TW573095B - Aryl aminofunctional silanes for epoxy laminates reinforced with glass fabrics - Google Patents

Abstract

Epoxy laminates with outstanding strength were obtained from glass fabrics finished with certain non-styryl arylalkyl aminofunctional alkoxysilane compounds having the formula, and its HCl salt wherein R, R1 and R2 may be the same or different and are independently selected from alkyl groups having 1 to 6 carbon atoms; and n has a value of 0 or 1, wherein the compounds are prepared using readily available starting materials without the need for styrenic double bond.

Description

573095 Bureau of Intellectual Property, Ministry of Economic Affairs B (Industrial and Consumer Cooperative Seal A7 ____B7_ V. Description of the Invention (^) Field of the Invention The present invention relates to a series of amine-functional silane coupling agents, which are used to enhance the manufacturing of epoxy resin laminates. Dressing liquid for glass fiber cloth. The amine-functional silane coupling agent not only has superior performance (up to the current standard product level), but also can be made from cheaper and easier-to-obtain raw materials than currently used. Related technical description in glass In the manufacture of fiber-reinforced plastic, the glass fiber or glass fiber cloth used must be treated with an organic functional silicon alkoxide (or silane coupling agent) in advance to make the interface between the glass and the substrate stronger, and resist water intrusion. The interface is particularly effective. The manufacturing of printed circuit boards using epoxy laminated boards generally uses amine-functional silane coupling agents, such as Z-6032 and Z-6224 by Dow Corning, and A- by Si (Crompton Corporation). 1128, especially Z-6032 and Z-6224. The process of manufacturing glass fiber reinforced epoxy laminates is as follows A few steps: (1) the glass fiber cloth is treated with a silane coupling agent aqueous solution (dressing liquid); (2) the glass fiber cloth is impregnated with an epoxy resin solution after drying; and then (3) is cured under heating and pressure. First The step is to prepare an aqueous solution of a silane coupling agent. The reason why the aqueous solution is selected is based on the consideration of the cost and safety (including flammable materials) of glass-fiber-finishing operations. In USP 3,8 1 One of the group of cationic amine-functional silane coupling agents disclosed in 9,67 5 is a coupling agent containing styryl (styry1) as shown in the following formula: This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) ) --------- Approval of clothes ------, 玎 ------ ^ (Please read the precautions on the back before filling this page) -4- 573095 A7 B7 Ministry of Economy Zhici Property Bureau a (Printed by Industrial and Consumer Cooperatives V. Description of Invention (2) CH2 = CHC6H4CH2NH (CH2) 2NH (CH2) 3Si (OCH3) 3-HCl (Z-6032)) It has created brilliant achievements in industrial use. Its For bonding organic polymers to inorganic substances, which covers almost all organic polymers Materials, such as polyolefins, unsaturated polyesters, phenolic plastics, epoxy resins, etc., are all in their ranks, and Wei is a “universal” coupling agent. Although the styrene group in this coupling agent does not contain vinyl (C = C What role does double bond) epoxy resin play, and whether it is necessary to use a coupling agent containing a styrene group? There have been many doubts and the price is high, but Z-6032 and its low-chloride Z-6224 can still be used. In the manufacture of epoxy resin laminates (printed circuit laminates) composite materials, it has maintained its dominance for 30 years. The present invention is based on trying to solve this long-standing mystery, and in view of the limited and expensive source of raw materials (that is, chloromethylstyrene) required to manufacture the product (because of difficult manufacturing, limited use, and the raw materials are being transported) And storage must be refrigerated to prevent polymerization from occurring), and anxious to find alternative materials that are cheaper and easier to obtain, in order to help reduce product costs. Based