公开(公告)号：CA674837A

公开(公告)日：1963-11-26

申请号：CA674837D

Applicant: BASF AG

Inventor： GEHM ROBERT ,  SCHMIDT OSWALD ,  MERTENS HEINRICH ,  GRUNWALD WOLFGANG ,  HEHL MANFRED

公开(公告)号：GB908229A

公开(公告)日：1962-10-17

申请号：GB219360

申请日：1960-01-21

Applicant: BASF AG

Inventor： GEHM ROBERT ,  SCHMIDT OSWALD ,  MERTENS HEINRICH ,  GRUNWALD WOLFGANG ,  HEHL MANFRED

IPC: C07D251/68

Abstract: A household detergent consisting of a mixture of tetrapropylene benzene sulphonate, oleyl sulphate, sodium perborate, magnesium silicate, sodium silicate, sodium tripolyphosphate, sodium tetrapyrophosphate, sodium sulphate, carboxymethyl cellulose and water is admixed with optical brightening agents which in their anionic form have the general formula:- in which X represents a 1-aza-4-thiocyclo-hex-1-yl-4,4-dioxide radical, a 2,6-dimethyl-1-aza-4-thiacyclohex-1-yl-4,4-dioxide radical or a radical of the formula:- and Y is a hydroxy group, an amino group, a monosubstituted amino group such as an alkylamino, cycloalkylamino, arylamino, hydroxyalkylamino or alkoxyalkylamino group, a disubstituted amino group such as a dialkylamino, di(hydroxyalkyl) amino or di(alkoxyalkyl) amino group, a pyrrolidino, piperidino or morpholino group, a 1-aza-4-thiacyclohex-1-yl-4,4-dioxide radical or a group of the formula or salts thereof with alkali metals, ammonia or primary, secondary or tertiary amines. Specification 874,519 is referred to.ALSO:The invention comprises optical brightening agents which in their anionic form have the general formula:- in which X represents a 1-aza-4-thiocyclo-hex-1-yl-4,4-dioxide radical, a 2,6-dimethyl-1-aza-4-thiacyclohex-1-yl-4,4-dioxide radical or a radical of the formula:- and Y is a hydroxy group, an amino group, a monosubstituted amino group such as an alkylamino, cycloalkylamino, arylamino, hydroxyalkylamino or alkoxyalkylamino group, a disubstituted amino group such as a dialkylamino, di(hydroxyalkyl) amino or di(alkoxyalkyl) amino group, a pyrrolidino, piperidino or morpholino group, a 1-aza-4-thiacyclohex-1-yl-4,4-dioxide radical or a group of the formula or salts thereof with alkali metals, ammonia or primary, secondary or tertiary amines. The above brightening agents are prepared by reacting in any order two mols. of a cyanuric halide with one mol. of an alkali metal salt of a 4,41-diamino-stilbene disulphonic acid of the formula:- and with two mols. of 1-aza-4-thia-cyclohexane-4,4-dioxide or two mols. of 2,6-dimethyl - 1 - aza-4-thiacyclohexane-4,4-dioxide, and further reacting the products obtained with aqueous alkali, ammonia, an alkylamine, a dialkylamine, a cycloalkylamine, a hydroxyalkylamine, a di(hydroxyalkyl) amine, an alkoxyalkylamine, a di(alkoxyalkyl) amine, an arylamine, pyrrolidine, morpholine, piperidine or 1 - aza-4-thiacyclo-hexane-4,4-dioxide or, after having reacted the said products or the initial compound (obtained by the reaction of cyanuric acid halide with 4,41-diaminostilbene disulphonic acid) with ammonia, the resulting compounds are treated with a mixture of aqueous formaldehyde and 1-aza-4-thiacyclohexane-4,4-dioxide or, after having reacted the initial compound (obtained by the reaction of cyanuric halide with 4,41-diaminostilbene disulphonic acid) with 2 mols. of aqueous alkali, a primary or secondary amine, pyrrolidine, piperidine or morpholine, the remaining chlorine substituents are replaced by means of ammonia and the resulting amino compound is condensed with formaldehyde and 2 mols. of 1-aza-4-thiacyclohexane-4,4-dioxide. Specification 874,519 is referred to.ALSO:Foils, films, felts, fibres, threads, yarns, flocks and woven and non-woven fabrics of natural, regenerated and synthetic material, such as leather, synthetic polymers (plastics), cotton, household washing, paper, native or regenerated cellulose and linear polyamides (e.g. polycaprolactam) are brightened by treatment with optical brightening agents which in their anionic form have the general formula:- in which X represents a 1-aza-4-thiocyclohex-1-yl-4,4-dioxide radical, a 2,6-dimethyl-1-aza-4-thiocyclohex-1-yl-4,4-dioxide radical or a radical of the formula:- and Y is a hydroxy group, an amino group, a monosubstituted amino group such as an alkylamino, cycloalkylamino, arylamino, hydroxyalkylamino or alkoxyalkylamino group, a disubstituted amino group such as a dialkylamino, di(hydroxyalkyl) amino or di(alkoxyalkyl) amino group, a pyrrolidino, piperidino or morpholino group, a 1-aza-4-thiocyclohex-1-yl-4,4-dioxide radical or a group of the formula or salts thereof with alkali metals, ammonia or primary, secondary or tertiary amines. Other ingredients which may be present in the aqueous treatment bath are formic acid, hydrogen peroxide, tetrapropylene benzene chromium trioxide to trichloracetic acid in solution in an aromatic hydrocarbon, e.g. toluene. Material treated by either process may be dried at an elevated temperature. Treatment enhances the adhesion of the fabric for materials of other high molecular synthetic or high molecular natural substances, e.g. gelatin, polyvinyl alcohol, polyvinyl butyral, polyethylene and polyamides. In an example, a polyethylene terephthalate fabric is bathed for 10 secs. in a solution of 100 parts by weight of water, 2.5 parts by weight of trichloracetic acid, 0.25 part by weight of chromium trioxide and 0.2 part by weight of a wetting agent, and is then dried in an oven. The dried fabric is then united with a polyamide film by pressing them together under the influence of heat.

