JP7169054B2 - resin foam composite - Google Patents

resin foam composite Download PDF

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JP7169054B2
JP7169054B2 JP2017141218A JP2017141218A JP7169054B2 JP 7169054 B2 JP7169054 B2 JP 7169054B2 JP 2017141218 A JP2017141218 A JP 2017141218A JP 2017141218 A JP2017141218 A JP 2017141218A JP 7169054 B2 JP7169054 B2 JP 7169054B2
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resin foam
joint
outer peripheral
resin
peripheral surface
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JP2019018512A (en
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裕一 有戸
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Asahi Kasei Construction Materials Corp
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Description

本発明は、樹脂発泡複合体に関する。より詳細には、極低温物質の保冷等に適した断熱材に供される樹脂発泡複合体に関するものである。 The present invention relates to resin foam composites. More specifically, the present invention relates to a resin foam composite that is used as a heat insulating material suitable for cold storage of cryogenic substances.

極低温用の断熱材は大きな温度差により歪が生じ亀裂が発生する事が懸念される。例えば、特許文献１に於いては、断熱材であるウレタンフォーム（以降ウレタン樹脂発泡体）の強化の為にウレタン樹脂発泡体内にガラスストランドを分散させ強度向上を図っているが、ガラスストランドの分散が悪いと大きな空間が出来、この空間が亀裂発生の原因になるため、ガラス繊維と樹脂発泡条件を最適化して大きな空間が出来ないようにした事例が開示されている。 It is feared that thermal insulation materials for cryogenic applications may be distorted and cracked due to a large temperature difference. For example, in Patent Document 1, glass strands are dispersed in the urethane resin foam in order to strengthen the urethane foam (hereinafter referred to as urethane resin foam) that is a heat insulating material, thereby improving the strength. If it is poor, a large space will be created, and this space will cause cracks to occur. Therefore, an example of optimizing the glass fiber and resin foaming conditions to prevent the creation of a large space has been disclosed.

特開昭６０－２５９４１４号公報JP-A-60-259414

しかしながら、特許文献１に記載の発明の様に、ウレタン樹脂発泡体の強度向上のためにウレタン樹脂発泡体内に密度の高いガラスストランドを入れると重量が増すばかりではなく、熱伝導率が上がり、断熱性能が損なわれるおそれもあった。 However, as in the invention described in Patent Document 1, if high-density glass strands are put into the urethane resin foam to improve the strength of the urethane resin foam, not only does the weight increase, but the thermal conductivity increases, resulting in heat insulation. There was also the possibility that performance would be impaired.

本発明は、液化ガスタンク等の極低温物質の保冷目的で用いた場合にも、亀裂が発生しにくく、かつ、施工性が高く、更に高い断熱性能を維持できる樹脂発泡複合体を提供することを目的とする。 An object of the present invention is to provide a resin foam composite that is less prone to cracking, has high workability, and can maintain high heat insulation performance even when used for the purpose of cold storage of cryogenic substances such as liquefied gas tanks. aim.

本発明者らは、上記課題を解決するため鋭意検討を行った結果、樹脂発泡体を接合して使用する際に、樹脂発泡体間の接合部の外周表面の窪みを特定数以下にすることにより本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors found that when resin foams are used by joining, the number of recesses on the outer peripheral surface of the joint between resin foams should be less than or equal to a specific number. The present invention was completed by the following.

すなわち、本発明は以下の［１］～［３］を提供する。
［１］
２個の樹脂発泡体が接合部を介して接合された構造を含む樹脂発泡複合体であって、前記接合部の外周表面に存在する深さ１ｍｍ以上の窪みの数が、前記接合部の外周表面の長さ１ｍあたり３個以下であり、前記接合部が接合材からなり、前記接合部の厚みが１００μｍ以上３０００μｍ以下であり、前記樹脂発泡体がフェノール樹脂発泡板であり、少なくとも１個の前記樹脂発泡体の熱伝導率が、０．００１Ｗ／ｍＫ以上０．０２８Ｗ／ｍＫ以下であり、前記樹脂発泡体が表面に、樹脂繊維からなる不織布及びガラス繊維混抄紙からなる群から選択される少なくとも１種の面材を備えており、前記接合部と、接合部に隣接する一方の前記樹脂発泡体を液体窒素に３０分間浸漬し、その後２３℃で２４時間経過した際、及び更に２４時間経過後に再度液体窒素で６０分間浸漬し、その後２３℃で２４時間経過した際における、前記接合部を挟む２つの前記樹脂発泡体の外周表面に生じる亀裂の数の和が０個である、液化ガスタンク用樹脂発泡複合体。 That is, the present invention provides the following [1] to [3].
[1]
A resin foam composite including a structure in which two resin foams are joined via a joint, wherein the number of depressions having a depth of 1 mm or more existing on the outer peripheral surface of the joint is the outer circumference of the joint. There are three or less per 1 m of surface length, the joint portion is made of a joint material, the thickness of the joint portion is 100 μm or more and 3000 μm or less, the resin foam is a phenolic resin foam plate, and at least one The resin foam has a thermal conductivity of 0.001 W/mK or more and 0.028 W/mK or less, and the surface of the resin foam is selected from the group consisting of a nonwoven fabric made of resin fibers and a glass fiber mixed paper. When the joint and one of the resin foams adjacent to the joint are immersed in liquid nitrogen for 30 minutes, and after 24 hours at 23 ° C., and a further 24 After the elapse of time, it is immersed again in liquid nitrogen for 60 minutes, and then after 24 hours at 23 ° C., the sum of the number of cracks generated on the outer peripheral surface of the two resin foams sandwiching the joint is 0. Resin foam composite for liquefied gas tanks .

［２］
前記接合部の外周表面に存在する深さ０．３ｍｍ以上１ｍｍ未満の窪みの数が、前記接合部の外周表面の長さ１ｍあたり１０個以下である［１］記載の樹脂発泡複合体。 [2]
The resin foam composite according to [1], wherein the number of depressions having a depth of 0.3 mm or more and less than 1 mm existing on the outer peripheral surface of the joint is 10 or less per 1 m of the length of the outer peripheral surface of the joint.

［３］
少なくとも１個の前記樹脂発泡体の密度が１５ｋｇ／ｍ３以上６０ｋｇ／ｍ３以下である［１］又は［２］に記載の樹脂発泡複合体。 [3]
The resin foam composite according to [1] or [2] , wherein at least one resin foam has a density of 15 kg/m 3 or more and 60 kg/m 3 or less.

本発明の樹脂発泡複合体は、上記構成を有することにより、液化ガスタンク等の極低温物質の保冷目的で用いた場合にも、亀裂が発生しにくく、かつ、施工性が高く、更に高い断熱性能を維持できる。 The resin foam composite of the present invention has the above configuration, so that even when used for cold storage of cryogenic substances such as liquefied gas tanks, cracks are less likely to occur, workability is high, and heat insulation performance is high. can be maintained.

図１は、本実施形態の樹脂発泡複合体の一例を示す概略図である。FIG. 1 is a schematic diagram showing an example of the resin foam composite of the present embodiment. 図２は、図１のＸ－Ｘ断面図である。FIG. 2 is a cross-sectional view taken along line XX of FIG. 図３は、接合部の外周表面に窪みが多数ある樹脂発泡複合体の接合部断面図である。FIG. 3 is a cross-sectional view of a joint of a resin foam composite having many depressions on the outer peripheral surface of the joint. 図４は、図３の接合部はみ出し部の拡大図である。FIG. 4 is an enlarged view of the joint protruding portion in FIG. 図５は、接合部の外周表面に窪みが多数ある樹脂発泡複合体の一例である。FIG. 5 shows an example of a resin foam composite having many depressions on the outer peripheral surface of the joint. 図６は、接合部の外周表面に存在する窪みの形状を示す一例である。FIG. 6 is an example showing the shape of the recesses present on the outer peripheral surface of the joint.

