JPH0610273B2 - Expandable copolymer resin particle composition - Google Patents
Expandable copolymer resin particle compositionInfo
- Publication number
- JPH0610273B2 JPH0610273B2 JP62102691A JP10269187A JPH0610273B2 JP H0610273 B2 JPH0610273 B2 JP H0610273B2 JP 62102691 A JP62102691 A JP 62102691A JP 10269187 A JP10269187 A JP 10269187A JP H0610273 B2 JPH0610273 B2 JP H0610273B2
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Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は発泡性共重合体樹脂粒子組成物に関する。さら
に詳しくは耐熱性ことに熱安定性にすぐれた発泡成形体
を得るための発泡性共重合体樹脂粒子組成物に関するも
のである。TECHNICAL FIELD The present invention relates to a foamable copolymer resin particle composition. More specifically, it relates to a foamable copolymer resin particle composition for obtaining a foamed molded article having excellent heat resistance and heat stability.
近年、とみに発泡性成形体に体する耐熱性の要求が高ま
っており、エアーコンディショナーの風洞，自動車のヘ
ットライナー，ドアトリム，インスツルメントパネル等
の構造部材、ソーラー関係の断熱材などに対して、高温
雰囲気下にあって寸法の安定した発泡成形体が求められ
ている。本発明の発泡性共重合体樹脂粒子組成物は主と
してこのような分野において有用なものである。In recent years, there has been an increasing demand for heat resistance of foamable molded bodies. For wind tunnels of air conditioners, automobile headliners, door trims, structural members such as instrument panels, and solar-related heat insulating materials, There is a demand for a foamed molded article having a stable dimension in a high temperature atmosphere. The expandable copolymer resin particle composition of the present invention is useful mainly in such fields.
（従来の技術） ポリスチレン粒子に易揮発性発泡剤を含ませ発泡性ポリ
スチレン粒子とし、これを水蒸気で加熱して予備発泡粒
子とした後金型に充填し再加熱して型内で粒子間を融着
させポリスチレン発泡成形体は広く知られている。しか
して、この発泡成形体は剛性が強く断熱性，保形成が良
い反面、脆弱で耐薬品性，耐油性にも劣る欠点があっ
た。(Prior Art) Polystyrene particles are made into expandable polystyrene particles by adding an easily volatile foaming agent, heated with steam to form pre-expanded particles, and then filled in a mold and reheated so that the space between particles in the mold is Fused polystyrene foam moldings are widely known. Although this foamed molded article has high rigidity and good heat insulation and retention, it is fragile and has poor chemical resistance and oil resistance.
このような欠点を改善するために、ポリスチレンの代わ
りに、アクリロニトリルとスチレン類との共重合体（特
開昭59-204629号公報）やこれに更に改良単量体成分を
含ませた多元共重合体を用いる提案がなされている。こ
のようなスチレン−アクリロニトリル系共重合体類を用
いることにより、基材樹脂自体の耐薬品性等が向上さ
れ、ひいてはこれを原料とする発泡成形体の耐薬品性，
耐油性等が改善されるとされている。In order to improve such a defect, instead of polystyrene, a copolymer of acrylonitrile and styrenes (JP-A-59-204629) or a multi-component copolymer containing further improved monomer components Proposals using coalescing have been made. By using such styrene-acrylonitrile-based copolymers, the chemical resistance and the like of the base resin itself is improved, and by extension, the chemical resistance of the foamed molded product using this as a raw material,
Oil resistance is said to be improved.
（発明が解決しようとする問題点） しかし、このようなスチレン−アクリロニトリル系共重
合体を基材樹脂とする発泡性樹脂粒子を用いて得られた
発泡成形体は、高温環境下（ことに100℃以上）におい
て熱変形を受け易く、ことに、軟化温度の高い基材樹脂
を用いた場合においても、成形体表面に凹凸が発生して
著しく外観が損なわれるという問題があった。そしてか
かる熱変形の発生は外観のみならず、他の材料と貼り合
わせて使用される場合の接着界面での剥離の危険性を招
く点でも問題となる。(Problems to be solved by the invention) However, the foamed molded product obtained by using the expandable resin particles having such a styrene-acrylonitrile-based copolymer as a base resin, has a high temperature environment (especially 100 However, even when a base resin having a high softening temperature is used, there is a problem that irregularities are generated on the surface of the molded product and the appearance is significantly impaired. The occurrence of such thermal deformation poses a problem not only in appearance but also in that there is a risk of peeling at an adhesive interface when used by being bonded to another material.
