JP2020179583A - Laminate and method for manufacturing the same - Google Patents
Laminate and method for manufacturing the same Download PDFInfo
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- JP2020179583A JP2020179583A JP2019083846A JP2019083846A JP2020179583A JP 2020179583 A JP2020179583 A JP 2020179583A JP 2019083846 A JP2019083846 A JP 2019083846A JP 2019083846 A JP2019083846 A JP 2019083846A JP 2020179583 A JP2020179583 A JP 2020179583A
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- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 title description 5
- 239000000835 fiber Substances 0.000 claims abstract description 161
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims description 26
- 229920005992 thermoplastic resin Polymers 0.000 claims description 9
- 239000004745 nonwoven fabric Substances 0.000 claims description 7
- 239000004753 textile Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 34
- 229920001971 elastomer Polymers 0.000 description 23
- 239000000806 elastomer Substances 0.000 description 16
- 238000001746 injection moulding Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 7
- 239000002649 leather substitute Substances 0.000 description 7
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- 238000005259 measurement Methods 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 5
- 230000035807 sensation Effects 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920001410 Microfiber Polymers 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 238000012935 Averaging Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- 239000012790 adhesive layer Substances 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
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- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- WNPMPFBJTYCQEL-UHFFFAOYSA-N carbonic acid;ethyl carbamate Chemical compound OC(O)=O.CCOC(N)=O WNPMPFBJTYCQEL-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001692 polycarbonate urethane Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- -1 propylene-ethylene Chemical group 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
Landscapes
- Injection Moulding Of Plastics Or The Like (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、人工皮革に代表される繊維構造体よりなる層と基盤樹脂層との接着性に優れる積層体に関する。また、いわゆるインモールド成形を用いた、インモールド材としての繊維構造体と樹脂、特に熱可塑性樹脂との積層体の製造方法に関する。 The present invention relates to a laminate having excellent adhesiveness between a layer made of a fiber structure typified by artificial leather and a base resin layer. The present invention also relates to a method for producing a laminate of a fiber structure as an in-mold material and a resin, particularly a thermoplastic resin, using so-called in-mold molding.
意匠性や触感に優れたインモールド材として、不織布や織物等の繊維構造体、繊維構造体を含む人工皮革や合成皮革等の皮革様素材、紙等のような繊維構造体を含む素材が用いられている。 As an in-mold material with excellent design and tactile sensation, fiber structures such as non-woven fabrics and textiles, leather-like materials such as artificial leather and synthetic leather including fiber structures, and materials including fiber structures such as paper are used. Has been done.
例えば、下記特許文献１は、特定の極細繊維束の繊維絡合体と高分子弾性体とからなる加飾成形用シートに三次元形状を賦与してプレフォーム成形体を成形し、得られたプレフォーム成形体を金型キャビィティに配置してインモールド射出成形することにより、表面に皮革様の外観が付与された加飾インモールド成形体を開示する。 For example, Patent Document 1 below is obtained by molding a preform molded product by imparting a three-dimensional shape to a decorative molding sheet composed of a fiber entangled body of a specific ultrafine fiber bundle and a polymer elastic body. Disclosed is a decorative in-mold molded product having a leather-like appearance on the surface by arranging the foam molded product in a mold cavity and in-mold injection molding.
しかしながら、従来から知られた一般的な繊維構造体を用いて加飾成形体を成形した場合、剥離強度が弱いという問題があり、特許文献１には剥離強度の詳細については記載されていない。 However, when a decorative molded product is molded using a conventional general fiber structure, there is a problem that the peel strength is weak, and Patent Document 1 does not describe the details of the peel strength.
また、上記問題に関して、繊維構造体と基盤樹脂の間に接着層を用いて密着性を向上させることも考えられるが、接着層を付与する工程が入るなど量産性の低下が懸念される。 Further, regarding the above problem, it is conceivable to use an adhesive layer between the fiber structure and the base resin to improve the adhesiveness, but there is a concern that the mass productivity may be lowered due to the inclusion of a step of applying the adhesive layer.
本発明の目的は、繊維構造体／樹脂なる積層体のインモールド成形において、より繊維構造体層と基盤樹脂層との接着性に優れる積層体を提供することにある。 An object of the present invention is to provide a laminate having more excellent adhesiveness between a fiber structure layer and a base resin layer in in-mold molding of a laminate of fiber structure / resin.
