JP2005162970A - Foam resin molded body - Google Patents
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Abstract
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本発明は、特定の粒度内容を有する、少なくとも粒子表面がリン酸カルシウム系化合物からなる発泡安定剤、及び、板状無機粒子、熱可塑性エラストマーから選ばれる少なくとも１種を含有してなる発泡樹脂成形体に関し、更に詳しくは、微細で均一な気泡を有し、軽量で、優れた機械的物性、寸法安定性を有する発泡樹脂成形体に関する。 The present invention relates to a foamed resin molded article having a specific particle size content and containing at least one selected from a foam stabilizer having at least a particle surface made of a calcium phosphate compound, plate-like inorganic particles, and a thermoplastic elastomer. More specifically, the present invention relates to a foamed resin molded article having fine and uniform air bubbles, light weight, excellent mechanical properties and dimensional stability.
樹脂の発泡成形とは、成形後の樹脂中に気泡を混在させる成形方法であり、優れた寸法安定性を有し、軽量で、しかも簡便に製造できる等の特徴から、多くの樹脂成形に応用されている。発泡成形の方法としては、樹脂に発泡剤を加えて射出成形する化学発泡法、または、射出成形する溶融状態の樹脂中に二酸化炭素、窒素等の不活性ガスを吹き込む物理発泡法が知られている。また、超臨界状ガスを用いて微細気泡を有する発泡成形体を得る超臨界発泡法が開発されている。一般的に発泡成形の材料として、ポリスチレン、ポリエチレン、ポリプロピレン等の汎用樹脂、ＡＢＳ、変性ポリフェニレンオキサイド等の樹脂が用いられている。発泡成形体は、発泡していない通常の成形体と比べると、軽量化と寸法安定性は向上するが、機械的物性が大幅に低下する問題がある。パソコンに代表されるＯＡ機器や家電製品、自動車部品等の更なる機械的物性の向上が要求されている。 Foam molding of resin is a molding method in which bubbles are mixed in the molded resin. It has excellent dimensional stability, is lightweight, and can be easily manufactured. Has been. As foam molding methods, there are known chemical foaming methods in which a foaming agent is added to a resin for injection molding, or physical foaming methods in which an inert gas such as carbon dioxide and nitrogen is blown into a molten resin to be injection molded. Yes. In addition, a supercritical foaming method for obtaining a foamed molded article having fine bubbles by using a supercritical gas has been developed. In general, general-purpose resins such as polystyrene, polyethylene, and polypropylene, and resins such as ABS and modified polyphenylene oxide are used as foam molding materials. The foamed molded product has a problem that the mechanical properties are greatly reduced, although the weight reduction and dimensional stability are improved as compared with a normal molded product that is not foamed. There is a demand for further improvement in mechanical properties of office automation equipment represented by personal computers, home appliances, automobile parts, and the like.
スチレン系樹脂を主体とし、これにポリプロピレン系樹脂を配合してなる樹脂成分を含む樹脂組成物に超臨界状ガスを浸透させて方法が提案されている（例えば、特許文献１参照）。しかし、この方法では、微細で均一な気泡が安定して得られず、スチレン系樹脂を主体とする樹脂組成物を用いるため、機械的物性が満足できるものではない。 A method has been proposed in which a supercritical gas is infiltrated into a resin composition containing a resin component mainly composed of a styrene-based resin and a polypropylene-based resin blended therein (see, for example, Patent Document 1). However, in this method, fine and uniform bubbles cannot be obtained stably, and the mechanical properties are not satisfactory because a resin composition mainly composed of a styrene resin is used.
また、ポリプロピレン系樹脂等の結晶性熱可塑性樹脂に、熱可塑性エラストマーなどの非晶性熱可塑性樹脂を配合してなる樹脂成分を含む樹脂組成物を、超臨界発泡法で発泡成形体を得る方法が提案されている（例えば、特許文献２参照）が、微細で均一な気泡が安定して得られず、機械的物性が満足できるものではない。 Also, a method of obtaining a foamed molded article by supercritical foaming with a resin composition containing a resin component obtained by blending a crystalline thermoplastic resin such as a polypropylene resin with an amorphous thermoplastic resin such as a thermoplastic elastomer. Has been proposed (for example, see Patent Document 2), but fine and uniform bubbles cannot be stably obtained, and the mechanical properties are not satisfactory.
更に、ポリオレフィン系樹脂に、完全に相溶しない熱可塑性エラストマーと、無機充填材を配合する方法が提案されている（例えば、特許文献３参照）が、微細で均一な気泡が安定して得られず、機械的物性が満足できるものではない。
本発明はかかる実情に鑑み、上記従来技術の問題点を解消し、微細で均一な気泡を有し、軽量で、優れた機械的物性、寸法安定性を有する発泡成形体を提供することを目的とするものである。 In view of such circumstances, the present invention aims to solve the above-mentioned problems of the prior art, and to provide a foamed molded article having fine and uniform bubbles, light weight, excellent mechanical properties and dimensional stability. It is what.
本発明者らは、上記問題を解決するために鋭意検討した結果、特定の粒度内容を有する、少なくとも粒子表面がリン酸カルシウム系化合物からなる発泡安定剤と、板状無機粒子及び／又は熱可塑性エラストマーとを含有することにより、微細で均一な気泡を有し、軽量で、優れた機械的物性、寸法安定性を有する発泡樹脂成形体が得られることを見いだし、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have found that a foaming stabilizer having a specific particle size and at least a particle surface made of a calcium phosphate compound, a plate-like inorganic particle and / or a thermoplastic elastomer, As a result, it was found that a foamed resin molded article having fine and uniform bubbles, light weight, excellent mechanical properties and dimensional stability was obtained, and the present invention was completed.
即ち、上記目的を達成するための本発明の請求項１は、下記の式（ａ）及び（ｂ）を満足する、少なくとも粒子表面がリン酸カルシウム系化合物からなる発泡安定剤と、板状無機粒子、熱可塑性エラストマーから選ばれる少なくとも１種とを含有してなることを特徴とする発泡樹脂成形体を内容とする。
（ａ）０．０１≦ｄｘ≦３０
（ｂ）２．５≦Ｖ≦３０
但し、
ｄｘ：電子顕微鏡写真により測定した平均粒子径（μｍ）
Ｖ ：ＪＩＳＫ５１０１−９１ ２１．１ 顔料試験方法の静置法による見掛け比容（ｍ ｌ／ｇ）
That is, claim 1 of the present invention for achieving the above object satisfies the following formulas (a) and (b), at least the surface of the particle is composed of a calcium phosphate compound, a plate-like inorganic particle, The content is a foamed resin molded article containing at least one selected from thermoplastic elastomers.
(A) 0.01 ≦ dx ≦ 30
(B) 2.5 ≦ V ≦ 30
However,
dx: average particle diameter (μm) measured by electron micrograph
V: JIS K5101-91 21.1 Apparent specific volume (ml / g) by the stationary method of the pigment test method
本発明の請求項２は、少なくとも粒子表面がリン酸カルシウム系化合物からなる発泡安定剤が更に下記の式（ｃ）及び（ｄ）を満足する請求項１記載の発泡樹脂成形体を内容とする。
（ｃ）１≦α≦５ α＝ｄ５０／ｄｘ
（ｄ）０≦β≦２ β＝（ｄ９０−ｄ１０）／ｄ５０
但し、
α ：分散係数
ｄ５０：マイクロトラックＦＲＡレーザー式粒度分布計により測定したふるい５０％平均 粒子径（μｍ）
ｄ９０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した通過側累計９０％ 粒子径（μｍ）
ｄ１０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した通過側累計１０％ 粒子径（μｍ）
A second aspect of the present invention includes the foamed resin molded article according to the first aspect, wherein the foam stabilizer having at least a particle surface made of a calcium phosphate compound further satisfies the following formulas (c) and (d).