本発明を実施するための形態（本明細書において、「本実施形態」と称する場合がある。）について詳細に説明する。 A mode for carrying out the present invention (which may be referred to as "the present embodiment" in this specification) will be described in detail.

本実施形態における樹脂発泡複合体は、２個の樹脂発泡体が、接合材を含む接合部を介して接合された構造を少なくとも有している。 The resin foam composite in the present embodiment has at least a structure in which two resin foams are joined via a joining portion containing a joining material.

ここで、本実施形態の樹脂発泡複合体を、図を用いて説明する。
本実施形態の樹脂発泡複合体１は、２個の樹脂発泡体２が接合部３を介して接合された構造を含む（図１参照）。本実施形態の樹脂発泡複合体１は、接合部３の外周表面の長さ１ｍあたりの、深さ１ｍｍ以上の窪みの数が１０個以下である。
ここで、本明細書において「接合部の外周表面」とは、樹脂発泡複合体１の表面、即ち樹脂発泡体２における接合部３と接する面と反対側の表面、に対して平行な接合部３の任意の断面における外周表面をいい、例えば、樹脂発泡体２と接合部３との界面に沿う断面の外周表面として良い（図２参照）。また、接合部３の外周表面の長さとは、接合部の外周表面に沿った長さをいう。本実施形態の樹脂発泡複合体の一例の接合部断面である図２では、接合部がはみ出している部分がないため、接合部の断面は樹脂発泡複合体の表面と略同一形状である。
２個の樹脂発泡体を接合する際、接合強度の観点から、重ね合わせる樹脂発泡体２の表面の全面に接合部３を設けることが通常である。この場合、２個の樹脂発泡体を押し合わせて接合させる時に、樹脂発泡複合体側面に接合部がはみ出した、接合部はみ出し部５が形成されることがある（図３参照）。「接合部はみ出し部」とは、樹脂発泡体外端形４から、樹脂発泡体の外側に接合部がはみ出している部分をいう（図３、４参照）。ここで、「樹脂発泡体外端形」とは、樹脂発泡複合体を厚さ方向に見た時の２個の樹脂発泡体が重なり合う部分の形状をいう（図３、４参照）。
図３は、接合部の外周表面に窪みが多数ある樹脂発泡体複合体の接合部の断面であり、樹脂発泡体外端形４から接合部がはみ出している接合部はみ出し部５を示す模式図である。また、図４は、図３の接合部はみ出し部５の拡大図である。接合部はみ出し部５には、窪み６が形成されることがある。
ここで、「窪み」とは、接合部はみ出し部５にある窪みをいい、接合部はみ出し部５の外端から樹脂発泡体外端形４に対して垂線をおろしこの垂線の長さ即ち距離Ｄが極大となる２つの隣り合う点７に挟まれ、該距離Ｄが極小となる点８を１つ含む窪みをいう（図４参照）。但し、上記距離Ｄは、樹脂発泡体外端形４の外端を基準として、樹脂発泡体外端形４の外側をプラスの値とし、内側をマイナスの値とする。また、幅Ｗ、即ち距離Ｄが極大となる２つの隣り合う点７間の距離Ｗ、深さＬ、即ち２つの隣り合う点７のうち距離Ｄが大きい点７と、極小となる点８の距離Ｄとの距離の差、とした時に、Ｌが３００μｍ以上であり、Ｗ／Ｌが１０．０以下となる窪みをいう。 Here, the resin foam composite of this embodiment will be described with reference to the drawings.
A resin foam composite 1 of the present embodiment includes a structure in which two resin foams 2 are joined via a joint 3 (see FIG. 1). In the resin foam composite 1 of the present embodiment, the number of depressions having a depth of 1 mm or more per 1 m length of the outer peripheral surface of the joint portion 3 is 10 or less.
Here, in this specification, the "peripheral surface of the joint" refers to the surface of the resin foam composite 1, that is, the surface of the resin foam 2 that is in contact with the joint 3 and the surface opposite to the joint that is parallel to the joint. 3, and for example, it may be the outer peripheral surface of a cross section along the interface between the resin foam 2 and the joint portion 3 (see FIG. 2). Further, the length of the outer peripheral surface of the joint portion 3 means the length along the outer peripheral surface of the joint portion. In FIG. 2, which is a joint cross-section of an example of the resin foam composite of the present embodiment, since there is no portion where the joint protrudes, the cross section of the joint has substantially the same shape as the surface of the resin foam composite.
When joining two resin foams, it is common to provide a joining portion 3 on the entire surface of the superimposed resin foams 2 from the viewpoint of joining strength. In this case, when the two resin foams are pressed together to be joined, a joint protruding portion 5 may be formed on the side surface of the resin foam composite (see FIG. 3). The term "protruding joint portion" refers to a portion where the joint protrudes outside the resin foam from the outer end shape 4 of the resin foam (see FIGS. 3 and 4). Here, the "outer shape of the resin foam" refers to the shape of the portion where two resin foams overlap each other when viewing the resin foam composite in the thickness direction (see FIGS. 3 and 4).
FIG. 3 is a cross section of a joint portion of a resin foam composite having many depressions on the outer peripheral surface of the joint portion, and is a schematic diagram showing a joint protruding portion 5 in which the joint portion protrudes from the resin foam outer edge shape 4. be. 4 is an enlarged view of the joint protruding portion 5 in FIG. A depression 6 may be formed in the joint protruding portion 5 .
Here, the "recess" means a recess in the joint protruding portion 5. A perpendicular line is drawn from the outer end of the joint protruding portion 5 to the resin foam outer end shape 4, and the length of this perpendicular, that is, the distance D is It is a depression that includes one point 8 that is sandwiched between two adjacent points 7 that are maximal and that has a minimal distance D (see FIG. 4). However, with respect to the distance D, the outer edge of the resin foam outer edge 4 is taken as a reference, the outer edge of the resin foam outer edge 4 is a positive value, and the inner edge is a negative value. Also, the distance W between two adjacent points 7 where the width W, that is, the distance D is maximum, and the depth L, that is, the point 7 where the distance D is the largest among the two adjacent points 7, and the point 8 where the distance D is the minimum. It refers to a dent in which L is 300 μm or more and W/L is 10.0 or less when the difference between the distance and the distance D is taken.

