Method of treating surface of molded article of polypropylene resin and method of coating said molded article

Abstract: The present invention provides a method which enables the surface of a molded article of a polypropylene resin to be modified to a surface suitable for coating, bonding, printing, etc. A molded article of a polypropylene resin comprising polypropylene, an ethylene-propylene copolymer rubber and an ethylene-acrylic acid or ethylene-methacrylic acid copolymer and optionally a filler is irradiated in the air with a light from a synthetic quartz low pressure mercury lamp having an output of 200 W for 60 sec with the distance between the surface of the molded article and the lamp being kept at about 10 cm.

Description: The present invention relates to a method of treating the surface of a molded article of a polypropylene resin formed particularly, but not exclusively, by injection molding or extrusion molding and a method of coating the molded article with a paint. More particularly, the present invention is concerned with a method of treating the surface of a molded article of a polypropylene resin comprising polypropylene, an ethylene-propylene copolymer rubber, and an ethylene-methylmethacrylate copolymer, and a coating method using the same. It is difficult to successfully coat, bond, and print, onto a molded polypropylene resin article because the polypropylene resin is non-polar. For this reason, various proposals have been made for successfully coating onto the surface of a molded article. For example, in order to further improve the compatibility of a molded polypropylene resin article (hereinafter often referred to as "molded article") with an adhesive or paint, a proposal has been made for the provision of an interlayer between the molded article and the adhesive or paint. A medium known as a so-called "primer" comprising a chlorinated polypropylene and toluene has been widely used as the interlayer. Sand blasting, chromic acid mixture treatment, flame treatment, corona discharge treatment and plasma treatment, have been proposed as a surface treatment method for modifying the surface of a molding to give a surface suitable for coating. However, in the conventional method wherein an interlayer is provided, the primer per se is expensive and an additional step, for forming the interlayer, is added to the method, so that the final cost of the product becomes high. Further, none of the conventional surface treatment methods such as sand blasting, chromic acid mixture treatment, flame treatment, corona discharge treatment and plasma treatment provided satisfactory results. Further, for example, the chromic acid mixture treatment has a problem that the waste solution should be made pollution-free. The present invention has been made under these circumstances, and we have now found it possible to solve the above-described problems and to provide a surface treatment method which will improve the coatability, adhesion and printability of the surface of a molded polypropylene resin article. WO 91/11483 discloses a method of irradiating the surface or a molded article or a composition by UV rays with a wavelength or 300 nm or less, said resin composition comprising (A) 50 to 95 % by weight of thermoplastic resin, (B) 5-50 % by weight of a funtionalized polyolefin resin and (C) 3 to 50 parts by weight based on (A) and (B) of a rubber. The molded articles provide good coatability, printability and adhesive properties. The present inventors have made extensive and intensive studies with a view to attaining the above-described aim. As a result, they have found that the irradiation of the surface of a molded article of a polypropylene resin comprising polypropylene, an ethylene-propylene copolymer rubber, and an ethylene-methylmethacrylate copolymer resin with ultraviolet rays having a dominant irradiation wavelength in a region of 300 nm or less enables the surface of the molded polypropylene resin article to be modified to give a surface suitable for coating, bonding and printing. According to one aspect of the present invention there is provided a method of treating the surface of a molded article of a polypropylene resin comprising irradiating a molded article of a resin composition comprising (A) 10 to 60 parts by weight of polypropylene, (B) 10 to 40 parts by weight of an ethylene-propylene copolymer rubber and (C) 30 to 60 parts by weight of an ethylene-methylmethacrylate copolymer resin (and optionally 40 parts by weight or less, based on 100 parts by weight of the composition comprising (A) the polypropylene resin, (B) the ethylene-propylene copolymer rubber and (C) the ethylene-methylmethacrylate copolymer resin, of a filler) with ultraviolet rays having an irradiation wavelength in a region of 300 nm or less. The method of coating a molded article of a polypropylene resin with a paint according to a further aspect of the invention comprises coating the polypropylene resin molding