公开(公告)号：FR1245962A

公开(公告)日：1960-11-10

申请号：FR816257

申请日：1960-01-21

Applicant: BASF AG

Inventor： GEHM ROBERT ,  SCHMIDT OSWALD ,  MERTENS HEINRICH ,  GRUNWALD WOLFGANG ,  HEHL MANFRED

IPC: C07D251/68

Abstract: A household detergent consisting of a mixture of tetrapropylene benzene sulphonate, oleyl sulphate, sodium perborate, magnesium silicate, sodium silicate, sodium tripolyphosphate, sodium tetrapyrophosphate, sodium sulphate, carboxymethyl cellulose and water is admixed with optical brightening agents which in their anionic form have the general formula:- in which X represents a 1-aza-4-thiocyclo-hex-1-yl-4,4-dioxide radical, a 2,6-dimethyl-1-aza-4-thiacyclohex-1-yl-4,4-dioxide radical or a radical of the formula:- and Y is a hydroxy group, an amino group, a monosubstituted amino group such as an alkylamino, cycloalkylamino, arylamino, hydroxyalkylamino or alkoxyalkylamino group, a disubstituted amino group such as a dialkylamino, di(hydroxyalkyl) amino or di(alkoxyalkyl) amino group, a pyrrolidino, piperidino or morpholino group, a 1-aza-4-thiacyclohex-1-yl-4,4-dioxide radical or a group of the formula or salts thereof with alkali metals, ammonia or primary, secondary or tertiary amines. Specification 874,519 is referred to.ALSO:The invention comprises optical brightening agents which in their anionic form have the general formula:- in which X represents a 1-aza-4-thiocyclo-hex-1-yl-4,4-dioxide radical, a 2,6-dimethyl-1-aza-4-thiacyclohex-1-yl-4,4-dioxide radical or a radical of the formula:- and Y is a hydroxy group, an amino group, a monosubstituted amino group such as an alkylamino, cycloalkylamino, arylamino, hydroxyalkylamino or alkoxyalkylamino group, a disubstituted amino group such as a dialkylamino, di(hydroxyalkyl) amino or di(alkoxyalkyl) amino group, a pyrrolidino, piperidino or morpholino group, a 1-aza-4-thiacyclohex-1-yl-4,4-dioxide radical or a group of the formula or salts thereof with alkali metals, ammonia or primary, secondary or tertiary amines. The above brightening agents are prepared by reacting in any order two mols. of a cyanuric halide with one mol. of an alkali metal salt of a 4,41-diamino-stilbene disulphonic acid of the formula:- and with two mols. of 1-aza-4-thia-cyclohexane-4,4-dioxide or two mols. of 2,6-dimethyl - 1 - aza-4-thiacyclohexane-4,4-dioxide, and further reacting the products obtained with aqueous alkali, ammonia, an alkylamine, a dialkylamine, a cycloalkylamine, a hydroxyalkylamine, a di(hydroxyalkyl) amine, an alkoxyalkylamine, a di(alkoxyalkyl) amine, an arylamine, pyrrolidine, morpholine, piperidine or 1 - aza-4-thiacyclo-hexane-4,4-dioxide or, after having reacted the said products or the initial compound (obtained by the reaction of cyanuric acid halide with 4,41-diaminostilbene