on this, while exploring the mystery of the C = C double bond in styryl, I unexpectedly discovered the superiority of a new group of non-styrene-based amine-functional silane coupling agents, which can not only be obtained from cheaper and easier raw materials Manufactured, and its performance as a glass fiber cloth dressing fluid passed or even exceeded the standards set by the industry (to reach the level of current benchmark products on the market). Summary of the Invention The present invention is to provide an aralkylamine-functional alkoxy sand compound represented by the following formula. The paper size is applicable to China National Standard (CNS) A4 (210X; 297 mm) (Please read first Note on the back, please fill out this page again) -5- 573095 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs printed A7 B7 V. Invention description (3) R] n I R-C6H4CH2NHCH2CH2NHCH2CH2CH2Si (OR2) 3.n ⑴ and its salt Acid salt, wherein R'R1 and R2 may be the same or different, and each is a fluorenyl group having 1 to 6 carbon atoms, and 11 is 0 or 1. This compound is used as a dressing liquid for reinforcing glass fiber cloth used in the manufacture of epoxy laminated boards. Detailed description of the invention The use of a silane coupling agent as a glass fabric finishes (glass fabrics finishes), its function is on the one hand through its silanol group (Si-OH) condensation with the surface of the inorganic glass Si-OH, to achieve The covalent bond between glass fiber and silane, on the other hand, the covalent bond between its organic functional group and the resin. In order to achieve an effective coupling effect, the silane group Si-OR (R usually represents Group or ethyl group) must first undergo hydrolysis to form Si-OH which is more soluble in water, and the latter is then condensed with Si-OΗ on the surface of the glass fiber to complete the covalent bonding of polyoxygen (si 1 ο X ane). On the other hand, the condensation reaction between the Si-OH homologous groups also proceeds simultaneously to form a polysiloxane that is insoluble in water and no longer has a coupling function and is turbid. Therefore, how to choose the stability that is most favorable to Si_0H is an important trick for preparing the hydrolysate; the production line at normal temperature must be able to maintain stability for at least two days. Furthermore, the water solubility of the coupling agent is of course a necessary condition for effective bonding with the surface of the glass fiber. After condensation, the finished product, that is, the composite laminate, has more water resistance. Therefore, a good coupling agent must strike an appropriate balance between ex-ante hydrophilicity and ex-post hydrophobicity. This paper size is applicable to the China National Standard (CNS) A4 specification (210X297 mm) " " -6- --------- batch clothes ------, 玎 ------ ^ (Please read the notes on the back before filling this page) 573095 A7 B7 V. Description of the invention (4) In the process of selecting amine-functional silane coupling agents in the present invention, a group of new non-styrene amines were unexpectedly found Based on the use of functional silane coupling agent as a glass fiber cloth finishing liquid for epoxy laminates, the performance can reach the current benchmark products in the market (as shown in Examples 5 and 6), and it can be cheaper from It is made from easier-to-obtain raw materials, and because it does not contain vinyl, it has good stability and does not worry about product deterioration, so the operation is very simple. The present invention solves the mystery of whether the C2C double bond functional group in the amine-functional silane coupling agent is necessary for many years, that is, the present invention confirms that the amine used in slope glass fiber cloth reinforced epoxy resin laminated board The functional silane coupling agent does not need to have a vinyl group, but can still achieve the same effect. The arylamine functional silane compound of the formula (I) provided by the present invention is printed by the Ministry of Economic Affairs, the Intellectual Property Department, the fourth bureau, and the consumer cooperation