本実施形態で使用する樹脂発泡体としては、例えば、フェノール樹脂発泡板、ウレタン樹脂発泡板、スチレン樹脂発泡板等の樹脂系の発泡板断熱材を使用することが出来る。熱伝導率が安定して小さい樹脂発泡板が好ましく、中でもフェノール樹脂発泡板は樹脂発泡板としては最も熱伝導率が小さく、特に好ましい。
本実施形態で使用する樹脂発泡体の熱伝導率の好ましい範囲は、０．００１Ｗ／ｍＫ以上０．０３５Ｗ／ｍＫ以下であり、より好ましくは０．００１Ｗ／ｍＫ以上０．０２８Ｗ／ｍＫ以下、さらに好ましくは０．００１Ｗ／ｍＫ以上０．０２１Ｗ／ｍＫ以下、特に好ましくは０．００１Ｗ／ｍＫ以上０．０１９Ｗ／ｍＫ以下である。２個の樹脂発泡体が接合部を介して接合された上記構造において、少なくとも１個の樹脂発泡体の熱伝導率が上記範囲であることが好ましく、２個の樹脂発泡体の熱伝導率が上記範囲であることがより好ましい。なお、本実施形態の樹脂発泡複合体の上記構造以外に樹脂発泡体が含まれる場合、該樹脂発泡体の熱伝導率は上記範囲であることが好ましい。
本実施形態で使用する樹脂発泡体の密度の好ましい範囲は、１５ｋｇ／ｍ3以上６０ｋｇ／ｍ3以下であり、より好ましくは２０ｋｇ／ｍ3以上５０ｋｇ／ｍ3以下である。密度が１５ｋｇ／ｍ3以上であれば、取扱い時に損傷し難い強度を持ち、６０ｋｇ／ｍ3以下であれば、軽量になるため施工性が高くなる。２個の樹脂発泡体が接合部を介して接合された上記構造において、少なくとも１個の樹脂発泡体の密度が上記範囲であることが好ましく、２個の樹脂発泡体の密度が上記範囲であることがより好ましい。なお、本実施形態の樹脂発泡複合体の上記構造以外に樹脂発泡体が含まれる場合、該樹脂発泡体の密度は上記範囲であることが好ましい。 As the resin foam used in the present embodiment, for example, a resin-based foam board heat insulating material such as a phenol resin foam board, a urethane resin foam board, or a styrene resin foam board can be used. A resin foam board with a stable and small thermal conductivity is preferable, and among them, a phenolic resin foam board is particularly preferable because it has the lowest thermal conductivity as a resin foam board.
A preferable range of thermal conductivity of the resin foam used in the present embodiment is 0.001 W/mK or more and 0.035 W/mK or less, more preferably 0.001 W/mK or more and 0.028 W/mK or less, and further It is preferably 0.001 W/mK or more and 0.021 W/mK or less, and particularly preferably 0.001 W/mK or more and 0.019 W/mK or less. In the above structure in which two resin foams are joined via a joint portion, the thermal conductivity of at least one resin foam is preferably within the above range, and the thermal conductivity of the two resin foams is preferably The above range is more preferable. In addition, when the resin foam composite of the present embodiment includes a resin foam other than the structure described above, the thermal conductivity of the resin foam is preferably within the above range.
A preferable density range of the resin foam used in the present embodiment is 15 kg/m 3 or more and 60 kg/m 3 or less, more preferably 20 kg/m 3 or more and 50 kg/m 3 or less. If the density is 15 kg/m 3 or more , it has a strength that makes it difficult to be damaged during handling. In the above structure in which two resin foams are joined via a joint portion, the density of at least one resin foam is preferably within the above range, and the density of the two resin foams is within the above range. is more preferable. In addition, when the resin foam composite of the present embodiment includes a resin foam other than the structure described above, the density of the resin foam is preferably within the above range.

本実施形態の樹脂発泡複合体は、接合材を含む接合部を介して接合されており、接合部の外周表面が滑らかであることが好ましい。
接合部の外周表面に存在する、深さ１ｍｍ以上の窪みの数が、接合部の外周表面の長さ１ｍあたり１０個以下であり、３個以下であることが好ましい。
また、接合部の外周表面に存在する深さ０．３ｍｍ以上１ｍｍ未満の窪みの数が、接合部の外周表面の長さ１ｍあたり１０個以下であることが好ましく、より好ましくは３個以下である。窪みの有無は目視やデジタル顕微鏡等で確認でき、窪みの幅及び深さはノギスで測定したり、デジタル顕微鏡で観察する事により測定することができる。 The resin foam composite of the present embodiment is bonded via a joint containing a bonding material, and the outer peripheral surface of the joint is preferably smooth.
The number of depressions having a depth of 1 mm or more present on the outer peripheral surface of the joint is 10 or less, preferably 3 or less, per 1 m of the length of the outer peripheral surface of the joint.
In addition, the number of depressions having a depth of 0.3 mm or more and less than 1 mm on the outer peripheral surface of the joint is preferably 10 or less, more preferably 3 or less, per 1 m of the length of the outer peripheral surface of the joint. be. The presence or absence of a dent can be confirmed visually or with a digital microscope, and the width and depth of the dent can be measured with a vernier caliper or observed with a digital microscope.

上記窪みの樹脂発泡複合体の厚み方向の形状について、図５、図６を用いて説明する。
図５は、樹脂発泡複合体の、２個の樹脂発泡体が接合部を介して接合された樹脂発泡複合体の一例の側面の概略図である。上記窪み６は、樹脂発泡複合体１の厚み方向において、窪み６の端が樹脂発泡体２と接合部３との界面、または、樹脂発泡体２と接合部３との界面に沿う断面に接していると、極低温時に樹脂発泡体に亀裂が発生しやすくなる（図５参照）。上記窪みは、厚み方向の一方の端が樹脂発泡体２と接合部３との界面に接しているもの（６Ｂ）、厚み方向の両方の端が樹脂発泡体２と接合部３との界面に接しているもの（６Ａ）、厚み方向の両方の端が何れも樹脂発泡体２と接合部３との界面に接していないもの（６Ｃ）がある。また、窪みの端が樹脂発泡体と接合部３との界面に接していない場合（６Ｃ）でも亀裂発生の原因になる可能性がある。（図５参照）
図６（Ａ）は、図４と同様、接合部はみ出し部５の拡大図であり、図６（Ｂ）（Ｃ）は、図６（Ａ）の接合部はみ出し部５にある窪み６の厚み方向断面（図６（Ａ）に示す線Ｙ－Ｙに沿う面により切断した時の断面）の例である。
図６（Ｂ）、図６（Ｃ）において、樹脂発泡体複合体の厚み方向全体にわたり、接合部はみ出し部５に窪み６が形成されている場合、厚み方向における窪み６の端は、図６（Ｂ）では樹脂発泡体２と接合部３との界面に接しており、図６（Ｃ）では、樹脂発泡体２の側面まではみ出している。樹脂発泡複合体の厚み方向における窪み６の端が、図６（Ｂ）、図６（Ｃ）のいずれの位置にある場合でも、亀裂発生の原因になる可能性がある。 The shape of the depression in the thickness direction of the resin foam composite will be described with reference to FIGS. 5 and 6. FIG.
FIG. 5 is a schematic side view of an example of a resin foam composite in which two resin foams are joined via a joint. In the thickness direction of the resin foam composite 1, the end of the recess 6 contacts the interface between the resin foam 2 and the joint 3 or the cross section along the interface between the resin foam 2 and the joint 3. Cracks tend to occur in the resin foam at extremely low temperatures (see Fig. 5). One end in the thickness direction of the recess is in contact with the interface between the resin foam 2 and the joint 3 (6B), and both ends in the thickness direction are in contact with the interface between the resin foam 2 and the joint 3. There is one that is in contact (6A) and one in which both ends in the thickness direction are not in contact with the interface between the resin foam 2 and the joint portion 3 (6C). In addition, even if the end of the recess does not touch the interface between the resin foam and the joint 3 (6C), it may cause cracks. (See Fig. 5)
FIG. 6(A) is an enlarged view of the joint protruding portion 5 as in FIG. 4, and FIGS. It is an example of a directional cross section (a cross section taken along the line YY shown in FIG. 6A).
6(B) and 6(C), when the recess 6 is formed in the joint protruding portion 5 over the entire thickness direction of the resin foam composite, the edge of the recess 6 in the thickness direction is In FIG. 6B, it is in contact with the interface between the resin foam 2 and the joint 3, and in FIG. The edge of the recess 6 in the thickness direction of the resin foam composite may cause cracking regardless of the position in FIG. 6(B) or FIG. 6(C).

