JPS60179426A - Flexible vinyl chloride resin/silicone composite molding and its production - Google Patents

Abstract

PURPOSE:To obtain the titled composite molding excellent in bonding strength and antithrombotic property, by subjecting the surface of a flexible vinyl chloride resin to a specified treatment before applying thereto a cured layer of an addition-polymerizable silicone composition. CONSTITUTION:The titled molding is obtained by treating the surface of a flexible vinyl chloride resin molding containing a stabilizer containing at least one metal selected from among Ca, Zn, Ba, Mg, and Al with low-temperature plasma or corona discharge, coating the treated surface with a layer (suitable thickness) of an addition-polymerizable silicone composition containing an organohydrogenpolysiloxane having at least two H atoms in the molecule in an amount sufficient to provide 0.8-6 Si-bonded H atoms per vinyl group in the vinyl resin molding, said silicone composition being used as such or as a solution in, for example, hexane, and heating the molding to 40-130 deg.C for 5min- 10hr to cure the film.

Description

[Detailed description of the invention] [Industrial application field] The present invention provides a vinyl chloride resin-silicone composite molded product C.
This is related to two things.

[Prior art] Vinyl chloride resin (1) is made more flexible by adding a plasticizer or a polymeric distomer (2).

It has been widely used for medical devices, food packaging, etc. because of its excellent transparency, adhesive properties, and high-frequency processability.

However, in the field of medical devices (2), vinyl chloride resin products have poor antithrombotic properties and tissue compatibility (2); A problem arises.

On the other hand, silicone has excellent antithrombotic properties and histocompatibility (
Second, although it is expected to be used as a medical material, 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 vinyl chloride resin C-silicone oil or to combine them with coatings, etc. However, with soft vinyl chloride resin (2), it was thought that it would be difficult to bond and integrate with silicone due to the influence of additives such as general C2 plasticizers.In order to overcome this problem, (2) Various methods have been proposed in which the surface of a soft vinyl chloride resin is treated with a primer and then a silicone layer is formed, but the process is complicated and most primers are ethyl acetate.

Since a solvent such as toluene is used, there is a concern that the solvent may remain, and there is also the problem that it may peel off over time even if it is bonded.

On the other hand, according to Japanese Unexamined Patent Publication No. 156083 (1983), the surface of vinyl chloride resin is treated with low-temperature plasma in advance,
After that, according to a method of forming a cured layer of room-temperature curing silicone of C=condensation type, and according to JP-A No. 58-32773 (2), the surface of the vinyl chloride resin material (2. It has been proposed that after forming a hardened layer, a silicone layer made of dimethylsiloxane or modified dimethylsiloxane (based on an alkyl group) is formed and modified. , condensation type RTV silicone rubber and silicone m
It is clear that the fat adheres to the vinyl resin surface.

However, condensation-type RTV v silicone rubber has a relatively high boiling point of acetic acid and oxime that are produced as by-products during the curing reaction, so it cannot be heated under reduced pressure at high temperatures of 150°C or higher for several hours, or in a temperature range where the soft vinyl chloride resin does not deform. If the unprinted product is not manipulated for a long time, silicone will not be able to exhibit its inherent biocompatibility such as antithrombotic properties. Furthermore, silicone resins generally lack adhesive strength, and their coatings themselves are hard, and when used in combination with flexible materials such as soft vinyl chloride resins, there is a risk that cracks may occur in the coating.

Addition polymerization type silicone rubber using a platinum catalyst or the like is available as a material that does not have such problems. This addition polymerization type silicone rubber is a low temperature curing type silicone rubber called LTV, which is cured for a short period of time (double cured) at a relatively low temperature of around 100°C, and has almost no by-products. It has excellent properties such as antithrombotic properties.The inventors investigated the adhesion between addition polymerization type silicone rubber, which has these excellent properties, and soft vinyl chloride resin, and surprisingly found C2. Through physical methods such as low-temperature plasma treatment, a combination of addition polymerized silicone rubber and soft vinyl chloride resin that can be bonded to soft vinyl chloride resin without pretreatment was discovered, and patent application No. 58-956 was filed.
No. 89 and Japanese Patent Application No. 58-203699.

