JP2013521359A - Anionic associative rheology modifier - Google Patents

Abstract

  The present invention relates to a novel anionic associative rheology modifier, its production method and application.

Description

  The present invention relates to a novel associative rheology modifier, its production method and application.

  There are often specific requirements for the rheological properties of cosmetic, pharmaceutical and industrial compositions. These compositions often cannot be converted into the desired application form without the use of additives, so-called thickeners. Examples of common low molecular weight thickeners are alkali metal and aluminum salts of fatty acids, fatty alcohols or waxes. However, depending on the field of use of the composition to be thickened, the use of known thickeners is often disadvantageous. For example, due to incompatibility, the thickening effect of such thickeners may not be sufficient, or mixing of the thickener into the composition may be hindered or incomplete. It is often difficult to provide products with complex property profiles using as little proportion or as few kinds of active substances as possible. For example, there is a need for a polymer for a cosmetic composition that has good conditioning or film-forming properties while at the same time acting as a thickener for the cosmetic composition. There is also an increasing consumer aesthetic demand for cosmetics and pharmaceuticals. For example, transparent gel compositions using such products are currently preferred. Accordingly, there is a need for polymers that are compatible with cosmetics and pharmaceuticals that are suitable to provide specific property profiles with respect to sensory properties, setting ability and rheological properties.

  Generally, a polymer thickener adjusts a viscosity with the molecular weight of a polymer. One drawback that often arises when using polymers as thickeners to prepare higher viscosity or gel compositions is that it is generally difficult to incorporate into cosmetic compositions as the molecular weight of the polymer increases. Finally, often only swelling of the polymer is observed, not the desired solution.

  Polymer rheology modifiers can be classified as either naturally derived or synthetically derived products. Examples of naturally derived products include starch, cellulose, alginate and protein. These naturally-derived polymers contain building blocks of polysaccharide units, or amino acids, to provide effective water soluble rheology modifiers. The grafting of selected groups onto the backbone of more widely used natural products (eg starch and cellulose) provides a large number of modified products developed to address specific application requirements. .

  Three common types of acrylic acid-based synthetic polymers comprise a group of products that have been used as rheology modifiers in various applications for many years. The first class is based on (meth) acrylic acid homopolymers, (meth) acrylic acid copolymers, (meth) acrylate esters and maleic acid, among others. This group is typically referred to as alkali swellable (or soluble) emulsions (ASE). Modification of the ASE polymer structure by incorporation of hydrophobic groups defines a second class of synthetic rheology modifiers known as hydrophobically modified alkali swellable emulsions (HASE). This group of polymers, more commonly referred to as associative thickeners, offers the potential to better control the rheology of the composition over a wider range of shear rates than conventional ASE class synthetic polymers. A third class of synthetic rheology modifiers are hydrophobically modified ethoxylated urethane resins (HEUR). This group of polymers typically consists of polyethylene glycol units of varying lengths joined by urethane bonds and terminated with hydrophobic end groups. Unlike ASEs and HASEs, HEUR rheology modifiers are non-ionic substances and their thickening mechanism activation is pH independent.

［式中、Ｒ^１はＣ_６〜Ｃ_２０アルキル、Ｃ_６〜Ｃ_２０アルケニル、Ｃ_５〜Ｃ_８シクロアルキル、フェニル、フェニル（Ｃ_１〜Ｃ_１２アルキル）または（Ｃ_１〜Ｃ_１２アルキル）フェニルであり、Ｒ^２は水素、メチルまたはフェニルであり、Ｒ^３およびＲ^４はそれぞれＨまたはＣ_１〜Ｃ_４アルキルであり、Ｘはハロゲン、Ｃ_１〜Ｃ_４アルコキシスルホニルオキシまたはＣ_１〜Ｃ_４アルカンスルホネートであり、ここで、Ｃ_１〜Ｃ_４アルカンスルホネートはまた、ベタイン構造の形成を伴ってＲ^３またはＲ^４として存在することもでき、ＹはＯまたはＮＨであり、ＡはＣ_１〜Ｃ_６アルキレンである］
で示されるオレフィン性不飽和第四級アンモニウム化合物またはそのようなアンモニウム化合物の混合物、Ｃ）０〜４９．９９重量％の式ＩＩＩ：

［式中、Ｒ^１、Ｒ^２およびＹは先に記載した意味を有し、Ｒ^５は水素、メチルまたはエチルであり、ｎは０〜２５の数である］
で示されるアクリレートまたはメタクリレート、Ｄ）０〜２９．８５重量％の別の共重合性モノマーおよびＥ）０．５〜２重量％の架橋剤としての、分子中に少なくとも２個のオレイン性不飽和基を有する化合物の１種以上とのラジカル重合により得ることができるコポリマーを記載している。 WO 93/22358 (BASF) is, A) of 50 to 99.99 wt%, olefinically unsaturated _C 3 -C ₅ monocarboxylic acid, olefinically unsaturated _C 4 -C ₈ dicarboxylic acids, their anhydrides, Or a mixture of such carboxylic acids or anhydrides and B) 0.1 to 29.95% by weight of formula I or II:

[Wherein R ¹ is C ₆ -C ₂₀ alkyl, C ₆ -C ₂₀ alkenyl, C ₅ -C ₈ cycloalkyl, phenyl, phenyl (C ₁ -C ₁₂ alkyl) or (C ₁ -C ₁₂ alkyl) phenyl. R ² is hydrogen, methyl or phenyl, R ³ and R ⁴ are each H or C ₁ -C ₄ alkyl, X is halogen, C ₁ -C ₄ alkoxysulfonyloxy or C ₁ -C ₄ An alkane sulfonate, wherein a C ₁ -C ₄ alkane sulfonate can also be present as R ³ or R ⁴ with the formation of a betaine structure, Y is O or NH, and A is C _1- C ₆ alkylene]
An olefinically unsaturated quaternary ammonium compound of the formula or a mixture of such ammonium compounds, C) 0 to 49.99% by weight of formula III:

[Wherein R ¹ , R ² and Y have the meanings described above, R ⁵ is hydrogen, methyl or ethyl, and n is a number from 0 to 25]
At least two oleic unsaturations in the molecule as D) 0-29.85% by weight of another copolymerizable monomer and E) 0.5-2% by weight of crosslinker Described are copolymers that can be obtained by radical polymerization with one or more of the group-containing compounds.

  WO 00/39176 (BF Goodrich) describes 0.05-20 mol% of an anionic monomer having at least one carboxy functional group, 10-45 mol% of a cationic monomer having at least one amino functional group, A hydrophilic amphoteric polymer formed by copolymerization of 35-95 mol% nonionic hydrophilic monomer, 0-10 mol% hydrophobic monomer and 0-1.5 mol% cross-linking monomer, about 50 ° C. Describes a polymer in which the monomers are selected such that a copolymer having a higher glass transition temperature is obtained and the cationic monomer and anionic monomer are present in a ratio of about 2:16.

［式中、Ｒ^１は水素またはＣ_１〜Ｃ_８アルキルであり、Ｘ^１はＯまたはＮＲ^２（ここで、Ｒ^２は水素、Ｃ_１〜Ｃ_８アルキルまたはＣ_５〜Ｃ_８シクロアルキルである）である］
で示されるα，β−エチレン性不飽和モノマー、ｂ）２５〜９０重量％の少なくとも１種のＮ−ビニルアミドおよび／またはＮ−ビニルラクタム、ｃ）０．５〜３０重量％の少なくとも１種の、ラジカル重合性α，β−エチレン性不飽和二重結合および一分子につき少なくとも１個のカチオン性有機基および／またはカチオン性基を有する化合物、ｄ）０〜３０重量％の少なくとも１種の式ＩＩ：

［式中、Ｒ^３は水素またはＣ_１〜Ｃ_８アルキルであり、Ｘ^２はＯまたはＮＲ^５（ここで、Ｒ^５は水素、Ｃ_１〜Ｃ_８アルキルまたはＣ_５〜Ｃ_８シクロアルキルである）であり、Ｒ^４は水素または直鎖Ｃ_１〜Ｃ_２２アルキル基である］
で示されるα，β−エチレン性不飽和モノマーを、組み込んだ状態で含んでなる水溶性または水分散性ポリマーおよびその塩の少なくとも１種を含んでなる化粧用組成物を記載している。 WO 01/62809 (BASF) a) 5 to 50% by weight of at least one formula I:

Wherein R ¹ is hydrogen or C ₁ -C ₈ alkyl and X ¹ is O or NR ² where R ² is hydrogen, C ₁ -C ₈ alkyl or C ₅ -C ₈ cycloalkyl. )]
B) 25-90% by weight of at least one N-vinyl amide and / or N-vinyl lactam, c) 0.5-30% by weight of at least one of the α, β-ethylenically unsaturated monomers represented by A compound having a radically polymerizable α, β-ethylenically unsaturated double bond and at least one cationic organic group and / or cationic group per molecule, d) 0 to 30% by weight of at least one formula II:

[Wherein R ³ is hydrogen or C ₁ -C ₈ alkyl, X ² is O or NR ⁵ (where R ⁵ is hydrogen, C ₁ -C ₈ alkyl or C ₅ -C ₈ cycloalkyl) And R ⁴ is hydrogen or a linear C ₁ -C ₂₂ alkyl group]
A cosmetic composition comprising at least one of a water-soluble or water-dispersible polymer and a salt thereof comprising an α, β-ethylenically unsaturated monomer represented by the formula:

  WO 03/053381 (BASF) describes at least one N-vinyl lactam, at least one anionic organic monomer and, optionally, in the presence of a polymer component having an ether group-containing or vinyl alcohol-derived repeating unit. A cosmetic composition comprising at least one water-soluble or water-dispersible copolymer obtained by radical copolymerization of further α, β-ethylenically unsaturated compounds which can be copolymerized is described.