かかる熱変形ことに凹凸の発生は、主として発泡成形体
中、ことに表面層に存在する残留発泡剤の再発泡により
生ずるものと考えられる。It is considered that such thermal deformation causes unevenness mainly due to refoaming of the residual foaming agent present in the foamed molded product, especially in the surface layer.
そこで本発明者は、表面の再発泡による熱変形ことに表
面の凹凸発生を防止するには、発泡成形中に残っている
発泡剤を減らせば良く、その手段として、予め発泡性樹
脂粒子の表面層付近に無数の微細なひび割れ（以下「微
細クラック」と呼ぶ）を入れ、その予備発泡粒子、さら
に発泡成形体の表面積を飛躍的に増大させて発泡剤の逸
散を促進する点について検討を行った。Therefore, the present inventor can reduce the amount of the foaming agent remaining during foam molding in order to prevent the occurrence of surface irregularities due to thermal deformation due to re-foaming of the surface. A number of fine cracks (hereinafter referred to as "fine cracks") are placed near the layers to study the pre-expanded particles and the point that the surface area of the foamed product is dramatically increased to promote the escape of the blowing agent. went.
従来、ポリスチレン発泡粒子においてこような微細クラ
ックを形成させる方法としては、針を用いた機械的な方
法（特公昭56−19809号公報）やパラフィン油、炭素数1
2〜30の高級脂肪酸のグリセライド等を被覆して成形時
に物理化学的に形成させる方法（特公昭61-18934号公
報）が知られている。Conventionally, as a method of forming such fine cracks in expanded polystyrene particles, a mechanical method using a needle (Japanese Patent Publication No. 56-19809), paraffin oil, carbon number 1
A method is known in which 2 to 30 higher fatty acid glycerides or the like are coated to form physicochemically during molding (Japanese Patent Publication No. 61-18934).
しかし、前者の方法は煩雑で特殊な装置を必要とする点
不利である。また、後者の方法をスチレン−アクリロニ
トリル系共重合体樹脂粒子に適用しても全く効果は現れ
ず、微細クラックを発生させることはできなかった。However, the former method is disadvantageous in that it is complicated and requires a special device. Further, even if the latter method was applied to the styrene-acrylonitrile-based copolymer resin particles, no effect was exhibited, and it was not possible to generate fine cracks.
（問題点を解決するための手段） 本発明者は、かかる状況に鑑み、鋭意研究を重ねた結
果、前者スチレン−アクリロニトリル系共重合体を基材
とする発泡性共重合体樹脂粒子に種々の油脂類のうち特
定の化合物を被覆させることにより、成形時に微細クラ
ックが効率良く発生して発泡剤の残留が防止又は抑制さ
れ、それにより得られた成形体の熱変形ことに表面変形
が著しく防止・抑制される事実を見出した。(Means for Solving Problems) The inventors of the present invention have conducted various studies in view of such circumstances, and as a result, various foamable copolymer resin particles based on the former styrene-acrylonitrile copolymer have been used. By coating a specific compound of oils and fats, fine cracks efficiently occur during molding and the residual foaming agent is prevented or suppressed, and the surface deformation due to thermal deformation of the resulting molded body is significantly prevented.・ We found the fact that it was suppressed.
かくして本発明によれば、アクリロニトリル系単量体残
基15〜40重量％，スチレン系単量体残基40〜85重量％及
び他の重合性単量体残基０〜30重量％より構成される共
重合体を基材樹脂とし、これに易揮発性発泡剤を１〜10
重量％含有してなる発泡性共重合体樹脂粒子の表面及び
／又は表面付近に、グリセリンのＣ6〜Ｃ9脂肪酸エステ
ルを存在させてなる発泡性共重合体粒子組成物が提供さ
れる。Thus, according to the present invention, it is composed of 15-40% by weight of acrylonitrile monomer residue, 40-85% by weight of styrene monomer residue and 0-30% by weight of other polymerizable monomer residue. The base resin is a copolymer of
Provided is an expandable copolymer particle composition in which a C 6 to C 9 fatty acid ester of glycerin is present on the surface and / or in the vicinity of the surface of the expandable copolymer resin particles contained in an amount of 1% by weight.
