JPH0519460B2 - - Google Patents

Description

[Detailed description of the invention]

OBJECT OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyolefin polymer molded article having an adhesive coating on its surface that strengthens the adhesion of paints, adhesives, etc. (Prior art) Polyolefin polymer, namely ethylene-propylene-diene terpolymer rubber (EPDM)
Polyolefin-based vulcanized rubber such as and ethylene-propylene copolymer rubber (EPM) and polyolefin-based synthetic resins such as polypropylene (PP) and polyethylene (PE) are natural rubber (NR) and styrene-butadiene copolymer rubber (SBR). , synthetic rubber such as polybutadiene rubber (BR), isobutylene-isoprene copolymer rubber (IIR), polychloroprene rubber (CR), acrylonitrile-butadiene copolymer rubber (NBR), polyisoprene rubber (IR), or ABS resin, polystyrene. Resin (PS), acrylonitrile-styrene copolymer resin (AS), ethylene-vinyl acetate copolymer resin (EVA)
Compared to synthetic resins such as
Because it is a polymer with excellent characteristics, it is now used in many fields. (Problems to be Solved by the Invention) However, since polyolefin-based vulcanized rubbers such as EPDM and EPM, and polyolefin-based synthetic resins such as PP and PE do not contain polar groups in the main chain of their molecules, The disadvantage is that even if paint or adhesive is applied to the surface, the resulting coating film is likely to peel off. Therefore, it is currently extremely difficult to coat these polyolefin polymers, or to adhere them to each other or to metals. Although many countermeasures have been attempted in the past to address these drawbacks, no satisfactory solution has yet been found. As a result of repeated research on the adhesive properties of the above-mentioned polyolefin-based polymer, the present inventors discovered an adhesive composition that has sufficient adhesion to the same polymer and various paints and adhesives, and thus arrived at the present invention. It is something. Structure of the Invention (Means for Solving the Problems) That is, the present invention comprises (a) a polyolefin polymer molded product, and (b) an allyl-type hydroxyl group at the molecular end, which is coated on the surface of the molded product. (c) a coating made of a polybutadiene polymer or its derivative;

[Formula] A reactive coating consisting of at least one of a compound containing a bond (wherein X is halogen), an alkyl hypohalide, or a hypochlorite;
The above-mentioned problems have been solved by devising a polyolefin-based polymer molded article with an adhesive coating. (Function) A coating made of a polybutadiene polymer or a derivative thereof containing an allyl-type hydroxyl group at the end of the molecule is provided on the surface of the molded article made of the above-mentioned polyolefin polymer.

[Formula] By forming a reactive coating consisting of at least one type of compound or alkyl hypohalide containing a bond (in the formula, X is halogen), the halogen in the reactive coating causes the allylic type to A polybutadiene polymer or its derivative containing a hydroxyl group is activated, and an adhesive film with excellent adhesion to polyolefin polymers, various paints, and adhesives is formed. (Example) Hereinafter, the structure of the polyolefin polymer molded article with an adhesive coating will be described in detail. First, polybutadiene polymer containing allyl type hydroxyl groups at the molecular ends is polybutadiene containing hydroxyl groups at both ends of the molecule and having an average molecular weight of 2,800, and is a liquid polymer with a hydroxyl value of 42 to 47 mgKOH/g and a viscosity of about 50 poise at room temperature. It is. The above-mentioned polybutadiene polymer is characterized in that it contains a hydroxyl group, particularly an allyl hydroxyl group, at the end of the molecule, and therefore exhibits high reactivity with various substances. Further, the above-mentioned polybutadiene polymer derivatives are those obtained by reacting a hydroxyl group at the end of the molecule with a compound having various functional groups according to a conventional method, and specifically, Terminal carboxyl groups such as A derivative formed by a condensation reaction between the hydroxyl group of and the molecular terminal hydroxyl group of the polybutadiene polymer, or a structural formula, Examples include intramolecular epoxy compounds of polybutadiene polymers represented by: In order to form a film made of the above-exemplified polybutadiene polymer or its derivative on the surface of the polyolefin polymer molded article, it is sufficient to dilute and lower the viscosity of these polymers with a solvent and then apply the coating. In addition, the solvents used at this time are saturated hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; chlorinated hydrocarbons such as ethyl chloride, chloroform, and carbon tetrachloride; acetic acid. Ester: A solvent appropriately selected from ketones, etc., or a mixed solvent of two or more. When diluting with these solvents, it is preferable that the solid content concentration is 30% or less, regardless of whether the above polybutadiene polymer or its derivatives are used; if it exceeds 30%, the solid content will precipitate at room temperature. There is a possibility that Note that the above-mentioned polybutadiene polymer and its derivatives are all one-component type, so they have a very long pot life, and if the viscosity increases due to evaporation of the solvent, the viscosity can be adjusted by adding the solvent again. Further, the coating method does not require any special equipment and can be easily applied using normal coating methods such as dipping, spraying, and brushing. Next, the alkyl hypohalides constituting the reactive coating include normal, secondary or tertiary alkyl hypohalides, particularly stable tertiary alkyl chlorides and bromides. Specifically, tertiary butyl hypochloride,
Tertiary butyl hypobromide, tertiary amyl hypochloride, tertiary amyl hypobromide and the like are particularly preferred, and halogen-substituted alkyl hypochlorides such as dichloro, trichloro or fluoromethyl hypochloride may also be used. . Also, in the molecule

