TW387865B - Reinforcing glass strands and composites resistant to corrosive media - Google Patents

Description

Printed by A7 'B7 of the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the Invention (1) The present invention relates to a glass stock (or "suspected dimension") used to strengthen organic and / or inorganic materials. The glass stock and / Or the material can be used in corrosive media (humid, NaC 1 thorium-containing media, acid media or alkaline media). The present invention also relates to a composition for coating the glass strand and a reinforced product (or "composite") obtained from the glass strand. It is known that glass strands are used to strengthen organic and / or inorganic materials. For some time, the most commonly used glass strand was the E glass strand, which contained a composition obtained from a Si02-A12-CaO system eutectic at 1 1 70 ° C. These glass strands are usually coated with a slurry composition during their manufacture to protect the glass strands from abrasion and improve the adhesion between the glass and the material to be strengthened (good adhesion is particularly helpful for obtaining good mechanical properties Compound). E-glass strands thus sizing are particularly suitable for use with thermoplastic or thermosetting organic materials and to produce composites with excellent mechanical properties. But in some media [such as when these glass strands are directly (that is, not protected by organic materials) merged with an alkaline material (such as cement) or when the composites made from these glass strands are in some corrosive media (Especially in cement or in a device that is in contact with water, salt or acid), these glass strands will deteriorate and their mechanical properties will deteriorate, resulting in their strengthening effect with Time has been reduced. At present, there have been attempts to solve this problem in various ways. Among them, it is particularly known to change the glass composition of the glass strands to improve the chemical resistance of these glass strands to highly alkaline media. . This composition called hafnium-resistant glass usually contains a high proportion of chromium oxide, and is a glass composition such as Na 2 0 — Z r02 — Si 02. The paper sizes of these books are in accordance with China National Standard (CNS) A4 (210X297 mm) ~ -4-· --........... --------- Loading --- --- Order ---- · Ί (Please read the notes on the back of the page before filling in this page) A7 B7 V. Description of the invention (2) Know the glass composition in GB 1, 29 0,528 〇However, although this type of glass is eroded to a lesser extent than E glass, its degradation phenomenon is slowed down, and the reduction of its mechanical properties may be significant under certain conditions. In addition, the use of these glass strands is currently limited to the direct strengthening of cement, and even if these glass strands are coated with a general slurry (such as those used to improve the adhesion of E glass strands to organic materials), their Adhesion is not as strong as E glass strands, so the benefits in strengthening organic materials are even more limited. Even if these glass strands are coated with conventional stocks (such as for coating E glass strands to make them suitable for weavers), weaving will still be difficult. It is also known to coat glass strands for strengthening cement with a primer. The purpose of this primer composition is to protect the surface of the glass strands from corrosion by the cement. Furthermore, many formulations have been proposed, such as coating glass strands with furan resin, but most of these formulations can only provide temporary protection. ”Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read first On the back • Note I, please fill out this page) As for other solutions (such as the addition of agents that reduce the alkalinity of the medium), they are only limited to specific uses, and the scope of application is very limited. In addition, other reinforcing materials (such as carbon stocks) Etc.) to produce composites with a corrosion-resistant medium, but the cost of this reinforcing material is higher than that of glass strands, so the rejection is still limited. The above disadvantages are overcome through the present invention. The present invention proposes to have a large and / or better strengthening effect in a long time in at least one corrosive medium such as a humid medium, Na C 1 thorium-containing medium, an acid medium, and an alkaline medium. The paper size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm). Printed by the Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs. A7 _B7 _ V. Description of the invention (3) Glass stocks, especially organic and / Or inorganic materials and used to obtain one or more mechanical properties in at least one corrosive medium such as humid medium, Na C 1 salt-containing medium, acid medium and alkaline medium before or after at least a considerable period of time. Improved glass strands, and / or glass strands whose deterioration has been substantially reduced in at least one of the above-mentioned media (meaning that the mechanical properties of the composites obtained from such glass strands decline less rapidly). The glass strand of the present invention is coated with a slurry composition containing at least one silane according to the following formula

