JPH01313346A - Production of antistatic glass fiber bundle, antistatic glass fiber roving, fiber material for reinforcing resin and sheet molding compound - Google Patents
Production of antistatic glass fiber bundle, antistatic glass fiber roving, fiber material for reinforcing resin and sheet molding compoundInfo
- Publication number
- JPH01313346A JPH01313346A JP63141578A JP14157888A JPH01313346A JP H01313346 A JPH01313346 A JP H01313346A JP 63141578 A JP63141578 A JP 63141578A JP 14157888 A JP14157888 A JP 14157888A JP H01313346 A JPH01313346 A JP H01313346A
- Authority
- JP
- Japan
- Prior art keywords
- agent
- glass fiber
- antistatic
- fiber bundle
- antistatic 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.)
- Granted
Links
- 239000003365 glass fiber Substances 0.000 title claims abstract description 56
- 229920005989 resin Polymers 0.000 title claims description 24
- 239000011347 resin Substances 0.000 title claims description 24
- 239000003677 Sheet moulding compound Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 230000003014 reinforcing effect Effects 0.000 title description 3
- 239000002657 fibrous material Substances 0.000 title 1
- 239000002216 antistatic agent Substances 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 55
- 239000000314 lubricant Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 10
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 9
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- 125000000129 anionic group Chemical group 0.000 claims abstract description 6
- 125000002091 cationic group Chemical group 0.000 claims abstract description 6
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract 4
- 239000003945 anionic surfactant Substances 0.000 claims abstract 4
- 238000004513 sizing Methods 0.000 claims description 37
- 239000012783 reinforcing fiber Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims 3
- CLVOYFRAZKMSPF-UHFFFAOYSA-N n,n-dibutyl-4-chlorobenzenesulfonamide Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(Cl)C=C1 CLVOYFRAZKMSPF-UHFFFAOYSA-N 0.000 claims 1
- 230000002787 reinforcement Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000000151 deposition Methods 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000010526 radical polymerization reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004040 coloring Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- -1 amphoteric Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
帯電防止性ガラス繊維束、帯電防止性ロービング、樹脂
補強用繊維体並びにシートモールディングコンパウンド
の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an antistatic glass fiber bundle, an antistatic roving, a resin reinforcing fiber body, and a sheet molding compound.
［従来の技術］
ブッシングから引出したガラス繊維に集束剤を附与して
所定本数集束して巻取り、加熱乾燥することにより製造
されたガラス繊ｍ末（ストランド）は繊維補強樹脂体（
ＦＲＰ）を製造する際の樹脂補強用繊維体として広く用
いられる。[Prior Art] Glass fibers (strands) produced by adding a sizing agent to glass fibers pulled out from a bushing, converging a predetermined number of fibers, winding them, and heating and drying them are made of fiber-reinforced resin bodies (
It is widely used as a resin reinforcing fiber when manufacturing FRP.
又上記のストランドは引揃えてロービングとなし、或は
そのまま、又は引揃えた状態で切断してチョツプドスト
ランド（ＣＳ）となし、或はストランド又はＣ８を移動
するコンベア上に堆積せしめてＣ３Ｍ（コンティニュア
スストランドマット）又はＣＭ（チョツプドストランド
マット）とした状態て補強繊維体として使用される。In addition, the above strands can be pulled together to form rovings, or cut as is or in the aligned state to form chopped strands (CS), or the strands or C8 can be deposited on a moving conveyor to form C3M. It is used as a reinforcing fiber body in the form of (continuous strand mat) or CM (chopped strand mat).
又Ｃ８を移動するコンベア上に堆積せしめてなるマット
状物にＭｇＯのような増粘剤を含む不飽和ポリエステル
樹脂のような熱硬化性樹脂を含浸させ、次いで養生して
樹脂粘度を上昇させてＳＭＣ（シートモールディングコ
ンパウンド）となし、ＦＲＰの製造に使用される。In addition, a mat-like material formed by depositing C8 on a moving conveyor is impregnated with a thermosetting resin such as an unsaturated polyester resin containing a thickener such as MgO, and then cured to increase the resin viscosity. SMC (Sheet Molding Compound) is used in the production of FRP.
このようなガラス繊維束に切断等の加工を施す際、静電
気が発生し、各種トラブルを生ずることかあるので、こ
れを防止する為集束剤に帯電防止剤を含有させる。When such a glass fiber bundle is subjected to processing such as cutting, static electricity is generated and may cause various troubles, so in order to prevent this, the sizing agent contains an antistatic agent.
帯電防止剤としてはノニオン系、カチオン系、両性イオ
ン系、アニオン系、或は無機塩類が知られている。Nonionic, cationic, amphoteric, anionic, and inorganic salts are known as antistatic agents.
［発明か解決しようとする課題］
従来技術は次のような問題点（解決すべき課題）を有す
る。[Problem to be solved by the invention] The conventional technology has the following problems (problems to be solved).
（１）充分な帯電防止効果を得るためには多量の帯電防
止剤を使用する必要かある。(1) In order to obtain a sufficient antistatic effect, it is necessary to use a large amount of antistatic agent.
