JPS62953B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a synthetic resin composition containing a blowing agent, in particular, a polyvinyl chloride resin composition. The present invention relates to an ink composition for forming an ink composition. Conventionally, in order to obtain synthetic resin products with uneven surfaces, an ink composition containing an agent that suppresses or accelerates the decomposition of the foaming agent (hereinafter referred to as a foaming inhibitor) is printed on a foaming resin composition containing a foaming agent. Then, the method of heating and foaming (for example, the method of
No. 28636) has been widely awarded. However, in this method, depending on the type of foam suppressor, the applied area of the ink composition may be significantly discolored or colored, resulting in poor appearance of the product, and therefore, the selection of pigments to be added to the ink composition is severely limited. . It goes without saying that the term "discoloration or coloration" used in the present invention is not caused by pigments intentionally added to the ink composition. Therefore, the present inventor developed an ink composition that can form an excellent uneven surface without causing discoloration or coloring when applied to the surface of a synthetic resin containing a foaming agent, particularly a vinyl chloride resin composition, and the foaming agent decomposes. As a result of repeated studies to develop a product, the present invention was arrived at. That is, the present invention contains 0.5 to 75% by weight of a foaming inhibitor, 0.5 to 75% by weight of a coloring inhibitor, and 20 to 75% by weight of a volatile solvent.
An ink composition for applying to the surface of a vinyl chloride resin composition comprising 85% by weight, 0 to 40% by weight of a pigment, and 0 to 25% by weight of a resin carrier for pigments, and containing a blowing agent, The coloring inhibitor is (a)
Carboxylate, phosphite, alcoholate, phenolate, mercaptide or alkylthioglycolate of Group A, Group B, Group A or Group A elements of the Periodic Table, (b) Thiourea compound, (c) Thione The present invention provides an ink composition characterized by being at least one selected from acid compounds, (d) thiuram compounds, and (e) epoxy compounds. Foam suppressants used in the present invention include (1) acids having at least two carboxyl groups or at least one carboxyl group and at least one hydroxyl group, such as maleic acid, fumaric acid, adipine; acid, salicylic acid, 1,2
(2) Organic acid anhydrides, such as phthalic anhydride, trimethic anhydride,
(3) organic acid halides, such as terephthaloyl chloride, (4) aromatic polyhydric alcohols or aromatic polyketones, such as hydroquinone, 1 (5) cyclic amines such as benzylamine, 8-hydroxyquinoline, 2-mercaptobenzothiazole, trithiocyanuric acid, 2-dibutylamino-4 , 6-dimethylcapto-s-triazine and 2-anilino-4,6-dimercapto-s-triazine. Among these, foam suppressants (1), (2), and (4) have good operability;
Although they provide an excellent uneven surface and are inexpensive, they are highly colored, so when these are used, the effects of the present invention are particularly pronounced. The coloring preventive agent used in the present invention is the above-mentioned (a)
~ (e) selected. Examples include (a) fats with 6 to 40 carbon atoms such as barium stearate, calcium salicylate, magnesium laurate, zinc heptylate, cadmium salicylate, tribasic lead maleate, tin ricinoleate, etc. Metal salts such as magnesium, calcium, strontium, barium, zinc, cadmium, lead or tin of group or aromatic carboxylic acids; such as dibasic lead phosphite, organic barium phosphite, organic cadmium phosphite, etc. Metal salts such as barium, lead or cadmium of phosphorous acid; zinc octadecyl alcoholate, calcium benzyl alcoholate, barium octyl phenolate, strontium aluminum phenolate, bis(octylthio)cadmium, S,S′,S″-trisoctadecylthiomalein Alcoholates, phenolates such as magnesium, calcium, strontium, barium, tin, antimony, zinc or lead, such as antimony acid, diptyltin bis(lauryl thioglycolate), di-n-octyltin mercaptide, alkoxy anhydrous polystanane diol alcoholate, etc. , mercaptide or alkylthioglycolate, (b) diptylthiourea, trimethylthiourea, etc., (c) thiolactic acid, etc., (d) tetramethylthiuram disulfide, tetraethylthiuram disulfide, etc., (e) 1,3-bis (glycidyloxy)benzene glycidol, epoxidized soybean