[Formula] Compounds with a bond (wherein X is halogen) include halogenated succinimides such as N-bromsuccinimide, isocyanuric acid halides such as trichloroisocyanuric acid and dichloroisocyanuric acid, and furthermore, such as dichlorodimethylhydantoin. Examples include halogenated hydantoins. Furthermore, examples of the hypochlorite include sodium hypochlorite, potassium hypochlorite, and calcium hypochlorite. In order to form an adhesive film on the surface of a polyolefin polymer molded article, the polyolefin polymer molded article coated with either the polybutadiene polymer solution or its derivative solution is coated with the above alkyl hypohalide in the molecule.

[Formula] Dip in a solution containing at least one type of compound having a bond (wherein X is halogen) or hypochlorite at room temperature for 30 seconds to several minutes, or spray or brush the same solution. This treatment activates the polybutadiene polymer or its derivatives with halogen, forming an adhesive film with excellent adhesion to polyolefin polymers, various paints, and adhesives. The concentration of the alkyl hypohalide in the solution is preferably 1 to 100 parts by weight, more preferably 25 to 100 parts by weight, based on 100 parts by weight of the solvent.
Less than 1 part by weight has almost no effect. Also, in the molecule

[Formula] The concentration of the compound with a bond (in the formula, X is halogen) is 0.5 to 5 parts by weight per 100 parts by weight of the solvent.
Parts by weight. There is no effect if it is less than 0.5 part by weight.
If the amount exceeds 5 parts by weight, there is a risk that unreacted substances will precipitate on the treated surface. Next, examples of solvents for alkyl hypohalides include various solvents used to dilute and lower the viscosity of the polybutadiene polymer or its derivatives, and

[Formula] In the case of a compound having a bond (wherein X is a halogen), water may be used in addition to the various solvents exemplified above, and in the case of hypochlorite, water is used. To form the above-mentioned reactive film, in addition to the above-mentioned halogen compound solution, an aqueous solution of chlorine, bromine or iodine; a mixture of hypohalite and an organic acid (Japanese Patent Publication No. 57-52216); Antimony (Japanese Patent Publication No. 50-23483); Aqueous solutions of alkali metals or alkaline earth metals, mixed aqueous solutions of fluoride ions and bromine (Japanese Patent Publication No. 53-27751); Mixtures of iodine and potassium iodide (Japanese Patent Publication No. 53-27751) ); Mixed aqueous solution of halogen oxychloride and concentrated hydrochloric acid (Special Publication Publication 1973-
22103); An aqueous mixed solution of alkali bromide and peroxodisulfuric acid may also be used. Next, in the polyolefin vulcanized rubber,
In addition to EPDM and EPM, we also use NR, SBR, IIR, CR, and NBR in amounts that do not lose these properties.
Rubber components such as ABS, PS, PE, PP,
It also includes those containing resin components such as EVA.
Further, the content of these rubber components or resin components is usually 1/2 or less of that of EPDM, EPM, etc. These polyolefin-based vulcanized rubbers contain commonly used formulations: sulfur, morpholine disulfide, dicumyl peroxide as vulcanizing agents, 2-mercaptobenzothiazole, zinc dimethyldithiocarbamate, and vulcanization accelerators. Tetramethylthiuram disulfide, phenyl-α-naphthylamine, 2,6-di-t- as an anti-aging agent, antioxidant, and ozone deterioration inhibitor.
Butyl-p-cresol, carbon black, magnesium carbonate, clay as a filler, dioctyl sebacate, mineral oil, etc. as a plasticizer are added. Hereinafter, the structure of the polyolefin-based polymer molded article with an adhesive coating will be explained in detail using Examples. Note that polybutadiene polymers and derivatives thereof having the compositions of Examples 1 to 8 below were used. Example 1 "R-45HT": A terminal hydroxyl group-containing polybutadiene polymer with a hydroxyl group content of 0.83 (mep/g), a hydroxyl value of 46.6 (mgKOH/g), and an average molecular weight of 2800. Example 2 "R-45M": Polybutadiene polymer containing terminal hydroxyl groups with a hydroxyl group content of 0.75 (mep/g), a hydroxyl value of 42.1 (mgKOH/g), and an average molecular weight of 2800. Example 3 "Poly bd CBC": "R-" in Example 1 above
A compound type polybutadiene polymer made by mixing ``45HT'' with carbon black. Example 4 "Poly bd HTP-4" At the end of the molecule, A polybutadiene polymer derivative having Example 5 "Poly bd R-45EPT" At the end of the molecule,