本発明の一局面は、上述したような繊維構造体において、繊維絡合体から成る繊維構造体層と、前記繊維構造体層の各繊維の隙間に浸潤して固着されている樹脂層とを備える繊維構造体／樹脂積層体であって、前記繊維絡合体の見掛け密度が０．１６〜０．７５ｇ／ｃｍ３の範囲内であり、かつ、下記式（１）で定義される前記繊維構造体の圧縮性Ｒが０．３０以下であることを特徴とする積層体である。
Ｒ＝（ｈ１−ｈ２）／ｈ１ （１）
ｈ１；荷重前繊維構造体厚さ（ｍｍ）、 ｈ２；荷重後繊維構造体厚さ（ｍｍ）
ここで、前記繊維絡合体がテキスタイル、不織布、紙、編み物からなる群より選ばれるいずれかであることが好ましい。
One aspect of the present invention includes a fiber structure layer made of a fiber entangled body and a resin layer infiltrated and fixed in the gaps between the fibers of the fiber structure layer in the fiber structure as described above. The fiber structure / resin laminate, the apparent density of the fiber entangled body is in the range of 0.16 to 0.75 g / cm 3 , and the fiber structure is defined by the following formula (1). It is a laminated body characterized by having a compressibility R of 0.30 or less.
R = (h1-h2) / h1 (1)
h1; Fiber structure thickness before loading (mm), h2; Fiber structure thickness after loading (mm)
Here, it is preferable that the fiber entanglement is selected from the group consisting of textiles, non-woven fabrics, paper, and knitting.
また、前記繊維構造体が、前記繊維絡合体と該絡合体に含浸された高分子弾性体から成り、前記繊維構造体の高分子弾性体と繊維絡合体の質量比（高分子弾性体の質量／繊維絡合体の質量）が５／９５〜４０／６０の範囲内であることが好ましい。
さらに、前記繊維構造体の構成繊維の少なくとも一部が高分子材料により被覆されているのが好ましい。
Further, the fiber structure is composed of the fiber entangled body and the polymer elastic body impregnated in the entangled body, and the mass ratio of the polymer elastic body to the fiber entangled body of the fiber structure (mass of the polymer elastic body). / Mass of fiber entanglement) is preferably in the range of 5/95 to 40/60.
Further, it is preferable that at least a part of the constituent fibers of the fiber structure is coated with a polymer material.
また、本発明の他の態様は、前記繊維構造体を成形用金型のキャビティに配置する工程と、前記繊維構造体が配置された金型を型締めし、前記繊維構造体の各繊維の隙間に溶融した熱可塑性樹脂を浸潤しつつ前記繊維構造体層に熱可塑性樹脂層を固着して形成する工程を備えた積層体の製造方法である。 Further, in another aspect of the present invention, a step of arranging the fiber structure in the cavity of the molding die and a mold in which the fiber structure is arranged are molded to form each fiber of the fiber structure. This is a method for producing a laminated body, which comprises a step of infiltrating the melted thermoplastic resin into the gaps and fixing the thermoplastic resin layer to the fiber structure layer to form the laminated body.
本発明によれば、いわゆるインモールド成形において接着性に優れる繊維構造体／樹脂なる積層体を得ることができる。 According to the present invention, it is possible to obtain a fiber structure / resin laminate having excellent adhesiveness in so-called in-mold molding.
本発明を達成するための具体的な手段の例を以下に述べる。まず、本発明に用いる繊維絡合体は、見掛け密度が０．１６〜０．７５ｇ／ｃｍ３の布帛であれば特に限定するものではなく、不織布、織編物で代表される布帛を用いることが可能であるが、例えば、皮革様の風合いや充実感や柔軟性に優れるため、三次元絡合不織布が好ましい。繊維絡合体の見掛け密度は、０．３５〜０．４７ｇ／ｃｍ３であることが好ましい。繊維構造体／樹脂積層体において、繊維絡合体の見掛け密度が低い程、各繊維の隙間が増大し、基盤樹脂の浸潤性が向上するため、優れた接着性が得られる。一方で、繊維絡合体の見掛け密度が低すぎる場合には、インモールド成形時に繊維の密度斑による浮模様（あらび）の表出や、成形時の圧縮により厚みが薄くなり柔軟性を失うなど、前記積層体の触感が低下する場合がある。加えて、繊維同士の纏まりが不十分となり、剥離強力が低下する場合がある。また、見掛け密度が高すぎる場合には、繊維絡合体内に樹脂が浸潤する隙間がなくなり、接着性が低下する傾向がある。 Examples of specific means for achieving the present invention are described below. First, the fiber entangled body used in the present invention is not particularly limited as long as it is a cloth having an apparent density of 0.16 to 0.75 g / cm 3, and a cloth typified by a non-woven fabric or a woven or knitted fabric can be used. However, for example, a three-dimensional entangled non-woven fabric is preferable because it is excellent in leather-like texture, fullness and flexibility. The apparent density of the fiber entangled body is preferably 0.35 to 0.47 g / cm 3 . In the fiber structure / resin laminate, the lower the apparent density of the fiber entangled bodies, the greater the gaps between the fibers and the improved infiltration of the base resin, so that excellent adhesiveness can be obtained. On the other hand, if the apparent density of the fiber entanglement is too low, floating patterns (roughness) may appear due to the density unevenness of the fibers during in-mold molding, or the thickness may become thin due to compression during molding, resulting in loss of flexibility. , The tactile sensation of the laminated body may be reduced. In addition, the fibers may not be sufficiently bundled with each other and the peeling strength may decrease. Further, when the apparent density is too high, there is no gap in which the resin infiltrates into the fiber entangled body, and the adhesiveness tends to decrease.
