JPH0431510B2 - - Google Patents

Description

[Detailed description of the invention]

OBJECT OF THE INVENTION (Field of Industrial Application) The present invention relates to a molding attached to the body, bumper, etc. of an automobile, and more specifically to a resin molding having a tape attached to the back surface thereof. (Prior Art) Moldings made of synthetic resin or synthetic rubber are attached to the bodies and bumpers of automobiles. The base material for the above molding is generally vinyl chloride resin or EPDM (ethylene-propylene-
Polyolefin-based vulcanized rubbers such as diene terpolymer rubber) and EPM (ethylene-propylene copolymer rubber) are used. A molding that is attached to the side of the body and has the function of preventing scratches caused by contact with other objects when opening a door, etc., as well as decoration, is called a side protection molding. It is now attached to the body etc. via tape). In other words, by adopting a method of attaching the molding base material to the body etc. via tape, the installation work is simplified, and since there is no need to drill holes in the body, there are advantages such as no rust occurring. It is from. The base material of the tape is generally a sponge made of polyethylene, acrylic rubber, chloroprene rubber, etc. in the form of a thin plate, nonwoven fabric, film, paper, or the like. In addition, the adhesives applied to the surface of the tape include butylene acrylate, butyl methacrylate,
Acrylic compositions containing an acrylic resin such as 2-ethylhexyl acrylate as a main component, or chloroprene compositions containing polychloroprene as a main component are common. (Problems to be Solved by the Invention) However, when the molding base material made of vinyl chloride resin is attached to a body etc., due to temperature differences between day and night and summer and winter,
The base material repeatedly contracts and expands. The base material shrinks due to the volatilization of low-molecular compounds in the resin. The plasticizers and stabilizers in the resin decompose and become low-molecular due to interaction with heat, light, moisture, etc. The adhesion of the adhesive (or pressure-sensitive adhesive) applied between the molding base material and the tape decreases due to various factors such as shrinkage of the base material due to volatilization in the air. It has been pointed out that the problem of In addition, polyolefin polymers such as EPDM, EPM, and polyethylene do not contain polar groups in the main chain of their molecules, so even if paint, adhesive, pressure-sensitive adhesive, etc. are applied to the surface, the adhesion of the coating film will be Known to be underpowered. Therefore, even if the molding base material and the tape are bonded together using adhesive or pressure-sensitive adhesive, if either the molding base material or the tape is made of polyolefin polymer, the problem is that the adhesion is insufficient. There is a point. As a result of repeated research aimed at solving the above-mentioned problems, the present invention aims to find a composition that has strong adhesion to resin moldings made of vinyl chloride resin, EPDM, etc., or tapes made of polyethylene, etc. As a result, the present invention was achieved. Structure of the Invention (Means for Solving Problems) The present invention comprises a molding base material and a tape attached to the back surface of the molding base material, and between the back surface of the molding base material and the tape, rubber and polyurethane The molding is characterized in that it is coated with an adhesive consisting of a mixture of polyisocyanate and a halogenating agent. (Function) By applying the adhesive having the above composition between the tape and the molding base material made of vinyl chloride resin or polyolefin polymer, the adhesion between the molding base material and the tape is significantly strengthened.
If this is attached to an adherend such as an automobile body or bumper, it will be difficult to peel off even after long-term use. [First Example] As shown in FIG. 1, the molding of this example includes a molding base material 1a made of vinyl chloride resin, a tape 3a made of a polyethylene foam 5 times larger, and the molding material 1a and the tape. The adhesive 2 is formed by coating between the holder 3a and the holder 3a. The molding base material 1a made of the above vinyl chloride resin is made of 170% vinyl chloride resin having the composition shown in Table 1 below.
It was extruded at ℃.

