JP6224997B2 - Composite molded body and method for producing the same - Google Patents
Composite molded body and method for producing the same Download PDFInfo
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- JP6224997B2 JP6224997B2 JP2013235183A JP2013235183A JP6224997B2 JP 6224997 B2 JP6224997 B2 JP 6224997B2 JP 2013235183 A JP2013235183 A JP 2013235183A JP 2013235183 A JP2013235183 A JP 2013235183A JP 6224997 B2 JP6224997 B2 JP 6224997B2
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- 239000002131 composite material Substances 0.000 title claims description 130
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 229920005989 resin Polymers 0.000 claims description 358
- 239000011347 resin Substances 0.000 claims description 358
- 239000006260 foam Substances 0.000 claims description 171
- 229920001187 thermosetting polymer Polymers 0.000 claims description 155
- 239000000463 material Substances 0.000 claims description 92
- 239000007788 liquid Substances 0.000 claims description 86
- 239000002994 raw material Substances 0.000 claims description 79
- 239000003822 epoxy resin Substances 0.000 claims description 18
- 229920000647 polyepoxide Polymers 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000123 paper Substances 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920013716 polyethylene resin Polymers 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 239000002985 plastic film Substances 0.000 claims description 4
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- 239000002759 woven fabric Substances 0.000 claims description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims 1
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- 238000010438 heat treatment Methods 0.000 description 14
- 238000000465 moulding Methods 0.000 description 12
- 239000011344 liquid material Substances 0.000 description 10
- 238000005452 bending Methods 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- -1 polypropylene Polymers 0.000 description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000805 composite resin Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012792 core layer Substances 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 239000004790 ingeo Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009734 composite fabrication Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013518 molded foam Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
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- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
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- Laminated Bodies (AREA)
Description
本発明は、シート材を備えた複合成形体及びその製造方法に関する。 The present invention relates to a composite molded body provided with a sheet material and a method for producing the same.
建築用部材や構造用部材等の物品の軽量化を図るために、複数個の発泡粒子が不飽和ポリエステル樹脂硬化物で一体化された複合軽量体が、従来技術として知られている（例えば、特許文献１参照）。また、成形体の意匠性を高めるために、樹脂成形品の表面に、加飾シートを接着及び固着させる方法が知られている（例えば、特許文献２参照）。 In order to reduce the weight of articles such as building members and structural members, a composite lightweight body in which a plurality of foam particles are integrated with an unsaturated polyester resin cured product is known as a conventional technique (for example, Patent Document 1). Moreover, in order to improve the designability of a molded object, the method of adhere | attaching and adhering a decorating sheet on the surface of a resin molded product is known (for example, refer patent document 2).
しかしながら、特許文献１に記載の複合軽量体と特許文献２に記載の方法とを組み合わせて複合軽量体にシート材を貼付する場合には、複合軽量体の表面にシート材を強固に固着させることが難しい場合があり、複合軽量体の使用中にシート材が剥がれてしまう場合があった。また、上記の場合には、一度、複合軽量体を形成させた後に、シート材を貼付、あるいは圧縮成形等により固着させる必要があり、生産性の観点からは課題を残すものであった。そこで、本発明は、シート材が強固に固着された複合成形体及びその製造方法を提供することを目的とする。 However, when the composite lightweight body described in Patent Document 1 and the method described in Patent Document 2 are combined to attach a sheet material to the composite lightweight body, the sheet material is firmly fixed to the surface of the composite lightweight body. In some cases, the sheet material may peel off during use of the composite lightweight body. Further, in the above case, it is necessary to form a composite lightweight body once and then fix the sheet material by sticking or compression molding, which leaves a problem from the viewpoint of productivity. Then, an object of this invention is to provide the composite molded object to which the sheet | seat material was firmly fixed, and its manufacturing method.
本発明者は、鋭意研究を重ねた結果、以下に示す構成を採用することにより、上記課題を解決し得ることを見出し、本発明を完成するに至った。
すなわち、本発明は、
［１］複数の樹脂発泡小片と、熱硬化性樹脂硬化物と、シート材とから構成される複合成形体であって、前記樹脂発泡小片間に前記熱硬化性樹脂硬化物が形成されていると共に、前記複合成形体の外形表面の少なくとも一部が、前記熱硬化性樹脂硬化物からなり、シート材が埋設された硬化物層によって形成されている複合成形体、
［２］前記シート材の基材は、紙、織布、不織布、プラスチックシート又は金属メッシュである、上記［１］に記載の複合成形体、
［３］前記複数の樹脂発泡小片は、相互に融着している、上記［１］又は［２］に記載の複合成形体、
［４］前記複合成形体の密度が１００〜６００ｇ／Ｌであり、前記複合成形体の体積に対して、前記熱硬化性樹脂硬化物の体積が３〜５５体積％である、上記［１］〜［３］のいずれかに記載の複合成形体、
［５］前記熱硬化性樹脂硬化物は、エポキシ系樹脂、不飽和ポリエステル系樹脂、ジシクロペンタジエン系樹脂、ウレタン系樹脂、シリコン系樹脂、フェノール系樹脂、メラミン系樹脂、ポリイミド系樹脂、ユリア系樹脂及びジアリルフタレート系樹脂からなる群から選択される少なくとも１種である、上記［１］〜［４］のいずれかに記載の複合成形体、
［６］前記樹脂発泡小片を構成する基材樹脂は、ポリスチレン系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、及びポリ塩化ビニル系樹脂からなる群から選択される少なくとも１種である、上記［１］〜［５］のいずれかに記載の複合成形体、
［７］型内に複数の樹脂発泡小片の集合体と、シート材とが積層された状態となるように配置する工程、前記型内に熱硬化性樹脂液体原料を導入し、前記樹脂発泡小片間及び前記シート材に前記熱硬化性樹脂液体原料を含浸させる工程、及び前記熱硬化性樹脂液体原料を硬化させる工程を順次含む、複合成形体の製造方法、
［８］前記集合体が、空隙率３〜３０体積％の樹脂発泡小片成形体である、上記［７］に記載の複合成形体の製造方法。
As a result of intensive studies, the present inventor has found that the above-described problems can be solved by adopting the configuration shown below, and has completed the present invention.
That is, the present invention
[1] A composite molded body composed of a plurality of resin foam pieces, a thermosetting resin cured product, and a sheet material, and the thermosetting resin cured product is formed between the resin foam pieces. And at least a part of the outer shape surface of the composite molded body is made of the thermosetting resin cured product, and is formed by a cured product layer in which a sheet material is embedded,
[2] The composite molded body according to the above [1], wherein the base material of the sheet material is paper, woven fabric, nonwoven fabric, plastic sheet or metal mesh,
[3] The composite molded body according to [1] or [2], wherein the plurality of resin foam pieces are fused to each other,
[4] The density of the composite molded body is 100 to 600 g / L, and the volume of the cured thermosetting resin is 3 to 55% by volume with respect to the volume of the composite molded body. To [3] a composite molded article according to any one of
[5] The thermosetting resin cured product is an epoxy resin, an unsaturated polyester resin, a dicyclopentadiene resin, a urethane resin, a silicon resin, a phenol resin, a melamine resin, a polyimide resin, or a urea resin. A composite molded article according to any one of the above [1] to [4], which is at least one selected from the group consisting of a resin and a diallyl phthalate resin;
[6] The base resin constituting the resin foam piece is at least one selected from the group consisting of polystyrene resin, polyethylene resin, polypropylene resin, polyester resin, polycarbonate resin, and polyvinyl chloride resin. The composite molded body according to any one of the above [1] to [5], which is a seed,
[7] A step of disposing an aggregate of a plurality of resin foam pieces and a sheet material in a mold, a thermosetting resin liquid raw material is introduced into the mold, and the resin foam pieces A step of impregnating the sheet material with the thermosetting resin liquid raw material, and a step of curing the thermosetting resin liquid raw material in order,
[8] The method for producing a composite molded body according to [7], wherein the aggregate is a resin foam small piece molded body having a porosity of 3 to 30% by volume.
本発明の複合成形体は、上記樹脂発泡小片間に熱硬化性樹脂硬化物が形成されているので、軽量であり、強度に優れるものである。また、上記熱硬化性樹脂硬化物層にシート材が埋設されているので、シート材自体が剥がれたり、傷ついたりする等の不具合がなく、シート材が強固に固着され、意匠性及び強度等が向上された高い複合成形体となる。
さらに、本発明の製造方法によれば、シート材により意匠性が高められた複合成形体を、従来よりも容易に製造することができる。
Since the thermosetting resin cured product is formed between the resin foam pieces, the composite molded body of the present invention is lightweight and has excellent strength. In addition, since the sheet material is embedded in the thermosetting resin cured product layer, there is no problem such as peeling or scratching of the sheet material itself, the sheet material is firmly fixed, and the design property and strength, etc. An improved high composite molding is obtained.
Furthermore, according to the manufacturing method of the present invention, it is possible to manufacture a composite molded body whose design properties are enhanced by a sheet material more easily than in the past.
以下、図面を参照して、本発明の一実施形態の複合成形体を説明するが、本発明は図面に記載されたものに限定されるものではない。図１は、本発明の一実施形態における複合成形体を厚さ方向に沿って切断したときの断面を示す略図である。 Hereinafter, although the composite molded object of one Embodiment of this invention is demonstrated with reference to drawings, this invention is not limited to what was described in drawing. FIG. 1 is a schematic diagram showing a cross section when a composite molded body according to an embodiment of the present invention is cut along the thickness direction.
本発明の一実施形態における複合成形体１は、複数の樹脂発泡小片１２と、熱硬化性樹脂硬化物３０と、シート材２０とから少なくとも構成される複合成形体である。樹脂発泡小片１２間には熱硬化性樹脂硬化物３０が形成されていると共に、複合成形体１の外形表面の一部が、熱硬化性樹脂硬化物からなりシート材２０が埋設された硬化物層３２によって形成されている。なお、シート材２０は、樹脂発泡小片１２に接していてもよいし、樹脂発泡小片１２とシート材２０との間に熱硬化性樹脂硬化物が存在していてもよい。 A composite molded body 1 according to an embodiment of the present invention is a composite molded body composed of at least a plurality of resin foam pieces 12, a thermosetting resin cured product 30, and a sheet material 20. A cured product in which a thermosetting resin cured product 30 is formed between the resin foam small pieces 12 and a part of the outer surface of the composite molded body 1 is made of a thermosetting resin cured product and the sheet material 20 is embedded. Formed by layer 32. The sheet material 20 may be in contact with the resin foam piece 12 or a thermosetting resin cured product may exist between the resin foam piece 12 and the sheet material 20.
上記複合成形体１は、複数の樹脂発泡小片１２と熱硬化性樹脂硬化物３０とを備え、樹脂発泡小片１２間に熱硬化性樹脂硬化物３０が形成されて、熱硬化性樹脂硬化物３０からなる網目構造が形成されることにより、複合成形体１の強度が大きく向上し、軽量性も担保される（複合成形体１から樹脂発泡小片１２のみを除いた部分である、熱硬化性樹脂硬化物の立体構造を、以下、「熱硬化性樹脂複合成形体の網目構造」という場合がある。）。なお、熱硬化性樹脂硬化物３０は、樹脂発泡小片１２間に、未硬化状熱硬化性樹脂（以下、「熱硬化性樹脂液体原料」ということがある）を含浸した後に、硬化して形成したものであることが好ましい。なお、熱硬化性樹脂硬化物３０は、樹脂発泡小片間１２だけでなく、樹脂発泡小片１２内に形成されていてもよい。樹脂発泡小片内に熱硬化性樹脂硬化物が形成されるものとしては、例えば、樹脂発泡小片が貫通孔を有する筒型形状の樹脂発泡小片である場合等が挙げられる。 The composite molded body 1 includes a plurality of resin foam pieces 12 and a thermosetting resin cured product 30, and the thermosetting resin cured product 30 is formed between the resin foam small pieces 12. By forming a network structure made of the above, the strength of the composite molded body 1 is greatly improved and the light weight is also ensured (a thermosetting resin that is a portion obtained by removing only the resin foam pieces 12 from the composite molded body 1). Hereinafter, the three-dimensional structure of the cured product may be referred to as “a network structure of a thermosetting resin composite molded body”. The thermosetting resin cured product 30 is formed by impregnating an uncured thermosetting resin (hereinafter sometimes referred to as “thermosetting resin liquid raw material”) between the resin foam pieces 12 and then curing. It is preferable that The thermosetting resin cured product 30 may be formed not only between the resin foam small pieces 12 but also within the resin foam small pieces 12. As what forms a thermosetting resin hardened | cured material in a resin foam small piece, the case where a resin foam small piece is a cylindrical-shaped resin foam small piece which has a through-hole, for example is mentioned.