本発明はさらに下記式（１）で定義される前記繊維構造体の圧縮性Ｒが０．３０以下である必要がある。
Ｒ＝（ｈ１−ｈ２）／ｈ１ （１）
ｈ１；荷重前繊維構造体厚さ（ｍｍ）、 ｈ２；荷重後繊維構造体厚さ（ｍｍ）
The present invention further requires that the compressible R of the fiber structure defined by the following formula (1) is 0.30 or less.
R = (h1-h2) / h1 (1)
h1; Fiber structure thickness before loading (mm), h2; Fiber structure thickness after loading (mm)
インモールド成形においては、型内に高い圧力で基盤樹脂が充填されるため、繊維構造体が基盤樹脂の圧力により圧縮され各繊維の隙間が減少してしまうおそれがある。そのため、接着性の観点では、圧縮性は小さい方が好ましく、０（変化なし）がもっとも好ましい。圧縮性が高く、各繊維の隙間が小さくなりすぎると、上記したように基板樹脂の浸潤が十分ではなく接着性に劣り剥離強度が低下することとなる。 In in-mold molding, since the base resin is filled in the mold at a high pressure, the fiber structure may be compressed by the pressure of the base resin and the gaps between the fibers may be reduced. Therefore, from the viewpoint of adhesiveness, the compressibility is preferably small, and 0 (no change) is most preferable. If the compressibility is high and the gap between the fibers is too small, the substrate resin is not sufficiently infiltrated as described above, the adhesiveness is poor, and the peel strength is lowered.
圧縮性を小さくする手段は、例えば、繊維絡合体の見掛け密度や繊維径、結合点の増大や繊維構造体の弾性率の向上などがあり、後述する風合いの観点から、適宜適切な圧縮性を決定する必要がある。 Means for reducing the compressibility include, for example, an increase in the apparent density and fiber diameter of the fiber entanglement, an increase in the bonding point, and an improvement in the elastic modulus of the fiber structure. From the viewpoint of the texture described later, appropriate compressibility is appropriately provided. You need to decide.
本発明の繊維絡合体を構成する繊維は、皮革様の風合いを得るため、平均繊度が０．９ｄｔｅｘ以下の極細繊維であることが好ましく、また強度が高くなる点から長繊維であることが好ましい。また、皮革様の風合いと機械強度を得る点で繊維絡合体を構成する繊維は、極細長繊維束三次元絡合不織布が最も好ましい。前記極細繊維は、複数樹脂を種々の方法で複合紡糸した後、一方の樹脂を溶解除去したり樹脂界面で分割したりする公知の方法で得ることができる。 The fibers constituting the fiber entanglement of the present invention are preferably ultrafine fibers having an average fineness of 0.9 dtex or less in order to obtain a leather-like texture, and are preferably long fibers from the viewpoint of increasing strength. .. Further, as the fiber constituting the fiber entangled body in terms of obtaining a leather-like texture and mechanical strength, an ultrafine long fiber bundle three-dimensional entangled non-woven fabric is most preferable. The ultrafine fibers can be obtained by a known method in which a plurality of resins are composite-spun by various methods and then one of the resins is dissolved and removed or divided at a resin interface.
前記繊維絡合体は、従来の人工皮革において最も一般的に実施されてきたように、目的の繊度に紡糸、延伸し、捲縮を付与した後で任意の繊維長にカットして、ステープルとし、カード、クロスラッパー、ランダムウェバー等を用いて複合繊維ウェブを製造するが好ましい。 The fiber entanglement is spun, stretched, crimped to the desired fineness, and then cut to an arbitrary fiber length to form a staple, as is most commonly practiced in conventional artificial leather. It is preferable to manufacture the composite fiber web using cards, cross wrappers, random webbers and the like.
