JPS5824386B2 - Alkali-resistant treated glass fiber - Google Patents
Alkali-resistant treated glass fiberInfo
- Publication number
- JPS5824386B2 JPS5824386B2 JP51012880A JP1288076A JPS5824386B2 JP S5824386 B2 JPS5824386 B2 JP S5824386B2 JP 51012880 A JP51012880 A JP 51012880A JP 1288076 A JP1288076 A JP 1288076A JP S5824386 B2 JPS5824386 B2 JP S5824386B2
- Authority
- JP
- Japan
- Prior art keywords
- treatment agent
- treated glass
- alkali
- alkali resistance
- glass cloth
- 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
Links
Landscapes
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Description
【発明の詳細な説明】
本発明は、アルカリ含有率の高いセメント、セメントモ
ルタル、セメントコンクリート等の無機水硬性セメント
マトリックスの補強材として使用可能な耐アルカリ性処
理ガラス繊維に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to alkali-resistant treated glass fibers that can be used as reinforcing materials for inorganic hydraulic cement matrices such as cements with high alkali content, cement mortars, and cement concretes.
従来より、アルカリ含有率の高い無機水硬性セメントマ
トリックスの補強材としてEガラス繊維、Cガラス繊維
等のガラス繊維を使用することは望ましくないものとさ
れている。Conventionally, it has been considered undesirable to use glass fibers such as E-glass fibers and C-glass fibers as reinforcing materials for inorganic hydraulic cement matrices having a high alkali content.
セメントマトリックスのアルカリ成分により、上記ガラ
ス繊維が著しく浸蝕され、補強材としての実用性がなか
ったためである。This is because the glass fibers were significantly eroded by the alkaline components of the cement matrix, making them impractical as reinforcing materials.
従って、上記ガラス繊維をアルカリ含有率の高い無機水
硬性セメントIJツクスの補強材として使用するために
は、さらに耐アルカリ性を向上させる必要がある。Therefore, in order to use the glass fiber as a reinforcing material for inorganic hydraulic cement IJTx with a high alkali content, it is necessary to further improve the alkali resistance.
本発明者等は、上記ガラス繊維の耐アルカリ性を向上さ
せるべく、種々の表面処理剤について鋭意検討した結果
、各種ゴムを主成分として含み、1且つ、少量のアミノ
シラン系又はメルカプトシラン系カップリング剤を含む
表面処理剤で処理し、処理剤組成物を表面に0.5重量
%以上付着せしめたガラス繊維の耐アルカリ性が非常に
優れている事を発見した。In order to improve the alkali resistance of the above-mentioned glass fibers, the present inventors conducted extensive studies on various surface treatment agents, and as a result, the present inventors discovered a method that contains various rubbers as a main component, and a small amount of an aminosilane-based or mercaptosilane-based coupling agent. It has been discovered that the alkali resistance of glass fibers treated with a surface treatment agent containing 0.5% by weight or more of the treatment agent composition on the surface is extremely excellent.
本発明の耐アルカリ性処理ガラス繊維は、比較的耐アル
カリ性の大きな各種ゴムと従来よりガラス繊維の表面処
理剤として使用されてきた各種カップリング剤の中で耐
水性及び耐アルカリ性付与効果の大きなアミノシラン系
又はメルカプトシラン系カップリング剤とを同時にガラ
ス繊維の表面に付着せしめたもので、耐アルカリ性に対
して、上記成分の相乗的効果により、従来の処理ガラス
繊維には得られなかった非常に高い耐アルカリ性を有す
る事を特徴とする。The alkali-resistant treated glass fiber of the present invention is based on various rubbers with relatively high alkali resistance and aminosilane-based which has a large effect of imparting water resistance and alkali resistance among various coupling agents conventionally used as surface treatment agents for glass fibers. Alternatively, a mercaptosilane coupling agent is attached to the surface of the glass fiber at the same time, and due to the synergistic effect of the above components on alkali resistance, it has extremely high resistance that cannot be obtained with conventionally treated glass fibers. It is characterized by being alkaline.
