JPH07508304A - Concentrated aqueous liquid detergent composition comprising polyvinylpyrrolidone and a terephthalate-based antifouling polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] A concentrate containing polyvinylpyrrolidone and a terephthalate-based antifouling polymer Aqueous liquid detergent composition wave technology branch The present invention relates to concentrated aqueous liquid detergent compositions. The composition according to the present invention Contains lupyrrolidone and a terephthalate-based antifouling polymer.

It is widely known in the art. Polyvinylpyrrolidone is used mainly for its fabric care properties. For use in agent compositions, for example, EP 262 897, EP 3 27927 and EP 203 486. child These documents include the use of polyvinylpyrrolidone in liquid detergent compositions. Ru.

Antifouling polymers based on terephthalates are also disclosed, for example in U.S. Pat. No. 4,116,8. No. 85, U.S. Pat. No. 4,132.680, EP No. 185,427 specification, EP 199 403 specification, EP 241985 specification and It is technically described in EP 241 984. These documents are also liquid Including detergent compositions.

A new trend in the field of detergent compositions is the formulation of so-called concentrated detergents. liquid In the context of aqueous detergents, this means containing less water and a greater total amount of active ingredients. means a product that The formulation of such concentrated detergent compositions poses certain problems. Ru.

In particular, formulating concentrated aqueous liquid detergent compositions containing polyvinylpyrrolidone Polyvinylpyrrolidone remains in these concentrated detergent matrices as moisture settles. This poses a problem because it becomes less soluble. The same problem occurs when base terephthalate This occurs in the case of antifouling polymers.

These problems result in products that have a cloudy appearance and present physical stability issues. do.

Amazingly, antifouling weights based on polyvinylpyrrolidone and terephthalate Both can improve the solubility of each other in the concentrated aqueous liquid detergent matrix. It has now been discovered that Thus, physically stable polymers containing both of the aforementioned While an aqueous liquid detergent composition containing only one of the , probably not very stable.

Combination of polyvinylpyrrolidone and terephthalate-based antifouling polymers is disclosed in British Patent No. 2,137,221 in the context of granular detergent compositions. It is. In this context, polyvinylpyrrolidone is a terephthalate antifouling polymer. It is said to protect against attack by alkaline virgoos.

Demonstration of invention The composition according to the invention comprises the usual cleaning ingredients, 2-35% water by weight of the total composition; 0.05 to 5% by weight of the composition of polyvinylpyrrolidone and thilphthalate as a base. A liquid detergent composition containing from 0.05% to 2% of a polymer.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is an antifouling polymer based on polyvinylpyrrolidone (A), terephthalate. Contains combined (B) and normal cleaning ingredients (C).

(A) Polyvinylpyrrolidone The composition according to the invention contains 0.05 to 5% by weight of polyvinylpyrrolidone, preferably Contains 0.25-2% by weight. Polyvinylpyrrolidone preferred for use herein has a molecular weight of 1000 to 1.00000, preferably 1500 to 20000, most Preferably it has 2,500 to 15,000.

(B) Antifouling polymer based on terephthalate The composition according to the present invention has a total composition of terephthalate in an amount of 0.05 to 2% by weight, preferably 0.1 to 0.5% by weight of the product. Contains a base antifouling polymer. Such antifouling polymers are described, for example, in U.S. Pat. No. 4,116,885, U.S. Pat. No. 4,132,680, EP No. Specification No. 185427, Specification EP No. 199 403, Specification EP No. 241 985 and EP 241 984.

Polymers suitable for use herein include formula 2 (%) Examples include polymers of In this formula, the moiety; (A-RIJ-R2)u(A-R3- A-R2) v+ A-R'-A- constitutes the oligomer or polymer main chain of the compound do. The main chain structure is important for adsorption of the polymer onto the fabric, while the end groups have antifouling properties. It is thought to give

The bond A part is essentially ie, the compounds of the present invention are polyesters. “A” used here The part is essentially The term "is a moiety" means that moiety A consists entirely of moieties or is a connecting moiety, e.g. means a compound partially substituted with Partial position at these other joins The degree of ventilation should be such that the antifouling properties are not adversely affected to any significant extent. . Preferably, all of the binding moieties A are moieties (i.e., occupies 100%), i.e., each A is either .

The R1 moiety is essentially a 4-phenylene moiety.

As used herein, the term "R1 moiety is essentially a 1,4-phenylene moiety" , the R1 moiety consists entirely of 1,4-phenylene moieties or partially consists of other arylene moieties. or alkalylene moiety, alkylene moiety, alkenylene moiety, or Refers to a compound substituted with a mixture.

1. Arylenes and alkalis that can be used partially in place of 4-phenylene As the lene moiety, 1,3-phenylene, 1,2-phenylene, 1,8-naphthi Ren, 1,4-naphthylene, 2,2-biphenylene, 4,4'-biphenylene, and mixtures thereof.

Partially substituted alkylene and alkenylene moieties include ethylene, 1 , 2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexame Tylene, 1,7-hebutamethylene, 1,8-octamethylene, 1゜4-cyclohe xylene, and mixtures thereof.

