由後述的製造方法1、製造方法3來製造積層體的情況且為特別是芯層（a）或芯層（A）為聚苯乙烯發泡體的情況下，為了避免由該聚苯乙烯發泡體的膨脹引起的成形不良，較佳為10小時半衰期溫度為90℃以下的聚合起始劑，更佳為80℃以下的聚合起始劑，特佳為70℃以下的聚合起始劑。作為此種聚合起始劑，例如可列舉：1,6-雙(第三丁基過氧化羰氧基)己烷、1,1-雙(第三丁基過氧化)環己烷、1,1-雙(第三戊基過氧化)環己烷、1,1-雙(第三己基過氧化)環己烷、過氧化二乙基乙酸第三丁酯、過氧化異丙基碳酸第三丁酯、過氧化2-乙基己基碳酸第三丁酯、過氧化異丙基碳酸第三戊酯、過氧化2-乙基己基碳酸第三戊酯、過氧化異丙基碳酸第三己酯、過氧化六氫對苯二甲酸二-第三丁酯、過氧化三甲基己酸第三戊酯、過氧化異壬酸第三戊酯、過氧化-2-乙基己酸第三己酯、戊酸4,4-二(第三丁基過氧化)正丁酯、過氧化2-乙基己酸1,1,3,3-四甲基丁酯、過氧化-2-乙基己酸第三丁酯、過氧化三甲基乙酸第三丁酯等。相對於樹脂組成物中的含聚合性不飽和基的化合物的總質量，聚合起始劑的添加量較佳為0.5質量%～3質量%的範圍。The resin composition (1) and the resin composition (2) may also contain a polymerization initiator. The polymerization initiator may be any conventional polymerization initiator without particular limitation, and an organic peroxide is particularly preferred. Examples of organic peroxides include diacyl peroxide compounds, peroxyester compounds, hydroperoxide compounds, ketone peroxide compounds, alkyl perester compounds, percarbonate compounds, and peroxyketal compounds. These may be used alone or in combination. Among them, in terms of shortening the molding time, a polymerization initiator having a temperature of 60° C. or above for obtaining a half-life of 10 hours is preferred. In addition, when a laminate is produced by the production method 1 or the production method 3 described later and in particular when the core layer (a) or the core layer (A) is a polystyrene foam, in order to avoid poor molding caused by the expansion of the polystyrene foam, a polymerization initiator having a 10-hour half-life temperature of 90°C or less is preferred, a polymerization initiator having a half-life temperature of 80°C or less is more preferred, and a polymerization initiator having a half-life temperature of 70°C or less is particularly preferred. Examples of such polymerization initiators include 1,6-bis(tert-butylperoxycarbonyloxy)hexane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-amylperoxy)cyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, tert-butylperoxydiethylacetate, tert-butylperoxyisopropylcarbonate, tert-butylperoxy-2-ethylhexylcarbonate, tert-amylperoxycarbonate, 2-ethylhexylperoxycarbonate, tert-butylperoxyisopropylcarbonate, 2-ethylhexylperoxycarbonate, tert-butyl ... 3-Amylhexyl carbonate, 3-isopropyl peroxycarbonate, di-3-butyl peroxyhexahydroterephthalate, 3-Amyl peroxytrimethylhexanoate, 3-Amyl peroxyisononanoate, 3-Amyl peroxy-2-ethylhexanoate, 4,4-di(3-butylperoxy)-butyl pentanoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 3-butyl peroxy-2-ethylhexanoate, 3-butyl peroxytrimethylacetate, etc. The amount of the polymerization initiator added is preferably in the range of 0.5 mass % to 3 mass % relative to the total mass of the polymerizable unsaturated group-containing compound in the resin composition.

所述樹脂組成物（1）、樹脂組成物（2）除所述各種化合物以外，亦可含有其他成分。作為其他成分，例如可列舉：熱塑性樹脂、聚合抑制劑、硬化促進劑、填充劑、低收縮劑、脫模劑、增黏劑、減黏劑、顏料、抗氧化劑、塑化劑、阻燃劑、抗菌劑、紫外線穩定劑、加強材、光硬化劑等。The resin composition (1) and the resin composition (2) may contain other components in addition to the above-mentioned various compounds. Examples of other components include thermoplastic resins, polymerization inhibitors, curing accelerators, fillers, low shrinkage agents, mold release agents, tackifiers, viscosity reducers, pigments, antioxidants, plasticizers, flame retardants, antibacterial agents, ultraviolet stabilizers, reinforcing materials, and light curing agents.

作為所述熱塑性樹脂，例如可列舉：聚醯胺樹脂、聚對苯二甲酸乙二酯樹脂、聚對苯二甲酸丁二酯樹脂、聚碳酸酯樹脂、胺基甲酸酯樹脂、聚丙烯樹脂、聚乙烯樹脂、聚苯乙烯樹脂、丙烯酸樹脂、聚丁二烯樹脂、聚異戊二烯樹脂及藉由共聚等將該些改質而得者。該些可單獨使用一種，亦可併用兩種以上。Examples of the thermoplastic resin include polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, urethane resin, polypropylene resin, polyethylene resin, polystyrene resin, acrylic resin, polybutadiene resin, polyisoprene resin, and modified versions thereof by copolymerization, etc. These may be used alone or in combination of two or more.

作為所述聚合抑制劑，例如可列舉：對苯二酚、三甲基對苯二酚、對-第三丁基鄰苯二酚、第三丁基對苯二酚、甲基對苯二酚（toluhydroquinone）、對苯醌、萘醌、對苯二酚單甲醚、啡噻嗪、環烷酸銅、氯化銅等。該些可單獨使用一種，亦可併用兩種以上。Examples of the polymerization inhibitor include hydroquinone, trimethylhydroquinone, p-tert-butylo-o-catechol, tert-butylhydroquinone, methylhydroquinone (toluhydroquinone), p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper cycloalkanoate, copper chloride, etc. These may be used alone or in combination of two or more.

作為所述硬化促進劑，例如可列舉：環烷酸鈷、辛烯酸鈷、辛烯酸氧釩、環烷酸銅、環烷酸鋇等金屬皂類；乙醯乙酸氧釩、乙醯乙酸鈷、乙醯丙酮酸鐵等金屬螯合化合物。另外，作為胺類，可列舉：N,N-二甲基胺基-對苯甲醛、N,N-二甲基苯胺、N,N-二乙基苯胺、N,N-二甲基-對甲苯胺、N-乙基-間甲苯胺、三乙醇胺、間甲苯胺、二乙三胺、吡啶、苯基嗎啉、哌啶、二乙醇苯胺等。該些可單獨使用一種，亦可併用兩種以上。Examples of the hardening accelerator include metal soaps such as cobalt cycloalkanoate, cobalt octenate, vanadium octenate, copper cycloalkanoate, and barium cycloalkanoate; and metal chelate compounds such as vanadium acetoacetate, cobalt acetoacetate, and iron acetopyruvate. In addition, examples of amines include N,N-dimethylamino-p-benzaldehyde, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, and diethanolaniline. These may be used alone or in combination of two or more.

作為所述填充劑，進行大致區分而有無機化合物、有機化合物。填充劑是主要出於調整成形物的強度、彈性係數、衝擊強度、疲勞耐久性等物性的目的而添加的成分。The fillers are roughly classified into inorganic compounds and organic compounds. Fillers are components added mainly for the purpose of adjusting the physical properties of the molded product, such as strength, elastic modulus, impact strength, fatigue durability, etc.

所述無機化合物例如可列舉：碳酸鈣、碳酸鎂、硫酸鋇、雲母、滑石、高嶺土、黏土、矽藻土、石棉、重晶石、氧化鋇、二氧化矽、矽砂、白雲石、石灰石、石膏、鋁微粉、中空球、氧化鋁、玻璃粉、氫氧化鋁、寒水石、氧化鋯、三氧化銻、氧化鈦、二氧化鉬、鐵粉等。有機化合物可列舉：纖維素、幾丁質等天然多糖類粉末、合成樹脂粉末等。作為合成樹脂粉末，可列舉包含硬質樹脂、軟質橡膠、彈性體或聚合物（共聚物）等的有機物的粉體、具有芯殼型等多層結構的粒子。作為合成樹脂粉末的具體例，可列舉：包含丁二烯橡膠、丙烯酸橡膠、胺基甲酸酯橡膠、矽橡膠等的粒子、聚醯亞胺樹脂粉末、氟樹脂粉末、酚樹脂粉末等。該些可單獨使用一種，亦可併用兩種以上。Examples of the inorganic compound include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, diatomaceous earth, asbestos, barite, barium oxide, silicon dioxide, silica sand, dolomite, limestone, gypsum, aluminum powder, hollow spheres, aluminum oxide, glass powder, aluminum hydroxide, calcite, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, iron powder, etc. Examples of the organic compound include natural polysaccharide powders such as cellulose and chitin, and synthetic resin powders. Examples of the synthetic resin powder include organic powders such as hard resins, soft rubbers, elastomers, or polymers (copolymers), and particles having a multilayer structure such as a core-shell type. Specific examples of synthetic resin powders include particles of butadiene rubber, acrylic rubber, urethane rubber, silicone rubber, etc., polyimide resin powder, fluororesin powder, phenol resin powder, etc. These may be used alone or in combination of two or more.