本発明に用いる共重合体樹脂を構成するアクリロニトリ
ル系単量体としては、アクリロニトリル，メタクリロニ
トリル，α−クロロアクリロニトリル，フマロニトリル
等が挙げられ、特にアクリロニトリルが好ましい。Examples of the acrylonitrile-based monomer constituting the copolymer resin used in the present invention include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like, and acrylonitrile is particularly preferable.
また、スチレン系単量体としては、スチレン，α−メチ
ルスチレン，ｔ−ブチルスチレン，ビニルトルエン，ビ
ニルキシレン，モノクロルスチレン，ジクロルスチレン
等が挙げられるが、特にスチレン及び／又はα−メチル
スチレンが好ましい。Further, examples of the styrene-based monomer include styrene, α-methylstyrene, t-butylstyrene, vinyltoluene, vinylxylene, monochlorostyrene, dichlorostyrene, and the like, but particularly styrene and / or α-methylstyrene. preferable.
一方、他の共重合可能な単量体としては、Ｎ−ラウリル
マレイミド，Ｎ−シクロヘキシルマレイミド，Ｎ−フェ
ニルマレイミド，Ｎ−メチルフェニルマレイミド，Ｎ−
ナフチルマレイミド，ビスマレイミド等のマレイミド系
単量体、メチルアクリレート，エチルアクリレート，ブ
チルアクリレート等のアクリレート系単量体、メチルメ
タクリレート，エチルメタクリレート等のメタクリレー
ト系単量体、アルリル酸，メタクリル酸等のビニルカル
ボン酸系単量体等が挙げられる。On the other hand, other copolymerizable monomers include N-lauryl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-methylphenyl maleimide, N-
Maleimide-based monomers such as naphthylmaleimide and bismaleimide; acrylate-based monomers such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylate-based monomers such as methyl methacrylate and ethyl methacrylate; vinyl such as allyl acid and methacrylic acid. Examples thereof include carboxylic acid type monomers.
これらの各単量体はそれぞれ２種以上用いられてもよ
い。Two or more kinds of each of these monomers may be used.
各単量体の共重合比は、得られた共重合体中のアクリロ
ニトリル系単量体残基が15〜40重量％、スチレン系単量
体残基が40〜85重量％及び他の重合性単量体残基が0〜3
0重量％となるように調整するのが適している。ここで
アクリロニトリル系単量体残基が少なすぎると、脆弱
さ，耐薬品性，耐油性等が不充分となり好ましくない。
一方、スチレン系単量体残基が少なすぎると発泡剤の保
持性が低下して高発泡倍率の成形体が得られず好ましく
ない。他の重合性単量体残基は必要に応じて共重合体の
物性を改良するために用いられ、せいぜい30重量％で充
分である。とくに、この重合性単量体として前記したマ
レイミド系単量体のうち、Ｎ−フェニルマレイミド等の
Ｎ−置換芳香族マレイミドを用いた場合には、基材樹脂
自体の軟化温度を著しく上昇でき、本願発明の効果とも
相俟って120℃程度の高温環境下においても成形体に優
れた寸法安定性，表面安定性を付与することができる。
この際のマレイミド系単量体残基の量としては0.5〜30
重量％が適しており、特に5〜20重量％が好ましい。The copolymerization ratio of each monomer is 15-40% by weight of the acrylonitrile-based monomer residue, 40-85% by weight of the styrene-based monomer residue in the obtained copolymer, and other polymerizability. 0 to 3 monomer residues
It is suitable to adjust to 0% by weight. If the amount of the acrylonitrile-based monomer residue is too small, the brittleness, chemical resistance, oil resistance and the like are insufficient, which is not preferable.
On the other hand, when the amount of the styrene-based monomer residue is too small, the retention of the foaming agent is lowered and a molded product having a high expansion ratio cannot be obtained, which is not preferable. Other polymerizable monomer residues are used to improve the physical properties of the copolymer as necessary, and 30% by weight is sufficient at most. Particularly, when N-substituted aromatic maleimide such as N-phenylmaleimide is used among the above-mentioned maleimide-based monomers as the polymerizable monomer, the softening temperature of the base resin itself can be remarkably increased. In combination with the effects of the present invention, it is possible to impart excellent dimensional stability and surface stability to a molded product even in a high temperature environment of about 120 ° C.
At this time, the amount of maleimide monomer residue is 0.5 to 30.
% By weight is suitable, particularly preferably 5 to 20% by weight.
