JPS6219772B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an embossing method for forming an embossing using a foamed thermoplastic resin material.

Generally, by selective foaming of thermoplastic materials,
There have already been proposals to produce so-called "chemically embossed" materials, and the present invention is a new approach. Regarding the structure of the present invention, there is Japanese Patent Publication No. 43-15713 (British Company Limited), which is important as an invention corresponding to the present invention. That is, the above invention involves forming a mixture of a thermoplastic resin material and a chemical blowing agent into a sheet, and applying an activator ink containing a decomposition accelerator for the chemical blowing agent to selected areas on the surface of the sheet. ,
heating temperature such that the applied zone of the sheet decomposes to a greater extent than the remaining zones, thereby causing a difference in the degree of expansion by the chemical blowing agent;
A method of embossing by selective expansion of thermoplastic material has been proposed, which consists of a period of time.
This invention is comparable in design and physical effects including embossing as a final product, for example, by using plastisol or organosol containing vinyl chloride resin and a chemical blowing agent on the surface of a non-foamed resin sheet. A product is printed with a pattern using a rotary screen printer, etc. and foamed at an appropriate heating temperature to give it an embossed effect, or a resin mixture containing a chemical foaming agent is formed into a sheet shape and heated and foamed. At least, compared to products embossed using embossing rolls, the surface is superior in smoothness, and the embossed effect can be expressed clearly and sharply even on delicate patterns. , the resin material can be easily applied or bonded to the sheet surface, which makes it possible to improve abrasion resistance, stain resistance, weather resistance, etc.
Furthermore, by adding a coloring agent to the activator ink and printing a pattern on the sheet, the zone expands and the colored zone and embossed zone match, so-called "synchronized embossing".
It has a number of excellent advantages, such as the ability to perform

Therefore, the applicant, Sanpo Jushi Kogyo Co., Ltd., recognized the usefulness of this patent about five years ago, and acquired the license from the patent owner, Phizons Limited of the United Kingdom. The above invention has been practiced to date. However, recently, a product with a much larger difference in thickness between the concave and convex regions than the patented product has appeared using a different manufacturing method, and the significance of this patent has decreased significantly. It had been deprived of righteousness, and improvements were desperately needed.

In order to improve this point and maintain its significance, the present inventors conducted intensive research and found that the surface of a sheet formed from a foamable mixture containing a chemical blowing agent in a thermoplastic resin material was selected. In the band where
An activator ink containing a decomposition accelerator for the blowing agent is applied, and a plastisol or organosol containing a vinyl chloride resin and a chemical blowing agent is applied to newly selected zones on the surface of this sheet. When we investigated the expansion emboss effect caused by the blowing agent and the decomposition accelerator for the blowing agent at appropriate heating temperatures and times, we discovered an emboss effect with dramatic irregularities that had not been previously achieved with the Huizons invention. Ivy.

That is, in the present invention, the activator ink 2 and the plastisol or organosol 3 are applied to the surface of a resin sheet 1 containing a foaming agent as shown in FIG. (See Figure 3).

FIG. 1-a shows this change in the chemically embossed coating state shown in FIG. 1a in the Faisons invention, and the state shown in FIG. 1b when this is expanded.

In the chemical embossing invented by Faisons, only the zone coated with the activator ink expands to form a convex portion, but the embossing depth is 0.5.
The limit is about 0.75 m/m, and it is possible to increase the thickness to 0.75 m/m by increasing the thickness of the sheet, but this increases the cost, and especially when the application is wallpaper, it is difficult to It has the major drawback of not being able to meet fuel standards.

In the present invention, a plastisol or organosol containing a vinyl chloride resin and a chemical blowing agent is applied by coating and adding a plastisol or organosol containing a vinyl chloride resin and a chemical blowing agent using a rotary screen printing method or the like in addition to the conventional chemical embossing method. As a result, the difference in expansion is dramatically expanded even with a small amount of sol attached.

