JP4332846B2 - Liquid composition - Google Patents

Description

Field of Invention

  The present invention relates to a liquid composition containing no colorant, which is used with an ink composition comprising a colorant.

  The ink jet recording method is a printing method in which recording is performed by flying small droplets of an ink composition and attaching them to a recording medium such as paper. This method has a feature that a high-resolution and clear image can be printed at high speed while using a relatively inexpensive apparatus. Conventionally, various ink compositions for use in recording by this ink jet recording method have been proposed. In recent years, there has been an increasing demand for higher quality recorded images, and in particular, various ideas have been made to further improve the color development and glossiness of recorded images.

In order to realize a high-quality image, it has been proposed to perform recording by adhering a second composition to a recording medium together with an ink composition. For example, JP-A-9-207424 (Patent Document 1) and JP-A-9-286940 (Patent Document 2) describe an ink composition having a specific composition and a reaction liquid containing polyallylamine as a recording medium. An ink jet recording method to be attached to a film is disclosed.
JP-A-9-207424 JP-A-9-286940

Summary of the Invention

  The present inventors have now found a composition having good performance as a liquid composition used by being attached to a recording medium together with an ink composition. In particular, there is a liquid mixture of the liquid composition and the ink composition (hereinafter sometimes referred to as “waste liquid”) in the cleaning cap while maintaining the high storage stability of the recorded material and maintaining good color development and gloss. The present inventors have found a liquid composition that allows a good cleaning operation without stagnation.

  Therefore, the present invention provides a liquid composition having good performance, in particular, the storage stability of the recorded matter is high, and the waste liquid does not stay in the cleaning cap while maintaining good color development and glossiness. An object of the present invention is to provide a liquid composition that enables a good cleaning operation.

（式中、
Ｒ_１、Ｒ_２、およびＲ_３は、それぞれ独立して炭素数１〜４のアルキル基を表し、
Ｘは下記（ｉ）〜（ｖ）のいずれかであり；
（ｉ） −ＣＯＮＨ_２、
（ｉｉ） −ＣＯＯＲ_４（ここで、Ｒ_４は炭素数１〜１２のアルキル基、または炭素数６〜１２のアリール基を表す）、
（ｉｉｉ）−ＣＯＲ_５（ここで、Ｒ_５は炭素数１〜１２のアルキル基を表す）、
（ｉｖ） −ＣＨ_２ＣＨ（Ｒ_６）−Ａ（ここで、Ｒ_６は水素原子またはメチル基を表し、Ａは−ＣＯＮＲ_７Ｒ_８（Ｒ_７およびＲ_８はそれぞれ独立して、水素原子、または、炭素数１〜８のアルキル基（このアルキル基は、ヒドロキシ基、ケト基、炭素数１〜４のモノアルキルアミノ基、ジ（炭素数１〜４のアルキル）アミノ基、またはトリ（炭素数１〜４のアルキル）アンモニウム基からなる群から選択される基により置換されていてもよい）を表すか、またはＮＲ_７Ｒ_８は一緒になってピペリジノ基またはモルホリノ基の環状アミノ基を表す。）、−ＣＮ、およびＣＯＯＲ_９（ここで、Ｒ_９は炭素数１〜８のアルキル基（このアルキル基は、ヒドロキシ基、ケト基、炭素数１〜４のモノアルキルアミノ基、ジ（炭素数１〜４のアルキル）アミノ基、およびトリ（炭素数１〜４のアルキル）アンモニウム基からなる群から選択される基で置換されていてもよい）からなる群から選択されるものである）、または、
（ｖ） −ＣＨ_２ＣＨ（ＯＨ）−Ｂ（ここで、Ｂは炭素数１〜８のアルキル基（このアルキル基は、ヒドロキシ基、炭素数１〜４のアルコキシ基、およびアルケニルオキシ基からなる群から選択される基により置換されていてもよい）を表す。）、
Ｙが、上記Ｘと同じ意味を表すか、または水素原子を表し、
ＸおよびＹは、繰り返し単位ごとに同じであっても、異なっていてもよい。）。 That is, the liquid composition according to the present invention comprises modified polyallylamine, polymer fine particles, an organic solvent, and water, does not contain a colorant, and is used by being attached to a recording medium together with the ink composition. A liquid composition comprising:
The modified polyallylamine contains repeating units (a) and (d) represented by the following formula as essential constituent monomers, and (b) and / or (c) as optional constituent monomers The liquid composition is:

(Where
R ₁ , R ₂ , and R ₃ each independently represents an alkyl group having 1 to 4 carbon atoms,
X is any one of the following (i) to (v);
(I) -CONH _2,
(Ii) -COOR ₄ (wherein R ₄ represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms),
(Iii) -COR ₅ (wherein, _{R 5} represents an alkyl group having 1 to 12 carbon atoms),
_{(Iv) -CH 2 CH (R} 6) -A ( wherein, _{R 6} represents a hydrogen atom or a methyl group, A is -CONR ₇ R _{8 (R 7} and _{R 8} are each independently a hydrogen atom, Or an alkyl group having 1 to 8 carbon atoms (the alkyl group is a hydroxy group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, a di (C1 to C4 alkyl) amino group, or tri (carbon Or an NR ₇ R ₈ together represents a cyclic amino group of a piperidino group or a morpholino group. ), -CN, and COOR ₉ (wherein R ₉ is an alkyl group having 1 to 8 carbon atoms (this alkyl group is a hydroxy group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, di (carbon Numbers 1-4 Kill) amino groups, and tri (those selected from the group consisting of may also be) optionally substituted by a group selected from the group consisting of alkyl) ammonium group having 1 to 4 carbon atoms), or,
(V) —CH ₂ CH (OH) —B (where B is an alkyl group having 1 to 8 carbon atoms (this alkyl group is composed of a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, and an alkenyloxy group). And optionally substituted with a group selected from the group).
Y represents the same meaning as X above, or represents a hydrogen atom,
X and Y may be the same or different for each repeating unit. ).

  According to the liquid composition of the present invention, a recorded matter excellent in storage stability can be realized while maintaining good color developability and glossiness. More specifically, it is possible to realize an image that hardly changes color.

Detailed description of the invention

Definitions In this specification, an alkyl group as a group or part of a group may be linear or branched.

式中、Ｒ_１、Ｒ_２、およびＲ_３は、それぞれ独立して炭素数１〜４のアルキル基を表し、特にメチル基であることが好ましい。 Modified polyallylamine The modified polyallylamine contained in the liquid composition according to the present invention is an essential component comprising a diallylalkylamine monomer unit represented by the following repeating unit (a) and an allylamine monomer unit represented by (c). And a copolymer comprising the dialkylallylamine monomer unit represented by (b) as an optional component (hereinafter sometimes referred to as a raw material copolymer) as a raw material, the amino group of the allylamine monomer shown below It is modified by a substituent.

In the formula, R ₁ , R ₂ , and R ₃ each independently represent an alkyl group having 1 to 4 carbon atoms, and is particularly preferably a methyl group.

The modified polyallylamine used in the present invention refers to one in which one or two hydrogen atoms of —NH _{2 in} the allylamine repeating unit (c) are substituted with any of the following (i) to (v).

That, (i) -CONH ₂ (hereinafter, referred to as a urea modified polyallylamine), (ii) -COOR ₂ (hereinafter, referred to as urethane-modified polyallylamine), (iii) -COR ₃ (hereinafter, referred to as acyl modified polyallylamine), _{(iv) -CH 2 CH (R} 4) -A ( hereinafter, referred to as Michael modified polyallylamine), _and, and the like (v) -CH 2 CH (OH ) -B ( hereinafter, referred to as alcohol-modified polyallylamine) .

  Hereinafter, each of the modified polyallylamine in the present invention will be described.

式中、Ｒ_１、Ｒ_２、およびＲ_３は、それぞれ独立して炭素数１〜４のアルキル基を表し、特にメチル基が好ましい。 (I) Urea-modified polyallylamine Urea-modified polyallylamine is a copolymer of the following repeating units (a), (b), (c) and (d1).

In the formula, R ₁ , R ₂ , and R ₃ each independently represent an alkyl group having 1 to 4 carbon atoms, and a methyl group is particularly preferable.

The proportion of the repeating unit ( b ) is preferably from 0 to 90%, more preferably from 0 to 80%, based on the total number of the constituent monomer units (a) and (b) constituting the modified polyallylamine. The proportion of the repeating units (a) and (b) is preferably from 5 to 95%, more preferably from 10 to 90%, particularly preferably from 20 to 80%, based on the total number of monomers constituting the modified polyallylamine. preferable. At this time, the degree of carbamoylation, that is, the ratio of (d1) to the total number of repeating units (c) and (d1) is preferably 60 to 100% from the viewpoint of the solubility and stability of the modified polyallylamine, and is preferably 90 to 100%. % Is more preferable, and 95 to 100% is particularly preferable.

式中、Ｒ_１、Ｒ_２、およびＲ_３は、それぞれ独立して炭素数１〜４のアルキル基を表し、特にメチル基が好ましい。また、Ｒ_４は炭素数１〜１２のアルキル基または炭素数６〜１２もアリール基を表す。 (Ii) Urethane-modified polyallylamine Urethane-modified polyallylamine is a copolymer of the following repeating units (a), (b), (c) and (d2).

In the formula, R ₁ , R ₂ , and R ₃ each independently represent an alkyl group having 1 to 4 carbon atoms, and a methyl group is particularly preferable. R ₄ represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.

When R ₄ is an alkyl group having 1 to 12 carbon atoms, a linear alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group is preferable. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, an o-tolyl group, and an m-tolyl group. A p-tolyl group is mentioned.

The proportion of the repeating unit ( b ) is preferably from 0 to 90%, more preferably from 0 to 80%, based on the total number of the constituent monomer units (a) and (b) constituting the modified polyallylamine. The proportion of the repeating units (a) and (b) is preferably from 5 to 95%, more preferably from 10 to 90%, particularly preferably from 20 to 80%, based on the total number of monomers constituting the modified polyallylamine. preferable. At this time, the degree of alkoxycarbonylation (or allyloxycarbonylation), that is, the ratio of (d2) to the total number of repeating units (c) and (d2) is 60% from the viewpoint of the solubility and stability of the modified polyallylamine. -100% is preferable, 90-100% is more preferable, and 95-100% is especially preferable.

式中、Ｒ_１、Ｒ_２、およびＲ_３は、それぞれ独立して炭素数１〜４のアルキル基を表し、特にメチル基が好ましい。また、Ｒ_５は炭素数１〜１２のアルキル基を表し、好ましくはメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−ノニル基が挙げられる。 (Iii) Acyl-modified polyallylamine The acyl-modified polyallylamine is a copolymer of the following repeating units (a), (b), (c) and (d3).

In the formula, R ₁ , R ₂ , and R ₃ each independently represent an alkyl group having 1 to 4 carbon atoms, and a methyl group is particularly preferable. R ₅ represents an alkyl group having 1 to 12 carbon atoms, preferably a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n -A heptyl group and n-nonyl group are mentioned.

The proportion of the repeating unit ( b ) is preferably from 0 to 90%, more preferably from 0 to 80%, based on the total number of the constituent monomer units (a) and (b) constituting the modified polyallylamine. The proportion of the repeating units (a) and (b) is preferably from 5 to 95%, more preferably from 10 to 90%, particularly preferably from 20 to 80%, based on the total number of monomers constituting the modified polyallylamine. preferable. At this time, the degree of acylation, that is, the ratio of (d3) to the total number of repeating units (c) and (d3) is preferably 60 to 100% from the viewpoint of the solubility and stability of the modified polyallylamine, and is preferably 90 to 100% is more preferable, and 95 to 100% is particularly preferable.

式中、Ｒ_１、Ｒ_２、およびＲ_３は、それぞれ独立して炭素数１〜４のアルキル基を表し、特にメチル基が好ましい。また、Ｒ_６は水素原子またはメチル基を表し、Ａは−ＣＯＮＲ_７Ｒ_８（Ｒ_７およびＲ_８はそれぞれ独立して、水素原子、または、炭素数１〜８のアルキル基（このアルキル基は、ヒドロキシ基、ケト基、炭素数１〜４のモノアルキルアミノ基、ジ（炭素数１〜４のアルキル）アミノ基、またはトリ（炭素数１〜４のアルキル）アンモニウム基からなる群から選択される基により置換されていてもよい）を表すか、またはＮＲ_７Ｒ_８は一緒になってピペリジノ基またはモルホリノ基の環状アミノ基を表す。）、−ＣＮ、およびＣＯＯＲ_９（ここで、Ｒ_９は炭素数１〜８のアルキル基（このアルキル基は、ヒドロキシ基、ケト基、炭素数１〜４のモノアルキルアミノ基、ジ（炭素数１〜４のアルキル）アミノ基、およびトリ（炭素数１〜４のアルキル）アンモニウム基からなる群から選択される基で置換されていてもよい）からなる群から選択されるものである。 (Iv) Michael-modified polyallylamine Michael-modified polyallylamine is a copolymer of the following repeating units (a), (b), (c), (d41), and / or (d42).

