JPH08864B2 - Porous cross-linked polyester bead lightening material and lightening composition containing the same - Google Patents
Porous cross-linked polyester bead lightening material and lightening composition containing the sameInfo
- Publication number
- JPH08864B2 JPH08864B2 JP3281506A JP28150691A JPH08864B2 JP H08864 B2 JPH08864 B2 JP H08864B2 JP 3281506 A JP3281506 A JP 3281506A JP 28150691 A JP28150691 A JP 28150691A JP H08864 B2 JPH08864 B2 JP H08864B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- bead
- composition
- reducing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
【発明の詳細な説明】Detailed Description of the Invention
【0001】[0001]
【産業上の利用分野】この発明は、多孔性架橋ポリエス
テルビード軽量化材およびそれを配合した軽量化組成物
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a porous crosslinked polyester bead lightweighting material and a lightweighting composition containing the same.
【0002】[0002]
【従来の技術】最近、燃費−大気汚染の関係で、自動車
の軽量化が世界的に強く求められている。また構造物か
らその大小あらゆる部品に至るまで、材料の軽量化を如
何に図るかについて、現在研究開発に莫大な経費が投じ
られている。2. Description of the Related Art Recently, there has been a strong demand worldwide to reduce the weight of automobiles due to the relationship between fuel consumption and air pollution. In addition, enormous expenses are currently invested in research and development for how to reduce the weight of materials, from structures to large and small parts.
【0003】自動車に限らず、航空機、車輌、および自
転車のような交通機関においても、同様の傾向がある。
また日常生活においても、家庭用品、履物、衣服、およ
びおもちゃなど、さらには建築部材などにも軽量化の波
が押寄せている。The same tendency is observed not only in automobiles but also in transportation such as aircrafts, vehicles, and bicycles.
Moreover, in daily life, the wave of weight reduction is also rushing to household products, footwear, clothes, toys, and even building materials.
【0004】現在、これらの研究開発が強力に行なわ
れ、ある程度は達成されているが、まだ不十分であり、
なお軽量化材料に対する要望には強いものがある。At present, these research and development activities have been strongly carried out and achieved to some extent, but they are still insufficient.
There is a strong demand for lightweight materials.
【0005】軽量化の方法には、比重の大きい材料を比
重の小さい材料に置換えることがよくなされており、た
とえば鉄からアルミ、さらにはプラスチックに代えられ
ている。また、ガラスから透明プラスチックに置換える
ことも行われている。In order to reduce the weight, it is common to replace a material having a large specific gravity with a material having a small specific gravity. For example, iron is replaced with aluminum, and further plastic is used. Also, glass is being replaced with transparent plastic.
【0006】もう1つの方法は、材料を発泡させるか、
あるいは空気を入れ込む方法であり、発泡セメント(L
AC)、スポンジゴム、発泡プラスチック、および軽量
化新聞などによく見かけられる一般的材料である。ま
た、これに類似した方法として、特定の材料に、軽量化
材を混合する方法もある。Another alternative is to foam the material, or
Alternatively, it is a method of injecting air, and foamed cement (L
AC), sponge rubber, expanded plastic, and lightweight newspapers are common materials. As a method similar to this, there is also a method of mixing a weight-reducing material with a specific material.
【0007】軽量化材として、内部に空隙を有する粉末
は、これまでにも知られており、たとえばシリカバルー
ン、ガラスバルーン、シラスバルーン、およびガロライ
トのようなシリカ系バルーンなどが知られている。これ
らのシリカ系バルーンは、シリカを主成分とする無機物
から形成されている。Powders having voids inside have been known as a weight-reducing material, and silica balloons such as silica balloons, glass balloons, shirasu balloons and gallolite are known. These silica-based balloons are formed from an inorganic material containing silica as a main component.
【0008】有機物から形成される軽量化材としては、
酢酸ビニル、アクリル酸、アクリル酸エステル、メタク
リル酸、メタクリル酸エステル、スチレン、塩化ビニリ
デンなどの熱可塑性樹脂から形成された中空あるいは多
孔性熱可塑性樹脂ビードが知られている。As a weight-reducing material formed of an organic material,
Hollow or porous thermoplastic resin beads formed from thermoplastic resins such as vinyl acetate, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, styrene, and vinylidene chloride are known.
【0009】[0009]
【発明が解決しようとする課題】しかしながら、シリカ
系バルーンではプラスチックおよびゴムなどに配合混練
する際にバルーンが破壊されてしまい、軽量化材として
の機能を達成できないという問題があった。However, silica-based balloons have a problem that the balloons are destroyed when they are compounded and kneaded with plastics and rubbers, and the function as a weight reducing material cannot be achieved.
【0010】また多孔性熱可塑性樹脂ビードでは、これ
をプラスチックおよびゴムなどに配合するため加熱混練
するが、その場合熱によってビードが変形または溶融し
てしまい、やはり軽量化材としての機能を達成できない
という問題があった。The porous thermoplastic resin beads are heated and kneaded in order to mix them with plastics and rubber, but in that case, the beads are deformed or melted by heat, and the function as a weight reducing material cannot be achieved. There was a problem.
【0011】この発明は、このような従来の問題点を解
消し、熱によって変形または溶融することがなく、かつ
混合工程の際にその気泡構造が破壊されることのない軽
量化材を提供することにある。The present invention solves the above-mentioned conventional problems, and provides a lightweight material which is neither deformed nor melted by heat and whose bubble structure is not destroyed during the mixing step. Especially.
【0012】[0012]
【課題を解決するための手段】この発明の軽量化材は、
不飽和ポリエステルとそれを架橋し得るビニル系単量体
とからなる油相中にアルカリ土類金属の酸化物および/
または水酸化物の水懸濁液を分散させて形成した油中水
型エマルジョンを懸濁安定材の水溶液中に再分散して架
橋硬化させ、これを乾燥させることによって形成した多
孔性架橋ポリエステルビード軽量化材である。The lightweight material of the present invention is
Alkaline earth metal oxide and / or in the oil phase consisting of unsaturated polyester and vinyl monomer capable of cross-linking it
Alternatively, a porous crosslinked polyester bead formed by redispersing a water-in-oil emulsion formed by dispersing an aqueous suspension of a hydroxide in an aqueous solution of a suspension stabilizer to crosslink and cure it, and then drying this. It is a lightweight material.
【0013】この発明のビード軽量化材の粒子径は、5
μm〜1mmであることが好ましく、さらに好ましくは
50〜200μmである。The particle diameter of the bead lightening material of the present invention is 5
The thickness is preferably 1 μm to 1 mm, more preferably 50 to 200 μm.
【0014】粒子径が5μmよりも小さくなると、粒子
が凝集し、粉末として仕上げることが難しくなり、取扱
いが面倒なものとなる。また粒子径が1mmより大きく
なると、軽量化させる対象物との混合の工程において、
軽量化材の空隙構造が破壊される場合がある。If the particle size is smaller than 5 μm, the particles agglomerate and it becomes difficult to finish them as powders, which makes the handling troublesome. When the particle size is larger than 1 mm, in the step of mixing with the object to be lightened,
The void structure of the lightweight material may be destroyed.
