JPH0112673B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a vinyl chloride resin-silicone composite molded product. PVC resin is made flexible by adding plasticizers or polymeric elastomers, has excellent transparency, and has good processability such as adhesiveness and high-frequency processability, so it has been widely used in medical devices, food packaging, etc. Ta. However, in the field of medical devices, vinyl chloride resin products have poor antithrombotic properties and tissue compatibility, which causes various problems when used in direct contact with blood or used in the body for long periods of time. On the other hand, although silicone is expected to be a medical material due to its excellent antithrombotic properties and tissue compatibility, its usage is still small due to its high price and low strength. In order to compensate for the advantages and disadvantages of both, many attempts have been made to incorporate silicone oil into vinyl chloride resin or to combine it with coatings, etc. However, in the case of soft vinyl chloride resins, it has generally been thought that it is difficult to firmly integrate them with silicone due to the influence of additives such as plasticizers. In order to overcome this problem, various methods have been proposed, such as applying a primer treatment to the surface of a soft vinyl chloride resin and then forming a silicone layer, but the process is complicated and many primers use ethyl acetate. Since solvents such as , toluene, etc. are used, there is concern that they may remain, and even if they are once bonded, they may peel off over time. On the other hand, according to JP-A No. 54-156083, etc., there is a method in which the surface of a vinyl chloride resin is treated with low-temperature plasma in advance, and then a cured layer of a condensation type room-temperature curing silicone rubber is formed. 58−
According to Publication No. 32773, after a hardened layer is formed in advance on the surface of a vinyl chloride resin material by plasma treatment or the like, a silicone resin layer made of dimethylpolysiloxane or dimethylpolysiloxane modified with an alkyl group is formed and modified. It is proposed to do so. Although it is clear that silicone resin can be fixed by these methods, it is difficult for plasma treatment to completely treat the inside of a tube with a small diameter or a long tube-like object to form a hardened layer. The present inventors have achieved antithrombotic properties directly onto the surface of soft vinyl chloride resin molded products, which has been considered difficult in the past, without forming a hardened layer such as plasma treatment or pretreatment such as primer treatment. As a result of intensive studies on silicone and vinyl chloride resins with the aim of forming an excellent silicone adhesion layer, we found that in addition to the amount of liquid plasticizer blended into the soft vinyl chloride resin, the amount of metal components in the compounding agent It was discovered that there is a combination of soft vinyl chloride resin and silicone that greatly affects the adhesion of addition-polymerized silicone, and surprisingly provides strong adhesion.After further investigation, the present invention was completed. I've reached it. In the present invention, the addition-polymerizable silicone refers to a vinyl group-containing polysiloxane represented by the general formula (1), an organohydrodiene polysiloxane represented by the general formula (2), and silica as a reinforcing material. A composition that can be solidified into an elastic body by addition polymerizing an inorganic composition using a platinum-based catalyst. [In the formula, R ₁ , R ₂ .R ₃ , R ₄ : monovalent same or different hydrocarbon groups, m is a positive integer] [In the formula, _R5 to _R8 : same or different monovalent hydrocarbon groups having 6 or less carbon atoms, n is a positive integer] More preferably, for improving the physical properties of the elastic body seen after solidification, or for other purposes. It is desirable to add various components to improve the adhesion to the material. Various components include, for example, vinyl group-containing resin-like copolymers that are compatible with the components shown in general formulas (1) and (2) as components that improve physical properties, and include, for example, the following: There are copolymers of general formulas (3) to (5). (CH ₂ = CH) (R ₉ ) (R ₁₀ ) SiO _0.5 ... (3) SiO ₂ ... (4) (R ₁₁ ) ₃ SiO _0.5 ... (5) [In the formula, R ₉ , R ₁₀ , R ₁₁ : Hydrocarbon groups of the same type or different types] In addition, as a component for improving adhesiveness, an epoxy compound, a carboxylic acid anhydride, or a compound of the general formula (6) is used.
These include acryloxyalkyl group-containing silanes or siloxanes, or unsaturated hydrocarbon-containing oxirane compounds. [In the formula, R ₁₂ : alkylene group R ₁₃ : CH ₃ or H group] These addition polymerization silicones can be used to form a hardened layer on the surface of a soft vinyl chloride resin molded product.