[Purpose of the invention]

As a result of intensive studies with the aim of improving adhesion by making further improvements to these, the present invention has developed physical treatments such as low-temperature plasma treatment and corona treatment on the surface of soft vinyl chloride resin molded products. After that, it was discovered that when an addition-polymerizable silicone composition was coated and cured, the adhesive strength was significantly improved, and the present invention was completed in step C2.

[Structure of the invention]

That is, the present invention provides a low-temperature plasma or corona-treated surface of a soft vinyl chloride resin molded article (= a vinyl chloride resin-silicone composite molded article provided with a hardened layer of an addition polymerizable silicone composition). This is related to two things.

In the present invention (additional poultry house type silicone), the general formula (
1) A vinyl group-containing polysiloxane represented by (2), and an organohydrogen polysiloxane represented by general formula (2) (2),
And if necessary, a composition consisting of an inorganic substance such as silica as a reinforcing agent is subjected to addition polymerization with a platinum-based catalyst, etc. , the organohydrogen silochitin units represented by the general formula (2) (2) are all vinyl groups represented by the general formula (1) (
: It is preferable that the organohydrogenpolysiloxane be contained in an amount sufficient to provide silicon atoms (two directly bonded hydrogen atoms) at a ratio of 0.8 or more, preferably 1 or more and 6 times, to

In addition, addition of an epoxy compound or an oxirane compound containing an unsaturated hydrocarbon group as a component of what is generally referred to as self-adhesive silicone rubber, or after solidification of an addition polymerization type silicone composition (2) General formulas (1) and (2) are used as components for improving the physical properties of the cured layer.
) (2 It is also possible to add a resin-like copolymer containing vinyl groups that is compatible with the components shown. For example, general formula f4)
, f5) and (6) copolymer organopolysiloxanes.

CH, = C-C-0-R,,, -Si = ...river, river, (3) 11 bird, O (CH, =, C) () (ru,) (rep 4) 8100-5
・・・・・・・・・(4) To Si ・・・・・・・・・
・・・・・・・・・・・・・・・・・・(5)(R111)
s S I Oo, a ・・・・・・・・・・・・・・・
(6) In the present invention, the soft vinyl chloride resin refers to vinyl chloride homopolymer, vinyl chloride lI/
-Ethylene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate terpolymer.

The main component is a copolymer mainly composed of vinyl chloride, such as a vinyl chloride-acrylic copolymer or a vinyl chloride-urethane copolymer, and is blended with a plasticizer that imparts flexibility. .

Examples of plasticizers include fatty acid esters such as phthalate esters including dioctyl phthalate, aliphatic dibasic acid esters such as dioctyl adipate and dibutyl sebaciate, polyester plasticizers, epoxidized soybean oil, and epoxidized It uses linseed oil, etc. Furthermore, the addition of non-liquid polymers that give flexibility, such as urethane and EVA, also falls into this category. Eggplant #neutralization 1
In addition to metal soaps such as calcium stearate, zinc stearate, magnesium stearate, and lead stearate, ester stabilizers such as organotin stabilizers, organosilicone stabilizers, and butyl stearate are used. preferably calcium stearate,
Lead stearate.

Metal soaps such as lead stearate and barium stearate,
and organic metal stabilizers and inorganic metal stabilizers of the above metals. Organotin stabilizers tend to inhibit the curing of silicone compositions despite physical treatments such as low-temperature plasma treatment, and care must be taken when using them.Also, phosphoric acid stabilizers Ester-based stabilizers such as and butyl stearate similarly cause curing inhibition when used in combination.

In addition, ultraviolet inhibitors, pigments, antistatic agents, X-ray contrast agents,
A lubricant and the like can also be added, and in this way, widely known formulations of the soft vinyl chloride resin in the present invention can be used.

The composite molded product of the present invention (second step) is a soft vinyl chloride resin molded product that has been subjected to low-temperature plasma-V keratinization, and has a hardened layer of the addition-polymerizable silicone composition described above. This is a low-temperature plasma and corona discharge treatment method for soft vinyl chloride resin molded articles.