［式中、基Ｒ^１〜Ｒ^３の１つは式：ＣＨ_２＝ＣＲ^４（ここで、Ｒ^４はＨまたはＣ_１〜Ｃ_４アルキルである）で示される基であり、それ以外の基Ｒ^１〜Ｒ^３は互いに独立してＨ、アルキル、シクロアルキル、ヘテロシクロアルキル、アリールまたはヘタリールであり、Ｒ^１およびＲ^２はそれらに結合しているアミド基と一緒に５〜８個の環原子を有するラクタムを形成していてもよく、Ｒ^２およびＲ^３はそれらに結合している窒素原子と一緒に五員〜七員複素環を形成していてもよく、ただし、基Ｒ^１、Ｒ^２およびＲ^３の炭素原子の和は最大８である］で示されるα，β−エチレン性不飽和アミド基含有化合物の少なくとも１種のラジカル共重合によって得ることができる両性コポリマーの少なくとも１種、または前記両性コポリマーの少なくとも１種を含んでなる高分子電解質錯体、およびそれらとは異なる少なくとも１種の更なる高分子電解質、並びにＢ）化粧用組成物に適したキャリヤーの少なくとも１種を含んでなる化粧用または医薬用組成物を記載している。 WO 2004/058837 (BASF) describes: A) a) a radically polymerizable α, β-ethylenically unsaturated double bond and at least one compound having at least one anionic organic group and / or an anionic group per molecule; 1) b) at least one compound having a radically polymerizable α, β-ethylenically unsaturated double bond and at least one cationic organic group and / or cationic group per molecule, c) formula:

[Wherein, ^{one of} the groups R ^{1 to} R ^{3 is} a group represented by the formula: CH ₂ ═CR ⁴ (wherein R ⁴ is H or C _{1 to} C ₄ alkyl), and other groups. R ^{1 to} R ³ are independently of each other H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, and R ¹ and R ² are 5 to 8 rings together with the amide group attached to them. May form a lactam having an atom, and R ² and R ³ may form a 5-membered to 7-membered heterocyclic ring together with the nitrogen atom bonded to them, provided that the group R ¹ , The sum of the carbon atoms of R ² and R ³ is at most 8.] At least one amphoteric copolymer obtainable by radical copolymerization of an α, β-ethylenically unsaturated amide group-containing compound represented by Or the bisexual copo Cosmetics comprising a polyelectrolyte complex comprising at least one of the mer, and at least one further polyelectrolyte different therefrom, and B) at least one carrier suitable for the cosmetic composition Or a pharmaceutical composition is described.

  WO 2006/044193 (ISP) and US 2007/0231286 A1 (ISP) are rheology modifiers / hairstyling resins that are cross-linked linear poly (vinylamide / polymerizable carboxylic acid) copolymers and their use in colored cosmetic compositions Is described.

  WO 2007/010035 A1 (BASF) is at least one of a1) a compound having a radically polymerizable α, β-ethylenically unsaturated double bond and at least one anionic organic group and / or an anionic group per molecule. Species, a2) radically polymerizable α, β-ethylenically unsaturated double bonds and at least one cationic organic group and / or compound having a cationic group per molecule, b) at least one molecule At least one of radically polymerizable crosslinking compounds having two α, β-ethylenically unsaturated double bonds, c) optionally a polyether group and / or a radically polymerizable olefinically unsaturated double bond An anionic group obtainable by radical copolymerization in the presence of at least one silicone compound having It describes the use of cationic and amphoteric copolymers as rheology modifiers for the composition in the hair cosmetics.

［式中、ＲおよびＲ_２はそれぞれ水素またはメチルであり、ｘは５〜８０の正の整数であり、ｙは０〜２０の整数であり、Ｒ_１はＣ_１〜２０アルキル、またはアルキル基が１〜２０個の炭素原子を有するアルキルフェニルである］
で示されるエステルを含んでなる増粘剤ポリマーを記載している。 US 4,230,844 (DuPont) has (i) about 1 to 99% by weight of at least one C ₃ -C ₆ unsaturated carboxylic acid, and (ii) about 1 to 99% by weight of at least one kind of formula:

[Wherein, R and R ₂ are each hydrogen or methyl, x is a positive integer of 5 to 80, y is an integer of 0 _{to 20} , and R ₁ is a C _1-20 alkyl or alkyl group] Is alkylphenyl having 1 to 20 carbon atoms]
A thickener polymer comprising an ester of the formula is described.

［式中、ＲおよびＲ_２はそれぞれ水素またはメチルであり、ｘは５〜８０の正の整数であり、ｙは０〜２０の整数であり、Ｒ_１はＣ_１〜２０アルキル、またはアルキル基が１〜２０個の炭素原子を有するアルキルフェニルである］
で示されるエステルから本質的になり、（ａ）〜（ｃ）の和が１００％となる増粘剤を記載している。 US 4,138,381 (DuPont) is a thickener comprising a polymer dissolved in a solvent at a concentration of up to 50% by weight of the composition, the solvent being at least one glycol, in preparation Containing up to 50% by weight of water, based on the weight of glycol, and the polymer is (a) about 10-98% by weight of at least one C ₃ -C ₆ unsaturated carboxylic acid, (b) about 1-50 % By weight of at least one alkyl acrylate or alkyl methacrylate in which the alkyl group has 1 to 30 carbon atoms, and (c) about 1 to 85% by weight of at least one formula:

[Wherein, R and R ₂ are each hydrogen or methyl, x is a positive integer of 5 to 80, y is an integer of 0 _{to 20} , and R ₁ is a C _1-20 alkyl or alkyl group] Is alkylphenyl having 1 to 20 carbon atoms]
It describes a thickener consisting essentially of an ester represented by the formula (a) to (c) with a sum of 100%.

US 5,015,708 describes polymerization initiators in solvents of aliphatic hydrocarbons (especially branched or unbranched, C _{3 to} C ₁₀ saturated hydrocarbons which are cyclic or acyclic, preferably heptane or cyclohexane). Polymerizing a reaction mixture of vinyl lactam (eg vinyl pyrrolidone or vinyl caprolactam), polymerizable carboxylic acid (eg acrylic acid or methacrylic acid) and hydrophobic monomer (eg lauryl methacrylate) in a predetermined composition range in the presence of The uncrosslinked precipitated terpolymer produced is described. The terpolymer is obtained as a white powder in high yield and can be easily filtered and dried.

US 6,025,431 is, (a) from about 5 to about 80 wt%, _C 1 -C ₆ alkyl esters and _C 1 -C ₆ acrylate selected from the group consisting of alkyl esters of methacrylic acid, acrylic acid monomer, (b) from about 5 to about 80 wt%, vinyl-substituted heterocyclic compound containing at least one nitrogen atom or sulfur atom, (meth) acrylamide, mono- or di _(C 1 -C ₄₎ alkylamino ( A monomer selected from the group consisting of C ₁ -C ₄ ) alkyl (meth) acrylate, and mono- or di (C ₁ -C ₄ ) alkylamino (C ₁ -C ₄ ) alkyl (meth) acrylamide, (c) 0 Up to about 30% by weight associative monomer, where all weight percentages are the total of monomers used to produce the polymer rheology modifier. It describes polymeric rheology modifier prepared by polymerization of based on the amount) (PRM), and cosmetic compositions suitable active substances (CAA).

［式中、ＲはＨまたは−ＣＨ_３であり、ｎは１〜４であり、Ｒ^１およびＲ^２はＣ_１〜４アルキルである］
で示されるエステル、または前記モノマーの混合物、および（ｂ）２０〜９８重量％の、式：

［式中、Ｒ^３はＣ_１〜２０アルキルであり、Ｒ^４はＨまたは−ＣＨ_３であり、Ｒ^５はＨであり、ｎは２〜１００であり、ｍは０〜５０である］
で示される重合性エチレン性不飽和化合物
を含んでなる水溶性コポリマーを記載している。 EP 3235 A1 (BASF) is, (a) of 80-2% by weight, ethylenically unsaturated _C 3 -C ₅ carboxylic acids, acrylamide dimethyl propane sulfonic acid, vinyl sulfonic acid or vinyl phosphonic acid, wherein:

[Wherein R is H or —CH ₃ , n is 1 to 4, and R ¹ and R ² are C _1-4 alkyl]
Or a mixture of said monomers, and (b) 20-98% by weight of the formula:

[Wherein R ³ is C _1-20 alkyl, R ⁴ is H or —CH ₃ , R ⁵ is H, n is 2 to 100, and m is 0 to 50]
A water-soluble copolymer comprising a polymerizable ethylenically unsaturated compound of the formula is described.

EP 11806 A1 (Dow Chemical) is (A) 15-60 to obtain an emulsion copolymer that is stable as an aqueous colloidal dispersion at an acidic pH below about 5.0, but is responsive to pH adjustment with a base. % By weight of a C _{3 to} C ₈ α, β-ethylenically unsaturated carboxylic acid monomer (preferably acrylic acid or methacrylic acid), or a mixture thereof with itaconic acid or fumaric acid, (B) 15-80% by weight A nonionic copolymerizable C ₂ -C ₁₂ α, β-ethylenically unsaturated monomer (preferably a monovinyl ester such as ethyl acrylate) or a mixture thereof with styrene, acrylonitrile, vinyl chloride or vinyl acetate, (C) 1 to 30% by weight of a specific nonionic vinyl surfactant (eg nonylphenoxypoly (ethylene) It describes an aqueous liquid emulsion polymer prepared by copolymerization of oxy) ₉ ethyl acrylate). Emulsion polymers adjusted to a pH of 5.5 to 10.5 or higher are useful as thickeners for aqueous systems including cosmetics, drilling mud, and aqueous coating compositions, particularly latex paints.

［式中、ＲはＨまたはＣＨ_３であり、ｎは少なくとも２であり、Ｒ^ｏはＣ_８〜Ｃ_３０アルキル、アルキルアリールまたは多環式アルキルである］
で示されるモノマー、（３）少なくとも３０重量％の少なくとも１種のＣ_１〜Ｃ_４アルキルアクリレートおよび／またはメタクリレート、および（４）０〜０．１重量％のポリエチレン製不飽和モノマーを、（１）、（２）、（３）および（４）の和が１００％となるように含有するコポリマーを記載している。 EP 13836 (Rohm & Haas) is (1) 20-69.5 wt.% Acrylic and / or methacrylic acid, (2) 0.5-25 wt.% Formula:

[Wherein R is H or CH ₃ , n is at least 2 and R ^o is C _{8 to} C ₃₀ alkyl, alkylaryl or polycyclic alkyl]
(3) at least 30% by weight of at least one C ₁ -C ₄ alkyl acrylate and / or methacrylate, and (4) 0 to 0.1% by weight of an unsaturated monomer made of polyethylene (1 ), (2), (3) and (4) are described as copolymers containing 100%.

EP 1690878 A1 (Rohm & Haas) is, (a) 25 to 45% of the carboxylic acid monomer residues, (b) 50-65% of _C 2 -C ₄ alkyl (meth) acrylate residues, (c). 2 to 20% of (i) alkyl (meth) acrylate, (ii) vinyl alkanoate, (iii) N-vinyl alkylamide and (iv) N-alkyl (meth) acrylamide at least one residue (6-18) And (d) from 0.01 to 2% of a residue of at least one crosslinker.

  WO 2003/061615 (Noveon) describes (a) at least one acidic vinyl monomer or salt thereof, (b) at least one nonionic vinyl monomer, (c) a first association having a first hydrophobic end group. (D) at least one monomer selected from the group consisting of a second associative monomer having a second hydrophobic end group, a semi-hydrophobic monomer, and combinations thereof, and optionally (e) a crosslinking monomer, A rheology-modified hairset, a polymer of a monomer mixture comprising a monomer selected from the group consisting of chain transfer agents and combinations thereof, in an effective amount for the hairset, an alkali-swellable and / or alkali-soluble associative polymer A hair set aqueous composition comprising: monomer (d) selected only from second associative monomers The first and second hydrophobic end groups of the associative monomers (c) and (d) are each independently selected from the same or different hydrocarbon species, and the first and second hydrophobic end groups are When selected from the same hydrocarbon species, a composition is described in which at least 8 carbon atoms in the molecular formula of the hydrophobic end group are different.