本発明の耐アルカリ性処理ガラス繊維の製造に用いられ
る表面処理剤の主成分として含まれるゴムとしては、ス
チレン、ブタジェンゴム(以下SBRと略す)、ニトリ
ル・ブタジェンゴム(以下NBRと略す)、天然ゴム(
以下NRと略す)、クロロプレンゴム(以下CRと略す
)、ポリイソプレンゴム、ブチルゴム、アクリル酸エス
テルゴム、シリコーンゴム、エチレンプロピレンゴム(
以下EPRと略す)等がある。Rubbers contained as main components of the surface treatment agent used in the production of the alkali-resistant treated glass fiber of the present invention include styrene, butadiene rubber (hereinafter abbreviated as SBR), nitrile-butadiene rubber (hereinafter abbreviated as NBR), natural rubber (
(hereinafter abbreviated as NR), chloroprene rubber (hereinafter abbreviated as CR), polyisoprene rubber, butyl rubber, acrylic ester rubber, silicone rubber, ethylene propylene rubber (
(hereinafter abbreviated as EPR), etc.
これらのゴムの中で、SBR,NBR,CR,NR,ア
クリル酸ゴム、シリコーンゴム乃至EPRが耐アルカリ
性に優れ、且つ、引張り強度の高い処理ガラス繊維を与
えるので特に望ましい。Among these rubbers, SBR, NBR, CR, NR, acrylic acid rubber, silicone rubber, and EPR are particularly desirable because they have excellent alkali resistance and provide treated glass fibers with high tensile strength.
本発明の耐アルカリ性処理ガラス繊維の製造に用いる表
面処理剤に少量含まれるアミノシラン系又はメルカプト
シラン系カップリング剤としては、従来よりガラス繊維
のカップリング剤として使用されてきたγ−アミノプロ
ピルトリエトキシシラン、N−(β−アミノエチル)−
γ−アミノプロピルトリメトキシシラン、N−(β−ア
ミノエチル)−γ−アミノプロピルメチルジメトキシシ
ラン、γ−メルカプトプロピルトリメトキシシラン等が
ある。The aminosilane or mercaptosilane coupling agent contained in a small amount in the surface treatment agent used in the production of the alkali-resistant treated glass fiber of the present invention is γ-aminopropyltriethoxy, which has been conventionally used as a coupling agent for glass fiber. Silane, N-(β-aminoethyl)-
Examples include γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-mercaptopropyltrimethoxysilane.
上記の表面処理剤としては、各種ゴムラテックスと少量
のアミノシラン系又はメルカプトシラン系カップリング
剤と必要に応じて各種改質材(柔軟剤、潤滑剤、帯電防
止剤、加硫剤、ゴム老化防止剤、加硫促進剤等)を水に
分散せしめたものが。The above surface treatment agents include various rubber latexes, a small amount of aminosilane-based or mercaptosilane-based coupling agents, and various modifiers (softeners, lubricants, antistatic agents, vulcanizing agents, rubber anti-aging agents) as needed. vulcanization accelerator, vulcanization accelerator, etc.) dispersed in water.
好ましいが、ベンゼン、トルエン、キシレン等の有機溶
媒に上記成分を溶解せしめたものでも良い。Although preferred, the above components may be dissolved in an organic solvent such as benzene, toluene, or xylene.
本発明の耐アルカリ性処理ガラス繊維の処理剤組成分の
付着量が、0.5重量%より少ない場合は、優れた耐ア
ルカリ性のものを得る事が期待できず。If the amount of the treatment agent component attached to the alkali-resistant treated glass fiber of the present invention is less than 0.5% by weight, it cannot be expected to obtain excellent alkali resistance.
また、30重量%より多くしても、耐アルカリ性に対す
る寄与率が小さくなり、コスト的にも高価になるので、
耐アルカリ性処理ガラス繊維の処理剤組成分の付着量は
0.5〜30重量%の範囲が望ましい。In addition, even if the amount is more than 30% by weight, the contribution to alkali resistance will be small and the cost will be high.
