JPH0343341B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a metal vapor deposition method for vinyl chloride resin products, and more specifically, a cured film layer of a cationic polymerizable resin composition that is cured by energy ray irradiation is provided on the surface of a vinyl chloride resin product. , which is characterized by applying metal vapor deposition thereon.

Taking advantage of the advantages of plastic, such as high productivity, excellent moldability, and light weight, metal processing has been applied to the surface of various plastic base materials to produce gold and silver thread, capacitors, insulation materials, and decorations. It is used in fields such as products, packaging materials, and reflective materials.
Examples of the method include a plating method, a hot stamping method, a vacuum evaporation method, a sputtering method, and an ion brating method. Among these, vacuum evaporation method,
The sputtering method is starting to attract attention as a low-cost and simple method that does not have the problem of waste liquid treatment. Polyester materials have a somewhat strong adhesion force with metals when vapor-deposited, so they are widely used in the film and sheet field, but metals can be vapor-deposited on plastic materials such as polyethylene, polypropylene, polystyrene, and hard polyvinyl chloride. Adhesion is weak, and metal vapor deposition is generally performed after applying a base coat.

Conventionally, vinyl chloride resin has been used for a wide range of purposes by being processed into hard, semi-hard, or soft products such as films, sheets, flat plates, molded products, and irregularly shaped products, but there are various problems with metal vapor deposition processing. There is a point. In particular, when attempting to perform metal vapor deposition on plasticized vinyl chloride resin products (films, sheets, molded products, etc.) obtained by blending plasticizers such as DOP with polyvinyl chloride, volatilization due to plasticizer bleed may occur. However, since the degree of vacuum did not reach the low level required for vapor deposition, the vapor deposited layer did not come into close contact with the substrate, making it impossible to industrially produce the desired metal vapor deposited product. For example, films made from plasticized vinyl chloride resin are widely used for various purposes because they have excellent processability such as high-frequency welding and fusing, and post-processability such as printing suitability. There is no known flexible metallized film product with excellent properties. This is because volatile substances such as plasticizers contained in the vinyl chloride film base material volatilize in vacuum, making it difficult to obtain a sufficiently high degree of vacuum and making it difficult to form a deposited film with good gloss. This is because sufficient adhesion with the film cannot be obtained, and in particular, a decrease in adhesion strength due to migration of the plasticizer after vapor deposition becomes a problem. Furthermore, as a pretreatment for metal vapor deposition on plastic substrates, etc., there is a method of applying an undercoat (base coat) for the purpose of improving vapor deposition suitability and adhesion of vapor-deposited metals. At present, it has not been possible to obtain a base coat with excellent performance as a base coat for metal deposition of soft vinyl chloride resin products obtained by blending.

However, in view of the above-mentioned circumstances, the present invention was completed as a result of extensive research into metal vapor deposition methods for vinyl chloride resin products, particularly vinyl chloride resin products containing plasticizers.

The purpose of the present invention is to provide a cured film layer (base coat layer) of a cationic polymerizable resin composition that is cured by energy ray irradiation on the surface of a base material of a vinyl chloride resin product, and to perform metal vapor deposition on the surface of the film layer. Therefore, we provide a method for manufacturing a metal-deposited vinyl chloride resin product that has excellent adhesion between the base material and the deposited film, and excellent metal deposition properties, smoothness, and durability by preventing the release of volatile substances contained in the base material. It's about doing.

Furthermore, the object of the present invention is to provide a cured coating layer of a cationic polymerizable resin composition that is cured by energy ray irradiation on the surface of a base material of a vinyl chloride resin product, and to perform metal vapor deposition on the surface of the coating layer. The object of the present invention is to provide a metal-deposited vinyl chloride resin product that has excellent adhesion between the base material and the deposited film, metal deposition properties, smoothness, durability, and the like.

The present invention will be explained in more detail below.

