A hindered amine compound having thesolubility in an acidic solution of 5.0xc3x9710xe2x88x923 eq./liter or less comprising at least two specific organic groups in a specific weight ratio in a molecule, or at least two specific monomeric units, which can be used as a stabilizer of a resin.

1. Field of the Invention
The present invention relates to a hindered amine compound, a resin composition comprising a hindered amine compound which achieves stabilizing effects (resistance to NOx, light stabilization, etc.) even after various processing processes, a resin composition comprising such a hindered amine compound which is sufficiently stabilized even after various processing processes, a polyurethane resin composition and fiber comprising such a hindered amine compound which is sufficiently stabilized even after various processing processes, and a method for the preparation of such a polyurethane fiber.
Furthermore, the present invention relates to a polyurethane resin composition and fiber which is stabilized against discoloration caused with NOx, and a method for the preparation of such a polyurethane fiber.
In addition, the present invention relates to a stretch fabric or knit comprising a polyurethane fiber and a non-stretch fiber such as a polyester fiber, a polyamide fiber, a cellulose fiber, etc.
2. Prior Art
Polyalkyl-substituted piperidine derivatives are called hindered amine compounds, and widely used as stabilizers of various resins since they have high stabilizing effects on resin materials.
Hindered amine compounds are usually used to suppress the degradation caused by light (UV rays). Hindered amine compounds of various structures are widely used depending on the kinds of resins to be stabilized, purposes, applications, etc.
Polyurethane resins are more easily deteriorated by various factors than other resins, and it is essential for polyurethane resins to compound stabilizers. Among the applications of polyurethane resin compositions, a polyurethane fiber particularly deteriorates since it has a large surface area per a unit weight.
Among the causes for the deterioration of polyurethane, even a slight amount of nitrogen oxides (NOx) discolor the polyurethane. Thus, it is highly desired to develop an effective stabilizer against NOx. Among others, hindered amine compounds have a high effect to suppress the discoloration of polyurethane with NOx, and thus various types of hindered amine compounds have been developed.
However, even polyurethane products which are stabilized by the compounding of hindered amine compounds often lose the stabilizing effects of the hindered amine compounds after secondary processing. One example of such a case is dyeing of polyurethane fibers. Fibers can be dyed by various methods depending on the kinds of fibers and applications of dyed fibers. In particular, fibers are often treated in an acidic aqueous solution. Hindered amine compounds form salts with acids in the acidic aqueous solution, since they are basic compounds. Thus, it is one reason why the stabilizing effects of the hindered amine compounds are lost that the hindered amine compounds form water-soluble salts and liberate from the fibers. Such a phenomenon is remarkable with low molecular weight hindered amine compounds, although high molecular weight hindered amine compounds having a molecular weight of several thousand to several ten thousand may encounter the same phenomenon. Therefore, the increase of the number of hindered amino groups in a molecule to improve the stabilizing effects lead to the easy liberation of the hindered amine compound by the treatment in the acidic solution. That is, the concentration of the hindered amino groups in a molecule has a close relationship with the liberation of a hindered amine compound from fibers, and the prevention of the liberation of hindered amine compounds is incompatible with the high stabilizing effects.
To ultimately prevent the liberation of hindered amine compounds, many literatures propose the reaction of the hindered amine compounds with polymers constituting resins. For example, the reaction of hindered amine compounds with polyurethane is disclosed in JP-A-53-1294, JP-A-53-39395, JP-A-5-155977, etc. However, when hindered amine compounds are reacted with resin polymers as disclosed in JP-A-53-1294 and JP-A-53-39395,the physical properties of the resins more or less deteriorate in comparison with unreacted resins. For example, when hindered amino groups are introduced at polymer chain ends using a hindered amine compound as a chain terminating agent, the increase of the number of terminal groups derived from the hindered amine compound to improve the stabilizing effects inevitably lead to the decrease of the molecular weight of the polymer. Accordingly, the improvement of the stabilizing effects by the increase of the number of terminal groups derived from hindered amine compounds is essentially incompatible with the improvement of physical properties by the increase of the molecular weight. Thus, it is impossible to increase both the physical properties and the stabilizing effects.
When a compound having a hindered amino group is incorporated as a side chain in a polymer chain, the molecular weight of the polymer is not influenced by the amount of the incorporated hindered amine compound, but the synthesis of the hindered amine compound and the polymerization of the polymer are complicated.
Even if polymers having hindered amino groups as side chains are prepared, the presence of bulky groups such as hindered amino groups in side chains has influences on the interaction of the polymer molecules and in turn on the physical properties of the polymers.
Many proposals have been made on the reaction of hindered amine compounds with polymers constituting resins other than polyurethane. For example, JP-A-5-262870, JP-A-6-207142, JP-A-6-240220 and JP-A-6-264029 disclose stabilized resins which are obtained by copolymerizing a polymerizable hindered amine monomeric compound having a carbon-carbon double bond with a polymerizable monomer constituting the resins. The polymerizable hindered amine monomeric compounds which are proposed in these Japanese patent applications are relatively easily copolymerized with the monomer constituting the resins, but the kinds of the resins to be copolymerized are limited to those of vinyl monomers.
Many proposals have been made on the use of copolymers of polymerizable hindered amine monomeric compounds and other polymerizable monomers as stabilizers of resins (see, for example, JP-A-5-112725, JP-A-9-3133, JP-A-10-46141, etc.)
These proposals can prevent the liberation of the hindered amine compounds by heat, or with neutral water or hot water. However, these proposals are not intended to prevent the liberation of the hindered amine compounds by the treatment with acids. Thus, they have the same drawbacks as those for the above high molecular weight hindered amine compounds.
JP-A-10-46141 discloses a polymer or a copolymer of a polymerizable hindered amine monomeric compound as a stabilizer which suppresses the yellowing of clothes during storage. However, the disclosed invention does not shape a compound as a product after compounding a hindered amine compound in a resin. Rather, the hindered amine compound is attached to shaped products such as finished clothes by post-processing. This process can stabilize the finished products, but the stability of intermediate products which are being processed prior to finishing cannot be improved. In particular, in the case of clothes, such a drawback is not negligible, since the processing from fibers to the finished products often takes a long time.
In the case of resins such as polyurethane which are particularly easily degraded, the resins themselves should have stability. Thus, stabilizers are compounded even in primary products prior to final products, and they should not lose stabilizing properties in the post-processing processes such as secondary processing.
Polyurethane is prepared from a polyisocyanate, a polymer diol having a relatively low molecular weight and a polyfunctional active hydrogen compound having a low molecular weight, and used in awide varietyof applications such as foams, elastomers, paints, synthetic leather, fibers, etc. because it has good mechanical properties and it is easily processed. In particular, polyurethane prepared using an aromatic isocyanate such as 4,4xe2x80x2-diphenylmethane diisocyanate as a polyisocyanate is broadly used since it has excellent mechanical properties.
However, polyurethane prepared from aromatic isocyanates has a drawback that it is heavily discolored with NOx. NOx is contained in combustion gas or exhaust gas, and it discolors polyurethane even in a very small amount. Therefore, the suppression of discoloration of polyurethane caused with NOx has been discussed for a long time. For example, phosphite ester antioxidants, aliphatic amine derivatives and hydrazine derivative are known as stabilizers which suppress the discoloration of polyurethane caused with NOx. Among them, the phosphite ester antioxidants, and hindered amine compounds as aliphatic amine derivatives are generally used since they achieve particularly high stabilizing effects.
However, the phosphite ester antioxidants and hindered amine compounds should be used in combination with phenol antioxidants to impart processing stability and heat resistance to polyurethane, since they have low effects to suppress thermal oxidation of polyurethane. It is known to use three stabilizers, that is, a phenol antioxidant, a phosphite ester antioxidant and a hindered amine compound, and the mixed stabilizer has a remarkable effect to prevent the discoloration of polyurethane. However, when a polyurethane resin composition containing such a mixed stabilizer is subjected to a secondary processing such as dyeing of fibers, the stabilizing effects of the mixed stabilizer are often greatly impaired. Such a polyurethane resin composition which loses the stabilizing effects by the secondary processing has a serious drawback since it has a large risk that a final product suffers from disoloration or deterioration.
Fabrics or knits comprising a polyurethane fiber and a non-stretch fiber such as a polyester fiber, a polyamide fiber or a cellulose fiber have good stretch properties. Thus they are used in a wide variety of applications, for example, the legs of panty hoses or socks; foundation garments or undergarments such as brassieres, girdles, bodysuits, etc.; sports wears such as swimming suits, leotards, etc.; outer garments such as ski pants, stretch denims, etc.; and the like. Furthermore, such fabrics and knits can be used in medical applications such as stretch bandages, stretch corsets, base cloths of stretch tapes, athletic supporters, etc.; base cloths of stretch boots; and the like.
However, since polyurethane has the above-described drawbacks, the stabilizing effects of stabilizers are often severely impaired, when stretch fabrics or knits comprising polyurethane fibers containing conventional stabilizers are dyed. Therefore, stretch fabrics or knits comprising such polyurethane fibers or their final products have problems that they are yellowed or deteriorated on exposure to an atmosphere containing NOx.
As described above, hindered amine compounds sometimes lose their stabilizing effects due to secondary processing such as dyeing, although they exhibit high stabilizing effects as stabilizers of resins.
Hitherto, no hindered amine compound has been provided, that is used as a stabilizer of resins and fibers, in particular, fibers which should be dyed under acidic conditions, and can exhibits satisfactory stabilizing effects without deteriorating the inherent properties of the resins even after the processing.
When hindered amine compounds are chemically bonded with polymers constituting resins, the obtained resins have good stability even after secondary processing, but their physical properties are greatly deteriorated.
Thus, it is highly desired to develop a stabilizer which can be compounded in a resin as a discrete stabilizer from the polymer constituting the resin, and achieves good stabilizing effects not only on resin materials but also on processed products which have been subjected to various processing steps such as dying. In particular, in the case of polyurethane, the intermolecular interaction greatly contributes to its good physical properties. Therefore, the introduction of a different structure in polymer chains largely deteriorates the physical properties, and the polyurethane having such a different structure in the polymer chain is easily discolored with NOx. Therefore, the above type of a stabilizer is highly important.
