JPH0234311B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a composite molded product of an olefin resin composition and an addition polymerizable silicone rubber. [Prior art] Generally, olefin resins, especially polyethylene,
Polypropylene and ethylene-propylene copolymers are inexpensive and have excellent toughness and rigidity, and are widely used as packaging materials and medical materials. However, these olefin resins are non-polar crystalline resins and are hardly soluble in solvents, so they have been considered extremely difficult to adhere to metals and plastics. Therefore, in the past, surface oxidation was performed by physical treatment such as corona discharge treatment or chemical treatment using a dichromic acid-sulfuric acid mixture to generate an oxide film containing polar groups such as carbonyl groups. Attempts have been made to bond treated products together using epoxy-polyamide adhesives, nitrile rubber adhesives, isocyanate adhesives, cyanoacrylate adhesives, etc., but none of them have been able to provide sufficient adhesive strength for practical use. are very few. Further, even if the olefin resin surface-treated in this manner is coated with another resin diluted with a solvent, in most cases it is easily peeled off and it is difficult to integrate the resin into a composite. [Object of the Invention] The object of the present invention is to provide high toughness and low cost.
By combining olefin resin, which has excellent rigidity and is widely used in medical devices and packaging materials, with silicone rubber, which is expensive and has poor strength but has excellent biocompatibility, it is resistant to hot water and autoclave treatment. The object of the present invention is to provide a durable material that does not peel off and is useful primarily for medical or industrial applications. [Structure of the Invention] The present inventors previously disclosed in Japanese Patent Application No. 58-203699, etc., that an addition polymerization type liquid silicone rubber of a specific formulation was coated on a soft vinyl chloride resin of a specific formulation and heated. However, in the course of further research, it was discovered that by adding organohydrogen polysiloxane to olefin resin, it was possible to bond strongly with almost all addition-polymerized silicone rubbers. The present inventors have discovered that it is possible to bond these materials, and have conducted intensive studies to complete the present invention. That is, the present invention provides at least an organohydrogensiloxane unit based on 100 parts by weight of the olefinic resin.
The present invention relates to a composite molded product of an olefin resin composition and an addition polymerizable silicone rubber, containing 0.01 to 10 parts by weight of organohydrogen polysiloxane of 30 mol % or more. The addition polymerization type liquid silicone rubber in the present invention is composed of a vinyl group-containing polysiloxane represented by the general formula (1), an organohydrogen polysiloxane represented by the general formula (2), and a platinum-based catalyst, If necessary, silica or the like is added as a reinforcing material, and it can be hardened into a rubber-like state by heating. In the formula, [R ₁ to _{R 4} : same or different monovalent hydrocarbon groups having 6 or less carbon atoms, m: positive integer] In the formula, [R ₅ , R ₇ to _{R 10} : Same or different monovalent hydrocarbon groups having 6 or less carbon atoms R ₆ : Hydrogen group or same or different monovalent hydrocarbon groups having 3 or less carbon atoms n: An integer of 2 or more and 100 or less l: 0 or a positive integer of 100 or less] In addition, as components generally referred to as self-adhesive silicone rubber, epoxy compounds, carboxylic acid anhydrides, and general formula (3) Even if it contains one or more of the acryloxyalkyl group-containing silanes or siloxanes shown, or the unsaturated hydrocarbon group-containing oxirane compounds, basically the formulas (1) and (2) There is no problem as long as the components shown in the following are included, and the addition of such components for improving adhesion further produces a synergistic effect. [In the formula, R: CH ₃ or H group, n: an integer of 1 or more and 3 or less] The olefin resin composition in the present invention is
The main components are low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene block copolymer, ethylene-propylene random copolymer, ethylene-propylene-diene terpolymer, A simple substance selected from ethylene copolymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, saponified ethylene-vinyl alcohol copolymer, ionomer, polybutadiene, butadiene copolymer, etc. The main component is a polymer or a mixture of two or more,
