JP2974368B2 - Aromatic resin molded product with picture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]

The present invention relates to a scented resin molded product with a pattern, and by the completion of the present invention, a pattern of various colors on the surface of a scented plastics product, that is, a figure, a character, a painting, a photograph,
Symbols, cartoons, functional displays, etc. can be freely added. Therefore, the present invention relates to daily necessities, electric / electronic equipment, communication equipment, transport equipment, agricultural goods, films, containers, decorations, sports goods, travel goods, transportation goods, stationery, artificial flowers, toys, sanitary goods, food goods. , Kitchenware, medical supplies,
Hospital supplies, makeup supplies, construction supplies, civil engineering supplies, packaging supplies,
It can provide useful products used in various fields such as daily necessities, footwear, cards, identification marks, and the like, and has an extremely large industrial application field. The scent of scented resin moldings is often aroma in general, but indoor insect repellent products, agricultural products, animal odor fragrance products, contact prevention products, dangerous goods products, etc. have a bad odor or unpleasant odor. In some cases, a fragrance may be used. However,
Generally, fragrances expressing flowers, fruits, spices, foods, perfumes, forests and the like are awarded as the most commonly used fragrances.

[Prior art]

Techniques that have long been well-known for products of scented resin compositions include sponges, gels, and the like impregnated with fragrances, and chewing gums, which are made by adding a fragrance to a natural resin and kneading them. Was. In recent years, a method of using a perfume packaged in cyclodextrin in addition to an adhesive base material for application (Japanese Patent Application Laid-Open No. 58-185372), an ink containing an emulsion containing an inorganic porous material impregnated with the perfume (particularly, No. 58-162677) or an ink obtained by adding a filler impregnated with a perfume to silica gel (JP-A-59-1452).
No. 98) has been developed. Further, a film obtained by impregnating an inorganic powder with a fragrance, kneading it with a polyolefin, and stretching (JP-A-62-227932), or a resin composition containing a fragrance and an ethylene / vinyl acetate copolymer as a main component (JP-A-62-27832) 1953-98
No. 352, JP-A-63-6099 and JP-A-2-51593) are also known. However, even with the above-mentioned known documents, there is no known technique for molding a product in each invention and applying a pattern to the molded product, and a practical method relating to this has been industrially implemented. The fact has never existed.

[Problems to be solved by the invention]

The present inventors consider that if a long-term stable fragrance can be imparted and painted on a molded product that has been actively used as a general-purpose plastics product, it is considered that it is extremely preferable in practical use and has long studied. In order to achieve this task, it was necessary to solve the following items. I. To find a component of a scented resin composition that retains a fragrance for a long period of time without changing the fragrance as much as possible, and to find a use ratio between the composition and the fragrance. B. Find conditions to avoid liquid bleed due to fragrance during molding, storage or painting. C. To select a painting method suitable for a molded article of a scented resin composition and to find a practical method thereof. D. To find the components of each layer including the picture layer that does not cause deterioration or peeling due to fragrance components. E. To establish a transfer method as an economical method that can be mass-produced industrially.

[Means for Solving the Problems]

