JP3175658B2 - Vinyl chloride resin molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin molded article. More specifically, the present invention relates to a vinyl chloride resin molded product which prevents surface migration of a plasticizer or the like, prevents contamination of the molded product surface, and has excellent water resistance.

[0002]

2. Description of the Related Art Vinyl chloride resins are relatively inexpensive, are unlikely to undergo chemical changes, and can be varied in properties over a wide range from hard to soft by blending with varying amounts of plasticizer. Therefore, there are many uses for both hard and soft materials such as hard pipes, floor materials, sheets, films, soft vinyl cloths, fibers, wall materials, sheets, films, household goods, and the like.

However, in a vinyl chloride resin molded article containing a plasticizer, after a long time, the plasticizer bleeds out to the surface of the molded article, migrates to other substances, or is extracted into water or a solvent. For example, there is a disadvantage that an undesirable phenomenon is exhibited. For example, when a soft vinyl chloride resin molded product comes into contact with the housing of an electric product such as a television, a video deck, or a personal computer made of a styrene resin such as ABS resin, impact-resistant polystyrene, or general-purpose polystyrene, a plasticizer is applied to the housing. Will migrate. This transition may result in contamination of the housing, resulting in a loss of aesthetics, a significant reduction in commercial value, and in some cases, reduced functionality.

[0004] When a molded article made of a vinyl chloride resin is used outdoors such as a floor material and a wall material and a tent, the plasticizer bleed out to the surface of the molded article is used. It has the disadvantage of being contaminated by dust, and when molded products are used for packaging, the bleed-out plasticizer reduces the printability on the film or adheres by heat sealing. Reduce the strength of the part.

Further, when the molded article is used for applications requiring water resistance, such as a waterproof canvas tent, a simple water tank, a water blocking plate, a water shielding sheet, etc., the plasticizer is washed away by the influence of rainwater, Problems such as whitening of the molded product, brittleness and breakage occur. As a method to solve these problems, the surface of the vinyl chloride resin molded product as shown below,
A method of coating with a specific resin or paint has been proposed. (I) A method of applying an acrylic resin (Japanese Patent Publication No. 46-29639)
(JP-A-50-28117, etc.) (II) A method of applying a fluororesin via an adhesive layer (JP-A-56-86748, JP-A-46-65161, JP-B-57-1)
(III) (III) A method of applying a mixture of a fluororesin and an acrylic resin (JP-A-63-21143, JP-A-46-65161,
JP-B-63-236, etc.)

However, (I) is not enough to prevent bleed out of the plasticizer or the like of the base material to the surface of the molded article, and (II) is due to the effect of the plasticizer or the like migrating to the adhesive layer. However, the adhesion and integration of the fluororesin and the substrate through the adhesive layer was not practically sufficient. As these improvements, (III) has been proposed, but the acrylic resin and the fluororesin are difficult to dissolve, so that the coating is opaque,
There was a disadvantage that the interfacial adhesion between the substrate and the fluororesin mixture was insufficient.

[0007]

Under such circumstances, the present inventors have attempted to prevent contamination of the surface of a molded article of a vinyl chloride resin, have excellent water resistance and durability, and have a substrate and a resin coating. As a result of intensive studies for the purpose of providing a vinyl chloride resin molded article having excellent adhesion, the present invention has been completed.

[0008]

The gist of the present invention resides in that, on the surface of a vinyl chloride resin molded product, 1 to 30% by weight of an alkyl (meth) acrylate monomer represented by the above general formula (I) is added. , Methyl methacrylate 50-
95% by weight, 4 to 30% by weight of a hydroxyalkyl (meth) acrylate monomer, and an α, β-unsaturated carboxylic acid containing one or more carboxyl groups in the molecule.
To 20% by weight, and the balance is mainly composed of two components, an acrylic polymer [A] obtained by copolymerizing another vinyl monomer copolymerizable with these compounds and a vinylidene fluoride resin [B]. The present invention resides in a molded article of a vinyl chloride resin formed with a coating of the composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 1. Vinyl Chloride Resin In the present invention, the vinyl chloride resin refers to not only polyvinyl chloride but also a copolymer containing vinyl chloride as a main component.
Examples of monomer compounds copolymerizable with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylonitrile, maleic acid, itaconic acid, acrylic acid, methacrylic acid, and vinyl acetate. These vinyl chloride resins may be produced by any of conventionally known production methods such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method.