after treating the surface in accordance with the present invention with a paint. Preferred embodiments will now be described. In practicing the present invention, the molded article may be in any form. Specifically, the invention may be applied to molded article in the form of a sheet, a film and a fiber, etc. The invention will now be described in detail. (A) Polypropylene The term "polypropylene" used in the present invention is generally intended to mean a crystalline polypropylene. The polypropylene includes at least one resin selected from (a) a homopolypropylene, (b) a polypropylene-α-olefin random copolymer produced by copolymerizing propylene with, for example, an α-olefin such as ethylene, butene-1, hexene-1, or 4-methyl-pentene-1, and (c) propylene-ethylene block copolymer. (a) Homopolypropylene A homopolypropylene having a melt index of 10 to 100 g/10 min is employed. When the melt index is smaller than 10 g/10 min, an injection molded article having an excellent appearance (in respect of flow mark and gloss) cannot be obtained. On the other hand, when the melt index exceeds 100 g/10 min, the properties, particularly impact strength, of the molded article decrease. (b) Propylene-α-olefin random copolymer A propylene-α-olefin random copolymer having an α-olefin content in the range of from 0.5 to 8 % by weight is employed. When the α-olefin content is higher than 8 % by weight, the properties, particularly heat resistance, of the molded article decrease. Preferably, the α-olefin has from 1 to 6 carbon atoms (exclusive of 3 carbon atoms). The α-olefin is preferably ethylene. The propylene-α-olefin random copolymer has a melt index in the range of from 10 to 100 g/10 min. The reason for this is the same as that in the case of the homopolypropylene. (c) Propylene-ethylene block copolymer The propylene-ethylene block copolymer has an ethylene content of 2 to 15 % by weight, an ethylene content of 20 to 60 % by weight in the propylene-ethylene copolymer portion and an intrinsic viscosity of 2 to 10 dl/g, preferably 3 to 8 dl/g, in the propylene-ethylene copolymer portion as measured in a tetralin solution at 135 °C. When the ethylene content is outside the above-described range, the impact strength of the molded article decreases. When the intrinsic viscosity is smaller than 2 dl/g, the impact strength of the molded article decreases. On the other hand, when the intrinsic viscosity exceeds 10 dl/g, the fluidity of the resin composition during molding decreases and the appearance of the molded article deteriorates. Further, the propylene-ethylene block copolymer has a melt index in the range of from 10 to 100 g/10 min. The reason for this is the same as that in the case of the homopolypropylene. The homopolypropylene (a), propylene-α-olefin random copolymer (b) and propylene-ethylene block copolymer (c) each may be produced, for example, by a reaction in the presence of a catalyst usually called a "Ziegler-Natta catalyst" comprising a combination of titanium trichloride with an alkyl aluminum compound. In the present invention, besides polypropylene, a modified polypropylene or mixture of a modified polypropylene with polypropylene may be used as the polypropylene (A). The term "modified polypropylene" is intended to mean a polypropylene modified by the grafting of an unsaturated carboxylic acid or its anhydride in an amount in the range of from 0.05 to 20 % by weight, preferably in the range of from 0.1 to 10 % by weight, onto the above-described polypropylene. Examples of the graft monomer in the modified polypropylene graft-modified with an unsaturated carboxylic acid or its anhydride include acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride and itaconic anhydride. Among them, maleic anhydride is particularly preferred. The graft monomer may be grafted onto polypropylene by various known methods. Examples of such methods include a method wherein polypropylene, a graft monomer and a radical initiator are melt-kneaded with each other within an extruder for grafting; a method which comprises dissolving polypropylene in an organic solvent, such as xylene, adding a radical generator to the solution in a nitrogen atmosphere, allowing a thermal reaction to proceed with stirring, cooling the reaction system after the completion of the reaction, washing and filtering the reaction mixture and drying the resultant solid to give a grafted polypropylene; a method wherein polypropylene is irradiated with ultraviolet rays or radioactive rays in the presence of a graft monomer; and a method wherein polypropylene is brought into contact with oxygen or ozone. (B) Ethylene-propylene copolymer rubber The term "ethylene-propylene copolymer rubber" used in the present invention is intended to mean an ethylene-propylene copolymer rubber having a propylene content of 10 to 70 % by weight and a Mooney viscosity (ML₁+₄, 100 °C) of 10 to 100. When the propylene content is outside the above-described range, the