In other words, the method of the present invention involves converting an energy beam-curable cationically polymerizable resin composition containing a compound that releases an active catalyst that initiates polymerization of the cationically polymerizable resin upon energy beam irradiation into a plasticized vinyl chloride resin containing a plasticizer. The resin composition is applied to the surface of the product and then irradiated with energy rays to cure and dry the resin composition to form a cured film layer on the surface of the vinyl chloride resin product. Next, the desired metal is heated and evaporated in a deposition tank maintained at 10 ^-2 to ^{10 -5} Torr.
This is easily achieved by condensing the metal vapor onto the cured coating layer of the vinyl chloride resin product to form a thin metal film layer approximately 200-5000 Å thick.
In the present invention, a top coat of a cationically polymerizable resin composition is further applied on the vapor deposited film, thereby protecting the metal vapor deposition film and improving its weather resistance.

The energy ray-curable cationic polymerizable resin composition used in the present invention can be cured and dried by extremely short energy ray irradiation, so it can be used for vinyl chloride resin products with weak heat resistance and solvent resistance, especially soft vinyl chloride resin. It enables continuous coating on products, has strong adhesion to the substrate surface and metal layer, and provides excellent vapor deposition suitability.

First, the energy ray-curable cationically polymerizable resin composition used in the present invention is a substance that initiates cationic polymerization upon irradiation with energy rays, which is polymerized or crosslinked to form a coating film when irradiated with energy rays. A cationic polymerizable resin composition containing a compound (photopolymerization initiator) that releases , for example, an epoxy resin composition that is polymerized by cationic ring-opening polymerization of an epoxy ring, cyclic ethers, lactones, vinyl compounds, etc. Cationically polymerizable compositions (for example, those described in Japanese Patent Publication No. 49-17040, as well as several other catalysts such as photosensitive onium salts described in Japanese Patent Publication No. 52-14278, etc.) are known. (However, some of them generate Lewis acids when irradiated with energy rays such as ultraviolet rays.) Among these, epoxy resin compositions that are polymerized by cationic ring-opening polymerization of epoxy rings are preferred.

Epoxy resins used in such epoxy resin compositions include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Here, preferred aromatic epoxy resins are polyglycidyl ethers of polyhydric phenols or their alkylene oxide adducts having at least one aromatic nucleus, such as bisphenol A or its alkylene oxide adducts and epichlorohydrin. Examples include glycidyl ether and epoxy novolac resin produced by the reaction of Preferred alicyclic epoxy resins include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, or compounds containing cyclohexene or cyclopentene rings, which are epoxidized with an appropriate oxidizing agent such as hydrogen peroxide or peracid. There are cyclohexene oxide- or cyclopentene oxide-containing compounds that can be obtained. Typical examples of polyglycidyl ethers include glycidyl ethers produced by reacting hydrogenated bisphenol A or its alkylene oxide adduct with epichlorohydrin. Further, representative examples of cyclohexene oxide or cyclopentene oxide-containing compounds include those represented by the following formula.

Preferred aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, and homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate. Typical examples include diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, and polypropylene glycol. Polyglycidyl ether of polyether polyol obtained by adding one or more alkylene oxides (ethylene oxide, propylene oxide) to aliphatic polyhydric alcohol such as diglycidyl ether, ethylene glycol, propylene glycol, and glycerin. , diglycidyl esters of aliphatic long chain dibasic acids. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenols, cresols, butylphenols, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to these, glycidyl esters of higher fatty acids, etc. may be blended as diluents. can.

The epoxy resin composition used in the present invention can contain these aromatic epoxy resins, alicyclic epoxy resins, or aliphatic epoxy resins alone or in a wide variety of combinations depending on the desired performance. Particularly preferable epoxy resin compositions from the viewpoint of adhesion to substrates and vapor deposition suitability are those mainly composed of alicyclic epoxy resins, and alicyclic epoxy resins having an epoxy group on the alicyclic ring [e.g. 3,4-epoxycyclohexylmethyl-3,4
-epoxycyclohexylcarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate] is preferably in the range of 10 to 95% by weight, more preferably 40 to 90% by weight.

