Chlorosulfonated propylene-based polymer composition and adhesive

Abstract

To provide a chlorosulfonated propylene-based polymer composition which can exhibit good adhesive properties between a resin such as polypropylene, which is a poorly adhesive material, and a metal such as an aluminum member, an aluminum alloy member or a stainless steel member without subjecting both to a specific surface treatment; and also to provide an adhesive.SOLUTION: Provided is a chlorosulfonated propylene-based polymer composition containing 0.1-50 pts.wt. of an alkaline earth metal oxide or hydroxide relative to 100 pts.wt.of a chlorosulfonated propylene-based polymer in which chlorine and a chlorosulfone group are bonded to a propylene-based polymer.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a chlorosulfonated propylene polymer composition in which chlorine and chlorosulfone groups are bonded to a propylene polymer, and an adhesive. [Background technology]

[0002] Traditionally, metals have been joined mainly by welding, riveting, and bolting, but with today's advances in science and technology, the performance and functionality of materials required has become more stringent, and there is a demand for adhesion between dissimilar materials. In order to meet these demands, attention has been focused on and development has been made in adhesive technology.

[0003] Furthermore, due to technological innovations in the automotive sector and elsewhere, it is expected that adhesion technologies for not only resin and metal components alone but also resin-metal composite materials, and especially for dissimilar materials such as polypropylene and metal, will become increasingly important in the future.

[0004] Polypropylene is widely used in a wide range of applications due to its excellent processability, physical properties, recyclability, and price. However, it is a poorly adhesive material, and it is difficult to ensure sufficient adhesive strength even when surface treatments are applied (see, for example, Non-Patent Document 1).

[0005] On the other hand, chlorosulfonated polyethylene has excellent heat resistance, weather resistance, ozone resistance, chemical resistance and bright color, and is therefore used in applications such as various hose cover materials, electric wire covering materials, packings, gaskets, rolls, and escalator handrails, and is also used in applications such as adhesives, coating agents, paints, and primers when dissolved in organic solvents.

[0006] However, chlorosulfonated polyethylene has insufficient adhesion to polypropylene resin, and although there have been studies on chlorosulfonated polyethylene latex for treating glass fibers for use in bonding rubber (see, for example, Patent Document 1), no studies have been conducted on bonding to metals, etc.

[0007] On the other hand, chlorosulfonated polypropylene has also been studied (for example, see Patent Document 2). However, an aqueous emulsion was prepared as a primer for polypropylene resin, and the adhesion of the coating film was evaluated, but adhesion to metals was not studied at all. [Prior art documents] [Non-patent literature]

[0008] [Non-Patent Document 1] Journal of the Adhesion Society of Japan Vol.54 No6(2018) Section 212~ [Patent documents]

[0009] [Patent Document 1] JP 2020-83918 A [Patent Document 2] JP 2008-127436 A Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention has been made in view of the above problems, and an object of the present invention is to provide a chlorosulfonated propylene polymer composition and an adhesive that can exhibit good adhesion to both resins, such as polypropylene, which are difficult-to-adhere materials, and metals, such as aluminum members, aluminum alloy members, and stainless steel members, without the need for any specific surface treatment. [Means for solving the problem]

[0011] The present inventors have conducted extensive research to solve the above problems and have completed the present invention. That is, the present invention relates to the following items [1] to [7].

[0012] [1] A chlorosulfonated propylene-based polymer composition comprising 0.1 to 50 parts by weight of an oxide or hydroxide of an alkaline earth metal per 100 parts by weight of a chlorosulfonated propylene-based polymer in which chlorine and chlorosulfone groups are bonded to a propylene-based polymer.

[0013] [2] The chlorosulfonated propylene polymer composition according to [1], wherein the chlorine content of the chlorosulfonated propylene polymer is 5.0 to 50.0%.

[0014] [3] The chlorosulfonated propylene polymer composition according to [1] or [2], wherein the chlorosulfonated propylene polymer has a sulfur content of 0.1 to 10.0%.

[0015] [4] The chlorosulfonated propylene polymer composition according to any one of [1] to [3], wherein the propylene polymer is a propylene homopolymer or an ethylene-propylene copolymer.

[0016] [5] The chlorosulfonated propylene polymer composition according to any one of [1] to [4], wherein the oxide or hydroxide of an alkaline earth metal is magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide.