作為所述脫模劑，例如可列舉：硬脂酸鋅、硬脂酸鈣、石蠟、聚乙烯蠟、巴西棕櫚蠟等。較佳為可列舉：石蠟、聚乙烯蠟、巴西棕櫚蠟等。該些可單獨使用一種，亦可併用兩種以上。Examples of the release agent include zinc stearate, calcium stearate, wax, polyethylene wax, and carnauba wax. Preferably, wax, polyethylene wax, and carnauba wax are used. These may be used alone or in combination of two or more.

作為所述增黏劑，例如可列舉氧化鎂、氫氧化鎂、氧化鈣、氫氧化鈣等金屬氧化物或金屬氫氧化物等；丙烯酸樹脂系微粒子等。該些增黏劑既可單獨使用亦可併用兩種以上。Examples of the thickener include metal oxides or metal hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide; acrylic resin-based fine particles, etc. These thickeners may be used alone or in combination of two or more.

作為所述阻燃劑，例如可列舉：含磷原子的化合物、含鹵素原子的化合物、含氮原子的化合物、水合金屬化合物、硼酸鹽、金屬氧化物、矽酮化合物等。該些阻燃劑既可單獨使用亦可併用兩種以上。Examples of the flame retardant include compounds containing phosphorus atoms, compounds containing halogen atoms, compounds containing nitrogen atoms, hydrated metal compounds, borates, metal oxides, silicone compounds, etc. These flame retardants may be used alone or in combination of two or more.

所述預浸體的製造方法並無特別限定，例如可列舉如下方法：使用靜態混合器、功率混合器、行星式混合器、捏合機等公知的混合機將基質樹脂（r）的各成分混合後，使其含浸於所述強化纖維（f）中，利用脫模膜夾住其，並利用壓延機進行壓延的方法等。於使基質樹脂（r）含浸於強化纖維（f）中時，亦可適當進行加溫等。The method for producing the prepreg is not particularly limited, and examples thereof include the following methods: mixing the components of the matrix resin (r) using a known mixer such as a static mixer, a power mixer, a planetary mixer, a kneader, etc., and then impregnating the matrix resin (r) into the reinforcing fiber (f), sandwiching the matrix resin (r) with a release film, and calendering the reinforced fiber (f). When the matrix resin (r) is impregnated into the reinforcing fiber (f), heating may be appropriately performed.

於使用所述樹脂組成物（1）、樹脂組成物（2）作為基質樹脂（r）的情況下，藉由將壓延後的片材於常溫～50℃下靜置而使樹脂組成物中的異氰酸酯基與羥基進行胺基甲酸酯化反應，可製成保存性或處理性優異的預浸體。另外，於使用所述樹脂組成物（1）、樹脂組成物（2）作為基質樹脂（r）的情況下，亦可使用在樹脂組成物的製備過程中一部分進行了胺基甲酸酯化反應者。When the resin composition (1) or the resin composition (2) is used as the base resin (r), the isocyanate group and the hydroxyl group in the resin composition undergo a urethanization reaction by leaving the sheet after rolling at room temperature to 50°C, thereby producing a prepreg having excellent storage stability and handling properties. In addition, when the resin composition (1) or the resin composition (2) is used as the base resin (r), a resin composition that has undergone a urethanization reaction partially during the preparation process of the resin composition may be used.

就容易處理且成形性亦優異的方面而言，所述預浸體的厚度較佳為0.02 mm以上，更佳為0.05 mm以上。另外，較佳為1.0 mm以下，更佳為0.5 mm以下。In terms of easy handling and excellent formability, the thickness of the prepreg is preferably 0.02 mm or more, more preferably 0.05 mm or more, and preferably 1.0 mm or less, more preferably 0.5 mm or less.

所述外層（B）可對所述預浸體進行加熱成形而獲得。作為加熱成形方法的一例，例如可列舉如下方法：將積層多個預浸體而成者投入預先加熱至110℃～160℃的模具中，利用壓縮成形機進行合模並賦形，於保持0.1 MPa～10 MPa的成形壓力的狀態下進行硬化的方法。進而，較佳為如下製造方法：使用具有剪刃（shear edge）的模具，於模具溫度130℃～160℃下保持1 MPa～8 MPa的成形壓力，每1 mm厚度的成形品加熱壓縮成形1分鐘～3分鐘的製造方法。預浸體的積層片數可根據成形性與所獲得的外層（B）的強度的平衡任意設定，就輕量性優異的方面而言，較佳為1片～20片的範圍。另外，積層預浸體時的預浸體的方向可考慮所期望的強度來任意設定，較佳為以成為類各向同性的方式進行積層。例如，較佳為以纖維方向成為相互不同的0°與90°的方式依序重疊。就所獲得的積層體的強度與輕量性的平衡的方面而言，外層（B）的厚度較佳為0.1 mm以上，更佳為0.4 mm以上，特佳為0.6 mm以上。另外，較佳為2.0 mm以下，更佳為1.5 mm以下。The outer layer (B) can be obtained by heat-forming the prepreg. As an example of a heat-forming method, for example, the following method can be cited: a plurality of prepregs are stacked and placed in a mold preheated to 110°C to 160°C, and the mold is closed and formed using a compression molding machine, and the prepreg is hardened while maintaining a molding pressure of 0.1 MPa to 10 MPa. Furthermore, the following manufacturing method is preferred: a mold with a shear edge is used, a molding pressure of 1 MPa to 8 MPa is maintained at a mold temperature of 130°C to 160°C, and a molding method of heat-compression molding is performed for 1 minute to 3 minutes per 1 mm thickness of the molded product. The number of prepreg layers can be arbitrarily set according to the balance between formability and the strength of the outer layer (B) obtained, and is preferably in the range of 1 to 20 sheets in terms of excellent lightness. In addition, the direction of the prepreg when laminating the prepreg can be arbitrarily set in consideration of the desired strength, and it is preferably laminated in a quasi-isotropic manner. For example, it is preferred to stack them in sequence in a manner such that the fiber directions are 0° and 90° different from each other. In terms of the balance between the strength and lightness of the obtained laminate, the thickness of the outer layer (B) is preferably 0.1 mm or more, more preferably 0.4 mm or more, and particularly preferably 0.6 mm or more. In addition, it is preferably 2.0 mm or less, and more preferably 1.5 mm or less.

本發明的積層體只要包括所述芯層（A）及所述外層（B）即可，如上所述，亦可為芯層（A）形成為多層，或者所述外層（B）形成為多層。另外，本發明的積層體亦可具有該些以外的其他層。該其他層可以所述芯層（A）為中心配置於兩側，亦可僅配置於一側。該其他層較佳為位於所述芯層（A）與所述外層（B）的中間。作為所述其他層，例如可列舉：金屬層、樹脂層、接著劑層等。於該情況下，所述芯層（A）與所述外層（B）的厚度相對於積層體的總厚度所占的比例較佳為80%以上，更佳為85%以上。The laminate of the present invention only needs to include the core layer (A) and the outer layer (B). As described above, the core layer (A) may be formed into multiple layers, or the outer layer (B) may be formed into multiple layers. In addition, the laminate of the present invention may also have other layers besides these. The other layers may be arranged on both sides with the core layer (A) as the center, or may be arranged on only one side. The other layers are preferably located between the core layer (A) and the outer layer (B). Examples of the other layers include: metal layers, resin layers, adhesive layers, etc. In this case, the ratio of the thickness of the core layer (A) and the outer layer (B) to the total thickness of the laminate is preferably 80% or more, more preferably 85% or more.

本發明的積層體的製造方法並無特別限定，可根據積層體的用途或所期望的形狀等並利用多種多樣的方法來製造。作為具體例的一部分，可列舉以下三個製造方法。以下，對該些製造方法進行說明。 （製造方法1）對將包含發泡體的芯層（a）及包含含有強化纖維（f）與基質樹脂（r）的預浸體的外層（b）積層而得的前驅物於壓縮所述芯層（a）的條件下進行加熱成形的積層體的製造方法 （製造方法2）使用接著劑將所述芯層（A）與所述包含纖維強化塑膠的外層（B）接著的積層體的製造方法 （製造方法3）對將所述芯層（A）及包含含有強化纖維（f）與基質樹脂（r）的預浸體的外層（b）積層而得的前驅物進行加熱成形的積層體的製造方法 The manufacturing method of the laminate of the present invention is not particularly limited, and it can be manufactured using a variety of methods according to the purpose of the laminate or the desired shape. As part of the specific examples, the following three manufacturing methods can be listed. These manufacturing methods are described below. (Manufacturing method 1) A method for manufacturing a laminated body in which a core layer (a) including a foam body and an outer layer (b) including a prepreg containing reinforcing fibers (f) and a matrix resin (r) are laminated and heat-formed under the condition of compressing the core layer (a) (Manufacturing method 2) A method for manufacturing a laminated body in which the core layer (A) and the outer layer (B) containing a fiber-reinforced plastic are bonded using a bonding agent (Manufacturing method 3) A method for manufacturing a laminated body in which a core layer (A) and an outer layer (b) including a prepreg containing reinforcing fibers (f) and a matrix resin (r) are laminated and heat-formed