In order to impart flexibility to the vinyl chloride resin serving as the base, 20 to 60 parts by weight of a plasticizer is blended with respect to 100 parts by weight of the resin. By setting the blending amount of the plasticizer in the above range, the desired soft vinyl chloride resin molded article can be imparted with excellent flexibility and mechanical properties. As the plasticizer, for example,
-Phthalic acid derivatives such as octyl phthalate, di-2-ethylhexyl phthalate, dibenzyl phthalate and diisodecyl phthalate; isophthalic acid derivatives such as dioctyl phthalate; adipic acid derivatives such as di-n-butyl adipate and dioctyl adipate; di-n-butyl malate Maleic acid derivatives such as tri-n-butyl citrate; itaconic acid derivatives such as monobutyl itaconate; oleic acid derivatives such as butyl oleate; ricinoleic acid derivatives such as glycerin monoricinoleate; Large oil, epoxy resin plasticizer and the like.

Further, in order to impart flexibility to the resin film, the present invention is not limited to the above-mentioned plasticizers. For example, a thermoplastic polyurethane resin, polyvinyl acetate or the like may be used. In addition to the plasticizer, the vinyl chloride-based resin may contain, if necessary, a known resin additive that is generally blended with a synthetic resin for molding, for example, a lubricant, a heat stabilizer, an antioxidant, and an ultraviolet absorber. Agents, antistatic agents, light stabilizers, surfactants, pigments, dyes, and the like.

Examples of the lubricant include higher fatty acids or metal salts thereof, various paraffins, higher alcohols, natural waxes, polyethylene waxes, fatty acid esters and fatty acid amides. As a heat stabilizer,
For example, calcium stearate, barium stearate, dibasic lead stearate, basic lead sulfite, dibasic lead phosphite, dibutyltin dilaurate, dibutyltin malate, dibutyltin mercaptide, β-diketone compound, or dioctyltin maleate Stabilizer,
And dioctyltin laurate-based stabilizers and dioctyltin mercaptide-based stabilizers.

Examples of the antioxidant include phenol-based, thiodipropionate, aliphatic sulfide and disulfide-based antioxidants. Specifically, 2,6-di-tert-butyl-4 -Methylphenol, 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), dilaurylthiodipropionate, and the like.

Examples of the ultraviolet absorber include benzotriazole, benzoate, benzophenone, cyanoacrylate and phenyl salicylate ultraviolet absorbers. Among them, a benzophenone-based ultraviolet absorber and / or a benzotriazole-based ultraviolet absorber are particularly preferred. Examples of the antistatic agent include polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene alkyl ether, glycerin fatty acid ester, and sorbitan fatty acid ester.

As the light stabilizer, for example, 2,2,6,6
Hindered amine light stabilizers containing tetramethylpiperidine units, and specifically, 4-acetoxy-
2,2,6,6-tetramethylpiperidine, bis (2
Hindered amine compounds such as 2,6,6-tetramethyl-4-piperidyl) adipate and tris (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate Can be

Examples of the surfactant include nonionic surfactants. Specific examples include surfactants such as sorbitan, glycerin and polyethylene glycol, and so-called antifogging agents such as alkylene oxide adducts of alkylphenols. In addition to the surfactant, a fluorine-based surfactant can be used. Specifically, H-bonded to C of a hydrophobic group of a normal surfactant is used.
And a surfactant in which a part or the whole thereof is substituted with F, and particularly a surfactant containing a perfluoroalkyl group or a perfluoroalkenyl group.

Examples of pigments or dyes include inorganic oxides such as titanium oxide, zinc white, lead white, gypsum, precipitated silica, carbon black, red iron, molybdenum red, cadmium yellow, graphite, titanium yellow, chromium oxide green, and ultramarine blue. Pigments: Organic pigments such as Permanent Red 4R, Hansa Yellow 10G, Benzidine Yellow GR, Permanent Carmine FB, Phthalocyanine Blue B, and Phthalocyanine Green.

The above various resin additives can be used alone or in combination of several kinds. The amount of the various resin additives to be added can be selected within a range that does not deteriorate the properties of the film, and usually within a range of 10 parts by weight or less based on 100 parts by weight of the vinyl chloride resin as the substrate. In order to mix a plasticizer and other resin additives with a vinyl chloride resin to obtain a vinyl chloride resin compound composition for molding, weigh each necessary amount, for example, a ribbon blender, a Banbury mixer. A conventionally known compounding machine or mixer such as a super mixer may be used.

By molding a vinyl chloride resin composition,
The shape of the vinyl chloride resin molded article of the present invention is not particularly limited, but a sheet, film, plate, or tubular form is suitable because of the ease of forming the coating. . As these molding methods, usually performed, for example, calender molding method, extrusion molding method,
What is necessary is just to employ | adopt suitably from an inflation molding method, an injection molding method, etc.