[Table] Adhesive 2 contains 4 to 300 parts by weight of polyurethane and 0.1 parts by weight of polyisocyanate per 100 parts by weight of rubber.
The composition was mixed in a proportion of ~50 parts by weight. In addition to polyolefin rubbers such as EPDM and EPM, the above-mentioned rubbers include polyisoprene (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), chloroprene rubber (CR), butyl rubber (IIR), and nitrile rubber (NBR). ), various synthetic rubbers such as acrylic rubber (ACM), and natural rubber (NR). These rubbers may be used unvulcanized depending on their properties, or they may be kneaded with various additives such as vulcanizing agents, vulcanization accelerators, antioxidants, and ozone deterioration inhibitors. It is also possible to do so. In the case of an adhesive using the above additive-containing rubber, the adhesive is applied to the molding (or tape) and then heated to form a vulcanization bond between the molding and the tape. Specific examples of the above-mentioned rubbers are shown in the table below, all of which are obtained by kneading the raw materials listed in the table with toluene added in an amount of about 10% of the total weight. (Hereinafter, all parts are by weight.)

【table】

[Table] Next, polyurethane is obtained by polymerizing polyester polyol (or polyether polyol) and polyisocyanate such that the isocyanate is in excess in molar ratio, then adding a chain extender and further polymerizing. Adhesive polyester urethane prepolymer (or polyether urethane prepolymer). Polyol components of polyester polyol include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5
Examples include -pentanediol, 1,6-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and trimethylolpropane. In addition, organic acid components include succinic acid, phthalic acid, phthalic anhydride, isophthalic acid, maleic acid,
Examples include dicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid. On the other hand, examples of polyether polyols include polyoxypropylene diol, polytetramethylene glycol ether, and polyoxyethylene diol. Further, as a chain extender, those exemplified as the polyol component of the polyester polyol may be used. Specific examples of the above-mentioned polyurethanes are shown below, and all of these are made by blending polyol and isocyanate in an organic solvent so that the isocyanate is in excess in molar ratio (solid content 35%), and then heating at 80°C in dry nitrogen gas. After carrying out a polymerization reaction for 3 hours, a chain extender was added and the polymerization reaction was further carried out at 80°C for 1 hour. The organic solvent used was 1,
It is a mixed solvent consisting of 1,1-trichloroethane/dimethylformamide=100/60 (weight ratio). Polyurethane-1: Polypropylene glycol (PPG) with a molecular weight of 2000 = 164 parts 4,4'-diphenylmethane diisocyanate (MDI) = 100 parts 1,6-hexanediol (1,6-HD) =
24.8 parts Polyurethane-2: Polyethylene adipate (PEA) with a molecular weight of 2000
= 164 parts Tolylene diisocyanate (TDI) = 69.6 parts 1,4-butanediol (1,4-BD) = 18.9
Part Polyurethane-3: Polybutylene adipate (PBA) with a molecular weight of 2000
= 200 parts. Polyurethane-5: PEA with a molecular weight of 2000 = 200 parts MDI = 100 parts, 1,6-HD = 37.8 parts Polyurethane-6: PBA with a molecular weight of 1000 = 100 parts Hydrogenated MDI = 104.9 parts 1,5-pentanediol (1, 5-PD)=
32.3 parts Polyurethane-7: PBA with a molecular weight of 1000 = 100 parts PPG with a molecular weight of 2000 = 400 parts MDI = 450 parts, 1,6-HD = 180.8 parts Next, as polyisocyanates, 2,4-tolylene diisocyanate, hydrogenated 2,4-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, 1,6-hexamethylene diisocyanate , various diisocyanates such as isophorone diisocyanate, or 4,4′,