A polyurethane resin composition containing a phosphite ester antioxidant, a phenol antioxidant and a hindered amine compound has high stability against degradation, but the stabilizing effects of the mixed stabilizer are sometimes lost after processing.
One object of the present invention is to provide a hindered amine compound which can be compounded in a resin as a discrete stabilizer from the polymer constituting the resin without deteriorating the properties of the resin, and achieves good stabilizing effects (e.g. resistance to NOx, light stabilization, etc.) on the resin even after the resin is subjected to various processing steps such as dying.
Another object of the present invention is to provide a polyurethane resin composition or fiber which has good light stability and is stabilized against discoloration caused by NOx not only in the form of an intermediate product but also in the form of a final product after various processing such as dyeing.
According to the first aspect of the present invention, there is provided a hindered amine compound having, in amolecule, at least one organic group (A1) selected from the group consisting of a monovalent organic group of the formula (1):
in which R is an alkyl group having 1 to 10 carbon atoms, which may optionally be substituted, and R1 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, which may optionally be substituted, or an alkoxy group having 1 to 10 carbon atoms, and a divalent organic group of the formula (2):
in which R is the same as defined above, wherein
(a) the number of the organic group (A1) is at least 1.3 moles per 1 kg of the hindered amine compound, and
(b) the solubility of the hindered amine compound is 5.0xc3x971031 3 eq./liter or less in an acidic solution.
According to the second aspect of the present invention, there is provided a hindered amine compound having, in a molecule, at least one organic group (A2) selected from the group consisting of a monovalent organic group of the formula (3):
in which R is an alkyl group having 1 to 10 carbon atoms, which may optionally be substituted, and R2is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, which may optionally be substituted, or an alkoxy group having 1 to 10 carbon atoms, and a divalent organic group of the formula (4):
in which R is the same as defined above, and at least one organic group (C1) selected from the group consisting of a cycloalkyl group having 5 to 10 carbon atoms and a cycloalkylene group having
5 to 10 carbon atoms,
wherein the weight percentages WA2 and WC1 of the organic groups (A2) and (C1), respectively, satisfy the following formulas (I) and (II):
40xe2x89xa6WA2+WC1xe2x89xa670xe2x80x83xe2x80x83(I)
0.6xe2x89xa6WA2/WC1xe2x89xa63xe2x80x83xe2x80x83(II)
According to the third aspect of the present invention, there is provided a hindered amine compound obtained by copolymerizing at least one polymerizable hindered amine monomeric compound (A3) of the formula (5):
in which R is an alkyl group having 1 to 10 carbon atoms, which may optionally be substituted, R3 is a hydrogen atom or a methyl group, R4 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, which may optionally be substituted, or an alkoxy group having 1 to 10 carbon atoms, and X1 is a xe2x80x94Oxe2x80x94 group or a xe2x80x94NHxe2x80x94 group, and at least one polymerizable monomer (C2) of the formula (6)
in which R5 is a hydrogen atom or a methyl group, R6 is a cycloalkyl group having 5 to 10 carbon atoms, and Y1 is a xe2x80x94Oxe2x80x94 group or a xe2x80x94NHxe2x80x94 group, wherein the weight percentages WA3 and WC2 of the components (A3) and (C2), respectively, satisfy the following formulas (III) and (IV):
80xe2x89xa6WA3+WC2xe2x89xa6100xe2x80x83xe2x80x83(III)
0.5xe2x89xa6WA3/WC2xe2x89xa62.3xe2x80x83xe2x80x83(IV)
According to the fourth aspect of the present invention, there is provided a hindered amine compound obtained by copolymerizing at least one polymerizable hindered amine monomeric compound (A4) of the formula (7):
in which R is an alkyl group having 1 to 10 carbon atoms, which may optionally be substituted, R7 is a hydrogen atom or a methyl group, R8 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, which may optionally be substituted, or an alkoxy group having 1 to 10 carbon atoms, and X2 is a xe2x80x94Oxe2x80x94 group or a xe2x80x94NHxe2x80x94 group, and at least one polymerizable monomer (D1) of the formula (8):
in which R9 is a hydrogen atom or a methyl group, R10 is a straight or branched alkyl group having 10 to 30 carbon atoms, and Y2 is a xe2x80x94Oxe2x80x94 group or a xe2x80x94NHxe2x80x94 group, wherein the weight percentages WA4 and WD1 of the components (A4) and (D1), respectively, satisfy the following formulas (V) and (VI):
80xe2x89xa6WA4+WD1xe2x89xa6100xe2x80x83xe2x80x83(V)
8.3xe2x89xa6WA4/WD1xe2x89xa62.3xe2x80x83xe2x80x83(VI)
According to the fifth aspect of the present invention, there is provided a hindered amine compound of the formula (9):
in which R is an alkyl group having 1 to 10 carbon atoms, which may optionally be substituted, R11 and R12 are the same or different and each a hydrogen atom or a methyl group, R13 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, which may optionally be substituted, or an alkoxy group having 1 to 10 carbon atoms, X and Y are the same or different and each a xe2x80x94Oxe2x80x94 group or a xe2x80x94NHxe2x80x94group, and n and m are positive integers satisfying the formula: 0.35xe2x89xa6n/mxe2x89xa61.75, and the sum of n and m is from 2 to 10000.
According to the sixth aspect of the present invention, there is provided a hindered amine compound of the formula (10):
in which R is an alkyl group having 1 to 10 carbon atoms, which may optionally be substituted, R14 and R15 are the same or different and each a hydrogen atom or a methyl group, R16 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, which may optionally be substituted, or an alkoxy group having 1 to 10 carbon atoms, R17 is a straight or branched alkyl group having 10 to 30 carbon atoms, X and Y are the same or different and each a xe2x80x94Oxe2x80x94 group or a xe2x80x94NHxe2x80x94 group, and n and m are positive integers satisfying the formula: 0.65xe2x89xa6n/mxe2x89xa62.50, and the sum of n and m is from 2 to 10000.
In a preferred embodiment, at least a part of the hindered amino groups of the above hindered amine compounds of the present invention form salts with at least one compound selected from the group consisting of organic carboxylic acids, carbon dioxide, phosphoric acid, phosphate esters, phosphorous acid and phosphite esters.
According to the seventh aspect of the present invention, there is provided a resin composition comprising at least one of the hindered amine compounds according to the first to sixth aspects of the present invention.
In a preferred embodiment, the above resin composition contains a phosphite ester antioxidant.
In another preferred embodiment, the resin in the above resin composition is polyurethane.
In the eighth aspect of the present invention, there is provided a resin composition comprising polyurethane, a phenol antioxidant, a phosphite ester antioxidant, and at least one of the hindered amine compounds according to the first to sixth aspects of the present invention, in which the amount of the phenol antioxidant is preferably from 0.1 to 2 wt. %, the amount of the phosphite ester is preferably from 0.1 to 2 wt. %, and the amount of the hindered amine compound is from 0.5 to 5 wt. %, based on the weight of polyurethane.
In a preferred embodiment, the above phosphite ester antioxidant is a hydrogenated bisphenol A-pentaerithritol phosphite polymer of the formula (11):
In another preferred embodiment, the above phenol antioxidant is aphenol compound which has the chemical structure of the formula (12):
whereom R18 is a tert.-butyl group, a sec-butyl group or a neopentyl group.
According to the ninth aspect of the present invention, there is provided a polyurethane fiber prepared from the polyurethane resin composition according to the seventh and eighth aspects of the present invention.
According to the tenth aspect of the present invention, there is provided a method for the production of a polyurethane fiber comprising the step of spinning the polyurethane resin composition according to the seventh and eighth aspects of the present invention.
According to the eleventh aspect of the present invention, there is provided a stretch fabric or knit comprising a polyurethane fiber according to the ninth aspect of the present invention, and a non-stretch fiber.
In a preferred embodiment, the above non-stretch fiber is at least one fiber selected from the group consisting of a polyester fiber, a polyamide fiber and a cellulose fiber.
In another preferred embodiment, the polyurethane fiber is a bare fiber or a composite fiber.
The mono- or divalent organic group (A1) in the hindered amine compound according to the first aspect of the present invention is at least one organic group selected from the group consisting of a monovalent organic group of the formula (1) and a divalent organic group of the formula (2).
When the organic group (A1) is a monovalent one, it is preferably bonded at the 4-position of the piperidine ring to other site of the compound.
R in the formula (1) or (2) is a substitutedor unsubstituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably methyl group.
R1 in the formula (1) is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or an alkoxyl group having 1 to 10 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred from the viewpoint of stabilizing effects, and a hydrogen atom or a methyl group is more preferable.
When the organic group (A1) is a divalent one, it is preferably bonded at the 1- and 4-positions of the piperidine ring to other sites of the compound. Preferred examples of the organic group (A1) include compounds of the following formulas (13) to (15):
The organic group (A1) may be a single organic group or a mixture of two or more organic groups, insofar as the above definitions are met. In addition, the organic group (A1) may be a mixture of at least one monovalent organic group and at least one divalent organic group. In particular, the organic group (A1) is preferably an organic group of the formula (13).
The number of the organic groups (A1) is at least 1.3 moles per 1 kg of the hindered amine compound. When the number of the organic groups (A1) is less than 1.3 moles, the stabilizingeffects may decrease since the number of effective sites of the compound, which contribute to the stabilization, becomes too small. Furthermore, as the number of the organic groups (A1) decreases, the increased amount of the hindered amine compound should be added to a resin composition to achieve the same effects, which is unfavorable from the viewpoint of the costs.
The number of the organic group (A1) is preferably at least 2.0 moles per 1 kg of the hindered amine compound from the viewpoint of stabilizing effects.
Herein, the solubility of a hindered amine compound in an acidic solution is measured as follows:
0.0200 g of a hindered amine compound is accurately weighed. When a hindered amine compound is in the form of a solution, the hindered amine compound is once recovered from the solution and then weighed, or the weight of the solution is weighed so that the weight of the hindered amine compound reaches the determined weight. To recover the hindered amine compound from the solution, any known method such as reprecipitation, recrystallization, evaporation of a solvent, etc. may be used.