disulphonic acid) with ammonia, the resulting compounds are treated with a mixture of aqueous formaldehyde and 1-aza-4-thiacyclohexane-4,4-dioxide or, after having reacted the initial compound (obtained by the reaction of cyanuric halide with 4,41-diaminostilbene disulphonic acid) with 2 mols. of aqueous alkali, a primary or secondary amine, pyrrolidine, piperidine or morpholine, the remaining chlorine substituents are replaced by means of ammonia and the resulting amino compound is condensed with formaldehyde and 2 mols. of 1-aza-4-thiacyclohexane-4,4-dioxide. Specification 874,519 is referred to.ALSO:Foils, films, felts, fibres, threads, yarns, flocks and woven and non-woven fabrics of natural, regenerated and synthetic material, such as leather, synthetic polymers (plastics), cotton, household washing, paper, native or regenerated cellulose and linear polyamides (e.g. polycaprolactam) are brightened by treatment with optical brightening agents which in their anionic form have the general formula:- in which X represents a 1-aza-4-thiocyclohex-1-yl-4,4-dioxide radical, a 2,6-dimethyl-1-aza-4-thiocyclohex-1-yl-4,4-dioxide radical or a radical of the formula:- and Y is a hydroxy group, an amino group, a monosubstituted amino group such as an alkylamino, cycloalkylamino, arylamino, hydroxyalkylamino or alkoxyalkylamino group, a disubstituted amino group such as a dialkylamino, di(hydroxyalkyl) amino or di(alkoxyalkyl) amino group, a pyrrolidino, piperidino or morpholino group, a 1-aza-4-thiocyclohex-1-yl-4,4-dioxide radical or a group of the formula or salts thereof with alkali metals, ammonia or primary, secondary or tertiary amines. Other ingredients which may be present in the aqueous treatment bath are formic acid, hydrogen peroxide, tetrapropylene benzene chromium trioxide to trichloracetic acid in solution in an aromatic hydrocarbon, e.g. toluene. Material treated by either process may be dried at an elevated temperature. Treatment enhances the adhesion of the fabric for materials of other high molecular synthetic or high molecular natural substances, e.g. gelatin, polyvinyl alcohol, polyvinyl butyral, polyethylene and polyamides. In an example, a polyethylene terephthalate fabric is bathed for 10 secs. in a solution of 100 parts by weight of water, 2.5 parts by weight of trichloracetic acid, 0.25 part by weight of chromium trioxide and 0.2 part by weight of a wetting agent, and is then dried in an oven. The dried fabric is then united with a polyamide film by pressing them together under the influence of heat.

公开(公告)号：GB924762A

公开(公告)日：1963-05-01

申请号：GB1691560

申请日：1960-05-13

Applicant: BASF AG

Inventor： STILZ WALTER ,  POMMER HORST ,  GEHM ROBERT ,  SCHMIDT OSWALD ,  MERTENS HEINRICH ,  HEHL MANFRED ,  GRUNWALD WOLFGANG