In addition, the epoxy equivalent of the alicyclic epoxy resin that can be used is not particularly strictly limited, and can be selected from a wide range, but generally
Epoxy-based cationic polymerizable resin compositions mainly composed of alicyclic epoxy resins having an epoxy equivalent within the range of 70 to 250 are effective from the viewpoint of preventing gases released from volatile substances in the base material and adhesion of deposited metals. Particularly preferred.

In addition, as a constituent component of the cationically polymerizable resin composition used in the present invention, cationically polymerizable compounds such as cyclic ethers, vinyl ethers, lactones, and vinyl compounds may be used as a main component, or in combination, in addition to the above-mentioned epoxy resins. You can also do it. In addition, the cationic polymerizable resin composition of the present invention may include olefin resins and acrylic resins other than the above-mentioned cationically polymerizable substances in order to improve the properties of paints or coatings, as long as the effects of the present invention are not impaired. , ester resin, petroleum resin, alkyd resin, polyether compound, polyether polyol compound, vinyl acetate resin, vinyl chloride resin, butyral resin, rubber resin, vinyl alcohol resin, acid anhydride resin Epoxy resin curing agents, pigments, dyes, various paint additives, etc. can be mixed and used.

On the other hand, the compound (photopolymerization initiator) that releases a substance that initiates polymerization or crosslinking of the cationic polymerizable resin when irradiated with energy rays, which is contained in the cationic polymerizable resin composition used in the present invention, is not particularly limited. Particularly preferred are the group of double salts, which are onium salts that release Lewis acids capable of initiating polymerization upon irradiation. Such compounds basically have the general formula [R ¹ _a R ² _b R ³ _c R ⁴ _d Z] ^+m [MX _o+n ] ^-
m [In the formula, the cation is onium, Z is N≡N,
S, Se, Te, P, As, Sb, Bi, O, halogen (for example I, Br, Cl), R ¹ , R ² , R ³ ,
R ⁴ is an organic group which may be the same or different. a, b, c, and d are each integers of 0 to 3, and a+b+c+d is equal to the valence of Z. M is a metal or metalloid that is the central atom of the halide complex, and B, P, As, Sb, Fe,
Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr,
Mn, Co, etc. X is a halogen, m is the net charge of the halide complex ion, and n is the number of halogen atoms in the halide complex ion. ].

Such catalyst precursors are known per se,
For example, compounds where z is N≡N are
It is described in No. 3708296, No. 3949143, No. 3794576, etc. Other onium catalyst precursors are described in Belgian Patent No. 828841, Belgian Patent No. 828669, French Patent No. 2270269, US Patent No. 4,139,655, etc.

The above diazonium compounds are described in the above US patents.
It can be obtained by the method described in No. 3708296, No. 3949143, etc. Compounds where Z is S, Se, Te, J. Knapozyk et al., JACS, 91 , 145
(1969), AL Maycock et al. J. Organic
Chemistry, 35 , No. 82532 (1970), Goethals et al.
Bul.Soc.Chim.Belg., 73 , 546 (1964), HM
It can be produced by the method described in Leicestar et al., JACS, 51 , 3587 (1929). Z is P, N, As,
Representative onium salts such as Sb and Bi are J.Goerdeler
Methoden der Organishen Chimie, 11/12,
591-640 (1958), K. Sasse, 12/1 , 79-112
(1963). A typical onium salt where Z is halogen is OAPtitsyna
Dokl.Adad.Nauk., SSSR, 163 , 383.
(1965), M. Drexler et al. JACS, 75 , 2705
(1953) and others. Furthermore, the onium salts referred to herein include pyrylium salts such as thiopyrylium described in U.S. Patent No. 4139655, and oxonium salts such as aryloxysulfoxonium salts described in JP-A-56-8428. It will be done.

Examples of other compounds that can be used to initiate the polymerization of epoxides are iodoform, α,α-dibromoparaxylene, bromoform, carbon tetrabromide, hexachloroparaxylene, and others described in U.S. Pat. No. 3,895,954. These are catalysts, bis(perfluoroalkylsulfonyl)methane salts, and organic halogen compounds such as diazonium salts of sulfonylmethane as described in US Pat. No. 3,586,616, German Patent No. 2,419,274, and the like.