Examples include various polyfunctional isocyanates such as 4''-triphenylmethane triisocyanate and tris-(p-isocyanate phenyl)-thiophosphate. 4 to 4 parts of polyurethane per 100 parts by weight of the example rubber.
What is necessary is to mix 300 parts by weight and polyisocyanate in a ratio of 0.1 to 50 parts by weight. If polyurethane is less than 4 parts by weight, it will not be effective.
Further, even if 300 parts by weight or less is added, no improvement in the effect is observed. Furthermore, in the case of polyisocyanate, if it is less than 0.1 part by weight, it will not be effective, and if it is more than 50 parts by weight, problems such as the hardness of the obtained adhesive will be too high and the pot life will be shortened. The organic solvents used are saturated hydrocarbons such as n-hexane and cyclohexane; benzene, toluene,
Aromatic hydrocarbons such as xylene; ethers such as dioxane and tetrahydrofuran; acetate esters such as ethyl acetate and propyl acetate; ketones such as acetone, cyclohexanone, and methylethiketone; or trichloroethane and dimethylformamide, etc. It is one kind of solvent or a mixture of two or more kinds. To manufacture the molding of this embodiment, a molding base material 1a made by extrusion molding of vinyl chloride resin is cut into a predetermined length, and then the above adhesive is applied to the back surface (or the surface of the tape 3a) of the molding material. The base material 1a and the tape 3a may be bonded together, and then the solvent may be evaporated by natural drying (or forced drying). Next, in order to measure the adhesion between the molding base material 1a and the tape 3a, a test was conducted using the following method. Test method: Adhesive 2 was applied to the back side of the polyvinyl chloride resin molding base material 1a and air-dried at room temperature for 30 minutes, then a tape 3a made of 5x polyethylene foam was attached and dried at 100°C for 2 minutes. Ta. Next, this mold was left at room temperature (25°C) for 20 days, and then in a constant temperature bath at 80°C for 5 hours.
Thereafter, the shear strength was measured at a tensile rate of 30 mm/min, and the results shown in Table 4 were obtained. The composition of the adhesive 2 used is as follows. All organic solvents used during mixing were toluene/cyclohexane/ethyl acetate = 1/1/1.
(weight ratio), and was adjusted so that the solid content concentration of Adhesive 2 was 37%. Test-1 Rubber-1 = 100 parts, Urethane-4 = 4 parts, TDI
= 10 parts of adhesive, Test-2 Rubber-1 = 100 parts, Urethane-5 = 50 parts, MDI
= 10 parts of adhesive, Test-3 (Adhesive-3) Rubber-2 = 100 parts, Urethane-2 = 50 parts, MDI
= 50 parts of adhesive, Test-4 (Adhesive-4) Rubber-4 = 100 parts, Urethane-2 = 50 parts, XDI
= 10 parts of adhesive, Test-5 (Adhesive-5) Rubber-2 = 100 parts, Urethane-3 = 300 parts,
Adhesive made by mixing 10 parts of MDI, Test-6 (Adhesive-6) Made by mixing 100 parts of rubber-3, 50 parts of urethane-6, and 10 parts of trimethylolpropane (TMP) + TDI Adhesive, Test-7 (Adhesive-7) Rubber-4 = 100 parts, Urethane-7 = 50 parts, TDI
= adhesive formed by mixing 10 parts, Test-8 (Comparative Example 1) Test-9 using only Rubber-1 (Comparative Example 2) Rubber-3 = 100 parts, Urethane-1 = 50 parts, MDI
= 60 parts of adhesive, Test-10 (Comparative Example 3) Rubber-4 = 100 parts, MDI = 10 parts of Adhesive, Test-11 (Comparative Example 4) Rubber-1 = 100 parts, urethane-4 = 400 parts, hydrogenated
Adhesive prepared by mixing 100 parts of MDI, Test-12 (Comparative Example 5) Chloroprene rubber adhesive (manufactured by Konishi Co., Ltd., "G
-17”) only used.