IPC: C11D1/00 ,  D06L3/12

Abstract: Substituted 1,4-bis-styryl benzenes of the general formula: in which X and X1 stand for carboxylic ester groups or N-alkyl carboxylic amide groups, are prepared by reacting terephthaladehyde with an ester of a carbalkoxy-benzylphosphonic acid or with an ester of a halogenmethylbenzoic acid, with the aid of a triarylphosphine and an alkali alcoholate, and if necessary converting the ester groups of the products into amide groups. These substituted 1,4-bis-styryl benzenes are optical brightening agents (Group IV(c)). In Example 1, the methyl ester of p-chlormethylbenzoic acid is stirred with triphenylphosphine in dimethylformamide at 80 DEG C. for 3 hours; and then terephthalaldehyde followed by sodium methylate are added. The product is 1,4-bis-(para-carbmethoxy-styryl)-benzene, and this is converted, by heating it with diethanolamine, into 1,4-bis-(para-carbodiethanolamidostyryl)-benzene Example 8 refers to 1,4-bis-(meta-carbdiethanolamido-styryl)-benzene. Example 9 describes the preparation of a mixture of 1,4-bis-(para-carbethoxy-styryl) - benzene, 1,4 - bis - (metacarbmethoxy-styryl)-benzene and 1-(para-carbmethoxy-styryl) - 4-(meta1-carbmethoxy-styryl)-benzene, by reacting terephthalaldehyde with a mixture of meta- and para-carbmethoxy-benzyl-phosphonic acid diethyl ester. The mixture of 1,4-bis-styryl-benzene diesters is then reacted with diethanolamine. Example 19 states that 1,4-bis-(meta-carb-N-cyclohexylisopropanol-amidostyryl)-benzene is obtained by reacting 1,4 - bis - (meta-carbmethoxy-styryl)-benzene with N-cyclohexyl-iso-propanolamine. It is stated that X and X1 in the general formula may stand for COO.C2H4OH, and similar groups. Compounds wherein the hydrogen atoms of the hydroxy groups in both the amides and the esters are substituted by glycol ether groups are obtained by the reaction of the amides or esters with ethylene oxide or propylene oxide. Specification 813,539 is referred to.ALSO:Substituted 1, 4-bis-styryl benzenes of the general formula in which X and X1 stand for carboxylic ester groups or N-alkyl carboxylic amide groups, act as brightening agents for textiles, paper and leather. The brightening agent is preferably used in aqueous medium in amounts of about 0,0015 to 0.05% with reference to the weight of the substrate to be brightened. In Example 1, previously bleached cotton fabric is treated, for 20 minutes, in a liquor, at 50 DEG to 60 DEG C., containing 0,003 to 0,01 grams per litre of the compound having the structure and 5 grams per litre of sodium sulphate decahydrate, the liquor to fabric ratio being 50:1. After rinsing and drying, the fabric has a dazzling whiteness of good fastness to light and washing. Examples 5, 6 and 7 relate to the use of the same compound for brightening polycaprolactam fabric, yellowish paper, and soiled clothing, respectively. Example 8 describes the use of 1, 4-bis-(metacarbdiethanolamidostyryl)-benzene for brightening cotton fabric. For the preparation of the brightening agents, (see Group IV(b)). Specification 813,539 is referred to.

公开(公告)号：BE589006A

公开(公告)日：1960-07-18

申请号：BE589006

申请日：1960-03-24

Applicant: BASF AG

Inventor： BALLI HEINZ ,  LEUCHS DIETER ,  HEHL MANFRED ,  GRUNWALD WOLFGANG ,  SCHMIDT OSWALD

IPC: C07D277/82 ,  C08K5/46 ,  C09B23/16 ,  D01F1/10 ,  D06L3/12 ,  D06P

公开(公告)号：AT215944B

公开(公告)日：1961-06-26

申请号：AT9860

申请日：1960-01-07

Applicant: BASF AG

Inventor： GEHM ROBERT DR ,  SCHMIDT OSWALD DR ,  MERTENS HEINRICH DR ,  GRUNWALD WOLFGANG ,  HEHL MANFRED

公开(公告)号：FR1257960A

公开(公告)日：1961-04-07

申请号：FR827274

申请日：1960-05-16

Applicant: BASF AG

Inventor： STILZ WALTER ,  POMMER HORST ,  GEHM ROBERT ,  SCHMIDT OSWALD ,  MERTENS HEINRICH ,  HEHL MANFRED ,  GRUNWALD WOLFGANG

