Taiga TATSUMI 1, ZhenHong WANG 1, Shinichi TAMURA 1,2, Yoshinori NISHINO 1,3 1

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1 Requested Article:Editorial Board GPI Journal Vol. 2, No. 2 GPI7G-047 Published in Dec 27, 2016 Technical report of auxiliary material Study of mat sizing agent of glass fiber 1st Report: Basic Properties of Olfine Taiga TATSUMI 1, ZhenHong WANG 1, Shinichi TAMURA 1,2, Yoshinori NISHINO 1,3 1 NBL Technovator Co., Ltd. 2 ISIR, Osaka University 3 NBL Material Co., Ltd. Abstract: This research is a report on research results on the surface activity and coupling effect of the sizing agent used for sizing materials of glass fiber mats. It is turned out that the effect of using an olefin surfactant as a CSM convergence aid for producing the effect of minimizing the amount of vat binder necessary for CSM forming is that the necessary binder amount can be drastically reduced to a maximum of 1/5. Keywords: nonionic surfactant, sizing agent, static surface tension, dynamic surface tension, wettability, defoaming properties Fig.1 Glass fiber mat 1. Introduction This research is a report on research results on the surface activity and coupling effect of the sizing agent used for sizing materials of glass fiber mats. Fig. 1 is a product of glass fiber mat. Generally, glass fiber mat made by cutting glass fiber and dispersing it on the flat surface and joining the fiber intersection with binder, Chopped Strand Mat (CSM) has 2400 tex (1300 μm) filament of 13 microns called multi end roving shown in Fig g / km) Cut the focused glass fiber (bundle) to about 50 mm, and mold a mat of 100 to 800 g/m2 shown in Fig. 1. This CSM is made by impregnating a matrix resin such as unsaturated polyester and dissolving the binder, dispersing the glass fiber to form a clay layer inside the reinforcing fiber and hardening and integrating the resin, whereby FRP (Fiber Reinforced Plastic) it can. In other words, it is necessary to Fig.2 glass fiber have a convergence aid that material has the function of temporarily bonding the glass fiber and focusing the mat binder, which does not adversely affect the curing of the resin, on the glass fiber contact point to impart wettability to the fiber surface. This includes the need to obtain a convergence effect to bundle the surface of the glass fiber bundle effectively by focusing the binder on the glass fiber contact point in Fig. 3, and on the contrary, to maintain the flexibility as a mat Other than the intersecting point of the Received on Nov 20, Revised on Dec 16, Accepted on Dec 25, Fig. 3 Mat(Glass fiber contact junction)[1] fibers as much as possible are required to bond and bond the fibers. At the same time, efficient bonding and bonding is a bonding between fiber bundles covering the glass fiber bundle surface without penetrating into the inside thereof. Further, it is difficult to dissolve in the matrix resin and does not hinder the performance of the resin. On the other hand, in order to obtain the coupling effect between the matrix and the glass fiber, a sizing agent constituting the glass fiber bundle to which the hydrolyzed silane coupling agent adheres that not to disturb the function. That is, guarantee the required performance of Fig. 4 showing the performance evaluation of CSM, maximize the bonding effect of the mat binder which does not adversely affect the FRP quality by minimizing the amount of expensive secondary raw material mat binder required for CSM molding As a result of applying research on CSM convergence aid (surfactant), we have succeeded to reduce the amount of binder necessary for CSM production to 1/5 of the required amount of powder mat binder while keeping quality deterioration to a minimum Successful molding of flexible mat. GPI Standards Committee Editorial Board

2 T. Tatsumi et al. / GPI Journal 2(2) (2016) Fig 4-1 Fiberglass mat test method. STYRENE MONOMER Fig 4-2. Mat binder dissolution test. the sizing agent used for the raw glass fiber filaments, nor does it dissolve the hydrolyzed silane coupling agent or other sizing agents. In other words, it was considered that Surfynol shown in Fig. 5 did not prevent the newly added surfactant of the emulsion binder necessary for mat processing by dissolving the filament sizing agent to which the newly added surfactant had already adhered. Further, at the time of FRP molding, it is necessary to dissolve all of the coupling agent by styrene monomer and recover it to the matrix resin. Auxiliaries applying glass fiber and matrix resin Surfynol surfactant (Nisshin Chemical Industry's name "OLFINE", acetylene glycol) are suitable for this purpose. As shown in Fig. 5, Surfynol is a nonionic surfactant having a bilaterally symmetrical structure and is applied to water-based materials in various fields as "wetting agent that does not easily foam". Environmental problems start to close up, and surfynol functions are suitable under circumstances where various materials are promoted to be water-based. It also meets the purpose for wetting, defoaming and even dispersion applications. It is a very stable glycol as a molecular structure, it has a small molecular weight, an effect of greatly lowering the surface tension, a wide range of adaptive materials, and when it is applied to a coating material, it remains on the coating film after passing through the baking step, it is reported that there is the merit of not having it. Olfine is blended with multifunctional surfynol surfactant and widely used for various applications. [2] Fig. 4-3 Lay-up and boiling test after bending strength for FRP 2.Characteristics of convergence aid used The used convergence aid (hereinafter referred to as "OLFIN") contains a large amount of surfactant for emulsification of mat binder as an emulsion type mat binder. Fig. 6 Comparison of physical properties between Surfynol (acetylene glycol) and general surfactant[2] 3. Characteristics of Olfine (Measurement of Surface Tension by Maximum Foam Pressure Method) Fig.5 Surfynol [2] (2,4,7,9-tetramethyl-5-decyne-4,7-diol) Furthermore, Global oil & gas Pipe Institute 246 it does not dissolve As shown in Fig. 6, Olfine has the Fig. 7 Principle of maximum bubble method[2]