Then, the weighed hindered amine compound is dissolved in 100 ml of a solvent. A used solvent is preferably a solvent in which the hindered amine compound is well dissolved, and which does not have a basicity, and is miscible with water.
Examples of such a solvent include lower alcohols (e.g. methanol, ethanol, propanol, etc.), amides (e.g. N,N-dimethylformamide, N,N-dimethylacetamide, etc.), ethers (e.g. tetrahydrofuran, dioxane, etc.), and the like. From these solvents, a solvent which can dissolve therein a hindered amine compound to be tested is suitably selected.
The solution of the hindered amine compound is then subjected to neutralization titration with a 1/100 N hydrochloric acid using potentiometric titration equipment (COMTITE-980 available from HIRANUMA Industries, Ltd.), a glass electrode (GE-101 available from HIRANUMA Industries, Ltd.) and a reference electrode (RE-101 available from HIRANUMA Industries, Ltd.).
The amount of a base (BA; unit: eq/kg) per 1 kg of the hindered amine compound is calculated according to he following equation:
BA=(Vxc3x97Fxc3x9710xe2x88x922)/0.0200xe2x80x83xe2x80x83(VII)
in which V is a titer (ml) and F is a factor of the 1/100 N hydrochloric acid.
1.200 g of acetic acid, and 0.250 g of anhydrous sodium acetate are accurately weighed, and dissolved in 1 liter of pure water in a graduated flask.
Using a base amount per 1 kg of a hindered amine compound, the weight (WA; unit: g) of the hindered amine compound for the solubility measurement is calculated so that the total base amount is 5.0xc3x9710xe2x88x925 mole according to the following equation:
WA=(5xc3x9710xe2x88x922)/BAxe2x80x83xe2x80x83(VIII)
in which BA is the base amount (eq/kg) per 1 kg of the hindered amine compound.
The hindered amine compound of the weight calculated according to equation (VIII) is accurately weighed, and charged in a glass ampoule together with 5 ml of the above prepared acidic solution and then sealed. The ampoule is heated at 100xc2x0 C. for 1 hour, cooled and then unsealed.
Three milliliters of the liquid in the ampoule, which has been filtered through a 0.45um filter, and ml of a 1/10 N aqueous sodium hydroxide solution were dissolved in 100 ml of a solvent. The solvent may be the same as that used in the above measurement of the base amount.
The mixed solution is subjected to neutralization titration with a 1/100 N hydrochloric acid using potentiometric titration equipment. As a blank, 3 ml of distilled water containing 3.6xc3x9710xe2x88x923 g of acetic acid and 0.75xc3x9710xe2x88x923 g of anhydrous sodium acetate and 1 ml of a 1/10 N aqueous sodium hydroxide solution were dissolved in 100 ml of the solvent, and then subjected to the neutralization titration.
The end point of the titration is a time when all the bases (the hindered amine compound, sodium acetate and sodium hydroxide) are titrated, and then a titer is determined.
The solubility (SA; unit: eq/liter) of the hindered amine compound in the acidic solution is calculated as the amount of the base dissolved in 1 liter of the acidic solution according to the following equation:
SA=(VSxe2x88x92VB)/300xe2x80x83xe2x80x83(IX)
in which VS is a titer (ml) for 3 ml of the sample solution and VB is a titer for 3 ml of the blank solution.
The hindered amine compound according to the first aspect of the present invention has a solubility of no larger than 5.0xc3x9710xe2x88x923 eq./liter, when the solubility is measured as described above. The smaller solubility is more preferred. The hindered amine compound has better properties, when its solubility is 2.5xc3x9710xe2x88x923 eq/liter or less.
The organic group (A2) of the hindered amine compound according to the second aspect of the present invention is at least one mono- or divalent organic group selected from the group consisting of a monovalent organic group of the formula (3) and a divalent organic group of the formula (4).
R in the formula (3) or (4) is a substitutedor unsubstituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably methyl group.
R2 in the formula (3) is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or an alkoxyl group having 1 to 10 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred from the viewpoint of stabilizing effects, and a hydrogen atom or a methyl group is more preferable.
When the organic group (A2) is a divalent one, it is preferably bonded at the 1- and 4-positions of the piperidine ring to other sites of the compound. Preferred examples of the organic group (A2) include compounds of the above formulas (13) to (15).
The organic group (A2) may be a single organic group or a mixture of two or more organic groups, insofar as the above definitions are met. In addition, the organic group (A2) may be a mixture of at least one monovalent organic group and at least one divalent organic group. In particular, the organic group (A2) preferably consists of the above structure (9).
The organic group (C1) in the hindered amine compound according to the second aspect of the present invention is at least one mono- or divalent organic group selected from the group consisting of a cycloalkyl group having 5 to 10 carbon atoms and a cycloalkylene group having 5 to 10 carbon atoms.
When the number of the carbon atoms in the organic group is small, the effect exerted by each group is small, so that the resin composition is not sufficiently stabilized after processing. When the number of carbon atoms is too large, the number of groups decreases, and thus the effects exerted by the whole groups decreases so that the sufficient stabilizing effects after the processing of a resin composition cannot be attained.
Preferably, the organic group (C1) is a cycloalkyl group having 5 to 10 carbon atoms.
A cycloalkyl group used herein means a group having at least one closed ring consisting of a plurality of carbon atoms which are covalently bonded. When one cycloalkyl group has two or more rings, the rings may share some carbon atoms. In a cycloalkyl group, each ring has at least 3 carbon atoms, preferably 5 or 6 carbon atoms.
A cycloalkyl group may have at least one straight or branched alkyl group having 1 to 5 carbon atoms as a substituent. Although the number of the substituent alkyl groups on a cycloalkyl group is not limited, the total number of carbon atoms of the substituent alkyl groups is generally 5 to 10. Preferably, a cycloalkyl group consists of carbon and hydrogen atoms.
Furthermore, a cycloalkyl group has only covalent bonds, and neither a double bond nor a triple bond, from the viewpoint of the stabilizing effects.
All the organic groups (C1) may the same groups, while they may comprise two or more different groups.
Preferred examples of the organic group (C1) are the groups of the following formulas (16) to (25):
wherein Z is a hydrogen atom, a straight or branched alkyl group having 1 to 5 carbon atoms, or a bonding site which is bonded with other site of a hindered amine compound, provided that the total number of carbon atoms in each formula does not exceed 10, and the number of bonding sites is 1 or 2.
Among them, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, a bornyl group, an isobornyl group and a decahydronaphthyl group are preferred. In particular, a cyclohexyl group and a isobornyl group are preferred.
The hindered amine compound according to the second aspect of the present invention has at least one organic group (A2) and atleastoneorganicgroup (C1) inonemolecule. Thetotalweight percentage of the organic group (A2) and the organic group (C1) in the hindered amine compound is preferably from 40 wt. % to 70 wt. %. When the total weight percentage of the two kinds of the organic groups is less than 40 wt. %, the hindered amine compound has low stabilizing effects, so that a large amount of the hindered amine compound should be compounded in a resin composition, whichisunfavorable fromtheviewpointof the costs. When the total weight percentage of the two kinds of the organic groups exceeds 70 wt. %, the stabilizing effects after the processing of a resin composition deteriorate, although the stabilizingeffectsprior to theprocessingrelativelyincrease. The total weight percentage of the two kinds of the organic groups is preferably from 50 wt. % to 60 wt. %.
In addition, a ratio of the weight percentage of the organic group (A2) to that of the organic group (C1) is preferably in the range between 0.6 and 3. When this ratio is less than 0.6, the stabilizing effects prior to the processing of a resin composition decrease, while when this ratio exceeds 3, the stabilizing effects after the processing of a resin composition deteriorate. This ratio is preferably in the range between 1.0 and 2.5.
The weight percentage of the organic group (A2) or the organic group (C1) is expressed in terms of a ratio of the formula weight of each organic group to the molecular weight of the hindered amine compound. When the hindered amine compound is a polymeric compound comprising repeating units, the weight percentage of each organic group can be calculated with the repeating units.
The hindered amine compound according to the third aspect of the present invention is obtained by copolymerizing at least one polymerizable hindered amine monomeric compound (A3) of the formula (5) and at least one polymerizable monomer (C2) of the formula (6). In addition, the weight percentages WA3 and WC2 of the components (A3) and (C2), respectively, should satisfy the following formulas (III) and (IV):
80 wt. % xe2x89xa6WA3+WC2xe2x89xa6100 wt. %xe2x80x83xe2x80x83(III)
0.5xe2x89xa6WA3/WC2xe2x89xa62.3xe2x80x83xe2x80x83(IV)
The weight percentage of each monomeric component is expressed in terms of a ratio of the weight of each monomeric component to the weight of the hindered amine compound. The weight of each monomeric component can be obtained by any one of conventional methods which are known as analyzing methods of polymers. Examples of quantitative analysis methods are the quantitative analysis with 1H-NMR, the quantitative analysis of the amount of a hindered amine component by neutralization titration, and the like. When it is difficult to quantitatively analyze a hindered amine compound, the weight percentage of the charged amount of each component may be used instead.
When the sum of the weight percentages of the components (A3) and (C2) is less than 80 wt. %, the stabilizingeffects cannot be attained with good balance after the processing of a resin composition. The sum of the weight percentages of the components (A3) and (C2) is preferably from 95 wt. % to 100 wt. %.
When the ratio of the weight percentage of the component (A3) to that of the component (C1) is less than 0.5, the hindered amine compound exerts low stabilizing effects prior to the processing of a resin composition, so that a large amount of the hindered amine compound should be compounded in a resin composition, which is unfavorable from the viewpoint of the costs. when this ratio exceeds 2.3, the stabilizing effects after the processing of a resin composition deteriorate, although the stabilizing effects prior to the processing are sufficient. This ratio is preferably in the range between 1.0 and 1.6.
R in the formula (5) is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably methyl group.
R3 in the formula (5) is a hydrogen atom or a methyl group, and a methyl group is preferable.
R4 in the formula (5) is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or an alkoxyl group having 1 to 10 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred from the viewpoint of stabilizing effects, and a hydrogen atom or a methyl group is more preferable.