IPC: C11D1/00 ,  D06L3/12 ,  D06L4/60 ,  D06L4/664

公开(公告)号：FR1253025A

公开(公告)日：1961-02-03

申请号：FR822979

申请日：1960-03-31

Applicant: BASF AG

Inventor： BALLI HEINZ ,  LEUCHS DIETER ,  HEHL MANFRED ,  GRUNWALD WOLFGANG ,  SCHMIDT OSWALD

IPC: C07D277/82 ,  C08K5/46 ,  C09B23/16 ,  D01F1/10 ,  D06L3/12

Abstract: Textile materials, i.e. fibres, flocks, yarns, threads, woven and non-woven fabrics and films, comprising polymers of acrylonitrile or cellulose acetate are optically brightened by incorporating into the polymers or into the cellulose acetate, before or during the spinning of the textile materials, an azamonomethine cyanine compound of the formula in which Y and Y1 are identical or different and each represents a hydrogenation, a methyl group of a methoxy group and X is an anion, e.g. an inorganic anion such as a chloride, bromide, iodide, perchlorate or sulphate anion or an organic anion such as an alkylsulphate or arylsulphonate anion. From 0,01 to 5% of brightening agent, with reference to the weight of the material to be brightened, may be used. Cellulose acetate, the acetyl content of which lies between 2 1/2 and 3 groups per anhydro-glycose unit, and polymers of acrylonitrile and copolymers thereof with vinyl chloride, vinyl acetate or methyl methacrylate containing more than 50% by weight of acrylonitrile, may be treated. Specifications 447,038, 461,668 and 461,688 are referred to.ALSO:Fibres, flocks, yarns, threads, woven and nonwoven fabrics and films comprising polymers of acrylonitrile or cellulose acetate are optically brightened by treating them with an azamonomethine cyanine compound of the formula in which Y and Y1 are identical or different and each represents a hydrogen atom, a methyl group or a methoxy group and X is an anion, e.g. an inorganic anion such as a chloride, bromide, iodide, perchlorate or sulphate anion or an organic anion such as an alkylsulphate or arylsulphonate anion. The brightening agents are preferably applied from aqueous solutions in amounts such that 0.01%-5% of the brightening agent, with reference to the weight of the material to be brightened, is applied. The brightening process may be carried out before or simultaneously with an alkali metal chlorite bleach. Cellulose acetates, the acetyl content of which lies between 2 1/2 and 3 groups per anhydroglucose unit, and polymers of acrylonitrile and copolymers thereof with vinyl chloride, vinyl acetate or methyl methacrylate containing more than 50% by weight of acrylonitrile, may be treated. Specifications 447,038, 461,668 and 461,688 are referred to.

公开(公告)号：DE1419003A1

公开(公告)日：1968-12-12

申请号：DE1419003

申请日：1959-11-06

Applicant: BASF AG

Inventor： WALTER STILZ DR ,  HORST POMMER DR ,  ROBERT GEHM DR ,  OSWALD SCHMIDT DR ,  HEINRICH MERTENS DR ,  HEHL MANFRED ,  GRUNWALD WOLFGANG