本実施形態の樹脂発泡複合体は、上記樹脂発泡体の表面に面材を備えていてもよい。面材としては、高分子繊維が好ましく、高分子繊維としては、例えば、樹脂繊維、ガラス繊維、セルロース繊維などが利用できる。好ましい繊維の形態としては、糸を織った布帛や、繊維を接着剤や熱融着により接着、あるいは機械的作用でからませて布状にした不織布やフェルト、また繊維を抄造法によりシート状に成形したもの等が使用できる。特に好ましい繊維の形態としては、ポリプロピレン繊維、ポリエチレンテレフタレート繊維、ナイロン繊維等の樹脂繊維からなる不織布やガラス繊維混抄紙があげられる。
本実施形態の樹脂発泡複合体は、樹脂発泡体表面に接合部を設けてもよいし、樹脂発泡体の表面に設けられた面材に粘着テープを設ける等により接合部を設けてもよい。 The resin foam composite of the present embodiment may have a face material on the surface of the resin foam. Polymer fibers are preferable as the face material, and resin fibers, glass fibers, cellulose fibers, and the like, for example, can be used as the polymer fibers. Preferred forms of the fibers include fabrics woven with threads, non-woven fabrics and felts formed by bonding fibers with an adhesive or heat fusion, or by mechanically entangling fibers, and sheets formed from fibers by a papermaking method. A molded product or the like can be used. Particularly preferred forms of fibers include non-woven fabrics made of resin fibers such as polypropylene fibers, polyethylene terephthalate fibers and nylon fibers, and glass fiber mixed papers.
The resin foam composite of the present embodiment may be provided with a joint on the surface of the resin foam, or may be provided with a joint by providing an adhesive tape on the face material provided on the surface of the resin foam.

本実施形態で使用する樹脂発泡体の厚みは、１０ｍｍ以上５００ｍｍ以下が好ましく、より好ましくは２０ｍｍ以上４００ｍｍ以下、さらに好ましくは３０ｍｍ以上３００ｍｍ以下である。
樹脂発泡体の厚みが１０ｍｍ以上であると断熱性能がより高まり、５００ｍｍ以下であると応力抵抗性が高まる。樹脂発泡体の厚みは、定規やノギス等で測定できる。 The thickness of the resin foam used in this embodiment is preferably 10 mm or more and 500 mm or less, more preferably 20 mm or more and 400 mm or less, and still more preferably 30 mm or more and 300 mm or less.
When the thickness of the resin foam is 10 mm or more, the heat insulation performance is enhanced, and when it is 500 mm or less, the stress resistance is enhanced. The thickness of the resin foam can be measured with a ruler, vernier caliper, or the like.

また、本実施形態の樹脂発泡複合体は、３個以上の樹脂発泡体を複合化して使用する場合に、発明の効果がより高まる事が期待でき、５個以上の樹脂発泡体を複合化して使用すると、より高い断熱性能を付与しながらも温度差により複合体が破壊しにくくなる効果が期待できる。本実施形態の樹脂発泡複合体において、接合部が２個以上ある場合、少なくとも１個の接合部において窪みの数が上記要件を満たすことが好ましく、全ての接合部において窪みの数が上記要件を満たすことがより好ましい。 Further, in the resin foam composite of the present embodiment, when three or more resin foams are combined and used, the effect of the invention can be expected to be further enhanced, and five or more resin foams are combined. When used, it can be expected to have the effect of making the composite less likely to break due to the temperature difference while providing higher heat insulation performance. In the resin foam composite of the present embodiment, when there are two or more joints, the number of dents in at least one joint preferably satisfies the above requirements, and the number of dents in all joints meets the above requirements. It is more preferable to satisfy

樹脂発泡複合体の好ましい厚みは４０ｍｍ以上２０００ｍｍ以下であり、より好ましくは５０ｍｍ以上１５００ｍｍ以下、更に好ましくは６０ｍｍ以上１２００ｍｍ以下である。樹脂発泡複合体の厚みが４０ｍｍ以上であると断熱性能がより高まり、２０００ｍｍ以下であると応力抵抗性が高まる。樹脂発泡複合体の厚みは、定規やノギス等で測定できる。 The thickness of the resin foam composite is preferably 40 mm or more and 2000 mm or less, more preferably 50 mm or more and 1500 mm or less, still more preferably 60 mm or more and 1200 mm or less. When the thickness of the resin foam composite is 40 mm or more, the heat insulating performance is enhanced, and when it is 2000 mm or less, the stress resistance is enhanced. The thickness of the resin foam composite can be measured with a ruler, vernier caliper, or the like.

本実施形態で使用する接合材としては、例えば、ウレタン系接着剤、ＳＢＲ系接着剤、ニトリルゴム系接着剤、アクリル系接着剤、エポキシ系接着剤、シリコーン系接着剤、酢ビ系接着剤、でんぷん糊、各種粘着剤、ニカワ等が挙げられる。中でも、低温耐性という観点から、ウレタン系接着剤、エポキシ系接着剤、シリコーン系接着剤、アクリル系接着剤、が好ましい。また、各種粘着剤を用いた場合、樹脂発泡複合体における接合材の外周表面が滑らかになりやすく、好ましい。 Examples of the bonding material used in the present embodiment include urethane-based adhesives, SBR-based adhesives, nitrile rubber-based adhesives, acrylic-based adhesives, epoxy-based adhesives, silicone-based adhesives, vinyl acetate-based adhesives, Examples include starch paste, various adhesives, glue, and the like. Among them, urethane-based adhesives, epoxy-based adhesives, silicone-based adhesives, and acrylic-based adhesives are preferable from the viewpoint of low temperature resistance. Moreover, when various adhesives are used, the outer peripheral surface of the bonding material in the resin foam composite is likely to be smooth, which is preferable.

本実施形態における接合部の厚みは、１μｍ以上５０００μｍ以下が好ましく、より好ましくは１０μｍ以上４０００μｍ以下であり、更に好ましくは１００μｍ以上３０００μｍ以下である。接合部の厚みは、目盛付き拡大鏡やデジタル顕微鏡、ＳＥＭ等で確認することが出来る。 The thickness of the joint portion in the present embodiment is preferably 1 μm or more and 5000 μm or less, more preferably 10 μm or more and 4000 μm or less, and still more preferably 100 μm or more and 3000 μm or less. The thickness of the joint can be confirmed with a magnifying glass with a scale, a digital microscope, an SEM, or the like.

本実施形態の樹脂発泡複合体は、例えば、液化ガスタンク断熱用や、極低温物質を貯蔵又は輸送する際の極低温タンクの保冷に利用でき、この場合、タンク表面温度と外気との温度差が１５０℃以上の貯蔵又は輸送用極低温タンクに、特に有意な効果を発現することができる。 The resin foam composite of the present embodiment can be used, for example, for thermal insulation of liquefied gas tanks or for cold storage of cryogenic tanks when storing or transporting cryogenic substances. In this case, the temperature difference between the tank surface temperature and the outside air is A particularly significant effect can be exhibited in cryogenic tanks for storage or transportation at 150° C. or higher.

