JPH0316976B2 - - Google Patents
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- Publication number
- JPH0316976B2 JPH0316976B2 JP9644083A JP9644083A JPH0316976B2 JP H0316976 B2 JPH0316976 B2 JP H0316976B2 JP 9644083 A JP9644083 A JP 9644083A JP 9644083 A JP9644083 A JP 9644083A JP H0316976 B2 JPH0316976 B2 JP H0316976B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- foam
- resin
- aromatic
- 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
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
【発明の詳細な説明】
本発明は、溶融したポリエステル系樹脂を混入
することを特徴とするポリイミド系樹脂混合フオ
ームの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyimide resin mixed foam, which is characterized by incorporating a molten polyester resin.
芳香族ポリイソシヤネートと芳香族酸無水物或
いは多官能性芳香族カルボン酸とを反応させるこ
とによつてポリイミド系樹脂フオームが生成する
ことは、例えば、米国特許第3300420号公報によ
つて既に明らかであり、更に種々の促進剤或いは
調整剤を加えることによつて、反応が促進される
ことも公知である。このようにして得られたポリ
イミド系フオームは、自消性と共に耐焔性があり
不燃材として有用な用途があるが、脆くそのまま
では使用に不適当であり改良が要望されていた。
本発明は、芳香族ポリイソシヤネートと芳香族酸
無水物、或いは多官能性芳香族カルボン酸とを反
応させてポリイミド系フオームを製造する際、溶
融したポリエステル系樹脂を混入することを特徴
とするポリイミド系樹脂混合フオームの製造方法
である。 It is already clear from, for example, U.S. Pat. No. 3,300,420 that a polyimide resin foam is produced by reacting an aromatic polyisocyanate with an aromatic acid anhydride or a polyfunctional aromatic carboxylic acid. It is also known that the reaction can be accelerated by adding various promoters or regulators. The polyimide foam thus obtained has self-extinguishing properties and flame resistance, and is useful as a noncombustible material, but it is brittle and unsuitable for use as it is, and improvements have been desired.
The present invention is characterized in that when a polyimide foam is produced by reacting an aromatic polyisocyanate with an aromatic acid anhydride or a polyfunctional aromatic carboxylic acid, a molten polyester resin is mixed therein. This is a method for producing a polyimide resin mixed foam.
本発明で使用する芳香族系ポリイソシアネート
とは、少なくとも２個のイソシアネート基を有す
る芳香族化合物にして、少なくとも１個のイソシ
アネート基を有する芳香環を少なくとも２個有す
る化合物を指し、例えば、ジフエニルメタン４，
4′ジイソシアネート（以下MDIと云う）、３，
3′ジメチルジフエニルメタン４，4′ジイソシアネ
ート、キシリレンジイソシアネート等が上げられ
る。 The aromatic polyisocyanate used in the present invention refers to an aromatic compound having at least two isocyanate groups, and a compound having at least two aromatic rings having at least one isocyanate group. For example, diphenylmethane 4 ，
4′ diisocyanate (hereinafter referred to as MDI), 3,
Examples include 3'dimethyldiphenylmethane, 4,4' diisocyanate, and xylylene diisocyanate.
通常、MDIを主体とする粗MDI（以下Ｃ−MDI
という）は常温で固体で毒性が少なく、取り扱い
易い為用いられることが多い。 Usually, crude MDI (hereinafter referred to as C-MDI) mainly consists of MDI.
) is often used because it is solid at room temperature, has little toxicity, and is easy to handle.
芳香族酸無水物或いは多官能性芳香族カルボン
酸としては、例えば無水トリメリツト酸、無水ピ
ロメリツト酸、及びトリメリツト酸、ピロメリツ
ト酸、等がある。芳香族酸無水物或いは多官能性
芳香族カルボン酸は、２種以上混合して用いるこ
とも可能である。耐熱性、自消性及び反応性の点
で無水トリメリツト酸、無水ピロメリツト酸、等
の芳香族酸無水物が好適に用いられる。 Examples of the aromatic acid anhydride or polyfunctional aromatic carboxylic acid include trimellitic anhydride, pyromellitic anhydride, trimellitic acid, pyromellitic acid, and the like. It is also possible to use a mixture of two or more kinds of aromatic acid anhydrides or polyfunctional aromatic carboxylic acids. Aromatic acid anhydrides such as trimellitic anhydride and pyromellitic anhydride are preferably used in terms of heat resistance, self-extinguishing property, and reactivity.
ポリエステル系樹脂は、ポリエチレンテレフタ
レート樹脂、ポリブチレンテレフタレート樹脂の
単体及びそれらの樹脂の共重合体等の熱可塑性ポ
リエステル系樹脂等が上げられる。 Examples of the polyester resin include thermoplastic polyester resins such as polyethylene terephthalate resin, polybutylene terephthalate resin, and copolymers of these resins.