複合成形体１の外形表面の少なくとも一部には、熱硬化性樹脂硬化物３０からなる硬化物層３２（以下、単に「熱硬化性樹脂層」又は「硬化物層」と表記することがある。）が形成されている。硬化物層３２は、複合成形体１における上記網目構造の周囲を被覆する被覆層であり、樹脂発泡小片１２が存在しない樹脂層である。網目構造の周囲を硬化物層３２が被覆することにより、複合成形体１の強度が向上すると共に、複合成形体１の表面の耐摩耗性をさらに向上させることができる。硬化物層３２の厚みは、０．１〜５ｍｍであることが好ましく、０．３〜３ｍｍであることがより好ましい。なお、上記硬化物層は、外形表面のうち少なくとも一部に渡って形成されていることが好ましく、外形表面の全面に形成されていることがさらに好ましい。 At least a part of the outer surface of the composite molded body 1 may be referred to as a cured product layer 32 (hereinafter simply referred to as “thermosetting resin layer” or “cured product layer”) made of the thermosetting resin cured product 30. .) Is formed. The cured product layer 32 is a coating layer that covers the periphery of the network structure in the composite molded body 1 and is a resin layer in which the resin foam pieces 12 do not exist. By covering the periphery of the network structure with the cured product layer 32, the strength of the composite molded body 1 can be improved and the wear resistance of the surface of the composite molded body 1 can be further improved. The thickness of the cured product layer 32 is preferably 0.1 to 5 mm, and more preferably 0.3 to 3 mm. In addition, it is preferable that the said hardened | cured material layer is formed over at least one part among external surfaces, and it is still more preferable that it is formed in the whole surface of an external surface.
また、上記複合成形体の外形表面の少なくとも一部が、上記熱硬化性樹脂硬化物からなり、シート材２０が埋設された硬化物層３２にて形成されている本発明の一実施形態においては、硬化物層３２にシート材２０が埋設されていることにより、優れた意匠性及び強度を付与することが可能となる。また、シート材２０が剥がれたり、傷ついたりする等の不具合がなく、長期にわたり高い意匠性を維持できる複合成形体１となる。なお、複合成形体１の外形表面が硬化物層３２により形成されている場合には、外形表面の一部の硬化物層３２にシート材２０が埋設されていても、外形表面の全部の硬化物層３２にシート材２０が埋設されていてもよい。 In one embodiment of the present invention, at least a part of the outer surface of the composite molded body is made of the cured thermosetting resin and is formed of a cured product layer 32 in which the sheet material 20 is embedded. In addition, since the sheet material 20 is embedded in the cured product layer 32, it is possible to impart excellent designability and strength. Further, there is no problem such that the sheet material 20 is peeled off or damaged, and the composite molded body 1 can maintain a high designability over a long period of time. When the outer shape surface of the composite molded body 1 is formed by the cured product layer 32, even if the sheet material 20 is embedded in a part of the cured product layer 32 of the outer shape surface, the entire outer surface is cured. The sheet material 20 may be embedded in the physical layer 32.
シート材２０としては、シート状の紙、織布、不織布、プラスチックシート、金属板、金属メッシュ、繊維マット等が挙げられる。これらの中でも、シート材２０は、熱硬化性樹脂液体原料が含浸され易い、紙、織布、不織布、プラスチックシート又は金属メッシュであることが好ましい。なお、金属メッシュの場合にはメッシュ部分に熱硬化性液体原料が入り込むことにより、シート材に熱硬化性液体原料が擬似的に含浸される。また、印刷及び着色等を行うことによって意匠性が付与されたシート材を用いることにより、複合成形体１に様々な意匠性を付与することもでき、強度を有するシート材を用いることでシート材を補強材として用い、複合成形体１の強度等の物性を向上させることもできる。 Examples of the sheet material 20 include sheet-like paper, woven fabric, nonwoven fabric, plastic sheet, metal plate, metal mesh, fiber mat, and the like. Among these, it is preferable that the sheet material 20 is paper, a woven fabric, a nonwoven fabric, a plastic sheet, or a metal mesh which is easily impregnated with the thermosetting resin liquid raw material. In the case of a metal mesh, the sheet material is pseudo-impregnated with the thermosetting liquid material by entering the mesh portion. Further, by using a sheet material imparted with design properties by performing printing, coloring, etc., various design properties can be imparted to the composite molded body 1, and a sheet material having strength can be used. Can be used as a reinforcing material to improve physical properties such as strength of the composite molded body 1.
シート材２０の基材は、熱硬化性樹脂液体原料が浸透又は透過できるシートであることが好ましい。これにより、シート材２０は、熱硬化性樹脂硬化物３０を介して一体化し、シート材２０が硬化物層３２に埋設されて、複合成形体１から分離することが抑制される。シート材２０の基材は、熱硬化性樹脂液体原料を浸透、透過できるものであれば特に限定されない。 The base material of the sheet material 20 is preferably a sheet through which the thermosetting resin liquid raw material can permeate or permeate. Thereby, the sheet material 20 is integrated via the thermosetting resin cured product 30, and the sheet material 20 is suppressed from being embedded in the cured product layer 32 and separated from the composite molded body 1. The base material of the sheet material 20 is not particularly limited as long as it can penetrate and permeate the thermosetting resin liquid raw material.
複合成形体１の密度は、好ましくは１００〜６００ｇ／Ｌであり、より好ましくは１２０〜４００ｇ／Ｌであり、さらに好ましくは１５０〜３５０ｇ／Ｌである。複合成形体１の密度が上記範囲内であれば、複合成形体１は、優れた軽量性及び優れた強度を有することになる。 The density of the composite molded body 1 is preferably 100 to 600 g / L, more preferably 120 to 400 g / L, and still more preferably 150 to 350 g / L. When the density of the composite molded body 1 is within the above range, the composite molded body 1 has excellent lightness and excellent strength.
複合成形体１中の熱硬化性樹脂硬化物３０の体積分率が３〜５５体積％であることが好ましい。熱硬化性樹脂硬化物３０の体積分率が上記範囲内であれば、網目構造を構成する熱硬化性樹脂硬化物３０により複合成形体１の強度が向上すると共に、軽量性も兼ね備えた、複合成形体１となる。上記観点から、熱硬化性樹脂硬化物３０の体積分率は、４〜４０体積％であることがさらに好ましい。なお、複合成形体１中の熱硬化性樹脂硬化物３０の体積分率は、複合成形体１の外形体積から樹脂発泡小片１２の真の体積及びシート材の外形体積の総計を差し引いた体積を、複合成形体１の外形体積で割り算して算出される。 The volume fraction of the thermosetting resin cured product 30 in the composite molded body 1 is preferably 3 to 55% by volume. If the volume fraction of the thermosetting resin cured product 30 is within the above range, the composite molded body 1 is improved in strength by the thermosetting resin cured product 30 constituting the network structure, and has a light weight. The molded body 1 is obtained. From the above viewpoint, the volume fraction of the thermosetting resin cured product 30 is more preferably 4 to 40% by volume. The volume fraction of the thermosetting resin cured product 30 in the composite molded body 1 is the volume obtained by subtracting the total of the true volume of the resin foam pieces 12 and the external volume of the sheet material from the external volume of the composite molded body 1. Then, it is calculated by dividing by the outer volume of the composite molded body 1.
［樹脂発泡小片］
樹脂発泡小片１２は気泡を含む樹脂小片である。なお、図１に示す樹脂発泡小片１２の気泡は省略されている。樹脂発泡小片１２は、例えば、発泡剤を含有する発泡性樹脂小片を加熱処理する等により発泡させることによって、又は、樹脂発泡体を粉砕することによって得られる。
[Resin foam pieces]
The resin foam piece 12 is a resin piece containing bubbles. In addition, the bubble of the resin foam small piece 12 shown in FIG. 1 is abbreviate | omitted. The resin foam piece 12 can be obtained, for example, by foaming a foamable resin piece containing a foaming agent by heat treatment or by pulverizing the resin foam.
樹脂発泡小片１２には、例えば、発泡粒子、発泡ストランド並びに発泡成形体及び押出発泡体の切断物又は粉砕物、鞍形状（チップ状）の発泡体等が挙げられる。これらの中で、樹脂発泡小片１２は、発泡粒子であることが好ましい。また、発泡粒子としては、貫通孔を有する、特開平０８−１０８４４１号公報等に記載の、筒状形状の発泡粒子を使用することもできる。なお、筒型発泡粒子を用いた場合には、筒孔の貫通孔部分にも熱硬化性樹脂液体原料が含浸し固化することから、さらに、熱硬化性樹脂硬化物の網目構造がさらに形成され易くなり、強度が向上した複合成形体となる。 Examples of the resin foam small pieces 12 include foam particles, foam strands, foamed molded products, cut or pulverized products of extruded foams, and foam-shaped (chip-shaped) foams. Among these, the resin foam pieces 12 are preferably foamed particles. Further, as the expanded particles, cylindrical expanded particles described in JP-A-08-108441 having a through hole can be used. When cylindrical foam particles are used, the thermosetting resin liquid raw material is also impregnated and solidified in the through hole portion of the cylindrical hole, so that a network structure of a thermosetting resin cured product is further formed. It becomes easy to be a composite molded body with improved strength.
樹脂発泡小片１２を構成する基材樹脂は、熱可塑性樹脂であることが好ましい。樹脂発泡小片１２を構成する好ましい基材樹脂には、例えば、ポリスチレン系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリカーボネート系樹脂、ポリ塩化ビニル系樹脂、並びに、ポリ乳酸系樹脂、ポリブチレンサクシネート及びポリエチレンテレフタレート等のポリエステル系樹脂等を挙げることができ、これらは、１種を単独で又は２種以上を混合して用いることができる。さらに好ましい基材樹脂としては、ポリエチレン系樹脂、ポリプロピレン系樹脂、及びポリ乳酸系樹脂等が挙げられる。 The base resin constituting the resin foam piece 12 is preferably a thermoplastic resin. Preferred base resins constituting the resin foam piece 12 include, for example, polystyrene resins, polyethylene resins, polypropylene resins, polycarbonate resins, polyvinyl chloride resins, polylactic acid resins, polybutylene succinates, and the like. Examples thereof include polyester resins such as polyethylene terephthalate, and these can be used alone or in admixture of two or more. More preferable base resin includes polyethylene resin, polypropylene resin, and polylactic acid resin.
なお、上記樹脂発泡小片１２の形状によって、樹脂発泡小片１２間に形成される熱硬化性樹脂硬化物３０の立体構造が決まる。このため、樹脂発泡小片１２の長手方向の寸法と短手方向の寸法の比（長手方向の寸法／短手方向の寸法、以下、「アスペクト比」という場合がある。）は１〜２であることが好ましい。アスペクト比がこの範囲内であれば、樹脂発泡小片１２間に形成される空隙が均一に分布されやすくなる。 The three-dimensional structure of the cured thermosetting resin 30 formed between the resin foam pieces 12 is determined by the shape of the resin foam pieces 12. For this reason, the ratio of the dimension in the longitudinal direction of the resin foam piece 12 to the dimension in the lateral direction (longitudinal dimension / dimension in the lateral direction, hereinafter sometimes referred to as “aspect ratio”) is 1 to 2. It is preferable. If the aspect ratio is within this range, the voids formed between the resin foam pieces 12 are likely to be uniformly distributed.
樹脂発泡小片１２の粒子径は、好ましくは、１．０〜３．５ｍｍであり、より好ましくは１．５〜３．２ｍｍである。ここで、樹脂発泡小片１２の粒子径とは、１００個の樹脂発泡小片１２の最大外形寸法の平均値である。樹脂発泡小片１２の粒子径が上記範囲内であると、熱硬化性樹脂液体原料は樹脂発泡小片１２間に浸透しやすくなると共に、複合成形体１の強度を高くすることができる。 The particle diameter of the resin foam piece 12 is preferably 1.0 to 3.5 mm, more preferably 1.5 to 3.2 mm. Here, the particle diameter of the resin foam pieces 12 is an average value of the maximum outer dimensions of 100 resin foam pieces 12. When the particle diameter of the resin foam pieces 12 is within the above range, the thermosetting resin liquid raw material can easily penetrate between the resin foam pieces 12 and the strength of the composite molded body 1 can be increased.