oil, epoxidized cottonseed oil, epoxy stearate, etc.Many of these color inhibitors are commercially available stabilizers and co-stabilizers for vinyl chloride resins, and crosslinking agents for rubber. It is easily available as an auxiliary agent.Some of the above coloring inhibitors themselves exhibit foaming suppressing effects, so depending on the type, unevenness can be further accentuated. By adding the inhibitor, it is possible to increase the amount of the inhibitor, so the degree of freedom in selecting uneven steps is expanded.Furthermore, it goes without saying that the use of the coloring inhibitor increases the degree of freedom in selecting the pigment.In the present invention Volatile solvents used include VM & P. naphtha, mineral spirits, hydrocarbons such as solvent naphtha, alcohols such as isopropyl alcohol, t-butyl alcohol, isobutyl alcohol, n-amyl alcohol, ethyl cellosolve,
butyl cellosolve, ethers or ether alcohols such as dioxane, ethyl acetate,
Examples include esters such as isopropyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and plasticizers such as dioctyl phthalate and dibutyl phthalate. In addition, as resin carriers for pigments, vinyl chloride or vinylidene chloride polymers such as vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinylidene chloride-acrylonitrile copolymer, methyl acrylate, acrylic Copolymers of acrylic monomers such as ethyl acid and methyl methacrylate with styrene, vinyl chloride, vinyl acetate, etc., cellulose derivatives such as nitrocellulose and cellulose acetate butyrate, short oils,
Examples include medium oil or long oil modified alkyd resins. The ratio of each component in the ink composition of the present invention is as described above, and is appropriately determined depending on the required unevenness level difference and the type of each component, but generally the foaming inhibitor is 0.5 to 75% ( The amount of the coloring inhibitor is preferably 0.5 to 75 (preferably 5 to 50)% by weight, and the other three components may be used in the same proportions as used in conventional ink compositions. That is, the volatile solvent is 20 to 85% by weight, the pigment is 0 to 40% by weight, and the resin carrier for the pigment is 0 to 25% (preferably 5 to 20%) by weight. Note that the amount of the resin carrier for pigments is preferably smaller than the sum of the amounts of the foaming inhibitor and the coloring inhibitor. As a method for applying the ink composition of the present invention to a foamable vinyl chloride resin composition, known methods such as gravure printing, rotary screen printing, silk screen printing, or transfer methods can be used. Note that the foamable vinyl chloride resin composition to which the ink composition of the present invention is applied includes:
Vinyl chloride homopolymer or this containing 60% by weight or more of vinyl chloride, vinyl acetate, vinyl ether,
Synthetic resins typified by copolymers with methyl acrylate, etc., common blowing agents such as azodicarbonamide, and plasticizers, stabilizers, fillers, pigments, and diluents added thereto as desired. Ordinary plastisols or organosols consisting of, for example, can be used. Although the mechanism of coloration has not yet been fully elucidated, it is thought that coloration occurs when the foaming inhibitor and the vinyl chloride polymer react with each other due to heating. Therefore, it is presumed that the presence of a coloring inhibitor in the reaction system effectively improves the thermal stability of the vinyl chloride polymer, thereby preventing coloring. Next, the present invention will be specifically explained with reference to Examples.
Note that the number of parts used for each compounding agent is based on weight. Example 1 The following foamable resin composition 1 was prepared by a mixing operation using three rolls, and this was applied to the surface of 0.15 mm thick flame retardant paper to a uniform thickness of about 0.18 mm. The coating was heated to 150° C. for 1 minute to solidify it as a semi-molten material and then cooled. Next, this cooled gelled coating was passed through a gravure printing machine, and the following Ink Composition 1 was printed in a pattern on its surface. Next, this was heated at 190° C. for 1.5 minutes to melt and foam, and then cooled to obtain a foam. The thickness of the foam is determined by the area where the ink composition is applied.