熱可塑性ポリエステル系樹脂は、無水トリメリ
ツト酸、無水ピロメリツト酸、等と反応して溶融
時に粘性を増加する作用があると共に、生成した
ポリイミド系樹脂混合フオームを柔軟なフオーム
にする効果を有する。ポリエステル系樹脂の混合
量は、Ｃ−MDI100重量部に対し14.3重量部〜572
重量部の範囲が望ましく、14.3重量部以下では、
脆さを改善するに至らず、又572重量部以上では、
自消性、耐熱性が著しく低下しポリイミド系樹脂
フオームの特性を失うと共に発泡が阻害されるた
め望ましくない。 The thermoplastic polyester resin has the effect of increasing viscosity when melted by reacting with trimellitic anhydride, pyromellitic anhydride, etc., and also has the effect of making the produced polyimide resin mixed foam into a flexible foam. The amount of polyester resin mixed is 14.3 parts by weight to 572 parts by weight per 100 parts by weight of C-MDI.
The preferred range is 14.3 parts by weight or less.
It does not improve the brittleness, and if it exceeds 572 parts by weight,
This is undesirable because self-extinguishing properties and heat resistance are significantly reduced, the properties of the polyimide resin foam are lost, and foaming is inhibited.
本発明で用いるものには、上記の成分以外に増
量剤或いは気泡調整剤として、超微粉子状の無水
シリカ及び反応を阻害しない限り粉状のアルミ
ナ、タルク等を用いてもよい。特に、BET法に
よつて測定した表面積が130m2／ｇ以上で、且つ
１次粒子の粒径が160ｍμ以下の超微粒子状の無
水シリカを添加した場合は、均一な気泡の発泡体
が得られやすく常用される。又、溶融粘度を増加
させるため、エポキシ樹脂、エポキシ樹脂と脂肪
酸の金属塩を用いてもよい。 In addition to the above-mentioned components, in addition to the above-mentioned components, ultrafine powdered anhydrous silica and powdered alumina, talc, etc. may be used as fillers or bubble control agents as long as they do not inhibit the reaction. In particular, when adding ultrafine anhydrous silica with a surface area of 130 m 2 /g or more and a primary particle size of 160 mμ or less as measured by the BET method, a foam with uniform cells cannot be obtained. Easy and regularly used. Furthermore, in order to increase the melt viscosity, an epoxy resin or a metal salt of an epoxy resin and a fatty acid may be used.
本発明によつて得られるポリエステル系樹脂と
ポリイミド系樹脂との混合フオームは、通常のポ
リウレタン発泡体と同様な用途に用いることが可
能であるが、耐熱性においてポリウレタン発泡体
より格段に優れるため、給湯管、給油管等の屈曲
部の断熱材として使用されて優れたものであり、
上記以外の耐熱性が要求される断熱材用にも使用
される。 The mixed foam of polyester resin and polyimide resin obtained by the present invention can be used for the same purposes as ordinary polyurethane foam, but it has much better heat resistance than polyurethane foam. It is excellent for use as insulation material for bent parts of hot water pipes, oil supply pipes, etc.
It is also used for insulation materials that require heat resistance other than those listed above.
以下に本発明の実施例を詳細に説明する。 Examples of the present invention will be described in detail below.
実施例 １
撹拌機と温度計を備えた反応容器に、ポリエチ
レンテレフタレート樹脂（以下PET樹脂と云う）
（イーストマン・ケミカル社製、KODAR）154.5
重量部を投入し、300℃迄急速に昇温し溶融した。
撹拌しながらＣ−MDI（住友バイエル社製、グレ
ード44V20）100重量部を加え高速で約30秒撹拌
し、無水ピロメリツト酸43.2重量部と超微粒子状
の無水シリカ（日本アエロジル社製、＃380）0.9
重量部の混合物を加え、約７秒間高速で撹拌した
後、撹拌を中止し発泡させた。得られたフオーム
は比重0.032の赤褐色で、強靭なものであつた。Example 1 Polyethylene terephthalate resin (hereinafter referred to as PET resin) was placed in a reaction vessel equipped with a stirrer and a thermometer.
(Manufactured by Eastman Chemical Company, KODAR) 154.5
Part by weight was added, and the temperature was rapidly raised to 300°C to melt it.
While stirring, add 100 parts by weight of C-MDI (manufactured by Sumitomo Bayer, grade 44V20), stir at high speed for about 30 seconds, and add 43.2 parts by weight of pyromellitic anhydride and ultrafine anhydrous silica (manufactured by Nippon Aerosil, #380). 0.9
After adding parts by weight of the mixture and stirring at high speed for about 7 seconds, stirring was stopped to allow foaming. The obtained foam was reddish brown with a specific gravity of 0.032 and was strong.
実施例 ２
PET樹脂を333.1重量部、Ｃ−MDIを100重量
部、無水ピロメリツト酸を43重量部とし、超微粒
子状の無水シリカ1.1重量部を用い実施例１と同
様にして反応させてフオームを得た。比重は
0.039であつた。Example 2 333.1 parts by weight of PET resin, 100 parts by weight of C-MDI, 43 parts by weight of pyromellitic anhydride, and 1.1 parts by weight of ultrafine anhydrous silica were reacted in the same manner as in Example 1 to form a foam. Obtained. The specific gravity is
It was 0.039.
