JPH0761679B2 - Cement structure composed of polyacetal - Google Patents
Cement structure composed of polyacetalInfo
- Publication number
- JPH0761679B2 JPH0761679B2 JP61127189A JP12718986A JPH0761679B2 JP H0761679 B2 JPH0761679 B2 JP H0761679B2 JP 61127189 A JP61127189 A JP 61127189A JP 12718986 A JP12718986 A JP 12718986A JP H0761679 B2 JPH0761679 B2 JP H0761679B2
- Authority
- JP
- Japan
- Prior art keywords
- polyacetal
- resistance
- stretching
- pressure
- present
- 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 - Fee Related
Links
- 229920006324 polyoxymethylene Polymers 0.000 title claims description 30
- 229930182556 Polyacetal Natural products 0.000 title claims description 29
- 239000004568 cement Substances 0.000 title claims description 13
- 239000003513 alkali Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 description 15
- 206010061592 cardiac fibrillation Diseases 0.000 description 13
- 230000002600 fibrillogenic effect Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000012530 fluid Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000012778 molding material Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polyoxymethylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacturing Of Tubular Articles Or Embedded Moulded Articles (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、耐薬品性、特に、耐アルカリ性に優れたポリ
アセタールの延伸体をセメントに複合したセメント構造
物に関する。本発明は、セメントとの複合材、例えば、
建築物、海洋構築物、漁しょう、道路などに用いること
ができる。TECHNICAL FIELD The present invention relates to a cement structure in which a stretched body of polyacetal having excellent chemical resistance, particularly alkali resistance, is combined with cement. The present invention is a composite material with cement, for example,
It can be used for buildings, marine structures, fishing boats, roads, etc.
従来、熱可塑性プラスチックを配向化して強度、弾性
率、熱安定性を改良する試みがなされている。比較的配
向化の容易なポリアセタールの場合も同様である。例え
ば、このような方法として、常圧下で加熱しながら２段
階で延伸する方法〔「ポリマー・エンジニアリング・ア
ンド・サイエンス（poly.Eng.＆Sci.）」，第14巻，第1
0巻，第682頁〕、誘電加熱下に超延伸を行う方法（特開
昭57−208216号公報）などがある。これらの方法によれ
ば、ポリアセタールの高強度、高弾性率、低熱収縮率化
は達成できるが、延伸中にフィブリル化を起こし、ボイ
ドが発生する。Heretofore, attempts have been made to orient thermoplastics to improve strength, elastic modulus and thermal stability. The same applies to the case of polyacetal, which is relatively easily oriented. For example, as such a method, a method of stretching in two steps while heating under normal pressure ["Polymer Engineering & Science (poly.Eng. &Sci.)", Volume 14, Volume 1
0, page 682], a method of performing super-stretching under dielectric heating (JP-A-57-208216) and the like. According to these methods, high strength, high elastic modulus and low heat shrinkage of polyacetal can be achieved, but fibrillation occurs during stretching and voids are generated.
本発明者らの実験によれば、フィブリル化とボイドの発
生は、常圧下での延伸において普通にみられる現象であ
り、ポリアセタールの場合、延伸倍率が10倍以上でフィ
ブリル化と失透が始まり、15倍以上で白化し、20倍以上
で白化と毛羽立ちが顕著になり、25〜30倍においてささ
くれと座屈が起こる。一般に耐薬品性は、延伸すると向
上するが、これは、配向することで薬品の作用を受けに
くい結晶部分が増すためと考えられる。しかし、15倍以
上になると、フィブリル化の影響が大きくなり、耐薬品
性はあまり改善されない。そして、フィブリル化とボイ
ドを多く含むほど耐薬品性は低い。また、延伸倍率が15
倍では、引張強度が1.2GPa、引張弾性率が25GPaであ
り、実用的に不足するという問題もある。According to the experiments conducted by the present inventors, fibrillation and generation of voids are phenomena commonly observed in stretching under normal pressure, and in the case of polyacetal, fibrillation and devitrification start at a stretching ratio of 10 times or more. , 15 times or more, whitening, 20 times or more, whitening and fluffing become noticeable, and 25 to 30 times wrinkling and buckling occur. Generally, the chemical resistance is improved by stretching, but it is considered that this is because the crystal parts which are not easily affected by the chemical increase due to the orientation. However, if it exceeds 15 times, the effect of fibrillation becomes large and the chemical resistance is not improved so much. And, the more the fibrillation and the more voids are contained, the lower the chemical resistance is. Also, the draw ratio is 15
If doubled, the tensile strength is 1.2 GPa and the tensile elastic modulus is 25 GPa, which is a problem in that it is practically insufficient.