  Anionic associative rheology modified polymers are commercially available, examples of which are Aculyn® 22 (INCI: acrylate / steareth-20 methacrylate copolymer; esters of methacrylic acid and steareth-20, acrylic acid, methacrylic acid Or copolymers with one or more of the monomers which are one of their simple esters), Aculyn® 28 (INCI: acrylate / Beheneth-25 methacrylate copolymer; esters of methacrylic acid and Behenes-25 and acrylic acid , Copolymers with one or more of the monomers that are one of methacrylic acid or one of their simple esters), Aculyn® 88 (INCI: acrylate / steareth-20 methacrylate cross-linked polymer; allyl ether of pentaerythritol or trimethylol Copolymer of steareth-20 methacrylate and one or more monomers that are one of acrylic acid, methacrylic acid or one of their simple esters, cross-linked with lopan allyl ether, and Tinovis® GTC (INCI: acrylate) / Beheneth-25 methacrylate copolymer).

WO 93/22358 WO 00/39176 WO 01/62809 WO 03/053381 WO 2004/058837 WO 2006/044193 US 2007/0231286 A1 WO 2007/010035 A1 US 4,230,844 US 4,138,381 US 5,015,708 US 6,025,431 EP 3235 A1 EP 11806 A1 EP 13836 EP 1690878 A1 WO 2003/061615

  There are many polymer thickeners already known and commercially available for cosmetic compositions, but can be easily incorporated into cosmetic compositions, while at the same time pH in the range of 5-9, preferably 6-8. There is still a need for thickeners that can rapidly thicken in value and have good film-forming and hair-setting properties. Furthermore, the long-term stability of such cosmetic compositions in combination with the acceptance of comparable high salt content is a property sought for current polymer thickeners. Other required properties include the ability to produce transparent gels, stabilization properties for particles, emulsions and foams, stability over a wide pH range, peroxide compatibility, shear stress, low temperature processability , And broad compatibility with other ingredients.

［式中、アルキレンオキシド単位は順不同であり、ｋおよびｌは互いに独立して０〜１０００の整数であり、ｋとｌの和は少なくとも５であり、Ｒ^８は水素またはＣ_１〜Ｃ_４アルキル、好ましくはメチルであり、Ｒ^９はＣ_８〜Ｃ_３０アルキル、Ｃ_８〜Ｃ_３０アルケニルまたはＣ_８〜Ｃ_３０アルキルアリールであり、ＸはＯまたは式：ＮＲ^１０（ここで、Ｒ^１０はＨ、アルキル、アルケニル、シクロアルキル、ヘテロシクロアルキル、アリールまたはヘタリールである）で示される基である］、
ｅ）０．０１〜２重量％の少なくとも１種の架橋剤、
ｆ）０．２〜５重量％の少なくとも１種の、式（Ｉ）：

［式中、＃は、ラジカル重合性α，β−エチレン性不飽和二重結合を有する基との結合部位であり、Ｒ^ａはＨまたはＣ_１〜Ｃ_４アルキルであり、Ｒ^ｂはＨまたはＣ_１〜Ｃ_４アルキルでり、即ちＲ^ａおよびＲ^ｂは共に（ＣＨ_２）_１〜４であり、Ｒ^ｃはＨまたはＣ_１〜Ｃ_３０アルキルである］
で示される基を有する更なるモノマー、
ｇ）０〜３０重量％の、ａ）〜ｆ）とは異なる更なるモノマー
を、ａ）〜ｇ）の合計が１００重量％となるように含んでなるポリマー
によって解決されることが見出された。 Surprisingly, these challenges are as polymerized units:
a) 25-85% by weight acrylic acid,
b) 10-60% by weight of N-vinylpyrrolidone,
c) 0.5 to 10% by weight of at least one cationic monomer,
d) 1 to 6% by weight of at least one compound d1) or d2):

Wherein the alkylene oxide units are in no particular order, k and l are each independently an integer from 0 to 1000, the sum of k and l is at least 5, and R ⁸ is hydrogen or C ₁ -C ₄ alkyl , Preferably methyl, and R ⁹ is C ₈ -C ₃₀ alkyl, C ₈ -C ₃₀ alkenyl or C ₈ -C ₃₀ alkylaryl, X is O or the formula: NR ¹⁰ (where R ¹⁰ is H , Alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl)]
e) 0.01-2% by weight of at least one crosslinking agent,
f) 0.2-5% by weight of at least one formula (I):

[Wherein # is a bonding site with a radically polymerizable α, β-ethylenically unsaturated double bond group, R ^a is H or C ₁ -C ₄ alkyl, and R ^b is H or C ₁ -C ₄ alkyl, ie, R ^a and R ^b are both (CH ₂ ) _1-4 and R ^c is H or C ₁ -C ₃₀ alkyl]
A further monomer having a group represented by
It has been found that this is solved by a polymer comprising g) 0-30% by weight of additional monomers different from a) -f) such that the sum of a) -g) is 100% by weight. It was.

In the present invention, the term “alkyl” includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are, for example, linear or branched C ₁ -C ₇ alkyl groups, preferably C ₁ -C ₆ alkyl groups, particularly preferably C ₁ -C ₄ alkyl groups. These are, among others, methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2- Trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl Include 3-heptyl, 2-ethylpentyl, 1-propyl butyl, octyl.

Suitable long chain _C 8 _{-C 30} alkyl groups and _C 8 _{-C 30} alkenyl groups are straight-chain and branched alkyl and alkenyl groups. Preferred in the present invention are predominantly linear alkyls such as are present in natural or synthetic fatty acids and fatty alcohols and also in oxo alcohols, which may optionally be additionally mono-, di- or polyunsaturated. It is a group. These include, for example, n-hexyl (ene), n-heptyl (ene), n-octyl (ene), n-nonyl (ene), n-decyl (ene), n-undecyl (ene), n-dodecyl ( Ene), n-tridecyl (ene), n-tetradecyl (ene), n-pentadecyl (ene), n-hexadecyl (ene), n-heptadecyl (ene), n-octadecyl (ene), n-nonadecyl (ene) ), Arakinyl (ene), behenyl (ene), lignocerinyl (ene), melicinyl (ene).

Cycloalkyl is preferably a _C 5 -C ₈ cycloalkyl, e.g., cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

  Aryl includes unsubstituted and substituted aryl groups, preferably phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, in particular phenyl, tolyl, xylyl or mesityl.

  In the following, a compound derived from acrylic acid and methacrylic acid is often referred to as an abbreviation with “(meth)” added to the compound derived from acrylic acid.

Monomer a): Acrylic acid In one embodiment of the invention, the polymer comprises 25-85% by weight of acrylic acid as polymerized units.
In another aspect of the invention, the polymer comprises 40-60% by weight acrylic acid as polymerized units.
In a preferred embodiment of the invention, the polymer comprises 65-75% by weight acrylic acid as polymerized units.

Monomer b): N-vinyl pyrrolidone In one embodiment of the invention, the polymer comprises 10 to 60% by weight of N-vinyl pyrrolidone as polymerized units.
In another aspect of the invention, the polymer comprises 20-50% by weight N-vinyl pyrrolidone as polymerized units.
In yet another embodiment of the present invention, the polymer comprises 10-25% by weight N-vinyl pyrrolidone as polymerized units.

Monomer c): Cationic monomer The polymer according to the invention comprises 0.3 to 10% by weight of at least one cationic monomer as polymerized units.
In the present invention, the term “cationic monomer” means a group (preferably an amine group) that can be cationically charged by either a monomer having a cationic charge, or protonation using an acid or quaternization using an alkylating agent. Means a monomer having In other words, the term “cationic monomer” can be used to indicate a cationically charged monomer and a monomer that can be cationically charged.

In one aspect of the invention, monomer c) is
1) Esters of α, β-ethylenically unsaturated monocarboxylic acids and dicarboxylic acids with amino alcohols,
2) Amides of α, β-ethylenically unsaturated monocarboxylic acids and dicarboxylic acids with diamines having at least one primary or secondary amino group,
3) N, N-diallylamine, N, N-diallyl-N-alkylamine and derivatives thereof,
4) vinyl-substituted and allyl-substituted nitrogen heterocyclic compounds,
5) comprising at least one compound selected from vinyl-substituted and allyl-substituted heterocyclic aromatic compounds, and 6) mixtures thereof.
In all of the monomers, suitable amine nitrogens may be monoalkylated or dialkylated.

  In one embodiment of the invention, preferred monomers c) are N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N , N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate. In one embodiment of the invention, N, N-dimethylaminoethyl (meth) acrylate is preferred.

In another aspect of the present invention, preferred monomer c) is N- [tert-butylaminoethyl] (meth) acrylamide, N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino). Ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (Dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide and N- [4- (dimethylamino) cyclohexyl] methacrylamide.
In one aspect of the invention, N- [3- (dimethylamino) propyl] methacrylamide (DMAPMAM) is preferred.
A particular embodiment relates to a polymer comprising N- [3- (dimethylamino) propyl] (meth) acrylamide as monomer c). In another aspect, monomer c) consists of N- [3- (dimethylamino) propyl] (meth) acrylamide.

  In another aspect of the invention, preferred monomers c) are N, N-diallylamine and N, N-diallyl-N-alkylamine.

  In another aspect of the invention, preferred monomers c) are vinyl-substituted and allyl-substituted nitrogen heterocyclic compounds different from vinyl imidazoles, such as 2-vinyl pyridine, 4-vinyl pyridine, 2-allyl pyridine and 4-allyl pyridine. It is.

［式中、Ｒ^５〜Ｒ^７は互いに独立して水素、Ｃ_１〜Ｃ_４アルキルまたはフェニルである］
で示される少なくとも１種のＮ−ビニルイミダゾール化合物を含んでなる。 In a preferred embodiment of the invention, the monomer c) is represented by the general formula (II) as the cationic monomer c):

[Wherein R ^{5 to} R ⁷ are each independently hydrogen, C _{1 to} C ₄ alkyl or phenyl]
At least one N-vinylimidazole compound represented by the formula:

Examples of compounds c) represented by general formula (II) are shown in Table 1 below.

  In a preferred embodiment of the invention, monomer c) is selected from N-vinylimidazole and N-vinylimidazole containing mixtures.

  A particularly preferred embodiment of the invention relates to a polymer in which monomer c) is N-vinylimidazole.