In conventional chemical embossing, the same color tone band colored by the activator ink has the same expansion rate, resulting in a smooth surface, but according to the present invention, the area coated with the activator colored ink and the colored band are the same. By shifting the sol application zone, it is possible to give not only a smooth surface but also a stepped surface to the sol zone, which is completely different from the conventional chemical embossing method in terms of design. Many expressions are now possible, and this is an epoch-making development in terms of design expression. Furthermore, in wallpaper applications, the depth of embossing can be increased without increasing the thickness of the sheet, which has the great advantage of not only cost benefits but also satisfying flame-retardant standards.

According to the invention, therefore, a foamable mixture containing a thermoplastic resin material and a chemical blowing agent is formed into a sheet, and a decomposition accelerator for the chemical blowing agent is contained in selected zones on the surface of the sheet. An activator ink is applied, and a plastisol or organosol containing a vinyl chloride resin and a chemical blowing agent is applied to newly selected zones on the surface of the sheet and brought into contact with the activator ink. The heating temperature and time are such that the areas of the sheet and the area to which the plastisol or organosol is applied decompose to a greater extent than the rest of the sheet, thereby causing differences in the degree of expansion. A method of embossing by selective expansion of a resin material is provided.

Even more surprisingly, by using a plastisol or organosol containing a chemical blowing agent in vinyl chloride resin and a decomposition accelerator for the chemical blowing agent, and combining it with an activator ink, the prediction was far exceeded. The embossed convex portion was also at an extremely acute angle with respect to the sheet surface, making it possible to further enhance the design. In the case of the chemical embossing method, applying the activator ink to the sheet and leaving it for about 45 hours at about 20℃ and about 25 hours at about 25℃ is the best way to expand it. Get favorable results.
This is because the decomposition accelerator of the activator ink needs time to penetrate into the sheet resin layer, but the decomposition accelerator contained in the sol is dispersed by sufficient stirring at the time of application. This has the advantage of not requiring elapsed time due to penetration; therefore,
It is possible to foam by heating at the same time as coating. That is, in FIG. 4, a vinyl chloride resin sol 4 containing an activator ink 2, a chemical foaming agent, and a decomposition promoter thereof is applied to the surface of a resin sheet 1 containing a chemical foaming agent, and then expanded. As shown in FIG. 5, additions were made to cause a difference in the degree of the difference.

“Plastisol” as used herein
The term refers to a paste prepared from a dispersed vinyl resin and a plasticizer. The term "organosol" also refers to a composition containing a dispersed vinyl resin, a plasticizer, a volatile solvent for the vinyl resin, and a diluent. The thermoplastic material can also be a condensation polymer, for example a polyamide (eg polycaprolactam or polyaminoundecanoic acid) or a polyester (eg terephthalate polyester). The thermoplastic material can be an addition polymer, for example a polymerization product of halogen-substituted olefins such as polyolefins (e.g. polyethylene or polypropylene), polyacrylates (e.g. polymethyl methacrylate), polystyrene or polyvinyl chloride. Among them, polyvinyl chloride and vinyl chloride-vinyl acetate copolymer are preferred.

The blowing agent can be any conventional blowing agent, and the decomposition temperature of the blowing agent is lowered in the presence of various compounds known as decomposition promoters. However, what is important here is to select a blowing agent appropriate for the polymer used, and the blowing agent is a substance that has a decomposition-promoting effect at a temperature at which the polymer or a composition containing the polymer becomes soft enough to expand. must be decomposed in the presence of Examples of blowing agents are azodicarbonamide, barium azodicarboxylate, PP ¹
-oxybis(benzenesulfonylhydrazide)
and PP ¹ -oxybis(benzenesulfonyl semicarbaside), but azodicarbonamide is particularly preferred, and the amount added is preferably 1 to 10 parts by weight per 100 parts by weight of the thermoplastic resin material. Preferably, the foamable mixture is prepared as a plastisol. And suitable plasticizers for preparing plastisols include phthalate esters (e.g. butylbenzyl phthalate, dioctyl phthalate, diisooctyl phthalate, diheptyl phthalate), adipate esters (e.g. dioctyl adipate), sebacic acid esters (e.g. dioctyl seba esters) and phosphate esters (eg, tricresyl phosphate and octyl diphenyl phosphate). The amount of plasticizer present in the foamable mixture is preferably between 25 and 200 parts by weight per 100 parts by weight of thermoplastic material.
30 to 70 parts by weight).