所述製造方法1是對將包含發泡體的芯層（a）及包含含有強化纖維（f）與基質樹脂（r）的預浸體的外層（b）積層而得的前驅物於壓縮所述芯層（a）的條件下進行加熱成形的方法。如上所述，所述外層（b）較佳為將多片預浸體重疊而成，具體而言，較佳為將1片～20片預浸體重疊而成。重疊預浸體時的積層方向可考慮所期望的強度來任意設定，較佳為以成為類各向同性的方式進行積層。例如，較佳為以纖維方向成為相互不同的0°與90°的方式依序重疊。所述芯層（a）與所述外層（b）可直接積層，亦可於它們之間設置接著層等其他層。另外，於利用製造方法1來製造積層體的情況下，為了防止於加熱形成步驟中形成芯層（a）的發泡體進一步發泡，形成所述外層（b）的預浸體的可成形溫度較佳為140℃以下，較佳為110℃以下。The manufacturing method 1 is a method of heat-forming a precursor obtained by laminating a core layer (a) including a foam body and an outer layer (b) including a prepreg containing reinforcing fibers (f) and a matrix resin (r) under the condition of compressing the core layer (a). As described above, the outer layer (b) is preferably formed by stacking multiple prepregs, and specifically, it is preferably formed by stacking 1 to 20 prepregs. The stacking direction when stacking the prepregs can be arbitrarily set in consideration of the desired strength, and it is preferably stacked in a quasi-isotropic manner. For example, it is preferably stacked in sequence in a manner that the fiber directions are 0° and 90°, which are different from each other. The core layer (a) and the outer layer (b) may be directly laminated, or other layers such as a bonding layer may be provided therebetween. In addition, when the laminate is manufactured using the manufacturing method 1, in order to prevent the foamed body forming the core layer (a) from further foaming in the heating forming step, the moldable temperature of the prepreg forming the outer layer (b) is preferably 140°C or less, and more preferably 110°C or less.

於所述製造方法1中，成形的條件並無特別限定，例如可列舉於80℃～140℃的溫度條件下、0.1 MPa～6 MPa的壓力條件下成形幾分鐘～幾十分鐘的方法等。對於模具，視需要亦可塗佈脫模劑，前驅物較佳為填充於模具中央。另外，亦可使用間隔物等來調整厚度，以使積層體的厚度成為規定的厚度。In the manufacturing method 1, the molding conditions are not particularly limited, and for example, a method of molding for several minutes to several ten minutes under a temperature condition of 80°C to 140°C and a pressure condition of 0.1 MPa to 6 MPa can be listed. A mold release agent can be applied to the mold as needed, and the precursor is preferably filled in the center of the mold. In addition, a spacer can be used to adjust the thickness so that the thickness of the laminate becomes a specified thickness.

所述製造方法2是使用接著劑將所述芯層（A）與所述包含纖維強化塑膠的外層（B）接著的方法。製造方法2中使用的芯層（A）與外層（B）如上所述。製造方法2中使用的接著劑並無特別限定，可根據積層體的用途或所期望的形狀等來選擇，例如可列舉：丙烯酸樹脂系、胺基甲酸酯樹脂系、橡膠系、聚酯樹脂系、環氧樹脂系、氰基丙烯酸酯樹脂系、矽酮樹脂系、改質矽酮樹脂系等。另外，接著劑可為單液型液狀、二液型液狀、片材狀、雙面膠帶狀等任意形狀。The manufacturing method 2 is a method of bonding the core layer (A) and the outer layer (B) comprising a fiber-reinforced plastic using an adhesive. The core layer (A) and the outer layer (B) used in the manufacturing method 2 are as described above. The adhesive used in the manufacturing method 2 is not particularly limited and can be selected according to the purpose of the laminate or the desired shape, for example, acrylic resin, urethane resin, rubber, polyester resin, epoxy resin, cyanoacrylate resin, silicone resin, modified silicone resin, etc. In addition, the adhesive can be in any shape such as a single-component liquid, a two-component liquid, a sheet, a double-sided tape, etc.

所述製造方法3是對將所述芯層（A）及包含含有強化纖維（f）與基質樹脂（r）的預浸體的外層（b）積層而得的前驅物進行加熱成形的方法。製造方法3中使用的芯層（A）如上所述。如上所述，所述外層（b）較佳為將多片預浸體重疊而成，具體而言，較佳為將1片～20片預浸體重疊而成。積層預浸體時的方向可考慮所期望的強度來任意設定，較佳為以成為類各向同性的方式進行積層。例如，較佳為以纖維方向成為相互不同的0°與90°的方式依序重疊。所述芯層（A）與所述外層（b）可直接積層，亦可於它們之間設置接著層等其他層。另外，於利用製造方法3來製造積層體的情況下，為了防止於加熱形成步驟中形成芯層（A）的發泡體進一步發泡，形成所述外層（b）的預浸體的可成形溫度較佳為140℃以下，較佳為110℃以下。The manufacturing method 3 is a method for heat-forming a precursor obtained by laminating the core layer (A) and the outer layer (b) including the prepreg containing reinforcing fibers (f) and the matrix resin (r). The core layer (A) used in the manufacturing method 3 is as described above. As described above, the outer layer (b) is preferably formed by stacking a plurality of prepregs, and specifically, it is preferably formed by stacking 1 to 20 prepregs. The direction when laminating the prepregs can be arbitrarily set in consideration of the desired strength, and it is preferably to laminate in a quasi-isotropic manner. For example, it is preferably to laminate in sequence in a manner such that the fiber directions become 0° and 90°, which are different from each other. The core layer (A) and the outer layer (b) may be directly laminated, or other layers such as a bonding layer may be provided therebetween. In addition, when the laminate is manufactured using the manufacturing method 3, in order to prevent the foamed body forming the core layer (A) from further foaming in the heating forming step, the moldable temperature of the prepreg forming the outer layer (b) is preferably 140°C or less, and more preferably 110°C or less.

於所述製造方法3中，成形的條件並無特別限定，例如可列舉於80℃～140℃的溫度條件下、0.1 MPa～6 MPa的壓力條件下成形幾分鐘～幾十分鐘的方法等。對於模具，視需要亦可塗佈脫模劑，前驅物較佳為填充於模具中央。另外，亦可使用間隔物等來調整厚度，以使積層體的厚度成為規定的厚度。In the manufacturing method 3, the molding conditions are not particularly limited. For example, a method of molding for several minutes to several ten minutes under a temperature condition of 80°C to 140°C and a pressure condition of 0.1 MPa to 6 MPa can be listed. A mold release agent can be applied to the mold as needed, and the precursor is preferably filled in the center of the mold. In addition, a spacer can be used to adjust the thickness so that the thickness of the laminate becomes a specified thickness.

本發明的積層體由於具有於為輕量的同時耐燃性或強度優異的特徵，因此除電池殼體以外，亦可適宜地用於航空航天器構件、鐵路車輛構件、住宅設備構件、電子機器構件、醫療機器構件、家電構件、汽車構件等多種用途。 [實施例] The laminate of the present invention has the characteristics of being lightweight and having excellent flame resistance or strength. Therefore, in addition to battery cases, it can also be suitably used in a variety of applications such as aerospace components, railway vehicle components, residential equipment components, electronic equipment components, medical equipment components, home appliance components, and automobile components. [Example]

其次，藉由實施例、比較例來更具體地說明本發明，以下，只要無特別說明，則「份」及「%」為質量基準。Next, the present invention will be described in more detail by way of examples and comparative examples. Hereinafter, unless otherwise specified, "parts" and "%" are by mass.

製造例1 預浸體（1）的製造 於設置有溫度計、氮氣及空氣導入管、冷卻冷凝器、攪拌機的1 L的燒瓶中投入環氧樹脂（迪愛生（DIC）股份有限公司製造的「艾匹克隆（EPICLON）152」）、四溴雙酚A型環氧樹脂（環氧當量365 g/當量、溴含量48.1質量%）365質量份、甲基丙烯酸84質量份、作為聚合抑制劑的第三丁基對苯二酚0.18質量份，於以1比1混合有氮氣與空氣的氣體的流通下，升溫至95℃。向其中放入作為觸媒的三苯基膦0.9質量份，升溫至105℃並反應12小時，由於酸價成為1以下，因此結束反應。冷卻至80℃附近後，自反應容器取出，獲得環氧甲基丙烯酸酯（1）。該樹脂的羥價為135 mgKOH/g。另外，該樹脂的(甲基)丙烯醯基當量為450 g/當量。 Production Example 1 Production of prepreg (1) In a 1 L flask equipped with a thermometer, nitrogen and air inlet pipes, a cooling condenser, and a stirrer, an epoxy resin ("Epiclon 152" manufactured by DIC Corporation), 365 parts by mass of tetrabromobisphenol A epoxy resin (epoxy equivalent 365 g/equivalent, bromine content 48.1% by mass), 84 parts by mass of methacrylic acid, and 0.18 parts by mass of tert-butylhydroquinone as a polymerization inhibitor were placed, and the temperature was raised to 95°C under the circulation of a gas mixed with nitrogen and air in a ratio of 1:1. 0.9 parts by mass of triphenylphosphine as a catalyst was added thereto, the temperature was raised to 105°C, and the reaction was allowed to proceed for 12 hours. Since the acid value became less than 1, the reaction was terminated. After cooling to about 80°C, the mixture was taken out from the reaction vessel to obtain epoxy methacrylate (1). The hydroxyl value of the resin was 135 mgKOH/g. In addition, the (meth)acrylic acid equivalent of the resin was 450 g/equivalent.

