JPH1057215A - Tableware formed out of highly functional thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To keep neutrality in taste and allow both of cleaning and washing processes to be repeated by making tableware using a composition formed out of highly func tional thermoplastic resin and irradiating a high energy radiation thereto. SOLUTION: Highly functional thermoplastic resin to be used, or polyarylene ether has a repetition unit I, and is expressed as shown in the formula, where (t) and (q) have a value between 0 and 3, and T, Q and Z are independent of one another. The amount of highly functional thermoplastic resin A contained in a composition is advantageously between 1 and 100wt.%, preferably between 10 and 90wt.% and particularly between 30 and 70wt.%. Also, the residue of the composition contains a thermosetting polymer B existing by volume advantageously between 0 and 99wt.%, preferably between 5 and 80wt.% and particularly between 10 and 60wt.%, and at the same time, other additives and a processing assistant C existing by a volume advantageously between 0 and 70wt.%, preferably between 5 and 60wt.% and particularly between 10 and 40wt.%. A laser to be used in this case is a CO2 laser (wavelength: 10.6μm) having a frequency multiplier (wavelength: 532, 355 and 256nm), preferably an excimer laser.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a food utensil formed from a high-performance thermoplastic resin (A). If desired, the utensil can be laser inscribed or provided with a pattern.

[0002] Furthermore, the present invention relates to a method for manufacturing the above-mentioned eating utensils, in which case a single pattern, for example an inscription, may be provided as required.

[0003]

2. Description of the Related Art In Asian countries, for hundreds of years,
Meals are eaten using chopsticks. The chopsticks are advantageously wooden. However, over the last few years, the use of wood has been reduced in some countries to protect forests.

Accordingly, synthetic materials, such as thermosetting resins or styrene polymers, have also been used for several years. However, this material has the disadvantage that if it is used repeatedly, it will become friable in the subsequent cleaning process and will lose its appeal and will soon have to be replaced.

[0005] In addition, metal chopsticks are used in a limited manner, but the metal chopsticks are relatively heavy and have a different feel from wooden ones. Also, metal chopsticks have an adverse effect on taste. This is because the use of metal chopsticks is only accepted by consumers.

In the Western world, eating utensils such as plastic knives, forks or spoons have also been evaluated and used in recent years. However, plastic meals that have been sold so far,
Similarly, plastic chopsticks have the disadvantages mentioned above.

[0007] The use of compositions based on polyethersulfone and other thermoplastics possible for kitchenware is known from the description of EP 0127852. As a required profile for this type of material, this European Patent states that it is particularly important for the heat resistance, diverse use and simple cleaning of kitchenware made from thermoplastics. I have. The ability to imprint the kitchenware described herein includes:
It is not mentioned in this European patent specification.

[0008] In addition, medical cups and surgical tweezers made from compositions based on polysulfone or polyethersulfone are known. The requirements for such products used in medicine are likewise significantly different from the requirements for eating utensils. That is, sensory properties such as, for example, gustatory neutrality do not play any role in such applications ("Ultrason in der medizintechni").
k ", Kunststoffe 83 (1993), 622-625).

[0009] It is also possible, in principle, to imprint a pattern on a thermoplastic molding material as used within the scope of the invention for producing eating utensils, for example by using high-energy radiation. Is also known. Thus, for example, the description of DE-A 44 16 129 describes the use of such molding materials for producing shaped articles which can be inscribed by using high-energy radiation, and thus also the inscription. The present invention relates to a method for producing a shaped article that can be subjected to the following. The method of imprinting shaped articles based on thermosetting or thermoplastic polymers or mixtures of these polymers themselves is the subject of DE-A-195 31 1490.5.

[0010]

SUMMARY OF THE INVENTION The object of the present invention, in connection with the prior art described above, is to avoid the drawbacks of plastic or non-wooden eating utensils which have hitherto been used, in particular eating utensils. Is to provide chopsticks. Therefore, the object of the present invention is to have a light, taste-neutral, pleasant sensational property for the user, which can be repeatedly cleaned and washed and, if necessary, sterilized with hot steam. It is to provide eating utensils that can be made to work. In addition, the utensil should have sufficient resilience to avoid breakage during use and / or cleaning and also have the mechanical strength required for repeated use. Moreover, the eating utensil must be simple, fast and inexpensive to be advantageously manufactured by injection molding, and must be recyclable. Also,
The materials used must be capable of laser inscription on the resulting eating utensils, or
It must be able to provide three patterns (prints).