3 Requested Article:Editorial Board GPI Journal Vol. 2, No. 2 GPI7G-047 Published in Dec 27, 2016 function of (1) lowering the dynamic surface tension, (2) suppressing the characteristics (increasing defoaming property). Normally, the dynamic surface tension is higher than the static surface tension shown in Fig. 11. The surface tension in the state close to the actual use condition is the dynamic surface tension, and it is important to control the dynamic surface tension. Fig. 12 compares the dynamic surface tensions of various surfactants. Olfine type has characteristics different from fluorine, silicon type and succinate type, and its dynamic surface tension is low. Fig. 8 Surface tension measuring device (by maximum bubble pressure method)[2] Fig. 9 Measurement of surface tension by maximum bubble pressure method (relationship between air pressure, surface tension and time)[3] It is a method to calculate the surface tension by measuring the maximum pressure (maximum bubble pressure) when bubbles are generated by letting gas flow through a capillary (probe) inserted in a liquid. In this study, the static surface tension was measured with one bubble per second, and the bubble generation rate was increased up to 10 bubbles per second. The foam maximum bubble pressure method was carried out using the measuring equipment shown in Fig. 8 under the principle shown in Fig.7. The advantage of the maximum bubble pressure method is that both dynamic surface tension and static surface tension can be measured by changing the bubble velocity. The interfacial tension (Fig. 9), which is rapidly generated by bubbles generated by nitrogen blowing, is similar to the measured interfacial tension value (Fig. 11) in the static state like the Du Nouy method (Fig. 10) [4]. Fig.12 Comparison of various surfactants (Evaluation by maximum bubble pressure method) 4-1 Wettability 4. Performance of Olfine An example of improvement of wettability by Olfine is shown in Fig.13. Fig. 13 Improvement of wettability by Olfine (Eg inkjet ink) Left: general surfactant, Right: Olfine The contact angle became smaller due to the addition of the Olfine (the contact angle became larger as the sphere was closer to it, and the wettability got worse). That is, Surfynol contributes to improvement of wettability. Fig.14 shows an example of improving the wettability of water based resin by Olfine. Fig. 10 Surface Fig. 11 Measurement of surface tension measuring tension by method according to Du device (by Du Nouy method (Obtain surface Nouy method) tension lamella length from stress Received on Nov 20, measurement length) [4] Revised on Dec 16, Accepted on Dec 25, GPI Standards Committee Editorial Board

4 T. Tatsumi et al. / GPI Journal 2(2) (2016) Fig.15 SEM photography of paper fiber (a)left:blank (b)middle:applied conventional surfactant (c)right:applied Olifine Fig. 16 Defoaming propert of Olfine (Left: blank, right: Olfine 0.1%) Fig.14 Improvement of wettability by adding Olfine (Left) Olfine addition (right) No additive Compared with the case where the resin unevenness was bad (the arrow part) without the additive (right part), the resin adhered to the whole when the olefin was added (left), resulting in a very beautiful finish. In the case of no additives, the object is considered to have insufficient wettability. 4-2 Defoaming properties Fig. 15 shows the results of improvement of defoaming property by using Olfine. The white line in the microphotograph was set to 100 μm (0.1 mm), and the enlargement ratio was set to 100 times. Fig. 15 (b) shows a general surfactant applied to Fig. 15 (a). There were dozens of small and large holes, even on the photograph. It is considered to be the influence of foam caused by surfactant. On the other hand, in Fig. 15 (c), no hole could be confirmed. Surfactant Surfynol contained in Olfine not only removes bubbles remaining on the surface (rupture effect) but also removes bubbles staying inside (surfactant suppressing effect), so even bubbles originating from non-surfactant As a result, the gap between the fibers of the paper is filled, and a clean surface without pinhole marks is obtained. Fig. 16 shows the results of photographing the coated surface with a microscope for improving the defoaming property with or without addition of the Olfine. On the right of the picture with the addition of the Olfine, unevenness on the left of the photo was not seen as without the Olfine, and it turned out that it was finished on a uniform dispersion surface. The scale in the figure is 1000 μm = 1 mm. 5. The effect of the use of Olfine 5.1 Adhesive bonding effect of mat binder Fig. 17 is an electron micrograph showing the adhesion state between glass fiber and mat binder. The glass fiber used was 2400 Tex multi-end E-glass, 50 mm cut roving which was mainly sized with 0.1% of silane coupling agent of 200 bundles of 11 to 13 m length of fiber and about 0.4% polyvinyl acetate (PVAc) converging material. This is the adhesion state confirmation test result of the mat binder emulsion containing 20 to 30% containing 1 to 3% of the Olfine aid. On the left side of Fig. 17, there is no loss of the glass filament forming sizing agent by the surfactant of the emulsion mat binder, and a mat binder having a new particle diameter adheres to the fiber surface. In the center picture, the mat binder does not invade much into the gaps between the fibers and is responsible for the filament binding effect. The right picture shows that the surfactant of the mat binder is insoluble in filament forming sizing agent. That is, Olfine is effective as a mat binder convergence aid. Global oil & gas Pipe Institute 248

