IMPREGNATION-PRINTED MOULDED ARTICLE

Abstract: A moulded plastic article carrying impregnated characters, symbols etc comprises a thermoplastic polyester resin formed from a mixture of (A) a polyester and (B) a polymer compound containing as its polymer skeleton at least one kind of material from the group consisting of butadienes, styrenes, acrylonitriles, and acrylates, the characters etc being impregnated from the surface into the interior of the article.

Description: This invention concerns an impregnation-printed moulded article comprising an article moulded of a composition consisting of a thermoplastic polyester resin (A) and, in mixture therewith, a thermoplastic plastic compound (B) containing as a polymer skeleton component unit at least one kind of material from the group consisting of butadienes, styrenes, acrylonitriles, and acrylates, the moulded article being impregnation-printed. Articles moulded of such a composition have excellent impregnation printability and can be advantageously used for such applications as keys (and more particularly key tops) for personal computers, word processors, typewriters, electronic calculators, telephone sets, and the like, which have characters, symbols, patterns, etc. impregnation-printed thereon. Prior Art and its Problems Recently, it is a general practice to form characters, symbols, patterns on moulded article surfaces to give some particular functions to the moulded articles. In such applications of moulded articles, and more particularly in those applications which involve very frequent use, such as keys (key tops in particular) for personal computers, word processors, typewriters, electronic calculators, and telephone sets, permanent properties against frictional wear are particularly required to ensure that the characters, symbols and the like formed on the moulded article surface are prevented from fading or vanishing away. Also, there are often cases where comfort in handling (good touch qualities) during use, prompt adaptability for varieties of characters and symbols and for diverse types of equipment. and good economical features are required. With known printing methods, such as dry offset printing, screen printing, and pad printing, it is impossible to provide prints of characters, symbols, and the like which have good performance properties against frictional wear. With any hot stamping method, or a method such that a part corresponding to a character or symbol on a moulded article is recessed in the mould, which recess is filled with an ink after moulding, one difficulty is that a concave and convex pattern is formed on the moulded article surface, which is often a source of discomfort in touching the moulded article when in use. Another difficulty is the lack of adaptability for varieties of characters and symbols, which fact is economically inconvenient. ln order to overcome these difficulties, one recent approach (the direct method) is to employ an impregnation printing method such that characters or symbols are printed directly on a moulded article by pad printing or screen printing techniques, using a special ink incorporating a sublimating dye. The moulded article is then heat treated so that the sublimating dye in the ink is impregnated and fixed into the moulded article interior. Another approach receiving attention (the heat transfer method) is that characters and/or symbols are printed in such aforesaid special ink on a release paper, the printed release paper is then placed on a moulded article and heat pressed thereon so that the dye in the ink is impregnated and fixed into the moulded article interior. Such impregnation printing, which permits the dye to penetrate deep into the resin, can provide good print with excellent wear resistance and good handling comfort during use; further it is adaptable for formation of various different characters and symbols and economical as well. However, such printing is not applicable to all types of resins. Depending upon the type of resin, the dye may not penetrate well into the resin, which results in a poor printing effect and inferior performance against frictional wear. In some uses, the dye may become diffused with the result of blurring and lack of clearness. In practice the impregnation printing technique is currently employed with only a limited variety of resins, including polyacetals and polybutylene terephthalates. An article in "Design Engineering", Vol 232 January 1985, Page 31, London GB, entitled "Printing development allows rationalisation of plastic moulding" describes the use of PBT for computer keytops. With many other types of resins, such as ABS resin and the like, impregnation printing involves the above-mentioned problems and, as such, it has not yet been reduced to practical application. Even with polyacetal and polybutylene terephthalate resins, there is a problem of blurring which arises from heating and improvements are required in this respect. Thus, development has been strongly demanded of resins which allow good ink impregnation and fixing during printing, assuring good stability of printed characters and symbols against wear, heat, ultraviolet rays, and other environmental conditions, and yet which have excellent mechanical, physical, and chemical properties. EP-A-0 201 627 which constitutes prior art according to Art. 54(3)(4) EPC for the following designated contracting states: BE, DE, FR GB, IT, NL, SE, describes a process for sublimation printing of plastics materials. It is stated that the process can be carried out with