2. Coating 2-1. Acrylic polymer [A] The acrylic polymer [A] of the present invention is an alkyl (meth)
Acrylate monomer 1 to 30% by weight, methyl methacrylate 50 to 95% by weight, hydroxyalkyl (meth)
4 to 30% by weight of an acrylate monomer, 0 to 20% by weight of an α, β-unsaturated carboxylic acid containing one or more carboxyl groups in a molecule, and other vinyl compounds whose balance can be copolymerized with these compounds It is a copolymer obtained by copolymerizing a monomer.

The alkyl (meth) acrylate monomer represented by the general formula (I) (alkyl ester of acrylic acid or methacrylic acid (hereinafter the same applies)) includes 2
-Ethylhexyl acrylate, decyl acrylate,
The alkyl group such as lauryl acrylate, myristyl acrylate and palmityl acrylate has 6 to 20 carbon atoms.
And alkyl methacrylates having 6 to 20 carbon atoms in the alkyl group such as 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, myristyl methacrylate, and palmityl methacrylate. These may be used alone or in combination of two or more.

If the amount of the alkyl (meth) acrylate monomer is more than 30% by weight, dust resistance and water resistance are undesirably reduced. If the content of methyl methacrylate is less than 50% by weight, the compatibility with the vinylidene fluoride resin is lowered, which is not preferable. Examples of the hydroxyalkyl (meth) acrylate monomer include hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, and 3-hydroxypropyl acrylate. Hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4
-Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxypentyl acrylate, 2-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate and the like.

When the proportion of the hydroxyalkyl (meth) acrylate in the acrylic resin is less than 4% by weight, the solubility with an organic solvent cannot be sufficiently exhibited, and on the other hand, it is more than 30% by weight. In such a case, the effect obtained is not so great as compared with the cost increase, which is not preferable. Α, which contains one or more carboxyl groups in the molecule
Examples of the β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, aconitic acid, fumaric acid, crotonic acid and the like.

The alkyl (meth) acrylate monomer represented by the above formula (I), methyl methacrylate, hydroxyalkyl (meth) acrylate monomer and other vinyl monomers copolymerizable with α, β-unsaturated carboxylic acid Examples of the body include alkyl acrylates having an alkyl group of 1 to 5 such as methyl acrylate, ethyl acrylate, n-propyl acrylate and isopropyl acrylate; and alkyl chain such as ethyl methacrylate, n-propyl methacrylate and isopropyl methacrylate. Is an alkyl methacrylate of 1 to 5;
Α, β-ethylenically unsaturated phosphonic acids such as ethylenesulfonic acid; hydroxyl-containing vinyl monomers such as hydroxyethyl of acrylic acid or methacrylic acid; acrylonitriles; acrylamides; glycidyl esters of (meth) acrylic acid Etc. These monomers may be used alone or in combination of two or more.

2-2. A predetermined amount of a polymerization monomer of the acrylic polymer [A] is mixed, charged into a polymerization vessel together with an organic solvent, a polymerization initiator and, if necessary, a molecular weight modifier are added, and the mixture is heated and polymerized with stirring. . For the polymerization, generally known methods such as a suspension polymerization method and a solution polymerization method are employed. In this case, examples of the polymerization initiator that can be used include a radical generation catalyst such as α, α-azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, and the like. As the molecular weight regulator, butyl mercaptan, n -Dodecyl mercaptan, tert-dodecyl mercaptan, β-mercaptoethanol and the like.

The organic solvent used for the polymerization includes methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol,
alcohols such as tert-amyl alcohol, n-hexyl alcohol and cyclohexanol; aromatic hydrocarbons such as benzene, toluene and xylene; acetates such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone and methyl-n-propyl Ketone, 2-hexanone,
Ketones such as 3-hexanone, di-n-propyl ketone, and di-n-amyl ketone cyclohexanone; tetrahydrofuran and the like, and these can be used alone or in combination of two or more.

2-3. Vinylidene fluoride resin [B] A vinylidene fluoride resin [B] is a homopolymer of vinylidene fluoride or a copolymer containing no vinylidene fluoride and other fluorine-containing unsaturated monomers and / or fluorine. Copolymers with possible monomers, and polymers in which some of these polymers are modified or modified, are also included. These vinylidene fluoride resins can be used alone or in combination of two or more, and may be used as a mixture with another fluorine-containing resin such as tetrafluoroethylene, chlorotrifluoroethylene, or fluoroethylene. Absent.