（２）多量の帯電防止剤を使用するとストランドを加熱
乾燥する際ストランドが着色し易い。(2) If a large amount of antistatic agent is used, the strands are likely to be colored when they are heated and dried.
（３）集束剤中に含まれる被膜形成剤、カップリンク剤
、潤滑剤等と帯電防止剤とか反応し、ストランドの性能
が低下し易い。例えばフイラメン１〜の剛性か低下し、
或は集束性か悪化し、ストランドかモノフィラメント状
になり、このストランドを補強用繊維体として使用する
際、樹脂の含浸性か不良となる。(3) The antistatic agent reacts with the film forming agent, coupling agent, lubricant, etc. contained in the sizing agent, and the performance of the strands tends to deteriorate. For example, the stiffness of filament 1 decreases,
Alternatively, the cohesiveness deteriorates and the strand becomes monofilament-like, resulting in poor resin impregnation when the strand is used as a reinforcing fiber.
特にＳＭＣを製造する場合、補強繊維体に含浸させる樹
脂は増粘されているため樹脂の含浸不良か生じ易い。Particularly when producing SMC, the resin used to impregnate the reinforcing fibers is thickened, so poor resin impregnation is likely to occur.
（４）集束剤と帯電防止剤の反応による性能の低下は両
者の組合せ如何によって変化する。このため帯電防止剤
による性能低下を少なくしようとすると、使用する集束
剤と帯゛准防止剤の種類か制限されてしまう。(4) The reduction in performance due to the reaction between the sizing agent and the antistatic agent varies depending on the combination of the two. For this reason, in order to reduce the deterioration in performance caused by antistatic agents, there are restrictions on the types of sizing agents and antistatic agents that can be used.
本発明者は上記課題を解決する為検討を重ね、帯電防止
剤を含まない集束剤を附与集束し、次いで好ましくは乾
燥してなるガラス繊維束の表面に帯電防止剤又は帯電防
止剤及び潤滑剤か被着せしめられている帯電防止性ガラ
ス繊維束、又はこの繊維束を引揃えたロービングをＦＲ
Ｐ補強繊維として使用し、或は上記帯電防止性ガラス繊
維束を用いてシートモールディングコンパウンド（ＳＭ
Ｃ）を製造することにより好適な結果の得られることを
見出し、特許出願を行った。The present inventor has made repeated studies to solve the above problems, and has applied a sizing agent that does not contain an antistatic agent to the surface of the glass fiber bundle, which is then preferably dried. FR is an antistatic glass fiber bundle coated with a chemical agent, or a roving made by aligning this fiber bundle.
Used as P reinforcing fibers or using the above antistatic glass fiber bundles to form sheet molding compounds (SM
It was discovered that suitable results could be obtained by producing C), and a patent application was filed.
本発明は、上記ガラス繊維束を補強繊維として使用して
得られるＦＲＰ、又はＳＭＣを使用して得られるＦＲＰ
の耐水性を向上させる為、研究を重ねた結果に基づく新
たな提案である。The present invention provides an FRP obtained by using the above-mentioned glass fiber bundle as a reinforcing fiber, or an FRP obtained by using SMC.
This is a new proposal based on the results of repeated research to improve the water resistance of.
［課題を解決するための手段］
Ｌ記目的を達成する為、本発明においては、帯電防止剤
を０．０５〜２ｗｔ％含む集束剤を附与集束し１次いで
好ましくは乾燥してなるガラス繊維束の表面に帯電防止
剤又は帯電防止剤及び潤滑剤を被着せしめた帯電防止性
ガラスｍ維束、又はこの！ａ維東を引揃えたロービング
をＦＲＰ補強繊維として使用する。[Means for Solving the Problems] In order to achieve the object L, in the present invention, glass fibers are formed by applying a sizing agent containing 0.05 to 2 wt% of an antistatic agent, sizing the glass fibers, and then preferably drying the glass fibers. Antistatic glass m fiber bundle with antistatic agent or antistatic agent and lubricant coated on the surface of the bundle, or this! a Roving made of ITO is used as FRP reinforcing fiber.
又本発明においては、ブッシングから引出したガラス繊
維に帯電防止剤を０，０５〜２ｗｔ％含む集束剤を附与
し、次いで好ましくは乾燥したガラス繊維束表面に帯電
防止剤又は帯電防止剤及び潤滑剤を被着せしめることに
より樹脂補強用繊維体を製造する。Further, in the present invention, a sizing agent containing 0.05 to 2 wt% of an antistatic agent is applied to the glass fibers pulled out from the bushing, and then preferably an antistatic agent or an antistatic agent and a lubricant are applied to the surface of the dried glass fiber bundle. A resin-reinforcing fiber body is manufactured by applying the agent.
