TW390896B - Surface modification and surface modifying coating methods for polyolefin resin products - Google Patents

Abstract

This invention related to the surface modification and surface modifying coating methods for polyolefin resin products. After agitated surface cleaning procedure, surface of polyolefin resin products is modified by the spraying aqueous ozone solution (65-85 DEG C). To assure uniformly surface modification and minimize ozone consumption, the spraying pressure A (kPa) and the distance B (cm) should satisfy A x B<-2> >= 0.07. Due to the well-controlled ozone spraying, both the overall processing time and ozone consumption were cut down without lowering surface modification quality.

Description

Λ7 Modification Year Q87.12. 1 4 V. Description of the Invention (2) Solution, K oxidizes the surface of the aforementioned polyolefin resin molded article. According to this method, the use of an organic solvent before the modification process can be omitted, and the surface of the resin molded article can be easily and uniformly modified. In addition, by subsequent coating, a coating film layer can be firmly formed on the surface of the resin shaped article. [Problems solved by the invention] 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 out this page). However, in the above-mentioned technology, for example, impregnating a polyolefin resin molding The method in the ozone aqueous solution at a predetermined temperature, therefore, although a certain excellent ultra-modification result can be obtained, there is a possibility that the following disadvantages occur. That is, as shown in FIG. 6, in the stage before the resin-molded article 51 is immersed in the ozone aqueous solution, power washing and washing by the water jet nozzle 52 is usually performed. It is implemented in the state of the machine 53. Therefore, in the process of immersion in the ozone aqueous solution, it is necessary to remove the resin molded article 51 from the conveyor 53 and move it to another immersion container 54 and maintain the immersion state. Moreover, in the power washing and cleaning, the surface of the resin molded article 51 toward the conveyor 53 (the back surface of the resin molded article 51) was insufficiently cleaned. Therefore, when the resin-molded article 51 is impregnated *, there is a possibility that the contaminated substance adhering to the back surface thereof will dissolve in the ozone water in the container 54 and become weak. As a result, the ozone aqueous solution is contaminated, and a good modification result cannot be obtained. In addition, it is necessary to warm all the ozone water solutions K in the container 54 with the heater 55 to maintain a constant temperature state of the ozone aqueous solution in the container 54. Therefore, the paper size of this guide is subject to the Chinese National Standard (CNS) A4 specification (210X297 cm) -5-a revision; ^ Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 _ ^ ____ £ 7 _ ^ _ 5. Description of the invention ( I) [Application fields in the industry] The present invention relates to a surface modification method and a surface coating method of a polyolefin resin molded article having a relatively low surface polarity, such as polypropylene. [Previous technology] When a polyolefin-based resin molded article having a small surface polarity represented by K polypropylene is used for secondary processing such as painting, the resin is first washed with a solvent such as trichloroethane. Surface modification and surface modification (concave-convex) of the molded product. Next, an M primer coating or an M plasma treatment is applied to the surface. Since these treatments are performed to polarize the surface, the resin form and the surface coating are firmly joined by K. However, in recent years, there has been a growing demand for cleaning with organic solvents such as trichloroethane and other halogenated hydrocarbons. Various aspects have begun to study new methods that can improve the surface of polyolefin-based resin moldings instead of the solvents mentioned above. One of the technologies corresponding to the above requirements is disclosed in, for example, Japanese Patent Laid-Open No. 3-1 03448. In this technique, a polypropylene resin molded article is treated under an ozone gas stream to oxidize its surface and modify its hydrophilicity. However, in the above-mentioned technique, a polypropylene resin molded article is treated under an ozone gas flow, so it is difficult to uniformly modify the entire surface of the resin molded article. That is, in order to uniformly modify the surface, it is necessary to make the ozone gas stream uniformly contact the entire surface * and to contact each surface for the same time. Therefore, if the resin molded object has a complicated shape, it is necessary to appropriately move the resin molded object or the airflow, otherwise the entire surface cannot be modified uniformly. As a result, it is very difficult to achieve uniform coating. _ In order to cope with the above-mentioned shortcomings, the present inventors have disclosed in Japanese Patent Japanese Patent Application No. Hei 5-1 6 3 6 1 9 that the polyolefin resin moldings are exposed to ozone water. The Chinese paper standard (CNS) A4 applies to the paper size. Specifications (210X297mm) _ 4-(Read the notes on the back first and then fill out this page)

V. Description of the invention (3 The additional cost of Yu can increase Λ7 B7

The reason is that the medium 4 5 containers contain liquid oxygen dissolved in water for a long period of time, and the user has no way to solve the problem. Concentrated oxygen odor high-increasing--f species 1 is provided in the question of the problem of Ju Qicheng. The solution is that the quality of the surface of the present invention is changed to form the aliphatic hydrocarbon alkenes, which is smaller than rts- Sexuality

The film coating and fruit quality are very good. The time is short. The amount of M can be reduced. The quality can be reduced. The quality can be changed in a series. 1 Apply the same surface at the same time. The table of contents and the quality of the French formula are modified to form the aliphatic hydrocarbon alkene polymer. The title of the question in the solution to the problem is clearly stated in the text. Nine substances are formed into a tree-like hydrocarbon alkene in contact with the water-soluble oxygen odor. The mist is sprayed. The odor is set and the oxygen surface is formed to form a resin. At the time of contacting the liquid dissolved water, oxygen, water, oxygen, and odor, the front spray (read the precautions on the back and then fill out this page). The Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs printed the distance to form the palm tree hydrocarbon When the liquid is full before the spraying