[0017] [6] The BET specific surface area of ​​the alkaline earth metal oxide or hydroxide is 50 to 300 m 2 The chlorosulfonated propylene polymer composition according to any one of [1] to [5], wherein the chlorosulfonated propylene polymer composition has a molecular weight of 1000 to 15000.

[0018] [7] An adhesive comprising the composition according to any one of [1] to [6]. Effect of the Invention

[0019] The composition and adhesive of the present invention exhibit good adhesion to various members including resin and metal members. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The present invention will be described in detail below.

[0021] A composition according to one embodiment of the present invention is a chlorosulfonated propylene-based polymer composition containing 0.1 to 50 parts by weight of an oxide or hydroxide of an alkaline earth metal per 100 parts by weight of a chlorosulfonated propylene-based polymer in which chlorine and chlorosulfone groups are bonded to a propylene-based polymer.

[0022] The chlorosulfonated propylene polymer may be any propylene polymer having chlorine and chlorosulfone groups bonded thereto.

[0023] The chlorine content of the chlorosulfonated propylene polymer is preferably 5.0% by weight or more, more preferably 8.0% by weight or more, and even more preferably 10.0% by weight or more, because excellent adhesion, particularly to low-polarity resins such as polypropylene, can be obtained. Also, the chlorine content is preferably 50.0% by weight or less, more preferably 40.0% by weight or less, even more preferably 35.0% by weight or less, and especially preferably 30.0% by weight or less, because excellent adhesion, particularly to low-polarity resins such as polypropylene, can be obtained.

[0024] The sulfur content of the chlorosulfonated propylene polymer is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, even more preferably 0.3% by weight or more, and particularly preferably 0.4% by weight or more, because excellent adhesion, particularly excellent adhesion to metal, can be obtained. In addition, the sulfur content is preferably 10.0% by weight or less, preferably 8.0% by weight or less, and even more preferably 5.0% by weight or less, because the stability of the polymer is excellent.

[0025] The chlorosulfonated propylene polymer may be obtained by any method, and for example, it can be obtained by chlorosulfonating a raw material propylene polymer that constitutes the chlorosulfonated propylene polymer.

[0026] Examples of propylene-based polymers that are raw materials for chlorosulfonated propylene-based polymers include propylene homopolymers, ethylene-propylene copolymers such as random polypropylenes in which ethylene is randomly copolymerized and block polypropylenes in which ethylene is block copolymerized, polypropylene terpolymers in which ethylene and α-olefins are copolymerized, syndiotactic polypropylene, atactic polypropylene, and long-chain branched polypropylene. Examples of α-olefins that are copolymerized into polypropylene terpolymers include 1-butene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene. Prime Polymer Co., Ltd. sells products under the trade name Prime Polypro (registered trademark), Japan Polypropylene Corporation sells products under the trade names Novatec (registered trademark) PP, Wintec (registered trademark), Newcon (registered trademark), Waymax (registered trademark), and Newstrene (registered trademark), and Sumitomo Chemical Co., Ltd. sells products under the trade names Noblen (registered trademark), Excellen (registered trademark), and Sumitic. Such polypropylene may be used alone or in combination of two or more. Since the propylene-based polymer used as a raw material has excellent adhesion to low polarity resins such as polypropylene and metals, it is preferable that the propylene-based polymer is a propylene homopolymer or an ethylene-propylene copolymer, more preferably an ethylene-propylene copolymer, and among the ethylene-propylene copolymers, it is particularly preferable that the block polypropylene is a block copolymerized with ethylene. Note that the block polypropylene is sometimes called impact resistant polypropylene, impact polypropylene, impact copolymer, ICP, etc., but these are also included. The content of the ethylene unit copolymerized in the random polypropylene or block polypropylene is preferably 30 mol% or less, more preferably 25 mol% or less, and even more preferably 20 mol% or less, since the adhesiveness to low polarity resins such as polypropylene and metals is excellent.

[0027] The method for obtaining the chlorosulfonated propylene-based polymer is not particularly limited, and examples thereof include a solution method in which a propylene-based polymer is uniformly dissolved in an inert solvent and reacted, a suspension method in which a propylene-based polymer is suspended in a solvent and reacted, a dissolution method in which a propylene-based polymer is dissolved in a solvent and reacted, etc. Among these, the solution method, which can uniformly chlorinate and chlorosulfonate the propylene-based polymer, is preferred.