本発明の基材となる共重合体樹脂粒子は、塊状−懸濁重
合，溶液重合，懸濁重合又は乳化重合等の方法で製造す
ることができるが、特に球状の樹脂粒子が簡便に得られ
る事から懸濁重合法が好ましい。The copolymer resin particles as the base material of the present invention can be produced by a method such as bulk-suspension polymerization, solution polymerization, suspension polymerization or emulsion polymerization, but particularly spherical resin particles can be easily obtained. Therefore, the suspension polymerization method is preferable.
懸濁重合法に使用できる分散剤としては、例えば部分鹸
化ポリビニルアルコール、ポリアクリル酸塩、ポリビニ
ルピロリドン、カルボキシメチルセルロース、メチルセ
ルロース等の有機化合物の他、ピロリン酸カルシウム、
リン酸カルシウム、炭酸カルシウム、リン酸マグネシウ
ム、ピロリン酸マグネシウム、酸化マグネシウム等の水
に難溶性の微粉末からなる無機化合物を挙げることがで
きる。分散剤として無機化合物を用いる際には、ドデシ
ルベンゼンスルフォン酸ソーダ等の界面活性剤を併用す
ることが好ましい。As the dispersant that can be used in the suspension polymerization method, for example, partially saponified polyvinyl alcohol, polyacrylate, polyvinylpyrrolidone, carboxymethylcellulose, other organic compounds such as methylcellulose, calcium pyrophosphate,
Examples of the inorganic compound include fine powders which are hardly soluble in water, such as calcium phosphate, calcium carbonate, magnesium phosphate, magnesium pyrophosphate, and magnesium oxide. When an inorganic compound is used as the dispersant, it is preferable to use a surfactant such as sodium dodecylbenzene sulfonate together.
また、上記重合法における重合開始剤は通常のポリスチ
レンの重合に使用されているもので良く、例えばベンゾ
イルパーオキサイド、ターシャリーブチルパーオキシベ
ンゾエート、ラウロイルパーオキサイド、ターシャリー
ブチルパーオキシイソブチレート、ターシャリーブチル
パーオキシラウレート、ターシャリーブチルパーオキサ
イド等の有機過酸化物、アゾビスイソブチロニトリル、
アゾビスジメチルバレロニトリル度のアゾ化合物等が挙
げられる。Further, the polymerization initiator in the above-mentioned polymerization method may be one used in the usual polymerization of polystyrene, for example, benzoyl peroxide, tertiary butyl peroxybenzoate, lauroyl peroxide, tertiary butyl peroxyisobutyrate, tertiary Organic peroxides such as butyl peroxylaurate, tertiary butyl peroxide, azobisisobutyronitrile,
Examples thereof include azo compounds having an azobisdimethylvaleronitrile degree.
重合処理は60〜140℃の温度で2〜20時間加熱することに
より行うのが適している。The polymerization treatment is suitably carried out by heating at a temperature of 60 to 140 ° C for 2 to 20 hours.
その他の重合条件については公知の条件を準用すること
ができる。Known conditions can be applied correspondingly to the other polymerization conditions.
また、上記共重合体樹脂粒子への発泡剤の含有は、樹脂
粒子を懸濁液に懸濁させた状態でこれに易揮発性発泡剤
を添加するか、上記懸濁重合途中に懸濁液中に易揮発性
発泡剤を添加することによって行うことができる。Further, the inclusion of the foaming agent in the copolymer resin particles, the easily volatile foaming agent is added to the resin particles suspended in the suspension, or the suspension during the suspension polymerization. It can be carried out by adding an easily volatile foaming agent therein.
易揮発性発泡剤としては、プロパン、ｎ−ブタン、ｉ−
ブタン、ｎ−ペンタン、ｉ−ペンタン、ｎ−ヘキサン等
の脂肪族炭化水素、メチルクロライド、エチルクロライ
ド、ジクロロジフルオロメタン、トリクロロフルオロメ
タン等のハロゲン化炭化水素を挙げることができ、好ま
しくはｎ−ブタン、ｉ−ブタンである。これらの易揮発
性発泡剤は単独に又は２種以上混合して使用でき、樹脂
粒子に対して１〜10重量％割合で含有するようにして使
用される。Examples of the easily volatile foaming agent include propane, n-butane, i-
Examples thereof include aliphatic hydrocarbons such as butane, n-pentane, i-pentane and n-hexane, and halogenated hydrocarbons such as methyl chloride, ethyl chloride, dichlorodifluoromethane and trichlorofluoromethane, and preferably n-butane. , I-butane. These easily volatile foaming agents can be used alone or as a mixture of two or more kinds, and are used so as to be contained in a ratio of 1 to 10% by weight with respect to the resin particles.
