TW396185B - Process for producing articles having a soft touch - Google Patents

Abstract

The invention relates to a process for producing a product that is pleasant to touch, essentially comprising the single-step injection moulding of a thermoplastic elastomer composition, chosen from the group comprising polyester block copolymers, polyurethanes and styrene block copolymers, which contains glass fibre. Preferably a polyether ester with a shore D hardness of between 30 and 50 and a MFI of 10-50 g/10 min. containing 35-55 wt. Glass fibre is used in the composition. The product obtained preferably has a stiffness of at least 2000 Mpa and a shore D hardness of less than 60.

Description

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (彳) The invention relates to a method for making articles with soft touch. Consumers are becoming more demanding about what they buy. In addition to being durable and easy to use, it also requires, for example, aesthetics. In addition to design, the latter is considered a perfect product surface. These aesthetic requirements now include, in addition to vision, a pleasing touch while touching the aforementioned products. Products that must meet the aforementioned requirements such as: electrical and electronic equipment (such as mobile phones, televisions and other audiovisual and recording equipment and so-called remote controls for personal systems) housings, handles, seat armrests, steering wheels, switches and keys. These products also need good toughness and must be able to withstand rough handling. In order to obtain products that meet these requirements, the method stated in this technique ’requires a complicated production method, which will significantly increase costs. References from recent market and technology observations include "Plastics News", July 21, 1997, 'Soft touches for soft-touch products'. According to it,' This product consists of The injection molding method is obtained from a tough polymer composition, and then covered with a soft polymer with a pleasing touch. After that, technical problems to be solved such as: the polymer composition used must have both toughness and rigidity, and the applied The adhesion of the coating to the tough polymer composition must be good. All of these requirements limit the choice of materials. For applications such as mobile phones, acrylonitrile-butadiene-styrene copolymers and polymers are commonly used. Carbonate (AB S + PC) and polyurethane coatings with long alcohol segments. Use less flexible polymers (eg, reinforced with glass fiber) This paper applies Chinese National Standards (CNS) A4 Specifications (210 × 297) -------- Packing II • ((Please read the precautions on the back before seeing this page) " τ--4-Printed by the Central Consumers Bureau of Ministry of Economic Affairs, Consumer Cooperatives A7 B7_____ 5. The description of the invention (2)) includes the defects of imperfect surface, so it is necessary to hide these defects with a thick and relatively expensive polyurethane coating. This coating is made by traditional equipment or continuous mold. According to other (known) methods described above, a fine texture with a pleasing touch is formed on the surface of a product formed of a tough polymer. An example is a texture equivalent to citrus peel. This The texture can sometimes be applied later, or it must be applied in the form of a negative film on the inner wall of the mold used to make the product, which is difficult and expensive, and is generally not the best choice for consumers. The inventors have now found a simple According to the method, a product having the aforementioned desired properties is obtained in a single operation. The method for producing a pleasing touch product according to the present invention comprises a glass fiber reinforced thermoplastic elastomer Ester-linked copolymers, polyurethane, and styrene-linked copolymers) were subjected to a single-step injection molding process. Polyether monoester copolymers are preferred. The glass fiber content in the composition varies widely, such as between 20 and 70% by weight based on the total composition. The preferred glass fiber content is between Between 30 and 60% by weight. The optimal content of glass fiber is between 35 and 55.5% by weight. The choice of glass fiber content depends on the toughness required of the product. In the best case, the toughness (Determined by flexural modulus) At least about 2 〇 〇 〇 Μ P a ο has known the high glass fiber content of the elastic composition 'but not on the market (please read the precautions on the back before, ^-, 4. this page) .Packing. _ The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -5- printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs «. A7 B7 V. The description of the invention (3) is for sale. Moulding applications. The type of fiberglass depends on the type of glass, size or size. The type chosen depends on the desired mechanical properties. Here, sizing is usually used to ensure a strong bond between the glass fiber and the thermoplastic elastomer matrix. Those skilled in the art can select commercially available glass fibers based on specific experiments. The higher the aspect ratio (length / diameter) of the fibers in the composition, the better, such as: at least about 20, preferably an aspect ratio of at least 30, and more preferably at least 40. ‘But these better aspect ratios should n’t hinder the possibility of using glass fibers with smaller aspect ratios to achieve satisfactory results for a particular application. The diameter of this fiber is usually between 1.5 and 35 mm, and the diameter of the fiber is preferably < 15 microns. When manufacturing such as electrical and electronic equipment casings, the composition also contains material fibers (such as steel fibers) that can absorb electromagnetic radiation, which often has its advantages. These fibers are added in an amount sufficient to protect them. The amount is measured individually. This composition can also contain general additives, such as: stabilizers that resist oxidative and light effects, processing aids (such as flow promoters, especially polytetrafluoroethylene), colorants and pigments, and additives ( (Eg clay and / or talc) and flame retardants as required. The thermoplastic elastomer used as the matrix material is selected from the group consisting of polyurethane, styrene-based copolymers and polyester-based copolymers. These polymers are described in, for example: Thermoplastic Elastomers (Thermoplastic Elastomers) 'Second Edition (Hanser Verlag, Munich (1 996), ISBN Bu 56990-205-4) Sections 2 and 3 This paper standard applies to Chinese National Standards (CNS ) A4 specification (210X297 mm) -6-(Please read the precautions on the back to reproduce, this page) Binding-booking printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 __B7 V. Invention Description (4), 4, Chapters 8 and 9. These are incorporated herein by reference. For practical reasons, especially the highly demanding processing conditions (such as low moisture content) and the processed product must take a long time to reach its final mechanical properties, so it is less desirable to use thermoplastic polyurethane. Ammunition. There are some problems in the processing of styrenic block copolymers: viscosity is closely related to shear force and its viscosity is very high especially when the shear force is small. Therefore, it is extremely demanding when it is processed by injection molding. Therefore, 'polyester-based copolymers are preferred, especially polyether-ester-based copolymers. They can be optionally mixed with crystalline polyalkylene esters such as polyethylene terephthalate (PBT). What was most surprising was the discovery that the use of these thermoplastic elastomeric compositions gave a pleasing touch and perfect surface in a single step injection molding operation. The toughness of the product obtained during the mold molding process can be changed by modifying the elastomer matrix and the glass fiber brightness. The choice of polyether monoester copolymers exhibits additional advantages: the surface properties can be substantially unchanged. This results in a considerable degree of change in toughness. Taking the crystallization rate into consideration, a polyether monoester-based copolymer containing a hard segment composed of a butyl terephthalate or a naphthalene succinate unit is preferable. As for the soft segment unit ', an alkylene oxide having 2 to 8 carbon atoms is preferred: In a more preferred case, the soft segment is mainly composed of propylene oxide and / or butylene oxide units. Ethylene oxide-based block copolymers have the disadvantage that they can absorb large amounts of water and the resulting products have poor dimensional stability. For the same reason, the polyether monoester copolymer is connected by polyester monoester and polyether monoamine. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). Note again # \ this page)