本実施形態の樹脂発泡複合体の製造方法としては、樹脂発泡体を接合材で接合した後に、（１）バンドソー等の切断機で接合部はみ出し部又は樹脂発泡複合体の外周を切断して、接合部の外周表面を滑らかにする方法；（２）接合部の外周表面にある接合部はみ出し部を溶剤で溶かして滑らかにする方法；（３）接合部の外周表面にある接合部はみ出し部を研磨により滑らかにする方法；（４）接着時に樹脂発泡複合体外周に離形性の良い当て板を当てて、はみ出す接合部の外周表面を滑らかにする方法；（５）変形しにくく滑らかな断面をもつシート状の粘着剤を用いて、接合する方法等が挙げられる。 As a method for producing the resin foam composite of the present embodiment, after bonding the resin foam with a bonding material, (1) the joint protruding portion or the outer periphery of the resin foam composite is cut with a cutting machine such as a band saw, Method of smoothing the outer peripheral surface of the joint ; (2) Method of dissolving the protruding portion of the joint on the outer peripheral surface of the joint with a solvent to smooth it; (3) Smoothing the protruding portion of the joint on the outer peripheral surface of the joint (4) A method of smoothing the outer peripheral surface of the protruding joint by applying a backing plate with good releasability to the outer periphery of the resin foam composite during bonding; (5) A smooth cross section that is difficult to deform. A method of bonding using a sheet-like adhesive having

樹脂発泡体の熱伝導率は以下の方法によって求めた。
＜樹脂発泡体の熱伝導率＞
樹脂発泡複合体を構成する樹脂発泡体の熱伝導率は、６００ｍｍ角に切り出した板状樹脂発泡体を、低温板５℃、高温板３５℃の条件で、平板熱流計法に従い、ＪＩＳ Ａ１４１２に準拠して測定した。 The thermal conductivity of the resin foam was obtained by the following method.
<Thermal conductivity of resin foam>
The thermal conductivity of the resin foam that constitutes the resin foam composite is measured by measuring the thermal conductivity of a plate-shaped resin foam cut into a 600 mm square under the conditions of a low temperature plate of 5 ° C. and a high temperature plate of 35 ° C. according to the flat plate heat flow meter method. Measured according to

以下に、実施例に基づいて本実施形態の樹脂発泡複合体をより詳細に説明する。
なお、実施例９、１０は、参考例として記載するものである。 EXAMPLES The resin foam composite of the present embodiment will be described in more detail below based on examples.
In addition, Examples 9 and 10 are described as reference examples.

（実施例１）
ウレタン系接着剤ＬＯＣＴＩＴＥ ＵＫ ５４００（ヘンケル社製）１ｋｇとＬＯＣＴＩＴＥ ＵＫ ８２０２（ヘンケル社製）４ｋｇをペール缶に計量し、均一に混合し接合材とした。
幅１５００ｍｍ×長さ１２００ｍｍ×厚み０．２ｍｍのＰＰシートに、幅１０００ｍｍ×長さ１０００ｍｍの枠を書き、枠の中に上記接合材を均一に塗布した。重量を測定した、幅１０００ｍｍ×長さ１０００ｍｍに切り出した全体厚み５０ｍｍ、密度２７ｋｇ／ｍ3の樹脂発泡体の両面に不織布面材を備えたフェノール樹脂発泡板１（旭化成建材（株）製）を、一方の不織布面材が下になるように、接合材が塗布されたＰＰシートの枠に合わせて伏せ、ＰＰシートとフェノール樹脂発泡板１とがずれない様に裏返し、ＰＰシートを押して、接合材をフェノール樹脂発泡板１の不織布面材に転写した。ＰＰシートをフェノール樹脂発泡板１から剥がし、小口に付着した接合材を拭き取った。接合材を転写した後のフェノール樹脂発泡板１の重量を測定し、転写前のフェノール樹脂発泡板１の重量から計算した、転写した接合材量は２９２ｇ／ｍ2であった。接合材を転写させた不織布面材上に、別途幅１０００ｍｍ×長さ１０００ｍｍに切り出したフェノール樹脂発泡板１の不織布面材が接合材を転写させた不織布面材に向くように、ずれない様に合わせ固定して、上に２０ｋｇの錘１０個をのせ、２４時間以上経過後に錘を外し、周囲を１０ｍｍずつバンドソーで切り取り、樹脂発泡複合体を得た。
接合部の外周表面は滑らかで、０．３ｍｍ以上の深さの窪みは無かった。用いたフェノール樹脂発泡板１の熱伝導率は、０．０２０Ｗ／ｍＫであった。 (Example 1)
1 kg of urethane-based adhesive LOCTITE UK 5400 (manufactured by Henkel) and 4 kg of LOCTITE UK 8202 (manufactured by Henkel) were weighed in a pail and uniformly mixed to obtain a bonding material.
A frame of 1000 mm width x 1000 mm length was drawn on a PP sheet of 1500 mm width x 1200 mm length x 0.2 mm thickness, and the bonding material was uniformly applied in the frame. A phenolic resin foam board 1 (manufactured by Asahi Kasei Construction Materials Co., Ltd.) having a non-woven fabric face material on both sides of a resin foam having a total thickness of 50 mm and a density of 27 kg/m 3 cut into 1000 mm width × 1000 mm length was measured. , so that one non-woven fabric surface material faces downward, it is turned over so that the PP sheet and the phenolic resin foam board 1 are not misaligned, and the PP sheet is pressed to join. The material was transferred to the nonwoven fabric surface material of the phenol resin foam board 1 . The PP sheet was peeled off from the phenol resin foam board 1, and the bonding material adhering to the edges was wiped off. The weight of the phenol resin foam board 1 after the transfer of the bonding material was measured, and the amount of the transferred bonding material calculated from the weight of the phenol resin foam board 1 before transfer was 292 g/m 2 . On the non-woven fabric face material to which the bonding material has been transferred, the non-woven fabric face material of the phenol resin foam board 1 separately cut into a width of 1000 mm and a length of 1000 mm is placed so as to face the non-woven fabric face material to which the bonding material has been transferred so as not to shift. They were fixed together and ten weights of 20 kg were placed thereon. After 24 hours or more, the weights were removed, and the periphery was cut off by a band saw at intervals of 10 mm to obtain a foamed resin composite.
The outer peripheral surface of the joint was smooth, and there were no depressions with a depth of 0.3 mm or more. The thermal conductivity of the phenol resin foam board 1 used was 0.020 W/mK.

（実施例２）
フェノール樹脂発泡板１を、全体厚み１００ｍｍ、密度２７ｋｇ／ｍ3の樹脂発泡体の両面に不織布面材を備えたフェノール樹脂発泡板２（旭化成建材（株）製）に変更し、接合材量が３１９ｇ／ｍ2で有った以外は、実施例１と同様にして樹脂発泡複合体を得た。こちらも実施例１と同様に接合部の外周表面の接合材は滑らかで０．３ｍｍ以上の深さの窪みは無かった。用いたフェノール樹脂発泡板２の熱伝導率は、０．０２０Ｗ／ｍＫであった。 (Example 2)
The phenolic resin foam board 1 was changed to a phenolic resin foam board 2 (manufactured by Asahi Kasei Construction Materials Co., Ltd.) having a total thickness of 100 mm and a density of 27 kg/m 3 with non-woven fabric facings on both sides. A resin foam composite was obtained in the same manner as in Example 1, except that it was 319 g/m 2 . In this case, similarly to Example 1, the bonding material on the outer peripheral surface of the bonding portion was smooth, and there were no depressions with a depth of 0.3 mm or more. The thermal conductivity of the phenol resin foam plate 2 used was 0.020 W/mK.

（実施例３）
フェノール樹脂発泡板１を、全体厚み５０ｍｍ、密度４０ｋｇ／ｍ3の樹脂発泡体の両面に不織布面材を備えたフェノール樹脂発泡板３（旭化成建材（株）製）に変更し、接合材量が２９５ｇ／ｍ2で有った以外は、実施例１と同様にして樹脂発泡複合体を得た。こちらも実施例１と同様に接合部の外周表面の接合材は滑らかで０．３ｍｍ以上の深さの窪みは無かった。用いたフェノール樹脂発泡板３の熱伝導率は、０．０２０Ｗ／ｍＫであった。 (Example 3)
The phenolic resin foam board 1 was changed to a phenolic resin foam board 3 (manufactured by Asahi Kasei Construction Materials Co., Ltd.) comprising a resin foam having a total thickness of 50 mm and a density of 40 kg/m 3 with non-woven fabric facings on both sides. A resin foam composite was obtained in the same manner as in Example 1, except that it was 295 g/m 2 . In this case, similarly to Example 1, the bonding material on the outer peripheral surface of the bonding portion was smooth, and there were no depressions with a depth of 0.3 mm or more. The thermal conductivity of the phenol resin foam plate 3 used was 0.020 W/mK.