In R-C6H4CH2NHCH2CH2NHCH2CH2CH2Si (OR2) 3-n (I) and its hydrochloride, R'R1 and R2 are preferably methyl, ethyl or propyl; and the compound is preferably the following compound: -CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 3. HCI potential

CH

CH installation ------ order ------ line (Please read the precautions on the back before filling this page) CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 3

CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 3HCI This paper size is applicable to Chinese National Standard (CNS) A4 specification (21 OX 297 mm) 573095 A7 B7 V. Description of the invention 5

Chi

-CH2NHCH2CH2NHCH2CH2CH2Si (〇CH2CH3) 3 CH3CH2-

CH2NHCH2CH2NHCH2CH2CH2Si (〇CH3) 3. HCI

CHUCK

CH2NHCH2CH2NHCH2CH2CH2Si (〇CH3) 3

CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 3 · HCI CH3CH2 · CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 2 (Please read the precautions on the back before filling out this page)-Install. CH3CH2

CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 3 HCI CH3CH2CH2 CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 3 Order CH3CH2CH2

CH2NHCH2CH2NHCH2CH2CH2Si (〇CH2CH3) 3HCI line ch3ch2ch2- Printed by the employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

CH3CH2CH

Chi

CH2NHCH2CH2NHCH2CH2CH2Si (〇CH2CH3) 2

CH 3

CH2NHCH2CH2NHCH2CH2CH2Si (〇CH3) 2. HCI This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -8- 573095 A7 B7 V. Description of the invention 6 ch3 ^

? H 3 CH2NHCH2CH2NHCH2CH2CH2Si (〇CH3) 2 CH.

CH. I 3 CH2NHCH2CH2NHCH2CH2CH2Si (〇CH2CH3) 2HCI

CH 3 CH? I 3 CH2NHCH2CH2NHCH2CH2CH2Si (〇CH2CH3) 2 CHXH,

CH,

CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 2 · HCI (Please read the precautions on the back before filling out this page)-Install · CH3CH:

CHUCK

CH. I 3 CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 2? Ch3 I 3 CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 2HCI CH. I 3 CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3). Associated Consumer Affairs Bureau, Intellectual Property Office, Ministry of Economic Affairs

CHXH ch3ch2ch2 CH3CH2CH:

CH. I 3 NHCH2CH2NHCH2CH2CH2Si (OCH3) 2 · HCI CH, I 3 -CH2NHCH2CH2NHCH2CH2CH2Si (OCH3). This paper size applies to the Chinese National Standard (CNS) A4 size (210X 297 mm) -9- 573095 B7 V. Description of the invention 7 ch3ch2ch ch3ch2ch