In the formula, R ₁ , R ₂ , and R ₃ each independently represent an alkyl group having 1 to 4 carbon atoms, and a methyl group is particularly preferable. R ₆ represents a hydrogen atom or a methyl group, A represents —CONR ₇ R ₈ (R ₇ and R ₈ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (this alkyl group is , A hydroxy group, a keto group, a C1-C4 monoalkylamino group, a di (C1-C4 alkyl) amino group, or a tri (C1-C4 alkyl) ammonium group. NR ₇ R ₈ together represents a piperidino group or a cyclic amino group of a morpholino group), —CN, and COOR ₉ (wherein R ₉ Is an alkyl group having 1 to 8 carbon atoms (this alkyl group is a hydroxy group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, a di (alkyl having 1 to 4 carbon atoms) amino group, and tri (carbon number). 1 to 4 alkyl) which may be substituted with a group selected from the group consisting of ammonium groups).

In addition, the group —CH ₂ CH ₂ (R ₆ ) -A is usually a Michael reaction adduct of an acrylic compound, but when the acrylamide adduct type (A is —CONR ₅ R ₆ type), —CH _{2 CH 2 CONH 2, -CH 2 CH} 2 CONHCH 3, -CH 2 CH 2 CON (CH 3) 2, -CH 2 CH 2 CONHC 2 H 5, -CH 2 CH 2 CON (C 2 H 5) 2, - _{CH 2 CH 2 CONH-nC 3} H 7, -CH 2 CH 2 CON (nC 3 H 7) 2, -CH 2 CH 2 CONH-iC 3 H 7, -CH 2 CH 2 CONHCH 2 O-nC 4 H 9 _{, -CH 2 CH 2 CONHCH 2 OH} , -CH 2 CH 2 CONHCH 2 CH 2 N (CH 3) 2, -CH 2 CH 2 CONHCH 2 CH 2 N (C 2 _{5) 2, -CH 2 CH 2} CONHCH 2 CH 2 CH 2 N (CH 3) 2, -CH 2 CH 2 CONHCH 2 CH 2 CH 2 N (C 2 H 5) 2, -CH 2 CH 2 CONHCH 2 CH ^{_{2 N + (CH 3) 3}} , -CH 2 CH 2 CONHCH 2 CH 2 N + (C 2 H 5) 3, -CH 2 CH 2 CONHCH 2 CH 2 CH 2 N + (CH 3) 3, -CH 2 _{CH 2 CONHCH 2 CH 2 CH 2} N + (C 2 H 5) 3, -CH 2 CH 2 CO- morpholino _group, -CH ₂ CH ₂ CO- piperidino _{group, -CH 2 CH (CH 3)} CONH 2, - _{CH 2 CH (CH 3) CONHCH} 3, -CH 2 CH (CH 3) CON (CH 3) 2, -CH 2 CH (CH 3) CONHC 2 H 5, -CH _{CH (CH 3) CON (C} 2 H 5) 2, -CH 2 CH (CH 3) CONH-nC 3 H 7, -CH 2 CH (CH 3) CON (nC 3 H 7) 2, -CH 2 CH _{(CH 3) CONH-iC 3} H 7, -CH 2 CH (CH 3) CONHCH 2 O-nC 4 H 9, -CH 2 CH (CH 3) CONHCH 2 OH, -CH 2 CH (CH 3) CONHCH 2 _{CH 2 N (CH 3) 2} , -CH 2 CH (CH 3) CONHCH 2 CH (CH 3) N (C 2 H 5) 2, -CH 2 CH (CH 3) CONHCH 2 CH 2 CH 2 N (CH _{3) 2, -CH 2 CH (} CH 3) CONHCH 2 CH 2 CH 2 N (C 2 H 5) 2, -CH 2 CH (CH 3) CONHCH 2 CH 2 N + (CH 3) 3, -C _{2 CH (CH 3) CONHCH 2} CH 2 N + (C 2 H 5) 3, -CH 2 CH (CH 3) CONHCH 2 CH 2 CH 2 N + (CH 3) 3, -CH 2 CH (CH 3) Examples thereof include CONHCH ₂ CH ₂ CH ₂ N ⁺ (C ₂ H ₅ ) ₃ , —CH ₂ CH (CH ₃ ) CO-morpholino group and —CH ₂ CH (CH ₃ ) CO-piperidino group.

Moreover, group _-CH 2 _CH 2 _(R 4) when -A is acrylonitrile adduct _type, -CH 2 _CH 2 CN, and _-CH 2 _CH (CH 3) CN and can be exemplified.

Further, when the group —CH ₂ CH ₂ (R ₄ ) —A is an acrylate adduct type, —CH ₂ CH ₂ COOCH ₃ , —CH ₂ CH ₂ COOC ₂ H ₅ , —CH ₂ CH ₂ COOC _{3 H 7, -CH 2 CH 2 COOC} 4 H 9, -CH 2 CH 2 COOCH 2 CH 2 N (CH 3) 2, -CH 2 CH 2 COOCH 2 CH 2 CH 2 N (CH 3) 2, -CH 2 _{CH 2 COOCH 2 CH 2 N (} C 2 H 5) 2, -CH 2 CH 2 COOCH 2 CH 2 CH 2 N (C 2 H 5) 2, -CH 2 CH 2 COOCH 2 CH 2 CH 2 N + (CH _{3) 3, -CH 2 CH 2} COOCH 2 CH 2 N + (C 2 H 5) 3, a _{-CH 2 CH 2 COOCH 2 CH 2} CH 2 N + (C 2 H 5) 3 Example It can be.

The proportion of the repeating unit ( b ) is preferably from 0 to 90%, more preferably from 0 to 80%, based on the total number of the constituent monomer units (a) and (b) constituting the modified polyallylamine. The proportion of the repeating units (a) and (b) is preferably from 5 to 95%, more preferably from 10 to 90%, particularly preferably from 20 to 80%, based on the total number of monomers constituting the modified polyallylamine. preferable. At this time, the degree of Michael adduct type conversion, that is, the ratio of (d41) and / or (d42) to the total number of repeating units (c) and (d41) and / or (d42) is the solubility of the modified polyallylamine. From the viewpoint of stability, 60 to 100% is preferable, 90 to 100% is more preferable, and 95 to 100% is particularly preferable.

  In addition, the ratio of (d42) to the total number of repeating units (d41) and (d42) is preferably 60 to 100%, more preferably 90 to 100%, and particularly preferably 95 to 100% from the viewpoint of waste liquid treatment. preferable.

式中、Ｒ_１、Ｒ_２、およびＲ_３は、それぞれ独立して炭素数１〜４のアルキル基を表し、特にメチル基が好ましい。また、Ｂは炭素数１〜８のアルキル基（このアルキル基は、ヒドロキシ基、炭素数１〜４のアルコキシ基、およびアルケニルオキシ基からなる群から選択される基により置換されていてもよい）を表す。 (V) Alcohol-modified polyallylamine The alcohol-modified polyallylamine is a copolymer of the following repeating units (a), (b), (c), (d51), and / or (d52).

In the formula, R ₁ , R ₂ , and R ₃ each independently represent an alkyl group having 1 to 4 carbon atoms, and a methyl group is particularly preferable. B is an alkyl group having 1 to 8 carbon atoms (this alkyl group may be substituted with a group selected from the group consisting of a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, and an alkenyloxy group). Represents.

  B is a hydroxy group, an alkyloxy group having 1 to 4 carbon atoms, or an alkyl group having 1 to 8 carbon atoms which may include an alkenyloxy group. Specifically, a methyl group, an ethyl group, a propyl group, Examples include butyl group, pentyl group, hexyl group, methoxymethyl, ethoxymethyl group, propyloxymethyl group, butoxymethyl group, pentoxymethyl group, hydroxymethyl group, and (2-propenyloxy) methyl group.

The group —CH ₂ CH ₂ (R ₆ ) —B is a 2-hydroxypropyl group, 2-hydroxybutyl group, 2-hydroxypentyl group, 2-hydroxyhexyl group, 2-hydroxyheptyl group, 2-hydroxyoctyl group, 3-methoxy-2-hydroxypropyl group, 3-ethoxy-2-hydroxypropyl group, 3-propyloxy-2-hydroxypropyl group, 3- (i-propyloxy) -2-hydroxypropyl group, 3-butoxy-2- Examples thereof include a hydroxypropyl group, a 3-pentoxy-2-hydroxypropyl group, a 2,3-dihydroxypropyl group, and a 3- (2-propenyl) 2-hydroxypropyl group.

The proportion of the repeating unit ( b ) is preferably from 0 to 90%, more preferably from 0 to 80%, based on the total number of the constituent monomer units (a) and (b) constituting the modified polyallylamine. The proportion of the repeating units (a) and (b) is preferably from 5 to 95%, more preferably from 10 to 90%, particularly preferably from 20 to 80%, based on the total number of monomers constituting the modified polyallylamine. preferable. At this time, the degree of hydroxyalkyl conversion, that is, the ratio of (d51) and / or (d52) to the total number of repeating units (c) and (d51) and / or (d52) is the ratio of the modified polyallylamine according to the present invention. In terms of solubility and stability, 60 to 100% is preferable, 90 to 100% is more preferable, and 95 to 100% is particularly preferable.

  Further, the ratio of (d52) to the total number of repeating units (d51) and (d52) is preferably 60 to 100%, more preferably 90 to 100%, and particularly preferably 95 to 100% from the viewpoint of waste liquid treatment. preferable.

  The structure of the modified polyallylamine has been described above. When there are a plurality of monomer units in which allylamine is modified, all the monomer units may be the same or may be composed of a plurality of different monomer units.

  The weight average molecular weight of the modified polyallylamine is preferably 12,000 or less, more preferably 200 to 8000, and particularly preferably 300 to 5000. When the molecular weight exceeds 12,000, the solubility of the modified polyallylamine in an organic solvent is lowered. On the other hand, when the molecular weight is less than 200, the performance of the recorded matter is deteriorated when used in the ink jet recording method. In addition, the “weight average molecular weight” in the present specification means a value in terms of polyethylene glycol measured by gel permeation chromatography (GPS) method.

  The raw material copolymer can be synthesized, for example, by the following method.

  The raw material copolymer can be produced by polymerizing an aqueous solution containing diallylalkylamine and monoallylamine as essential components and optionally containing dialkylallylamine in the presence of a polymerization initiator. In this case, the monomer concentration in the aqueous solution is 10 to 80% by weight, preferably 15 to 70% by weight. As diallylalkylamine, methyldiallylamine is preferably used because of the high solubility of the modified product. Moreover, it is preferable that 0-90% of the dialkylallylamine which is an arbitrary component is contained with respect to a diallylalkylamine monomer, and it is more preferable that 0-80% is contained.

  As the polymerization initiator, a compound having a water-soluble azo group such as 2,2'-azobis (2-amidinopropane) dihydrochloride is preferably used. The polymerization initiator is preferably 0.1 to 30 mol% based on the total amount of monomers. The polymerization time is 3 to 100 hours, preferably 5 to 70 hours.

  The weight average molecular weight of the raw material copolymer is preferably 200 to 12,000, more preferably 200 to 8000, and particularly preferably 300 to 5000. When the molecular weight is in the above range, the resulting modified polyallylamine dissolves well in the solvent constituting the ink, and the attacking property to the parts used in the ink jet recording apparatus is suppressed, so that the ink flow path component can be It does not attack and is preferable.

The modified polyallylamine contained in the liquid composition according to the present invention is a reagent capable of substituting an amino group with a substituent having 1 to 12 carbon atoms, such as an N-carbamoylation reagent or an alkoxycarbonylation reagent. , An allyloxycarbonylating reagent, an acylating reagent, or an acrylic compound capable of Michael addition reaction or a 1,2-epoxyalkane compound which may have a substituent, is present in the raw material copolymer. N, N-dialkylallylamine and N-substitution are obtained by modifying some or all of the hydrogen atoms of —NH ₂ of the allylamine monomer to “—NH-substituent” or / and “—N-disubstituent”. A copolymer with allylamine can be obtained.