Si (R i) (R 2) (R 3) (R 4) where • R! And R 2 are alkoxy groups; • R 3 is an alkoxy group or a group consisting mainly of carbon, hydrogen, and possible nitrogen; • R 4 is a base mainly composed of carbon, hydrogen, and possible nitrogen, and contains at least one unsaturated ring, which is replaced by at least one unsaturated chain co-rolled with the ring. The present invention is also related to coating The slurry composition of the glass strand, the composition containing at least one silane according to the above formula. The "composition j containing" means "a composition whose initial composition is one", regardless of the change of the composition in the composition. Similarly, "coated glass strands (coated glass strands j means" glass strands that have been coated with "), and the coating is subjected to general treatment of the glass strands (especially after drying). And / or after the polymerization operation) The situation is irrelevant · This & Zhang scale is applicable to the Chinese solid standard (CNS > A4 specification (210X297 mm) -------- r equipment ----- order ( Please read the note at the back of the page 项 -item before filling out this page) -6-Printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by Aigong Consumer Cooperative A7 B7 V. Description of the invention (4) The glass strand of the present invention is prepared by known methods. Generally speaking, the glass strand of the present invention is manufactured in the following manner: mechanically pulling the molten glass stream from one or more bushing nozzles into one or more fa n of continuous filaments, The monofilament is then coated with the slurry composition of the present invention before being assembled into strands. The glass strand is then wound on a rotating support before distribution or other operations (for indirect cutting, weaving extraction) • or distributed Formed on a moving conveyor or on a permeation stretcher Later cutting (direct cutting under the bushing). The state of the glass strand of the present invention depends on the application, and it can be wound into a continuous winding glass strand (roving, cake, tapered cone, etc.) ), Can be cut into strands, mat-like (entangled with skein-like flakes), total ribbon, ribbon, and mesh, etc. These various glass strands are usually from 5 to 2 4 in diameter Monofilament. The glass strand of the present invention can be made of any type of glass generally used to make glass strands for strengthening. The glass strand of the present invention can be an E glass strand, a so-called "R glass" type glass strand (mechanical Strong) or glass strands of "S glass" based on silica, alumina, magnesia, and possibly lime, and glass strands of alkali-resistant glass, etc. Especially when the glass strand of the present invention is E glass When it is stock, it should be obtained from the following ingredients which are mainly contained in weight percentage: 52-58% Si〇2 '12-16% A12〇3' 16 -2 5% CaO '4-1 3% B203, -6% MgO, 0—2% rhenium metal oxide (basically Na20 and / or K20). This glass may also contain other materials containing no more than 1% each Other ingredients, such as fluorine, Ti02, Cu0, Ba0, Zn0, Zr02, L i 0 2, 503, etc. * In addition, it can also be used for other paper sizes that can be used for strengthening. Use China National Sample Rate (CNS) Α4 specification (210X297 Mm) — -H ϋ nn ^ — — — — — Order 3 \, (please read the note on the back Ϋ-item before filling out this page) -7-A7 B7 glass stock but less frequently mentioned in this use Glass 9 is especially chemically resistant glass containing the following main components expressed as percentages of heavy children: 5 7 to 59% S i 0 2, 1 1 to 13% A 1 2 0 3, 2 0 to 2 2% C a 0, 2 — 5% Μ g 0, 0 — 0 • 5% B 2 〇3 2 -3% T i 0 2% 0 — 3% Z η 0 0 • 9 — 1% N a 2 〇 and / Or K 2〇 or glass containing acid-resistant medium with the following main composition expressed as a percentage by weight: 60-6 6% S i 0 2, 2-6% A 1 2 0 3 > 1 4-1 5% C a 0 1 — 3% Mg 0, 2-7% B 2 〇3 7 — 10% Ν a 2〇 and / or K 2〇> 0 — 0 4% F e 2 〇3 0 The glass strand of the present invention is preferably a so-called Γ-resistant glass strand. This type of glass usually contains zirconia Zr 0 2 0. These glass strands may be selected from any existing resistant glass strands (such as GB 1%). 2 9 0, 5 2 8, US 4 9 3 4 5 9 0 3 7, US 4 > 0 3 6 »6 5 4 5. Description of the invention (5) Please read first

Note

I

(Patent, US 4,014,705, US 3,859,106, etc.), and should preferably contain at least 5 mole% 2Zr02. According to a preferred implementation system of the present invention, the glass constituting the glass strand contains Si0 2, Zr02 and at least one samarium oxide (Na 2 0 is preferred) as the main components. The alkali-resistant glass composition particularly used for manufacturing the glass strand of the present invention is the composition described in GB 1,290,528, which mainly contains the following ingredients expressed in mole percentages: 62-75% SiO2, 7-11% Zr02, 13-21% R2〇'l — ι〇% R 〇, 0 — 4% A 1203, 〇— 6% B2 03, 〇— 5% This paper size applies to China National Standard (CNS) A4 specifications (210X297 (Mm) 8 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 —— ___B7 V. Description of Invention (6)