In the case of the R1 moiety, the degree of partial substitution with moieties other than 1,4-phenylene is The antifouling properties of the material should not be adversely affected to any significant extent. General The acceptable degree of partial substitution will depend on the backbone length of the compound, i.e. A longer backbone has more partial substitutions for the 1,4-phenylene moiety. Can be done.

Usually, R1 is about 50% to 100% (1,4-)unishine of the 1,4-phenylene moiety. Compounds consisting of a portion other than O (about 50%) have adequate antifouling activity. for example , isophthalic acid (1,3-) unishin) vs. terephthalic acid (1°4-) unishin) The polyester produced according to the present invention using a 40:60 molar ratio of It has excellent antifouling activity. However, most polyesters used in textile manufacturing Consisting of ethylene terephthalate units, typically 1 for best antifouling activity. ．． It is desirable to minimize the degree of partial substitution with moieties other than 4-phenylene.

Preferably, the R1 portion consists entirely of 1,4-phenylene moieties (i.e., 100 %), ie each R1 moiety is 1°4-phenylene.

The R moiety is essentially an ethylene moiety, or an 01-C4 alkyl or alkoxy moiety. It is a substituted ethylene moiety with a substituent. The "R2 part" used here is Ren moiety, or C'''' C4 alkyl or alkoxy substituent substituent The term "is an ethylene moiety" means that the R2 moiety is all ethylene or substituted ethylene. or partially substituted with other compatible moieties do. Examples of these other moieties include 1°3-propylene, 1,4-butylene , 1,5-pentylene, 1,6-hexamethylene, etc. linear C-C6 alkylene moieties, 1,2-cycloalkylene moieties such as 1,2-cyclohexylene, 1,4 -1,4-cyclohexylene, 1゜4-dimethylenecyclohexylene, etc. loalkylene part, polyoxyalkylated 1,2-hydroxyalkylenes such as, and -CHCH0CH2CH20CH2CH2-1-CHCH0CH2CH2- etc. The oxyalkylene moiety of

In the case of the R2 moiety, the degree of partial substitution with these other moieties is such that the antifouling properties of the compound are It should be such that it does not have a significant negative impact. generally acceptable The degree of partial substitution will depend on the backbone length of the compound, i.e. the longer the backbone , can have more partial substitutions. Usually R2 is ethylene or a substituted ethylene Compounds consisting of 20% to 100% tyrene in part (0 to about 80% in other compatible parts) has suitable antifouling activity. For example, diethylene glycol (-CHCH20 Using a molar ratio of CH2CH2-) to ethylene glycol (ethylene) of 75:25 The polyesters produced according to the invention have adequate antifouling activity. deer However, for the best antifouling activity, such It is desirable to minimize partial substitutions. (When manufacturing the polyester according to the present invention) , small amounts of these oxyalkylene moieties (as dialkylene glycols) , typically produced from glycols in a side reaction and then incorporated into polyesters. ). Preferably R2 is ethylene or substituted ethylene partially 80-10 0% and other compatible portions from 0 to about 20%.

In the case of the R2 moiety, suitable ethylene or substituted ethylene moieties include ethylene. 1,2-propylene, 1゜2-butylene, 1,2-hexylene, 3-methoxylene C-1.2-propylene and mixtures thereof. Preferably R2 The moieties are essentially ethylene moieties, 1,2-propylene moieties or mixtures thereof. be. Formulating with a higher percentage of ethylene moiety tends to improve the antifouling activity of the compound. Ru. Surprisingly, the formulation of a higher percentage of 1,2-propylene moieties reduces the water content of the compound. It tends to improve solubility.

In the case of the R3 moiety, preferred substituted C-C hydrorubylene moieties include the substituted 02 ~C12 alkylene, alkenylene, arylene, alkali metal and similar Some parts can be mentioned. Substituted alkylene or alkenylene moieties can be linear, Can be branched or cyclic. Also, all R3 parts are the same (for example, all substituted arylene) or a mixture (e.g., substituted arylene and substituted alkyl) (mixture with kylene).

Preferred R3 moieties are those that are substituted 1,3-phenylene moieties.

The substituted R3 moiety preferably has only one -503M substituent. M is H or a compatible water-soluble cation. As a suitable water-soluble cation water-soluble alkali metals, such as potassium (K+) and especially sodium ( Na+), and ammonium [wherein R1 and R2 are each C-C hydrodynamic group] is a building group (e.g., alkyl, hydroxyalkyl) or - together with 4 to 6 forming a cyclic or heterocyclic ring of carbon atoms (e.g. piperidine, morpholine) ; R3 is C'''' C20 hydrocarbyl group; R4 is H (ammonium) or 01-C2o hydrocarbyl group (quaternary amine)] Also suitable are substituted ammonium cations having . Typical substituted ammonium Cationic groups are those in which R4 is H (ammonium) or 01-C4 alkyl, especially methyl (quaternary amine), R1 is C-C alkyl, especially C-C alkyl, R and R 3 is each C-C alkyl, especially methyl.

The R3 moiety with substituents provides a branched backbone compound.