X1 in the formula (5) is a xe2x80x94Oxe2x80x94 group or a xe2x80x94NHxe2x80x94 group, and a xe2x80x94Oxe2x80x94 group is preferable.
The polymerizable hindered amine monomeric compound (A3) is a single compound of the formula (5) or a mixture of two or more compounds of the formula (5), which may be the compounds of the formula (5) wherein each of R3, R4 and X1 is the same or different. The most preferred combination of R3, R4 and X1 is such that R3 is a methyl group, R4 is a hydrogen atom and X1 is a xe2x80x94Oxe2x80x94 group.
Preferred examples of the polymerizable hindered amine monomeric compound (A3) include 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, N-(2,2,6,6-tetramethyl-4-piperidyl) methacrylamide, N-(1,2,2,6,6-pentamethyl-4-piperidyl) methacrylamide, N-(2,2,6,6-tetramethyl-4-piperidyl) acrylamide, N-(1,2,2,6,6-pentamethyl-4-piperidyl) acrylamide, etc. Among them, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and 1,2,2,6,6-pentamethyl-4-piperidyl acrylate are more preferred. The most preferred compound is 2,2,6,6-tetramethyl-4-piperidyl methacrylate.
The component (A3) may be a mixture of two or more compounds as defined above with any composition. In particular, it is preferred to use 2,2,6,6-tetramethyl-4-piperidyl methacrylate alone.
R5 in the formula (6) is a hydrogen atom or a methyl group, and a methyl group is preferable.
R6 in the formula (6) is a cycloalkyl group having 5 to 10 carbon atoms or its derivative. When the number of carbon atoms in R6 is too small, the effect exerted by each group is small. When the number of carbon atoms is too large, the number of groups decreases, and thus the effects exerted by the whole groups decreases so that the sufficient stabilizing effects after the processing of a resin composition cannot be attained.
A cycloalkyl group used herein means a group having at least one closed ring consisting of a plurality of carbon atoms which are covalentlybonded. Whenonecycloalkyl group hastwoormore rings, the rings may share some carbon atoms. In a cycloalkyl group, each ring has at least 3 carbon atoms, preferably 5 or 6 carbon atoms.
A cycloalkyl group may have at least one straight or branched alkyl group having 1 to 5 carbon atoms as a substituent. Although the number of the substituent alkyl groups on a cycloalkyl group is not limited, the total number of carbon atoms of the substituent alkyl groups is generally 5 to 10. Preferably, a cycloalkyl group consists of carbon and hydrogen atoms.
Furthermore, a cycloalkyl group has only covalent bonds, and neither a double bond nor a triple bond, from the viewpoint of the stabilizing effects. The bonding site of R6 with X2 may be either a carbon atom on the cycloalkyl group, or on an alkyl group which may be present as a substituent on the cycloalkyl group.
Specific examples of R6are the compounds of the following formulas (26) to (35):
wherein Z is a hydrogen atom, a straight or branched alkyl group having 1 to 5 carbon atoms or a bonding site with Y1, provided that the total number of carbon atoms in each formula does not exceed 10, and one of Z""s is a bonding site with Y1.
Preferable examples of R6 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a decahydronaphtyl group, a norbornyl group, a bornyl group, an isobornyl group, etc. Among them, a cyclohexyl group and an isobornyl group are more preferred.
Y1 in the formula (6) is a xe2x80x94Oxe2x80x94 group or a xe2x80x94NHxe2x80x94 group, and the xe2x80x94Oxe2x80x94 group is preferable.
The polymerizable monomeric compound (C2) is a single compound of the formula (6) or a mixture of two or more compounds of the formula (6), which may be the compounds of the formula (6) wherein each of R5, R6 and Y1 is the same or different. The most preferred combination of R5, R6 and Y1 is such that R5 is a methyl group, R6 is a cyclohexyl group and Y1 is a xe2x80x94Oxe2x80x94 group.
Preferred examples of the polymerizable monomeric compound (C2) include cyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, cyclononyl methacrylate, cyclodecyl methacrylate, decahydronaphthyl methacrylate, norbornyl methacrylate, bornyl methacrylate, isobornyl methacrylate, cyclopentyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, cyclononyl acrylate, cyclodecyl acrylate, decahydronaphtyl acrylate, norbornyl acrylate, bornyl acrylate, isobornyl acrylate, N-cyclopentyl methacrylamide, N-cyclohexyl methacrylamide, N- cycloheptyl methacrylamide, N-cyclooctyl methacrylamide, N-cyclononyl methacrylamide, N-cyclodecyl methacrylamide, N-decahydronaphtyl methacrylamide, N-norbornyl methacrylamide, N-bornyl methacrylamide, N-isobornyl methacrylamide, N-cyclopentyl methacrylamide, N-cyclohexyl acrylamide, N-cycloheptyl acrylamide, N-cyclooctyl acrylamide, norbornyl methacrylate, norbornyl acrylate, N-norbornylacrylamide, N-cyclononyl acrylamide, N-cyclodecyl acrylamide, N-decahydronaphthyl acrylamide, N-norbornyl acrylamide, N-bornyl acrylamide, N-isobornyl acrylamide, etc. Preferable examples of the polymerizable monomeric compound (C2) include cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl methacrylate, isobornyl acrylate, etc. Among them, cyclohexyl methacrylate is more preferable.
In the hindered amine compound according to the third aspect of the present invention, the most preferred combination of the polymerizable hindered amine monomeric compound (A3) and the polymerizable monomer (C2) is the combination of 2,2,6,6-tetramethyl-4-piperidyl methacrylate and cyclohexyl methacrylate.
The hindered amine compound according to the fourth aspect of the present invention is a hindered amine compound obtained by copolymerizing at least one polymerizable hindered amine monomeric compound (A4) of the formula (7) and at least one polymerizable monomer (D1) of the formula (8). In addition, the weight percentages WA4 and WD1 of the components (A4) and (D1), respectively, satisfy the following formulas (V) and (VI):
80xe2x89xa6WA4+WD1xe2x89xa6100xe2x80x83xe2x80x83(V)
xe2x80x830.3xe2x89xa6WA4/WD1xe2x89xa62.3xe2x80x83xe2x80x83(VI)
The weight percentage of each monomeric component is expressed in terms of a ratio of the weight of each monomeric component to the weight of the hindered amine compound. The weight of each monomeric component can be obtained by any one of conventional methods which are known as analyzing methods of polymers. Examples of quantitative analysis methods are the quantitative analysis with 1H-NMR, the quantitative analysis of the amount of a hindered amine component by neutralization titration, and the like. When it is difficult to quantitatively analyze a hindered amine compound, the weight percentage of the charged amount of each component may be used instead.
When the sum of the weight percentages of the components (A4) and (D1) is less than 80 wt. %, the stabilizingeffects cannot be attained with good balance after the processing of a resin composition. The sum of the weight percentages of the components (A4) and (D1) is preferably from 95 wt. % to 100 wt. %.
When the ratio of the weight percentage of the component (A4) to that of the component (D1) is less than 0.3, the hindered amine compound exerts low stabilizing effects prior to the processing of a resin composition, so that a large amount of the hindered amine compound should be compounded in a resin composition, which is unfavorable from the viewpoint of the costs. when this ratio exceeds 2.3, the stabilizing effects after the processing of a resin composition deteriorate, although the stabilizing effects prior to the processing are sufficient. This ratio is preferably in the range between 0.7 and 1.6.
R in the formula (7) is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably methyl group.
R7 in the formula (7) is a hydrogen atom or a methyl group, and a methyl group is preferable.
R8 in the formula (7) is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or an alkoxyl group having 1 to 10 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred from the viewpoint of stabilizing effects, and a hydrogen atom or a methyl group is more preferable.
X2 in the formula (7) is a xe2x80x94Oxe2x80x94 group or a xe2x80x94NHxe2x80x94 group, and a xe2x80x94Oxe2x80x94 group is preferable.
The polymerizable hindered amine monomeric compound (A4) is a single compound of the formula (7) or a mixture of two or more compounds of the formula (7), which may be the compounds of the formula (7) wherein each of R7, R8 and X2 is the same or different. Preferably, each of R7, R8 and X2 is the same. The most preferred combination of R7, R8 and X2 is such that R7 is a methyl group, R8 is a hydrogen atom and X2 is a xe2x80x94Oxe2x80x94 group.
Preferred examples of the polymerizable hindered amine monomeric compound (A4) include 2,2,6, 6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, N-(2,2,6,6-tetramethyl-4-piperidyl) methacrylamide, N-(1,2,2,6,6-pentamethyl-4-piperidyl) methacrylamide, N-(2,2,6,6-tetramethyl-4-piperidyl) acrylamide, N-(1,2,2,6,6-pentamethyl-4-piperidyl) acrylamide, etc. Among them, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and 1,2,2,6,6-pentamethyl-4-piperidyl acrylate are more preferred. The most preferred compound is 2,2,6,6-tetramethyl-4-piperidyl methacrylate.
The component (A4) may be a mixture of two or more compounds as defined above with any composition. In particular, it is preferred to use 2,2,6,6-tetramethyl-4-piperidyl methacrylate alone.
R9 in the formula (8) is a hydrogen atom or a methyl group, and a methyl group is preferable.
R10 in the formula (8) is a straight or branched alkyl group having 10 to 30 carbon atoms. When the number of carbon atoms in R10 is too small, the effect exerted by each group is small. When the number of carbon atoms is too large, the number of groups decreases, and thus the effects exerted by the whole groups decreases so that the sufficient stabilizing effects after the processing of a resin composition cannot be attained.
Preferable examples of alkyl groups for R10 include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a docosyl group, a tetracosyl group, a hexacosyl group, an octacosyl group, a triacontyl group, an isostearyl group, etc. More preferable examples include a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, etc.
Y2 is a xe2x80x94Oxe2x80x94 group or a xe2x80x94NHxe2x80x94 group, and a xe2x80x94Oxe2x80x94 group is preferable.