For example, the foamable mixture may contain 1 per 100 parts by weight of resin.
Suitably it contains ~80 parts by weight of filler. Preferably, the foamable mixture contains a stabilizer for the resin material. When a decomposition accelerator is attached to the sheet, the stabilizer is a tin compound (for example, dibutyltin malate, dibutyltin laurate, and tin mercaptide (barium compounds (barium caprylate, barium caproate, barium laurate, and barium myristate)). A combination of a barium compound and a zinc or cadmium compound, preferably a fatty acid soap, is preferred.The amount of the stabilizer added is suitably 0.2 to 5 parts by weight per 100 parts by weight of the thermoplastic resin material.

The foamable mixture may also contain other ingredients necessary to obtain the desired product.

These additional ingredients include plasticizers, solvents, diluents, spreading agents, pigments, dyes, hardeners, viscosity modifiers,
Includes fillers and other stabilizing agents.

The foamable mixture can be made into a sheet by extruding, casting, rolling, or spreading the mixture. Preferably, the foamable mixture is spread as a plastisol on a suitable surface, optionally with a support, and then the plastisol is allowed to gel. That is, the plastisol is heated for a period of time sufficient to cause the plastisol layer to become hard and non-tacky, but insufficient to cause the blowing agent to decompose.
The sheet is preferably gelled by heating for 0.5 to 2 minutes at a temperature of 120 DEG to 150 DEG C., although it may be gelled in a shorter period of time, particularly at higher temperatures.

Thus, the support in these embodiments is formed of a release material such as a resinous material, paper, woven fabric, impregnated glass fiber, impregnated felt fiber, or paper coated with, for example, a silicone, alginate or casein composition. obtain.

The decomposition accelerator used in the activator ink can be any of a number of compounds that lower the decomposition temperature of the blowing agent, including compounds of zinc (e.g. zinc oxide, zinc caprylate, zinc sulfate and zinc fatty acid soaps), cadmium compounds (e.g. zinc oxide, zinc caprylate, zinc sulfate and zinc fatty acid soaps), e.g. cadmium caprylate, cadmium caproate, cadmium laurate, cadmium myristate and cadmium fatty acid soap), lead compounds (e.g. lead carbonate, zinc phthalate,
Decomposition accelerators such as lead phosphite and lead stearate), urea, borax, ethanolamine, glycols and benzenesulfonehydrazine,
Particular preference is given to zinc compounds such as zinc caprylate or zinc nitrate. The activator ink comprises a mixture of a solution or dispersion of a decomposition accelerator and a solution or dispersion of a film-forming or binder resin and a dye or pigment, the dispersion preferably being an ester such as ethyl acetate. .

Further suitable film formers or binder resins include polyvinyl chloride or copolymers of vinyl chloride and vinyl acetate, acrylic resins, polyurethanes, cellulose acetate, polyesters, polystyrenes, rubbers, epoxy resins, silicones and other polymers. There is.
The solvent or dispersant for the film former or binder preferably acts as a dispersant for the vinyl chloride derived polymer or copolymer used in the swellable mixture. This is because in this manner the activator ink improves the transfer of the degradation accelerator to the expandable mixture sheet. Suitable solvents include ketones (e.g. cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone), esters (e.g. ethyl acetate), chlorinated hydrocarbons (e.g. ethylene dichloride, methylene chloride), aromatic hydrocarbons (e.g. toluene, xylene) and nitro compounds. (eg nitrobenzene, nitropropane).