(C) 1 ≦ α ≦ 5 α = d50 / dx
(D) 0 ≦ β ≦ 2 β = (d90−d10) / d50
However,
α: Dispersion coefficient d50: Sieve 50% average particle diameter (μm) measured by Microtrac FRA laser particle size distribution analyzer
d90: Cumulative passage side 90% measured by Microtrac FRA laser particle size distribution meter Particle diameter (μm)
d10: Passage side cumulative 10% measured by Microtrac FRA laser particle size distribution meter Particle diameter (μm)
本発明の請求項３は、リン酸カルシウム系化合物のＣａ／Ｐの原子比が５．５６以下である請求項１又は２記載の発泡樹脂成形体を内容とする。 A third aspect of the present invention includes the foamed resin molded article according to the first or second aspect, wherein the Ca / P atomic ratio of the calcium phosphate compound is 5.56 or less.
本発明の請求項４は、リン酸カルシウム系化合物が、化学式Ｃａ10（ＰＯ4 ）6 ・（ＯＨ）2 のヒドロキシアパタイトである請求項１〜３のいずれか１項に記載の発泡樹脂成形体を内容とする。 Claim 4 of the present invention is that the calcium phosphate compound is hydroxyapatite of the chemical formula Ca 10 (PO 4 ) 6. (OH) 2. Content of the foamed resin molded article according to any one of claims 1 to 3 And
本発明の請求項５は、 樹脂１００重量部に対して、少なくとも粒子表面がリン酸カルシウム系化合物からなる発泡安定剤が０．０１〜１０重量部、板状無機粒子が１〜５０重量部、熱可塑性エラストマーが０．０１〜２０重量部である請求項１〜４のいずれか１項に記載の発泡樹脂成形体を内容とする。 According to claim 5 of the present invention, with respect to 100 parts by weight of the resin, 0.01 to 10 parts by weight of the foam stabilizer composed of at least a calcium phosphate compound on the particle surface, 1 to 50 parts by weight of the plate-like inorganic particles, thermoplasticity An elastomer is 0.01-20 weight part, The content is the foaming resin molding of any one of Claims 1-4.
本発明の発泡成形体は、微細で均一な気泡を有し、軽量で、優れた機械的物性及び寸法安定性を備えている。 The foamed molded product of the present invention has fine and uniform bubbles, is lightweight, and has excellent mechanical properties and dimensional stability.
本発明の発泡樹脂成形体は、下記の式（ａ）及び（ｂ）を満足する、少なくとも粒子表面がリン酸カルシウム系化合物からなる発泡安定剤と、板状無機粒子、熱可塑性エラストマーから選ばれる少なくとも１種とを含有してなることを特徴とする。
（ａ）０．０１≦ｄｘ≦３０
（ｂ）２．５≦Ｖ≦３０
但し、
ｄｘ：電子顕微鏡写真により測定した平均粒子径（μｍ）
Ｖ ：ＪＩＳＫ５１０１−９１ ２１．１ 顔料試験方法の静置法による見掛け比容（ｍ ｌ／ｇ）
The foamed resin molded article of the present invention satisfies the following formulas (a) and (b), at least one selected from a foam stabilizer in which at least the particle surface is made of a calcium phosphate compound, plate-like inorganic particles, and a thermoplastic elastomer. It is characterized by containing a seed.
(A) 0.01 ≦ dx ≦ 30
(B) 2.5 ≦ V ≦ 30
However,
dx: average particle diameter (μm) measured by electron micrograph
V: JIS K5101-91 21.1 Apparent specific volume (ml / g) by the stationary method of the pigment test method
本発明における発泡安定剤の平均粒子径ｄｘ（μｍ）は、０．０１≦ｄｘ≦３０であり、好ましくは、０．１≦ｄｘ≦２０、より好ましくは、０．２≦ｄｘ≦１０である。ｄｘが０．０１μｍ未満の場合、粒子の凝集が強く、樹脂中への分散が低下し、微細で均一な気泡が得られないため、機械的物性を低下させるので好ましくない。また、ｄｘが３０μｍを超える場合、発泡安定剤の個数が極端に少なくなり、微細な気泡が得られないため好ましくない。
尚、平均粒子径ｄｘは、走査型電子顕微鏡を用いて、異なった視野から約１００個の単粒子と認めることが出来る粒子のみを計測した。測定粒子径は定方向径について測定し、このようにして得られた粒子径から求めた個数平均径である。但し、一次粒子が針状・柱状ないし不定形の場合は、一つの一次粒子の最長径と最短径の積の平方根をｄｘとする。
The average particle diameter dx (μm) of the foam stabilizer in the present invention is 0.01 ≦ dx ≦ 30, preferably 0.1 ≦ dx ≦ 20, and more preferably 0.2 ≦ dx ≦ 10. . When dx is less than 0.01 μm, the aggregation of particles is strong, the dispersion in the resin is reduced, and fine and uniform bubbles cannot be obtained. Further, when dx exceeds 30 μm, the number of foam stabilizers becomes extremely small, and fine bubbles cannot be obtained, which is not preferable.
The average particle diameter dx was measured only for particles that can be recognized as about 100 single particles from different fields of view using a scanning electron microscope. The measured particle diameter is a number average diameter determined from the particle diameter obtained by measuring the unidirectional diameter. However, when the primary particles are acicular, columnar, or amorphous, the square root of the product of the longest diameter and the shortest diameter of one primary particle is defined as dx.
本発明における発泡安定剤の見掛け比容Ｖ（ｍｌ／ｇ）は、２．５≦Ｖ≦３０であり、好ましくは、３≦Ｖ≦２０であり、より好ましくは、８≦Ｖ≦２０である。Ｖが３０を超える場合、樹脂との混合が困難で、分散性低下の原因となり、粉塵等のハンドリング面での問題もあり好ましくない。また、Ｖが２．５未満の場合は、樹脂中に存在する粒子個数が少なくなり、微細で均一な気泡が得られないので好ましくない。 The apparent specific volume V (ml / g) of the foam stabilizer in the present invention is 2.5 ≦ V ≦ 30, preferably 3 ≦ V ≦ 20, and more preferably 8 ≦ V ≦ 20. . When V exceeds 30, it is difficult to mix with resin, which causes a decrease in dispersibility, and there is a problem in handling such as dust, which is not preferable. On the other hand, when V is less than 2.5, the number of particles present in the resin decreases, and fine and uniform bubbles cannot be obtained.
本発明における発泡安定剤の粒子組成は、少なくとも粒子表面がリン酸カルシウム系化合物であり、樹脂との親和性が高いという観点から、リン酸カルシウム系化合物が好ましく、また樹脂中の粒子個数を多くし、微細な気泡を得るという観点から、見掛け比容が大きいものが好ましく、例えば、花弁状多孔質構造を有するリン酸カルシウム系化合物が好ましい。 The particle composition of the foam stabilizer in the present invention is preferably a calcium phosphate compound from the viewpoint that at least the particle surface is a calcium phosphate compound and has a high affinity with the resin. From the viewpoint of obtaining bubbles, those having a large apparent specific volume are preferable. For example, calcium phosphate compounds having a petal-like porous structure are preferable.