樹脂発泡小片１２は、特に、特開２００４−０６８０１６号公報に記載されているような、鞘芯構造の発泡粒子を用いることが好ましい。鞘芯構造の発泡粒子における鞘層を形成する基材樹脂を熱硬化性樹脂原料との親和性が高いものを選択し、芯層を形成する基材樹脂を熱硬化性樹脂原料に不溶性のものとすることにより、樹脂発泡小片１２と熱硬化性樹脂硬化物３０との接合がより良好となり、強度の高い複合成形体１を得ることができる。 In particular, the resin foam piece 12 is preferably foamed particles having a sheath core structure as described in Japanese Patent Application Laid-Open No. 2004-0668016. The base resin that forms the sheath layer in the foam particles having the sheath core structure is selected to have a high affinity with the thermosetting resin raw material, and the base resin that forms the core layer is insoluble in the thermosetting resin raw material. By doing so, joining of the resin foam small piece 12 and the thermosetting resin cured product 30 becomes better, and the composite molded body 1 having high strength can be obtained.
樹脂発泡小片１２として好ましい鞘芯構造の発泡粒子は、例えば、鞘層が非晶性ポリ乳酸樹脂である鞘芯型のポリ乳酸系樹脂発泡粒子である。非晶性ポリ乳酸樹脂は熱硬化性樹脂に溶解又は膨潤しやすい特性を有していることから、発泡粒子と熱硬化性樹脂液体原料との間の親和性を高くすることができる。したがって、樹脂発泡小片表面に対する熱硬化性樹脂液体原料のぬれ性が良好になるので、熱硬化性樹脂液体原料は、樹脂発泡小片１２間の空隙に浸透しやすくなる。 The foam particles having a sheath core structure preferable as the resin foam small piece 12 are, for example, sheath core type polylactic acid resin foam particles whose sheath layer is an amorphous polylactic acid resin. Since the amorphous polylactic acid resin has the property of being easily dissolved or swollen in the thermosetting resin, the affinity between the foamed particles and the thermosetting resin liquid raw material can be increased. Therefore, since the wettability of the thermosetting resin liquid raw material with respect to the surface of the resin foam small pieces becomes good, the thermosetting resin liquid raw material easily penetrates into the gaps between the resin foam small pieces 12.
一方、鞘芯型のポリ乳酸系樹脂発泡粒子の芯層には、結晶性ポリ乳酸樹脂を用いることが好ましい。結晶性ポリ乳酸系樹脂は、熱硬化性樹脂液体原料に対して溶解や膨潤しにくい。このため、樹脂発泡小片１２間の空隙に熱硬化性樹脂液体原料が浸透しても、発泡粒子全体が溶けることなく、発泡粒子の形状が維持される。このようなポリ乳酸系樹脂発泡粒子は、例えば、特開２０１２−０２５８６９号公報に記載の方法により調製することができる。 On the other hand, a crystalline polylactic acid resin is preferably used for the core layer of the sheath-core type polylactic acid-based resin expanded particles. The crystalline polylactic acid-based resin is difficult to dissolve or swell with respect to the thermosetting resin liquid raw material. For this reason, even if the thermosetting resin liquid raw material penetrates into the gaps between the resin foam small pieces 12, the shape of the expanded particles is maintained without melting the entire expanded particles. Such polylactic acid-based resin expanded particles can be prepared, for example, by the method described in JP2012-025869A.
樹脂発泡小片１２の嵩密度は、好ましくは１５ｇ／Ｌ〜２５０ｇ／Ｌであり、より好ましくは１５〜１００ｇ／Ｌであり、さらに好ましくは１５〜９０ｇ／Ｌであり、さらに好ましくは１５〜８０ｇ／Ｌである。樹脂発泡小片１２の嵩密度が上記範囲内であれば、軽量であり、かつ強度が高い熱硬化性樹脂複合成形体の網目構造を形成しやすくなる。 The bulk density of the resin foam pieces 12 is preferably 15 g / L to 250 g / L, more preferably 15 to 100 g / L, still more preferably 15 to 90 g / L, and further preferably 15 to 80 g / L. L. When the bulk density of the resin foam small pieces 12 is within the above range, it is easy to form a network structure of a thermosetting resin composite molded body that is lightweight and has high strength.
樹脂発泡小片１２には、市販されている発泡粒子又は発泡体を使用することができる。例えば、株式会社ジェイエスピーのポリプロピレン系樹脂発泡体である商品名「ピーブロック（登録商標）」のうち、嵩密度が１５〜９０ｇ／Ｌである発泡粒子、同社のポリエチレン系樹脂発泡体である商品名「エルブロック（登録商標）」のうち、嵩密度が１５〜８０ｇ／Ｌである発泡粒子、株式会社ジェイエスピーの発泡性ポリスチレン樹脂粒子、商品名「スチロダイヤ （登録商標）」を予備発泡機で所定の嵩密度に発泡させたポリスチレン樹脂発泡粒子、株式会社ジェイエスピーのポリ乳酸系樹脂発泡体である商品名「ＬＡＣＴＩＦ（登録商標）」のうち、嵩密度が１５〜２００ｇ／Ｌである発泡粒子等を樹脂発泡小片１２として使用できる。また、特公昭５３−１３１３号公報、ＷＯ２０１２／０８６３０５号公報、特開２０１２−０２５８６９号公報等に記載されている発泡粒子も樹脂発泡小片１２として使用できる。 Commercially available foam particles or foam can be used for the resin foam piece 12. For example, among the product name “PiBlock (registered trademark)” which is a polypropylene resin foam of JSP Corporation, expanded particles having a bulk density of 15 to 90 g / L, and a product which is a polyethylene resin foam of the same company Of the name “L-Block (registered trademark)”, expandable particles having a bulk density of 15 to 80 g / L, expandable polystyrene resin particles of JSP Co., Ltd., and trade name “Styrodia® (registered trademark)” are pre-expanded Expanded polystyrene resin foam particles having a predetermined bulk density, expanded particles having a bulk density of 15 to 200 g / L among the trade name “LACTIF (registered trademark)” which is a polylactic acid resin foam of JSP Co., Ltd. Can be used as the resin foam pieces 12. Further, expanded particles described in Japanese Patent Publication No. 53-1313, WO2012 / 086305, Japanese Patent Application Laid-Open No. 2012-025869, and the like can also be used as the resin foam pieces 12.
樹脂発泡小片１２は、複合成形体１を成形する型内で、複数の樹脂発泡小片１２が接触、接着、又は融着して形成される集合体として、複合成形体１内で存在している。なお、その集合体は、複数の樹脂発泡小片を型内成形して得られる、樹脂発泡小片同士が加熱融着された、樹脂発泡小片成形体であることが好ましい。例えば、特開平２−２９９８２２号公報、特開平５−１４７１２０号公報等に記載されているように、複数の樹脂発泡小片１２を型内成形することによって樹脂発泡小片成形体は得られる。なお、図面の説明では、樹脂発泡小片１２は、樹脂発泡小片成形体として複合成形体１内に存在している。 The resin foam piece 12 exists in the composite molded body 1 as an aggregate formed by contacting, adhering, or fusing a plurality of resin foam pieces 12 in a mold for molding the composite molded body 1. . In addition, it is preferable that the aggregate is a resin foam small piece molded body obtained by heat-sealing resin foam small pieces obtained by in-mold molding a plurality of resin foam small pieces. For example, as described in JP-A-2-299822, JP-A-5-147120 and the like, a resin foam small piece molded body is obtained by molding a plurality of resin foam small pieces 12 in a mold. In the description of the drawings, the resin foam small piece 12 exists in the composite molded body 1 as a resin foam small piece molded body.
樹脂発泡小片成形体は連通した空隙を有していることが好ましく、その空隙率は、好ましくは３〜３０体積％であり、より好ましくは５〜２５体積％である。空隙率が上記範囲内であると、複合成形体１の強度を高くし、かつ複合成形体１を軽量化するのに適切な量の熱硬化性樹脂液体原料を樹脂発泡小片成形体に浸透させることができる。 It is preferable that the resin foam small piece molded body has continuous voids, and the porosity is preferably 3 to 30% by volume, more preferably 5 to 25% by volume. When the porosity is within the above range, an amount of a thermosetting resin liquid material appropriate for increasing the strength of the composite molded body 1 and reducing the weight of the composite molded body 1 is permeated into the resin foam small piece molded body. be able to.
なお、樹脂発泡小片成形体の空隙率は、例えば、以下の方法により求めることができる。
温度２３℃、相対湿度５０％の環境下で２４時間以上放置した樹脂発泡小片成形体から直方体試験片を切り出し、その試験片の外形寸法より嵩体積Ｖａ［ｃｍ3］を求める。次に、その試験片を温度２３℃のエタノールの入ったメスシリンダー中に金網等の道具を使用して沈め、軽い振動等を加えることにより成形体中の空隙に存在している空気を脱気する。そして、金網等の道具の体積を考慮して水位上昇分より読みとられる試験片の真の体積Ｖｂ［ｃｍ3］を測定する。求められた試験片の嵩体積Ｖａ［ｃｍ3］と真の体積Ｖｂ［ｃｍ3］から、次式により空隙率Ｙ［％］を求める。
空隙率Ｙ［％］＝〔（Ｖａ−Ｖｂ）／Ｖａ〕×１００・・・（１）
In addition, the porosity of a resin foam small piece molded object can be calculated | required with the following method, for example.
A rectangular parallelepiped test piece is cut out from a resin foam small piece that has been allowed to stand for 24 hours or more in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and a bulk volume Va [cm 3 ] is determined from the outer dimensions of the test piece. Next, the test piece is submerged in a graduated cylinder containing ethanol at a temperature of 23 ° C. using a tool such as a wire mesh, and the air present in the voids in the molded body is degassed by applying a light vibration or the like. To do. Then, the true volume Vb [cm 3 ] of the test piece read from the rise in the water level is measured in consideration of the volume of the tool such as a wire mesh. From the obtained bulk volume Va [cm 3 ] and the true volume Vb [cm 3 ], the porosity Y [%] is obtained by the following formula.
Porosity Y [%] = [(Va−Vb) / Va] × 100 (1)
樹脂発泡小片成形体の嵩密度は、好ましくは１５〜２５０ｇ／Ｌであり、より好ましくは２０〜２３０ｇ／Ｌである。樹脂発泡小片成形体の嵩密度が上記範囲内であれば、高い強度を有し、軽量である複合成形体１を得ることができる。 The bulk density of the resin foam small piece molding is preferably 15 to 250 g / L, more preferably 20 to 230 g / L. When the bulk density of the resin foam small piece is within the above range, the composite molded body 1 having high strength and light weight can be obtained.
なお、樹脂発泡小片成形体の嵩密度は、樹脂発泡小片成形体の重量を、樹脂発泡小片成形体１０の外形寸法から求められた容積で割り算し、さらに［ｋｇ／ｍ3］に単位換算することにより求めることもできる。 The bulk density of the resin foam small piece is obtained by dividing the weight of the resin foam small piece by the volume obtained from the outer dimensions of the resin foam small piece 10 and further converting the unit to [kg / m 3 ]. Can also be obtained.
［熱硬化性樹脂硬化物］
熱硬化性樹脂硬化物３０は、樹脂発泡小片１２間に、熱硬化性樹脂液体原料が含浸された後に硬化したものであり、三次元網目構造を形成している。また、複合成形体１の外形表面においては、熱硬化性樹脂硬化物は硬化物層３２を形成し、硬化物層３２にはシート材２０が埋設される。
[Thermosetting resin cured product]
The thermosetting resin cured product 30 is cured after the thermosetting resin liquid raw material is impregnated between the resin foam small pieces 12 and forms a three-dimensional network structure. Further, on the outer surface of the composite molded body 1, the cured thermosetting resin forms a cured product layer 32, and the sheet material 20 is embedded in the cured product layer 32.
熱硬化性樹脂硬化物３０には、例えば、エポキシ系樹脂、不飽和ポリエステル系樹脂、ジシクロペンタジエン系樹脂、ウレタン系樹脂、シリコン系樹脂、フェノ−ル系樹脂、メラミン系樹脂、ポリイミド系樹脂、ユリア系樹脂、ジアリルフタレート系樹脂及びこれらの変性樹脂等を挙げることができる。なお、熱硬化性樹脂硬化物３０はこれらの樹脂の、２種以上の混合物であってもよい。また、シート材２０との意匠性の観点からは、透明である熱硬化性樹脂３０を用いることが好ましい。 Examples of the thermosetting resin cured product 30 include epoxy resins, unsaturated polyester resins, dicyclopentadiene resins, urethane resins, silicone resins, phenol resins, melamine resins, polyimide resins, Examples include urea resins, diallyl phthalate resins, and modified resins thereof. The thermosetting resin cured product 30 may be a mixture of two or more of these resins. Further, from the viewpoint of design with the sheet material 20, it is preferable to use a thermosetting resin 30 that is transparent.
