TW425436B - Process for treating a metallic surface, method of bonding a metallic surface to another surface, and method for improving the adhesion properties of a metallic surface - Google Patents

Abstract

The invention provides a process for treating a metallic surface, other than a clean aluminium or aluminium alloy surface, which comprises treating the surface with an organosilane and exposing the surface to a laser.

Description

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 42543 6 A7 _B7____ 5. Description of the Invention (I) The present invention relates to a method for treating a metal surface, especially to improve its adhesion. Β We have published World Patent Application No. 96 / No. 23037 describes a method for treating the surface of a golden hurricane. The metal is aluminum or aluminum alloy to improve its adhesion. This method includes treating a clean metal surface with an organosilane and exposing the surface to a laser. We have now unexpectedly discovered that before bonding or other methods (where surface adhesion is important) | Organic silanes and laser treatments can also be applied to the pretreatment of other gold surfaces, but also for unclean aluminum Pre-treatment of aluminum or aluminum alloy surface "Therefore, the present invention provides a method for treating metal surface, instead of a clean aluminum or aluminum alloy metal surface, which method comprises treating the surface with an organosilane and exposing the surface to a laser under. The surface of the golden tincture can be any surface of the golden tincture. Examples of suitable gold alloys include steel, such as stainless steel, iron in the form of ferrous iron, titanium, magnesium 'copper, gold, nickel or chromium or alloys of the metal. Metal surfaces can also be unclean aluminum or aluminum alloy surfaces-metal surfaces can be treated with organic silanes and lasers in either order. However, it is best to first apply an organosilane to the metal surface and expose the coated surface to laser light. It is also possible to expose the surface to a laser, apply an organosilane, and then expose the surface to the laser. The metal surface can be clean: for example, it can be degreased | Usually using any standard method, such as wiping with a solvent such as acetone, 3 This paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -J ---.--------- Clothing -------- Order -------- Line (Read the precautions on the back before filling in this Page> 4254 3 6 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention) Steam degreasing, immersion with or without ultrasonic treatment, or use of alkaline degreasing agents. The method of the present invention can also be used to treat unclean metal surfaces, for example, when it is greasy or when it ages * organosilanes can be compounds of formula I:

RnSi (ORl) m (I) where R is an organic functional group, which may be reactive or non-reactive, R1 is alkyl, alkoxyalkyl, or fluorenyl, η is 1 or 2 *, and m is 2 or 3 such that n + m = 4. Preferably η is 1 and m is 3β. Examples of organic functional groups R include alkyl, phenyl, vinyl, acryloxyalkyl, glycidyloxyalkyl and the like, wherein alkyl "has 1 to 4 carbons. Atoms. When R1 is alkyl, lower alkyls having 1 to 4 carbon atoms are preferred, and more preferably methyl or ethyl. When R1 is alkoxyalkyl, each alkyl moiety It preferably has 1 to 4 carbon atoms. The alkoxyalkyl group R1 is most preferably a methoxyethyl group. When R1 is a fluorenyl group, it is more fluorene with 2 to 4 carbon atoms, and the acetamyl group is most preferable. Specific examples of suitable silanes are: CH2 = C (CH3) COO (CH2) 3Si (OCH3) 3 0 / \ CH2— CHCH20 (CH2) 3Si (0CH3) 3 CH3Si (OCH3) 3 C6H5Si (OCH3) 3 CH3 (CH2 ) 2Si (OCH3) 3 HS (CH2) 3Si (OCH3) 3 4 This paper is applicable to the national standard of the country < CNS) A4 specification (210 X 297 mm) -11 Clothing --- I ---- Order i! * Line (please read the precautions on the back before filling this page) Α7 4 25 4 3 β ___ Β7_ V. Description of the invention (1) CH2 = CHSi (OOCCH3) 3 CH2 = CHSi (OCH2CH3) 3 CH2 = CHSi (OCH3) 3