[0011]

According to the present invention, there is provided an ink jet recording head comprising a composition comprising a high-performance thermoplastic resin (A).
It has been found that this is achieved by the described eating utensils.

[0012] Claim 2 describes a method for producing a meal with one pattern, and claim 3 describes a high-performance thermoplastic resin with one pattern. A food utensil obtainable by a method comprising irradiating a food utensil formed from.

[0013]

DETAILED DESCRIPTION OF THE INVENTION As used herein, the term "eating utensils" includes knives, forks, spoons, but especially chopsticks as primarily used in Asia. .

The above composition is a high-performance thermoplastic resin (A)
Consists of A list of suitable high performance thermoplastics can be found, for example, in Kunststoff-Taschenbuch.
-Taschenbuch) (ed. By Saechtling), 1989 edition, where the sources are also mentioned. The production of such high-performance thermoplastics is known per se to the person skilled in the art. Further details of some preferred plastic molds are described below.

1. Polyarylene Ether The polyarylene ether used according to the invention comprises a repeating unit I:

[0016]

Embedded image

[0017]

In this case, t and q are each 0,
It can take the values 1, 2, or 3. T, Q and Z may be each independently the same or different. These T, Q and Z are -O-, -SO
It can be a chemical bond or group selected from _2- , -S-, C = O, -N = N- or S = O. Further, T, Q and Z are represented by the formula -R ^a C = CR ^b -or-
CR ^c R ^d-wherein R ^a and R ^b are each a hydrogen atom or a C ₁ -C ₁₀ -alkyl group, R ^c and R ^d are each a hydrogen atom, a C ₁ -C ₁₀ -alkyl group, such as methyl, ethyl, n- propyl, isopropyl, tert-butyl, n- _hexyl, C 1 _{-C 10} - alkoxy groups such as methoxy, ethoxy, n- propoxy,
Isopropoxy, n-butoxy or a C ₆ -C ₁₈ -aryl group such as phenyl or naphthyl]. Also, the groups R ^c and R
^d, together with the carbon atoms to which they are attached a cyclic aliphatic ring, preferably C ₅ -C 7 _- may also form a cycloalkyl ring. Also, this cycloalkyl ring is
It can also have one or more substituents. Preferred substituents _are, C 1 _{-C 10} - embraces alkyl groups such as methyl, ethyl, n- propyl or isopropyl, in particular methyl. Preferably, a polyarylene ether A is described, wherein T, Q and Z are each —O—, —SO ₂ —, C ＝ O, one chemical bond or a group of the formula —CR ^c R ^d —. . Preferred groups R ^c and R
^d includes a hydrogen atom and a methyl group. Among groups T, Q and Z, at least one is, -SO ₂ - or C =
O. Ar and Ar ¹ are a C ₆ -C ₁₈ -aryl group such as 1,5-naphthyl, 1,6-naphthyl,
2,7-Naphthyl, 1,5-anthryl, 9,10-anthryl, 2,6-anthryl, 2,7-anthryl or biphenyl, especially phenyl. Said aryl groups are advantageously unsubstituted. However, the aryl group is
C ₁ -C ₁₀ - alkyl groups such as methyl, ethyl, n
- propyl, isopropyl, tert-butyl, n- _hexyl, C 6 _{-C 18} - aryl group such as phenyl or _naphthyl, C 1 _{-C 10} - alkoxy groups such as methoxy, ethoxy, n- propoxy, isopropoxy, n
-It can have a substituent selected from butoxy or a halogen atom. Among these, preferred substituents include methyl, phenyl, methoxy and chlorine.

Some particularly suitable repeating units are shown below:

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

Particularly preferably, the repeating unit (I ₁ )
Compositions having a polyarylene ether having (I ₂ ), (I ₂₅ ) or (I ₂₆ ) as component A are described. The composition is, for example, 100 repeating units (I ₁ ).
Includes compositions having as a high performance thermoplastic (A) a polyarylene ether having about 100 mole% and 100 mole% of repeating units (I ₂ ).