From the viewpoint of workability, it is preferable that the material be cured within 10 hours at a temperature of 40 to 120°C. Compositions in which various components are added to addition-polymerizable silicone are as reported in Japanese Patent Publication No. 55-45098 or Japanese Patent Application Laid-Open No. 53-33256, etc.
It is a well-known fact that it strongly adheres to metals, ceramics, etc. However, there have been no reports yet that these addition-polymerizable silicone compositions strongly adhere to soft vinyl chloride resins, and it has even been said that adhesion between silicone and soft vinyl chloride resins is extremely difficult. . In the present invention, the soft vinyl chloride resin includes vinyl chloride homopolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate terpolymer, vinyl chloride The main ingredients are vinyl chloride-based copolymers, such as acrylic copolymers, vinyl chloride-urethane copolymers, and other copolymers, with plasticizers added to give them flexibility. Examples of plasticizers include phthalate esters including dioctyl phthalate, dioctyl adipate,
Fatty acid esters such as aliphatic dibasic acid esters such as dibutyl sebacate, polyester plasticizers,
It uses epoxidized soybean oil, epoxidized linseed oil, etc. Furthermore, the addition of non-liquid polymers, such as urethane and EVA, which impart flexibility to the vinyl chloride resin, also falls within this category. Additives such as ultraviolet inhibitors and antistatic agents can also be used. Furthermore, as stabilizers that impart heat resistance and thermal stability, in addition to metal soaps such as calcium stearate, zinc stearate, magnesium stearate, and lead stearate, organotin stabilizers, organosilicone stabilizers, butyl Ester stabilizers such as stearate can be used, but calcium stearate and zinc stearate are preferred. In the present invention, widely known formulations of the soft vinyl chloride resin can be used, but as the soft vinyl chloride resin that strongly adheres to addition-polymerized silicone, it is preferable to use the liquid plastic resin. When the weight of the agent (Y part) and the weight of the metal component (X part) in other compounding agents are 100 parts by weight of the main component soft vinyl chloride resin,
It satisfies the relationship of the formula: 0<X≦0.08−0.025/100×Y (7) More preferably, it satisfies the relationship of formula (8). 0 < Even if a large amount of plasticizer is blended to provide sufficient amount of plasticizer, if the amount is less than 320 parts by weight, preferably less than 200 parts by weight, the relationship of formula (7), preferably formula (8) is satisfied. We have discovered that by reducing the amount of stabilizer, it is possible to bond with addition-type silicone while maintaining flexibility and thermal stability. However, if the relationship of formula (7) is not satisfied, for example, molding is made from a soft vinyl chloride resin composition in which 100 parts by weight of dioctyl phthalate and 0.1 part of metal soap (converted to metal weight) are added to 100 parts by weight of vinyl chloride resin. Even if an attempt is made to provide a cured layer of additional silicone on the cured sheet, vulcanization of the silicone will be prevented at the interface between the two, and even if it is cured, the adhesion to the soft vinyl chloride resin will be extremely weak. The composite molded article according to the present invention is produced by coating a pre-molded soft vinyl chloride resin composition with addition polymerization type silicone to a desired thickness without performing any pretreatment such as a primer. The cured layer is formed at a temperature of 120°C to 120°C, preferably 70°C to 10°C, for 10 minutes to 10 hours, preferably 30 minutes to 3 hours. This hardened layer adheres extremely firmly to the surface of the molded product, does not deteriorate in adhesive strength over time, and does not deteriorate even when subjected to harsh treatments such as autoclaving, and is used in applications such as medical equipment, food packaging, etc. The range is extremely wide. Furthermore, the effect is even higher with polymer blend-based and copolymer-based soft vinyl chloride resins. The thus obtained molded product of the present invention has excellent antithrombotic properties, is free from residual by-products such as acetic acid, alcohol, and oxime, which are seen in condensed RTV silicone, and is useful for medical purposes, especially when used with blood. It is suitable for direct contact circuits, catheters, drains, and other long-term indwelling applications. Examples of the present invention will be given below and will be explained in more detail. Example 1 Various soft vinyl chloride resin compositions as shown in Table 1 were roll-kneaded at 160°C for 5 minutes, and then
Press molding was performed at 200°C for 4 minutes to create a sheet with a thickness of 0.5 m/m. These sheets are 20m/m x 50
Cut into pieces of m/m and use various types of silicone (20
0.5 g) was laminated onto an area of m/m x 20 m/m and left to heat at 110° C. for 1 hour to cure. Various performances of these test pieces are shown in Table 1. In Table 1, the adhesive strength is 180 by Tensilon universal testing machine.
According to the measurement results of degree peel, the autoclave was heated to 120℃.
This test was conducted for one hour.

