JPH02185537A - Laminated molding of inorganic material and polyvinyl chloride resin and preparation thereof - Google Patents

Abstract

PURPOSE:To prevent a plasticizer from causing bleedout and to obtain the title laminate molding with an inorg. material layer strongly laminated and adhered by subjecting a base material of a molding consisting of a PVC resin material to a specified treatment and then forming an inorg. material layer. CONSTITUTION:The surface of a base material of a molding pref. consisting of a PVC resin material is treated with a low temp. plasma in an inert inorg. gas atmosphere pref. contg. CO and/or Ar to form a crosslinked PVC layer and the surface of this crosslinked layer is treated with a low temp. plasma in an inorg. gas atmosphere contg. an oxidative gas (e.g. O2) to form a modified PVC layer. Then, one or more inorg. material layers (e.g. an Al layer) are formed on this modified layer by, e.g. vacuum deposition to obtain the title laminate molding constituting the base material of the molding consisting of the PVC resin material, said crosslinked layer, said modified layer and said inorg. material layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an inorganic material-polyvinyl chloride resin laminate molded article and a method for producing the same.

More specifically, the present invention relates to an inorganic material comprising a base made of a molded article made of a polyvinyl chloride resin material, and an inorganic material layer, such as a metal layer or an inorganic metal compound layer, firmly laminated and bonded thereon. The present invention relates to a polyvinyl chloride resin laminate molded article and a method for manufacturing the same.

[Conventional technology]

Various attempts have been made to form a metal vapor deposited layer on the surface of a polyvinyl chloride resin molded article substrate. In general, polyvinyl chloride resin molded products contain a large amount of plasticizer, so the plasticizer bleeds out onto the surface of the molded product over time, making it easy for the metal deposited layer to peel off from the base. was of little practical use. As a solution to these problems, Japanese Patent Application Laid-open No. 199245/1983 describes
A method is disclosed in which a polyester plasticizer with relatively little bleed-out is used and the amount added is limited to 20 to 40 parts by weight. However, with this method, the adhesive force between the substrate surface and the metal vapor deposited layer was still insufficient, and the flexibility of the molded article itself was insufficient. Also, JP-A-5
No. 9-96137 discloses a method in which a plasma polymerized film of a silicon compound is deposited on the surface of a polyvinyl chloride resin molded article, and a metallizing treatment is performed on the polymerized film layer. In this method, the plasma polymerization method has the disadvantage that the reproducibility of the produced polymer film is low, and in particular, it is extremely difficult to form a large area polymer film with good reproducibility.
Moreover, the adhesive strength of the laminated article obtained in this way is
It was unsatisfactory.

[Problem to be solved by the invention]

When the surface of a molded article made of polyvinyl chloride resin material is subjected to low-temperature plasma treatment, a polyvinyl chloride crosslinked layer is formed, and this crosslinked layer prevents the plasticizer in the polyvinyl chloride resin material from bleeding out. Although it is effective for
The adhesion of the surface of this crosslinked layer to an inorganic material coating layer such as a metal film and its durability are unsatisfactory.

The present invention solves the above-mentioned problems and has a polyvinyl chloride resin molded article base and an inorganic material layer that is firmly and durablely laminated and bonded to the substrate. It is an object of the present invention to provide a vinyl resin laminate molded article and a method for manufacturing the same.

[Means and actions to solve the problem]

The inorganic material-polyvinyl chloride resin laminate molded article of the present invention is formed by subjecting a molded article base made of a polyvinyl chloride resin material and a surface portion of the base to low-temperature plasma treatment in an inert inorganic gas atmosphere. a polyvinyl chloride crosslinked layer; a polyvinyl chloride modified layer formed by subjecting the surface portion of the crosslinked layer to low temperature plasma treatment in an inorganic gas atmosphere containing an oxidizing gas;
and one or more inorganic material layers laminated and bonded on the modified layer.

In addition, the method for manufacturing an inorganic material-polyvinyl chloride resin laminate molded article of the present invention includes subjecting the surface portion of a molded article base made of a polyvinyl chloride resin material to a low-temperature plasma treatment in an inert inorganic gas atmosphere to form a polychlorinated article. A vinyl crosslinked layer is formed, a polyvinyl chloride modified layer is formed by subjecting the surface portion of the crosslinked layer to low temperature plasma treatment in an oxidizing gas-containing inorganic gas atmosphere, and at least one inorganic layer is formed on the modified layer. forming a layer of material.