5 Requested Article:Editorial Board GPI Journal Vol. 2, No. 2 GPI7G-047 Published in Dec 27, 2016 Fig. 17 Electron micrograph showing the adhesion state between glass fiber and mat binder (Left) Mat binder adheres to fiber surface (center) Filament bundling effect by binder (right) Do not remove sizing material Fig.18 Characteristics of use of acrylic emulsion binder (effect by Olfine auxiliaries) [5] 5.2 Characteristics of using acrylic emulsion binder [4] Fig. 18 shows the test results of the mat strength and the required amount of binder obtained by adding an olefin aid to an acrylic emulsion using 100 multi-ended and 200-cut rovings. The necessary emulsion mat binder strength is 5 kg in terms of 100 mm width. The allowable flexural rigidity is 5 cm in cantilever rating of 125 mm length. The mechanical strength characteristic that the standard addition amount under the same conditions when no olefin was added by this binder was 1.2% indicates that a test result was obtained in which the required binder amount was reduced by about 50% owing to the addition of Olfine. As a result, the necessary strength and flexibility were obtained under the best production conditions, the binder usage amount was changed from 1.2% to 0.5% in the case of using 100 multi-end, 0.6% in 1.4% in 200 lines (the dry weight ratio ). In addition, when using a flexible type emulsion binder of PVAc type, the addition amount is about 3.5% as standard. 5.3 Quality performance of product CSM Fig. 19 is a photograph comparing the effect of CSM using olefin aid on the glass fiber interface of the FRP molded article by conducting the boiling deterioration test [4] of the molded article. The resin used is about 65% wt in ISO type polyester resin. Compared with the CSM using VE type powder binder which does not affect the glass fiber interface, use of the right olfine clearly showed less interfacial deterioration (judged by degree of whitening) as compared with the center without using olfine. That is, the use of an olefin aid indicates less inhibition of the effect of the coupling agent with the glass fiber. Received on Nov 20, Revised on Dec 16, Accepted on Dec 25, GPI Standards Committee Editorial Board

6 T. Tatsumi et al. / GPI Journal 2(2) (2016) Fig. 19 Corrosion resistance evaluation results of CSM products using Olfine 6 Conclusion The water-soluble emulsion mat binder is a product in which PVAc, EVA, acrylic and PET type particles are dispersed in an ionic surfactant at a concentration of 2.5% to 8%. For CSM products using this binder, it is necessary to add about 3.5% LOI, at least 1.2% or more is required even when high strength and high flexibility acrylic type is used, and the interface deterioration with glass fiber The resulting emulsion binder is excellent in flexibility but whitening is regarded as a drawback. In this study, we have successfully solved this problem by using nonionic surfactant, Olfine, and reported the results. 1) We confirmed the strength up that the filament binding binder effect can be evaluated. 2) It was confirmed that deterioration of glass fiber interface at CSM product was improved. 3) There was a defoaming effect, eliminating the problem of bubbles occurring at about 300% amount of shower and excessive emulsion vacuum. Shinichi Tamura, Yoshinori Nishino, "Analysis of autonomous concentration of mat binder particles to cross point of glass fiber bundles by electric field", GPI Journal Vol. 2, No. 2, pp (2016). [2] Olfine catalog, Nisshin Chemical Industry Co., Ltd. (2016) [3] urface_tention/ [4] Kenji Aoki, Research on Coatings No. 156, pp (2014). [5] Taiga Tatsumi, ZhenHong Wang, Hiroyuki Doi, Shinichi Tamura, Yoshinori Nishino, "Quality evaluation and test methods of chopped strand glass fiber mat",gpi Journal Vol. 2, No. 2, pp (2016). Acknowledgement This paper is the result of the development of emulsion binder and CSM production facility for glass fibers which we have been collaborating with Nisshin Chemical Industry Co., Ltd. in the past and given the reporting opportunity, we will announce the results. I thank you for your support. Reference [1] Taiga Tatsumi, ZhenHong Wang, Hiroyuki Doi, Global oil & gas Pipe Institute 250