このようにして得られた繊維ウェブを、目的とする目付の不織布を得るため、複数枚重ね合わせ、ニードルパンチングを含む絡合処理によって、繊維を実質的に切断することなく、厚み方向に繊維を配向させつつ繊維同士を絡合させて複合繊維絡合体とする。 In order to obtain a non-woven fabric having a desired basis weight from the fiber web thus obtained, a plurality of sheets are laminated and an entanglement process including needle punching is performed to cut the fibers in the thickness direction without substantially cutting the fibers. The fibers are entangled with each other while being oriented to form a composite fiber entangled body.
本願発明においては、前記繊維絡合体にさらに高分子弾性体を浸潤させることにより、繊維構造体層を形成することができる。このような繊維構造体としては、従来いわゆる人工皮革と称されている。高分子弾性体の含有割合は、繊維構造体層の高分子弾性体と繊維絡合体の質量比（高分子弾性体の質量／繊維絡合体の質量）が、５／９５〜４０／６０、さらには、１２／８８〜２６／７４の範囲であることが好ましい。高分子弾性体の含有割合は高い程、繊維同士の纏まりが強固になり繊維束となることで、樹脂の浸潤する隙間が増大し、接着性は向上する。一方で、高分子弾性体の割合が高すぎる場合には、得られる積層体の触感が劣る（ゴムライクになる）傾向がある。高分子弾性体の割合が低すぎる場合には、繊維同士の纏まりが不十分となり、繊維構造体の繊維／繊維界面にて剥離が発生する場合がある。 In the present invention, the fiber structure layer can be formed by further infiltrating the fiber entangled body with a polymer elastic body. Such a fiber structure is conventionally called so-called artificial leather. The content ratio of the polymer elastic body is such that the mass ratio of the polymer elastic body to the fiber entangled body (mass of the polymer elastic body / mass of the fiber entangled body) of the fiber structure layer is 5/95 to 40/60, and further. Is preferably in the range of 12/88 to 26/74. The higher the content ratio of the polymer elastic body, the stronger the bundle between the fibers and the bundle of fibers, so that the gap in which the resin infiltrates increases and the adhesiveness improves. On the other hand, when the proportion of the polymer elastic body is too high, the tactile sensation of the obtained laminated body tends to be inferior (becomes rubber-like). If the proportion of the polymer elastic body is too low, the fibers may not be sufficiently bundled with each other, and peeling may occur at the fiber / fiber interface of the fiber structure.
高分子弾性体としては、ゴム、エラストマーなどが特に限定なく使用される。その具体例としては、例えば、ブタジエンゴム，イソプレンゴム，クロロプレンゴム，スチレン−ブタジエンゴムなどのジエン系ゴム；ニトリルゴム，水素化ニトリルゴムなどニトリル系ゴム；アクリルゴムなどのアクリル系ゴム；ポリエーテルウレタンゴム，ポリエステルウレタンゴムなどのウレタン系ゴム；シリコーン系ゴム；エチレン−プロピレンゴムなどのオレフィン系ゴム；フッ素系ゴム；スチレン−ブタジエンブロック共重合体，スチレン−イソプレンブロック共重合体，スチレン−ブタジエン−スチレンブロック共重合体，スチレン−イソプレン−スチレンブロック共重合体，アクリロニトリル−ブタジエン−スチレン共重合体，アクリロニトリル−スチレン共重合体，もしくはこれらの水添物又はエポキシ化物などのポリスチレン系エラストマー；プロピレン−エチレン・プロピレンゴム共重合体などのオレフィンとゴム成分との共重合体、又はその水添物などのポリオレフィン系エラストマー；ポリエーテルウレタンエラストマー，ポリエステルウレタンエラストマー，ポリエーテルエステルウレタンエラストマー，ポリカーボネートウレタンエラストマー，ポリエーテルカーボネートウレタンエラストマー，ポリエステルカーボネートウレタンエラストマーなどのポリウレタン系エラストマー；ポリエーテルエステルエラストマー，ポリエステルエステルエラストマーなどのポリエステル系エラストマー；ポリエステルアミドエラストマー，ポリエーテルエステルアミドエラストマーなどのポリアミド系エラストマー；塩化ビニル系エラストマーなどのハロゲン系エラストマー；などが挙げられる。これらは、単独で用いても、二種以上を組み合わせて用いてもよい。上記高分子弾性体の中では、ポリウレタン系、ポリエステル系、ポリアミド系などのエラストマー、特に、ポリウレタン系エラストマーが好ましい。 As the polymer elastic body, rubber, elastomer and the like are used without particular limitation. Specific examples thereof include diene rubbers such as butadiene rubber, isoprene rubber, chloroprene rubber, and styrene-butadiene rubber; nitrile rubbers such as nitrile rubber and hydride nitrile rubber; acrylic rubbers such as acrylic rubber; and elastomer urethane. Urethane-based rubbers such as rubber and polyester urethane rubber; Silicone-based rubbers; Olefin-based rubbers such as ethylene-propylene rubber; Fluorine-based rubbers; styrene-butadiene block copolymers, styrene-isoprene block copolymers, styrene-butadiene-styrene Block copolymers, styrene-isoprene-styrene block copolymers, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene copolymers, or polystyrene-based elastomers such as hydrogenated products or epoxidized products of these; propylene-ethylene. Polypolymers of olefins such as propylene rubber copolymers and rubber components, or polyolefin-based elastomers such as hydrogenated products thereof; polyether urethane elastomers, polyester urethane elastomers, polyether ester urethane elastomers, polycarbonate urethane elastomers, polyether carbonates Polyurethane elastomers such as urethane elastomers and polyester carbonate urethane elastomers; Polyester elastomers such as polyether ester elastomers and polyester ester elastomers; Polyamide elastomers such as polyesteramide elastomers and polyether esteramide elastomers; Halogen-based elastomers such as vinyl chloride elastomers Elastomer; etc. These may be used alone or in combination of two or more. Among the above polymer elastic bodies, polyurethane-based, polyester-based, polyamide-based and other elastomers, particularly polyurethane-based elastomers are preferable.