In one embodiment of the invention, the polymer comprises 0.3 to 5% by weight of at least one cationic monomer c) as polymerized units.
In another embodiment of the invention, the polymer comprises 0.5 to 3% by weight of at least one cationic monomer c) as polymerized units.
In yet another embodiment of the invention, the polymer comprises 0.5 to 2% by weight of at least one cationic monomer c) as polymerized units.

  In one embodiment of the invention, the molar ratio of acrylic acid a) to monomer c) is at least 10: 1. In another aspect of the invention, the molar ratio of acrylic acid a) to monomer c) is at least 20: 1. In yet another aspect of the invention, the molar ratio of monomer a) to monomer c) is at least 30: 1. In yet another aspect of the invention, the molar ratio of monomer a) to monomer c) is at least 40: 1.

In one embodiment of the invention, the molar ratio of monomer a) to monomer c) is at most 120: 1. In another aspect of the invention, the molar ratio of monomer a) to monomer c) is up to 100: 1.
In another aspect of the invention, the molar ratio of monomer a) to monomer c) is up to 50: 1.

  In a preferred embodiment of the invention, the molar ratio of monomer a) to monomer c) is in the range of 30: 1 to 120: 1, more preferably in the range of 40: 1 to 100: 1. In another aspect of the invention, the molar ratio of monomer a) to monomer c) ranges from 40: 1 to 50: 1.

Preferably, the cationic organic group and / or the cationic group of monomer c) is a nitrogen-containing machine, such as primary, secondary and tertiary amino groups, quaternary ammonium groups. The nitrogen-containing group is preferably a tertiary amino group or a quaternary ammonium group. Charged cationic groups can be generated from amine nitrogens either by protonation with acids or quaternization with alkylating agents. Acids include, for example, carboxylic acids such as lactic acid, or inorganic acids such as phosphoric acid, sulfuric acid and hydrochloric acid. Alkylating agents, for example, C ₁ -C ₄ alkyl halide or sulfate, for example, ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. Protonation or quaternization is preferably carried out after polymerization.

In one embodiment of the invention, monomer c) is copolymerized in a substantially non-quaternized state and remains in a non-quaternized state after polymerization.
In another aspect of the invention, monomer c) is copolymerized in a substantially non-quaternized state and is at least partially quaternized after polymerization.
In yet another embodiment of the present invention, monomer c) is copolymerized in a substantially quaternized state and is fully quaternized after polymerization.

The “substantially unquaternized state” of monomer c) means at least 90 mol%, preferably at least 95 mol%, more preferably at least 99 mol%, even more preferably at least 99.9 mol% of monomer. c) means not quaternized until after polymerization.
The term “post-polymerization” refers to a maximum of 1%, preferably a maximum of 0.1%, more preferably a maximum of 0.01%, even more preferably a maximum of 0.001% of the total monomer initially polymerizable. Is still polymerizable, i.e., still has monoethylenic unsaturation.

  For various experimental reasons, monomers c that are already cationic (ie protonated or quaternized) before or during polymerization, without intentionally carrying out protonation / quaternization. ) May always be present in small amounts.

式中、アルキレンオキシド単位は順不同であり、ｋおよびｌは互いに独立して０〜１０００の整数であり、ｋとｌの和は少なくとも５であり、Ｒ^８は水素またはＣ_１〜Ｃ_４アルキル、好ましくはメチルであり、Ｒ^９はＣ_８〜Ｃ_３０アルキル、Ｃ_８〜Ｃ_３０アルケニルまたはＣ_８〜Ｃ_３０アルキルアリールであり、ＸはＯまたは式：ＮＲ^１０（ここで、Ｒ^１０はＨ、アルキル、アルケニル、シクロアルキル、ヘテロシクロアルキル、アリールまたはヘタリールである）で示される基である。 Monomer d)
The polymer according to the invention comprises 1 to 6% by weight of at least one compound d1) or d2) as polymerized units.
In a preferred embodiment of the invention, the polymer comprises 2 to 4% by weight of at least one compound d1) or d2) as polymerized units.

Wherein the alkylene oxide units are in any order, k and l are each independently an integer from 0 to 1000, the sum of k and l is at least 5, R ⁸ is hydrogen or C ₁ -C ₄ alkyl, Preferably it is methyl, R ⁹ is C ₈ -C ₃₀ alkyl, C ₈ -C ₃₀ alkenyl or C ₈ -C ₃₀ alkylaryl, X is O or the formula: NR ¹⁰ (where R ¹⁰ is H, Alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl).

In one preferred embodiment of the invention, R ⁸ is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, particularly preferably hydrogen. , Methyl or ethyl. Most preferably R ⁸ is methyl.

  In one preferred embodiment of the invention, k is an integer in the range 1 to 500, in particular 3 to 250, and l is an integer in the range 0 to 100.

In one preferred embodiment of the invention, R ⁹ of monomers d1) and d2) is n-octyl, 1,1,3,3-tetramethylbutyl, ethylhexyl, n-nonyl, n-decyl, n-undecyl, It is selected from tridecyl, myristyl, pentadecyl, palmityl, heptadecyl, octadecyl, nonadecyl, arakinyl, behenyl, lignoselenyl, serotinyl, melinyl, palmitoleinyl, oleyl, linolyl, linolenyl, stearyl, lauryl.
In a particularly preferred embodiment of the invention, R ⁹ of monomers d1) and d2) is selected from palmityl, heptadecyl, octadecyl, nonadecyl, arakinyl, behenyl, and mixtures of two or three thereof.
In another preferred embodiment of the invention, R ⁹ of monomers d1) and d2) is selected from two and three mixtures of even numbered alkyl residues (eg C ₁₆ , C ₁₈ , C ₂₀ and C ₂₂ ). The

  X in formula d1) is preferably O or NH.

Suitable polyether (meth) acrylates d1) are, for example, condensation products of (meth) acrylic acid and polyetherol. Suitable polyetherols can be readily prepared by reaction of ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with starter alcohol R ⁹ —OH. The alkylene oxides can be used alone, alternately or as a mixture. The polyether (meth) acrylate d1) can be used by itself or in a mixture for preparing the polymers according to the invention.

In one embodiment of the invention, the polymer comprises as polymerized units at least one compound d1) selected from polyether (meth) acrylates terminated with C ₈ -C ₂₂ alkyl groups.

Preferred monomers d1) of the present invention are esters of methacrylic acid and ethoxylated C ₁₆ -C ₁₈ alkyl alcohols having a degree of ethoxylation (k in formula d1) of 10 to 40, preferably 20 to 30.
In one embodiment of the invention, monomer d1) is supplied as a mixture with methyl methacrylate and / or methacrylic acid.
In one preferred embodiment of the present invention, commercially available C ₁₈ -PEG 1100 MA (Plex® 6877-O, CAS number: 70879-51-5 (APG 1100 MA), manufacturer: Evonik) is at least 1 Select as seed monomer d1).

［式中、Ｒ^８は水素またはメチルであり、ｋは５〜８０、好ましくは１０〜５０の正の整数であり、Ｒ^９はＣ_８〜１５アルキル、またはアルキル基が８〜２０個の炭素原子を有するアルキルフェニル、好ましくは

（ここで、Ｒ^１０はＣ_８〜２０アルキルである）である］
で示される。 In another aspect of the present invention, monomer d1) may be prepared using the alcohol and acid described in column 3, lines 36-75, as described in US 3,708,445. it can.
This particular monomer d1) has the formula:

[Wherein R ⁸ is hydrogen or methyl, k is a positive integer of 5 to 80, preferably 10 to 50, and R ⁹ is C _{8 to 15} alkyl, or an alkyl group having ₈ to 20 carbons. Alkylphenyl having an atom, preferably

(Where R ¹⁰ is C _8-20 alkyl)]
Indicated by

Suitable allyl alcohol alkoxylates d2) are, for example, the etherification products of allyl chloride with the corresponding polyetherols. Suitable polyetherols can be readily prepared by reaction of ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with water or starter alcohol R ⁹ —OH. The alkylene oxides can be used alone, alternately or as a mixture. The allyl alcohol alkoxylate d2) can be used by itself or in a mixture for preparing the polymers of the invention.

Monomer e)
The polymer according to the invention comprises 0.01 to 2% by weight of at least one crosslinking agent e) in the copolymerized state. Preferred crosslinking agents are compounds having at least two polymerizable ethylenically unsaturated nonconjugated double bonds.

  Suitable crosslinking agents e) are, for example, (meth) acrylic acid esters, allyl ethers or vinyl ethers of at least dihydric alcohols. In the present invention, the OH group of the parent alcohol may be completely or partially etherified or esterified. However, the crosslinking agent has at least two ethylenically unsaturated groups.

  Examples of parent alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3 -Butanediol, 1,4-butanediol, but-2-ene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentyl glycol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-biphenyl (Hydroxymethyl) cyclohexane, hydroxypivalic acid neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane, diethylene glycol, triethylene Glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thiopentane-1,5-diol, and in each case polyethylene glycol, polypropylene glycol and polytetrahydrofuran having a molecular weight of 200-10000 is there. Besides homopolymers of ethylene oxide and propylene oxide, block copolymers of ethylene oxide or propylene oxide, or copolymers having incorporated ethylene oxide groups and propylene oxide groups can also be used. Examples of parent alcohols having 3 or more OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, triethoxycyanuric acid, sorbitan, sugar, For example, sucrose, glucose and mannose. Polyhydric alcohols can also be used as the corresponding ethoxylates or propoxylates after reaction with ethylene oxide or propylene oxide. Polyhydric alcohols can also be first converted to the corresponding glycidyl ether by reaction with epichlorohydrin. Ethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate are preferred.

Another suitable crosslinker e) is a vinyl ester or a monounsaturated alcohol and an ethylenically unsaturated C ₃ -C ₆ carboxylic acid (eg acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid) and Ester. Examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol, 10- Undecen-1-ol, cinnamyl alcohol, citronellol, crotyl alcohol or cis-9-octadecen-1-ol. However, it is also possible to esterify monounsaturated alcohols using polybasic carboxylic acids (eg malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid).

  Another suitable crosslinker e) is an ester of an unsaturated carboxylic acid (for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid) and said polyhydric alcohol.

  Suitable crosslinking agents e) are also linear or branched, linear or cyclic, aliphatic or aromatic hydrocarbons having at least two double bonds, for example divinylbenzene, divinyltoluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane, or polybutadiene having a molecular weight of 200-20000. Double bonds must not be conjugated in the case of aliphatic hydrocarbons.

  Also suitable as crosslinkers e) are at least difunctional amines of acrylamide, methacrylamide and N-allylamine. Such amines are, for example, 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, Piperazine, diethylenetriamine or isophoronediamine. Likewise suitable are amides of allylamines with unsaturated carboxylic acids (for example acrylic acid, methacrylic acid, itaconic acid, maleic acid) or at least dibasic carboxylic acids as described above.

  In addition, triallylamine and triallyl monoalkylammonium salts, such as triallylmethylammonium chloride or methyl sulfate, are also suitable as crosslinking agents e).