（実施例４）
フェノール樹脂発泡板１を、全体厚み６０ｍｍ、密度２５ｋｇ／ｍ3の樹脂発泡体の両面に不織布面材を備えたフェノール樹脂発泡板４（旭化成建材（株）製）に変更し、接合材量が２８４ｇ／ｍ2で有った以外は、実施例１と同様にして樹脂発泡複合体を得た。こちらも実施例１と同様に接合部の外周表面の接合材は滑らかで０．３ｍｍ以上の深さの窪みは無かった。用いたフェノール樹脂発泡板４の熱伝導率は、０．０２０Ｗ／ｍＫであった。 (Example 4)
The phenolic resin foam board 1 was changed to a phenolic resin foam board 4 (manufactured by Asahi Kasei Construction Materials Co., Ltd.) having a total thickness of 60 mm and a density of 25 kg/m 3 with non-woven fabric facings on both sides. A resin foam composite was obtained in the same manner as in Example 1, except that it was 284 g/m 2 . In this case, similarly to Example 1, the bonding material on the outer peripheral surface of the bonding portion was smooth, and there were no depressions with a depth of 0.3 mm or more. The thermal conductivity of the phenol resin foam board 4 used was 0.020 W/mK.

（実施例５）
フェノール樹脂発泡板１を、全体厚み２５ｍｍ、密度２７ｋｇ／ｍ3の樹脂発泡体の両面に不織布面材を備えたフェノール樹脂発泡板５（旭化成建材（株）製）に変更し、接合材量が２７７ｇ／ｍ2で有った以外は、実施例１と同様にして樹脂発泡複合体を得た。こちらも実施例１と同様に接合部の外周表面の接合材は滑らかで０．３ｍｍ以上の深さの窪みは無かった。 (Example 5)
The phenolic resin foam board 1 was changed to a phenolic resin foam board 5 (manufactured by Asahi Kasei Construction Materials Co., Ltd.) having a total thickness of 25 mm and a density of 27 kg/m 3 with non-woven fabric facings on both sides. A resin foam composite was obtained in the same manner as in Example 1, except that it was 277 g/m 2 . In this case, similarly to Example 1, the bonding material on the outer peripheral surface of the bonding portion was smooth, and there were no depressions with a depth of 0.3 mm or more.

（実施例６）
接合材量が９１ｇ／ｍ2で、接合の際に上に乗せる２０ｋｇの錘を１個にし、周囲をバンドソーで切り取らなかった以外は、実施例１と同様にして樹脂発泡複合体を得た。接合部の外周表面には、凹凸が有り０．３ｍｍ以上の深さの窪みは５個確認されたが、１ｍｍ以上の窪みは無かった。 (Example 6)
A foamed resin composite was obtained in the same manner as in Example 1, except that the amount of bonding material was 91 g/m 2 , one weight of 20 kg was placed on the bonding material, and the periphery was not cut off with a band saw. The outer peripheral surface of the joint portion had irregularities, and although five depressions with a depth of 0.3 mm or more were confirmed, there were no depressions of 1 mm or more.

（実施例７）
接合材量が１１５ｇ／ｍ2で、接合の際に上に乗せる２０ｋｇの錘を１個にし、周囲をバンドソーで切り取らなかった以外は、実施例３と同様にして樹脂発泡複合体を得た。接合部の外周表面には、凹凸が有り０．３ｍｍ以上の深さの窪みは４個確認されたが、１ｍｍ以上の窪みは無かった。 (Example 7)
A resin foam composite was obtained in the same manner as in Example 3, except that the bonding material amount was 115 g/m 2 , one weight of 20 kg was placed on top during bonding, and the periphery was not cut with a band saw. The outer peripheral surface of the joint portion had irregularities, and although four dents with a depth of 0.3 mm or more were confirmed, there were no dents of 1 mm or more.

（実施例８）
接合材量が１００ｇ／ｍ2で、接合の際に上に乗せる２０ｋｇの錘を１個にし、周囲をバンドソーで切り取らなかった以外は、実施例４と同様にして樹脂発泡複合体を得た。接合部の外周表面には、凹凸が有り０．３ｍｍ以上の深さの窪みは４個確認されたが、１ｍｍ以上の窪みは無かった。 (Example 8)
A resin foam composite was obtained in the same manner as in Example 4, except that the amount of the bonding material was 100 g/m 2 , one weight of 20 kg was placed on top during bonding, and the periphery was not cut off with a band saw. The outer peripheral surface of the joint portion had irregularities, and although four dents with a depth of 0.3 mm or more were confirmed, there were no dents of 1 mm or more.

（実施例９）
接合材量が１７２ｇ／ｍ2で、接合の際に上に乗せる２０ｋｇの錘を１個にし、周囲をバンドソーで切り取らなかった以外は、実施例１と同様にして樹脂発泡複合体を得た。接合部の外周表面には、凹凸が有り０．３ｍｍ以上の深さの窪みは１６個確認され、そのうち４個が１ｍｍ以上の深さがあった。 (Example 9)
A foamed resin composite was obtained in the same manner as in Example 1, except that the bonding material amount was 172 g/m 2 , one weight of 20 kg was used for bonding, and the periphery was not cut with a band saw. The outer peripheral surface of the joint portion had irregularities, and 16 depressions with a depth of 0.3 mm or more were confirmed, of which 4 had a depth of 1 mm or more.

（実施例１０）
接合材量が２００ｇ／ｍ2で、接合の際に上に乗せる２０ｋｇの錘を１個にし、周囲をバンドソーで切り取らなかった以外は、実施例１と同様にして樹脂発泡複合体を得た。接合部の外周表面には、凹凸が有り０．３ｍｍ以上の深さの窪みは２７個確認され、そのうち８個が１ｍｍ以上の深さがあった。 (Example 10)
A foamed resin composite was obtained in the same manner as in Example 1, except that the bonding material amount was 200 g/m 2 , one weight of 20 kg was placed on top during bonding, and the periphery was not cut with a band saw. The outer peripheral surface of the joint portion had irregularities, and 27 depressions with a depth of 0.3 mm or more were confirmed, of which 8 had a depth of 1 mm or more.

（実施例１１）
フェノール樹脂発泡板２を３回積層し夫々の接合材量が、３３５ｇ／ｍ2、３６２ｇ／ｍ2、２８７ｇ／ｍ2で有った以外は、実施例１と同様にして樹脂発泡複合体を得た。こちらも実施例１と同様に接合部の外周表面の接合材は滑らかで０．３ｍｍ以上の深さの窪みは無かった。用いたフェノール樹脂発泡板２の熱伝導率は、０．０２０Ｗ／ｍＫであった。 (Example 11)
A resin foam composite was produced in the same manner as in Example 1, except that the phenolic resin foam board 2 was laminated three times and the amounts of the respective bonding materials were 335 g/m 2 , 362 g/m 2 and 287 g/m 2 . Obtained. In this case, similarly to Example 1, the bonding material on the outer peripheral surface of the bonding portion was smooth, and there were no depressions with a depth of 0.3 mm or more. The thermal conductivity of the phenol resin foam plate 2 used was 0.020 W/mK.

