Acrylic modified chlorinated polyolefin resin composition and the production method thereof

Abstract

The invention relates to a novel acrylic modified chlorinated polyolefin resin composition and production method that will enable primer or paint systems to adhere to the surface in the automotive sector. The invention in particular, relates to a novel acrylic modified chlorinated polyolefin resin composition that will enable single-component (1K) or double component (2K-polyurethane) primer and / or single layer paint systems to adhere directly to thermoplastic polyolefin (TPO) and thermoplastic alloy surfaces without the need for adhesion enhancing pretreatments.

Description

[0001] ACRYLIC MODIFIED CHLORINATED POLYOLEFIN RESIN COMPOSITION AND THE PRODUCTION METHOD THEREOF

[0002] Technical Field

[0003] The invention relates to a novel acrylic modified chlorinated polyolefin resin composition that will enable primer or paint systems to adhere to the surface in the automotive sector and the production method thereof.

[0004] In particular, the invention relates to a novel acrylic modified chlorinated polyolefin resin composition which enables single component (1 K) or double component (2K- polyurethane) primer and / or single layer paint systems to adhere directly to thermoplastic polyolefin (TPO) and thermoplastic alloy surfaces without the need for adhesion enhancing pretreatments.

[0005] State of the Art

[0006] Thermoplastic polyolefin (TPO), widely used in the automotive industry, are plastics that combine semi crystalline polyolefin thermoplastic and amorphous elastomeric contents. Due to the apolar structure of thermoplastic polyolefins (TPOs) and low surface tension energy, it is a challenging process to ensure that primer or paint systems adhere to these surfaces. Therefore, in the art, adhesive surface pretreatments such as flame, plasma or UV light exposure are applied that increase the polarity of the surface (increases the surface energy) and provide functional groups on the surface that can interact with the coating. However, these procedures cause both extra cost and time loss.

[0007] In addition to the pretreatments in the present art, adhesion enhancing methods are also applied in the form of applying chlorinated polyolefins to the surface as a separate layer before the paint or coating systems or by entering the chlorinated polyolefin solution into the primer or paint system to be applied. However, these methods also have disadvantages. Its application in a separate layer causes extra time and energy loss as well as creates an extra layer on the surface, thus causing the surface to become heavier. The addition of chlorinated polyolefins in the form of a solution into the paint system causes decomposition in the paint system due to their low compatibility with other resins, and as a result, it brings application difficulties. Therefore, there is a need for a resin composition consisting of both acrylic monomers and chlorinated polyolefin, the main structure of which will have both acrylic resin properties and the ability of chlorinated polyolefin to adhere to the surface.

[0008] As a result, due to the abovementioned disadvantages and the insufficiency of the current solutions regarding the subject matter, a development is required to be made in the relevant technical field.

[0009] The Objective of the Invention

[0010] The objective of the invention is to solve the abovementioned disadvantages by being inspired from the current conditions.

[0011] The main objective of the invention is to provide a resin composition that has acrylic resin properties and the ability of chlorinated polyolefin to adhere to the surface. Since the main structure of the composition consists of both acrylic monomers and chlorinated polyolefin, the primer or paint systems to be used have both acrylic resin properties and the ability of chlorinated polyolefin to adhere to the surface.

[0012] The objective of the invention is to provide a resin composition that will enable single component (1 K) or double component (2K-polyurethane) primer and / or single layer paint systems to adhere directly to the thermoplastic polyolefin (TPO) and thermoplastic alloy surfaces without the need for adhesion enhancing pretreatment that can create extra cost, energy and labor.

[0013] In order to fulfill the aforementioned objectives, the invention is a novel acrylic modified chlorinated polyolefin resin composition that enable paint and primer systems to adhere to thermoplastic polyolefin (TPO) and thermoplastic alloy surfaces, comprising chlorinated Polyolefin Resin, Aromatic Hydrocarbon solvent, radical initiator, Acrylate / Methacrylate Monomer 1 , Acrylate / Methacrylate Monomer 3 with Hydroxyl Functional Group, Inhibitor Solution.