これらの樹脂の中でも、取り扱い性等の観点から、熱硬化性樹脂硬化物３０は、特に好ましくはエポキシ樹脂である。エポキシ樹脂は、１分子に２個以上のエポキシ基を含有するものが特に好ましい。このようなエポキシ樹脂には、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ（アセトアルデヒド）型エポキシ樹脂、グリシジルエステル型エポキシ樹脂及び脂環式エポキシ樹脂等が挙げられる。 Among these resins, the thermosetting resin cured product 30 is particularly preferably an epoxy resin from the viewpoint of handleability and the like. The epoxy resin is particularly preferably one containing two or more epoxy groups per molecule. Examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD (acetaldehyde) type epoxy resins, glycidyl ester type epoxy resins, and alicyclic epoxy resins.
熱硬化性樹脂硬化物３０により形成される、硬化物層３２の表面硬度は、好ましくは、バーコル硬度で２０以上である。これにより、硬化物層は擦過等からシート材２０を十分に保護することができる。なお、バーコル硬度は、ＪＩＳ Ｋ７０６０（１９９５）に準拠して測定することができる。 The surface hardness of the cured product layer 32 formed by the thermosetting resin cured product 30 is preferably 20 or more in Barcol hardness. Thereby, the hardened | cured material layer can fully protect the sheet | seat material 20 from abrasion. The Barcol hardness can be measured according to JIS K7060 (1995).
熱硬化性樹脂硬化物３０は、樹脂発泡小片１２間の空隙における樹脂発泡小片１２の表面と強固に接着していることが好ましい。樹脂発泡小片１２間の空隙に熱硬化性樹脂硬化物３０が入り込み、樹脂発泡小片１２の表面と強固に接着していることにより、さらに強度を向上させることができる。このような観点からは、熱硬化性樹脂硬化物３０としてエポキシ樹脂を用いた場合、樹脂発泡小片１２の基材樹脂は、ポリ乳酸樹脂及びポリプロピレン系樹脂等が特に好ましい。 It is preferable that the thermosetting resin cured product 30 is firmly bonded to the surface of the resin foam piece 12 in the gap between the resin foam pieces 12. The thermosetting resin cured product 30 enters the gaps between the resin foam small pieces 12 and is firmly bonded to the surface of the resin foam small pieces 12, whereby the strength can be further improved. From this point of view, when an epoxy resin is used as the thermosetting resin cured product 30, the base resin of the resin foam piece 12 is particularly preferably a polylactic acid resin or a polypropylene resin.
［複合成形体］
本発明の一実施形態における複合成形体１は、例えば、外壁デザイン用パネル並びに室内意匠パネルとして使用できる。また、複合成形体１は、自動車、鉄道、船舶、飛行機等の移動媒体の金属外板パネルの代替品としても使用できる。
[Composite molded body]
The composite molded body 1 according to an embodiment of the present invention can be used as, for example, an outer wall design panel and an indoor design panel. The composite molded body 1 can also be used as a substitute for a metal outer panel of a moving medium such as an automobile, a railway, a ship, and an airplane.
次に、図２を参照して、本発明の一実施形態における複合成形体１の製造方法を説明する。図２は、本発明の一実施形態における複合成形体１の製造方法を説明するための図である。なお、図２に示す樹脂発泡小片１２内の気泡は省略されている。また、樹脂発泡小片１２は、樹脂発泡小片成形体１０の形態で、本発明の一実施形態における製造方法で使用される。 Next, with reference to FIG. 2, the manufacturing method of the composite molded object 1 in one Embodiment of this invention is demonstrated. Drawing 2 is a figure for explaining the manufacturing method of composite fabrication object 1 in one embodiment of the present invention. Note that the bubbles in the resin foam piece 12 shown in FIG. 2 are omitted. Moreover, the resin foam small piece 12 is the form of the resin foam small piece molded object 10, and is used with the manufacturing method in one Embodiment of this invention.
［複合成形体の製造方法］
本発明の一実施形態における複合成形体の製造方法は、型内に複数の樹脂発泡小片の集合体と、シート材とが積層された状態となるように配置する工程（工程（Ａ））、型４０内に熱硬化性樹脂液体原料５０を導入し、樹脂発泡小片１２間及びシート材２０に熱硬化性樹脂液体原料５０を含浸させる工程（工程（Ｂ））、及び熱硬化性樹脂液体原料５０を硬化させる工程（工程（Ｃ））を順次含む。なお、複数の樹脂発泡小片１２が接触、接着、又は融着して形成される集合体であれば、型４０内に配置するものは樹脂発泡小片成形体１０に限定されない。
[Method for producing composite molded body]
The method for producing a composite molded body according to an embodiment of the present invention includes a step of placing a collection of a plurality of resin foam pieces and a sheet material in a mold (step (A)), A step (step (B)) of introducing a thermosetting resin liquid raw material 50 into the mold 40 and impregnating the resin foam small pieces 12 and the sheet material 20 with the thermosetting resin liquid raw material 50; and a thermosetting resin liquid raw material The process of hardening 50 (process (C)) is included sequentially. In addition, what is arrange | positioned in the type | mold 40 is not limited to the resin foam small piece molded object 10 if it is the aggregate | assembly formed by the some resin foam small piece 12 contacting, adhere | attaching, or melt | fusion.
［工程（Ａ）］
上述したように、工程（Ａ）では、複数の樹脂発泡小片１２の樹脂発泡小片成形体１０を、所定形状を有する型４０内に配置すると共に、樹脂発泡小片成形体１０の外形表面１４にシート材２０を配置する。なお、シート材２０は、樹脂発泡小片成形体１０の外形表面１４に配置された状態となっていればよいが、シート材２０が樹脂発泡小片成形体１０の外形表面１４に確実に配置されているようにするために、画鋲、ピン、両面テープ等の固定手段を使用して、樹脂発泡小片成形体１０の外形表面１４にシート材２０を固定してもよい。例えば、図２（ａ）に示すように、外形表面１４にシート材２０を配置した樹脂発泡小片成形体１０を、所定形状の型４０内に配置する。
[Step (A)]
As described above, in the step (A), the resin foam small piece molded body 10 of the plurality of resin foam small pieces 12 is disposed in the mold 40 having a predetermined shape, and a sheet is formed on the outer surface 14 of the resin foam small piece molded body 10. The material 20 is arranged. In addition, the sheet material 20 should just be in the state arrange | positioned at the external shape surface 14 of the resin foam small piece molded object 10, However, The sheet material 20 is arrange | positioned reliably at the external shape surface 14 of the resin foam small piece molded object 10. Therefore, the sheet material 20 may be fixed to the outer surface 14 of the resin foam small piece molded body 10 by using fixing means such as a thumbtack, a pin, and a double-sided tape. For example, as shown in FIG. 2A, the resin foam small piece molded body 10 in which the sheet material 20 is disposed on the outer surface 14 is disposed in a mold 40 having a predetermined shape.
型４０は、所定形状の内部空間４２を型４０内に有する、成形用の型である。型４０の内部空間４２の形状は、作製する複合成形体の形状により決まる。ところで、樹脂発泡小片成形体１０の大きさが型４０の内部空間４２に比べて小さすぎると、得られる複合成形体中の熱硬化性樹脂硬化物の割合が高くなり、複合成形体の軽量化が図れない場合がある。このため、型４０の内部空間４２は、所望の硬化物層の厚さに応じて、樹脂発泡小片成形体１０の大きさを変え、型４０と樹脂発泡小片成形体１０との間隙を調整することより決定される。 The mold 40 is a mold for molding having an inner space 42 of a predetermined shape in the mold 40. The shape of the internal space 42 of the mold 40 is determined by the shape of the composite molded body to be produced. By the way, if the size of the resin foam small piece 10 is too small as compared with the internal space 42 of the mold 40, the ratio of the thermosetting resin cured product in the obtained composite formed body becomes high, and the weight of the composite formed body is reduced. May not be possible. For this reason, the internal space 42 of the mold 40 changes the size of the resin foam small piece molded body 10 according to the desired thickness of the cured product layer, and adjusts the gap between the mold 40 and the resin foam small piece molded body 10. It is decided from that.
なお、シート材２０を配置した樹脂発泡小片成形体１０の外形表面１４が下側になるように型４０内に樹脂発泡小片成形体１０を配置することが好ましい。熱硬化性樹脂液体原料が型４０内に導入されると、樹脂発泡小片成形体１０は熱硬化性樹脂液体原料内で浮く場合があるからである。重しのようにシート材２０の上に載っていた樹脂発泡小片成形体１０が熱硬化性樹脂液体原料内で浮くとともに、シート材の素材や形状によってはシート材２０も浮き上がる場合があることから、シート材２０を配置した樹脂発泡小片成形体１０の外形表面１４が下側になるように配置して、シート材２０の外側の面２２を熱硬化性樹脂液体原料で確実に被覆されるようにすることが好ましい。また、樹脂発泡小片成形体１０にシート材２０が固定されている場合、シート材２０は樹脂発泡小片成形体１０と一緒に浮き上がる。この場合も、シート材２０の外側の面２２は熱硬化性樹脂液体原料で確実に被覆される。なお、シート材が埋設された硬化物層は、複数の面に跨って形成させたり、曲面に形成させることも可能である。 In addition, it is preferable to arrange | position the resin foam small piece molded object 10 in the type | mold 40 so that the external surface 14 of the resin foam small piece molded object 10 which has arrange | positioned the sheet material 20 may become a lower side. This is because when the thermosetting resin liquid material is introduced into the mold 40, the resin foam small piece molded body 10 may float in the thermosetting resin liquid material. The resin foam small piece molded body 10 placed on the sheet material 20 like a weight floats in the thermosetting resin liquid raw material, and the sheet material 20 may also float depending on the material and shape of the sheet material. The outer surface 14 of the resin foam small piece 10 in which the sheet material 20 is disposed is disposed on the lower side so that the outer surface 22 of the sheet material 20 is reliably covered with the thermosetting resin liquid raw material. It is preferable to make it. When the sheet material 20 is fixed to the resin foam small piece molded body 10, the sheet material 20 floats together with the resin foam small piece molded body 10. Also in this case, the outer surface 22 of the sheet material 20 is reliably covered with the thermosetting resin liquid raw material. In addition, the hardened | cured material layer by which the sheet | seat material was embed | buried can be formed ranging over several surfaces, or can also be formed in a curved surface.
［工程（Ｂ）］
上述したように、工程（Ｂ）では、図２（ｂ）に示すように、型４０内に熱硬化性樹脂液体原料５０を導入し、樹脂発泡小片１２間及びシート材２０に熱硬化性樹脂液体原料５０を含浸させる。
[Step (B)]
As described above, in step (B), as shown in FIG. 2B, the thermosetting resin liquid raw material 50 is introduced into the mold 40, and the thermosetting resin is formed between the resin foam small pieces 12 and the sheet material 20. The liquid raw material 50 is impregnated.
樹脂発泡小片１２間及びシート材２０に熱硬化性樹脂液体原料を含浸させる方法には、例えば、型４０の内部空間４２を減圧して浸透させる方法（減圧法）、及び熱硬化性樹脂液体原料を加圧して含浸させる方法（加圧法）がある。なお、減圧と加圧を同時に併用して行い、熱硬化性樹脂液体原料を導入することも可能である。 Examples of the method of impregnating the resin foam small pieces 12 and the sheet material 20 with the thermosetting resin liquid raw material include, for example, a method in which the internal space 42 of the mold 40 is decompressed and permeated (decompression method), There is a method (pressurization method) of impregnating with pressure. It is also possible to introduce a thermosetting resin liquid raw material by simultaneously performing decompression and pressurization.