The present inventors have conducted various studies in order to solve the above-mentioned problems, but have now finally completed the present invention to which attention should be paid. That is, the present inventors have found that polyolefin 80 to 95% by weight, olefin / ester monomer copolymer 3 to 10
Wt%, fragrance 0.2-4.0 wt% and ester wax
When molding a scented resin composition containing 0.3 to 3.0% by weight, or after pressing, the surface side including the picture layer of the transfer foil is pressure-bonded to the surface of the molded article, and a high-quality scented resin with picture pattern is formed. They found that they could get the goods. Here, the olefin / ester monomer copolymer is defined as ethylene / vinyl acetate copolymer, ethylene / vinyl acetate copolymer modified resin, ethylene / vinyl acetate / vinyl chloride copolymer and ethylene / (meth) acrylate copolymer. It is at least one copolymer selected from the group consisting of coalescing, and the ester wax is at least one wax selected from the group consisting of higher fatty acid esters, higher alcohol esters, and animal and vegetable oils and fats. Polyolefins include polyethylene (low density polyethylene LDPE, high density polyethylene HDPE), polypropylene, polybutylene, polybutadiene, ethylene / propylene copolymer, ethylene / α-olefin copolymer, modified polyethylene, modified polypropylene, polyolefin petroleum resin, etc. And mixtures of two or more of which are particularly important industrially are polyethylene and polypropylene. The olefin / ester-based monomer copolymer is a single one or a mixture of two or more of the above-mentioned ones. The industrially important one is an ethylene / vinyl acetate copolymer and its modified resin (for example, a partially hydrolyzed product thereof). is there. The ester wax may be one of those described above or 2
A mixture of more than one species, but specific examples of industrially important ones include para rubber seed oil, rice wax, cashew seed oil, kapok oil, cocoa butter, 12-hydroxystearate, palm oil, palm kernel oil. , Wood wax, coconut oil, tallow, lard, horse fat, sheep fat, whale wax, dense wax, carbana wax, candelilla wax, shellac wax, palm wax,
Montan wax, wool fat, hardened fish oil, softened whale oil, hardened oil of squid oil, hardened oil of soybean oil, hardened oil of bran oil, hardened oil of jojoba oil, hardened castor oil, hardened rapeseed oil, palmitic acid ester, myristic acid ester, Stearic acid ester, monomyristin, monostearin, octadecyl acetate, stearyl acetate, oil-based synthetic wax (Ito wax-E, Kao wax 85-P, Custer wax, synchro wax) and the like. In the present invention, it is desirable to use a good product having as little odor and color as possible among these. The fragrance used in the present invention is mainly a liquid fragrance that does not contain a so-called solvent, and a typical composition thereof is
Top note 15-35% by weight, middle note 10-30% by weight, base note (last note) 45-65% by weight. The fragrance used in the present invention in the form of a natural fragrance, a synthetic fragrance, or a mixture of both, includes fragrance type, flavor type, spicy type and the like, and any of them can be effectively used in the present invention. These fragrances are blended to form a scented resin composition. In this case, the following considerations are required. It is desirable that the fragrance is uniformly distributed and dissolved in the resin composition and does not cause liquid bleed due to a change in temperature. Further, it is desirable that the weight loss due to the fragrance of the fragrance is extremely slow, and that the molded product hardly undergoes volume shrinkage and does not drop off or peel off the patterned portion. It is also preferred that the desired odor is preserved over a long period, sometimes for several years, without causing significant modulation of the fragrance during the process of the present invention and during storage of the molded article. With regard to liquid bleed, it is necessary to distinguish between plasticizer migration (migration) and leachability (bleeding and blooming), which determine the commercial value of plastics. In other words, these are probably appearance or sensory evaluation terms, and are standard test methods (eg, AS
(TM or ISO) is being enacted, but at present there is no way to measure it accurately. However, as for the leaching property, the bleeding of a plasticizer in a vinyl chloride resin compound in BS2571-1955 and a liquefied vinyl resin sheet in BS1763, 2739-1956 are specified in British Standard BS2571-1955, which can be applied mutatis mutandis. In addition, blooming is a term often used when treating the leachability of a solid rather than a liquid, and is a term for the expression "white powder blows" on the surface of a so-called rubber or the like.
The liquid bleed of the present inventors is intended to judge a more bleeding phenomenon that is more sensitive than the bleeding test of the British standard, and the gradient of the concentration of the fragrance between the inside and the surface of the plastic molded article is different. If the diffusion of the fragrance from the inside to the surface becomes large, it becomes impossible to apply the pattern by the transfer according to the present invention, and the intended high quality fragrant resin molded product with a pattern cannot be obtained. Thus, the finished appearance of the product of the present invention also has value as a considerably more sensitive liquid bleed detection method. The present inventors have conducted a number of studies on these points and found that 80 to 95% by weight of polyolefin is particularly preferable.