將二苯基甲烷二異氰酸酯（巴斯夫依諾阿酷聚胺基甲酸酯（BASFINOAC polyurethane）股份有限公司製造的「魯普拉奈特（LUPRANATE）MI」）13質量份、之前獲得的環氧(甲基)丙烯酸酯樹脂（1）80質量份、乙烯性不飽和單量體（丁二醇二甲基丙烯酸酯）20質量份及聚合起始劑（化藥阿克蘇（KAYAKU AKZO）股份有限公司製造的「托高諾斯（Trigonox）122-C80」、有機過氧化物、10小時半衰期溫度87℃）11.3質量份混合，獲得基質樹脂（1）。使用預浸體製造裝置，使基質樹脂（1）以樹脂質量含有率成為35%的方式含浸於硝子纖維（日本電氣硝子股份有限公司製造的「ER1620F」、硝子纖維的單位面積重量162 g/m ²）中，獲得厚度為0.13 mm的預浸體（1）。 13 parts by mass of diphenylmethane diisocyanate (LUPRANATE MI manufactured by BASF Innoac Polyurethane Co., Ltd.), 80 parts by mass of the previously obtained epoxy (meth)acrylate resin (1), 20 parts by mass of an ethylenically unsaturated monomer (butylene glycol dimethacrylate), and 11.3 parts by mass of a polymerization initiator (Trigonox 122-C80 manufactured by KAYAKU AKZO Co., Ltd., organic peroxide, 10-hour half-life temperature 87°C) were mixed to obtain a base resin (1). Using a prepreg manufacturing apparatus, a base resin (1) was impregnated into glass fiber ("ER1620F" manufactured by Nippon Electric Glass Co., Ltd., glass fiber weight per unit area 162 g/m ² ) so that the resin mass content was 35%, thereby obtaining a prepreg (1) having a thickness of 0.13 mm.

製造例2 預浸體（2）的製造 將二苯基甲烷二異氰酸酯（巴斯夫依諾阿酷聚胺基甲酸酯（BASFINOAC polyurethane）股份有限公司製造的「魯普拉奈特（LUPRANATE）MI」）13質量份、製造例1中獲得的環氧(甲基)丙烯酸酯樹脂（1）80質量份、乙烯性不飽和單量體（丁二醇二甲基丙烯酸酯）20質量份及聚合起始劑（化藥阿克蘇（KAYAKU AKZO）股份有限公司製造的「托高諾斯（Trigonox）421-70」、有機過氧化物、10小時半衰期溫度65℃）18.1質量份混合，獲得基質樹脂（2）。使用預浸體製造裝置，使基質樹脂（2）以樹脂質量含有率成為35%的方式含浸於硝子纖維（日本電氣硝子股份有限公司製造的「ER1620F」、硝子纖維的單位面積重量162 g/m ²）中，獲得厚度為0.13 mm的預浸體（2）。 Production Example 2 Production of prepreg (2) 13 parts by mass of diphenylmethane diisocyanate ("LUPRANATE MI" manufactured by BASF Innoac Polyurethane Co., Ltd.), 80 parts by mass of the epoxy (meth)acrylate resin (1) obtained in Production Example 1, 20 parts by mass of an ethylenically unsaturated monomer (butylene glycol dimethacrylate) and 18.1 parts by mass of a polymerization initiator ("Trigonox 421-70" manufactured by KAYAKU AKZO Co., Ltd., organic peroxide, 10-hour half-life temperature 65°C) were mixed to obtain a base resin (2). Using a prepreg manufacturing apparatus, the base resin (2) was impregnated into glass fiber ("ER1620F" manufactured by Nippon Electric Glass Co., Ltd., glass fiber unit area weight 162 g/m ² ) so that the resin mass content was 35%, thereby obtaining a prepreg (2) having a thickness of 0.13 mm.

製造例3 預浸體（3）的製造 將聚亞甲基聚苯基聚異氰酸酯與二苯基甲烷二異氰酸酯的混合物（東曹股份有限公司製造的「米魯奈特（Millionate）MR-200」、聚亞甲基聚苯基聚異氰酸酯的含量55質量～65質量）100質量份、甲基丙烯酸羥基乙酯59質量份、雙酚A的環氧乙烷加成物（三洋化成股份有限公司製造的「紐坡魯（Newpol）BPE-20」、羥基當量164 g/當量）24質量份、雙酚A的環氧乙烷加成物（三洋化成股份有限公司製造的「紐坡魯（Newpol）BPE-40」、羥基當量204 g/當量）31質量份、聚合起始劑（化藥阿克蘇（KAYAKU AKZO）股份有限公司製造的「托高諾斯（Trigonox）122-C80」、有機過氧化物）2.1質量份混合，獲得基質樹脂（2）。使用預浸體製造裝置，使基質樹脂（3）以樹脂質量含有率成為35%的方式含浸於硝子纖維（日本電氣硝子股份有限公司製造的「ER1620F」、硝子纖維的單位面積重量162 g/m ²）中，獲得厚度為0.13 mm的預浸體（3）。 Production Example 3 Production of Prepreg (3) 100 parts by mass of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate ("Millionate MR-200" manufactured by Tosoh Co., Ltd., content of polymethylene polyphenyl polyisocyanate 55 to 65 parts by mass), 59 parts by mass of hydroxyethyl methacrylate, 24 parts by mass of an ethylene oxide adduct of bisphenol A ("Newpol BPE-20" manufactured by Sanyo Chemical Co., Ltd., hydroxyl equivalent 164 g/equivalent), and 24 parts by mass of an ethylene oxide adduct of bisphenol A ("Newpol BPE-40" manufactured by Sanyo Chemical Co., Ltd., hydroxyl equivalent 204 g/equivalent) were mixed. g/equivalent) and 2.1 parts by mass of a polymerization initiator (Trigonox 122-C80 manufactured by KAYAKU AKZO Co., Ltd., an organic peroxide) were mixed to obtain a base resin (2). Using a prepreg manufacturing apparatus, the base resin (3) was impregnated into glass fiber (ER1620F manufactured by Nippon Electric Glass Co., Ltd., a unit area weight of the glass fiber of 162 g/m ² ) so that the resin mass content was 35%, thereby obtaining a prepreg (3) with a thickness of 0.13 mm.

製造例4 預浸體（4）的製造 將聚亞甲基聚苯基聚異氰酸酯與二苯基甲烷二異氰酸酯的混合物（東曹股份有限公司製造的「米魯奈特（Millionate）MR-200」、聚亞甲基聚苯基聚異氰酸酯的含量55質量%～65質量%）100質量份、甲基丙烯酸羥基乙酯59質量份、雙酚A的環氧乙烷加成物（三洋化成股份有限公司製造的「紐坡魯（Newpol）BPE-20」、羥基當量164 g/當量）24質量份、雙酚A的環氧乙烷加成物（三洋化成股份有限公司製造的「紐坡魯（Newpol）BPE-40」、羥基當量204 g/當量）31質量份、聚合起始劑（化藥阿克蘇（KAYAKU AKZO）股份有限公司製造的「托高諾斯（Trigonox）122-C80」、有機過氧化物）2.1質量份混合，獲得基質樹脂（3）。使用預浸體製造裝置，使基質樹脂（4）以樹脂質量含有率成為34%的方式含浸於碳纖維（東麗股份有限公司製造的「T700SC」、碳纖維的單位面積重量100 g/m ²）中，獲得厚度為0.1 mm的預浸體（4）。 Production Example 4 Production of Prepreg (4) 100 parts by mass of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate ("Millionate MR-200" manufactured by Tosoh Co., Ltd., polymethylene polyphenyl polyisocyanate content of 55% to 65% by mass), 59 parts by mass of hydroxyethyl methacrylate, 24 parts by mass of an ethylene oxide adduct of bisphenol A ("Newpol BPE-20" manufactured by Sanyo Chemical Co., Ltd., hydroxyl equivalent of 164 g/equivalent), and 24 parts by mass of an ethylene oxide adduct of bisphenol A ("Newpol BPE-40" manufactured by Sanyo Chemical Co., Ltd., hydroxyl equivalent of 204 g/equivalent) were mixed. g/equivalent) and 2.1 parts by mass of a polymerization initiator (Trigonox 122-C80 manufactured by Kayaku Akzo Co., Ltd., an organic peroxide) were mixed to obtain a base resin (3). Using a prepreg manufacturing apparatus, the base resin (4) was impregnated into carbon fibers (T700SC manufactured by Toray Industries, Ltd., carbon fiber unit area weight 100 g/m ² ) so that the resin mass content became 34%, thereby obtaining a prepreg (4) with a thickness of 0.1 mm.

