JPS6234781B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a weather-resistant polymer sheet with good adhesion. There are many polymers such as polyethylene and polypropylene that have good weather resistance, especially resistance to ozone deterioration, but a common drawback of these polymers is that they cannot be used together or with other materials. It is difficult to adhere. Conventionally, surface treatments such as corona discharge and buffing have been performed to improve the adhesion of various materials made of these polymers, but these methods are complicated and have little effect, so they are not generally recommended methods. It's hard to say. Therefore, weather-resistant polymers are used only in specific areas that do not require adhesive operations or do not require significant adhesive strength, and are used in adhesive applications to enable more widespread use in areas that require weather resistance. It was hoped to improve sexuality. Based on the above background, the present invention aims to provide a sheet made of a polymer composition that has good adhesiveness and good weather resistance. That is, the present invention has a weather-resistant polymer and a 1,2-polybutadiene resin as the second component as essential components, and the ratio of the weather-resistant polymer to the second component is 80:
The present invention relates to a weather-resistant polymer composition with good adhesion, characterized in that the surface of the sheet is treated with a halogen molecule or a pseudohalogen compound in a weight ratio of 20 to 10:90. The weather-resistant polymer that is the first component used in the composition of the present invention includes polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-acrylic acid copolymer,
In addition to single polymers and copolymers that do not substantially contain double bonds in the main chain, such as metal ion crosslinked ethylene-acrylic acid copolymers and polyisobutylene, ethylene-propylene-nonconjugated diene polymers It also includes copolymers having a small amount, usually 3% by weight or less, of unsaturated bonds in the main chain, such as isobutylene-isoprene copolymers. Polymers having more than 3% by weight of unsaturated bonds in the main chain are not used because their weather resistance decreases. Next, 1,2-polybutadiene, which is used as a second component in the composition of the present invention and does not contain an unsaturated bond in its main chain and has an unsaturated group in its side chain, can adhere without impairing the weather resistance of the composition. It is blended with the first component for the purpose of improving properties. As mentioned above, the second component does not contain unsaturated bonds in its main chain, so it has fairly good ozone deterioration resistance, and since it has unsaturated groups in its side chains, it can be surface-treated to improve adhesion. It is possible. Other desirable conditions for the second component are that it has good compatibility with the weather-resistant polymer and excellent mechanical properties. For this reason, as the second component,
1,2-polybutadiene, especially syndiotactic 1,2 which has an internal crystalline region and has high tensile strength.
-Polybutadiene is preferably used. The second component does not contribute to improving adhesion unless it is added in an amount of at least 20% by weight, where the sum of the weather-resistant polymer and the second component is 100. In order to improve adhesion, it is preferable to have a larger amount of the second component, and the effect is particularly noticeable when it is 30% by weight or more. This is because when a certain amount or more of the second component is added, unsaturated groups in the side chains of the second component appear on the surface of the blend in an amount sufficient for adhesion. On the other hand, if the amount of the second component is too large, the hardness of the composition will increase, flexibility will be lost, and deterioration due to ultraviolet light will become noticeable. Added. In order to further improve adhesive performance, the surface of the sheet formed by blending the weather-resistant polymer and the second component must be treated with a treatment agent, that is, a halogen molecule or a pseudohalogen compound (halogenoid). The halogen molecules used in the present invention include chlorine, bromine, iodine, and their 0.1 to
In addition to a 20% concentration aqueous solution or organic solvent solution, it includes a compound that generates halogen molecules in the presence of an acid, such as an aqueous solution of hypochlorous acid or hypobromous acid. Examples of pseudohalogen compounds (halogenoids) include halogenated isocyanates, N-monohaloalkyl urethanes, N,N-dihaloalkyl urethanes, N,N-dihaloallylsulfonamides, sulfur halides, sulfenyl halides, and halomethyl Ether, thiocyanogen, azide iodide, azide bromide, iodine chloride, iodine bromide, trichloroacetate iodide, acetate bromide, iodine nitrate, alkyl hypohalide, alkylthionyl chloride, allylthionyl chloride, nitrosyl chloride , nitrosyl bromide, halogenated isocyanuric acid, halogenated methylhydantoin, and the like. Among the above-mentioned processing agents, pseudohalogen compounds, especially halogenated isocyanates, N,N-dihaloalkyl urethanes, N,N-dihaloallylsulfonamides, alkyl hypohalides, and halogen Preferred are halogenated isocyanuric acid and halogenated methylhydantoin. Specifically, iodized isocyanate, N,N
-dichloroethyl urethane, N,N-dibromoethyl urethane, N,N-dichloropropylurethane, N,N-dibromopropylurethane, N,N
-dichlorobenzyl urethane, N,N-dibromobenzyl urethane, N,N-dichlorotoluenesulfonamide, N,N-dibromotoluenesulfonamide, tertiary butylhypochloride, trichloroisocyanuric acid, dichloroisocyanuric acid, dibromodimethylhydantoin, Compounds such as dichloromethylhydantoin. The above pseudohalogen compounds (halogenoids) must be dissolved in an appropriate solvent during actual processing.
