Refill with polyhydroxybutyric acid as binder and pen with refill

Abstract

The invention relates to a cartridge for writing, drawing, drawing and / or cosmetic pens, comprising a binder, a filler, a colorant and further additives, and having the following components: 5 to 65% by weight of a binder comprising polyhydroxybutyric acid and / or a copolymer having polyhydroxybutyric acid as a first polymer and a second polymer, the present invention relates to a composition comprising, by weight, 33 to 85% of a filler having a colorant, 2 to 33% of one or more waxes, 0 to 1% of other additives such as stabilizers, lubricants, and the like.

Description

Technical Field

[0001] The invention relates to a refill based on a biodegradable binder for a writing pen, a drawing pen, a painting pen and / or a cosmetic pencil having the features of claim 1. The invention also relates to a pen having a refill. Background Art

[0002] Pen refills having polymers produced from crude oil are known for use in writing, drawing, painting and / or applying makeup.

[0003] Document EP 2644407 A1 describes a polymer-bonded expanded lead with a biodegradable binder and graphite as a colorant. In the case of this lead, the strength and coverage of the stroke can be partially optimized, especially in pencil leads.

[0004] Furthermore, document DE 19855325 A1 describes a coating of a colored pen core or pencil core based on cellulose and a biodegradable polymer. A large number of biopolymers for coating the pen core are described here, but no indication is given as to how a pen core with such a biopolymer can be realized.

[0005] A polymer-bound colored and graphite refill is known from document WO 2010 / 006742 A1. This refill contains a polymer binder, wax, palm oil and fillers. Most polymer refills are based on crude oil products and are therefore directly related to the price and availability of oil. In addition, refills based on crude oil-derived polymers consume naturally occurring non-renewable resources.

[0006] In addition, polymer-bound colored and graphite refills are known from document US Pat. No. 2,988,784 A. Such refills contain polymer binders based on cellulose esters, in particular cellulose acetate, waxes and fillers. Although these refills are constructed from natural raw materials and can therefore be completely degraded, they are mostly composed of the naturally occurring raw material wood. However, due to the high demand for wood, it is becoming increasingly difficult and expensive to purchase high-quality wood. In addition, the dwindling reserves of natural wood are greatly consumed by the production of pens with cellulose esters. Summary of the invention

[0007] The object of the present invention is therefore to develop a refill and a pen for writing, drawing and / or painting having such a refill, wherein the refill constitutes an environmentally friendly alternative without losing essential properties, such as sharpenability, color, strength, covering power of the stroke and / or erasability of the refill.

[0008] The subject matter of the invention is a refill having the features of claim 1 and a pen having the features of claim 7. Preferred or advantageous embodiments of the invention are apparent from the dependent claims and the following description.

[0009] The invention relates to a refill for a writing pen, a drawing pen, a painting pen and / or a cosmetic pen, which is composed of a filler, a colorant, a binder and other additives. The refill can be configured as a colored refill or a pencil refill.

[0010] Pen refills for writing, drawing, painting and / or cosmetics are understood to be, in particular, pen refills which are firmly introduced into a shaft material, such as wood or an extruded mixture, such as a polymer mixture, wherein the pen refill can be sharpened. Alternatively, the pen refill can be movably supported in a rigid sleeve. Examples of this are wooden pencils and pen refills for mechanical pens, such as so-called mechanical pencils or mechanical pens. In this case, the pen refill has, in particular, an outer diameter in the range of about 0.3 mm to 6 mm.

[0011] According to the present invention, the refill has the following composition with respect to the refill, in particular with respect to the total weight of the refill:

[0012] 5 to 65% by weight of a binder comprising polyhydroxybutyric acid and / or a copolymer having polyhydroxybutyric acid as a first polymer and a second polymer,

[0013] 33 to 85% by weight of filler with colorant,

[0014] 2 to 33% by weight of one or more waxes,

[0015] 0 to 1 wt% of other additives such as stabilizers, lubricants.

[0016] According to the invention, the binder comprises polyhydroxybutyric acid. Polyhydroxybutyric acid is abbreviated as PHB and is registered in particular with Chemical Abstracts Service under CAS number: 26063-00-3. Depending on the number of monomers in the polymer, the properties of PHB as a polymer may vary slightly. Polyhydroxybutyric acid is thermoplastic and biodegradable.

[0017] Alternatively or in addition, the binder comprises a copolymer with polyhydroxybutyric acid as the first polymer. A copolymer is to be understood as a polymer consisting of, in particular, exactly two polymers. The polymers of the copolymer are chemically bonded. In a copolymer based on polyhydroxybutyric acid, the first polymer is polyhydroxybutyric acid. The second polymer is selected according to the requirements of the properties. Preferably, the second polymer can be biomanufactured and / or is biodegradable. Particularly preferably, the second polymer is more flexible than polyhydroxybutyric acid.