【0015】この発明のビード軽量化材は、空隙率が2
0〜90容量%であることが好ましく、さらに好ましく
は40〜80容量%である。空隙率が20容量%より小
さくなると軽量化の効果が十分に得られない場合があ
り、また90容量%以上を超えると軽量化材の空隙構造
が破壊されやすくなる。The bead weight reducing material of the present invention has a porosity of 2
It is preferably 0 to 90% by volume, and more preferably 40 to 80% by volume. If the porosity is less than 20% by volume, the effect of weight reduction may not be sufficiently obtained, and if it exceeds 90% by volume, the void structure of the weight-reducing material is likely to be destroyed.
【0016】この発明のビード軽量化材は、最終工程で
乾燥することによって得られるが、水分5%以下に乾燥
することが好ましい。The bead weight-reducing material of the present invention is obtained by drying in the final step, but it is preferable to dry it to a water content of 5% or less.
【0017】この発明のビード軽量化材は、内部の空隙
率に比較して表面における孔の存在が少ないことが特徴
である。このように表面において孔が少ないために軽量
化対象物が孔内部に進入することが抑制され、より軽量
化の効果を十分に発揮することができる。The bead weight-reducing material of the present invention is characterized in that the number of pores on the surface is small as compared with the internal porosity. Since the number of holes on the surface is small as described above, it is possible to prevent the object to be lightened from entering the inside of the hole, and it is possible to sufficiently exert the effect of further weight reduction.
【0018】この発明のビード軽量化材は、不飽和ポリ
エステルとビニル系単量体とからなる油相中にアルカリ
土類金属酸化物および/または水酸化物の水懸濁液を分
散させて形成した油中水型エマルジョンを懸濁安定剤の
水溶液中に再分散して架橋硬化させた後、これを乾燥す
ることによって得ることができる。The bead weight-reducing material of the present invention is formed by dispersing an aqueous suspension of an alkaline earth metal oxide and / or hydroxide in an oil phase composed of an unsaturated polyester and a vinyl monomer. The obtained water-in-oil emulsion can be obtained by redispersing the emulsion in an aqueous solution of a suspension stabilizer to crosslink and cure it, and then drying it.
【0019】この発明のビード軽量化材の原料として用
いられる不飽和ポリエステルとしては、特に限定される
ものではなく、たとえば、α,β−不飽和酸もしくはそ
れと飽和酸との混合物と二価アルコールもしくは三価ア
ルコールとを重合させたものなどを挙げることができ
る。The unsaturated polyester used as a raw material for the bead weight-reducing material of the present invention is not particularly limited and includes, for example, α, β-unsaturated acid or a mixture thereof and a dihydric alcohol. Examples thereof include those obtained by polymerizing a trihydric alcohol.
【0020】不飽和酸としては、たとえば、フマル酸、
マレイン酸、イタコン酸などが、飽和酸としてはたとえ
ば、フタル酸、テレフタル酸、コハク酸、グルタル酸、
テトラヒドロフタル酸、アジピン酸、およびセバチン酸
などが挙げられる。Examples of unsaturated acids include fumaric acid,
Maleic acid, itaconic acid, etc., as the saturated acid, for example, phthalic acid, terephthalic acid, succinic acid, glutaric acid,
Examples include tetrahydrophthalic acid, adipic acid, sebacic acid, and the like.
【0021】また二価アルコールおよび三価アルコール
としては、たとえば、エチレングリコール、ジエチレン
グリコール、プロピレングリコール、ネオペンチルグリ
コール、1,3−プロパンジオール、1,6−ヘキサン
ジオール、トリメチロールプロパンなどが挙げられる。Examples of dihydric alcohols and trihydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 1,3-propanediol, 1,6-hexanediol and trimethylolpropane.
【0022】不飽和ポリエステルの酸価は特に限定され
ないが、油中水型エマルジョンの安定性を考慮すると、
5〜30mgKOH/g程度の酸価を有する不飽和ポリ
エステルを使用するのが好ましい。The acid value of the unsaturated polyester is not particularly limited, but considering the stability of the water-in-oil emulsion,
It is preferable to use an unsaturated polyester having an acid value of about 5 to 30 mg KOH / g.
【0023】この発明のビード軽量化材の原料となるビ
ニル系単量体としては、特に制限されず、たとえば、ス
チレン、クロルスチレン、ビニルトルエン、ジビニルベ
ンゼン、アクリル酸、メチルアクリレート、アクリロニ
トリル、エチルアクリレート、およびジアリルフタレー
トなどが挙げられる。The vinyl monomer as a raw material for the bead weight reducing material of the present invention is not particularly limited, and examples thereof include styrene, chlorostyrene, vinyltoluene, divinylbenzene, acrylic acid, methyl acrylate, acrylonitrile, ethyl acrylate. , And diallyl phthalate.
【0024】不飽和ポリエステルとビニル系単量体の配
合割合は特に制限されないが、通常、不飽和ポリエステ
ル100重量部に対してビニル系単量体50〜200重
量部程度配合すればよい。The mixing ratio of the unsaturated polyester and the vinyl monomer is not particularly limited, but usually 50 to 200 parts by weight of the vinyl monomer may be added to 100 parts by weight of the unsaturated polyester.
【0025】不飽和ポリエステルとビニル系単量体に乳
化剤として添加されるアルカリ土類金属の酸化物および
/または水酸化物(以下「アルカリ土類金属塩」とい
う)としては、特に制限されず、たとえば、酸化マグネ
シウム、酸化カルシウム、酸化バリウム、酸化ストロン
チウム、水酸化マグネシウム、水酸化カルシウム、水酸
化バリウム、水酸化ストロンチウムなどが挙げられる。The alkaline earth metal oxide and / or hydroxide (hereinafter referred to as "alkaline earth metal salt") added to the unsaturated polyester and the vinyl monomer as an emulsifier is not particularly limited, Examples thereof include magnesium oxide, calcium oxide, barium oxide, strontium oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and strontium hydroxide.
【0026】アルカリ土類金属塩の使用量は特に制限さ
れないが、油相100重量部に対し、通常0.01〜2
0重量部程度、好ましくは0.1〜5重量部程度とすれ
ばよい。アルカリ土類金属塩を懸濁するための水の使用
量は、油相100重量部に対し、10〜800重量部程
度、好ましくは50〜400重量部程度とすればよい。The amount of the alkaline earth metal salt used is not particularly limited, but is usually 0.01 to 2 per 100 parts by weight of the oil phase.
It may be about 0 parts by weight, preferably about 0.1 to 5 parts by weight. The amount of water used for suspending the alkaline earth metal salt may be about 10 to 800 parts by weight, preferably about 50 to 400 parts by weight, based on 100 parts by weight of the oil phase.
【0027】アルカリ土類金属塩の水への懸濁方法は特
に制限されず、たとえば、ボールミル、高速攪拌器など
で十分に懸濁すればよい。The method of suspending the alkaline earth metal salt in water is not particularly limited, and it may be sufficiently suspended using, for example, a ball mill or a high speed stirrer.
【0028】油相にアルカリ土類金属塩の水懸濁液を加
えて油中水型エマルジョンを形成するには、攪拌などの
一般的な方法が採用できる。たとえば、油相中にアルカ
リ土類金属塩の水懸濁液を徐々に添加し、ディスパーミ
ル、コロイドミルなどで激しく攪拌すればよい。攪拌速
度は特に制限されないが、通常攪拌羽根の周速度が10
〜60m/秒程度、好ましくは15〜30m/秒程度で
あればよい。In order to form a water-in-oil emulsion by adding an aqueous suspension of an alkaline earth metal salt to the oil phase, a general method such as stirring can be adopted. For example, an aqueous suspension of an alkaline earth metal salt may be gradually added to the oil phase and vigorously stirred with a disper mill, a colloid mill or the like. The stirring speed is not particularly limited, but the peripheral speed of the stirring blade is usually 10
It is about 60 to 60 m / sec, preferably about 15 to 30 m / sec.