リン酸カルシウム系化合物のＣａ／Ｐの原子比は、花弁状多孔質構造を有するリン酸カルシウム系化合物の割合であり、見掛け比容の高さという観点から、５．５６以下が好ましく、３．３３以下がさらに好ましい。下限については特に限定されないが、粒子の安定性という観点から１．６０以上が好ましく、１．６７以上が更に好ましい。また、粒子の安定性という観点から、リン酸カルシウム系化合物が、化学式Ｃａ10（ＰＯ4 ）6 ・（ＯＨ）2 のヒドロキシアパタイトであることが好ましい。 The Ca / P atomic ratio of the calcium phosphate compound is the ratio of the calcium phosphate compound having a petal-like porous structure, and is preferably 5.56 or less, and more preferably 3.33 or less from the viewpoint of high apparent specific volume. preferable. The lower limit is not particularly limited, but is preferably 1.60 or more and more preferably 1.67 or more from the viewpoint of particle stability. From the viewpoint of particle stability, the calcium phosphate compound is preferably a hydroxyapatite having the chemical formula Ca 10 (PO 4 ) 6. (OH) 2 .
上記の如き本発明における発泡安定剤は、例えば、後記する混合条件及び熟成条件により得られるが、上記式（ａ）〜（ｄ）で表される平均粒子径ｄｘ、見掛け比容Ｖ、分散係数α、シャープネスβをコントロールする際に、特に大きく影響する混合条件としては、混合、熟成時の撹拌羽根周速、Ｃａ／Ｐの原子比である。撹拌羽根周速が低すぎた場合、混合、熟成時に凝集が起こり、平均粒子径ｄｘが大きくなりすぎたり、分散係数α、シャープネスβにも悪影響を及ぼし、撹拌羽根周速が高すぎる場合、撹拌力によって水懸濁液温度が急激に上昇してしまい、反応系の温度コントロールが困難になるだけでなく、製造コストにも大きく影響する。また、Ｃａ／Ｐの原子比が高すぎた場合、粒子に占める多孔質構造を有するリン酸カルシウム系化合物の割合が小さくなるため、見掛け比容Ｖが低下してしまい、Ｃａ／Ｐの原子比が低すぎた場合、リン酸カルシウム系化合物粒子自体が形成できなくなる傾向にある。 The foam stabilizer in the present invention as described above can be obtained by, for example, the mixing conditions and the aging conditions described later, but the average particle diameter dx, the apparent specific volume V, the dispersion coefficient represented by the above formulas (a) to (d). The mixing conditions that particularly affect the control of α and sharpness β are the stirring blade peripheral speed during mixing and aging, and the atomic ratio of Ca / P. If the stirring blade peripheral speed is too low, agglomeration occurs during mixing and ripening, the average particle diameter dx becomes too large, or the dispersion coefficient α and sharpness β are adversely affected. The water suspension temperature rises rapidly due to the force, which not only makes it difficult to control the temperature of the reaction system, but also greatly affects the production cost. Further, if the Ca / P atomic ratio is too high, the ratio of the calcium phosphate compound having a porous structure in the particles is small, so that the apparent specific volume V is lowered and the Ca / P atomic ratio is low. When too much, it exists in the tendency for the calcium-phosphate type compound particle itself to become unable to form.
本発明における発泡安定剤の調製方法については特に制限はないが、例えば、炭酸カルシウムを分散した水系中で、水可溶性リン酸、又は、水可溶性リン酸塩とを徐々に反応させて、核材表面で花弁状多孔質リン酸カルシウム系化合物を生成させることにより調製される。具体的には、特定の核材となる炭酸カルシウムの水懸濁液分散体と燐酸の希釈水溶液及び／又は特定の燐酸２水素カルシウムの水懸濁液分散体及び／又は特定の燐酸水素カルシウム２水塩の水懸濁液分散体を特定の割合で特定の混合条件において混合、特定の熟成条件で熟成後、乾燥する方法が例示される。 The method for preparing the foam stabilizer in the present invention is not particularly limited. For example, in a water system in which calcium carbonate is dispersed, a water-soluble phosphoric acid or a water-soluble phosphate is gradually reacted to form a core material. It is prepared by generating a petal-like porous calcium phosphate compound on the surface. Specifically, an aqueous suspension dispersion of calcium carbonate and a diluted aqueous solution of phosphoric acid and / or an aqueous suspension dispersion of specific calcium dihydrogen phosphate and / or specific calcium hydrogen phosphate 2 as a specific core material An example is a method in which an aqueous suspension dispersion of a water salt is mixed at a specific ratio under specific mixing conditions, aged under specific aging conditions, and then dried.
以下に、本発明の発泡安定剤を構成するリン酸カルシウム系化合物の内、特に好ましく用いることのできる花弁状多孔質ヒドロキシアパタイトを主成分とした場合の調製方法について、より具体的に例示する。 Hereinafter, the preparation method in the case where the main component is petal-like porous hydroxyapatite which can be particularly preferably used among the calcium phosphate compounds constituting the foam stabilizer of the present invention will be illustrated more specifically.
粒度分布測定器（（株）島津製作所製ＳＡ−ＣＰ３）により測定した平均粒子径が０．１〜５μｍである炭酸カルシウムの水懸濁液分散体と燐酸の希釈水溶液及び／又は粒度分布測定器（（株）島津製作所製ＳＡ−ＣＰ３）により測定した平均粒子径が２〜１０μｍであるリン酸二水素カルシウムの水懸濁液分散体及び／又は粒度分布測定器（（株）島津製作所製ＳＡ−ＣＰ３）により測定した平均粒子径が２〜１０μｍであるリン酸水素カルシウム二水塩の水懸濁液分散体をＣａ／Ｐの原子比が１６．７〜１．６０となる割合で水中で下記の混合条件で混合後、更に下記の熟成条件で熟成を行い、脱水、水洗を行い、３００度以下の乾燥雰囲気下で乾燥し、解砕仕上げを行う。 An aqueous suspension of calcium carbonate and a dilute aqueous solution of phosphoric acid and / or a particle size distribution measuring device having an average particle size of 0.1 to 5 μm measured by a particle size distribution measuring device (SA-CP3 manufactured by Shimadzu Corporation) An aqueous suspension dispersion of calcium dihydrogen phosphate and / or a particle size distribution measuring instrument (SA Shimadzu Corporation SA) having an average particle size of 2 to 10 μm as measured by (SA-CP3 manufactured by Shimadzu Corporation) -An aqueous suspension dispersion of calcium hydrogen phosphate dihydrate having an average particle diameter of 2 to 10 μm measured by CP3) in water at a ratio of the Ca / P atomic ratio of 16.7 to 1.60. After mixing under the following mixing conditions, aging is further performed under the following aging conditions, followed by dehydration and water washing, drying in a dry atmosphere of 300 ° C. or less, and crushing finish.
（混合条件）
炭酸カルシウムの水懸濁液分散体固形分濃度 １〜１５重量％
燐酸の希釈水溶液濃度 １〜５０重量％
混合攪拌羽根の周速 ０．５〜５０ｍ／秒
混合時間 ０．１〜１５０時間
混合系水懸濁液温度 ０〜８０℃
混合系の水懸濁液ｐＨ ５〜９
（熟成条件）
熟成系のＣａ濃度 ０．４〜５重量％
熟成時間 ０．１〜１００時間
熟成系水懸濁液温度 ２０〜８０℃
熟成系水懸濁液ｐＨ ６〜９
攪拌羽根の周速 ０．５〜５０ｍ／秒
(Mixing conditions)
Calcium carbonate aqueous suspension dispersion solid content concentration 1-15 wt%
1-50% by weight of dilute aqueous solution
Peripheral speed of mixing stirring blade 0.5 to 50 m / second Mixing time 0.1 to 150 hours Mixing system water suspension temperature 0 to 80 ° C.