製造例5 預浸體（5）的製造 將聚亞甲基聚苯基聚異氰酸酯與二苯基甲烷二異氰酸酯的混合物（東曹股份有限公司製造的「米魯奈特（Millionate）MR-200」、聚亞甲基聚苯基聚異氰酸酯的含量55質量%～65質量%）100質量份、甲基丙烯酸羥基乙酯59質量份、雙酚A的環氧乙烷加成物（三洋化成股份有限公司製造的「紐坡魯（Newpol）BPE-20」、羥基當量164 g/當量）24質量份、雙酚A的環氧乙烷加成物（三洋化成股份有限公司製造的「紐坡魯（Newpol）BPE-40」、羥基當量204 g/當量）31質量份、聚合起始劑（化藥阿克蘇（KAYAKU AKZO）股份有限公司製造的「托高諾斯（Trigonox）122-C80」、有機過氧化物）2.1質量份混合，獲得基質樹脂（3）。使用SMC製造裝置，使基質樹脂（4）以樹脂質量含有率成為43%的方式含浸於如下碳纖維，即切成1/2吋且無規地散佈的碳纖維（東麗股份有限公司製造的「T700SC」、碳纖維的單位面積重量1150 g/m ²）中，獲得厚度為1.6 mm的預浸體（5）。 Production Example 5 Production of Prepreg (5) 100 parts by mass of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate ("Millionate MR-200" manufactured by Tosoh Co., Ltd., polymethylene polyphenyl polyisocyanate content of 55% to 65% by mass), 59 parts by mass of hydroxyethyl methacrylate, 24 parts by mass of an ethylene oxide adduct of bisphenol A ("Newpol BPE-20" manufactured by Sanyo Chemical Co., Ltd., hydroxyl equivalent of 164 g/equivalent), and 24 parts by mass of an ethylene oxide adduct of bisphenol A ("Newpol BPE-40" manufactured by Sanyo Chemical Co., Ltd., hydroxyl equivalent of 204 g/equivalent) were mixed. g/equivalent) and 2.1 parts by mass of a polymerization initiator (Trigonox 122-C80 manufactured by Kayaku Akzo Co., Ltd., an organic peroxide) were mixed to obtain a base resin (3). Using an SMC manufacturing device, the base resin (4) was impregnated with the following carbon fibers cut into 1/2 inch and randomly dispersed (T700SC manufactured by Toray Industries, Ltd., carbon fiber unit area weight 1150 g/ ^m2 ) so that the resin mass content became 43%, and a prepreg (5) with a thickness of 1.6 mm was obtained.

實施例1～實施例4及比較例1 按照下述要領來製造積層體（1）～積層體（9）及積層體（1'），並進行各種評價試驗。將各積層體的評價結果示於表1及表2中。 Example 1 to Example 4 and Comparative Example 1 Laminar bodies (1) to (9) and (1') were manufactured according to the following procedures and various evaluation tests were performed. The evaluation results of each laminate are shown in Table 1 and Table 2.

實施例1 積層體（1）的製造 將製造例1中獲得的預浸體（1）切斷成298 mm×218 mm及298 mm×218 mm的大小，以預浸體的纖維方向成為相互不同的0°方向與90°方向的方式依序積層8片。將其填充於塗佈有脫模劑的平面板模具的中央，於壓力4 MPa、上模溫度140℃、下模溫度135℃、成形時間3分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×1 mm的外層（B1）。依據日本工業標準（Japanese Industrial Standards，JIS）K 7017而測定的外層（B1）的彎曲彈性係數為24.6 GPa。 將厚度為4 mm的發泡苯乙烯板（牛尾馬泰克斯（ushiomtx）股份有限公司製造的「巴利希魯德（BARI-SHIELD）」、於表面塗敷有阻燃劑的苯乙烯珠粒的發泡體、密度0.04 g/cm ³、發泡倍率60倍）切斷成298 mm×218 mm的大小後，填充於平面板模具的中央，於上模溫度30℃、下模溫度30℃、成形時間5分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×2 mm的芯層（A1）。芯層（A1）的厚度方向上的壓縮率為50%，比重為0.08 g/cm ³，根據壓縮率而算出的發泡體單元的縱橫比為2。 使用阻燃性雙面膠帶（日東電工製造的「No.5011N」、厚度0.15 mm），於芯層（A1）的兩面貼合所述外層（B1）各1片，獲得積層體（1）。 Example 1 Production of a laminate (1) The prepreg (1) obtained in Production Example 1 was cut into pieces of 298 mm × 218 mm and 298 mm × 218 mm in size, and eight pieces were laminated in order so that the fiber directions of the prepreg were in mutually different 0° and 90° directions. The prepreg was filled in the center of a flat plate mold coated with a mold release agent, and compression molding was performed under the conditions of a pressure of 4 MPa, an upper mold temperature of 140°C, a lower mold temperature of 135°C, and a molding time of 3 minutes to obtain an outer layer (B1) of 300 mm × 220 mm × 1 mm. The flexural modulus of the outer layer (B1) measured in accordance with Japanese Industrial Standards (JIS) K 7017 was 24.6 GPa. A 4 mm thick expanded styrene sheet ("BARI-SHIELD" manufactured by Ushiomtx Co., Ltd., a foamed body with styrene beads coated with a flame retardant on the surface, density 0.04 g/cm ³ , expansion ratio 60 times) was cut into 298 mm × 218 mm pieces and filled in the center of a flat plate mold. The sheet was compressed and molded at an upper mold temperature of 30°C, a lower mold temperature of 30°C, and a molding time of 5 minutes to obtain a core layer (A1) of 300 mm × 220 mm × 2 mm. The compression ratio of the core layer (A1) in the thickness direction was 50%, the specific gravity was 0.08 g/cm ³ , and the aspect ratio of the foam unit calculated from the compression ratio was 2. Using a flame-retardant double-sided adhesive tape ("No.5011N" manufactured by Nitto Denko, thickness 0.15 mm), one sheet of the outer layer (B1) was adhered to both sides of the core layer (A1) to obtain a laminate (1).

實施例2 積層體（2）的製造 將製造例1中獲得的熱硬化性預浸體（1）切斷成298 mm×218 mm及298 mm×218 mm的大小，以預浸體的纖維方向成為相互不同的0°方向與90°方向的方式依序積層4片。將其填充於塗佈有脫模劑的平面板模具的中央，於壓力4 MPa、上模溫度140℃、下模溫度135℃、成形時間3分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×0.5 mm的外層（B2）。依據JIS K 7017而測定的外層（B2）的彎曲彈性係數為24.6 GPa。 將厚度為10 mm的發泡苯乙烯板（牛尾馬泰克斯（ushiomtx）股份有限公司製造的「巴利希魯德（BARI-SHIELD）」、於表面塗敷有阻燃劑的苯乙烯珠粒的發泡體、密度0.04 g/cm ³、發泡倍率60倍）切斷成298 mm×218 mm的大小後，填充於平面板模具的中央，於上模溫度30℃、下模溫度30℃、成形時間5分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×2 mm的芯層（A2）。芯層（A2）的厚度方向上的壓縮率為80%，比重為0.20 g/cm ³，根據壓縮率而算出的發泡體單元的縱橫比為5。 使用阻燃性雙面膠帶（日東電工製造的「No.5011N」、厚度0.15 mm），於芯層（A2）的兩面貼合所述外層（B2）各1片，獲得積層體（2）。 Example 2 Production of a laminate (2) The thermosetting prepreg (1) obtained in Production Example 1 was cut into pieces of 298 mm × 218 mm and 298 mm × 218 mm in size, and four pieces were laminated in order so that the fiber directions of the prepreg were in mutually different 0° and 90° directions. The prepreg was filled in the center of a flat plate mold coated with a mold release agent, and compression molding was performed under the conditions of a pressure of 4 MPa, an upper mold temperature of 140°C, a lower mold temperature of 135°C, and a molding time of 3 minutes to obtain an outer layer (B2) of 300 mm × 220 mm × 0.5 mm. The flexural modulus of the outer layer (B2) measured in accordance with JIS K 7017 was 24.6 GPa. A 10 mm thick expanded styrene sheet ("BARI-SHIELD" manufactured by Ushiomtx Co., Ltd., a foamed body with styrene beads coated with a flame retardant on the surface, density 0.04 g/cm ³ , expansion ratio 60 times) was cut into 298 mm × 218 mm pieces and filled in the center of a flat plate mold. The sheet was compressed and molded at an upper mold temperature of 30°C, a lower mold temperature of 30°C, and a molding time of 5 minutes to obtain a core layer (A2) of 300 mm × 220 mm × 2 mm. The compression ratio of the core layer (A2) in the thickness direction was 80%, the specific gravity was 0.20 g/cm ³ , and the aspect ratio of the foam unit calculated from the compression ratio was 5. Using a flame-retardant double-sided adhesive tape ("No.5011N" manufactured by Nitto Denko, thickness 0.15 mm), one sheet of the outer layer (B2) was adhered to both sides of the core layer (A2) to obtain a laminate (2).