【0029】油中水型エマルジョンを再分散させる懸濁
安定剤としては、たとえば、ポリビニルアルコール、部
分ケン化ポリビニルアルコール、ヒドロキシメチルセル
ロース、ヒドロキシエチルセルロースなどが挙げられ
る。Examples of the suspension stabilizer for redispersing the water-in-oil emulsion include polyvinyl alcohol, partially saponified polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl cellulose and the like.
【0030】懸濁安定剤は単独でまたは2種以上の混合
物で使用できる。水溶液中の懸濁安定剤の濃度は、目的
とする多孔性ポリエステル樹脂粒子の粒子径などに応じ
て適宜選択すればよいが、通常0.1〜10重量%程度
とすればよい。The suspension stabilizers can be used alone or as a mixture of two or more kinds. The concentration of the suspension stabilizer in the aqueous solution may be appropriately selected according to the particle diameter of the target porous polyester resin particles and the like, but is usually about 0.1 to 10% by weight.
【0031】油中水型エマルジョンを懸濁安定剤の水溶
液中に再分散するときの攪拌速度は、得ようとする多孔
性架橋ポリエステルビード軽量化材の粒子径などに応じ
て適宜選択することができる。一般的には、攪拌速度が
速いと小さい粒子径のものが得られる、攪拌速度が遅い
と大きいものが得られる。The stirring speed at the time of redispersing the water-in-oil emulsion in the aqueous solution of the suspension stabilizer may be appropriately selected depending on the particle diameter of the porous crosslinked polyester bead lightweighting material to be obtained. it can. Generally, when the stirring speed is high, a small particle size is obtained, and when the stirring speed is low, a large particle size is obtained.
【0032】再分散体中の油中水型エマルジョンを架橋
硬化する方法は、通常の方法で行なうことができる。た
とえば、再分散体を攪拌しながら、重合開始剤を加えて
架橋硬化させればよい。重合開始剤としては、不飽和ポ
リエステル樹脂の重合開始剤として用いられるものを使
用することができる。具体的には、たとえば、過酸化ベ
ンゾイル、メチルエチルケトンパーオキサイド、クメン
パーオキサイド、t−ブチルパーオキサイドなどの有機
過酸化物、過硫酸アンモニウム、過硫酸ナトリウム、過
硫酸カリウムなどの無機過酸化物、メチルエチルケトン
パーオキサイド−コバルト有機酸塩、クメンハイドロパ
ーオキサイド−コバルト有機酸塩などのレドックス系重
合開始剤などが挙げられる。The method of crosslinking and hardening the water-in-oil emulsion in the redispersion can be carried out by a usual method. For example, a polymerization initiator may be added to crosslink and cure the redispersion while stirring. As the polymerization initiator, those used as a polymerization initiator for the unsaturated polyester resin can be used. Specifically, for example, organic peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, cumene peroxide and t-butyl peroxide, inorganic peroxides such as ammonium persulfate, sodium persulfate and potassium persulfate, and methyl ethyl ketone peroxide. Examples thereof include redox polymerization initiators such as oxide-cobalt organic acid salts and cumene hydroperoxide-cobalt organic acid salts.
【0033】重合開始剤は、不飽和ポリエステルおよび
ビニル系単量体の油相中に加えておいてもよい。また2
成分からなるレドックス系重合開始剤は、一方の成分を
油相に加え、もう一方の成分を再分散体に加えておいて
もよい。The polymerization initiator may be added in the oil phase of the unsaturated polyester and the vinyl monomer. Again 2
As for the redox-based polymerization initiator composed of the components, one component may be added to the oil phase and the other component may be added to the redispersion.
【0034】重合開始剤の使用量は特に制限されない
が、通常油相100重量部に対して、0.5〜5重量部
程度とすればよい。重合温度は特に制限されないが、通
常10〜40℃程度でよい。また攪拌速度も特に制限さ
れないが、通常攪拌羽の周速度を1〜10m/秒程度と
すればよい。The amount of the polymerization initiator used is not particularly limited, but it is usually 0.5 to 5 parts by weight per 100 parts by weight of the oil phase. Although the polymerization temperature is not particularly limited, it is usually about 10 to 40 ° C. The stirring speed is also not particularly limited, but the peripheral speed of the stirring blade is usually about 1 to 10 m / sec.
【0035】架橋硬化後の乾燥は、一般には加熱乾燥に
よって行なうことができる。加熱温度としては特に制限
されないが、通常80〜120℃程度で行なえばよい。Drying after crosslinking and curing can be generally performed by heat drying. The heating temperature is not particularly limited, but it is usually about 80 to 120 ° C.
【0036】この発明のビード軽量化材を混合すること
により軽量化する対象物は特に限定されるものではない
が、たとえば、SMCおよびBMCなどの繊維強化不飽
和ポリエステル樹脂、油粘土および紙粘土、接着剤、シ
ーラント、合成木材、人工大理石などのプラスチックコ
ンクリート、セメントコンクリート、床材および壁紙な
どのペーストPVC成形品、カーペットバッキング材、
ブイなどの浮力材、紙ボード、天井材、プラスチック成
形品ならびにゴム成形品などに添加して軽量化を図るこ
とができる。The object to be lightened by mixing the bead weight-reducing material of the present invention is not particularly limited, but for example, fiber reinforced unsaturated polyester resin such as SMC and BMC, oil clay and paper clay, Adhesives, sealants, synthetic wood, plastic concrete such as artificial marble, cement concrete, paste PVC molded products such as flooring and wallpaper, carpet backing materials,
It can be added to buoyancy materials such as buoys, paper boards, ceiling materials, plastic molded products and rubber molded products to reduce the weight.
【0037】繊維強化不飽和ポリエステル樹脂に配合す
る場合は、不飽和ポリエステル樹脂100重量部に対
し、この発明のビード軽量化材5〜1000重量部、さ
らに好ましくは10〜500重量部配合することが好ま
しい。5重量部より少ないと十分に軽量化の効果が得ら
れず、1000重量部より多くなると、不飽和ポリエス
テル樹脂組成物の粘度が高くなり、成型がしにくくな
る。When blended with the fiber reinforced unsaturated polyester resin, the bead weight-reducing material of the present invention is blended in an amount of 5 to 1000 parts by weight, preferably 10 to 500 parts by weight, based on 100 parts by weight of the unsaturated polyester resin. preferable. If the amount is less than 5 parts by weight, the effect of sufficiently reducing the weight cannot be obtained, and if the amount is more than 1000 parts by weight, the viscosity of the unsaturated polyester resin composition becomes high and molding becomes difficult.
【0038】油粘土にこの発明のビード軽量化材を添加
する場合、油粘土100重量部に対し、この発明のビー
ド軽量化材5〜500重量部、さらに好ましくは10〜
300重量部配合することが好ましい。5重量部より少
ないと軽量化の効果が十分に得られず、500重量部よ
り多いと、油粘土の粘度が高くなり、細工がしにくくな
る。When the bead lightening material of the present invention is added to the oil clay, the bead lightening material of the present invention is 5 to 500 parts by weight, more preferably 10 to 100 parts by weight of the oil clay.