The amount of the treatment agent component deposited on the alkali-resistant treated glass fiber is preferably in the range of 0.5 to 30% by weight.
以下実施例により本発明を説明する。The present invention will be explained below with reference to Examples.
本実施例の耐アルカリ性評価方法は、耐アルカリ性処理
ガラス繊維をPH=12に調整した60℃の水酸化カル
シウム溶液中に所定時間浸漬した後、0.1%希塩酸で
洗浄し、さらに充分水洗した。The alkali resistance evaluation method of this example was to immerse the alkali resistance treated glass fiber in a 60°C calcium hydroxide solution adjusted to pH=12 for a predetermined time, wash it with 0.1% dilute hydrochloric acid, and then rinse thoroughly with water. .
後乾燥したものを引張試験用試料とした。The post-dried sample was used as a tensile test sample.
引張り試験は、テンシロン引張り試験機(ボールドウィ
ン株式会社製品)を使用し、温度20℃、湿度60%の
室内で、スパン1501m、ヘットスピード200ii
/分で測定した。The tensile test was carried out using a Tensilon tensile tester (manufactured by Baldwin Corporation) in a room at a temperature of 20°C and a humidity of 60%, with a span of 1501 m and a head speed of 200 II.
/min.
なお、水酸化カルシウム溶液の炭酸化を防ぐために密栓
をした状態でガラス繊維を浸漬した。Note that the glass fibers were immersed in the calcium hydroxide solution with the solution closed tightly to prevent carbonation.
実施例 1
ヒートクリーニングしたガラスクロスを、下記のA配合
の処理剤に浸漬し、次いでニップローラーにはさみ余分
の処理剤を除去した後、110℃で120分間乾燥し、
処理剤の付着量が0.51重量%の処理ガラスクロスを
作成する。Example 1 A heat-cleaned glass cloth was immersed in a treatment agent of the following composition A, then sandwiched between nip rollers to remove excess treatment agent, and dried at 110°C for 120 minutes.
A treated glass cloth with a coating amount of treatment agent of 0.51% by weight is prepared.
同様にしてB。C乃至り配合の処理剤を用いて、処理剤
の付着量が、それぞれ5.2重量%、10.2重量%乃
至19.8重量%の処理ガラスクロスを作成する。Similarly, B. Treated glass cloth with a coating amount of treatment agent of 5.2% by weight and 10.2% by weight to 19.8% by weight, respectively, is prepared using treatment agents of C to 10% by weight.
上記処理ガラスクロスを巾25龍、長さ300闘の試料
に切断し、耐アルカリ性の試験を行なった。The above-mentioned treated glass cloth was cut into samples with a width of 25 mm and a length of 300 mm, and an alkali resistance test was conducted.
その結果を次表に示す。実施例の試料番号1〜4の試料
は、比較例の未処理試料乃至酢酸ビニル処理試料に比し
、引張り強度の初期値が非常に高く、耐アルカリ性も非
常に優れていることがわかる。The results are shown in the table below. It can be seen that the samples of sample numbers 1 to 4 of the examples have very high initial values of tensile strength and are also very excellent in alkali resistance, compared to the untreated samples to the vinyl acetate treated samples of the comparative examples.
実施例 2
一般のガラスクロスを、下記の配合の処理剤に浸漬し、
次いでニップローラーにはさみ余分の処理剤を除去した
後、110℃で120分間乾燥し、処理剤の付着量が1
0.2重量%の処理ガラスクロ上記処理ガラスクロスを
巾25mm、長さ300mrrtの試料に切断し、耐ア
ルカリ性の試験を行なった。Example 2 A common glass cloth was dipped in a treatment agent with the following composition,
Next, after removing the excess treatment agent with a nip roller, it was dried at 110°C for 120 minutes until the amount of treatment agent attached was 1.