Cl (CH2) 3Si (OCH3) 3 and CH2 = CHSi (OCH2CH2OCH3) 3 This silane can be used as a solution in water or organic solvents. If water is used as the solvent and the silane is difficult to dissolve, a small amount of non-ionic wetting agent can be added to the water before the silane is added. Alternatively, silane can be used as an emulsion. Suitable organic solvents include alcohols, esters, ethers, ketones and chlorinated hydrocarbons. Preferred alcohols are alkanols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, hexanol and decanol. The preferred esters are Ci-CU alkyl esters of fatty acids such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate. The preferred ethers are dialkyl ethers (such as diethyl ether), butoxyethanol and cyclic ethers (such as tetrahydrofuran). The preferred chlorinated hydrocarbons are dichloromethane, 1,2-dichloroethane. And chloroform. Preferred ketones are lower aliphatic ketones such as propionate and methyl ethyl ketone. If desired, a mixture of these solvents can be used. The most preferred solvents are polar solvents such as ketones, especially acetone. Water and / or carboxylic acids can also be added to a suitable organic solvent as part of the solution. The solution can contain any concentration of silane, preferably from 1 to 10 weight percent silane (based on the total weight of the solution). The organosilane solution can be applied by any suitable method, for example, 'wiping, brushing or spraying on the area to be treated. 5 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 g t) I ---- I I --- IIII. ^ — — — — — — II ^ * ΙΙΙΙΪ — I — ^ 4 (Please (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the employee Du 1 * ^-4 25 4 3 6 A7 ___B7 Degreasing of metal surfaces (when required) The coating and laser treatment of the organosilane solution can be performed by automatic equipment (such as robots). Any suitable laser can be used, such as 400 millijoules per pulse. Suitable lasers include Nd: YAG lasers such as excimer lasers and Q-switches. Others are well known in the literature. In order to process at high speed and not damage the metal surface through unacceptably high energy concentration, good results are obtained using an unfocused laser. In order to avoid damaging the surface of the golden beast, the actual power level required depends on the actual surface to be treated and the specific laser used. This can be easily determined by simple experiments. After the surface of the gold tincture is treated by the method of the present invention, the surface is ready for bonding or other methods (where surface adhesion is important) such as coating or encapsulation. Adhesion can be adhered to another surface using an adhesive or, for example, by applying a coating to the other surface. When bonded to another surface, the other surface may be metallic or non-metallic. If it is golden, it can be processed in the same way as above if necessary. When the treated surface is bonded to another surface | This can be achieved using any adhesive, such as a 1- or 2-component epoxy or polyurethane adhesive. The adhesive used is preferably capable of reacting with the organic silane used in the method of the present invention. The method of the present invention provides excellent bonding performance, rapid processing, cleansing method, ecologically superior to traditional wet " method and sandblasting method, and allows the use of.-=-IIII-- ^ illlm---- — — — (Please read the notes on the back before filling out this page) 6 This paper size is applicable to the national standard (CNS) A4 specification (210 X 297 g t) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 25 4 3 6 A7 ______B7 V. Description of the Invention (ί) Use a wide range of adhesives and be able to locally treat the area to be bonded. The method of the present invention can significantly improve the adhesion of metal surfaces. The invention is illustrated by the following examples. Example 1 In this example, the metal used is an aluminum alloy (L 165), stainless steel, a magnesium alloy (greater than 90 percent magnesium, less than 8 percent aluminum, and less than 2 percent zinc ) And Titanium (ASTM Level 2). These metals are tested using different surface conditions: a) Uncleaned, that