  Urea derivatives, N-vinyl compounds of at least bifunctional amides, cyanurates or urethanes, such as urea, ethylene urea, propylene urea or N-vinyl compounds of tartaric diamide, such as N, N′-divinylethylene urea or N, N'-divinylpropylene urea is also suitable.

  Another suitable crosslinking agent e) is divinyldioxane, tetraallylsilane or tetravinylsilane.

  It is of course also possible to use mixtures of the compounds e).

  In one preferred embodiment of the invention, the crosslinking agent e) comprises at least one ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol triallyl ether, methylene bisacrylamide, N, N′— Divinylethylene urea, triallylamine and triallyl monoalkylammonium salts.

  In one preferred embodiment of the invention, the crosslinker e) is pentaerythritol triallyl ether (PETAE, CAS number: 1471-17-6) or comprises pentaerythritol triallyl ether.

［式中、＃は、ラジカル重合性α，β−エチレン性不飽和二重結合を有する基との結合部位であり、Ｒ^ａはＨまたはＣ_１〜Ｃ_４アルキルであり、Ｒ^ｂはＨまたはＣ_１〜Ｃ_４アルキルであり、即ちＲ^ａおよびＲ^ｂは共に（ＣＨ_２）_１〜４であり、Ｒ^ｃはＨまたはＣ_１〜Ｃ_３０アルキルである］
で示される基を有する更なるモノマーを含んでなる。 Monomer f)
The polymer of the present invention has, as polymerized units, 0.2 to 5% by weight of at least one formula (I):

[Wherein # is a bonding site with a radically polymerizable α, β-ethylenically unsaturated double bond group, R ^a is H or C ₁ -C ₄ alkyl, and R ^b is H or C ₁ -C ₄ alkyl, ie, R ^a and R ^b are both (CH ₂ ) _1-4 and R ^c is H or C ₁ -C ₃₀ alkyl]
And further monomers having the group represented by

［式中、Ｒ^１はＨまたはＣＨ_３であり、Ｒ、Ｒ’は互いに独立してＨまたは有機基であるか、或いは互いに結合していてもよく、ＧはＯまたはＮＨである］
で示される化合物から選択される。 Preferably, the at least one monomer f) has the general formula (Ia):

[Wherein R ¹ is H or CH ₃ , R and R ′ are each independently H or an organic group, or may be bonded to each other, and G is O or NH]
Is selected from the compounds represented by:

であるか、２−（２−オキソ−１−イミダゾリジニル）エチルメタクリレートを含んでなる。 In one particularly preferred embodiment of the invention, the monomer f) is 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate (CAS number: 86261-90-7), also known as ureido methacrylate (UMA):

Or comprises 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate.

  In one embodiment of the invention, the polymer is a by-product of the synthesis of ureido methacrylate, as described in DE 4301673 (herein incorporated by reference), in particular hydroxyethylethyleneurea (CAS number: 3699). -54-5) and a structural unit derived from N- (methacryloyloxyethyl) -N ′-(methacryloyl) ethyleneurea (CAS number: 157312-17-9).

  A preferred polymer of the present invention comprises 0.5-2% by weight of 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate (ureido methacrylate, UMA) as polymerized units.

Monomer g)
The polymers according to the invention comprise, as polymerized units, 0 to 30% by weight of further monomers g) different from a) to f). In one embodiment of the invention, the polymer comprises 1-20% by weight of such further monomers g) as polymerized units. In another embodiment of the invention, the polymer comprises 1 to 10% by weight of further monomers g) as polymerized units.

  In one embodiment of the invention, the at least one monomer g) is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, methyl ethacrylate, ethyl eth Acrylate, n-propyl ethacrylate, isopropyl ethacrylate, n-butyl ethacrylate, tert-butyl ethacrylate, isobutyl ethacrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, 2-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, isopentyl acrylate, neopentyl acrylate, n-octyl (meth) acrylate, 1,1, 3 3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) Acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, arakinyl (meth) acrylate, behenyl (meth) acrylate, lignoselenyl (meth) acrylate, serotinyl (meth) acrylate, Melicinyl (meth) acrylate, palmitoleinyl (meth) acrylate, oleyl (meth) acrylate, linoleyl (meth) acrylate, linolenyl (meth) acrylate , Stearyl (meth) acrylate, lauryl (meth) acrylate, phenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, cyclohexyl (meth) acrylate, ureido (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and mixtures thereof Selected from the group.

One preferred embodiment of the present invention is as described above, wherein at least one monomer g) is selected from esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₈ alkanols. A good polymer.

At least one monomer g) of preferably from _C 1 -C ₆ alkyl (meth) acrylate, more preferably from _C 1 -C ₄ alkyl (meth) acrylates, e.g., methyl (meth) acrylate, ethyl (meth) Acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, methyl ethacrylate, ethyl ethacrylate, n-propyl ethacrylate, isopropyl ethacrylate, n-butyl ethacrylate, tert-butyl ethacrylate It is selected from the group consisting of rate, isobutyl ethacrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate.

  In one preferred embodiment of the invention, the at least one monomer g) is methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate and Selected from the group consisting of those mixtures.

［式中、Ｒ^１は式：ＣＨ_２＝ＣＲ^４−（ここで、Ｒ^４はＨまたはＣ_１〜Ｃ_４アルキルである）で示され、Ｒ^２およびＲ^３は互いに独立してＨ、アルキル、シクロアルキル、ヘテロシクロアルキル、アリールまたはヘタリールであるか、またはＲ^２およびＲ^３はそれらに結合している窒素原子と一緒に五員〜八員窒素複素環を形成しているか、或いは
Ｒ^２は式：ＣＨ_２＝ＣＲ^４−で示され、Ｒ^１およびＲ^３は互いに独立してＨ、アルキル、シクロアルキル、ヘテロシクロアルキル、アリールまたはヘタリールであるか、またはＲ^１およびＲ^３はそれらに結合しているアミド基と一緒に５〜８個の環原子を有するラクタムを形成している］で示される化合物から選択され、モノマーａ）〜ｆ）のいずれとも異なる。 In another aspect of the invention, the at least one monomer g) has the general formula VI):

[Wherein R ¹ is represented by the formula: CH ₂ ═CR ⁴ — (wherein R ⁴ is H or C ₁ -C ₄ alkyl), and R ² and R ³ are independently of each other H, alkyl , Cycloalkyl, heterocycloalkyl, aryl or hetaryl, or R ² and R ³ together with the nitrogen atom bound to them form a 5- to 8-membered nitrogen heterocycle, or R ² Is represented by the formula: CH ₂ ═CR ⁴ — and R ¹ and R ³ are independently of each other H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or R ¹ and R ³ are A lactam having 5 to 8 ring atoms in combination with the amide group to which it is attached], and is different from any of the monomers a) to f).

In one embodiment of the invention, the preferred monomer g) is an N-vinyl lactam that is different from any of the monomers a) to f). Suitable monomers g) are unsubstituted N-vinyl lactams and, for example, one or more C ₁ -C ₆ alkyl substituents (eg methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert N-vinyl lactam derivatives, which may have -butyl and the like. These include, for example, N-vinyl piperidone, N-vinyl caprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N -Vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam and mixtures thereof.

  In one embodiment of the invention, the preferred monomer g) is N-vinylcaprolactam, N-vinylformamide, acrylamide, N, N-dimethylacrylamide or mixtures thereof.

  In another aspect of the invention, a suitable monomer g) is an amide of (meth) acrylic acid that is different from any of the monomers a) to f). Such amides include, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, Ni-propyl (meth) acrylamide, N -(N-butyl) (meth) acrylamide, N- (sec-butyl) (meth) acrylamide, N- (tert-butyl) (meth) acrylamide, N- (n-pentyl) (meth) acrylamide, N- ( n-hexyl) (meth) acrylamide, N- (n-heptyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (tert-octyl) (meth) acrylamide, N- (1, 1,3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylami N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth) acrylamide, N-tridecyl (meth) acrylamide, N-myristyl (meta) ) Acrylamide, N-pentadecyl (meth) acrylamide, N-palmityl (meth) acrylamide, N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-arakinyl (meth) acrylamide, N-behenyl (meth) acrylamide , N-lignoselenyl (meth) acrylamide, N-serotinyl (meth) acrylamide, N-mericinyl (meth) acrylamide, N-palmitreinyl (meth) acrylamide, N-oleyl (meth) acrylamide, N-linolyl (meth) acrylic Bromide, N- linolenyl (meth) acrylamide, N- stearyl (meth) acrylamide, N- lauryl (meth) acrylamide.

  In yet another aspect of the invention, suitable monomers g) are 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, 2-hydroxyethyl ethacrylamide, 2-hydroxypropyl acrylamide, 2-hydroxypropyl methacrylamide, 3-hydroxypropyl acrylamide, 3-hydroxypropyl methacrylamide, 3-hydroxybutyl acrylamide, 3-hydroxybutyl methacrylamide, 4-hydroxybutyl acrylamide, 4-hydroxybutyl methacrylamide, 6-hydroxyhexyl acrylamide, 6-hydroxyhexyl methacryl Amides, 3-hydroxy-2-ethylhexyl acrylamide and 3-hydroxy-2-ethylhexyl methacrylamide.

  In yet another aspect of the invention, the at least one monomer g) is vinyl acetate, vinyl propionate, vinyl butyrate, ethylene, propylene, isobutylene, butadiene, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, chloride. It is selected from vinyl, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.

In yet another embodiment of the invention, at least one monomer g) different from acrylic acid is a radically polymerizable α, β-ethylenically unsaturated double bond and at least one anionic organic group per molecule and And / or selected from monomers having an anionic group. Such monomers g) include monoethylenically unsaturated mono and dicarboxylic acids having 3 to 25, preferably 3 to 6 carbon atoms, which may be used as salts or anhydrides. . Examples thereof are methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid. Such monomers g) also include half-esters of monoethylenically unsaturated C _4-10 (preferably C _4-6 ) dicarboxylic acids (eg maleic acid), such as monomethyl maleate. Such monomers g) are monoethylenically unsaturated sulfonic acids and phosphonic acids such as vinyl sulfonic acid, allyl sulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3 -Also included are acrylicoxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid and allylphosphonic acid. Such monomers g) also include salts of said acids, in particular sodium, potassium and ammonium salts, and salts with amines. Such monomers g) may be used as such or as a mixture with one another. All these weight fractions relate to the acid form. In one embodiment of the invention, component g) is methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, Selected from aconitic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid and mixtures thereof.

  In one preferred embodiment of the invention, the at least one monomer g) is methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesacone. Selected from acids, glutaconic acid, aconitic acid and mixtures thereof.