[0014] The invention is a production method of of novel acrylic modified chlorinated polyolefin resin composition that enable paint and primer systems to adhere to thermoplastic polyolefin (TPO) and thermoplastic alloy surfaces, comprising the following process steps; i. Preparing and homogenization of the chlorinated polyolefin solution in the temperature range of 75-95 O, ii. Adding radical initiator to the homogeneous chlorinated polyolefin solution and keeping it in the temperature range of 75-95 'C unt il the solution becomes active, iii. The preparation of balanced addition mixture comprises monomers, the radical initiator and the Aromatic Hydrocarbon solvent, iv. Mixing the prepared balanced addition mixture by adding it to the chlorinated polyolefin solution at the reaction temperature and then obtaining the resin solution by maintaining the mixture at the reaction temperature until the reaction reaches the determined acid value, v. Adding the inhibitor solution to the resulting resin solution at the reaction temperature and mixing, vi. Ensuring that the resin composition reaches the final solid value by adding Aromatic Hydrocarbon solvent to the resin solution.

[0015] The structural and characteristic features and all the advantages of the invention will be understood more clearly due to the detailed description given below, and therefore the evaluation should be made while taking this detailed description into consideration.

[0016] Detailed Description of the Invention

[0017] In this detailed description, the resin composition and preferred structures of the invention are described only for a better understanding of the subject.

[0018] The present invention relates to a novel acrylic modified chlorinated polyolefin resin composition and production method thereof that enable paint and primer systems to adhere to thermoplastic polyolefin (TPO) and thermoplastic alloy surfaces. Since the main structure of the invention consists of both acrylic monomers and chlorinated polyolefin, the primer or paint systems to be used have both acrylic resin properties and the ability of chlorinated polyolefin to adhere to the surface.

[0019] Inventive composition in its most basic form, comprises chlorinated Polyolefin Resin, Aromatic Hydrocarbon solvent, radical initiator, Acrylate / Methacrylate Monomer 1 , Acrylate / Methacrylate Monomer 3 with Hydroxyl Functional Group, Inhibitor Solution. The composition comprises chlorinated Polyolefin Resin in the range of 5-25% by weight, Aromatic Hydrocarbon solvent in the range of 33.5-62.5%, radical initiator in the range of 0.75-2.25%, Acrylate / Methacrylate Monomer 1 in the range of 2.5-7.5%, Acrylate / Methacrylate Monomer 3 with Hydroxyl Functional Group in the range of 2.5- 7.5% and Inhibitor Solution in the range of 2.5-7.5% by weight. The composition additionally comprise Acrylate / Methacrylate Monomer 2 and / or Acrylate / Methacrylate Monomer 4 with the Acid Functional Group.

[0020] A preferred example of the inventive composition comprise; chlorinated Polyolefin Resin in the range of 5-25%, Aromatic Hydrocarbon solvent in the range of 33.5- 62.5%, radical initiator in the range of 0.75-2.25%, Acrylate / Methacrylate Monomer 1 in the range of 2.5-7.5%, Acrylate / Methacrylate Monomer 2 in the range of 10-30%, Acrylate / Methacrylate Monomer 3 with Hydroxyl Functional Group in the range of 2.5- 7.5%, Acrylate / Methacrylate Monomer 4 with Acid Functional Group in the range of 0.25-0.75% and Inhibitor Solution in the range of 2.5-7.5% by weight. Resin composition recipes are given in Table 1 .

[0021] Table 1. Resin composition recipes within the scope of the invention

[0022] The Radical Initiator mentioned in our invention is selected from, but not limited to, organic peroxides, azo compounds.

[0023] The Acrylate / Methacrylate Monomer 1-2 mentioned in our invention is selected from the group comprising, but not limited to: butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate.

[0024] The acrylate / methacrylate monomer 3 with hydroxyl functional group mentioned in our invention is selected from the group comprising, but not limited to, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate.

[0025] The acrylate / methacrylate monomer 4 with acid functional group mentioned in our invention is selected from the group comprising, but not limited to acrylic acid, methacrylic acid.

[0026] The aromatic Hydrocarbon Solvent mentioned in our invention is selected from the group comprising, but not limited to, benzene, toluene, xylene, ethyl benzene.