-A-CCR-A-RA)) The R3 moiety having the -RA moiety is a crosslinked main chain compound give. In fact, the synthetic methods used to produce branched backbone compounds typically gives at least some crosslinked backbone compounds.

part C(RO) (CH(Y) CH20) n) - and -((OCH(Y)CH 2) n(OR)m]- moiety -(RO)- and =(CH(Y)CH20)- are mixed together, preferably -(R50)- and -(CH(Y)CH2 0) A partial block can be formed. Preferably, -(R50) part The minute block is placed next to the main chain of the compound. R5 is the part -R-A-R"- , m is 1 and the moiety -R-A-R''- is preferably placed next to the main chain of the compound. In the case of R5, the preferred C-C alkylene is C 3H6 (propylene); when R is C3-C4 alkylene, m is Preferably it is from 0 to about 5, most preferably O. R6 is preferably a metal It is tyrene or 1,4-phenylene.

The moiety -(CH(Y)CH20)- is preferably the moiety -((RO)(C at least about 75% by weight of H(Y)CH20)n)-, most preferably 1 00% by weight (m is O).

each part The Y substituent of -C(RO)(CH(Y)CH20)n)- is an ether moiety -CH(OCH2CH2) pO-X, or more typically this agent is a mixture of Tel moieties and H; p can be from 0 to 100, but typically is 0. When the Y substituent is a mixture, the moiety -(CH(Y)CH20) n- is the following part (where n is at least 1 and the sum of n + n2 is the value of n) It can be expressed as Typically, n1 has an average value of about 1 to about 10 . part and -(CHCHO)- can be mixed together with 2 2 R2 However, typically and -(CHCHO) Part of the block is shaped like 2 2 R2 to be accomplished. X is H, C-C4 alkyl or (wherein R7 is C-C alkyl) ). X is preferably methyl or ethyl, most preferably is methyl. The value of each n is at least about 6, but preferably at least is also about 10. The value of each n is typically from about 12 to about 113. Typically each The value of n is within the range of about 12 to about 43.

The main chain portion -(A-R1-A-R2)- and -(A-R3-A-R2)- are - can be mixed together, or -(A-R1-A-R2)- and - (A-R3-A-R2) can form a partial block. The value of u+v is determined by the present invention. of the compound must be at least about 3 to have significant antifouling activity. It was found that The maximum value of u+v is generally determined by the manufacturing method of the compound. 25, i.e., the compounds of the present invention may be oligomeric or or low molecular weight polymers. In comparison, polyester used in textile manufacturing typically have a much higher molecular weight, e.g. from about 50 to about 250 molecules. Contains tylene terephthalate units. Typically, the sum of u+v is the compound of the invention. It is about 3 to about 10 in the case of a product.

In general, the larger the value of u+v, the less soluble the compound is (particularly when the R3 moiety does not have a substituent -COOM or -So3M). Also, n As the value of u+v increases, the value of u+v increases as the compound adheres better to the fabric during washing. It should increase as much as possible. R3 part is a substituent (branched main chain compound) or When having a bridge backbone compound), the value of W is typically at least 1; Determined by the compound manufacturing method.

In the case of these branched backbone compounds and crosslinked backbone compounds, the value of u+v+w is It is about 3 to about 25.

Preferred compounds of this type of polymer have the formula (all R1 moieties are 1,4-phenylene The 122 portion is essentially an ethylene portion, a 1,2-propylene portion, or the like. all R3 moieties are calylum or preferably sodium 5 -Suluo0-1unifinylene moiety or a substituent at the 5-position a substituted 1,3-phenylene moiety having; the R4 moiety is a R1 or R3 moiety; or a mixture thereof; each X is ethyl or preferably methyl; each n1 is 1 to about 5: the sum of each n + n2 is about 12 to about 43: W is O When u+v is about 3 to about 10: When W is at least 1, u+v+w is about 3 to about 10) It is a block polyester with

Particularly preferred block polyesters are those in which V is O, i.e. linear block polyesters. It is polyester. In the case of these most preferred linear block polyesters is typically about 3 to about 8. These linear block polyester Among them, those in which U is about 3 to about 5 are the most water-soluble.

Other polymers suitable for use here include the formula % (formula %) Examples include polymers of In this formula, the moiety is the oligomeric or polymeric backbone of the compound. Configure. Groups X-[(OCHCH(Y)) (OR4))- and 2 nm and -C(Ro)(CH(y)CH20)n)-X are generally oligomers/ It is attached at the end of the polymer backbone.

The bond A part is essentially ie, the compounds of the present invention are polyesters. “A” used here The term "a part is essentially a part" means that a part is is all part consisting of or a connecting part, e.g. H^ means a compound partially substituted with Partial position at these other joins The degree of ventilation should be such that the antifouling properties are not adversely affected to any significant extent. . (i.e., occupies 100%), i.e., each A is either.

The R1 moiety is essentially a 1,4-phenylene moiety.

As used herein, the term "rR1g is essentially a 1,4-phenylene moiety" , the R1 moiety consists entirely of 1,4-phenylene moieties or partially consists of other arylene moieties. or alkalylene moiety, alkylene moiety, alkenylene moiety, or Refers to a compound substituted with a mixture.

