JP2007106904A - Liquid bleaching agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid bleaching agent composition which excels in a bacterium-proofing/mildew-proofing effect, exhibits bleaching/detergency after storage, and does not deteriorate a liquid feeling. <P>SOLUTION: The liquid bleaching agent composition comprises a nonionic surface active agent (a), a quaternary ammonium salt (b) represented by formula (1) (wherein one or two of R<SP>11</SP>to R<SP>14</SP>are hydrocarbon groups having one phenol group or 8-36C aliphatic hydrocarbon groups and the remaining are 1-5C alkyl groups, and the total carbon number of R<SP>11</SP>to R<SP>14</SP>is 19 or more, and X<SP>-</SP>is a halogen ion or a 1-3C alkyl sulfate ion), and the content of the component (a) in the composition is 1-50 mass% and the content of the component (b) is 0.1-10 mass%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid bleach composition.

  Nonionic surfactants are widely used in laundry detergents and bleaching agents because of their high surface activity and excellent detergency. Liquid bleaches based on hydrogen peroxide are preferred because they can be used for colors and patterns and can be applied directly to dirt. Although hydrogen peroxide exhibits a bleaching effect when used with a weak alkaline detergent, it is very difficult to increase the pH of the product in terms of hydrogen peroxide stability. Thus, hydrogen peroxide stabilization technology has been developed, and Patent Literature 1 discloses a technology for stabilizing hydrogen peroxide by combining two types of nonionic surfactants. Patent Document 2 discloses a liquid bleaching agent in which a phenol derivative is blended as a hydrogen peroxide stabilizer and the pH is adjusted to 4-7.

On the other hand, cationic surfactants are widely used in detergents and softeners because they adsorb on clothes and have antibacterial and deodorizing effects. Patent Document 3 discloses a liquid detergent composition containing a cationic surfactant as an antibacterial agent, and Patent Document 4 discloses a cationic surfactant as an antibacterial / deodorant agent for clothing. Formulated softeners are disclosed.
JP 2001-200300 A Japanese Patent Laid-Open No. 11-181492 Japanese Patent Laid-Open No. 2002-60788 JP 2001-146681 A

  Hydrogen peroxide can exert a bleaching effect and a sterilization / deodorization effect by using it in a pH range of weak alkalinity or higher. However, when the liquid bleach composition in Patent Documents 1 and 2 is stored for a long period of time, the non-ionic surfactant is decomposed by hydroxy radicals generated from hydrogen peroxide, resulting in deterioration of the liquid feeling and decomposition of the composition. Accelerated, resulting in decreased bleaching and cleaning capabilities.

  In addition, when the liquid compositions of Patent Documents 3 and 4 are used, the antibacterial effect on clothes is exhibited, but the sterilization effect and the antibacterial / antifungal effect of the washing tub are low, and the bacteria are removed from the clothes and the washing tub after washing. An unpleasant odor from the origin arises.

  Accordingly, an object of the present invention is to provide a liquid bleaching composition that is excellent in antibacterial and antifungal effects, exhibits bleaching and detergency even after storage, and does not deteriorate the liquid feeling.

  The present inventors have found that a liquid bleaching composition containing a specific quaternary ammonium salt in a specific ratio can solve the above problems.

That is, this invention contains the following (a) component, (b) component, and (c) component, the content of (a) component in a composition is 1-50 mass%, Content of (b) component Provides a liquid bleach composition in which is from 0.1 to 10% by weight.
(A) Nonionic surfactant (b) Quaternary ammonium salt represented by the general formula (1)

[Wherein, one or two of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are a hydrocarbon group having one phenyl group or a linear or branched aliphatic hydrocarbon group having 8 to 36 carbon atoms] And the remainder is a linear or branched alkyl group having 1 to 5 carbon atoms. However, the total carbon number of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is 19 or more. X ⁻ is a halogen ion or an alkyl sulfate ion having 1 to 3 carbon atoms. ]
(C) Hydrogen peroxide or a compound that generates hydrogen peroxide in water

  The liquid bleach composition of the present invention is excellent in antibacterial and antifungal effects, does not deteriorate liquid feeling, and can exhibit bleaching and detergency even after storage.