  In the present invention, the content of the modified polyallylamine may be appropriately determined from the viewpoint of improving the color developability and glossiness of the recorded matter. According to a preferred embodiment of the present invention, the content of the modified polyallylamine is preferably 0.00. It is 1 to 30% by weight, more preferably 0.1 to 10% by weight, and still more preferably 0.5 to 5% by weight.

  In the present invention, modified polyallylamine and polyallylamine or a derivative thereof may be mixed and added. When mixed and added, the total content thereof is preferably 0.1 to 30% by weight, more preferably 0.1 to 10% by weight, and still more preferably 0.5 to 5% by weight.

Polymer fine particles The liquid composition according to the present invention comprises polymer fine particles. In the present invention, the polymer fine particles are preferably anionic polymer fine particles and / or nonionic polymer fine particles, and more preferably a combination of one or more anionic polymer fine particles and one or more nonionic polymer fine particles is used. .

  According to a preferred embodiment of the present invention, the polymer fine particles are added to the liquid composition as an emulsion obtained by dispersing (mixing) in an aqueous medium. By adding as an emulsion, the stability and storage stability of the liquid composition are improved, the reliability is further increased, and a high-quality recorded image can be obtained.

  According to a preferred embodiment of the present invention, the emulsion is selected from the group consisting of an emulsion emulsion, a sol emulsion, an anionic polyethylene emulsion or a modified product thereof, an anionic polypropylene emulsion or a modified product thereof, and a mixture thereof. According to the embodiment of the present invention, the anionic polyethylene emulsion or the anionic polypropylene emulsion is a carboxylated modified product, a sulfonated modified product, or the like.

  The fine polymer particles preferably have an average particle size of 10 to 200 nm or less, a glass transition temperature (Tg; measured according to JIS K6900) of 50 ° C. or less, and a minimum film-forming temperature (MFT) of 20 ° C. or less. The weight average molecular weight (Mw) is 5,000 to 1,000,000, preferably 6,000 to 600,000.

  In the present invention, the content of the polymer fine particles is preferably 0.1 to 20.0% by weight, more preferably 0.2 to 5.0% by weight, and still more preferably 0.1% by weight with respect to the total amount of the liquid composition. 5 to 3.0% by weight. In the present specification, the content of the polymer fine particles is a solid content conversion amount.

  In the present invention, the liquid composition preferably further comprises 0.1 to 30.0% by weight of polyethyleneimine or polyallylamine, thereby significantly improving the glossiness in the non-printed portion of the recorded image. Can be realized.

  Hereinafter, each polymer fine particle in the preferable aspect of this invention is demonstrated.

1. Anionic polymer fine particles Preferred examples of emulsions obtained by mixing and dispersing anionic polymer fine particles in an aqueous medium include emulsified emulsions, sol type emulsions, anionic polyethylene emulsions or modified products thereof, anionic polypropylene emulsions or the like thereof. Examples thereof include those selected from the group consisting of modified products and mixtures thereof. These emulsions will be described below.

(1) Emulsifying emulsion In the present invention, an "emulsifying emulsion" refers to a polymer that uses a surfactant to disperse a monomer in a solvent when synthesizing polymer fine particles. The fine particles have a particle size of approximately 70 μm or more.

  The glass transition temperature (Tg; measured in accordance with JIS K6900) of the emulsified emulsion is preferably 30 ° C. or less, more preferably 10 ° C. or less, from the viewpoint of improving the gloss and the stability of the recorded image.

  The weight average molecular weight (Mw) of the anionic polymer fine particles constituting the emulsified emulsion is preferably 100,000 to 1,000,000, more preferably from the viewpoint of improving the glossiness and the stability of the recorded image. 400,000 to 600,000. When the weight average molecular weight (Mw) is within this range, the storage stability is enhanced, and the glossiness in the non-printed portion of the recorded image can be improved.

  The average particle size of the anionic polymer fine particles constituting the emulsion emulsion is preferably 70 nm or more, more preferably 100 to 200 nm, and particularly preferably 110 to 150 nm. When the average particle diameter of the anionic polymer fine particles is within this range, the anionic polymer fine particles can easily form an emulsion in water, the storage stability is improved, and a high-quality recorded image can be obtained.

  The minimum film-forming temperature (MFT) of the emulsified emulsion is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, from the viewpoint of improving glossiness and improving the stability of recorded images. When the minimum film-forming temperature (MFT) is within this range, it is possible to further improve the glossiness in the non-printed portion of the recorded image.

(2) Sol-type emulsion In the present invention, a “sol-type” emulsion means that a surfactant for dispersing a monomer in a solvent is substantially unnecessary when a polymer fine particle is synthesized, and an emulsion is formed. The particle size of the polymer fine particles is about 70 μm or less.

  The glass transition temperature (Tg; measured according to JIS K6900) of the sol-type emulsion is preferably 50 ° C. or less, more preferably 30 ° C. or less, more preferably from the viewpoint of improving the gloss and stability of the recorded image. It is 20 degrees C or less.

  The weight average molecular weight (Mw) of the anionic polymer fine particles constituting the sol-type emulsion is preferably 1,000 to 1,000,000, more preferably from the viewpoint of improving glossiness and improving the stability of recorded images. Is from 3,000 to 500,000, particularly preferably from 5,000 to 15,000. When the weight average molecular weight (Mw) is within this range, the ejection stability is improved, and the glossiness of the non-printed portion of the recorded image can be improved.

  The average particle diameter of the anionic polymer fine particles constituting the sol-type emulsion is preferably 70 nm or less, more preferably 50 nm or less. If the average particle size of the anionic polymer fine particles is within this range, the anionic polymer fine particles can easily form an emulsion in water, the sol-type dispersion state is stabilized, the storage stability is improved, and a high-quality recorded image is obtained. It is done.

  The minimum film-forming temperature (MFT) of the sol-type emulsion is preferably 20 ° C. or less, more preferably 0 ° C. or less, from the viewpoint of improving glossiness and improving the stability of recorded images. When the minimum film-forming temperature (MFT) is within this range, it is possible to further improve the glossiness in the non-printed portion of the recorded image.

  Preferable specific examples of the sol type emulsion include alkali-soluble emulsions and sulfone group-containing emulsions.

  The alkali-soluble emulsion preferably has a pH adjusted with a base, preferably an inorganic base, more preferably an alkali metal hydroxide or alkaline earth metal hydroxide. The acid value of this emulsion is preferably 40 or less.

  An alkali-soluble emulsion comprises an ethylenically unsaturated carboxylic acid monomer and a monomer copolymerizable with this monomer in the presence of an alcoholic hydroxyl group-containing water-soluble polymer compound or copolymerizable surfactant. An emulsion obtained by dispersing a polymer obtained by polymerization in an aqueous medium is preferable.

  Examples of ethylenically unsaturated carboxylic acid monomers include ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid and methacrylic acid; ethylenically unsaturated polycarboxylic acids such as itaconic acid, maleic acid, fumaric acid, and butenetricarboxylic acid. Monovalent carboxylic acid monomers; partial ester monomers of ethylenically unsaturated polyvalent carboxylic acids such as monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleate; many such as maleic anhydride and citraconic anhydride Can be mentioned, and one or a mixture of two or more of these may be used. Among these, acrylic acid or methacrylic acid is particularly preferable.

  The monomer copolymerizable with the ethylenically unsaturated carboxylic acid monomer is not particularly limited. For example, aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, and chlorostyrene; Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, ethyl hexyl (meth) acrylate, (meth ) (Meth) acrylate monomers such as octyl acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate; cyano group-containing ethylenic groups such as (meth) acrylonitrile Unsaturated monomer; ethylenically unsaturated glycidyl ether such as allyl glycidyl ether Ethylenically unsaturated amide monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3 -Conjugated diene monomers such as butadiene and 1,3-pentadiene; carboxylic acid vinyl ester monomers such as vinyl acetate and the like, and one or a mixture of two or more of these can be used. Among these, an ethylenically unsaturated carboxylic acid ester monomer is preferable in terms of excellent light resistance and glossiness of an image, and in particular, (meth) such as methyl (meth) acrylate and ethyl (meth) acrylate. Acrylic acid ester monomers are more preferred.

  The alcoholic hydroxyl group-containing water-soluble polymer compound is preferably a vinyl alcohol polymer. Specifically, the alcoholic hydroxyl group-containing water-soluble polymer compound contains 5 to 25 alcoholic hydroxyl groups per 1,000 molecular weight, but is highly water-soluble. Molecular compounds are preferred. For example, vinyl alcohol polymers such as polyvinyl alcohol and various modified products thereof; saponified products of copolymers of vinyl acetate and acrylic acid, methacrylic acid or maleic anhydride; alkyl cellulose, hydroxyalkyl cellulose, alkyl hydroxyalkyl cellulose, etc. Cellulose derivatives; starch derivatives such as alkyl starch and carboxymethyl starch; gum arabic, tragacanth gum; polyalkylene glycol, and the like. One or a mixture of two or more of these can be used.

  The copolymerizable surfactant is a surfactant having one or more polymerizable vinyl groups in the molecule. For example, sodium propenyl-2-ethylhexylsulfosuccinate, polyoxyethylene sulfate (meth) acrylate , Anionic polymerizable surfactants such as polyoxyethylene alkyl propenyl ether sulfate ammonium salt, (meth) acrylic acid polyoxyethylene ester phosphoric acid ester; polyoxyethylene alkyl benzene ether (meth) acrylic acid ester, polyoxyethylene alkyl ether Anionic polymerizable surfactants such as (meth) acrylic acid esters can be mentioned, and one or a mixture of two or more of these can be used. Among these, polyoxyethylene alkylpropenyl ether sulfate ammonium salt is preferable because it has an excellent balance between the emulsifying and dispersing performance of the monomer and the copolymerizability with the monomer.

  The sulfonic acid group-containing emulsion is preferably a diene sulfonic acid group-containing emulsion or a non-diene sulfonic acid group-containing emulsion.

  The sulfonic acid group-containing emulsion is obtained by sulfonating a polymer or copolymer obtained by singly or copolymerizing monomers described later (see JP-A-11-217525), or sulfonation. Examples include emulsions obtained by dispersing a polymer obtained by homopolymerizing or copolymerizing a monomer in an aqueous medium, and a diene sulfonic acid group-containing emulsion having a diene monomer as an essential component or a diene monomer as an essential component. And non-diene sulfonic acid group-containing emulsions.

  Examples of the monomer used to obtain the diene sulfonic acid group-containing emulsion include a diene monomer and other monomers that can be used in combination with the diene monomer.

  Specific examples of the diene monomer include diene compounds having 4 to 10 carbon atoms, such as 1,3-butadiene, 1,2-butadiene, 1,3-pentadiene, 1,2-pentadiene, 2, 3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,3-hexadiene, 2,4-hexadiene, 2,3-dimethyl-1, 3-butadiene, 2-ethyl-1,3-butadiene, 1,2-heptadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,3-heptadiene, 2,5-heptadiene, 3,4-heptadiene, 3,5-heptadiene, cycloheptadiene, etc. can be mentioned, one or more of these The mixture can be used.

  Specific examples of other monomers that can be used in combination with the diene monomer include aromatic monomers such as styrene, α-methylstyrene, O-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, and (meth) acrylic acid. Mono- or dicarboxylic acid or dicarboxylic acid anhydride such as methyl, ethyl (meth) acrylate, alkyl (meth) acrylate such as butyl (meth) acrylate, (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid , Vinyl cyanide compounds such as (meth) acrylonitrile, vinyl chloride, vinylidene chloride, vinyl methyl ethyl ketone, vinyl acetate, (meth) acrylamide, glycidyl (meth) acrylate, etc., one or two of these A mixture of the above can be used.

  When these other monomers are used in combination, the amount of diene monomer used is preferably 0.5% by weight or more, more preferably 1% by weight or more, and still more preferably 5% by weight or more.

  The diene-based co-emulsion obtained by copolymerization with the above-described diene-based monomer or another monomer that can be used in combination with the diene-based monomer may be any copolymer including a random copolymer and a block copolymer.

  Preferred polymers include, for example, isoprene homopolymer, butadiene homopolymer, isoprene-styrene random copolymer, isoprene-styrene block copolymer, styrene-isoprene-styrene ternary block copolymer, and butadiene-styrene random copolymer. Examples thereof include a copolymer, a butadiene-styrene block copolymer, a styrene-butadiene-styrene block copolymer, a styrene-butadiene-styrene ternary block copolymer, and an ethylene-propylene-diene ternary block copolymer. More preferable copolymers include, for example, isoprene-styrene block copolymer, styrene-isoprene-styrene ternary block copolymer, butadiene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene- Examples thereof include a butadiene-styrene ternary block copolymer.