is, " as received ", which is gold, as shipped from the supplier, The surface has not been changed at all. B) Clean, that is, "degreased"-"as received", the metal is degreased by means of a trichloroethane vapor degreasing tank. C) The aging effect is 'as received', " metal is subjected to 40 ° C / 100% relative humidity, seven days of artificial aging in a humidity chamber " suitable for lap shear sample coupons, It is erected on the substrate of the holding jig, and on the strip of about 25 mm at the end of each row of the area to be bonded, the primer solution is used to "prime" (primed). Allow the primer to air dry for five minutes at room temperature before placing the laser on the XY mount. Lacquer is a solution containing 81.5 parts by weight of ethanol, 2.8 parts by weight of glacial acetic acid, 9.4 parts by weight of deionized water, and 6.3 parts by weight of gamma-glycidyloxypropyltrimethoxysilane. 7 Paper Size Applicable to Chinese national standard (CNS > A4 specification (210 X 297 mm) J ------- Hi ---- clothing ----- order · 1111 line {Please read the notice on the back before filling in this (Page) A7-4 25 43 6 _B7_ V. Description of the Invention (G) The laser used in this example is an excimer laser with an operating pulse frequency of 30 Hz. Three levels of energy density (low, medium, and high) are used. ) For each group of samples to obtain a scattered exposure. The energy density is changed by inserting an attenuator and glass filter in the beam, or by changing the small spot area and keeping the beam energy constant. Use a fixture to create a lap The shear joint, so that all metals (except magnesium alloys) have a consistent overlap of 12.5 mm x 25 mm. Initial experiments with magnesium alloys indicate that for the thickness of the swatches, 1 3 12.5 mm 2 The bonding area is too large, and the substrate is sticking. The front of the adhesive is broken. Therefore, for magnesium alloys alone, the overlap is reduced to 5 mm X 25 mm. The adhesive is a component epoxy paste adhesive, which is a kind of butadiene · propylene Nitrile rubber modified bisphenol-A epoxy resin using dicyandiamine and chlorotoluron as curing agents. All joints are cured at 150 ° C for 30 minutes. Also without primer and thunder Control group experiment of pre-treatment to demonstrate the effect of pre-treatment. The lap shear strength of the prepared joint was measured according to ISO 4587 (but the test speed was set to 10 mm per minute). The lap shear strength is recorded, and the failure mode is also recorded with reference to the description of ISO 10365. Before the lap shear strength is measured, an accelerated aging test is also performed to determine the durability of the joint and the effect of pretreatment. Adopt two kinds of accelerated aging technologies: 8 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) I ----- Order ·- ------- Consumption cooperation by employees of the Intellectual Property Bureau of the Ministry of Online Economy Du 2 4 5 4 3 6 A7 ______B7__ V. Description of the invention (^)) 5) 14 days ^ / Kauplasma test, which involves It is heated to about 70 ° C for 14 days under high humidity conditions, and then cooled to _2 (rc, and before the test, the sample is allowed to warm to room temperature and stored for 2 hours. B) According to the mechanical test part 'aging procedure AP8 (taken from ASTM 8117-94) for 1000 hours of salt spray (only 350 hours for magnesium). In the table presented below, ‘All lap shear strengths are indicated in millions of psi (MPa). The abbreviations used describe the main types of damage observed for each group of samples: AF = adhesion damage SF = substrate damage CF = cohesion damage control group The results of the experiment except for the condition of the "quot 洁" group have degreasing In addition, these results are obtained by using the substrate without any pretreatment. J ^ ------ I 'clothing --- 1 ---- order ---- 1 ---- line (Jing first read the precautions on the back before filling in this page) Staff Consumption of Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative 9 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 public love) 42543 6 A7 B7 V. Hair (No primer or laser pre-treatment results on the stand