It is used in concentrations of 0.1 to 20% by weight, preferably 1 to 15% by weight. Specific examples of solvents when the above treatment agent in the present invention is used as an organic solvent solution include carbon tetrachloride, chloroform, halogenated hydrocarbons such as dichloromethane, benzene, nitrobenzene, halogenated benzene, toluene, aromatic hydrocarbons such as xylene, etc. Hydrocarbons, chain or cyclic ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF), and dioxane, esters such as ethyl acetate, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane,
Examples include ketones such as acetone, cyclohexanone, and methyl ethyl ketone (MEK); alcohols such as ethanol, ethylene glycol, and tertiary butyl alcohol; among others, tetrahydrofuran (THF), dioxane, acetone, benzene, toluene, and tetrachloride. Carbon, chloroform, methyl ethyl ketone (MEK), ethyl acetate, and ethanol are preferably used. The method of treating the sheet with the treatment agent is as follows:
Any industrial means capable of bringing the treatment agent into contact with the sheet surface can be employed, such as application with a brush or brush, spraying, or dipping. The surface of the sheet of the present invention treated with the above-mentioned treatment agent maintains a smooth surface and is indistinguishable from the sheet before treatment in appearance. The performance of the composition also remains unchanged before and after treatment. Adhesion to this treated sheet does not deteriorate even after one year or more after treatment. Further, in a preferred embodiment, the adhesive performance is better preserved by covering and protecting the treated sheet surface with a film, gummed tape, etc. to prevent staining. It is of course possible to incorporate fillers such as carbon black, silica, calcium carbonate, calcium silicate, and lignin, and softeners such as mineral oil, vegetable oil, and synthetic plasticizers into the composition. Further, if necessary, a vulcanizing agent such as sulfur, peroxide, quinoid, vulcanizing aid, etc. may be added to the composition, and the sheet may be formed by molding and vulcanizing, and then subjected to the above-mentioned surface treatment. Furthermore, the composition of the present invention may include a metal,
It is also possible to use a core material such as organic fiber or glass fiber, or a reinforcing material embedded therein. The sheet made of the weather-resistant polymer and the second component obtained by the surface treatment of the present invention has significantly improved adhesion without impairing the properties of conventional weather-resistant polymers, and can be used as an adherend. In addition to the sheet of the present invention, it can be used to connect with metal, rubber, plastic, wood, glass, etc., and in particular, a waterproof sheet,
Extremely effective for bonding joints of gaskets, belts, etc. In order to bond the sheet of the present invention and the adherend, polyurethane resin, epoxy resin, phenolaldehyde resin, polyhydric phenolaldehyde resin,
This is done by interposing nitrile rubber cement or the like on the adhesion surface and compressing it. The present invention will be explained in more detail below using examples. Example 1 As shown in Table 1 below, various amounts of syndiotactic 1 were added to ethylene-propylene-ethylidene norbornene copolymer (manufactured by Japan Synthetic Rubber Co., Ltd., JSREP33, iodine value 26, hereinafter referred to as EPDM). ,2-
Polybutadiene (Japan Synthetic Rubber, JSR
The physical properties and adhesive performance of a vulcanized rubber blended with RB820 (hereinafter referred to as PB) were evaluated. The basic composition is
For a total of 100 parts by weight of EPDM and PB, HAF Black 50, process oil 5, stearic acid 2, N
-isopropyl-N'-phenyl-p-phenylenediamine 1, paraffin wax 1, rosin 2 as a tackifier, zinc white 5, sulfur 2, N
-oxydiethylene-2-benzothiazolesulfenamide 1 part by weight, and the vulcanization conditions were 160
℃ for 20 minutes. Adhesion was evaluated as follows. Prepare two vulcanized rubber sheets 60 mm wide x 150 mm long x 2 mm thick, and apply an acetone solution containing 5% by weight N,N'-dichloro-p-toluenesulfonamide to the adhesive surface with a brush. I processed it. Add 100 parts of Adiprene L-213 (manufactured by DuPont, -NCO content 9.4%) as an adhesive to the treated surface, and add MOCA (3,3'-dichloro-4,4'-diaminodiphenylmethane, Dupont) as a hardening agent. (manufactured by S.A.) was dissolved in 125 g of acetone and mixed to make an adhesive.
This urethane solution was applied before the vulcanized rubber treatment, and after drying, the two rubber sheets were bonded together using a pressure roller, left at room temperature for 24 hours, and then punched out using an inch cutter to obtain an adhesive test piece A. Separately, a sheet of thermoplastic urethane resin (DN4818, manufactured by Nippon Polyurethane) with a thickness of 1 mm was sandwiched between two vulcanized rubber sheets whose surface had been treated in the same manner, and the sheet was pressed with an iron at 200°C for 40 seconds. , and the melt-adhesive pieces were similarly punched out using an inch cutter B to obtain an adhesive test piece B. Each test piece was subjected to a T-peel test using a tensile tester at a speed of 50 mm/min. The results obtained are shown in the attached drawings. In the drawings, curve 1 shows the results for test piece A, and curve 2 shows the results for test piece B. We also investigated the weather resistance of vulcanized rubber. In the ozone deterioration resistance test, the size of the vulcanized rubber was 20 mm in width and 70 mm in length.
mm, 2 mm thick sheet was stretched by 40% and the temperature was 40
The occurrence of cracks was investigated after deterioration for 168 hours at ℃ and ozone concentration of 90 ppHm. In addition, in the ultraviolet ray deterioration test, vulcanized rubber (thickness 2 mm) was punched out with a JIS No. 3 dumbbell, the test piece was placed under a 400 W mercury lamp at a distance of 15 cm (approximately 19,000 μW), and after being irradiated with ultraviolet rays for 8 hours, the tensile speed was set at 30 mm. The rate of decrease was calculated by comparing it with the first one. The above test results are also listed in Table 1 below.