Water suspension pH of mixed system 5-9
(Maturation conditions)
Aging Ca concentration 0.4 to 5 wt%
Aging time 0.1 to 100 hours Aging water suspension temperature 20 to 80 ° C
Aged aqueous suspension pH 6-9
Stirring blade peripheral speed 0.5-50m / sec
本発明における発泡安定剤の分散係数αは、１≦α≦５が好ましく、１≦α≦２がより好ましい。αが５を超える場合、凝集による粗大粒子が多く存在することを意味し、微細な気泡が得られない傾向にある。またαは１未満の場合、粒子の凝集が起こり、樹脂中での分散状態が不均一になるので、均一な気泡が得られない傾向にある。 The dispersion coefficient α of the foam stabilizer in the present invention is preferably 1 ≦ α ≦ 5, and more preferably 1 ≦ α ≦ 2. When α exceeds 5, it means that there are many coarse particles due to aggregation, and fine bubbles tend not to be obtained. On the other hand, when α is less than 1, the particles are aggregated and the dispersion state in the resin becomes non-uniform, so that uniform bubbles tend not to be obtained.
本発明における発泡安定剤のシャープネスβは、０≦β≦２が好ましく、０≦β≦１がより好ましい。βが２を超える場合、粒度分布がブロードなことを意味し、微小粒子、粗大粒子、またその両方の含有率が多くなるため、微細で均一な気泡が得られない傾向にある。 The sharpness β of the foam stabilizer in the present invention is preferably 0 ≦ β ≦ 2, more preferably 0 ≦ β ≦ 1. When β exceeds 2, it means that the particle size distribution is broad, and the content of fine particles, coarse particles, or both increases, so that fine and uniform bubbles tend not to be obtained.
本発明における発泡安定剤は、粒子の分散性や安定性等をさらに高めるために、シランカップリング剤やチタネートカップリング剤等のカップリング剤、有機酸、例えば脂肪酸、樹脂酸、アクリル酸等のα、βモノエチレン性不飽和カルボン酸及び、そのエステル類、シュウ酸、クエン酸、酒石酸等の有機酸、フッ酸等の無機酸、それらの重合物及び共重合物、それらの塩、又はそれらのエステル類等の表面処理剤、界面活性剤やヘキサメタリン酸ソーダ、ピロリン酸、ピロリン酸ソーダ、トリポリリン酸、トリポリリン酸ソーダ、トリメタリン酸、ハイポリリン酸等の縮合リン酸及びその塩等を、常法に従い添加又は表面処理してもさしつかえない。これらは単独で又は必要に応じ２種以上組み合わせて用いられる。
表面処理は湿式、乾式のいずれでもよい。湿式の場合の表面処理条件としては特に制限されないが、表面処理剤濃度１〜２０重量％、表面処理時間１０〜６０分、攪拌羽根の周速０．５〜３０ｍ／秒が好ましい。
表面処理量は、発泡安定剤に対して０．０１〜５０重量％が好ましい。０．０１未満では処理効果が充分でなく、一方、５０重量％を超えると、凝集の原因となり、機械的物性が低下する傾向にある。
In order to further improve the dispersibility and stability of the particles, the foam stabilizer in the present invention is a coupling agent such as a silane coupling agent or a titanate coupling agent, an organic acid such as a fatty acid, a resin acid, or acrylic acid. α, β monoethylenically unsaturated carboxylic acid and esters thereof, organic acids such as oxalic acid, citric acid and tartaric acid, inorganic acids such as hydrofluoric acid, polymers and copolymers thereof, salts thereof, or thereof Surface treatment agents such as esters, surfactants and sodium hexametaphosphate, pyrophosphoric acid, sodium pyrophosphate, tripolyphosphoric acid, sodium tripolyphosphate, trimetaphosphoric acid, and high polyphosphoric acid, and salts thereof according to conventional methods Addition or surface treatment is acceptable. These may be used alone or in combination of two or more as required.
The surface treatment may be either wet or dry. Although it does not restrict | limit especially as surface treatment conditions in the case of wet, Surface treatment agent density | concentration 1-20 weight%, surface treatment time 10-60 minutes, and the peripheral speed of a stirring blade 0.5-30 m / sec are preferable.
The surface treatment amount is preferably 0.01 to 50% by weight with respect to the foam stabilizer. If it is less than 0.01, the treatment effect is not sufficient. On the other hand, if it exceeds 50% by weight, it causes aggregation and mechanical properties tend to be lowered.
本発明における板状無機粒子は、発泡安定剤を起点に発生した気泡同士の接触、接合を防止するため、板状形状を有する無機粒子であれば特に制限はなく、タルク、マイカ、ナノ分散した層状珪酸塩、カオリン、ガラスフレーク等が例示できる。これらは単独で又は必要に応じ２種以上組み合わせて用いられる。これらの中では、微細な粒子径で、良好な分散性を有し、樹脂ともなじみの良好なタルクが好ましい。平均粒子径は、機械的物性、成形物の外観等の観点から、２０μｍ以下が好ましく、１０μｍ以下が更に好ましい。 The plate-like inorganic particles in the present invention are not particularly limited as long as they are inorganic particles having a plate-like shape in order to prevent contact and bonding between bubbles generated from the foam stabilizer, and talc, mica, and nano-dispersed particles are used. Examples thereof include layered silicate, kaolin, and glass flakes. These may be used alone or in combination of two or more as required. Among these, talc having a fine particle size, good dispersibility, and good compatibility with the resin is preferable. The average particle diameter is preferably 20 μm or less, more preferably 10 μm or less, from the viewpoint of mechanical properties, appearance of the molded product, and the like.
本発明における熱可塑性エラストマーは、例えば、ブタジエンゴム、スチレン−ブタジエンゴム、エチレン−プロピレンゴム（ＥＰＲ）、エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）、水素添加スチレン−ブタジエン共重合体エラストマー（ＨＳＢＲ）、スチレン−（エチレン・ブチレン）−エチレンブロック共重合体エラストマー（ＳＥＢＣ）、エチレン−（エチレン・ブチレン）−エチレンブロック共重合体エラストマー（ＣＥＢＣ）、シリコーンゴム、フッ素ゴム、エチレンアクリルゴムなどが例示できる。これらは単独で又は必要に応じ２種以上組み合わせて用いられる。 Examples of the thermoplastic elastomer in the present invention include butadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), hydrogenated styrene-butadiene copolymer elastomer (HSBR), styrene- (Ethylene / butylene) -ethylene block copolymer elastomer (SEBC), ethylene- (ethylene / butylene) -ethylene block copolymer elastomer (CEBC), silicone rubber, fluororubber, ethylene acrylic rubber and the like can be exemplified. These may be used alone or in combination of two or more as required.