[0018] It has surprisingly been shown that high-quality refills can be produced using polyhydroxybutyric acid and / or copolymers comprising polyhydroxybutyric acid as the first polymer as a binder, wherein polyhydroxybutyric acid constitutes an environmentally friendly alternative due to its biodegradability.

[0019] In one embodiment, the binder contains only polyhydroxybutyric acid. In another embodiment, the binder contains only a copolymer containing polyhydroxybutyric acid as the first polymer and a second polymer. In another embodiment, the binder contains a mixture of polyhydroxybutyric acid and a copolymer containing polyhydroxybutyric acid as the first polymer and a second polymer.

[0020] In particular, the filler is selected from the group comprising hexagonal boron nitride, phyllosilicates, chalk, barite, color pigments and / or colorless pigments or mixtures thereof. This enables the manufacture of a refill having optimized costs and mechanical properties.

[0021] The filler can additionally include graphite and / or carbon black, which also serve as colorants. Preferably, for black lead, graphite and / or carbon black are selected as filler and colorant, either alone or as a mixture thereof. In particular, black lead is referred to as pencil lead or graphite lead.

[0022] The colorant is used to color the refill so that colored grinding dust can be seen when writing. In particular, the colorant is selected from the group consisting of titanium dioxide, zinc sulfide, color pigments, carbon black, graphite and / or mixtures thereof. Thus, the color of the refill can be selected.

[0023] Other additives include stabilizers and lubricants.

[0024] Stabilizers are added to the refills in order to reduce the aging processes of the polymer. Thus, the action of heat, light, ozone and oxygen can lead to aging processes which become evident in a deterioration of the properties, for example as a color change.

[0025] In particular, a lubricant is added to the refill so that the refill does not get stuck in the sleeve in the case of a mechanical pencil or a retractable pen. In addition, the lubricant causes the pen to be guided more easily on the page and improves the transfer of the colorant of the refill to the writing surface, such as wood, paper, concrete, asphalt, skin. In particular, the lubricant comprises palm oil.

[0026] In one embodiment, the copolymer has a weight ratio of polyhydroxybutyric acid as the first polymer to the second polymer in the range of 1:10 to 10:1, preferably in the range of 5:10 to 10:5, especially with respect to the total weight of the binder.

[0027] In another embodiment, the second polymer of the copolymer comprises poly(3-hydroxyvaleric acid). Poly(3-hydroxyvaleric acid) is known in particular by the name poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and / or as PHV (CAS: 83120-66-5). It can be biomanufactured and is biodegradable.

[0028] In particular, the binder contains only a copolymer of polyhydroxybutyric acid as a first polymer and poly(3-hydroxyvaleric acid) as a second polymer, the weight ratio of the first polymer to the second polymer being in the range of 1:10 to 10:1, preferably in the range of 5:10 to 10:5, in particular with respect to the total weight of the binder.

[0029] In particular, the binder comprises a mixture of polyhydroxybutyric acid, poly (3-hydroxyvaleric acid) and / or polylactic acid. The binder preferably consists of a mixture. A mixture of polymers is referred to as a blend.

[0030] PLA is the name used for polylactic acid, which may be referred to as polylactide and / or polylactic acid, among others. In particular, PLA is also registered with Chemical Abstracts Service under CAS number: 9051-89-2. Depending on the number of monomers in the polymer, the properties of PLA as a polymer may vary slightly.

[0031] PLA is a thermoplastic. PLA has the advantage that it can be produced on a bio-based basis, so that the use of petroleum-based raw materials in pens is significantly reduced or completely avoided. For example, PLA is obtained from corn and belongs to polyester as a synthetic polymer. Therefore, pure PLA is preferably made from renewable raw materials and is not based on fossil raw materials, such as petroleum.

[0032] In particular, the binder comprises a mixture of polyhydroxybutyric acid, poly (3-hydroxyvaleric acid) and polylactic acid. In particular, the binder comprises a mixture of polyhydroxybutyric acid and poly (3-hydroxyvaleric acid). In particular, the binder comprises a mixture of poly (3-hydroxyvaleric acid) and polylactic acid. In particular, the binder comprises a mixture of polyhydroxybutyric acid and polylactic acid.

[0033] Thus, in the case of biodegradable binders, a selection can be made with regard to properties such as wear resistance, mechanical strength.