更に又本発明においては、ブッシングから引出したガラ
ス繊維に帯電防止剤を０５０５〜２ｗｔ％含む集束剤を
附与集束、し次いで乾燥してなるガラスｍ維東又はその
引揃え物に帯電防止剤又は帯電防止剤及び潤滑剤とを含
む後処理液を塗布し、次いで好ましくは加熱下に再度乾
燥したガラス繊維又はその引揃え物を切断し、移動する
コンベア上に堆積せしめてマット状物となし、該マット
状物に増粘剤を含む液状の熱硬化性樹脂を含浸させた後
、養生することによりＳＭＣを製造する。Furthermore, in the present invention, a sizing agent containing 0505 to 2 wt % of an antistatic agent is applied to the glass fibers pulled out from the bushing, the sizing agent is applied to the glass fibers pulled out from the bushing, and the antistatic agent or applying a post-treatment liquid containing an antistatic agent and a lubricant, and then cutting the glass fibers or their alignments, preferably dried again under heating, and depositing them on a moving conveyor to form a mat-like material; SMC is manufactured by impregnating the mat-like material with a liquid thermosetting resin containing a thickener and then curing it.
次に本発明を更に具体的に説明する。Next, the present invention will be explained in more detail.
ブッシングから引出した直径３〜２５終、好ましくは９
〜１６ルのガラス繊維に集束剤を塗布し、３０〜ｓ、ｏ
ｏｏ本、好ましくは５０〜１，０００本程本捏束し、ス
トランドとする。Diameter pulled out from bushing 3-25, preferably 9
Apply a sizing agent to ~16 liters of glass fiber, and apply a sizing agent to it for 30~s, o.
000 pieces, preferably about 50 to 1,000 pieces, are kneaded into a strand.
集束剤としては０．０５〜２ｗｔ％程度の帯電防止剤、
１〜１５ｗｔ％程度の被膜形成剤、０．０１〜２ｗｔ％
程度の潤滑剤、０．０１〜５ｗｔ％程度のカップリング
剤を含むものが好適に使用てきる。As a sizing agent, an antistatic agent of about 0.05 to 2 wt%,
Film forming agent of about 1 to 15 wt%, 0.01 to 2 wt%
A lubricant containing approximately 0.01 to 5 wt % of a coupling agent can be suitably used.
被膜形成剤としてはポリ酢醜ビニール等を、潤滑剤とし
てはノニオン系或はカチオン系界面活性剤又は油剤等を
、カップリンク剤としてはシランカップリング剤等を用
いるのか適当である。It is appropriate to use polyvinyl acetate or the like as the film forming agent, a nonionic or cationic surfactant or oil agent as the lubricant, and a silane coupling agent as the coupling agent.
ガラス繊維に対する集束剤の附与丑は、固型分として０
．３〜３ｗｔ％好ましくは０．５〜２ｗｔ％とするのが
適当である。The amount of sizing agent added to glass fibers is 0 as a solid content.
．． A suitable amount is 3 to 3 wt%, preferably 0.5 to 2 wt%.
このように集束剤中に微量の帯電防止剤を含有せしめる
ことにより、前述した先願の効果を損なうことなく、し
かも上記のストランドを補強繊維として使用して得られ
るＦＲＰ、或は上記ＳＭＣを使用して得られるＦＲＰの
耐水性を向上せしめうろことが見出された。By including a small amount of antistatic agent in the sizing agent, the above-mentioned effect of the previous application is not impaired, and FRP obtained by using the above-mentioned strands as reinforcing fibers or the above-mentioned SMC can be used. It has been found that the water resistance of FRP obtained by this process can be improved.
Ｌ述のストランドに帯電防止剤を被着せしめる。Apply an antistatic agent to the strands described in L.
被着の手段に特に限定はなく、帯電防止剤を含む後処理
液をストランドに噴霧し、或はロールコータ−を用いて
塗布しても良く、或は又ストランドをテンションバーの
下面に接して張力を与えつつ移動せしめながら、テンシ
ョンバーの上面に本溶液を所定割合で、好ましくは定量
ポンプを用いて供給し、後処理溶液をテンションバーの
下面に流下せしめストランドに後処理液を接触せしめて
塗布することによってストランドに帯電防止剤を被着さ
せることもできる。There is no particular limitation on the means of application, and a post-treatment liquid containing an antistatic agent may be sprayed onto the strand or applied using a roll coater, or the strand may be placed in contact with the lower surface of the tension bar. While applying tension and moving the strand, supply this solution at a predetermined ratio to the upper surface of the tension bar, preferably using a metering pump, and allow the post-treatment solution to flow down to the lower surface of the tension bar and contact the strand with the post-treatment solution. The strands can also be coated with antistatic agents by coating.
後処理液の塗布によって被着せしめる帯電防止剤の量は
、ガラス繊維に対し０．Ｏ１〜１ｗｔ％程度て充分効果
をうることかできる。The amount of antistatic agent deposited by applying the post-treatment liquid is 0.0. A sufficient effect can be obtained with about 1 to 1 wt% of O.