[0028] The solvent used in the chlorosulfonation by the solution method is not particularly limited, and examples thereof include carbon tetrachloride, trichloroethane, tetrachloroethane, chloroform, chlorobenzene, and the like from the viewpoints of solubility and reactivity, and trichloroethane is particularly preferred because of its favorable reactivity.

[0029] The chlorosulfonating agent used in chlorosulfonating the propylene polymer is not particularly limited, and sulfurous acid gas, chlorine, sulfuryl chloride, etc. may be used alone or in combination. In addition, a catalyst for promoting the chlorosulfonation reaction may be used as necessary. Examples of the catalyst include azo compounds and organic peroxides. Examples of the azo compounds include α,α'-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc., and examples of the organic peroxides include benzoyl peroxide, acetyl peroxide, t-butyl peroxide, t-butyl perbenzoate, etc. Azo compounds are preferred because they are highly stable in handling, and α,α'-azobisisobutyronitrile is particularly preferred because they allow moderate chlorination and chlorosulfonation reactions to proceed. Furthermore, amino compounds such as pyridine and quinoline, and phosphate compounds may be added as co-catalysts for promoting the chlorosulfonation reaction as necessary.

[0030] The chlorinating agent used for chlorinating the propylene polymer is not particularly limited, and chlorinating agents such as chlorine gas, thionyl chloride, and sulfuryl chloride may be used alone or in combination. In addition, a catalyst for promoting the chlorination reaction may be used as necessary. Examples of the catalyst include azo compounds and organic peroxides. Examples of the azo compounds include α,α'-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, and 2,2'-azobis(2,4-dimethylvaleronitrile), and examples of the organic peroxides include benzoyl peroxide, acetyl peroxide, t-butyl peroxide, and t-butyl perbenzoate. Azo compounds are preferred because they are highly stable in terms of handling, and α,α'-azobisisobutyronitrile is particularly preferred because they allow moderate chlorination and chlorosulfonation reactions to proceed. Furthermore, amino compounds such as pyridine and quinoline, and phosphate compounds may be added as co-catalysts for promoting the chlorination reaction as necessary.

[0031] The reaction temperature during chlorosulfonation or chlorination is not particularly limited and can be appropriately selected according to the melting point of the raw material polymer, and in particular, taking into consideration reactivity and handling, it is preferably 50 to 150° C., and more preferably 60 to 130° C. In addition, the reaction pressure during chlorosulfonation or chlorination is not particularly limited and is, for example, 0 to 1.0 MPa, and is preferably 0 to 0.6 MPa in order to allow the chlorosulfonation and chlorination reactions to proceed appropriately.

[0032] After the chlorosulfonation or chlorination reaction is completed, sulfur dioxide gas or hydrogen chloride remaining in the reaction solution can be removed by introducing nitrogen. There is no problem even if the sulfur dioxide gas or hydrogen chloride is removed under reduced pressure.

[0033] Furthermore, additives such as antioxidants and stabilizers may be added either before or after the chlorosulfonation or chlorination reaction. The type of additive is not particularly limited, and examples thereof include hindered phenol-based antioxidants such as 4-t-butylcatechol, 2,6-di-t-butyl-p-cresol, triethylene glycol bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], and epoxy compounds such as epoxidized polybutadiene and bisphenol A diglycidyl ether, which may be used alone or in combination of two or more. The timing of adding the additive is not particularly limited, but in consideration of the ease of operation and the efficiency of the additive, it is preferable to add the additive after the chlorosulfonation or chlorination reaction and after removing the remaining gas.

[0034] The method for separating the polymer and the solvent from the chlorosulfonated or chlorinated product polymer solution is not particularly limited, but for example, steam distillation, a drum dryer, a vented extruder, etc. can be used.

[0035] The content of the alkaline earth metal oxide or hydroxide contained in the chlorosulfonated propylene polymer composition of the present invention is 0.1 to 50 parts by weight based on 100 parts by weight of the chlorosulfonated propylene polymer composition. Furthermore, in order to obtain excellent metal adhesion and durability, the content of the alkaline earth metal oxide or hydroxide is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and even more preferably 2 parts by weight or more. In order to obtain good fluidity during processing, the content is preferably 45 parts by weight or less, more preferably 40 parts by weight or less, and even more preferably 35 parts by weight or less.

