JP2021024959A - Production method of polymer particle - Google Patents

Abstract

To provide a method for producing polymer particles that provide excellent fastness of printing in washing and color hardly degraded even by washing of many times when used as ink for textile.SOLUTION: A production method of polymer particles includes the steps of: producing a liquid containing a particulate polymer having a chromophore by polymerization; and filtering the liquid by a plurality of filter membranes. The plurality of filter membranes includes a first filter membrane having an average pore diameter of 7 μm or less that the liquid penetrates first after polymerization and a second filter membrane having an average pore diameter of 1 μm or less.SELECTED DRAWING: None

Description

The present invention relates to a method for producing polymer particles.

Inkjet printing is a method of dyeing the woven fabric by ejecting ink droplets onto various woven fabrics (textiles) that have been pretreated in advance using an inkjet printer.

Textile inks used for inkjet printing contain dyes that are water-soluble compounds, pigments that are insoluble particles, and the like as dye components. When performing inkjet printing using a textile ink containing a dye, after ejecting droplets of the textile ink onto the woven fabric, the dye that has not penetrated the woven fabric is subjected to a cleaning treatment such as steam treatment, water washing treatment, or soaping treatment. It is common to remove and suppress discoloration. However, the dye is gradually eluted from the printed woven fabric by repeated washing, and the color tends to gradually fade.

On the other hand, when inkjet printing is performed using a textile ink containing a pigment, it is said that discoloration during washing is unlikely to occur even if the cleaning treatment after printing is not performed. However, in pigments, only the surface of the particles contributes mainly to the color development property, and the inside of the particles does not contribute significantly to the color development property, so that the color development efficiency per unit volume tends to be low. Therefore, textile inks containing pigments do not have sufficient color development after printing. Therefore, in order to improve the color-developing property after printing, it has been proposed to use polymer particles having a chromophore as a textile ink (see Patent Document 1).

International Publication No. 2017/154854

However, the printed matter printed with the textile ink using the polymer particles having such a chromophore does not have sufficient fastness at the time of washing, and bleeding and fading occur after a large number of washings.

Therefore, in some aspects of the present invention, when used as a textile ink, the printed material has excellent fastness during washing, and polymer particles whose color development property does not easily decrease even after a large number of washings are produced. The purpose is to provide a method.

The present invention has been made to solve at least a part of the above-mentioned problems, and can be realized as any of the following aspects.

One aspect of the present invention includes a step of obtaining a liquid containing a particulate polymer having a color-developing group by polymerization and a step of filtering the liquid by a plurality of filter membranes, and the plurality of filter membranes are the liquids. Is a method for producing polymer particles, which comprises a first filter film having an average pore size of 7 μm or less and a second filter film having an average pore size of 1 μm or less.

In one aspect of the present invention, when the average pore size of the first filter film is A and the average pore size of the second filter film is B, it is preferable that 1 <A / B ≦ 7 is satisfied.

In one aspect of the present invention, it is preferable that the plurality of filter membranes further include a third filter membrane in which the liquid permeates after the second filter membrane and the average pore size is 1 μm or less.

In one aspect of the present invention, it is preferable that the polymer particles are an ink agent for textiles.

According to any aspect of the present invention, when used as a textile ink, the printed material has excellent fastness during washing, and polymer particles whose color development property is unlikely to deteriorate even after a large number of washings are produced. A method can be provided.

Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be noted that the present invention is not limited to the embodiments described below, but should be understood to include various modifications implemented without changing the gist of the present invention.

In the present specification, the numerical range described by using "~" means that the numerical values described before and after "~" are included as the lower limit value and the upper limit value.

<Method for producing polymer particles>
The method for producing polymer particles according to an embodiment of the present invention is
A step of obtaining a liquid (dispersion liquid) containing a particulate polymer having a color-developing group by polymerization (polymerization step), and a step of filtering the liquid with a plurality of filter films (filtration step).
To be equipped.

The plurality of filter membranes used in the filtration step include a first filter membrane in which the liquid first permeates after polymerization and has an average pore size of 7 μm or less, and a second filter membrane having an average pore size of 1 μm or less. ..

In the manufacturing method, when used as a textile ink through such a filtration step, the printed material has excellent fastness during washing, and the color development property does not easily decrease even after many washings. Particles can be obtained. The reason why such an effect occurs is not clear, but by performing filtration using the above two filter membranes in this order, the particle size of the obtained polymer particles can be improved, such as an appropriate particle size and its uniformity. It is presumed that the distribution is optimized and the polymer particles can be fixed to the fiber in a good state in which the polymer particles are evenly dispersed.

