JPH024618B2 - - Google Patents

Description

[Detailed description of the invention]

This invention aims to produce a polyvinyl chloride sheet containing a metal pigment that has excellent metallic luster, is clear, has little detachment of the metal pigment from the sheet, and has little transfer of the metal pigment to a molding machine, etc. This relates to a manufacturing method. Conventionally, metal pigments have been widely used as pigments for kneading into polyvinyl chloride sheets. However, with conventional metal pigments, the metal pigment particles are made fine by the high shearing force applied when blending them with polyvinyl chloride, and the hydrogen chloride generated from the polyvinyl chloride due to heat and light is It acts on the surface, causing discoloration or blackening, and loss of metallic luster and clarity.Also, since polyvinyl chloride and metal pigments have poor affinity, during processing and molding,
It is often observed that metal pigments adhere to metal surfaces of molding machines and the like (for example, plate-out onto rolls), and that metal pigments desorb from surfaces after sheet formation. Therefore, in order to suppress the discoloration of metal pigments, titanium oxide etc. are added (for example, JP 54-138048), and stabilizers are added to prevent the transfer of metal pigments to the metal roll surface of molding machines. Many attempts have been made to improve this by adding metal pigments, reducing the amount of metal pigments added, or adjusting working conditions such as temperature, but these results in a decrease in the sharpness and metallic feel of the sheet, or completely prevent plate-out. Because of this, it is necessary to stop the machine and clean the roll surface, and it is also necessary to apply an overcoat to prevent the metal pigment from detaching from the sheet surface. A product with excellent kneading of metal pigments into a sheet has not yet been obtained. This invention was made to overcome these conventional problems, and it is a polyvinyl chloride resin containing a compound A having a polymerizable double bond and at least one epoxy group. A metal pigment-containing polyvinyl chloride sheet is produced by adding a metal pigment whose surface is coated with a polymer B produced by reacting, mixing and melting, and then molding the melt. The present invention provides a method. The vinyl chloride resin used in this invention is a polyvinyl chloride homopolymer, vinylidene chloride, ethylene, propylene, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, vinyl ether, vinyl ester, maleic anhydride, etc., and vinyl chloride. Binary or ternary copolymers of , ethylene vinyl acetate copolymers, chlorinated polyethylene, etc. and vinyl chloride graft copolymers, etc. can be mentioned, and examples of the above acrylic esters include methyl acrylate, acrylic acid Ethyl etc. as methacrylic ester,
Methyl methacrylate, ethyl methacrylate, etc.
Examples of the vinyl ether include vinyl isobutyl ether, and examples of the vinyl ester include vinyl acetate and vinyl caproate. Further, mixed polymers of such polyvinyl chloride resins and epoxy resins, acrylic resins, polyolefin resins, etc. can also be used for this invention. Next, the metal pigments in this invention are aluminum, copper, zinc, iron, nickel, and alloys thereof, and the shape of these pigments is usually flaky, but is not particularly limited to this. Furthermore, examples of the compound A having a polymerizable double bond and at least one epoxy group include epoxidized polybutadiene, glycidyl acrylate, glycidyl methacrylate, cyclohexene vinyl monoxide, divinylbenzene monoxide, etc. Of course, it is also possible to form a copolymer by using a mixture with other polymerizable monomers. Here, examples of the polymerizable monomer include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylnitrile,
Vinyl acetate, vinyl propionate, acrylic acid,
There are acrylic esters, methacrylic acid, methacrylic esters, crotonic acid, itaconic acid, citraconic acid, oleic acid, maleic acid, maleic anhydride, divinylbenzene, etc. Acrylic esters include methyl acrylate, ethyl acrylate, n-Butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, cyclohexyl acrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, etc., and methacrylic acid esters include methyl methacrylate, ethyl methacrylate,
n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, hydroxyethyl methacrylate,
Hydroxypropyl methacrylate, methoxyethyl methacrylate, butoxyethyl methacrylate,
Examples include cyclohexyl methacrylate. Polymer B coating the metal pigment in this invention
The amount of is 1 per 100 parts by weight of the metal content of the metal pigment.
~15 parts by weight, preferably 5 to 10 parts by weight.
This is because if the amount is less than 1 part by weight, the desired effect of the present invention cannot be obtained, while if it exceeds 15 parts by weight, the cost will only increase and no particular improvement in performance will be observed. The method for coating a metal pigment with a polymer B of the compound A is to coat the compound A in the presence of a polymerization initiator in an organic solvent in which the compound A is soluble and the polymer B is substantially insoluble. The surface of the metal pigment is coated by reaction polymerization, and organic solvents include aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, and mineral spirits, and aromatic substances such as benzene, toluene, and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, trichlorobenzene, perchlorethylene, trichlorethylene, alcohols such as methanol, ethanol, n-propyl alcohol, n-butanol, 2-propanone, 2-butanone Ketones such as ethyl acetate, esters such as propyl acetate, tetrahydrofuran, diethyl ether, ethyl propyl ether, etc., and polymerization initiators include di-t-butyl peroxide, acetyl peroxide, benzoyl peroxide. , lauroyl peroxide, cumyl hydroperoxide, t-butyl hydroperoxide and other organic peroxides, and azo compounds such as α-α'-azobisisobutyronitrile. The polymerization reaction temperature is preferably in the range of 60 to 200℃,