1. Arylenes and alkalis that can be used partially in place of 4-phenylene Len moieties include 1,3-two-biphenylene, and mixtures thereof. It will be done.

Partially substituted alkylene and alkenylene moieties include ethylene, 1 ．． 2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexame Tylene, 1,7-hebutamethylene, 1,8-octamethylene, 1゜4-cyclohe xylene, and mixtures thereof.

These other arylene, alkali metal, alkylene and alkenylene moieties can be unsubstituted or at least one ~So3M, -COOM .

-A-R7-(A-R-A-R7-] -X substituent or another R1 moiety at least one moiety -A-R7-[:A-R1-A-R7) -A- (formula where R7 is the moiety R2 or R3): W is 0 or less. At least 1. Preferably, these substituted R1 moieties include only one -803 M, -COOM or -A-R7-[A-R-A-R7-○) -x substituent. M is H or Can be a compatible water-soluble cation. Suitable water-soluble cations include water Soluble alkali metals, such as potassium (K+) and especially sodium (Na) , as well as ammonium (NH+)+ can be mentioned. formula In formula C, R1 and R2 each represent a C-C hydrocarbyl group (e.g., alkyl, hydrogen hydroxyalkyl) or -cyclic or heterocyclic of 4 to 6 carbon atoms form a ring (e.g. piperidine, morpholine): R3 is a 01-C28 hydrocarbon. is a rubyl group; R4 is H (ammonium) or 01-C2o hydrocarbyl group (quaternary amine)] Also suitable are substituted ammonium cations having . Typical substituted ammonium Cationic groups are those in which R4 is H (ammonium) or C1-C4 alkyl, especially methyl (quaternary amine), R is C-Calkyl, especially 012-C alkyl, R and R3 is each C-C alkyl, especially methyl.

A R1 moiety with a group provides a branched backbone compound.

-A-R7-(A-R1-A-R7) The R1 portion having a part of -A is the crosslinking main gives a chain compound. In fact, the synthetic methods used to produce branched backbone compounds are Typically, at least some crosslinked backbone compounds are provided.

In the case of the R1 moiety, the degree of partial substitution with moieties other than 1,4-phenylene is The antifouling properties of the material should not be adversely affected to any significant extent. General The acceptable degree of partial substitution will depend on the backbone length of the compound, i.e. A longer backbone has more partial substitutions for the 1,4-phenylene moiety. Can be done.

Usually, R1 is about 50% to 100% (1,4-)unilene of 1,4-phenylene moiety Compounds consisting of 0 to about 50% of the rest have adequate antifouling activity. but However, most polyesters used in textile manufacturing contain ethylene terephthalate units. Therefore, moieties other than 1,4-phenylene are usually used for the best antifouling activity. It is desirable to minimize the degree of partial substitution in . Preferably, the R1 portion is entirely 1,4-phenylene moieties (i.e., 100%), ie, each R1 moiety is 1. It is 4-phenylene.

The R moiety is essentially a substituted ethyl group having 01-C4 alkyl or alkoxy substituents. This is the Len part. As used herein, the "R2 moiety is essentially C-c alkyl or alkyl. The term "substituted ethylene moiety having alkoxy substituent" means that the R2 moiety is entirely of the invention consisting of substituted ethylene moieties but partially substituted with other compatible moieties. means a compound. Examples of these other moieties include ethylene, 1,3-propylene lene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, etc. Linear 02-c6 alkylene moiety, 1°2-cyclo such as 1,2-cyclohexylene loalkylene moiety, 1,4-cyclohexylene, 1,4-dimethylenecyclohexylene 1,4-cycloalkylene moieties such as silene, polyoxyalkylated 1,2-hydroxyalkylenes such as, and -CHCH Secondary xyalkylene moieties such as OCHCH2- are included.

In the case of the R2 moiety, the degree of partial substitution with these other moieties will depend on the antifouling properties and and solubility should not be adversely affected to any significant extent. General The acceptable degree of partial substitution depends on the desired antifouling properties and solubility, the main chain length of the compound ( i.e., longer backbones can generally have more partial substitutions), and the type of moiety included (e.g., larger moiety substitutions on ethylene moieties are (generally decreases solubility).

Typically, R2 is partially substituted ethylene from 20% to 100% (other compatible moieties 0 to about 80%). %) has adequate antifouling activity. However, the best antifouling activity It is generally desirable to minimize such partial substitutions for stability and solubility. Yes. (When producing the polyester according to the present invention, a small amount of oxyalkylene moiety ( dialkylene glycols) are produced from glycols in a side reaction, and then (sometimes incorporated into polyester). Preferably R2 is substituted ethylene It consists of 80-100% part and 0-about 20% other compatible parts. R2 part In some cases, suitable substituted ethylene moieties include 1,2-propylene, 1,2-butylene, Examples include tyrene, 3-methoxy-1°2-propylene and mixtures thereof. . Preferably, the R2 moiety is essentially a 1,2-propylene moiety.