Fe203 '0-2% CaF2' Ο-4% T i Ο 2, R2〇 represents one or more rhenium metal oxides (preferably Na2〇) and Li20 which is selectively used (up to 2%), R ^ 0 is one or more components selected from the group consisting of ochre metal oxide, Z η ◦ and M η 〇. The reason why the alkali-resistant glass strand according to the present invention is particularly suitable for the purpose of the present invention will be described below. The slurry composition of the coated glass strand of the present invention may be an aqueous or anhydrous composition, or may contain, for example, less than 5% by weight of a compound solely as a solvent. In most cases, the composition of the present invention is an aqueous composition containing 70 to 98% by weight of water, and is an aqueous dispersion (emulsion, suspension, emulsion and / or suspension mixture). Or as a solution "As defined by the present invention, this composition contains at least one glass selected from the specific silanes that conform to the previous definition, and the glass coated with the slurry composition of the present invention containing one or more such silanes It can be used to strengthen organic and / or inorganic materials to produce at least one corrosive medium such as humid medium, Na C 1 salt-containing medium, acid medium and alkaline medium. More than one compound with improved mechanical properties, etc .; and / or a compound with better mechanical properties maintained after a period of time (mechanical properties are less rapidly degraded). The improvement in properties depends on the type of glass strands being coated, the material being strengthened, and the corrosive medium. "Improved mechanical properties (improved mechanical properties)" as used herein refers to the same glass strands that are not coated with the slurry composition of the present invention (especially at the size of this paper, the Chinese National Standard (CNS) A4 specification applies) 210 X 297 mm) n -------- r f'installation ------- order -------. 1 rf. · 'I, y (please read the back of the M first Note the year and fill in this page again.) A7 ___B7_ V. Description of the invention (7) Generally the same glass strands coated with a paste containing other silanes other than the silanes used in the present invention) have improved mechanical properties compared with In the best case, when the glass strands of the present invention are alkali-resistant glass strands, it seems that the bonding of these glass strands to organic materials (especially thermosetting materials) can be greatly improved. Composites having mechanical properties before ageing in a corrosive medium (regardless of the medium) or after aging for at least a considerable period of time compared to alkali resistance of the same organic material and generally not coated with the slurry composition of the present invention Glass strands (especially those containing other silanes than those used in the present invention) Slurry-coated alkali-resistant glass strands) are better composites. Therefore, the alkali-resistant glass strands coated with the paste of the present invention can be used not only for corrosive inorganic materials (for example, non-hardened materials such as cement ), And it is unexpectedly and beneficially used to strengthen organic materials that may or may not be used in highly corrosive media such as cement. Printed by Shellfish Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs (please read the "Notes on the back" before filling out this page). It must be specified here that the durable glass strands coated with the composition of the present invention can be woven. So that it can be used in applications such as making meshes (for walls) [this meshing is made of several types of films coated with protective substances (usually, butadiene, polyvinyl chloride, acrylic, etc.) Made of E-glass strands of polymers). In this application, the use of alkali-resistant glass strands (direct strengthening of alkaline media (such as cement) is better than E-glass strands from the beginning, so there is no need to protect them with organic substances for road applications) To avoid the use of additional protective substances "organic materials and other glass strands coated with the slurry of the present invention (if the paper size is applicable to the Chinese National Standard (CNS) A4 size (210X297 mm) — -10-economic A7 B7 printed by the Consumers' Cooperative of the Ministry of Standards and Standards of the People's Republic of China V. Description of the invention (8) The compound obtained by the invention of the R glass stock or E glass stock) is at least some corrosive media before aging or after at least a considerable period of time The mechanical properties after aging have also improved, but in many cases the degree of improvement is not as significant as that of the alkali-resistant glass strand of the present invention. More specifically, if the composite is highly stressed in an acid medium, even if the compound is used, The E glass strand of the invention does not improve the mechanical strength of the composite. Similarly, the use of the E glass strand of the present invention in an alkaline medium does not improve the mechanical strength. There is also no significant improvement in the mechanical properties of the composites. In addition, the mechanical properties of the composites after aging in humid media and / or Na C 1 salty media have also been observed for some time. The results were found in Eben The invention of the R glass strand is much shorter than the case of the alkali-resistant glass strand according to the present invention. However, the R glass strand or the E glass strand of the present invention makes it possible to produce a composite with particularly improved mechanical strength ( The reason is that the R glass strand or E glass strand has good adhesion to the organic material at the beginning.) The R4 group of the silane in the definition of the present invention is preferably R 5 Φ R β where φ is Unsaturated ring, this ring should be a benzene ring, and it should be a para isomer. • Re is an unsaturated chain conjugated to the ring. The better is when Re = — (CH = CH) m_: H , m is an integer of 1 to 4, especially for the reason of three-dimensional obstacles, where = 1 is particularly good, and it can also be 2. This paper is also applicable to the Chinese National Standard (CNS) A4 (210X297 mm) '- --11---------〗-Magnesium ------ Order & Please read the back-C NoteΫ. (This page) Printed by the Ministry of Economic Affairs_Central Bureau of Standards Consumer Cooperatives A7 B7 V. Description of Invention (9) • R5 is an aliphatic chain containing one or more alkyl groups and possible amine groups (the [etc.] amine group It may be related to other components of the slurry and / or to the reinforced material (some kind of coupling interaction), the number of atoms in the main chain is 4-20, especially for reasons of steric obstacles. This chain can be branched and unsaturated (especially on its branch). This aliphatic bond preferably contains one or more alkyl and amine groups, but it is more advantageous to have at least 4 carbon atoms and mostly alkyl groups (for example, this chain contains at least 3 times more amine groups than amine groups). Alkyl group is more favorable): it should be composed of connected groups that meet the following formula:-(CH2) n_NH —, where η is an integer, can be changed depending on the group, and less than 4 is more favorable, and in each of its The end is terminated with an alkyl group. For example: R 5 = — (C Η 2) „-Ν Η-(CH2)„ ._NH — (C Η 2), where η, η > and n'S4e The R3 group of the silane in the definition of the present invention may be R4 type or r5 type group or alkoxy group, and alkoxy group is preferred. The alkoxy group of the silane of the present invention is preferably selected from ethoxy and methoxy. According to a preferred implementation system of the present invention, the slurry composition used in the present invention contains at least one silane as defined above, wherein: R 1 == R2 = — C Η 〇 »R 4 =, R 5 =-(C Η 2) a- Ν Η-(CH2) 2-NH-CH2-, and

