JPS61195134A - Foam of polyamide resin - Google Patents
Foam of polyamide resinInfo
- Publication number
- JPS61195134A JPS61195134A JP3545885A JP3545885A JPS61195134A JP S61195134 A JPS61195134 A JP S61195134A JP 3545885 A JP3545885 A JP 3545885A JP 3545885 A JP3545885 A JP 3545885A JP S61195134 A JPS61195134 A JP S61195134A
- Authority
- JP
- Japan
- Prior art keywords
- nylon
- resin
- foam
- polyamide resin
- blowing agent
- 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.)
- Pending
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、軽量パネル、軽量成形体、断熱材、緩衝材、
クッション材として利用されるポリアミド樹脂発泡体に
関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to lightweight panels, lightweight molded bodies, heat insulating materials, cushioning materials,
The present invention relates to a polyamide resin foam used as a cushioning material.
ポリアミド樹脂発泡体に関しては、その優れた樹脂の性
質を生かす目的で種々の発泡方法が研究されており、例
えば、特公昭51−42145号、特公昭51−344
25号、特公昭39−22214号、特開昭51−50
366号、特開昭51−67366号及び特開昭53−
106770号の公報に開示された技術がある。これら
従来の方法による発泡体は、ナイロン6、ナイロン6.
6、ナイロン11、ナイロン12、ナイロン6.10、
ポリへキサメチレンイソフタラミド、ポリへキサメチレ
ンテレフタラミド、ポリメタキシリレンアジパミド及び
これらの共重合体を基材樹脂として使用するものである
。Regarding polyamide resin foam, various foaming methods have been studied in order to take advantage of the excellent properties of the resin.
No. 25, Japanese Patent Publication No. 39-22214, Japanese Patent Publication No. 51-50
No. 366, JP-A-51-67366 and JP-A-53-
There is a technique disclosed in Publication No. 106770. These conventional foams include nylon 6, nylon 6.
6, nylon 11, nylon 12, nylon 6.10,
Polyhexamethylene isophthalamide, polyhexamethylene terephthalamide, polymethaxylylene adipamide, and copolymers thereof are used as the base resin.
従来技術によるポリアミド樹脂発泡体は、気泡が均質で
なく、局部的に数mmの大きさの空洞が散在し、外観が
悪く、曲げ強さ、衝撃強さ、局部圧縮強さ等物理的性能
が劣り、産業上の使用には不十分なものであった。又、
これら気泡の不均一性を改良するためにポリアミド樹脂
にイオン性共重合体を混合して発泡する方法が特開昭5
3−106770号公報に示されているが、ポリアミド
樹脂本来の耐熱性、耐溶剤性等が劣り、気泡が極度に小
さくなり、気泡壁に部分的にピンホールが生じやすく独
立気泡率の低い発泡体しか得られなかった。Conventional polyamide resin foams have non-homogeneous cells, locally scattered cavities several millimeters in size, poor appearance, and poor physical performance such as bending strength, impact strength, and local compressive strength. It was inferior and unsatisfactory for industrial use. or,
In order to improve the non-uniformity of these bubbles, a method of foaming by mixing an ionic copolymer with a polyamide resin was proposed in JP-A No. 5.
3-106770, polyamide resin's inherent heat resistance, solvent resistance, etc. are poor, the bubbles become extremely small, and pinholes are likely to occur partially on the cell walls, resulting in foaming with a low closed cell ratio. All I got was the body.
本発明の目的は、これら従来の欠点を改良したポリアミ
ド樹脂発泡体、即ち、均質な気泡構造を有し、曲げ強さ
、衝撃強さ、局部圧縮強さ等の物理性能に優れ、耐熱性
、耐溶剤性等に優れたポリアミド樹脂発泡体を提供する
ことである。The object of the present invention is to provide a polyamide resin foam that improves these conventional drawbacks, that is, has a homogeneous cell structure, has excellent physical properties such as bending strength, impact strength, and local compressive strength, and has excellent heat resistance and An object of the present invention is to provide a polyamide resin foam having excellent solvent resistance and the like.
即ち、本発明は、ナイロン4.6樹脂を発泡剤で膨脹さ
せることにより得られる見掛は密度が0.005〜0.
8 g /−の範囲の均質な気泡構造を有するポリアミ
ド樹脂発泡体に関するものである。That is, in the present invention, the apparent density obtained by expanding nylon 4.6 resin with a foaming agent is 0.005-0.