materials such as acrylonitrile butadiene styrene, cellulose acetate polyamides, polycarbonates, polyesters such as polybutylene terephthalate or a mixture of said polymers such as polycarbonate/ABS or polycarbonate/PBT. Summary of the Invention The present inventors made a series of studies into the possiblities of solving these problems in order to produce satisfactory impregnation-printed moulded articles, and as a result they found that impregnation printing, with such excellent print effect that had never been achieved, could be made with mouldings of a composition consisting of a thermoplastic polyalkylene terephthalate resin (A) blended with a thermoplastic polymer compund (B) containing as a polymer skeleton unit at least one kind of material from the group consisting of butadienes, styrenes, acrylonitriles, and acrylates, all of which had been considered to be unsuitable for impregnation printing. This finding led to the present invention. Thermoplastic polyalkylene terephthalate resins (A) used in the invention are homopolyesters, copolyesters, and the like which are produced through polycondensation of a dicarboxylic acid compound and a dihydroxy compound, or polycondensation of oxycarboxylic compounds, or polycondensation of a tricomponent mixture of them. One kind of such resin may be used alone, or two or more kinds of such resin may be used in mixture. Preferably, polybutylene terephthalate is advantageously used. If desired, the polyester may be one modified through such known techniques as crosslinking or graft polymerization. The thermoplastic polymer compound (B) may be any of such materials as, for example, acrylo-nitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, methylmethacrylate-butadiene-styrene (MBS) resin, ethylene-ethylacrylate (EEA) resin, acrylonitrile-EPDM-styrene (AES) resin, acrylonitrile-styrene-special acrylic rubber (AAS) resin, polymethyl methacrylate (PMMA) resin, and butadiene or acrylonitrile rubber. These resins may be used either singly or in a mixture of two or more kinds, with good effect. The present invention thus provides a moulded article comprising a thermoplastic polyester resin incorporating a mixture of (A) one or more polyalkylene terephthalate resins and (B) a polymer produced from at least one kind of material from the group consisting of butadienes, styrenes, acrylonitrile and acrylates, the resin being impregnated with printing dye which extends from the surface to the interior of the article. The mixture ratio of the two components for production of such moulded article is: thermoplastic polyalkylene terephthalate (A)/specific thermoplastic polymer compound (B) = 99 ∼ 1/1 ∼ 99 (percent by weight). Preferably, such ratio is 95 ∼ 10/5 ∼ 90 (percent by weight), more preferably 90 ∼ 30/10 ∼ 70 (percent by weight). More strictly, an optimum value is often found within the range of 80 ∼ 40/20 ∼ 60 (percent by weight). In the present invention, it is possible to further add known additives and/or fillers to aforesaid composition of which a moulded article is formed, to such extent as is reasonably compatible with the impregnation printability of the moulded article and according to the purpose for which the moulded article is used. For example, any of the following may be added: stabilizers for anti-oxidation and weathering purposes, lubricants, plasticizers, nucleating agents, parting agents, anti-static agents, surface active agents, and the like; glass fibers, metal fibers, potassium titanate, glass flakes, glass heads, micas, talc, wollastonite, calcium carbonate, titanium oxide, alumina, silicon carbide, boron nitride, ceramics, metal powder, and the like inorganic compounds in fibrous, lamellar, granular, and powdery forms. Methods for preparation of moulded articles in the present invention are not particularly limited. Any conventional method may be employed. For example, one method is such that all component materials for construction of a moulded article are mixed together and the mixture is melted, kneaded, and extruded by means of an extruder, the mixture being thereby pelletized;thereafter, the moulding operation is carried out. Another method applicable is such that pellets of different compositions are first prepared and they are mixed and moulded into any desired mouldings. Another method is such that all component materials are loaded into a moulding machine so that mouldings of the desired composition are produced. Impregnation printing techniques employed in the invention are not particularly limited. Any known method may be employed. For example, one method is such that characters, symbols, or the like are printed in a special ink incorporating a sublimating dye directly on the moulded article by employing conventional printing techniques, such as pad printing, screen printing, or the like, then heat treatment is effected to permit the dye in the ink to become penetrated and fixed into the moulded article interior. Another method is such that characters, symbols, or the like are printed with aforesaid special ink on a release paper, and then the printed release paper is placed on the moulded article and is heat pressed thereon so that the dye in the ink is penetrated and fixed into the moulded part interior. [Examples] The following examples and comparative examples are given to further illustrate the invention. It is to be understood, however, that the invention is not limited to these examples. In the following examples and comparative examples, impregnation printing and evaluation were carried out