（減圧法）
内部空間４２を減圧する場合、不図示の減圧吸引用のバルブを開いて、真空ポンプ等により内部空間４２は減圧される（減圧工程）。なお、少なくとも、熱硬化性樹脂液体原料５０の導入時には、減圧度が内部空間４２で均一になっていることが好ましい。内部空間４２が均一の減圧度となることにより、熱硬化性樹脂液体原料５０はシート材２０及び樹脂発泡小片成形体１０に均一に浸透し、強度の高い複合成形体１が得られる。
(Decompression method)
When the internal space 42 is decompressed, the decompression suction valve (not shown) is opened, and the internal space 42 is decompressed by a vacuum pump or the like (decompression process). At least when the thermosetting resin liquid raw material 50 is introduced, the degree of reduced pressure is preferably uniform in the internal space 42. When the internal space 42 has a uniform degree of reduced pressure, the thermosetting resin liquid raw material 50 uniformly penetrates into the sheet material 20 and the resin foam small piece molded body 10, and the composite molded body 1 having high strength is obtained.
内部空間４２を減圧にするとき、−０．０１〜−０．１ＭＰa（Ｇ）で行われるが、熱硬化性樹脂液体原料５０の沸点が下がるため、沸騰現象による気泡が熱硬化性樹脂液体原料５０に生ずるおそれがある。このため、内部空間４２の圧力は、より好ましくは−０．０２〜−０．０８ＭＰａ（Ｇ）である。 When the internal space 42 is depressurized, it is performed at -0.01 to -0.1 MPa (G). However, since the boiling point of the thermosetting resin liquid raw material 50 is lowered, bubbles due to the boiling phenomenon are generated in the thermosetting resin liquid raw material. 50 may occur. For this reason, the pressure of the internal space 42 is more preferably −0.02 to −0.08 MPa (G).
内部空間４２の減圧は、熱硬化性樹脂液体原料５０を内部空間４２に導入する前に行われることが好ましい。これにより、熱硬化性樹脂液体原料５０を樹脂発泡小片成形体１０の空隙に均等かつ隈なく浸透させることができる。 The internal space 42 is preferably decompressed before the thermosetting resin liquid raw material 50 is introduced into the internal space 42. Thereby, the thermosetting resin liquid raw material 50 can be penetrated evenly and uniformly in the voids of the resin foam small piece molded body 10.
熱硬化性樹脂液体原料５０の導入は準静的に行われることが好ましい。準静的な状態とは、レイノルズ数で定義される層流の状態であり、乱流の状態は含まない。熱硬化性樹脂液体原料５０を層流の状態で導入することにより、熱硬化性樹脂液体原料５０が気泡を巻き込むこと等を抑制することができる。これにより、熱硬化性樹脂複合成形体１０の網目構造の欠損を防止することができる。 The introduction of the thermosetting resin liquid raw material 50 is preferably performed quasi-statically. The quasi-static state is a laminar state defined by the Reynolds number and does not include a turbulent state. By introducing the thermosetting resin liquid raw material 50 in a laminar flow state, it is possible to prevent the thermosetting resin liquid raw material 50 from involving bubbles. Thereby, the defect | deletion of the network structure of the thermosetting resin composite molded object 10 can be prevented.
（加圧法）
例えば、熱硬化性樹脂液体原料５０の不図示の導入口で熱硬化性樹脂液体原料５０に圧力をかけて熱硬化性樹脂液体原料５０は内部空間４２に導入される。熱硬化性樹脂液体原料５０の加圧は、ピストンプランジャー等による機械的な圧縮により一般的に行われる。しかし、熱硬化性樹脂液体原料５０を収容している不図示のタンクを気体等で加圧して、熱硬化性樹脂液体原料５０を加圧してもよい。ただし、タンク内で熱硬化性樹脂液体原料５０が空気又は水蒸気成分と接触することにより、熱硬化性樹脂液体原料５０が変性もしくは失活するおそれがある場合は、ピストンプランジャー等による機械的な圧縮により熱硬化性樹脂液体原料５０に圧力をかけることが好ましい。熱硬化性樹脂液体原料５０を内部空間４２に導入するときの熱硬化性樹脂液体原料５０に適用する圧力は、好ましくは０．５ＭＰａ（Ｇ）以下である。加圧された熱硬化性樹脂液体原料５０はシート材２０及び樹脂発泡小片１２間に浸透する。
(Pressure method)
For example, the thermosetting resin liquid material 50 is introduced into the internal space 42 by applying pressure to the thermosetting resin liquid material 50 at an inlet (not shown) of the thermosetting resin liquid material 50. The thermosetting resin liquid raw material 50 is generally pressurized by mechanical compression using a piston plunger or the like. However, the thermosetting resin liquid raw material 50 may be pressurized by pressurizing a tank (not shown) containing the thermosetting resin liquid raw material 50 with gas or the like. However, when the thermosetting resin liquid raw material 50 comes into contact with air or a water vapor component in the tank and there is a possibility that the thermosetting resin liquid raw material 50 is denatured or deactivated, it is mechanically operated by a piston plunger or the like. It is preferable to apply pressure to the thermosetting resin liquid raw material 50 by compression. The pressure applied to the thermosetting resin liquid raw material 50 when introducing the thermosetting resin liquid raw material 50 into the internal space 42 is preferably 0.5 MPa (G) or less. The pressurized thermosetting resin liquid raw material 50 penetrates between the sheet material 20 and the resin foam piece 12.
（樹脂発泡小片成形体）
樹脂発泡小片成形体１０を用いる場合には、内部空間４２に熱硬化性樹脂液体原料５０を導入するときの初期の段階で、樹脂発泡小片成形体１０は熱硬化性樹脂液体原料５０から浮き上がる。これにより、樹脂発泡小片成形体１０の底側から熱硬化性樹脂液体原料５０は樹脂発泡小片成形体１０に浸透していき、樹脂発泡小片１２間に含浸することになる。また、樹脂発泡小片成形体１０の空隙内に残っている気体は、樹脂発泡小片成形体１０の上側から排出されるので、樹脂発泡小片成形体１０の空隙内に残っている気体は効率よく樹脂発泡小片成形体１０から排出される。したがって、樹脂発泡小片成形体１０に含浸された熱硬化性樹脂液体原料５０の中に気泡が残留することを抑制できる。
(Resin foam small piece molding)
When the resin foam small piece molded body 10 is used, the resin foam small piece molded body 10 floats up from the thermosetting resin liquid raw material 50 at the initial stage when the thermosetting resin liquid raw material 50 is introduced into the internal space 42. Thereby, the thermosetting resin liquid raw material 50 permeates into the resin foam small piece molded body 10 from the bottom side of the resin foam small piece molded body 10 and is impregnated between the resin foam small pieces 12. Further, since the gas remaining in the gap of the resin foam small piece molded body 10 is discharged from the upper side of the resin foam small piece molded body 10, the gas remaining in the gap of the resin foam small piece molded body 10 is efficiently resinized. The foamed small piece compact 10 is discharged. Therefore, it is possible to suppress the bubbles from remaining in the thermosetting resin liquid raw material 50 impregnated in the resin foam small piece molded body 10.
内部空間４２に熱硬化性樹脂液体原料５０が導入された後の、型４０の内部空間４２を形成する壁と樹脂発泡小片成形体１０との間の隙間の厚さは、好ましくは０．１〜５ｍｍであり、より好ましくは０．２〜３ｍｍである。型４０の内部空間４２を形成する壁と樹脂発泡小片成形体１０との間の隙間に、熱硬化性樹脂液体原料５０が回り込むことにより、樹脂発泡小片成形体１０の外形表面が硬化物層にて形成される。 The thickness of the gap between the wall forming the internal space 42 of the mold 40 and the resin foam small piece molded body 10 after the thermosetting resin liquid raw material 50 is introduced into the internal space 42 is preferably 0.1. -5 mm, more preferably 0.2-3 mm. When the thermosetting resin liquid raw material 50 wraps around the gap between the wall forming the internal space 42 of the mold 40 and the resin foam small piece molded body 10, the outer surface of the resin foam small piece molded body 10 becomes a cured product layer. Formed.
（シート材）
内部空間４２に導入した熱硬化性樹脂液体原料５０はシート材２０にも浸透することが好ましい。シート材２０が熱硬化性樹脂液体原料に対する透過性を有することにより、型４０の内部空間４２を形成する壁とシート材２０との間隙及びシート材と樹脂発泡小片成形体１０との隙間に、熱硬化性樹脂液体原料が存在して硬化物層３２（図１参照）を形成し、シート材２０が硬化物層３２（図１参照）に埋設されることとなる。
(Sheet material)
The thermosetting resin liquid raw material 50 introduced into the internal space 42 preferably penetrates into the sheet material 20. Since the sheet material 20 is permeable to the thermosetting resin liquid raw material, in the gap between the wall forming the internal space 42 of the mold 40 and the sheet material 20 and the gap between the sheet material and the resin foam small piece molded body 10, The thermosetting resin liquid raw material is present to form a cured product layer 32 (see FIG. 1), and the sheet material 20 is embedded in the cured product layer 32 (see FIG. 1).
（熱硬化性樹脂液体原料）
上述したように、液体状熱硬化性樹脂液体原料５０は、熱硬化性樹脂硬化物３０の硬化前の組成物である。熱硬化性樹脂液体原料５０は硬化剤を含んでもよい。硬化剤は、液体状熱硬化性樹脂成分と反応して硬化物を生成し得るものであれば特に限定されない。熱硬化性樹脂硬化物３０がエポキシ樹脂の場合、硬化剤には、例えば、メチルヘキサヒドロフタル酸無水物等の酸無水物、ノボラック型フェノール樹脂、クレゾールノボラック型エポキシ樹脂等のフェノール樹脂、無水フタル酸誘導体、ジシアンジアミド、イミダゾール化合物、アルミニウムキレート及びＢＦ3等のルイス酸のアミン錯体等が挙げられ、これらは、１種を単独で又は２種以上を混合して用いてもよい。
(Thermosetting resin liquid raw material)
As described above, the liquid thermosetting resin liquid raw material 50 is a composition before the thermosetting resin cured product 30 is cured. The thermosetting resin liquid raw material 50 may contain a curing agent. The curing agent is not particularly limited as long as it can react with the liquid thermosetting resin component to produce a cured product. When the thermosetting resin cured product 30 is an epoxy resin, examples of the curing agent include acid anhydrides such as methylhexahydrophthalic anhydride, phenol resins such as novolac type phenol resins and cresol novolac type epoxy resins, and phthalic anhydride. Examples include acid derivatives, dicyandiamide, imidazole compounds, aluminum chelates, and amine complexes of Lewis acids such as BF 3. These may be used alone or in combination of two or more.
硬化剤の添加量は、熱硬化性樹脂の種類、硬化剤の種類等によっても異なる。例えば、エポキシ樹脂の場合、そのエポキシ当量によっても異なるが、硬化剤の添加量は、例えば、エポキシ樹脂１００質量部に対して、好ましくは２〜１５０質量部である。 The addition amount of the curing agent varies depending on the type of thermosetting resin, the type of curing agent, and the like. For example, in the case of an epoxy resin, although it changes also with the epoxy equivalent, the addition amount of a hardening | curing agent becomes like this. Preferably it is 2-150 mass parts with respect to 100 mass parts of epoxy resins.
熱硬化性樹脂液体原料５０は、架橋モノマー、硬化促進剤、添加剤等をさらに含むことができる。 The thermosetting resin liquid raw material 50 can further include a crosslinking monomer, a curing accelerator, an additive, and the like.
熱硬化性樹脂液体原料５０は溶剤を含まないことが好ましい。溶剤は、熱硬化性樹脂複合成形体の網目構造を構成している網目構造壁の内部に、気泡を生じさせるおそれがあるからである。網目構造壁の内部には、可能な限り気泡が存在しないことが好ましい。網目構造壁の内部の気泡は、熱硬化性樹脂複合成形体の網目構造の強度を低下させ、これにより複合成形体１の強度も低下するからである The thermosetting resin liquid raw material 50 preferably contains no solvent. This is because the solvent may cause bubbles in the interior of the network wall constituting the network structure of the thermosetting resin composite molded body. It is preferable that bubbles are not present as much as possible inside the network wall. This is because air bubbles inside the network structure wall reduce the strength of the network structure of the thermosetting resin composite molded body, thereby reducing the strength of the composite molded body 1.