The R3 moiety is essentially a polyoxyethylene moiety -(CHCH20), -CH2CH It is 2-. As used herein, the [R3 moiety is essentially a polyoxyethylene moiety -(C 2Q for “HCHO) -H2CH2-” The word R3 consists entirely of this polyoxyethylene moiety or other compatible moieties. means a compound of the invention which further includes. Examples of these other parts include C3 to C6 oxyalkylene moieties such as xypropylene and oxybutylene, poly Polyoxyalkylene moieties such as oxypropylene and polyoxybutylene, Examples include polyoxyalkylated chemicals such as 2-hydroxyalkylene oxide. Ru. The degree of inclusion of these other parts will have a negative effect on the antifouling properties of the compound. It should be such that it does not occur. Typically, in the compounds of the present invention, polyol The xyethylene moiety accounts for about 50-100% of each R3 moiety. Preferably, The lyoxyethylene moiety accounts for about 90-100% of each R3 moiety.

(During the production of the polyester according to the present invention, a very small amount of oxyalkylene moiety is , is bonded to the polyoxyethylene moiety in a side reaction, and thus assembled into the R3 moiety. ).

In the case of polyoxyethylene moieties, the value of q is at least about 9, preferably or at least about 12.

The value of q typically ranges from about 12 to about 180. Typically, the value of q is from about 12 to about It is within the range of 90.

part ((RO) (CH(Y) CH20) n] - and one [(○CH(Y) CH) (OR4)] - part 2n m -(RO)- and -(CH(Y)CH20)- are mixed together or preferably -(R40)- and -(CH(Y)CH20) form a partial block. can be done. Preferably, the -(R40) moiety block is the main chain of the compound. placed next to. When R4 is the moiety -R2-A-R"-, m is 1 and ; and the moiety -R-A-R"- is preferably located next to the main chain of the compound . In the case of R4, the preferred 03-C alkylene is CH (propylene); When R4 is C3-C4 alkylene, m is preferably from 0 to about 10. , most preferably 0. R5 is preferably methylene or 1,4-phenylene. It's Niren.

The moiety -(CH(Y)CH20)- is preferably the moiety -[(RO)m( at least about 75% by weight of CH(Y)CH20)n)-, most preferably It accounts for 100% by weight (m is 0).

The Y substituent of each moiety C(RO) (CH(Y)CH20)n) is H1 ether part -CH(OCH2CH2), O-X, or a mixture of this nityl moiety and H Yes; p can be from 0 to 100, but is typically 0. typically , Y substituents are all H. Y substituent is a mixture of ether moiety and H sometimes part -(CH(Y) CH20) n- represents the following moiety (where nl is at least 1, and the sum of n1 + n2 is the value of n) It can be expressed as Typically, nl has an average value of about 1 to about 10.

part and -(CHCH○)- can be mixed together with 2 2 R2 However, typically CH2(OCH2CH2)pO-x and -(CHCHO) Part of the block is shaped like 2 2 R2 to be accomplished. X is H, C-C4 alkyl or (wherein R is 01-C4 alkyl) can be). X is preferably methyl or ethyl, most preferably Or methyl. The value of each n is at least about 6, but preferably less than Both are about 10. The value of each n is typically from about 12 to about 113. Typically, The value of each n is within the range of about 12 to about 45.

Main chain part -(A-R"-A-R")- and -(A-R1-A-R3) part blocks can be formed, but more typically they are randomly mixed together. this In the case of the main chain portion of The average value can be from about 1 to about 20; the average value for u+v is from about 3 to about 70. . The average values of u1■ and u+v are generally determined by the method of preparation of the compound.

Generally, the larger the average value of ■, the thicker the average value of u + V, the smaller the average value of u + V. The smaller the size, the more soluble the compound. Typically, the average value of U is between about 5 and about 20, and the average value of ■ is about 1 to about 10; the average value of u+v is about 6 to about 30 It is. Generally, the ratio of U to V is at least about 1, typically from about 1 to about It is 6.

Preferred compounds of this type of polymer have the formula (where each R1 is a 1,4-phenylene moiety). R2 is essentially a 1,2-propylene moiety; R3 is essentially a polyoxyethylene moiety; Len part -(CH2C20) -CH2CH2-; each X is ethyl or preferably methyl; each n is from about 12 to about 45; q is from about 12 to about 90; The average value is about 5 to about 20; the average value of V is about 1 to about 10; The average value is about 6 to about 30; the U to V ratio is about 1 to about 6) It is a polyester with

Highly preferred polymers for use herein are of the formula: It can also be a chain group, each X having H1 from 1 to about 4 carbon atoms, preferably from 1 to 2 carbon atoms. selected from the group consisting of alkyl or acyl groups (most preferably alkyl)] It is a polymer of n is selected for water solubility, generally from about 10 to about 50, preferably or about 10 to about 25. The selection of U is based on relatively high ionic strength. This is critical for formulation into liquid detergents with a high degree of strength. Most substances with U greater than 5 preferably less than about 10 mol%, more preferably less than 5 mol%, most preferably or less than 1 mol%. Furthermore, at least 20 mol% of substances in which U is 3 to 5, Preferably there should be at least 40 mol%.

The R1 moiety is essentially a 1,4-phenylene moiety.