實施例3 積層體（3）的製造 將製造例1中獲得的熱硬化性預浸體（1）切斷成298 mm×218 mm及298 mm×218 mm的大小，以預浸體的纖維方向成為相互不同的0°方向與90°方向的方式依序積層3片。填充於塗佈有脫模劑的平面板模具的中央，利用壓縮成形機於壓力4 MPa、上模140℃、下模135℃、成形時間3分鐘的條件下進行壓縮成形，獲得寬度300 mm×220 mm×0.35 mm的外層（B3）。依據JIS K 7017而測定的外層（B3）的彎曲彈性係數為24.6 GPa。 將厚度為20 mm的發泡苯乙烯板（牛尾馬泰克斯（ushiomtx）股份有限公司製造的「巴利希魯德（BARI-SHIELD）」、於表面塗敷有阻燃劑的苯乙烯珠粒的發泡體、密度0.04 g/cm ³、發泡倍率60倍）切斷成298 mm×218 mm的大小後，填充於平面板模具的中央，於上模溫度30℃、下模溫度30℃、成形時間5分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×2 mm的芯層（A3）。芯層（A3）的厚度方向上的壓縮率為90%，比重為0.40 g/cm ³，根據壓縮率而算出的發泡體單元的縱橫比為10。 使用阻燃性雙面膠帶（日東電工製造的「No.5011N」、厚度0.15 mm），於芯層（A3）的兩面貼合所述外層（B3）各1片，獲得積層體（3）。 Example 3 Production of a laminate (3) The thermosetting prepreg (1) obtained in Production Example 1 was cut into pieces of 298 mm × 218 mm and 298 mm × 218 mm in size, and three pieces were laminated in order so that the fiber directions of the prepreg were in mutually different 0° and 90° directions. The pieces were filled in the center of a flat plate mold coated with a mold release agent, and compression molding was performed using a compression molding machine under the conditions of a pressure of 4 MPa, an upper mold temperature of 140°C, a lower mold temperature of 135°C, and a molding time of 3 minutes to obtain an outer layer (B3) with a width of 300 mm × 220 mm × 0.35 mm. The flexural modulus of the outer layer (B3) measured in accordance with JIS K 7017 was 24.6 GPa. A 20 mm thick expanded styrene sheet ("BARI-SHIELD" manufactured by Ushiomtx Co., Ltd., a foamed body with styrene beads coated with a flame retardant on the surface, density 0.04 g/cm ³ , expansion ratio 60 times) was cut into 298 mm × 218 mm pieces and filled in the center of a flat plate mold. The sheet was compressed and molded at an upper mold temperature of 30°C, a lower mold temperature of 30°C, and a molding time of 5 minutes to obtain a core layer (A3) of 300 mm × 220 mm × 2 mm. The compression ratio of the core layer (A3) in the thickness direction was 90%, the specific gravity was 0.40 g/cm ³ , and the aspect ratio of the foam unit calculated from the compression ratio was 10. Using a flame-retardant double-sided adhesive tape ("No.5011N" manufactured by Nitto Denko, thickness 0.15 mm), one sheet of the outer layer (B3) was adhered to both sides of the core layer (A3) to obtain a laminate (3).

實施例4 積層體（4）的製造 將厚度為20 mm的發泡苯乙烯板（牛尾馬泰克斯（ushiomtx）股份有限公司製造的「巴利希魯德（BARI-SHIELD）」、於表面塗敷有阻燃劑的苯乙烯珠粒的發泡體、密度0.04 g/cm ³、發泡倍率60倍）切斷成298 mm×218 mm的大小後，填充於平面板模具的中央，於上模溫度30℃、下模溫度30℃、成形時間5分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×1.5 mm的芯層（A4）。芯層（A4）的厚度方向上的壓縮率為92.5%，比重為0.53 g/cm ³，根據壓縮率而算出的發泡體單元的縱橫比為13.3。 使用阻燃性雙面膠帶（日東電工製造的「No.5011N」、厚度0.15 mm），於芯層（A4）的兩面貼合實施例2中獲得的外層（B2）各1片，獲得積層體（4）。 Example 4 Production of a laminate (4) A 20 mm thick foamed styrene sheet ("BARI-SHIELD" manufactured by Ushiomtx Co., Ltd., a foamed body of styrene beads coated with a flame retardant on the surface, density 0.04 g/ ^cm3 , foaming ratio 60 times) was cut into pieces of 298 mm × 218 mm and filled in the center of a flat plate mold. The pieces were compression molded at an upper mold temperature of 30°C, a lower mold temperature of 30°C, and a molding time of 5 minutes to obtain a core layer (A4) of 300 mm × 220 mm × 1.5 mm. The compression rate of the core layer (A4) in the thickness direction was 92.5%, the specific gravity was 0.53 g/cm ³ , and the aspect ratio of the foam unit calculated from the compression rate was 13.3. Using a flame-retardant double-sided adhesive tape ("No.5011N" manufactured by Nitto Denko, thickness 0.15 mm), one sheet of the outer layer (B2) obtained in Example 2 was attached to both sides of the core layer (A4) to obtain a laminate (4).

實施例5 積層體（5）的製造 將製造例2中獲得的預浸體（2）切斷成298 mm×218 mm及298 mm×218 mm的大小，以預浸體的纖維方向成為相互不同的0°方向與90°方向的方式依序積層8片。將其貼合於切斷成298 mm×218 mm的大小且厚度為20 mm的發泡苯乙烯板（牛尾馬泰克斯（ushiomtx）股份有限公司製造的「巴利希魯德（BARI-SHIELD）」、於表面塗敷有阻燃劑的苯乙烯珠粒的發泡體、密度0.04 g/cm ³、發泡倍率60倍）的兩面後，填充於塗佈有脫模劑的平面板模具的中央，設置4 mm的間隔物，於壓力4 MPa、上模溫度105℃、下模溫度100℃、成形時間5分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×4 mm的積層體（5）。 依據JIS K 7017而測定的外層的彎曲彈性係數為24.6 GPa。 Example 5 Production of a laminate (5) The prepreg (2) obtained in Production Example 2 was cut into pieces of 298 mm×218 mm and 298 mm×218 mm, and eight pieces were sequentially laminated so that the fiber directions of the prepreg were in mutually different 0° and 90° directions. After being attached to both sides of a 20 mm thick expanded polystyrene board (BARI-SHIELD manufactured by Ushiomtx Co., Ltd., a foamed body of styrene beads coated with a flame retardant on the surface, density 0.04 g/cm ³ , and expansion ratio 60 times) cut into 298 mm × 218 mm sizes, the sheet was filled in the center of a flat plate mold coated with a mold release agent, a 4 mm spacer was set, and compression molding was performed under the conditions of a pressure of 4 MPa, an upper mold temperature of 105°C, a lower mold temperature of 100°C, and a molding time of 5 minutes to obtain a 300 mm × 220 mm × 4 mm laminate (5). The flexural modulus of the outer layer measured in accordance with JIS K 7017 is 24.6 GPa.

實施例6 積層體（6）的製造 將厚度為20 mm的發泡苯乙烯板（牛尾馬泰克斯（ushiomtx）股份有限公司製造的「巴利希魯德（BARI-SHIELD）」、於表面塗敷有阻燃劑的苯乙烯珠粒的發泡體、密度0.04 g/cm ³、發泡倍率60倍）切斷成298 mm×218 mm的大小後，填充於平面板模具的中央，於上模溫度30℃、下模溫度30℃、成形時間5分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×4 mm的芯層（A4）。於芯層（A4）的兩面，將製造例2中獲得的預浸體（2）切斷成298 mm×218 mm及298 mm×218 mm的大小，以預浸體的纖維方向成為相互不同的0°方向與90°方向的方式依序積層8片，將所得的預浸體貼合於兩面後，填充於塗佈有脫模劑的平面板模具的中央，設置4 mm的間隔物，於壓力4 MPa、上模溫度105℃、下模溫度100℃、成形時間5分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×4 mm的積層體（6）。 依據JIS K 7017而測定的外層的彎曲彈性係數為24.6 GPa。 Example 6 Production of a laminate (6) A 20 mm thick expanded polystyrene sheet ("BARI-SHIELD" manufactured by Ushiomtx Co., Ltd., a foam of styrene beads coated with a flame retardant on the surface, density 0.04 g/ ^cm3 , and expansion ratio 60 times) was cut into pieces of 298 mm × 218 mm and filled in the center of a flat plate mold. The sheet was compression molded at an upper mold temperature of 30°C, a lower mold temperature of 30°C, and a molding time of 5 minutes to obtain a core layer (A4) of 300 mm × 220 mm × 4 mm. On both sides of the core layer (A4), the prepreg (2) obtained in Manufacturing Example 2 was cut into 298 mm × 218 mm and 298 mm × 218 mm in size, and eight sheets were stacked in sequence so that the fiber directions of the prepreg were mutually different at 0° and 90°. The obtained prepreg was bonded to both sides and filled in the center of a flat plate mold coated with a mold release agent, a 4 mm spacer was set, and compression molding was performed under the conditions of a pressure of 4 MPa, an upper mold temperature of 105°C, a lower mold temperature of 100°C, and a molding time of 5 minutes to obtain a 300 mm × 220 mm × 4 mm laminate (6). The flexural modulus of the outer layer measured in accordance with JIS K 7017 was 24.6 GPa.