（実施例１２）
フェノール樹脂発泡板２を７回積層し、夫々の接合材量が２９８ｇ／ｍ2、３２２ｇ／ｍ2、３１０ｇ／ｍ2、２９３ｇ／ｍ2、３４１ｇ／ｍ2、２８９ｇ／ｍ2、３０８ｇ／ｍ2で有った以外は、実施例１と同様にして樹脂発泡複合体を得た。こちらも実施例１と同様に接合部の外周表面の接合材は滑らかで０．３ｍｍ以上の深さの窪みは無かった。用いたフェノール樹脂発泡板２の熱伝導率は、０．０２０Ｗ／ｍＫであった。 (Example 12)
The phenol resin foam board 2 was laminated seven times, and the respective bonding material amounts were 298 g/m 2 , 322 g/m 2 , 310 g/m 2 , 293 g/m 2 , 341 g/m 2 , 289 g/m 2 , 308 g/m 2 . A resin foam composite was obtained in the same manner as in Example 1, except that 2 was used. In this case, similarly to Example 1, the bonding material on the outer peripheral surface of the bonding portion was smooth, and there were no depressions with a depth of 0.3 mm or more. The thermal conductivity of the phenol resin foam plate 2 used was 0.020 W/mK.

（実施例１３）
幅１０００ｍｍ×長さ１０００ｍｍに切り出した両面に不織布面材を備えた全体厚み５０ｍｍのフェノール樹脂発泡板１の片面の不織布面材に両面粘着テープ（ＤＣＸ－１０８０ スリーエムジャパン（株））をフェノール樹脂発泡板１からはみ出ない様に全面に貼り、剥離紙を剥がした粘着面に、別途幅１０００ｍｍ×長さ１０００ｍｍに切り出した全体厚み５０ｍｍのフェノール樹脂発泡板１を、ずれない様に合わせ固定した。固定後、上に２０ｋｇの錘１０個を乗せて２４時間経過後、錘を外し、樹脂発泡複合体を得た。こちらも実施例１と同様に接合部の外周表面の接合材は滑らかで０．３ｍｍ以上の深さの窪みは無かった。 (Example 13)
Phenolic resin foaming with double-sided adhesive tape (DCX-1080 3M Japan Co., Ltd.) on one side of the nonwoven fabric surface material of a phenolic resin foam board 1 with a total thickness of 50mm and having nonwoven fabric surface materials on both sides cut into a width of 1000mm x length 1000mm A phenol resin foam board 1 having a total thickness of 50 mm, which was separately cut into a width of 1,000 mm and a length of 1,000 mm, was aligned and fixed on the adhesive surface from which the release paper was peeled off. After fixing, 10 weights of 20 kg were placed on top, and after 24 hours, the weights were removed to obtain a foamed resin composite. In this case, similarly to Example 1, the bonding material on the outer peripheral surface of the bonding portion was smooth, and there were no depressions with a depth of 0.3 mm or more.

（比較例１）
接合材量が３３８ｇ／ｍ2で、周囲をバンドソーで切り取らなかった以外は、実施例１と同様にして樹脂発泡複合体を得た。接合部の外周表面には、接合材がはみ出ていて、０．３ｍｍ以上の深さの窪みは１１２個確認され、そのうち４９個が１ｍｍ以上の深さがあった。 (Comparative example 1)
A resin foam composite was obtained in the same manner as in Example 1, except that the bonding material amount was 338 g/m 2 and the periphery was not cut off with a band saw. The bonding material protruded from the outer peripheral surface of the joint, and 112 depressions with a depth of 0.3 mm or more were confirmed, of which 49 had a depth of 1 mm or more.

（比較例２）
接合材量が３５６ｇ／ｍ2で、周囲をバンドソーで切り取らなかった以外は、実施例２と同様にして樹脂発泡複合体を得た。比較例１と同様に接合部の外周表面には、接合材がはみ出ていて、０．３ｍｍ以上の深さの窪みは１２２個確認され、そのうち５０個が１ｍｍ以上の深さが有った。 (Comparative example 2)
A resin foam composite was obtained in the same manner as in Example 2, except that the bonding material amount was 356 g/m 2 and the periphery was not cut off with a band saw. As in Comparative Example 1, the bonding material protruded from the outer peripheral surface of the bonded portion, and 122 depressions with a depth of 0.3 mm or more were confirmed, of which 50 had a depth of 1 mm or more.

（比較例３）
接合材量が３４０ｇ／ｍ2で、周囲をバンドソーで切り取らなかった以外は、実施例３と同様にして樹脂発泡複合体を得た。比較例１と同様に接合部の外周表面には、接合材がはみ出ていて、０．３ｍｍ以上の深さの窪みは８４個確認され、そのうち２６個が１ｍｍ以上の深さが有った。 (Comparative Example 3)
A resin foam composite was obtained in the same manner as in Example 3, except that the bonding material amount was 340 g/m 2 and the periphery was not cut off with a band saw. As in Comparative Example 1, the bonding material protruded from the outer peripheral surface of the bonding portion, and 84 depressions with a depth of 0.3 mm or more were confirmed, of which 26 had a depth of 1 mm or more.

（比較例４）
接合材量が３３３ｇ／ｍ2で、周囲をバンドソーで切り取らなかった以外は、実施例４と同様にして樹脂発泡複合体を得た。比較例１と同様に接合部の外周表面には、接合材がはみ出ていて、０．３ｍｍ以上の深さの窪みは８８個確認され、そのうち３９個が１ｍｍ以上の深さが有った。 (Comparative Example 4)
A resin foam composite was obtained in the same manner as in Example 4, except that the bonding material amount was 333 g/m 2 and the periphery was not cut off with a band saw. As in Comparative Example 1, the bonding material protruded from the outer peripheral surface of the bonded portion, and 88 depressions with a depth of 0.3 mm or more were confirmed, of which 39 had a depth of 1 mm or more.

（比較例５）
接合材量が２９５ｇ／ｍ2で、周囲をバンドソーで切り取らなかった以外は、実施例５と同様にして樹脂発泡複合体を得た。比較例１と同様に接合部の外周表面には、接合材がはみ出ていて、０．３ｍｍ以上の深さの窪みは６０個確認され、そのうち２３個が１ｍｍ以上の深さが有った。
樹脂発泡複合体の製造に用いた上記フェノール樹脂発泡板１～５の熱伝導率は、０．０２０Ｗ／ｍＫであった。 (Comparative Example 5)
A resin foam composite was obtained in the same manner as in Example 5, except that the bonding material amount was 295 g/m 2 and the periphery was not cut with a band saw. As in Comparative Example 1, the bonding material protruded from the outer peripheral surface of the bonded portion, and 60 depressions with a depth of 0.3 mm or more were confirmed, of which 23 had a depth of 1 mm or more.
The thermal conductivity of the phenol resin foam plates 1 to 5 used in the production of the resin foam composite was 0.020 W/mK.

