JP5723526B2 - Oral composition - Google Patents

Description

  The present invention relates to an oral composition that can impart a good refreshing feeling to the mouth.

  Various refreshing agents are blended in oral compositions such as dentifrices, bad breath suppressants, mouth fresheners, mouth-soluble tablets, and gums for the purpose of imparting a refreshing feeling when applied to the oral cavity. Among the refreshing agents, menthol is widely used because it has a strong cooling effect, but it is also known to have a stimulating effect at the same time as a refreshing sensation, and when it is increased, it may cause irritation that is painful. (Patent Document 1). On the other hand, the composition of patent document 1 is mix | blending caffeine or its salt as a stimulus improving agent with respect to irritation | stimulation of cooling components, such as menthol. In addition, the solid preparation for oral cavity described in Patent Document 2 has two or more layers, reduces the amount of menthol blended in the layer that can be quickly dissolved, and gradually increases the amount of menthol dissolved to give a feeling of irritation. It is relaxed. The liquid oral cavity composition described in Patent Document 3 contains xylitol in order to reduce irritation and hotness of menthol.

  On the other hand, ginger oleoresin is known as a warming agent (for example, Patent Document 4), and Shogaol contained in ginger oleoresin is known as a pungent component (for example, Non-Patent Document 1). As described, ginger oleoresin is also known to have strong irritation and fragrance as a warming agent. And the composition for oral cavity of patent document 5 mix | blends oleoresin, such as ginger and a pepper, and concrete of Iris, etc. in order to improve the acidity and astringency of phytic acid which are not reduced with fragrance | flavors, such as peppermint. Is described.

JP 2001-302518 A JP-A-10-53518 JP 2000-178152 A JP 2001-279227 A Japanese Patent Publication No. 7-72124

"Synthetic fragrance" published by Chemical Industry Daily, 2005 revised edition P152-153 J. et al. W. Published by Hassler, "Applied technology of activated carbon", Techno System Co., Ltd., P16-17, 1976

However, the composition containing menthol described in Patent Documents 1 to 3 is intended to alleviate irritation when containing menthol, and in particular, when the menthol contains a large amount of menthol, It is intended to reduce bitterness, and does not describe means for amplifying and enhancing the refreshing feeling of menthol while suppressing irritation of menthol.
The subject of this invention is providing the composition for oral cavity which can reinforce the refreshing feeling of menthol, even if content of menthol is a range which is hard to feel the irritation | stimulation and pain which a tongue tingles.

  Therefore, the present inventor examined the change in taste by using various ingredients in combination with menthol, and surprisingly, when using a specific purified ginger oleoresin, the menthol refreshment was completely enhanced, and the concentration was high. It was found that a refreshing feeling equivalent to or better than that of menthol was obtained and that the refreshing refreshing feeling persisted, and the present invention was completed.

That is, the present invention contains (A) menthol 0.2 to 0.8% by mass, and (B) purified ginger oleoresin in which the content of gingiberene is less than 1 part by mass relative to 1 part by mass of shogaol in terms of solid content And the composition for oral cavity whose mass ratio (A / B) of the solid content conversion amount of (A) and (B) is 2-80 is provided.
Moreover, this invention is (A) The composition for oral cavity containing 0.2-0.8 mass% of menthol, (B) The content of Genghiberen with respect to 1 mass part of shogaol in conversion of solid content is less than 1 mass part. A method for enhancing the refreshing feeling of menthol contained in a composition for oral cavity, comprising purified ginger oleoresin that is (A) and (B) and having a mass ratio (A / B) of 2 to 80. is there.

  When the composition for oral cavity of the present invention is applied to the mouth, the refreshing feeling of menthol is enhanced, and a refreshing refreshing feeling equal to or higher than that of increasing menthol is obtained, and its action is sustained.

It is a figure which shows the analysis result of (GC-FID) of the ginger oleoresin before the process by activated carbon and after a process. It is the figure which expanded and showed a part of analysis result of FIG. It is a figure which shows the effect of the refreshing feeling (clean feeling) by combined use of menthol and refined ginger oleoresin. It is a figure which shows the addition effect of the refined ginger oleoresin with respect to a menthol 0.2 mass% compounding composition.