It is preferable to add 300 parts by weight. If the amount is less than 5 parts by weight, the effect of reducing the weight cannot be sufficiently obtained, and if the amount is more than 500 parts by weight, the viscosity of the oil clay becomes high and it becomes difficult to make the work.
【0039】接着剤に対しこの発明のビード軽量化材を
配合する場合は、接着剤100重量部に対し、この発明
のビード軽量化材5〜200重量部、さらに好ましくは
10〜150重量部配合することが好ましい。5重量部
より少ないと十分に軽量化の効果が得られず、200重
量部より多いと、接着力が低下する。When the bead weight-reducing material of the present invention is added to the adhesive, 5 to 200 parts by weight, more preferably 10 to 150 parts by weight of the bead-lightening material of the present invention is added to 100 parts by weight of the adhesive. Preferably. If it is less than 5 parts by weight, the effect of sufficiently reducing the weight cannot be obtained, and if it is more than 200 parts by weight, the adhesive strength is lowered.
【0040】熱可塑性樹脂に対しこの発明のビード軽量
化材を配合する場合は、熱可塑性樹脂100重量部に対
し、この発明のビード軽量化材5〜500重量部、さら
に好ましくは10〜300重量部配合することが好まし
い。5重量部より少ないと十分に軽量化の効果が得られ
ず、500重量部より多いと、熱可塑性樹脂成形品の強
度が低下する。When the bead weight-reducing material of the present invention is added to a thermoplastic resin, the bead-lightening material of the present invention is 5 to 500 parts by weight, and more preferably 10 to 300 parts by weight, relative to 100 parts by weight of the thermoplastic resin. It is preferable to mix them in parts. If the amount is less than 5 parts by weight, the effect of sufficiently reducing the weight cannot be obtained, and if the amount is more than 500 parts by weight, the strength of the thermoplastic resin molded article decreases.
【0041】ゴムに対しこの発明のビード軽量化材を配
合する場合は、ゴム100重量部に対し、この発明のビ
ード軽量化材5〜300重量部、さらに好ましくは10
〜200重量部配合することが好ましい。5重量部より
少ないと十分に軽量化の効果が得られず、300重量部
より多いと、ゴム成形品の強度が低下する。When the bead weight-reducing material of the present invention is added to rubber, the bead-lightening material of the present invention is 5 to 300 parts by weight, more preferably 10 parts by weight, relative to 100 parts by weight of the rubber.
It is preferable to mix it in an amount of up to 200 parts by weight. If the amount is less than 5 parts by weight, the effect of sufficiently reducing the weight cannot be obtained, and if the amount is more than 300 parts by weight, the strength of the rubber molded product decreases.
【0042】[0042]
【発明の作用効果】この発明のビード軽量化材は、その
内部に、0.2〜2μm程度の小泡を多数有しており、
また素材が不飽和ポリエステル樹脂の硬化物からなるた
め、軽量化の対象物と混合する工程においても従来のシ
リカ系バルーンのようにその構造が破壊されることはな
い。The bead weight-reducing material of the present invention has a large number of small bubbles of about 0.2 to 2 μm therein.
Further, since the material is a cured product of an unsaturated polyester resin, its structure is not destroyed unlike the conventional silica balloon even in the step of mixing with the object of weight reduction.
【0043】また不飽和ポリエステルの架橋硬化物から
なるものであるため、従来の熱可塑性樹脂から形成され
たビードのように加熱混練によって変形または溶融した
りすることもない。Since it is composed of a cross-linked cured product of unsaturated polyester, it is not deformed or melted by heating and kneading unlike the beads formed of conventional thermoplastic resins.
【0044】したがって、この発明に従うビード軽量化
材は、プラスチック、ゴム、紙ボードおよび接着剤など
に混合して、従来にはない優れた軽量化の効果を発揮す
るものである。Therefore, the bead weight-reducing material according to the present invention, when mixed with plastic, rubber, paper board, adhesive or the like, exerts an excellent weight-reducing effect which has never been obtained.
【0045】また従来のシリカ系バルーンの場合は、バ
ルーンの構造が破壊すると素材がシリカを主成分とする
ため、たとえば油粘土や紙粘土などに配合すると破壊し
た破片によって指などを傷付けるおそれがあったが、こ
の発明のビード軽量化材はこのような破壊が生じず、ま
たたとえ破壊が生じたとしても不飽和ポリエステル樹脂
をベースとしているため、指などを傷付けるおそれがな
い。Further, in the case of the conventional silica type balloon, when the structure of the balloon is destroyed, the material mainly contains silica. Therefore, if it is mixed with oil clay or paper clay, for example, there is a possibility that the broken pieces may injure a finger or the like. However, the bead weight-reducing material of the present invention does not cause such breakage, and even if breakage occurs, since it is based on the unsaturated polyester resin, there is no risk of scratching a finger or the like.
【0046】また、この発明のビード軽量化材は内部に
多数の小泡を有する構造であるため、内部の小泡の径や
その空隙率などを広い範囲でコントロールすることがで
き、種々の用途に適合するビード軽量化材とすることが
できる。Further, since the bead weight-reducing material of the present invention has a structure having a large number of small bubbles inside, it is possible to control the diameter of the small bubbles inside and the porosity thereof in a wide range, and various applications are possible. The bead lightening material that conforms to
【0047】[0047]
実施例1 不飽和ポリエステル樹脂[商品名:エポラックN−14
B,酸価12,スチレン含有量40%,日本触媒株式会
社製]65重量部、スチレン35重量部およびナフテン
酸コバルト(コバルト含有量6重量%)0.4重量部を
ディスパー攪拌機で、23.3m/秒の周速で攪拌しな
がら、水300重量部に酸化マグネシウム1重量部を添
加しボールミルに3時間かけて分散させた水懸濁液を徐
々に加えて、油中水型エマルジョンを得た。Example 1 Unsaturated polyester resin [trade name: Epolak N-14
B, acid value 12, styrene content 40%, manufactured by Nippon Shokubai Co., Ltd.] 65 parts by weight, styrene 35 parts by weight and cobalt naphthenate (cobalt content 6% by weight) 0.4 parts by weight with a disper stirrer. While stirring at a peripheral speed of 3 m / sec, 1 part by weight of magnesium oxide was added to 300 parts by weight of water, and the water suspension dispersed in a ball mill for 3 hours was gradually added to obtain a water-in-oil emulsion. It was
【0048】次に、このエマルジョンに、PVA(重合
度2000,けん化度80%)4.0重量%水溶液30
0重量部を加え、プロペラ攪拌機で8m/秒の周速で1
0分間攪拌した。Next, to this emulsion, 30% PVA (polymerization degree 2000, saponification degree 80%) 4.0% by weight aqueous solution was added.
Add 0 parts by weight, and propeller stirrer at a peripheral speed of 8 m / s to 1
Stirred for 0 minutes.
【0049】さらに硬化触媒MEKPO1.5重量部を
添加し、30℃で緩やかに攪拌を続け、不飽和ポリエス
テル粒子のスラリーを得た。Further, 1.5 parts by weight of the curing catalyst MEKPO was added, and stirring was continued gently at 30 ° C. to obtain a slurry of unsaturated polyester particles.
【0050】このポリエステル粒子をろ過し、得られた
ポリエステル粒子のケーキを105℃で1昼夜乾燥し、
水分1.5%、粒子径15〜150μm、空隙率79%
の多孔性架橋ポリエステルビード軽量化材(以下この軽
量化材を「軽量化材A」という)を得た。The polyester particles were filtered, and the obtained polyester particle cake was dried at 105 ° C. for one day.