以上のように、これまでの方法では、高い耐薬品性と、
高強度、高弾性率を共に満足するポリアセタール延伸体
を得ることができなかった。すなわち、従来のポリアセ
タール延伸体は、耐アルカリ性が低いという問題があっ
たので、高い耐アルカリ性と高強度、高弾性率を必要と
するセメントの複合材には不適当であり、セメントと複
合するという実例は皆無であった。As described above, in the conventional methods, high chemical resistance and
It was not possible to obtain a polyacetal stretched product that satisfies both high strength and high elastic modulus. That is, since the conventional polyacetal stretched product has a problem of low alkali resistance, it is unsuitable for a cement composite material that requires high alkali resistance, high strength, and high elastic modulus, and is said to be combined with cement. There were no examples.
このような事情のもとで、本発明者らは、鋭意研究を重
ねた結果、高い耐薬品性と高強度・高弾性率をポリアセ
タールを得るには、フイブリル化を抑制しながら15倍以
上に高延伸する必要があることを見い出した。一方、本
発明者らは、先に、延伸中に生じるフイブリル化の抑制
と10倍以上の高延伸を達成することで、高密度・高弾性
率のポリアセタールが得られるこを見い出した〔特開昭
60−183122号公報〕。本発明者らは、これらの知見に基
づいて、本発明を成すに至った。Under these circumstances, the inventors of the present invention have conducted extensive studies, and in order to obtain polyacetal having high chemical resistance and high strength / high elastic modulus, the fibrillation is suppressed to 15 times or more. It has been found that high stretching is necessary. On the other hand, the present inventors previously found that a polyacetal having a high density and a high elastic modulus can be obtained by suppressing the fibrillation that occurs during stretching and achieving a high stretching of 10 times or more [Patent Document 1] Akira
60-183122]. The present inventors have completed the present invention based on these findings.
すなわち、本発明は、耐アルカリ性に優れた引張弾性率
30GPa以上、見掛け密度1.42g/cm3以上を有するポリアセ
タールが複合されていることを特徴とするセメント構造
物を提供するものである。That is, the present invention is a tensile modulus having excellent alkali resistance.
The present invention provides a cement structure characterized by being compounded with a polyacetal having an apparent density of 30 GPa or more and an apparent density of 1.42 g / cm 3 or more.
本発明のポリアセタールとは、別名ポリオキシメチレン
ともよばれ、ホモポリマー及びコポリマーである。The polyacetal of the present invention, which is also known as polyoxymethylene, is a homopolymer and a copolymer.