[(A) component]
The liquid bleach composition of the present invention contains a nonionic surfactant as component (a).

  The nonionic surfactant is a polyoxyalkylene alkyl ether type nonionic surfactant having an oxyethylene group and / or oxypropylene group, or a polyglyceryl alkyl having a glyceryl group, from the viewpoint of suppressing deterioration of the liquid feeling. Ether type nonionic surfactant is preferable, selected from polyoxyalkylene alkyl ether type nonionic surfactant having oxyethylene group and oxypropylene group, and polyglyceryl alkyl ether type nonionic surfactant having glyceryl group At least one selected from the group consisting of polyoxyalkylene alkyl ether type nonionic surfactants having an oxyethylene group and an oxypropylene group is particularly preferred.

  Further, as the component (a), at least one selected from a polyoxyalkylene alkyl ether type nonionic surfactant having an oxyethylene group and an oxypropylene group and a polyglyceryl alkyl ether type nonionic surfactant having a glyceryl group It is also preferable to use a mixture of (referred to as (a1) component) and a polyoxyethylene alkyl ether type nonionic surfactant (referred to as (a2) component), and the mass ratio of (a1) component to (a2) component is From the viewpoint of suppressing deterioration of the liquid feeling, (a1) / (a2) = 1/30 to 30/1 is preferable.

  The polyoxyalkylene alkyl ether type nonionic surfactant having an oxyethylene group and an oxypropylene group as the component (a1) may be arranged in any form of a random copolymer or a block copolymer, Of these, block copolymers are preferred. As the form of the block copolymer, a compound represented by the following general formula (2) is preferable.

^{_{R 21 -O- (C 2 H 4}} O) p - (C 3 H 6 O) q - (C 2 H 4 O) r H (2)
[Wherein, R ²¹ is a hydrocarbon group having 8 to 18 carbon atoms, and p, q, and r are each independently a number of 1 to 10 indicating the number average addition mole number of the oxyalkylene group. ]
In the general formula (2), R ²¹ is a hydrocarbon group having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, more preferably an alkyl group or an alkenyl group, and still more preferably an alkyl group. p, q, and r are each independently a number of 1 to 10 indicating the number average addition mole number of the oxyalkylene group, and a number of 2 to 8 is preferable.

  The polyglyceryl alkyl ether type nonionic surfactant having a glyceryl group as the component (a1) is preferably a compound represented by the following general formula (3).

R ²² —O— (C ₃ H ₆ O ₂ ) _s —H (3)
Wherein, R ²² is a hydrocarbon group having 8 to 18 carbon atoms, a group represented by C ₃ H ₆ O ₂ is a linear or branched, s is 1 to 10 showing a number-average molar number of addition It is. ]
In the general formula (3), R ²² is a hydrocarbon group having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, more preferably an alkyl group or an alkenyl group, and still more preferably an alkyl group. s is the number of 1-10 which shows a number average addition mole number, and the number of 2-6 is preferable.

[Component (b)]
The liquid bleach composition of this invention contains the quaternary ammonium salt represented by the said General formula (1) as (b) component.

In the general formula (1), R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each a hydrocarbon group having one phenyl group or a straight chain or branched chain having 8 to 36 carbon atoms. An aliphatic hydrocarbon group, and the remainder is a linear or branched alkyl group having 1 to 5 carbon atoms. Examples of the hydrocarbon group having one phenyl group include a phenyl group and a benzyl group.

Among these, one or two of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are an alkyl group having 8 to 36 carbon atoms, a phenyl group or a benzyl group, particularly an alkyl group having 16 to 22 carbon atoms, and the rest. Is preferably an alkyl group having 1 to 3 carbon atoms, particularly a methyl group or an ethyl group. R ¹¹ , R ¹² , R ¹³ and R ^{14 have} a total carbon number of 19 or more, preferably 19 to 40, and more preferably 19 to 32.

X ⁻ is a halogen ion or an alkyl sulfate ion having 1 to 3 carbon atoms, preferably a chlorine ion, a methyl sulfate ion, or an ethyl sulfate ion.