繊維構造体を射出成形金型２内にセットした状態で射出成形することにより、繊維構造体層２と基盤樹脂層３とが一体化された積層体であるインモールド成形品（繊維構造体／樹脂なる積層体４）を得る。具体的には、次のようにして行うとよい。 An in-mold molded product (fiber structure /) which is a laminated body in which the fiber structure layer 2 and the base resin layer 3 are integrated by injection molding with the fiber structure set in the injection molding die 2. A resin laminate 4) is obtained. Specifically, it may be performed as follows.
まず、キャビティ型とコア型とからなる射出成形金型１内にインモールド加飾シートとしての繊維構造体をセットする。インモールド加飾シート（繊維構造体）をキャビティ面に固定するためには、キャビティ面に吸引孔を形成して吸引固定するなどの手段がある。次いで、型締め後、溶融した熱可塑性樹脂をゲート部５よりキャビティ内に充満させ射出成形を行う（図１参照）。そして、冷却、型開きして、繊維構造体層２と基盤樹脂層３とが一体化された繊維構造体／樹脂積層体４としてインモールド成形品を得ることができる（図２参照）。 First, a fiber structure as an in-mold decorative sheet is set in an injection molding die 1 composed of a cavity mold and a core mold. In order to fix the in-mold decorative sheet (fiber structure) to the cavity surface, there is a means such as forming a suction hole in the cavity surface and sucking and fixing the sheet. Next, after molding, the cavity is filled with the molten thermoplastic resin from the gate portion 5 to perform injection molding (see FIG. 1). Then, by cooling and opening the mold, an in-mold molded product can be obtained as a fiber structure / resin laminate 4 in which the fiber structure layer 2 and the base resin layer 3 are integrated (see FIG. 2).
本発明における樹脂は、熱可塑性樹脂、好ましくは射出成形グレードの熱可塑性樹脂が好ましく用いられ、具体的には、ＡＢＳ（アクリルブチルスチレン），ＰＣ（ポリカーボネート），ＰＭＭＡ（アクリル），及びＡＢＳ＋ＰＣの群から選択された１つの素材、好ましくはＡＢＳ又はＰＭＭＡ、さらに好ましくはＡＢＳである。また、基盤樹脂層の厚さは、製品に応じて任意に設定され、本実施の形態では、約３ｍｍである。基盤樹脂層の原料である熱可塑性樹脂は、射出成形機で加熱溶融され、繊維構造体がキャビティ側に装着された金型の中に射出されて、前記繊維構造体裏面の各繊維の隙間に浸潤しながら繊維構造体に固着されている。 As the resin in the present invention, a thermoplastic resin, preferably an injection-molded grade thermoplastic resin is preferably used, and specifically, a group of ABS (acrylic butyl styrene), PC (polycarbonate), PMMA (acrylic), and ABS + PC. One material selected from, preferably ABS or PMMA, more preferably ABS. The thickness of the base resin layer is arbitrarily set according to the product, and is about 3 mm in the present embodiment. The thermoplastic resin, which is the raw material of the base resin layer, is heated and melted by an injection molding machine, and the fiber structure is injected into a mold mounted on the cavity side to fill the gaps between the fibers on the back surface of the fiber structure. It is fixed to the fiber structure while infiltrating.
以下、本発明を実施例によりさらに具体的に説明する。なお、本発明は実施例により何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to the examples.