[0027] The inhibitor solution mentioned in our invention is obtained by dissolving the compound selected from 1-4 benzenediol, hydroquinone monomethyl ether, tertbutyl catechol, etc. in aromatic hydrocarbon solvent (benzene, toluene, xylene, ethyl benzene, etc.).

[0028] The subject of the invention which is a production method of novel acrylic modified chlorinated polyolefin resin composition that enable the paint and primer systems to adhere to thermoplastic polyolefin (TPO) and thermoplastic alloy surfaces comprise the following process steps: i. Preparing and homogenization of the chlorinated polyolefin solution in the temperature range of 75-95 O, ii. Adding radical initiator to the homogeneous chlorinated polyolefin solution and keeping it in the temperature range of 75-95 'C unt il the solution becomes active, iii. The preparation of balanced addition mixture containing monomers, the radical initiator and the Aromatic Hydrocarbon solvent, iv. Mixing the prepared balanced addition mixture by adding it to the chlorinated polyolefin solution at the reaction temperature and then obtain the resin solution by keeping the mixture at the reaction temperature until the reaction reaches the determined acid value , v. Adding the inhibitor solution to the resulting resin solution at the reaction temperature and mixing, vi. Ensuring that the resin composition reaches the final solid value by adding Aromatic Hydrocarbon solvent to the resin solution.

[0029] Herein, the chlorinated polyolefin solution is prepared as follows; chlorinated polyolefin resin in solid (pellet) form weighed in the specified ratios and hydrocarbon solvent weighed in accordance with the specified ratios are added to the reaction balloon, the temperature is preferably adjusted to 75-95cC. Whe n the solid resin starts to melt, the mechanical mixer is adjusted to 90-105 rpm (rotations / minute) and the resin is dissolved homogeneously in the hydrocarbon solvent. This process preferably takes place within 1 hour. Then, radical initiator is added to the homogeneous chlorinated polyolefin solution.

[0030] The preferred embodiment of the method, in the process step (ii), the radical initiator is kept in the temperature range of 75-95 'C for 1 hou r until the added solution becomes active.

[0031] Preferred embodiment of the method; in the process step (iii), Acrylate / Methacrylate Monomer 1 , Acrylate / Methacrylate Monomer 3 with Hydroxyl Functional Group, radical initiator and Aromatic Hydrocarbon solvent are mixing at room temperature to prepare the balanced addition mixture. The preferred embodiment of the method; in the process step (iii), the radical initiator, aromatic hydrocarbon solvent, acrylate / methacrylate monomer 1 , acrylate / methacrylate monomer 3 with hydroxyl functional group, acrylate / methacrylate monomer 2 and / or acrylate / methacrylate monomer 4 with acid functional group are mixing to prepare the balanced addition mixture.

[0032] Herein, in the preferred embodiment of the method, the reaction temperature mentioned in the process step (iv) is in the range of 75-95cC. The balanced additional mixture is added to the chlorinated polyolefin solution at a temperature of 75-95 G for 2-4 hours and the mixture is kept for 3-5 hours at a temperature range of 75-95 G in order for the reaction to reach the determined acid value. Here, while adding the balanced addition mixture, the mixer is set at 120-140 rpm (rotations / minute) and remains at the specified rpm until the end of the reaction.

[0033] In the preferred embodiment of the method, the reaction temperature mentioned in the process step (v) is in the range of 75-95 G.

[0034] In the preferred embodiment of the method, the aromatic hydrocarbon solvent mentioned in the process step (vi) is added to the resin solution in the temperature range of 60-70 G.

[0035] In order to obtain a preferred example of the invention, the following processes are followed:

[0036] 1 st Step: Preparation and homogenization of chlorinated polyolefin solution in the temperature range of 75-95 G,

[0037] 2nd Step: Adding a radical initiator in the range of 75-95 G into a homogeneous chlorinated polyolefin solution and keeping the solution in the temperature range of 75- 95 G for 1 hour until it becomes active.