In one embodiment of the invention, the at least one monomer g) is methyl methacrylate (MMA) or comprises methyl methacrylate.
In another aspect of the invention, the at least one monomer g) is methacrylic acid (MAA) or comprises methacrylic acid.
In yet another aspect of the present invention, the at least one monomer g) is or comprises a mixture of methacrylic acid (MAA) and methyl methacrylate (MMA).

In one aspect of the invention, monomers d) and g) are used as a mixture to produce a polymer. Mixtures of such monomers d) and g) are, for example, mixtures containing methacrylic acid esters and methyl methacrylate of the ethoxylated (25 mol EO) C ₁₆ -C ₁₈ fatty alcohol spectrum (eg Plex® 6877-O ), Or a mixture containing C ₁₆ -C ₁₈ (EO) ₂₅ methacrylate and methacrylic acid (eg, Lutencryl® 250).

  In one aspect of the invention, monomers f) and g) are used as a mixture to produce a polymer. Mixtures of such monomers f) and g) are, for example, mixtures containing 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate and methyl methacrylate (for example Plex® 6844-O in methyl methacrylate). 25% by weight of N- (2-methacryloyloxyethyl) ethylene urea).

The following table shows exemplary composition ranges of monomers a) to g) for the four polymers I to IV of the present invention. The numbers are given in units of% by weight and the sum of a) to g) is 100% by weight. a) is acrylic acid, b) is N- vinylpyrrolidone, c) is preferably N- vinylimidazole, d) is preferably _C 16 _~C 18 PEG-25 methacrylate (i.e. monomers d) are Formula d1) wherein R ⁸ is methyl, X is oxygen, k is about 25, l is 0, R ⁹ is a mixture of C ₁₆ alkyl and C ₁₈ alkyl, and e) is Preferably pentaerythritol triallyl ether (PETAE), f) is preferably 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate (CAS number: 86261-90), also known as ureido methacrylate (UMA). -7) and g) is preferably methyl methacrylate and / or methacrylic acid.

One aspect of the present invention is as polymerized units:
a) 36-45% by weight acrylic acid,
b) 38-43% by weight of N-vinylpyrrolidone,
c) 2-4% by weight of N-vinylimidazole,
d) 3 to 5% by weight of _C 16 _~C 18 PEG-25 methacrylate,
e) 0.4 to 0.8% by weight of at least one crosslinking agent, preferably PETAE,
f) 0.5-4% by weight of ureido methacrylate,
g) 5 to 16% by weight of further monomers different from a) to e), preferably a mixture of methacrylic acid and methyl methacrylate, so that the sum of a) to g) is 100% by weight. It is a polymer.

Another aspect of the present invention is as polymerized units,
a) 55-65% by weight acrylic acid,
b) 20-30% by weight of N-vinylpyrrolidone,
c) 1-3 wt% N-vinylimidazole,
d) 2 to 4% by weight of _C 16 _~C 18 PEG-25 methacrylate,
e) 0.3-0.6% by weight of at least one crosslinking agent, preferably PETAE,
f) 1-3% by weight of ureido methacrylate,
g) 6 to 12% by weight of further monomers different from a) to e), preferably a mixture of methacrylic acid and methyl methacrylate, such that the sum of a) to g) is 100% by weight. It is a polymer.

Still another embodiment of the present invention is a polymerization unit,
a) 68-73 wt% acrylic acid,
b) 12-20% by weight of N-vinylpyrrolidone,
c) 0.5-3 wt% N-vinylimidazole,
d) 2 to 4% by weight of _C 16 _~C 18 PEG-25 methacrylate,
e) 0.3-0.6% by weight of at least one crosslinking agent, preferably PETAE,
f) 0.2-1.5% by weight of ureido methacrylate,
g) 5 to 10% by weight of further monomers different from a) to e), preferably a mixture of methacrylic acid and methyl methacrylate, such that the sum of a) to g) is 100% by weight. It is a polymer.

Still another embodiment of the present invention is a polymerization unit,
a) 75-85% by weight acrylic acid,
b) 8-15% by weight of N-vinylpyrrolidone,
c) 0.5-3 wt% N-vinylimidazole,
d) 1 to 5% by weight of _C 16 _~C 18 PEG-25 methacrylate,
e) 0.3-0.7% by weight of at least one crosslinking agent, preferably PETAE,
f) 0.2-1.5% by weight of ureido methacrylate,
g) 1 to 7% by weight of further monomers different from a) to e), preferably a mixture of methacrylic acid and methyl methacrylate, so that the sum of a) to g) is 100% by weight. It is a polymer.

Precipitation Polymerization The polymer of the present invention is preferably prepared by a precipitation polymerization process.
Accordingly, the present invention further provides a process for producing the polymer of the present invention, wherein the polymerization is precipitation polymerization.

  In certain embodiments of precipitation polymerization, at least two radical initiators having different decomposition temperatures and / or half-lives at specific polymerization temperatures are used. As a result, a copolymer having a particularly low residual monomer content can be obtained. This occurs especially when an initiator that decomposes at high temperatures is added before the end of the precipitation of the polymer, preferably before the start of the precipitation of the polymer.

  During precipitation polymerization, the monomer can be dissolved in a reaction medium containing monomer and solvent but no product polymer. The resulting polymer becomes insoluble and precipitates under such polymerization conditions. Thereby, higher molecular weight copolymers can be obtained than other polymerization methods (eg solution polymerization). Such copolymers with a relatively high molecular weight are very advantageous as rheology modifiers, in particular as thickeners.

  Precipitation polymerization is preferably carried out in a solvent in which each monomer used can be dissolved at least 10% by weight (at 20 ° C., 1 bar) and gives a visually clear solution.

  Precipitation polymerization is carried out, for example, in an ester such as ethyl acetate or butyl acetate and / or in a hydrocarbon such as cyclohexane or n-heptane as a solvent. In one embodiment of the invention, a mixture of ethyl acetate and cyclohexane is used as the solvent.

  The resulting polymer particles may precipitate from the reaction solution and be separated by known methods such as vacuum filtration.

  The polymerization temperature is preferably in the range of about 30 to 120 ° C, particularly preferably 40 to 100 ° C.

  Suitable initiators for radical polymerization are peroxo compounds and / or azo compounds which are common for this purpose, such as alkali metal peroxodisulfate or ammonium peroxodisulfate, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, peroxides. Di-tert-butyl, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permaleate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis (o -Toluoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, ert-butyl hydroperoxide, 2,2′-azobis (2,4-dimethylvaleronitrile), azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylbutyronitrile) (Wako (registered) V65), tert-butyl peroctoate (CAS number: 13467-82-8), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (Trigonox® 101). .

  In order to produce a polymer having a minimum residual monomer content, a post-polymerization step may be carried out following the first polymerization (main polymerization). Such post-polymerization may use the same or different initiator system as the main polymerization. The temperature of the post-polymerization step is preferably the same as the main polymerization temperature, more preferably higher than the main polymerization temperature. The reaction temperature during the main polymerization is preferably at most 100 ° C., and the reaction temperature during the post-polymerization is preferably at most 130 ° C.

In certain embodiments, at least two radical initiators that allow for essentially independent initiation in at least two phases are used in the preparation of the polymers of the present invention. Thereby, a polymer with a particularly low residual monomer content can be obtained.
[0494] to [0508] of US 2008/0199416 A1, which is incorporated herein by reference, describes such methods in detail.

  After polymerization, the precipitated polymer is separated from the reaction mixture. For this, methods known to those skilled in the art may be used. Such methods are filtration, centrifugation, solvent evaporation or a combination of these methods. The polymer may be further purified by a conventional washing step using the same solvent used in the polymerization.

  The resulting dry polymer powder can advantageously be converted to an aqueous solution or dispersion by dissolution or redispersion in water. Finely divided copolymers have the advantage of good solubility, easy transportability and usually show a low tendency to microbial attack.

Monomer or polymer acid groups may be partially or fully neutralized with a base. Bases that may be used to neutralize the polymer are alkali metal bases such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate, and alkaline earth metal bases such as Calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate, and amines. Suitable amines are, for example, C ₁ -C ₆ alkylamine, preferably n- propylamine and n- butylamine, dialkylamines, preferably diethyl propylamine and dipropyl methylamine, trialkylamines, preferably triethylamine and triisopropylamine It is an amine. Preferred are amino alcohols such as trialkanolamines such as triethanolamine, alkyl dialkanolamines such as methyl or ethyldiethanolamine, dialkylalkanolamines such as dimethylethanolamine, and 2-amino-2-methyl- 1-propanol. Particularly for use in hair treatment compositions, 2-amino-2-methyl-1-propanol, 2-amino-2-ethylpropane-1,3-diol, diethylaminopropylamine and triisopropanolamine are acid group-containing polymers. It was found to be particularly useful for neutralization of The neutralization of the acid groups may be carried out using a mixture of two or more bases, such as a mixture of sodium hydroxide solution and triisopropanolamine. Depending on the intended use, neutralization may be carried out partially or completely.

In one embodiment of the invention, the acrylic acid monomer is at least partially neutralized prior to polymerization. In one aspect of the invention, the acrylic acid monomer is at least partially neutralized with (NH ₄ ) HCO ₃ prior to polymerization. In another aspect of the invention, the acrylic acid monomer is at least partially neutralized with triethanolamine prior to polymerization.

  In one preferred embodiment of the invention, precipitation polymerization is carried out in the presence of at least one surfactant. Preferably, the surfactant has an HLB value of 10 or less.

  Using HLB values (W.C.Griffin, J. Soc. Cosmetic Chem. 1 (1949) 311), emulsifiers can be classified according to the ratio of hydrophilic groups to lipophilic groups (HLB = hydrophilic lipophilic balance).

  Suitable surfactants having an HLB value of 10 or less are described, for example, in Karl-Heinz Schrader, Grundlagen und Rezepturen der Kosmetika, 2nd edition, Verlag Huethig, Heidelberg, pages 395-397, which is cited here. And incorporate it here.

  The measurement of the HLB value of an emulsifier is known to those skilled in the art and is described, for example, on page 394 of the above document. Another suitable surfactant having an HLB value of 10 or less is described, for example, in US Pat. No. 4,375,533, column 7, lines 26-60, which is incorporated herein by reference. The use of surfactants in the precipitation polymerization of cross-linked polyacrylic acid has already been described in US 4,420,596 and US 4,375,533.