＜樹脂発泡複合体の耐低温特性＞
実施例１～１３及び比較例１～５で作製し、接合部の外周表面の窪みを確認した樹脂発泡複合体を、液体窒素に浮かべ、上から押さえつけて、一番下側の接合部が完全に液体窒素に浸漬するように沈めた。３０分間経過後に樹脂発泡複合体を取り出し、２４時間以上室温（２３℃）で静置した。静置後の樹脂発泡複合体の接合部の外周表面に水性インクを塗って亀裂の有無を目視で確認した。亀裂の有無及び数を確認した後、２４時間以上室温（２３℃）で静置し、水性インクが完全に乾いたことを確認後、もう一度樹脂発泡複合体を、液体窒素に浸漬し、６０分間経過後、樹脂発泡複合体を取り出し、２４時間以上室温（２３℃）で静置した。
静置後、樹脂発泡複合体周縁部に水性インクを塗って亀裂の有無及び数を目視で確認した。
なお、亀裂とは、樹脂発泡体に入る亀裂をいい、亀裂の数とは、液体窒素に浸漬した接合部を挟む２つの樹脂発泡体の外周表面に発生する亀裂の数の和をいう。 <Low Temperature Resistance of Resin Foam Composite>
The resin foam composites prepared in Examples 1 to 13 and Comparative Examples 1 to 5, and in which depressions on the outer peripheral surface of the joint were confirmed, were floated on liquid nitrogen and pressed from above, so that the lowest joint was complete. immersed in liquid nitrogen. After 30 minutes had passed, the resin foam composite was taken out and allowed to stand at room temperature (23°C) for 24 hours or more. A water-based ink was applied to the outer peripheral surface of the joint portion of the resin foam composite after standing, and the presence or absence of cracks was visually confirmed. After confirming the presence and number of cracks, leave at room temperature (23 ° C.) for 24 hours or more, confirm that the water-based ink is completely dry, and then immerse the resin foam composite again in liquid nitrogen for 60 minutes. After the passage of time, the resin foam composite was taken out and allowed to stand at room temperature (23° C.) for 24 hours or longer.
After standing still, water-based ink was applied to the periphery of the resin foam composite, and the presence or absence of cracks and the number of cracks were visually confirmed.
The cracks refer to cracks entering the resin foam, and the number of cracks refers to the sum of the number of cracks generated on the outer peripheral surfaces of the two resin foams sandwiching the joint immersed in liquid nitrogen.

実施例と比較例の結果を表１にまとめた。
実施例が示す通り、樹脂発泡複合体の接合部に１ｍｍ以上の窪みが多いと液体窒素へ浸漬した際に亀裂が発生する事が確認できた。
実施例６～１０では、転写した接合材の量が少なく、２個の樹脂発泡体の接着性能が若干低下した。本実施形態の樹脂発泡複合体において、接合する樹脂発泡体の接合強度の観点から、樹脂発泡体の表面全面（例えば、樹脂発泡体外端形全面）に接合部が設けられることが好ましい。 Table 1 summarizes the results of Examples and Comparative Examples.
As shown in the examples, it was confirmed that if there were many depressions of 1 mm or more in the joint portion of the resin foam composite, cracks would occur when immersed in liquid nitrogen.
In Examples 6 to 10, the amount of the transferred bonding material was small, and the adhesion performance of the two resin foams was slightly lowered. In the resin foam composite of the present embodiment, from the viewpoint of the bonding strength of the resin foam to be bonded, it is preferable that the bonding portion is provided on the entire surface of the resin foam (for example, the entire outer end shape of the resin foam).

Figure 0007169054000001
Figure 0007169054000001

本発明は、液化石油ガス（ＬＰＧ）、液化天然ガス（ＬＮＧ）、液化水素（ＬＨ2）、液化窒素（ＬＮ2）、液化酸素（ＬＯ2）、液化ヘリウム（ＬＨｅ）等の極低温物質を貯蔵又は輸送する際の極低温タンクに適した樹脂発泡複合体である。 The present invention uses cryogenic substances such as liquefied petroleum gas (LPG), liquefied natural gas (LNG), liquefied hydrogen ( LH2), liquefied nitrogen ( LN2), liquefied oxygen ( LO2), and liquefied helium (LHe). It is a resin foam composite suitable for cryogenic tanks during storage or transportation.

１ 樹脂発泡複合体
２ 樹脂発泡体
３ 接合部
４ 樹脂発泡体外端形
５ 接合部はみ出し部
６ 窪み
６Ａ 厚み方向の両方の端が樹脂発泡体２と接合部３との界面に接している窪み
６Ｂ 厚み方向の片方の端が樹脂発泡体２と接合部３との界面に接している窪み
６Ｃ 厚み方向の端が樹脂発泡体と接合部３との界面に接していない窪み
７ 距離Ｄが極大となる点
８ 距離Ｄが極小となる点
Ｄ 樹脂発泡体外端形４の外端と接合部はみ出し部の外端との、樹脂発泡体外端形４に対して垂直方向の距離
Ｗ 幅
Ｌ 深さ 1 Resin foam composite 2 Resin foam 3 Joint 4 Resin foam outer end shape 5 Joint protruding portion 6 Hollow 6A Hollow 6B in which both ends in the thickness direction are in contact with the interface between the resin foam 2 and the joint 3 Recess 6C whose one end in the thickness direction is in contact with the interface between the resin foam 2 and the joint 3 Recess 7 whose end in the thickness direction is not in contact with the interface between the resin foam and the joint 3 When the distance D is maximum Point 8 Point D at which the distance D becomes minimum D Distance between the outer end of the resin foam outer end shape 4 and the outer end of the joint protruding portion in the direction perpendicular to the resin foam outer end shape 4 W Width L Depth

Claims (3)

２個の樹脂発泡体が接合部を介して接合された構造を含む樹脂発泡複合体であって、
前記接合部の外周表面に存在する深さ１ｍｍ以上の窪みの数が、前記接合部の外周表面の長さ１ｍあたり３個以下であり、
前記接合部が接合材からなり、
前記接合部の厚みが１００μｍ以上３０００μｍ以下であり、
前記樹脂発泡体がフェノール樹脂発泡板であり、
少なくとも１個の前記樹脂発泡体の熱伝導率が、０．００１Ｗ／ｍＫ以上０．０２８Ｗ／ｍＫ以下であり、
前記樹脂発泡体が表面に、樹脂繊維からなる不織布及びガラス繊維混抄紙からなる群から選択される少なくとも１種の面材を備えており、
前記接合部と、接合部に隣接する一方の前記樹脂発泡体を液体窒素に３０分間浸漬し、その後２３℃で２４時間経過した際、及び更に２４時間経過後に再度液体窒素で６０分間浸漬し、その後２３℃で２４時間経過した際における、前記接合部を挟む２つの前記樹脂発泡体の外周表面に生じる亀裂の数の和が０個である、
液化ガスタンク用樹脂発泡複合体。 A resin foam composite including a structure in which two resin foams are joined via a joint,
The number of depressions having a depth of 1 mm or more existing on the outer peripheral surface of the joint is 3 or less per 1 m length of the outer peripheral surface of the joint,
The joint portion is made of a joint material,
The joint portion has a thickness of 100 μm or more and 3000 μm or less,
The resin foam is a phenol resin foam board,
At least one resin foam has a thermal conductivity of 0.001 W/mK or more and 0.028 W/mK or less ,
The resin foam has, on its surface, at least one surface material selected from the group consisting of a nonwoven fabric made of resin fibers and a glass fiber mixed paper,
The joint and one of the resin foams adjacent to the joint are immersed in liquid nitrogen for 30 minutes, and then immersed in liquid nitrogen for 60 minutes after 24 hours at 23 ° C. and after a further 24 hours, After 24 hours at 23 ° C., the sum of the number of cracks generated on the outer peripheral surfaces of the two resin foams sandwiching the joint is 0.
Resin foam composite for liquefied gas tanks . 前記接合部の外周表面に存在する深さ０．３ｍｍ以上１ｍｍ未満の窪みの数が、前記接合部の外周表面の長さ１ｍあたり１０個以下である、請求項１記載の樹脂発泡複合体。 2. The resin foam composite according to claim 1, wherein the number of depressions having a depth of 0.3 mm or more and less than 1 mm existing on the outer peripheral surface of the joint is 10 or less per 1 m of the length of the outer peripheral surface of the joint. 少なくとも１個の前記樹脂発泡体の密度が１５ｋｇ／ｍ３以上６０ｋｇ／ｍ３以下である請求項１又は２に記載の樹脂発泡複合体。 The resin foam composite according to claim 1 or 2 , wherein at least one resin foam has a density of 15 kg/m3 or more and 60 kg/m3 or less.
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