[0036] The alkaline earth metal oxide or hydroxide contained in the chlorosulfonated propylene polymer composition of the present invention is not particularly limited, and examples thereof include beryllium oxide, beryllium hydroxide, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, strontium oxide, strontium hydroxide, barium oxide, and barium hydroxide, which may be used alone or in combination of two or more. Magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide are preferred because they are easy to handle and provide excellent metal adhesion, and magnesium oxide or calcium hydroxide are more preferred, with magnesium oxide being even more preferred.

[0037] The BET specific surface area of ​​the alkaline earth metal oxide or hydroxide is preferably 50 m because it provides excellent metal adhesion and durability. 2 / g or more, more preferably 70m 2 / g or more, more preferably 100m 2 In order to provide good fluidity during processing, the BET specific surface area is preferably 300 m 2 / g or less, and more preferably 250m 2 / g or less, and more preferably 200m 2 / g or less.

[0038] The composition and adhesive according to an embodiment of the present invention may further contain various additives as necessary. Examples of such additives include tackifiers, waxes, crosslinking agents, crosslinking assistants, acid acceptors, plasticizers, viscosity regulators, flexibility agents, inorganic fillers, antioxidants, antiaging agents, UV absorbers, adhesion promoters, and silane coupling agents, and the like, which can be added to the adhesive. The amounts of these additives may be conventional amounts, as long as they do not violate the object of the present invention.

[0039] The composition and adhesive of one embodiment of the present invention can be used as an adhesive that has excellent adhesion to various substrates, and in particular, is excellent in bonding dissimilar materials between metals and resins such as polypropylene. In the case of metals, for example, iron, stainless steel, steel, carbon steel, aluminum, etc., as well as alloys thereof, metal oxides, metal hydroxides, etc., and also substrates having these at least on the surface, the adhesive exhibits excellent adhesion regardless of the presence or absence of surface treatment or surface modification such as primer treatment. EXAMPLES

[0040] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0041] In the examples, the ethylene content of the propylene polymer, and the chlorine content, sulfur content, melting point, heat of crystal fusion, molecular weight, and adhesive strength of the chlorosulfonated propylene polymer were measured as described below.

[0042] [Measurement of chlorine content and sulfur content] The chlorine content in the chlorosulfonated propylene polymer was determined by burning the sample in a combustion flask method, absorbing the resulting hydrochloric acid in pure water, and then quantifying it with an automatic titrator using a 0.05 mol / l silver nitrate aqueous solution. The sulfur content was measured by the oxygen combustion flask method in accordance with JIS K6233 (1998 edition).

[0043] The chlorosulfonated propylene polymer composition was prepared by the following method.

[0044] [Raw materials] The following commercially available products were used as raw materials for the synthesis of the chlorosulfonated propylene-based polymer. Propylene-based polymer: Polypropylene (manufactured by Japan Polypropylene Corporation, product name: Novatec (registered trademark) BC03B, melt mass flow rate (JIS K 7210): 30 g / 10 min.) Sulfuryl chloride (FUJIFILM Wako Pure Chemical Industries, Ltd.) α,α'-Azobisisobutyronitrile (FUJIFILM Wako Pure Chemical Industries, Ltd.) Pyridine (FUJIFILM Wako Pure Chemical Industries, Ltd.) 1,1,2-Trichloroethane (Tokyo Chemical Industry Co., Ltd.) CSM: Chlorosulfonated polyethylene (manufactured by Tosoh Corporation, product name: TOSO-CSM (registered trademark) TS-320) Magnesium oxide (manufactured by Kyowa Chemical Industry Co., Ltd., product name: Kyowamag (registered trademark) 150, BET specific surface area: 144 m 2 / g) [Synthesis of chlorosulfonated propylene polymer] In a nitrogen atmosphere, a propylene-based polymer and 1,1,2-trichloroethane were added in a glass pressure reactor according to Table 1, and dissolved at 130°C. After completion of dissolution, the reaction liquid was cooled to 120°C. Pyridine was added to this polymer solution according to Table 1. Under a condition of 120°C, a 1,1,2-trichloroethane solution of α,α'-azobisisobutyronitrile adjusted to 2g / L was dropped at a rate of 0.1mL / min, while sulfuryl chloride was added at a rate of 0.8mL / min, and the pressure was adjusted to 0.25MPaG. After adding sulfuryl chloride for a predetermined time according to Table 1, the temperature and pressure were lowered, and nitrogen gas was introduced at 100°C and normal pressure at a rate of 150mL / min for 1 hour. A predetermined amount of magnesium oxide was added to the obtained reaction liquid according to Table 1, and the mixture was stirred and mixed. The solvent was distilled off from the obtained reaction liquid using a double drum dryer, and a chlorosulfonated propylene-based polymer was obtained.