On the other hand, in addition to the above-mentioned patent of the British company Faisons Limited, there is also a patent of the British company Concorium and Nan Incorporated (Patent Application Publication 1973)
-28636). This patent is based on a concept opposite to that of the Faisons patent, and attempts to create an embossed effect by using a decomposition inhibitor for a chemical foaming agent without using a decomposition accelerator for the chemical foaming agent. It is.

In the process of researching the chemical embossing method, the present inventors found that by adding the Congolium patent to the above-mentioned method, unevenness that could not be imagined by itself appeared, and it was found that the carving blade rather than the chemical embossing method appeared. It gives the impression that a person has been cut off, and although in principle it is an application of the aforementioned patent, the effect far exceeds expectations.

To explain this effect with reference to FIG. 6, an activator ink 2, a deactivator ink 5 containing a chemical foaming agent for suppressing decomposition, a chemical foaming agent, and a chemical foaming agent on the surface of a resin sheet 1 containing a chemical foaming agent. A vinyl chloride resin sol 4 containing a decomposition accelerator is applied and heated to cause different degrees of expansion (Figure 7).The unevenness is extremely large, especially in wallpaper applications. Although there are weight restrictions in the standards, the embossing depth can be increased without increasing the thickness of the sheet, which has the great advantage of not only cost benefits but also meeting the flame-retardant standards.

The decomposition inhibitor used in the deactivator ink can be any of a number of compounds that increase the decomposition temperature of the blowing agent, including organic acids (e.g., maleic acid, fumaric acid, adipic acid, and phthalic acid), halogenated organic acids ( For example, galefthaloyl chloride, tetrachlorophthalic anhydride), organic acid anhydrides (e.g. maleic anhydride, trimellitic anhydride), polyaromatic alcohols and ketones with two functional groups (e.g. hydroquinone), and 6- to 10-membered There are other decomposition inhibitors such as ring amines (eg benzine amine), but trimellitic anhydride or maleic anhydride is particularly preferred.

Sheet stabilizers when applying both activator and deactivator inks include lead compounds (e.g. dibasic lead phosphite), zinc compounds (zinc laurate, zinc stearate) and Cadmium compounds (cadmium caprylate, cadmium caproate, cadmium laurate, cadmium myristate), etc. are preferred.

The decomposition accelerator and decomposition inhibitor contained in the activator ink and the deactivator ink range from 2% by weight to 25% by weight.
% by weight is desirable (preferably from 5% to 20% by weight).

The solids content of the activator ink or deactivator ink is suitably about 5 to 30% by weight.

Next, the present invention will be explained with reference to examples.

In the examples, parts are by weight.

Blend 1 Plastisol blended polyvinyl chloride resin (dispersed type) 100 parts DOP (dioctyl phthalate) 60 Epoxidized soybean oil 6 Dibutyltin dilaurate 1.2 Azodicarbonamide 3.5 Filler (calcium carbonate) 30 Pigment 10 Blend 2 Plastisol blended vinyl chloride resin (Dispersed type) 100 parts DOP (dioctyl phthalate) 60 Epoxidized soybean oil 6 Dibasic lead phosphite 2 Azodicarbonamide 3.5 Filler (calcium carbonate) 30 Pigment 10 Compound 3 Vinyl chloride resin with activator ink ( Dispersed type) 20 parts acrylate polymer 30 Toluene 75 MEK 175 MIBK 30 Ethyl acetate 65 Pigment 8 Zinc caprate 40 Blend 4 Vinyl chloride-vinyl acetate copolymer with deactivator ink 20 parts MEK 120 Pigment 35 Anhydrous Trimeriz Acid 25 Example 1 Plastisol of Formulation 1 was applied to wallpaper backing paper and heated at 150°C for 30 seconds to gel and form a layer of 0.14 mm thick.
A sheet of m/m was obtained.