As a low temperature plasma treatment method, 10-3 to 10 Tor
The molded article is treated by glow discharge in a gas that does not have plasma polymerizability under a pressure of r. As the plasma condition, for example, between the electrodes (213.56 MH
z, a power of 10 to 1000 W may be applied, and the molded product may be treated for several tens of seconds to several tens of minutes, preferably for one minute to nine minutes. Low-temperature plasma treatment (2) The plasma non-polymerizable gas used is Ar5He1CO,,CO
, N, etc. Special Publication No. Sho 57-1540, Special Publication No. Sho 57-1
The gases described in Publication No. 541, etc. (2) can be used alone or in a mixed system.

Further, as a corona discharge treatment method, a commercially available apparatus can be used, and the treatment conditions are, for example, a high frequency voltage of 4 and V.

The applied voltage is preferably 8 to 30 V, preferably 10 to 20 V, and the distance between the electrode plates may be any distance as long as discharge can occur, but it is better to be as short as possible. The corona discharge treatment is preferably carried out under such conditions, and as the atmospheric gas, air, CO, Co, , N, , Ar, Ne, etc. can be used alone or in a mixed system.

In this way, general methods such as coating, dipping, and spraying can be used to form a hardened layer of addition polymerization silicone on the surface of the physically (2-treated) soft vinyl chloride resin molded product. Can be applied. Addition polymerization type silicone composition can be used as it is, or a solution diluted with hechitin etc. can be applied to the desired thickness (two layers, 40°C to 130°C).
℃, preferably 80℃ to 120℃ for 5 minutes to 10 minutes.
It is desirable to form the cured layer over a period of time, preferably 10 minutes to 3 hours.

〔Effect of the invention〕

The adhesiveness of the silicone rubber-soft vinyl chloride resin molded product obtained in this way is 1.5 to 2.5% higher than that of a composite directly bonded without plasma treatment or corona discharge treatment. It has twice the adhesive strength, and further has the advantage that it can be bonded even if the ratio of organohydrogensiloxane groups to vinyl groups in the silicone rubber composition is low.

This adhesion mechanism is thought to be primarily due to the reaction between the vinyl groups in the vinyl chloride resin and the hydrogen atoms directly bonded to silicon atoms, but there are also hydroxyl groups and carbonyl groups generated during plasma treatment and corona discharge treatment. Furthermore, it is presumed that vinyl groups and the like contribute in part to the reaction (C2), and van der Waals force due to polarity (2 groups) is involved in adhesion C2.

In addition, it is said that low-temperature plasma treatment has a large effect on preventing the elution of plasticizers in vinyl chloride resins (2).
With regard to =, silicone composites (with respect to =, there is not much effect.

The composite according to the present invention (2) has excellent antithrombotic properties, and has no residual acetic acid, alcohol, oxime, etc. as seen in (2) condensed RTV silicone rubber C2, and is suitable for medical use, especially (2) when it comes into direct contact with blood. It is suitable for use in blood bags, catheters, etc.

The present invention will be explained in detail below using Example C2.

Example 1 Sheets of soft vinyl chloride resin with two formulations as shown in Table 1 (2) were molded using a 4 (lφ extruder) to a thickness of 0.8 x. Two types of primary silicone rubber were prepared as rubbers.

(Silicone A) Trimethylsiloxane unit 10 mo1%, dimethylsiloxane unit per 100 parts by weight of dimeterpolysiloxane having a viscosity of 18.0OOC8 at 5°C (2) and having vinyldimeternyl groups at both ends of one molecular chain. 49mo1
%, 5 parts by weight of polysiloxane consisting of 50 mo1% of methyl hydrogen siloxane units, and parts by weight of silica.

and isopropyl alcohol of chloroplatinic acid (platinum content 3%)
) was adjusted by adding 0.2 parts by weight.

(Silicone B) 100 parts of dimethylpolysiloxane having a viscosity of 12,00C8 at 5°C and having pinyldimethylmonlyl groups at both ends of the molecular chain (2 to 12 mol of trimethylsiloxane units in the methylhydrogen polysiloxane component) %, 8 parts of polysiloxane consisting of 53 mo1% of dimethylsiloxane units and 35 mo1% of methylhydrogen siloxane units, 30 parts of silica, and 0.1 part by weight of an isopropyl alcohol solution of chloroplatinic acid (platinum content: 5%). .