All 2 is a pre-set and succinct system of hydrocarbon olefin polymerization, especially the lower MV 5 8 and the upper M V 5 6 are liquid water-soluble oxygen at a temperature of II. Forming the Fat Tree Range Fan ΛBi, please use φ as the registered item of Mingfa 2 The Fan Range Request, the paper size applies to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) -6-Correction page Λ7 Revised Year Q87.12. 1 4 V. Description of the Invention (2) Solution, K oxidizes the surface of the aforementioned polyolefin resin molded article. According to this method, the use of an organic solvent before the modification process can be omitted, and the surface of the resin molded article can be easily and uniformly modified. In addition, by subsequent coating, a coating film layer can be firmly formed on the surface of the resin shaped article. [Problems solved by the invention] 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 out this page). However, in the above-mentioned technology, for example, impregnating a polyolefin resin molding The method in the ozone aqueous solution at a predetermined temperature, therefore, although a certain excellent ultra-modification result can be obtained, there is a possibility that the following disadvantages occur. That is, as shown in FIG. 6, in the stage before the resin-molded article 51 is immersed in the ozone aqueous solution, the power washing of the water jet nozzle 52 is usually performed. However, this washing is carried by placing the resin-molded article 51 on the conveyance. It is implemented in the state of the machine 53. Therefore, in the process of immersion in the ozone aqueous solution, it is necessary to remove the resin molded article 51 from the conveyor 53 and move it to another immersion container 54 and maintain the immersion state. Moreover, in the power washing and cleaning, the surface of the resin molded article 51 toward the conveyor 53 (the back surface of the resin molded article 51) was insufficiently cleaned. Therefore, when the resin-molded article 51 is impregnated *, there is a possibility that the contaminated substance adhering to the back surface thereof will dissolve in the ozone water in the container 54 and become weak. As a result, the ozone aqueous solution is contaminated, and a good modification result cannot be obtained. In addition, it is necessary to warm all the ozone water solutions K in the container 54 with the heater 55 to maintain a constant temperature state of the ozone aqueous solution in the container 54. Therefore, the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 cm) -5 a correction; ^ -r bucket / j-二 Λ7 87.12. 14 B7 V. Surface of the description of the invention (4) The modification method is to directly coat the surface of the polyolefin-based resin molded article having the modified surface with a coating film layer of the polyolefin-based resin molded article whose special mold is the main point. In addition, the invention described in item 3 of the scope of patent application is that the surface of the polyolefin-based resin molded article whose surface is modified by the surface modification method described in item 1 of the application patent, directly forms a primer coating layer. A surface coating method of a polyolefin-based resin molded article characterized by forming a coating film layer on the primer coating layer is a gist. [Function] Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) According to the above. The invention described in the first item of the scope of patent application, contact the sprayed ozone aqueous solution with the polyolefin system Resin molding. At this time, the surface of the polyolefin resin molded article is oxidized by the oxidizing power of ozone remaining in the water and becomes polarized. At this time, regardless of the shape of the polyolefin-based resin molded article, the ozone aqueous solution can surely contact the entire surface of the resin molded article. Therefore, an oxidation reaction is uniformly performed on each surface of the resin molded article, and it is not easy to cause a reaction streak in each part. In addition, since the ozone aqueous solution comes in contact with the surface of the resin molded product in the form of M spray, the amount of ozone per unit time that is in contact with the surface of the resin molded product is large. In addition, the interfacial film diffusion layer of the ozone aqueous solution formed on the surface of the resin molded article is thin. Then, an aqueous ozone solution hits the interface film from the diffusion layer. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 light and light). 7 Correction page V. Description of the invention (3) Λ7 B7

The reason is that the medium 4 5 containers contain liquid oxygen dissolved in water for a long period of time, and the user has no way to solve the problem. Concentrated oxygen odor high-increasing--f species 1 is provided in the question of the problem of Ju Qicheng. The solution is that the quality of the surface of the present invention is changed to form the aliphatic hydrocarbon alkenes, which is smaller than rts- Sexuality

The film coating and fruit quality are very good. The time is short. The amount of M can be reduced. The quality can be reduced. The quality can be changed in a series. 1 Apply the same surface at the same time. The table of contents and the quality of the French formula are modified to form the aliphatic hydrocarbon alkene polymer. The title of the question in the solution to the problem is clearly stated in the text. Nine substances are formed into a tree-like hydrocarbon alkene in contact with the water-soluble oxygen odor. The mist is sprayed. The odor is set and the oxygen surface is formed to form a resin. At the time of contacting the liquid dissolved water, oxygen, water, oxygen, and odor, the front spray (read the precautions on the back and then fill out this page). The Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs printed the distance to form the palm tree hydrocarbons. When the liquid is full before the spraying

