JPS60137644A - Composite molded material of soft vinyl chloride group resincomposition and addition polymerization type silicone rubber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a composite molded product of a vinyl chloride resin composition and an addition polymerizable silicone rubber.0 [Prior Art] Vinyl chloride resin linear plasticizer Alternatively, it has been widely used in medical devices, food packaging, etc. because it is given flexibility by adding polymeric nidistomer, etc., has excellent transparency, and has good processability such as adhesiveness and high frequency processability. However, in the field of medical devices, vinyl chloride resin products have antithrombotic properties,
Due to its poor tissue compatibility, various problems arise when it is used in direct contact with blood or in applications where it is used in the body for a long period of time.

On the other hand, although silicone is expected to be used as a medical material due to its excellent antithrombotic properties and tissue compatibility, its usage is still limited due to its high price and low mechanical strength.

In order to compensate for the advantages and disadvantages of both, many attempts have been made to combine them into bases, such as J) and J:'-rings, in which silicone oil is mixed with vinyl chloride resin. 0
However, in soft vinyl chloride resins, additives such as plasticizers are generally used. It was thought that it would be difficult to bond and integrate with silicone due to the influence of the material. 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 acetic acid. Since solvents such as ethyl and toluene 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-54-156083, etc., a method is disclosed in which the surface of a vinyl chloride resin is treated with low-temperature plasma in advance, and then a condensation-type cured layer of silicone rubber is formed at room temperature. According to Publication No. 58-32773, a hardened layer is formed in advance on the surface of a vinyl chloride resin material by plasma treatment or the like, and then a silicone made of dimethylpolysiloxane or dimethylpolysiloxane modified with an alkyl group is fixed. It has been proposed to form a layer and modify it.

[Purpose of the invention]

Although it is clear that the silicone fixing layer can be fixed by these methods, it is difficult to completely treat the inside of a tube having a small diameter or a long tube-like object by plasma treatment to form a hardened layer. □ The present inventors have previously achieved a method of directly resisting the surface of a soft vinyl chloride resin molded product, which has been considered difficult in the past, without forming a hardened layer such as plasma treatment or performing any pretreatment such as primer treatment. With the aim of forming a silicone adhesive layer with anti-thrombotic properties, we have carefully studied silicone and vinyl chloride resin.
(I discovered that there is a combination of vinyl resin and silicone, and patent application No. 58-203699 and No. 58-2
Completed the invention shown in 03700 fc. After that, further studies were carried out to find a method that would be advantageous in terms of manufacturing and to make money. ,...: [Structure of the invention] In the course of further improvement and study, the present inventors added organohydrogenpolycaroxane to a soft vinyl chloride resin. We discovered that it is possible to bond with silicone rubber with a fully perforated additional type.
After extensive research, we have completed the present invention.

That is, in the present invention, the organohydrogensiloxane unit is at least 3.0 mol per 100 parts by weight of vinyl chloride, vinyl-based resin.
'J or higher organohydrogenpolysiloxane o, o,
A soft vinyl chloride resin composition, which is characterized by providing a hard layer of addition polymerized silicone rubber on the surface of a molded article made of a soft vinyl chloride resin composition containing 10 parts by weight. The object of the present invention is to provide a composite 4-molded product of resin/resin composition eyelids and attachment: weighted mold silicone rubber. .

The soft salt and vinyl resin composition in the first invention are:
Vinyl chloride homopolymer, blue ethylene chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-
The main components are copolymers mainly composed of vinyl chloride and vinyl, such as ethylene-vinyl acetate terpolymer, vinyl chloride-acrylic acid copolymer, vinyl chloride-urethane copolymer, and organohydrogen. Contains polysiloxane, plasticizers, stabilizers, etc.

Organo hydrogen, su, white, xane, general formula (1
) is an organohydrogensiloxy group-containing polysiloxane having 1. At least 30 mo1% or more of organohydrogensiloxane units, preferably 40 mo
It contains 1% or more. Even more preferred is an organohydrogenpolysiloxane containing at least one vinyl group in its molecule, represented by general formula (2) and having excellent compatibility with vinyl resins.

It is shown in these general formulas (1) and (2). The amount of organohydrogenpolysiloxane to be added to the vinyl chloride resin strength varies depending on the PK contained in the organohydrogen siloxane group, but is generally 0.00 to 10 violet parts of the vinyl chloride resin.
0.01 to 10 parts by weight Preferably, the optimum range is 0.5 to 5.0 parts by weight. Otherwise, the lubricity will be too strong, making processing difficult and resulting in a significant loss of transparency. Particularly for applications requiring transparency, 0.01 to 10 parts by weight of vinyl group-containing organohydrogen polysiloxane represented by general formula (2) is preferably used.
．． It is suitable to add a portion of Ojutsuki.