[0038] 3rd Step: Preparing the balanced addition mixture by mixing radical initiator, Aromatic Hydrocarbon solvent, Acrylate / Methacrylate Monomer 1 , Acrylate / Methacrylate Monomer 3 with Hydroxyl Functional Group, Acrylate / Methacrylate Monomer 2 and / or Acrylate / Methacrylate Monomer 4 with Acid Functional Group at room temperature,

[0039] 4th Step: Adding the balanced Addition Mixture to the chlorinated polyolefin solution for 2-4 hours at a temperature range of 75-95 G and th en obtaining the resin solution by keeping the mixture at a temperature range of 75-95 'C and for 3-5 hours until the reaction reaches the determined acid value,

[0040] 5th Step: Addition of Inhibitor Solution to the resulting resin solution in the temperature range of 75-95 O,

[0041] 6th Step: For reaching the Final Solid Value of the Resin, adding of Aromatic Hydrocarbon solvent at 60-70cC.

[0042] In our invention, it is not required to have acid modification in order to make acrylic modification in chlorinated polyolefin. The lack of acid modification ensures that the final resin both have a cost advantage manner and ability to adhere paint system to difficult thermoplastic surfaces without the need for pre-treatment.

[0043] Aromatic Hydrocarbon Solvent: Before proceeding to the acrylic modification stage of the reaction, the chlorinated polyolefin in pellet form must be made into a homogeneous solution in order to react efficiently. In our invention, aromatic hydrocarbons are used as the solvents which provides the best dissolution of chlorinated polyolefin.

[0044] Another important function of Aromatic Hydrocarbon Solvents is to increase the penetration on thermoplastic polyolefin (TPO) to the surface after the primer or paint system is applied. Aromatic hydrocarbon solvents can penetrate the surface more easily and allow the crystalline layer in the top layer of the thermoplastic polyolefin surface to swell. With this swelling, it allows the resin to reach the amorphous structure in the lower layer of the surface and increase the surface-resin interaction.

[0045] Inhibitor solution: The most important problem of chlorinated polyolefin resins with acrylic modification is the long-term stabilization of the final resin at high and low temperatures (not increasing viscosity and / or not occurring gelation). In our invention, the widening of the temperature ranges and the extending of the duration of this stabilization takes place thanks to the inhibitor solution used during the reaction.

[0046] Before the 1 K or 2K primer or paint system prepared with acrylic modified chlorinated polyolefin resin, which is the subject of our invention, is applied to the surface, the following potential impurities must be removed from the surface. Otherwise, these impurities will adversely affect the adhesion performance of the applied paint.

[0047] Plasticizer, lubricant, fire retardant, UV stabilizers, filler and monomers etc. accumulated on the surface of the thermoplastic. - Possible sanding dusts, dusts from the air line, fiber particles, etc.

[0048] The comparisons obtained from three different runs of the acrylic modified chlorinated polyolefin resin composition, which is the subject of our invention, and two commercial resins are given in Table 2. It is seen that the resin, which is the subject of our invention, has low viscosity. Table 2 Resin composition comparison data

Claims

CLAIMS1. A novel acrylic modified chlorinated polyolefin resin composition for adhesion of paint and primer systems to thermoplastic polyolefin (TPO) and thermoplastic alloy surfaces, characterized by comprising; chlorinated Polyolefin Resin, Aromatic Hydrocarbon solvent, radical initiator, Acrylate / Methacrylate Monomer 1 , Acrylate / Methacrylate Monomer 3 with Hydroxyl Functional Group, Inhibitor Solution.

2. The composition according to claim 1 , characterized in that; the said Acrylate / Methacrylate Monomer 1 is selected from the group comprising, but not limited to, butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate.

3. The composition according to claim 1 , characterized in that; the said Acrylate / Methacrylate Monomer 3 with Hydroxyl Functional Group is selected from the group comprising, but not limited to, 4-hydroxybutyl acrylate, 4- hydroxybutyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate.

4. The composition according to claim 1 , characterized in that; the said radical initiator is selected from the group comprising, but not limited to, organic peroxides, azo compounds.

5. The composition according to claim 1 , characterized by comprising;Chlorinated Polyolefin Resin in the range of 5-25%Aromatic Hydrocarbon solvent in the range of 33.5-62.5%Radical initiator in the range of 0.75-2.25%Acrylate / Methacrylate Monomer 1 in the range of 2.5-7.5%Acrylate / Methacrylate Monomer 3 with Hydroxyl Functional Group in the range of 2.5-7.5%Inhibitor Solution in the range of 2.5-7.5% by weight.