Furthermore, as proposed in U.S. Pat. No. 4,156,035, the cationic polymerizable resin composition used in the present invention may be blended with an acrylate or methacrylate compound and a carbonyl photosensitizer to improve coating film performance and curing properties. It is also possible to improve.

The above-mentioned cationic polymerizable resin composition can be applied to the surface of the base material of a vinyl chloride resin product using conventionally known methods such as a roll coater, a gravure coater,
It can be applied by coating methods such as gravure offset, flow coating, screen printing, spraying and dipping methods. At that time, in order to improve paintability and adhesion to the base material, the surface of the base material must be pretreated with alcohol treatment, corona discharge treatment, etc. before application, or within the range where there are no adverse effects such as a decline in performance. An organic solvent can be added to the resin composition for coating. The thickness of the cured film is not critical and can vary widely depending on the type of metal to be deposited, the type of PVC resin substrate, etc., but in general
A range of about 0.5 to 30μ is appropriate, preferably 1 to 30μ.
It can be about 10μ. Energy rays for applying the cationically polymerizable resin composition of the present invention to the base material of vinyl chloride resin products to form a cured film include ultraviolet rays, electron beams, and radiation. This is a preferable method from a practical point of view. Furthermore, the formation of a cured film using the cationic polymerizable resin composition can be performed by applying heat treatment to the base material or while applying the heat treatment, or by applying heat treatment and energy ray irradiation after applying the resin composition to the base material. It can be promoted even more effectively by using them together.

Next, metal vapor deposition on the surface of the vinyl chloride resin product provided with the cured film layer of the cationic polymerizable resin composition is performed using a conventionally known method such as a resistance heating method, an electron beam heating method, a high frequency induction heating method, etc. This can be carried out by a method such as a vapor deposition method, a sputtering method, or an ion plating method. Metals or metal compounds that can be deposited include iron, silicon, aluminum, tin, selenium, germanium, antimony, lead, chromium, nickel,
Single metals such as bismuth, gold, silver, platinum, palladium, copper, indium, arsenic, tellurium, cadmium, magnesium, zinc, manganese, gallium, beryllium, cobalt, mixtures of these metals, or at least one of these metals Examples include alloys containing these metals, or compounds containing these metals, such as oxides.

The degree of vacuum during vapor deposition can be varied over a wide range depending on the type of metal or metal compound used, the vapor deposition method, and the like. The thickness of the vapor-deposited metal or metal compound is also not critical, and can be varied widely depending on the type of metal or metal compound, the required performance of the final product, etc., but it is generally 150 to 5000 Å. , preferably 250~
A suitable range is 3000 Å, more preferably 400 to 1500 Å.

The vapor deposited film formed on the vinyl chloride resin product provided with the cured film layer in this way is firmly attached to the base material via the undercoat cured film layer, and during vapor deposition, it is not contained in the base material. It was not susceptible to the effects of volatile substances such as plasticizers and had extremely excellent gloss, and no phenomenon such as a decrease in adhesion of the deposited metal due to migration of the plasticizer after deposition was observed. Depending on the intended use of vapor-deposited vinyl chloride resin products, they can be used as is without further treatment, but usually a top coat is applied to the vapor-deposited film or laminated to protect the vapor-deposited film. Do this. The top coat can be selected from among many known paints depending on the required physical properties of the final product, but for vinyl chloride resin products that are unsuitable for high-temperature treatment, coats with high adhesion to vapor-deposited metals, weather resistance, etc. An energy beam-curable cationic polymerizable resin composition that has excellent physical properties and fast curing is preferred.

Furthermore, the base coat, intermediate paint and top coat used in the metal vapor deposition method of the present invention may be colored by adding dyes or pigments, and the metal vapor deposited products obtained by the method of the present invention may be embossed, laminated or printed. It is also possible to perform post-processing such as machining.

Examples of vinyl chloride resin base materials that can be used in the present invention include polyvinyl chloride, vinyl chloride and ethylene, vinyl acetate, vinylidene chloride, acrylonitrile,
Examples include plasticized vinyl chloride resins containing plasticizers obtained by copolymers and graft polymers with propylene, maleic esters, etc. alone or in combination. Furthermore, in the vinyl chloride resin base material containing a plasticizer, a plasticizer having low volatility and retention property is particularly preferable.