There are no particular restrictions on the plasticizers added to the vinyl chloride-based w/fat, but phthalate esters such as dioctyl phthalate, which have little negative effect on adhesion with addition-polymerized silicone, and epoxidized soybean oil ,
Preferably, epoxidized linseed oil or the like is used.

In addition, as stabilizers that impart heat resistance and thermal stability, in addition to metal soaps such as calcium stearate, zinc stearate, barium stearate, magnesium stearate, and aluminum stearate, among the above stabilizers, Metal organometallic stabilizers are particularly preferred, and one or more of the metals listed above are used in the stabilizer. However, organotin stabilizers, ester stabilizers such as pudelstearate, phosphoric acid, and type 5 stabilizers inhibit the curing of addition-polymerized silicone rubbers. Since it also inhibits the effect of the addition of organohydrogen polysiloxane added to the system resin, they cannot be used together.

The addition polymerization type silicone rubber in the present invention includes: 1. As is known, a vinyl group-containing polysiloxane represented by the general formula (3)/, an organohydrogen polysiloxane represented by the general formula (4), and a reinforcing agent; A composition that can be solidified into a bullet by addition-polymerizing a composition consisting of an inorganic substance such as silica using a platinum-based catalyst, and is not particularly limited. This category also includes those in which an epoxy compound, carboxylic acid anhydride, etc. are added as a third component to improve adhesion.

The manufacturing capability of the composite molding of the soft vinyl chloride resin composition and the addition-polymerized silicone resin composition according to the present invention is not particularly limited, but it can be made soft by adding Lugano hydrogen polysiloxane, for example. After kneading the vinyl chloride-based resin composition with a heated roll, it is made into slits, and the resulting molding material is molded by an extrusion method, press method, injection molding method, etc., and added to the surface of the molded product. By coating a polymerizable liquid silicone rubber by dipping, spraying, etc., and then curing the addition polymerization liquid silicone rubber in a heating furnace, etc., adhesive integration with a 1μ-shaped product can be achieved at the same time. That's why.

The present inventors previously proposed in Japanese Patent Application No. 58-203699 that an excessive amount of organohydrogen polysiloxane in an addition-polymerized liquid silicone rubber was added to the extent that the physical properties after assimilation were not significantly impaired. □Therefore, it has already been discovered that strong adhesion can be achieved with a soft vinyl chloride resin of a particular formulation, and the adhesion mechanism is due to residual vinyl groups in the vinyl chloride resin or heating. It is presumed that this is the result of an addition reaction of organohydrogensiloxy groups in the addition-polymerizable liquid silicone rubber to the unsaturated double bonds formed.

The present invention is based on the injection technology, and it has been discovered that by adding organohydrogen polysiloxane to soft vinyl chloride resin in advance, it is possible to combine it with addition polymerization type silicone rubber. Based on the facts, the adhesion mechanism is based on the addition reaction of organohydrogen siloxy groups of organohydrogen polysiloxane blended in soft vinyl chloride resin to vinyl groups in addition polymerized silicone rubber, and chlorination. - It can be assumed that this is the result of an addition reaction of organohydrogensiloxy groups in the addition-polymerized cone rubber to the vinyl groups remaining in the vinyl resin or to the unsaturated double bonds generated by heating, both of which proceed simultaneously.

Here, an addition reaction between the organohydrogensiloxy groups of the organohydrogenpolysiloxane in the soft vinyl chloride resin composition and the vinyl groups in the vinyl chloride resin occurs during heating and crosstalk of the core composition, and the organohydrogenpolysiloxane Although it is possible that the activity of the siloxane decreases, since there is no catalyst in the soft vinyl chloride resin composition that can act as a catalyst for the addition reaction, the reaction occurs inside the soft vinyl chloride resin composition. ζ Ruko! :ti is considered to be extremely small. That is, the organohydrogenpolysiloxane added to the soft vinyl chloride resin composition starts an addition reaction only when it comes into contact with addition polymerization type liquid silicone rubber containing a platinum thread catalyst and is heated. It is thought that this contributes to improving adhesive strength.

[Effects of the invention゛]′″′ □ The thus obtained composite molded product of the soft vinyl chloride resin composition and the addition-polymerized silicone rubber is strongly adhesively integrated□, and the soft vinyl chloride resin composition Although it has the toughness and rigidity of a silicone resin, its surface is coated to match the antithrombotic properties and tissue compatibility of addition polymerized silicone rubber, and its surface is extremely flat. ,
It is useful in various applications, especially in the medical field.