[Table] Example 2 As shown in Table 2 below, isoprene-isoptylene rubber (IIR-268 manufactured by Nippon Synthetic Rubber, hereinafter referred to as IIR)
The physical properties and adhesive performance of vulcanized rubber blended with various amounts of PB were evaluated. The basic composition is based on the total amount of IIR and PB of 100 parts by weight.
HAF black 50, process oil 5, stearic acid 2, N-isopropyl-N'-phenyl-p
-Phenylenediamine 1, paraffin wax 1, rosin 2, zinc white 5, sulfur 2, N-oxyethylene-2-benzothiazolesulfenamide 1, tetramethylenethiuram monosulfide
0.5 parts by weight each, and the vulcanization time was 20 minutes at 160°C. The physical properties of the vulcanizate were evaluated for tensile properties and ozone deterioration resistance. For adhesion evaluation, as in Example 1, an acetone solution containing 5% by weight N,N'-dichloro-p-toluenesulfonamide was applied to the vulcanized surface, and after surface treatment, 50% by weight of N,N'-dichloro-p-toluenesulfonamide was applied to the vulcanized surface. Adiprene L-
Test piece C was prepared by applying an adhesive of an acetone solution of 213/MOCA (100/25), bonding the two sheets together, and leaving them at room temperature to harden. The test results are shown in Table 2.