  Specific examples of the component (b) include cetyl trimethyl ammonium salt; trimethyl stearyl ammonium salt; benzyl cetyl dimethyl ammonium salt; benzyl dimethyl stearyl ammonium salt. From the viewpoint of suppressing deterioration of the liquid feeling, benzylcetyldimethylammonium salt is preferable.

[Component (c)]
The liquid bleach composition of the present invention contains hydrogen peroxide or a compound that generates hydrogen peroxide in water as the component (c). Examples of the compound that generates hydrogen peroxide in water include percarbonate and perborate.

[Liquid bleach composition]
The liquid bleach composition of this invention contains (a) component, (b) component, and (c) component as an essential component.

  Content of (a) component in the composition of this invention is 1-50 mass% from a viewpoint of suppressing deterioration of a liquid feeling, 15-40 mass% is preferable, and 20-35 mass% is more preferable. .

  Content of (b) component in the composition of this invention is 0.1-10 mass% from a viewpoint of suppressing deterioration of a liquid feeling, 0.2-5 mass% is preferable, 0.3- 3 mass% is more preferable.

  The content of the component (c) in the composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.5 to 5% by mass as hydrogen peroxide from the viewpoint of obtaining an excellent bleaching effect. 1 to 4.5% by mass is more preferable.

  The liquid bleach composition of the present invention preferably contains a sequestering agent having a phosphonic acid group or its base as the component (d). Examples of the sequestering agent having a phosphonic acid group or its base include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, and ethanehydroxy. 1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, phosphonic acid selected from methanehydroxyphosphonic acid, or an alkali metal salt or alkanolamine salt thereof, 2-phosphonobutane- And phosphonocarboxylic acids selected from 1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, or alkali metal salts or alkanolamine salts thereof. Preferred are phosphonic acids or their alkali metal salts, especially ethane-1-hydride. Carboxy-1,1-diphosphonic acid or alkali metal salts thereof are preferred.

  The content of the component (d) in the composition of the present invention is preferably 0.05% by mass or more and less than 0.3% by mass from the viewpoint of obtaining the stability of hydrogen peroxide, and is 0.1 to 0.25% by mass. % Is more preferable, and 0.15-0.2 mass% is still more preferable.

  The liquid bleach composition of the present invention is used as a component (e) in order to impart a pH jump effect, that is, to keep the pH of the composition low during storage and to increase the pH when diluted in use. , At least one compound selected from boric acid, borax and borate, and (f) a compound having at least one site each having one hydroxyl group on each of adjacent carbon atoms as component ( It is preferable to contain in the ratio from which the f) component / (e) component molar ratio will be 1.5-2.7.

  Examples of the borate of the component (e) include sodium borate, potassium borate, ammonium borate, sodium tetraborate, potassium potassium borate, and ammonium ammonium borate.

  Specific examples of the component (f) include the following compounds (1) to (4).

(1) Glycerin, diglycerin, triglycerin, alkyl glyceryl ether having 1 to 10 carbon atoms of alkyl group, alkyl diglyceryl ether, alkyl triglyceryl ether; glycerol or glycol selected from ethylene glycol and 1,2-propylene glycol (2) Sugar alcohols selected from sorbitol, mannitol, maltose, inositol, phytic acid (3) Reduction selected from glucose, apiose, arabinose, galactose, lyxose, mannose, galose, aldose, idose, talose, xylose, fructose Sugars (4) A polysaccharide selected from starch, dextran, xanthan gum, guar gum, curdlan, pullulan, amylose and cellulose.

  In the present invention, the sugar alcohols of the above (2) are particularly preferable, and sorbitol is particularly preferable from the viewpoint of stability and bleaching / washing effect. Note that the reducing saccharide of (3) requires caution when it is used because a reducing aldehyde group that affects the stability of hydrogen peroxide exists in the molecule.