ここで本発明における耐薬品性とは、通常、耐アルカリ
性、耐酸性、耐酸化性、耐溶剤性、耐塩水性、耐熱水性
を意味するが、必要に応じて、これ以外の耐薬品性も含
まれる。耐酸化性とは、酸化材による分解、空気中の酸
素による加熱分解に対する耐久性であり、耐溶剤性と
は、一般溶剤による膨潤や特殊溶剤による溶解に対する
耐久性である。上記の耐薬品性のうち、耐アルカリ性、
耐酸性、耐酸化性、耐溶剤性が本発明によつて顕著に改
良される。耐塩水性、耐熱水性については、ポリアセタ
ールが本来もつている高い耐久性のために、差がなかつ
た。本発明では、上記の耐薬品性を改良するために、フ
イブリル化を抑制しながら高度に配向させることに特徴
がある。フイブリル化を抑制するために流体加圧を行
う。加圧は、成形材料の径方向に対して等方向に加えら
れる。流体は、圧力媒体であると同時に加熱媒体でもあ
る。通常、取扱いが容易で熱伝導が良く均一加熱に有利
なことから液体を用いるが、所望ならば気体でもよい。
この流体は、ポリアセタールに対し実質的に不活性であ
り、延伸温度において流動性を示すものである限り制限
はない。これらの流体に加えられる圧力としては、10〜
1000kg/cm2、好ましくは100〜800kg/cm2の範囲が選ばれ
るが所望ならばさらに高い圧力を用いることもできる。Here, the chemical resistance in the present invention usually means alkali resistance, acid resistance, oxidation resistance, solvent resistance, salt water resistance, hot water resistance, but if necessary, also includes other chemical resistance. Be done. Oxidation resistance is resistance to decomposition by an oxidant and thermal decomposition by oxygen in the air, and solvent resistance is resistance to swelling with a general solvent and dissolution with a special solvent. Of the above chemical resistance, alkali resistance,
Acid resistance, oxidation resistance and solvent resistance are significantly improved by the present invention. There was no difference in salt water resistance and hot water resistance due to the high durability inherent in polyacetal. The present invention is characterized in that it is highly oriented while suppressing fibrillation in order to improve the above chemical resistance. Fluid pressurization is performed to suppress fibrillation. The pressure is applied isotropically to the radial direction of the molding material. The fluid is both a pressure medium and a heating medium. Usually, a liquid is used because it is easy to handle, good in heat conduction, and advantageous for uniform heating, but a gas may be used if desired.
There is no limitation as long as this fluid is substantially inert to polyacetal and exhibits fluidity at the stretching temperature. The pressure applied to these fluids is 10 to
1000 kg / cm 2, preferably is the range of 100~800kg / cm 2 is selected may be used a higher pressure if desired.
一般に延伸倍率を高くするほど、大きな圧力を必要と
し、又、圧力を大きくするほど物性の改善効果は上がる
傾向がある。この圧力は、少なくとも５秒程度、好まし
くは30〜300秒連続的に加えるのが望ましい。本発明で
は延伸時の温度も重要であり、延伸時の圧力下における
ポリアセタールの軟化点を超えない温度で行うことが必
要である。この軟化点は、同じ物質においても圧力の増
大に従つて上昇する。軟化点よりも高い温度では、分子
配向が十分に進行しないため弾性率が著しく低下するの
で好ましくない。延伸温度は、圧力、延伸倍率などに関
係する。一般に、圧力が1000kg/cm2までで、延伸倍率が
15〜30倍の範囲であれば、130〜184℃、好ましくは160
〜180℃の範囲内が適当である。次に、本発明において
は、原料のポリアセタール成形材料を周囲の流体を介し
て均一に加圧し、かつ軟化点を超えない温度に加熱した
状態で15倍以上に高延伸することが必要である。延伸
は、例えば供給ロールと引取ロールとの回転比を変える
などして、供給速度よりも、引取速度を大きくすること
によつて行うことができる。通常、延伸倍率は15倍〜30
倍、好ましくは18倍〜26倍の範囲が良い。延伸倍率を大
きくすることは、耐薬品性を改良することと、実用的な
高い引張強度と引張弾性率を得るために重要である。15
倍以上延伸すれば、顕在化したフイブリル化が抑制され
た状態で、見掛け密度が1.43g/cm3以上、90％以上の配
向度、80％以上の結晶化度が得られ、これは、耐薬品性
を著しく改善し、又、引張強度が1.3PGa以上、引張弾性
率が30GPa以上の実用的な値が得られる。延伸倍率が18
〜26倍の範囲は、また、顕在化したフイブリル化が抑制
され得る範囲であり、かつ、引張強度、引張弾性率が最
高に達する範囲であるので好ましい。Generally, the higher the draw ratio, the higher the pressure required, and the higher the pressure, the more the effect of improving the physical properties tends to increase. It is desirable to apply this pressure continuously for at least about 5 seconds, preferably 30 to 300 seconds. In the present invention, the temperature during stretching is also important, and it is necessary to perform the stretching at a temperature that does not exceed the softening point of the polyacetal under the pressure during stretching. This softening point increases with increasing pressure even in the same material. At a temperature higher than the softening point, the molecular orientation does not proceed sufficiently and the elastic modulus is significantly lowered, which is not preferable. The stretching temperature is related to the pressure, the stretching ratio and the like. Generally, the draw ratio is up to 1000 kg / cm 2
In the range of 15 to 30 times, 130 to 184 ℃, preferably 160
A temperature within the range of to 180 ° C is suitable. Next, in the present invention, it is necessary to uniformly press the raw material polyacetal molding material through the surrounding fluid and highly stretch it 15 times or more while heating it to a temperature not exceeding the softening point. The stretching can be performed by increasing the take-up speed rather than the supply speed, for example, by changing the rotation ratio between the supply roll and the take-up roll. Normally, the draw ratio is 15 to 30
The range is preferably double, preferably 18 to 26 times. Increasing the draw ratio is important for improving chemical resistance and obtaining practically high tensile strength and tensile elastic modulus. 15
Stretching more than twice yields an apparent density of 1.43 g / cm 3 or more, a degree of orientation of 90% or more, and a degree of crystallinity of 80% or more in a state in which the visible fibrillation is suppressed. The chemical properties are remarkably improved, and practical values such as tensile strength of 1.3 PGa or more and tensile elastic modulus of 30 GPa or more are obtained. Draw ratio is 18
The range of up to 26 times is preferable because it is a range in which the actualized fibril formation can be suppressed and the tensile strength and the tensile elastic modulus reach the maximum.