It concerns a polyamide resin foam with a homogeneous cell structure in the range of 8 g/-.
本発明のポリアミド樹脂発泡体は、ナイロン4゜6樹脂
を基材樹脂とするものである。ナイロン4゜6樹脂は、
特開昭56−149430号、特開昭56−14943
1号、及び特開昭58−83029号の公報に記載され
ている方法で重合される樹脂で、1.4−ジアミノブタ
ンとアジピ酸との重縮合反応によって得られる線状ポリ
マーである。The polyamide resin foam of the present invention uses nylon 4°6 resin as a base resin. Nylon 4゜6 resin is
JP-A-56-149430, JP-A-56-14943
It is a linear polymer obtained by the polycondensation reaction of 1,4-diaminobutane and adipic acid.
本発明におけるナイロン4.6樹脂は、硫酸中(濃度0
.5 g /100m1 、25℃)での相対粘度が1
.8以上のものであれば良く、特に2.5以上のものが
、発泡性及び得られた発泡体の物性が優れるため好まし
い。The nylon 4.6 resin in the present invention is prepared in sulfuric acid (concentration 0).
.. 5 g/100m1, relative viscosity at 25°C) is 1
.. It may be 8 or more, and 2.5 or more is particularly preferable because the foamability and the physical properties of the obtained foam are excellent.
本発明のナイロン4.6樹脂は、本発明の目的から外れ
ない範囲で他のポリアミド樹脂のブレンド或いは共重合
により変性させられたものであっても良い。又、工業的
な生産性、特定の物性の改良のために添加する変性樹脂
を含有するものであっても良い。The nylon 4.6 resin of the present invention may be modified by blending or copolymerizing with other polyamide resins without departing from the object of the present invention. Furthermore, it may contain a modified resin added to improve industrial productivity and specific physical properties.
本発明のポリアミド樹脂発泡体は、その見杉)c+重密
度o、oos〜0.8 g /−の範囲のものである。The polyamide resin foam of the present invention has a weight density o, oos to 0.8 g/-.
0.005 g /dより小さい密度を有する発泡体は
、緩iE材、クッション材としての性能が劣るので好ま
しくない、又、0.8g/cjより大きい密度を有する
発泡体は、軽量パネル、軽量成形体としてその効果が著
しく小さく好ましくない。Foams with a density smaller than 0.005 g/d are undesirable because they have poor performance as loose iE materials and cushioning materials, and foams with a density larger than 0.8 g/cj are undesirable for use in lightweight panels and cushioning materials. As a molded product, the effect is extremely small, which is not preferable.
本発明のポリアミド樹脂発泡体は、ナイロン4゜6樹脂
に公知の発泡剤を均一に含有させ、膨脹させることによ
り得られるもので、使用する発泡剤、発泡方法は特に限
定されるものではない0例えば、ナイロン4.6樹脂を
押出機で加熱熔融し、揮発性の低沸点化合物を加圧注入
し樹脂と均一に混合した後、冷却装置により発泡温度ま
で冷却し、低圧系に開口したノズル部から押出し、発泡
させる方法、ナイロン4.6樹脂ペレツトに揮発性の低
沸点化合物を含浸させた発泡性組成物を型に入れて加熱
発泡させる方法、ナイロン4.6樹脂に加熱により分解
してガスを放出する化合物を混合し射出成形、或いは押
出成形により発泡成形する方法等が使用される。The polyamide resin foam of the present invention is obtained by uniformly incorporating a known blowing agent into nylon 4゜6 resin and expanding it, and the blowing agent used and the foaming method are not particularly limited. For example, nylon 4.6 resin is heated and melted in an extruder, a volatile low-boiling compound is injected under pressure and mixed uniformly with the resin, and then cooled to the foaming temperature by a cooling device, and a nozzle part opened to a low-pressure system. A method in which nylon 4.6 resin pellets are impregnated with a volatile low-boiling point compound to form a foaming composition is placed in a mold and foamed by heating, and a method in which nylon 4.6 resin is decomposed by heating to form a gas. A method is used in which a compound that releases a compound is mixed and the mixture is foam-molded by injection molding or extrusion molding.