CK CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 2 where the methyl substituent on the phenyl group is a single ortho, meta or para substituent, or a mixture thereof; the same applies to the case where the substituent is any other substituent , Such as methyl, ethyl, propyl and so on. The present invention also provides a substrate that is water resistant and can enhance the adhesion to epoxy resin, which includes glass fiber cloth CH coated with the silane compound of the present invention. The present invention is further illustrated by the following examples, but the examples are not intended to be used. To limit the scope of the invention. Some consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed Example 1 Preparation of CH3CH2C6H4CH2NH (CH2) 2NH (CH2) 3Si (〇CH3) 3.HCl The chemical reaction formula for the compound of the above formula is as follows: CH3CH2C6H4CH2C1 + H2N (CH2) 2NH (CH2 ) 3Si (〇CH3) 3 Example 1 The title compound was purchased from 226 g (1.0 moles) of 2-aminoethyl (3-aminopropyl) trimethoxylithium (A -1 1 2 0 ' cr 〇mpt ο n C ο 1 ρ 〇rati ο η), add a 2000 ml glass container equipped with a thermometer, an addition funnel, a reflux condenser and a stirrer and heat to 60 ° C. Then from the addition funnel, divide 156 g (lo K) le of ethyl ethyl chloride with 57 g of anhydrous methanol, and divide the labor hours. The paper size applies the Chinese National Standard (CNS) A4 ^ (210X297 mm) --- ------ Batch of clothing ------ 1T ------ ^ (Please read the precautions on the back before filling this page) -10- 573095 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation of the invention 5. Description of the invention (8) Xu was added while maintaining the reflux state (65-70 ° C) for 2.5 hours, and the reaction was completed (the amount of free chlorine (C1 ·) titrated by silver nitrate was close to the theoretical value of 3.73%, which was verified) The total yield was 950 g. Other physical properties were as follows: specific gravity at 25 ° C, 0.901; refractive index iid25, 1.396; C1 ·, 3.70%. Example 2 Preparation of CH3CH2C0H4CH2NH (CH2) 2NH (CH2) 3Si (OCH3) 3 was prepared by neutralizing the title compound of Example 1 with NaOH in an alcohol solution. The chemical reaction formula is as follows: CH3CH2C6H4CH2NH (CH2) 2NH (CH2) 3Si (〇CH〇3.HCl + Na〇H / CH3〇H- > NaCl + Example 2 title compound. 150 g of a methanol solution containing 40 g of NaOH was slowly dropped into the solution while rapidly stirring. 940 g of the product obtained in Example 1, the resulting NaCl precipitate was removed by filtration to obtain 1022 g of a transparent product, and other physical properties were as follows: specific gravity at 25 ° C, 0.879; refractive index nD25, 1.389; C1 ·, 0.3%. Example 3 Preparation of CH3CH2C6H4CH2NH (CH2) 2NH (CH2: hSiCH3 (〇CH3) 2.HCl The chemical reaction formula for preparing the compound of the above formula is as follows: CH3CH2C6H4CH2C1 + H2N (CH2) 2NH (CH2) 3SiCH3 (〇CH3) 2 ◊ Example 3 The title compound followed the procedure of Example 1. 210 g (1.02 moles) of 2-aminoethyl (3-aminopropyl) methyldimethoxysilane (KBM 602, Shin-Etsu Chemical), 156 g (1.0 mole) of ethyl benzyl chloride mixed with 5 50 g of anhydrous methanol This paper is sized for China National Standard (CNS) A4 (210X297 cm) Binding line (please read the precautions on the back before filling this page) -11-573095 Printed by A7 B7, Industrial and Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (9) The product reacted with 915g, the other properties are as follows · Specific gravity at 20 ° C, 0.890; refractive index nd25, 1.4040; C1, 3.87%. Example 4 Water solubility test 1 g of the title compound of Example 1 was slowly dropped into 100 ml of agitation containing 1 % Glacial acetic acid aqueous solution. The solution was milky white at first and gradually turned to be clear after 45 minutes. Z-6032 prepared in the same way turned to be clear after 20 minutes, but became cloudy after being left for less than a week. The former remained clear for more than two weeks. Example 5 Adhesive strength test A. Preparation of dressing solution: 10 g of acetic acid was diluted in 1,000 ml of deionized water and 6.7 g of the title compound of Example 1 was added slowly while stirring. The resulting solution was stirred at room temperature for about an hour to obtain a clear aqueous solution of amine-functional silane (effective concentration: 0.27%). B. Treatment of glass fiber cloth 1. Heat-cleaned 7628 type glass fiber cloth Soak at room temperature A dressing liquid formulated to 2.5 minutes. The excess solution was squeezed out by a roller and heated at 115T for 30 minutes. 