  In the present invention, the pH of the liquid bleach composition during storage at 4.0C is preferably 4.0 to 7.0, while the pH is preferably increased by diluting with water during use. When the diluted solution is diluted with 1000 times volume of water, the pH at 20 ° C. of the diluted solution is 8.5 or more and less than 10.5, and more preferably 9 or more and less than 9.5. From the viewpoint of obtaining. In order to obtain such a pH jump effect, it is preferable to blend the component (e) and the component (f) in the above ratio in the composition of the present invention.

  Here, the following equilibrium reaction exists between the component (e) and the component (f).

  In the present invention, it is preferable that the di-form is a main component of the pH jump system so that the pH of the diluted solution is 8.5 or more and less than 10.5. In the liquid bleach composition, the component (e) It is preferable that 70-100 mol% of this is a di-form. In addition, from the viewpoint of obtaining a sufficient pH jump effect and a bleaching / washing effect, the proportion of the component (e) which is a mono-form is preferably 0 to 5 mol%, and in the component (e), boric acid, borax or The proportion of the borate present alone is preferably 0 to 25 mol%.

  Further, if the component (f) is present excessively, the stability of hydrogen peroxide may be impaired, so care must be taken in the ratio of the components (e) and (f). Therefore, in the present invention, the molar ratio of component (f) / component (e) (however, in the case of borax and sodium tetraborate, it contains 4 boron atoms and is considered to be 4 equivalents), preferably 1.5 to Mixing at a ratio of 2.7, more preferably 2.0 to 2.7, and even more preferably 2.2 to 2.7, both the excellent pH jump effect of the present invention and the stability of hydrogen peroxide Can be obtained.

  In the present invention, when the component (e) and the component (f) are blended in the liquid bleach composition, the liquid bleach composition is converted into the above mono- and di-form compounds. The contents of the component (e) and the component (f) in the invention are the content of the component (e) and the component (f) that are present alone, and the content of the mono- and di-forms. And (f) means the sum total of the quantity which added the quantity which converted the quantity of the component. The content of the component (e) in the composition of the present invention is preferably 0.05 to 1% by mass, more preferably 0.15 to 0.5% by mass, and still more preferably 0.2 to 0.5% as a boron atom. 0.4% by mass. Content of (f) component in the composition of this invention becomes like this. Preferably it is 3-35 mass%, More preferably, it is 5-30 mass%, More preferably, it is 10-20 mass%.

The content of the converted mono- and di-forms can be calculated by using a combination of boron ( ¹¹ B) NMR spectroscopy and ICP emission analysis.

  The liquid bleach composition of the present invention preferably contains a bleach activator as the component (g). The bleach activator means a compound that generates an organic peracid by reacting with an inorganic peroxide. As the bleach activator of the component (g), at least one selected from alkanoyloxybenzene sulfonic acid having 8 to 14 carbon atoms in the alkanoyl group, alkanoyloxybenzene carboxylic acid, or a salt thereof can be cited, and good storage From the viewpoint of obtaining stability, an alkanoyloxybenzenesulfonic acid or alkanoyloxybenzenecarboxylic acid having a branched alkanoyloxy group having 8 to 14 carbon atoms, or a salt thereof is preferred, and α of the carbon atom forming the ester bond of the alkanoyloxy group More preferred are alkanoyloxybenzene sulfonic acids or alkanoyloxybenzene carboxylic acids having a side chain at the position or β-position or salts thereof.

  Examples of the alkanoyloxy group having a side chain at the α-position or β-position of the carbon atom forming the ester bond include 2-ethylhexanoyl group, 2-propylheptanoyl group, 3,5,5-trimethylhexanoyl group, and the like. Benzenesulfonic acid or benzenecarboxylic acid (benzoic acid) having a branched alkanoyloxy group or a salt thereof is particularly preferable. As the salt, sodium salt, potassium salt, and magnesium salt are preferable, and sodium salt is particularly preferable from the viewpoint of solubility.

  Specific examples of the component (g) include compounds represented by the following formulas (g-1) to (g-4), and compounds represented by the formulas (g-1) to (g-2) include: preferable.

  The content of the component (g) in the composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, from the viewpoint of developing an excellent bleaching effect. More preferably, ˜2 mass%.