[Second example]

As shown in Fig. 2, the mall of this embodiment has the following features:
It is composed of a molding base material 1b made of EPDM, a tape 3b made of a five-fold foam of chloroprene rubber, and an adhesive 2 applied between the molding material 1b and the tape 3b. The molding base material 1b made of the above EPDM is shown in Table-5.
It was manufactured by extruding EPDM having the composition shown in the figure below and then vulcanizing it at 200°C for 5 minutes.

[Table] To manufacture the molding of this example, after cutting the molding base material 1b made of extrusion molded EPDM into a predetermined length, adhesive 2 is applied to the back surface (or the surface of the tape 3b). The molding base material 1b and the tape 3b are bonded together, and then the solvent is evaporated by natural drying (or forced drying). The adhesive 2 is a composition in which 100 parts by weight of rubber is mixed with 4 to 300 parts by weight of polyurethane and 0.002 to 20 parts by weight of a halogenating agent, and a preferable halogenating agent contains in the molecule:

A compound containing the formula: (wherein X represents a halogen), an alkyl hypohalide, and a hypochlorite. In the molecule,

Compounds containing [Formula] (wherein X represents halogen) include halogenated succinimides such as N-bromsuccinimide; isocyanuric acid halides such as dichloroisocyanuric acid and trichloroisocyanuric acid; halogenated succinimides such as dichlorodimethylhydantoin; Hydantoin can be exemplified. Examples of the alkyl hypohalides include normal, secondary, and tertiary alkyl hypohalides, particularly stable tertiary alkyl hypochlorides, and tertiary alkyl hypobromides. Examples of hypochlorite include sodium hypochlorite, calcium hypochlorite, and potassium hypochlorite, but when using these hypochlorites, an emulsifier is added to make an emulsion. A adhesive type adhesive may be used. Other halogenating agents include chlorine, bromine or their aqueous solutions, mixtures of hypochlorite and organic acids (Japanese Patent Publication No. 57
-52216), antimony pentafluoride (Japanese Patent Publication No. 50-23483), aqueous solutions of alkali metals or aqueous alkaline earth metals, mixtures of sulfur fluoride and bromine (Japanese Patent Publication No. 1983-23483),
27751), a mixture of iodine and potassium iodide (Tokukosho
53-27751), a mixed aqueous solution of a halogen oxyacid and concentrated hydrochloric acid (Japanese Patent Publication No. 46-22103), a mixed aqueous solution of alkali bromide and peroxodisulfuric acid, and various other halogen compounds. To produce this adhesive, add 4 to 4 to 4 parts of polyurethane to 100 parts by weight of the above-mentioned rubber in an organic solvent.
What is necessary is to mix 300 parts by weight and a halogenating agent at a ratio of 0.002 to 20 parts by weight. If polyurethane is less than 4 parts by weight, it will not be effective.
Further, even if 300 parts by weight or more is added, no improvement in the effect is observed. Furthermore, in the case of a halogenating agent, there is no effect if it is added in an amount of 0.002 parts by weight or less, and no improvement in the effect is observed even if it is added in an amount of 20 parts by weight or more. Next, in order to measure the adhesion between the molding base material 1b and the tape 3b, a test was conducted using the following method. Test method: Adhesive 2 was applied to the back surface of the molding base material 1b and air-dried at room temperature for 30 minutes, then tape 3b was attached and dried at 100° C. for 2 minutes. Next, this mold was left at room temperature (25°C) for 20 days, and then in a constant temperature bath at 80°C for 5 hours.
Thereafter, the shear strength was measured at a tensile rate of 30 mm/min, and the results shown in Table 6 were obtained. The composition of the adhesive 2 used is as follows. All organic solvents used during mixing were toluene/cyclohexane/ethyl acetate = 1/1/1.
The solid content concentration of Adhesive 2, which is a mixed solvent consisting of (weight ratio), was adjusted to 37%. Test-13 (Adhesive-9) Rubber-1 = 100 parts, Urethane-4 = 4 parts, N-
Adhesive made by mixing bromsuccinimide (NBSI) = 0.4 parts, Test-14 (Adhesive-10) Rubber-1 = 100 parts, Urethane-6 = 50 parts, t-
Alkyl hypochloride (t-BHC) = 0.002
Test-15 (Adhesive-11) Rubber-1 = 100 parts, Urethane-7 = 50 parts, tt-
Adhesive made by mixing 20 parts of BHC, Test-16 (Adhesive-12) Rubber-1 = 100 parts, Urethane-1 = 300 parts, t-
Adhesive made by mixing BHC = 0.002 parts, Test-17 (Adhesive-13) Rubber-2 = 100 parts, Urethane-2 = 50 parts, t-
Adhesive made by mixing 0.1 part of BHC, Test-18 (Adhesive-14) Adhesion made by mixing 100 parts of rubber-2, 300 parts of urethane-2, and 0.1 part of trichloroisocyanuric acid (TCIA) Test-19 (Adhesive-15) Rubber-3 = 100 parts, Urethane-2 = 50 parts,
Adhesive made by mixing TCIA = 0.05 part, Test-20 (Adhesive-16) Rubber-3 = 100 parts, Urethane-2 = 300 parts,
Adhesive made by mixing TCIA = 0.05 part, Test-21 (Adhesive-17) Rubber-4 = 100 parts, Urethane-2 = 50 parts,
Adhesive made by mixing TCIA = 0.05 part, Test-22 (Adhesive-18) Rubber-4 = 100 parts, Urethane-2 = 300 parts,
Adhesive made by mixing 0.05 parts of TCIA, Test-23 (Comparative Example 6) Adhesive made by mixing 100 parts of Rubber-1 and 0.4 parts of t-BHC, Test-24 (Comparative Example 7) Rubber -1 = 100 parts, urethane -2 = 3 parts,
Adhesive prepared by mixing NBSI = 0.4 parts, Test-25 (Comparative Example 8) Rubber-1 = 100 parts, Urethane-3 = 20 parts,
Adhesive prepared by mixing NBSI = 25 parts, Test-26 (Comparative Example 9) Rubber-1 = 100 parts, Urethane-5 = 50 parts,
Adhesive prepared by mixing NBSI = 0.0005 parts, Test-27 (Comparative Example 10) Rubber-1 = 100 parts, Urethane-2 = 350 parts, t-
Adhesive made by mixing 0.04 parts of BHC, Test-28 (Comparative Example 11) Only acrylic adhesive (manufactured by Mitsubishi Chemical Industries, Ltd., "Dianal") was used.