A7 B7__Fifth, invention description (5) Copolymer is preferred. The molecular weight of the soft segment is preferably between 400 and 300, and the concentration of the soft segment is between 10 and 65% by weight based on the polyether monoester copolymer. It is preferably between 20 and 60% by weight. Therefore, the Shore D hardness of the matrix can be between 30 and 75, preferably between 30 and 50 (measured according to I S 0 R 8 6 8). Here, a very big advantage lies in an unusual phenomenon: in addition to the high content of glass fiber, the hardness of the softened polyetherester which is strengthened is only slightly higher than that of the unreinforced one, which can obtain the required high Toughness without affecting the pleasing touch. In a preferred case, the molecular weight of the thermoplastic elastomer is selected so that its melt viscosity (expressed as the melt flow index MF I, measured at 230 ° C and 2.16 kg according to ASTM D 1238, the unit is grams per 10 minutes ) Between 50 and 10, preferably between 30 and 15, MFI is about 25 grams / 10 minutes is best. The injection molding process is performed under conditions typically used for thermoplastic elastomers. These conditions are listed in the product manual attached to the raw material supplier. Glass fiber-containing thermoplastic elastomer compositions can be obtained from composite components in a general manner, such as by mixing a solid phase (powder or particulate) polymer with glass fibers. This composition can then be sent directly to the extruder of an injection molding machine. In another method, glass fibers and thermoplastic elastomers and other additives, as appropriate, are mixed in the molten state, which is usually the preferred method. General melt-mixing equipment can be used for this purpose. It is better to use an extruder. After that, the glass fiber and the thermoplastic elastomer are sent to the entrance at the same time. In another embodiment, first melt (please read the precautions on the back before ^^ this page) • The size of the paper is bound to the Chinese national standard (CNS ) A4 size (210 × 297 mm) -8-Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 ___B7 V. Description of the invention (6) Spring material, and then introduce the glass fiber into this melt. In the example mentioned later The larger the fiber length in the composition, the more favorable it is for the toughness of the injection molded product. According to the present invention, the glass fiber is well dispersed in the product. This is even more so. The so-called 'tactile touch' is a subjective feeling. Although dedicated to investigation, its characteristics cannot be determined with a single physical parameter. Parameters such as roughness, hardness and surface abrasion resistance Participate here. Therefore, consumer objects use the so-called tactile judging panel to get the most accurate surface average evaluation possible. In the example of this application specification, this is used Quantitative evaluation method. Unless otherwise stated in the experiment, the composition is obtained by mixing with the help of Werner and Pfleiderer ZSK 53 double-strand screw extruder. The glass fiber is introduced into the melted polymer, and the composition is obtained. Samples were formed by injection molding for mechanical testing, and the test of the mobile phone casing was performed by a user evaluation panel. The mobile phone casing was based on this technical statement (continuously molded with AB S / PC and polyurethane Ester-coated and patterned ABS / PC injection molding), which was also tested by a judging panel.