  The composition of the present invention preferably contains a hydrogen peroxide stabilizer (radical trapping agent) as the component (h) from the viewpoint of hydrogen peroxide stability. As radical trapping agents, phenol derivatives are generally known and disclosed in JP-A-11-181492. In the present invention, a compound having a phenolic hydroxyl group or an ester derivative or an ether derivative of a phenolic hydroxyl group can be preferably used as the phenol derivative. Specific examples of such compounds include cresol, thymol, chlorophenol, bromophenol, methoxyphenol, nitrophenol, hydroxybenzoic acid, salicylic acid, hydroxybenzenesulfonic acid, 4-phenolsulfonic acid, and 2,6-ditertiary. Examples include butyl-p-cresol, naphthol, hydroquinone, catechol, pyrogallol, phenoxyethanol and the like. Among these, a preferable compound has a redox potential (OP) 0 (25 ° C.) of 0.3 described in GEPenketh, J. Appl. Chem., Vol 7, pages 512 to 521 (1957). It is a compound of -1.25V, More preferably, it is a compound of 0.6-0.75V. Furthermore, a radical trapping agent with high solubility is more effective from the viewpoint of ease of blending, and a hydrophobic parameter logP value of 3 or less showing solubility is preferable. From the above-mentioned oxidation-reduction potential and solubility point, 4-methoxyphenol, 4-hydroxybenzoic acid, 4-phenolsulfonic acid, hydroquinone, and catechol are preferable. These phenolic radical trapping agents may be used alone or in combination of two or more. As for the compounding quantity of (h) component in the composition of this invention, 0.01-2.0 mass% is preferable, More preferably, it is 0.1-1.0 mass%.

  The pH of the liquid bleach composition of the present invention at 20 ° C. is preferably 4.0 to 11.0, more preferably 4.0 to 7.0, still more preferably 4.2 to 6.5, particularly preferably. Is 4.5 to 5.5. As a pH adjuster for adjusting to such pH, it is preferable to use an inorganic acid selected from hydrochloric acid and sulfuric acid, and an inorganic base selected from sodium hydroxide and potassium hydroxide.

  The liquid bleach composition of the present invention is used in a method of bleaching / washing by diluting in water, and the water to be diluted is 600 to 2000 times by mass, preferably 700 to 1500 times by mass with respect to the liquid bleach composition. It is. Moreover, it is preferable that pH at 20 degreeC of the solution diluted by such magnification becomes 8.5 or more and less than 10.5, especially 8.5 or more and less than 9.5. By using such a cleaning solution, an excellent bleaching / cleaning effect can be obtained.

Example 1
Liquid bleach compositions having the compositions shown in Tables 1 and 2 were prepared using the following components. Using the obtained liquid bleach composition, the storage stability of hydrogen peroxide, the washability before and after storage, the cloud point, and the washing tank odor after washing were evaluated by the following methods. The results are shown in Tables 1 and 2.

<Compounding ingredients>
Component (a) _{(a1) -1; CH 3 (} CH 2) 11 -O- (C 2 H 4 O) p - (C 3 H 6 O) q - (C 2 H 4 O) r -H ( number Average addition mole number p = 7, q = 2 and r = 3)
_{(A1) -2; CH 3 (} CH 2) 11 -O- (CH 2 CH (OH) CH 2 O) - (CH (CH 2 OH) CH 2 O) - (CH 2 CH (OH) CH 2 O ) -H
(A2) -1; CH ₃ (CH ₂ ) ₁₁ —O— (C ₂ H ₄ O) _p —H (number average added mole number p = 8)
(B) component (b) -1; cetyltrimethylammonium chloride (b) -2; trimethylstearylammonium chloride (b) -3; benzylcetyldimethylammonium chloride (b) -4; benzyldimethylstearylammonium chloride (b ′) Ingredient (Comparative product of ingredient (b))
(B) '-1; ethyltrimethylammonium chloride (b)'-2; hexyltrimethylammonium chloride (b) '-3; benzyltrimethylammonium chloride (c) component (c) -1; hydrogen peroxide (d) component (D) -1; ethane-1-hydroxy-1,1-diphosphonic acid (e) component (e) -1; boric acid (f) component (f) -1; sorbitol (g) component (g) -1 Compound (g) -2 represented by formula (g-2); compound represented by formula (g-1) (h) component (h) -1; 4-sodium phenolsulfonate <peroxidation Evaluation Method for Storage Stability of Hydrogen>
80 g of the liquid bleach composition was placed in a 100 mL glass sample bottle and stored at 30 ° C. for 1 week. The liquid bleach composition before and after storage was titrated with a 1 / 10N permanganic acid standard solution, the amount of effective oxygen was determined, and the hydrogen peroxide residual rate was measured by the following formula.