［繊維絡合体の見掛け密度の測定］
繊維構造体における繊維絡合体の単位面積あたりの質量（ｇ／ｃｍ２）を厚さ（ｃｍ）で除した値を局所見掛け密度（ｇ／ｃｍ３）とし、繊維絡合体の任意の１０箇所について測定した局所見掛け密度を算術平均した値を、その繊維絡合体の見掛け密度とする。なお、厚さは、ＪＩＳ Ｌ１０９６に準じて圧力２３．５ｋＰａ（２４０ｇｆ／ｃｍ２）で測定される。
[Measurement of apparent density of fiber entanglement]
The value obtained by dividing the mass (g / cm 2 ) per unit area of the fiber entanglement in the fiber structure by the thickness (cm) is defined as the local apparent density (g / cm 3 ), and for any 10 points of the fiber entanglement. The value obtained by arithmetically averaging the measured local apparent densities is taken as the apparent density of the fiber entanglement. The thickness is measured at a pressure of 23.5 kPa (240 gf / cm 2 ) according to JIS L1096.
［繊維構造体の圧縮性の測定］
繊維構造体を５０±３ｍｍの正四角形に裁断し、複数枚を２０ｍｍ±５ｍｍになるよう重ね、この時の高さｈ１を測定する。次に２００ｇの荷重をかけて厚さ方向に圧縮させ、この時の高さｈ２を測定する。この測定を各３回行うことで、ｈ１，ｈ２の平均値を算出し、下記式（１）より圧縮性Ｒとした。
Ｒ＝（ｈ１−ｈ２）／ｈ１ （１）
ただし、ｈ１；荷重前繊維構造体厚さ（ｍｍ）、 ｈ２；荷重後繊維構造体厚さ（ｍｍ）である。
[Measurement of compressibility of fiber structure]
The fiber structure is cut into a regular quadrangle of 50 ± 3 mm, and a plurality of sheets are stacked so as to have a length of 20 mm ± 5 mm, and the height h1 at this time is measured. Next, a load of 200 g is applied to compress the material in the thickness direction, and the height h2 at this time is measured. By performing this measurement three times each, the average value of h1 and h2 was calculated, and the compressibility R was obtained from the following formula (1).
R = (h1-h2) / h1 (1)
However, h1; fiber structure thickness before loading (mm), h2; fiber structure thickness after loading (mm).
［繊維構造体層の高分子弾性体と繊維絡合体の質量比（高分子弾性体の質量／繊維絡合体の質量）の測定］
繊維構造体層の高分子弾性体と繊維絡合体の質量比Ｗ１は、下式（２）により得ることができる。
Ｗ１＝（ＷＷ−ＷＤ）／ＷＤ （２）
＝［｛（ＷＷ−ＷＤ）／ＷＷ｝×１００］／｛（ＷＤ／ＷＷ）×１００｝ （２）’
ただし、ＷＤ：高分子弾性体の溶液または水分散液を含浸する前の繊維構造体の目付（ｇ／ｍ２）、
ＷＷ：高分子弾性体の溶液または水分散液を含浸した後の繊維構造体の目付（ｇ／ｍ２）である。
[Measurement of mass ratio of polymer elastic body and fiber entanglement in fiber structure layer (mass of polymer elastic body / mass of fiber entanglement)]
The mass ratio W 1 of the polymer elastic body of the fiber structure layer and the fiber entangled body can be obtained by the following equation (2).
W 1 = (W W -W D ) / W D (2)
= [{(W W -W D ) / W W} × 100] / {(W D / W W) × 100} (2) '
However, W D: basis weight of the fibrous structure prior to impregnation of a solution or dispersion of the elastic polymer (g / m 2),
W W : The basis weight (g / m 2 ) of the fiber structure after being impregnated with a solution of a polymer elastic body or an aqueous dispersion.