本発明においては、集束剤中に混入する帯電防止剤の量
は微量であるので、集束剤との関連において使用しうる
帯電防止剤の種類が制限をうけることはなくアニオン系
、ノニオン系、カチオン系、両性イオン系、無機塩類等
各種のものか使用てきるが、＃水性向上の見地からは
を用いるのか特に望ましい。In the present invention, since the amount of antistatic agent mixed into the sizing agent is very small, there are no restrictions on the types of antistatic agents that can be used in conjunction with the sizing agent, including anionic, nonionic, and cationic antistatic agents. A variety of compounds can be used, including aqueous, amphoteric, and inorganic salts, but it is particularly desirable to use # from the standpoint of improving aqueous properties.
又本発明においては後処理液中に潤滑剤を１〜３０ｗｔ
％、好ましくは５〜１５ｗｔ％程度含有させておくこと
もでき、ストランドの潤滑性を一層向上させることがで
きる。In addition, in the present invention, 1 to 30 wt of lubricant is added to the post-treatment liquid.
%, preferably about 5 to 15 wt%, to further improve the lubricity of the strand.
なお、潤滑剤としてはノニオン系或はカチオン系界面活
性剤又は油剤が好適に使用できる。Note that as the lubricant, nonionic or cationic surfactants or oil agents can be suitably used.
ストランドに対する本溶液の附与は、ストランド水中の
水分か０．１ ｗｔ％以下の状態て行うのか好ましく、
本発明の効果を一層向上させることかできる。水分を減
少させる工業的手段としては加熱炉を用いた加熱乾燥、
減圧乾燥を行うのが好適である。It is preferable that the solution is applied to the strands at a water content of 0.1 wt% or less in the strand water.
The effects of the present invention can be further improved. Industrial methods to reduce moisture include heating and drying using a heating furnace;
Drying under reduced pressure is preferred.
なおストランドに対する後処理液の附与は個々のストラ
ンドに対し別々に行うこともできるが、多数のストラン
ドを引揃えてロービングとなす際、多数のストランドに
同時に附与するのが実際的である。Although the application of the post-treatment liquid to the strands can be carried out separately for each strand, when a large number of strands are arranged to form a roving, it is practical to apply the post-treatment liquid to a large number of strands at the same time.
後処理液を附与したストランド、或はロービングは、３
０〜ｌＯＯ°Ｃ１好ましくは５０〜８０℃において加熱
乾燥するのか適当であり、リボナイゼイションを向上さ
せる効果を得ることがてきる。Strands or rovings to which post-treatment liquid has been applied are 3
It is appropriate to dry by heating at a temperature of 0 to 100°C, preferably 50 to 80°C, and the effect of improving ribonization can be obtained.
上述の本発明ストランド或はロービングはそのまま、或
は切断し、又は連続した状態でマット状物とし、或は製
織して布状物となしてＦＲＰの補強用に好適に用いるこ
とができる。The above-mentioned strands or rovings of the present invention can be suitably used for reinforcing FRP as they are, cut into pieces, or made into a mat-like material in a continuous state, or woven into a cloth-like material.
又本発明のストランド或はロービングの切断物（ＣＳ）
を用いてＳＭＣを製造することもできる。Also, the strand or roving cut product (CS) of the present invention
SMC can also be manufactured using.
［作 用］
帯電防止剤の大部分をストランドの表面にのみ被着させ
ることにより所望の帯電防止効果をうるのに必要な帯電
防止剤の使用量を減少させる。[Function] By depositing most of the antistatic agent only on the surface of the strand, the amount of antistatic agent required to obtain the desired antistatic effect is reduced.
又帯電防止剤を０．０５〜２ｗｔ％含む集束剤を附かし
てガラス＃ａ雌を集束してストランドとなし、次いでこ
のストランド表面に帯電防止剤を被着させることにより
、集束剤成分と帯電防止剤の反応を防止し、ストランド
の性能を向上させ、着色を防止し、更に又このストラン
ドを補強繊維として使用して得られるＦＲＰ、又はこの
ストランドを使用して得られるＳＭＣの耐水性を向上さ
せる。In addition, by applying a sizing agent containing 0.05 to 2 wt% of an antistatic agent and converging glass #a female into a strand, and then coating the surface of this strand with an antistatic agent, the sizing agent component can be combined with the sizing agent component. It prevents the reaction of the antistatic agent, improves the performance of the strand, prevents coloring, and also improves the water resistance of FRP obtained by using this strand as a reinforcing fiber or SMC obtained by using this strand. Improve.
このようなストランドをＦＲＰ補強用として用いること
により樹脂の含浸性を良好ならしめる。By using such strands for reinforcing FRP, resin impregnation properties are improved.
この効果はＳＭＣ製造の場合特に著しい。This effect is particularly significant in SMC production.
帯電防止剤の被着をストランド乾燥後に行うことにより
、北記効果を一層向上させる。By applying the antistatic agent after drying the strand, the Hokki effect is further improved.
又帯電防止剤と共に潤滑剤を附ケすることによりストラ
ンドの潤滑性を一層向上させる。Furthermore, by adding a lubricant together with an antistatic agent, the lubricity of the strands is further improved.
更に又帯電防止剤附与後ストランドを加熱乾燥するこに
とよりリボナイゼーションを向上させる。Furthermore, ribonization can be improved by heating and drying the strand after adding the antistatic agent.