Hytrel ®, polyether monoester copolymer 1) 'Shore D hardness 52, from DuPont de Nemours ---------- • ·. * ((Please read the precautions on the back before \ i : This page) The paper size of the edition is applicable to China National Standard for Ladder (CNS) A4 (21〇 × 2ί > 7 mm) -9-398185 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) ArnUel ® Polyether Monoester Copolymer 11, Shore D hardness 40-5 5 from DSM Arnitel®, Polyether Monoacetate Copolymer 2), ShoreD Hardness 3 8 'from DSM Elastollan ® 1185A10, poly Ether-urethane group copolymer, ShoreD hardness 39, from Elastogram / BASF (MF I is 90 and 8 respectively) Glass fiber: OCF ® 429YZ, from Owens-Corning, length '4.5 mm ; 10 microns in diameter. The present invention will now be further described with reference to the following examples and comparative examples, but it is not intended to limit the present invention by these examples. Example test method The properties of the surface of the obtained product are determined by the following tests: Hardness: Shore D, according to ISO R 868 Perfection: Observed with the naked eye + no obvious irregularities are observed 0 small defects-irregular surfaces 1 Based on butadiene phthalate hard segment and butylene oxide soft segment 2 Based on butadiene terephthalate hard segment and polypropylene oxide soft segment whose end is ethylene oxide The evaluation is the average of the evaluation by a judging panel composed of users --------- installed II • ·.. C (Please read the precautions on the back before refurbishing. ¾ • this page)-Order 11. This paper The scale adopts the Chinese National Standard (CNS) A4 specification (210X297 mm) -10- 396185 ---- ~ i •, the description of the invention (8) makes it as objective as possible. + At least 80% of the panelists found it interesting 0 No difference ~ At least 80% of the panelists gave a negative evaluation Bending property: flexural modulus IS ◦ 178 Impact resistance: Izod notched ISO R 180 (2 3. (:) MFI: ASTMD 1 2 3 8 The composition under test and its results are listed in Table I. I Comparative Example The phone casing was obtained according to the state of the art, that is, A) after polymerization with a long alcohol segment. The urethane-coated ABS + PC and B) ABS + PC with a patterned surface were evaluated by members of the judging panel (+) and no difference (0). Note: The phone case with a pattern on the surface may slip out of the hand. (Please read the precautions on the back before dreaming about this page) -Pack