本発明の発泡成形体における発泡安定剤の配合量は、微細で均一な気泡を数多く得、発泡成形体の重量増を抑えるという観点から、樹脂１００重量部に対して０．０１〜１０重量部が好ましく、０．０５〜５重量部がより好ましい。 The blending amount of the foam stabilizer in the foamed molded product of the present invention is 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin from the viewpoint of obtaining a large number of fine and uniform cells and suppressing an increase in the weight of the foamed molded product. Is preferable, and 0.05 to 5 parts by weight is more preferable.
板状無機粒子の配合量は、気泡同士の接合を防ぎ、微細で均一な気泡を得、発泡成形体の重量増を抑えるという観点から、樹脂１００重量部に対して、１〜５０重量部が好ましく、１０〜４０重量部がより好ましい。 The compounding amount of the plate-like inorganic particles is 1 to 50 parts by weight with respect to 100 parts by weight of the resin from the viewpoint of preventing bonding of bubbles, obtaining fine and uniform bubbles, and suppressing an increase in the weight of the foamed molded product. Preferably, 10-40 weight part is more preferable.
熱可塑性エラストマーの配合量は、樹脂自体の機械的物性を損なうことなく、気泡同士の接合を防ぎ、微細で均一な気泡を得るという観点から、樹脂１００重量部に対して、０．０１〜２０重量部が好ましく、０．０５〜１０重量部がより好ましい。 The blending amount of the thermoplastic elastomer is 0.01 to 20 with respect to 100 parts by weight of the resin from the viewpoint of preventing bonding between the bubbles and obtaining fine and uniform bubbles without impairing the mechanical properties of the resin itself. Part by weight is preferable, and 0.05 to 10 parts by weight is more preferable.
本発明の発泡安定剤に配合される他の成分としては、特に制限はないが、必要に応じて合成シリカ等の無機粒子を目的に応じて１種又は２種以上配合してもさしつかえない。また、リン酸カルシウム系化合物では、花弁状構造を有しない非晶質リン酸カルシウム（略号ＡＣＰ、化学式Ｃａ3 （ＰＯ4 ）2 ・ｎＨ2 Ｏ）、フッ素アパタイト（略号ＦＡＰ、化学式Ｃａ10（ＰＯ4 ）6 Ｆ2 ）、塩素アパタイト（略号ＣＡＰ、化学式Ｃａ10（ＰＯ4 ）6 Ｃ12）、ヒドロキシアパタイト（略号ＨＡＰ、化学式Ｃａ10（ＰＯ4 ）6 （ＯＨ）2 ）、リン酸八カルシウム（略号ＯＣＰ、化学式Ｃａ8 Ｈ2 （ＰＯ4 ）6 ・５Ｈ2 Ｏ）、リン酸三カルシウム（略号ＴＣＰ、化学式Ｃａ3 （ＰＯ4 ）2 ）、リン酸水素カルシウム（略号ＤＣＰ、化学式ＣａＨＰＯ4 ）、リン酸水素カルシウム二水和物（略号ＤＣＰＤ、化学式ＣａＨＰＯ4 ・２Ｈ2 Ｏ）等の本発明の徐放体用花弁状多孔質基材と異なる、花弁状構造を有しないリン酸カルシウム系化合物を目的に応じて１種又は２種以上配合してもさしつかえない。 The other components to be blended in the foam stabilizer of the present invention are not particularly limited, but one or more inorganic particles such as synthetic silica may be blended according to the purpose as needed. In addition, in calcium phosphate compounds, amorphous calcium phosphate (abbreviation ACP, chemical formula Ca 3 (PO 4 ) 2 .nH 2 O), fluorapatite (abbreviation FAP, chemical formula Ca 10 (PO 4 ) 6 F) having no petal-like structure is used. 2 ), chlorine apatite (abbreviation CAP, chemical formula Ca 10 (PO 4 ) 6 C 12 ), hydroxyapatite (abbreviation HAP, chemical formula Ca 10 (PO 4 ) 6 (OH) 2 ), octacalcium phosphate (abbreviation OCP, chemical formula Ca 8 H 2 (PO 4 ) 6 · 5H 2 O), tricalcium phosphate (abbreviation TCP, chemical formula Ca 3 (PO 4 ) 2 ), calcium hydrogen phosphate (abbreviation DCP, chemical formula CaHPO 4 ), calcium hydrogen phosphate Different from the petal-like porous substrate for sustained release of the present invention such as dihydrate (abbreviated DCPD, chemical formula CaHPO 4 · 2H 2 O), calcium phosphate without petal-like structure Depending on the purpose, one or more of the um-based compounds may be blended.
本発明の発泡成形体に用いることのできる樹脂としては、特に制限はなく、通常の熱可塑性樹脂を用いることができる。具体例としては、ポリエチレン樹脂、ポリプロピレン樹脂、ポリ塩化ビニル樹脂等の汎用プラスチック、ポリアミド樹脂、ＡＢＳ樹脂、熱可塑性ポリエステル、ポリカーボネート樹脂、ポリアセタール樹脂、ポリフェニレンサルファイド樹脂、ポリフェニレンエーテル樹脂、ポリサルフォン樹脂、ポリエーテルサルフォン樹脂、ポリエーテルイミド樹脂、ポリエーテルエーテルケトン樹脂等のエンジニアリングプラスチック等を挙げることができる。また、熱硬化性樹脂としては、フェノール樹脂、ユリア樹脂、メラミン樹脂、不飽ポリエステル、ジアリルフタレート樹脂、エポキシ樹脂、ケイ素樹脂、ポリウレタン、ポリイミドなどが挙げられ、これらの樹脂の共重合体、混合物、変性物などでもよい。これらは単独で又は必要に応じ２種以上組み合わせて用いられる。 There is no restriction | limiting in particular as resin which can be used for the foaming molding of this invention, A normal thermoplastic resin can be used. Specific examples include general-purpose plastics such as polyethylene resin, polypropylene resin, and polyvinyl chloride resin, polyamide resin, ABS resin, thermoplastic polyester, polycarbonate resin, polyacetal resin, polyphenylene sulfide resin, polyphenylene ether resin, polysulfone resin, and polyethersulfone. Examples thereof include engineering plastics such as phon resin, polyetherimide resin, and polyetheretherketone resin. Examples of thermosetting resins include phenolic resins, urea resins, melamine resins, unsaturated polyesters, diallyl phthalate resins, epoxy resins, silicon resins, polyurethanes, polyimides, etc., and copolymers of these resins, mixtures, A modified product may be used. These may be used alone or in combination of two or more as required.
本発明の発泡成形体に用いることのできる発泡剤は、特に制限はなく、物理的発泡法では、二酸化炭素や窒素等の不活性ガスを用いればよく、化学的発泡法では、例えば、アゾ系化合物、ニトロソ系化合物、スルホニルヒドラジド系化合物、スルホニルセミカルバジド系化合物、複素環式窒素含有化合物、カーボネート系化合物及びカルボキシレート系化合物から選ばれた発泡剤であり、例えば、アゾジカルボンアミド、アゾジカルボン酸バリウム、ジニトロソペンタメチレンテトラミン、４，４’−オキシ−ビス−（ベンゼンスルホニル）ヒドラジド、３．３’−ジスルホンヒドラジドジフェニルスルホン、トリヒドラジン−Ｓ−トリアジン、５−フェニルテトラゾール、５−フェニルテトラゾールのカルシウム塩、ジイソプロピルヒドラゾカルボキシレート等が挙げられる。これらは単独で又は必要に応じ２種以上組み合わせて用いられる。
配合量は、発泡成形体中０．０１〜１０重量％が好ましい。発泡剤と共に、尿素系、有機酸系、金属塩系の発泡助剤を併用してもかまわない。また、機械的強度、耐熱性、寸法安定性、電気的性質等の性能を付加する目的で、本発明の発泡安定剤以外にも無機充填剤を配合してもかまわない。
The foaming agent that can be used for the foamed molded article of the present invention is not particularly limited. In the physical foaming method, an inert gas such as carbon dioxide or nitrogen may be used. In the chemical foaming method, for example, an azo type is used. A blowing agent selected from a compound, a nitroso compound, a sulfonyl hydrazide compound, a sulfonyl semicarbazide compound, a heterocyclic nitrogen-containing compound, a carbonate compound and a carboxylate compound, such as azodicarbonamide, barium azodicarboxylate , Dinitrosopentamethylenetetramine, 4,4′-oxy-bis- (benzenesulfonyl) hydrazide, 3.3′-disulfonhydrazide diphenylsulfone, trihydrazine-S-triazine, 5-phenyltetrazole, 5-phenyltetrazole calcium Salt, diisopropylhydrazo Rubokishireto, and the like. These may be used alone or in combination of two or more as required.