All 2 is a pre-set and succinct system of hydrocarbon olefin polymerization, especially the lower MV 5 8 and the upper M V 5 6 are liquid water-soluble oxygen at a temperature of II. Formation of the fatty acid tree range ΛΒ profit is specially requested to be used as the item of Mingfa 2 The application of the paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) -6-Revised page 5 Description of the invention (5 Λ7 B7 Amendment date b7.12. 14 The diffusion layer compresses the diffusion layer. The diffusion layer is discontinuously disturbed by the compression. As a result, ozone molecules can be shortened through the diffusion phase. The time it takes to reach the surface of the resin molding can suppress the decrease in ozone concentration, and can further promote the oxidation reaction. Furthermore, unlike the case where the resin molding is immersed in an ozone aqueous solution, a sprayed ozone aqueous solution is sprayed on the resin molding. Therefore, the ozone solution can be contacted with the resin molding in a series of processes. At the same time, the sprayed ozone solution is heated as much as possible before spraying the resin molding. The temperature of the liquid can be high, which can avoid the decomposition of ozone during the maintenance period. Therefore, compared with the case of immersion, it can also maintain a high concentration of ozone at high temperatures. In addition, only the aqueous solution sprayed with warming on the resin molding is Yes, so you can save energy for heating (please read the precautions on the back before filling this page), 1T printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, and the invention described in the second patent application scope is in-use application The surface modification method described in item 1 of the patent scope directly modifies the surface of the polyolefin-based resin molded product to form a coating film layer. Therefore, the coating film layer can be firmly bonded to a uniformly oxidized and polarized surface Adding the invention described in item 3 of the scope of patent application is to use the surface modification method described in item 1 of the scope of patent application to modify the surface of the polyolefin-based resin molded article directly to form a primer coating layer. The paper size applied on the bottom layer is in accordance with China National Standard (CNS) A4 specification (210 × 297 male f) 8-Correction page -r bucket / j-二 Λ7 87.12. 14 B7 It is stated that the surface modification method described in the item (4), the surface coating method of directly modifying the surface of the polyolefin-based resin molded article with the modified surface, and forming the coating layer of the polyolefin-based resin molded article whose special mold is the gist is the main point. In addition, the invention described in item 3 of the scope of patent application is that the surface of the polyolefin-based resin molded article whose surface is modified by the surface modification method described in item 1 of the application patent, directly forms a primer coating layer. The surface coating method of forming a polyolefin-based resin molded article with a coating film layer on the bottom coating layer as a feature is the main point. [Function] Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in (This page) According to the invention described in the above item 1 of the patent application scope, a sprayed ozone solution is contacted with the polyolefin resin molded article. At this time, the surface of the polyolefin resin molded article is oxidized by the oxidizing power of ozone remaining in the water and becomes polarized. At this time, regardless of the shape of the polyolefin-based resin molded article, the ozone aqueous solution can surely contact the entire surface of the resin molded article. Therefore, an oxidation reaction is uniformly performed on each surface of the resin molded article, and it is not easy to cause a reaction streak in each part. In addition, since the ozone aqueous solution comes in contact with the surface of the resin molded product in the form of M spray, the amount of ozone per unit time that is in contact with the surface of the resin molded product is large. In addition, the interfacial film diffusion layer of the ozone aqueous solution formed on the surface of the resin molded article is thin. Then, an ozone solution hits the interface film from the diffusion layer. The paper size applies the Chinese National Standard (CNS) Α4 specification (210X297). 7 Correction page

V. Description of the invention (6 coating layers are formed. Therefore, the bottom coating layer can be firmly bonded to the uniformly oxidized and polarized surface. It is not necessary to choose a special base material or implement a special baking treatment method. In addition, the coating film layer is firmly bonded to the base coating layer. As described above, according to the surface modification method of the polyolefin / resin molded article of the present invention and the surface coating method thereof, a polyolefin resin having a small surface polarity When the surface of the formed article is modified, it can be used in a short period of time to obtain excellent results and the strength of the coating film. At the same time, the modification can be implemented in a series of processes and the energy cost can be reduced. [Embodiment] The embodiment of the present invention is described below according to the illustration. It is 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) as shown in Figure 2 As shown, for example, a resin product 1 such as a face-protecting pole for an automobile is composed of a resin molded product 2 and a coating film layer 3 formed on the surface. The resin molded product 2 is formed by molding polypropylene with a metal mold. The surface is modified (oxidized). In this embodiment, the surface of the resin molding 2 is directly coated with M. Second, according to the process diagram of the reforming device shown in FIG. 1 When the resin product 1 is manufactured, the surface modification process from the time when the resin molded product 2 is formed to the pre-painting stage will be described below. As shown in the figure, when the surface of the resin molded product 2 is modified, use Power This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 g) -9-Revised page V. Description of the invention (5 Λ7 B7 Amends the date b7.12. 14 The diffusion layer and compresses the diffusion layer. Also, The diffusion layer is discontinuously disturbed due to the compression. As a result, the time for ozone molecules to reach the surface of the resin molded article through the diffusion phase can be shortened, the decrease in ozone concentration can be suppressed, and the oxidation reaction can be further promoted. When the resin-molded article is immersed in an ozone solution, it is sufficient to spray the sprayed ozone-water solution onto the resin-molded article. Therefore, the ozone-water solution can be brought into contact with the resin-molded article in a series of processes. At the same time, it is sufficient to heat the aqueous solution to a high temperature before spraying the sprayed ozone aqueous solution on the resin molding to avoid the decomposition of ozone during the maintenance period. Therefore, compared with the case of immersion, it can also maintain a high concentration at high temperatures. In addition, it only needs to be heated and sprayed on the aqueous solution of the resin molding, so it can save heating energy (please read the precautions on the back before filling this page), printed by the Consumer Cooperative of the Central Standard Bureau of the Ministry of Economic Affairs At the same time, the invention described in item 2 of the scope of patent application is to directly form a coating film layer on the surface of a polyolefin-based resin molded article whose surface is modified by the surface modification method described in item 1 of the scope of patent application. The layer can be firmly bonded to the uniformly oxidized and polarized surface. Add M * The invention described in the third item of the patent application scope is to use the surface modification method described in the first patent application scope to modify the surface aggregation. On the surface of the olefin-based resin molded article, an undercoat layer is directly formed. This paper is also coated on the bottom layer with the Chinese national standard (CNS) A4 specification (210 × 297 male f). 8-Revised page Λ7. Ministry of Economic Affairs, Central Standards Bureau, Off-line Consumer Cooperative, Yin Cebo. Weep these 14 ^ --- -. 'ϋ — — ^ V. Description of the invention (7) Cleaning and washing device 4 and surface modification device 5. In the series of processes, a conveyor 6 is used, and the resin molded product 2 is moved by the conveyor 6 to, for example, the aforementioned power cleaning and washing device 4 on the right side of the figure to wash and remove the surface of the resin molded product 2 The device for pollution is provided with a pump and a nozzle 7 (not shown). From the tip of the nozzle 7, a sprayed water is sprayed onto the resin molded product 2. The surface modification device 5 includes an ozone generator 8, a heater 9, a nozzle 10, a drainage 11, a hose for connecting the components, and the like. The ozone generator 8 is capable of dissolving ozone in water while changing oxygen into ozone. In addition, the ozone generator 8 is provided with a pump (not shown) therein, and can send an ozone aqueous solution to the heater 9 under pressure. In addition, the heater 9 provided in the middle of the hose has a structure capable of heating the flowing ozone solution to a predetermined temperature. The nozzle 10 provided at the tip of the hose is arranged so that the heated ozone aqueous solution sent from the heater 9 side can contact the resin molded product 2 in a spray form. At this time, when the spray pressure when the front ozone water solution is brought into contact is A (kPa), and the distance between the tip of the nozzle for spraying the front ozone water solution and the aforementioned polyolefin-based resin molding is 8 ((: 111), it can satisfy The conditions of /^.8-220.07 are suitable. In addition, the discharge port 11 is an ozone solution stored below the conveyor 6 and stored in contact with the resin molding 2. The ozone solution stored at the discharge port 11 is 12 and M—the fixed speed was introduced into the ozone generator again (please read the precautions on the back before filling this page)