The polymerizable monomeric compound (D1) is a single compound of the formula (8) or a mixture of two or more compounds of the formula (8), which may be the compounds of the formula (8) wherein each of R9, R10 and Y2 is the same or different. Preferably, each of R9, R10 and Y2 is the same. The most preferred combination of R9, R10 and Y2 is such that R9 is a methyl group, R10 is an octadecyl group and Y2 is a xe2x80x94Oxe2x80x94 group.
Preferable examples of the polymerizable monomeric component (D1) include dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, N-dodecyl methacrylamide, N-tetradecyl metharylamide, N-hexadecyl methacrylamide, N-octadecyl methacrylamide, N-dodecyl acrylamide, N-tetradecyl acrylamide, N-hexadecyl acrylamide, N-octadecyl acrylamide, etc.
In the hindered amine compound according to the fourth aspect of the present invention, the most preferred combination of the polymerizable hindered amine monomeric compound (A4) and the polymerizable monomer (D1) is the combination of 2,2,6,6-tetramethyl-4-piperidyl methacrylate and octadecyl methacrylate.
The hindered amine compounds according to the fifth and sixth aspects of the present invention are the copolymer of the compound of the formula (5) and the compound of the formula (6), and the copolymer of the compound of the formula (7) and the compound of the formula (8), respectively.
The hindered amine compounds according to the third, fourth, fifth and sixth aspects of the present invention can be synthesized from the above described compounds as the raw materials. It may be possible to copolymerize at least one of known polymerizable monomers which are not essential components of the hindered amine compounds of the present invention, insofar as the effects of the present invention are not impaired.
The polymerization reaction may be carried out by any known methods. A radical polymerization method is preferable, and a solution polymerization method, in which raw materials are reacted in a solvent in the presence of a radical polymerization initiator, is more preferable since the method is simple and the reaction can be easily controlled. Any solvent may be used, insofar as it does not react with radicals, and the polymerizable monomers and produced copolymers can be dissolved in it. Specific examples of such solvents include hydrocarbons (e.g. toluene, benzene, xylene, etc.), esters (e.g. ethyl acetate, butyl acetate, etc.), ketones (e.g. acetone, methyl ethyl ketone, etc.), alcohols (e.g. methanol, ethanol, isopropanol, n-butanol, etc.), N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoneamide, etc.), ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, etc.), and the like.
Any known polymerization initiator may be used in the present invention. In particular, azo compounds are preferable. Specific examples of azo compound include 2,2xe2x80x2-azobis(2-diaminopropane) dihydrochloride, 1,1xe2x80x2-azobis(cyclohexane-1-carbonitrile), 2,2xe2x80x2-azobis(2-methylbutyronitrile), 2,2xe2x80x2-azobis(isobutyronitrile), 2,2xe2x80x2-azobis(2,4-dimethylvaleronitrile), 2,2xe2x80x2-azobis(4-methoxy-2,4-dimethylvaleronitrile), 4,4xe2x80x2-azobis(4-cianovaleric acid), dimethyl 2,2xe2x80x2-azobisisobutyrate, 2,2xe2x80x2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2xe2x80x2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride dihydrate, 2,2xe2x80x2-azobis]2-(2-imidazolin-2-yl)propane], 2,2xe2x80x2-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2xe2x80x2-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)methyl]propionamide}, 2,2xe2x80x2-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2xe2x80x2-azobisisobutylamide dihydrate, 2,2xe2x80x2-azobis[2-(hydroxymethyl)propionitrile], 2,2xe2x80x2-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2xe2x80x2-azobis(2,4,4-trimethylpentane), etc.
The concentration of the polymerizable monomers at the charging is not limited, and is preferably from 20 to 70 wt %. A solvent may be supplemented, as the polymerization reaction proceeds.
The amount of the polymerization initiator added can be freely changed according to the intended degree of polymerization. The amount of the polymerization initiator is usually from 0.01 to 2 wt. % of the weight of the polymerizable monomers. The polymerization initiator as such or the solution of the polymerization initiator may be added to the polymerization system. The polymerization initiator may be added all at once, or portion by portion.
If necessary, any known chain transfer agent may be used.
The reaction temperature is not limited, and is preferably from 50 to 100xc2x0 C.
The reaction time is not limited either, and is preferably from 1 to 24 hours.
The content of unreacted polymerizable monomers remained in the polymer composition is not limited, and is preferably not larger than 20 wt. % of the polymer weight. When the amount of the unreacted polymerizable monomers in the hindered amine compound is too large, they themselves deteriorate the compound and thus the stabilizing effects of the hindered amine compound may impaired. The obtained polymer may be used in the form of a solution, or it maybe purified by any known purification method such as reprecipitation, the removal of the solvent, column chromatography, etc., and then used.
R in the formula (9) is a substitutedorunsubstitutedalkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and methyl group is more preferable. R11 and R12 in the formula (9) are the same or different and each a hydrogen atom or methyl group, preferably each a methyl group. R13 in the formula (9) is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably hydrogen atom or methyl group, and hydrogen atom is more preferable. X and Y in the formula (9) are the same or different and each a xe2x80x94Oxe2x80x94 group or a xe2x80x94NHxe2x80x94 group, preferably each a xe2x80x94Oxe2x80x94 group. In formula (9), n/m is from 0.35 to 1.75, preferably from 0.70 to 1.70, and sum of n and m is from 2 to 10000, preferably from 5 to 1000.
R in the formula (10) is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and methyl group is more preferable. R14 and R15 in the formula (10) are the same or different and each a hydrogen atom or methyl group, preferably each a methyl group. R16 in the formula (10) is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably hydrogen atom or methyl group, and hydrogen atom is more preferable. R17 in the formula (10) is a straight or branched alkyl group having 10 to 30 carbon atoms. Preferable example for R17 include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a docosyl group, a tetracosyl group, a hexacosyl group, anoctacosyl group, a triacontyl group, an isostearyl group, etc, and a dodecyl group, tetradecyl group, a hexadecyl group, and an octadecyl group are more preferable. X and Y in the formula (10) are the same or different and each a xe2x80x94Oxe2x80x94 group or a xe2x80x94NHxe2x80x94 group, preferably each a xe2x80x94Oxe2x80x94 group. In formula (10), n/m is from 0.65 to 2.50, preferably from 1.30 to 2.30, and sum of n and m is from 2 to 10000, preferably from 5 to 1000.
The molecular weight of the hindered amine compound is not limited, and is preferably from 1,000 to 500,000. When the molecular weight is less than 1,000, the mobility of the compound in the resin increases so that the compound may bleed out. When the molecular weight exceeds 500,000, the compound may have adverse influences on the properties of the resin, and it may have less stabilizing effects than the compound having the smaller molecular weight. Preferably, the molecular weight of the hindered amine compound is from 2,000 to 200,000. The hindered amine compound having a suitable molecular weight can be used in accordance with applications and purposes.
The molecular weight of the hindered amine compound can be measured by any known method such as a gel permeation chromatographic method, a light scattering method, an osmotic pressure method, etc.
In the hindered amine compound of the present invention, at least a part of the hindered amino groups may form salts with at least one compound selected from the group consisting of organic carboxylic acids, carbon dioxide, phosphoric acid compounds, phosphate esters, phosphorous acid compounds and phosphite esters. It is possible to adjust the basicity or solubility of the hindered amine compound by forming the salts of at least a part of the hindered amine groups with the above compound(s) without deteriorating the inherent stabilizing function of the hindered amine compound.
Organic carboxylic acids are preferably those having 1 to 10 carbon atoms. In particular, saturated carboxylic acids are preferable. In addition, monocarboxylic acids are more preferable than polycarboxylic acids. Specific examples of organic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, acetoacetic acid, pyruvic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, naphthoacetic acid, phenylacetic acid, etc.
Phosphoric acid compounds include phosphoric acid and its salts with basic compounds such as amines, metal ions, etc., and phosphorous acid compounds include phoshorous acid and its salts with basic compounds such as amines, metal ions, etc.
Phosphate esters are preferably monoesters or diesters of phosphoric acid, while phosphate esters may be polymeric compounds a part of which has a monoester or diester structure of phosphoric acid. Phosphite esters are preferably monoesters or diesters of phosphorous acid, while phosphite esters may be polymeric compounds a part of which has a monoester or diester structure of phosphorous acid. The phosphate or phosphite esters may be partial salts with basic compounds such as amines, metal ions, etc.
The hindered amine compounds of the present invention can be used as stabilizers of known resins. Examples of such resins include polyurethane, polyamide, polyester, polyolefin, polystyrene, and mixtures or blends thereof.
The resin composition of the present invention contains a phosphite ester antioxidant and/or a phenol antioxidant.
A phosphite ester antioxidant may be any known compound, and a suitable compound is selected by taking into account its solubility in a solvent, compatibility with the resins such as polyurethane, and the like. Examples of phosphite ester antioxidants include tetrakis(2,4-di-tert.-butylphenyl) 4,4xe2x80x2-biphenylenephosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert.-butylphenyl) phosphite, distearylpentaerithritol diphosphite, di(2,4-di-tert.-butylphenyl)pentaerithritol diphosphite, di(2,6-di-tert.-butyl-4-methylphenyl)pentaerithritol diphosphite, triphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, 4,4xe2x80x2-butylidene-bis(3-methyl-6-tert.-butylphenyl-ditridedyl) phosphite, cyclic neopentantetrayl (octadecylphosphite), tris(mono- and/or dinonylphenyl) phosphite, diisodecylpentaerithritol diphosphite, 2,2-methylenebis(4,6-di-tert.-butylphenyl)octyl phosphite, bis(tridecyl)pentaerithritol diphosphite, bis(nonylphenyl)-pentaerithritol diphosphite, hydrogenated bisphenol A-pentaerithritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, tetraphenyltetra(tridecyl)pentaerithritol tetraphosphite, tetra(tridecyl)-4,4xe2x80x2-isopropylidenediphenyl diphosophite, tetraphenyldipropyleneglycol diphosphite, etc. Among them, hydrogeneated bisphenol A-pentaerithritol phosphite polymer and hydrogenated bisphenol A phosphite polymer are preferable. The phosphite ester antioxidant is compounded in polyurethane in an amount such that the degradation of polyurethane can be sufficiently suppressed in the practical application. Two or more phosphite ester antioxidants may be used. The amount of the phosphite ester antioxidant(s) is preferably from 0.1 to 2 wt. % of the weight of polyurethane.