85 to 93% by weight, 3 to 10% by weight of olefin / ester monomer copolymer, particularly preferably 5 to 8% by weight, and fragrance 0.2
To 4.0% by weight, particularly preferably 0.3 to 3.0% by weight and ester wax 0.3 to 3.0% by weight, particularly preferably 0.4 to 2.5%.
% By weight is suitable as the scented resin composition of the present invention. When the content is out of these ranges, liquid bleed will be observed, and a change in scent will be observed. It is becoming. However, it is permissible to add a small amount of a heat stabilizer, an antioxidant, a photodegradation inhibitor, an isomerization inhibitor, etc. to the scented resin composition as an additive in order to stabilize the fragrance. When the use ratio of the above resin composition is maintained, general fillers, pigments and the like may be used in the same manner as other polyolefin molded products. The transfer foil referred to in the present invention means that a mat layer, a release layer, a protective layer, a pattern layer (single or multilayer), an anchor layer, and an adhesive layer are formed on a base film (often a polyethylene terephthalate (PET) film). It has a stacked structure (some of these layers may be omitted or moved back and forth in some cases). Among the layers of the transfer foil, each component of the protective layer to the adhesive layer is exposed to the radiant vapor of the fragrance from the surface of the molded article of the fragrant resin composition after bonding. It should be of a structure that makes it suitable for use, but should not have a particularly high affinity for perfume. As a result of many studies on the transfer foils of the present inventors, the chemical structure that is considered to be a preferable component in the layer has an ester bond, and generally has -OCO-, -COO-,- Polymers or oligomers containing NHCOO-, -OCOO-, etc. as functional groups and other hydrocarbon groups such as hydrocarbon groups, halogens, acid amide groups, cyano groups, alkoxy groups (ether groups), etc. Alternatively, a mixture of these and a small amount of filler or additive may be blended. Pressing and bonding the side including the pattern layer of the transfer foil to the surface of the molded product during or after molding the effective resin composition,
This shows that the patterning on the surface of the molded product may be performed by either simultaneous transfer of molding or transfer after molding. First, a simple example of the transfer foil will be described.
For example, a release layer made of a thermoplastic acrylate resin is applied to a PET film for a transfer film by a gravure printing method or a roll coating method. A pattern is printed thereon by a gravure printing method or an offset printing method using a colored ink (a pigment kneaded with an acrylate / vinyl ester resin composition as a binder). At this time, the ink is diluted with a convenient solvent (eg, methyl ethyl ketone, toluene, acetate, methyl isobutyl ketone) so that the viscosity of the ink can be appropriately maintained. If multi-color printing is required, change the printing surface of the film after printing each ink.
Dry at 60-150 ° C. and then, if necessary, apply a polyurethane-containing ink as an anchor layer. This anchor layer is divided into two or multiple layers of a front anchor layer and a rear anchor layer, and can be applied with a slightly changed composition, or even omitted in some cases. When a two-layer or multi-layer anchor layer is used, an aluminum vapor-deposited film is often sandwiched between them. Next, an adhesive solution containing a vinyl chloride-vinyl acetate copolymer or chlorinated polyolefin is applied and dried. To form a final layer.
In the simultaneous transfer of the molding, there is a case where the adhesive layer may be omitted. In the case of simultaneous transfer of molding, insert this transfer foil into the mold of the molding machine so that the printing surface comes to the injection nozzle side, keep the mold temperature at 50 ° C or less, and transfer the scented resin composition from the nozzle to 120 ~. 1
Injection injection is performed at 70 ° C. After cooling, the mold is opened and the painted molded product is peeled off from the PET film to obtain a product. On the other hand, in the case of transfer after molding, a molded product molded into a predetermined shape by a normal plastic molding machine is placed on a table, and the adhesive side of the transfer paper is placed thereon as if it is in contact with the surface of the molded product, Pressure is applied to the PET film using a heated mold or silicone rubber mold. After decompression, the PET film is peeled off to obtain a product with a picture. With this transfer printing method, not only flat printing but also curved printing is possible. When the liquid bleed occurs during the transfer, irregularities are generated on the transfer surface, and the picture portion is peeled off. However, as long as the conditions specified in the present invention are maintained, a beautiful scented resin molded product with a picture can be obtained. It gives good yield. The product of the present invention thus obtained has a pattern completely adhered to the plastic surface, does not fall off or peel off in normal use, and generally has a certain degree of flexibility so that deformation of the substrate It can be deformed according to. The release of the fragrance from the scented resin molded product is large from the non-transfer surface, but is small from the transferred picture surface, so that there is an effect of helping to retain the fragrance.