［式中、Ａは、２５℃で１重量％以上の水中溶解性を有し、２００〜５００００の分子量Ｍ_ｗを有し、Ｂと共有結合するよう選択される親水性構成単位であり、
Ｂは、３００〜６００００の分子量Ｍ_ｗを有し、２５℃で１重量％未満の水中溶解性を有し、Ａと共有結合できる疎水性構成単位であり、
ＣおよびＤは、ＡまたはＢであってよく、同じ基または異なった基であってよい末端基であり、
ｗは０または１であり、
ｘは１以上の整数であり、
ｙは０または１であり、
ｚは０または１である］
で示される。 Thus, the present invention performs precipitation polymerization in the presence of at least one surfactant selected from linear block copolymers having hydrophobic building blocks having a length greater than 5 nm (calculated by the cosine law). A method as described above is also provided. The linear block copolymer has the following formula:

[In the formula, A, has a 1 wt% or more solubility in water at 25 ° C., it has a molecular weight _{M w} of the 200 to 50,000, a hydrophilic structural unit is selected to covalently bind is B,
B has a molecular weight _{M w} of the 300 to 60,000, have a solubility in water of less than 1% by weight at 25 ° C., a hydrophobic structural unit capable of covalently bonding with A,
C and D may be A or B and are end groups that may be the same or different groups;
w is 0 or 1,
x is an integer greater than or equal to 1,
y is 0 or 1;
z is 0 or 1]
Indicated by

［式中、Ｒ_１およびＲ_２は末端基であり、互いに同じまたは異なっていてよく、ＺおよびＱとは異なり、
Ｚは、２５℃で１重量％未満の水中溶解性を有する疎水性構成単位であり、
Ｑは、２５℃で１重量％超の水中溶解性を有する親水性構成単位であり、
ｍおよびｎは１以上の整数であり、分子量Ｍ_ｗが１００〜２５００００となるように選択される］
で示されるランダム櫛形コポリマーから選択される界面活性剤の少なくとも１種の存在下で沈澱重合を実施する、先に記載した方法を提供する。 The present invention further includes the following formula:

[Wherein R ₁ and R ₂ are end groups and may be the same or different from each other, unlike Z and Q,
Z is a hydrophobic constituent unit having solubility in water of less than 1% by weight at 25 ° C.
Q is a hydrophilic structural unit having solubility in water of more than 1% by weight at 25 ° C.
m and n are integers of 1 or more, and are selected such that the molecular weight _Mw is 100 to 250,000]
There is provided a process as described above, wherein the precipitation polymerization is carried out in the presence of at least one surfactant selected from random comb copolymers represented by:

In one preferred embodiment of the invention, the surfactant is selected from 12-hydroxystearic acid block copolymers, more preferably 12-hydroxystearic acid block copolymers with polyethylene oxide. The 12-hydroxystearic acid block copolymer is particularly preferably an ABA block copolymer.
1) Hypermer® B239: a block copolymer of polyhydroxy fatty acid (PFA) and polyethylene oxide (PEO) having a M _w of about 3500;
2) Hypermer® B246: a block copolymer of polyhydroxy fatty acid (PFA) and polyethylene oxide (PEO) having a M _w of about 7500;
3) Hypermer® B261: a block copolymer of polyhydroxy fatty acid (PFA) and polyethylene oxide (PEO) having a M _w of about 9600;
4) Hypermer® 2234: nonionic polymer surfactant compound;
5) Hypermer® LP6: polymeric fatty acid ester having a M _w of about 4300;
6) Hypermer® lL2296: nonionic polymer surfactant compound;
7) Hypermer® A-109: block copolymer of fatty acid or long chain alkylene group and ethylene oxide;
8) Hypermer® A-409: block copolymer of fatty acid or long chain alkylene group and ethylene oxide;
9) Pecosil® PS-100: Dimethicone copolyol phosphate polymer having 5 to 12 mol of ethylene oxide per mol of hydrophilic units;
10) Pecosil® WDS-100: Dimethicone copolyol phosphate polymer with 5-12 mol of propylene oxide per mol of hydrophilic units.
Useful surfactants are disclosed in EP 584771 Bl, page 23, lines 2 to 37, which is incorporated herein by reference.

In another aspect of the invention, the surfactant is
A copolymer of polydimethylsiloxane and organic glycol,
A substance having the INCI name dimethicone PEG-7 phosphate,
-Polyethylene glycol-containing polyester,
・ Polyoxyethylene-glycerol-fatty acid ester,
・ Polyamide wax,
Selected from the group consisting of neutral waxes and mixtures thereof.

Another surfactant is a copolymer of polydimethylsiloxane and an organic glycol, such as a material having the INCI name PEG / PPG-25 / 25 dimethicone (eg Belsil® DMC 6031), and the INCI name dimethicone copolyol acetate. (Eg Belsil® DMC 6032).
Another suitable commercially available dimethicone PEG-7 phosphate (INCI) is, for example, Pecosil® PS-100.

  Another suitable commercially available dimethicone is an aminoalkyl substituted dimethicone, such as methoxy PEG / PPG-7 / 3 aminopropyl dimethicone (Abil® Soft AF 100 from Evonik). Aminoalkyl substituted surfactants result in higher solids during precipitation polymerization compared to using non-aminated surfactants.

In one preferred embodiment of the invention, the monomer is polymerized by precipitation polymerization in the presence of methoxy PEG / PPG-7 / 3 aminopropyl dimethicone.
In another preferred embodiment of the invention, the monomer is polymerized by precipitation polymerization in the presence of PEG / PPG-25 / 25 dimethicone.
In yet another preferred embodiment of the invention, the monomer is polymerized by precipitation polymerization in the presence of Leophen RW ECO (mixture of various ethoxylated long chain fatty alcohols, BASF).

  Commercially available polyethylene glycol-containing polyesters that may be used as surfactants in precipitation polymerization are Hypermer® brands, particularly block copolymers of grades B239, B246, B261, 2234, LP6, A-109, A-409 ( EP 584771 B1, page 10, lines 25-42).

  A commercially available polyoxyethylene-glycerol-fatty acid ester suitable as a surfactant is also polyglyceryl-2 dipolyhydroxystearate (INCI), such as Dehymuls® PGPH (Cognis).

  Another suitable surfactant is a compound having the INCI name PEG-7 hydrogenated castor oil, such as Arlacel® 989, Cremophor® WO7 (BASF) or Dehymuls® HRE 7 (Cognis), PEG-2 hydrogenated castor oil such as Arlacel® 582, sorbitan monooleate / propyl glyceryl 4 / 3-ricinoleate such as Arlacel® 1689 (Croda), sorbitan stearate and sucrose cocoate such as Arlartone ( Registered trademark) 2121 (Croda), Solves-20 beeswax, eg Atlas® G-1726 (Croda).

  Another suitable surfactant is a polyamide wax, such as Kahl Wax 6635 (Kahl & Co). Other suitable commercially available natural waxes are, for example, fatty acid esters, mixtures of fatty acids and fatty alcohols, such as beeswax, berry wax, rice wax (Kahl & Co).

  Suitable beeswax is in particular beeswax having CAS number 8006-40-4 (white) or 8012-89-3. Suitable beeswax has the INCI (EU) name Cera Alba, synthetic beeswax, PEG-7 dimethicone beeswax. A particularly suitable beeswax is the beeswax having the INCI (EU) name Cera Alba.

  A suitable berry wax is, for example, a berry wax (Berry Wax 6290 (Kahl & Co) or Botaniwax® OT (Botanigenics, Inc)) having the INCI name Rhus Verniciflua Peel Wax.

  Suitable rice waxes are in particular rice waxes having CAS number 8016-60-2 or rice waxes having the INCI name Oryza Sativa (Rice) blanc wax. Such rice waxes are Cerewax® (Chemyunion Quimica LTDA), ESP® Rice Bran Wax (Earth Supplied Products, LLC), Florabeads® RBW (Floratech Americas), Naturebead® R20 (Micro Powders, Inc., Personal Care Division), Oryza Soft (registered trademark) "COS" (Cosmetochem International Ltd.), ORYZA (registered trademark) Wax (Ichimaru Pharcos Company, Ltd.), Ricebran Wax SP 8000 (Strahl & Pitsch, Inc.), Rice Wax No. 1 (Tri-K Industries), Rice Wax 2811 (Kahl).

  The amount of surfactant present during precipitation polymerization is 0.001 to 50% by weight, preferably 0.01 to 20% by weight, particularly preferably 0, based on a total amount of 100% by weight of components a) to g). .1 to 10% by weight.

  The polymers obtainable by the process according to the invention can be used as sole gel formers in cosmetic compositions because of their thickening effect. Furthermore, the polymers of the present invention are also suitable for use in combination with conventional gel formers.

  The polymer of the present invention is an aqueous composition in the fields of daily necessities, personal care, building industry, fabrics for paper coating slips, pigment printing pastes, aqueous colorants, leather treatment compositions, cosmetic compositions, pharmaceuticals and agrochemicals. In products, it may be used especially as a thickener.

  Also, the polymers of the present invention are easy to handle, enable the use of continuous production methods using in-line static mixers, can be processed using membrane pumps, and when diluted using turbine mixers and high-speed propellers Allows the preparation of transparent products, can be used with electrolytes, supports the stabilization of hydrophobic (low solubility) components, nonionic, anionic, zwitterionic and some Compatible with cationic surfactants, can stabilize suspensions, are gentle, smooth, non-sticky, non-tacky, in compositions at pH 5.5-12 It is stable, increases viscosity, stabilizes hydrogen peroxide, and allows flexible selection of preservative systems.

Another aspect of the present invention is a cosmetic composition comprising the polymer of the present invention.
Non-limiting examples of cosmetic compositions comprising the polymers of the present invention include anti-dandruff shampoos, bath foams, curl activators, hair removal agents, emulsifier-free compositions, facial cleansing foams, hair styling gels, liquid soaps, lotions, moisturizing Cream, shampoo, shower gel, skin mask, waterless hand cleaner and wave set.

  The invention will now be described in more detail with reference to the following non-limiting examples.

abbreviation:
VP: N-vinylpyrrolidone MAA: methacrylic acid AA: acrylic acid MMA: methyl methacrylate VI: N-vinylimidazole EAc: ethyl acetate PETAE: pentaerythritol triallyl ether C _16-18 alkyl-PEG-MA: alkoxylated with 25 mol of ethylene oxide Methacrylic acid ester of _C16-18 fatty alcohol
Plex® 6877-O: C _16-18 alkyl-PEG ₁₁₀₀ -methacrylate in MMA [75:25 w: w]
Lutencryl® 250: C _16-18 alkyl-PEG ₁₁₀₀ -methacrylate in MMA [50:50 w: w]
LUMA: C _16-18 alkyl-PEG ₁₁₀₀ -methacrylate
Plex® 6844-O: 25 wt% N- (2-methacryloyloxyethyl) ethylene urea in MMA

I) Preparation of polymers Preferably, the polymers of the present invention are prepared by precipitation polymerization.