［実施例１］
帯電防止剤としてＣ１□１１２５Ｎ” ＣＩｌ：Ｉ・
ＣＩ−を固型ルを８ｗＬ％、潤滑剤としてノニオン系界
面活性剤を０．５ ｗｔ％、カップリング剤としてシラ
ンカップリンク剤を０．２ ｗＬ％含むサイジング剤を
ガラス繊維に対し固型分として１．ｓ ｗｔ％附与附与
１４０℃に１２１＋ｒ加熱乾燥してストランドｌとした
。[Example 1] As an antistatic agent, C1□1125N” CIl:I・
A sizing agent containing 8 wL% of solid CI-, 0.5 wt% of a nonionic surfactant as a lubricant, and 0.2 wL% of a silane coupling agent as a coupling agent was added to the solid content of the glass fiber. As 1. s wt % was applied and dried by heating at 140° C. for 121+r to obtain a strand 1.
このストランドに帯電防止剤として
０１□１１□５−Ｎ÷−６１１３・ＣＩ−の１０％溶液
を、ロールコ」
の表面に被着させ、ストランドＩＩを得た。A 10% solution of 01□11□5-N÷-6113.CI- was applied to this strand as an antistatic agent on the surface of Rollco to obtain Strand II.
帯電防止剤の被着量はガラス繊維の０．０５ｗＬ％てあ
った。The amount of antistatic agent applied was 0.05 wL% of the glass fiber.
ト記ストランドＩ、ＩＩを用い、スタティックフォトメ
ーターを使用し、印加電圧８ＫＶ、温度２５°Ｃ１湿度
５０％の条件で帯電圧、半減期を測定した結果を別表に
示す。Using strands I and II, the charging voltage and half-life were measured using a static photometer at an applied voltage of 8 KV, temperature of 25° C., and humidity of 50%. The results are shown in the attached table.
ストランドＩＩは集束性、切断時の分散不良を生するこ
となく、液状熱硬化性樹脂の含浸性も良好てあり、着色
を生ずることもなかった。Strand II did not exhibit poor cohesiveness or dispersion during cutting, had good impregnability with the liquid thermosetting resin, and did not cause coloring.
［実施例２コ
Ｃ１１゜
実施例１の Ｃ１゜１１□％ Ｎ”−（：１１：１−
ＣＩ−に代え、ＣＨ。[Example 2 C11゜Example 1 C1゜11□% N”-(:11:1-
CH instead of CI-.
ｌｈ
（：＋ａｌｌ：＋ｙ Ｎ◆−Ｃ２１１，、・Ｃ２Ｈ，
、ＳＯ，−を用いて得られた（：ｌＩ：１
ストランド（ストランド■）について同様な測定を行っ
た結果を別表に示す。lh (:+all:+y N◆-C211,,・C2H,
The results of similar measurements performed on the (:lI:1 strand (strand ■) obtained using , SO, - are shown in the attached table.
なお、ストランド■の集束性共他の性質はストランドＩ
Ｉと同等であった。In addition, the convergence and other properties of strand ■ are similar to those of strand I.
It was equivalent to I.
［比較例１］ 実施例１で用いられた集束剤中に ＣＨ。[Comparative example 1] In the sizing agent used in Example 1 CH.
Ｃｌ８１１３７ Ｎ” Ｃ２１１５・Ｃ２１１５Ｓ
Ｏ４−を混入し、（混入よう定めた）実施例１と同様に
して得られたストランド■について同様な測定を行った
結果を別表に示す。Cl81137 N” C2115/C2115S
The results of similar measurements performed on strand (2) obtained in the same manner as in Example 1 with O4- mixed therein (specified to be mixed) are shown in the attached table.
なお、このストランド■は分散性、樹脂の含浸性かスト
ランドエ、Ｈに比して不良であり、このストランドを用
いて製造したＦＲＰ中に約５％の不良品か発生した。It should be noted that this strand (3) had poor dispersibility and resin impregnation properties compared to strands (E) and (H), and about 5% of the FRPs produced using this strand were defective.
又このストランド■は黄色に着色した。Also, this strand (■) was colored yellow.
別 表
［実施例３］
実施例１．２のストランドＩＩ、ｍを２．５ ｃｍの長
さに切断し、この切断物を７５０ｇｒ／ｒｒｆの割合で
堆請させたＣ８に、次の組成を有する樹脂組成物を含浸
させ、ガラス含有１２５ｗｔ％のＳＭＣを製造した。Attached Table [Example 3] Strand II, m of Example 1.2 was cut into a length of 2.5 cm, and the following composition was added to C8, which was deposited at a rate of 750 gr/rrf. A 125 wt % glass-containing SMC was manufactured by impregnating the resin composition with the resin composition.
不飽和ポリエステル樹脂 ７０重量部低収縮剤
３０重量部炭酸カルシウム １５
０重量部Ｔ Ｂ Ｐ Ｂ ０．０２
重量部ステアリン酸亜鉛 ０．０５ｉ量部Ｍｇ
Ｏｏ、ｏ＋重量部
樹脂の含浸性は良好てあり、含浸不良に起因する不良品
か発生することはなかった。Unsaturated polyester resin 70 parts by weight Low shrinkage agent
30 parts by weight calcium carbonate 15
0 parts by weight T B P B 0.02
Part by weight Zinc stearate 0.05i Part by weight Mg
Oo, o+parts by weight The impregnability of the resin was good, and no defective products were produced due to poor impregnation.