The molded article base of the laminated molded article of the present invention is made of a polyvinyl chloride resin material. The polyvinyl chloride resin used in the present invention includes soft polyvinyl chloride resin, hard polyvinyl chloride resin, copolymer resin of vinyl chloride and olefins such as ethylene, propylene, or isobutylene, and copolymer resin of vinyl chloride and styrene. Copolymer resins, copolymer resins of vinyl chloride and dienes such as butadiene, or isoprene, copolymer resins of vinyl chloride and acrylic acid, halogenated olefins, or vinyl acetate, and the above resins, Modifying resin, e.g. 8BS
, 5BR1 or a mixed resin with rubber such as NBR.

There are no particular restrictions on the type or amount of plasticizer added to the polyvinyl chloride resin, and any generally usable plasticizer may be included.

Furthermore, the polyvinyl chloride resin material used in the present invention may contain an organic compound having an acryloyl group and/or a methacryloyl group at the molecular end. Such acryloyl or methacryloyl group-containing organic compounds improve the efficiency of crosslink formation by low-temperature plasma treatment of polyvinyl chloride, prevent bleed-out of the plasticizer, and, as a result, improve adhesion to the inorganic material layer. It is effective for improving

As the acryloyl group- or methacryloyl group-containing organic compound, those represented by the following -Funenin (I) to (V) are preferred.

A-←M→ER(1) A,-←M,-)-τA2 (n)A
:l-E-M2---N-→Download A4
(m) A5-←M, →, Tr-A, (■) A, -←M4-N-+TTM, -A1. (V)A,
A.

(However, "two people (1) to (V), A, A,, A2
A.3. A,,A,A,,A,,A,,A7. A, and A1 each independently represent an acryloyl group or a methacryloyl group, and M, M, and M2 each independently represent an aliphatic dihydric alcohol residue. , M, , M, and M5 each independently represent an aliphatic trihydric alcohol residue,
R is an alkyl group, an alkyl group substituted with at least one hydroxyl group, an alkyl group substituted with at least one carboxyl group, a phenyl group, an alkylphenyl group, a substituted with at least one hydroxyl group represents a member selected from a phenyl group, an alkylphenyl group, and a phenyl group and an alkylphenyl group substituted with at least one carboxyl group, N represents a dibasic acid residue,
nl represents an integer of 0 or 1 or more, n2 n3 .
n4 and n5 each independently represent an integer of 1 or more).

Examples of the compound represented by the above -Funenin (1) include phenylpolyethylene glycol acrylate (methacrylate), p-(nonylphenyl)polyethylene glycol acrylate-1-(methacrylate), and 2-hydroxo-
Examples include 3-phenoxypropyl acrylate (methacrylate), monophthalate ester ethylene glycol acrylate-1-(methacrylate-1.), and 2-ethylhexyl acrylate (methacrylate).

- Compounds represented by Funato (■) and (III) include polyethylene glycol acrylate (dimethacrylate 1-1), polyethylene glycol monoacrylate monomethacrylate, tripropylene glycol diacrylate (dimethacrylate), tripropylene Glycol monoacrylate monomethacrylate-1-11,4
-Butylene glycol diacrylate (dimethacrylate 1-
1.), 1.4-butylene glycol monoacrylate monomethacrylate, phthalic acid ethylene glycol oligoester diacrylate (dimethacrylate), and phthalic acid ethylene glycol oligoester monoacrylate monomethacrylate.

Examples of the compound of general formula (IV) include pentaerythritol triacrylate (trimethacrylate). −
Examples of the polyfunctional oligoester compound of Funato (V) include phthalic acid pentaerythritol oligoester triacrylate acrylate). In the compounds of the above-Funenin (1) to (V), M, M. , an aliphatic dihydric alcohol residue represented by M2, M3.

In at least one kind of molecular chain of the aliphatic trihydric alcohol residue represented by M 4 and M s and the dibasic acid residue represented by N, there is an isocyanate group and an epoxy group. At least one selected type may be included.

In addition, the polyvinyl chloride resin material used in the present invention may contain appropriate amounts of stabilizers, fillers, flame retardants, flame retardants, antioxidants, ultraviolet absorbers, and antifungal agents depending on the purpose. , lubricant,
It may also contain pigments and the like.

The molded article substrate used in the present invention is made of polyvinyl chloride resin material by any suitable method such as extrusion molding, injection molding, canleder molding, inflation molding, compression molding, coating, or dipping. It can be obtained by molding into desired shapes and dimensions using a molding method. The shaped article substrate may also include suitable reinforcing materials made from synthetic, semi-synthetic, natural fibers, etc. incorporated for the purpose of increasing physical strength.