A polybutadiene polymer derivative having the formula: Example 6 "Poly bd R-45EPI" Structural formula, An intramolecular epoxy compound of polybutadiene polymer represented by Example 7 “Poly bd R-45ACR” At the end of the molecule, A polybutadiene polymer derivative having Example 8 "Poly bd R-45MA" Maleic acid ester derivative of the above Example 1 "R-45HT". (The following are all product names of Idemitsu Petrochemical Co., Ltd.) First, a rubber compound having the composition shown in Table 1 was prepared at 160%
℃ for 30 minutes to produce a 2 mm thick base material made of EPDM.

[Table] Next, the above EPDM base material was used as a test piece, which was immersed in a 5% toluene solution of the polybutadiene polymer or its derivative having the composition of Examples 1 to 8 above for 1 minute, air-dried for 30 minutes, and then subjected to the following procedure. The samples were immersed in the halogen-containing compound solutions of Examples 9 to 22 for 30 seconds and then air-dried at room temperature for 30 minutes to form an adhesive film on the surface. Example 9 Toluene/trichloroisocyanuric acid = 99/1
A solution consisting of (weight ratio) was prepared. Example 10 N-bromsuccinimide was used in place of trichloroisocyanuric acid in the solution of Example 9 (others are the same as Example 9). Example 11 The amount of trichloroisocyanuric acid in the solution of Example 9 was (Others are the same as Example 9.) Example 12 The amount of trichloroisocyanuric acid in Example 9 was reduced to 2.
(Others are the same as in Example 9). Example 13 The amount of trichloroisocyanuric acid in Example 9 was reduced to 5
(Others are the same as in Example 9). Example 14 The amount of trichloroisocyanuric acid in Example 9 was
100 times (others are the same as in Example 9). Example 15 Xylene/tertiary butyl hypochloride =
A solution consisting of 75/25 (weight ratio) was prepared. Example 16 Xylene/tertiary butyl hypochloride =
A solution consisting of 100/75 (weight ratio) was prepared. Example 17 Xylene/tertiary butyl hypochloride =
A solution consisting of 100/50 (weight ratio) was prepared. Example 18 Toluene/trichloroisocyanuric acid/tertiary butyl hypochloride = 99/1/20 (weight ratio)
A solution consisting of was prepared. Example 19 Toluene/trichloroisocyanuric acid/tertiary butyl hypochloride = 99/1/30 (weight ratio)
A solution consisting of was prepared. Example 20 Sodium hypochlorite with an available chlorine concentration of approximately 0.4%
An aqueous solution was prepared by adding 2 c.c. of glacial acetic acid to 100 c.c. Example 21 Sodium hypochlorite with an available chlorine concentration of approximately 0.5%
An aqueous solution was prepared by adding 2.5 cc of glacial acetic acid to 100 cc. Example 22 Sodium hypochlorite with an available chlorine concentration of approximately 0.5%
An aqueous solution was prepared by adding 5 c.c. of glacial acetic acid to 100 c.c.
Next, Table 2 shows the combinations of the 5% toluene solution of the polybutadiene polymer or its derivative used and the halogen compound-containing solution.

[Table] Next, a urethane paint obtained by reacting a urethane compound having the composition shown in Table 3 in dry nitrogen gas at 80°C for 3 hours was applied to each test piece on which the adhesive film had been formed. and cured at room temperature for 24 hours.