  The composition for oral cavity of this invention contains 0.2-0.8 mass% of (A) menthol. Here, examples of menthol include l-menthol and dl-menthol, and l-menthol is preferable in terms of a refreshing feeling. As menthol, in addition to menthol refined from natural oil, menthol synthesized from citronella oil, thymol, myrcene or the like may be blended, or peppermint oil itself containing menthol may be blended. The content of menthol in the composition for oral cavity is 0.2 to 0.8% by mass, preferably 0.2 to 0.6% by mass, from the balance of refreshing feeling (clean feeling) and suppression of irritation and pungent taste. Further, 0.3 to 0.5% by mass is preferable. Even if 0.2% by mass of menthol alone is added to the composition for oral cavity, a strong refreshing sensation cannot be obtained, but the combined use of the purified ginger oleoresin of the present invention enhances the refreshing sensation and contains menthol. Even if the amount is 0.2% by mass, a refreshing sensation of about 5 times the menthol content is obtained, and the refreshing sensation (clean feeling) is maintained.

(B) Purified ginger oleoresin used in the present invention contains other scent components such as gingivalene in addition to shogaol, and the content of gingivalene per 1 part by mass of shogaol in terms of solid content of ginger oleoresin Is less than 1 part by mass. That is, in the purified ginger oleoresin, the mass ratio (B2 / B1) of (B1) shogaol and gingiberene (B2) is less than 1, and this mass ratio (B2 / B1) is more preferably 0.9 or less. 0.8 or less is preferable. In addition, 1-6 mass% is preferable and, as for content of gingiberene in refined ginger oleoresin, 2-5 mass% is more preferable.
Moreover, (B) refined ginger oleoresin contains fragrance components such as β-sesquiferlandene, γ-muololene, α-farnesene, etc., and the contents of β-sesquiferlandene and γ-muololene are each in a mass ratio. The content is preferably less than ½ of the content of shogaol. The mass ratio of purified ginger oleoresin to shogaol is preferably 10 to 60%, more preferably 15 to 50% for β-sesquiferlandene. The content of α-farnesene in the purified ginger oleoresin is preferably 0.1 to 0.8% by mass, and more preferably 0.2 to 0.75% by mass. The content of β-sesquiferlandene in (B) purified ginger oleoresin is preferably 0.1 to 2.8% by mass, more preferably 1.0 to 2.7% by mass, and the content of γ-muololene. The amount is preferably 1.9 to 2.5% by mass. Here, shogaol is also called 6-shogaol, and the chemical names are 1- (4-hydroxy-3-methoxyphenyl) -4-decen-3-one, 1- (3-methoxy-4-hydroxyphenyl) ) -4-decen-3-one, and Zingiberene is also called α-Zingiberene, and its chemical name is (R) -5-[(S) -1,5-dimethyl-4-hexenyl] -2-methyl -1,3-cyclohexadiene.

  (B) The content of the purified ginger oleoresin in the oral composition is 2 to 80 in terms of mass ratio (A / B) with menthol from the viewpoint of improving a refreshing feeling, a refreshing feeling, and a refreshing feeling. Furthermore, 5-50 are preferable and 10-40 are especially preferable. By setting the mass ratio of (A) menthol and (B) purified ginger oleoresin to 2 to 80, the refreshing feeling of menthol contained in the composition for oral cavity can be enhanced.

  Such purified ginger oleoresin is obtained by extracting ginger with an organic solvent and further purifying it. Although the purification method is not particularly limited, a purification method including an activated carbon treatment step in which ginger oleoresin is brought into contact with activated carbon is preferable, and further, purification including a step in which ginger oleoresin is brought into contact with an organic solvent or a mixed solution of an organic solvent and water. The method is preferred. The purified ginger oleoresin preferably has a shogaol content of 4 to 16% by mass in terms of solid content of paste or solid from which the solvent has been removed by vacuum concentration, thin film concentration or the like, and 5 What is 10 mass% is preferable.

  Preferred (B) purified ginger oleoresin of the present invention has a Gardner color number (Shogaol 0.01% by mass ethanol solution) (see “JIS K0071-3 Color Test Method for Chemical Products, Part 2, Gardner Color Number”). From the viewpoint of the appearance of the product, it is preferably 1 to 4, more preferably 1 to 3, and further preferably 1 to 2. The Shogaol 0.01% by mass ethanol solution is an adjustment solution prepared by adjusting (B) purified ginger oleoresin with an ethanol solution so that the Shogaol content is 0.01% by mass.