この範囲において、見掛け密度は1.43〜1.46g/cm3、引
張強度は1.4〜2.0GPa、引張弾性率は32〜56GPaに達す
る。また、耐アルカリ性（実施例で行つた60℃のIN−水
酸化ナトリウム水溶液に浸漬した時の引張強度保持率）
はほぼ100％保持される。延伸倍率が30倍をこえると切
断を生じるおそれがある。In this range, the apparent density reaches 1.43 to 1.46 g / cm 3 , the tensile strength reaches 1.4 to 2.0 GPa, and the tensile elastic modulus reaches 32 to 56 GPa. Also, alkali resistance (retention rate of tensile strength when immersed in 60 ° C IN-sodium hydroxide aqueous solution as in the example)
Is almost 100% retained. If the draw ratio exceeds 30 times, cutting may occur.
上記の見掛け密度は、フイブリル化の程度を示すための
尺度である。フイブリル化が抑制されているほど高密度
である。本発明では、通常、見掛け密度を1.42g/cm3以
上とする。1.42g/cm3は延伸前のポリアセタール材料
（したがつてフイブリル化していない。）の密度であ
り、これは、所定のポリアセタールを窒素気流下200℃
で加熱溶融後、20℃まで放冷した試料で測定した。The apparent density is a measure for indicating the degree of fibrillation. The higher the fibrillation is suppressed, the higher the density. In the present invention, the apparent density is usually 1.42 g / cm 3 or more. 1.42 g / cm 3 is the density of the polyacetal material (thus not fibrillated) before stretching, which is the specified polyacetal at 200 ° C under nitrogen flow.
The sample was heated and melted at 20 ° C., and then allowed to cool to 20 ° C., and then measured.
見掛け密度は1.43〜1.46g/cm3、さらに好ましくは、1.4
4〜1.46g/cm3の範囲にするのが良い。さらに、本発明の
配向性は、90％以上の配向度と80％以上の結晶化度を有
する必要がある。The apparent density is 1.43 to 1.46 g / cm 3 , and more preferably 1.4.
It is good to set it in the range of 4 to 1.46 g / cm 3 . Furthermore, the orientation of the present invention must have a degree of orientation of 90% or more and a degree of crystallinity of 80% or more.
以上のように、本発明の方法で、耐薬品性が、大きく改
善されるのは、フイブリル化を抑制したことで、緻密な
構造となり、これは、フイブリル化し、ボイドを含んだ
構造にくらべて、著しく欠陥が少なく、緻密なため表面
から内部に物質が進入するのが困難になつたためと考え
られる。As described above, in the method of the present invention, the chemical resistance is greatly improved by suppressing the fibrillation, resulting in a dense structure, which is fibrillated, as compared with the structure containing voids. It is considered that it is difficult for the substance to enter the inside from the surface due to the fact that there are few defects and it is dense.