This paper size applies to China National Standard (CNS) Α4 size (210X 297 mm) -10-Correction page

V. Description of the invention (6 coating layers are formed. Therefore, the bottom coating layer can be firmly bonded to the uniformly oxidized and polarized surface. It is not necessary to choose a special base material or implement a special baking treatment method. In addition, the coating film layer is firmly bonded to the base coating layer. As described above, according to the surface modification method of the polyolefin / resin molded article of the present invention and the surface coating method thereof, a polyolefin resin having a small surface polarity When the surface of the formed article is modified, it can be used in a short period of time to obtain excellent results and the strength of the coating film. At the same time, the modification can be implemented in a series of processes and the energy cost can be reduced. [Embodiment] The embodiment of the present invention is described below according to the illustration. It is 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) as shown in Figure 2 As shown, for example, a resin product 1 such as a face-protecting pole for an automobile is composed of a resin molded product 2 and a coating film layer 3 formed on the surface. The resin molded product 2 is formed by molding polypropylene with a metal mold. The surface is modified (oxidized). In this embodiment, the surface of the resin molding 2 is directly coated with M. Second, according to the process diagram of the reforming device shown in FIG. 1 When the resin product 1 is manufactured, the surface modification process from the time when the resin molded product 2 is formed to the pre-painting stage will be described below. As shown in the figure, when the surface of the resin molded product 2 is modified, use Power This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 male t) -9-Correction page __— L7—_ | 87-.12.1 4 employment charge __ 5. Description of invention (15) Object 2 (test When the entire surface of the sheet P) is a craftsman noodle, the composition of the ozone water solution may be sprayed from various aspects. Regarding the items that are not listed in the scope of the patent application, the technical ideas that can be grasped from the above-mentioned embodiments and The effects are described below. (A) In the method for modifying the surface of a polyolefin / resin molded article described in item 1 of the patent application, or in the surface coating method described in items 2 and 3 of the patent application, spraying ozone is used. During the previous stage of contact with the aqueous solution, heat the aforementioned Oxygen solution is its characteristic. Due to the above-mentioned structure, the ozone concentration of the ozone solution can be increased, and the efficiency of surface modification can be further improved by using M. [Simplified description of the drawing] Drawing 1 is a concrete example of the invention and a practical example of the invention A system diagram of a surface modification device, etc. Figure 2 is a cross-sectional view showing a tree cell product in an embodiment. Figure 3 is a graph showing a relationship between water temperature and ozone solubility coefficient in an embodiment.-Central Ministry of Economic Affairs Printed by the Consumer Bureau of the Standards Bureau. Figure 4 is a diagram showing a model of experimental equipment when surface modification / testing is performed in one embodiment. Figure 5 is a diagram showing resin products in other embodiments embodying the present invention. Sectional view. Figure 6 is a general view of the surface modification device of the prior art. [Explanation of component numbers] 1 Resin products 2 Resin moldings 18 _ (Please read the precautions on the back before filling this page ) This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) Λ7 Yin Zebo, Consumer Work Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 泣 weet these 14 ^ -----. 'Ϋ — — ^ V. Invention description 7) cleaning device 4 cleaning and surface modification means 5. In the series of processes, a conveyor 6 is used, and the resin molded product 2 is moved by the conveyor 6 to, for example, the aforementioned power cleaning and washing device 4 on the right side of the figure to wash and remove the surface of the resin molded product 2 The device for pollution is provided with a pump and a nozzle 7 (not shown). From the tip of the nozzle 7, a sprayed water is sprayed onto the resin molded product 2. The surface modification device 5 includes an ozone generator 8, a heater 9, a nozzle 10, a drainage 11, a hose for connecting the components, and the like. The ozone generator 8 is capable of dissolving ozone in water while changing oxygen into ozone. In addition, the ozone generator 8 is provided with a pump (not shown) therein, and can send an ozone aqueous solution to the heater 9 under pressure. In addition, the heater 9 provided in the middle of the hose has a structure capable of heating the flowing ozone solution to a predetermined temperature. The nozzle 10 provided at the tip of the hose is arranged so that the heated ozone aqueous solution sent from the heater 9 side can contact the resin molded product 2 in a spray form. At this time, when the spray pressure when the front ozone water solution is brought into contact is A (kPa), and the distance between the tip of the nozzle for spraying the front ozone water solution and the aforementioned polyolefin-based resin molding is 8 ((: 111), it can satisfy The conditions of /^.8-220.07 are suitable. In addition, the discharge port 11 is an ozone solution stored below the conveyor 6 and stored in contact with the resin molding 2. The ozone solution stored at the discharge port 11 is 12 and M—the fixed speed was introduced into the ozone generator again (please read the precautions on the back before filling this page)