[0034] Other copolymers based on polyhydroxybutyric acid are also possible and increase the options for selecting different properties. Thus, the mechanical properties, in particular machinability, coloring, strength, stroke coverage, erasability, etc., as well as the production costs can be adjusted.

[0035] In a preferred embodiment, the refill has a binder content preferably in the range of 8 to 50 weight %, preferably in the range of 15 to 27 weight %, relative to the total mass of the refill. This has the advantage that the binder content can optimize the costs for production while providing mechanical properties in the refill.

[0036] In another embodiment, the refill has at least one wax or a mixture of waxes as the wax mixture. The at least one wax is selected from the group consisting of fatty acids, stearates, montan wax, amide wax, carnauba wax, beeswax, paraffin wax, polyolefin wax, polyethylene wax, polyethylene vinyl acetate wax and mixtures thereof. In addition, the wax includes other additives. A plurality of different waxes can be used as the wax mixture.

[0037] Preferably, the wax comprises a mixture of polyethylene wax and / or polyethylene vinyl acetate wax.

[0038] Preferably, at least one wax is selected from the group comprising calcium stearate and / or ethylenebisstearamide (EBS). Ethylenebis(stearamide) is especially known by the name of distearylethylenediamide and / or as EBS (especially CAS: 110-30-5). Calcium stearate (CAS: 1592-23-0) is also part of the list of European food additives, known as E470a. In particular, the wax comprises biopolymers from the company Deurex.

[0039] In another embodiment, the refill has a colorant content in the range of 0 to 10% by weight relative to the refill.

[0040] In another embodiment, the refill has the following composition with respect to the refill, in particular with respect to the total weight of the refill:

[0041] 8 to 50% by weight of a binder comprising polyhydroxybutyric acid and / or a copolymer having polyhydroxybutyric acid as a first polymer and a second polymer,

[0042] 40% to 80% by weight of filler with colorant,

[0043] 5 to 28% by weight of one or more waxes,

[0044] 0 to 1 wt% of other additives such as stabilizers, lubricants.

[0045] In particular, the adhesion promoter is used when the refill is used in a pen with a shaft. The adhesion promoter has the following advantages: the refill is arranged immovably in the shaft. Therefore, the refill does not move into the shaft when light pressure is applied during writing.

[0046] Another subject of the invention is a pen with a refill as described above. The pen is in particular designed as a writing pen, a drawing pen, a painting pen and / or a cosmetic pen. The pen has a refill and a rod, wherein the rod preferably surrounds the refill concentrically and / or coaxially. The refill is preferably arranged with the rod to prevent movement and / or immovably relative to each other. In particular, the refill is permanently fixed in the rod in a non-detachable manner and / or cannot be removed in a non-destructive manner. Alternatively, the refill is movably supported in the pen. For example, the pen is designed as an automatic pencil or a movable pen. DETAILED DESCRIPTION

[0047] Other features, advantages and effects of the present invention are apparent from the following description of preferred embodiments of the present invention:

[0048] The refill according to the invention is preferably produced as a refill thread at approximately 150 to 200° C. by an extrusion process or a coextrusion process after the components of the refill have been mixed and granulated.

[0049] The shape of the refill cross section is adjusted in the extrusion head. When producing refills for mobile pens, the refill wire is additionally cut to a certain length. In the case of refills for stem pens, the refill is wrapped with stem material as a further process step.

[0050] Exemplary ingredients for the refills are shown below.

[0051] Example 1: A refill with the following composition:

[0052] 17.5 wt% polyhydroxybutyric acid as a binder,

[0053] 67.5% by weight of talc and / or kaolin as filler,

[0054] 7% by weight of carbon black as colorant,

[0055] 3% by weight of polyethylene wax as wax,

[0056] 5% by weight of polyethylene vinyl acetate wax was used as the wax.

[0057] A high filler content in combination with a biodegradable binder is advantageous, as it allows the production of largely biodegradable refills.

[0058] Example 2: A pencil lead having the following composition is used as the lead:

[0059] 60% by weight of a copolymer of polyhydroxybutyric acid and poly(3-hydroxyvaleric acid) in a weight ratio of 2:1, in particular corresponding to 40% by weight of polyhydroxybutyric acid and 20% by weight of a copolymer of polyhydroxybutyric acid and poly(3-hydroxyvaleric acid) as binder, with respect to the total weight of the binder,

[0060] 34 wt. % of graphite and carbon black, in particular graphite and carbon black in a weight ratio of 1:2 as fillers and colorants,

[0061] 2% by weight of polyethylene wax as wax,

[0062] 4% by weight of polyethylene vinyl acetate wax was used as the wax.

[0063] The copolymer reduces the proportion of crystalline regions and makes the wear of the lead and thus writing easier.