［比較例２］
比較例１のストランド■を用いて、実施例３と同様なＳ
ＭＣを製造した。[Comparative Example 2] Using the strand ■ of Comparative Example 1, the same S as in Example 3 was prepared.
MC was manufactured.
樹脂の含浸性は不良て、不良品発生率は５％てあった。The impregnability of the resin was poor, and the incidence of defective products was 5%.
［実施例４コ
実施例３のＳＭＣを用いて製造したＦＲＰを１００°Ｃ
の水中に８０間放置した場合、成形品表面のふくれか生
じなかった。[Example 4] The FRP manufactured using the SMC of Example 3 was heated at 100°C.
When the molded product was left in water for 80 hours, only blistering occurred on the surface of the molded product.
［比較例３］
実施例４のストランド■、■に代え、被膜形成剤、潤滑
剤、カップリング剤の種類及び含有量はストランドＩＩ
、ｍの製造に用いられた集束剤と同一・であるか、帯電
防止剤を全く含まない集束剤を使用して得られたストラ
ンドを用い、実施例４と同様に試験を行った場合著しい
ふくれを生した。[Comparative Example 3] In place of strands ■ and ■ in Example 4, the types and contents of the film forming agent, lubricant, and coupling agent were those of strand II.
When a test was conducted in the same manner as in Example 4 using a strand obtained using a sizing agent that was the same as the sizing agent used in the production of , m or did not contain any antistatic agent, significant blistering was observed. gave birth to
［発明の効果］
所定の性能を得るのに必要な帯電防止剤の使用！１℃を
減少し、帯電防止効果を高める。[Effect of the invention] Use of antistatic agent necessary to obtain the desired performance! Reduces temperature by 1℃ and enhances antistatic effect.
ストランドの集束性の低下、着色を防止し、樹脂の含浸
性を高め、均質なＦＲＰ、ＳＭＣをうる。Prevents deterioration of strand cohesiveness and coloring, improves resin impregnation, and obtains homogeneous FRP and SMC.
又ＦＲＰの耐水性を向上させる。It also improves the water resistance of FRP.
帯電防止剤と集束剤の組合せ可能な範囲を特徴するFeatures a range of possible combinations of antistatic agents and sizing agents
Claims (25)
与集束してなるガラス繊維束の表面に帯電防止剤又は帯
電防止剤及び潤滑剤を被着せしめたことを特徴とする帯
電防止性ガラス繊維束。(1) Charging characterized by having an antistatic agent or an antistatic agent and a lubricant coated on the surface of a glass fiber bundle obtained by applying and converging a sizing agent containing 0.05 to 2 wt% of an antistatic agent. Anti-resistant glass fiber bundle.
与集束し、次いで乾燥してなるガラス繊維束の表面に帯
電防止剤又は帯電防止剤及び潤滑剤を被着せしめたこと
を特徴とする帯電防止性ガラス繊維束。(2) An antistatic agent or an antistatic agent and a lubricant are applied to the surface of the glass fiber bundle that is obtained by applying a sizing agent containing 0.05 to 2 wt% of an antistatic agent and then drying it. Characteristic antistatic glass fiber bundle.
ン系、アニオン系或は両性系の界面活性剤であることを
特徴とする請求項１、又は２記載の帯電防止性ガラス繊
維束。(3) The antistatic glass fiber bundle according to claim 1 or 2, wherein the antistatic agent is an inorganic salt, or a cationic, nonionic, anionic, or amphoteric surfactant.
量はガラス繊維の０．０１〜１ｗｔ％であることを特徴
とする請求項１、２又は３記載の帯電防止性ガラス繊維
束。(4) The antistatic glass fiber bundle according to claim 1, 2 or 3, wherein the amount of the antistatic agent deposited on the surface of the glass fiber bundle is 0.01 to 1 wt% of the glass fiber. .
剤を含むことを特徴とする請求項１、２、３又は４記載
の帯電防止性ガラス繊維束。(5) The antistatic glass fiber bundle according to claim 1, 2, 3, or 4, wherein the sizing agent contains a film forming agent, a coupling agent, or a lubricant.
であることを特徴とする請求項１、２、３、４又は５記
載の帯電防止性ガラス繊維束。(6) The amount of sizing agent added is 0.3 to 3 wt% of the glass fiber.
The antistatic glass fiber bundle according to claim 1, 2, 3, 4 or 5, characterized in that:
は油剤であることを特徴とする請求項１、２、３、４、
５又は６記載の帯電防止性ガラス繊維束。(7) Claims 1, 2, 3, 4, wherein the lubricant is a nonionic or cationic surfactant or an oil agent.