  The diene sulfonic acid group-containing polymer used in the present invention is a polymer obtained by hydrogenating a part or all of the residual double bond based on the diene polymer and / or its precursor monomer. It may be sulfonated by a known sulfonation method, for example, the method described in the Chemical Society of Japan, New Experimental Chemistry Course (Vol. 14, page III.1773) or JP-A-2-227403.

  Examples of the sulfonating agent include sulfuric anhydride, sulfuric acid, chlorosulfonic acid, fuming sulfuric acid, hydrogen sulfite (Li salt, Na salt, K salt, Rb salt, Cs salt, etc.) and the like. The amount of the sulfonating agent is preferably 0.005 to 1.5 mol, more preferably 0.01 to 1.0 mol in terms of anhydrous sulfuric acid, with respect to 1 mol of the polymer.

  The diene sulfonic acid group-containing emulsion is preferably used in a state obtained by allowing water and / or a basic compound to act on the product sulfonated as described above. Examples of the basic compound include alkali metal hydroxides, alkali metal alkoxides, alkali metal carbonates, aqueous ammonia, organometallic compounds, amines, and the like. The basic compound can be used alone or in combination of two or more. The usage-amount of a basic compound is 2 mol or less with respect to 1 mol of used sulfonating agents, Preferably, it is 1.3 mol or less.

Examples of the monomer used to obtain the non-diene sulfonic acid group-containing emulsion include vinyl monomers such as allyl sulfonic acid, vinyl sulfonic acid, or methacryl sulfonic acid obtained by reacting isobutylene with sulfur trioxide, Alternatively, a styrenic monomer such as sodium p-styrenesulfonate (for example, Spiromer, manufactured by Tosoh Corporation), or a general formula CH ₂ ═C (CH ₃ ) —COO (AO) _n SO ₃ Na (A: A monomer having a sulfonyl group such as a methacrylic acid ester monomer represented by (lower alkylene group) (for example, Eleminol RS-30, manufactured by Sanyo Chemical Co., Ltd.), and sodium, potassium and lithium salts of the monomer Etc.

  The non-diene sulfonic acid group-containing emulsion can also be obtained by copolymerizing a monomer having no sulfonic acid group with the monomer having the sulfonic acid group.

  Examples of other copolymerizable monomers include aromatic monovinyl compounds such as styrene, ethylvinylbenzene, α-methylstyrene, fluorostyrene, vinylpyrine, butyl acrylate, 2-ethylhexyl acrylate, β-methacryloyloxyethyl hydrodiene phthalate, N Acrylate monomers such as N, N-dimethylaminoethyl acrylate, 2-ethylhexyl methacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, N, N'-dimethylaminoethyl methacrylate, glycidyl methacrylate Cyanation of methacrylic acid ester monomers such as acrylonitrile and methacrylonitrile A vinyl compound, a silicon | silicone modified monomer, a macromonomer etc. can be mentioned. Furthermore, conjugated double bond compounds such as butadiene and isoprene, vinyl ester compounds such as vinyl acetate, 4-methyl-1-pentene, and other α-olefin compounds may be mentioned. Among the copolymerizable monomers, styrene, methyl methacrylate, and acrylonitrile are preferable.

  The amount of the copolymerizable monomer used is usually 1 to 93% by weight, preferably 5 to 80% by weight of the polymerizable monomer.

  Non-diene-based sulfonic acid group-containing emulsion is the above sulfonic acid group-containing monomer or other monomer copolymerizable with the sulfonic acid group-containing monomer, for example, in a polymerization solvent such as water or an organic solvent, Radical polymerization is performed using a radical polymerization initiator, a chain transfer agent or the like.

  The non-diene sulfonic acid group-containing emulsion obtained by copolymerizing the non-diene monomer may be any copolymer including a random copolymer and a block copolymer.

(3) Anionic polyethylene emulsion or modified product thereof, and anionic polypropylene emulsion or modified product thereof The melting point of anionic polyethylene emulsion or modified product thereof, and anionic polypropylene emulsion or modified product thereof is glossy and stable in recorded images. From the viewpoint of improving properties, it is preferably 70 ° C. or higher. Moreover, these particle diameters are preferably 200 nm or less, and the average particle diameter is preferably 160 nm or less.

  A commercially available product can be used as the anionic polyethylene emulsion, for example, as AQUACER507 from Big Chemie Japan. AQUACER 507 is an anionic oxidized high-density polyethylene emulsion having a melting point of 130 degrees, a pH of 10, a particle size of 100 nm to 200 nm, and an average particle size of 150 nm.

2. Nonionic polymer fine particles Specific examples of emulsions obtained by mixing and dispersing nonionic polymer fine particles in an aqueous medium include a nonionic polyethylene emulsion or a modified product thereof, a nonionic polypropylene emulsion or a modified product thereof, and a mixture thereof. Those selected from the group can be mentioned.

  The melting point of the nonionic polyethylene emulsion or a modified product thereof, or the polypropylene emulsion or the modified product thereof is preferably 70 ° C. or higher from the viewpoint of improving the gloss and improving the stability of the recorded image. The particle size is preferably 200 nm or less, and the average particle size is preferably 160 nm or less.

  Commercially available products of these emulsions can be used. For example, AQUACER 513, AQUACER 593, AQUACER 543 and the like are available from Big Chemie Japan.

  AQUACER 513 is a nonionic oxidized high-density polyethylene emulsion having a melting point of 130 ° C., a pH of 9, a particle size of 100 to 200 nm, and an average particle size of 150 nm. AQUACER 593 is a nonionic oxidized high-density polypropylene emulsion having a melting point of 160 ° C., a pH of 9, a particle size of 100 to 200 nm, and an average particle size of 150 nm. AQUACER 543 is a mixture of AQUACER 593 and nonylphenol.

Water and organic solvent The liquid composition in the present invention comprises water and an organic solvent.

  As the water, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used. In addition, the use of water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is preferable because generation of mold and bactea can be prevented when the ink composition is stored for a long period of time.

  Examples of the organic solvent contained in the liquid composition according to the present invention include glycol ether compounds, alkyldiol compounds, and polyhydric alcohol compounds. By using these compounds as an organic solvent, it is excellent in clogging property and ejection stability, and the image quality of a recorded image can be improved without significantly reducing the color development property and glossiness.

  The content of these compounds (the total amount when a plurality of types are mixed) is preferably 1.0% by weight or more and 70% by weight or less in the liquid composition from the viewpoint of improving the image quality, and more preferably 10 to 50% by weight.

  Examples of the glycol ether compounds include triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and the like. In particular, triethylene glycol monobutyl ether is suitable.

  The content of the glycol ether compound is preferably 0.1 to 30.0% by weight in the liquid composition, more preferably 1.0 to 20.0% by weight, and particularly preferably 2.0 to 10.0% by weight.

  Examples of the alkyldiol compound include 1,2-hexanediol, 1,2-pentanediol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, and 2-methyl-2,4- A pentanediol etc. are mentioned. In particular, 1,2-hexanediol is preferred.

  The content of the alkyldiol compound is preferably 0.1 to 30.0% by weight in the liquid composition, more preferably 1.0 to 20.0% by weight, and particularly preferably 2.0 to 2.0% by weight. -10.0 wt%.

  Examples of the polyhydric alcohol compound include water-soluble organic solvents such as glycerin, ethylene glycol, triethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, dipropylene glycol, and tetraethylene glycol. In particular, glycerin is suitable.

  The content of the polyhydric alcohol compound in the liquid composition is preferably 0.1 to 50.0% by weight, more preferably 1.0 to 40.0% by weight, and particularly preferably 8. 0 to 30.0% by weight.

  The liquid composition according to the present invention can further contain any one of an acetylene glycol compound, an acetylene alcohol compound, and a polysiloxane compound as a surfactant. Thereby, the discharge stability of the liquid composition can be improved without significantly deteriorating the color developability and glossiness.

  The content of the surfactant in the liquid composition is preferably 0.1 to 10.0% by weight, more preferably 0.1 to 3.0% by weight, and particularly preferably 0.3 to 2.0% by weight.

  Further, as a result of the addition of the surfactant, the surface tension of the liquid composition is preferably 15 to 45 dyn / cm, more preferably 20 to 40 dyn / cm, and particularly preferably 25 from the viewpoint of improving permeability. ~ 35 dyn / cm.

  In the present invention, acetylene glycol compounds preferably used as surfactants include Olphine E1010, STG, Y (all trade names, manufactured by Nissin Chemical Co., Ltd.), Surfynol 82, 104, 440, 465, 485 (any Also, a commercial product such as a trade name, manufactured by Air Products and Chemicals Inc. can be used.

  Examples of acetylene alcohol compounds preferably used in the present invention include 3,5-dimethyl-1-hexyne-3ol, 2,4-dimethyl-5-hexyn-3-ol, and Surfinol 61 (trade name, Air Products and Chemicals Inc.) can be used.

（ここで、Ｒ_１〜Ｒ_９は、独立してＣ_１〜Ｃ_６アルキル基を表し、ｊ、ｋおよびｘは独立して１以上の整数を表し、ＥＯはエチレンオキシ基を表し、ＰＯはプロピレンオキシ基を表し、ｍおよびｎは０以上の整数を表すが、ｍ＋ｎは１以上の整数を表し、繰り返し単位ＥＯおよびＰＯは、その順序は問わず、ランダムであってもブロックであってもよい。）
具体的には、ビックケミー・ジャパン社製のＢＹＫ３４７、同３４８等が使用できる。 As the polysiloxane compound preferably used in the present invention, compounds represented by the following general formula can be used.

(Wherein R _{1 to} R ₉ independently represent a C _{1 to} C ₆ alkyl group, j, k and x independently represent an integer of 1 or more, EO represents an ethyleneoxy group, and PO represents Represents a propyleneoxy group, m and n represent an integer of 0 or more, m + n represents an integer of 1 or more, and the repeating units EO and PO may be random or block regardless of their order. Good.)
Specifically, BYK347 and 348 manufactured by Big Chemie Japan can be used.

Other Components The liquid composition according to the present invention can further contain a solvent generally used in an aqueous ink composition for ink jet recording, if necessary. Examples of such a solvent include 2-pyrrolidone, triethanolamine, sugar and the like.

Specific examples of sugars include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, Examples include glucitol, sorbitol, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose and the like. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature, such as alginic acid, α-cyclodextrin, and cellulose. The derivatives of these saccharides are represented by reducing sugars of the saccharides described above (for example, sugar alcohol (general chemical formula HOCH ₂ (CHOH) _n CH ₂ OH (where n represents an integer of 2 to 5)). ), Oxidized sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thio sugars, etc. Particularly preferred are sugar alcohols, and specific examples include maltitol, sorbit, etc. Commercially available products include HS. -300, 500 (registered trademark of Hayashibara Shoji) etc. can be obtained.

  The liquid composition according to the present invention comprises a nozzle clogging preventive agent, an antiseptic, an antioxidant, a conductivity adjusting agent, a pH adjusting agent, a viscosity adjusting agent, a surface tension adjusting agent, an oxygen absorber, an ultraviolet absorber, and a chelating agent. Etc. can be further added.

  Specific examples of the preservative include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazolin-3-one (Abisia) Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel TN) and the like.

  Furthermore, specific examples of pH adjusters, solubilizers, or antioxidants include amines such as diethanolamine, triethanolamine, propanolamine, morpholine, and modified products thereof, potassium hydroxide, sodium hydroxide, hydroxide. Inorganic salts such as lithium, ammonium hydroxide, quaternary ammonium hydroxide (such as tetramethylammonium), carbonates such as potassium carbonate, sodium carbonate, lithium carbonate, and other phosphates, or N-methyl-2-pyrrolidone, urea And L-ascorbic acid and salts thereof, such as ureas such as thiourea and tetramethylurea, allophanates such as allophanate and methylallohanate, and biurets such as biuret, dimethylbiuret and tetramethylbiuret. Specific examples of ultraviolet absorbers include Ciba Geigy's Tinuvin 328, 900, 1130, 384, 292, 123, 144, 622, 770, 292, Irgacor 252, 153, Irganox 1010, 1076, 1035, MD1024, and lanthanide oxides. Can be mentioned. Specific examples of the chelating agent include ethylenediaminetetraacetic acid (EDTA).