實施例7 積層體（7）的製造 將製造例3中獲得的預浸體（3）切斷成298 mm×218 mm及298 mm×218 mm的大小，以預浸體的纖維方向成為相互不同的0°方向與90°方向的方式依序積層8片。將其填充於塗佈有脫模劑的平面板模具的中央，於壓力4 MPa、上模溫度140℃、下模溫度135℃、成形時間3分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×1 mm的外層（B4）。依據JIS K 7017而測定的外層（B4）的彎曲彈性係數為23.2 GPa。 將厚度為20 mm的發泡苯乙烯板（牛尾馬泰克斯（ushiomtx）股份有限公司製造的「巴利希魯德（BARI-SHIELD）」、於表面塗敷有阻燃劑的苯乙烯珠粒的發泡體、密度0.04 g/cm ³、發泡倍率60倍）切斷成298 mm×218 mm的大小後，填充於平面板模具的中央，於上模溫度30℃、下模溫度30℃、成形時間5分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×2 mm的芯層（A3）。芯層（A3）的厚度方向上的壓縮率為90%，比重為0.40 g/cm ³，根據壓縮率而算出的發泡體單元的縱橫比為10。 使用阻燃性雙面膠帶（日東電工製造的「No.5011N」），於芯層（A3）的兩面貼合所述外層（B4）各1片，獲得積層體（7）。 Example 7 Production of a laminate (7) The prepreg (3) obtained in Production Example 3 was cut into pieces of 298 mm × 218 mm and 298 mm × 218 mm in size, and eight pieces were laminated in sequence so that the fiber directions of the prepreg were in mutually different 0° and 90° directions. The prepreg was filled in the center of a flat plate mold coated with a mold release agent, and compression molding was performed under the conditions of a pressure of 4 MPa, an upper mold temperature of 140°C, a lower mold temperature of 135°C, and a molding time of 3 minutes to obtain an outer layer (B4) of 300 mm × 220 mm × 1 mm. The flexural modulus of the outer layer (B4) measured in accordance with JIS K 7017 was 23.2 GPa. A 20 mm thick expanded styrene sheet ("BARI-SHIELD" manufactured by Ushiomtx Co., Ltd., a foamed body with styrene beads coated with a flame retardant on the surface, density 0.04 g/cm ³ , expansion ratio 60 times) was cut into 298 mm × 218 mm pieces and filled in the center of a flat plate mold. The sheet was compressed and molded at an upper mold temperature of 30°C, a lower mold temperature of 30°C, and a molding time of 5 minutes to obtain a core layer (A3) of 300 mm × 220 mm × 2 mm. The compression ratio of the core layer (A3) in the thickness direction was 90%, the specific gravity was 0.40 g/cm ³ , and the aspect ratio of the foam unit calculated from the compression ratio was 10. Using a flame-retardant double-sided adhesive tape ("No.5011N" manufactured by Nitto Denko), one sheet of the outer layer (B4) is adhered to both sides of the core layer (A3) to obtain a laminate (7).

實施例8 積層體（8）的製造 將製造例4中獲得的預浸體（4）切斷成298 mm×218 mm及298 mm×218 mm的大小，以預浸體的纖維方向成為相互不同的0°方向與90°方向的方式依序積層8片。將其填充於塗佈有脫模劑的平面板模具的中央，於壓力4 MPa、上模溫度140℃、下模溫度135℃、成形時間3分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×1 mm的外層（B5）。依據JIS K 7017而測定的外層（B5）的彎曲彈性係數為61.5 GPa。 將厚度為20 mm的發泡苯乙烯板（牛尾馬泰克斯（ushiomtx）股份有限公司製造的「巴利希魯德（BARI-SHIELD）」、於表面塗敷有阻燃劑的苯乙烯珠粒的發泡體、密度0.04 g/cm ³、發泡倍率60倍）切斷成298 mm×218 mm的大小後，填充於平面板模具的中央，於上模溫度30℃、下模溫度30℃、成形時間5分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×2 mm的芯層（A3）。芯層（A3）的厚度方向上的壓縮率為90%，比重為0.40 g/cm ³，根據壓縮率而算出的發泡體單元的縱橫比為10。 使用阻燃性雙面膠帶（日東電工製造的「No.5011N」），於芯層（A3）的兩面貼合所述外層（B5）各1片，獲得積層體（8）。 Example 8 Production of a laminate (8) The prepreg (4) obtained in Production Example 4 was cut into pieces of 298 mm × 218 mm and 298 mm × 218 mm in size, and eight pieces were laminated in sequence so that the fiber directions of the prepreg were in mutually different 0° and 90° directions. The prepreg was filled in the center of a flat plate mold coated with a mold release agent, and compression molding was performed under the conditions of a pressure of 4 MPa, an upper mold temperature of 140°C, a lower mold temperature of 135°C, and a molding time of 3 minutes to obtain an outer layer (B5) of 300 mm × 220 mm × 1 mm. The flexural modulus of the outer layer (B5) measured in accordance with JIS K 7017 was 61.5 GPa. A 20 mm thick expanded styrene sheet ("BARI-SHIELD" manufactured by Ushiomtx Co., Ltd., a foamed body with styrene beads coated with a flame retardant on the surface, density 0.04 g/cm ³ , expansion ratio 60 times) was cut into 298 mm × 218 mm pieces and filled in the center of a flat plate mold. The sheet was compressed and molded at an upper mold temperature of 30°C, a lower mold temperature of 30°C, and a molding time of 5 minutes to obtain a core layer (A3) of 300 mm × 220 mm × 2 mm. The compression ratio of the core layer (A3) in the thickness direction was 90%, the specific gravity was 0.40 g/cm ³ , and the aspect ratio of the foam unit calculated from the compression ratio was 10. Using a flame-retardant double-sided adhesive tape ("No.5011N" manufactured by Nitto Denko), one sheet of the outer layer (B5) is adhered to both sides of the core layer (A3) to obtain a laminate (8).

實施例9 積層體（9）的製造 將製造例5中獲得的預浸體（5）切斷成290 mm×212 mm的大小。將其1片填充於塗佈有脫模劑的平面板模具的中央，於壓力10 MPa、上模溫度145℃、下模溫度145℃、成形時間3分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×1.5 mm的外層（B5）。依據JIS K 7017而測定的外層（B5）的彎曲彈性係數為29 GPa。 將厚度為20 mm的發泡苯乙烯板（牛尾馬泰克斯（ushiomtx）股份有限公司製造的「巴利希魯德（BARI-SHIELD）」、於表面塗敷有阻燃劑的苯乙烯珠粒的發泡體、密度0.04 g/cm ³、發泡倍率60倍）切斷成298 mm×218 mm的大小後，填充於平面板模具的中央，於上模溫度30℃、下模溫度30℃、成形時間5分鐘的條件下進行壓縮成形，獲得300 mm×220 mm×2 mm的芯層（A3）。芯層（A3）的厚度方向上的壓縮率為80%，比重為0.20 g/cm ³，根據壓縮率而算出的發泡體單元的縱橫比為5。 使用阻燃性雙面膠帶（日東電工製造的「No.5011N」），於芯層（A3）的兩面貼合所述外層（B5）各1片，獲得積層體（9）。 Example 9 Production of a laminate (9) The prepreg (5) obtained in Production Example 5 was cut into pieces of 290 mm × 212 mm in size. One piece of the prepreg (5) was filled in the center of a flat plate mold coated with a mold release agent, and compression molding was performed under the conditions of a pressure of 10 MPa, an upper mold temperature of 145°C, a lower mold temperature of 145°C, and a molding time of 3 minutes to obtain an outer layer (B5) of 300 mm × 220 mm × 1.5 mm. The flexural modulus of the outer layer (B5) measured in accordance with JIS K 7017 was 29 GPa. A 20 mm thick expanded styrene sheet ("BARI-SHIELD" manufactured by Ushiomtx Co., Ltd., a foamed body with styrene beads coated with a flame retardant on the surface, density 0.04 g/cm ³ , expansion ratio 60 times) was cut into 298 mm × 218 mm pieces and filled in the center of a flat plate mold. The sheet was compressed and molded at an upper mold temperature of 30°C, a lower mold temperature of 30°C, and a molding time of 5 minutes to obtain a core layer (A3) of 300 mm × 220 mm × 2 mm. The compression ratio of the core layer (A3) in the thickness direction was 80%, the specific gravity was 0.20 g/cm ³ , and the aspect ratio of the foam unit calculated from the compression ratio was 5. Using a flame-retardant double-sided adhesive tape ("No.5011N" manufactured by Nitto Denko), one sheet of the outer layer (B5) is adhered to both sides of the core layer (A3) to obtain a laminate (9).

比較例1 積層體（1'）的製造 將厚度為2 mm的發泡苯乙烯板（牛尾馬泰克斯（ushiomtx）股份有限公司製造的「巴利希魯德（BARI-SHIELD）」、於表面塗敷有阻燃劑的苯乙烯珠粒的發泡體、密度0.04 g/cm ³、發泡倍率60倍）切斷成300 mm×220 mm的大小，製成芯層（A1'）。 使用阻燃性雙面膠帶（日東電工製造的「No.5011N」、厚度0.15 mm），於芯層（A1'）的兩面貼合實施例1中獲得的外層（B1）各1片，獲得積層體（1'）。 Comparative Example 1 Production of a laminate (1') A 2 mm thick foamed styrene sheet ("BARI-SHIELD" manufactured by Ushiomtx Co., Ltd., a foamed body of styrene beads coated with a flame retardant on the surface, density 0.04 g/cm ³ , foaming ratio 60 times) was cut into 300 mm × 220 mm pieces to prepare a core layer (A1'). Using a flame retardant double-sided tape ("No.5011N" manufactured by Nitto Denko, thickness 0.15 mm), one sheet of the outer layer (B1) obtained in Example 1 was attached to both sides of the core layer (A1') to obtain a laminate (1').