発泡剤としては、例えばプロパン、ブタン、ペンタン、
ヘキサン等の脂肪族炭化水素、ベンゼン等の芳香族炭化
水素、シクロヘキサン等の脂環族炭化水素、塩化メチル
、塩化メチレン、クロロホルム、塩化エタン、1.2−
ジクロルエタン、1.1−ジクロルエタン等の塩化炭化
水素、モノクロロジフルオロメタン、モノクロロトリフ
ルオロメタン、ジクロロジフルオロメタン、トリクロロ
フルオロメタン、ジクロロテトラフルオロエタン、トリ
クロロトリフルオロエタン、1−クロロ−1,1−ジフ
ルオロエタン、バーフルオロシ゛クロブタン等の塩化・
フッ化炭化水素、メタノール、エタノール等のアルコー
ル、アセトン、メチルエチルケトン等のケトン、エチル
エーテル、石油エーテル等のエーテル、アセトニトリル
等のニトリル等の揮発性低沸点化合物、バリウムアゾジ
カルボキシレート、トリヒドラジノトリアジン、p−ト
ルエンスルホニルセミカルバジド等の分解型発泡剤、蓚
酸ナトリウム、マロン酸カルシウム等金属炭酸塩若しく
は重炭酸塩或いはこれらと燐のオキシ酸との混合物等、
加熱によりガスを発生する化合物等がある。Examples of blowing agents include propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as benzene, alicyclic hydrocarbons such as cyclohexane, methyl chloride, methylene chloride, chloroform, ethane chloride, 1.2-
Chlorinated hydrocarbons such as dichloroethane, 1,1-dichloroethane, monochlorodifluoromethane, monochlorotrifluoromethane, dichlorodifluoromethane, trichlorofluoromethane, dichlorotetrafluoroethane, trichlorotrifluoroethane, 1-chloro-1,1-difluoroethane, bar Chlorinated fluorocyclobutane, etc.
Fluorinated hydrocarbons, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, ethers such as ethyl ether and petroleum ether, nitriles such as acetonitrile, volatile low-boiling compounds, barium azodicarboxylate, trihydrazinotriazine , decomposition type blowing agents such as p-toluenesulfonyl semicarbazide, metal carbonates or bicarbonates such as sodium oxalate and calcium malonate, or mixtures of these with phosphorus oxyacids, etc.
There are compounds that generate gas when heated.
これら発泡剤は単独或いは混合して使用することができ
る。These blowing agents can be used alone or in combination.
これらの発泡剤の内、塩化メチレン、クロロホルム、ト
リクロロフルオロメタン、ジクロロフルオロメタン、ジ
クロロジフルオロメタン、塩化エチル、アセトンから選
ばれた1種以上を含有する発泡剤が特に均質な気泡構造
を持つ見掛は密度0.1g/cd以下の高発泡体を与え
るのに有利である。Among these blowing agents, blowing agents containing one or more selected from methylene chloride, chloroform, trichlorofluoromethane, dichlorofluoromethane, dichlorodifluoromethane, ethyl chloride, and acetone have a particularly homogeneous cell structure. is advantageous in providing a highly foamed product with a density of 0.1 g/cd or less.
本発明のポリアミド樹脂発泡体を製造するにあたり、そ
の目的に応じて着色剤、酸化防止剤、紫外線吸収剤、無
機充填材、核剤、滑剤、帯電防止剤等通常使用される各
種添加剤を添加しても良い。When producing the polyamide resin foam of the present invention, various commonly used additives such as colorants, antioxidants, ultraviolet absorbers, inorganic fillers, nucleating agents, lubricants, and antistatic agents are added depending on the purpose. You may do so.
本発明の発泡体の形状は、その使用目的に応じ糸状、フ
ィルム状、シート状、板状、筒状、粒状であっても良く
、場合により異形成形体、複雑形状成形体であっても良
く、未発泡ないしは密度の異なる複合構造体であっても
良い。The shape of the foam of the present invention may be thread-like, film-like, sheet-like, plate-like, cylindrical, or granular, depending on the purpose of use, and depending on the case, it may be a irregularly shaped body or a complex-shaped molded body. , it may be an unfoamed structure or a composite structure with different densities.