Water content 1.5%, particle size 15-150 μm, porosity 79%
A porous crosslinked polyester bead lightening material (hereinafter, this lightening material is referred to as "lightening material A") was obtained.
【0051】この軽量化材Aを市販の不飽和ポリエステ
ル樹脂(リゴラックM411,昭和高分子株式会社製)
に配合し、硬化触媒BPO2重量部を添加し、120℃
で加圧成形し、不飽和ポリエステル樹脂軽量化組成物を
得た。A commercially available unsaturated polyester resin (Rigolac M411, Showa Polymer Co., Ltd.) is used as the weight-reducing material A.
And 2 parts by weight of the curing catalyst BPO are added to 120 ° C.
And pressure-molded to obtain an unsaturated polyester resin lightweight composition.
【0052】軽量化材Aの配合量は、表1に示すよう
に、不飽和ポリエステル樹脂100重量部に対し、2、
9、30、200、500、1200重量部と変化させ
た(比較例1−1,本発明例1−2〜1−5,比較例1
−6)。As shown in Table 1, the compounding amount of the weight-reducing material A is 2, with respect to 100 parts by weight of the unsaturated polyester resin.
9, 30, 200, 500, 1200 parts by weight (Comparative Example 1-1, Inventive Examples 1-2 to 1-5, Comparative Example 1
-6).
【0053】得られた不飽和ポリエステル樹脂の比重お
よび充填剤の破壊率(%)を表1に示した。なお、軽量
化材Aを1200重量部配合したものは、成形品にクラ
ックが発生し、不飽和ポルエステル樹脂組成物が得られ
なかった。Table 1 shows the specific gravity of the obtained unsaturated polyester resin and the destruction rate (%) of the filler. In addition, when 1200 parts by weight of the weight-reducing material A was mixed, cracks were generated in the molded product, and the unsaturated polyester resin composition could not be obtained.
【0054】ここで破壊率は次式により算出される数値
である。Here, the destruction rate is a numerical value calculated by the following equation.
【0055】[0055]
【数1】 [Equation 1]
【0056】ここで、計算比重Aは、マイクロバルーン
など空洞を有した充填剤を組成物の配合して、空洞がす
べて壊れた場合の配合組成物の比重を示しており、破壊
率100%のときの比重を示している。Here, the calculated specific gravity A represents the specific gravity of the compounded composition in the case where a filler having voids such as microballoons is compounded in the composition and all the voids are broken, and the fracture rate is 100%. It shows the specific gravity when.
【0057】また計算比重Bは、マイクロバルーンなど
空洞を有した充填剤を組成物の配合して、空洞がまった
く壊れない場合の配合組成物の比重、すなわち破壊率0
%のときの比重を示している。The calculated specific gravity B is the specific gravity of the compounded composition when the composition is compounded with a filler having cavities such as microballoons, that is, the fracture rate is 0.
The specific gravity is shown when%.
【0058】比較として、軽量化材Aの代わりに重質炭
酸カルシウムを用い、不飽和ポリエステル樹脂100重
量部に対し100重量部配合した不飽和ポリエステル樹
脂組成物を作製し、その比重および充填剤の破壊率を表
1に示した(比較例1−7)。For comparison, heavy calcium carbonate was used in place of the weight-reducing material A, and an unsaturated polyester resin composition was prepared by mixing 100 parts by weight with 100 parts by weight of the unsaturated polyester resin. The destruction rate is shown in Table 1 (Comparative Example 1-7).
【0059】また比較として、軽量化材Aの代わりに、
シリカ系バルーンのQ−cel−300(旭ガラス株式
会社製,比重0.21)30重量部を配合し、不飽和ポ
リエステル樹脂組成物を作成した(比較例1−8)。こ
の組成物の比重および破壊率を表1に示した。For comparison, instead of the lightweight material A,
30 parts by weight of a silica-based balloon Q-cel-300 (manufactured by Asahi Glass Co., Ltd., specific gravity 0.21) was blended to prepare an unsaturated polyester resin composition (Comparative Example 1-8). The specific gravity and destruction rate of this composition are shown in Table 1.
【0060】[0060]
【表1】 [Table 1]
【0061】実施例2 市販の不飽和ポリエステル樹脂(リゴラックM411,
昭和高分子株式会社製)100重量部に実施例1で得た
軽量化材A9重量部または30重量部配合し、さらにガ
ラス繊維100重量部,硬化触媒BPO2重量部を添加
し、120℃で加圧成形し、不飽和ポリエステル樹脂軽
量化組成物を得た(本発明例2−1,2−2)。得られ
た組成物の比重および破壊率を表1に示した。Example 2 Commercially available unsaturated polyester resin (Rigolac M411,
100 parts by weight of Showa Polymer Co., Ltd.) was mixed with 9 parts by weight or 30 parts by weight of the weight-reducing material A obtained in Example 1, 100 parts by weight of glass fiber and 2 parts by weight of curing catalyst BPO were added, and the mixture was heated at 120 ° C. It pressure-molded and the unsaturated polyester resin lightweight composition was obtained (Examples 2-1 and 2-2 of this invention). The specific gravity and destruction rate of the obtained composition are shown in Table 1.
【0062】比較として、軽量化材Aの代わりに重質炭
酸カルシウムを用い、不飽和ポリエステル樹脂100重
量部に対し100重量部配合した不飽和ポリエステル樹
脂組成物を得た(比較例2−3)。その比重および破壊
率を表1に示した。As a comparison, an unsaturated polyester resin composition was obtained in which heavy calcium carbonate was used instead of the weight-reducing material A, and 100 parts by weight of 100 parts by weight of the unsaturated polyester resin was mixed (Comparative Example 2-3). . The specific gravity and destruction rate are shown in Table 1.
【0063】また比較として、軽量化材Aの代わりに、
シリカ系バルーンのQ−cel−300(旭ガラス株式
会社製比重0.21)8重量部を配合し、不飽和ポリエ
ステル樹脂組成物を得た(比較例2−4)。その比重お
よび破壊率を表1に示した。For comparison, instead of the lightweight material A,
8 parts by weight of silica-based balloon Q-cel-300 (specific gravity 0.21 manufactured by Asahi Glass Co., Ltd.) was blended to obtain an unsaturated polyester resin composition (Comparative Example 2-4). The specific gravity and destruction rate are shown in Table 1.
【0064】実施例3 実施例1の軽量化材Aの製造において、水300重量部
を水100重量部にし、他の条件は同様にして、多孔性
架橋ポリエステル粒子のスラリーを得た。このポリエス
テル粒子をろ過して得られたケーキを、105℃で1昼
夜乾燥し、水分1.0%、粒子径20〜130μm、空
隙率49%の多孔性架橋ポリエステルビード軽量化材
(以下この軽量化材を「軽量化材B」という)を得た。Example 3 In the production of the weight-reducing material A of Example 1, 300 parts by weight of water was changed to 100 parts by weight of water, and the other conditions were the same to obtain a slurry of porous crosslinked polyester particles. A cake obtained by filtering the polyester particles is dried at 105 ° C. for one day, and has a moisture content of 1.0%, a particle diameter of 20 to 130 μm, and a porosity of 49%. The chemical material was referred to as “lightweight material B”).