Example 30:
AA / VP / VI / Lutencryl 250 / Plex 6877-O / PETAE // Belsil® 6031 (77/12/1/8/2 / 1.5% w / w) copolymer initial introduction: 345 g acetic acid Ethyl (Eac)
305 g cyclohexane
8.4 g Belsil® DMC 6031
0.4 g tert-butyl peroctoate feed 1: 170 g ethyl acetate
150g cyclohexane
431.2g acrylic acid
67.2 g N-vinylpyrrolidone
5.6 g N-vinylimidazole
44.8 g Lutencryl® 250
11.2g Plex (R) 6877-O
2.8g PETAE
11.2 g NH ₄ HCO ₃
Feed 2: 67 g ethyl acetate
60g cyclohexane
1g tert-butyl peroctoate
0.12 g Wako (registered trademark) V 50
Feed 3: 320 g ethyl acetate
280 g cyclohexane

  The stirred reaction vessel was filled with the initial charge, kept under a nitrogen atmosphere, and the initial charge was heated to 70 ° C. Feed 1 was added continuously for 3 hours and Feed 2 was added continuously for 5 hours. After the addition of feed 1 was completed, feed 3 was added continuously for 1.5 hours. After the addition of Feed 2 was complete, the reaction mixture was heated to 75 ° C. and held at 75 ° C. for 3 hours, then heated to 100 ° C. and held at 100 ° C. for an additional 4 hours. The reaction mixture was then cooled, filtered, washed with ethyl acetate / cyclohexane and dried at 80 ° C./vacuum for 24 hours.

  The total monomer amounts listed in the table below are given in weight% units.

II) Application of polymer In the following, “polymer selected from No. 1 to 35” refers to polymer No. 1 to No. 35. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35.

Hair gel containing non-ionic hair set
CTFA wt%
Phase 1:
No. Polymer selected from 1 to 35 2.0
Luviskol® K90 polyvinylpyrrolidone 1.5
46.5 distilled water
Further additives: pH adjusted to 6.7-7.2 using preservatives such as Euxyl® K100, perfume and other triethanolamine (50% strength solution).
Phase 2:
Distilled water up to 100 Preparation method:
Phase 1 was weighed and homogenized with stirring at a temperature in the range of 20-50 ° C. After about 3 hours, a milky dispersion was formed. Triethanolamine was added with stirring. After about 2 hours, a (substantially) homogeneous high viscosity gel was formed. Phase 2 was then added to phase 1 with slow stirring. The gel was stirred for an additional hour at room temperature. As a result, a stable and transparent gel was obtained.

Hair gel containing poly (vinyl pyrrolidone / vinyl acetate)
CTFA wt%
Phase 1:
No. Polymer selected from 1 to 35 2.0
Luviskol® VA64 poly (vinyl pyrrolidone 1.5
/ Vinyl acetate)
46.5 distilled water
Further additives: pH adjusted to 6.7-7.2 using preservatives such as Euxyl® K100, perfume and other triethanolamine (50% strength solution).
Phase 2:
Distilled water up to 100 Preparation method:
Phase 1 was weighed and homogenized with stirring at a temperature in the range of 20-50 ° C. After about 3 hours, a milky dispersion was formed. Triethanolamine was added with stirring. After about 2 hours, a (substantially) homogeneous high viscosity gel was formed. Phase 2 was then added to phase 1 with slow stirring. The gel was stirred for an additional hour at room temperature. As a result, a stable and transparent gel was obtained.

Hair gel containing cationic hair polymer
CTFA wt%
Phase 1:
No. Polymer selected from 1 to 35 2.2
Luviskol® K90 polyvinylpyrrolidone 0.8
Luviquat® Supreme (BASF AG) Polyquaternium-68 0.5
46.5 distilled water
Further additives: pH adjusted to 6.7-7.2 using preservatives such as Euxyl® K100, perfume and other triethanolamine (50% strength solution).
Phase 2:
Distilled water up to 100 Preparation method:
Phase 1 was weighed and homogenized with stirring at a temperature in the range of 20-50 ° C. After about 3 hours, a milky dispersion was formed. Triethanolamine was added with stirring. After about 2 hours, a (substantially) homogeneous high viscosity gel was formed. Phase 2 was then added to phase 1 with slow stirring. The gel was stirred for an additional hour at room temperature. This gave a stable and substantially transparent gel.

Gel that can be freely hair set
CTFA wt%
Phase 1:
No. Polymer selected from 1 to 35 2.0
Luviskol (registered trademark) K90 polyvinylpyrrolidone 1.0
D-Panthenol, USP Panthenol 0.2
Glycerol 0.1
Distilled water 46.7
Further additives: pH adjusted to 6.7-7.2 using preservatives such as Euxyl® K100, perfume and other triethanolamine (50% strength solution).
Phase 2:
Distilled water up to 100 Preparation method:
Phase 1 was weighed and homogenized with stirring at a temperature in the range of 20-50 ° C. After about 3 hours, a milky dispersion was formed. Triethanolamine was added with stirring. After about 2 hours, a (substantially) homogeneous high viscosity gel was formed. Phase 2 was then added to phase 1 with slow stirring. The gel was stirred for an additional hour at room temperature. This gave a stable and substantially transparent gel.

Set form
CTFA wt%
Phase 1:
No. Polymer selected from 1 to 35 0.5
Water 28.0
Adjusted to a pH of 6.8 using triethanolamine (50% strength solution).
Phase 2:
Luviset (R) Clear 1.2
Water 60.0
Cremophor (registered trademark) A25 CETEARETH-25 / BASF 0.2
Comperlan (registered trademark) KD Coamide DEA / Henkel 0.1
Additional additives: Perfume, preservatives, etc. Dimethyl ether 10.0
Preparation method:
Phase 1: The polymer was charged into water with stirring. While stirring, the polymer was neutralized with triethanolamine and dissolved. Phase 2 was added to Phase 1 with slow stirring. Filled into a bottle and added propellant gas.

Set form
CTFA wt%
Phase 1:
No. Polymer selected from 1 to 35 0.8
Water 37.7
Adjusted to a pH of 6.8 using triethanolamine (50% strength solution).
Phase 2:
Luviskol® VA 64 1.2
Cremophor (registered trademark) A25 CETEARETH-25 / BASF 0.2
Comperlan (registered trademark) KD Coamide DEA / Henkel 0.1
Water 50.0
Additional additives: Perfume, preservatives, etc. Dimethyl ether 10.0
Preparation method:
Phase 1: The polymer was charged into water with stirring. While stirring, the polymer was neutralized with triethanolamine and dissolved. Phase 2 was added to Phase 1 with slow stirring. Filled into a bottle and added propellant gas.

Shampoo (without adding salt)
CTFA wt%
Phase 1:
No. Polymer selected from 1 to 35 1.0
Water 48.0
Adjusted to a pH of 6.8 using triethanolamine (50% strength solution).
Phase 2:
Texapon (registered trademark) NSO 28% concentration Sodium laureth sulfate 50.0
/ Henkel
Comperlan (registered trademark) KD Coamide DEA / Henkel 1.0
Additional additives: Preparation methods such as fragrances and preservatives:
Phase 1 and phase 2 were weighed separately and dissolved with stirring and mixed. Phase 2 was added to Phase 1 with slow stirring.

shampoo
CTFA wt%
Phase 1:
No. Polymer selected from 1 to 35 1.0
Polyvinylpyrrolidone K30 0.5
Water 47.5
Phase 2:
Texapon (registered trademark) NSO 28% concentration Sodium laureth sulfate 50.0
/ Henkel
Comperlan (registered trademark) KD Coamide DEA 1.0
Further additives: appropriate amount, perfume oil, preservative preparation method:
Phase 1 and phase 2 were weighed separately and dissolved with stirring and mixed. Phase 2 was added to Phase 1 with slow stirring.

Claims (12)

As polymerized units,
a) 25-85% by weight acrylic acid,
b) 10-60% by weight of N-vinylpyrrolidone,
c) 0.3 to 10% by weight of at least one cationic monomer,
d) 1 to 6% by weight of at least one compound d1) or d2):

Wherein the alkylene oxide units are in no particular order, k and l are each independently an integer from 0 to 1000, the sum of k and l is at least 5, and R ⁸ is hydrogen or C ₁ -C ₄ alkyl And R ⁹ is C ₈ -C ₃₀ alkyl, C ₈ -C ₃₀ alkenyl or C ₈ -C ₃₀ alkylaryl, X is O or the formula: NR ¹⁰ (where R ¹⁰ is H, alkyl, alkenyl , A cycloalkyl, heterocycloalkyl, aryl or hetaryl)]
e) 0.01-2% by weight of at least one crosslinking agent,
f) 0.2-5% by weight of at least one formula (I):

[Wherein # is a bonding site with a radically polymerizable α, β-ethylenically unsaturated double bond group, R ^a is H or C ₁ -C ₄ alkyl, and R ^b is H or C ₁ -C ₄ alkyl, ie, R ^a and R ^b are both (CH ₂ ) _1-4 and R ^c is H or C ₁ -C ₃₀ alkyl]
A further monomer having a group represented by
g) A polymer comprising 0 to 30% by weight of further monomers different from a) to f) such that the sum of a) to g) is 100% by weight. At least one cationic monomer c) is represented by the general formula (II):

[Wherein R ^{5 to} R ⁷ are each independently hydrogen, C _{1 to} C ₄ alkyl or phenyl]
The polymer of Claim 1 selected from the vinylimidazole compound shown by these.   The polymer according to claim 2, wherein the at least one cationic monomer c) is N-vinylimidazole. At least one monomer f) is represented by the general formula (Ia):

[Wherein R ¹ is H or CH ₃ , R and R ′ are each independently H or an organic group, or may be bonded to each other, and G is O or NH]
The polymer in any one of Claims 1-3 selected from the compound shown by these.   5. A polymer according to any one of claims 1 to 4, wherein at least one monomer f) is ureido methacrylate. The at least one monomer g) is selected from methacrylic acid, α, β-ethylenically unsaturated monocarboxylic acids and esters of dicarboxylic acids with C ₁ -C ₈ alkanols, and mixtures thereof. 6. The polymer according to any one of 5. At least one monomer g) is methacrylic acid, C 1 _-C 6 _(meth) acrylate, and mixtures thereof, the polymer according to claim 6. At least one compound d1) is selected from polyether (meth) acrylate terminated with C ₈ -C ₂₂ alkyl group, a polymer according to any one of claims 1 to 7.   9. A polymer according to any preceding claim, wherein the molar ratio of compound a) to c) is at least 4: 1. As polymerized units,
a) 65-75% by weight acrylic acid,
b) 10-25% by weight of N-vinylpyrrolidone,
c) 0.5-2% by weight of N-vinylimidazole,
d) 1 to 6% by weight of _C 16 _~C 18 PEG-25 methacrylate,
e) 0.5-1.5% by weight of at least one crosslinking agent,
f) 0.5-2% by weight of ureido methacrylate,
g) 1 to 6% by weight methacrylic acid and / or 1 to 6% by weight methyl methacrylate, so that the sum of a) to g) is 100% by weight. The polymer described in 1.   A cosmetic composition comprising the polymer according to claim 1.   The adjustment method of the viscosity of an aqueous composition including adding the polymer in any one of Claims 1-10 to an aqueous composition.