JPS60187549A - Flexible vinyl chloride group resin-silicon group multilayerlaminate - 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 flexible vinyl chloride resin-silicone multilayer laminate.

[Prior art]

Conventionally, for bonding soft vinyl chloride resins together, solvents with high solubility for vinyl chloride resins, such as acetone, methyl ethyl ketone, cyclohexanone, and tetrahydrofuran, have been used, or vinyl chloride-vinyl acetate copolymer resins have been used in these solvents. , acrylic ester copolymer resin,
Adhesives prepared by dissolving co-condensed polyester resin, thermoplastic polyurethane, etc., or hot-melt adhesives such as thermoplastic polyurethane, co-condensed polyester, etc. have been used.

In addition, in the case of adhesion between soft vinyl chloride resin and other materials,
For example, when the other party is metal, nitrile comb-7-[-
/ -! J-Sock thermoplastic polyurethanes, two-part polyurethanes, carboxylated neoprenes, and the like have been used. As described above, adhesion of soft vinyl chloride resin, including adhesion of similar materials, is always difficult due to the presence of plasticizers, and there are a limited number of adhesives that can be used.

Furthermore, soft vinyl chloride side bending has poor heat resistance,
Since it is difficult to leave the adhesive for a long time at a temperature higher than that, for example, an adhesive using a solvent has a problem in that the solvent remains in the resin. Moreover, many of the above-mentioned adhesives have poor heat resistance and water resistance, and a phenomenon in which adhesive strength decreases when exposed to autoclave or raw water, for example, is observed. Furthermore, some adhesives often have odor and hygiene problems when used for food or medical purposes. Furthermore, when adhering soft vinyl chloride resin, it is desirable that the adhesive itself be a nidistomer, and there has been no light contact agent that satisfies all of the above-mentioned problems.

The present invention has discovered a silicone that does not have the above-mentioned problems and can firmly bond soft vinyl chloride resins to each other and to polyurethane, polycarbonate, silicone, metals, ceramics, glass, etc., and has conducted various studies. In addition, it has been completed.

Examples of silicone-based adhesives include so-called condensation-type cold-curing silicones, such as acetic acid-removed type, alcohol-eliminated type, and oxime-eliminated type, which are known as RTv silicone rubbers. Furthermore, regarding these RTV silicone rubbers, according to Japanese Patent Application Laid-Open No. 54-156083,
A method has been proposed in which a hardened adhesive layer of RTV silicone rubber is formed after the surface of a soft vinyl chloride resin is subjected to low-temperature plasma treatment in advance, but the by-products such as acetic acid, alcohol, and oxime are treated with normal soft chloride. At the heat-resistant temperature of vinyl resin, complete removal is impossible, and hygiene remains a problem.

In addition, as described in JP-A-55-45098 or JP-A-53-33256,
It is said that addition-polymerizable silicone compositions with various components added firmly adhere to metals, ceramics, etc., and it is known that they adhere to metals, ceramics, hard vinyl chloride resins, polycarbonate, etc. It is a fact. However, there have been no reports yet that these silicone compositions strongly adhere to soft vinyl chloride fats.In fact, it has been said that adhesion with soft vinyl chloride fats is extremely difficult. be.

On the other hand, the present inventors discovered that the organohydrogensiloxane units represented by the general formula (3) are hydrogens bent and bonded to silicon atoms at a ratio of 1 to 6 times the total vinyl groups represented by the general formula (21). A sufficient amount of the hydrogen J in one molecule to give an atom
D. It was discovered that the adhesion force with soft vinyl chloride ribs (fat) increases greatly when organohydrogen polysiloxane having two or more children is contained.
No. 699 was filed.

In general, so-called self-adhesive silicone rubbers include epoxy compounds, carboxylic acid anhydrides, silanes or siloxanes containing an acryloxyalkyl group represented by general formula (1), or unsaturated carbonized silicone rubbers. Contains a hydrogen group-containing oxirane compound, etc., and furthermore, organohydrogensiloxane units shown in general formula (3) are directly bonded to silicon atoms at a ratio of 1 to 6 times the total vinyl groups shown in general formula (2). If the adhesive contains a sufficient amount of organohydrogenpolysiloxane having two or more hydrogen atoms in one molecule to provide hydrogen atoms, the same adhesive effect can be obtained.