【0065】この軽量化材Bを、市販の不飽和ポリエス
テル樹脂(リゴラックM411,昭和高分子株式会社
製)100重量部に21重量部配合して加圧成形し、不
飽和ポリエステル樹脂軽量化組成物を得た(本発明例
3)。得られた樹脂組成物の比重および破壊率を表1に
示す。21 parts by weight of this weight-reducing material B was mixed with 100 parts by weight of a commercially available unsaturated polyester resin (Rigolac M411, Showa Polymer Co., Ltd.) and pressure-molded to obtain an unsaturated polyester resin weight-reducing composition. Was obtained (Example 3 of the present invention). Table 1 shows the specific gravity and destruction rate of the obtained resin composition.
【0066】表1から明らかなように、この発明に従う
軽量化材を不飽和ポリエステル樹脂に配合する場合、不
飽和ポリエステル樹脂100重量部に対するこの発明に
従う軽量化材の配合量は、5〜1000重量部が好まし
く、さらに好ましくは10〜500重量部であることが
わかる。As is clear from Table 1, when the lightening material according to the present invention is blended with the unsaturated polyester resin, the compounding amount of the lightening material according to the present invention relative to 100 parts by weight of the unsaturated polyester resin is 5 to 1000 parts by weight. It can be seen that parts are preferable, and more preferably 10 to 500 parts by weight.
【0067】実施例4 実施例1で得た軽量化材Aにセリサイト10重量部を予
め混合しておき、流動パラフィン10重量部、マイクロ
クリスタリンワックス7重量部、グリセリン1.6重量
部、ステアリン酸カルシウム1.0重量部、カリ石鹸
0.4重量部等を混合し、50〜70℃で加熱して均一
な液状物とした。この液状物とセリサイトおよび軽量化
材Aの混合粉末とを擂解機で混合し、ついでニーダータ
イプの攪拌機で60〜90℃の温度で混合し、油粘土組
成物を作成した。Example 4 10 parts by weight of sericite was mixed in advance with the weight-reducing material A obtained in Example 1, and 10 parts by weight of liquid paraffin, 7 parts by weight of microcrystalline wax, 1.6 parts by weight of glycerin, and steer 1.0 parts by weight of calcium phosphate, 0.4 parts by weight of potassium soap and the like were mixed and heated at 50 to 70 ° C. to obtain a uniform liquid substance. This liquid substance and the mixed powder of sericite and the weight-reducing material A were mixed with a disintegrator and then with a kneader type stirrer at a temperature of 60 to 90 ° C. to prepare an oil clay composition.
【0068】軽量化材Aの配合は、軽量化材A以外の油
粘土組成物100重量部に対し、それぞれ3重量部、2
3重量部、100重量部、および800重量部となるよ
うに配合した(比較例4−1,本発明例4−2および4
−3,比較例4−4)。The composition of the weight-reducing material A was 3 parts by weight and 2 parts by weight, respectively, relative to 100 parts by weight of the oil clay composition other than the weight-reducing material A.
3 parts by weight, 100 parts by weight, and 800 parts by weight were compounded (Comparative Example 4-1, Invention Examples 4-2 and 4).
-3, Comparative Example 4-4).
【0069】また比較として、軽量化材Aの代わりにQ
−cel−300を油粘土組成物100重量部に対し、
23重量部配合して油粘土軽量化組成物を作成した(比
較例4−5)。For comparison, instead of the lightweight material A, Q
-Cel-300 to 100 parts by weight of the oil clay composition,
23 parts by weight were compounded to prepare an oil clay lightweight composition (Comparative Example 4-5).
【0070】得られた油粘土組成物中における充填剤の
破壊率を表2に示した。The destruction rate of the filler in the obtained oil clay composition is shown in Table 2.
【0071】[0071]
【表2】 [Table 2]
【0072】実施例5 実施例1において得られた軽量化材Aとエポキシ樹脂
(エピコート815,シェル石油化学株式会社製)とを
混合し接着剤組成物を作製した。軽量化材Aの配合量
は、エポキシ樹脂100重量部に対し、それぞれ2重量
部、10重量部、150重量部、および300重量部と
なるように変化させた(比較例5−1,本発明例5−2
および5−3,比較例5−4)。Example 5 The lightening material A obtained in Example 1 and an epoxy resin (Epicoat 815, manufactured by Shell Petrochemical Co., Ltd.) were mixed to prepare an adhesive composition. The compounding amount of the weight-reducing material A was changed to be 2 parts by weight, 10 parts by weight, 150 parts by weight, and 300 parts by weight, respectively, with respect to 100 parts by weight of the epoxy resin (Comparative Example 5-1 and the present invention). Example 5-2
And 5-3, Comparative Example 5-4).
【0073】このようにして得られた接着剤組成物10
0重量部に対し、エチレントリアミン5重量部を添加し
て硬化させ、60℃で1時間さらにアフターキュアーを
行なった。Adhesive composition 10 thus obtained
To 0 part by weight, 5 parts by weight of ethylenetriamine was added and cured, and after-curing was further performed at 60 ° C. for 1 hour.
【0074】得られた接着剤組成物の比重およびせん断
強さを表3に示した。せん断強さは、両面鉄金属による
接着層のせん断強さ(kg/cm)である。The specific gravity and shear strength of the obtained adhesive composition are shown in Table 3. The shear strength is the shear strength (kg / cm) of the adhesive layer made of ferrous metal on both sides.
【0075】比較として、軽量化材Aの代わりに重質炭
酸カルシウムをエポキシ樹脂100重量部に対して10
0重量部配合したエポキシ樹脂接着剤組成物を作製した
(比較例5−5)。この接着剤組成物の比重およびせん
断強さも表3に示した。For comparison, heavy calcium carbonate instead of the weight-reducing material A was added to 10 parts by weight of 100 parts by weight of the epoxy resin.
An epoxy resin adhesive composition containing 0 parts by weight was prepared (Comparative Example 5-5). The specific gravity and shear strength of this adhesive composition are also shown in Table 3.
【0076】また比較として、配合充填剤を加えていな
いエポキシ樹脂のみの硬化物を作製した(比較例5−
6)。この接着剤硬化物についても比重およびせん断強
さを表3に示した。For comparison, a cured product of only the epoxy resin containing no compounded filler was prepared (Comparative Example 5-
6). The specific gravity and shear strength of this cured adhesive are also shown in Table 3.
【0077】[0077]
【表3】 [Table 3]
【0078】実施例6 不飽和ポリエステル樹脂〔商品名ポリマール9802,
武田薬品株式会社製〕60重量部、スチレン40重量
部、およびナフテン酸コバルト(コバルト含有量6%)
をディスパー攪拌機で25m/秒の周速で攪拌しなが
ら、水200重量部に水酸化ストロンチウム1重量部を
添加し、ボールミルで3時間かけて分散させた水懸濁液
を徐々に添加し、油中水型エマルジョンを得た。Example 6 Unsaturated polyester resin (trade name: Polymer 9802,
Takeda Pharmaceutical Co., Ltd.] 60 parts by weight, styrene 40 parts by weight, and cobalt naphthenate (cobalt content 6%)
With stirring at a peripheral speed of 25 m / sec with a disper stirrer, was added hydroxide strike b Nchiumu 1 part by weight to 200 parts by weight of water, it was gradually added an aqueous suspension prepared by dispersing for 3 hours in a ball mill A water-in-oil emulsion was obtained.