熱硬化性樹脂液体原料５０の粘度は、好ましくは１００〜１００００ｍＰａ・ｓであり、より好ましくは２００〜８０００ｍＰａ・ｓである。熱硬化性樹脂液体原料５０の粘度が上記範囲内であれば、樹脂発泡小片１２間に、熱硬化性樹脂液体原料５０を均一にかつ容易に浸透させることができる。なお、本明細書において粘度は、ＪＩＳ Ｋ６９０１（２００８）のブルックフィールド型粘度計法に基づいて測定された値である。 The viscosity of the thermosetting resin liquid raw material 50 is preferably 100 to 10000 mPa · s, and more preferably 200 to 8000 mPa · s. If the viscosity of the thermosetting resin liquid raw material 50 is within the above range, the thermosetting resin liquid raw material 50 can be uniformly and easily penetrated between the resin foam pieces 12. In the present specification, the viscosity is a value measured based on the Brookfield viscometer method of JIS K6901 (2008).
熱硬化性樹脂液体原料５０の粘度を調整するために、揺変性付与剤等の粘度を高くする添加剤及び粘度低下剤等の粘度を低くする添加剤を必要に応じて熱硬化性樹脂液体原料５０に添加することができる。この場合、粘度調整後の熱硬化性樹脂液体原料の粘度を測定する。 In order to adjust the viscosity of the thermosetting resin liquid raw material 50, an additive for increasing the viscosity such as a thixotropic agent and an additive for decreasing the viscosity such as a viscosity reducing agent are used as necessary. 50 can be added. In this case, the viscosity of the thermosetting resin liquid raw material after viscosity adjustment is measured.
［工程（Ｃ）］
工程Ｃでは、型４０内に導入された熱硬化性樹脂液体原料５０を硬化させる。熱硬化性樹脂液体原料５０を硬化する際には、熱硬化性樹脂液体原料５０の硬化特性に対応した温度に型を加熱すること等によって、型４０内部の熱硬化性樹脂液体原料５０を硬化させる。なお、硬化条件は、特段に規定されるものではなく、熱硬化性樹脂は、１液性ではなく、２液以上の複数液混合から構成されてもよい。硬化手段としては、目的とする硬化物が得られれば特段に規定されるものではなく、ラジカル反応、重縮合反応、メタセシス反応等の一般的な化学反応を伴う形態で硬化させることができる。これにより、図１に示す本発明の一実施形態における複合成形体１が完成する。
[Step (C)]
In step C, the thermosetting resin liquid raw material 50 introduced into the mold 40 is cured. When the thermosetting resin liquid material 50 is cured, the thermosetting resin liquid material 50 inside the mold 40 is cured by heating the mold to a temperature corresponding to the curing characteristics of the thermosetting resin liquid material 50. Let The curing conditions are not particularly defined, and the thermosetting resin may be composed of a mixture of two or more liquids instead of one liquid. The curing means is not particularly defined as long as the desired cured product is obtained, and can be cured in a form accompanied by a general chemical reaction such as a radical reaction, a polycondensation reaction, a metathesis reaction or the like. Thereby, the composite molded object 1 in one Embodiment of this invention shown in FIG. 1 is completed.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
なお、複合成形体、樹脂発泡小片成形体、樹脂発泡小片等の物性は、以下の方法により測定した。 The physical properties of the composite molded body, the resin foam piece, the resin foam piece and the like were measured by the following methods.
（樹脂発泡小片の嵩密度）
樹脂発泡小片の嵩密度は、樹脂発泡小片を無作為に抜き出し、気温２３℃、相対湿度５０％の大気圧下において、容積１Ｌのメスシリンダーの中に、静電気を除去しつつ自然堆積状態となるように多数の発泡小片を１Ｌの目盛まで収容し、次に、収容された発泡小片の重量を測定することにより求めた。
(Bulk density of resin foam pieces)
The bulk density of the foamed resin pieces is selected by randomly extracting the foamed resin pieces, and in a 1 L graduated cylinder at a temperature of 23 ° C. and a relative humidity of 50%, the static density is removed while being naturally deposited. Thus, many foam pieces were accommodated to the scale of 1L, and it calculated | required by measuring the weight of the accommodated foam pieces next.
（樹脂発泡小片の粒径）
樹脂発泡小片の粒径は、任意の樹脂発泡小片１００個について各々の最大直径を測定し、算出した値の平均値を樹脂発泡小片の平均径として示した。
(Particle size of resin foam piece)
As for the particle diameter of the resin foam pieces, the maximum diameters of 100 arbitrary resin foam pieces were measured, and the average value of the calculated values was shown as the average diameter of the resin foam pieces.
（樹脂発泡小片成形体の空隙率）
樹脂発泡小片成形体の空隙率は、温度２３℃、相対湿度５０％の環境下で２４時間以上放置した樹脂発泡小片成形体から直方体試験片を切り出し、該試験片の外形寸法より嵩体積Ｖａ［ｃｍ3］を求める。次いで該試験片を温度２３℃のエタノールの入ったメスシリンダー中に金網等の道具を使用して沈め、軽い振動等を加えることにより予備成形体中の空隙に存在している空気を脱気する。そして、金網等の道具の体積を考慮して水位上昇分より読みとられる該試験片の真の体積Ｖｂ［ｃｍ3］を測定する。求められた試験片の嵩体積Ｖａ［ｃｍ3］と真の体積Ｖｂ［ｃｍ3］から、次式により空隙率Ｙ［％］を求めた。
空隙率Ｙ［％］＝〔（Ｖａ−Ｖｂ）／Ｖａ〕×１００・・・（１）
(Porosity of molded resin small piece)
The porosity of the resin foam small piece was determined by cutting out a rectangular parallelepiped test piece from a resin foam small piece molded body that was allowed to stand for 24 hours or more in an environment of a temperature of 23 ° C. and a relative humidity of 50%. cm 3 ]. Next, the test piece is submerged in a graduated cylinder containing ethanol at a temperature of 23 ° C. using a tool such as a wire mesh, and the air present in the voids in the preform is degassed by applying a light vibration or the like. . Then, the true volume Vb [cm 3 ] of the test piece read from the rise in water level is measured in consideration of the volume of a tool such as a wire mesh. From the obtained bulk volume Va [cm 3 ] and the true volume Vb [cm 3 ], the porosity Y [%] was obtained by the following formula.
Porosity Y [%] = [(Va−Vb) / Va] × 100 (1)
（複合成形体の密度）
複合成形体の密度は、複合成形体の重量を水没法にて求められる複合成形体の体積で除して得られるとして求めた。なお、該密度は、シート材を含む、複合成形体の全体の密度を意味する。
(Composite molded body density)
The density of the composite molded body was determined as being obtained by dividing the weight of the composite molded body by the volume of the composite molded body determined by the submersion method. The density means the overall density of the composite molded body including the sheet material.
（熱硬化性樹脂硬化物により形成される網目径）
網目径の測定方法は、以下のようにして行った。得られた複合成形体を厚み方向に２分割し、顕微鏡を使用して切断面の拡大写真を撮影し、次に、写真上に複合成形体の表面の硬化物層を除いた部分から中心付近を通り反対側の表面まで達する直線を引き、直線と交わっている樹脂発泡小片の数を数える。そして、直線の長さ（実際の長さ）を樹脂発泡小片の数で除して、網目径を求め、この操作を複合成形体の５箇所について同様に行ない、得られる測定値の最大値とした。
(Net diameter formed by thermosetting resin cured product)
The method for measuring the mesh diameter was as follows. Divide the resulting composite molded body into two in the thickness direction, take an enlarged photograph of the cut surface using a microscope, and then remove the cured product layer on the surface of the composite molded body from the vicinity of the center Draw a straight line that passes through to the opposite surface and count the number of resin foam pieces that intersect the straight line. Then, the length of the straight line (actual length) is divided by the number of resin foam pieces to obtain a mesh diameter, and this operation is similarly performed for five locations of the composite molded body, and the maximum value of the obtained measurement value is obtained. did.
（複合成形体中の熱硬化性樹脂硬化物の体積分率）
複合成形体中の熱硬化性樹脂硬化物の体積分率（Ｉ）は、例えば、複合成形体の体積をＧとし、発泡小片成形体の体積をＨ、シート材の体積をＦとして、下式により求めることができる。
熱硬化性樹脂硬化物の体積分率Ｉ［％］＝〔（１００−Ｈ−Ｆ）／Ｇ〕×１００
(Volume fraction of cured thermosetting resin in composite molded body)
The volume fraction (I) of the thermosetting resin cured product in the composite molded body is, for example, the following formula: G is the volume of the composite molded body, H is the volume of the foamed small piece molded body, and F is the volume of the sheet material. It can ask for.
Volume fraction of thermosetting resin cured product I [%] = [(100−HF) / G] × 100
（複合成形体の内層密度）
複合成形体の内部から無作為に少なくとも５箇所から切り出した試験片の密度（内層密度）の標準偏差を密度の算術平均で除した値である変動係数を百分率で表示して１０％以内の範囲にあることが好ましく、８％以下であることが好ましい。なお、該内層密度は、表層の硬化物層部分を除いた密度として定義される。内層密度の変動係数が上記範囲内である場合には、複合成形体の内層密度のバラツキが小さいことから、強度の均一性に特に優れ、局所的に材料破壊等が進行して物性が低下してしまうことがなく、良好な複合成形体である。従って、従来よりも曲げ弾性率等の機械的物性に優れた複合成形体となる。
(Inner layer density of composite molded body)
The coefficient of variation, which is a value obtained by dividing the standard deviation of the density (inner layer density) of the test piece randomly cut from at least 5 locations from the inside of the composite molded body by the arithmetic average of the density, expressed as a percentage, is within 10%. Preferably, it is 8% or less. The inner layer density is defined as the density excluding the cured product layer portion of the surface layer. When the variation coefficient of the inner layer density is within the above range, since the variation of the inner layer density of the composite molded product is small, the strength uniformity is particularly excellent, and material destruction progresses locally, resulting in a decrease in physical properties. This is a good composite molded body. Therefore, the composite molded body is superior in mechanical properties such as flexural modulus compared to the conventional one.
なお、上記内層密度は、硬化物層部分を除く複合成形体の内部から任意に切り出した、直方体状の試験片の重量と３次元寸法を測定し計算した体積から、単位換算して内層密度（ｋｇ／ｍ3）を求めることができる。また、直方体状に切り出すのが困難な場合は、任意形状に切り出し、重量を測定したのちに、水を入れたメスシリンダーに試験片を沈めて、その標線変化から体積を測定（水没法）し、密度を計算することができる。なお、上記測定の場合には、試験片は硬化物層を含まないものとする。 The inner layer density is the inner layer density (in terms of units) calculated from the weight and three-dimensional dimensions of a rectangular parallelepiped specimen arbitrarily cut out from the inside of the composite molded body excluding the cured product layer portion. kg / m 3 ) can be obtained. If it is difficult to cut into a rectangular parallelepiped shape, cut it into an arbitrary shape, measure the weight, submerge the test piece in a graduated cylinder containing water, and measure the volume from the change in the marked line (submersion method) And the density can be calculated. In the case of the above measurement, the test piece does not include a cured product layer.
（複合成形体の耐傷性評価）
複合成形体の表面を、先端が尖った針を用いて、２５０ｇｆの荷重を与えながら１ｃｍ／秒の速度で引っ掻いた。
〇：シート材の印刷には影響がない
×：シート材の印刷部分が剥がれたり、傷つきが生じる。
(Scratch resistance evaluation of composite moldings)
The surface of the composite molded body was scratched at a speed of 1 cm / second while applying a load of 250 gf using a needle with a sharp tip.
○: No effect on printing of sheet material ×: Printed portion of sheet material is peeled off or damaged.
（接着性の評価）
複合成形体を構成する樹脂発泡小片成形体と熱硬化性樹脂の網目構造壁との接着性を確認する方法としては、曲げ破壊にて確認することができる。より具体的には、ＪＩＳ Ｋ７２２１に準拠して、通常は幅２０ｍｍ、厚さ１０ｍｍ、長さ２００ｍｍの試験片に切り出した後、支点間（スパン）１００ｍｍに設定した３点曲げ試験を、荷重速度５ｍｍ／秒で試験片中央部に曲げ荷重を与え、試験片が割れ折れるまで試験を行った後、その破断面を検証した。破断面において樹脂発泡小片が材料破壊している数が多いほど、接着性は高いと評価できるが、材料破壊した発泡小片の数（Ｎｂ）と材料破壊しなかった発泡小片の数（Ｎｎ）を比較し、その比Ｎｂ／Ｎｎの値が１以上でなければ、接着性があるとは評価できない。すなわち、本発明の複合成形体の接着性確認法において、Ｎｂ／Ｎｎの比の値は、１以上であることが好ましい。Ｎｂ／Ｎｎの値が１未満の場合は、曲げ、引張、せん断等の力学的強度が十分に発現しない虞があるため、好ましくない。
(Adhesive evaluation)
As a method for confirming the adhesiveness between the resin foam small piece molded body constituting the composite molded body and the network wall of the thermosetting resin, it can be confirmed by bending fracture. More specifically, in accordance with JIS K7221, a three-point bending test set to 100 mm between fulcrums (span) is usually performed after cutting into a test piece having a width of 20 mm, a thickness of 10 mm, and a length of 200 mm. A bending load was applied to the central portion of the test piece at 5 mm / second, and the test was conducted until the test piece was broken, and then the fracture surface was verified. It can be evaluated that the larger the number of resin foam pieces that have broken the material on the fracture surface, the higher the adhesiveness. However, the number of foam pieces that have been destroyed (Nb) and the number of foam pieces that have not been destroyed (Nn) In comparison, if the ratio Nb / Nn is not 1 or more, it cannot be evaluated that there is adhesiveness. That is, in the method for confirming the adhesiveness of the composite molded body of the present invention, the value of the Nb / Nn ratio is preferably 1 or more. When the value of Nb / Nn is less than 1, it is not preferable because mechanical strength such as bending, tension, and shearing may not be sufficiently exhibited.