次に、図面に従つて本発明の実施態様の一例を説明す
る。第１図は、本発明方法を実施するのに好適な装置の
説明図である。ポリアセタールの長尺体（Ａ）はドラム
１、繰出ローラ２を経て一段目の延伸装置（Ｂ）へ供給
され、さらに引取ローラ３を経て二段目の延伸装置
（Ｃ）へ供給され、引取ローラ４を経て巻取ローラ５に
巻取られる。延伸装置（Ｂ），（Ｃ）は、供給口6,7を
有する保圧部材8,9と取出口10,11を有する保圧部材12,1
3を両端に備え、かつ、取出口側に媒体導入口14,15を、
また供給口側に媒体排出口16,17をそれぞれ設けた円筒
状容器18,19から構成され、この中は、媒体として加圧
流体（Ｄ），（Ｅ）が満たされている。長尺体（Ａ）
は、この延伸装置（Ｂ），（Ｃ）中に通過する間に、加
圧流体（Ｄ），（Ｅ）により所要の圧力で加圧され、ヒ
ーター20,21により加熱された加圧流体を介して加熱さ
れながら延伸処理される。Next, an example of an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is an explanatory view of an apparatus suitable for carrying out the method of the present invention. The elongated body (A) of polyacetal is supplied to the first-stage stretching device (B) through the drum 1 and the feeding roller 2, further supplied to the second-stage stretching device (C) through the take-up roller 3, and then the take-up roller. It is wound around a winding roller 5 via 4. The stretching devices (B) and (C) include pressure holding members 8 and 9 having supply ports 6 and 7 and pressure holding members 12 and 1 having take-out ports 10 and 11.
3 at both ends, and medium introduction ports 14 and 15 on the outlet side,
Further, it is composed of cylindrical containers 18 and 19 respectively provided with medium discharge ports 16 and 17 on the supply port side, and the medium is filled with pressurized fluids (D) and (E). Long body (A)
Is pressurized at a required pressure by the pressurized fluids (D) and (E) while passing through the stretching devices (B) and (C), and is heated by the heaters 20 and 21. It is stretched while being heated.
上記の保圧部材は、延伸装置内の圧力低下をもたらさな
いようなシールを有している。加圧は、ポンプ22,23で
行い、圧力の調整は調圧弁24,25で行う。延伸装置の外
部に設けた26,27は、保温のためのジヤケツトである。The pressure-holding member has a seal that does not cause a pressure drop in the stretching device. The pressurization is performed by the pumps 22 and 23, and the pressure is adjusted by the pressure adjusting valves 24 and 25. 26 and 27 provided outside the stretching device are jackets for keeping heat.
長尺体（Ａ）は、丸棒、角棒、異形体、チユーブ、シー
ト、板、テープ、糸、フイルムなど任意の形状を有する
ものが加工できる。The elongated body (A) can be processed into any shape such as a round bar, a square bar, a deformed body, a tube, a sheet, a plate, a tape, a thread, and a film.
次に、実施例により本発明をさらに詳細に説明する。な
お実施例中の密度は、JISK7112−1980の乳沈法により、
無水炭酸カリウムの水溶液を用いて、温度20±0.5℃に
おいて測定した。引張弾性率は、バイブロンIII EA型
（東洋ボールドウイン社製）を用い、23℃において測定
した。さらに、引張強度はインストロン引張試験機を用
い、JISK7113−1981に準じて23℃で測定した。これらの
数値の算出に必要な延伸体の断面積は、一定長の試料の
重量と、前記のようにして求めた密度を用いて計算し
た。耐アルカリ性は、試料を60℃の１規定水酸化ナトリ
ウムに所定時間浸漬した後、重量、引張強度、引張弾性
率を測定し、その保持率をみた。耐酸性は、60℃の5wt
％−塩酸水溶液に浸漬し、同様に、保持率をみた。耐酸
化性は、JIS K 7212−1977に準拠して測定した。温度13
0℃に加熱した空気の恒温槽に入れ、所定時間後の引張
強度の保持率をみた。耐溶剤性は、1cmの長さにカツト
した試料を溶剤抽出し、重量保持率をみた。Next, the present invention will be described in more detail with reference to examples. Incidentally, the density in the examples, by the milk sedimentation method of JIS K7112-1980,
The measurement was performed at a temperature of 20 ± 0.5 ° C. using an aqueous solution of anhydrous potassium carbonate. The tensile elastic modulus was measured at 23 ° C. using Vibron III EA type (manufactured by Toyo Baldwin Co., Ltd.). Furthermore, the tensile strength was measured at 23 ° C. according to JIS K7113-1981 using an Instron tensile tester. The cross-sectional area of the stretched body necessary for calculating these numerical values was calculated using the weight of a sample of a constant length and the density obtained as described above. The alkali resistance was determined by immersing the sample in 1N sodium hydroxide at 60 ° C. for a predetermined time, measuring the weight, tensile strength, and tensile elastic modulus, and checking the retention rate. Acid resistance is 5wt at 60 ℃
% -Hydrochloric acid aqueous solution, the retention rate was checked in the same manner. The oxidation resistance was measured according to JIS K 7212-1977. Temperature 13
It was placed in a thermostatic chamber of air heated to 0 ° C., and the retention rate of tensile strength after a predetermined time was observed. For solvent resistance, a sample cut into a length of 1 cm was subjected to solvent extraction, and the weight retention rate was observed.