[Purpose of the invention]

The purpose of the present invention is to solve the problems of adhesion of soft vinyl chloride resins as described above. The present invention attempts to propose a multilayer soft vinyl chloride resin-silicone layered body having a silicone adhesive layer that overcomes the above problems.

[Fourteenth aspect of the invention] That is, the present invention provides a structure in which at least one layer is made of soft vinyl chloride (ν
It is a multi-layer laminate made of J-type resin, which is made of soft vinyl chloride resin! i'i is an addition polymerization type silicone composition in which the adjoining layer further comprises 1 to 6 hydrogen atoms connected to a silicon atom per vinyl group in the composition; Regarding a soft vinyl chloride resin-silicone multilayer laminate, /l' is long enough to contain organohydrogen polysiloxane having two or more hydrogen atoms in one molecule, in an amount sufficient to provide hydrogen atoms. It is.

. The silicone composition that adheres to the soft vinyl chloride resin, which is a requirement for implementing the present invention, has hydrogen atoms directly bonded to silicon atoms, and the physical properties after curing are on the order of It is an essential condition that the organohydrogen polysiloxane containing two or more hydrogen atoms in one molecule is contained in an amount sufficient to give the adhesive in excess without causing any damage to the adhesive. Addition of an improver has a synergistic effect on adhesion with the soft vinyl chloride resin, and can also improve adhesion with other layer materials.

The addition polymerization type silicone rubber in the present invention includes a vinyl group-containing polysiloxane represented by the general formula (2), an organohydrogen polysiloxane represented by the general formula (3), and optionally a reinforcing agent. A composition made of an inorganic material such as silica is solidified into an elastic body by addition polymerization using a platinum-based catalyst.

In addition, the general formula (2
) and (31) By adding a vinyl group-containing resin-like copolymer that is compatible with the components shown in (31), the strength of the silicone film can be improved. For example, the following general formula (4) There are organopolysiloxane copolymers of (5) and (6).

(cr12=c1i) (R11XR12)siOo, 5
---------(4) Sioz......(5) (R15) 5 S roo......(6) Regarding adhesion with soft vinyl chloride hardwood, please refer to the patent application 58
As stated in No. 203700, it has been discovered that conventional addition-polymerized silicone rubbers can be firmly adhered to the primer coat layer of organohydrogenpolysiloxane containing at least 30 nZot- or more of organo-Mizuya siloxane units. Ta. In this case, in order to further increase the adhesive strength with the third layer, it is desirable to add the aforementioned adhesion improver and reinforcing agent.

Vinyl chloride resins as soft vinyl chloride-based thin surface components that form the multilayer body include vinyl chloride homopolymers, vinyl chloride-ethylene copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride- Ethylene-vinyl acetate terpolymer, vinyl chloride-acrylic copolymer, vinyl chloride-
Refers to copolymers mainly composed of vinyl chloride, such as urethane copolymers.

Examples of plasticizers that impart flexibility to vinyl chloride resins include phthalate esters such as dioctyl phthalate, fatty acid esters such as aliphatic dibasic acid esters such as dioctyl adipate and dibutyl sebachet, and polyesters. system plasticizer, trimellitic acid ester,
Examples include epoxidized soybean oil and epoxidized linseed oil. Furthermore, the addition of non-liquid polymers such as urethane and EVA also falls within this category.

Stabilizers that improve heat resistance and thermal stability include metal soaps such as calcium stearate, zinc stearate, and magnesium stearate, as well as organotin stabilizers, organosilicone stabilizers, and esters such as butyl stearate. Although system stabilizers and the like can be used, metal soaps such as calcium, zinc, magnesium, and lead, organic metal stabilizers, and inorganic metal stabilizers are preferred. Organotin stabilizers are a factor that inhibits the curing of silicone compositions, and their use is preferably avoided when the amount of plasticizer is large.

In addition, ultraviolet inhibitors, pigments, antistatic agents, X-ray contrast agents,
A lubricant etc. can also be added.