Temperatures lower or higher than this are not preferred because the polymerization time becomes longer or the efficiency of the polymerization initiator decreases. Note that in order to increase the polymerization efficiency, the polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen, helium, or argon. The resin-coated metal pigment thus obtained is
To add it to polyvinyl chloride resin, it can be added in the form of a paste containing a solvent, in a powder form without a solvent, in a paste form mixed with wax, fatty acid metal soap, plasticizer, etc., or in the form of a resin powder or pellet. It is conceivable to melt and mix metal pigments, plasticizers, stabilizers, etc. to form a master batch (pellet or sheet form), and then add the appropriate amount of plasticizer, reinforcing agent, filler, etc. Stabilizers, colorants, antistatic agents, antioxidants, etc. can also be added and mixed. Here, in order to mix and melt these mixtures, a conventional ribbon mixer, kneader, Henschel mixer, super mixer, two-roll mixer, Banbury mixer, Alternatively, an extruder etc. may be used, and in order to further shape the melt, in addition to calendering, T
Extrusion processing using a die or a round die, etc. can be used. The amount of the metal pigment added to the polyvinyl chloride resin is usually 1 to 10 parts by weight per 100 parts by weight of the polyvinyl chloride resin.
In this way, the polyvinyl chloride sheet coated with polymer B and kneaded with metal pigment has superior metallic luster compared to conventional products, is clear without discoloration or blackening, and has excellent gloss on the sheet surface. It was extremely excellent, with little color unevenness, almost no transfer of metal pigment to the processing and molding machine, and little falling off of the metal pigment from the sheet surface. Examples and comparative examples are shown below. [Example 1] In a 2-four neck flask, 2.0 g of epoxidized polybutadiene, 3.0 g of 1,6-hexanediol diacrylate, 0.8 g of acrylic acid, 1000 g of mineral spirits, and Alpaste (registered trademark)
(Aluminum paste manufactured by Toyo Aluminum Co., Ltd.:
MG-1000, metal content 71.0%) was added, and the mixture was stirred and mixed while introducing nitrogen gas. temperature in the system
The temperature was raised to 80°C, 1 g of α-α'-azobisisobutyronitrile was added, and the mixture was reacted at 80°C for 6 hours. After the reaction was completed, the mixed solution was filtered and concentrated to obtain a resin-coated aluminum paste. Analysis of this revealed that the resin-coated aluminum content was 65%, and the resin-coated aluminum paste was washed and filtered with n-hexane, powdered, and mixed acid (hydrochloric acid: nitric acid: water =
When the aluminum content was dissolved in a ratio of 1:1:2), the remaining resin content was filtered, dried and weighed, it was found that 1.2 parts by weight of the polymer was coated on 100 parts by weight of aluminum. Ta. [Example 2] Into a four-necked flask, 3.6 g of epoxidized polybutadiene, 5.3 g of 1,6-hexanediol diacrylate, 1.5 g of acrylic acid, 1000 g of mineral spirits, and aluminum paste (as described in Example 1) were added. ) 250g, and hereafter Example 1
A resin-coated aluminum paste was obtained in the same manner.
As a result of the same analysis, the resin-coated aluminum content was 63%, and the amount of resin coated was 63%.
The amount was 3.3 parts by weight per 100 parts by weight. [Example 3] In a four-necked flask, 6.5 g of glycidyl methacrylate, 9.5 g of 1,6-hexanediol diacrylate, 2.5 g of acrylic acid, 1000 g of mineral spirits, and aluminum paste (as described in Example 1) were added. Add 250g, and hereafter Example 1
A resin-coated aluminum paste was obtained in the same manner.
As a result of the same analysis, the resin-coated aluminum content was 59%, and the amount of resin coated was aluminum.
The amount was 7.5 parts by weight per 100 parts by weight. [Comparative Example 1] In a four-necked flask, 1.3 g of epoxidized polybutadiene, 2.2 g of 1,6-hexanediol diacrylate, 0.8 g of acrylic acid, 1000 g of mineral spirits, and aluminum paste (the one described in Example 1) were added. ) 250g, and hereafter Example 1
A resin-coated aluminum paste was obtained in the same manner.
As a result of the same analysis, the resin-coated aluminum content was 72.0%, and the amount of resin coated was 72.0%.
The amount was 0.7 parts by weight per 100 parts by weight. [Example 4] The resin-coated aluminum pastes obtained in Examples 1 to 3 and Comparative Example 1, and the untreated ALPASTE [registered trademark] (aluminum paste manufactured by Toyo Aluminum Co., Ltd.: MG-
1000, metal content 71.0%), 100 parts by weight of polyvinyl chloride (Nippon Zeon Co., Ltd.: Zeon 103EP), DOP48
Parts by weight, 2 parts by weight of epoxidized soybean oil, Barium-
To 100 parts by weight of a composition containing 2 parts by weight of a zinc-based stabilizer, add so that the metal content is 2.5 parts by weight,
The mixture was kneaded for 5 minutes using two rolls to form a kneaded sheet with a thickness of about 1 mm. After making the kneaded sheet in this way, the two rolls were subsequently used to prepare the plate-out test formulation, namely 100 parts by weight of polyvinyl chloride;
A composition containing 50 parts by weight of DOP, 1 part by weight of epoxidized soybean oil, and 1 part by weight of cadmium stearate stabilizer was kneaded at 165°C for 5 minutes to transfer and incorporate the metal pigments attached to the roll surface. A sheet was prepared. The color, gloss, plateout, pigment desorption phenomenon, etc. of the obtained sheet were observed, and the results are summarized in the table.

[Table] Note: “Slightly” in the table means that there is no problem in practical use.

Claims (1)

[Claims] 1 100 parts by weight of polyvinyl chloride resin, metal pigment
has a polymerizable double bond per 100 parts by weight, and
After adding 1 to 10 parts by weight of a metal pigment whose surface is coated with 1 to 15 parts by weight of a polymer produced by reacting a compound having at least one epoxy group, mixing and melting, the melt is shaped. 1. A method for producing a polyvinyl chloride sheet containing a metal pigment, characterized in that it is processed.