A phenol antioxidant may be any known compound, and a suitable compound is selected by taking into account its solubility in a solvent, compatibility with the resin such as polyurethane, and the like. Examples of phenol antioxidants include pentaerithritol tetrakis [3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert.-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert.-butylphenyl)butane, 1,3,5-tris(4-tert.-butyl-3-hydroxy-2,6-dimethyl)isocyanuric acid, 1,3,5-tris(4-sec.-butyl-3-hydroxy-2,6-dimethyl)isocyanuric acid, 1,3,5-tris(4-neopentyl-3-hydroxy-2,6-dimethyl)isocyanuric acid, 2,2xe2x80x2-methylenebis(4-methyl-6-tert.-butylphenol), 4,4xe2x80x2-butylidenebis(4-methyl-6-tert.-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert.-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert.-butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis{2-[3-(3-tert.-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethyleneglycol bis[3-(3-tert.-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionate], N,Nxe2x80x2-hexamethylenebis(3,5-di-tert.-butyl-4-hydroxy-hydrocinnamide), diethyl 3,5-di-tert.-butyl-4-hydroxybenzylphosphonate, tris(3,5-di-tert.-butyl-4-hydroxybenzyl) isocyanurate, isooctyl 3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionate, N,Nxe2x80x2-bis[3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionyl]hydrazine, a polycondensate of p-chloromethylstyrene and p-cresol, a polycondensate of p-chloromethylstyrene and divinylbenzene, a reaction product of isobutylene with a polycondensate of p-cresol and divinylbenzene, etc. Among them, 1,3,5-tris(4-tert.-butyl-3-hydroxy-2,6-dimethyl)isocyanuric acid, 1,3,5-tris(4-sec.-butyl-3-hydroxy-2,6-dimethyl)isocyanuric acid and 1,3,5-tris(4-neopentyl-3-hydroxy-2,6-dimethyl)isocyanuric acid are preferable, and 1,3,5-tris(4-tert.-butyl-3-hydroxy-2,6-dimethyl)isocyanuric acid is more preferable. The phenol antioxidant is compounded in polyurethane in an amount such that the degradation of polyurethane can be sufficiently suppressed in the practical application. Two or more phenol antioxidants may be used. The amount of the phenol antioxidant(s) is preferably from 0.1 to 2 wt. % of the weight of polyurethane.
A resin composition containing the hindered amine compound of the present invention can be shaped or molded by any known method, and processed by any known method.
The application of the resin composition is not limited, and the resin composition can be shaped in the form of fiber, film, sheet, molded article, foam, artificial leather, elastomer, paint, adhesive, non-woven fabric, and the like.
The resin composition containing the hindered amine compound of the present invention has excellent properties for the fiber application.
Examples of fibers include synthetic fibers such as polyurethane fiber, polyester fiber, polyamide fiber, acrylic fiber, acetate fiber, rayon fiber, polynosic fiber, cupra fiber, polyethylene fiber, polypropylene fiber, poly(vinirydene chloride) fiber, poly(vinyl chloride) fiber, etc. Inparticular, the hindered amine compound of the present invention is suitable for polyurethane resins and polyurethane fibers, and more suitable for polyurethane fibers.
Polyurethane used in the present invention may be any known polyurethane such as polyether polyurethane, polyester polyurethane, polycarbonate polyurethane, etc.
Such polyurethane can be obtained by reacting a polyisocyanate, a polymer diol, and optionally a low molecular weight polyfunctional active-hydrogen compound.
Examples of polyisocyanates include 4,4xe2x80x2-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4xe2x80x2-dicyclohexylmethane diisocyanate, xylylene diisocyanate, and mixtures thereof. Among them, 4,4xe2x80x2-diphenylmethane diisocyanate is preferable.
A polymer diol is a substantially linear polymer having hydroxyl groups at both ends and a molecular weight of 600 to 7,000. Examples of polymer diols include polyether polyols (e.g. polytetramethylene ether glycol, polypropylene ether glycol, polyethylene ether glycol, polypentamethylene ether glycol, etc.), copolyether polyols having two or more alkylene groups having 1 to 6 carbon atoms (e.g. copoly(tetramethylene-neopentylene) ether diol, copoly(tetramethylene-2-methylbutylene) ether diol, copoly(tetramethylene-2,3-dimethylbutylene)ether diol, copoly(tetrametylene-2,2-dimethylbutylene) ether diol, etc.), polyester polyols prepared from at least one dibasic acid (e.g. adipic acid, sebacic acid, maleic acid, itaconic acid, azelaic acid, malonic acid, succinic acid, glutaric acid, suberic acid, dodecanedicarboxylic acid, xcex2-methyladipic acid, hexahydroterephthalic acid, etc.) with at least one glycol (e.g. ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-dimethylolcyclohexane, etc.), polyetherester diol, polylactone diol, polycarbonate diol, and the like.
A low molecular weight polyfunctional active-hydrogen compound may be a compound having two or more active hydrogen atoms reactive with isocyanate groups (chain extender). Examples of chain extenders include polyamines (e.g. ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminopropane, diethylenetriamine, triethylenetetramine, etc.), polyols (e.g. ethylene glycol, butanediol, etc.), polyhydrazide, polysemicarbazone, polyhydroxyamine, water, hydrazine, and mixtures thereof.
In addition to a chain extender, a compound having only one active hydrogen atom reactive with an isocyanate group may be used as a chain terminator. Examples of a compound having only one active hydrogen atom in a molecule include dialkylamines (e.g. diethylamine, dimethylamine, dibutylamine, diethanolamine, etc.), monoalkylamines (e.g. ethylamine, n-propylamine, isopropylamine, n-butylamine, tert.-butylamine, ethanolamine, etc.), monohydric alcohols (e.g. n-butanol, etc.), dehydrated condensates of diamine and ketones (e.g. a 1:1 reaction product of ethylenediamine and acetone), N,N-dimethylhydrazine, and mixtures thereof.
Polyurethane may be prepared by any conventional polymerization methods such as melt polymerization, solution polymerization, etc. A polymerization method may be a one-shot method in which all raw materials are mixed and reacted at once, or a prepolymer method in which a prepolymer is first prepared and then chain extended. A suitable amount of a reaction rate regulator such as an organic acid (e.g. acetic acid, p-toluenesulfonic acid, etc.) or carbon dioxide may be added at any step of the polymerization reaction. The reaction rate regulator is preferably added after the formation of the prepolymer and prior to the termination of a chain-extending reaction. The reaction rate regulator may be added together with a chain extender or a chain terminator.
The obtained polyurethane can be shaped by any conventional method and used in respective applications.
The hindered amine compound of the present invention may be compounded in a resin in any step, for example, up to a spinning step in the case of the production of fibers. The hindered amine compound of the present invention may be compounded in raw materials for polymerization, insofar as it has no influence on the polymerization reaction of the raw materials to produce a resin, or a resin from which fibers are produced. Alternatively, the hindered amine compound of the present invention may be compounded in a resin, or a resin from which fibers are produced, after the termination of the polymerization reaction, preferably after the termination of the polymerization reaction and prior to the shaping of the resin.
The hindered amine compound of the present invention may be used together with any conventional additives such as antioxidants (e.g. phenol antioxidants, phosphite ester antioxidants, thioether antioxidants, etc.), UV ray absorbers (e.g. benzotriazole UV ray absorbers, benzophenone UV ray absorbers, triazine UV ray absorbers, etc.), metal deactivators (e.g. dihydrazide derivative metal deactivators, oxalic acid derivative metal deactivators, etc.), anti-sticking agents (e.g. magnesium stearate, higher fatty acid amides, higher fatty acid esters, polyorganosilanes, polytetrafluoroethylene, etc.), inorganic fine particles (e.g. titanium dioxide, magnesium oxide, zinc oxide, hydrotalcite, barium sulfate, magnesium silicate, calcium silicate, etc.), flame retardants, antifungals, and the like.
When the hindered amine compound of the present invention is compounded in fibers, and a resin composition is melt spun, the hindered amine compound may be compounded in the raw material resin by melt kneading.
Among the other additives, the UV ray absorber is preferably compounded in a polyurethane resin composition, since it can significantly improve the light stability of the polyurethane resin composition. A suitable UV ray absorber may be selected from conventional UV ray absorbers such as benzotriazole UV ray absorbers, benzophenone UV ray absorbers, triazine UV ray absorbers, oxalinide UV ray absorbers, and the like depending on the purpose. Among them, benzotriazole UV ray absorbers and triazine UV ray absorbers are preferable.
Specific examples of benzotriazole UV ray absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert.-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert.-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert.-amylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert.-butylphenyl)benzotriazole, 2-(2-hydroxy-5-methyl-3-(3,4,5,6-tetrahydrophthalimidoylomethyl)phenyl]benzotriazole, 2-(2-hydroxy-5-tert.-butylphenyl)benzotriazole, 2-(2-hydroxy-5-tert.-octylphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(xcex1,xcex1-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol], a condensate of methyl-3-[3-tert.-butyl-5-(2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol, etc.
Examples of triazine UV ray absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2,4-di(2xe2x80x2,4xe2x80x2-dimethylphenyl)-6-(2xe2x80x3-hydroxy-4xe2x80x3-n-octyloxyphenyl)-1,3,5-triazine, etc.
Among those UV ray absorbers, 2-(2-hydroxy-3,5-di-tert.-amyl)benzotriazole and 2-[2-hydroxy-3,5-bis(xcex1,xcex1-dimethylbenzyl)phenyl]-2H-benzotriazole are preferable.
The above UV ray absorbers may be used independently or in admixture of two or more.
The amount of the UV ray absorber is preferably from 0.1 to 2.0 wt. % of the weight of polyurethane.