This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -10-Correction page amends A7 bucket Q B7 87.! 2. 补充 Supplement V. Description of invention (丨 6) Employees of Central Bureau of Standards, Ministry of Economic Affairs Printed by a consumer cooperative 3 Coating layer 4 Power cleaning and cleaning device 5 Surface modification device 6 Conveyor 7 Nozzle 8 Ozone generator 9 Heater 10 Nozzle 11 Discharge outlet 12 Tube 13 Drying device 31 Oxygen cylinder 32 Oxygen generator 33 Valve 34 Backflow prevention valve 35 Mixer 36 Spring 37 Mixer 38 Heater 39 Excess gas separation gate 40 Valve 41 Condensation gate 42 Activated carbon extinguisher 43 Aspirator (Please read the precautions on the back before filling this page)

This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -19-Revised page Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (8) 8. The relationship of the ozone solubility coefficient to water temperature is as shown in FIG. 3. That is, the more the water temperature rises, the more difficult it is for ozone to dissolve, and as the temperature rises, ozone becomes easier to decompose. In contrast, it is generally known that the reaction speed (surface modification speed) increases when the water temperature is high. Therefore, the heater 9 should be appropriately heated and adjusted so that the ozone concentration is as high as possible and the temperature of the ozone solution is preferably as high as possible. Specifically, the above-mentioned temperature M is preferably 65 ° 0 to 85 ° 0. In addition, the surface-modified resin molded article 2 by the surface-modifying device 5 is provided in the coating process after being dried by the drying device 13. Next, the method of modifying the surface of the resin molded article 2 using the above-mentioned surface modifying device 5 and the like, and the effects during the modification will be described below. First, a resin molded article 2M formed into a predetermined shape by a metal cross piece is placed on a conveyor in operation with its intentional side facing upward, and moved to the right in FIG. 1. Then, the cleaning device 4 is cleaned by the power, and sprayed water is sprayed onto the surface of the resin molded product 2 from the tip of the nozzle 7. Thus, contaminants such as dust adhering to the surface of the resin-made garment 2 can be cleaned. However, at this time, the non-patterned surface of the resin molded article 2 which does not need to be painted is facing the conveyor 6 side. Therefore, the non-circular case surface was not sufficiently cleaned. V Next, the resin molding 2 is moved to the right side of the figure by the conveyor 6 described above, and is transferred to the surface modification device 5. At this time, the sprayed ozone aqueous solution was in contact with the resin molded product 2. The surface of the resin molded article 2 is oxidized and polarized by the oxidizing power of ozone remaining in the contacted water. At this time, none of this paper size applies to Chinese national standards (CNS> Α4 size (210 × 297 mm) _ ι ι _ (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1 Amendment. A 7 years. Monthly power% B7 87J2.I4 V. Description of the invention (17) (Please read the notes on the back before filling in this page)

44 Mounting table 45 Glass tank 47 Primer coating tank 51 Resin-shaped product 52 Water jet nozzle 53 Conveyor 54 Container 55 Loader This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) —20-Revised page A7 B7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shelley Consumer Cooperative, V. Description of the invention (9) 1 I On the shape of the resin molding 2 (in this example, the bumper 1 of the car | the shape of the rod) But the ozone solution In order to at least surely contact the entire surface of the pattern ^ -X 1 'I surface 0, therefore, it is necessary to uniformly perform the 1 1 1 line on each surface of each resin molded product 2 The oxidation reaction is not easy to cause reverse r / fty in each part 牕Spot 〇1 • 5 Back 1 I Then the surface-modified resin molded product 2 is as described above. Dry from the injection 1 1 Drying device 13 and transferred to the painting process. Thinking 1 1 Re 1 In this embodiment Oxygen solution M is sprayed on the surface of the resin-molded product 2 so that it comes into contact with the surface of the resin-molded product 2 per unit of time on this page 1. The amount of ozone is large, so the entire product is immersed in the resin-molded product. 1 It can shorten the contact time when ozone water is dissolved in the oxygen solution. Because of 1 1 this short-time modification treatment can obtain good coating film adhesion (can be fixed 1 and I solidly join the coating film layer 3) 〇 As a result, the productivity can be significantly improved 〇 ozone solution Μ spray m The interface film diffusion layer 1 1 of the ozone aqueous solution formed on the surface of the resin molded product 2 is thin because of the contact with the surface of the resin molded product 1 1 I. Further, the ozone aqueous solution is in contact with the interface film diffusion Λ layer due to collision. Therefore, the diffusion layer is compressed, and the diffusion layer is disturbed by the compression and becomes discontinuous. As a result, the ozone molecules can be reduced to the surface of the resin molded product through the diffusion phase, and the reduction of the ozone concentration can be suppressed. Promote the 1 1 oxidation reaction. Therefore, the contact time of the ozone water solution can be shortened. Further, it is different from immersing the resin molding in the ozone water solution, as long as the sprayed ozone water is used. The liquid can contact the resin molded object, so the ozone aqueous solution can be contacted in a series of processes. That is, after the power cleaning and washing, I j is different from the resin molded object once it is removed from the conveyor and immersed in the container 1 1 Advanced technology in 1 &gt; Modification can be performed on conveyor 6. As a result, 1 paper size applies the Chinese National Standard (CNS) 8-4 specifications (210X297 mm) -12-Printed by Zhengong Cooperative Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 __ B7____ 5. Explanation of the invention (i〇) Quality equipment and devices dome K and reduce costs. Adding K, this embodiment is different from the prior art in which the ozone solution in the container needs to be heated &gt; The ozone solution is heated by the heater 9 before the ozone solution is brought into contact with the resin molded article. Therefore, it is possible to suppress the decomposition of ozone while maintaining the high temperature state to a minimum. Therefore, the ozone concentration in the sprayed ozone aqueous solution can be increased, and the efficiency of modification can be improved. With M, in this embodiment, it is sufficient to heat a portion of the aqueous solution in contact with the resin-molded article 2, and therefore, less energy is used for heating. As a result, energy costs can be reduced. [Experiment] In order to confirm the above-mentioned effect, various experiments of surface modification methods were implemented and the results of measuring the modification results were as follows. 1 (Manufacturing and simple cleaning of polyolefin resin molding) First, in this embodiment, a homopolymer of polypropylene was used as the polyolefin resin. Then, the above polymer was formed into a size of "100x50x3mm" and used as a test piece P. Then, the above test ΗP was cleaned and washed with K power. That is, water with a water temperature of "(30 ° C) and a water pressure of" 100 kPa "is washed on the surface of the test piece P to remove dust and the like attached to the surface. (Apparatus) Second, the surface used for surface modification The experimental device is described below. However, the device used here is completely experimental. The same device as the surface modification device 5 described in the above embodiment is used as a means (flowing means) for contacting the test piece P with the ozone aqueous solution. That is, As shown in Figure 4, the paper size of the test paper from the nozzle 10 applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ~ &quot; -13 — (Please read the precautions on the back before filling this page)