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 ``To 100 parts by weight of vinyl chloride resin (Toyo Soda special product 700D), 0.04 parts by weight of zinc stenarate, 0.02 parts by weight of stearin-calcium, 56 parts by weight of diethylhexyl phthalate, in terms of metal weight. Epoxidized soybean oil 5
Add the parts by weight to the basic soft vinyl chloride resin composition (
Table 1).

On the other hand, as organohydrogenpolysiloxane Al, 25°C
The viscosity is about 40C8, and the methylhydrogen siloxane unit in one molecule is about 70 mol %.
Contains 70% methylhydrogen polysiloxane.
Pegisan solution i! I! I IM'd you. Further, as organohydrogenpolysiloxane JI62 having a vinyl group in the molecule, a 14k n-hexane solution containing 703iit of polysiloxane shown in formula (5) was prepared.

Next, organohydrogenpolysoxane 41 and A2 were added to the basic soft vinyl chloride resin composition as shown in Table 1, and as a comparative example, they were not added, respectively, at 190°C in a blender. After kneading for about 7 minutes, the mixture was granulated. These molding materials were heated at 180℃, 5
A sheet with a thickness of 0.5% was obtained by press molding for a minute. From this sheet, two sheets with a size of 2° x 50% were made, and the commercially available addition-polymerized liquid silicone rubber shown in Table 1 was prepared with a thickness of 1% and a contact area of 20% on the top and bottom sides x approx. %, and heated in a constant temperature bath at 100° C. for 60 minutes to cure the addition polymerizable liquid silicone rubber. The thus obtained test pieces were subjected to a 180° peel test at room temperature and their adhesive strength was compared. The results are as shown in Table 1, and it is clear that the soft vinyl chloride resin composition of the present invention can be firmly bonded to a commercially available addition polymerization type liquid silicone rubber. .

Example 2 Vinyl chloride resin (Jumin Chemical Industry ■llj S-101
) 100 parts by weight of gold, 0.04 parts by weight of zinc stearate, 0.01 parts by weight of calcium stearate, 40 parts by weight of dioctyl phthalate, 6 parts by weight of epoxidized soybean oil, and formula (6) 1.2 parts by weight of a 50 wt% n-hexane solution of methylhydrogen polysiloxane shown by was mixed in a blender and then granulated.
．． A tube with an inner diameter of 5% and an outer diameter of 7% was molded using an extrusion mill.

On the other hand, addition polymerization type liquid silicone rubber (Shin-Etsu Chemical Co., Ltd.
1! i! A 20 wt% toluene solution of KE-1920) was prepared. Next, the tube was cut into a length of 1 m, and about 10 cc of the toluene solution of the liquid silicone rubber was collected using a syringe, and the tube was fixed vertically and injected into the tube from above. Coating was done. Then, after air drying for 30 minutes, it was dried in a hot air dryer at 105
C. for 95 minutes to obtain a two-layer tube (tube A) having an outer surface made of soft vinyl chloride resin and an inner surface made of addition-polymerized silicone rubber. In exactly the same manner, a two-layer tube (comparative tube) was prepared without adding methylhydrogen polysiloxane.
-I got it.

These two tubes were immersed in a 30 wt % ethanol aqueous solution to remove the air inside, and were ultrasonically cleaned for about 30 minutes. Each tube was taken out for cleaning, cut and pasted vertically with a knife, and visually observed. In Tube A of the present invention, the soft vinyl chloride resin layer and addition polymerization type silicone rubber layer remained neatly adhered. On the other hand, small pieces of exfoliated silicone rubber were present on the inner surface of the tube in the comparative example, and several parts of the tube-shaped 11 addition polymerized silicone rubber were observed to have exfoliated. It was done.

Patent applicant: Sumitomo Bakelite Co., Ltd. Patent applicant: Fuji Systems Co., Ltd.

Claims (3)

[Claims] (1) 0.01 to 10 parts of organohydrogenpolysiloxane having an organohydrogensiloxane concentration of at least 30 mol 4 or more per 100 parts by weight of vinyl chloride resin.
A soft vinyl chloride resin composition and an addition polymerizable silicone rubber, characterized in that a cured layer of an addition polymerizable silicone rubber is provided on the surface of a molded article made of a soft vinyl chloride resin composition containing parts by weight. composite molded product. (2) A soft vinyl chloride resin composition and an addition polymerizable silicone rubber according to claim (1), wherein the organo-aqueous bulk polysiloxane has at least one vinyl group in the molecule. Composite molded product with. (3) A patent claim characterized in that the metal in the stabilizer used in the soft vinyl chloride resin composition is one or more of calcium, zinc, barium, magnesium, and aluminum. A composite molded product of the soft vinyl chloride resin composition described in scope (1) and an addition polymerizable silicone rubber.