Those containing a relatively large number of unsaturated double bonds in the molecule are preferred. For example, polyethylene originally has a CH ₂ linear molecular structure as shown in formula (4), but depending on the polymerization conditions, polyethylene has the structure of formulas (5), (6), and ( 7) Unsaturated double bonds as shown in formula 7) are often formed in the molecular chain. Even in the case of high-density polyethylene, it is well known that terminal vinyl groups have been confirmed from infrared spectroscopy, and it is preferable that many such unsaturated double bonds remain. The olefin resin composition of the present invention is obtained by adding an organohydrogen polysiloxane to an olefin resin containing such an unsaturated double bond. The organohydrogen polysiloxane is a polysiloxane containing an organohydrogen siloxane group represented by the general formula (8), and contains at least 30 mol% or more, preferably 40 mol% or more, of organohydrogen siloxane units. Furthermore, organohydrogen polysiloxanes represented by general formula (9) containing unsaturated hydrocarbon groups such as vinyl groups in the molecule can also be used. In the formula [R ₁ : hydrogen group or monovalent hydrocarbon group having 3 or less carbon atoms R ₂ to _{R 5} : monovalent hydrocarbon group having 6 or less carbon atoms m: 0 or a positive integer of 100 or less n: 3 Positive integer greater than or equal to 100] In the formula [R ₁ , R ₂ : one is a vinyl group or an allyl group, the other is a vinyl group or an allyl group, or 1 having 3 or less carbon atoms
valent hydrocarbon group _R3 to _R7 : monovalent hydrocarbon group having 6 or less carbon atoms x: 0 or a positive integer of 100 or less y: a positive integer of 3 or more and 100 or less] These general formulas (8), The amount of the organohydrogenpolysiloxane shown in (9) and (9) added to the olefinic resin varies depending on the content of the organohydrogensiloxane group, but is generally 0.01 to 10 parts by weight per 100 parts by weight of the olefinic resin. Preferably 0.5
The optimal amount is between 5.0 parts by weight, and if it is less than 0.01 parts by weight, the adhesive strength will be insufficient, and if it exceeds 10 parts by weight, it will become too slippery and difficult to process.
Significant whitening may occur. The adhesion mechanism in the present invention is basically deduced from Japanese Patent Application No. 58-203699, which is an earlier patent filed by the present inventors. It is thought that the adhesion mechanism is almost the same as that between soft vinyl chloride resin and silicone rubber. That is, the addition reaction of the hydrosilyl group in the addition polymerizable liquid silicone rubber to the unsaturated hydrocarbon group in the olefinic resin and/or organohydrogen polysiloxane present in the olefinic resin composition, and the olefinic resin. The adhesion is thought to be due to the addition reaction of the hydrosilyl group in the organohydrogen polysiloxane present in the composition to the unsaturated hydrocarbon group in the addition-polymerizable liquid silicone rubber. Since the adhesive uses an addition reaction, its adhesive strength is extremely strong. The additives added to the olefin resin in the olefin resin composition of the present invention are not particularly limited, but BHT as an antioxidant,
Phosphite esters, mercaptan compounds, organic disulfide compounds, or organic tin compounds as light stabilizers tend to inhibit the addition reaction in the present invention, so please refrain from using them. It is preferable to reduce the amount of addition as much as possible. The method for producing a composite molded product of silicone rubber and olefin resin in the present invention is not particularly limited, but may include an addition polymerization type liquid silicone rubber or dissolving the addition polymerization type liquid silicone rubber in a solvent such as toluene or hexane. The solution is coated on the surface of a pre-molded article made of an olefin resin composition by a dipping method, a spraying method, etc., and the temperature is 40 to 130°C, preferably the highest temperature at which thermal deformation does not occur in practical terms. The mixture is heated for 3 minutes to 5 hours, preferably 10 minutes to 2 hours. The composite molded product of the olefin resin composition and silicone rubber according to the present invention can be used in the medical field, for example, for cannulae, blood-related medical devices such as vascular catheters, and urinary-related medical devices such as ureteral catheters. The present invention provides an excellent composite molded product that can be widely applied to various applications such as silicone, and combines the antithrombotic properties and tissue compatibility of silicone with the toughness and stiffness of olefin resin. Further, this composite molded product can be applied not only to the medical field but also to a wide range of fields such as packaging materials such as retort packaging and industrial applications by taking advantage of silicone rubber's non-toxicity and hot water resistance. [Effects of the Invention] The effects of the present invention will be explained below with reference to Examples. Example 1 As organohydrogen polysiloxane No. 1, 25°C
An n-hexane solution was prepared containing 70% by weight of methylhydrogen polysiloxane having a viscosity of about 50 CS and having about 60 mol% of methylhydrogensiloxane units in one molecule. In addition, as organohydrogen polysiloxane No. 2 having a vinyl group in the molecule,
n containing 70% by weight of polysiloxane shown in formula (10)
- Prepared a heptane solution. [In the formula, m = 25-30 n = 70-75] On the other hand, low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd.)