［繊維構造体層と基盤樹脂層とからなる積層体の剥離強力測定方法］
長さ２００ｍｍ、巾５０ｍｍ、厚さ３ｍｍの繊維構造体層と基盤樹脂層とからなる積層体を、長さ１２５ｍｍ、巾２０ｍｍに切り出し、繊維構造体を端部から長さ８０ｍｍ程度剥離する。繊維構造体層および基盤樹脂層それぞれの端部を、初期間隔１００ｍｍにセットした引張試験機の上下それぞれのチャックに挟んで、引張速度５ｍｍ／分での引張時間に対応した、繊維構造体層と基盤樹脂層との接着部分の剥離強力を測定し、チャートに記録する。チャート上に得られた引張時間−剥離強力曲線の剥離強力がほぼ一定している箇所についての平均値を読み取り、その試験片の剥離強力値とした。１種類の繊維構造体について、任意の試験片３個の剥離強力測定値を算術平均した値を、その繊維構造体の剥離強力値とした。
[Method for measuring the peeling strength of a laminate consisting of a fiber structure layer and a base resin layer]
A laminate composed of a fiber structure layer having a length of 200 mm, a width of 50 mm and a thickness of 3 mm and a base resin layer is cut out to a length of 125 mm and a width of 20 mm, and the fiber structure is peeled off from the end by about 80 mm in length. The ends of the fiber structure layer and the base resin layer are sandwiched between the upper and lower chucks of a tensile tester set at an initial interval of 100 mm, and the fiber structure layer and the fiber structure layer correspond to the tensile time at a tensile speed of 5 mm / min. Measure the peeling strength of the adhesive part with the base resin layer and record it on the chart. The average value of the tension time-peeling strength curve obtained on the chart at the points where the peeling strength was almost constant was read and used as the peeling strength value of the test piece. For one type of fiber structure, the value obtained by arithmetically averaging the peel strength measurement values of three arbitrary test pieces was defined as the peel strength value of the fiber structure.
［実施例１］
繊維構造体における布帛（繊維絡合体）の見掛け密度が０．３９ｇ／ｃｍ３であり、前記繊維構造体の高分子弾性体／繊維絡合体の質量比が１２／８８である人工皮革（図３参照）を、直圧式油圧成形機（（株）名機製作所製のＭ−１００Ｃ−ＡＳ−ＤＭ）の型のキャビティ部に前記人工皮革を装着した状態で、基盤樹脂層の材料としてＡＢＳ樹脂を射出成形することで、厚さ３ｍｍ、巾５０ｍｍ、長さ２００ｍｍの繊維構造体／樹脂なる積層体を得た。射出成形の条件は、樹脂温度２３５℃、金型温度５０℃、射出ピーク圧７８ＭＰａとした。
得られた積層体について上述した評価方法により、剥離強力を評価した。このときの剥離強力は、０．６９Ｎ／ｍｍと高いものであった。本実施例で得られた積層体は、しっとり感と柔軟性を兼ね備えており、優れた触感を有するものであった。
[Example 1]
Artificial leather in which the apparent density of the cloth (fiber entangled body) in the fiber structure is 0.39 g / cm 3 and the mass ratio of the polymer elastic body / fiber entangled body of the fiber structure is 12/88 (FIG. 3). Refer to), with the artificial leather attached to the cavity of the direct pressure type hydraulic molding machine (M-100C-AS-DM manufactured by Meiki Seisakusho Co., Ltd.), and ABS resin as the material of the base resin layer. By injection molding, a fiber structure / resin laminate having a thickness of 3 mm, a width of 50 mm, and a length of 200 mm was obtained. The conditions for injection molding were a resin temperature of 235 ° C., a mold temperature of 50 ° C., and an injection peak pressure of 78 MPa.
The peeling strength of the obtained laminate was evaluated by the above-mentioned evaluation method. The peeling strength at this time was as high as 0.69 N / mm. The laminate obtained in this example had both a moist feeling and flexibility, and had an excellent tactile sensation.
［実施例２］
繊維構造体層の高分子弾性体と繊維絡合体の質量比を下記のように変更した以外は、実施例１と同様の方法で積層体を得た。評価結果を表１に示す。
[Example 2]
A laminate was obtained in the same manner as in Example 1 except that the mass ratio of the polymer elastic body and the fiber entangled body of the fiber structure layer was changed as follows. The evaluation results are shown in Table 1.
［実施例３］
繊維絡合体の見掛け密度を下記のように変更した以外は、実施例１と同様の方法で積層体を得た。評価結果を表１に示す。
[Example 3]
A laminate was obtained in the same manner as in Example 1 except that the apparent density of the fiber entangled body was changed as follows. The evaluation results are shown in Table 1.
［実施例４］
繊維絡合体の見掛け密度を下記のように変更した以外は、実施例１と同様の方法で積層体を得た。評価結果を表１に示す。
[Example 4]
A laminate was obtained in the same manner as in Example 1 except that the apparent density of the fiber entangled body was changed as follows. The evaluation results are shown in Table 1.
［実施例５］
繊維構造体層の高分子弾性体と繊維絡合体の質量比を下記のように変更した以外は、実施例１と同様の方法で積層体を得た。本実施例で得られた積層体は、高分子弾性体と繊維絡合体の質量比が高いため、しっとり感や柔軟性が若干劣るものの、剥離強力は十分に高いものであった。評価結果を表１に示す。
[Example 5]
A laminate was obtained in the same manner as in Example 1 except that the mass ratio of the polymer elastic body and the fiber entangled body of the fiber structure layer was changed as follows. Since the laminated body obtained in this example has a high mass ratio of the polymer elastic body and the fiber entangled body, the moist feeling and flexibility are slightly inferior, but the peeling strength is sufficiently high. The evaluation results are shown in Table 1.