2. After drying, cut the fabric into 5 X 25 cm2 test pieces for tensile strength test. 3 · Tensile strength is tested at a tensile speed of Instr011 10cin / min. Its paper size at break is applicable to China National Standard (CNS) A4 (210 X 297 mm) --------- ^- ----- 1T ------ ^ (Please read the notes on the back before filling out this page) -12- Printed by the Employee Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 573095 A7 __ B7 V. Description of the invention (_ ) 10 値 measured when cracking, the results are shown in Table 1. The RTS (relative tensile strength) in Table 1 is the tensile strength of the 7628 glass fiber cloth treated with 0.67% Z-6224. 128.7 kg / 5cm is 10 0. Table 1 The 7628 glass fiber cloth treated with silane Tensile strength Z-6224 Silane (40% solids) Example 1 (40% solids; silane body) Example 3 Silane (40% solids) Silane-free Silane concentration Tensile strength (kg / 5cm) RTS% Tensile strength Strength (kg / 5cm) RTS% Tensile strength (kg / 5cm) RTS% Tensile strength (kg / 5cm) RTS% 0.40% 110.4 85.8 122.9 95.5 0.50% 122.2 94.9 0.67% 128.7 100 140.4 109 140 109 1.00% 131.6 102 139.1 108 0.00% 54.3 42 Example 6 Water resistance of a multilayer laminated board made of epoxy resin conforming to the specifications for FR-4 A. Preparation of epoxy resin paint solution formula: epoxy resin ... ... Araldite 8011A-80, 143 parts hardener ------------ dicyandiamide, 4 parts This paper size applies Chinese National Standard (CNS) A4 specifications ( 210X 297 mm) gutter (please read the precautions on the back before filling this page) -13- 573095 Ministry of Economic Affairs A7 _ _ B7_ printed by the Property Cooperative Consumer Cooperative V. Description of the Invention (H) Accelerator ............ Methylimidazoline, 0.2 parts of solvent …… —— …… Dimethyl Formamidine B. Preparation of laminated board 4-layer laminated board: 7628 type long glass fiber cloth was treated with a silane dressing solution as in Example 5B-1, and then impregnated with the aforementioned lacquer (Example 6A); at 150 ° C Pre-cured for 5 minutes. The temperature was gradually increased to 190 ° C during 15 minutes, and the pressure was gradually increased to 35 kg / cm2 for pressure curing and maintained for 2 hours. Hot water resistance test (1) Pressure cooker: The standard test conditions are a temperature of about 1 21 ° C (under steam), a gauge pressure (gauge pressure + 1 a t m = absolute pressure) of 1 a t m, and a time of 1 hour. The severe test conditions are a temperature of about 132 ° C (under steam), a gauge pressure (gauge pressure +1 a t m = absolute pressure) of 2 a t m, and the time is 1 hour or 2 hours. Laminate samples were immersed in a pressure cooker for 1 hour and 2 hours under boiling conditions as described above. (2) Welding bath: After the above steps of the pressure cooker, according to the IPC-TM-650 test method, the sample is immersed in a soldering bath maintained at 500 ° C for 10 ° F (260 = t5 ° F) for 20 seconds. The results are shown in Table 2. The dressing liquid used was the dressing liquid of Example 1, which was prepared according to the procedure of Example 5A. --------- Batch of clothes ------ 1T ------ ^ (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X 297 feet) -14- 573095 A7 B7 V. Description of the invention (12) Table 2 Numbering standard for water resistance samples of multilayer laminated boards made of FR-4 epoxy resin printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economy Test Severe test (1 hour) Severe test (2 hours) 1 No foaming, no foaming, no foaming 2 No foaming, no foaming, no foaming 3 No foaming, no foaming, no foaming 4 No foaming, no foaming No foaming 5 No foaming No foaming --------- ^ ------- 1T ------ ^ (Please read the precautions on the back before filling in this Page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -15-