0.2% by weight treated glass cloth The treated glass cloth described above was cut into samples with a width of 25 mm and a length of 300 mrrt, and an alkali resistance test was conducted.
その結果を次表に示す。スを作成する。The results are shown in the table below. create a
実施例の試料番号5の試料は、比較例の未処理試料乃至
ポリエステル処理試料に比し、引張り強度の初期値が非
常に高く、耐アルカリ性も非常に優れていることがわか
る。It can be seen that the sample No. 5 of the example has a very high initial value of tensile strength and is also very excellent in alkali resistance, compared to the untreated sample or the polyester-treated sample of the comparative example.
実施例 3
ヒートクリーニングしたガラスクロスを、下記の配合の
処理剤に浸漬し、次いでニップローラーにはさみ余分の
処理剤を除去した後、150℃で15分間乾燥し、処理
剤の付着量が10.3重量%の処理ガラスクロスを作成
する。Example 3 A heat-cleaned glass cloth was immersed in a treatment agent of the following composition, then placed between nip rollers to remove excess treatment agent, and dried at 150° C. for 15 minutes until the amount of treatment agent attached was 10. A 3% by weight treated glass cloth is prepared.
上記処理ガラスクロスを巾25mm、長さ300闘の試
料に切断し、耐アルカリ性の試験を行なった。The above-mentioned treated glass cloth was cut into samples with a width of 25 mm and a length of 300 mm, and an alkali resistance test was conducted.
その結果を次表に示す。The results are shown in the table below.
実施例の試料番号6の試料は、比較例の未処理試料乃至
エポキシ処理試料に比し、引張り強度の初期値が非常に
高く、耐アルカリ性も非常に優れていることがわかる。It can be seen that the sample No. 6 of the example has a very high initial value of tensile strength and is also very excellent in alkali resistance, compared to the untreated sample or the epoxy-treated sample of the comparative example.
実施例 4
ヒートクリーニングしたガラスクロスを、下記の配合の
処理剤に浸漬し、次いでニップローラーにはさみ余分の
処理剤を除去した後、150℃で15分間乾燥し、処理
剤の付着量が9.2重量%の処理ガラスクロスを作成す
る。Example 4 A heat-cleaned glass cloth was immersed in a treatment agent of the following composition, then placed between nip rollers to remove excess treatment agent, and dried at 150° C. for 15 minutes until the amount of treatment agent attached was 9. A 2% by weight treated glass cloth is prepared.
上記処理ガラスクロスを巾25mm、長さ300mmの
試料に切断し、耐アルカリ性の試験を行なった。The treated glass cloth was cut into samples with a width of 25 mm and a length of 300 mm, and an alkali resistance test was conducted.
その結果を次表に示す。実施例の試料番号7の試料は、
比較例の未処理試料に比し、引張り強度の初期値が非常
に高く、耐アルカリ性も非常に優れていることがわかる
。The results are shown in the table below. Sample number 7 in the example is:
It can be seen that the initial value of the tensile strength is very high and the alkali resistance is also very excellent compared to the untreated sample of the comparative example.
。実施例 5
ガラス繊維紡糸時に、ブッシング直下で、下記の配合の
処理剤(−サイジング剤)でフィラメント(太さ10μ
)をサイジング処理し1本に束ねた太さ125グラム/
1000m100Oチック・ス)のガラスストランドを
125℃で6時間乾燥し、ガラスストランドの耐アルカ
リ性試験を行なつた。. Example 5 During glass fiber spinning, a filament (thickness 10μ
) is sized and bundled into a single piece with a thickness of 125 grams/
A glass strand of 1000 ml (1000 ml) was dried at 125° C. for 6 hours, and an alkali resistance test of the glass strand was conducted.
その結果を次表に示す。実施例の試料番号8のガラスス
トランド試料は、比較例の酢酸ビニル系サイジング処理
ガラスストランドに比し、耐アルカリ性が非常に優れて
いる事がわかる。The results are shown in the table below. It can be seen that the glass strand sample of Sample No. 8 of the Example has much better alkali resistance than the vinyl acetate-based sizing-treated glass strand of the Comparative Example.