【0079】次にこのエマルジョンをPVA(重合度2
000,ケン化度80%,和光純薬工業株式会社製)の
3.0重量部%水溶液160重量部と、ヒドロキシエチ
ルセルロース[商品名ナトロゾール250HHR,ハー
キュレス株式会社製]の1重量%水溶液90重量部の混
合物を加え、プロペラ攪拌機を用い周速10m/秒で1
0分間攪拌した。Next, this emulsion was mixed with PVA (polymerization degree 2
000, saponification degree 80%, Wako Pure Chemical Industries, Ltd.) 3.0 parts by weight aqueous solution 160 parts by weight, and hydroxyethyl cellulose [trade name Natrosol 250HHR, manufactured by Hercules Co., Ltd.] 90% by weight aqueous solution. 1) at a peripheral speed of 10 m / sec using a propeller stirrer.
Stirred for 0 minutes.
【0080】さらに硬化触媒MEKPO1.5重量部を
添加し、30℃で緩やかに攪拌を続け、不飽和ポリエス
テルを架橋硬化させて、白色の多孔性架橋ポリエステル
粒子のスラリーを得た。Further, 1.5 parts by weight of the curing catalyst MEKPO was added, and the mixture was continuously stirred gently at 30 ° C. to crosslink and cure the unsaturated polyester to obtain a slurry of white porous crosslinked polyester particles.
【0081】このポリエステル粒子を水洗ろ過して得た
ケーキを120℃で1昼夜乾燥し、水分05%、粒子径
10〜50μm、空隙率65%の架橋ポリエステルビー
ド軽量化材(以下この軽量化材を「軽量化材C」とい
う)を得た。A cake obtained by washing and filtering the polyester particles with water was dried at 120 ° C. for one day and night, and a cross-linked polyester bead lightweight material having a water content of 05%, a particle diameter of 10 to 50 μm and a porosity of 65% (hereinafter referred to as this lightweight material. Is referred to as "lightening material C").
【0082】この軽量化材Cを、市販のABS樹脂(商
品名JSR ABS 15,日本合成ゴム株式会社製)
に、180℃で5分間熱ロールで混練した後、約90℃
で加圧成形し、ABS樹脂軽量化組成物を得た。This weight-reducing material C is made of a commercially available ABS resin (trade name JSR ABS 15, manufactured by Japan Synthetic Rubber Co., Ltd.).
After kneading with a hot roll at 180 ℃ for 5 minutes,
Was pressure-molded to obtain an ABS resin lightweight composition.
【0083】軽量化材Cの配合量は、ABS樹脂100
重量部に対し、1重量部、20重量部、300重量部、
および700重量部となるように配合した(比較例6−
1,本発明例6−2および6−3,比較例6−4)。The blending amount of the lightening material C is 100% ABS resin.
1 part by weight, 20 parts by weight, 300 parts by weight,
And 700 parts by weight (Comparative Example 6-
1, Inventive Examples 6-2 and 6-3, Comparative Example 6-4).
【0084】得られたABS樹脂組成物の比重、破壊
率、および引張り強さを表4に示した。Table 4 shows the specific gravity, fracture rate and tensile strength of the obtained ABS resin composition.
【0085】なお、比較として軽量化材Cの代わりに熱
可塑性プラスチックバルーン[商品名マツモトマイクロ
スフェアーF80ED,比重0.024,松本樹脂株式
会社製]をABS樹脂100重量部に対し30重量部配
合し、他は上記と同様にして加圧成形し、ABS樹脂成
形物を得た(比較例6−6)。このABS樹脂組成物の
比重、破壊率および引張り強さについても表4に示す。For comparison, instead of the weight-reducing material C, 30 parts by weight of thermoplastic balloon [trade name Matsumoto Microsphere F80ED, specific gravity 0.024, manufactured by Matsumoto Resin Co., Ltd.] was blended with 100 parts by weight of ABS resin. Then, pressure molding was carried out in the same manner as above except that an ABS resin molded product was obtained (Comparative Example 6-6). Table 4 also shows the specific gravity, fracture rate and tensile strength of this ABS resin composition.
【0086】上記の実施例において、不飽和ポリエステ
ル樹脂60重量部およびスチレン40重量部の代わり
に、それぞれ50重量部および50重量部とし、水20
0重量部の代わりに水960重量部として、その他の条
件は同様にして多孔性架橋ポリエステル粒子のスラリー
を作製した。In the above example, instead of 60 parts by weight of unsaturated polyester resin and 40 parts by weight of styrene, 50 parts by weight and 50 parts by weight, respectively, were added, and water 20
Instead of 0 part by weight, 960 parts by weight of water was used, and under the other conditions, a slurry of porous crosslinked polyester particles was prepared.
【0087】この多孔性架橋ポリエステル粒子のスラリ
ーをろ過して、得られたケーキを120℃で1昼夜乾燥
した。この結果、水分0.2%粒子径20〜80μm、
空隙率92%の多孔性架橋ポリエステルビード軽量化材
(以下この軽量化材を「軽量化材D」という)を得た。The slurry of the porous crosslinked polyester particles was filtered, and the obtained cake was dried at 120 ° C. for one day. As a result, the water content is 0.2%, the particle diameter is 20 to 80 μm,
A lightweight material for the porous crosslinked polyester beads having a porosity of 92% (hereinafter, referred to as "lightweight material D") was obtained.
【0088】この軽量化材D5重量部を、ABS樹脂1
00重量部に、180℃で5分間熱ロールで混練した
後、190℃で加圧成形し、比重1.00のABS樹脂
組成物を得た(比較例6−5)。この得られたABS樹
脂組成物についても、その比重、破壊率および引張り強
さを表4に示した。ABS resin 1 was added to 5 parts by weight of this lightweight material D.
100 parts by weight of the mixture was kneaded with a hot roll at 180 ° C. for 5 minutes and then pressure-molded at 190 ° C. to obtain an ABS resin composition having a specific gravity of 1.00 (Comparative Example 6-5). Table 4 shows the specific gravity, fracture rate and tensile strength of the obtained ABS resin composition.
【0089】[0089]
【表4】 [Table 4]
【0090】実施例7 実施例6で得られた軽量化材CをEPDM(商品名EP
−21,日本合成ゴム株式会社製)に配合した。配合量
はEPDM100重量部に対し、それぞれ1重量部、2
0重量部、200重量部、および400重量部となるよ
うに配合した(比較例7−1,本発明例7−2および7
−3,比較例7−4)。またEPDM100重量部に対
し、ZnO5重量部、ステアリン酸1重量部、AccC
Z1重量部、AccTT1.5重量部、AccBZ0.
5重量部、硫黄2重量部、およびプロセスオイル(PW
−380)15重量部を加えて温度60℃でロール混練
した後、160℃で10分間加圧成形し、EPDM軽量
化組成物を得た。Example 7 The lightening material C obtained in Example 6 was used as EPDM (trade name EP
-21, manufactured by Japan Synthetic Rubber Co., Ltd.). The compounding amount is 1 part by weight and 2 parts by weight with respect to 100 parts by weight of EPDM, respectively.
It was blended so as to be 0 parts by weight, 200 parts by weight, and 400 parts by weight (Comparative Example 7-1, Inventive Examples 7-2 and 7).
-3, Comparative Example 7-4). 5 parts by weight of ZnO, 1 part by weight of stearic acid, 100 parts by weight of EPDM, and AccC
Z1 parts by weight, AccTT 1.5 parts by weight, AccBZ0.
5 parts by weight, 2 parts by weight of sulfur, and process oil (PW
-380) 15 parts by weight was added, and the mixture was roll-kneaded at a temperature of 60 ° C., and then pressure-molded at 160 ° C. for 10 minutes to obtain an EPDM lightweight composition.