respectively according to the following method: Test piece Flat plate (50mm × 70mm × 3mm) Impregnation Printing Method Each test piece was degreased by supersonic cleaning in 1,1,1-trichloroethane, then dried. Then, printing was effected directly on the test piece with an ink of SMX PBT (India ink) F-1/reducer liquid WKLTD (a product of Toyo Ink K.K.) = 10/1 and by employing the pad printing technique, and the printed plate was heated and baked at 160°C for 8 min. (if the resin is melted or softened at that temperature, heating/baking was effected at a temperature that was 20 ∼ 30°C lower than the melting or softening temperature of the resin, for 30 ∼ 60 min.) so that the ink was penetrated and fixed into the resin. Finally, the surface was cleaned with solvent and then dried. Evaluation Method Immediately after each test piece was impregnation-printed, and also after the impregnation-printed test piece was treated for 240 hrs in a thermo-hygrostat of 80°C and 95% RH, evaluation was made with respect to the following: Appearance (print clearness, ink blur, and the like) Visual observation was made by the naked eye and also by a 10X magnifier. Evaluation was made in 10 steps. Ink Adhesion Print peel test by cellophane tape, and wipe-off test with solvent. Print resistance to wear 10,000-time wear test with plastic eraser. Examples 1 ∼ 5 and Comparative Examples 1 ∼ 2 A polybutylene terephthalate (PBT) resin having an inherent viscosity (I.V.) of 0.75 and an acrylonitrile-butadienestyrene (ABS) resin (a product of Ube Industries, Ltd,: Sicolac GSM) were mixed in each respective ratio shown in Table 1, and the mixture was extruded by a twin-screw extruder into pellets. Test pieces were prepared from these pellets by injection moulding and impregnation-printed. The so-printed test pieces were respectively evaluated. For comparison, test pieces moulded of PBT resin and ABS resin respectively were prepared and evaluated in similar manner. The results are shown in Table 1. Nothing abnormal was observed with either the examples or the comparative examples in the evaluation of ink adhesion and print resistance to wear. Examples 6 ∼ 13 and Comparative Examples 3 ∼ 7 A PBT resin having an inherent viscosity of 0.75 was mixed with AS resin, MBS resin, EEA resin, AES resin, or PMMA resin. Test pieces were treated and evaluated in same manner as in Examples 1 ∼ 5. Their respective compositions and evaluation results are shown in Table 2. With either the examples or the comparative examples, nothing abnormal was found in the tests as to ink adhesion and print wear resistance. Examples 14 ∼ 16 and Comparative Example 8 Polyethylene terephthalate (PET) resin was mixed with ABS resin. Test pieces were evaluated in same way as in Examples 1 ∼ 5. For comparison, test pieces composed of PET resin alone (and those of ABS resin alone) were also evaluated in the same manner. Results are shown in Table 3. With these examples and comparative examples, nothing abnormal was observed in the tests as to ink adhesion and wear resistance. As may be clearly understood from the foregoing examples and comparative examples, by using as a substrate for impregnation printing a moulded article of a composition consisting of a thermoplastic polyalkylene terephthalate resin blended with a thermoplastic polymer compound having as its polymer skeleton at least one kind of material selected from the group consisting of butadienes, styrenes, acrylonitriles, and acrylates, all of which have been previously considered to be unsuitable for impregnation-printing, it is now possible to obtain an impregnation-printed moulded article having improved impregnation printability, much better print clarity, better ink adhesion, remarkably less ink blurring due to heat treatment, and much better performance against frictional wear as compared with articles moulded from the individual resins independently.

Claims: A moulded article comprising a thermoplastic polymeric resin incorporating a mixture of (A) one or more polyalkylene terephthalate resins and (B) a polymer produced from at least one kind of material from the group consisting of butadienes, styrenes, acrylonitriles and acrylates, the resin being impregnated with printing dye which extends from the surface into the interior of the article. A moulded article as set forth in claim 1, wherein the polyalkylene terephthalate resin (A) is a polybutylene terephthalate resin. A moulded article as set forth in claim 1 or claim 2, wherein the polymer (B) is an acrylonitrile butadiene styrene (ABS) resin. A moulded article as set forth in any one of claims 1 to 3, wherein the polymer (B) is an acrylonitrile styrene (AS) resin. A moulded article as set forth in claim 1 or claim 2, wherein the polymer (B) is a methylmethacrylate butadiene styrene (MBS) resin. A moulded article as set forth in claim 1 or claim 2, wherein the polymer (B) is an ehtylene ethylacrylate (EEA) resin. A moulded article as set forth in claim 1 or claim 2, wherein the polymer (B) is a polyacrylate resin. A moulded article as set forth in any preceding claim, wherein the proportion of polymer (B) is 5 to 90% of the total weight of polyalkylne terephthalate resin (A) plus polymer (B). A moulded article as set forth in any preceding claim, wherein the proportion of polymer (B) is 30 to 70% of the total weight of polyalkylene terephthalate resin (A) plus polymer (B).

Inventors: FUKUI, KIITIRO, SATO, TSUNENOBU
Applicants: POLYPLASTICS CO. LTD.
Application year: 1987
Main classification: B41M1
IPC codes: B41M1, C08L67, C09B5