[Table] Types of silicone A, B, C, and D are as follows, where A and B are addition polymerization type silicones, and C and D are condensation type silicones. (Silicone A) 12 mol% of trimethylsiloxy units, 48 mol% of dimethylsiloxy units, and methylhydrogensiloxy units per 100 parts of dimethylpolysiloxane with a viscosity of 12000CS at 25°C and a dimethylvinylsilyl group at the end of the molecular chain. It was prepared by adding 12 parts of polysiloxane containing 40 mol%, 30 parts of silica, 2.0 parts of methacryloxypropyltrimethoxysilane, and 0.1 part of an isopropyl alcohol solution of chloroplatinic acid (platinum content: 5%). (Silicone B) The viscosity at 25°C is 1300CS, and the viscosity at 25°C is
The content of methylhydrodiene siloxy groups in methylhydrodiene polysiloxane is 50CS.
5 parts of 50 mol%, 0.2 parts of isopropyl alcohol solution of chloroplatinic acid (platinum content 5%), 25 parts of silica, and 2 parts of the epoxy compound with the following structural formula.
Department, Adjustment was made by adding 0.5 part of phthalic anhydride. (Silicone C) Condensation silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KE-42-RTV) (Silicone D) Condensation-type silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KE-45-RTV) As described above, the soft silicone of the example It can be seen that the vinyl chloride resin-silicone composite molded sheet is strongly bonded and integrated, and there is very little deterioration due to autoclaving or change over time. Example 2 100 parts by weight of vinyl chloride resin (S-101 manufactured by Sumitomo Chemical Co., Ltd.), 65 parts by weight of dioctyl phthalate, 0.05 parts by weight of calcium stearate and zinc stearate in terms of metal weight, and 7 parts by weight of epoxidized soybean oil. A resin composition containing the following was extruded into a film to obtain a film with a thickness of 0.1 m/m. This film was coated with various silicones diluted with n-hexane to a thickness of approximately 60 μm after curing, the solvent was evaporated at room temperature, and the samples were cured by heating at 100°C for 2 hours. . These films were subjected to a blood agglutination test using the Imai-Nose method. Lower film is 30m/m x 30
m/m, and the overlying film was cut to 15 m/m x 15 m/m so that the silicone surface was in contact with the blood. Immediately after blood collection, 0.25 ml of fresh ACD blood from a dog was dripped onto the lower film, 0.025 ml of 3.8% calcium chloride aqueous solution was added, and after stirring well, the upper film was placed and left in an atmosphere of saturated steam at 37°C. The cells were incubated for 5, 10, and 20 minutes, and after each period, uncoagulated blood was washed away with 50 c.c. of distilled water. Then, only the clot was fixed with 37% formalin.
After washing with water and drying, the weight of the blood clot was measured. The results are shown in Table 2.

【table】

[Table] As described above, it is clear that the soft vinyl chloride resin silicone composite film of the present invention is firmly fixed and integrated and has excellent antithrombotic properties.

Claims (1)

[Scope of Claims] 1. A composite molded article comprising a hardened layer of an addition polymerizable silicone composition on the surface of a soft vinyl chloride resin molded article, wherein the soft vinyl chloride resin has a chloride resin as a main component. For 100 parts by weight of vinyl resin,
A soft vinyl chloride-based product containing a liquid plasticizer in an amount of less than 320 parts by weight, and characterized in that the ratio of the blended liquid plasticizer to the metal components in other compounding agents is expressed by the following formula: Resin-silicone composite molded product. O<Y≦0.08−0.025/100×Y (Y: Weight of liquid plasticizer (parts), X: Weight of metal component in compounding agent (parts)) 2 Compounding agent contained in the composition of soft vinyl chloride resin Claim 1, characterized in that the metal component therein is calcium and/or zinc.
A soft vinyl chloride resin-silicone composite molded article as described in . 3. The soft chloride according to claim 1 or 2, wherein the addition polymerization silicone is a self-adhesive addition polymerization silicone that hardens within 10 hours at a temperature of 40 to 120°C. Vinyl resin-silicone composite molded product.