Specific examples of vinyl chloride resin products to which the present invention can be applied include vinyl chloride film sheets, vinyl chloride boards, vinyl chloride synthetic leather, vinyl chloride flooring,
The method of the present invention can be applied to the metallization of all plasticized vinyl chloride resin products containing plasticizers, including vinyl chloride extrusions and molded products, vinyl chloride irregular products, and the like.

More specific fields of application of vinyl chloride resin products to which the present invention can be applied include vinyl chloride films and sheets for miscellaneous goods and decoration (furoshiki, shower curtains, tablecloths, raincoats, toys, maps, stickers, stickers, labels, Gold and silver thread, adhesive tape, desk mat, display, projection, playing cards, cards, bags, pencil cases, covers, covers, footwear, bands, shoes, hats, artificial flowers, malls, handicrafts, sequins, wrapping strings, ribbons, advertising (for printed matter, stamping foil, etc.), agricultural vinyl chloride film sheets (for hotbeds, gardening greenhouses, tunnels, mulching, shading, insect prevention, heat retention, etc.), vinyl chloride film sheets for food packaging containers (jams, butter, frozen desserts, etc.) For Western confectionery, delicacy tsukudani, pickled cups, margarine, tofu, egg packets, fruit packets, food packets, cap stickers,
For gaskets, stretch, shrink, etc.)
PVC film and sheets for non-food packaging (lightweight containers, seedling containers, cosmetics, stationery, toys, furniture, pharmaceuticals, etc.), PVC film and sheets for building materials and furniture
Sheets (mats, carpets, wall materials, ceiling materials,
Decorative plywood, furniture, insulation materials, reflective materials, light shielding materials, laminated steel plates, etc.), vinyl chloride film for lamination,
Sheets (PVC steel plates, special plywood, credit cards, food packaging, paper processing, etc.), PVC leather (chair upholstery, vehicle seats, bags, quilting, etc.)
Beds, cushion surface materials, wall covering materials, interior decoration materials, furniture surface materials, carpets, shoes, sandals, chemical shoes, hats, raincoats,
Reflective sheets, ceiling materials, vinyl flooring, table mats, accordion doors, stationery, tarpaulins, etc.), industrial vinyl chloride plates (tanks, baskets, etc.), electrical and communication vinyl chloride plates (instrument panels, electric refrigerators, etc.) (for parts, electric washing machines, etc.), PVC boards for construction and vehicles (for roofs, wainscoting, ceilings, rain gutters, insulation materials, arcades, terraces, curtains, blinds, slats, heat reflectors, tiles, decorative boards, etc.) ,
PVC boards for miscellaneous goods (stationery, fluorescent lanterns, sinks, etc.), other PVC boards (toys, laminates, advertising signs, signboards, etc.), corrugated PVC boards for housing, corrugated PVC boards for agriculture (greenhouses) , light shielding, etc.), PVC pipes and fittings (for water supply, building materials, electric wires, agriculture, etc.)
(for industrial use, gas use, interior design, etc.), PVC shaped products and molded products (for rain gutters, decking materials, ceiling materials, wall materials, furniture, miscellaneous goods, containers, lids, etc.), PVC extruded products (hoses, tubes, etc.) etc.), vinyl chloride flooring materials (tiles, sheets, cushion floors, pine, etc.)
Examples include.

The metal vapor deposition method of the present invention is useful for semi-rigid and soft vinyl chloride resin base materials containing plasticizers, especially for films and sheet products for which conventional metal vapor deposition is industrially difficult. The present invention provides a method. Note that the method of the present invention can also be applied to other metallization processing methods for vinyl chloride resin base materials, such as chemical plating, electroplating, electroless plating, and the like.

Hereinafter, typical examples of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In the examples, "parts" means parts by weight.