  In addition, the viscosity (absolute viscosity) of the preferred (B) purified ginger oleoresin of the present invention is an ethanol solution adjusted to 4% by mass of shogaol from the viewpoint of easy blending, at a temperature of 20 ° C. Preferably it is 1cP-30cP, More preferably, it is 5cP-25cP, More preferably, it is 10cP-25cP. The viscosity is a viscosity measured at 20 ° C. with a vibration viscometer (“VM-1A” manufactured by Yamaichi Electronics Co., Ltd.).

  The content of the (B) purified ginger oleoresin of the present invention in the oral composition is 0.005 to 0.1 mass in terms of solid content of the paste or solid from which the solvent has been removed by methods such as vacuum concentration and thin film concentration. % Is preferable, 0.01 to 0.08 mass% is more preferable, and 0.02 to 0.06 mass% is particularly preferable.

  In the purification of the above ginger oleoresin, it is preferable to bring ginger oleoresin into contact with an organic solvent or a mixture of an organic solvent and water before the activated carbon treatment step. The ratio of the organic solvent to water in this step is preferably 60:40 to 100: 0, more preferably 60:40 to 90:10, further preferably 60:40 to 85:15, particularly 60:40. : 40-80: 20 is preferable.

  Examples of the organic solvent used for the purification include lower alcohols having 1 to 4 carbon atoms such as methanol, ethanol and propanol, acetone, dimethyl ether, hexane, chloroform, dichloromethane, toluene, ethyl acetate, acetonitrile and the like. Preferred are lower alcohols and acetone, more preferred are methanol and ethanol, and even more preferred is ethanol because it dissolves in water and the solvent can be easily removed. You may use these individually or in combination of 2 or more types.

  Although the usage-amount of said organic solvent or the liquid mixture of an organic solvent and water is not limited, Preferably it is 5 mass parts or more with respect to 1 mass part of ginger oleoresin (solid content conversion), More preferably, it is 8-30. Part by mass, more preferably 10 to 20 parts by mass.

  The step of bringing ginger oleoresin into contact with the above organic solvent or a mixture of an organic solvent and water may be performed by specifically dissolving or suspending ginger oleoresin in an organic solvent or a mixture of an organic solvent and water. If necessary, techniques such as stirring and ultrasonic treatment can be employed.

  The purification step of ginger oleoresin preferably includes an activated carbon treatment step for contacting with activated carbon. Further, after the step of contacting with an organic solvent or a mixed solution of organic solvent and water, this organic solvent, water and ginger oleoresin. It is preferable to perform an activated carbon treatment step in which the mixed solution is brought into contact with activated carbon. The activated carbon used in the activated carbon treatment step is preferably one having a pore size distribution of 15 to 40 mm, more preferably a pore size distribution of 15 to 25 mm, from the viewpoint of decolorization effect and adsorption effect of viscous substances and the like. It is preferable. Here, the pore size distribution means the relationship between the pore size and the pore volume, and the pore size distribution of the present invention indicates that measured by the gas adsorption method.

  As the activated carbon having the above pore size distribution, carbonaceous raw materials such as wood flour (sawdust), coconut shell, coal, pitch, coke and other carbonaceous materials such as plant materials and mineral materials are carbonized so as to have a predetermined pore size distribution. And activated ones. Especially, what uses plant materials, such as wood flour (sawdust) and a coconut shell, is preferable, and it is more preferable to use wood flour (sawdust).

  Any activation method may be used as long as it can form a predetermined pore size distribution. For example, when obtaining activated carbon having a pore size distribution of 15 to 25%, a raw material of wood flour (sawdust) is activated by a steam method. (Refer to Non-Patent Document 2), and in the case of obtaining activated carbon having a pore size distribution of 25 to 40%, a method of activating the raw material of wood flour (sawdust) by the zinc chloride method (chemical activation method) ( Non-patent document 2).

  Moreover, as a commercial item of activated carbon, for example, those having a pore size distribution of 15 to 25%, white birch A, white birch B, white birch M, white birch P, granular white birch (all are trade names of Nippon Envirochemicals) ; Dazai K type, Dazai P type (both are trade names of Futura Chemical Co., Ltd.); Ohira Uminefeng, Ohira MA (trade names of Taihei Chemical Sangyo), etc. Moreover, carborafine, strong white rabbit, refined white rabbit, special white rabbit (all are trade names of Nippon Environmental Chemicals Co., Ltd.); Dazai S type (trade names of Nimura Chemical Co., Ltd.) Etc.