impact strength of the molded article decreases. When the Mooney viscosity is less than 10, the mechanical properties of the molded article deteriorate, while when the Mooney viscosity exceeds 100, the appearance of the molded article becomes poor due to a lowering in the fluidity of the resin composition during molding. In the present invention, the ethylene-propylene copolymer rubber includes an ethylene/propylene/non-conjugated diene copolymer rubber. (C) Ethylene-methylmethacrylate copolymer resin. The ethylene content of the ethylene-methylmethacrylate copolymer resin is in the range of from 50 to 95 % by weight. When the ethylene content is less than 50 % by weight, the heat resistance of the molded article deteriorates. On the other hand, when the ethylene content exceeds 95 % by weight, the co-monomer content becomes so low that the ultraviolet irradiation according to the present invention provides no improvement in the coatability, adhesion and printability of the molded article. (D) Percentage composition The resin composition used in the molding according to the present invention comprises (A) 10 to 60 parts by weight of at least one polypropylene selected from (a) a homopolypropylene, (b) a propylene-α-olefin random copolymer and (c) a propylene-ethylene block copolymer, (B) 10 to 40 parts by weight of an ethylene-propylene copolymer rubber and (C) 30 to 60 parts by weight of an ethylene-methylmethacrylate copolymer. When the content of the ethylene-methylmethacrylate resin (C) exceeds 60 parts by weight, the heat resistance of the molded article decreases. In the present invention, when a filler comprising an inorganic filler and/or a glass fiber is incorporated in the resin composition, the proportion of the filler is preferably up to 40 parts by weight based on 100 parts by weight of the composition comprising (A)polypropylene, (B) an ethylene-propylene copolymer rubber and (C) a copolymer resin. This is because when molding is carried out with the use of a resin composition containing an inorganic filler and/or a glass fiber in an amount exceeding 40 parts by weight, the impact resistance of the resultant molded article remarkably decreases. When molding is carried out the use of a resin composition free from any of the inorganic filler and the glass fiber, although the heat resistance, rigidity and dimensional stability of the molded article are poor, the molded article has an improved impact strength. When an inorganic filler is used in combination with a glass fiber, the proportions of the inorganic filler and the glass fiber are preferably 20 to 80 % by weight and 80 to 20 % by weight, respectively. In practicing the present invention, if necessary, the resin composition used in the molding may contain various additives such as pigments, ultraviolet absorbers, heat stabilizers, flame retardants, antistatic agents, weathering agents, forming agents, antioxidants and plasticizers. Further, in practicing the invention, when a molded article of a polypropylene resin is produced, if necessary, the resin composition used in the molding may contain an ethylene-propylene-non-conjugated copolymer rubber, a propylene-butene rubber, an isoprene-butylene rubber, polyisoprene, polybutadiene, and styrene block copolymers, for example, rubber-like substances such as a styrene-butadiene rubber, a styrene-butadiene-styrene block copolymer, a partially hydrogenated styrene-butadiene block copolymer, a styrene-isoprene block copolymer and a partially hydrogenated styrene-isoprene block copolymer in such an amount as will not spoil various properties of the molded article of the resin. (E) Blending method and molding method There is no particular limitation on the process for producing the polypropylene resin composition used in the molding in the present invention, and use may be made of a conventional process. It is also effective to use a process which comprises melt-mixing the polypropylene (A) with the ethylene-propylene copolymer rubber (B) and the copolymer resin (C) and evaporating the solvent or precipitating the composition in a non-solvent. In fact, however, a process wherein the components are kneaded with each other in a molten state is preferred from an industrial standpoint. A Banbury mixer, an extruder, a roll, various kneaders commonly used in the art may be used for the melt kneading. In the kneading, it is preferred that individual resin components be previously homogeneously blended in the form of a pellet in an apparatus such as a tumbler or a Henschel mixer. If necessary, however, the blending may be omitted, and the resin components may be separately fed at a constant feed rate to a kneading device. The kneaded resin composition can be molded by injection molding, extrusion molding and various other molding methods. Further, in the present invention, it is also possible to use a method wherein, without conducting the step of kneading, the components are dry-blended with each other