実施例 6
ヒートクリーニングしたガラスクロスを、下記の配合の
処理剤に浸漬し、次いでニップローラーにはさみ余分の
処理剤を除去した後、150℃で15分間乾燥し、処理
剤の付着量が10.0重量%の処理ガラスクロスを作成
する。Example 6 A heat-cleaned glass cloth was immersed in a treatment agent of the following composition, then placed between nip rollers to remove excess treatment agent, and dried at 150° C. for 15 minutes until the amount of treatment agent attached was 10. A 0% by weight treated glass cloth is prepared.
上記処理ガラスクロスを巾25mm、長さ300關の試
料に切断し、耐アルカリ性の試験を行なった。The above-mentioned treated glass cloth was cut into samples with a width of 25 mm and a length of 300 mm, and an alkali resistance test was conducted.
その結果を次表に示す。実施例 7
ヒートクリーニングしたガラスクロスを、下記の配合の
処理剤に浸漬し、次いでニップローラーにはさみ余分の
処理剤を除去した後、150℃で15分間乾燥し、処理
剤の付着量が9.8重量%の処理ガラスクロスを作成す
る。The results are shown in the table below. Example 7 A heat-cleaned glass cloth was immersed in a treatment agent of the following composition, then placed between nip rollers to remove excess treatment agent, and dried at 150° C. for 15 minutes until the amount of treatment agent adhered was 9. An 8% by weight treated glass cloth is made.
上記処理ガラスクロスを巾25mm、長さ300mmの
試料に切断し、耐アルカリ性の試験を行なった。The treated glass cloth was cut into samples with a width of 25 mm and a length of 300 mm, and an alkali resistance test was conducted.
その結果を次表に示す。実施例 8
ヒートクリーニングしたガラスクロスを、下記の配合の
処理剤に浸漬し、次いでニップローラーにはさみ余分の
処理剤を除去した後、150°Cで15分間乾燥し、処
理剤の付着量が5.5重量%の処理ガラスクロスを作成
する。The results are shown in the table below. Example 8 A heat-cleaned glass cloth was immersed in a treatment agent with the following composition, and then the excess treatment agent was removed by nip rollers, and the cloth was dried at 150°C for 15 minutes until the amount of treatment agent attached was 5. .5% by weight treated glass cloth is prepared.
上記処理ガラスクロスを巾25mm、長さ300關の試
料に切断し、耐アルカリ性の試験を行なった。The above-mentioned treated glass cloth was cut into samples with a width of 25 mm and a length of 300 mm, and an alkali resistance test was conducted.
その結果を次表に示す。実施例 9
ヒートクリーニングしたガラスクロスを、下記の配合の
処理剤に浸漬し、次いでドクターローラーで余分の処理
剤を除去した後、150℃で30分間乾燥し、処理剤の
付着量が12.2重量%の処理ガラスクロスを作成する
。The results are shown in the table below. Example 9 A heat-cleaned glass cloth was immersed in a treatment agent with the following composition, and then the excess treatment agent was removed using a doctor roller, and then dried at 150°C for 30 minutes, resulting in an adhesion amount of treatment agent of 12.2 % by weight to create a treated glass cloth.
*上記処理ガラスクロスを巾25
mm、長さ300mmの試料に切断し、耐アルカリ性の
試験を行なった。*Width 25mm of the above treated glass cloth
Samples were cut into 300 mm long samples and tested for alkali resistance.
その結果を次表に示す。さらに比較のために、ヒートク
リーニングクロスを下記内容の処理剤に浸漬し、次いで
ニップローラーにてはさみ余分の処理剤を除去した後、
150℃で15分間乾燥し、処理剤の付着量が10重量
%の処理ガラスクロスを作成する。The results are shown in the table below. For further comparison, a heat cleaning cloth was immersed in the processing agent described below, and then the excess processing agent was removed using a nip roller.