Re = — CH = CH2, that is, 1-vinylfluorenyl-4_methyl-amine ^ Paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -------- f Pack- ---— Order. .1. (Please read the note ν ^^^ on the back before filling this page) -12-A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (10) Ethylamine The amount of silane in the slurry composition according to the present invention in the slurry composition of the present invention is approximately bounded between 0-5 to 20% by weight of the dry extract of the composition. It is better to be 2% to 15% of the weight of the child > and to reset the %% from 4 to 5 to 1 3 to be the best 0. The improvement of the mechanical properties of the compound is observed ~ Generally, with this inclusion Increasing (except when using E glass strand in acid medium 9 will be explained below) 〇 If the silane content of the present invention is less than 0-5 wt% > the improvement of mechanical properties is not significant if it is less than 2 weight % 9 changes The degree of goodness is not very large. If it is higher than 15% by weight, the cost of this slurry will increase greatly and there is no improvement in nature. Cases in which mechanical properties are reduced 0 In addition to the above-mentioned containing at least one kind of silane, the slurry composition of the present invention may contain one or more silanes commonly used as coupling agents »especially one or more silicon compounds used in slurry Such as gamma — methacrylic acid oxypropyl • If · —— · 碁 dimethoxysilane, gamma-gl yc idoxy propyl trimethoxysilane, etc. (these) silicon firing may be between glass reinforced materials In this case, the content of other silanes other than the silicon courtyard defined by the present invention is generally lower than 1 2 weight 1:% of the dry extract of the composition of the present invention, and less than 5 reset% is more than Good 0 The biggest content of all sand yards The amount does not exceed 25% of the reset of the dry extract of the composition of the present invention. This slurry composition may also contain other coupling agents (such as titanates > zirconates, etc.) or used to promote glass strands. Organic compounds that are coupled to certain organic materials 0 According to a preferred embodiment of the present invention 9 The composition for coating the glass strand, in addition to containing the silicon courtyard of the present invention, includes at least-* kinds of adhesives »ie, please Read the back first. Please fill in the paper size of the note and use the Chinese National Standard (CNS) A4 specification (210X297 mm) -13-A7 _____B7_ V. Description of the invention (11) The monofilament is bonded together (whole) in the glass strand. Pharmaceutical, this adhesive is a compound with ring gas functional group, preferably a polymer with at least partially polymerized functional group and at least one epoxy functional group. This "prepolymer" is, for example, bisphenol A or bisphenol F diepoxidized derivative, epoxy phenol novolac resin or epoxy cresol novolac resin, phenyl glycidyl ether, triglycidyl ether of p-aminophenol, cyclohexane Dimethyl diglycidyl ether and the like. In the composition of the present invention, at least one silane defined in the present invention and at least one adhesive containing at least one epoxy functional group are used in combination for a composite obtained from these glass strands and organic and / or inorganic materials. The result is that the mechanical properties in the acidic medium before aging, at least for a considerable period of time, and after aging have been further improved or even unexpectedly, and these composites and glass strands can also obtain special characteristics. Good corrosion resistance (less rapid deterioration of mechanical properties caused by a period of time in corrosive media), especially better corrosion resistance than using a composition containing only one of these ingredients in a considerable amount ( Multiplication effect). Printed by the Central Labor Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative (please read the V note on the back before filling out this page). This composition may contain one or more than one kind of adhesive in addition to the epoxy functional adhesive. Other adhesives, such as those with polyester functional groups (such as polyethylene vinyl esters) or replacing the adhesives with epoxy functional groups with these other adhesives, but the latter is related to the use of epoxy functional groups. Adhesive implementation The system is less favorable than the following, which will be explained below. The amount of adhesive should be 0-85% by weight of the dry extract of the composition, generally 50-75% by weight. At least 85% of these adhesives should be epoxy-functional adhesives. Agent. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm). Printed by Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7 B7. 5. Description of the invention (l2) According to a more advantageous implementation system of the present invention, in principle, When glass strands are used for the direct strengthening of alkaline materials such as cement, the composition contains at least one phosphonic acid or phosphine in addition to at least one of the foregoing silanes and at least one epoxy-functional adhesive. Acid derivatives Sodium butanephosphine tricarboxylate, hydroxyethane diphosphonic acid, sodium hydroxyethane diphosphonic acid, and the like. Coating a glass strand with a composition containing at least one silane of the present invention and at least one phosphonic acid or a phosphonic acid derivative For the glass strand of the present invention or a composite obtained from the glass strand of the present invention, excellent corrosion resistance properties are obtained, This is especially the case when the glass strands are directly bonded to an alkaline organic material such as cement. The use of at least one silane as defined in the present invention, at least one phosphonic or phosphonic acid derivative, and at least one epoxy functional group-containing adhesive in the composition to coat the glass strand of the present invention produces at least some corrosive properties. Media (such as alkaline media) have unexpected aging resistance, especially glass strands that are better than using a composition containing only one or two of these ingredients in equal amounts. This multiplicative effect is particularly pronounced when glass strands are used directly with alkaline inorganic materials such as cement. The amount of phosphonic acid is generally 0 to 40% by weight of the dry extract of the composition, and the amount of phosphonic acid is 10% of the dry extract of the composition when the glass strand is directly bonded to an inorganic material such as cement. — 40% by weight is particularly good》 In addition to the ingredients described above, the composition of the present invention may also contain other ingredients, especially those commonly used in slurry compositions * such as lubricants, film-forming agents, textile agents ( textile agents), antistatic agents, this paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ~~ — -15--------- '' i equipment ----- 丨Order «\ (please read the note I on the back side before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, printed A7 B7 V. Description of the invention (13) Emulsifiers, surfactants, wetting agents, etc. The proportion of these agents is preferably less than 30% by weight of the dry extract of the composition, and in most cases the composition contains at least one lubricant, such as a fatty acid ester or a fatty alcohol derivative. Drying the composition for at