以下の実施例で用いたポリアセタール成形材料は、テナ
ツク3010〔旭化成工業（株）製、ポリアセタールの登録
商標名、密度1.42g/cm3（常圧）、軟化点174℃（常
圧）〕のチユーブ（外径4.5mm、内径1.0mm）である。The polyacetal molding material used in the following examples is a tube of Tenac 3010 (produced by Asahi Kasei Corporation, registered trademark of polyacetal, density 1.42 g / cm 3 (normal pressure), softening point 174 ° C. (normal pressure)). (Outer diameter 4.5 mm, inner diameter 1.0 mm).
参考例１〜５及び参考比較例１〜３ ポリアセタール成形材料を、第１図に示す装置で、加圧
流体としてシリコーンオイルを用い、第１表に示す処理
条件下において、連続的に15〜26倍に延伸した。このよ
うにして得た試料の物性及び耐アルカリ性の結果を第１
表に示す。なお、比較のために、常圧下で延伸したもの
と、延伸前のポリアセタール成形材料についての結果も
併記した。Reference Examples 1 to 5 and Reference Comparative Examples 1 to 3 Polyacetal molding materials were continuously treated for 15 to 26 under the treatment conditions shown in Table 1 using silicone oil as a pressurized fluid in the apparatus shown in FIG. It was stretched twice. The results of physical properties and alkali resistance of the sample thus obtained are
Shown in the table. For comparison, the results for the polyacetal molding material stretched under normal pressure and the polyacetal molding material before stretching are also shown.
参考例６及び参考比較例４〜５ 参考例３で得た延伸倍率20倍の試料の耐酸性を調べた。
その結果を第２表に示す。なお、比較のために、参考比
較例２常圧下で延伸したもの及び参考比較例３延伸前の
成形材料で得た試料についての結果も併記した。 Reference Example 6 and Reference Comparative Examples 4 to 5 The samples having a draw ratio of 20 times obtained in Reference Example 3 were examined for acid resistance.
The results are shown in Table 2. For comparison, the results of the sample obtained by stretching in Reference Comparative Example 2 under normal pressure and the sample obtained in Reference Comparative Example 3 before stretching are also shown.
この結果から、常圧下で延伸した試料と未延伸材料は、
薬液が内部に浸透するのに対し、本発明の方法による試
料は、表面から徐々に溶解するが、内部には、薬液が浸
透しないことがわかる。 From this result, the sample stretched under normal pressure and the unstretched material,
It can be seen that the drug solution permeates inside, whereas the sample according to the method of the present invention gradually dissolves from the surface, but the drug solution does not penetrate inside.
参考例７及び参考比較例６〜７ 参考例３で得た試料の温度130℃における空気中の酸素
に対する耐酸化性を調べた。その結果を第３表に示す。
なお比較のために、参考比較例２常圧下で延伸したもの
及び参考比較例３延伸前の成形材料の試料についての結
果も併記した。また、参考例３の試料を100℃で2300時
間耐酸化性の処理を行い、その表面を電子顕微鏡で観察
した結果を第２図に参考比較例２の試料を100℃で1500
時間耐酸化性の処理したものの表面を電子顕微鏡で観察
した結果を第３図に示す。Reference Example 7 and Reference Comparative Examples 6 to 7 The samples obtained in Reference Example 3 were examined for oxidation resistance to oxygen in the air at a temperature of 130 ° C. The results are shown in Table 3.