2-4. Coating Acrylic polymer [A] and vinylidene fluoride resin [B] were blended in an amount of 5 to 50 parts by weight [A] and 50 [B].
Preferably, it is 95 parts by weight. If the ratio of the polymer [A] to the resin [B] is too small, the adhesion of the formed film to the substrate surface is poor, and the film is easily peeled off, which is not preferable. On the other hand, when the ratio of the polymer [A] to the resin [B] is too large, the effect of preventing migration of a plasticizer or the like of the formed film, stain resistance, and water resistance are not sufficient, which is not preferable.

In the above coating composition, in addition to these components,
Auxiliary components such as antioxidants, neutralizers, ultraviolet absorbers, light stabilizers, antistatic agents, pigments, dyes, foaming agents, lubricants and the like can be added. It can be used after being dispersed and / or dissolved in an organic solvent. Examples of the organic solvent include, for example, heptane and cyclohexane as aliphatic hydrocarbons;
Benzene, toluene, xylene, etc. as aromatic hydrocarbons; methanol, ethanol, isopropyl alcohol, polyoxyethylene glycol, etc. as alcohols: chloroform, tetrachloride hydrocarbon, chlorobenzene, etc. as halogenated hydrocarbons; methyl acetate, allyl as esters Acetate, ethyl stearate, etc .;
Amines such as trimethylamine, diphenylamine,
Hexamethylenediamine, etc .; and dimethylformamide, dimethylacetamide, dioxane, diethyl ether, diethylenedithioglycol, diacetone alcohol, benzonitrile, dimethylsulfoxide, etc., which can be used alone or in combination of two or more. .

In order to form a film on the surface of the vinyl chloride resin molded product, various known methods are applied depending on the shape of the molded product. For example, when forming a film in a solution state, doctor blade coating, gravure roll coating, air knife coating, reverse roll coating, deep coating, curtain roll coating, spray coating,
An application method such as a rod coating method is used.

In the case where the above coating composition is formed as a single coating without being in a solution state, coextrusion, extrusion coating, extrusion lamination, and lamination are used. As a method for forming a film, as a method for drying a solvent in the case of using a coating method, for example, there are an air drying method, a hot air drying method, an infrared drying method, a far infrared drying method, and the like. Hot air drying is advantageous. In this case, the temperature condition is in the range of 50 ° C. to 200 ° C., and the time is preferably selected from 10 seconds to 15 minutes.

When the above resin coating composition is applied to the surface of a vinyl chloride resin molded article to form a coating, the amount of the coating is determined by applying an undercoat, excluding the coating, and drying and solidifying by an application method. Is preferably in the range of 0.1 to 10 g / m ² . When the amount is less than 0.1 g / m ^2, the effect of preventing the plasticizer in the vinyl chloride resin molded product from migrating to the surface is insufficient, and when the amount is 10 g / m ² or more, the coating amount is too large, It is economically disadvantageous, especially when the vinyl chloride resin molded product to be coated is a film-like structure, its mechanical strength may be reduced,
Not preferred. Particularly, a range of 0.5 to 5 g / m ² is preferable.

Before applying the above coating composition, the surface of the vinyl chloride resin molded product is previously washed with alcohol or water, subjected to plasma discharge treatment or corona discharge treatment, or subjected to another paint or primer. May be subjected to a pretreatment such as undercoating.

[0034]

Industrial Applicability The vinyl chloride resin molded article according to the present invention is rich in adhesion between the base film and the coating derived from the coating composition formed on the surface thereof. Since the performance can be maintained at a high level, it is extremely useful as molded articles such as flooring materials, wall materials, desk mats, and covering materials for electric wires.

[0035]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to embodiments, but the present invention is not limited to the following examples unless it exceeds the gist. Examples 1-4, Comparative Examples 1-4

I. Preparation of base film Polyvinyl chloride (average degree of polymerization = 1400) 100 parts by weight Dioctyl phthalate 50 parts by weight Epoxidized soybean oil 3 parts by weight Barium-zinc composite liquid stabilizer 1.5 parts by weight Barium stearate 0.2 parts by weight A resin composition consisting of 0.4 parts by weight of zinc stearate was prepared, mixed and stirred for 10 minutes by a super mixer, and then kneaded on a mill roll heated to 180 ° C. to obtain a base film having a thickness of 0.3 mm. Was adjusted.

II. Preparation of Acrylic Polymer [A] In a reactor equipped with a thermometer, a stirrer, a reflux condenser and a nozzle for adding raw materials, 70 parts by weight of methyl ethyl ketone, 30 parts by weight of toluene, 1.0 part by weight of benzoyl peroxide and 100 parts by weight of the mixture of the monomers shown in the table were charged, and while stirring under a nitrogen gas stream, 0.5 part by weight of benzoyl peroxide was further added at 70 ° C. for 3 hours, and the reaction was carried out for about 3 hours. The acrylic polymer shown in Table 1 was obtained continuously at the same temperature.