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Claims (1)

Public--1 396185 A & CD * 12.S 8al years of repair 6. Appendix 1 (A) (Please read the precautions on the back before filling this page) Patent No. 87 1 1 66 1 5 Amendments to the scope of the Chinese application for patents in the Republic of China 1988. Amendments in February 1. A method for making a piece with a soft touch, one feature is that it contains a thermoplastic good elastic material composition fan-single-table abrupt injection Molding procedure 'This thermoplastic, elastomeric, and elastomeric composition includes polyester-based copolymers, polyurethane, and styrene-based copolymers containing glass fibers.' Wherein the hardness of the thermoplastic elastomer (in terms of Shore D represents) between 3 (and 7 5), and the melt viscosity of the thermoplastic elastomer (expressed as the melt flow index MFI, measured according to ASTM D1238 'at 230 ° C, 2.16 kg, the unit is g / 1 (0 minutes) is between 50 and 10 ° 2. The method of the first item of the scope of patent application 'wherein-', the thermoplastic elastomer is a polyether monoester copolymer. Employees of the Bureau of Intellectual Property, Ministry of Economic Affairs Printed by Consumer Cooperatives 3. If method 1 or 2 of the scope of patent application is 'where' The glass fiber content is 20 to 70% by weight based on the total composition. 4. The method 'wherein' the glass fiber is as described in item 3 of the patent application. The content is 35 to 55% by weight based on the total composition. ° 5. The method according to item 1 of the scope of patent application 'wherein' the hardness of the thermoplastic elastomer (represented by Shore D) is between 30 and 50. 6. The method according to item 1 of the scope of patent application 'where 'The melt viscosity of thermoplastic elastomers (expressed as the melt flow index MF 1') According to the paper size, the Chinese National Standard (CNS) A4 specification (210 X 297 male «) is published--1 396185 A & CD * 12. S 8al Year of Repair 6. Attachment 1 (A) to the scope of patent application (please read the notes on the back before filling this page) No. 87 1 1 66 1 No. 5 Chinese Patent Application Amendment of the Republic of China 8 8 years 1 2 Month Correction 1. A method of manufacturing a piece with a soft touch, one feature is that it contains a thermoplastic good elastic material composition fan-single-table flash injection molding process' this thermoplastic, elastic material composition contains Polyester block copolymer, polyurethane and styrene block copolymer Polymer containing glass fibers' where the hardness of the thermoplastic elastomer (represented by Shore D) is between 3 (and 7 5) and the melt viscosity of the thermoplastic elastomer (represented by the melt flow index MFI, according to ASTM D1238 'Measured at 230 ° C, 2.16 kg, the unit is grams / 10 minutes) between 50 and 10 ° 2. If the method of the scope of patent application No. 1' its-in, 'thermoplastic The projectile is a polyether monoester copolymer. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3. The method of applying for item 1 or 2 of the scope of patent application, wherein the glass fiber content is 20 to 70% by weight based on the total composition. 4. The method according to item 3 of the patent application 'wherein' the glass fiber. The content is 35 to 55 wt% based on the total composition ° 5. The method according to item 1 of the patent scope 'where' the thermoplastic elastomer The hardness (expressed as Shore D) is between 30 and 50 °. 6. The method according to item 1 of the scope of the patent application, where 'The melt viscosity of the thermoplastic elastomer (indicated by the melt flow index MF 1') According to the paper size, the Chinese National Standard (CNS) A4 specification (210 X 297 public «) 396185 A8B8C8D8 6. The scope of patent application ASTM D1238, measured at 23 ° C, 2.16 kg (the unit is grams per 10 minutes) is between 30 and 15. 7 _-A product obtained by the method according to the first item of the patent application, wherein the product has a toughness (expressed in flexural modulus) of at least 2000 MPa. 8 .—A product obtained by the method according to the scope of patent application No. 1 ', in which the Shore D hardness is lower than 6 ◦. (Please read the precautions on the back before filling this page) -------. 1 Order ·· -------- Line, Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, Paper Size Applicable to China National Standard (CNS) A4 (210 X 297 mm) -2-