least 5% by weight. The invention can be manufactured by mixing all ingredients simultaneously or adding these ingredients in several steps. The silane of the present invention is generally added to the composition in a hydrolyzed state. After mixing the active ingredients, a solvent (especially water) can be added to the mixture to obtain the desired composition and ratio. If the composition of the present invention is an aqueous dispersion, the dry extractability of the composition is approximately between 2 and 30% reset of the composition. This composition is usually sunk on the monofilaments before the monofilaments are combined into strands, for reasons explained above. However, the composition for coating glass strands can be deposited in several steps. For example, the silane of the present invention can be immersed in a hydrolyzed state and has nothing to do with the other components in the composition, but it is preferable that these other components are deposited before the silane is brought into direct contact with the glass constituting the glass strand. The loss of ignition (loss of ignition) of the glass stocks should be between 0.2 and 4% by weight * of the glass stocks, and 0.3-2% by weight of the glass stocks are preferred. These glass stocks are effective Reinforce organic and / or inorganic materials and produce composites with improved mechanical properties in corrosive media. The composite obtained from the glass strand of the present invention includes at least one organic material and / or at least one inorganic material and glass strand, at least some of which have a glass paper size that conforms to China National Standard (CNS) A4 (210X297 mm) ~ ' —Lb-(Please read the note on the back? Then fill in this page) 'Binding · Order A7 B7 V. Description of the invention (14) The stock is the glass stock of the present invention. The glass strand of the present invention is suitable for thermosetting materials (vinyl esters, polyesters, phenol resins, epoxides, acrylic polymers, etc., and vinyl esters are more advantageous because they are more corrosion resistant than other organic materials) and / Or cementitious materials (cement, concrete, stucco, stone sales, compounds formed by the reaction of lime, silica and water, etc.). Reinforcement of cement materials may be achieved directly or indirectly (merged with organic materials before being added to cement). The following non-limiting examples are intended to illustrate the glass strands and composites of the present invention, and the mechanical properties of the composites prepared from the glass strands of the present invention before and after aging and the mechanical properties of the composites produced from conventional glass strands. Comparison of properties * Comparative Example 1 In this example, a glass monofilament with a diameter of 14 was drawn by drawing a molten glass stream. This glass has the following composition (expressed in weight percentage) -------- (; , Installed-f--2Λ (please read the note on the back first, and then fill out this page) Order the durable glass printed by the Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs: S i 0 2 6 1 6% A 1 2 〇3 0 • g% Z r 0 2 1 6-8% C a 0 5 • 4% N a 2 〇1 4 • 7% K 2〇0 * 3% F β 2 〇3 0-0 5% Gas 0 2 6% This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 17-Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of Invention (15) A7 _____B7 T i 0 2 0 1% S 0 3 0.05% These monofilaments contain 1 heavy layer during their passage and before assembly into strands:% are ethoxylated Lubricant based on phenol (sold under the GAF product name “IGEPAL C 0 880”), 0.15 wt% gamma-methacryloxypropyltrimethoxysilane (sold under the product name “SiUuest A 174” ), The rest of the slurry composition is coated with water, these glass strands obtained from a monofilament combination and having a linear density ("yarn count (yarnc unt)") of 300 g / km (t ex) are cakes The glass strands are then wound and dried with hot air at 130 ° C. The glass strands are then pulled out of the wound package to produce plaques with parallel glass strands in accordance with NF 5 7 — 15 2 standards. The reinforced The resin is a polyester resin sold by Cray-Valley under the trade name M 4 02, in which 15 parts of Cray-Valley is sold under the trade name "F 8 0 10 C" for every 100 parts by weight of the polyester resin. 16.5 parts of styrene and 1 · 5 parts of Ciba-Geigy accelerators sold under "THM 60". The mechanical properties of these pUciues in terms of bending are before aging and immersion at 9 8 ° C Measured after 24 hours in water (accelerated aging) according to standard ISO 1 78. Its bending strength (For glass extrapolated to 100%) before aging is 1 1 2 OMP a (standard deviation for 10 plaques is 12 2MP a), and after aging is 186 MPa (standard deviation is 20 MPa) ). The size of this paper is in Chinese National Standard (CNS) A4 (210X297 mm) ------- r. Packing ------ Order (please read the t note on the back before filling this page)- 18-A7 _B7 _ V. Description of the invention (16) Example 1 was carried out in the same manner as in Comparative Example 1, but 1- (vinylfluorenyl-4-methylamino-ethylamino) propyltrimethoxysilane was used instead of gamma. -Methacryloxypropyltrimethoxysilane, the former is added as a solution of its hydrochloride in methanol. This solution is sold by Dow Corning under the name "Silane Z-6 032". For the glass child extrapolated to 100%, the crossbow strength is 2111 MPa before aging (standard deviation for 10 plaques is 159 MPa), and it is 616 MPa after aging (standard deviation is 2 6 M P a). From the above comparison, it was found that the use of the glass strand of the present invention greatly improves the bending strength of the composite made of the glass strand and the organic material, and the aging resistance in a humid medium is also improved. After 7 days of accelerated aging in a wet medium, the loss of mechanical properties is much smaller than the loss of mechanical properties observed with glass stocks coated with silanes that do not meet the definition of the present invention. Example 2 Packing -------- ^ ,! Packing ------- Order (please read and read the t note on the back before filling in this ΪΓ). Manufacture alkali-resistant glass strands in the same way as in Comparative Example 1. Wrap the package, but change the slurry composition of Comparative Example 1 to a material containing 0.08 wt% 1- (vinylfluorenyl-4-methylaminoethylamino) propyltrimethoxysilane (as the hydrochloride Methanol solution added), 0.25% by weight (N-fluorenylaminoethyl) aminopropyltrimethoxysilane (added in the form of a hydrochloride methanol solution, this solution is SiO and "Silquest A 1128" The seller of the product name), 1.80 reset% diethylene glycol adipic acid ester. ¥ Paper size is applicable to the Chinese national standard (€ Yang) 8 4 specifications (210 father 297 mm) ~ Central Bureau of Standards, Ministry of Economic Affairs Printed by the Industrial and Consumer Cooperatives A7 B7 V. Description of the Invention (17) Agent ("Naxol 25 00 SH" by Scott Bader) Seller name), 0.42% reset lubricant polyethylene glycol emulsifier (based in BP Chemicals' Breox 2000 "seller's name), while the remaining group is a water slurry of the present compositions. The dry extract is approximately 2.6 reset for the composition? ό. Secondly, these glass strands are drawn from the wound package to produce plaques with parallel glass strands in accordance with NF 5 7-15 2 standards. The reinforced resin is a vinyl ester resin sold by Dow Chemicals under the trade name Derakane 41 1_45, in which 0.75 5 replacement parts are added from 8 1 ^ 〇 to "100