The polyarylene ether may be a copolymer or block copolymer in which a polyarylene ether segment or a segment of another thermoplastic resin is present, such as a polyamide, polyester, aromatic polycarbonate, polyester carbonate, polysiloxane, polyimide or polyetherimide. It may be. The numerical average of the molecular weights _Mn of the blocks or graft chains in the copolymer is generally from 1000 to 30000 g /
In the molar range. The blocks of different structures may be arranged selectively or randomly. The weight ratio of polyarylene ether in the copolymer or block copolymer is generally at least 10% by weight. The weight ratio of polyarylene ether can be up to 97% by weight. Preferably, copolymers or block copolymers having a weight ratio of polyarylene ether of up to 90% by weight are described. Particular preference is given to using copolymers and block copolymers having from 20 to 80% by weight of polyarylene ether.

Generally, the polyarylene ether is 10
It has a numerical average molecular weight _Mn in the range of 000 to 60000 g / mol and a relative viscosity of 1.25 to 1.95. The relative viscosity depends on the solubility of the polyarylene ether, depending on the solubility of the N-methylpyrrolidone at a concentration of 1% by weight or in a mixture of phenol and dichlorobenzene at a weight ratio of 1: 1. It is determined at 20 ° C. or 25 ° C. in solution or in a 0.5% strength by weight solution of 96% strength sulfuric acid, respectively.

The polyarylene ether having the repeating unit I is known per se and can be obtained by a known method.

The polyarylene ether is formed, for example, by condensing an aromatic dihalogen compound and an aromatic bisphenol alkali metal salt. The polyarylene ether can be obtained, for example, by self-condensing an alkali metal salt of an aromatic halogen phenol in the presence of a catalyst. German Offenlegungsschrift 38 43 438 provides, for example, an extensive list of suitable monomers. A suitable method is described, inter alia, in US Pat.
No. 38, U.S. Pat. No. 4,180,837, DE-A-27 38 962 and EP-A-0 00 361. Also, polyarylene ethers having a carbonyl function are, inter alia, WO 84/0389.
2, it can also be obtained by electrophilic (Friedel Crafts) polycondensation. In the case of electrophilic polycondensation, the carbonyl bridge is formed by reacting a dicarboxylic acid chloride or phosgene with an aromatic compound having two hydrogen atoms that can be replaced by an electrophilic substituent. Alternatively, it is formed by polycondensation of an aromatic carboxylic acid chloride itself containing both acid chloride groups and alternative hydrogen atoms.

Preferred processing conditions for the synthesis of polyarylene ethers are described, for example, in EP-A-1131.
No. 12 and EP-A-135130. A particularly preferred method consists in reacting the monomers in an aprotic solvent, in particular in N-methylpyrrolidone, in the presence of anhydrous alkali metal carbonates, especially potassium carbonate. Reacting the monomers in solution has been found to be equally advantageous in many cases.

Depending on the synthesis conditions, the polyarylene ethers can have different end groups.

Examples which may be mentioned are halogen atoms,
In particular, they are chlorine, phenoxy or benzyloxy, hydroxy, anhydride, epoxy or carboxy. The synthesis of such polyarylene ethers is known to those skilled in the art.

2. Polyesters Suitable polyesters are known per se and have been described in publications. Polyester has an aromatic ring derived from an aromatic dicarboxylic acid in the main chain. Moreover, aromatic ring, for example a halogen atom such as chlorine or or may be substituted by bromine or C ₁ -C _4, -
It may be substituted by alkyl groups such as methyl, ethyl, isopropyl or n-propyl and n-butyl, isobutyl or tert-butyl.

The polyester can be produced by a method known per se by reacting an aromatic dicarboxylic acid, an ester or an ether-forming derivative thereof with an aliphatic dihydroxy compound.

Preferred dicarboxylic acids which may be mentioned are naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 10 mol% of aromatic dicarboxylic acid, aliphatic or cycloaliphatic dicarboxylic acid,
For example, it can be replaced by adipic acid, azelaic acid, sebacic acid, dodecandioic acid and cyclohexanedicarboxylic acid.