A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (U.) 1 I m piece of P sprayed ozone spray solution. In addition to the above flow 1 I water means M, each means outside the use of the following device 0 namely. As shown in the figure, '* 1 ozone generator 32 is connected to the oxygen cylinder 31 r The ozone generated at this place is required The structure of 1 1 1 is supplied to the mixer 35 through the valve 33 and the backflow prevention gate 34. The ozone solution (water) is pressure-fed by the read back 1 II pump 36. The ozone solution (water) is supplied to the mixer 35. 1 I means 1 in the combiner 35. 9 ozone is dissolved in the ozone water solution (water) 〇 Furthermore, the ozone water-soluble matters 1 I and 1 '' liquid and __. Part of the ozone is 9 introduced under the '-mixer 37 at the same time it. The above-mentioned dissolution is continued at this place. Also added on the page of this mixer 37 is added to this page '— ^ 4. The device 38 is added with an ozone solution to a predetermined temperature.In order to introduce the excess gas into the 1 gate 39, then 1 the excess ozone passes from the separation gate 39 through the valve 40 and condensate. 1 The gate 41 is introduced into the activated carbon converter 42 〇 In the activated carbon converter 42 Inside> 1 I Ozone decomposes into oxygen. This oxygen is discharged from the aspirator 43. Another * 1 1 The ozone solution passing through the aforementioned excess gas separation gate 39 is sprayed on the mounting table 44 through the flowing water device described above. The test piece P (The ozone Λ aqueous solution is stored in the glass tank 45 of the mounting table 44 and then re-guided; | | Into the aforementioned pump 36 〇 Repeatedly implement the above-mentioned series of flow I process 〇1 I In the above device, the ozone concentration of the ozone solution in front of each flowing water device is 11 degrees for the plant 5 ^ 6 Ρ Ρ IB J, and the hydrogen ion concentration (ρ Η) is "approximately 5.5 Jt temperature 1 plant 70 ° cj 9 running water The amount is 4.5 liters per minute (sample 1 4) t 6.0 liters per minute 1 sample 5 to 8 j 〇 t t processing time 100 seconds] In addition,-aspects 1 * use silent discharge type Device (produced by Sugawara Corporation, brand name 1 OZSC -5 A) as the ozone generator 32 »The amount of ozone gas produced at that time was the factory 1 1 This paper size applies to the Chinese National Standard (CNS) A4 specification (2I0X297 mm ） The paper size printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 V. Description of the invention (12) 3 g / hour ". Furthermore, the ozone water concentration measuring device (manufactured by Hagiwara Corporation, trade name: Kentaro) was used to measure the concentration of the ozone aqueous solution. In addition, the treatment K immersed in the ozone aqueous solution as described above is compared at the same time (sample) 〇 (Experimental content) Using the above device, replace the appropriate nozzle 10 Μ while changing the spray pressure A, change the tip of the nozzle 10 and The distance B between the resin molded articles 2 is modified, and the drying and coating are performed thereafter. The paint used for this coating was a urethane paint (manufactured by Kansai Paint Co., Ltd., trade name: S F X 2000). Μ "80 ° C" After drying the paint to form a coating film layer, a peel strength test was performed on the coating film layer. To measure the peeling strength, a tensile tester (Tenslon: T en s h 丨 1 ο η) was used to measure the peeling strength of the coating film layer (but the pulling angle was "180 degrees" and the pulling speed was "50 mm / sec"). (Experimental results) Table 1 shows the values of A · B-2 when each of the above-mentioned processing conditions was changed, and the results of measuring the peel strength of the coating film layer in the center portion of the test piece P. (Please read the notes on the back before filling this page)