  The amount of activated carbon used in the activated carbon treatment process is not particularly limited as long as it does not exceed the adsorption capacity, but it reduces the loss of active ingredients and does not reduce the efficiency of removing unnecessary components such as coloring components. Preferably it is 0.001-1 mass part with respect to 1 mass part of gin (solid content conversion), More preferably, it is 0.0625-0.5 mass part, More preferably, it is 0.1-0.5. Part by mass.

  The activated carbon in the activated carbon treatment step may be granular or powdery, and any activated carbon may be used, but may be appropriately selected according to the method of active edge treatment.

As a means for contacting an organic solvent or a mixed solution of an organic solvent and water, or a means for contacting with activated carbon, any method such as a patch method or a continuous treatment using a column may be employed. For example, by adding powdered activated carbon to a mixture of ginger oleoresin, organic solvent and water, stirring, selectively adsorbing unnecessary components, and then obtaining a filtrate from which unnecessary components have been removed by filtration, or granules For example, a method in which an unnecessary component is selectively adsorbed by continuous treatment using a column packed with an activated carbon or the like and the active component is eluted is exemplified. Since ginger oleoresin can be purified continuously, it is preferably performed by a method such as continuous treatment using an activated carbon column.
Operation temperature at this time becomes like this. Preferably it is 5-60 degreeC, More preferably, it is 20-40 degreeC.

  Further, in order to increase the recovery rate of the active ingredient, activated carbon that has been brought into contact with a mixed solution of ginger oleoresin and an organic solvent or an organic solvent and water is further brought into contact with a mixed solution of an organic solvent and water. The active ingredient may be recovered.

The obtained purified ginger oleoresin may be further purified repeatedly by the above method, or may be purified by combining known methods such as an organic solvent precipitation method such as ethanol.
Moreover, you may remove an organic solvent suitably by methods, such as vacuum concentration and thin film concentration.

  The resulting purified ginger oleoresin can be used as it is after being concentrated or diluted.

  The oral composition of the present invention preferably contains a sugar alcohol in order to further enhance the cooling effect. As the sugar alcohol, those having a high cooling effect are preferable, and erythritol, xylitol, mannitol, and sorbitol are preferable, and erythritol and sorbitol are particularly preferable from the viewpoint of cooling effect and shape retention. The content of the sugar alcohol in the oral composition is preferably 10 to 95% by mass from the point of obtaining a refreshing refreshing effect and the shape retention when the oral composition is a solid composition, Furthermore, 40-95 mass% is preferable, and 50-95 mass% is especially preferable.

  The form of the composition for oral cavity of the present invention is not limited as long as it is applied to the mouth, and examples thereof include foods such as dentifrices, tablets, chewing gums, refreshing sweets in the mouth, and oral hygiene devices such as dental floss and cloth. , Dentifrices, tablets, chewing gums, and refreshing confections in the mouth, and solid oral compositions selected from tablets, refreshing confections in the mouth, and chewing gums are particularly preferable.

  In the case of dentifrice, among these compositions, abrasives, binders, moisturizers, surfactants, sweeteners, fragrances, bactericides, preservatives, cleaning aids, other active ingredients, etc. it can.

  In the case of tablets, chewing gums and the like, excipients, thickeners, disintegrants, binders, sweeteners, gum bases and the like can be blended. In the case of tablets and chewing gum, tragacanth gum, gum arabic gum, etc. are blended as binders and thickeners. There is a rough feel on the tongue and throat. On the other hand, it has been found that when the menthol and purified ginger oleoresin of the present invention are combined, the taste of tragacanth gum and the like is improved. The content of gum arabic and gum tragacanth is preferably 1/8 to 15/2, more preferably 1/4 to 15/4, in terms of mass ratio with menthol from the point of improving the taste (trant gum etc./menthol) 1-3 are especially preferable.