Among the aliphatic dihydroxy compounds, preferably diols having 2 to 6 carbon atoms, especially 1,2
-Ethanediol, 1,4-butanediol, 1,6-
Hexanediol, 1,4-hexanediol, 1,4
Cyclohexanediol and neopentyl glycol or mixtures thereof are described.

Particularly preferred polyesters include
It can be formed from a polyalkylene terephthalate derived from an alkanediol having 6 carbon atoms. Of these, polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate are particularly preferred.

The viscosity of the polyester is generally from 60 to 20.
0 ml / g (measured at 25 ° C. in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (1: 1 by weight)).

3. Polymethacrylates Among these polymethacrylates, they are based on polymethyl methacrylate (PMMA) as well as methyl methacrylate and are named, for example, Lucryl® from BASF or Plexiglas® from Roehm. Particular mention may be made of copolymers containing up to 40% by weight of other copolymerizable monomers, such as can be obtained under the name of).

4. Polyamides Preferably, polyamides are described which are generally partially crystalline, aliphatic and have any type of partially aromatic or amorphous structure. A corresponding product is available from BASF under the trade name Ultramid®.

5. Polyimides The polyimides used according to the invention are known. The synthesis of this polyimide is described, for example, in US Pat.
7, US Pat. No. 3,847,869, US Pat. No. 3,850,885, US Pat.
No. 42, U.S. Pat. No. 3,855,178, U.S. Pat. No. 3,888,558, U.S. Pat.
No. 511, U.S. Pat. No. 4,024,110,
These are described in U.S. Pat. No. 4,250,279 and German Offenlegungsschrift 440 4891.2.

Furthermore, polyimides are known from the description of EP-A-389092. Such polyimides are used in the production of liquid crystal displays. This is because polyimide helps the alignment of the liquid crystal. Specific diamines having a cycloaliphatic ring for preparing polyimides for the same application are described in EP-A-368604 and EP-A-439362.

Further, diamines for preparing polyimides of this type are described in EP-A-379,006.

Polyimides (or polyetherimides) which are advantageously used within the scope of the invention are described in DE-A-39 27 399 and have the following repeating units:

[0043]

Embedded image

Is provided.

The term polyimide as used herein includes homopolymers, copolymers, terpolymers and block polymers. The Staudinger number of the polyimide used is, for example, N-
0.1 to 3 dl / g, preferably 0.3 to 1.5 dl, measured at 25 DEG C. in methylpyrrolidone or methylene chloride
/ G, especially 0.3-1 dl / g.

As will be clear from the above description, the thermoplastic resin (A) is preferably a polyarylene ether, polyamide, polyester, polymethacrylate, polysiloxane, polyimide, polyetherimide, its copolymer, block copolymer or its copolymer. A mixture of two or more of the above.

It is clear that mixtures of high performance thermoplastics (A) and / or thermosetting polymers (B) may be used.

[0048] In connection with suitable thermosetting polymers, Kunststo-Taschenbuch, supra, is used.
ff-Taschenbuch) (ed. by Saechtling), 1989 edition, in which the sources are also mentioned.

The amount of high-performance thermoplastic resin (A) in the composition is advantageously from 1 to 100% by weight, preferably from 10 to 90% by weight, in particular from 30 to 70% by weight. The residue of such a composition is advantageously between 0 and 99% by weight, preferably between 5 and 8%.
Thermosetting polymer (B) present in an amount of 0% by weight, in particular 10 to 60% by weight, and preferably in an amount of 0 to 70% by weight, preferably 5 to 60% by weight, in particular 10 to 40% by weight Other additives and processing aids (C) present in, for example, fibrous or particulate fillers, such as glass fiber or mineral fillers, such as wollastonite, rubber-elastic polymers (eg EP rubber, EPDM rubber, TPU, Core-shell polymer),
It consists of a UV stabilizer, a nucleating agent, a plasticizer, a flame retardant, an antioxidant and a heat stabilizer, wherein the proportion of the components present is 1
Add up to 00%.

In order to improve the printability or inscription of the eating utensil according to the invention, the composition for forming the eating utensil may comprise fine powders as additives, inorganic black pigments based on iron oxides, To this is added an iron oxide pigment having a spinel or inverse spinel structure, an inorganic transition metal salt, carbon black or ash, respectively, from the residue of the dry-distillable biomass, or a mixture thereof.