Trigonox 239 "catalyst sold under the trade name of 0.88% by weight

Accelerators sold by Akzo under the brand name "NL 5 1P" ° The mechanical properties of these plaques in bending are such that the specimen undergoes forced bending deformation in a liquid corrosive medium at 40 ° C Measured after 3 to 7 days according to standard I SO 1 78. For the amount of glass inserted to 100%, measured after performing the "stress corrosion" test in a 1 N sulfuric acid solution, a 1 N sodium hydroxide solution, distilled water, and a salt solution containing 37 g of NaCl per liter, respectively. The flexural strength (expressed as MPa) is shown in Table I, and the standard deviations for the 6 test items are shown in parentheses. Example 3 The same procedure as in Example 2 was performed, but this time the slurry composition was changed. The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -------- ^ V ----- It (please read the note _ on the back _ and then fill out this I)- 20-Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed A7 B7 V. Description of the invention (I8) 1-vinylethyl-4-methylaminoethylaminopropyltrimethoxysilane and (N-fluorenylamine) The amount of ethyl) aminopropyltrimethoxysilane, the former is 0.2% by weight of the composition, and the latter is the composition of the composition. The reset results are shown in Table I. It can be seen from the table that when used for coating When the amount of the silane of the present invention is increased in the glass-coated composition, the compound is in the medium regardless of the corrosive medium used. Accelerated aging bending strength of 3 days and 7 days Example 4 were improved by the same procedure of Example 2, but this time using the following composition (expressed in weight percent children) of E glass Glass yarns obtained. S i 0 2 5 5% A 1 2 0 3 1 5% B 2 〇3 7% Μ g 〇3% C a 0 19% N a 2 〇0 3% K 2 〇0-2% F e 2 〇 3 0 • 3% Fluorine 0 3% The results are shown in Table I e This paper size applies to China National Standard (CNS) A4 (210X297 mm) _ 21 _ --------- '. -----— Order ------% /, i · ...-\ (Please read the back and note Ϋ-item before filling out this page) Printed by A7, Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs B7 V. Description of the invention (19) Example 5 The same procedure as in Example 3 was performed, but this time the glass strand obtained by using E glass with the composition shown in Example 4 was used. The results are shown in Table 1. When the amount of the silane of the present invention contained in the composition for coating glass strands is increased, the flexural strength of the composite after 3 to 7 days of accelerated aging in distilled water or a salt solution is improved. Example 6 The same procedure as in Example 2 was performed, but this time a glass strand obtained using R glass composed of the following (expressed as a percentage of heavy child) · S i 0 2 60 0% A 1 2 0 3 2 5% M g 0 6% C a 0 9% The results are shown in Table I. Example 7 was carried out in the same manner as in Example 3, but this time a glass strand obtained using R glass having the composition shown in Example 6 was used. The results are shown in Table 1. As a result, it can be seen that the bending strength of the composite is improved after 3 days of accelerated aging in a corrosive medium (regardless of the medium), and after 7 days of accelerated aging in an acid medium or an alkaline medium. Therefore, the size of the glass stock paper used in the present invention is applicable to the Chinese National Standards (CNS) Λ4 grid (210X297 mm). Packing-(Please read the note on the back · Please note the item before filling in this page) Order-22-A7 B7 V. Description of the invention (20) It can reduce the deterioration of glass strands and composites in corrosive media. Example 8 was performed according to the phase synchronization of Example 2, but the slurry composition of Example 2 was changed to a solution containing 0.5% by weight of 1- (vinylfluorenyl-4-methylaminoethylamino) propyltrimethoxysilane. (Added in the state of hydrochloride), 0.1% reset Polyzamide silane sold under the trade name "Silquest A 1387" by 0 Si, 3% by weight by Scott Bader Polyester adhesive sold under the brand name "Naxol 2500 SH", 0.6% by weight of a polyethylene glycol lubricant sold under the brand name "Breox 2000" by BP Chemicals, and a slurry composition consisting essentially of water. The dry extract is 4.5% by weight »Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the _ Note on the back and fill in this page before filling in this page) For the machine made in the same way as in Example 2 Bending property is measured according to the standard I SO 1 78 before aging and after the specimen has been subjected to forced bending deformation in a liquid corrosive medium at 40 ° C for 7 days. For extrapolating to a glass content of 100%, the flexural strength (expressed as MP a) measured after the stress corrosion test was performed in a 1 N sulfuric acid solution and a 1 N sodium hydroxide solution are shown in Table Π. . Example 9 was carried out in the same manner as in Example 8, except that the polyester adhesive in the slurry composition was replaced with an epoxy adhesive sold by Shell under the name "EPI-REZ 3510 W 60". The results are shown in Table II. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 _ B7 V. Description of the invention (21) As can be seen from the results, the silane and the ring having the present invention are used in combination in the glass-coated composition. Oxygen functional adhesives make the composites obtained from these glass strands and organic materials have unexpected mechanical properties before or after aging in corrosive media, and can obtain glasses with excellent corrosion resistance. Strands and Compounds. Comparative Example 2 A winding roll of an alkali-resistant glass strand was manufactured in the same manner as in Comparative Example 1. However, the slurry composition of Comparative Example 1 was replaced with a paste containing 0.25% reset%. (Please read the precautions on the back before filling this page) (N —Methylaminoethyl) Aminopropyltrimethoxysilane (added in the form of a hydrochloride solution, this solution is named "Dynasilan 1161" by Hiils Sales), 10% by weight of fluorene molecular weight polyvinyl acetate-based adhesive (added in the solution state sold by Vinamul under the name "Vinamul R 841 46"), 2 reset% by ethoxylated sorbose Sorbitan monooleate is a lubricant based on ICI under the trade name of "Tween 80" and fatty acid (under the trade name of Sidobre SinnovaU "Lutostat N 68"). The rest are basically water based. Slurry composition. The dry extract is approximately 12% by weight.