積層體的厚度的評價 將芯層（A）及外層（B）（兩層）的合計厚度作為積層體的厚度進行評價。再者，於本評價中，於積層體的製造步驟中使用的雙面膠帶的厚度不包含於積層體的厚度中。 Evaluation of the thickness of the laminate The total thickness of the core layer (A) and the outer layer (B) (two layers) is evaluated as the thickness of the laminate. In this evaluation, the thickness of the double-sided tape used in the manufacturing step of the laminate is not included in the thickness of the laminate.

積層體的比重的測定 將芯層（A）及外層（B）（兩層）的合計重量除以積層體的體積而得的數值作為比重進行評價。再者，於本評價中，於積層體的製造步驟中使用的雙面膠帶的重量與體積不包含於積層體的重量與體積中。 Determination of specific gravity of laminate The total weight of the core layer (A) and the outer layer (B) (two layers) is divided by the volume of the laminate and the value is evaluated as the specific gravity. In addition, in this evaluation, the weight and volume of the double-sided tape used in the manufacturing step of the laminate are not included in the weight and volume of the laminate.

耐燃性的評價 使用氣體燃燒器，使火焰接觸積層體單面的中心部，以與積層體接觸的明火的溫度成為1000℃的方式調整火焰的位置，並加熱6分鐘。對積層體的未進行明火加熱的面的中心部的表面溫度進行測定，於加熱時的最高溫度下進行評價。 Evaluation of flame resistance Use a gas burner to bring the flame into contact with the center of one side of the laminate, adjust the position of the flame so that the temperature of the open flame in contact with the laminate becomes 1000°C, and heat for 6 minutes. Measure the surface temperature of the center of the surface of the laminate that is not heated by the open flame, and evaluate at the highest temperature during heating.

積層體的強度的評價 算出彎曲剛性（D）作為表示積層體的強度的指標並進行評價。 彎曲剛性（D）是根據以下的式來算出。 D=（（E1×t1）×（E2×t2）×（T+tc） ²）/4λ（E1×t1+E2×t2） 此處，E為外層（B）的彎曲彈性係數[kN/mm ²]（上層E1、下層E2），t為外層（B）的厚度[mm]（上層t1、下層t2），tc為芯層（A）的厚度[mm]，T為積層體的厚度[mm]。λ可以1-（泊松比） ²的形式算出，但作為各向異性材料的係數而使用0.99。 將超過鋼板的平均值即4.5 kN‧mm ²者評價為A，將其以下者評價為B。 Evaluation of the strength of the laminate The flexural rigidity (D) is calculated as an index representing the strength of the laminate and evaluated. The flexural rigidity (D) is calculated according to the following formula. D = ((E1×t1)×(E2×t2)×(T+tc) ² )/4λ(E1×t1+E2×t2) Here, E is the flexural elastic modulus [kN/mm ² ] of the outer layer (B) (upper layer E1, lower layer E2), t is the thickness of the outer layer (B) [mm] (upper layer t1, lower layer t2), tc is the thickness of the core layer (A) [mm], and T is the thickness of the laminate [mm]. λ can be calculated as 1-(Poisson's ratio) ² , but 0.99 is used as the coefficient of anisotropic materials. Those exceeding the average value of steel plates, i.e. 4.5 kN‧mm ² , are evaluated as A, and those below are evaluated as B.

[表1]    實施例1 實施例2 實施例3 實施例4 實施例5 預浸體的種類 （1） （1） （1） （1） （2） 芯層（A）的厚度[mm] 2 2 2 1.5 2 芯層（A）的壓縮率[%] 50 80 90 92.5 90 芯層（A）的發泡體單元的縱橫比 2 5 10 13.3 10 外層（B）的厚度[mm] 1 0.5 0.35 0.5 1 積層體整體的厚度[mm] 4 3 2.7 2.5 4 積層體的比重[g/m ³] 1.04 0.80 0.81 1.11 1.20 耐燃性[℃] 290 260 270 250 220 彎曲剛性的評價 A A A A A [Table 1] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Types of Prepreg (1) (1) (1) (1) (2) Thickness of core layer (A) [mm] 2 2 2 1.5 2 Compression ratio of core layer (A) [%] 50 80 90 92.5 90 Aspect ratio of the foam unit of the core layer (A) 2 5 10 13.3 10 Thickness of outer layer (B) [mm] 1 0.5 0.35 0.5 1 Overall thickness of the laminate [mm] 4 3 2.7 2.5 4 Specific gravity of laminate [g/m ³ ] 1.04 0.80 0.81 1.11 1.20 Flame resistance[℃] 290 260 270 250 220 Evaluation of bending stiffness A A A A A

[表2]    實施例6 實施例7 實施例8 實施例9 比較例1 預浸體的種類 （2） （3） （4） （5） （1） 芯層（A）的厚度[mm] 2 2 2 2 2 芯層（A）的壓縮率[%] 90 90 90 80 0 芯層（A）的發泡體單元的縱橫比 10 10 10 5 1 外層（B）的厚度[mm] 1 1 1 1.5 1 積層體整體的厚度[mm] 4 4 4 5 4 積層體的比重[g/m ³] 1.20 1.12 0.97 0.99 1.02 耐燃性[℃] 220 240 200 280 320 彎曲剛性的評價 A A A A A [Table 2] Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Comparison Example 1 Types of Prepreg (2) (3) (4) (5) (1) Thickness of core layer (A) [mm] 2 2 2 2 2 Compression ratio of core layer (A) [%] 90 90 90 80 0 Aspect ratio of the foam unit of the core layer (A) 10 10 10 5 1 Thickness of outer layer (B) [mm] 1 1 1 1.5 1 Overall thickness of the laminate [mm] 4 4 4 5 4 Specific gravity of laminate [g/m ³ ] 1.20 1.12 0.97 0.99 1.02 Flame resistance[℃] 220 240 200 280 320 Evaluation of bending stiffness A A A A A

Claims (8)

一種積層體，包括：芯層（A），將發泡體沿厚度方向壓縮而成；及外層（B），包含纖維強化塑膠。A laminate comprises: a core layer (A) formed by compressing a foam body in the thickness direction; and an outer layer (B) comprising a fiber-reinforced plastic. 如請求項1所述的積層體，其中，所述芯層（A）的壓縮率以厚度換算計為40%以上。The laminate according to claim 1, wherein the compression rate of the core layer (A) is 40% or more in terms of thickness. 如請求項1所述的積層體，其中，所述芯層（A）的發泡體單元的縱橫比為2以上。The laminate according to claim 1, wherein the aspect ratio of the foamed unit of the core layer (A) is 2 or more. 如請求項1所述的積層體，其中，所述外層（B）是對包含強化纖維（f）與基質樹脂（r）的預浸體進行加熱成形而獲得，所述基質樹脂為含有聚異氰酸酯化合物（r1）與多羥基(甲基)丙烯酸酯化合物（r2）的樹脂組成物（1）或含有聚異氰酸酯化合物（r1）、單羥基(甲基)丙烯酸酯化合物（r3）及多羥基化合物（r4）的樹脂組成物（2）。A laminate as described in claim 1, wherein the outer layer (B) is obtained by heat-forming a prepreg comprising reinforcing fibers (f) and a matrix resin (r), and the matrix resin is a resin composition (1) containing a polyisocyanate compound (r1) and a polyhydroxy (meth)acrylate compound (r2) or a resin composition (2) containing a polyisocyanate compound (r1), a monohydroxy (meth)acrylate compound (r3) and a polyhydroxy compound (r4). 一種積層體的製造方法，製造如請求項1至4中任一項所述的積層體，且所述積層體的製造方法中，對將芯層（a）與外層（b）積層而得的前驅物於壓縮所述芯層（a）的條件下進行加熱成形，所述芯層（a）包含發泡體，所述外層（b）包含含有強化纖維（f）與基質樹脂（r）的預浸體。A method for manufacturing a laminate, wherein the laminate as described in any one of claims 1 to 4 is manufactured, and in the method for manufacturing the laminate, a precursor obtained by laminating a core layer (a) and an outer layer (b) is heat-formed under the condition of compressing the core layer (a), wherein the core layer (a) includes a foamed body and the outer layer (b) includes a prepreg containing reinforcing fibers (f) and a matrix resin (r). 一種積層體的製造方法，製造如請求項1至4中任一項所述的積層體，且所述積層體的製造方法中，使用接著劑將所述芯層（A）與包含所述纖維強化塑膠的外層（B）接著。A method for manufacturing a laminate, comprising manufacturing the laminate as described in any one of claims 1 to 4, wherein the core layer (A) is bonded to the outer layer (B) comprising the fiber-reinforced plastic using a bonding agent. 一種積層體的製造方法，製造如請求項1至4中任一項所述的積層體，且所述積層體的製造方法中，對將所述芯層（A）與外層（b）積層而得的前驅物進行加熱成形，所述外層（b）包含含有強化纖維（f）與基質樹脂（r）的預浸體。A method for manufacturing a laminate, wherein the laminate as described in any one of claims 1 to 4 is manufactured, and in the method for manufacturing the laminate, a precursor obtained by laminating the core layer (A) and the outer layer (b) is heat-formed, and the outer layer (b) includes a prepreg containing reinforcing fibers (f) and a matrix resin (r). 一種電池殼體，使用如請求項1至4中任一項所述的積層體。A battery case using the laminate as described in any one of claims 1 to 4.