The fine powder has an essentially smooth surface structure and differs from the high-performance thermoplastic resin (A1) present in the composition and is selected from polyarylene ethers and polyimides. And spherical particles containing at least one high-performance thermoplastic resin (A2) as an essential component. The amount of fine powder when present in the composition is from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight, in particular from 0.5 to 3% by weight.

The fine powder which can be used according to the invention is, surprisingly, whether it melts the high-performance thermoplastic resin (A2), dissolves this high-performance thermoplastic resin (A),
Alternatively, it can be obtained by reducing the viscosity of the high-performance thermoplastic resin (A) using an appropriate liquid, followed by spray condensation or spray drying. Such fine powders or their preparation are described in DE-A-43 00 326.
The particles obtainable according to DE-A-43 300 326 have a regular, circular and substantially pore-free surface. The average particle size (volume average) is generally 1 μm or more. This average particle size may be low, but is usually at least 0.5 μm. Generally, the average particle size is 80μ.
m. This average particle size can be slightly larger, for example 100 μm. The average particle size is preferably from 2 to 70 μm, particularly preferably from 5 to 50 μm
m, especially 10 to 20 μm. For some applications, an average particle size of up to 300 μm is also required. Also, the average particle size can be even larger, for example 350 μm, but average particle sizes above 500 μm are:
Usually, there are no other advantages for applications such as the production of eating utensils according to the invention. The particles generally have the density of the underlying high-performance thermoplastic (A2). However, the density of the particles may be slightly lower, for example when sealing small amounts of gas.

The fine powder has a narrow particle size distribution. One criterion for the width of the particle size distribution is the relative span factor Δ (AH Lefebvre: “Atomization and Spra
ys ", Hemisphere publishing Corporation, 1989, 1st
00, see equation 3.40). The relative span factor of the fine powder according to the invention is generally between 1 and 2. However, this relative span factor may be higher, but is typically less than or equal to 2.5. Preferably, span factors of up to about 1.5 are described. Particularly preferably, a span factor of less than 1 is described.

In addition, the compositions used according to the invention can contain 1 to 200 ppm, preferably 5 to 100 ppm, of pigment as additive (C).

Such additives are, for example, bone ash obtainable from calcined or ground animal bones. Proper milling and post-treatment of raw bone char leads to products which vary in color purity and particle size.

Conventional bone ash generally has the following suitable composition: 85-90% by weight of calcium phosphate, 7.5-12% by weight of carbon, up to 1.5% by weight of water.

The pH is generally in the range from 7 to 9, especially 7.0.
The density is in the range of 5 to 8.5 and the density is 1.8 to 3.
0 g / cm ^3, preferably in the range of approximately 2.1 to 2.5 g / cm ^3.

Bone ash suitable for the composition used according to the invention is, for example, Hoover Color Corpora
is available under the name “Bone Black” from tiontion).

Suitable carbon blacks are in principle described, for example, in Encyclopedia of Chemical Technology, Volume 3, page 34 et seq. (Interscience Encyclopedia, New York).
It is described in.

Further, a suitable pigment is iron oxide black (Fe
₃ O ₄ ), spinel black (Cu (Cr, Fe) ₂ O ₄ ) and manganese black (manganese dioxide and silicon dioxide;
A mixture with iron oxide). Further, a copper phthalocyanine pigment can also be used.

As another additive for improving printability or inscription, the composition comprises from 0.01 to 4% by weight of an inorganic black pigment based on iron oxide as an essential component, It can also be present as an additive in an amount of preferably 0.02 to 3% by weight, in particular 0.02 to 1% by weight. Preferred iron oxide pigments have a spinel or inverse spinel structure.