6. The composition according to claim 1 , characterized in that; the composition further comprises Acrylate / Methacrylate Monomer 2.

7. The composition according to claim 6, characterized in that; the said Acrylate / Methacrylate Monomer 2 selected from, but not limited to, butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate.

8. The composition according to claim 1 , characterized in that; the total composition further comprises Acrylate / Methacrylate Monomer 4 with Acid Functional Group.

9. The composition according to claim 8, characterized in that; the said Acrylate / Methacrylate Monomer 4 with Acid Functional Group is selected from, but not limited to, acrylic acid or methacrylic acid.

10. The composition according to any one of the preceding claims, characterized by comprising;Chlorinated Polyolefin Resin in the range of 5-25%Aromatic Hydrocarbon solvent in the range of 33.5-62.5%Radical initiator in the range of 0.75-2.25%Acrylate / Methacrylate Monomer 1 in the range of 2.5-7.5% Acrylate / Methacrylate Monomer 2 in the range of 10-30% Acrylate / Methacrylate Monomer 3 with Hydroxyl Functional Group in the range of 2.5-7.5%,Acrylate / Methacrylate Monomer 4 with Acid Functional Group in the range of 0.25-0.75%Inhibitor Solution in the range of 2.5-7.5% by weight.

11. A production method of novel acrylic modified chlorinated polyolefin resin composition that enable paint and primer systems to adhere to thermoplastic polyolefin (TPO) and thermoplastic alloy surfaces, characterized by comprising; following the process steps: i. Preparing and homogenization of the chlorinated polyolefin solution in the temperature range of 75-95 G,ii. Adding radical initiator to homogeneous chlorinated polyolefin solution and keeping it in the temperature range of 75-95 'C until the solution becomes active, iii. Preparation of balanced addition mixture comprises monomers, radical initiator and Aromatic Hydrocarbon solvent, iv. Mixing the prepared balanced addition mixture by adding it to the chlorinated polyolefin solution at the reaction temperature and then obtaining the resin solution by keeping the mixture at the reaction temperature until the reaction reaches the determined acid value, v. Adding the inhibitor solution to the resulting resin solution and mixing at the reaction temperature, vi. Ensuring that the resin composition reaches the final solid value by adding Aromatic Hydrocarbon solvent to the resin solution.

12. The method according to claim 11 , characterized in that; the solution in which the radical initiator is added in the process step (ii) is kept for 1 hour in the temperature range of 75-95 'C until it becomes acti ve.

13. The method according to claim 1 1 , characterized in that; in the process step (iii), the balanced addition mixture prepared by mixing Acrylate / Methacrylate Monomer 1 , Acrylate / Methacrylate Monomer 3 with the Hydroxyl Functional Group, radical initiator and Aromatic Hydrocarbon solvent at room temperature.

14. The method according to claim 1 1 , characterized in that; in the process step(iii), the balanced addition mixture prepared by mixing radical initiator, aromatic hydrocarbon solvent, acrylate / methacrylate monomer 1 , acrylate / methacrylate monomer 3 with hydroxyl functional group, acrylate / methacrylate monomer 2 and / or acrylate / methacrylate monomer 4 with acid functional group.

15. The method according to claim 1 1 , characterized in that; the reaction temperature mentioned in the process step (iv) is in the temperature range of 75-95tC.

16. The method according to claim 1 1 , characterized in that; in the process step(iv), the balanced addition mixture is added to the chlorinated polyolefin solution by mixing at a reaction temperature of 75-95 G and for 2-4 hours.

17. The method according to claim 11 , characterized in that; in the process step (iv), the mixture is kept in the temperature range of 75-95 'C for 3-5 hours in order for the reaction to reach the determined acid value.

18. The method according to claim 11 , characterized in that; the reaction temperature mentioned in the process step (v) is in the range of 75-95cC.

19. The method according to claim 11 , characterized in that; the aromatic hydrocarbon solvent mentioned in the process step (vi) is added in the temperature range of 60-70cC.

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