  Further, an organic solvent such as alcohol may be contained for the purpose of adjusting the viscosity and bleeding on the recorded material. Specific examples thereof include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, sec-butanol, tert-butanol, i-butanol, n-pentanol and the like. A monohydric alcohol is particularly preferable.

  The content of the high-boiling organic solvent in the liquid composition is preferably 0.1 to 30.0% by weight, more preferably 1.0 to 10.0% by weight, and particularly preferably 2.0 to 5.0% by weight.

Ink composition An ink jet recording method according to another aspect of the present invention is carried out by printing the liquid composition and the ink composition on a recording medium, respectively. The ink composition comprises at least a colorant, water, and a water-soluble organic solvent. Hereinafter, each component constituting the ink composition will be described.

1. Colorant In the ink composition, a pigment or a dye is used as a colorant, and a pigment is preferably used. As the pigment, inorganic pigments and organic pigments can be used. As the inorganic pigment, in addition to titanium oxide and iron oxide, carbon black produced by a known method such as a contact method, a furnace method, or a thermal method can be used. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), pigment chelates (eg, basic pigment chelates, acidic pigment chelates), nitro pigments, nitroso pigments, aniline black, and the like.

  Examples of carbon black used as black ink include No. 1 manufactured by Mitsubishi Chemical. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B, etc. are Raven 5750, 5250, 5000, 3500, 1255, 700, etc. manufactured by Columbia, and Regal 400R, 330R, 660R, Mogu L, Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, manufactured by Cabot, Inc. Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex35, U, V, 140U, Special Black 6, 5, 4A, 4, etc. manufactured by Degussa.

  Examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14C, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 108, 109, 110, 113, 114, 116, 117, 120, 128, 129, 133, 138, 139, 147, 150, 151, 153, 154, 155, 156, 167, 172, 173, 180, 185, 195 and the like.

  Examples of pigments used in magenta ink include C.I. I. Pigment Red 1, 2, 3, 5, 7, 9, 10, 11, 12, 14, 17, 18, 23, 30, 31, 38, 42, 48 (Ca), 48 (Mn), 57 (Ca) 57: 1, 67, 88, 112, 114, 122, 123, 144, 147, 149, 150, 151, 166, 168, 170, 171, 175, 176, 177, 178, 179, 184, 185, 187 202, 209, 219, 224, 245, etc., and C.I. I. And CI pigment violet 19.

  Examples of pigments used for cyan ink include C.I. I. Pigment Blue 1, 2, 3, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15:34, 16, 18, 22, 25, 60, 65, 66, C.I. I. Bat Blue 4, 60 and the like.

  Examples of pigments used in red ink include C.I. I. Pigment red 17, 49: 2, 112, 149, 177, 178, 188, 255, 264 and the like.

  Examples of pigments used in violet ink include C.I. I. Pigment violet 3, 9, 19, 23, 31, 32, 33, 36, 38, 43, 50 and the like.

  The particle size of these pigments is preferably 200 nm or less, more preferably 100 nm or less.

  The content of the pigment in the ink composition is 0.01 to 10% by weight, preferably 0.1 to 6.0% by weight, and more preferably 0.5 to 4.0% by weight.

  The pigment as the colorant is preferably added to the ink as a pigment dispersion using a dispersant. Examples of the dispersant include natural polymers. Specific examples include proteins such as glue, gelatin, casein, and albumin, natural rubbers such as gum arabic and tragacanth, glucosides such as saponin, alginic acid, propylene glycol alginate, triethanolamine alginate, and alginic acid such as ammonium alginate. Derivatives, cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, ethylhydroxycellulose, and the like.

  Synthetic polymers are preferably used as the dispersant. Polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic acid. Acrylic resins such as ester copolymers, acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene- Styrene-acrylic resins such as α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer , Vinyl naphthalene-acrylic acid copolymer, vinyl Naphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid Examples thereof include vinyl acetate copolymers such as copolymers and salts thereof.

  Among these, a copolymer of a monomer having a hydrophobic group and a monomer having a hydrophilic group, and a polymer comprising a monomer having both a hydrophobic group and a hydrophilic group in the molecular structure are particularly preferable. The copolymer may be either a random copolymer or a block copolymer. Examples of the salt include salts with diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol, morpholine, and the like.

  These copolymers have a weight average molecular weight of about 1,000 to 1,000,000, preferably about 3,000 to 500,000, and more preferably 5,000 to 300,000.

  When the following self-dispersing pigment is used as the pigment, a dispersant may not be added. However, when the self-dispersing pigment is not used, the content of the dispersing agent is 0.001 to 14. It is 0.0% by weight, preferably 0.01 to 9.0% by weight, and particularly preferably 0.05 to 6.0% by weight.

  In the ink composition according to the present invention, as a colorant, a pigment that can be dispersed and / or dissolved in water without a dispersant, that is, a pigment generally referred to as a self-dispersing pigment can be preferably used. This pigment can be dispersed and / or dissolved in water without a dispersant by a surface treatment in which at least one functional group of carbonyl group, carboxyl group, hydroxyl group, or sulfone group or a salt thereof is bonded to the surface of the pigment. It was made possible. Specifically, a functional group or a molecule containing a functional group is grafted on the surface of the pigment by physical treatment such as vacuum plasma or chemical treatment (for example, oxidation treatment with hypochlorous acid, sulfonic acid, etc.). Can be obtained by: In the present invention, the functional group grafted on one pigment particle may be single or plural. The type and degree of the functional group to be grafted may be appropriately determined in consideration of dispersion stability in the ink, color density, drying property on the front surface of the ink jet head, and the like. The pigment used for the self-dispersing pigment may be the same as the pigment described above.

  In the present invention, a state where the pigment is stably present in water without a dispersant is expressed as “dispersion and / or dissolution”. In many cases, it is difficult to clearly distinguish whether a substance is dissolved or dispersed. In the present invention, as long as the pigment can be stably present in water without a dispersant, such a pigment can be used regardless of whether the state is dispersed or dissolved. Therefore, in the present specification, a pigment that can exist stably in water without a dispersant is sometimes referred to as a colorant, but it does not mean that even a pigment in a dispersed state is excluded.

2. Water, organic solvent, and other components The ink composition according to the present invention comprises water and a water-soluble organic solvent. Water, the organic solvent, and other components can be the same as those of the liquid composition.

  The ink composition can be prepared by a conventional method, for example, it can be produced by dispersing and mixing the above-described components by an appropriate method. Preferably, first, ion-exchanged water, a pigment, a dispersant, an organic solvent, and, if necessary, other components are dispersed in a suitable dispersing machine (for example, a ball mill, a sand mill, an attritor, a roll mill, an agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, jet mill, ang mill, etc.) to prepare a uniform pigment dispersion. Next, ion-exchanged water, an organic solvent, and other components as necessary are sufficiently stirred at room temperature to prepare an ink solvent. The pigment dispersion is gradually added dropwise to a state where the ink solvent is stirred with a suitable stirrer, and the mixture is sufficiently stirred. After sufficiently stirring, filtration is performed to remove coarse particles and foreign matters that cause clogging, thereby obtaining a target ink composition.

  When a self-dispersing pigment is used as a colorant, an ink composition can be obtained in the same manner as described above except that the pigment is surface-treated and the pigment itself is dispersed.

According to another aspect of the ink cartridge invention, an ink cartridge containing the liquid composition is provided. This ink cartridge may be configured to contain only the liquid composition alone, or may be configured to contain both the liquid composition and the ink composition.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.

  Hereinafter, allylamine may be referred to as “AA”, N, N-dimethylallylamine as “DMAA”, and diallylmethylamine as “DAMA”. Further, unless otherwise specified, “%” represents weight%.

1. Production of modified polyallylamine
Production Example 1
Production of modified PAA-1 (copolymer of DAMA and AA (5/5)) In a 2000 ml four-necked separable flask equipped with a stirrer, Dimroth reflux, and thermometer, a concentration of 58.80% Was charged with 159.10 g of a monoallylamine hydrochloride aqueous solution, 212.20 g of an N, N-diallylmethylamine hydrochloride aqueous solution having a concentration of 69.58%, and 834.70 g of distilled water. The monomer aqueous solution was heated to 65 ° C., 54.24 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added as a radical initiator, and polymerization was performed for 48 hours.

  After completion of the polymerization, 193.30 g of a 50% aqueous sodium hydroxide solution was added dropwise under ice cooling to neutralize hydrochloric acid. After completion of neutralization, unreacted monomers were distilled off at 50 ° C. under reduced pressure (10.6 kPa).

  The solution obtained here was subjected to electrodialysis, desalted, and an aqueous solution 1055 of a copolymer of free type N, N-dimethylallylamine and allylamine having a concentration of 14.35% (copolymerization ratio 5: 5). .43 g was obtained.

  A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an isopropanol solvent to obtain copolymer hydrochloride. The results of elemental analysis were C = 50.02, H = 9.01, and N = 11.32. These values agreed with the calculated values C = 49.80, H = 9.19, N = 11.64.

Production Example 2a
Production of modified PAA-2a (copolymer of DAMA and carbamoylated AA (5/5)) In a 1000 ml four-necked separable flask equipped with a stirrer, Dimroth reflux, and thermometer, Production Example 1 Was charged with 586.35 g of an aqueous copolymer solution of 14.35% free type N, N-diallylmethylamine and allylamine obtained in (1), and 104.17 g of 35% hydrochloric acid was added dropwise under ice cooling. Subsequently, the mixture was heated to 50 ° C., and 455.07 g of a sodium cyanate aqueous solution having a concentration of 7.5% was added dropwise to carry out the reaction for 24 hours.

  After completion of the reaction, 42.00 g of 50% sodium hydroxide was added dropwise under ice cooling to neutralize unreacted hydrochloric acid.

  The solution obtained here was subjected to electrodialysis, desalted, and a copolymer of free type N, N-diallylmethylamine and carbamoylated allylamine having a concentration of 11.30% (copolymerization ratio 5: 5). )) 907.00 g (yield 97%) of an aqueous solution was obtained. The copolymer had a weight average molecular weight of 1800.

  The copolymer was concentrated to a solid, and the solubility at 10% in various solvents was examined. As a result, this polymer was insoluble in acetone and acetonitrile, but dissolved in methanol, ethanol, isopropanol, DMSO, and DMF. This result shows that the copolymer of the present invention is dissolved in an organic solvent as compared with the allylamine polymer.

  A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an acetone solvent to obtain copolymer hydrochloride. This result shows that the modified polyallylamine of the present invention can be a cationic polymer.

  The results of elemental analysis were C = 53.58, H = 8.92, and N = 16.64. These values agreed with the calculated values C = 53.32, H = 8.95, and N = 16.96. Further, the molar fraction of carbamoylation calculated from neutralization titration of copolymer hydrochloride was 46.76%, which was almost the same as the result of elemental analysis.

Production Example 2b
Production of modified PAA-2b (copolymer of DAMA and carbamoylated AA (3/7)) In Production Example 1, 127.32 g of N, N-diallylmethylamine hydrochloride aqueous solution having a concentration of 69.58%, In the same manner as in Production Example 1 except that 222.75 g of 58.80% monoallylamine and 747.78 g of distilled water were used, free type N, N-diallylmethylamine and allylamine having a concentration of 14.50% As a result, 889.95 g of a copolymer (copolymerization ratio 3: 7) aqueous solution was obtained.

  In Example 2a, a free type having a concentration of 11.52% was prepared in the same manner as in Production Example 2a, except that 505.67 g of the aqueous copolymer solution, 637.10 g of the aqueous sodium cyanate solution, and 25.20 g of the aqueous sodium hydroxide solution were used. A 85.10 g (yield 95%) aqueous solution of a copolymer of N, N-diallylmethylamine and carbamoylated allylamine (copolymerization ratio 3: 7) was obtained. The weight average molecular weight of this copolymer was 1500.

Production Example 2c
Production of modified PAA-2c (copolymer of DAMA and carbamoylated AA (7/3)) In Production Example 1, 29.08 g of a 69.58% N, N-diallylmethylamine hydrochloride aqueous solution, In the same manner as in Production Example 1 except that 95.46 g of 58.80% monoallylamine and 921.66 g of distilled water were used, free type N, N-diallylmethylamine and allylamine having a concentration of 14.81% 1218.26 g of a copolymer (copolymerization ratio 7: 3) aqueous solution was obtained.