The activator ink of Formulation 3 was applied as a pattern on a part of the surface of the sheet, and then plastisol of Formulation 2 was applied on the same pattern in a layer of 0.15 m/m using a rotary screen printing machine. Printed. This was heated at 200°C for 75 seconds to foam and expand. The maximum thickness difference after expansion was 1.15 m/m. (See Figures 2 and 3) Example 2 Plastisol of Formulation 1 was applied to wallpaper backing paper and heated at 150°C for 30 seconds to gel and give a thickness of 0.14 mm.
A sheet of m/m was obtained.

The activator ink of Formulation 3 was applied as a pattern on a part of the surface of the sheet, and then 4.2 parts of zinc caprylate, which is a blending accelerator for chemical blowing agents, was added to the plastisol of Formulation 2 on the same pattern. Using a rotary screen printing device, printing was performed in a layer with a thickness of 0.15 m/m. this
It was heated at 200°C for 75 seconds to foam and expand. The maximum thickness difference after expansion was 1.55 m/m (Fig. 4,
Figure 5).

Example 3 Plastisol of Formulation 2 was applied to wallpaper backing paper and heated at 150°C for 30 seconds to gel, resulting in a thickness of 0.14 mm.
A sheet of m/m was obtained.

Apply the activator ink of Formulation 3 as a pattern on the surface of the sheet, then apply the deactivator ink of Formulation 4 to the area other than the same pattern, and then apply it to the surface of the sheet. On the same coating pattern of the activator ink, 4.2 parts of zinc caprylate was added to the plastisol of Formulation 2 in the same manner as in Example 2, and a thickness of 0.15 m/cm was printed using a rotary screen printing device.
Printed in m layers. This was heated at 200°C for 75 seconds to foam and expand. The maximum thickness difference after expansion is
1.81 m/m (Figures 6 and 7) All of the final products according to the examples had excellent embossed surfaces, and if necessary, a coating layer could be applied or applied to the sheet surface. It is possible to bond them together, thereby improving the abrasion resistance of the ink.

[Brief explanation of the drawing]

FIGS. 1a and 1b are explanatory diagrams of a known embossing method,
FIGS. 2 to 7 are explanatory diagrams of the embossing method according to the present invention. 1... Foamable mixture sheet, 1'... Foamable mixture after foaming, 2... Activator ink coating layer,
2'...Activator ink coating layer after foaming, 3...
Plastisol or organosol coating layer, 3'...
...The sol coating layer after foaming, 4...The sol added with a decomposition accelerator, 4'...The sol of 4 after foaming, 5...
...Deactivator ink coating layer.

Claims (1)

[Claims] 1. A foamable mixture containing a thermoplastic resin material and a chemical blowing agent is formed into a sheet, and a decomposition accelerator for the blowing agent is contained in selected zones on the surface of the sheet. An activator ink or a deactivator ink containing a decomposition inhibitor for the foaming agent is applied, and plastisol or a polyvinyl chloride resin containing a chemical foaming agent is applied to a newly selected zone on the surface of the sheet. The parts of the sheet coated with the organosol that are in contact with the activator ink and the zones coated with the plastisol or organosol are decomposed to a greater extent than the remaining zones, and are also in contact with the deactivator ink. The heating temperature and time are selected so as to cause a smaller degree of decomposition in the areas of the sheet than in the remaining zones, thereby causing a difference in the degree of foaming expansion of the sheet and the plastisol or organosol from place to place. A thermoplastic resin embossing method characterized by forming an emboss by selectively expanding a thermoplastic resin material. 2. By performing the same method using a plastisol or organosol containing a chemical blowing agent in vinyl chloride resin that is attached to the surface of the sheet, and a material that further contains a decomposition accelerator for the chemical blowing agent, the thermoplastic resin material can be A method for embossing a thermoplastic resin according to claim 1, wherein the embossing is formed by selective expansion.