なお、このようにして得られる発泡性共重合体樹脂粒子
中には、他の成分、例えば、酸化防止剤、紫外線吸収
剤、着色剤等の種々の添加剤が任意に含まれていてもよ
い。The expandable copolymer resin particles thus obtained may optionally contain other components, for example, various additives such as an antioxidant, an ultraviolet absorber and a colorant. .
以上述べた発泡性共重合体樹脂粒子にグリセリンのＣ6
〜Ｃ9脂肪酸エステルを被覆処理させることにより本発
明の発泡性共重合体樹脂粒子組成物が得られる。ここで
用いるグリセリンのＣ6〜Ｃ9脂肪酸エステルとしては、
グリセリンカプリル酸エステルが好ましく、グリセリン
トリカプリル酸エステルがより好ましい。このようなグ
リセリンＣ6〜Ｃ9脂肪酸エステルの使用量は、発泡性共
重合体樹脂粒子に対して0.001〜0.5重量％が好ましい。
0.001重量％未満では、微細クラックを発生させる効果
は少なく、0.5重量％を超過すると微細クラックの発生
効果は飽和になり経済性の点で不利であると共に発泡性
共重合体樹脂粒子が互いにベトツキ状態となるので、予
備発泡機の計量ホッパー等への搬送は困難となり、実質
上連続状態での予備発泡操作はできなくなるため好まし
くない。C 6 of glycerin above-mentioned foamable copolymer resin particles
The foamable copolymer resin particle composition of the present invention can be obtained by coating with a C 9 fatty acid ester. As the C 6 to C 9 fatty acid ester of glycerin used here,
Glycerin caprylic acid ester is preferable, and glycerin tricaprylic acid ester is more preferable. The amount of the glycerin C 6 to C 9 fatty acid ester used is preferably 0.001 to 0.5% by weight based on the expandable copolymer resin particles.
If it is less than 0.001% by weight, the effect of generating fine cracks is small, and if it exceeds 0.5% by weight, the effect of generating fine cracks is saturated, which is disadvantageous in terms of economy, and the expandable copolymer resin particles are in a sticky state with each other. Therefore, it becomes difficult to convey the pre-foaming machine to a weighing hopper or the like, and the pre-foaming operation in a substantially continuous state cannot be performed, which is not preferable.
なお、用いるグリセリンのＣ6〜Ｃ9脂肪酸エステルは混
合脂肪酸エステルであってもよく、また、少なくともこ
の脂肪酸エステルが上記量含まれておれば、他の高級脂
肪酸エステルを含有する混合脂肪酸エステルの形態で用
いられていてもよい。Incidentally, C 6 -C 9 fatty acid esters of glycerin used may be a mixed fatty acid ester, also, at least if the fatty ester is I contains amounts above, the form of the mixed fatty acid esters containing other higher fatty acid esters May be used in.
上記被覆処理する方法には特に制限はなく、例えば、連
続式もしくは回分式の混合機中で発泡性共重合体樹脂粒
子と上記エステルを流動混合する方法、発泡性共重合体
樹脂粒子を耐圧容器中で懸濁重合状態で製造する際、そ
の工程で懸濁液中に上記エステルを分散させて付着させ
る方法などで行えばよい。これにより、グリセリン脂肪
酸エステルは樹脂粒子の表面及び／又は表面付近（表面
層内）に含有されることとなる。The method of coating treatment is not particularly limited, for example, a method of fluidly mixing the expandable copolymer resin particles and the ester in a continuous or batch mixer, a pressure resistant container for the expandable copolymer resin particles. In the case of production in the suspension polymerization state, the method may be carried out by a method of dispersing and adhering the above ester in the suspension at that step. As a result, the glycerin fatty acid ester is contained on the surface of the resin particles and / or near the surface (inside the surface layer).