7. The antistatic glass fiber bundle according to 5 or 6.
ガラス繊維の０．０１〜１ｗｔ％であることを特徴とす
る請求項１、２、３、４、５、６又は７記載の帯電防止
性ガラス繊維束。(8) The amount of the lubricant deposited on the surface of the glass fiber bundle is 0.01 to 1 wt% of the glass fiber. antistatic glass fiber bundle.
帯電防止性ガラス繊維束の引揃え物よりなることを特徴
とする帯電防止性ロービング。(9) An antistatic roving comprising an array of antistatic glass fiber bundles according to claim 1, 2, 3, 4, 5, 6, 7, or 8.
剤を０．０５〜２ｗｔ％含む集束剤を附与し、次いで好
ましくは乾燥したガラス繊維束表面に帯電防止剤を被着
せしめることを特徴とする樹脂補強用繊維体の製造法。(10) A sizing agent containing 0.05 to 2 wt% of an antistatic agent is applied to the glass fibers pulled out from the bushing, and then the antistatic agent is preferably applied to the surface of the dried glass fiber bundle. A method for producing a fibrous body for resin reinforcement.
剤を０．０５〜２ｗｔ％含む集束剤を附与集束し次いで
乾燥してなるガラス繊維束又はその引揃え物に帯電防止
剤を含む後処理液を塗布することによって帯電防止剤を
被着し、次いで好ましくは加熱下に再度乾燥することを
特徴とする樹脂補強用繊維体の製造法。(11) A post-treatment liquid containing an antistatic agent is applied to the glass fiber bundle or the aligned product obtained by applying a sizing agent containing 0.05 to 2 wt% of an antistatic agent to the glass fibers pulled out from the bushing, converging the bundle, and then drying it. 1. A method for producing a resin-reinforcing fibrous body, which comprises applying an antistatic agent by coating the material, and then drying it again, preferably under heating.
うことを特徴とする請求項１０又は１１記載の樹脂補強
用繊維体の製造法。(12) The method for producing a resin-reinforcing fiber body according to claim 10 or 11, characterized in that drying before application of the post-treatment liquid is carried out under heating or under reduced pressure.
オン系、アニオン系或は両性系の界面活性剤であること
を特徴とする請求項１０、１１又は１２記載の樹脂補強
用繊維体の製造法。(13) Production of a resin reinforcing fiber body according to claim 10, 11 or 12, wherein the antistatic agent is an inorganic salt, or a cationic, nonionic, anionic or amphoteric surfactant. Law.
の量はガラス繊維の０．０１〜１ｗｔ％であることを特
徴とする請求項１１、１２又は１３記載の樹脂補強用繊
維体の製造法。(14) The resin reinforcing fiber body according to claim 11, 12 or 13, wherein the amount of the antistatic agent deposited on the surface of the glass fiber bundle is 0.01 to 1 wt% of the glass fiber. Manufacturing method.
滑剤を含むことを特徴とする請求項１１、１２、１３又
は１４記載の樹脂補強用繊維体の製造法。(15) The method for producing a resin reinforcing fiber body according to claim 11, 12, 13, or 14, wherein the sizing agent contains a film forming agent, a coupling agent, or a lubricant.
％であることを特徴とする請求項１１、１２、１３、１
４又は１５記載の樹脂補強用繊維体の製造法。(16) The amount of sizing agent added is 0.3 to 3 wt of glass fiber.
%, Claims 11, 12, 13, 1
4 or 15. The method for producing a resin reinforcing fiber body according to 15.
求項１１、１２、１３、１４、１５又は１６記載の樹脂
補強用繊維体の製造法。(17) The method for producing a resin reinforcing fiber body according to claim 11, 12, 13, 14, 15, or 16, wherein the post-treatment liquid also contains a lubricant.
又は油剤であることを特徴とする請求項１７記載の樹脂
補強用繊維体の製造法。(18) The method for producing a resin reinforcing fiber body according to claim 17, wherein the lubricant is a nonionic or cationic surfactant or an oil agent.
剤を０．０５〜２ｗｔ％含む集束剤を附与集束し次いで
乾燥してなるガラス繊維束又はその引揃え物に帯電防止
剤又は帯電防止剤及び潤滑剤とを含む後処理液を塗布し
、次いで好ましくは加熱下に再度乾燥したガラス繊維又
はその引揃え物を切断し、移動するコンベア上に堆積せ
しめてマット状物となし、該マット状物に増粘剤を含む
液状の熱硬化性樹脂を含浸させた後、養生することを特
徴とするシートモールディングコンパウンドの製造法。(19) A sizing agent containing 0.05 to 2 wt% of an antistatic agent is applied to the glass fibers pulled out from the bushing, the bundle is bundled and then dried, and an antistatic agent or an antistatic agent is added to the glass fiber bundle or an array thereof. A post-treatment liquid containing a lubricant is applied, and then the glass fibers or their alignments are cut again preferably under heating and deposited on a moving conveyor to form a mat-like material. A method for producing a sheet molding compound, which comprises impregnating a sheet molding compound with a liquid thermosetting resin containing a thickener and then curing the compound.