[Table 1] Sample No. Spray pressure A Distance BA · B-2 Peel strength 1 0 (impregnation) — — 40M 2 40 35 0.033 ^ 50 3 100 35 0.082 800 4 150 35 0.122 1000 5 40 15 0.178 1100 6 40 20 0.100 700 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (13) 7 40 30 0.044 150 8 40 40 0.025 10 0 Unit: spray pressure A, ..kPa, distance B: cm, peel strength : ... N / m. From the above results, it can be understood that, in the method of the M example, spraying the ozone aqueous solution in the form of K spray can obtain better adhesion of the coating film than the dipping treatment. In addition, increase the value of Α · Β_2, in other words, set the spray pressure as high as possible and the distance B as short as possible (especially the value of A · Β-2 is set to Q. 0 7 or more), and K can be significantly improved. The coating film is adhesive. [Additional test] ^ Next, except for the temperature K of the ozone aqueous solution, the treatment was performed under the same conditions as in the above-mentioned Sample 3, and the peel strength (coating film adhesion strength) when the temperature was changed was measured. The results are shown in Table 2. [Table 2]

Aqueous solution temperature 50 ° C 70 ° C 80 t: 90 1C Then the strength Δ 〇 ◎ X ◎ ... very strong, ○ ... strong, △ ... slightly strong, X ... weak. As can be understood from Table 2 above, when the ozone solution K is sprayed in a spray state, the adhesion strength of the coating film varies depending on the temperature of the ozone solution. That is, when the temperature of the aqueous ozone solution is higher than 8 5 ° C, * ozone is hardly dissolved in water, and the amount of decomposition from the ozone generator to the substrate also becomes large. Therefore, the desired modification properties cannot be obtained. When the temperature of the ozone aqueous solution is lower than 65 ° C, although the ozone concentration can be increased, the reactivity of the aqueous solution itself is poor, and the desired modification result cannot be obtained. In addition, the present invention is not limited to the above embodiments. For example, it can be configured as follows: This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -16-(Please read the precautions on the back before filling this page ), -'Β Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (14). (1) In the foregoing embodiment, the resin product 1 is composed of a resin molded product 2 and a coating film layer 3 formed on the surface. However, as shown in FIG. The structure of the undercoat layer 47 may be interposed between the film layers 3. At this time, the primer layer 47 can be firmly bonded to the surface of the resin molded article 2 which is uniformly oxidized and polarized. As a result, it is not necessary to use a specially selected primer material, or a special method is not required for the baking treatment. At the same time, the coating film 3 can be firmly bonded to the primer coating layer 47. (2) In the foregoing embodiment, an example in which a simple washing is performed by the power washing and washing device 4 at a stage before the modification is implemented, but the washing process may be omitted. (3) In the foregoing embodiment, polypropylene is used as the material of the poly (hydrocarbon) resin molded article. However, as long as the material is made of M polyolefin, it can be applied to polyethylene resin molded articles. , And those equipped with other secondary components, etc., the surface modification of any resin molding. Moreover, its shape is not limited to the shape of the bumper, for example, grid panels, decorations, garnishes, spoilers! Flow boards, lights, signs, badges, wheel covers, and other car accessories M and any other Shapers. (4) In the foregoing embodiment, the heater 9 and 38 are provided in the stage immediately before the spraying of the ozone solution on the resin molded article 2 (test piece P), but it may be provided in the earlier stage. Therefore, if necessary, it may be provided in the glass tank 45 shown in the foregoing embodiment. (5) In the foregoing embodiment, the composition of the intended surface (upper surface) of the resin molding 2 (test piece P) was sprayed in a misty manner with the ozone aqueous solution M 嗔, but the paper size of the resin molding is subject to the Chinese National Standard (CNS) Α4 specifications (210 × 297 mm) _ 丨 7 _ ~ (Please read the precautions on the back before filling this page) #. 、 1Τ

-Λ V __— L7—_ | 87-.12.1 4 hire charge __ V. Description of the invention (15) When the entire surface of the object 2 (test piece P) is a craftsman noodle, the composition of the ozone spray solution from various aspects is also can. The technical ideas and effects which can be grasped from the above-mentioned embodiments regarding items not included in the scope of patent application are described below. (a) In the method for modifying the surface of a polyolefin / resin molded article according to item 1 of the scope of patent application, or the surface coating method described in items 2 and 3 of the scope of patent application, in the stage immediately before contacting the sprayed ozone aqueous solution It is characteristic that the aforementioned ozone solution is heated. Due to the above structure, the ozone concentration of the ozone aqueous solution can be increased, and the efficiency of surface modification can be further improved by using M. [Brief Description of the Drawings] Drawing 1 is a system diagram showing a concrete version, a surface modification device, and the like in the actual example of the invention. FIG. 2 is a cross-sectional view showing a dendritic product according to an embodiment. Fig. 3 is a graph showing the relationship between water temperature and ozone solubility coefficient in an embodiment. -Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Figure 4 is a schematic diagram showing the experimental equipment when the surface modification / test is implemented in one embodiment. Fig. 5 is a cross-sectional view showing a resin product in another embodiment embodying the present invention. FIG. 6 is a general view of a surface modification device and the like of the prior art. [Description of component numbers] 1 Resin products 2 Resin molded products 18 _ (Please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) Amend A7 Bucket Q B7 87.! 2. Η Supplement V. Description of the invention (丨 6) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 3 Coated film 4 Power cleaning and cleaning device 5 Surface modification device 6 Conveyor nozzle 7 8 Ozone generator 9 Heater 10 Nozzle 11 Discharge port 12 Tube 13 Dryer 31 Oxygen cylinder 32 Oxygen generator 33 Valve 34 Backflow prevention valve 35 Mixer 36 Spring 37 Mixer 38 Heater 39 Excess gas separation gate 40 Valve 41 Condensation Gate 42 Activated carbon extinguisher 43 Aspirator (Please read the precautions on the back before filling this page)