（曲げ弾性率）
本発明において複合成形体の曲げ弾性率の測定は、ＪＩＳ Ｋ７２０３（１９８２）に基づいて行った。長さ１５０ｍｍ×横２５ｍｍ×厚さ３０ｍｍ（製品厚み）のものを複合成形体から、任意の箇所において１０箇所切出して試験片を作製した。なお、該試験片には、厚み方向の上下面には硬化物層が存在し、側面には硬化物層が存在しない。測定は、支点先端のＲ＝５ｍｍ、圧子先端のＲ＝５ｍｍ、支点間距離５０ｍｍ、曲げ速度１０ｍｍ／分の条件にて行った。なお、１０個の試験片を測定し平均値を求め、その値をその試験片の曲げ弾性率とした。
(Flexural modulus)
In the present invention, the flexural modulus of the composite molded body was measured based on JIS K7203 (1982). A specimen having a length of 150 mm, a width of 25 mm, and a thickness of 30 mm (product thickness) was cut out from the composite molded body at an arbitrary location to produce a test piece. The test piece has a cured product layer on the upper and lower surfaces in the thickness direction, and no cured product layer on the side surface. The measurement was performed under the conditions of R = 5 mm at the tip of the fulcrum, R = 5 mm at the tip of the indenter, a distance between the fulcrums of 50 mm, and a bending speed of 10 mm / min. In addition, ten test pieces were measured, the average value was calculated | required, and the value was made into the bending elastic modulus of the test piece.
（比曲げ剛性）
本発明における比曲げ剛性は、上述の方法により求められた、曲げ弾性率Ｅ（ＭＰａ）の値及び複合成形体の密度ρ（ｋｇ／ｍ3）から次式：Ｅ1/3／ρにより求めた値である。なお、複合成形体の比曲げ剛性は、０．０２〜０．０４［（ＭＰａ）1/3（Ｋｇ／ｍ3）-1］であることが好ましい。
(Specific bending stiffness)
The specific bending rigidity in the present invention is obtained by the following formula: E 1/3 / ρ from the value of the flexural modulus E (MPa) and the density ρ (kg / m 3 ) of the composite molded body obtained by the above method. Value. The specific bending rigidity of the composite molded body is preferably 0.02 to 0.04 [(MPa) 1/3 (Kg / m 3 ) −1 ].
（加熱体積変化率）
複合成形体における２３０℃、１０分の加熱後の加熱体積変化率が０〜−３％となることが好ましい。加熱体積変化率は、熱硬化性樹脂硬化物により形成される三次元網目構造の気泡壁部分に形成される気孔が応力点となって大きくなると考えられる。したがって、上記範囲内であれば、圧縮強度や曲げ強度等の物性が低下することなく、良好な複合成形体となる。上記観点から、加熱体積変化率は、０〜−２．５％であることがより好ましい。
(Heating volume change rate)
The heating volume change rate after heating at 230 ° C. for 10 minutes in the composite molded body is preferably 0 to −3%. It is considered that the heating volume change rate increases with pores formed in the bubble wall portion of the three-dimensional network structure formed by the thermosetting resin cured product as stress points. Therefore, if it is in the said range, physical properties, such as compressive strength and bending strength, will not fall, but it will become a favorable composite molded object. From the above viewpoint, the heating volume change rate is more preferably 0 to −2.5%.
加熱体積変化率の測定は、以下のようにして行った。まず、各実施例、比較例において作製した複合成形体の、試験前の体積Ｂを測定した。次いで、複合成形体を温度２３０℃のオーブンにて１０分加熱した後、温度２３℃、相対湿度５０％の条件下に６０分保管した。そして、加熱後の複合成形体の体積Ｃを測定した。
加熱体積変化率をＡとすると、式：Ａ＝（Ｂ−Ｃ）／Ｂ×１００にて体積変化率を求めた。なお、試験片のサイズは、縦５０ｍｍ×横５０ｍｍ×厚み２５ｍｍとして行った。また、試験片には、硬化物層が除かれた試験片を用いた。その結果を後述の表２に示す。
The heating volume change rate was measured as follows. First, the volume B before the test of the composite molded body produced in each example and comparative example was measured. Next, the composite molded body was heated in an oven at a temperature of 230 ° C. for 10 minutes, and then stored for 60 minutes under conditions of a temperature of 23 ° C. and a relative humidity of 50%. And the volume C of the composite molded object after a heating was measured.
When the heating volume change rate is A, the volume change rate was obtained by the formula: A = (BC) / B × 100. The size of the test piece was 50 mm long × 50 mm wide × 25 mm thick. Moreover, the test piece from which the hardened | cured material layer was removed was used for the test piece. The results are shown in Table 2 below.
実施例１
（発泡小片成形体の製造）
ネイチャーワークス社製のポリ乳酸、グレード名：「Ｉｎｇｅｏ４０６０Ｄ」の非発泡層の鞘層、及び同社のグレード名：「Ｉｎｇｅｏ２００３Ｄ」の発泡芯層からなる鞘芯型ポリ乳酸発泡粒子を樹脂発泡小片として用いた。鞘層と芯層の質量比率は５／９５であった。該発泡粒子を型内成形して発泡小片成形体を得た。成形には、開放し、閉鎖し得る金型〔有効寸法：長さ（ｌ）３００×幅（ｗ）３００×深さ（ｔ）５０（ｍｍ）〕を使用した。型内を空気で０．１ＭＰａ（Ｇ）に保持した金型内に樹脂発泡小片を充満した後、金型内の空気圧を０.０ＭＰａ（Ｇ）に戻した。次いで金型に付属する排気弁を開放した状態で元圧０．３ＭＰａ（Ｇ）のスチームを５秒間導通した後に、排気弁を閉鎖し、０．０２ＭＰａ（Ｇ）のスチームを型に導入し５秒間保持した。その後、直ちに型を開放し、１５秒の水冷冷却を行い、型を開放して、型で成形した平板状の発泡小片成形体を取り出した。成形体は、４０℃のオーブン中で２４時間乾燥した後に、７０℃のオーブンに移し、２４時間の熱処理が施された。熱処理後の発泡小片成形体の寸法は長さ（ｌ）２９５×幅（ｗ）２９５×厚み（ｔ）４８（ｍｍ）であり、嵩密度８４ｋｇ／ｍ3を有する、後述の表１に示す空隙率のポリ乳酸製の発泡小片成形体（発泡粒子型内成形体）を得た。成形品は、厚さ２８ｍｍにカットして平板とした。
Example 1
(Manufacture of foamed small pieces)
Polylactic acid manufactured by Nature Works, grade name: “Ingeo 4060D” non-foamed sheath layer, and company grade name: “Ingeo 2003D” foamed core layer used as resin foam small pieces It was. The mass ratio of the sheath layer to the core layer was 5/95. The foamed particles were molded in-mold to obtain a foamed small piece compact. For molding, a mold that can be opened and closed [effective dimension: length (l) 300 × width (w) 300 × depth (t) 50 (mm)] was used. After filling the mold in which the inside of the mold was kept at 0.1 MPa (G) with air, the resin foam pieces were filled, and the air pressure in the mold was returned to 0.0 MPa (G). Next, with the exhaust valve attached to the mold open, steam with an original pressure of 0.3 MPa (G) is conducted for 5 seconds, then the exhaust valve is closed, and 0.02 MPa (G) steam is introduced into the mold. Held for 2 seconds. Thereafter, the mold was immediately opened, cooled with water for 15 seconds, the mold was opened, and the flat foamed small piece molded body molded with the mold was taken out. The molded body was dried in an oven at 40 ° C. for 24 hours, then transferred to an oven at 70 ° C., and subjected to heat treatment for 24 hours. The dimensions of the molded foam piece after the heat treatment are length (l) 295 × width (w) 295 × thickness (t) 48 (mm), and have a bulk density of 84 kg / m 3. A foamed small piece molded product made of polylactic acid (foamed particle in-mold molded product) was obtained. The molded product was cut to a thickness of 28 mm to form a flat plate.
（複合成形体の製造）
有効内寸３００(ｌ)×３００(ｗ)×３０(ｔ)（ｍｍ）である、熱硬化性樹脂の導入口と排出口を有する樹脂型（ＦＲＰ型）を上型とし、２ｍｍ厚みのＳＵＳ板を下型とした、上下一対の、密閉空間を形成できる型の内部に、上記のポリ乳酸製の発泡小片成形体を配置すると共に、発泡小片成形体の外形表面に接するようにして、発泡小片成形体の下面に、中性紙を配置した（配置工程）。次いで、下型との境界部に設けられた液状原料の導入口を閉鎖して型内を密閉した後に、上型の中央頂部に設けた排出口から−０．０４ＭＰａ（Ｇ）で減圧した（減圧工程）。型内が−０．０４ＭＰａ（Ｇ）となったのを確認した後に、予め調合しておいたエポキシ系熱硬化性樹脂液状原料を、導入口を開いて型内へ導入した。エポキシ系樹脂には、１００質量部の三菱化学株式会社製ｊＥＲ８０７と１１質量部の三菱化学株式会社製のトリエチレンテトラミン（ＴＥＴＡ）とからなる熱硬化性樹脂液体原料を用いた。なお、この熱硬化性樹脂液体原料の粘度は、後述の表１に示す。
(Manufacture of composite moldings)
A resin mold (FRP type) having an effective inner dimension of 300 (l) x 300 (w) x 30 (t) (mm) and having a thermosetting resin inlet and outlet and an upper mold is 2 mm thick SUS. Place the above-mentioned polylactic acid foamed compact molded body inside a pair of upper and lower molds that can form a sealed space, with the plate as the lower mold, and foam so as to contact the outer surface of the foamed small molded body Neutral paper was placed on the bottom surface of the small piece compact (placement step). Next, after closing the inlet of the liquid raw material provided at the boundary with the lower die and sealing the inside of the die, the pressure was reduced by -0.04 MPa (G) from the outlet provided at the central top of the upper die ( Decompression step). After confirming that the inside of the mold became −0.04 MPa (G), an epoxy-based thermosetting resin liquid raw material prepared in advance was introduced into the mold by opening the inlet. As the epoxy resin, a thermosetting resin liquid raw material composed of 100 parts by mass of jER807 manufactured by Mitsubishi Chemical Corporation and 11 parts by mass of triethylenetetramine (TETA) manufactured by Mitsubishi Chemical Corporation was used. The viscosity of the thermosetting resin liquid raw material is shown in Table 1 described later.
導入口に接続した１０ｍｍφのシンプレックスチューブを介して、型の減圧状態を推進力に、混練した熱硬化性樹脂液体原料（以下、「液体樹脂」ということがある。）を吸引し型内へ層流状態を維持しながら且つ気孔の混入に配慮しながら導入した。なお、導入時にわたり型内の圧力を−０．０４ＭＰａ（Ｇ）に維持した。導入時の液体樹脂量を３０ｇ／分から２００ｇ／分の間で制御しながら熱硬化性樹脂液体原料を導入し、最終的に上型の排出口から液状樹脂が排出されるまで、熱硬化性樹脂液体原料の導入を継続して行った（導入工程）。液体樹脂の導入に要した時間は１０分であった。導入が終了した時点で、導入口を閉鎖し、排出口から減圧を継続しながら２４時間の間、型を静置した状態（室内の気温:２３℃、湿度:６０％ＲＨ）で保持した。 A kneaded thermosetting resin liquid raw material (hereinafter sometimes referred to as “liquid resin”) is sucked into the mold through a 10 mmφ simplex tube connected to the introduction port with the reduced pressure state of the mold as a driving force. It was introduced while maintaining the flow state and taking into account the mixing of pores. Note that the pressure in the mold was maintained at -0.04 MPa (G) throughout the introduction. The thermosetting resin liquid raw material is introduced while controlling the amount of liquid resin at the time of introduction between 30 g / min and 200 g / min, and finally the thermosetting resin is discharged until the liquid resin is discharged from the upper mold outlet. The liquid raw material was continuously introduced (introduction process). The time required for introducing the liquid resin was 10 minutes. When the introduction was completed, the inlet was closed, and the mold was kept stationary (indoor temperature: 23 ° C., humidity: 60% RH) for 24 hours while continuing to reduce pressure from the outlet.