[Table] Example 3 As shown in Table 3, low density polyethylene (Yukalon MS30, manufactured by Mitsubishi Yuka, hereinafter referred to as LD-PE) and various amounts of PB were mixed and blended using a high temperature (120°C) roll. The physical properties and adhesive properties of sheets melt-molded in a press at 150°C were evaluated. The adhesion method was carried out in the same manner as in Example 1, and the obtained test piece was designated as D. The test results are also listed in Table 3.

[Table] Example 4 As shown in Table 4, Surlyn 1555 is a metal ion crosslinked product of ethylene and acrylic acid copolymer.
(Na ion type, made by Mitsui Polychemicals, hereinafter referred to as Surlyn) and various amounts of PB were mixed in a high temperature roll and melt-formed in a press at a temperature of 150°C. The physical properties and adhesive properties of the sheet were the same as in Example 1. It was evaluated as follows. The adhesion method was carried out in the same manner as in Example 1, and the obtained sample was designated as Test Piece E. The test results are shown in Table 4.

[Table] Example 5 A vulcanized rubber sheet made of a blend of EPDM and PB was bonded to a metal (iron piece). The vulcanized sheet produced in Experiment No. 1d (EPDH/PB=70/30) of Example 1 was surface-treated with a 5% by weight DCTS acetone solution. On the other hand, after the iron (SS41) surface was subjected to shotplast treatment, it was cleaned with acetone, and then Chemlock 218 (manufactured by Huurin Chemical Co., USA), which is an adhesive between metal and cast urethane, was applied with a brush. Adiprene L-213/MOCA as adhesive
(100/25) was applied with a brush to the treated vulcanized rubber and metal surfaces using a 50% by weight acetone solution.
After the solvent had evaporated, the two pieces were pasted together and fixed with cellophane tape, and left at room temperature for 48 hours to cure and bond. The adhesive piece was pulled at the same speed as in Example 1.
Peeling was performed at 180° at 50 mm/sec and the adhesive strength was evaluated. As a result, cohesive failure of the vulcanized rubber occurred at an adhesive strength of 75 kg/25 mm. As a result, a metal composite protected by a vulcanized sheet with excellent weather resistance was obtained.

[Brief explanation of the drawing]

The attached drawings show test pieces A and B of Example 1.
It is a curve diagram showing the relationship between EPDM/PB blend ratio and peeling force.

Claims (1)

[Claims] 1. A weather-resistant polymer and a second component, 1,2-polybutadiene resin, are essential components, and the weight ratio of the weather-resistant polymer and the second component is in the range of 80:20 to 10:90. 1. A weather-resistant polymer sheet with good adhesion, characterized in that the surface of the sheet molded from a composition comprising the above-mentioned composition is treated with a halogen molecule or a pseudohalogen compound. 2. The weather-resistant polymer sheet with good adhesion according to claim 1, wherein the weather-resistant polymer does not contain unsaturated bonds in its main chain or has 3% by weight or less of unsaturated bonds. 3 The weather-resistant polymer is polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid copolymer, metal ion of ethylene-acrylic acid copolymer A crosslinked product having good adhesive properties and durability according to claim 1 or 2, which is at least one selected from crosslinked products, polyisobutylene, ethylene-propylene-nonconjugated diene copolymers, and isobutylene-isoprene copolymers. Polymer sheet. 4 Weather-resistant polymer and second component in weight ratio of 70:30
A weather-resistant polymer sheet with good adhesion according to claim 1, 2 or 3, which has a ratio of 1 to 30:70. 5 Claims 1 to 4 in which the second component is a syndiotactic 1,2-polybutadiene resin
A weather-resistant polymer sheet with good adhesion as described in any one of the above items.