The blending amount is preferably 0.01 to 10% by weight in the foamed molded product. A urea-based, organic acid-based, or metal salt-based foaming aid may be used in combination with the foaming agent. In addition to the foam stabilizer of the present invention, an inorganic filler may be blended for the purpose of adding performance such as mechanical strength, heat resistance, dimensional stability, and electrical properties.
このような無機充填剤としては、例えば、ガラス繊維、アスベスト繊維、カーボン繊維、シリカ繊維等の繊維状充填剤や、カーボンブラック、グラファイト、シリカ、石英粉末、ガラスビーズ、ガラスバルーン、ガラス紛、珪酸カルシウム、珪酸アルミニウム、カオリン、タルク、クレー、珪藻土、酸化鉄、酸化チタン、酸化亜鉛、炭酸カルシウム、炭酸マグネシウム、リン酸カルシウム、硫酸カルシウム、硫酸バリウム等の粒状充填剤が挙げられる。これらは単独で又は必要に応じ２種以上組み合わせて用いられる。無機充填剤の配合量は、発泡成形体中０〜８０重量％が好ましい。８０重量％を超えると成形性が低下する。 Examples of such inorganic fillers include fibrous fillers such as glass fiber, asbestos fiber, carbon fiber, and silica fiber, carbon black, graphite, silica, quartz powder, glass beads, glass balloons, glass powder, and silicic acid. Examples thereof include particulate fillers such as calcium, aluminum silicate, kaolin, talc, clay, diatomaceous earth, iron oxide, titanium oxide, zinc oxide, calcium carbonate, magnesium carbonate, calcium phosphate, calcium sulfate, and barium sulfate. These may be used alone or in combination of two or more as required. As for the compounding quantity of an inorganic filler, 0 to 80 weight% is preferable in a foaming molding. If it exceeds 80% by weight, the moldability is lowered.
本発明の成形発泡成形体には、微細な気泡の安定性を高めるためる目的で、界面活性剤を配合してもかまわない。例えば、カチオン系、アニオン系、非イオン系等が挙げられ、配合量は、発泡成形体中０．０５〜５重量％が好ましい。 In the molded foam molded article of the present invention, a surfactant may be blended for the purpose of enhancing the stability of fine bubbles. For example, a cationic type, an anionic type, a nonionic type etc. are mentioned, and a compounding quantity has a preferable 0.05-5 weight% in a foaming molding.
本発明の発泡成形体には、成型時に発泡した樹脂が金型に充填された後、結晶化を促進させる目的で、結晶核剤を配合することも有効である。例えば、ボロンナイトライド等の窒化物、カオリン、タルク、クレー等の粘土類、金属の酸化物、炭酸塩、硫酸塩、珪酸塩、有機酸塩等のが挙げられる。これらは単独で又は必要に応じ２種以上組み合わせて用いられる。また、これと併用して結晶成長速度を増大させるため、リン酸エステル類を配合するのも好ましい。 It is also effective to add a crystal nucleating agent to the foamed molded article of the present invention for the purpose of promoting crystallization after the resin foamed at the time of molding is filled in the mold. Examples thereof include nitrides such as boron nitride, clays such as kaolin, talc, and clay, metal oxides, carbonates, sulfates, silicates, and organic acid salts. These may be used alone or in combination of two or more as required. Moreover, in order to increase the crystal growth rate in combination with this, it is also preferable to add phosphate esters.
本発明の発泡成形体には、一般に熱可塑性樹脂及び熱硬化性樹脂に添加される公知の物質、例えば、酸化防止剤、難燃剤、染料や顔料等の着色剤、潤滑剤等も要求物性に応じ適宜添加してもかまわない。 In the foamed molded article of the present invention, known substances generally added to thermoplastic resins and thermosetting resins, for example, antioxidants, flame retardants, coloring agents such as dyes and pigments, lubricants, and the like have required physical properties. It may be added as appropriate.
本発明の発泡成形体の成形用材料の調製は、特に制限はないが、本発明の発泡安定剤と、樹脂、発泡剤、及びその他の成分を成形前にブレンドする方法、発泡剤以外の成分の全部または一部を含む樹脂組成物を調製しておき、これに発泡剤またはこれと残りの成分をブレンドする方法、発泡剤の分解温度以下で軟化する樹脂に発泡剤を混練したマスターバッチを調製し、他の成分とブレンドする方法等のいずれでも問題ない。 The preparation of the molding material of the foamed molded product of the present invention is not particularly limited, but the foam stabilizer of the present invention and a method of blending the resin, foaming agent and other components before molding, components other than the foaming agent A resin composition containing all or part of the above is prepared, a foaming agent or a method of blending this with the remaining components, and a master batch in which the foaming agent is kneaded with a resin that softens below the decomposition temperature of the foaming agent. There is no problem in any of the methods of preparing and blending with other components.
本発明の発泡成形体の成形方法は、特に制限はないが、射出成形、押出成形、ブロー成形等、通常の方法で成形することができるが、特に射出成形による方法が簡便であり、好ましい。微細で均一な気泡を得るという観点から、二酸化炭素、窒素等の不活性ガスを用いる物理的発泡方法がより好ましい。 The method for molding the foamed molded article of the present invention is not particularly limited, but can be molded by a usual method such as injection molding, extrusion molding, blow molding, etc. The method by injection molding is particularly simple and preferable. From the viewpoint of obtaining fine and uniform bubbles, a physical foaming method using an inert gas such as carbon dioxide and nitrogen is more preferable.
本発明の発泡成形体の発泡倍率は、特に制限はないが、１．０２〜４．０となるようにするのが好ましい。
発泡倍率とは、下記の如く定義される。
発泡倍率＝発泡剤を添加しない場合の成形体の比重／発泡剤を添加した成形体の比重
発泡倍率が１．０２未満では、成形体の軽量化、寸法安定性の向上にほとんど期待できない。逆に発泡倍率が４．０を越えると、大幅に機械的物性が低下し、成形の制御も極めて困難である。より好ましい発泡倍率は、１．１〜２である。
The expansion ratio of the foamed molded product of the present invention is not particularly limited, but is preferably 1.02 to 4.0.
The expansion ratio is defined as follows.
Foaming ratio = specific gravity of molded product without adding foaming agent / specific gravity of molded product with added foaming agent When the expansion ratio is less than 1.02, almost no improvement can be expected in weight reduction and dimensional stability of the molded product. On the other hand, if the expansion ratio exceeds 4.0, the mechanical properties are significantly lowered, and the control of molding is extremely difficult. A more preferable expansion ratio is 1.1 to 2.