Clean and unclean ageing initial degeneration salt mist initial degeneration salt mist initial degeneration salt mist initial degeneration salt mist aluminum 31.58 11.99 0.10 7.88 3.44 2.75 L165 AF AF AF AF AF AF stainless steel 23.98 18.77 22.37 23.50 16.20 21.23 23.18 16.62 22.26 AF AF AF AF AF AF AF AF AF Magnesium alloy 24.84 0.11 21.54 0.14 4.47 2.63 AF AF AF AF AF AF titanium 29.12 11.51 20.80 27.66 12.94 19.03 28.27 17.51 24.32 AF AF AF AF AF AF AF AF AF primer / laser experiment Results Again, the results presented are in millions of Baskas (MPa), and the main damage forms are indicated (the salt spray of magnesium alloys results in substrate damage under several conditions) "Low, Medium and The high indication refers to the proper beam energy used. --—— — If— ^. — J — — — — — Order * ΙΪΙ — — —!. (Please read the notes on the back before filling out this page) 10 copies of paper printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Standards apply to China National Standard (CNS) A4 (210 X 297 mm) 4 2 5 4 3 6

The first 14 days degenerate salt mist low middle low 1% low middle high stainless 29.81 29.92 29.86 26.92 27.32 27.01 25.76 25.53 27.30 steel CF CF CF CF CF CF CF CF CF magnesium 24.06 24.79 26.51 10,05 10.25 8.65 gold CF CF CF 1SF, 1SF, 2SF, 2AF 2AF 1AF Titanium 34.81 35.83 35.44 27.96 23.83 31.61 25.60 31.27 33.06 CF CF CF AF AF CF AF AF CF A7 ______B7_ V. Description of the invention (1) Table 2 was obtained ^ "Clean" (to Grease / primer / laser) lap shear joint results: _ I ----- II ----- 'clothing --- ι! Ϊ order · --I ----- line (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 (210x297 mm)

The first 14 days degenerate salt fog low middle high low middle low aluminum high 43.92 36.05 37.39 39.72 39.33 35.38 37.13 38.99 L.165 CF CF CF CF CF CF CF CF CF CF CF CF CF CF CF CF Magnesium alloy 26.32 26.98 23.97 9.07 11.46 10.48 CF CF CF AF AF AF titanium 35.07 35.22 35.82 24.09 30.61 ^ 32.05 27.80 30.12 33.44 CF CF CF AF CF CF AF AF CF A7 __ 5. Description of the invention (~) Table Three results from "unclean" (as received / primed / laser) lap shear joint: (Please read the precautions on the back before filling in this purchase) Clothing ---- ---- Order * -------- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size is applicable to China National Standard (CNS) A4 (210x297 mm) --425436 A7 _ B7 V. Description of the invention () Table 4 results from "aged" (40 ° C / 100% relative humidity 7 days / primer / laser) lap shear joints:

The first 14 days degenerate salt fog low middle high low middle high low medium high aluminum 23.80 23.09 19.44 25.15 26.33 24.69 24.25 22.84 17.70 L165 AF CF AF CF CF CF AF AF AF stainless steel 29.73 29.92 29.84 26.41 27.36 26.97 26.86 25.54 27.95 CF CF CF CF CF CF CF CF CF Magnesium alloy 15.73 19.02 20.16 14.83 16.04 15.54 CF CF CF 1SF, 1SF, 2SF, 2AF 2AF 1AF titanium 33.56 34.28 35.16 26.60 25.41 30.25 27.90 28.03 33.41 CF CF CF AF AF CF AF AF CF You can observe the lap shear joint Destruction mode, and get a simple indication of substrate adhesiveness or adhesion. The following observed forms of destruction can be displayed: I 1 II II II Government _ — Ϊ! IJ Order · — 11 — Line (Please read the notice on the back before filling this page) Printed AF by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperative -It shows the poor interface adhesion between the substrate and the adhesive. CF_ The interface adheres well, so the damage is obvious from the adhesive in Table 1. The samples without primer or laser pretreatment showed adhesion damage (AF ). It can be inferred that the interface bonding between the substrate and the adhesive is not optimal for good adhesion1 so the adhesion shows poor performance under accelerated aging conditions, regardless of the initial strength. 