実施例 ３
PET樹脂を571.4重量部、Ｃ−MDIを100重量
部、無水ピロメリツト酸を43重量部とし、超微粒
子状の無水シリカ1.1重量部を用い実施例１と同
様にして反応させてフオームを得た。比重は
0.064であつた。Example 3 571.4 parts by weight of PET resin, 100 parts by weight of C-MDI, 43 parts by weight of pyromellitic anhydride, and 1.1 parts by weight of ultrafine anhydrous silica were reacted in the same manner as in Example 1 to form a foam. Obtained. The specific gravity is
It was 0.064.
実施例 ４
PET樹脂のグレードを鐘淵化学工業(株)社製、
ベルベツトEF−６に変え、該PET樹脂が99重量
部とタルク１重量部からなる配合物を予め押出し
溶融した後、粉砕したものを333重量部と、Ｃ−
MDIを100重量部、無水ピロメリツト酸を43重量
部とし、超微粒子状の無水シリカ1.1重量部を用
い実施例１と同様にして反応させてフオームを得
た。比重は0.051であつた。Example 4 PET resin grade manufactured by Kanebuchi Chemical Industry Co., Ltd.
Instead of Velvet EF-6, a mixture consisting of 99 parts by weight of the PET resin and 1 part by weight of talc was extruded and melted in advance, and then pulverized, and 333 parts by weight of C-
A foam was obtained by reacting 100 parts by weight of MDI, 43 parts by weight of pyromellitic anhydride, and 1.1 parts by weight of ultrafine anhydrous silica in the same manner as in Example 1. The specific gravity was 0.051.
実施例 ５
PET樹脂を実施例４と同様のグレードとし該
PET樹脂が98.4重量部とエポキシ樹脂１重量部と
ステアリン酸カルシユーム0.6重量部からなる配
合物を予め押出し溶融した後、粉砕したものを
333重量部と、Ｃ−MDIを100重量部、無水ピロ
メリツト酸を43重量部とし、超微粒子状の無水シ
リカ1.1重量部を用い実施例１と同様にして反応
させてフオームを得た。比重は0.037であつた。Example 5 The same grade of PET resin as in Example 4 was used.
A mixture consisting of 98.4 parts by weight of PET resin, 1 part by weight of epoxy resin, and 0.6 parts by weight of calcium stearate was extruded and melted in advance, and then pulverized.
333 parts by weight, 100 parts by weight of C-MDI, 43 parts by weight of pyromellitic anhydride, and 1.1 parts by weight of ultrafine anhydrous silica were reacted in the same manner as in Example 1 to obtain a foam. The specific gravity was 0.037.
実施例 ６
PET樹脂を三菱レーヨン製ダイヤナイトKR−
461とし、PET樹脂を357.3重量部、Ｃ−MDIを
100重量部、無水トリメリツト酸を53.3重量部と
し、超微粒子状の無水シリカ1.3重量部を用い実
施例１において、同様にして反応させてフオーム
を得た。比重は0.11であつた。Example 6 PET resin was molded into Mitsubishi Rayon Diamondite KR-
461, 357.3 parts by weight of PET resin, and C-MDI.
A foam was obtained by reacting in the same manner as in Example 1 using 100 parts by weight, 53.3 parts by weight of trimellitic anhydride, and 1.3 parts by weight of ultrafine anhydrous silica. The specific gravity was 0.11.
Claims (1)
或いは多官能性芳香族カルボン酸とを反応させて
ポリイミド系フオームを製造する際、溶融したポ
リエステル系樹脂を混入することを特徴とするポ
リイミド系樹脂混合フオームの製造方法。1. A polyimide resin mixture characterized by mixing a molten polyester resin when producing a polyimide foam by reacting an aromatic polyisocyanate with an aromatic acid anhydride or a polyfunctional aromatic carboxylic acid. Method of manufacturing foam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9644083A JPS59219341A (en) | 1983-05-30 | 1983-05-30 | Production of mixed polyimide resin foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9644083A JPS59219341A (en) | 1983-05-30 | 1983-05-30 | Production of mixed polyimide resin foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59219341A JPS59219341A (en) | 1984-12-10 |
| JPH0316976B2 true JPH0316976B2 (en) | 1991-03-06 |
Family
ID=14165072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9644083A Granted JPS59219341A (en) | 1983-05-30 | 1983-05-30 | Production of mixed polyimide resin foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59219341A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02150434A (en) * | 1988-12-01 | 1990-06-08 | Sekisui Plastics Co Ltd | Production of polyester-based rein foam |
| GB2561573B (en) * | 2017-04-18 | 2023-02-15 | Univ Bath | Air filters |
-
1983
- 1983-05-30 JP JP9644083A patent/JPS59219341A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59219341A (en) | 1984-12-10 |
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