Secondly, these glass strands are taken out from the embroidered winding package, and then placed in a CPA_CΕΜ I 4 2.5 type (standard NF P15-301) artificial Portland cement in a water / cement ratio of 0.4. Paste, and note that some glass strands will extend beyond the wet cement. The cement is then hardened at room temperature for 1 hour and then in water for 2 3 hours. The tensile strength of the glass strands held in the cement block is in accordance with the national standard (CNS) A4 size (210X297 gong) applicable to the aging of this paper. &Quot; -24-Printed by the Shell Industry Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Install A7 B7 V. Description of the invention (22) and test on an Instron tension tester before aging in 80 ° C water for 4 days. The results (expressed as MP a) are listed in Table Π, and the residual strength (ie, the strength after aging, expressed as a percentage of the initial strength) is also listed in this table. Example 1 0 was performed in the same steps as in Comparative Example 2, where The same slurry composition is used, but (N-fluorenylaminoethyl) aminopropyltrimethoxysilane is removed, and the amount of 1- (ethylenefluorenyl-4) is further included in an amount of 5% by weight relative to the dry extract of the composition. Monomethylaminoethylamino) propyltrimethoxysilane, and contains a children's lubricant and an adhesive so that it has the same 12% dry extract. The results are shown in Table II. Example 11 was carried out in the same procedure as in Example 10, wherein the same slurry composition was used, but an adhesive based on bisphenol A diglycidyl ether (sold by DSM Italia under the name "Neoxil 8294" ) Equivalent replacement of polyvinyl acetate adhesive. The dry extract amount of this composition was 12% by weight. The results are not in Table Π. Example 1 2 was carried out in the same steps as in Example 11 in which the same size was used to combine the paper size and the Chinese National Standard (CNS) A4 specification (210X297 mm) was applied. ---- Order / · .... S% (please read the note on the back of the page before filling in this page) -25-A7 _B7_ V. Description of the invention (23), but further contains a dry extract relative to the composition The output was 18% by weight of hydroxyethanediphosphonic acid and a small amount of lubricant and adhesive sold by Protex under the name "Masquol P 210 j." The same 12% by weight dry extract was obtained. The results are shown in Table Π When the glass strand is coated with the composition of the present invention *, it can be found that the tensile strength is improved both before and after accelerated aging. When the composition further contains an epoxy functional group adhesive and / Or phosphonic acid, the degree of improvement is greater. It has also been found that when the composition contains, in addition to at least one silane of the present invention, at least one adhesive having an epoxy functional group and at least one phosphonic acid, then Corrosion resistance in alkaline media is also apparent. The loss of degree is small. The glass strand of the present invention can be used for manufacturing various composites, especially for directly strengthening cement (use: meshing for walls, etc.) or for indirectly strengthening cement (use: substitution of rebars for concrete with pultruded rods, etc.) ) E -------- Λ., Install ------- order / ·, ..ά% (Please read the notes on the back before filling in this 萸) Zhengong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs The printed paper size is applicable to China National Standard (CNS) A4 (210X297mm) -26-

A B7 V. Description of Invention (24)