F101), ethylene-propylene copolymer (S-131 manufactured by Sumitomo Chemical Co., Ltd.), and propylene homopolymer (FS-1012 manufactured by Sumitomo Chemical Co., Ltd.) were prepared, and 100% of each of these simple olefin resins was prepared. Organohydrogenpolysiloxane No. 1 and No. 2 based on parts by weight
A mixture to which the amounts shown in Table 1 were added, and a mixture to which it was not added as a comparative example, were kneaded in a blender at 190 to 220°C for about 10 minutes, and then granulated. These molding materials were each press-molded at 190 to 220°C for 5 minutes to obtain sheets each having a thickness of 0.5 m/m. Two sheets each with a size of 20 m/m x 50 m/m were made from these sheets, and the commercially available addition-polymerized liquid silicone rubber shown in Table 1 was coated with a thickness of 1.
m/m, contact surface top and bottom each 20m/m x approx. 25m/m
Place the scissors so that the
The addition polymerization type liquid silicone rubber was cured by heating for a minute. Using the test pieces thus obtained, a 180° peel test was conducted at room temperature to compare the adhesive strength. The results are shown in Table 1, and it is clear that the olefin resin composition of the present invention can be firmly bonded and integrated with a general commercially available addition polymerization type liquid silicone rubber.

[Table] Example 2 Low density polyethylene (F101 manufactured by Sumitomo Chemical Co., Ltd.)
80% by weight n-hexane solution of methylhydrogen polysiloxane represented by formula (11) based on 100 parts by weight
After mixing 1.5 parts by weight in a blender, granulation was performed,
Inner diameter 5m/m, outer diameter 7m/m using 40m/m extruder
A tube was molded. [In the formula, J = 33-40 K = 60-67] On the other hand, a 20% by weight toluene solution of an addition polymerization type liquid silicone rubber (KE-1920 manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared. Next, the tube was cut into a length of 1 m, and about 10 c.c. of the toluene solution of the liquid silicone rubber was collected with a syringe and injected into the tube to coat the inner surface of the tube. Then, after air drying for 30 minutes, in a hot air dryer,
The tube was heated at 100° C. for 2 hours to obtain a two-layer tube (tube A) having an outer surface of low-density polyethylene and an inner surface of addition-polymerized silicone rubber. In exactly the same manner, a two-layer tube (comparative tube) was obtained without adding methylhydrogen polysiloxane. Five of each of these two types of tubes were ultrasonically cleaned in a 50% ethanol aqueous solution. After cleaning, a total of 10 tubes were taken out, cut vertically with a knife, and visually observed. In tube A according to the present invention, all 5 tubes were completely glued and integrated. Partial peeling was observed in 4 out of 5 comparative tubes, and 1 of them
It was found that the silicone rubber layer of the book was peeled off while remaining almost like a tube, indicating that its adhesiveness was insufficient and had large variations.

Claims (1)

[Claims] 1. Organohydrogenpolysiloxane containing at least 30 mol% of organohydrogensiloxane units is contained in an amount of 0.01 to 10% by weight based on 100 parts by weight of olefin resin.
A composite molded article of an olefin resin composition and an addition polymerization type silicone rubber, characterized in that a cured layer of addition polymerization type silicone rubber is provided on the surface of the molded article made of the olefin resin composition containing parts by weight. . 2. A composite molded product of the olefin resin composition and addition polymerizable silicone rubber according to claim 1, wherein the organohydrogen polysiloxane has a vinyl group or an allyl group in the molecule. 3 The olefin resin is polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, ethylene-propylene-diene terpolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, etc. It is characterized by being one or a mixture of two or more selected from polymers, ethylene copolymers such as saponified ethylene-vinyl alcohol copolymers, ionomer resins, polybutadiene, and butadiene copolymers. , a composite molded product of the olefin resin composition according to claim 1 and an addition polymerizable silicone rubber. 4 The olefin resin is polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, ethylene-propylene-diene terpolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, etc. One or more selected from polymers, ethylene copolymers such as saponified ethylene-vinyl alcohol copolymers, ionomer resins, polybutadiene, and butadiene copolymers, and thermoplastic resins other than the above. A composite molded product of the olefin resin composition according to claim 1 and an addition polymerizable silicone rubber, which is a mixture.