at the time of the injection molding or extrusion molding and directly blended during melt processing to obtain a molded article. (F) Surface treatment method and coating method In the present invention, the surface of a molded article formed by molding the above-described polypropylene resin composition is irradiated with ultraviolet rays. The light applied to the surface of the molded article is a light having a wavelength of 300 nm or less, particularly preferably ultraviolet rays having wavelengths of 254 nm and 185 nm as a dominant active wavelength. The stronger the intensity of the light, the better the results. The ultraviolet irradiation time is preferably about 20 sec to 10 min, more preferably 30 sec to 5 min. This is because when the ultraviolet irradiation time is shorter than 20 sec, the effect of improving the coatability, adhesion, printability of the molded article of the composition may be unsatisfactory, while when the ultraviolet irradiation time is longer than 10 min, not only the profitability is poor but also the surface of the molded article of the resin composition may unfavorably begin to deteriorate. A synthetic quartz low pressure mercury lamp is preferably used as a lamp for applying the ultraviolet rays to the molded article. This is because in this type of mercury lamp, the intensity of a light having a wavelength of 254 nm and 185 nm is higher than that of a natural quartz low pressure mercury lamp. In practicing the present invention, it is preferred to degrease the molded article prior to the irradiation of the surface of the molded article of a polypropylene resin with ultraviolet rays. Water or an aqueous solution of an alkali and alcohols such as ethanol and isopropyl alcohol may be used as a solvent for degreasing the surface of the molded article of a polypropylene resin. Examples of the method of bringing the degreasing solution into contact with the surface of the molded article of a polypropylene resin include coating, wiping and spraying. The molded article irradiated with ultraviolet rays may then be coated with a paint. Preferred examples of the paint used in the present invention include epoxy, polyester, acrylic and urethane paints. In particular, since urethane paint is flexible, it is extensively used in parts of automobiles and motorbikes. Examples of urethane paint include paints having a urethane structure, such as acrylic urethanes, polyester urethanes and other modified urethanes. EXAMPLES The present invention will now be described in more detail with reference to the following EXAMPLES. However, materials and numerical conditions such as mixing ratio of the materials, treatment temperature and treatment time used in the following EXAMPLES are merely a preferred embodiment falling within the scope of claims of the present invention. Therefore, it should be understood that the present invention is not limited to these materials and numerical conditions only. 〈Method of evaluating coatability (initial adhesion)〉 The surface treatment effect of the molded articles subjected to the surface treatment method in the following EXAMPLES and COMPARATIVE EXAMPLES was evaluated as follows. The surface of the molded article subjected to the surface treatment was coated with a paint, and 100 cross-cuts each having a side length of 2 mm (10 cross-cuts x 10 cross-cuts) were cut by means of a razor on the coating of the coated molded article. A cellophane tape (trade name of a tape manufactured by Nichiban Co., Ltd.) having a width of 24 mm was contact-bonded onto the coating by means of a finger. Then, the end face of the tape was grasped, and the tape was peeled off at a breath. The number of cross-cuts remaining unpeeled (percentage remaining cross-cuts (%)) was counted to evaluate the coatability. EXAMPLE 1 30 parts by weight of a propylene-ethylene random block copolymer having a melt index of 30 g/10 min and an ethylene content of 3 % by weight (hereinafter referred to as "PP-1"), 30 parts by weight of an ethylene-propylene copolymer rubber having a propylene content of 28 % by weight and a Mooney viscosity (ML₁+₄, 100 °C) of 45 (hereinafter referred to as "EPR-1") and 40 parts by weight of an ethylene-methyl methacrylate copolymer (methyl methacrylate content: 15 % by weight; hereinafter referred to as "EMMA-1") were blended with each other, and preliminarily blended with each other in a tumbler for 20 min. The blend was pelletized by melt-kneading at a temperature of 250 °C through the use of a TEX 44SS-30BW-2V type twin-screw extruder manufactured by The Japan Steel Works, Ltd. The resultant pellet was molded at 220 °C by means of an injection molding machine (model FS-75N) manufactured by Nissei Plastic Industrial Co., Ltd. into a molded article in a sheet form. The resultant molded article was put in front of an ultraviolet irradiation device equipped with a synthetic quartz low pressure mercury lamp. The distance between the lamp and the surface of the