[Table] *Material Destruction From the above test results, it was found that by using the adhesive 2 of this example, the adhesion between the molding base material 1b and the tape 3b was significantly improved. In addition, test 24 (comparative example 7) has a small proportion of polyurethane in the adhesive, so test 26 (comparative example 9)
Because the proportion of halogenated agent in the adhesive is small,
In Test 27 (Comparative Example 10), the shear strength was reduced because the proportion of polyurethane in the adhesive was excessive. This molding can be attached to an automobile body or bumper by applying a commercially available acrylic adhesive or chloroprene rubber adhesive to the other side of the tape, as in the first embodiment. In particular, when the tape is made of polyolefin polymer, it may be coated with the adhesive of the present invention. It should be noted that the present invention is not limited to the above embodiments, and for example, prior to applying the adhesive 2, the surface of the molding base material (or tape) made of polyolefin polymer is subjected to corona discharge treatment, plasma treatment, etc. By doing so, the adhesion between the adhesive 2 and the molding base material (or tape) can be further strengthened. As an example, conditions for performing corona discharge treatment are shown below. Corona discharge treatment conditions: Power: 1KW Electrode: Knife-shaped electrode length: 300mm Electrode-base material spacing: 1.0mm Effects of the invention As detailed above, the molding has extremely high adhesion between the molding base material and the tape. This invention has the effect of making it stronger, and by attaching it to the adherend (automobile body or bumper),
It is less likely to peel off even after long-term use.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing the molding of the first embodiment, and FIG. 2 is a sectional view showing the molding of the second embodiment. 1a, 1b...mole, 3a, 3b...tape, 2...adhesive.

Claims (1)

[Claims] 1. Consisting of a molding base material and a tape attached to the back surface of the molding base material, and between the back surface of the molding base material and the tape, rubber, polyurethane, polyisocyanate, or a halogenating agent. A molding characterized in that it is formed by applying an adhesive consisting of a mixture of. 2 The adhesive contains 4 to 300 parts by weight of polyurethane and 0.1 to 0.1 parts by weight of polyisocyanate per 100 parts by weight of rubber.
The molding according to claim 1, wherein the molding is mixed in a proportion of 50 parts by weight. 3. The molding according to claim 1, wherein the adhesive is a mixture of 4 to 300 parts by weight of polyurethane and 0.02 to 20 parts by weight of a halogenating agent to 100 parts by weight of rubber.