【Example】

The present inventors have conducted a number of experiments on the above-mentioned present invention and clarified the superiority of the present invention.However, in order to further explain the technical content of the present invention, several representative examples were extracted and described below. It will be shown as an example. Therefore, the present invention should not be construed as being limited to only the examples described below, and it is possible to arbitrarily modify the embodiments without departing from the spirit and the spirit of the present invention. Of course. Example 1 (Transfer Foil A) An acrylic-modified melamine resin solution is applied to a commercially available PET film having a matte surface and dried to form a release layer. An ethylene-acrylate copolymer solution is applied thereon and dried to form a protective layer. Next, red and blue polka dots are printed and dried using a red ink and a blue ink using an acrylate resin as a binder. Then, a urethane resin paint is applied on this, dried, covered with a mask cover, and subjected to aluminum vacuum deposition to disperse a metallic polka dot pattern. Then, a urethane paint is applied thereon and dried, and then a chlorinated polypropylene solution is applied and dried to form a hot melt adhesive layer. The transfer foil thus obtained is designated as A. Example 2 (Transfer Foil B) An acrylic-modified epoxy resin solution is applied to a PET film whose surface has been subjected to electric discharge machining and dried to form a release layer. An ethylene / vinyl acetate copolymer-modified resin solution is applied thereon, and after drying, a three-color printing of a flower pattern is carried out by a conventional method. After drying, an acrylic-modified polyvinyl chloride solution is applied and dried. The transfer foil thus obtained is designated as B. Example 3 (Transfer Foil C) An acrylic-modified polyvinyl chloride paint using a one-year calendar in black letters instead of the floral design of the transfer foil B, and using titanium oxide and barium sulfate as white pigments Then, a chlorinated polypropylene paint is applied and dried. The transfer foil thus obtained is designated as C. Example 4 850 g of LDPE (density 0.92), 100 g of ethylene-vinyl acetate copolymer, 40 g of jasmine-based floral bouquet blended oil as a flavor, 20 g of 12-hydroxystearic acid ester (mp. 55 ° C.) 20 g, carnauba wax (mp) (82.degree. C.), 10 g is put in a nitrogen stream, sealed, heated and dissolved, followed by stirring. When a uniform solution is obtained, the contents are drawn out of ice water under reduced pressure from an outlet provided at the bottom of the pressure cooker and solidified. The solidified product is crushed in a nitrogen stream to obtain pellets of the scented resin composition. Put these pellets into a small injection molding machine,
Injection molding is performed under the conditions of 0 ° C. and a mold temperature of 50 ° C. to form a plate having a thickness of 2 mm. No liquid bleed is observed from the surface of the plate-like material, but if the above mixing ratio changes, for example, a fragrance
If 50 g were not used and 12-hydroxystearic acid ester and carnauba wax were not incorporated, liquid bleeding would occur, which would be detrimental to subsequent transfer printing. After the adhesive layer of the transfer foil A was brought into close contact with the surface of the plate-like material, a pressure of 10 kg / cm ² was applied from above the PET film with a silicone sponge heated to 175 ° C. for 3 seconds, followed by cooling. And PE
When the T film is peeled off, it becomes a fragrant resin molded product with a picture on which a beautiful polka dot pattern is transferred and printed. The aroma of this product emits jasmine scent for about 6 months when left indoors. Example 5 70 g of ethylene-vinyl acetate copolymer, 30 g of natural white oil as a flavor, 10 g of refined rice wax, and 5 g of jojoba oil-hardened oil
Is heated to 80 ° C. in a nitrogen stream to melt and then cooled to crush the solid to form pellets of the scented resin composition. LDPE (specific gravity 0.92) 500g, HDPE (specific gravity 0.96) 500g
And 50g of silica powder are mixed and once put on a pelletizer, then put into an injection molding machine, resin temperature 170 ° C, molding pressure 100kg
Under the processing condition of / cm ² , it is molded into the shape of a fan. The pattern may be transferred to the molded article after molding by the same method as in Example 4, but the simultaneous molding transfer may be performed using the transfer foil B as follows. That is, the transfer foil B is clamped to the frame fitting set on the core side of the molding die. The clamp is as to face the surface side including the picture layer to the injection nozzle, 160 ° C. After the mold is closed, and injection molded at 200 kg / cm ^2, the molded product was peeled off from the PET film to open the mold By taking it out, it is possible to attach a pattern to only the front side of the fan's bone. If a pattern is also required on the back side, a pattern can be applied after molding according to the fourth embodiment. By attaching a translucent film from both sides of the bone, this fan becomes a beautiful product with the scent of a white platform. Example 6 60 g of an ethylene / vinyl acetate copolymer and 15 g of a purified shellac wax (mp. 100 ° C.) were heated and melted.
-Add 20 g of phenylethyl alcohol (a component of rose oil) to make a completely homogeneous solution. To this solution, 50 g of fine powder of talc in pharmacopoeia is added and cooled while kneading to form a white powder. This white powder is mixed with 300 g of polypropylene powder, placed in a small extruder, heated to 200 ° C. and pressured from 500 to 60
Extruded at 0 kg / cm ² to form a sheet. After adhering the adhesive-coated surface of the transfer foil C to the surface of the sheet-like material, the sheet is inserted into a heating press, and a 200 ° C hot plate is pressed from above the PET film at a pressure of 20 kg / cm ² and taken out a few seconds after pressing. After cooling
After peeling off the PET film, it is cut into a suitable size, and a calendared fragrance sheet that emits a rose odor for about six months can be obtained as a base for stationery. In this example, β-phenylethyl alcohol was used as a fragrance. However, it is a matter of course that a base note has a better scent retention effect than a middle note. If a pattern is printed on the underside of the underlay using a transfer foil of another mode, a scented resin molded article with a double-sided pattern having higher added value can be obtained.