The surface portion of the polyvinyl chloride resin molded article substrate of the present invention is modified into a crosslinked layer. This polyvinyl chloride crosslinked layer is applied to the surface of the substrate in an inert inorganic gas atmosphere.
It is formed by performing low temperature plasma treatment. The inert inorganic gas includes at least one member selected from -carbon oxide (CO) gas and argon (Ar) gas, and in addition to the above gases, inert gases such as helium, neon, nitrogen, etc. , and small amounts of nitrous oxide, nitrogen dioxide, oxygen, air, carbon dioxide, hydrogen, chlorine, hydrogen chloride, bromine cyanide, tin bromide, sulfur, sulfur dioxide gas, hydrogen sulfide, etc., which do not impede the purpose of the present invention. may be included as long as

The low-temperature plasma treatment in an inert gas atmosphere is generally preferably performed under a pressure of 0.01 to 1 QTorr.

There are no particular limitations on the conditions for generating low-temperature plasma, but for example,
A power of 10 to 500 W at 13.561 Hz may be applied between the electrodes. Sufficient results can be obtained by either polar discharge or non-polar discharge. The plasma treatment time varies depending on the applied voltage, but generally a few seconds to several tens of minutes is sufficient.

There are various plasma processing methods other than those mentioned above. For example, low frequency, microwave, direct current, etc. can be used as the discharge frequency band, and plasma generation methods include glow discharge, corona discharge, and spark. You can choose between discharge, silent discharge, etc. In addition to the external electrode, the electrode used may be an internal electrode, a coil type, capacitive coupling, or inductive coupling. However, no matter what method you use,
Care must be taken to ensure that the surface of the substrate is not altered by discharge heat.

The polyhinyl chloride crosslinked layer thus formed can prevent plasticizer from bridging from inside the substrate onto its surface.

In the present invention, on the surface portion of the polyhinyl chloride crosslinked layer,
A polyvinyl chloride modified layer is formed.

This modified layer is formed by subjecting the surface portion of the polyvinyl chloride crosslinked layer to low-temperature plasma treatment in an inorganic gas atmosphere containing an oxidizing gas.

Oxygen is generally used as the oxidizing gas, but nitrous oxide (No), nitrogen dioxide (NO2), etc. may also be used. Inorganic gases used as diluting gases along with oxidizing gases include nitrogen, carbon oxide, hydrogen, chlorine, halides such as hydrogen chloride, bromine cyanide, and tin bromide, sulfur, sulfur dioxide gas, hydrogen sulfide, etc. sulfides, etc. C:t and oxidizing gas (oxygen) are present in this inorganic gas atmosphere at 20% by volume or more, preferably from 60% to 60% by volume.
The conditions for generating low temperature plasma, which is preferably contained at a content of 100% by volume, are the same as described above.

Although the mechanism of action of low-temperature plasma treatment in an oxidizing gas-containing atmosphere is not fully clear, (a) functional groups, such as oxygen-containing functional groups, are formed on the surface portion of the polyvinyl chloride crosslinked layer.

(b) Remove contaminants (substances that reduce adhesion) on the surface.

etc. are possible.

However, even if the surface of the polyvinyl chloride crosslinked layer is subjected to cleaning treatment, for example, ultrasonic cleaning treatment in various solvents, no particular adhesion improvement effect is observed. It is presumed that the effect is mainly due to the introduction of highly adhesive functional groups.

In general, low-temperature plasma treatment in an inorganic gas atmosphere containing CO and/or Ar does not substantially introduce oxygen-containing functional groups onto the substrate surface; however, when the surface to be treated is exposed to the atmosphere after treatment, the surface The radicals remaining in
A small amount of oxygen-containing functional groups may be introduced by reacting with oxygen in the atmosphere, but the introduction of this level of functional groups does not allow for a practically sufficient level of adhesion to inorganic materials on the substrate surface. cannot be improved.

For example, when calculating the polar force component in a three-component system using extended Hawks 2, the surface tension of the surface of the polyvinyl chloride crosslinked layer treated with CO gas plasma is 9.2 dynes/cm, but 0□ The surface tension of the gas plasma-treated polyvinyl chloride modified layer surface is 12.3 dynes/(-m
improve.

In the present invention, at least one inorganic material layer is formed on the polyvinyl chloride modified layer.

Although there are no particular limitations on the method for forming the inorganic material layer, dry methods such as vacuum evaporation, sputtering, and ion silating are generally used.

The inorganic materials used in the present invention include 8! Ti,
Cr, Mn, l? e, Ni, Cu,
Metals like Zn, Sn etc., ZnO+MgO
, In2O3+ 5n02.5iOz, etc., metal sulfides such as MoS, CdS, ZnS, etc., and metal fluorides such as MgF, and CaF2. These inorganic materials are selected depending on the intended use of the molded article and the required functions and characteristics.