This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -19-Revised page Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy 1 Revised. A 7 years. Monthly power% B7 87J2.I4 V. Invention Instructions (17) (Please read the cautions on the back before filling out this page)

44 Mounting table 45 Glass tank 47 Bottom coating tank 51 Forming resin 52 Water jet nozzle 53 Conveyor 54 Container 55 Adding container This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) — 20-Revised page

Claims (1)

Α8 Amendment Notice B8 C8 D8 January Q '37 .12.14. For the scope of patent application, please read the precautions on the back before filling out this page. 1. A method for modifying the surface of polyolefin resin moldings. The sprayed ozone solution is in contact with the polyolefin-based resin molding to oxidize the surface of the polyolefin-based resin molding, and the spray pressure when the ozone-water solution is in contact is set to A (kPa). When the distance between the JT tip and the polyolefin-based resin molded product is B (cm), X can satisfy the condition of B-2 ， 0.07, and the temperature / degree of the above-mentioned odor and oxygen aqueous solution is set to 85TM or lower. 2. A surface coating method for a polyolefin-based resin molded article, which is characterized in that a mist-like ozone aqueous solution is contacted with a polyalkylene hydrocarbon resin molded article, so that the surface of the aforementioned polyolefin fume resin molded article It is oxidized and the spray pressure when the ozone solution is contacted is set to A (k P qJ, when the nozzle for spraying the ozone solution described above is at a distance of B (cib) from the ^ polyolefin resin molded article I, It can meet the conditions of Α · B-2 S0.0J, and, before setting, the temperature of the ozone-soluble solvent is 6 5 ° CK to 85CK, and the surface of the modified olefin resin molding is modified. On the surface of the modified polymer, the coating layer is formed on the surface of the resin modified product. 3 — — Surface coating method of polypolycarbonate resin molded product, which It is characterized by economic and central standards bureau, industrial and consumer cooperation printing *. Spraying ozone aqueous solution-contacting the polyolefin-based resin molding, oxidizing the surface of the aforementioned "poly shoulder-hydrocarbon-resin molding", and , By setting the spray-fog when the aforementioned odorous aqueous solution is in contact- The force is A (kPa). When the distance between the tip of the nozzle for spraying the ozone solution and the polyalkylene resin resin molded product is B (cm), the condition of the force can be satisfied. B-2 &amp; 0. Ί) 7 And, before setting _ although the temperature of the ozone solution is 65t: W at 85ΌM, M will be; ^ the surface of the modified polyolefin-based grease molding, and | the modified paper size on this surface is applicable to China National Standards (CNS) Α4 Specification (210X297 mm) 1 Α8 Amendment Notice B8 C8 D8 Month Q '37.12.14. For the scope of patent application, please read the notes on the back before filling in this page 1. A polyolefin resin A method for modifying the surface of a molded product is particularly characterized by contacting a sprayed ozone aqueous solution with a polyolefin-based resin molded product, oxidizing the surface of the polyolefin-based resin molded product, and setting a spray when the ozone-water solution is contacted. When the pressure is A (kPa) and the distance between the spray JT tip for spraying the ozone solution and the polyolefin resin molded product is B (cm), X can satisfy the condition of B-2 衾 0.07, and the odor is set. ', The temperature / degree of the oxygen aqueous solution is lower than 85TM. 2. A surface coating method for a polyolefin-based resin molded article, which is characterized in that a mist-like ozone aqueous solution is contacted with a polyalkylene hydrocarbon resin molded article, so that the surface of the aforementioned polyolefin fume resin molded article It is oxidized and the spray pressure when the ozone solution is contacted is set to A (k P qJ, when the nozzle for spraying the ozone solution described above is at a distance of B (cib) from the ^ polyolefin resin molded article I, It can meet the conditions of Α · B-2 S0.0J, and, before setting, the temperature of the ozone-soluble solvent is 6 5 ° CK to 85CK, and the surface of the modified olefin resin molding is modified. On the surface of the modified polymer, the coating layer is formed on the surface of the resin modified product. 3 — — Surface coating method of polypolycarbonate resin molded product, which It is characterized by economic and central standards bureau, industrial and consumer cooperation printing *. Spraying ozone aqueous solution-contacting the polyolefin-based resin molding, oxidizing the surface of the aforementioned "poly shoulder-hydrocarbon-resin molding", and , By setting the spray-fog when the aforementioned odorous aqueous solution is in contact- The force is A (kPa). When the distance between the tip of the nozzle for spraying the ozone solution and the polyalkylene resin resin molded product is B (cm), the condition of the force can be satisfied. B-2 &amp; 0. Ί) 7 And, before setting _ although the temperature of the ozone solution is 65t: W at 85ΌM, M will be; ^ the surface of the modified polyolefin-based grease molding, and | the modified paper size on this surface is applicable to China National Standards (CNS) A4 specification (210X297 mm) 1 c Printed by A8 S9O806? 88 D8 of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, the scope of the patent application releases the resin molding, and the surface of the object is formed to the bottom coating The coating layer ', meanwhile, on this coating layer, a coating film-layer is formed. nn 1 ^ 1 I m ^ i i-I In · n ^ i I (Please read the precautions on the back before filling in this page) Order. This paper size applies the Chinese National Standard (CNS) A4 specification (210X25 »7mm)