（作 用） グリセリンのＣ6〜Ｃ9脂肪酸エステルの存在で成形時に
微細クラックが発生し、表面積が飛躍的に増大した発泡
成形体が得られる。そのため発泡成形体は、成形中、成
形後を通じて発泡剤の逸散性が良好となり、結局発泡成
形体中に残留する発泡剤は非常に少ないものとなる。Fine cracks during molding occurs in the presence of a C 6 -C 9 fatty acid esters of (created for) glycerol, foamed molded article obtained surface area is greatly increased. Therefore, in the foamed molded product, the dispersibility of the foaming agent is improved throughout the molding and after the molding, and the amount of the foaming agent remaining in the foamed molded product is extremely small.
また、グリセリンのＣ6〜Ｃ9脂肪酸エステルの存在で予
備発泡時に粒子同士が結合することもなく、しかも発泡
成形時の融着も悪化させることもない。It no binding between the particles during prefoaming in the presence of a C 6 -C 9 fatty acid esters of glycerol, yet also fused during foam molding never worsen.
（実施例） 実施例１ 発泡性共重合体樹脂粒子としては、a)アクリロニトリル
20重量％、スチレン80重量％を単量体組成として構成さ
れ、b)100ml中1gのテトラヒドロフラン溶液で温度30±
0.2℃の条件下、オストワルド粘度計にて測定した比粘
度ηspが1.12である共重合体樹脂粒子（粒子径は0.7〜
1.0mm）に発泡剤として、ブタンを3.9重量％含有してい
るものを用いた。(Example) Example 1 As the expandable copolymer resin particles, a) acrylonitrile was used.
It is composed of 20% by weight and 80% by weight of styrene as a monomer composition.
Copolymer resin particles having a specific viscosity ηsp of 1.12 measured with an Ostwald viscometer (particle size of 0.7 to
A foaming agent containing 1.0% of butane and 3.9% by weight of butane was used.
そこで、グリセリントリカプリル酸エステルを上記発泡
性共重合体樹脂粒子に対して0.10重量％混合して、ポリ
エチレン袋に入れて充分に振り、発泡性共重合体樹脂粒
子の表面処理を行い本発明の試料（発泡性共重合体樹脂
粒子組成物）を作製した。Therefore, 0.10% by weight of glycerin tricaprylate is mixed with the expandable copolymer resin particles, and the mixture is put in a polyethylene bag and shaken well to perform surface treatment of the expandable copolymer resin particles. A sample (foamable copolymer resin particle composition) was prepared.
次に、バッチ式発泡機によって、この試料700ｇを水蒸
気で加熱し、カサ倍率10倍に予備発泡させ、粒子表面に
おける微細クラックの発生の有無をルーペで調べその
後、閉鎖型の金型（400×200×10mm）に充填し水蒸気で
再び加熱することにより板状の発泡成形体を得た。Next, 700 g of this sample was heated with steam using a batch type foaming machine to pre-foam with a bulk ratio of 10 times, and the presence or absence of fine cracks on the particle surface was examined with a magnifying glass and then closed mold (400 x It was filled in 200 × 10 mm) and heated again with steam to obtain a plate-shaped foam molded article.
ここで得られた発泡成形体を60℃の乾燥室内で４時間乾
燥した後、ガスクロマトグラフで残存する発泡剤（ブタ
ン）の量を調べた。The foamed molded product obtained here was dried in a drying chamber at 60 ° C. for 4 hours, and then the amount of the remaining foaming agent (butane) was examined by gas chromatography.
また耐熱試験として85℃の熱風循環式恒温槽内に24時間
放置し、発泡成形体表面における、再発泡による凹凸の
状態を調べた。Further, as a heat resistance test, it was left in a hot air circulation type constant temperature bath at 85 ° C. for 24 hours, and the state of unevenness due to refoaming on the surface of the foamed molded product was examined.
測定結果を表１に示す。The measurement results are shown in Table 1.
実施例２ 発泡性共重合体樹脂体粒子としては、a)アクリロニトリ
ル30重量％、α−メチルスチレン70重量％を単量体組成
として構成され、b)100ml中1gのテトラヒドロフラン溶
液で温度30℃±0.2℃の条件下、オスワルド粘度計にて
測定した比粘度ηspが0.811である共重合体樹脂粒子
（粒子径は0.7〜1.0mm）に発泡剤としてブタン3.7重量
％含有しているものを用い、耐熱試験の温度を105℃と
した以外は実施例１と同様にして評価を行った。Example 2 As the expandable copolymer resin particles, a) 30% by weight of acrylonitrile and 70% by weight of α-methylstyrene were used as a monomer composition, and b) a solution of 1 g of tetrahydrofuran in 100 ml was used at a temperature of 30 ° C ±. Under conditions of 0.2 ℃, using a butane 3.7 wt% as a foaming agent in the copolymer resin particles (particle size 0.7 ~ 1.0 mm) having a specific viscosity ηsp measured by an Oswald viscometer of 0.811, Evaluation was performed in the same manner as in Example 1 except that the temperature of the heat resistance test was 105 ° C.