0.55mm, and the remaining part was 0.95mm, and had a deep uneven pattern. The area where the ink composition was applied did not change color, and the color tone of the pigment was faithfully reproduced. This product also became a decorative wall paper with excellent appearance and feel. Resin composition 1 Vinyl chloride polymer for plastisol 100 parts Dioctyl phthalate 55 Dodecylbenzene 10 Titanium dioxide 7 Na-Zn composite stabilizer 3 Azodicarbonamide 3 Ink composition 1 Vinyl chloride-vinyl acetate copolymer 8.5 parts Methyl ethyl ketone 46.5 Toner containing 60% titanium dioxide 15.0 Phthalic anhydride 10.0 Barium stearate 20.0 Comparative Example 1 A similar experiment was conducted using the following ink composition 2 instead of ink composition 1 in Example 1. The area turned brown and the color tone of the pigment was significantly impaired. Ink composition 2 Vinyl chloride-vinyl acetate copolymer 11.5 parts Methyl ethyl ketone 53.0 Toner containing 60% titanium dioxide 23.5 Phthalic anhydride 10.0 Example 2 Expandable resin composition 2 was placed on 0.75 mm thick asbestos paper whose binder was synthetic rubber. uniform thickness 0.25
mm and heated at 150° C. for 30 seconds to solidify as a semi-molten material. On the other hand, a transfer paper for the transfer method was obtained by printing Ink Composition 3 in a pattern on the surface of release paper using a gravure printing machine and air drying. Next, the transfer paper is layered so that the ink composition is in contact with the surface of the solidified resin composition, heated for 5 seconds from the transfer paper side with an infrared heater, and immediately after that, both layers are placed on a roll with a linear pressure of 1 kg/cm. The ink composition was transferred to the gelled film, and after cooling, the release paper of the transfer paper was removed. Resin composition 2 Vinyl chloride polymer for plastisol 80 parts Vinyl chloride polymer for blend 20 Dioctyl phthalate 40 Butyl benzyl phthalate 8 Titanium dioxide 3 Zinc oxide 2 Azodicarbonamide 3 Ink composition 3 Vinyl chloride-vinyl acetate copolymer 8.5 Part methyl ethyl ketone 46.5 Toner containing 60% titanium dioxide 15.0 Trimellitic anhydride 10.0 Zinc salicylate 20.0 Next, non-foaming resin composition 3 was applied to a thickness of about 0.18 mm on the gelled film in order to improve wear resistance. The resin composition is applied and heated at 210℃ for 2 minutes to melt both resin compositions, decompose the foaming agent, and then cooled to form three layers: a transparent and strong resin layer, a foam layer, and an asbestos layer. Got a prepared sheet. This sheet was a product with an uneven surface that was depressed in the area where the ink composition was applied, and whose color tone faithfully reproduced that of the pigment, making it an excellent floor decoration material. Resin composition 3 Vinyl chloride polymer for plastisol 70 parts Vinyl chloride polymer for blend 30 Dioctyl phthalate 40 Epoxidized soybean oil 2 Ba-Zn stabilizer 3 Example 3 Resin composition in place of resin composition 1 in Example 1 When a similar experiment was conducted with the exception that ink compositions 4 and 5 were used in place of ink composition 1 to perform two-stage gravure printing on product 4, no coloring was observed in the area where the ink composition was applied. First, even the area coated with uncolored ink composition 4 showed the same degree of whiteness as the area not coated with