Example 1 3,4-epoxycyclohexylmethyl-3,
60 parts of 4-epoxycyclohexylcarboxylate (epoxy equivalent: 131-143), bis(3,4-
20 parts of epoxycyclohexylmethyl) adipate (epoxy equivalent: 180-200), 1,4-butanediol diglycidyl ether (epoxy equivalent: 125-200)
143) Cationic polymerizable resin composition (epoxy equivalent: 152) consisting of 20 parts, 1 part of silicone surfactant, and 3 parts of photopolymerization initiator PP-33 (manufactured by Asahi Denka Kogyo)
was applied to the surface of a 100μ thick soft vinyl chloride film (plasticizer content: 40 parts per 100 parts of polyvinyl chloride) using a gravure coater to a thickness of about 4μ, and UV curing was performed in the same manner as in Example 2. After heating, aluminum metal was vacuum evaporated under conditions of evaporation temperature of 1400° C., evaporation speed of 90 m/min, degree of vacuum of 1×10 ⁻⁴ Torr, and distance of 30 cm between the evaporation source and the film. The aluminum vapor-deposited film thus obtained exhibited excellent metallic luster and adhesion of the vapor-deposited film.

In addition, a cationically polymerizable UV-curable paint (manufactured by Asahi Denka Kogyo, product name AD-7200) is applied to a thickness of 6μ as a top coat on this vapor-deposited film. A vinyl chloride film product was obtained. On the other hand, when this aluminum evaporated film was superimposed on a 200 μm thick polyvinyl chloride film and subjected to high frequency welding, the high frequency processability was good.

Comparative Example 1 When aluminum was directly deposited on the surface of the same soft vinyl chloride film as used in Example 1 without providing a cured film layer of the cationic polymerizable resin composition, a shiny mirror surface was not formed. , and showed no adhesion of the deposited metal to the substrate.

Comparative Example 2 50 parts of diacrylate compound of bisphenol A diglycidyl ether (epoxy equivalent: 190), 30 parts of trimethylolpropane triacrylate,
20 parts of 1,6-hexanediol diacrylate,
A radically polymerizable ultraviolet curable resin composition containing 0.2 parts of a silicone surfactant and 2 parts of benzophenone was obtained.

This is made into a 100μ thick soft vinyl chloride film (contains 40 parts of plasticizer per 100 parts of polyvinyl chloride).
It was applied to the surface to a film thickness of 5μ and exposed under a high-pressure mercury lamp (80w/cm, 4kw) installed at a height of 10cm.
A cured film was obtained by irradiating ultraviolet light at a rate of m/min.

Vacuum deposition was performed on the surface of the soft vinyl chloride film having this coating layer in the same manner as in Example 3, but a glossy mirror surface was not formed and cracks were observed on the surface. Adhesion was poor.

Claims (1)

[Scope of Claims] 1. A compound that releases a substance that initiates cationic polymerization upon irradiation with energy rays and a cationic polymerizable resin that initiates cationic polymerization with the compound is applied to the surface of a plasticized vinyl chloride resin product containing a plasticizer. providing a cured coating layer of a cationic polymerizable resin composition that is cured by energy ray irradiation,
A method for metal vapor deposition of a plasticized vinyl chloride resin product containing a plasticizer, which comprises performing metal vapor deposition on the surface of the coating layer, and further applying a top coat of a cationic polymerizable resin composition on the vapor deposited film. 2. The plasticizer according to claim 1, wherein the cationic polymerizable resin composition contains 10 to 95% by weight of an alicyclic epoxy resin having an epoxy group on an alicyclic ring as an essential component. A metal vapor deposition method for plasticized vinyl chloride resin products containing. 3. Claim 1 or 2, characterized in that the cationically polymerizable resin composition contains 40 to 90% by weight of an alicyclic epoxy resin having an epoxy group on an alicyclic ring as an essential component. A metal vapor deposition method for plasticized vinyl chloride resin products containing a plasticizer. 4. Contains the plasticizer according to claim 2 or 3, characterized in that the epoxy equivalent of the alicyclic epoxy resin having an epoxy group on the alicyclic ring is within the range of 70 to 250. A metal vapor deposition method for plasticized vinyl chloride resin products.