[0038]

[Table 1]

III. Acrylic polymer [A] of the type and amount shown in Table 2
And a commercially available vinylidene fluoride resin [B] were added thereto, and methyl ethyl ketone was added thereto to have a solid content of 20% by weight to obtain a coating composition. The coating composition was applied to one surface of the substrate film prepared by the above method using a # 5 bar coater. The applied film was kept in an oven at 130 ° C. for 1 minute to evaporate the solvent. The amount of coating on each of the obtained films was about 3 g /
m ² .

[0040]

[Table 2]

V. Evaluation of Film The performance of the film was evaluated by the following methods, and the results are shown in Table 3. Initial appearance The appearance of the film was visually observed. The evaluation criteria are as follows. A: Colorless and excellent in transparency.・ ・ ・: Somewhat white, but transparent. Δ: White and translucent. X: cloudy and devitrified.

Film Flexibility Each film was cut into a width of 5 cm and a length of 15 cm, and folded back at right angles to the length direction at an interval of 2 cm. In this state, a load of 2 kg was applied from above and left in a thermostat kept at 15 ° C. for 24 hours. Then, the load was removed, the fold of the film was extended, and the appearance of the coating was visually observed. The evaluation criteria in this test are as follows.・ ・ ・: No change was observed in the film at the fold portion. Δ: Cracks are observed in the film at the fold. ×: Cracks are remarkably observed in the film at the fold.

Stain resistance Each of the contaminants was allowed to adhere to the film surface of the film, allowed to stand at room temperature for 24 hours, and the contaminants were wiped off with absorbent cotton, and traces were observed. The evaluation criteria are as follows. A: No trace is observed at all.・ ・ ・: No trace is observed on 2/3 or more of the coating. Δ: Traces are observed in 2/3 or more of the coating. ×: Traces are observed on the entire surface of the coating.

Water Resistance Test A large number of test pieces of 4 cm × 5 cm were prepared and 50
The film was immersed in a water bath maintained at a temperature of 12 ° C., and after 12 hours and 24 hours, several films of each type were taken out and dried, and then the appearance of the film was visually observed. The evaluation criteria in this test are as follows. A: No change in appearance was observed in the coating.・ ・ ・: Whitening was observed in a part of the coating. Δ: Whitening was observed on the entire surface of the coating. ×: Whitening was observed on the entire surface of the film and peeling of the film was partially observed, or the film was completely peeled.

Adhesion evaluation (acceleration test) 300 cc of water (50 ° C.) was placed in a 500 cc beaker, and the beaker was coated with a sample so that the surface on which the coating was formed was inside the beaker. ° C), tilt the beaker 10 degrees off the ground and 2/3 from the bottom
And left in a constant temperature room at 25 ° C. for 5 hours.
Using the obtained film, a cellophane tape was adhered to the surface on which the coating was formed, and when the cellophane tape was peeled off,
The state of peeling of the coating was visually observed. The evaluation criteria are as follows. ◎: The film was completely removed without peeling.・ ・ ・: A part (less than 1/3) of the coating was peeled off. Δ: One-third or more and less than two-thirds of the coating peeled off. ×: Two-thirds of the coating peeled off.

[0046]

[Table 3]

Continuation of the front page (56) References JP-A-10-96198 (JP, A) JP-A-3-124439 (JP, A) JP-A-62-240332 (JP, A) JP-A-62-156951 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (2)

(57) [Claims] 1. An alkyl (meth) acrylate monomer represented by the general formula (I) of 1 to 30% by weight, methyl methacrylate of 50 to 95% by weight, and a hydroxyalkyl (meth) acrylate monomer 4 on a surface of a vinyl chloride resin molded product. Α, β-unsaturated carboxylic acid containing one or two or more carboxyl groups in the molecule
The main components are two components of an acrylic polymer [A] and a vinylidene fluoride resin [B] obtained by copolymerizing another vinyl monomer copolymerizable with these compounds, with the balance being the weight%. A molded article of a vinyl chloride resin formed with a coating of the composition. Embedded image (In the formula, R ¹ represents a hydrogen or methyl group, and n represents an integer of 6 to 20.) 2. The vinyl chloride resin molded article according to claim 1, wherein the component [A] is 5 to 50 parts by weight and the component [B] is 50 to 95 parts by weight.