the ink composition. The thickness of the product was 0.75 mm in the area where ink composition 4 was applied, 0.85 mm in the area where ink composition 5 was applied, and 1.05 mm in the remaining area, making it a decorative wall paper with excellent appearance and feel. Resin composition 4 Vinyl chloride for plastisol - 100 parts Vinyl acetate copolymer (vinyl acetate 5% by weight) Dialkyl (C7-10) phthalate 60 Titanium dioxide 5 Zn-based composite stabilizer 3 Azodicarbonamide 3.5 Antimony trioxide 3 Ink Composition 4 Vinyl chloride-vinyl acetate copolymer 10 parts Methyl ethyl ketone 55 Trimellitic anhydride 10 D-n-octyltin mercaptide 25 Ink composition 5 Vinyl chloride-vinyl acetate copolymer 10 parts Methyl ethyl ketone 48 Cyanine blue pigment 5 Phosphorus Tricresyl acid 10 Trimethic anhydride 11 Dibutylthiourea 16 Examples 4 to 13 and Comparative Example 2 The following experiments were carried out except that the following foamable resin composition 5 or 6 and ink composition 6, 7, 8, 9, 10 or 11 were used. A wall decoration paper was obtained in the same manner as in Example 1. The results are shown in the table. Resin composition 5 Vinyl chloride polymer for plastisol (degree of polymerization
800) 35 parts Vinyl chloride polymer for plastisol (degree of polymerization 1350) 35 Vinyl chloride polymer for blending 30 Dioctyl phthalate 50 Tricresyl phosphate 5 Dodecylbenzene 8 Ca-Zn stabilizer 3 Azodicarbonamide 4 Cyanine blue Pigment 3 Resin composition 6 Vinyl chloride polymer for plastisol 100 parts Calcium carbonate 30 Dioctyl phthalate 45 Diisodecyl phthalate 10 Mineral spirit 5 Ca-Zn composite stabilizer 3 Azodicarbonamide 2.5 P,P'-oxybis(benzenesulfonyl) semicarbazide) 0.5 Titanium dioxide 5 Antimony trioxide 2 Ink composition 6 Vinyl chloride-vinyl acetate copolymer 10 parts methyl ethyl ketone 46.5 Toner containing 60% titanium dioxide 13.5 Salicylic acid 13 Thiolactic acid 17 Ink composition 7 Vinyl chloride-vinyl acetate Copolymer 10 parts Methyl ethyl ketone 46.5 Toner containing 60% titanium dioxide 13.5 Trimellitic anhydride 7 Tetraethylthiuram disulfide 23 Ink composition 8 Vinyl chloride-vinyl acetate copolymer 10 parts Methyl ethyl ketone 46.5 Toner containing 60% titanium dioxide 13.5 Trimellitic anhydride 10 Epoxidized soybean oil 20 Ink composition 9 Vinyl chloride-vinyl acetate copolymer 10 parts Methyl ethyl ketone 46.5 Toner containing 60% titanium dioxide 13.5 Hydroquinone 7 Dibutyl tin bis (lauryl thioglycolate) 23 Ink composition 10 Vinyl chloride-vinyl acetate Copolymer 10 parts methyl ethyl ketone 46.5 Toner containing 60% titanium dioxide 13.5 Salicylic acid 10 Dibasic lead phosphite 20 Ink composition 11 Vinyl chloride-vinyl acetate copolymer 10 parts methyl ethyl ketone 48 Toner containing 60% titanium dioxide 20 Trimethic anhydride 22 [Table]

Claims (1)

[Claims] 1 Foaming inhibitor 0.5~75% by weight, coloring inhibitor 0.5~
75% by weight, volatile solvent 20-85% by weight, pigment 0-40
An ink composition for application to the surface of a vinyl chloride resin composition comprising 0 to 25% by weight of a resin carrier for pigments and containing a blowing agent, wherein the coloring inhibitor is ( a) Group a of the periodic table,
Carboxylate, phosphite, alcoholate, phenolate, mercaptide or alkylthioglycolate of group b, group a or group a element, (b) thiourea compound, (c) thionic acid compound, (d) thiuram An ink composition comprising at least one selected from a compound and (e) an epoxy compound.