[Table] Next, the adhesion of the urethane coating formed on the surface of each of the above test pieces was investigated by a goblin test. As a result, all base materials had sufficient adhesion (100/100).
showed that. The compositions of Comparative Examples 1 to 3 below are conventionally used as primer coating agents for polyolefin polymers. Comparative Example 1 A composition was prepared by diluting "Betsukosol J-534" (manufactured by Dainippon Ink & Chemicals, an anima oil-modified long oil alkyd resin) with a mineral base and further adding cobalt naphthenate as a desiccant. Comparative Example 2 A composition was prepared by diluting "Orestar M55-80A" (manufactured by Mitsui Toatsu, a moisture-curing polyurethane resin) with toluene. Comparative Example 3 A composition was prepared by diluting "Ester Resin-20" (manufactured by Toyobo Co., Ltd., saturated polyester resin) with a mixed solvent of methyl ethyl ketone/toluene = 1/9 (weight ratio). Next, the compositions of Comparative Examples 1 to 3 were added to the compositions of Comparative Examples 1 to 3 above.
It was applied to an EPDM base material, and then a urethane paint with the composition shown in Table 3 above was applied, and after curing for 24 hours, the adhesion of the paint film was examined by a goblin test, but no adhesion was found in either case. (0/100). Next, usage examples in which the structure of the present invention is applied to various molded articles for automobiles will be explained. Usage Example 1 Glass Run The polyolefin vulcanized rubber for glass runs used in the sliding parts of the window glass of door frames has the composition shown in Table 1, as an example. After extrusion molding of EPDM compound with this composition, 160℃
The mixture was vulcanized for 30 minutes to produce a glass run for automobiles. Next, this molded product was immersed in the polybutadiene solution of Example 1 for 1 minute, air-dried for 30 minutes at room temperature, and then immersed in the halogen compound-containing solution of Example 9.
Dipping for 30 seconds and air drying at room temperature for 30 minutes formed an adhesive film. Next, a urethane paint having the composition shown in Table 4 was applied and cured at room temperature for an additional 24 hours.

[Table] The urethane prepolymers in Table 4 are made by reacting the formulations having the compositions shown in Tables 5 and 6 in dry nitrogen gas at 80°C for 30 minutes, and each of the urethanes obtained. It was prepared by mixing at a ratio of 100/40 (weight ratio).

【table】

[Table] Usage example 2 Door weather strip The weather strip that seals the gap between the car body and the door is an example of a weather strip with the composition shown in Table 7.
It was manufactured by extruding an EPDM compound and then vulcanizing it at 200°C for 5 minutes.

[Table] Next, this weather strip was immersed in the polybutadiene solution of Example 2 for 1 minute, air-dried for 30 minutes at room temperature, and then soaked in the halogen compound-containing solution of Example 10 for 30 seconds, and then dried at room temperature for 30 minutes. Air dried for a minute to form an adhesive film. Next, the formulation in Table 8 was heated to 80°C in dry nitrogen gas.
℃ for 3 hours, and then 24.8 parts of 1,6-hexanediol and 170 parts of dimethylformamide were added and reacted for 20 minutes at 80℃ in dry nitrogen gas.The resulting urethane paint was applied on top of the mixture for 24 hours. hardened. Then dimethyl silicone oil (100,000 cSt)
A 5% solution of toluene was applied onto the urethane coating.

[Table] Usage Example 3 Electrostatic flocking products Some of the glass run products in Usage Example 1 have electrostatic flocking done using short fibers on the glass sliding parts. This glass run was immersed in the polybutadiene solution of Example 3 for 1 minute and air-dried at room temperature for 30 minutes, then immersed in the polybutadiene solution of Example 11 and air-dried at room temperature for 30 minutes. Furthermore, the formulations in Table 9 were added to
After applying the urethane adhesive obtained by reacting at 100°C for 3 hours, a pile of nylon 66 short fibers was electrostatically flocked, and the same urethane adhesive was cured with hot air at 100°C for 3 minutes to form electrostatic flocking. Got the product.

[Table] Next, the abrasion resistance of the coating films applied to the surfaces of the adhesive coated molded products of Use Examples 1 and 3 was tested using the following method. Test machine: KI type abrasion tester Test conditions: Friction element glass (thickness 5 mm) Load: 3 kg Friction element cycle: 60 times/min Friction element stroke: 145 mm The molded product was attached to the above testing machine and tested under the conditions described above. rubbed the surface. As a result, good results were obtained in which no peeling of the coating film was observed even after repeated friction 50,000 times. In addition, the abrasion resistance of the coating film applied to the surface of the adhesive coated molded product of Use Example 3 was tested using the following method. Testing machine: Reciprocating abrasion tester Test conditions: Friction element: Glass (thickness: 5 mm) Friction element cycle: 60 times/min Friction element stroke: 145 mm The molded product was attached to the above testing machine, and its surface was tested under the conditions described above. was rubbed. As a result, good results were obtained in that no peeling of the coating film was observed even after repeated friction 20,000 times. In addition, a 180 degree bending test was conducted to check the followability of each of the molded products of Usage Examples 1 to 3, and all of them showed extremely good followability, and the flexibility and flexibility, which are characteristics of polyolefin-based vulcanized rubber, were was not damaged in any way. Usage Example 4 Resin Molding Moldings attached to the side surfaces of automobile bodies are attached to the body via double-sided adhesive tapes made of polyethylene foam or the like. Therefore, a molding was manufactured by extrusion molding a vinyl chloride resin having the formulation shown in Table 10 at 170°C, and the following tests were conducted using this molding.