As used herein, the term "R1 moiety is essentially a 1,4-phenylene moiety" , the R1 moiety consists entirely of 1,4-phenylene moieties or partially consists of other arylene moieties. or alkalylene moiety, alkylene moiety, alkenylene moiety, or Refers to a compound substituted with a mixture.

1. Arylenes and alkalis that can be used partially in place of 4-phenylene As the lene moiety, 1,3-phenylene, 1,2-phenylene, 1,8-naphthi Ren, 1,4-naphthylene, 2,2-biphenylene, 4,4'-biphenylene, and mixtures thereof.

Partially substituted alkylene and alkenylene moieties include ethylene, 1 ．． 2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexame Tylene, 1,7-hebutamethylene, 1,8-octamethylene, 1゜4-cyclohe xylene, and mixtures thereof.

In the case of the R1 moiety, the degree of partial substitution with moieties other than 1,4-phenylene is The antifouling properties of the material should not be adversely affected to any significant extent. General The acceptable degree of partial substitution will depend on the backbone length of the compound, i.e. Longer backbones have more moiety substitution for the 1,4-phenylene moiety. Can be done.

Usually, R1 is 1,4-phenylene partially 50% to 100% (1,4-)unilene Compounds consisting of 0 to about 50% of the rest have adequate antifouling activity. for example , isophthalic acid (1,3-unilene) vs. terephthalic acid (1°4-phenylene) The polyester produced according to the present invention using a 40:60 molar ratio of It has excellent antifouling activity. However, most polyesters used in textile manufacturing Consisting of ethylene terephthalate units, typically 1 for best antifouling activity. ．． It is desirable to minimize the degree of partial substitution with moieties other than 4-phenylene.

Preferably, the R1 portion consists entirely of 1,4-phenylene moieties (i.e., 100 %), ie each R1 moiety is 1°4-phenylene.

In the case of the R2 moiety, suitable ethylene or substituted ethylene moieties include ethylene. 1,2-propylene, 1゜2-butylene, 1,2-hexylene, 3-methoxylene C-1.2-propylene and mixtures thereof. Preferably R2 The moiety is essentially an ethylene moiety, or preferably a 1,2-propylene moiety or It is a mixture of them. Formulating with a higher percentage of ethylene moiety increases the antifouling activity of the compound. Although there is a tendency to improve, the percentages included are limited by water solubility. amazing In particular, the incorporation of a higher percentage of 1°2-propylene moiety improves the water solubility of the compound. , thus improving the ability to formulate isotropic aqueous detergent compositions without significantly compromising antifouling activity. There is a tendency to do good.

In the case of the present invention, using 1.2-propylene moieties or similar branched equivalents maximizes the incorporation of a substantial proportion of antifouling ingredients into heavy-duty liquid detergent compositions. This is extremely important in order to limit the Preferably, about 75% to about 100% of the R2 portion %, more preferably about 90% to about 100%, is the 1,2-propylene moiety.

Generally, antifouling ingredients that are soluble in cold (15°C) ethanol can also be used in the compositions of the present invention. Useful.

The value of n averages at least about 10, but a distribution of n values exists. The value of each n is , usually from about 10 to about 50. Preferably, the value of each n averages from about 10 to about 25 It is.

A preferred method for producing the antifouling component is a typical method in which a substantial portion of the antifouling component is made of a substance in which U is 6 or more. The polymer having the distribution is heated at a low temperature, for example, from about 0°C to about 15°C, preferably about 13°C. The following essentially consists of a step of extraction with absolute ethanol.

The ethanol soluble fraction virtually disintegrates long polymers and isotropically heavy duty. - much easier to incorporate into liquids, especially those with large amounts of bilge. Ru. Polymers with a U of about 3 or less have inherent value in providing antifouling effects. No, but can be more easily formulated than higher U values.

A more preferable method for producing the antifouling component is a direct synthesis method.

A more comprehensive disclosure of antifouling ingredients and their preparation can be found at Eugen P. Gosselink Co-pending U.S. Patent Application No. 684,511 filed December 21, 1984 Specification (incorporated herein by reference).

The most preferred polymers for use herein have the formula (wherein X is methyl and n is 16, R1 is a 1°4-phenylene moiety, and R2 is 1,2-propylene. and U is essentially from 3 to 5).

(C) Normal cleaning ingredients The composition according to the invention is a concentrated liquid detergent containing 2 to 35% water by weight of the total composition. Ru. Preferred compositions according to the invention contain 5 to 25% water by weight of the total composition.

The composition according to the invention further comprises conventional cleaning ingredients.

Such ingredients are selected from surfactants and builders and mixtures thereof. Ru.

Surfactant materials suitable for use herein include nonionic surfactants, anionic surfactants, on surfactants, cationic surfactants, zwitterionic surfactants and mixtures thereof Examples include organic surfactants selected from the following.