Production Example 1
In a 100 mL glass screw vial, 2 g of ginger oleoresin (manufactured by Givodan) was added as a raw material and dissolved in 50 mL of a 95% by mass ethanol aqueous solution.
2 g of various activated carbons (white birch WH2C, white birch P, carborafine, all manufactured by Nippon Enviro Chemicals) were added to each ginger oleoresin dispersion. After stirring for 2 hours at room temperature using a shaker to adsorb the colored, viscous and odorous components to the activated carbon, the solution is filtered with a 0.45 μm filter, and the filtrate is subjected to high performance liquid chromatography (HPLC). It was measured. The measurement conditions are as follows: Column: inert syl-ODS-3 (GL-Science, 2.1 × 150 mm), 0.1% TFA is flowed, and the moving bed is set to 100% MeCN concentration over 30 minutes from the start of measurement (0 minutes). 100% MeCN for 40 minutes, flow rate: 0.2 mL / min, temperature: 40 ° C., measurement wavelength: 254 nm (UV). At this time, ginger oleoresin was brought into contact with 50 mL of a 95% by mass ethanol aqueous solution, and the concentration of shogaol after mixing was set to 100%.
Moreover, 1.5 mL of filtrate was put into a 2 mL capacity glass screw vial, and a panel (two people) was used to compare the odor (irritating odor) level and the degree of color reduction with the ginger oleoresin solution.
At this time, ginger oleoresin was brought into contact with 50 mL of a 95% by mass ethanol aqueous solution, and the color and odor after mixing were used as a reference.
Here, “odor” means a strong irritating odor peculiar to ginger.

Table 1 below shows the Shogaol recovery rate, visual color reduction degree, and odor level in each processed product obtained as a result of HPLC analysis. The coloring level and odor level indicate the result of discussion between the two panelists.
As shown in Table 1, the Shogaol recovery rate was the same for all three types. On the other hand, carborafine (25-40 Å) and white cocoon P (15-25 Å) were found to have a high color removal effect and an irritating odor mitigating effect, and carborafine (25-40 Å) was the most excellent in terms of the color removal effect. . Therefore, the result that the pore diameter distribution of activated carbon was excellent in 15-40cm was obtained.

1 and 2 show the results of gas chromatographic analysis (GC-FID) of the components of ginger oleoresin before and after the treatment with the activated carbon (carbophylan). Table 2 shows the analysis results of each component of the purified ginger oleoresin by the GC-FID peak analysis of FIG. 1 (FIG. 2).
The measurement conditions of GC-FID are: apparatus: 6890N (Agilent Technology), column: DB-1 (length 30 m, inner diameter 0.25 mm, membrane pressure: 0.25 μm), column flow rate: 1 mL / min, column temperature: 40 ° C (5 minutes) → (temperature rise at 20 ° C./minute)→320° C. (10 minutes), detector: FID (hydrogen flame ion detector), detector temperature: 300 ° C., carrier gas: He. The content of shogaol contained in the ginger oleoresin before and after treatment is the peak area by GC-FID measurement using commercially available shogaol (No.199-14111 for pharmacopoeia crude drug test by Wako Pure Chemical Industries, Ltd.) as a standard solution. We asked for the standard. The content of components other than Shogaol is based on p-cymene (p-cymene) (Acros Organics No.111762500), which is a homologous substance, as a standard solution and based on the peak area measured by GC-FID. Asked. In addition, the measurement conditions of GC-FID of the standard solution are also the same as the measurement conditions of the above ginger oleoresin.

  As shown in Table 2, in the purified ginger oleoresin after the treatment with activated carbon, the content of gingiberene is decreased with respect to the content of shogaol. Specifically, the content of gingivalene before the activated carbon treatment was higher than that of shogaol and contained about 1.7 times the mass ratio of shogaol. The mass ratio with respect to oar was reduced to about 0.8 times. In addition, β-sesquiferlandene and γ-muololene have a content of less than ½ of the content of shogaol by weight ratio due to the activated carbon treatment. In addition, α-farnesene was a small solid content of 12.5% by mass, and it was confirmed that the components that cause these stimulating scents were reduced.

Tablets (tablets) were produced according to the compositions shown in Tables 3 and 4. The content in the table is% by mass.
Example 1
Tablets 1 to 10 were produced according to the formulation in Table 3 using the purified ginger oleoresin obtained in Production Example 1 (using carborafine). Tablets 1 to 10 were produced by charging 0.7 g of a mixture according to the formulation shown in Table 3 into a 12 mm diameter mold and applying a load of 2 t with a press machine.