molded article was kept at about 10 cm, and the molded article was irradiated with ultraviolet rays (UV) having a dominant active wavelength of 254 nm and 185 nm in an air atmosphere for 60 sec to conduct a surface treatment. The lamp (manufactured by Sen Lights Corp.) had an output of 200 W. The irradiation dose of light having a wavelength of 254 nm from the lamp was 840 mJ/cm². The surface of the molded article subjected to an ultraviolet irradiation treatment was spray-coated with an acrylic urethane paint (RECRACK®#440S manufacture by Fujikura Kasei Corp.), and the coating was baked and dried at 80°C for 30 min. Thereafter, the initial adhesion of the coating of the coated molded article was measured by the above-described coatability evaluation method. The results are given in Table 1. COMPARATIVE EXAMPLE 1 The initial adhesion of the coating of the coated molded article was measured in the same manner as that of EXAMPLE 1, except that no ultraviolet irradiation was conducted. The results are given in Table 1. COMPARATIVE EXAMPLE 2 The initial adhesion of the coating of the coated molded article was measured in the same manner as that of EXAMPLE 1, except that the molding was conducted through the use of a resin composition comprising 70 parts by weight of PP-1 and 30 parts by weight of ERP-1. The results are given in Table 1. EXAMPLE 2 The initial adhesion of the coating of the coated molded article was measured in the same manner as that of EXAMPLE 1, except that the molding was conducted through the use of a resin composition comprising a mixture of 28 parts by weight of PP-1 with 44 parts by weight of EMMA-1 and 28 parts by weight of an ethylene-propylene copolymer rubber having a propylene content of 22 % by weight and a Mooney viscosity (ML₁+₄, 100 °C) of 35 (hereinafter referred to as "EPR-2"), added to the mixture, 10 parts by weight, based on 100 parts by weight of the mixture, of calcium carbonate (ESCALON®#200 manufactured by Hayashi Kasei Corp.; hereinafter referred to as "filler"). The results are given in Table 2. COMPARATIVE EXAMPLE 3 The initial adhesion of the coating of the coated molded article was measured in the same manner as that of EXAMPLE 2, except that no ultraviolet irradiation was conducted. The results are given in Table 2. As is apparent from EXAMPLE 2 with COMPARATIVE EXAMPLE 3, the irradiation of ultraviolet rays having a wavelength of 300 nm or less is useful for improving the coatability of the molded article also when the molded article contains a filler. EXAMPLE 3 The initial adhesion of the coating of the coated molded article was measured in the same manner as that of EXAMPLE 1, except that the molding was conducted through the use of a resin composition comprising a mixture of 45 parts by weight of PP-1 with 25 parts by weight of EPR-2 used in Example 2 and 30 parts by weight of EMMA-1. The results are given in Table 3. COMPARATIVE EXAMPLE 4 The initial adhesion of the coating of the coated molded article was measured in the same manner as that of EXAMPLE 3, except that no ultraviolet irradiation was conducted. The results are given in Table 3. Mixing ratio of components of resin composition (parts by weight) Ultraviolet irradiation Paint used in coating Initial adhesion (%) PP-1 EPR-1 EMMA-1 EX.1 30 30 40 irradiated RECRAC®#440S 95 Comp. Ex.1 30 30 40 not irradiated ditto 0 Comp. Ex.2 70 30 0 irradiated ditto 30 Mixing ratio of components of resin composition (parts by weight) Ultraviolet irradiation Paint used in coating Initial adhesion (%) PP -1 EPR -1 EMMA -1 filler EX.2 28 28 44 10 irradiated RECRAC®#440S 99 Comp. Ex.3 28 28 44 10 not irradiated ditto 0 Mixing ratio of components of resin composition (parts by weight) Ultraviolet irradiation Paint used in coating Initial adhesion (%) PP-1 EPR-2 EMMA-1 EX.3 45 25 30 irradiated RECRAC®#440S 96 Comp. Ex.4 45 25 30 not irradiated ditto 0 As is apparent also from the above-described description, according to the method for treating the surface of a molded article of the present invention, the surface of a molded article of a polypropylene resin comprising polypropylene, an ethylene-propylene copolymer rubber and an ethylene-methylmethacrylate copolymer (and optionally containing a filler) can be modified to a surface suitable for coating, bonding, and printing. Further, the method of the present invention does not advantageously produce a waste solution and therefore is a nonpolluting method as compared with, for example, the chromic acid mixture treatment method. According to the coating method of the present invention, a desired coating can be easily formed on a molded article of a polypropylene resin comprising polypropylene, an ethylene-propylene copolymer rubber and an ethylene-methylmethacrylate copolymer (and optionally containing a filler). Therefore, the present inventions can contribute to an improvement in the value of the molded article and an expansion of the applications of the molded article.