Suitable anionic surfactant salts are selected from the group of sulfonates and sulfates. It will be done. Such anionic surfactants are well known in detergent technology and are used in commercial detergents. It has found a wide range of applications in the field. Preferred anionic water-soluble sulfonates or Sulfates have alkyl groups having about 8 to about 22 carbon atoms in their molecular structure. like this Examples of preferred anionic surfactant salts include, for example, tallow oil, palm oil, palm kernel In sulfating 08-018 fatty alcohols derived from oil and coconut oil The reaction product thus obtained; an alkyl group having about 9 to 15 carbon atoms; Killbenzene sulfonate, sodium alkyl glyceryl ether sulfonate ; ether sulfates of fatty alcohols derived from tallow and coconut oil; Coconut fatty acid monoglyceride sulfate and coconut fatty acid monoglyceride dosulfonates; and para-dosulfonates having about 8 to about 22 carbon atoms in the alkyl chain; It is a water-soluble salt of finsulfonic acid. For example, U.S. Patent No. 3,332.880 Sulfonated olefin surfactants, such as those detailed herein, can also be used. anion Neutralizing cations for synthetic sulfonates and/or sulfates are available in detergent technology. Sodium, potassium, alkanol ammonium widely used in It is represented by a common cation such as

The preferred anionic synthetic surfactant component here is water of alkylbenzenesulfonic acid. Soluble salts, preferably sodium alkylbenzene sulfonates, preferably alkyl Sodium alkylbenzenesulfonate having about 10 to 13 carbon atoms in the group Represented by um. Another anionic surfactant component preferred herein is the alkaline surfactant component. It is a sodium alkyl sulfate having about 10-15 carbon atoms in the kill group.

Nonionic surfactants suitable for use herein include reactive hydrogen atoms, e.g. For example, hydrocarbons with hydroxyl, carboxyl, or amino groups and ethylene It is also produced by condensation with oxide in the presence of an acid or base catalyst. and has the general formula RA (CHCH20)nH (wherein R represents a hydrophobic moiety). , A represents a group supporting a reactive hydrogen atom, and n represents an ethylene oxide moiety. (representing the average number of ). R is typically about 8-2 It has 2 carbon atoms. They are combinations of propylene oxide and low molecular weight compounds. It can also be produced by condensation. n typically varies from about 2 to about 24.

A preferred class of nonionic ethoxylates are fatty alcohols containing 12 to 15 carbon atoms. and about 4 to 10 moles of ethylene oxide per mole of fatty alcohol. Therefore, it is expressed as Suitable ethoxylates of this type include C12-C 15 oxo alcohol and 3 to 9 moles of ethylene oxide per mole of alcohol condensate with.

Narrow cut 014-C15 oxo alcohol and 1 mole of fatty (oxo) alcohol condensate with 3 to 9 moles of ethylene oxide per mol, narrow cut C12 to C1 3 fatty (oxo) alcohols and 6.5 moles of ethyl alcohol per mole of fatty alcohol. condensation product with ) 01°-C coconut fatty alcohol condensates having 4-8.

Fatty oxo alcohols are primarily linear, but depending on processing conditions and raw material olefins. It can have a degree of branching depending on the chain, especially short chains such as methyl branches. branch 15% to 50% (wt%) is often found in commercial oxo alcohols .

Suitable cationic surfactants include the formula RRRRN, where R1, R2, and and R3 are methyl groups, R4 is 012-15 alkyl group, or R1 is is an ethyl or hydroxyethyl group, R and R are methyl groups, and R4 is C12-15 alkyl group) quaternary ammonium compounds.

As a zwitterionic surfactant, the aliphatic moiety can be linear or branched; one of the aliphatic substituents has about 8 to about 24 carbon atoms and the other substituent has at least Aliphatic quaternary ammonium, phosphonium containing one anionic water-solubilizing group , and derivatives of sulfonium compounds. Particularly preferred zwitterionic substances are: U.S. Pat. No. 3,925°262 to Rollin et al., issued February 9, 1975. and U.S. Pat. No. 3,929,6 to Rollin et al., issued December 30, 1975. Ethoxylated ammonium sulfonates and ethoxylated ammonium sulfonates disclosed in No. 78 ammonium sulfate.

Semipolar nonionic surfactants include alkyl or hydride having about 8 to about 28 carbon atoms. one loxyalkyl moiety and an alkyl group having from 1 to about 3 carbon atoms and a hydroxyalkyl moiety; two moieties selected from the group consisting of alkyl groups (these may optionally be combined to form a ring Examples include water-soluble amine oxides containing

R2-C-N-Z (In the formula, R1 is H, C 1-4 hydrocarbyl, 2-hydro roxyethyl, 2-hydroxypropyl or a mixture thereof, R2 is C 5-31 hydrocarbyl, and Z is at least 3 hydrocarbyls directly attached to the chain. Polyhydroxyhydrocarbyl with linear hydrocarpyl chain with roxyl or its alkoxylated derivative) polyhydroxy fatty acid amide surfactant Agents are also suitable. Preferably R is methyl and R2 is C11-15 alkyl or alkenyl linear chain, or a mixture thereof, and Z is a reductive amination reaction. Derived from reducing sugars such as glucose, fructose, maltose, and lactose be done.

The composition according to the invention may further include a builder system. polycarboxylate and fatty acids, substances such as ethylenediaminetetraacetate, aminopolyphos Sequestering agents such as phonates, especially ethylenediaminetetramethylene phosphorus Any commonly used Conventional builder systems are also suitable for use herein. For obvious environmental reasons Although not preferred, phosphate builders can also be used here.