本発明において、ナイロン4.6樹脂からなる発泡体が
、従来から知られているポリアミド樹脂発泡体に比べ、
気泡が均質で機械的、熱的緒特性に優れた発泡体である
理由は必ずしも明らかではないが、ナイロン4.6樹脂
の化学構造から来る発泡剤との親和性、溶解性、溶融状
態から冷却される過程での結晶化挙動、溶融粘弾性挙動
等の熱的挙動が他のポリアミドと異なり発泡に適した特
性範囲にあるためと考えられる。従来このようなナイロ
ン4.6の特殊性は知られていなかった。In the present invention, the foam made of nylon 4.6 resin has a higher
The reason why the cells are homogeneous and has excellent mechanical and thermal characteristics is not necessarily clear, but the chemical structure of nylon 4.6 resin allows for affinity with blowing agents, solubility, and cooling from the molten state. This is thought to be because the thermal behavior such as crystallization behavior and melt viscoelastic behavior during the foaming process is in a range of properties suitable for foaming, unlike other polyamides. Conventionally, such special characteristics of nylon 4.6 were unknown.
以下、本発明を実施例で詳細に説明する。実施例におい
て部とは重量部である。又、発泡体の特性値は以下の方
法により測定したものである。Hereinafter, the present invention will be explained in detail with reference to Examples. In the examples, parts are parts by weight. Further, the characteristic values of the foam were measured by the following method.
(1)発泡体の見掛は密度
JISに6767に記載の方法に準じて、試験片の重量
と体積を測定して求めた。(1) The appearance of the foam was determined by measuring the weight and volume of the test piece according to the method described in Density JIS 6767.
(2)発泡体の気泡径
発泡体試験片を2m−以下の薄片に切断し、10倍に拡
大した投影像の気泡の寸法を測定した。最大気泡径は試
験片中の最大の気泡径、最小の気泡径は最小気泡径の値
であり、平均気泡径はランダムに選んだ30個の気泡に
ついて測定した気泡径の算術平均値である。(2) Cell size of foam The foam test piece was cut into thin pieces of 2 m or less, and the size of the bubbles was measured in a projected image magnified 10 times. The maximum bubble diameter is the maximum bubble diameter in the test piece, the minimum bubble diameter is the minimum bubble diameter, and the average bubble diameter is the arithmetic mean value of the bubble diameters measured for 30 randomly selected bubbles.
(3)独立気泡率
ASTM 02856に記載のエアピラノメータ法によ
り測定した。(3) Closed cell rate Measured by the air pyranometer method described in ASTM 02856.
実施#J 1
1.4−ジアミノブタン及びアジピン酸とから重縮合に
より得たナイロン4.6樹脂(0,5g/100m1濃
度、25℃での硫酸中での相対粘度3.5)を口径4〇
−鵬の押出成形機に供給し、300℃に加熱熔融させ、
押出機先端部に取付けた発泡剤注入口よりジクロロジフ
ルオロメタン10部と塩化メチル5部の混合物を樹脂1
00部当たり15部供給し、加熱用圧下樹脂と均一に混
合し、押出機出口側に接続した冷却装置により250℃
に冷却した後、口径31のノズル孔から大気圧下に吐出
し発泡させた。得られた発泡体は密度0.040 g
/cd、平均気泡径0.6−蒙、最大気泡径1m■、最
小気泡径0.4mm 、独立気泡率85%の均質な気泡
構造を有するものであた。得られた発泡体は弾力性に富
み、曲げた時に局部的な破損による座屈がなく機械的強
度に優れたものであった。又、150℃の高温に96時
間曝露させても収縮、変形等がなく優れた耐熱性を示し
た。Implementation #J 1 Nylon 4.6 resin obtained by polycondensation from 1,4-diaminobutane and adipic acid (concentration 0.5 g/100 ml, relative viscosity 3.5 in sulfuric acid at 25° C.) was 〇-Feed to Peng's extrusion molding machine, heat and melt at 300℃,
A mixture of 10 parts of dichlorodifluoromethane and 5 parts of methyl chloride was added to 1 part of the resin through the blowing agent injection port attached to the tip of the extruder.
15 parts per 100 parts, mixed uniformly with the compressed resin for heating, and heated to 250°C by a cooling device connected to the exit side of the extruder.
After cooling to , the mixture was discharged under atmospheric pressure through a nozzle hole with a diameter of 31 to cause foaming. The resulting foam has a density of 0.040 g
/cd, an average cell diameter of 0.6 mm, a maximum cell diameter of 1 m, a minimum cell diameter of 0.4 mm, and a closed cell ratio of 85%. The obtained foam was highly elastic and had excellent mechanical strength without buckling due to local damage when bent. Further, even when exposed to a high temperature of 150° C. for 96 hours, there was no shrinkage or deformation, and excellent heat resistance was exhibited.