[0045] [Preparation of adhesive composition] The chlorosulfonated polymer and magnesium oxide were added to a sealed container according to Tables 2 and 3, and 1,1,2-trichloroethane was added so that the concentration of the chlorosulfonated polymer was 10% by weight, and the mixture was dissolved and mixed. During this process, the mixture was heated to about 80° C. as necessary. The 1,1,2-trichloroethane was distilled off from the resulting mixture using a double drum dryer, to obtain an adhesive composition.

[0046] An adhesive was prepared using the adhesive composition by the method described below.

[0047] [How to make adhesive] The adhesive composition was applied to a 0.5 mm thick mold, preheated at 140°C for 3 minutes, and subjected to 50 kgf / cm 2 , then 100kgf / cm 2 After 5 minutes of heat pressing, 50kgf / cm at 23℃ 2 The mixture was then cooled and pressed for 3 minutes to prepare a 0.5 mm sheet of adhesive.

[0048] The adhesive obtained was evaluated for adhesive strength by the following adhesive strength evaluation method.

[0049] [Method for evaluating tensile shear adhesive strength] Using the adhesive, test pieces for measuring tensile shear adhesive strength were prepared under heat press conditions of 160°C in accordance with JIS K6850, and the tensile shear adhesive strength was measured. The test pieces used were pure aluminum (A1050P) (thickness 3.0 mm, width 25 mm, length 100 mm) and polypropylene (thickness 3.0 mm, width 25 mm, length 100 mm).

[0050] Adhesion to aluminum was rated as excellent when it was 10 MPa or more and poor when it was below that, and adhesion to polypropylene was rated as excellent when it was 5 MPa or more and poor when it was below that.

[0051] As shown in Table 2, Examples 1 to 8 were evaluated as excellent for both metal and polypropylene, and the results showed excellent adhesion to both polypropylene and metal. Comparative Examples 1 to 3 were excellent in adhesion to polypropylene but poor in adhesion to metal. Comparative Example 4 was poor in adhesion to both metal and polypropylene.

[0052] [Table 1]

[0053] [Table 2]

[0054] [Table 3] [Industrial Applicability]

[0055] Since the present invention exhibits good adhesion to both resins such as polypropylene, which are difficult to bond, and metals such as aluminum members, aluminum alloy members, and stainless steel members, without the need for any specific surface treatment, it can be used as a bonding material for these members by bonding methods similar to conventional methods, and can be used in a wide range of applications.

Claims

1. A chlorosulfonated propylene-based polymer composition comprising 100 parts by weight of a chlorosulfonated propylene-based polymer in which chlorine and chlorosulfone groups are bonded to a propylene-based polymer, and 0.1 to 50 parts by weight of an oxide or hydroxide of an alkaline earth metal.

2. 2. The chlorosulfonated propylene polymer composition according to claim 1, wherein the chlorine content of the chlorosulfonated propylene polymer is 5.0 to 50.0% by weight.

3. 2. The chlorosulfonated propylene polymer composition according to claim 1, wherein the sulfur content of the chlorosulfonated propylene polymer is 0.1 to 10.0% by weight.

4. The chlorosulfonated propylene polymer composition according to claim 1, wherein the propylene polymer is a propylene homopolymer or an ethylene-propylene copolymer.

5. 2. The chlorosulfonated propylene polymer composition according to claim 1, wherein the alkaline earth metal oxide or hydroxide is magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide.

6. The BET specific surface area of ​​the alkaline earth metal oxide or hydroxide is 50 to 300 m ２ The chlorosulfonated propylene polymer composition according to claim 1, wherein the chlorosulfonated propylene polymer composition has a molecular weight of 1000 to 15000.

7. An adhesive comprising the composition according to any one of claims 1 to 6.

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