Table I Example of printing by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Acid medium 3 810 1602 1304 518 1522 2001 (40) (172) (431) (243) (402) ( 199) 7 681 834 0 0 1207 1508 (31) (65) (255) (233) Hydroxide 3 864 1340 2129 2142 1524 1642 Sodium medium (85) (108) (38) (217) (372) (372) ( 393) 7th 627 657 1979 1822 1325 1535 (94) (152) (118) (229) (320) (251) Distilled water 3 795 1536 2067 2241 1530 1986 Medium (47) (82) (220) (102) (300) (139) 7th 634 771 1835 2144 1142 1109 (37) (67) (83) (151) (254) (165) NaCl 3rd 935 1670 2065 2231 1512 1935 Salt medium (101) (246) (133) (123) (352) (315) 7th 679 931 2019 2235 1273 1275 (51) (72) (150) (119) (257) (291) This paper size applies to China National Standards (CNS) A4 Specifications (210X297mm) (Please read the notes on the back before filling this page) -27-387865 V. Description of Invention (25) Table Π A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 8 Example 9 Acid media Before aging 2 195 2275 7 835 2230 Sodium hydroxide medium Before aging 2195 2275 7 655 2125 -------- ^-** (Please read the precautions on the back before filling this page) Order

V This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297mm) -28-S87865 V. Description of Invention (26) A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs m Comparative Example Example Example 2 10 11 12 Strength before aging 1032 1422 1830 1621 (MPa) After 4 days 日 strength 303 385 640 736 (MPa) Residual strength (%) 29 27 35 45 {Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) A4 (210X297 mm) -29-

Claims (1)

387865 Α8 Β8 C8 D8 VI. Announcement of the scope of patent application This Annex la: Patent Application No. 85111096 Chinese Application for Patent Scope Amendment May 1987 Amendment 1. A glass stock for strengthening organic and / or inorganic materials, This glass strand is coated with a sizing composition containing at least one silane according to the following formula: SR 1) (R 2) (R 3) (R where • R i and ruler 2 are 〇1— (: 5 Alkoxy group: • R4 is a group mainly composed of carbon, hydrogen and possible nitrogen, and meets the following formula: R 5 Φ R 6 -------- factory table-(Please read the back first Please pay attention to this page, please fill in this page) It is printed by Shelley Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs • Φ is a benzene ring; • Re is an unsaturated chain conjugated to the ring; • Rs is an aliphatic chain and contains an alkyl group And possible amine groups, the number of atoms in the main chain is 4 to 20:. R3 is a R4 or R5 type or (: 1-(: 5 alkoxy). 2. as the first item in the scope of patent application The glass stock is characterized in that the paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) 387865 Α8 Β8 C8 D8 VI. Announcement of the scope of patent application This appendix la: Patent application No. 85111096 Amendment of the scope of Chinese application for patent Amendment of the Republic of China May 1987 Amendment 1. A kind of glass stock used to strengthen organic and / or inorganic materials A sizing composition containing at least one silane according to the formula SR 1) (R 2) (R 3) (R where • R i and ft 2 are 〇1 — (: 5 alkoxy: • R4 is based only on carbon, hydrogen and possible nitrogen, and meets the following formula: R 5 Φ R 6 -------- Factory table-(Please read the notes on the back before filling (On this page) Printed by Shelley Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs • Φ is a benzene ring; • Re is an unsaturated chain conjugated to the ring; • Rs is an aliphatic chain containing an alkyl group and a possible amine group The number of atoms in the main chain is 4 to 20:. R3 is a R4 or R5 type radical or (: 1-(: 5 alkoxy). 2. If the glass strand of item 1 of the scope of patent application, It is characterized in that this paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 387865 ll _ D8 6. Scope of patent application The composition further contains at least one adhesive having at least one epoxy functional group. 3. The glass strand according to item 1 or 2 of the patent application scope, characterized in that the composition further contains at least one phosphonic acid or a phosphonic acid derivative. 4_ The glass strand of claim 1 or 2, characterized in that the composition further contains at least one adhesive with at least one epoxy functional group and at least one phosphonic acid or phosphonic acid derivative. 5. If applied The glass strands in the scope of patents No. 1 or 2 are characterized by being obtained from a thorium-resistant glass strand. 6. —A slurry composition for glass strands, containing at least one silane Si (R!) (R2) (R3) (R4), which conforms to the following formula: where R1 and ruler 2 are: (1 — C5 alkoxy; • R4 is based on carbon, hydrogen, and possible nitrogen only * Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) and conform to the following formula Where: R 5 Φ R β where • Φ is a benzene ring: • Re is an unsaturated chain conjugated to the ring: This paper uses the Chinese national standard (CNS M4 specification (210X297 mm)) _? _ ABCD 387865 VI Scope of patent application • r5 is an aliphatic chain containing an alkyl group and a possible amine group, and the number of atoms in the main chain is 4 to 20: • R3 is a 114-type or R5-type group or a Ci_C5 alkoxy group. 7 The composition according to item 6 of the patent application, characterized in that it contains at least one adhesive having at least one epoxy functional group and / or at least one phosphonic acid or phosphonic acid derivative. 8. A composite comprising at least one An organic and / or inorganic material and containing glass strands, at least one of the glass strands These are the glass stocks described in claims 1 to 5 of the scope of patent application 9. The composites according to claim 8 of the scope of patent application are characterized by containing at least one cement material. J ---------- (Please read the precautions on the back before filling out this page.) Order the printed paper of the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 3