For comparison, the results of Reference Comparative Example 2 drawn under normal pressure and Sample of the molding material before Reference Comparative Example 3 drawing are also shown. Further, the sample of Reference Example 3 was subjected to oxidation resistance treatment at 100 ° C. for 2300 hours, and the result of observing the surface with an electron microscope is shown in FIG.
FIG. 3 shows the result of observing the surface of the one treated with time oxidation resistance with an electron microscope.
参考例８及び参考比較例８〜９ 参考例３で得た試料の耐溶剤性を調べた。溶剤は、ガソ
リン、ヘキサフルオロイソプロパノールを用いて溶剤抽
出した。なお比較のために、参考比較例２及び参考比較
例３の試料についても行つた。その結果を第４表に示
す。 Reference Example 8 and Reference Comparative Examples 8 to 9 The solvent resistance of the samples obtained in Reference Example 3 was examined. The solvent was solvent-extracted using gasoline and hexafluoroisopropanol. For comparison, samples of Reference Comparative Example 2 and Reference Comparative Example 3 were also tested. The results are shown in Table 4.
なお、第４表において参考比較例８は、溶剤が内部にま
で浸透しているのに対し、参考例８は、内部への浸透は
みられない。 In Table 4, in Reference Comparative Example 8, the solvent permeated to the inside, whereas in Reference Example 8, no permeation into the interior was observed.
実施例１〜２ 本発明のポリアセタールをセメントの複合材として用い
る場合を想定して、セメントの上澄み液を用いた耐アル
カリ性を調べた。ポリアセタールとしては、テナツク30
10のチユーブ（外径14mm、内径4mm）を本発明の方法に
より、第１段目の延伸条件として温度155℃、圧力60Kg/
cm2、延伸倍率８倍、第２段目の延伸条件として、温度1
72℃、圧力300Kg/cm2、最終延伸倍率22倍に延伸して得
た線径2.8mm、見掛け密度1.45g/cm2、引張強度1.60GP
a、引張弾性率35GPaの半透明のポリアセタール線材（実
施例１）、および７本の該線材を撚り合わせてつくった
撚線（実施例２）を用いた。セメントの上澄み液は、重
量比でボルトランドセメント１に水４を加えて混合液を
つくり、該混合液を90℃で24時間混合撹拌して得た液の
上澄みをとってつくった。上澄み液のPHは約12.6であつ
た。該上澄み液に、上記のポリアセタール線材および撚
線を90℃で24時間浸漬し、重量、強度の保持率を調べ
た。その結果を第５表に示す。Examples 1-2 Assuming that the polyacetal of the present invention is used as a composite material for cement, alkali resistance was examined using a supernatant of cement. Tenac 30 as polyacetal
Ten tubes (outer diameter 14 mm, inner diameter 4 mm) were drawn by the method of the present invention as the first stage drawing conditions at a temperature of 155 ° C. and a pressure of 60 Kg /
cm 2 , the draw ratio is 8 times, and the second drawing condition is a temperature of 1
72 ℃, pressure 300Kg / cm 2 , final draw ratio 22 times drawn wire diameter 2.8mm, apparent density 1.45g / cm 2 , tensile strength 1.60GP
a, a semi-transparent polyacetal wire having a tensile elastic modulus of 35 GPa (Example 1), and a twisted wire (Example 2) formed by twisting seven of these wires. The cement supernatant liquid was prepared by adding water 4 to Voltland cement 1 in a weight ratio to prepare a mixed liquid, and mixing and stirring the mixed liquid at 90 ° C. for 24 hours to obtain a supernatant of the liquid. The pH of the supernatant was about 12.6. The above polyacetal wire and the twisted wire were immersed in the supernatant liquid at 90 ° C. for 24 hours, and the weight and strength retention rates were examined. The results are shown in Table 5.
結果から明らかな様に、本発明のポリアセタールは、セ
メントの複合材としての好ましい性質を有している。 As is clear from the results, the polyacetal of the present invention has desirable properties as a cement composite material.