オン系、アニオン系或は両性系の界面活性剤であること
を特徴とする請求項１９記載のシートモールディングコ
ンパウンドの製造法。(20) The method for producing a sheet molding compound according to claim 19, wherein the antistatic agent is an inorganic salt, or a cationic, nonionic, anionic, or amphoteric surfactant.
着せしめた帯電防止剤の量はガラス繊維の０．０１〜１
ｗｔ％であることを特徴とする請求項１８、１９又は２
０記載のシートモールディングコンパウンドの製造法。(21) The amount of antistatic agent deposited on the surface of the glass fiber bundle by applying the post-treatment liquid is 0.01 to 1% of the amount of glass fiber.
Claim 18, 19 or 2, characterized in that it is wt%.
A method for producing a sheet molding compound according to 0.
滑剤を含むことを特徴とする請求項１８、１９、２０又
は２１記載のシートモールディングコンパウンドの製造
法。(22) The method for producing a sheet molding compound according to claim 18, 19, 20 or 21, wherein the sizing agent contains a film forming agent, a coupling agent, or a lubricant.
％であることを特徴とする請求項１８、１９、２０、２
１又は２２記載のシートモールディングコンパウンドの
製造法。(23) The amount of sizing agent added is 0.3 to 3 wt of glass fiber.
%, Claims 18, 19, 20, 2
23. The method for producing a sheet molding compound according to 1 or 22.
又は油剤であることを特徴とする請求項１９、２０、２
１、２２又は２３記載のシートモールディングコンパウ
ンドの製造法。(24) Claims 19, 20, 2, wherein the lubricant is a nonionic or cationic surfactant or an oil agent.
24. The method for producing a sheet molding compound according to 1, 22 or 23.
着せしめた潤滑剤の量はガラス繊維の０．０１〜１ｗｔ
％であることを特徴とする請求項１９、２０、２１、２
２、２３又は２４記載のシートモールディングコンパウ
ンドの製造法。(25) The amount of lubricant deposited on the surface of the glass fiber bundle by applying the post-treatment liquid is 0.01 to 1wt of the glass fiber.
%, Claims 19, 20, 21, 2
The method for producing a sheet molding compound according to 2, 23 or 24.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63141578A JP2563826B2 (en) | 1988-06-10 | 1988-06-10 | Manufacturing method of antistatic glass fiber bundle, antistatic roving, resin reinforcing fiber and sheet molding compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63141578A JP2563826B2 (en) | 1988-06-10 | 1988-06-10 | Manufacturing method of antistatic glass fiber bundle, antistatic roving, resin reinforcing fiber and sheet molding compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01313346A true JPH01313346A (en) | 1989-12-18 |
| JP2563826B2 JP2563826B2 (en) | 1996-12-18 |
Family
ID=15295247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63141578A Expired - Fee Related JP2563826B2 (en) | 1988-06-10 | 1988-06-10 | Manufacturing method of antistatic glass fiber bundle, antistatic roving, resin reinforcing fiber and sheet molding compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2563826B2 (en) |
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| JPH0292844A (en) * | 1988-09-27 | 1990-04-03 | Taikisha Ltd | Cloth |
| JP2014058436A (en) * | 2012-08-20 | 2014-04-03 | Nippon Electric Glass Co Ltd | Surface treatment agent coating apparatus and surface treatment agent coating method, and glass roving |
| CN104986952A (en) * | 2015-07-01 | 2015-10-21 | 安徽丹凤电子材料股份有限公司 | Preparation technology of anti-static glass fiber |
| EP3106442A1 (en) | 2015-06-15 | 2016-12-21 | Shin-Etsu Quartz Products Co., Ltd. | Sizing agent for quartz glass fibers, quartz glass fiber, quartz glass yarn, and quartz glass cloth |
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| JPH01298044A (en) * | 1988-03-31 | 1989-12-01 | Ppg Ind Inc | Chemically treated glass fiber for reinforcing thermosetting resin matrix |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0292844A (en) * | 1988-09-27 | 1990-04-03 | Taikisha Ltd | Cloth |
| JP2014058436A (en) * | 2012-08-20 | 2014-04-03 | Nippon Electric Glass Co Ltd | Surface treatment agent coating apparatus and surface treatment agent coating method, and glass roving |
| JP2017186731A (en) * | 2012-08-20 | 2017-10-12 | 日本電気硝子株式会社 | Method for producing glass roving |
| EP3106442A1 (en) | 2015-06-15 | 2016-12-21 | Shin-Etsu Quartz Products Co., Ltd. | Sizing agent for quartz glass fibers, quartz glass fiber, quartz glass yarn, and quartz glass cloth |
| US10104768B2 (en) | 2015-06-15 | 2018-10-16 | Shin-Etsu Quartz Products Co., Ltd. | Sizing agent for quartz glass fibers, quartz glass fiber, quartz glass yarn, and quartz glass cloth |
| CN104986952A (en) * | 2015-07-01 | 2015-10-21 | 安徽丹凤电子材料股份有限公司 | Preparation technology of anti-static glass fiber |
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| Publication number | Publication date |
|---|---|
| JP2563826B2 (en) | 1996-12-18 |
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