<Evaluation method for cleanability before and after storage>
80 g of the liquid bleach composition was placed in a 100 mL glass sample bottle and stored at 30 ° C. for 1 week. After mixing 1 mL of the liquid bleach composition before and after storage and 4 ° DH to adjust to 1000 mL, a model sebum soil-contaminated cloth (4 sheets) was subjected to a cleaning test at 20 ° C. and 80 rpm using a tartometer. The reflectance of the cloth surface before and after the washing treatment was measured, and the washing rate was obtained by the following formula.
-Preparation of Sebum Dirt-Contaminated Cloth Sebum-dirt contaminated cloth (artificial contaminated cloth) was prepared by uniformly applying 2 g of model sebum dirt having the following composition to a 10 cm x 10 cm cotton cloth. The composition of the model sebum soil is 60% by weight cottonseed oil, 10% by weight cholesterol, 10% by weight oleic acid, 10% by weight palmitic acid, and 10% by weight liquid and solid paraffin.

<Measurement method of cloud point before and after storage>
80 g of the liquid bleach composition was placed in a 100 mL glass sample bottle and stored at 50 ° C. for 1 month. The temperature (cloud point) at which the liquid bleach composition before and after storage was gradually heated to become cloudy was measured.

<Odor evaluation method for washing tub>
After mixing 30 mL of liquid bleach composition and 4 ° DH and adjusting to 30 L, the test of washing 4 kg of underwear using a fully automatic washing machine (Matsushita Electric Industrial Co., Ltd .; NA-F60K2 type) was repeated 60 times. It was. 7 levels of washing tank odor after cumulative washing (0: no odor, 1: very slightly odor, 2: weak odor, 3: clear odor, 4: strong odor, 5: very strong odor, 6: very strong odor ), And sensory evaluation was performed.

Claims (4)

The following (a) component, (b) component, and (c) component are contained, (a) component content in a composition is 1-50 mass%, (b) Component content is 0.1-10. Liquid bleach composition that is weight percent.
(A) Nonionic surfactant (b) Quaternary ammonium salt represented by the general formula (1)

[Wherein, one or two of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are a hydrocarbon group having one phenyl group or a linear or branched aliphatic hydrocarbon group having 8 to 36 carbon atoms] And the remainder is a linear or branched alkyl group having 1 to 5 carbon atoms. However, the total carbon number of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is 19 or more. X ⁻ is a halogen ion or an alkyl sulfate ion having 1 to 3 carbon atoms. ]
(C) Hydrogen peroxide or a compound that generates hydrogen peroxide in water   Furthermore, the liquid bleach composition of Claim 1 containing the sequestering agent which has a phosphonic acid group or its base as (d) component.   (A) The component is at least one selected from a polyoxyalkylene alkyl ether type nonionic surfactant having an oxyethylene group and an oxypropylene group, and a polyglyceryl alkyl ether type nonionic surfactant having a glyceryl group The liquid bleach composition according to claim 1 or 2. The component (a) is at least one selected from a polyoxyalkylene alkyl ether type nonionic surfactant having an oxyethylene group and an oxypropylene group and a polyglyceryl alkyl ether type nonionic surfactant having a glyceryl group (( a1) component) and a polyoxyethylene alkyl ether type nonionic surfactant (referred to as component (a2)), and the mass ratio (a1) / (a2) between component (a1) and component (a2) ) Is 1/30 to 30/1, The liquid bleach composition according to claim 1 or 2.