IPC: C11D1/00 ,  D06L3/12

Abstract: Substituted 1,4-bis-styryl benzenes of the general formula: in which X and X1 stand for carboxylic ester groups or N-alkyl carboxylic amide groups, are prepared by reacting terephthaladehyde with an ester of a carbalkoxy-benzylphosphonic acid or with an ester of a halogenmethylbenzoic acid, with the aid of a triarylphosphine and an alkali alcoholate, and if necessary converting the ester groups of the products into amide groups. These substituted 1,4-bis-styryl benzenes are optical brightening agents (Group IV(c)). In Example 1, the methyl ester of p-chlormethylbenzoic acid is stirred with triphenylphosphine in dimethylformamide at 80 DEG C. for 3 hours; and then terephthalaldehyde followed by sodium methylate are added. The product is 1,4-bis-(para-carbmethoxy-styryl)-benzene, and this is converted, by heating it with diethanolamine, into 1,4-bis-(para-carbodiethanolamidostyryl)-benzene Example 8 refers to 1,4-bis-(meta-carbdiethanolamido-styryl)-benzene. Example 9 describes the preparation of a mixture of 1,4-bis-(para-carbethoxy-styryl) - benzene, 1,4 - bis - (metacarbmethoxy-styryl)-benzene and 1-(para-carbmethoxy-styryl) - 4-(meta1-carbmethoxy-styryl)-benzene, by reacting terephthalaldehyde with a mixture of meta- and para-carbmethoxy-benzyl-phosphonic acid diethyl ester. The mixture of 1,4-bis-styryl-benzene diesters is then reacted with diethanolamine. Example 19 states that 1,4-bis-(meta-carb-N-cyclohexylisopropanol-amidostyryl)-benzene is obtained by reacting 1,4 - bis - (meta-carbmethoxy-styryl)-benzene with N-cyclohexyl-iso-propanolamine. It is stated that X and X1 in the general formula may stand for COO.C2H4OH, and similar groups. Compounds wherein the hydrogen atoms of the hydroxy groups in both the amides and the esters are substituted by glycol ether groups are obtained by the reaction of the amides or esters with ethylene oxide or propylene oxide. Specification 813,539 is referred to.ALSO:Substituted 1, 4-bis-styryl benzenes of the general formula in which X and X1 stand for carboxylic ester groups or N-alkyl carboxylic amide groups, act as brightening agents for textiles, paper and leather. The brightening agent is preferably used in aqueous medium in amounts of about 0,0015 to 0.05% with reference to the weight of the substrate to be brightened. In Example 1, previously bleached cotton fabric is treated, for 20 minutes, in a liquor, at 50 DEG to 60 DEG C., containing 0,003 to 0,01 grams per litre of the compound having the structure and 5 grams per litre of sodium sulphate decahydrate, the liquor to fabric ratio being 50:1. After rinsing and drying, the fabric has a dazzling whiteness of good fastness to light and washing. Examples 5, 6 and 7 relate to the use of the same compound for brightening polycaprolactam fabric, yellowish paper, and soiled clothing, respectively. Example 8 describes the use of 1, 4-bis-(metacarbdiethanolamidostyryl)-benzene for brightening cotton fabric. For the preparation of the brightening agents, (see Group IV(b)). Specification 813,539 is referred to.

公开(公告)号：GB895084A

公开(公告)日：1962-05-02

申请号：GB1134960

申请日：1960-03-31

Applicant: BASF AG

Inventor： BALLI HEINZ ,  LEUCHA DIETER ,  HEHL MANFRED ,  GRUNWALD WOLFGANG ,  SCHMIDT OSWALD

IPC: C07D277/82 ,  C08K5/46 ,  C09B23/16 ,  D01F1/10 ,  D06L3/12

Abstract: Textile materials, i.e. fibres, flocks, yarns, threads, woven and non-woven fabrics and films, comprising polymers of acrylonitrile or cellulose acetate are optically brightened by incorporating into the polymers or into the cellulose acetate, before or during the spinning of the textile materials, an azamonomethine cyanine compound of the formula in which Y and Y1 are identical or different and each represents a hydrogenation, a methyl group of a methoxy group and X is an anion, e.g. an inorganic anion such as a chloride, bromide, iodide, perchlorate or sulphate anion or an organic anion such as an alkylsulphate or arylsulphonate anion. From 0,01 to 5% of brightening agent, with reference to the weight of the material to be brightened, may be used. Cellulose acetate, the acetyl content of which lies between 2 1/2 and 3 groups per anhydro-glycose unit, and polymers of acrylonitrile and copolymers thereof with vinyl chloride, vinyl acetate or methyl methacrylate containing more than 50% by weight of acrylonitrile, may be treated. Specifications 447,038, 461,668 and 461,688 are referred to.ALSO:Fibres, flocks, yarns, threads, woven and nonwoven fabrics and films comprising polymers of acrylonitrile or cellulose acetate are optically brightened by treating them with an azamonomethine cyanine compound of the formula in which Y and Y1 are identical or different and each represents a hydrogen atom, a methyl group or a methoxy group and X is an anion, e.g. an inorganic anion such as a chloride, bromide, iodide, perchlorate or sulphate anion or an organic anion such as an alkylsulphate or arylsulphonate anion. The brightening agents are preferably applied from aqueous solutions in amounts such that 0.01%-5% of the brightening agent, with reference to the weight of the material to be brightened, is applied. The brightening process may be carried out before or simultaneously with an alkali metal chlorite bleach. Cellulose acetates, the acetyl content of which lies between 2 1/2 and 3 groups per anhydroglucose unit, and polymers of acrylonitrile and copolymers thereof with vinyl chloride, vinyl acetate or methyl methacrylate containing more than 50% by weight of acrylonitrile, may be treated. Specifications 447,038, 461,668 and 461,688 are referred to.