［比較例１］
繊維絡合体の見掛け密度を下記のように変更した以外は、実施例１と同様の方法で積層体を得た。本比較例で得られた積層体は、優れた触感を有していたものの、高い見掛け密度により樹脂が浸潤する隙間がなくなったことで、剥離強力は測定限界を下回るものであった。評価結果を表１に示す。
[Comparative Example 1]
A laminate was obtained in the same manner as in Example 1 except that the apparent density of the fiber entangled body was changed as follows. Although the laminate obtained in this comparative example had an excellent tactile sensation, the peeling strength was below the measurement limit because there were no gaps for the resin to infiltrate due to the high apparent density. The evaluation results are shown in Table 1.
［比較例２］
繊維構造体層の高分子弾性体と繊維絡合体の質量比、および繊維絡合体の見掛け密度を下記のように変更（図４参照）した以外は、実施例１と同様の方法で積層体を得た。本比較例で得られた積層体は、見掛け密度が低いため、繊維同士の纏まりが不十分となり剥離強力が小さかった。評価結果を表１に示す。
[Comparative Example 2]
The laminate was prepared in the same manner as in Example 1 except that the mass ratio of the polymer elastic body and the fiber entangled body of the fiber structure layer and the apparent density of the fiber entangled body were changed as follows (see FIG. 4). Obtained. Since the laminated body obtained in this comparative example had a low apparent density, the fibers were not sufficiently bundled with each other and the peeling strength was small. The evaluation results are shown in Table 1.
１ 射出成形金型
２ 繊維構造体層
３ 基盤樹脂層
４ 繊維構造体／樹脂なる積層体
５ ゲート部
1 Injection molding mold 2 Fiber structure layer 3 Base resin layer 4 Fiber structure / resin laminate 5 Gate
Claims (5)
Ｒ＝（ｈ１−ｈ２）／ｈ１ （１）
ｈ１；荷重前繊維構造体厚さ（ｍｍ）、 ｈ２；荷重後繊維構造体厚さ（ｍｍ） It is a laminate including a fiber structure layer made of a fiber entangled body and a resin layer infiltrated and fixed in the gaps between the fibers of the fiber structure layer, and the apparent density of the fiber entangled body is 0. A laminate characterized in that it is in the range of 16 to 0.75 g / cm 3 and the compressibility R of the fiber structure defined by the following formula (1) is 0.30 or less.
R = (h1-h2) / h1 (1)
h1; Fiber structure thickness before loading (mm), h2; Fiber structure thickness after loading (mm)
The step of arranging the fiber structure in the cavity of the molding die and the mold in which the fiber structure is arranged are molded, and the molten thermoplastic resin is infiltrated into the gaps between the fibers of the fiber structure. The method for producing a laminate according to any one of claims 1 to 4, further comprising a step of fixing and forming a thermoplastic resin layer to the fiber structure layer.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5580582A (en) * | 1979-12-03 | 1980-06-17 | Asahi Chemical Ind | Artificial leather |
| JP2004091960A (en) * | 2002-08-30 | 2004-03-25 | Kuraray Co Ltd | Method for producing suede-like artificial leather |
| JP2004291637A (en) * | 2003-03-13 | 2004-10-21 | Toray Ind Inc | Synthetic resin molding and its manufacturing process |
| WO2015076204A1 (en) * | 2013-11-21 | 2015-05-28 | 東レ株式会社 | Sheet-like article |
| JP2017065216A (en) * | 2015-10-02 | 2017-04-06 | 株式会社クラレ | Method for manufacturing laminated molding having in-mold material containing fiber structure integrated with surface thereof |
-
2019
- 2019-04-25 JP JP2019083846A patent/JP7340950B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5580582A (en) * | 1979-12-03 | 1980-06-17 | Asahi Chemical Ind | Artificial leather |
| JP2004091960A (en) * | 2002-08-30 | 2004-03-25 | Kuraray Co Ltd | Method for producing suede-like artificial leather |
| JP2004291637A (en) * | 2003-03-13 | 2004-10-21 | Toray Ind Inc | Synthetic resin molding and its manufacturing process |
| WO2015076204A1 (en) * | 2013-11-21 | 2015-05-28 | 東レ株式会社 | Sheet-like article |
| JP2017065216A (en) * | 2015-10-02 | 2017-04-06 | 株式会社クラレ | Method for manufacturing laminated molding having in-mold material containing fiber structure integrated with surface thereof |
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| JP7340950B2 (en) | 2023-09-08 |
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