Before forming one layer of such a soft vinyl chloride resin molding and compositing it with another third layer and the addition polymerizable silicone composition of the present invention, a primer is applied to the soft vinyl chloride resin molding. Treatment, plasma treatment, etc. can be applied in advance. In the case of priming, a thin layer of a known silicone primer can be applied;
Furthermore, as described in Japanese Patent Application No. 58-203700, a thin layer of organohydrogen polysiloxane containing at least 30 yioA% of organo-Mizuya siloxane units may be provided. Furthermore, the adhesion can be further improved by performing low-temperature plasma treatment, corona discharge treatment, or ultraviolet irradiation treatment.

When such primer treatment or physical treatment is performed, in the addition polymerization type silicone composition before curing, as described in claim 1, organo-Kiyo in the addition polymerization type silicone composition is Adhesion is possible even if the ratio of polysilo and xane to vinyl groups is low.

The method for producing a multilayer laminate includes a soft vinyl chloride resin molded product and other layers, such as soft vinyl chloride resin, silicone,
The photopolymerizable silicone composition of the present invention is sandwiched between glass, ceramic, metal, etc., or coated on at least one side of the layer to bring them into contact to form an adhesive layer, or thereafter. While applying pressure, the temperature is 40°C to 130°C, preferably 80°C to 12°C.
At 0°C, 10 minutes to 10 hours, preferably 30 minutes to 3 hours.
The addition polymerizable silicone composition may be crosslinked and cured by heating for a period of time. Alternatively, a cured layer of addition polymerizable silicone rubber may be formed on the surface of the soft vinyl chloride resin molded article by heating under the same conditions as above, and then composited with other layers. good.

In this method, the composite can be formed without using a solvent, but in some cases, a solvent such as hexane or toluene may be used as a diluent in order to adjust the viscosity of the addition polymerizable silicone composition.

The soft vinyl chloride resin-silicone multilayer laminate thus obtained can withstand a high temperature of 130°C, which is the limit of the heat resistance of soft vinyl chloride resin, with some exceptions, and can be peeled off by autoclaving, hot water, etc. There is no risk of deterioration in strength, and there are no reaction products from the adhesive layer, so it is highly hygienic. Therefore, it can be applied to packaging containers such as retort containers, industrial products such as cosmetic glasses, and medical applications.

〔Effect of the invention〕

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

EXAMPLE In preparing the multilayer laminate, adhesiveness with various materials was evaluated.

The soft vinyl chloride resin composition shown in Table 1 was roll-kneaded at 160° C. for 5 minutes, and then press-molded at 200° C. for 4 minutes to create a sheet with a thickness of 1.0%. This sheet 2
The pieces were cut into pieces of 0% x 50% and laminated with the materials shown in Table 1 through various silicones (thickness 1%), and left to heat at 110°C for 1 hour to harden.
A peel test was conducted. Example N [L 6 was prepared by coating the sheet surface with a thin layer of primer in advance and heating it at 100°C.
Dry for o minutes. In addition, in Example N [L 7, the first
Plasma treatment was performed under the conditions shown in the table.

One step was carried out at 120° C. for 1 hour.

*1 (vinyl chloride resin) 5X-DH manufactured by Sumitomo Chemical *
2 (Silicone A) 12 mol% of trimethylsiloxane units, 40 mol% of dimethylsiloxane units based on 100 parts by weight of dimethylpolysiloxane, which has a viscosity of 16,000 cs at 25°C and has vinyldimethylsilyl groups at both ends of the molecular chain.
, 7 parts by weight of polysiloxane consisting of 48 mo1% of methylhydrogen siloxane units, 25 parts by weight of silica, and an isopropyl alcohol solution of chloroplatinic acid (platinum content: 5%).
．． Adjustments were made by adding 3 parts by weight.

*3 (Silicone B) 10 mot% of trimethylsiloxane units and 45 mot of dimethylsiloxane units based on 100 parts by weight of dimethylpolysiloxane which has a viscosity of 12.0OOcs at 25°C and has vinyldimethylsilyl groups at both ends of the molecular chain.
%, 10 parts by weight of polysiloxane consisting of 45 mot% of methylhydrogen siloxane units, 20 parts by weight of silica, and an isopropyl alcohol solution of chloroplatinic acid (platinum content: 3%)
It was adjusted by adding 0.5 parts by weight of.