測定結果を表１に示す。The measurement results are shown in Table 1.
実施例３ 発泡性共重合体樹脂粒子としては、a)アクリロニトリル
25重量％、α−メチルスチレン65重量％、Ｎ−フェニル
マレイミド10重量％を単量体組成として構成され、b)10
0ml中1gのテトラヒドロフラン溶液で温度30℃±0.2℃の
条件下、オストワルド粘度計にて測定した比粘度ηspが
0.564であり、且つc)常圧沸点100℃以上の溶剤成分量が
0.47重量％であるＮ−置換マレイミド系共重合樹脂粒子
（粒子径は0.7〜1.0mm）に発泡剤としてブタンを3.6重
量％含有しているものを用い、耐熱試験の温度を115℃
として以外は実施例１と同様にして作業を行った。測定
結果を表１に示す。Example 3 As the expandable copolymer resin particles, a) acrylonitrile was used.
25% by weight, 65% by weight of α-methylstyrene, 10% by weight of N-phenylmaleimide as a monomer composition, and b) 10
The specific viscosity ηsp measured with an Ostwald viscometer under the condition of a temperature of 30 ° C ± 0.2 ° C with 1 g of tetrahydrofuran solution in 0 ml is
0.564, and c) the amount of solvent component having a boiling point of 100 ° C or higher at atmospheric pressure
0.47% by weight of N-substituted maleimide copolymer resin particles (particle diameter is 0.7 to 1.0 mm) containing 3.6% by weight of butane as a foaming agent, and the heat resistance test temperature is 115 ° C.
Operations were performed in the same manner as in Example 1 except for the above. The measurement results are shown in Table 1.
実施例４，５ 実施例３においてグリセリントリカプリル酸エステルの
量を各々0.05重量％（実施例４）、0.30重量％（実施例
５）とした以外、同様にして本発明の発泡性共重合体樹
脂粒子組成物を作製した。Examples 4 and 5 In the same manner as in Example 3, except that the amounts of glycerin tricaprylic acid ester were 0.05% by weight (Example 4) and 0.30% by weight (Example 5), respectively, the foamable copolymer of the present invention was obtained. A resin particle composition was prepared.
測定結果をまとめて表１に示す。The measurement results are summarized in Table 1.
比較例１，２，３ 実施例１，２，３においてそれぞれグリセリントリカプ
リル酸エステルを使用しなかった以外、同様の作業を行
った。Comparative Examples 1, 2, 3 The same operation was performed except that glycerin tricaprylic acid ester was not used in Examples 1, 2, and 3, respectively.
測定結果をまとめて表２に示す。The measurement results are summarized in Table 2.
比較例４〜９ 実施例３において、グリセリントリカプリル酸エステル
のかわりに表２に示した添加化合物をそれぞれ0.10重量
％使用した。Comparative Examples 4 to 9 In Example 3, 0.10% by weight of the additive compound shown in Table 2 was used instead of the glycerin tricaprylic acid ester.
測定結果をまとめて表２に示した。The measurement results are summarized in Table 2.
比較例１０ 100ml中1gのトルエン溶液の30±0.2℃における比粘度が
1.22で、且つその粒径が0.7〜1.0mmのポリスチレン樹脂
粒子に発泡剤としてブタンを4.3重量％含有しているも
のを発泡性樹脂粒子として用いた以外は実施例１と同様
にして評価を行った。Comparative Example 10 The specific viscosity of 1 g of a toluene solution in 100 ml at 30 ± 0.2 ° C.
Evaluation was conducted in the same manner as in Example 1 except that polystyrene resin particles having a particle diameter of 0.7 to 1.0 mm and containing butane at 4.3 wt% as a foaming agent were used as the expandable resin particles. It was
ところが予備発泡において、カサ倍率6.1倍までしか発
泡せず、また成形においても予備発泡粒子同志が接着せ
ず全く発泡成形体は得られなかった。However, in the pre-expansion, the expansion ratio was up to 6.1 times, and the pre-expanded particles did not adhere to each other in the molding, so that the foam-molded article could not be obtained at all.