以下に本発明を実施例を挙げてさらに詳しく説明するが、本発明は、その要旨を越えない限り、以下の実施例に制限されるものではない。 EXAMPLES The present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
（発泡安定剤の調製）
先ず以下の実施例、比較例において使用する炭酸カルシウムの水懸濁液分散体ａ、及びｂの調製方法について記載する。
(Preparation of foam stabilizer)
First, the preparation method of the aqueous suspensions a and b of calcium carbonate used in the following examples and comparative examples will be described.
「炭酸カルシウムの水懸濁液分散体ａ」
比重１．０５５で温度が８℃の石灰乳（水酸化カルシウムの水懸濁液）７０００リッターに、炭酸ガス濃度２７重量％の炉ガスを２４ｍ3 の流速で導通しｐＨ９まで炭酸化反応を行い、その後４０〜５０℃で５時間撹拌熟成を行うことにより粒子間のアルカリを溶出させｐＨ１０．８として分散させ、電子顕微鏡写真より測定した平均粒子径０．０５μｍで粒度分布測定器（（株）島津製作所製ＳＡ−ＣＰ３）により測定した平均粒子径が０．４８μｍである炭酸カルシウムの水懸濁液分散体を調製した。
"Aqueous suspension of calcium carbonate dispersion a"
A carbonation reaction is carried out to pH 9 by passing 7000 liters of lime milk (calcium hydroxide aqueous suspension) with a specific gravity of 1.055 at a flow rate of 24 m 3 through 7000 liters of lime milk (water suspension of calcium hydroxide). Then, the mixture was aged and aged at 40 to 50 ° C. for 5 hours to elute the alkali between the particles and disperse it as pH 10.8. An aqueous suspension of calcium carbonate having an average particle size of 0.48 μm measured by Shimadzu SA-CP3) was prepared.
「炭酸カルシウムの水懸濁液分散体ｂ」
丸尾カルシウム製重質炭酸カルシウム「スーパーＳＳＳ」（１．２ｍ2 ／ｇ）に水を添加混合後、ＴＫホモミキサー（５０００ｒｐｍ，１５分間）にて撹拌分散させて固形分濃度２５％の電子顕微鏡写真より測定した平均粒子径３μｍで粒度分布測定器（（株）島津製作所製ＳＡ−ＣＰ３）により測定した平均粒子径が３．４μｍである炭酸カルシウムの水懸濁液分散体ｂを調製した。
"Water dispersion of calcium carbonate b"
After adding water to Maruo calcium heavy calcium carbonate “Super SSS” (1.2 m 2 / g), mixing and stirring and dispersing with TK homomixer (5000 rpm, 15 minutes), electron micrograph of solid content concentration 25% A water suspension dispersion b of calcium carbonate having an average particle diameter of 3.4 μm and an average particle diameter of 3.4 μm measured with a particle size distribution measuring instrument (SA-CP3 manufactured by Shimadzu Corporation) was prepared.
上記炭酸カルシウム水懸濁液分散体ａ、ｂを用い下記の方法により、発泡安定剤Ａ〜Ｅを調製した。即ち、炭酸カルシウムの水懸濁液とリン酸の希釈水溶液を表１に記載の混合条件で混合反応させた後、５重量％のステアリン酸石鹸を１０％の熱水溶液とし表面処理を行い、常法で脱水、乾燥後、解砕を行った。 Foam stabilizers A to E were prepared by the following method using the calcium carbonate aqueous suspension dispersions a and b. That is, a water suspension of calcium carbonate and a diluted aqueous solution of phosphoric acid were mixed and reacted under the mixing conditions shown in Table 1, and then surface treatment was performed using 5% by weight of stearic acid soap as a 10% hot aqueous solution. After dehydration and drying by the method, crushing was performed.
得られた発泡安定剤Ａ〜Ｅ、及び市販のリン酸カルシウム（商品名：リン酸三カルシウム、米山化学工業株式会社製）の粉体物性を表２に示す。
また、粒子表面を比較するために、発泡安定剤Ｂと市販のリン酸カルシウムの粒子構造を示す電子顕微鏡写真をそれぞれ図１、図２に示す。
図１より、発泡安定剤２は花弁状多孔質構造を有しており、また図２より市販のリン酸カルシウムは微細な粒子の凝集物であり、花弁状多孔質構造を有するものではないことがわかる。
Table 2 shows the powder physical properties of the obtained foam stabilizers A to E and commercially available calcium phosphate (trade name: tricalcium phosphate, manufactured by Yoneyama Chemical Co., Ltd.).
Moreover, in order to compare the particle | grain surface, the electron micrograph which shows the particle structure of the foam stabilizer B and commercially available calcium phosphate is shown in FIG. 1, FIG. 2, respectively.
As can be seen from FIG. 1, the foam stabilizer 2 has a petal-like porous structure, and from FIG. 2, commercially available calcium phosphate is an aggregate of fine particles and does not have a petal-like porous structure. .
（発泡成形体の製造）
実施例１、２ 比較例１〜４
ＰＰ樹脂１００重量部、発泡安定剤１重量部、板状無機粒子（浅田製粉製「ＪＭ２０９」）１０重量部、熱可塑性エラストマー（クラレエラストマーカンパニー製「セプトン１０５０」）３重量部を、射出成形機によって混練し、発泡安定剤を配合した樹脂ペレットを得た。該樹脂ペレットを射出成形機のシリンダー内で溶融し、超臨界状態の二酸化炭素ガスを浸透させ、金型へ射出して発泡成形品を得た。
成形品の製造条件は、シリンダー温度２００℃、射出速度１００mm／秒、溶融樹脂射出量はキャビティ容量の約５割、金型温度８０℃、冷却時間９０秒とした。成形品の発泡倍率は約１．３倍である。
(Manufacture of foam moldings)
Examples 1 and 2 Comparative Examples 1 to 4
100 parts by weight of PP resin, 1 part by weight of foam stabilizer, 10 parts by weight of plate-like inorganic particles (“JM209” manufactured by Asada Milling), 3 parts by weight of thermoplastic elastomer (“Septon 1050” manufactured by Kuraray Elastomer Company) To obtain resin pellets containing a foam stabilizer. The resin pellet was melted in a cylinder of an injection molding machine, impregnated with carbon dioxide gas in a supercritical state, and injected into a mold to obtain a foam molded product.
The manufacturing conditions of the molded product were a cylinder temperature of 200 ° C., an injection speed of 100 mm / second, a molten resin injection amount of about 50% of the cavity volume, a mold temperature of 80 ° C., and a cooling time of 90 seconds. The expansion ratio of the molded product is about 1.3 times.
実施例３、５
熱可塑性エラストマーを無添加とする以外は実施例１と同様に行い、発泡成形品を得た。
Examples 3 and 5
A foam molded article was obtained in the same manner as in Example 1 except that no thermoplastic elastomer was added.
比較例６
発泡安定剤と熱可塑性エラストマーを無添加とする以外は実施例１と同様に行い、発泡成形品を得た。
Comparative Example 6
A foam molded article was obtained in the same manner as in Example 1 except that the foam stabilizer and the thermoplastic elastomer were not added.
実施例４、６
板状無機粒子を無添加とする以外は実施例１と同様に行い発泡成形品を得た。
Examples 4 and 6
A foam molded article was obtained in the same manner as in Example 1 except that no plate-like inorganic particles were added.