The polyurethane fiber of the present invention can be prepared by spinning the polyurethane resin composition of the present invention. When the resin composition is spun by a wet or dry spinning method, the hindered amine compound of the present invention can be compounded in a spinning dope by mixing the hindered amine compound as such or in the form of a solution with the spinning dope. Spinning machines or spinning conditions are not limited, and any conventional spinning method can be selected according to the composition of the resin composition, applications, purposes, the properties of fibers, etc. The hindered amine compound of the present invention is suitable as a stabilizer of fibers, in particular, polyurethane fibers. Among the polyurethane fibers, those produced by wet or dry spinning of a polyurethane solution is significantly stabilized with the hindered amine compound of the present invention.
The hindered amine compound of the present invention is compounded in a resin composition in an amount such that the stabilizing function is well exerted in accordance with the kinds and applications of resins or fibers. Although not limited, the amount of the hindered amine compound of the present invention is preferably from 0.05 to 10 wt. % of the weight of the resin or fiber. In particular, the amount of the hindered amine compound of the present invention is from 0.5 to 5 wt. % in the case of the polyurethane resin composition or the polyurethane fiber.
A polyester fiber, which is used in combination with a polyurethane fiber in a stretch fabric or knit of the present invention, may be any conventionally used polyester fiber. A typical example of such a polyester fiber is a polyethylene terephthalate fiber.
A polyamide fiber, which is used in combination with a polyurethane fiber in a stretch fabric or knit of the present invention, may be any conventionally used polyamide fiber such as fibers of Nylon 6, Nylon 66 and Nylon 46, their cation-dyeable modified fibers, as well as polyamide-polyester composite fibers. Fibers having any fineness and cross section can be used.
A cellulose fiber, which is used in combination with a polyurethane fiber in a stretch fabric or knit of the present invention, may be any conventionally used cellulose fiber such as cotton fibers, rayon fibers, their blended fibers with polyester fibers, and composite fibers with Nylon/polyester filaments. Fibers having any fineness can be used.
A fiber, which is used in combination with a polyurethane fiber in a stretch fabric or knit of the present invention, may be any non-stretch fiber, for example, fur such as wool, cashmere, alpaca, etc., silk, acrylic fiber, promix fiber, and the like.
A polyurethane fiber used in a stretch fabric or knit of the present invention is usually in the form of a bare yarn, or a composite elastic yarn such as a single-covering yarn, a double-covering yarn, a core spun yarn or a ply yarn.
The stretch fabric or knit of the present invention comprises the polyurethane elastic yarn, and a non-stretch yarn of a polyester fiber, a polyamide fiber, a cellulose fiber, and the like.
A stretch fabric may be a plain weave, a twill weave, a satin weave, etc., which uses the polyurethane yarn as a warp and/or a weft. A stretch knit may be a circular knit such as a plain stitch, an interlock stitch, a rib stitch, a purl stitch, and their modificatins, or a warp knit such as a tricot, a Russel cord, etc.
The texture of knitting can be a half stitch, a reverse half stitch, a double demby stitch, a double atlas stitch, et. in the case of a tricot, or a power net, a half power net, a satin net, a triconet, etc. in the case of a Russel cord.

Hindered amine compound, resin composition, polyurethane fiber and production method and use thereof


A stretch film comprising a base film made of a stretchable plastic film material, a multiplicity of holes in the base film arranged in several columns along a main direction, at least one reinforcement strip made of a stretchable plastic film material. The reinforcement strip is arranged and fixed on the base film in an area between two adjacent columns of holes. The thickness of the base film is greater than or equal to the thickness of the reinforcement strip and the width (w) of the reinforcement strip is as great as possible, but is such that the reinforcement strip does not contact or overlap the holes in the adjacent columns of holes. The reinforcement strip may be fixed to the base film so as to be inseparable and indistinguishable from the base film.

1. Field of the Invention
The present invention relates to a stretch film. In particular, the present invention relates to a stretch film product for palletizing.
2. Description of the Prior Art
For packing or wrapping pallets, bales of straw, fruit etc. it is known that perforated plastic stretch films are used in order to provide sufficient stretchability of the packaging film as well as ventilation of the products to be packed. Known from EP 0 820 856 A1 is a pre-stretched plastic stretch film in which holes are formed by a thermal irradiation method without contacting the film and thus without waste of film material, for example, caused by punching out holes.
Known from EP 0 909 721 A1 is a perforated extensible palletizing film comprising a longitudinally elongated thin sheet of extensible plastics provided with ventilation holes and longitudinal reinforcement elements which are made of extensible plastics and are adapted to increase the strength of the film in the pulling direction.
Similar perforated stretch films are known from WO 01/60709 A1 and WO 02/094674 A1.
The perforations of these stretch films represent a macro perforation in which holes having a diameter of at least 5 mm are provided in a base film. Films with significantly smaller perforations represent a micro perforation and are irrelevant to the present invention.
The above should not be confused with film products on which slits or small punctures have been made initially with the intention that these increase, break or open (resulting in large openings) as a result of the film being stretched during usage in a wrapping machine with a prestretching system.
In practice, a number of problems may arise in connection with the above-described macro-perforated stretch films comprising reinforcing elements. Namely, the stretch films are normally used by automatic or semi-automatic stretch wrapping machines, for example, in order to wrap products stacked on pallets. To ensure good material utilization, it is desirable to stretch the stretch film during the wrapping operation by e.g. 100 to 250% as compared to the stock of film material still on a winding drum. To this end, considerable force is required which can be significantly increased by reinforcing elements fixed onto the stretch film, so that in the end the wrapping machine, under special conditions, is no longer capable of providing sufficient stretching of the stretch film for lack of sufficient power.
On the other hand, if the wrapping machine is strong enough to provide the desired stretching, there is the danger that the forces acting on the products to be wrapped are too great. If the products are, for example, boxes, there is the risk that the stretch film and/or the reinforcing elements fixed thereto, press the products or their packages together and damage them.
Further there is the danger that the additional reinforcing elements have not been fixed onto the base film by the manufacturer with sufficient reliability. In this case the respective reinforcement element which, for example, is formed as an elongated plastic film strip, can detach itself from the carrier film and become engaged in a nip roll of a wrapping machine, thereby obstructing the film feed path.
In addition, it has been found in the case of the films known from the prior art that the respective carrier films or base films hardly contributes to strength. Basically, they serve rather only to carry the reinforcement elements, which predominantly ensure the desired strength. Accordingly, the material of the base film is utilized insufficiently.
The reinforcement elements fixed onto the base film may convey to the observer an impression of poor optical properties and poor appearance of a pallet wrapped in the stretch film, thereby detracting from the overall impression of the pallet and the valence of the products stacked thereon.

This patent is subject to a terminal disclaimer.


The method and apparatus for measuring a content of vaporous hydrogen peroxide in a gaseous medium within an enclosure includes a irradiating a portion of the gaseous medium with light, measuring an absorbance of light in a selected near-infrared wavelength range, and calculating the content of vaporous hydrogen peroxide from the measured absorbance of light.

The present invention relates to a method and apparatus for measuring a concentration of vaporous hydrogen peroxide. More particularly, the present invention relates to a method and apparatus that measures the concentration of vaporous hydrogen peroxide continuously in an enclosure.
Hydrogen peroxide has wide commercial use. In the pharmaceutical industry, hydrogen peroxide is commonly used as a sterilant. For instance, hydrogen peroxide is used to sterilize enclosures and equipment of sterile operations. The equipment is located in a sealed enclosure known as an isolation barrier that protects the equipment from contamination. Periodically, the equipment and barrier are shut down for cleaning and sterilization. During sterilization, vaporous hydrogen peroxide is introduced into the barrier. A prior art technique to ensure proper sterilization includes placing biological indicators or challenges within the barrier prior to the sterilization cycle. After the sterilization cycle, which may proceed for one to three hours, the biological challenges are removed from the barrier. The biological challenges are then cultured to promote any growth. Culturing typically takes a minimum of eight hours.
Analysis of the biological challenges determines if any bacteria has survived the sterilization process. If all of the bacteria has been killed, the equipment and the barrier have been properly sterilized. Otherwise, if any bacteria has survived, the sterilization cycle must be repeated.
A significant disadvantage of using biological challenges is the inherent delay necessary to culture the biological challenges after they have been removed from the barrier. The ability of the biological challenges to survive in the presence of vaporous hydrogen peroxide is dependent upon the duration and concentration level of vaporous hydrogen peroxide during the sterilization cycle. If the concentration level of vaporous hydrogen peroxide was sufficiently high for a suitable time period, the biological challenges will not survive and sterilization would be complete.
Although it is well known that vaporous hydrogen peroxide in a sufficient concentration and time duration will kill bacteria and sterilize, a system or method to measure the concentration level of vaporous hydrogen peroxide has not been disclosed.

Method and apparatus for measuring vaporous hydrogen peroxide


A dishwasher having an improved structure by which a basket is easily withdrawn, the dishwasher including a case, a basket arranged within the case to receive objects to be washed, a rail provided on an inner wall of the case in order to guide the basket such that the basket is withdrawn forward of the case, a link unit mounted to the basket to lift the basket, and an auxiliary unit connected to the link unit such that lifting force acts on the basket based on a position of the basket.

1. Field
The following description relates to a dishwasher having an improved structure by which a basket is easily withdrawn.
2. Description of the Related Art
In general, a dishwasher is a device spraying high pressure wash water onto one or more objected to be washed such as dishes to wash the objects and typically undergoes a preliminary washing process, for example, a main washing process, a rinsing process, and a drying process. Dishwashing is performed by spraying only wash water without detergent to wash contaminants off of the objects in the preliminary washing process, and then simultaneously inserting detergent using a detergent supply unit while spraying wash water in the main washing process.
The dishwasher typically includes a cabinet provided with a washing bath therein, a pump to generate a wash water pressure, a basket which receives objects to be washed and is installed movably in a forward and backward direction within the washing bath, spray units to spray wash water onto the basket, a connection passage through which the pump and the spray units are connected, and a passage switching valve to selectively move wash water from the pump to the multiple spray units, thereby washing the objects to be washed by the wash water sprayed from the spray units.
The basket includes an upper basket provided at an upper portion of the washing bath and a lower basket provided at a lower portion thereof.