In the laminate molded article of the present invention, the polyvinyl chloride crosslinked layer formed on the base material prevents bleed-out of plasticizer etc. to the surface, and furthermore, the modified layer formed on the crosslinked layer has no effect on inorganic materials. It exhibits extremely high adhesion, especially to almost all metals, compared to the untreated case.
It has 20 times more adhesive strength. taste, )°, C
Shows extremely high adhesion to r, Ni, 1, and Cn.

Although the polyvinyl chloride modified layer of the present invention also exhibits improved adhesion to metal oxides, sulfides, and fluorides,
Its durability may not always be sufficient. In such a case, a single metal layer with excellent adhesiveness and durability, preferably Cr, Ni, etc., is first applied on the modified polyvinyl chloride layer within a range that does not impair the function of the intended inorganic material layer.
, Mn or Cu may be formed as a single anchor metal layer, and an inorganic material layer having a desired function may be formed thereon.

Generally, there is no particular limitation on the thickness of the anchor metal single layer, and it is generally preferably 10 to 500 angstroms, more preferably 10 to 300 angstroms. If the thickness of the anchor metal single layer is greater than 500 angstroms, the anchoring effect tends to decrease and there is also the disadvantage of increased cost.

〔Example〕

The present invention will be further explained below with reference to Examples.

Example 1゜PVC (polyvinyl chloride resin, trademark: Denka 5S103)
) 100 parts by weight, DOP (dioctyl phthalate)
60 parts by weight, 3 parts by weight of EPS (epoxidized soybean oil),
A composition containing 2 parts of T3a Z n-based stabilizer was formed into a film with a thickness of 0.1 man by heating rolls (film ■). Also, in the same composition as above, D
A composition containing 50 parts by weight of OP and 10 parts by weight of tetraethylene glycol diacrylate was made into a film having a thickness of 0.1 mm in the same manner as described above (film ■). Each of these films I and H was heated and adhered to both sides of a fabric using polyester multifilament 1000 denyl yarns as the warp and weft at a density of 11 threads/25.4 mm to create a polyvinyl chloride resin sheet. . The obtained sea 1-1 and
The plasma treatment described in the table was performed, and then metal AI was applied to a thickness of 400 mm using the resistance heating evaporation method. , vapor deposited layers were laminated. The conditions for forming a crosslinked layer using low-temperature plasma are as follows: CO/Ar (7/3) mixed gas is used as the atmospheric gas;
The internal pressure was 0.4 Torr, and the applied power was 100 W for 5 minutes. In addition, the modified layer forming treatment conditions are as follows: 02 gas is used as the atmospheric gas, and the pressure inside the vessel is 0.55To.
rr, and the applied power was 500 W for 30 seconds.

i: I ^j' of the molded article of 22 parts of metal Δ! -i'V
Table 1 shows the measurement results of the adhesive force between c.

Apply 20 g of adhesive (manufactured by Toagosei ■, FS-175) to one side of the untreated sheet using gravure coating.
It was applied with a coating amount of rd. The adhesive side of this sheet,
The metal surface of the metal laminate sheet is welded using a welding machine (YF-7000 manufactured by Shiraki Hinita), and the width of the sheet is 3.
I made it to cm. This test piece was subjected to Instron T (manufactured by Toyo Seiki Co., Ltd.), and its peel strength was measured.

The Toshio J■8 roasted metal laminate sheet was left in a constant temperature and humidity chamber (KAISER manufactured by Kanizai) with an ambient temperature of 50°C and humidity of 90% for 500 hours, and then the peel strength was measured according to the adhesive force measurement method described above. did.

From the results in Table 1, it can be seen that by performing the two-step process of forming a crosslinked layer and forming a modified layer, the adhesive strength of the polyvinyl chloride resin (1B) material sheet was significantly improved and it exhibited excellent durability. Recognize. It is also seen that by adding a compound having a (meth)acrylic [Iyl group to the polyvinyl chloride resin material, the adhesive strength is improved even more.

Example 2゜Example 1 was applied to the sheet ■ to which the film I of Example 1 was attached.
Under the same conditions as above, we created a product in which only the crosslinked layer formation process was performed (comparative example) and a product in which the modified layer formation process was performed after the formation of the crosslinked layer (example of the present invention).
A plurality of inorganic material layers listed in the table were sequentially deposited and laminated to obtain a metal laminated PVC sheet. For these products, the initial adhesive strength and the adhesive strength after the durability test were measured. The results are shown in Table 2.