[Table] (a) As shown in Figure 1, the polybutadiene solution of Example 1 was spray-coated on one side of the tape 3 made of 5x polyethylene foam, and after air-drying at room temperature for 30 minutes, the same tape 3 was applied. The adhesive coating 4 was formed by dipping in the halogen compound-containing solution of Example 9 for 30 seconds and air drying at room temperature for 30 minutes. Next, G-17 was applied as adhesive 5a on the same film 4.
(manufactured by Konishi, CR adhesive) and the other side is coated with a commercially available acrylic adhesive 6 for double-sided tape to prepare a double-sided adhesive tape 7a. A resin molding 2 was attached to an acrylic-painted iron plate 1. (b) The solution of Example 10 was used as the halogen compound-containing solution in (a) above. (Others are the same as in (a).) (c) The solution of Example 15 was used as the halogen compound-containing solution in (a) above. (Others are the same as in (a).) (d) In (a) above. The solution of Example 20 was used as the halogen compound-containing solution (Others are the same as in (a).) (e) Next, as shown in Figure 2, one side of the tape 3 made of 5x polyethylene foam was Example 2
After spraying a polybutadiene solution of Example 9 and air drying at room temperature for 30 minutes, the same tape 3 was dipped in the halogen compound-containing solution of Example 9 for 30 seconds and then air-dried at room temperature for 30 minutes to form adhesive coating 4.
was formed. Next, Dial 882 (manufactured by Mitsubishi Rayon, acrylic adhesive) was applied as the adhesive 5b on the film 4, and a commercially available acrylic adhesive 6 for double-sided tape was applied to the other surface, and the double-sided adhesive tape 7b was applied. Adjust this double-sided adhesive tape 7b
A molding 2 made of vinyl chloride resin was attached to an acrylic-painted iron plate 1 through the . (f) The solution of Example 10 was used as the halogen compound-containing solution in (e) above (others are the same as in (e)). (g) The solution of Example 15 was used as the halogen compound-containing solution in (e) above. (Others are the same as (e).) (h) The solution of Example 20 was used as the halogen compound-containing solution in (e) above (Others are the same as (e).) (i) Comparison As Example 1, as shown in FIG. 3, only the above-mentioned G-17 was applied as the adhesive 5a to one side of a tape 3 made of a 5x polyethylene foam (others were the same as in (a)). (j) As Comparative Example 2, as shown in FIG. 4, only the above-mentioned Dial 882 was applied as the adhesive 5b to one side of a tape 3 made of 5x polyethylene foam (others were the same as in (e)). Next, a tensile shear test was conducted on each of the moldings 2 of (a) to (j) above at a tensile speed of 30 mm/min, and the results shown in Table 11 were obtained.

[Table] From the above test results, it was found that the adhesion of the paint and adhesive applied to the surface of the automotive polyolefin polymer moldings with adhesive coatings in each of the above usage examples was extremely strong. Effects of the Invention As detailed above, by forming an adhesive film on the surface of a molded product made of polyolefin vulcanized rubber or polyolefin synthetic resin, the adhesion of paints and adhesives applied thereon can be improved. It will be extremely strong. Therefore, this adhesive coated polyolefin polymer molded product is an excellent invention that can be used not only for various molded products for automobiles but also for a wide range of applications.

[Brief explanation of the drawing]

1 and 2 are cross-sectional views showing an attachment structure for a molding with an adhesive coating according to the present invention, and FIGS. 3 and 4 are cross-sectional views showing an example of a conventional molding attachment structure, respectively. 2...Mall, 4...Adhesive film.

Claims (1)

[Scope of Claims] 1 (a) a polyolefin polymer molded article; (b) a coating formed by coating on the surface of the molded article and made of a polybutadiene polymer or a derivative thereof containing an allyl-type hydroxyl group at the molecular end; (c) A reactive coating formed by coating on the surface of the same coating and consisting of at least one of a compound containing a [formula] bond (wherein X is a halogen) in the molecule, an alkyl hypohalide, or a hypohalite. , a polyolefin polymer molded article with an adhesive coating.