13 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs · 4 25 4 3 6 A7 _______B7___ V. Description of the invention (Po Tables 2 to Tables Four shows that the damage form of the joint between aluminum and stainless steel is CF, which indicates that the adhesion of the substrate has been improved by primer and laser treatment. Titanium shows that the damage form of the initial sample is improved to CF under all three metal conditions. When using a high energy density setting, the two accelerated aging tests also show improvements in the destruction form to CF »Magnesium alloys are not suitable for regression testing because of their own poor environmental resistance. The destruction form of the starting sample was improved to CF However, there is still some substrate damage (SF) after the salt spray test. The main damage form of magnesium alloys is AF after environmental aging. The strength of the magnesium treated by the primer and laser is after the salt spray, Significant improvement over those without primer and laser pre-treatment. The above shows that the primer and laser pre-treatment add some improvements in the form of destruction from AF to CF, at least for all tested metals. This is the case at the beginning. After the environmental aging, the damage forms of aluminum, stainless steel and titanium have also been improved. Example 2 A stainless steel plate was wiped with acetone to remove fat. A solution of glacial acetic acid, 9.4 parts by weight of deionized water and 6.3 parts by weight of 7-glycidoxypropyltrimethoxysilane was primed. The board was then exposed to a Q-switched Nd: YAG laser. The two treated boards are bonded with two-component cold-cured edge oxygen resin adhesive. The resin component is a bisphenol A epoxy resin based paste. The hardened component is a fatty amine curing agent and an amine-based ending. The butadiene acrylonitrile polymer-based mixture is filled with "the resulting joint has a lap shear strength of 17.3. / J — Ί II II installed! 1 order · — — — --- — line (Please read the intentions on the back before filling this page) 14 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) A7 f-42543 6 ______B7__ 5. Description of the invention (ί $) million Baska, a form of CF destruction. Without primer and laser treatment The reference sample was destroyed at 16.3 million Baska, which is a form of AF destruction. [Window Example 3 Repeated the use of Example 2 except that the laser used in Example 1 was changed to a carbon dioxide laser. The resulting joints were overlapped. The shear strength is 17.9 million bascars. Example 4 An oily aluminum alloy (L 165) with different pretreatment combinations, among which: (P) Ethanol containing 81.5 halo parts, 2.8 parts by weight Primer a solution of glacial acetic acid, 9.4 parts by weight of deionized water, and 6.3 parts by weight of r · glycidyloxypropyltrimethoxysilane. (L) Exposure to excimer laser. Two pieces of treated aluminum alloy were bonded with a one-part epoxy resin. This is a bisphenol-A epoxy resin based paste containing the reaction product of a bisphenol-F epoxy resin and a carboxy-terminated butadiene acrylonitrile polymer. The curing agent contains dicyandiamine and a particulate accelerator. Ill ill —---- II, clothing — II order · 1 !! line (please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 15 This paper size is applicable to Chinese national standards ( CNS) A4 specification (210 X 297 mm) 5 2 4 7 7 Α β 5. Description of the invention (/ f) The results obtained are as follows:

Dealing with the average intensity destruction form after 14 days of degeneration (million pascals) PL 32.3 CF 28 CF LP 28.4 AF 24.8 CF LPL 37.3 CF 31.3 CF and J \ S \ 25.9 50% AF (please first (Please read the notes on the back and fill in this page) -¾ .--- I--I ^-I ------ This paper printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs is compliant with the national standard of Xinhua ( CNS) A4 size (210 X 297 male f)

Claims (1)

-425 43 6 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 6. Patent application methods. Instead of clean aluminum or aluminum alloy surfaces, this method includes: treating the surface with an organic silane, and applying The surface is exposed to laser light. 2. The method according to item 1 of the patent application | where the metal surface is the surface of iron, titanium, magnesium 'copper, gold, nickel, chromium, or an alloy of the metal in the form of steel, ferrous iron. 3. The method according to item 1 or 2 of the patent application, wherein an organic silane is first coated on the surface of the gold tincture, and then the coated surface is exposed to a laser. 4. The method of claim 1 or 2, wherein the organosilane has the following general formula: RnS i (OR ^) m where R is an organic functional group, which may be reactive or non-reactive, R1 Is an alkyl, alkoxyalkyl, or fluorenyl group, n is 1 or 2 and m is 2 or 3, so that n + m-4 β 5. The method according to item 1 or 2 of the patent application scope, wherein the silane is soluble in Use water and / or a solution in an organic solvent. 6. The method as claimed in claim 5 wherein the solution contains from 1 to 10 weight percent of an organosilane. 7. The method of claim 1 or 2, in which the laser is an unfocused laser. 8. For the method of applying for item 1 or 2 of the patent scope, wherein the surface of the gold tincture is an unclean surface. 1 This paper size is applicable to the national standard of difficulty (CNS > A4 specification (210 X 297 mm) (please read the special benzene item on the back before filling this page) --V -------- Order-- ------- Line ί — 6 3 4 5 2 4 8888 A8B8C8D8 Employee Cooperative Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Application for Patent Scope 9. Such as the method of applying for scope 1 or 2 of the patent scope 'where the metal surface Is the surface of stainless steel. 10. The method of claim 1 or 2 in which the metal surface is a surface of iron in the form of ferrous iron. 11. The method of claim 1 or 2 in which the metal surface is The surface of titanium or its alloy "12. The method according to item 1 or 2 of the patent application, wherein the metal surface is the surface of magnesium or its alloy. 13. The method according to item 1 or 2 of the patent application, wherein the surface of gold tincture It is the surface of copper or its alloy. 14. The method according to item 1 or 2 of the patent application, wherein the metal surface is the surface of gold or its alloy. 15. The method according to item 1 or 2, in which the gold is applied The surface of rhenium is the surface of nickel or its alloy. Method, wherein the surface of the gold tincture is the surface of chromium or its alloy. 17. The method according to item 8 of the patent application scope, wherein the surface of the gold carving is the surface of aluminum or aluminum alloy. N 1 8 methods of bonding the metal surface to another , Which comprises: treating the metal surface by any of the methods in the aforementioned patent application range, and then bonding it to another surface with an adhesive. 19. The method according to claim 18 in the patent application scope, wherein the other surface is a metal Or non-metallic. 2 This paper is sized for China National Standard (CNS) A4 (210 * 297 mm) (Please read the notes on the back before filling this page) -1 ^ n I ϋ n 1 n (9 1 * 1 a tt IIK 1 n 1 > n ϋ f · n 5 2 4 Zhong 08 6. Application for patent scope 20. For the method of applying for patent scope No. 18, in which the other surface is gold • Surfaces treated by the method of any one of claims 1 to 17. 21. A method for improving the adhesion of a metal surface, which includes: applying any one of the claims 1 to 17 of the scope of the patent Method to treat the metal surface, and then apply a coating On the treated surface. ≪ Please read the notes on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Industrial Consumer Cooperatives 3 · -i — — — — — • 11111111 1— III i I Hi I —Ί — — — — — — — — — — — — — This paper size applies to the Chinese National Standard (CNS) A4 specifications < 210 X 297 mm) Λ.… People 21, ··-^:,-· > Application Date _---------------- Case No. ° e ί ί ο ο 6 1 Category (the above blocks are filled in by this Office) Year Month Η 425436 || Patent Instruction I. Name of Invention New Chinese Method for Treating Metal Surfaces · Method for Bonding Metal Surfaces to Another — Surface Method and Method for Improving the Adhesion of Metal Surface English Process for Treating a Metallic Surface, Method of Bondinj; a Metallic Surface to Another Surface, and itethod for Improving the Adhesion Properties of a Metallic Surface Name Yoken Sauer__ Invention 1-Creation Λ Nationality German Residence and Residence 4310 Rheinfeld, Switzerland, 8 Sucher Street Name (Name) Bart Chemical Holding Co., Ltd. Switzerland 3. Applicant's residence and domicile (storage) Name of representative at No. 141 Chongbei Street, Bafer City, Switzerland 4057 1. Enlin Alvhell 2. Hans 1 Peifu Weitling 1 Binding Book Paper Size: China National Samples (CNS) A * »Natural (210X297 mm) Pack -425 43 6 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 6. Patent application methods. Instead of clean aluminum or aluminum alloy surfaces, this method includes: treating the surface with an organic silane, and applying The surface is exposed to laser light. 2. The method according to item 1 of the patent application | where the metal surface is the surface of iron, titanium, magnesium 'copper, gold, nickel, chromium, or an alloy of the metal in the form of steel, ferrous iron. 3. The method according to item 1 or 2 of the patent application, wherein an organic silane is first coated on the surface of the gold tincture, and then the coated surface is exposed to a laser. 4. The method of claim 1 or 2, wherein the organosilane has the following general formula: RnS i (OR ^) m where R is an organic functional group, which may be reactive or non-reactive, R1 Is an alkyl, alkoxyalkyl, or fluorenyl group, n is 1 or 2 and m is 2 or 3, so that n + m-4 β 5. The method according to item 1 or 2 of the patent application scope, wherein the silane is soluble in Use water and / or a solution in an organic solvent. 6. The method as claimed in claim 5 wherein the solution contains from 1 to 10 weight percent of an organosilane. 7. The method of claim 1 or 2, in which the laser is an unfocused laser. 8. For the method of applying for item 1 or 2 of the patent scope, wherein the surface of the gold tincture is an unclean surface. 1 This paper size is applicable to the national standard of difficulty (CNS > A4 specification (210 X 297 mm) (please read the special benzene item on the back before filling this page) --V -------- Order-- ------- line ί —