From the results in Table 2, it can be seen that even inorganic materials such as MgF2, which have low adhesiveness to PVC, can be significantly improved in adhesiveness by the method of the present invention (two-stage plasma treatment). Further, by providing the first layer (anchor layer) δ of a single metal, the adhesive strength and durability of MgF2 P V C-\ are significantly improved.

Among them, a metal vapor deposited layer consisting of ■n, Cu, Cr, and Ni has a particularly excellent anchoring effect.

The thickness of the first layer (anchor layer) is 10 to 500 mm.
It can be seen that within the range of 1 to 1, the obtained laminate exhibits stable adhesive strength and vinegar durability.

Example 3 Film II prepared in Example I was used as is. This was subjected to plasma treatment as shown in Table 3 under the same conditions as in Example 1, and then a third layer was applied using a resistance heating evaporation method.
After the anchor metals shown in the table were deposited, an ITO film with a thickness of 1000 mm was further laminated by sputtering to produce a transparent conductive laminated film. Table 3 shows the measurement results of the adhesive strength, conductivity, and light transmittance of these laminated films after the initial adhesive strength/durability test. The conductivity is expressed by the volume resistivity value measured by the four-probe method, and the light transmittance is
Convenience - Expressed by transmittance of light having a wavelength of 550 nm.

The metal itself must have good light transmittance, and it is preferable to use a metal that has a light transmittance of at least 50% at a thickness of at least 150 angstroms. Representative metals such as Cu,
Examples include Mn.

From the results in Table 3, it can be seen that the adhesive strength and durability of the ITO film formed on the PVC surface are significantly improved by the method of the present invention. In addition, the thickness of Cu or Mn is 10~
It can be seen that within the range of 150 angstroms, a good transparent conductive laminated film without significant decrease in light transmittance can be obtained.

Example 4゜The sheet ■ to which the film ■ of Example 1 was attached was
Plasma treatment was performed under the same conditions as shown in Table 4 (inventive examples and comparative examples). After that, from the sputtering method G,
A Cr layer with a thickness of 100 mm as an anchor layer, and a 1-
A Ti layer with a thickness of 500 layers was formed as a bulge layer. Table 4 shows the evaluation results of the anti-icing properties of this sheet. For comparison, similar tests were also conducted on a silicone-coated steel plate that has excellent anti-icing properties and a steel plate coated with an anti-icing paint (Deflo S manufactured by Kansai Paint Co., Ltd.).

Take a test piece of Shunsui Bosai 11 people and place it on a steel plate with a thickness of 9 mm and an area of 100 x 100 mm using adhesive so that there are no irregularities.
At an ambient temperature of 20°C, fresh water was sprayed to form ice on the test piece to a thickness of 10 m [lI].

Thereafter, the adhesion between the test piece and the ice was measured by applying a shear load. This operation was repeated several times to evaluate durability.

From the results in Table 4, it can be seen that an anti-icing sheet with excellent durability can be obtained by the method of the present invention.

〔Effect of the invention〕

The inorganic material-polyvinyl chloride resin laminate molded article obtained by the present invention has excellent adhesive strength between the base made of the polyvinyl chloride resin material and the inorganic material layer, and has good durability. In particular, it is possible to improve the adhesive strength and durability of the polyvinyl chloride resin material substrate, even to metals or metal compounds with low adhesive strength, without deteriorating their functionality.

Therefore, the present invention is useful for providing laminated molded articles having various functions such as excellent conductivity, heat insulation, and/or decorative properties by firmly laminating and bonding various inorganic material layers on a substrate. It is something.

Claims (1)

[Claims] 1. A molded article base made of a polyvinyl chloride resin material;
A polyvinyl chloride crosslinked layer is formed on the surface of the base by subjecting it to low-temperature plasma treatment in an inert inorganic gas atmosphere, and a polyvinyl chloride crosslinked layer is formed on the surface of the crosslinked layer by subjecting it to a low temperature plasma treatment in an inert inorganic gas atmosphere. An inorganic material-polyvinyl chloride resin laminate comprising a polyvinyl chloride modified layer formed by low-temperature plasma treatment and one or more inorganic material layers laminated and bonded on the modified layer. Molded articles. 2. A polyvinyl chloride crosslinked layer is formed by subjecting the surface portion of a molded article base made of a polyvinyl chloride resin material to low-temperature plasma treatment in an inert inorganic gas atmosphere, and the surface portion of the crosslinked layer contains an oxidizing gas. An inorganic material-polyvinyl chloride resin laminated layer comprising forming a polyvinyl chloride modified layer by performing low temperature plasma treatment in an inorganic gas atmosphere, and forming at least one inorganic material layer on the modified layer. Method of manufacturing a molded article.