  In Example 2a, a free type having a concentration of 11.12% was prepared in the same manner as in Production Example 2a, except that 641.18 g of the above copolymer aqueous solution, 273.04 g of sodium cyanate aqueous solution, and 58.80 g of sodium hydroxide aqueous solution were used. 940.95 g (yield 97%) of an aqueous solution of a copolymer of N, N-diallylmethylamine and carbamoylated allylamine (copolymerization ratio 7: 3) was obtained. The weight average molecular weight of this copolymer was 2100.

Production Example 3
Production of modified PAA-3 (copolymer of DAMA and methoxycarbonylated AA (5/5)) In a 1000 ml four-necked separable flask equipped with a stirrer, Dimroth reflux, and thermometer 1 was charged with 586.35 g of an aqueous copolymer solution of free type N, N-diallylmethylamine and allylamine having a concentration of 14.35% obtained in No. 1, and heated to 50 ° C. to give dimethyl carbonate having a purity of 99%. 77g was dripped and reaction was performed for 24 hours.

  After completion of the reaction, by-produced methanol was removed under reduced pressure (80 mmHg) at 50 ° C., and a copolymer of free type N, N-diallylmethylamine and methoxycarbonylated allylamine having a concentration of 22.44% (copolymerization) Ratio 5: 5) 494.19 g (98% yield) of aqueous solution was obtained. The weight average molecular weight of this copolymer was 1900.

  A part of this aqueous copolymer solution was converted into a hydrochloride, and reprecipitated with an isopropanol solvent to obtain a copolymer hydrochloride. The results of elemental analysis were C = 54.69, H = 8.62 and N = 10.37. These values agreed with the calculated values C = 54.85, H = 8.82 and N = 10.66. Moreover, as a result of calculating the methoxycarbonylation mole fraction by neutralization titration of copolymer hydrochloride, it was 49.88%, which almost coincided with the result of elemental analysis.

Production Example 4
Production of modified PAA-4 (copolymer of DAMA and acetylated AA (5/5)) In a 1000 ml 4-neck separable flask equipped with a stirrer, Dimroth reflux, and thermometer, Production Example 1 Was charged with 586.35 g of a copolymer aqueous solution of free type N, N-diallylmethylamine and allylamine obtained in 1.35%. Under ice-cooling, 54.69 g of acetic anhydride having a purity of 98% was added dropwise only in the amount of 1/2 mol of allylamine, and the content was adjusted to 42.00 g of sodium hydroxide having a concentration of 50% corresponding to the molar amount of acetic acid by-produced. The procedure was repeated, and the whole amount of acetic anhydride was added dropwise to carry out the reaction for 24 hours.

  The solution obtained here was subjected to electrodialysis, desalted, and a copolymer of free type N, N-diallylmethylamine and acetylated allylamine having a concentration of 15.12% (copolymerization ratio 5: 5). ) 695.50 g (yield 100%) of an aqueous solution was obtained. The weight average molecular weight of this copolymer was 1900.

  A part of this aqueous copolymer solution was converted into a hydrochloride, and reprecipitated with an isopropanol solvent to obtain a copolymer hydrochloride. The results of elemental analysis were C = 58.31, H = 9.16, and N = 11.07. These values agreed with the calculated values C = 58.41, H = 9.40, and N = 11.35. Moreover, as a result of calculating the acetylation molar fraction by neutralization titration of copolymer hydrochloride, it was 50.06%, which almost coincided with the result of elemental analysis.

Production Example 5
Production of modified PAA-5 (copolymer of DAMA and monocarbamoylethylated AA (5/5)) In a 1000 ml four-necked separable flask equipped with a stirrer, Dimroth reflux, and thermometer. 586.35 g of a 14.35% -concentration free type N, N-diallylmethylamine-allylamine copolymer aqueous solution obtained in Example 1 was charged, heated to 50 ° C., and acrylamide with a concentration of 50%. 63 g was dropped and the reaction was performed for 24 hours. In this way, 631.93 g of an aqueous solution (copolymerization ratio 5: 5) of a free type N, N-diallylmethylamine having a concentration of 18.56% and monocarbamoylethylated allylamine (yield 98%). ) The copolymer had a weight average molecular weight of 1800.

  A part of this aqueous copolymer solution was converted into a hydrochloride, and reprecipitated with an isopropanol solvent to obtain a copolymer hydrochloride. The results of elemental analysis were C = 56.48, H = 8.99, and N = 15.38. These values agreed with the calculated values C = 56.61, H = 9.50, N = 15.24. Moreover, as a result of calculating the monopropyl amidation mole fraction by neutralization titration of the copolymer hydrochloride, it was 49.03%, which almost coincided with the result of elemental analysis.

Production Example 6
Production of modified PAA-6 (copolymer of DAMA and dicarbamoylethylated AA (5/5)) In Production Example 5, except that 149.27 g of acrylamide was used, a concentration of 23. A 647.03 g (yield 97%) aqueous solution of a copolymer of 27% free type N, N-diallylmethylamine and dicarbamoylethylated allylamine (copolymerization ratio 5: 5) was obtained. The copolymer had a weight average molecular weight of 1800.

  A part of this aqueous copolymer solution was converted into a hydrochloride, and reprecipitated with an isopropanol solvent to obtain a copolymer hydrochloride. The results of elemental analysis were C = 55.18, H = 8.75, and N = 15.81. These values agreed with the calculated values C = 55.40, H = 9.01, N = 16.15. Moreover, as a result of calculating the dipropylamidation molar fraction by neutralization titration of copolymer hydrochloride, it was 48.71% and was almost in agreement with the result of elemental analysis.

Production Example 7
Production of modified PAA-7 (copolymer of DAMA and monoethoxy-2-hydroxypropylated AA (5/5)) 1000 ml 4-neck separable flask equipped with stirrer, Dimroth reflux, and thermometer Into this, 586.35 g of an aqueous copolymer solution of free type N, N-diallylmethylamine and allylamine having a concentration of 14.35% obtained in Production Example 1 was charged and heated to 50 ° C. to obtain a purity of 100%. Of ethyl glycidyl ether was added dropwise and reacted for 24 hours. In this way, 614.87 g of a copolymer (copolymerization ratio 5: 5) aqueous solution of free type N, N-diallylmethylamine having a concentration of 21.99% and monoethoxy-2-hydroxypropylated allylamine (copolymerization ratio 5: 5) Yield 100%). The copolymer had a weight average molecular weight of 1800.

  A part of this aqueous copolymer solution was converted into a hydrochloride, and reprecipitated with an isopropanol solvent to obtain a copolymer hydrochloride. The results of elemental analysis were C = 58.50, H = 9.99, and N = 9.08. These values were in agreement with the calculated values C = 58.71, H = 10.18, N = 9.13. Moreover, as a result of calculating the monoethoxy-2-hydroxypropylation mole fraction from neutralization titration of copolymer hydrochloride, it was 50.12%, which almost coincided with the results of elemental analysis.

Production Example 8
Production of modified PAA-8 (copolymer of DAMA and diethoxy-2-hydroxypropylated AA (5/5)) In Example 7, except that 107.24 g of ethyl glycidyl ether was used, the same as Example 7 644.36 g of a copolymer (copolymerization ratio 5: 5) of free type N, N-diallylmethylamine having a concentration of 28.62% and diethoxy-2-hydroxypropylated allylamine (yield 99%) ) The copolymer had a weight average molecular weight of 1800.

  A part of this aqueous copolymer solution was converted into a hydrochloride, and reprecipitated with an isopropanol solvent to obtain a copolymer hydrochloride. The results of elemental analysis were C = 58.56, H = 9.98, and N = 6.73. These values coincided with the calculated values C = 58.73, H = 10.10, and N = 6.85. Moreover, as a result of calculating diethoxy-2-hydroxypropylation mole fraction from neutralization titration of copolymer hydrochloride, it was 49.71%, which almost coincided with the result of elemental analysis.

Production Example 9
Production of Modified PAA-9 (Ternary Copolymer of DAMA, AA and Carbamoylated AA (5/3/2)) In Production Example 2a, 273.04 g of an aqueous sodium cyanate solution and 58. A copolymer of free type N, N-diallylmethylamine having a concentration of 11.75%, monocarbamoylethylated allylamine and allylamine in the same manner as in Production Example 1 except that 80 g was used (copolymerization ratio 5 : 3: 2) 817.70 g (99% yield) of an aqueous solution was obtained. The copolymer had a weight average molecular weight of 1800.

Production Example 10
Production of Modified PAA-10 (Ternary Copolymer (5/3/2) of DAMA, AA and Methoxycarbonylated AA) Example 3 except that 28.66 g of dimethyl carbonate was used in Production Example 3. 494.19 g (yield 98) of a free-form N, N-diallylmethylamine, methoxycarbonylated allylamine and allylamine copolymer (copolymerization ratio 5: 3: 2) having a concentration of 19.33%. %). The copolymer had a weight average molecular weight of 1800.

Production Example 11
Production of Modified PAA-11 (Ternary Copolymer of DAMA, AA, and Acetylated AA (5/3/2)) In Production Example 4, 32.81 g of acetic anhydride and 25.20 g of an aqueous sodium hydroxide solution were added. Except that it was used, in the same manner as in Production Example 4, a free aqueous solution of N, N-diallylmethylamine, acetylated allylamine and allylamine having a concentration of 13.74% (copolymerization ratio 5: 3: 2) 704.15 g (yield 100%) was obtained. The copolymer had a weight average molecular weight of 1800.

Production Example 12
Production of Modified PAA-12 (Ternary Copolymer (5/3/2) of DAMA, AA, and Monocarbamoylethylated AA) Production Example 5 except that 44.78 g of acrylamide was used in Production Example 5 In the same manner as described above, 611.07 g of a free type N, N-diallylmethylamine having a concentration of 17.26%, a copolymer of monocarbamoylethylated allylamine and allylamine (copolymerization ratio 5: 3: 2) ( Yield 98%). The copolymer had a weight average molecular weight of 1800.

Production Example 13
Production of modified PAA-13 (ternary copolymer of DAMA, monoethoxy-2-hydroxypropylated AA, and AA (5/3/2)) In Production Example 7, 32.17 g of ethyl glycidyl ether was used. A copolymer of free type N, N-diallylmethylamine, monoethoxy-2-hydroxypropylated allylamine and allylamine having a concentration of 19.57% (copolymerization ratio 5) : 3: 2) 586.51 g (yield 100%) of an aqueous solution was obtained. The copolymer had a weight average molecular weight of 1800.

Production Example 14
Production of Modified PAA-14 (Ternary Copolymer of DAMA, DMAA and Carbamoylated AA (1/1/1)) 1000 ml 4-neck Separa equipped with a stirrer, Dimroth reflux and thermometer In a bull flask, 212.20 g of a 69,58% N, N-diallylmethylamine hydrochloride aqueous solution, 191.66 g of a 63.45% N, N-dimethylallylamine hydrochloride aqueous solution, and a concentration of 58.80. % Monoallylamine hydrochloride aqueous solution 159.10 g and distilled water 646.40 g were charged. This aqueous monomer solution was heated to 65 ° C., 54.24 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added as a radical polymerization agent, and a polymerization reaction was carried out for 48 hours.

  After completion of the reaction, 273.28 g of a 50% aqueous sodium hydroxide solution was added dropwise under ice cooling to neutralize hydrochloric acid. After completion of neutralization, unreacted monomers were distilled off at 50 ° C. under reduced pressure (10.6 kPa).

  The obtained solution was subjected to electrodialysis, desalted, and a free type copolymer of N, N-diallylmethylamine, N, N-dimethylallylamine and allylamine having a concentration of 14.82% (polymerization ratio 1: 1: 1) 1504.87 g of aqueous solution was obtained.

  To 5700.04 g of the obtained aqueous copolymer solution, 104.17 g of 35% hydrochloric acid was added dropwise under ice cooling, followed by heating to 50 ° C. and 300.35 g of a 7.5% aqueous sodium cyanate solution. Was added dropwise to carry out the reaction for 24 hours.

  The solution thus obtained was subjected to electrodialysis, desalted, and a free type of N, N-diallylmethylamine, N, N-dimethylallylamine and carbamoylated allylamine having a concentration of 12.13%. 782.09 g (yield 96%) of a polymer (polymerization ratio 1: 1: 1) aqueous solution was obtained. The copolymer had a weight average molecular weight of 1700.