Claims (1)

571? 95 A8 B8 C8 D8 VI. Application for patent scope 1 1. An arylamine functional silane compound I R-C6H4CH2NHCH2CH2NHCH2CH2CH2Si (OR2) 3-n and its hydrochloride salt, of which R'R1 and R2 may be the same or different, and are each an alkyl group having 1 to 6 carbon atoms; and η is 0 or 1. 2. For example, the compound in the scope of patent application, wherein the compound is -CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 3 · HCI, and .CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 3 where the methyl group on the phenyl group is alone ortho, meta or para A substituent, or a mixture thereof. 3. For example, the compound in the first scope of the patent application, where the compound is: ^^^-CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 3 HCI CH potential (CH,, and (please read the precautions on the back before filling out this page) Silk CH potential CH2NHCH2CH2NHCH2CH2CH2Si (〇CH2CH3) '2 ^' '3/3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, where the methyl group on the phenyl group is a single ortho, meta or para substituent or a mixture thereof. 4. The compound according to item 1 of the patent application scope, wherein the compound is ch3ch2- CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 3. HCI, and this paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) -16- 573095 A8 B8 C8 D8 Patent application scope 2 CHXH. CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 3 wherein the ethyl group on the phenyl group is a single ortho, meta or para substituent, or a mixture thereof. 5. The compound according to item 1 of the patent application scope, wherein the compound is / r ^ y-CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 3HCI CH3CH2 /, and CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 3 CHXH, wherein the ethyl group on the phenyl group is alone ortho, meta Sub- or para-substituents, or mixtures thereof. 6. For the compound in the first item of the patent application scope, the compound is ^^^)-CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 3 · HCI ch3ch2ch2-, and CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 3 (Please read the notes on the back before filling in this page) . · 1T silk ch3ch2ch2 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where the propyl group on the phenyl group is a single ortho, meta or para substituent, or a mixture thereof. 7. The compound according to item 1 of the scope of patent application, wherein the compound is ^^ y ~ CH2NHCH2CH2NHCH2CH2CH2Si (〇CH2CH3) 3HCI CH3CH2CH2-, and this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -17- 573095 A8 B8 C8 D8 Patent application scope 3 ch3ch2ch2. Repair CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 3 wherein the propyl group on the phenyl group is a single ortho, meta or para substituent or a mixture thereof. 8. The compound according to item 1 of the patent application scope, wherein the compound is CHU CH. I CH2NHCH2CH2NHCH2CH2CH2Si (〇CH3) 2 · HCI, and ch3 I 3 CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 2 (Please read the notes on the back before filling out this page)-Equipment · CH where the methyl group on the phenyl group is a separate ortho and meta Sub- or para-substituents, or mixtures thereof. 9. The compound as claimed in claim 1, wherein the compound is CH. CH. CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 2.HCI, and 1T-dart Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, CH, CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 2 where the methyl group on the phenyl group is a single ortho, meta or para substituent or a mixture thereof. 10. The compound according to item 1 of the patent application scope, wherein the compound is CH. CHXH. CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 2 · HCI, and this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -18- 573095 8 88 8 ABCD patent application scope 4 ch3ch2 · ch3 I 3CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 2 wherein the ethyl group on the phenyl group is a single ortho, meta or para substituent, or a mixture thereof. 11. The compound as claimed in claim 1 wherein the compound is CH. CH3CH2- CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 2HCI, and (Please read the precautions on the back before filling out this page)-Install CH, / (f ^ VCH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 2 ch3ch2 / <-/ where the ethyl group on the phenyl group is separate Ortho, meta, or para are taken as a substituent, or a mixture thereof. 12. The compound according to item 1 of the scope of patent application, wherein the compound is CH, ch3ch2ch repair H2NHCH2CH2NHCH2CH2CH2Si (OCH3) 2. HCI, and the Ministry of Economy Printed by the Intellectual Property Bureau employee consumer cooperative ch3ch2ch2 CH, CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) 2 wherein the propyl group on the phenyl group is a single ortho, meta or para substituent, or a mixture thereof. 1 3. If the compound in the scope of the patent application item 1, the compound is the size of this paper applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 19- 573095 A8 B8 C8 D8 Patent scope CH3CH2CH2.5 CH, CH2NHCH2CH2NHCH2CH2CH2Si (OCH2CH3) 2HCI and CH, ch3ch2ch2 NHCH2CH2NHCH2CH2CH2Si (〇CH2CH3) 2 where the propyl group on the phenyl group is a single ortho, meta or para substituent, or a mixture thereof. 14. A substrate that is water-resistant and can enhance the adhesion to epoxy resin, which includes glass fiber cloth coated with the compound as described in the first patent application scope (please read the precautions on the back before filling this page) Ministry of Economic Affairs The paper size printed by the Intellectual Property Bureau's Consumer Cooperatives applies the Chinese National Standard (CNS) A4 specification (210x297 mm) -20-Announcement, Annex Application Date September 30, 91 Case No. 91122520 I Category Η 1 Q1 ( The above columns are filled by this Office.) Patent Application No. 91122520-Electricity ^ Specification Amendment Page 8 η A4 C4 || 鋈 Patent Specification Amended November, 1991 573095 Invention w I. The name of the new Chinese language is based on glass iron Aryl aminofunctional si lanes for epoxy laminates reinforced with glass fabrics Name (1) Zhuang Huigan (1) Republic of China 1 Invention 2 I. Creative Nationality (1 ) 3, 1st Floor, No. 374, Wenhua 2nd Road, Section 1, Wenkou Road, Linkou Township, Beixian County (1) Zhuang Yuangan (Name) Nationality (1) Republic of China (1) 13th, 11th Floor, No. 374, Section 1, Wenhua 2nd Road, Linkou, Dabei County, Applicant's Residence, Residence (Office) Name of Representative (1) National Standard (CNS) A4 specification (210X297 mm) Hold