Next, the above two types of soft vinyl chloride resin sheets were subjected to low temperature plasma treatment under the following conditions. The various sheets mentioned above were placed in a vacuum chamber (for two people, after reducing the pressure to 0.05 Torr l, the chamber was filled with 300 ml of argon gas at a speed of 7 minutes) (
The internal pressure of the chamber was maintained at approximately 0.15 Torr, and then a plasma treatment was performed by discharging the sample at 00 W using a 13.56 MHz high-frequency internal electrode for 5 minutes.

Next (=, various sheets (=), each sheet that was not subjected to plasma treatment was prepared.

These sheets were cut into 2 pieces each with a size of 20~50~, and each silicone A and silicone B were cut so that the thickness was 1% and the contact area was 20% x about 25% (=C2). The scissors were left in an oven at 105°C (1100 minutes), returned to room temperature (-), and subjected to a 180° beer test. The results are shown in Table 1 (==).

Comparative Examples ■, ■ (=Compared with Examples ■ and ■C2, After the surface of the vinyl chloride resin molded product of the present invention (=) was plasma treated, the silicone rubber of the present invention was sandwiched and heated. The adhesion strength of the test piece was dramatically improved compared to (2) which was not subjected to plasma treatment.However, as is clear from the comparative examples If the formulations of the silicone rubber and the vinyl chloride resin are outside the scope of the present invention, not only the conditions but also the formulations of the vinyl chloride resin, the effect of the plasma treatment is hardly seen.

Example 2 Vinyl chloride resin (8X-DH manufactured by Sumitomo Chemical Co., Ltd.) 10
0 parts by weight, 35 parts by weight of dioctyl phthalate, 0.02 parts by weight of calcium stearate (in terms of metal weight), 0.03 parts by weight of zinc stearate (in terms of metal weight),
and 8 parts by weight of epoxidized soybean oil were roll-kneaded at 170°C and then subjected to brene molding at 190°C for 5 minutes.

In this way, three sheets of 300%; , in air and in argon gas.

On the other hand, as a silicone rubber, 100 parts by weight of dimethylpolysiloxane having a viscosity of 15,000C8 at 25°C (= 15,000C8) and having vinyldimethylsilyl groups at both ends of the molecular chain (10mol% of trimethylsiloxane units, 35 mo1%, 5 parts by weight of polysiloxane consisting of 55 mo1% methylhydrogen siloxane units, 20 parts by weight of silica, and 0.1 part by weight of an isopropyl alcohol solution of chloroplatinic acid (platinum content: 5%).

Mouthpiece Using the above two types of vinyl chloride resin sheets and the above silicone rubber, test pieces were prepared in the same manner as in Example 1, and a 180° peel test was conducted. The results are shown in Table 2, and it can be seen that the corona discharge treated vinyl chloride resin sheet of the present invention C2 has significantly improved adhesive strength compared to the untreated vinyl chloride resin sheet (2).

Table 2

Claims (4)

[Claims] (1) Surface C of a soft vinyl chloride resin molded product (2) Composite molded product having a hardened layer of an addition polymerizable silicone composition (2) The surface of the soft vinyl chloride resin molded product is A soft vinyl chloride resin-silicone composite molded product characterized by being subjected to plasma treatment or corona treatment. (2) The addition-polymerizable silicone composition provides 0.8 to 6 hydrogen atoms directly bonded to silicon atoms per vinyl group in the composition (200% of the hydrogen atoms in one molecule). The soft vinyl chloride resin-silicone composite molded article according to claim 1, which contains an organohydrogen polysiloxane having two or more atoms. (3) Claim 1, characterized in that the metal in the stabilizer used in the soft vinyl chloride resin is one or more of calcium, zinc, barium, magnesium, and aluminum. A soft vinyl chloride resin-silicone composite molded article as described in 1. (4) Surface of soft vinyl chloride resin: When providing a cured layer of addition polymerizable silicone composition (2. At least 40°C
A method for producing a soft vinyl chloride resin-silicone composite molded product, characterized by heating and curing at a temperature above.