*4 (Silicone C) Condensation type RTV silicone rubber.

Ia Etsu Kagaku Kogyobin 3 KE-42RTV *5 (hard vinyl chloride resin) Sumitomo Chemical ■ S-101 *6 (silicone rubber) Tone Silicone ■ SH851U *7 (primer) Viscosity at 25℃ An n-hexane solution containing 5.0% by weight of a methylhydrogen polysiloxane having a molecular weight of about 40 cs and a methylhydrogensiloxane unit of about 65 mots per molecule.

*8 (Plasma treatment) Argon gas was introduced into the chamber at a rate of 250 ml per minute, and the internal pressure of the chamber was maintained at approximately 0.1 Torr.
The battery was discharged for 7 minutes at an applied power of 500 W using a 13.56 MH2O high-frequency internal electrode.

As described above, the multilayer composite of the present invention, which has a basic structure in which soft vinyl chloride resin is adjoined to addition-polymerized silicone rubber and further has other materials in instant contact with its surface, can be firmly bonded and integrated. Furthermore, it can be seen that the adhesive strength can be further improved by pretreatment with a primer or the like.

Patent applicant Sumitomo Bakelite Co., Ltd. Fuji Systems Co., Ltd. Continued from page 1 ■ Inventor Akira Igarashi [phase] Inventor Nobuhisa Kawaguchi 47 Akiba-cho, Totsuka-ku, Yokohama Fuji Systems Co., Ltd. Yokohama Tech ↓ Inside the Yokohama "Hama Factory"

Claims (1)

[Scope of Claims] (1) A multilayer laminate in which at least one layer is made of a soft vinyl chloride resin, the layer adjacent to the soft vinyl chloride resin is an addition polymerization type silicone composition, and The addition polymerizable silicone composition has a vinyl group 1 in the composition.
A soft material characterized by containing an organohydrogenpolysiloxane having two or more hydrogen atoms per molecule in a sufficient amount to provide 1 to 6 hydrogen atoms perpendicular to each silicon atom. Vinyl chloride thread resin - silicone multilayer a)
゛F-layer body. (21) A multi-Ri laminate in which at least one layer is made of a soft vinyl chloride resin, and the layer adjacent to the soft vinyl chloride resin contains at least 30 f organohydrogensiloxane units?
The soft vinyl chloride resin-silicone composition according to claim 1, wherein the soft vinyl chloride resin-silicone composition is an adjoining addition polymerization type silicone composition with a primer layer of organohydrogen polysiloxane having a content of +ot% or more. system multilayer laminate. (3) A silicone in which the addition polymerizable silicone composition contains at least one of an epoxy compound, a carboxylic acid anhydride, and an acrylic compound represented by the general formula (1) as a component for improving adhesiveness. A soft vinyl chloride resin-silicone multilayer laminate according to claim 11 or (2), which is a composition. (4) In the soft vinyl chloride resin composition Claim (1) or (1), wherein the metal in the stabilizer used is one or more of calcium, zinc, lead, barium, magnesium, and aluminum. The soft vinyl chloride resin-silicone multilayer laminate described in item 2). (5) In the multilayer laminate including at least the soft vinyl chloride front fat layer and the addition polymerizable silicone composition layer, the other layers are , soft vinyl chloride resin, hard vinyl chloride (1 degree month), glass, polyurethane, polycarbonate, polyethylene, ethylene-acetic acid copolymer, ethylene-vinyl alcohol copolymer d, polyvinyl alcohol, The soft vinyl chloride resin-silicone yarn N11R according to claim 11 or (2) is characterized by comprising at least one layer selected from the group consisting of gold E6 and ceramic. (6) In a multilayer laminate including at least a soft vinyl chloride resin layer and a (=j-added dispersed silicone composition layer), at least one side between each layer is subjected to low-temperature plasma treatment or corona discharge treatment. or ultraviolet irradiation treatment.
), (4), and (5).