  A part of this aqueous copolymer solution was converted into a hydrochloride, and reprecipitated with an isopropanol solvent to obtain a copolymer hydrochloride. The results of elemental analysis were C = 51.83, H = 9.13, and N = 14.97. These values agreed with the calculated values C = 52.03, H = 9.28, and N = 15.17. Moreover, as a result of calculating the carbamoylation mole fraction by neutralization titration of copolymer hydrochloride, it was 31.84%, which almost coincided with the result of elemental analysis.

2. Measurement of Weight Average Molecular Weight of Polymer The weight average molecular weight (Mw) of the polymer was measured by gel permeation chromatography (GPC method) using Hitachi L-6000 type high performance liquid chromatograph. The eluent flow path pump is Hitachi L-6000, the detector is Shodex RI SE-61 differential refractive index detector, the column is Asahi Pack's water-based gel filtration type GS-220HQ (exclusion limit molecular weight 3,000) and GS- 620HQ (exclusion limit molecular weight 2 million) and a double connection were used. The sample was adjusted to a concentration of 0.5 g / 100 ml with an eluent, and 20 μl was used. A 0.4 mol / l sodium chloride aqueous solution was used as an eluent. The column temperature was 30 ° C. and the flow rate was 1.0 ml / min. A calibration curve was determined using polyethylene glycol having a molecular weight of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, 23000 or the like as a standard sample, and the Mw of the polymer was determined based on the calibration curve.

3. Preparation of polymer fine particles Each polymer fine particle was prepared according to the following. The glass transition temperature Tg of the polymer fine particles was measured according to JIS K6900, and the turbidity was measured at a cell width of 10 mm using a turbidimeter (WATER-ANALYZER2000 manufactured by Nippon Denshoku Industries Co., Ltd.).

(1) A reaction vessel equipped with an emulsified emulsion stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 900 g of ion-exchanged water and 3 g of sodium lauryl sulfate, and the temperature was raised to 70 ° C. while purging with nitrogen under stirring. The internal temperature was kept at 70 ° C., 4 g of potassium persulfate was added as a polymerization initiator, and after dissolution, 450 g of ion exchange water, 3 g of sodium lauryl sulfate, 20 g of acrylamide, 300 g of styrene, 640 g of butyl acrylate, and 30 g of methacrylic acid were previously added. The emulsion prepared by adding with stirring was dropped into the reaction solution continuously over 4 hours. After completion of the dropwise addition, aging was performed for 3 hours. The obtained emulsified emulsion was cooled to room temperature, and then ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the solid content to 40% and pH 8.

  The polymer fine particles in this emulsified emulsion have a glass transition temperature (Tg) of 15 ° C., an average particle size of 130 nm, a weight average molecular weight (Mw) of 500,000, a minimum film-forming temperature (MFT) of 0 ° C., and turbidity. It was 30 mg / l or more.

(2) Sol type emulsion (alkali-soluble emulsion)
A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 130 parts of ion exchange water and 2 parts of potassium persulfate, and the temperature was raised to 80 ° C. It was prepared in advance by adding 280 parts of ion exchange water, 55 parts of ethyl acrylate, 37 parts of methyl acrylate, 6 parts of methacrylic acid, 3 parts of octyl thioglycolate as a molecular weight regulator, and 2.5 parts of polyvinyl alcohol with stirring. The dispersion of the monomer mixture was continuously added over 4 hours for polymerization. After completion of the continuous addition, the reaction was performed at 80 ° C. for 30 minutes.

  Next, 10% aqueous sodium hydroxide solution in an amount corresponding to the charged methacrylic acid and an equimolar amount of sodium hydroxide was added to the reactor, followed by heat treatment at 80 ° C. for 1 hour, followed by addition of an appropriate amount of ion-exchanged water and solidification. An alkali-soluble emulsion having a partial concentration of 15% was obtained. This alkali-soluble emulsion had an acid value of 40 and a pH of 9.2.

  The polymer fine particles in this alkali-soluble emulsion have a glass transition temperature Tg (measured according to JIS K6900) of 25 ° C., an average particle size of 50 nm or less, a weight average molecular weight (Mw) of 11,000, and a minimum film-forming temperature (MFT). Was 15 ° C. and turbidity was 30 mg / l or less.

(3) Sol type emulsion (sulfone group-containing emulsion)
Into a glass reaction vessel, 100 g of dioxane was added, and 11.8 g of anhydrous sulfuric acid was added thereto while maintaining an internal temperature of 25 ° C., and the mixture was stirred for 2 hours to obtain an anhydrous sulfuric acid-dioxane complex.

  Next, the total amount of the complex obtained above in 100 g of THF solution (concentration = 15%) of styrene / isoprene / styrene ternary block copolymer (10/80/10 weight ratio, Mw = 100000) The solution was added while maintaining the temperature, and further stirred for 2 hours to obtain a solution.

  1200 g of water, 7.1 g of sodium hydroxide, and 1 g of sodium dodecylbenzenesulfonate were placed in a flask, and the internal temperature was kept at 40 ° C. Into this, the whole amount of the above solution was added dropwise over 1 hour while maintaining the internal temperature at 40 ° C. After dropping, the mixture was stirred at 40 ° C. for 2 hours, and then the solvent was removed by distillation under reduced pressure while leaving water to obtain a sulfone group-containing emulsion having a concentration of 15%. The sulfonic acid content in the solid content was 1.2 mmol / g.

  The polymer fine particles in this sulfone group-containing emulsion emulsion have a glass transition temperature Tg of 25 ° C., an average particle size of 50 nm or less, a weight average molecular weight (Mw) of 10,000, a minimum film-forming temperature (MFT) of 15 ° C., and turbidity. Was 30 mg / l or less.

4). A liquid composition comprising a respective compositions adjusted following liquid composition was prepared.

Example 1a
Modified PAA-2a 5.0% (solid content conversion)
Emulsified emulsion 2.0% (solid content conversion)
Glycerin 25.0%
Triethylene glycol monobutyl ether 3.0%
Olfine E1010 0.3%
Water remaining
Example 1b
A liquid composition of Example 1b was obtained in the same manner as Example 1a, except that the emulsion emulsion was replaced with a sol emulsion (alkali-soluble emulsion) in Example 1a.

Example 1c
A liquid composition of Example 1c was obtained in the same manner as in Example 1a, except that the emulsion emulsion was replaced with a sol emulsion (sulfone group-containing emulsion) in Example 1a.

Example 1d
In Example 1a, the liquid composition of Example 1d was obtained in the same manner as in Example 1a, except that the emulsion emulsion was changed to AQUACER 593 (manufactured by Big Chemie Japan), which was a modified polypropylene emulsion.

Example 1e
A liquid composition of Example 1e was obtained in the same manner as Example 1a, except that in Example 1a, the emulsified emulsion was replaced with AQUACER 513 (manufactured by Big Chemie Japan), which was a modified polypropylene emulsion.

Examples 2b-14
In Example 1c, liquid compositions of Examples 2a to 14 were obtained in the same manner as Example 1c except that modified PAA-2a was replaced with modified PAA-2b to 14.

Comparative Example 1
A liquid composition having the following compositions was prepared in the same manner as in Example 1a.

Unmodified PAA (PAA-01 manufactured by Nitto Boseki Co., Ltd.)
5.0% (solid content conversion)
Glycerin 25.0%
Triethylene glycol monobutyl ether 3.0%
Olfine E1010 0.3%
Water remaining
Comparative Example 2
In Comparative Example 1, a liquid composition of Comparative Example 2 was obtained in the same manner as Comparative Example 1 except that the unmodified PAA was changed to modified PAA-1.

Comparative Example 3
In Comparative Example 1, the non-modified PAA was replaced with dimethyl-modified PAA (the number of dimethyl AA monomers: 95: 5 to 100: 0 and no other modified AA monomers). Obtained a liquid composition of Comparative Example 3 in the same manner as Comparative Example 1.

Comparative Example 4
In Comparative Example 1, a liquid composition of Comparative Example 4 was obtained in the same manner as Comparative Example 1 except that unmodified PAA was not added.

  When the surface tension of the above liquid composition was measured by CBVP-Z manufactured by Kyowa Interface Science Co., Ltd., the surface tensions of the liquid compositions of Examples 1a to 14 and Comparative Examples 1 to 4 were all. It was 25-35 dyn / cm.

５．評価試験
（１）光沢度試験
実施例１ａ〜１４および比較例１〜４における各液体組成物と、インク組成物とをインクジェットプリンタ（セイコーエプソン株式会社製；ＭＣ−２０００）に充填し、インクジェット専用紙（セイコーエプソン株式会社製；ＰＭ写真用紙）に、７２０×７２０ｄｐｉにて、Ｄｕｔｙ４０％で印刷を行った。 5. Preparation of Ink Composition Each ink composition shown in Table 1 below was prepared by the following operation. First, a pigment and a resin (styrene-acrylic acid copolymer) are mixed and dispersed in a sand mill (manufactured by Yasukawa Seisakusho) with glass beads (1.7 mm in diameter, 1.5 times the weight of the mixture (weight)) for 2 hours. I let you. Thereafter, the glass beads were removed, other additives were added, and the mixture was stirred at room temperature for 20 minutes. Filtration through a 10 μm membrane filter gave a pigment ink.

5. Evaluation Test (1) Glossiness Test Each liquid composition in Examples 1a to 14 and Comparative Examples 1 to 4 and the ink composition are filled into an ink jet printer (Seiko Epson Corporation; MC-2000) and used exclusively for ink jet. Printing was performed on paper (manufactured by Seiko Epson Corporation; PM photographic paper) at 720 × 720 dpi with a duty of 40%.

  “Duty” is a value calculated by the following equation.

duty (%) = number of actual printing dots / (vertical resolution × horizontal resolution) × 100
(Where “actual printing dot number” is the actual number of printing dots per unit area, and “vertical resolution” and “horizontal resolution” are the resolutions per unit area. 100% duty is a single color for a pixel. Means the maximum ink weight.)
The glossiness of each obtained recorded matter was tested as follows. “GP-200” manufactured by Murakami Color Materials Research Co., Ltd. is used. 12V50W, incident beam stop diameter 1 mm, reflected light stop diameter 1.5 mm, ND10 filter, incident angle 45 degrees, turn angle 0 degree, standard mirror plate 42. The maximum glossiness value was measured as 5. A higher glossiness value indicates higher gloss imparting properties.

  The results were evaluated according to the following criteria.

S: Maximum gloss is 50 or more AA: Maximum gloss is 45 or more A: Maximum gloss is 40 or more B: Maximum gloss is 30 or more and less than 40 C: Maximum gloss is 20 or more and less than 30 D: Maximum gloss The degree is 10 or more and less than 20 E: The maximum glossiness is less than 10 The evaluation results are as shown in Tables 2 and 3.

(2) Color development test (plain paper)
The liquid composition and the ink composition in Examples 1a to 14 and Comparative Examples 1 to 4 were filled in an ink jet printer (Seiko Epson Corporation; MC-2000) and placed on plain paper (Xerox 4024) at 720 × 720 dpi. Printed. At this time, the ink composition was printed at 70% duty, and at the same time, the liquid composition was printed at 10% duty.

  The optical density of the obtained recorded matter was measured. The optical density was measured using a Gretag Macbeth SPM50 manufactured by Gretag Co., with a D50 light source, no filter, and a viewing angle of 2 °.

  The results were evaluated according to the following criteria.

  S: It is difficult to visually confirm an uncolored portion, and the OD value increases by 0.08 or more than when the liquid composition is not printed.

  AA: It is difficult to visually confirm the uncolored portion, and the OD value increases by 0.06 or more than when the liquid composition is not printed.

  A: Uncolored portions are difficult to visually confirm, and the OD value increases by 0.03 or more than when the liquid composition is not printed.

  B: An uncolored portion can be easily confirmed visually, and the OD value does not increase by 0.03 or more than when the liquid composition is not printed.

  The evaluation results were as shown in Tables 2 and 3.

(3) Waste liquid treatment performance test of cap having no nonwoven fabric Each liquid composition and ink composition in Examples 1a to 14 and Comparative Examples 1 to 4 were filled in an ink jet printer (Seiko Epson Corporation; MC-2000). Thereafter, the recording head cleaning (pressing the printer cleaning button once) and the nozzle check pattern printing were repeated. This test operation was performed 10 times to evaluate whether the nozzle check pattern was printed normally, and the state of the waste liquid in the cap was observed. Whether the check pattern has been printed normally in all 10 test operations and the liquid composition in which the waste liquid did not stay in the cap has been subjected to 90 more test operations, and has the check pattern been printed normally? Evaluation was made and the state of the waste liquid in the cap was observed. Further, for the liquid composition in which the check pattern was normally printed in all 90 test operations and no waste liquid remained in the cap, this test operation was further performed 100 times in an environment of 40 ° C. Evaluated.