（発明の効果） 本発明の発泡性共重合体樹脂粒子組成物を用いて成形し
た発泡成形体は、単なるスチレン−アクリロニトリル系
共重合体樹脂からなる発泡性樹脂粒子を用いて成型した
ものに比して、高温環境下における耐熱変形性ことに表
面安定性に優れ、ことに成形体としての熱許容温度を5
〜10℃程度も向上させることができる。 (Effect of the Invention) The foamed molded product molded using the expandable copolymer resin particle composition of the present invention has a higher ratio than that molded using the expandable resin particles made of a simple styrene-acrylonitrile copolymer resin. In addition, it has excellent heat distortion resistance in a high temperature environment and excellent surface stability.
It can be improved up to about 10 ° C.
従って、種々の耐熱性を要求される成形品を製造する原
料として極めて有用なものである。Therefore, it is extremely useful as a raw material for producing molded products that require various heat resistances.
Claims (5)
％，スチレン系単量体残基40〜85重量％及びその他の重
合性単量体残基0〜30重量％より構成される共重合体を
基材樹脂とし、これに易揮発性発泡剤を1〜10重量％含
有してなる発泡性共重合体樹脂粒子の表面及び／又は表
面付近に、グリセリンのＣ6〜Ｃ9脂肪酸エステルを存在
させてなる発泡性共重合体樹脂粒子組成物。1. A copolymer composed of 15-40% by weight of acrylonitrile-based monomer residues, 40-85% by weight of styrene-based monomer residues and 0-30% by weight of other polymerizable monomer residues. A C 6 to C 9 fatty acid ester of glycerin is formed on the surface and / or near the surface of the expandable copolymer resin particles containing a polymer as a base resin and an easily volatile foaming agent in an amount of 1 to 10% by weight. A foamable copolymer resin particle composition in which the above is present.
リセリンカプリル酸エステルである特許請求の範囲第１
項記載の樹脂粒子組成物。2. The C 6 -C 9 fatty acid ester of glycerin is glycerin caprylic acid ester.
The resin particle composition according to the item.
発泡性樹脂粒子に対して0.001〜0.5重量％用いられる特
許請求の範囲第１項記載の樹脂粒子組成物。3. A C 6 -C 9 fatty acid ester of glycerin,
The resin particle composition according to claim 1, which is used in an amount of 0.001 to 0.5% by weight based on the expandable resin particles.
−メチルスチレンである特許請求の範囲第１項記載の樹
脂粒子組成物。4. The styrene-based monomer is styrene and / or α
-The resin particle composition according to claim 1, which is methylstyrene.
トリルである特許請求の範囲第１項記載の樹脂粒子組成
物。5. The resin particle composition according to claim 1, wherein the acrylonitrile-based monomer is acrylonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62102691A JPH0610273B2 (en) | 1987-04-24 | 1987-04-24 | Expandable copolymer resin particle composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62102691A JPH0610273B2 (en) | 1987-04-24 | 1987-04-24 | Expandable copolymer resin particle composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63268749A JPS63268749A (en) | 1988-11-07 |
| JPH0610273B2 true JPH0610273B2 (en) | 1994-02-09 |
Family
ID=14334275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62102691A Expired - Lifetime JPH0610273B2 (en) | 1987-04-24 | 1987-04-24 | Expandable copolymer resin particle composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0610273B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2468916T3 (en) | 2011-08-31 | 2014-06-17 | Basf Se | Coated expandable polymer particles |
| DE102012217659A1 (en) | 2012-09-27 | 2014-03-27 | Basf Se | Expandable polymer particle useful for producing foam molded part or block of foam which is useful in e.g. furniture, construction and stand construction automotive industry, comprises polymerized styrene and/or alpha-methyl styrene |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5856568B2 (en) * | 1977-02-04 | 1983-12-15 | 日立化成工業株式会社 | Novel expandable styrenic resin particles and their manufacturing method |
| JPS5511135A (en) * | 1978-07-10 | 1980-01-25 | Hitachi Ltd | High strength, strain-inducing alloy for power or displacement transducer and manufacture thereof |
| JPS56112944A (en) * | 1980-02-14 | 1981-09-05 | Badische Yuka Co Ltd | Expandable styrene resin particle |
-
1987
- 1987-04-24 JP JP62102691A patent/JPH0610273B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63268749A (en) | 1988-11-07 |
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