The spinel lattice unit cell has 32 oxygen atoms packed and sealed in a substantially cubic shape. In the case of the standard spinel structure, eight Me ²⁺ ions are located at the center point of the octahedron formed from four O ²⁻ ions (position in the octahedron). In the case of the inverse spinel structure, the cation distribution is different. M
Half of the e ³⁺ ions occupy tetrahedral locations and the other half are co-distributed with Me ⁺² ions at octahedral locations. Also, a transition between two structures having a random distribution of cations is possible. The standard and reverse structures are
The formulas Me ²⁺ [Me ₂ ³⁺ ] O ₄ and Me ³⁺ [Me
^{2 +} Me ³⁺ ] O ₄ . Ferrites include representatives of two structural formulas: zinc ferrite
It has the standard structure Zn [Fe ₂ ] O ₄ , but in the case of magnesium ferrite, the cations are mainly distributed as in the case of the inverse spinel: Fe ³⁺ [Mg ²⁺ Fe ³⁺ ] O _4. ing.

Examples of divalent metals are Mg, Fe (II), Z
n, Mn, Co, Ni and Cu; examples of trivalent metals are Al, Fe (III), V, Cr or titanium. Preferred iron oxide pigments include magnetite (reverse spinel Fe ³⁺ [Fe ²⁺ Fe ³⁺ ] O ₄ ), Cr ³⁺ [Cu
^II, a mixed phase pigment consisting of ^Fe II] _{O 4} and _{Fe 2 O 3 / Mn 2 O} 3.

The preparation of mixed-phase pigments is known from the description of DE 195 490.5.

Another method for producing iron oxide pigments is
Known to those skilled in the art; Roempp Chemie Lexikon, 9th edition,
It is known from the examples described in Georg Thieme (Stuttgart, New York) 1994, p. 1096.

The most customary production method is the aniline method. When nitrobenzene is reduced in an acid solution to form aniline, the reducing agent cast iron is used in the form of fine shavings. This cast iron is oxidized during processing, resulting in iron oxide, usually having a black grey. If the process is carried out in a special way by using suitable additives, such as iron (II) salts and aluminum salts, a strongly colored iron oxide black slurry is obtained. After washing and filtration, the slurry is worked up to yield iron oxide black.

In order to optimize the optical properties of the pigment,
narrow primary particle size range for e ₃ O _4, for example 0.1 to 1
Sticking to μm is preferred. The particle size of a suitable black pigment is adjusted by micronization, ie by special milling by using superheated steam. This results in a relatively homogeneous particle size distribution.

The primary particle size and its distribution are usually measured by sieve analysis, sedimentation analysis and known calculation methods (for example, with an electron microscope).

Advantageously, as commercially available black pigments,
Pigment Black 11, Echtschwarz 100 and Bay Ferrox
ferrox (registered trademark)) black grade (manufactured by Bayer)
Can be mentioned.

In one preferred embodiment of the eating utensil according to the invention, the composition additionally comprises, as an additive for better contrast of the pattern or inscription:
0.005 to 5% by weight of inorganic fiber metal salt, preferably 0.0
It is present in an amount of from 1 to 2% by weight, in particular from 0.02 to 1% by weight. The transition metal converts the d electron into an outer electron shell (d ¹ -d
¹⁰ ) An element contained in the above.

Among the inorganic transition metal salts, those which have been found to be particularly suitable are those in which the transition metal has an electron configuration from d ⁶ to d ¹⁰ , preferably d ⁹ , ie Cu, Ag,
Au, especially Cu and Ag. Further, preferred as inorganic transition metal salts are halides and sulfates. Particularly preferred are chloride, bromide and sulfate.

The compositions used according to the invention can be processed by methods known per se for shaping polymers, resulting in eating utensils having the properties mentioned in the introductory part of the description. Preferably, an injection molding method is described.

Furthermore, according to the present invention, there is provided a meal implement having a pattern or inscription, characterized by irradiating the meal implement according to the invention with high-energy radiation. A method of manufacturing is provided. This irradiation is usually performed using a laser. Furthermore, according to the present invention, there is provided a meal provided with one pattern and obtainable by a method comprising irradiating a meal formed from a composition comprising the high performance thermoplastic resin (A). You. The advantage of this laser inscription or printing is that it is simple, fast and accurate, non-contact (no mechanical stress or contamination of the work piece), versatile (computer controlled), clean and clean It is a treatment method without chemicals. A particular advantage of this method is that individual inscriptions can be made on the plastic parts. This is because layout changes can be made easily and quickly using a computer.

The two methods are laser printing /
A distinction can be made in relation to the inscription, ie the inscription by the mask (projection) and the inscription by the polarization (scanning of the laser beam).