[0064] Example 3: A refill with the following composition:

[0065] 26 wt% polyhydroxybutyric acid as a binder,

[0066] 55% by weight of layered silicate as filler,

[0067] 10% by weight of red pigment as colorant,

[0068] 5% by weight of polyethylene wax as wax,

[0069] 3% by weight of polyethylene vinyl acetate wax as wax,

[0070] 1% by weight of palm oil was used as lubricant.

[0071] Example 4: A refill with the following composition:

[0072] 7 wt% poly(3-hydroxyvaleric acid) as a binder,

[0073] 81% by weight of graphite as filler,

[0074] 2 wt% carbon black as colorant,

[0075] 6% by weight of ethylenebisstearamide as wax,

[0076] 4% by weight of calcium stearate as wax.

[0077] Example 5: A refill with the following divisions:

[0078] 40% by weight of a copolymer of polyhydroxybutyric acid and poly(3-hydroxyvaleric acid), in particular in a ratio of 1:4, as a binder, in particular corresponding to 8% by weight of polyhydroxybutyric acid and 32% by weight of poly(3-hydroxyvaleric acid), based on the total weight of the binder,

[0079] 46 wt.% barite as filler,

[0080] 10% by weight of yellow pigment as colorant,

[0081] 2% by weight of polyethylene wax as wax,

[0082] 2% by weight of calcium stearate as wax.

[0083] Example 6: A refill with the following composition:

[0084] 16% by weight of a mixture or blend of polyhydroxybutyric acid and polylactic acid, in particular in a ratio of 3:1, as a binder, preferably corresponding to 12% by weight of polyhydroxybutyric acid and 4% by weight of polylactic acid,

[0085] 74 wt% hexagonal boron nitride as filler,

[0086] 5% by weight of carbon black and titanium dioxide pigments as colorants,

[0087] 4% by weight of ethylene bisstearamide as wax,

[0088] 6% by weight of polyethylene vinyl acetate wax was used as the wax.

[0089] Example 7: A refill having the following composition:

[0090] 26% by weight of a mixture or blend of polyhydroxybutyric acid and polylactic acid, in particular in a ratio of 27:10, as a binder, preferably corresponding to 19% by weight of polyhydroxybutyric acid and 7% by weight of polylactic acid,

[0091] 55% by weight of layered silicate as filler,

[0092] 10 wt% green pigment as colorant,

[0093] 5% by weight of polyethylene wax as wax,

[0094] 3% by weight of polyethylene vinyl acetate wax as wax,

[0095] 1% by weight of palm oil was used as lubricant.

[0096] With the aid of these examples, refills with biodegradable binders can be manufactured.

Claims

1. A refill for a writing pen, a drawing pen, a painting pen and / or a cosmetic pen, comprising a binder, a filler, a colorant and other additives, It is characterized in that The refill has the following ingredients: 5 to 65 wt % of a binder comprising polyhydroxybutyric acid and / or a copolymer having polyhydroxybutyric acid as a first polymer and a second polymer, 33 to 85% by weight of filler with colorant, 2 to 33% by weight of one or more waxes, 0 to 1% by weight of other additives, such as stabilizers, lubricants.

2. The pen refill according to claim 1, characterized in that: The binder is biodegradable.

3. The refill according to any one of the preceding claims 1 or 2, characterized in that: The copolymer has a weight ratio of polyhydroxybutyric acid as the first polymer and the second polymer in the range of 1:10 to 10:1, preferably in the range of 5:10 to 10:

5.

4. A refill according to any one of the preceding claims, characterized in that The second polymer of the copolymer includes poly(3-hydroxyvaleric acid).

5. A refill according to any one of the preceding claims, characterized in that The copolymer of the binder having polyhydroxybutyric acid and poly(3-hydroxyvaleric acid) as the second polymer comprises a weight ratio in the range of 1:10 to 10:1, preferably in the range of 5:10 to 10:

5.

6. A refill according to any one of the preceding claims, characterized in that The binder comprises a mixture of polyhydroxybutyric acid, poly (3-hydroxyvaleric acid) and / or polylactic acid.

7. A refill according to any one of the preceding claims, characterized in that The refill comprises a binder content in the range of 8 to 50% by weight, preferably in the range of 15 to 27% by weight, relative to the refill.

8. A refill according to any one of the preceding claims, characterized in that The lead comprises a wax content in the range of 2 to 33% by weight, preferably in the range of 5 to 28% by weight, relative to the lead.

9. A refill according to any one of the preceding claims, characterized in that The core includes a colorant content in a range of 0 to 10% by weight relative to the core.

10. A pen having a refill according to any one of the preceding claims.