Since the lower basket has a structure to store the objects to be washed in a state of being arranged at the lower portion of the washing bath and moving forward, the objects may be inserted into or withdrawn from the lower basket in a state in which a user bends down. Therefore, this may very inconvenient for the user and may not be good for the user's health. In particular, in terms of a structure of the dishwasher, the lower basket is relatively larger in size than the upper basket and heavy objects are received in the lower basket and washed. Accordingly, it may be hard to insert or withdraw these objects into or from the lower basket.


The present invention is directed to a one piece blank of foldable sheet material cut and scored so that it is divided into a series of connected wall forming panels which when assembled provides a trio of diamond shaped cartons for packaging articles, each carton connected to another carton by a common edge. The present invention is also directed to a one piece trio of diamond shaped cartons for packaging articles, each carton connected to another carton by a common edge.

Many types of cartons for packaging articles are known. However, these cartons have not been suitable for use when several cartons are desired, such as those where each carton is attached to another carton, particularly diamond shaped cartons. The preparation of such an arrangement generally requires the use of several different blanks that must be glued together to form the final carton.
U.S. Pat. No. 1,998,147 (F. C. Stegman) discloses a bottle carton consisting of a longitudinal series of vertical hexagonal individual bottle receiving cells with a shock absorbing support at the bottom of the cells to prevent damage to the bottles. Each cell is a complete structural unit even when separated from the other cells. The bottle carton comprises a combination of a pair of duplicate blanks cut, scored, connected and set up to provide a longitudinal series of vertical hexagonal individual bottle-receiving cells. The blanks have vertical weakened lines between the cells facilitating their separation, and leaving when separated vertical laterally-projecting flanges at opposite angles of the cells. The lower portions of the blanks are cut and scored to provide semi-hexgonal half bottom panels folded inwardly from opposite side walls of the cells in vertically spaced relation to the lower ends of the other side walls. The edges of the walls adjacent the panels are bevelled to prevent binding of the panels as they are folded inwardly. The bottom panels have at their inner edges downturned bottom flanges extending between the vertical flanges and providing with the lower ends of the other walls, a shock absorbing support for the bottom of the cell which is in an elevated position. A means is provided for connecting the vertical and bottom flanges of the cells so that each cell is a complete structural unit even when separated from the other cells of the series. F. C. Stegman does not teach a trio carton wherein each carton is attached by a common edge or axis to another carton because the blanks of F. C. Stegman have vertical weakened lines between the cells facilitating their separation and when separated leave vertical laterally-projecting flanges at opposite angles of the cells.
U.S. Pat. No. 2,342,623 (S. A. Aquino) discloses a one piece multicompartment container provided with a central partition. The container comprises at least six relatively flat side members fastened together in polygonal shape, wherein the top members and bottom members cooperate with the side members. A partition is provided dividing the column enclosed by the side members into two compartments, each defined by an odd number of the side members and one of the top and bottom members. The partition comprises two separate panel elements, arranged back to back. Each panel has a height of about the height of the side walls and extends between opposite sides formed by the side members. An edge portion of the cover member and an edge portion of the bottom member of each compartment is attached to the top and bottom edges respectively of the panel elements of the partition which forms a wall of the respective compartment. The bottom member of each compartment is attached at its opposite edge to one of the side members at the lower edge portion, whereby the bottom of each compartment is supported both by the partition and by one of the side members.
U.S. Pat. No. 3,004,696 (R. W. McCormick) discloses a polygonal compartmented container formed with partitions to provide a plurality of compartments, and having a bottom construction which includes a plurality of prismatic portions enabling the container to be positioned on uneven ground or to be interlocked with the prismatic portions of a similar container. The polygonal compartmented container is formed from foldable paperboard and comprises a plurality of elongated panels arranged in tubular form and hingedly connected in series at their longitudinal edges along parallel lines. A fold line extends at right angles, centrally across the panels, to divide the assembled panel group into two half sections. Two sets of fold lines each extend at acute angles to the central fold line and form a plurality of adjoined, endwise aligned, diamond shaped areas, located symmetrically along the central fold line with their transverse axes coinciding with alternate hinge lines of the panel group and with their apexes located at the intersections of the central fold line with the remaining alternate hinge lines of the panel group. One of the half sections of the assembled panels comprises inner partitions and is folded over along the central fold line and enclosed inside the other half section comprising the container outer walls. The outer walls and the enclosed inner partitions are collapsible to flat tubular form. The diamond shaped areas when the tubular construction is in expanded form, is collapsible inwardly and axially of the expanded tube, whereby to cause the pairs of partition panels adjoined to the inner sides of the respective diamond shaped areas to expand inwardly of the tube and form with the side wall panels on the other side of the respective diamond shaped areas similar compartments, each having a symmetrical diamond shape in cross-section.
U.S. Pat. No. 3,403,835 (J. M. Schwaner) discloses a multi-cell container assembly formed of separate unitary cells which have certain panels of each cell secured in face-to-face relationship permitting the container to be folded into a flat contour. The multi-cell container assembly comprises a plurality of polygonal container subassemblies each joined to each of its adjacent subassemblies at a single side panel to form one or more L-shaped, attached series of subassemblies. Further panels of the subassemblies within the bight of the L-shaped series are positioned in abutting relation to form a multi-cell container assembly in which at least two panels of each polygonal subassembly is reinforced by an adjacent subassembly panel.
U.S. Pat. No. 4,062,487 (Bliss) discloses a carton blank for a four-sided carton having a recessed double thickness handle formed as a part of the top closure. The carton blank comprises four rectangular side wall panels of equal size positioned in lateral alignment and connected by vertical fold lines. The side panels are defined along their top and bottom edges by horizontal fold lines. Bottom closure flaps are connected along the bottom edge of the side wall panels. A top closure for the blank is connected along the top edge of the blank including a first triangular handle section. The triangular section is formed as an isosceles triangle having a base equal to the width of a first adjacent pair of the side wall panels and having a center fold line extending vertically from the apex of the triangle to the point of intersection of the top edge fold line and the vertical hinge line connecting the first pair of adjacent side wall panels. The first triangular handle section has a slot cut on each side of the vertical fold line and is positioned along the diagonally positioned fold lines. A pair of fold lines extends diagonally from the point of intersection of the top edge hinge line and the hinge line connecting the first pair of adjacent side wall panels and intersecting the outer edges of the first triangular handle section. A second triangular handle section substantially similar in size and configuration to the first triangular handle section is connected along the top edge of the remaining two adjacent side wall panels. A pair of insertable tabs is formed as a part of and extends vertically from the second triangular handle section adjacent the apex of the second section. The tabs are formed in width substantially equal to or slightly less than the length of the slots. Die cut apertures are formed in that portion of each of the triangular handle sections on either side of each vertical fold line and above each of the diagonally positioned fold lines.
U.S. Pat. No. 4,601,390 (Rosenthal et al.) discloses a repeatably usable collapsible hand carrier for bottles of standard size. The carrier is fabricated of flexible panel material and has a structure comprising: A. front and rear side panels provided with complementary handle extensions; B. left and right end panels hingedly joined to the end edges of the side panels; C. a bottom panel hingedly joined to the bottom edges of the side panels and disconnected from the end panels, the bottom panel and the end panels all having a center fold to create a gusset whereby the carrier may be collapsed after use into a flat state by pressing the side panels together, and in doing so, causing the bottom panel and the end panel gussets to fold out, and the carrier may be erected for reuse by pulling the side panels apart; and D. four snap-in corner sections formed at the junctions of the side and end panels. Each section is defined by a pair of parallel slots spaced from the top and bottom edges of the panels and extends horizontally from the center fold of the related end panel and a vertical fold line on the related side panel. When the hand carrier is erected and a corner section is pressed in at its junction, the section then reverses itself to set up within the interior of the carrier a corner cell adapted to accommodate a single standard bottle.
U.S. Pat. No. 4,856,706 (VanDerStraten) discloses a packing device comprising a continuous row or at least one element in a flat extended position. Each element is composed of a bottom, a top panel, at least one end wall and side walls. The elements are hingeably connected together substantially along longitudinal ribs formed between the bottoms to form the continuous row of elements. The packing device is made from one unitary blank and the row of elements can be rolled up from its flat extended position to a closed polygonal block having a casing. End faces are provided in which the interconnected bottoms and the side walls of the elements are combined to form the casing and the end faces, respectively, of the block.
U.S. Pat. No. 5,107,985 (Bezrutczyk) discloses a display carton for holding and displaying an article including a tubular container structure and a tubular drawer structure by which an article is displayed by opening and closing the drawer. The carton is made from a unitary blank of foldable sheet material, such as paper board, and comprises a plurality of container panels foldably interconnected along primary fold lines to form a tubular container structure open at its ends. Container end closure flaps are provided foldably joined to the container panels and secured in overlapped relation to close the ends of the tubular container structure. An opening is provided in at least one of the container panels defining an opening to the interior of the container structure; a plurality of drawer panels are provided foldably interconnected along secondary fold lines to form a tubular drawer structure open at its ends, one of the drawer panels being joined to one of the container panels along a hinge line; drawer end closure flaps are provided joined to the drawer panels and secured in overlapped relation to close the ends of the tubular drawer structure. The drawer structure is hingedly connected to the container structure with respect to the hinge line for movement through the opening between a first closed position situated within the interior of the container structure and a second open position situated at least in part outside of the container structure.
U.S. Pat. No. 5,601,231 (Cai) discloses a multi-partitioned meal tray or container for holding food products. The container is made from a unitary blank and comprises a planar base and a plurality of straight, equal length sidewalls having respective bottom edges integrally joined to the planar base. Each of the sidewalls has opposed ends joined at an obtuse angle to corresponding ends of adjacent sidewalls to define corners. The plurality of sidewalls and the corners define a periphery of the container. The container further comprises a plurality of integral internal partitions extending along the planar base. Each of the internal partitions has first and second ends. At least two of the internal partitions each have its first end joined to a respective one of the corners. At least two of the internal partitions have their second ends joined together. A further one of the internal partitions has a first end joined to the periphery of the container and a second end joined to the second ends of the at least two of the internal partitions.

One piece trio of diamond shaped cartons