In this specification, mainly a frequency multiplier (wavelength 5
CO ₂ lasers having a 32,355,256Nm) (wavelength 10.6 [mu] m), preferably Nd: YAG laser (wavelength 1064 nm) or ND: YAG laser and in particular a UV laser is used, is preferably excimer laser . Lasers used in the method according to the invention are commercially available.

The energy density of the laser used is:
^{Generally, 0.3mJ / cm 2 ~50J / cm} 2, in preferably in the range from ^{0.5mJ / cm 2 ~20J / cm 2} , in particular 1
It is in the range of mJ / cm ^{2 to} 10 J / cm ² .

If a pulsed laser is used, the frequency of the pulses is generally in the range from 0.1 to 10000 Hz, preferably from 0.5 to 5000 Hz, in particular from 1 to 1000 Hz, and the pulse length (of the individual pulses) The duration is preferably in the range from 0.1 to 1000 ns, preferably from 1 to 5000 ns, in particular from 1 to 100 ns.

The extinction coefficient of the plastics to be treated is often not high enough to induce a color change in the polymer material at the said wavelengths and thus produce a readily readable imprint having a high contrast. However, this problem is overcome by mixing in the additives described above, where the additives are strongly absorbed at the wavelength used and transfer the absorbed energy to the surrounding polymer matrix. Thus, according to the method of the present invention, a food utensil that can be inscribed or imprinted in any manner and that can read the inscription or imprint well is provided.

As used herein, the intensity and duration of the illumination affects the contrast, depth of penetration and surface structure of the shaped product. More detailed information on this subject can be found, for example, in the two relevant publications Kunststoffe 81 (199
1), 4th edition, pp. 341 et seq. And Kunststoff 78 (19
88), 8th edition, pages 688 et seq., Which relate to laser inscription of shaped articles formed from thermoplastics. Further, German Patent Application No. 3936926, German Patent No. 3619670, German Patent No. 3044722, German Patent Application No. 4416129.8 and European Patent Application Publication No. 190997 can be mentioned.

[0080]

【Example】

Examples Materials used: Product Manufacturer-ULTRASON S2010 natural (polysulfone) BASF AG-ULTRASON E2010 natural (polyethersulfone) B
ASF AG-Ultem 1010 Natural General Electric Plastics-Polystyrene 158K (polystyrene) BASF A
G Manufacturing conditions: Product Composition temperature (° C) Mold temperature (° C)-ULTRASON S2010 natural 320 130-ULTRASON E2010 natural 360 140-polyetherimide (Ultem 1010) 370 140-polystyrene 230 70 20 pieces of each material Food utensils were tested under real conditions. In one test cycle, the meals were each successively mixed with hot curry sauce (60 ° C.), tomato ketchup (60 ° C.) and vegetable oil (130 ° C.).
Contact was made for 0 minutes. Thereafter, the eating utensils were stored in hot water at 80 ° C. to which 1% of an alkaline detergent had been added for 60 minutes (dish washing process). Each test implement, except for those that were lost prematurely, was subjected to 1000 test cycles.

Thereafter, the chopsticks were subjected to a mechanical test and a visual evaluation.

Results: Tensile strength (N / mm ² ) Initial state After 100 working cycles-ULTRASON S2010 natural 78 92-ULTRASON E2010 natural 93 107-polyetherimide (Ultem 1010) 105 110-polystyrene 40 destroyed Visual evaluation after 1000 working cycles-ULTRASON S2010 Natural No discoloration, no formation of stress cracks-ULTRASON E2010 Natural No discoloration, very little formation of stress cracks-Polyetherimide (Ultem 1010) Discoloration, Medium formation of stress cracks-polystyrene destroyed after 5 working cycles

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Peter Wolf, Germany Kirchheim Römerstraße 14 (72) Inventor Helmut Geer, Germany Danstadt-Schauernheim Ringstrasse 20

Claims (3)

[Claims] 1. A food utensil formed from a high-performance thermoplastic resin (A). 2. A method for manufacturing a meal with one pattern, the method comprising: irradiating the meal with a high-energy radiation to the meal according to claim 1. 3. A meal provided with a pattern and obtainable by a method comprising irradiating a meal formed from a high-performance thermoplastic resin (A).