【The invention's effect】

The present invention relates to a molded scented resin article with a picture, and for the first time, it is possible to impart a scent and a picture to a plastics product by an industrially advantageous method. Therefore, the product of the present invention can be provided to various markets by applying to plastics products having various functions which cannot be produced by the conventional technology.
Therefore, it can be said that the effect of the present invention is truly enormous.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Isao Yamamoto, Inventor Kenichi Kamono, Examiner at Nissha Printing Co., Ltd., 3 Mibuhanai-cho, Nakagyo-ku, Kyoto-shi, Kyoto (58) Field surveyed (Int.Cl. ⁶ , DB name) ) B32B 33/00 B32B 27/18 C08J 5/00 C08L 23/00

Claims (3)

(57) [Claims] 1. 80 to 95% by weight of a polyolefin, 3 to 10% by weight of an olefin / ester monomer copolymer, 0.2 of a fragrance
~ 4.0% by weight and ester wax 0.3 ~ 3.0% by weight
A molded scented resin article with a pattern, characterized in that the surface side including the pattern layer of the transfer foil is pressure-bonded to the surface of the molded article during or after molding the scented resin composition containing 2. The olefin / ester monomer copolymer is ethylene / vinyl acetate copolymer, ethylene / vinyl acetate copolymer modified resin, ethylene / vinyl acetate / vinyl chloride copolymer and ethylene / (meth) acrylate. The patterned odorous resin molded product according to claim 1, which is at least one copolymer selected from the group consisting of copolymers. 3. The molded article of a fragrant resin with a picture according to claim 1, wherein the ester wax is at least one wax selected from the group consisting of higher fatty acid esters, higher alcohol esters, and animal and vegetable fats and oils.