  The above results were evaluated according to the following criteria.

  S: The check pattern is printed normally in all 100 test operations under an environment of 40 ° C., and there is no waste liquid remaining in the cap.

  AA: The check pattern is normally printed in all 100 test operations under an environment of 20 ° C., and there is no waste liquid remaining in the cap.

  A: In an environment of 20 ° C., the check pattern is printed normally in all 10 test operations, and no waste liquid stays in the cap.

  B: The check pattern is printed normally in all 10 test operations in an environment of 20 ° C., but there is a slight retention of the waste liquid in the cap.

  C: The check pattern may not be printed normally under an environment of 20 ° C., and the waste liquid remains in the cap.

  The evaluation results were as shown in Tables 2 and 3.

(4) Evaluation of waste liquid treatment performance of cap having nonwoven fabric The nonwoven fabric was attached to the cap of the inkjet printer, and the same evaluation as in the evaluation (3) was performed. The evaluation results were as shown in Tables 2 and 3.

(5) Evaluation of printing stability After filling each liquid composition and ink composition in Examples 1a to 14 and Comparative Examples 1 to 4 into an ink jet printer (Seiko Epson Corporation; MC-2000), 40 ° C. Under the environment, 200 sheets of Duty 100% were continuously printed on A4 PM photographic paper at 720 * 720 dpi. Thereafter, a nozzle check pattern was printed without cleaning. Further, in the following evaluation criteria, when it was A, 400 sheets were continuously printed (a total of 600 sheets), and then a nozzle check pattern was printed without cleaning. It was evaluated according to the following criteria.

  AA: Both the check patterns after continuous printing of 200 sheets and after continuous printing of 600 sheets are printed normally.

  A: The check pattern after continuous printing of 200 sheets is printed normally, but the check pattern after continuous printing of 600 sheets is not printed normally (however, it can be printed normally by one cleaning).

  B: Check pattern after continuous printing of 200 sheets is not printed normally (however, it can be printed normally by one cleaning).

The evaluation results were as shown in Tables 2 and 3.

Claims (15)

A liquid composition comprising a modified polyallylamine, polymer fine particles, an organic solvent, and water, not containing a colorant, and being attached to a recording medium together with an ink composition,
The modified polyallylamine contains repeating units (a) and (d) represented by the following formula as essential constituent monomers, and (b) and / or (c) as optional constituent monomers,
A liquid composition having a glass transition temperature point of the polymer fine particles of 50 ° C. or lower:

(Where
R ₁ , R ₂ , and R ₃ each independently represents an alkyl group having 1 to 4 carbon atoms,
X is any one of the following (i) to (v);
(I) -CONH _2,
(Ii) -COOR ₄ (wherein R ₄ represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms),
(Iii) -COR ₅ (wherein, _{R 5} represents an alkyl group having 1 to 12 carbon atoms),
_{(Iv) -CH 2 CH (R} 6) -A ( wherein, _{R 6} represents a hydrogen atom or a methyl group, A is -CONR ₇ R _{8 (R 7} and _{R 8} are each independently a hydrogen atom, Or an alkyl group having 1 to 8 carbon atoms (the alkyl group is a hydroxy group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, a di (C1 to C4 alkyl) amino group, or tri (carbon Or an NR ₇ R ₈ together represents a cyclic amino group of a piperidino group or a morpholino group. ), -CN, and COOR ₉ (wherein R ₉ is an alkyl group having 1 to 8 carbon atoms (this alkyl group is a hydroxy group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, di (carbon Numbers 1-4 Kill) amino groups, and tri (those selected from the group consisting of may also be) optionally substituted by a group selected from the group consisting of alkyl) ammonium group having 1 to 4 carbon atoms), or,
(V) —CH ₂ CH (OH) —B (where B is an alkyl group having 1 to 8 carbon atoms (this alkyl group is composed of a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, and an alkenyloxy group). And optionally substituted with a group selected from the group).
Y represents the same meaning as X above, or represents a hydrogen atom,
X and Y may be the same or different for each repeating unit. ). A liquid composition comprising a modified polyallylamine, polymer fine particles, an organic solvent, and water, not containing a colorant, and being attached to a recording medium together with an ink composition,
The modified polyallylamine contains repeating units (a) and (d) represented by the following formula as essential constituent monomers, and (b) and / or (c) as optional constituent monomers,
A liquid composition having a minimum film-forming temperature of the polymer fine particles of 20 ° C. or lower:

(Where
R ₁ , R ₂ , and R ₃ each independently represents an alkyl group having 1 to 4 carbon atoms,
X is any one of the following (i) to (v);
(I) -CONH _2,
(Ii) -COOR ₄ (wherein R ₄ represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms),
(Iii) -COR ₅ (wherein, _{R 5} represents an alkyl group having 1 to 12 carbon atoms),
_{(Iv) -CH 2 CH (R} 6) -A ( wherein, _{R 6} represents a hydrogen atom or a methyl group, A is -CONR ₇ R _{8 (R 7} and _{R 8} are each independently a hydrogen atom, Or an alkyl group having 1 to 8 carbon atoms (the alkyl group is a hydroxy group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, a di (C1 to C4 alkyl) amino group, or tri (carbon Or an NR ₇ R ₈ together represents a cyclic amino group of a piperidino group or a morpholino group. ), -CN, and COOR ₉ (wherein R ₉ is an alkyl group having 1 to 8 carbon atoms (this alkyl group is a hydroxy group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, di (carbon Numbers 1-4 Kill) amino groups, and tri (those selected from the group consisting of may also be) optionally substituted by a group selected from the group consisting of alkyl) ammonium group having 1 to 4 carbon atoms), or,
(V) —CH ₂ CH (OH) —B (where B is an alkyl group having 1 to 8 carbon atoms (this alkyl group is composed of a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, and an alkenyloxy group). And optionally substituted with a group selected from the group).
Y represents the same meaning as X above, or represents a hydrogen atom,
X and Y may be the same or different for each repeating unit. ). A liquid composition comprising a modified polyallylamine, polymer fine particles, an organic solvent, and water, not containing a colorant, and being attached to a recording medium together with an ink composition,
The modified polyallylamine contains repeating units (a) and (d) represented by the following formula as essential constituent monomers, and (b) and / or (c) as optional constituent monomers,
The polymer fine particles are anionic polymer fine particles,
The organic solvent is one or a combination of two or more selected from the group consisting of glycol ether compounds, alkyl diol compounds, and polyhydric alcohol compounds,
The emulsion obtained by dispersing the anionic polymer fine particles in an aqueous medium is selected from the group consisting of a sol emulsion, an anionic polyethylene emulsion or a modified product thereof, an anionic polypropylene emulsion or a modified product thereof, and a mixture thereof. And
Liquid composition wherein the sol-type emulsion is an alkali-soluble emulsion and / or a sulfone group-containing emulsion:

(Where
R ₁ , R ₂ , and R ₃ each independently represents an alkyl group having 1 to 4 carbon atoms,
X is any one of the following (i) to (v);
(I) -CONH _2,
(Ii) -COOR ₄ (wherein R ₄ represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms),
(Iii) -COR ₅ (wherein, _{R 5} represents an alkyl group having 1 to 12 carbon atoms),
_{(Iv) -CH 2 CH (R} 6) -A ( wherein, _{R 6} represents a hydrogen atom or a methyl group, A is -CONR ₇ R _{8 (R 7} and _{R 8} are each independently a hydrogen atom, Or an alkyl group having 1 to 8 carbon atoms (the alkyl group is a hydroxy group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, a di (C1 to C4 alkyl) amino group, or tri (carbon Or an NR ₇ R ₈ together represents a cyclic amino group of a piperidino group or a morpholino group. ), -CN, and COOR ₉ (wherein R ₉ is an alkyl group having 1 to 8 carbon atoms (this alkyl group is a hydroxy group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, di (carbon Numbers 1-4 Kill) amino groups, and tri (those selected from the group consisting of may also be) optionally substituted by a group selected from the group consisting of alkyl) ammonium group having 1 to 4 carbon atoms), or,
(V) —CH ₂ CH (OH) —B (where B is an alkyl group having 1 to 8 carbon atoms (this alkyl group is composed of a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, and an alkenyloxy group). And optionally substituted with a group selected from the group).
Y represents the same meaning as X above, or represents a hydrogen atom,
X and Y may be the same or different for each repeating unit. ). A liquid composition comprising a modified polyallylamine, polymer fine particles, an organic solvent, and water, not containing a colorant, and being attached to a recording medium together with an ink composition,
The modified polyallylamine contains repeating units (a) and (d) represented by the following formula as essential constituent monomers, and (b) and / or (c) as optional constituent monomers,
The polymer fine particles are nonionic polymer fine particles,
The organic solvent is one or a combination of two or more selected from the group consisting of glycol ether compounds, alkyl diol compounds, and polyhydric alcohol compounds,
An emulsion obtained by dispersing the nonionic polymer fine particles in an aqueous medium is selected from the group consisting of a nonionic polyethylene emulsion or a modified product thereof, a nonionic polypropylene emulsion or a modified product thereof, and a mixture thereof. There is a liquid composition:

(Where
R ₁ , R ₂ , and R ₃ each independently represents an alkyl group having 1 to 4 carbon atoms,
X is any one of the following (i) to (v);
(I) -CONH _2,
(Ii) -COOR ₄ (wherein R ₄ represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms),
(Iii) -COR ₅ (wherein, _{R 5} represents an alkyl group having 1 to 12 carbon atoms),
_{(Iv) -CH 2 CH (R} 6) -A ( wherein, _{R 6} represents a hydrogen atom or a methyl group, A is -CONR ₇ R _{8 (R 7} and _{R 8} are each independently a hydrogen atom, Or an alkyl group having 1 to 8 carbon atoms (the alkyl group is a hydroxy group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, a di (C1 to C4 alkyl) amino group, or tri (carbon Or an NR ₇ R ₈ together represents a cyclic amino group of a piperidino group or a morpholino group. ), -CN, and COOR ₉ (wherein R ₉ is an alkyl group having 1 to 8 carbon atoms (this alkyl group is a hydroxy group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, di (carbon Numbers 1-4 Kill) amino groups, and tri (those selected from the group consisting of may also be) optionally substituted by a group selected from the group consisting of alkyl) ammonium group having 1 to 4 carbon atoms), or,
(V) —CH ₂ CH (OH) —B (where B is an alkyl group having 1 to 8 carbon atoms (this alkyl group is composed of a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, and an alkenyloxy group). And optionally substituted with a group selected from the group).
Y represents the same meaning as X above, or represents a hydrogen atom,
X and Y may be the same or different for each repeating unit. ).   5. The modified polyallylamine according to claim 1, wherein the repeating unit (b) comprises 0 to 90% of the repeating unit (b) with respect to the total number of the repeating units (a) and (b). Liquid composition.   The modified polyallylamine comprises 5 to 95% of the repeating units (a) and (b) based on the total number of the repeating units (a), (b), (c) and (d). Item 6. The liquid composition according to any one of Items 1 to 5.   7. The modified polyallylamine according to claim 1, wherein the repeating unit (d) comprises 60 to 100% of the total number of the repeating units (c) and (d). Liquid composition.   The liquid composition according to any one of claims 1 to 7, wherein the modified polyallylamine has a weight average molecular weight of 12,000 or less. The alkali-soluble emulsion comprises an ethylenically unsaturated carboxylic acid monomer and a monomer copolymerizable with the ethylenically unsaturated carboxylic acid monomer. The liquid composition according to claim 3 , wherein a polymer obtained by polymerization in the presence of a surfactant is dispersed in an aqueous medium. The liquid composition according to claim 3 , wherein the sulfone group-containing emulsion is a diene sulfonic acid group-containing emulsion and / or a non-diene sulfonic acid group-containing emulsion.   The liquid composition according to claim 1 or 2, wherein the organic solvent is one or a combination of two or more selected from the group consisting of glycol ether compounds, alkyl diol compounds, and polyhydric alcohol compounds.   The liquid composition according to claim 1, which is used in an inkjet recording method.   An ink cartridge containing the liquid composition according to claim 1. A liquid composition according to any one of claims 1 to 12,
An ink set comprising an ink composition comprising at least a colorant, a water-soluble organic solvent, and water.   An ink jet recording method for performing recording by attaching the liquid composition according to any one of claims 1 to 12 and the ink composition according to claim 14 to a recording medium.