Polycarboxylate builders suitable for use herein include citric acid, Preferably in the form of a water-soluble salt, formula R-CH(COOH)CH2(COOH) (wherein R is C1o-2o alkyl or alkenyl, preferably C12-16 or R is a hydroxyl, sulfo, sulfoxyl or sulfone substituent Examples include derivatives of succinic acid (which can be substituted with ). A specific example is laurilus succinate, myristyl succinate, valmityl succinate, 2-dodecenylate Examples include rusuccinate and 2-tetradecenyl succinate. succinate Builders preferably include sodium salts, potassium salts, ammonium salts and amine salts. It is used in the form of water-soluble salts, including the lukanol ammonium salt.

Other suitable polycarboxylates are oxodisuccinate and tartrate. Mixtures of monosuccinic acid and tartrate disuccinic acid, e.g. U.S. Pat. It is described in the specification of No. 63°071.

Fatty acid builders suitable for use herein include saturated or unsaturated C1o-18 fats. fatty acids and corresponding soaps. Preferred saturated species have 12 to 16 saturated species in the alkyl chain. carbon atoms. A preferred unsaturated fatty acid is oleic acid.

Preferred builder systems for use herein include citric acid and fatty acids and Consists of a mixture with succinic acid derivatives. The builder system according to the invention preferably 5-35% by weight of the composition.

The composition according to the invention preferably contains an enzyme. Suitable fermenters for use here The substances include proteases, lipases, cellulases and amylases and their mixtures. It is a compound. Compositions according to the invention may also include enzyme stabilization systems. What kind of communication Conventional enzyme stabilization systems are also suitable and preferred for use herein. is boric acid or its derivative, 1,2-propanediol, carboxylic acid, and Based on a mixture of them.

The composition can contain a series of further optional ingredients.

Examples of such additives include solvents, alkanolamines, pH adjusters, and foam control agents. conditioners, emulsifiers, agents that improve mechanical compatibility in connection with enamel-coated surfaces, fragrances, Examples include dyes, bactericides, brighteners, and fabric softeners.

The invention is further illustrated in the following examples.

weight% II Alkylbenzene sulfonate 186C13-15 alkyl 3-ethoxylate Sulfate - 12C13-15 alcohol 7 ethoxylate 13 5C 12-14N-Methylgelcosamide 9 Atmospheric pressure distilled palm kernel fatty acid 1111 Dodecylsuccinic anhydride 4.2- Citric acid 1.85 Diethylenetriaminepentamethylenephosphonic acid 11 Ethanol 12 Propanediol 11 9.8 Sodium hydroxide 0.6- Potassium hydroxide 2.2- Monoethanolamine 9 12.6 Enzyme 0.7 15 Boric acid 1.22 Calcium chloride 0.02 - Ethoxylated tetraethylenepentamine G, 5 0.5 Fragrance 0.6 0.5 PVP O,51,0 Terephthalate-based polymer 0.46 0.46 Water 2319 Trace components balance (assumed to be 100%) The PVP used in both examples is Luwiskol from BASF. R) K 12 (molecular weight 2500).

The terephthalate polymer used in both examples is where X is Me.

n is 16, R is 1.4 phenylene, R2 is 1,2-propylene, U is essentially 3- The above preferred polymer is No. 5.

Free of terephthalate-based antifouling polymers, PvP and terephthalate Similar combinations containing either antifouling polymers based on A composition was also prepared. All compositions were then stored at room temperature (approximately 20°C). tone The as-made compositions all had the same appearance. After two weeks of storage, which weight The composition is transparent and does not contain terephthalate-based antifouling polymers. It was observed that the compositions containing no It was done.

Continuation of front page (81) Designated countries 0A (BF, BJ, CF, CG.

CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AU, BB, BG, BR, BY, CA, CZ, FI, HU, JP, KP, K R, KZ, LK, MG, MN, MW, No, NZ, PL, R○, RU, SD.

SK, UA, US, VN

Claims (6)

[Claims] 1. Liquid detergent compositions containing conventional cleaning ingredients and 2 to 35% water by weight of the total composition 0.05 to 5% by weight of the total composition of polyvinylpyrrolidone and tereph A liquid detergent characterized in that it contains 0.05% to 2% of a polymer based on tallate. agent composition. 2. A liquid detergent composition according to claim 1, comprising from 5 to 25% water by weight of the total composition. 3. Claim comprising from 0.25 to 2% by weight of the total composition of said polyvinylpyrrolidone. 3. The composition according to 1 or 2. 4. In the previous claim, the polyvinylpyrrolidone has a molecular weight of 2,500 to 15,000. A composition according to any one of the claims. 5. 0.1% to 0.5% of the above-mentioned terephthalate-based polymer. A composition according to any one of claims. 6. The above terephthalate-based polymer has the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein X is methyl, n is 16, and R1 is a 1,4-phenylene moiety , R2 is a 1,2-propylene moiety, and u is essentially 3 to 5) A composition according to any one of the preceding claims, which is a polymer.