(Evaluation method)
For evaluation, 4 expert panelists ate tablets 1 to 10, and evaluated the refreshing feeling (clean feeling) and the stimulation felt on the tongue. The refreshing feeling is evaluated on a five-point scale, and 5 is evaluated as 1 to 5 where 5: extremely refreshing and refreshing feeling is maintained, 1: 1 refreshing feeling is not sustained and the average value of 4 persons is evaluated. The evaluation value was used. The evaluation of the stimuli felt on the tongue was evaluated as “x” when the tongue felt tingling and felt pain, and “○” when almost no tingling sensation was felt.

  The evaluation results of tablets 1 to 10 are shown in Table 3 and FIG. As shown in Table 3 and FIG. 3, tablets 1 to 5 containing menthol of the present invention and purified ginger oleoresin have a higher refreshing feeling (fresh feeling) than tablets 6 to 10 not containing purified ginger oleoresin. The effect was observed to persist. In particular, tablets 2 to 5 containing 0.2% by mass or more of menthol have a high refreshing feeling as compared to tablets 10 or more containing only 1% by mass of menthol, and the amount of menthol is less than 1% by mass. For No. 4, there was no tingling irritation to the tongue, and a high evaluation of refreshing feeling was obtained.

(Example 2)
Moreover, according to prescription of Table 4, the tablets 11-17 were prepared similarly to (Example 1), and the refreshing feeling (clean feeling) and the irritation | stimulation to a tongue were evaluated similarly to (Example 1). The evaluation results are shown in Table 4 and FIG. As shown in Table 4 and FIG. 4, the tablet 11 containing only menthol had a low feeling of refreshing and the refreshing effect of the refreshing feeling was weak, but tablets 12 to 15 containing menthol and purified ginger oleoresin were refreshing. It was recognized that the effect of maintaining a refreshing feeling was improved. On the other hand, the tablets 16 to 18 containing only purified ginger oleoresin were evaluated with little refreshing feeling and no durability even when containing 1.0% by mass of purified ginger oleoresin.

  The following tablets 19 and 20 were produced, and the refreshing feeling (clean feeling) and the irritation felt on the tongue were evaluated in the same manner as in Example 1.

Example: Tablet 19
Sorbitol (98%) 50%
Erythritol 45%
Sucralose 0.03%
Calcium stearate 1.0%
Menthol 0.4%
Purified ginger oleoresin (* 1) 0.02%
Dextrin adjustment
Total 100%
Refreshing feeling (clean feeling) 5
Stimulation on the tongue ○
* 1: Production example 1

Example: Tablet 20
Sorbitol 95%
Sucralose 0.03%
Calcium stearate 1.0%
Menthol 0.4%
Purified ginger oleoresin (* 1) 0.02%
Tragant gum 1.0%
Dextrin adjustment
Total 100%
Refreshing feeling (clean feeling) 5
Stimulation on the tongue ○
* 1: Production example 1

Claims (6)

(A) Menthol 0.2-0.8 wt%, and (B) to the next ginger oleoresin the step of contacting a mixture of ethanol or ethanol and water, contacting the resulting mixture on activated carbon obtained was purified by performing, and purified content of zingiberene for shogaol 1 part by mass in terms of solid content is less than 1 part by mass ginger oleoresin 0.01 to 0.08 wt%
The composition for oral cavity containing (A) and the mass ratio (A / B) of (B) which is 5-80.   (B) The composition for oral cavity according to claim 1, wherein the purified ginger oleoresin contains 4 to 16% by mass of shogaol in terms of solid content.   (B) The purified ginger oleoresin contains 1 to 6% by mass of gingivalene in terms of solid content, and the content of gingivalene with respect to 1 part by mass of shogaol in terms of solid content is 0.9 parts by mass or less. Or the composition for oral cavity of 2.   Furthermore, the composition for oral cavity of any one of Claims 1-3 containing sugar alcohol.   Furthermore, the composition for oral cavity of any one of Claims 1-4 containing tragacanth gum.   (B) In purified ginger oleoresin, the content of β-sesquiferlandene is less than 1/2 of the content of shogaol by mass ratio, and the content of γ-mulolene is the content of shogaol by mass ratio The composition for oral cavity of any one of Claims 1-5 less than 1/2.

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