２４時間経過の後に、型を開放し、複合成形品を取り出した。次いで、８０℃に加温してあるオーブン中に３時間放置し、硬化を完結した。 After 24 hours, the mold was opened and the composite molded product was taken out. Then, it was left in an oven heated to 80 ° C. for 3 hours to complete the curing.
硬化を完結した複合成形品は、３００(ｌ)×３００(ｗ)×３０(ｔ)（ｍｍ）の平板状複合成形品であった。なお、液体樹脂の安定供給を維持するためのマニホールド部（インジェクション成形のランナーに相当する部位）や、バリ部位は切断除去した。 The composite molded product that completed the curing was a plate-shaped composite molded product of 300 (l) × 300 (w) × 30 (t) (mm). In addition, the manifold part (part corresponding to the injection molding runner) for maintaining the stable supply of the liquid resin and the burr part were cut and removed.
実施例２
（発泡小片成形体の製造）
基材樹脂がポリプロピレン系樹脂とポリ乳酸樹脂の混合樹脂からなる発泡粒子を樹脂発泡小片として用いた。該発泡粒子を型内成形して発泡小片成形体を得た。成形は、開放し、閉鎖し得る金型（有効寸法３００(ｌ)×３００(ｗ)×５０(ｔ)（ｍｍ））を使用して、型内を空気で０．１ＭＰａ（Ｇ）に保持した金型内に樹脂発泡小片を充満した後、金型内の空気圧を０.０ＭＰａ（Ｇ）に戻した。次いで金型に付属する排気弁を開放した状態で元圧０．３ＭＰａ（Ｇ）のスチームを５秒間導通した後に、排気弁を閉鎖し、０．０２ＭＰａ（Ｇ）のスチームを型に導入し５秒間保持した。その後、直ちに型を開放し、１５秒の水冷冷却を行い、型を開放して、型で成形した平板状の発泡小片成形体を取り出した。成形体は、４０℃のオーブン中で２４時間乾燥した後に、７０℃のオーブンに移し、２４時間の熱処理が施された。熱処理後の発泡小片成形体の寸法は２９５（ｌ）×２９５（ｗ）×４８（ｔ）（ｍｍ）であり、後述の表１に示す発泡小片成形体を得た。成形品は、厚さ２８ｍｍにカットして平板とした。
Example 2
(Manufacture of foamed small pieces)
Foamed particles in which the base resin was a mixed resin of a polypropylene resin and a polylactic acid resin were used as resin foam pieces. The foamed particles were molded in-mold to obtain a foamed small piece compact. Molding is performed by using a mold (effective dimension 300 (l) x 300 (w) x 50 (t) (mm)) that can be opened and closed, and the inside of the mold is maintained at 0.1 MPa (G) with air. After filling the mold with the resin foam pieces, the air pressure in the mold was returned to 0.0 MPa (G). Next, with the exhaust valve attached to the mold open, steam with an original pressure of 0.3 MPa (G) is conducted for 5 seconds, then the exhaust valve is closed, and 0.02 MPa (G) steam is introduced into the mold. Held for 2 seconds. Thereafter, the mold was immediately opened, cooled with water for 15 seconds, the mold was opened, and the flat foamed small piece molded body molded with the mold was taken out. The molded body was dried in an oven at 40 ° C. for 24 hours, then transferred to an oven at 70 ° C., and subjected to heat treatment for 24 hours. The size of the foamed small piece compact after the heat treatment was 295 (l) × 295 (w) × 48 (t) (mm), and the foam small piece compact shown in Table 1 described later was obtained. The molded product was cut to a thickness of 28 mm to form a flat plate.
（複合成形体の製造）
実施例２の複合成形体の製造は、表１の条件で実施例１の複合成形体の製造と同様な方法で実施された。得られた複合成形体の物性等を後述の表２に示す。
(Manufacture of composite moldings)
The composite molded body of Example 2 was manufactured in the same manner as the composite molded body of Example 1 under the conditions shown in Table 1. The physical properties and the like of the obtained composite molded body are shown in Table 2 described later.
比較例１
実施例１で得られたポリ乳酸系樹脂発泡小片成形体（寸法は２９５（ｌ）×２９５（ｗ）×２８（ｔ）（ｍｍ）であり、８４ｋｇ／ｍ3の嵩密度を有する空隙率１０％のポリ乳酸製の発泡小片成形体）を挿入した。型枠は下型に密着する構造であり、下型を減圧状態とすることで、発泡小片成形体を介して、発泡小片成形体の上面から下面に向けて差圧を形成させた（上面は開放されている）。エポキシ系樹脂は三菱化学株式会社製ｊＥＲ８０７を１００質量部と三菱化学株式会社社製ＴＥＴＡを１１質量部とからなる熱硬化性樹脂液体原料を用いた。上面から、発泡小片成形体の上面を被覆するように、熱硬化性樹脂液体原料を流し込んだ。なお、導入時の減圧は−０．０４ＭＰａ（Ｇ）とした。液体原料が発泡小片成形体に吸入されるのを確認した後に、脱型し、２４時間放置した。次いで、８０℃に加温してあるオーブン中に３時間放置し、硬化を完結し、３００（ｌ）×３００（ｗ）×３０（ｔ）（ｍｍ）の平板状複合成形品を得た。比較例１の複合成形体の製造工程の条件を表１に、得られた複合成形体の構成及び評価結果について表２に示す。なお、上記方法では、シート材（中性紙）を発泡小片成形体外面に配置しても、硬化物層内にシート材を埋設させることができなかった。そこで、複合成形体の外形表面に、市販の加飾シート材（加飾フィルム）を貼付した。従って、複合成形体の製造と、加飾シートの貼付という２工程を経るものであった。また、得られた加飾複合成形体は、加飾シートが剥がれやすく、耐久性に劣るものであった。
Comparative Example 1
Polylactic acid-based resin foamed small piece molded body obtained in Example 1 (the dimensions are 295 (l) × 295 (w) × 28 (t) (mm), and the porosity is 10 and the bulk density is 84 kg / m 3. % Foamed small piece made of polylactic acid). The mold frame is a structure that is in close contact with the lower mold, and by setting the lower mold in a reduced pressure state, a differential pressure is formed from the upper surface of the foam piece molded body to the lower surface via the foam piece molded body (the upper surface is Open). As the epoxy resin, a thermosetting resin liquid raw material composed of 100 parts by mass of jER807 manufactured by Mitsubishi Chemical Corporation and 11 parts by mass of TETA manufactured by Mitsubishi Chemical Corporation was used. A thermosetting resin liquid raw material was poured from the upper surface so as to cover the upper surface of the foamed small piece molded body. The reduced pressure during the introduction was set to -0.04 MPa (G). After confirming that the liquid raw material was sucked into the foamed small piece compact, it was removed from the mold and left for 24 hours. Subsequently, it was left in an oven heated to 80 ° C. for 3 hours to complete the curing, and a 300 (l) × 300 (w) × 30 (t) (mm) flat composite molded product was obtained. Table 1 shows the conditions of the production process of the composite molded body of Comparative Example 1, and Table 2 shows the configuration and evaluation results of the obtained composite molded body. In the above method, the sheet material could not be embedded in the cured product layer even when the sheet material (neutral paper) was disposed on the outer surface of the foamed small piece molded body. Therefore, a commercially available decorative sheet material (decorative film) was attached to the outer surface of the composite molded body. Therefore, it has undergone two steps of manufacturing a composite molded body and attaching a decorative sheet. Moreover, the obtained decorative composite molded body was inferior in durability because the decorative sheet was easily peeled off.
１ 複合成形体
１０ 樹脂発泡小片成形体
１２ 樹脂発泡小片
２０ シート材
３０ 熱硬化性樹脂硬化物
３２ 硬化物層
４０ 型
４２ 内部空間
５０ 熱硬化性樹脂液体原料
DESCRIPTION OF SYMBOLS 1 Composite molded object 10 Resin foam small piece molded body 12 Resin foam small piece 20 Sheet material 30 Thermosetting resin cured material 32 Hardened material layer 40 Type 42 Internal space 50 Thermosetting resin liquid raw material
Claims (7)
前記複合成形体の密度が１００〜６００ｇ／Ｌであり、
前記複合成形体の体積に対して、前記熱硬化性樹脂硬化物の体積が３〜５５体積％であり、前記樹脂発泡小片間に前記熱硬化性樹脂硬化物が形成されていると共に、前記複合成形体は、前記樹脂発泡小片間に熱硬化性樹脂硬化物で構成される網目構造を有しており、前記複合成形体の外形表面の少なくとも一部が、前記熱硬化性樹脂硬化物からなりシート材が埋設された硬化物層によって形成されている複合成形体。 A composite molded body composed of a plurality of resin foam pieces, a thermosetting resin cured product, and a sheet material,
The density of the composite molded body is 100 to 600 g / L,
The volume of the thermosetting resin cured product is 3 to 55% by volume with respect to the volume of the composite molded body, and the thermosetting resin cured product is formed between the resin foam pieces, and the composite The molded body has a network structure composed of a thermosetting resin cured product between the resin foam small pieces , and at least a part of the outer surface of the composite molded body is made of the thermosetting resin cured product. A composite molded body formed by a cured product layer in which a sheet material is embedded.
る、請求項１に記載の複合成形体。 The composite molded body according to claim 1, wherein the base material of the sheet material is paper, woven fabric, non-woven fabric, plastic sheet, or metal mesh.
。 The composite molded body according to claim 1 or 2, wherein the plurality of resin foam pieces are fused to each other.
ンタジエン系樹脂、ウレタン系樹脂、シリコン系樹脂、フェノール系樹脂、メラミン系樹
脂、ポリイミド系樹脂、ユリア系樹脂及びジアリルフタレート系樹脂からなる群から選択
される少なくとも１種である、請求項１〜３のいずれか１項に記載の複合成形体。 The cured thermosetting resin is epoxy resin, unsaturated polyester resin, dicyclopentadiene resin, urethane resin, silicon resin, phenol resin, melamine resin, polyimide resin, urea resin and diallyl. The composite molded article according to any one of claims 1 to 3 , which is at least one selected from the group consisting of phthalate resins.
ポリプロピレン系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、及びポリ塩化ビ
ニル系樹脂からなる群から選択される少なくとも１種である、請求項１〜４のいずれか１
項に記載の複合成形体。 The base resin constituting the resin foam piece is a polystyrene resin, a polyethylene resin,
Any one of Claims 1-4 which is at least 1 sort (s) selected from the group which consists of a polypropylene-type resin, a polyester-type resin, a polycarbonate-type resin, and a polyvinyl chloride-type resin.
The composite molded article according to item.
する工程、
前記型内に熱硬化性樹脂液体原料を導入し、前記樹脂発泡小片間及び前記シート材に前
記熱硬化性樹脂液体原料を含浸させる工程、及び
前記熱硬化性樹脂液体原料を硬化させ、熱硬化性樹脂硬化物で構成される網目構造を前記樹脂発泡小片間に形成する工程を順次含む、複合成形体の製造方法。 A step of arranging the aggregate of a plurality of resin foam pieces and a sheet material in a mold,
Introducing a thermosetting resin liquid raw material into the mold, and impregnating the thermosetting resin liquid raw material between the resin foam pieces and the sheet material; and curing the thermosetting resin liquid raw material to perform thermosetting A method for producing a composite molded body, which sequentially includes a step of forming a network structure composed of a cured resin material between the resin foam pieces .
の複合成形体の製造方法。 The manufacturing method of the composite molded object of Claim 6 which the said aggregate | assembly consists of a resin foam small piece molded object with the porosity of 3-30 volume%.
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