実施例７
発泡安定剤を０．５重量部とする以外は実施例１と同様に行い発泡成形品を得た。
Example 7
A foam molded article was obtained in the same manner as in Example 1 except that the foam stabilizer was 0.5 parts by weight.
実施例８
発泡安定剤を８重量部とする以外は実施例１と同様に行い発泡成形品を得た。
Example 8
A foam molded article was obtained in the same manner as in Example 1 except that the foam stabilizer was 8 parts by weight.
実施例９
板状無機粒子を３重量部とする以外は実施例１と同様に行い発泡成形品を得た。
Example 9
A foam molded article was obtained in the same manner as in Example 1 except that the amount of the plate-like inorganic particles was 3 parts by weight.
実施例１０
板状無機粒子を４５重量部とする以外は実施例１と同様に行い発泡成形品を得た。
Example 10
A foam molded article was obtained in the same manner as in Example 1 except that the amount of the plate-like inorganic particles was 45 parts by weight.
実施例１１
熱可塑性エラストマーを０．０５重量部とする以外は実施例１と同様に行い発泡成形品を得た。
Example 11
A foam molded article was obtained in the same manner as in Example 1 except that the thermoplastic elastomer was 0.05 parts by weight.
実施例１２
熱可塑性エラストマーを１５重量部とする以外は実施例１と同様に行い発泡成形品を得た。
Example 12
A foam molded article was obtained in the same manner as in Example 1 except that the thermoplastic elastomer was 15 parts by weight.
比較例７
発泡安定剤と板状無機粒子を無添加とする以外は実施例１と同様に行い発泡成形品を得た。
Comparative Example 7
A foam molded article was obtained in the same manner as in Example 1 except that the foam stabilizer and the plate-like inorganic particles were not added.
比較例５
板状無機粒子及び熱可塑性エラストマーを無添加にする以外は実施例１と同様に行い発泡成形品を得た。
Comparative Example 5
A foam molded article was obtained in the same manner as in Example 1 except that the plate-like inorganic particles and the thermoplastic elastomer were not added.
比較例８
発泡安定剤、板状無機粒子及び熱可塑性エラストマー全て無添加にする以外は実施例１と同様に行い発泡成形品を得た。
Comparative Example 8
A foamed molded article was obtained in the same manner as in Example 1 except that all of the foam stabilizer, the plate-like inorganic particles, and the thermoplastic elastomer were not added.
比較例９
発泡安定剤を無添加にする以外は実施例１と同様に行い発泡成形品を得た。
Comparative Example 9
A foam molded article was obtained in the same manner as in Example 1 except that no foam stabilizer was added.
実施例１〜１２、比較例１〜９で得られた発泡成形体について下記の方法により発泡状態を下記の基準により評価した。結果を表３に示す。
（評価方法）
発泡成形品を切断し、切断面に現れた発泡セルの大きさ、分布と、均一性（成形体全体の発泡セルの分布）を電子顕微鏡視野で観察することによって発泡状態を評価した。均一性については、成形体のゲート付近、中央、エンドの３箇所で確認した。
About the foaming molding obtained in Examples 1-12 and Comparative Examples 1-9, the foaming state was evaluated by the following method by the following method. The results are shown in Table 3.
(Evaluation methods)
The foamed molded product was cut, and the foamed state was evaluated by observing the size, distribution, and uniformity of foamed cells appearing on the cut surface (distribution of the foamed cells throughout the molded body) with an electron microscope. About uniformity, it confirmed in three places near the gate of a molded object, the center, and an end.
（評価基準）
発泡セル１０〜３０μｍで分布状態が均一である ５
発泡セル１０〜５０μｍで分布状態が若干不均一である ４
発泡セル５０〜１５０μｍで分布状態が若干不均一である ３
発泡セル５０〜２００μｍで分布状態が不均一である ２
発泡セル３０〜３００μｍで分布状態が不均一である １
(Evaluation criteria)
Uniform distribution with foamed cells of 10-30 μm 5
The distribution state is slightly non-uniform in foamed cells of 10-50 μm 4
The distribution state is slightly non-uniform in the foam cell of 50 to 150 μm 3
The distribution state is not uniform in the foam cell of 50 to 200 μm 2
The distribution state is not uniform in the foam cell of 30 to 300 μm 1
叙上のとおり、本発明の発泡成形体は、微細で均一な気泡を有するとともに、軽量で、優れた機械的物性及び寸法安定性を有し、パソコンに代表されるＯＡ機器や家電製品、自動車部品等の更なる機械的物性の向上が要求されている分野にも有用である。 As described above, the foamed molded article of the present invention has fine and uniform bubbles, is lightweight, has excellent mechanical properties and dimensional stability, and is used for office automation equipment and home appliances such as personal computers and automobiles. It is also useful in fields where further improvements in mechanical properties such as parts are required.
Claims (5)
（ａ）０．０１≦ｄｘ≦３０
（ｂ）２．５≦Ｖ≦３０
但し、
ｄｘ：電子顕微鏡写真により測定した平均粒子径（μｍ）
Ｖ ：ＪＩＳＫ５１０１−９１ ２１．１ 顔料試験方法の静置法による見掛け比容（ｍ ｌ／ｇ） And satisfying the following formulas (a) and (b), at least the surface of the particle contains a foaming stabilizer composed of a calcium phosphate compound, and at least one selected from plate-like inorganic particles and thermoplastic elastomer. Characteristic foamed resin molding.
(A) 0.01 ≦ dx ≦ 30
(B) 2.5 ≦ V ≦ 30
However,
dx: average particle diameter (μm) measured by electron micrograph
V: JIS K5101-91 21.1 Apparent specific volume (ml / g) by the stationary method of the pigment test method
（ｃ）１≦α≦５ α＝ｄ５０／ｄｘ
（ｄ）０≦β≦２ β＝（ｄ９０−ｄ１０）／ｄ５０
但し、
α ：分散係数
ｄ５０：マイクロトラックＦＲＡレーザー式粒度分布計により測定したふるい５０％平均 粒子径（μｍ）
ｄ９０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した通過側累計９０％ 粒子径（μｍ）
ｄ１０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した通過側累計１０％ 粒子径（μｍ） The foamed resin molded article according to claim 1, wherein the foam stabilizer comprising at least a particle surface of a calcium phosphate compound further satisfies the following formulas (c) and (d).
(C) 1 ≦ α ≦ 5 α = d50 / dx
(D) 0 ≦ β ≦ 2 β = (d90−d10) / d50
However,
α: Dispersion coefficient d50: Sieve 50% average particle diameter (μm) measured by Microtrac FRA laser particle size distribution analyzer
d90: Cumulative passage side 90% measured by Microtrac FRA laser particle size distribution meter Particle diameter (μm)
d10: Passage side cumulative 10% measured by Microtrac FRA laser particle size distribution meter Particle diameter (μm)
With respect to 100 parts by weight of the resin, at least 0.01 to 10 parts by weight of a foam stabilizer composed of a calcium phosphate compound on the particle surface, 1 to 50 parts by weight of plate-like inorganic particles, and 0.01 to 20 parts by weight of a thermoplastic elastomer. It is a part, The foamed resin molding of any one of Claims 1-4.
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| EP3342809A1 (en) * | 2016-12-28 | 2018-07-04 | Toyota Jidosha Kabushiki Kaisha | Composite material and method of producing the same |
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