第１図は、本発明の方法に用いるのに適した装置の一例
を示す断面略解図、第２図は実施例３で得た試料の耐酸
化性処理を行つた後の試料表面における繊維の形状を示
す電子顕微鏡写真拡大図、第３図は、比較例２で得た試
料の耐酸化性処理を行つた後の試料表面における繊維の
形状を示す電子顕微鏡写真拡大図である。 （Ａ）……長尺成形材料、（Ｂ），（Ｃ）……延伸装
置、（Ｄ），（Ｅ）……加圧流体、１……ドラム、２…
…繰出ローラ、3,4……引取ローラ、５……巻取ロー
ラ、6,7……供給口、8,9,12,13……保圧部材、10,11…
…取出口、14,15……媒体導入口、16,17……媒体排出
口、18,19……円筒状容器、20,21……ヒーター、22,23
……ポンプ、24,25……調圧弁、26,27……保温ジヤケツ
トFIG. 1 is a schematic cross-sectional view showing an example of an apparatus suitable for use in the method of the present invention, and FIG. 2 is a diagram showing the fibers on the surface of the sample obtained by subjecting the sample obtained in Example 3 to the oxidation resistance treatment. FIG. 3 is an enlarged view of an electron microscope photograph showing the shape, and FIG. 3 is an enlarged view of the electron microscope photograph showing the shape of the fiber on the sample surface after the oxidation resistance treatment of the sample obtained in Comparative Example 2. (A) ... long molding material, (B), (C) ... stretching device, (D), (E) ... pressurized fluid, 1 ... drum, 2 ...
… Feeding roller, 3,4 …… Take-up roller, 5 …… Take-up roller, 6,7 …… Supply port, 8,9,12,13 …… Pressure holding member, 10,11…
… Outlet, 14,15 …… Medium inlet, 16,17 …… Medium outlet, 18,19 …… Cylindrical container, 20, 21 …… Heater, 22,23
...... Pump, 24,25 …… Regulator, 26,27 …… Insulation jacket
───────────────────────────────────────────────────── 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 Ｄ０２Ｊ 1/22 Ｊ Ｂ２９Ｋ 59:00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location D02J 1/22 J B29K 59:00
Claims (1)
上、見掛け密度1.42g/cm3以上を有するポリアセタール
が複合されていることを特徴とするセメント構造物。1. A cement structure comprising a composite of polyacetal having a tensile elastic modulus of 30 PGa or more and an apparent density of 1.42 g / cm 3 or more, which is excellent in alkali resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61127189A JPH0761679B2 (en) | 1986-06-03 | 1986-06-03 | Cement structure composed of polyacetal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61127189A JPH0761679B2 (en) | 1986-06-03 | 1986-06-03 | Cement structure composed of polyacetal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62284725A JPS62284725A (en) | 1987-12-10 |
| JPH0761679B2 true JPH0761679B2 (en) | 1995-07-05 |
Family
ID=14953888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61127189A Expired - Fee Related JPH0761679B2 (en) | 1986-06-03 | 1986-06-03 | Cement structure composed of polyacetal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0761679B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE307786T1 (en) * | 2001-09-10 | 2005-11-15 | 3M Innovative Properties Co | FIBER REINFORCED CEMENT COMPOSITES |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5510423A (en) * | 1978-07-07 | 1980-01-24 | Mitsui Petrochemical Ind | Composition for cement and its manufacture |
| JPS5878937A (en) * | 1981-11-05 | 1983-05-12 | Toshiba Corp | Document feeding device |
| JPS58145655A (en) * | 1981-12-30 | 1983-08-30 | 牧 恒雄 | Concrete reinforcement material |
| JPS5945960A (en) * | 1983-05-06 | 1984-03-15 | 三井化学株式会社 | Manufacture of blend for cement |
| JPS60183122A (en) * | 1984-02-29 | 1985-09-18 | Asahi Chem Ind Co Ltd | Manufacturing of polyacetal of high strength and coefficient of high elasticity |
-
1986
- 1986-06-03 JP JP61127189A patent/JPH0761679B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62284725A (en) | 1987-12-10 |
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