Claims: A method of treating the surface of a molded article of a polypropylene resin, comprising irradiating a molded article of a resin composition with ultraviolet rays having an irradiation wavelength in a region of 300 nm or less, said resin composition comprising (A) 10 to 60 parts by weight of at least one polypropylene selected from (a) a homopolypropylene having a melt index of 10 to 100 g/10 min, (b) a propylene-α-olefin random copolymer having a melt index of 10 to 100 g/10 min and an α-olefin content of from 0.5 to 8% by weight, wherein said α-olefin has from 1 to 6 carbon atoms, and (c) a propylene-ethylene block copolymer having an ethylene content of 2 to 15 % by weight and a melt index of 10 to 100 g/10 min, the propylene-ethylene copolymer portion having an ethylene content of 20 to 60 % by weight and an intrinsic viscosity of 2 to 10 dl/g as measured in a tetralin solution at 135°C, (B) 10 to 40 parts by weight of an ethylene-propylene copolymer rubber having a propylene content of 10 to 70 % by weight and a Mooney viscosity (ML₁+₄, 100 °C) of 10 to 100, (C) 30 to 60 parts by weight of an ethylene-methylmethacrylate copolymer resin having an ethylene content of 50 to 95 % by weight, and 0 to 40 parts by weight, based on 100 parts by weight of the composition comprising (A) propylene, (B) the ethylene-propylene copolymer rubber and (C) the copolymer resin, of a filler comprising one or both of an inorganic filler and a glass fiber. A method of coating a molded article of a polypropylene resin, comprising the steps of irradiating a molded article of a resin composition with ultraviolet rays having an irradiation wavelength in a region of 300 nm or less said resin composition comprising (A) 10 to 60 parts by weight of at least one polypropylene selected from (a) a homopolypropylene having a melt index of 10 to 100 g/10 min, (b) a propylene-α-olefin random copolymer having a melt index of 10 to 100 g/10 min and an α-olefin content of from 0.5 to 8% by weight, wherein said α-olefin has from 1 to 6 carbon atoms, and (c) a propylene-ethylene block copolymer having an ethylene content of 2 to 15 % by weight and a melt index of 10 to 100 g/10 min, the propylene-ethylene copolymer portion having an ethylene content of 20 to 60 % by weight and an intrinsic viscosity of 2 to 10 dl/g as measured in a tetralin solution at 135 °C, (B) 10 to 40 parts by weight of an ethylene-propylene copolymer rubber having a propylene content of 10 to 70 % by weight and a Mooney viscosity (ML₁+₄, 100 °C) of 10 to 100, (C) 30 to 60 parts by weight of an ethylene-methylmethacrylate copolymer resin having an ethylene content of 50 to 95 % by weight, and 0 to 40 parts by weight, based on 100 parts by weight of the composition comprising (A) propylene, (B) the ethylene-propylene copolymer rubber and (C) the copolymer resin, of a filler comprising one of or both of an inorganic filler and a glass fiber; and coating the irradiated molded article with a paint.

Inventors: SHINONAGA HIDEO, SOGABE SATORU, SHINONAGA, HIDEO, SOGABE, SATORU
Applicants: SUMITOMO CHEMICAL CO, SUMITOMO CHEMICAL COMPANY LIMITED
Application year: 1992
Main classification: B05D3
IPC codes: C08L53, B29C35, C08J7, B05D3, B05D7, C08L23, B29C59