It is dried at 150° C. for 15 minutes to produce a treated glass cloth with a coating amount of 10% by weight of the treatment agent.
E SBRラテックス
(小野田CXB、小野田建材■製品) 69.0脱
イオン 31.0F SB
Rラテックス
(小野田CXB、小野田建材■製品) 69.0γ
、グリシドキシプロピルトリメトキシシラン 0.
6脱イオン水 30.4G S
BRラテックス
(小野田CXB、小野田建材■製品) 69.0γ
、メタアクリロキシプロピルトリ
メトキシシラン 0.6脱イオン水
30.4上記処理ガラスクロスを
幅25mm、長さ300mmの試料に切断し、耐アルカ
リ性の試験を行なった。E SBR latex (Onoda CXB, Onoda Kenzai product) 69.0 deionized 31.0F SB
R latex (Onoda CXB, Onoda Kenzai product) 69.0γ
, glycidoxypropyltrimethoxysilane 0.
6 Deionized water 30.4G S
BR latex (Onoda CXB, Onoda Kenzai product) 69.0γ
, methacryloxypropyltrimethoxysilane 0.6 deionized water
30.4 The above-treated glass cloth was cut into samples with a width of 25 mm and a length of 300 mm, and an alkali resistance test was conducted.
Claims (1)
系又はメルカプトシラン系カップリング剤を含む組成物
をガラス繊維に対して05乃至30重量%表面に付着せ
しめた事を特徴とする耐アルカリ性処理ガラス繊維。1. An alkali-resistant treated glass fiber characterized by having a composition containing rubber as a main component and a small amount of an aminosilane-based or mercaptosilane-based coupling agent adhered to the surface of the glass fiber in an amount of 05 to 30% by weight. .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP51012880A JPS5824386B2 (en) | 1976-02-10 | 1976-02-10 | Alkali-resistant treated glass fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP51012880A JPS5824386B2 (en) | 1976-02-10 | 1976-02-10 | Alkali-resistant treated glass fiber |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60084400A Division JPS60260446A (en) | 1985-04-22 | 1985-04-22 | Alkali resistant glass fiber |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5296296A JPS5296296A (en) | 1977-08-12 |
JPS5824386B2 true JPS5824386B2 (en) | 1983-05-20 |
Family
ID=11817716
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP51012880A Expired JPS5824386B2 (en) | 1976-02-10 | 1976-02-10 | Alkali-resistant treated glass fiber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5824386B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH064942Y2 (en) * | 1987-10-29 | 1994-02-09 | ぺんてる株式会社 | Applicator with valve |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55126553A (en) * | 1979-03-24 | 1980-09-30 | Daiichi Kasei Kk | Glass fiber surface treating method |
JPH01239169A (en) * | 1988-03-11 | 1989-09-25 | Asahi Glass Co Ltd | Surface-treating agent for silica fiber |
BRPI0802008A8 (en) * | 2008-05-09 | 2017-12-26 | O Nascimento Engenharia E Consultoria Ltda | MANUFACTURING PROCESS OF FIBERCEMENT COMPOSITES USING CEMENTIUM MATERIALS REINFORCED WITH INORGANIC FIBERS CHEMICALLY MODIFIED BY ORGANOSILANES |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4917817A (en) * | 1972-06-09 | 1974-02-16 | ||
JPS5031191A (en) * | 1973-07-03 | 1975-03-27 |
-
1976
- 1976-02-10 JP JP51012880A patent/JPS5824386B2/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4917817A (en) * | 1972-06-09 | 1974-02-16 | ||
JPS5031191A (en) * | 1973-07-03 | 1975-03-27 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH064942Y2 (en) * | 1987-10-29 | 1994-02-09 | ぺんてる株式会社 | Applicator with valve |
Also Published As
Publication number | Publication date |
---|---|
JPS5296296A (en) | 1977-08-12 |
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