比較例1
実施例1においてポリアミド樹脂をナイロン6(相対粘
度2.3 ”) 、ナイロン6.6(相対粘度2.5)
にそれぞれ変えて同様の方法で発泡させた。その結果を
第1表に示した。Comparative Example 1 In Example 1, the polyamide resins were nylon 6 (relative viscosity 2.3") and nylon 6.6 (relative viscosity 2.5").
Foaming was carried out in the same manner using different methods. The results are shown in Table 1.
(以下余白)
第1表
第1表から、本発明の発泡体が気泡構造が均質で優れた
発泡体であることが明らかである。又、ナイロン6、ナ
イロン6.6の発泡体は曲げると気泡の粗大な部位から
座屈を起こし、かつ、150℃に加熱すると変形を起こ
し物性の劣るものであった。(The following is a blank space) Table 1 From Table 1, it is clear that the foam of the present invention has a homogeneous cell structure and is an excellent foam. In addition, when the foams of nylon 6 and nylon 6.6 are bent, buckling occurs from the coarse portions of the cells, and when heated to 150° C., the foams are deformed and have poor physical properties.
実施例2、比較例2
1.4−ジアミノブタンとアジピン酸とから重縮合によ
り得た種々の相対粘度を有するナイロン4.6樹脂ペレ
ツト(粒径1.5a+m ) 100部と塩化メチレン
200部を攪拌機つきの500ccオートクレーブに入
れ、混合物を120℃で塩化メチレンの蒸気圧下に12
時間攪拌混合した後、室温に冷却してペレットを取り出
した。それぞれの樹脂ペレット中の塩化メチレンの含有
量は第2表のとおりであった。Example 2, Comparative Example 2 100 parts of nylon 4.6 resin pellets (particle size 1.5a+m) having various relative viscosities obtained by polycondensation from 1,4-diaminobutane and adipic acid and 200 parts of methylene chloride were added. The mixture was placed in a 500cc autoclave equipped with a stirrer and heated at 120°C under the vapor pressure of methylene chloride for 12 hours.
After stirring and mixing for a period of time, the mixture was cooled to room temperature and the pellets were taken out. The methylene chloride content in each resin pellet was as shown in Table 2.
得られた発泡性樹脂ペレットをそれぞれ250℃の油浴
中に浸漬し発泡させた。浸漬時間を30秒間隔で変えて
発泡させ、その中の最も高発泡したものの見掛は密度は
第2表のとおりであった。The resulting foamable resin pellets were each immersed in an oil bath at 250°C to foam. The immersion time was varied at 30 second intervals to cause foaming, and the one with the highest foaming had an apparent density as shown in Table 2.
第2表
第2表より相対粘度が1.8以上のナイロン4.6樹脂
が優れた発泡体となることが明らかである。From Table 2, it is clear that nylon 4.6 resin having a relative viscosity of 1.8 or more makes an excellent foam.
本発明のポリアミド樹脂発泡体は、ポリアミド樹脂とし
ての優れた緒特性を具備すると共に、優れた均質な気泡
構造を有する発泡体である。The polyamide resin foam of the present invention is a foam that has excellent elastic properties as a polyamide resin and also has an excellent homogeneous cell structure.
Claims (1)
より得られる見掛け密度が0.005〜0.8g/cm
^3の範囲の均質な気泡構造を有するポリアミド樹脂発
泡体。(1) The apparent density obtained by expanding nylon 4,6 resin with a foaming agent is 0.005 to 0.8 g/cm
Polyamide resin foam with a homogeneous cell structure in the range of ^3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3545885A JPS61195134A (en) | 1985-02-25 | 1985-02-25 | Foam of polyamide resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3545885A JPS61195134A (en) | 1985-02-25 | 1985-02-25 | Foam of polyamide resin |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS61195134A true JPS61195134A (en) | 1986-08-29 |
Family
ID=12442343
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3545885A Pending JPS61195134A (en) | 1985-02-25 | 1985-02-25 | Foam of polyamide resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61195134A (en) |
-
1985
- 1985-02-25 JP JP3545885A patent/JPS61195134A/en active Pending
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