【0091】得られたEPDM組成物の比重、破壊率お
よび引張り強さを表5に示す。なお、比較として、軽量
化材Cの代わりにシラスバルーン(商品名ウインライ
ト,比重0.45,伊地知化成株式会社製)30重量部
を配合し、上記と同様にしてEPDM組成物を作製した
(比較例7−5)。得られたEPDM組成物の比重、破
壊率および引張り強さを表5に示す。Table 5 shows the specific gravity, fracture rate and tensile strength of the obtained EPDM composition. As a comparison, 30 parts by weight of Shirasu balloon (trade name Winlite, specific gravity 0.45, manufactured by Ichichi Kasei Co., Ltd.) was blended in place of the lightening material C, and an EPDM composition was prepared in the same manner as above ( Comparative Example 7-5). Table 5 shows the specific gravity, fracture rate and tensile strength of the obtained EPDM composition.
【0092】また比較として、配合充填剤を充填してい
ないEPDM組成物を作製した(比較例7−6)。この
EPDM組成物についても、同様に比重、破壊率、およ
び引張り強さを表5に示した。For comparison, an EPDM composition not filled with the compounding filler was prepared (Comparative Example 7-6). The specific gravity, fracture rate and tensile strength of this EPDM composition are also shown in Table 5.
【0093】[0093]
【表5】 [Table 5]
【0094】実施例8 不飽和ポリエステル樹脂の配合量および水の量を適当に
変化させることにより、空隙率が10%から92%まで
の種々の軽量化材を作製し、この軽量化材をABS樹脂
(比重1.05)に配合した。Example 8 Various weight-reducing materials having a porosity of 10% to 92% were produced by appropriately changing the blending amount of unsaturated polyester resin and the amount of water. It was mixed with a resin (specific gravity 1.05).
【0095】配合割合は、ABS樹脂100重量部に対
し軽量化材30重量部とした。得られた組成物の比重を
測定し、組成物の比重と軽量化材の空隙率との関係を図
1に示した。The blending ratio was 30 parts by weight of the lightweight material based on 100 parts by weight of the ABS resin. The specific gravity of the obtained composition was measured, and the relationship between the specific gravity of the composition and the porosity of the lightweight material is shown in FIG.
【0096】図1から明らかなように、軽量化材の空隙
率が30%ぐらいから軽量化効果があらわれ、90%を
越えると急激に軽量化効果が低下することが分かる。As is apparent from FIG. 1, the weight-reducing effect is exhibited when the porosity of the weight-reducing material is about 30%, and the weight-reducing effect is sharply reduced when the porosity exceeds 90%.
【図1】軽量化材の空隙率と、軽量化材を配合した組成
物の比重との関係を示す図である。FIG. 1 is a diagram showing the relationship between the porosity of a lightweight material and the specific gravity of a composition containing the lightweight material.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 C08J 3/24 CFE Z C08K 3/20 C08L 67:00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08J 3/24 CFE Z C08K 3/20 C08L 67:00
Claims (6)
ビニル系単量体とからなる油相中にアルカリ土類金属の
酸化物および/または水酸化物の水懸濁液を分散させて
形成した油中水型エマルジョンを懸濁安定剤の水溶液中
に再分散して架橋硬化させ、これを乾燥させることによ
って得られる、粒子径が5μm〜1mmであり、かつ空
隙率が30〜90容量%である多孔性架橋ポリエステル
ビート軽量化材。1. An aqueous phase of an oxide and / or hydroxide of an alkaline earth metal dispersed in an oil phase composed of an unsaturated polyester and a vinyl monomer capable of crosslinking the polyester. The water-in-oil emulsion is redispersed in an aqueous solution of a suspension stabilizer, crosslinked and cured, and dried to obtain a particle size of 5 μm to 1 mm and a porosity of 30 to 90% by volume. A porous crosslinked polyester beet lightweight material.
対し、請求項1に記載の多孔性架橋ポリエステルビード
軽量化材を5〜1000重量部配合したことを特徴とす
る、不飽和ポリエステル樹脂軽量化組成物。2. An unsaturated polyester resin lightening composition comprising 100 parts by weight of an unsaturated polyester resin and 5 to 1000 parts by weight of the porous crosslinked polyester bead lightweighting material according to claim 1. Stuff.
記載の多孔性架橋ポリエステルビード軽量化材を5〜5
00重量部配合したことを特徴とする、油粘土軽量化組
成物。3. The porous crosslinked polyester bead weight-reducing material according to claim 1 to 5 parts by weight per 100 parts by weight of oil clay.
An oil clay lightening composition, characterized in that it is blended in an amount of 00 parts by weight.
記載の多孔性架橋ポリエステルビード軽量化材を5〜2
00重量部配合したことを特徴とする、接着剤軽量化組
成物。4. The porous cross-linked polyester bead weight-reducing material according to claim 1 to 5 parts by weight per 100 parts by weight of the adhesive.
An adhesive weight-reducing composition, characterized by being compounded in an amount of 00 parts by weight.
項1に記載の多孔性架橋ポリエステルビード軽量化材を
5〜500重量部配合したことを特徴とする、熱可塑性
樹脂軽量化組成物。5. A thermoplastic resin weight-reducing composition, characterized in that 5 to 500 parts by weight of the porous crosslinked polyester bead weight-reducing material according to claim 1 is blended with 100 parts by weight of the thermoplastic resin.
載の多孔性架橋ポリエステルビード軽量化材を5〜30
0重量部配合したことを特徴とする、ゴム軽量化組成
物。6. The porous crosslinked polyester bead weight-reducing material according to claim 1 is added to 5 to 30 parts by weight of rubber.
A rubber weight-reducing composition, characterized by containing 0 part by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3281506A JPH08864B2 (en) | 1991-10-28 | 1991-10-28 | Porous cross-linked polyester bead lightening material and lightening composition containing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3281506A JPH08864B2 (en) | 1991-10-28 | 1991-10-28 | Porous cross-linked polyester bead lightening material and lightening composition containing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05148384A JPH05148384A (en) | 1993-06-15 |
JPH08864B2 true JPH08864B2 (en) | 1996-01-10 |
Family
ID=17640136
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3281506A Expired - Lifetime JPH08864B2 (en) | 1991-10-28 | 1991-10-28 | Porous cross-linked polyester bead lightening material and lightening composition containing the same |
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JP (1) | JPH08864B2 (en) |
Families Citing this family (3)
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---|---|---|---|---|
JP4820010B2 (en) * | 2001-03-09 | 2011-11-24 | 日本ユピカ株式会社 | Porous cured product and method for producing the same |
JP5064299B2 (en) * | 2008-05-26 | 2012-10-31 | 日東電工株式会社 | Method for producing dry powder of porous polymer particles |
US10308804B2 (en) | 2016-07-13 | 2019-06-04 | Illinois Tool Works Inc. | Unsaturated polyester composition for autobody repair with improved adhesion to metal substrates |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS513845B2 (en) * | 1971-10-05 | 1976-02-06 | ||
JPS5026866A (en) * | 1973-04-13 | 1975-03-19 | ||
JPS503170A (en) * | 1973-04-24 | 1975-01-14 | ||
JPS5516163A (en) * | 1978-07-22 | 1980-02-04 | Semedain Kk | Semi-permanent fixing method of lid at manhole and handhole |
-
1991
- 1991-10-28 JP JP3281506A patent/JPH08864B2/en not_active Expired - Lifetime
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