Further, by using a polymer having a chromophore as a textile ink, inkjet printing can be easily performed, the color development property after printing is excellent, and sufficient washing resistance is obtained. The following reasons can be inferred as the reason for this. Since the polymer is usually a water-insoluble dye, it can exhibit sufficient washing resistance without performing a washing treatment at the time of printing. In addition, the polymer can be easily and surely adjusted in size to an appropriately small size, and the surface area per unit volume can be relatively increased. As a result, it is presumed that by using the above-mentioned polymer, excellent color development properties equal to or higher than those of textile inks using dyes can be exhibited.

[Polymerization process]
In the polymerization step, a liquid containing a polymer having a chromophore is obtained by polymerization. The polymer is in the form of particles. The obtained liquid may be a dispersion liquid in which a particulate polymer is dispersed in a dispersion medium. This dispersion may be, for example, an aqueous dispersion using water as a dispersion medium. A part of the polymer may be dissolved in the dispersion medium.

(Polymer)
The obtained polymer preferably has a structural unit (I) derived from a monomer having a chromophore. The polymer may further have a second structural unit (hereinafter, also referred to as “structural unit (II)”) having no chromophore.

(Structural unit (I))
The structural unit (I) is derived from a monomer having a chromophore. Examples of the monomer having this chromophore include i) a salt of a cationic chromophore and an anion having an anionic group and a polymerizable unsaturated group (hereinafter, also referred to as “compound (a1)”).
ii) A salt of an anionic chromophore and a cation having a cationic group and a polymerizable unsaturated group (hereinafter, also referred to as "compound (a2)"),
iii) A compound having an electrically neutral chromophore and a polymerizable unsaturated group (hereinafter, also referred to as “compound (a3)”),
iv) A salt of a cationic chromophore having a polymerizable unsaturated group and an anion,
v) Examples thereof include a salt of an anionic chromophore having a polymerizable unsaturated group and a cation.

Among these, compound (a1) is preferable from the viewpoint of increasing the fastness to a large number of washings when one embodiment of the present invention is adopted. In particular, when a polymer having a structural unit (I) derived from the compound (a1) is used, the color development property and the like after a large number of washings may be easily deteriorated depending on the conventional filtration method. The reason for this is not clear, but it is presumed that the presence of a cationic chromophore or an anionic group tends to cause agglutination of particles, and the variation in particle size tends to be particularly large. Therefore, when the polymer has a structural unit (I) derived from the compound (a1), the variation in the obtained polymer particles is remarkable by applying the method for producing polymer particles according to the embodiment of the present invention. It is considered that the effect of improving the fastness during washing is particularly sufficiently exhibited.

Here, the “cationic chromophore” as used herein refers to an atomic group having a positive charge. When the atomic group has a functional group having a positive charge and a functional group having a negative charge, and the total of these charges becomes a positive charge, it is included in the cationic chromophore. .. Further, the "anionic chromophore" refers to an atomic group having a negative charge. In addition, when the atomic group has a functional group having a positive charge and a functional group having a negative charge, and the total of these charges becomes a negative charge, it is included in the anionic chromophore. .. Further, in the present specification, it is an atomic group that does not correspond to a cationic color group or an anionic color group, and has neither a positively charged functional group nor a negatively charged functional group, or Even if it has a functional group having a positive charge and a functional group having a negative charge, the atomic group having the same number of functional groups and being electrically neutral as a whole is "electrically neutrally colored". "Dan".

(Compound (a1))
Compound (a1) is a salt of a cationic chromophore and an anion having an anionic group and a polymerizable unsaturated group. The cationic chromophore constitutes a cation of compound (a1).

Examples of the cationic chromophore include triarylmethane chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore, xanthene chromophore, squarylium chromophore, and quinophthalone chromophore. A group, a kumarin chromophore, etc. can be mentioned. Among these, triarylmethane chromophore, xanthene chromophore and coumarin chromophore are preferable. In addition, as the above-mentioned cationic chromophore, in the color index (CI: The Society of Dyersand Colorists), C.I. I. It is also possible to use cations of dyes classified as basic.

As the cationic chromophore, an atomic group having an absorption maximum of 360 nm or more and 830 nm or less is preferable, and an atomic group having an absorption maximum of 380 nm or more and 780 nm or less is more preferable.

The triarylmethane chromophore is preferably represented by the following formula (1). The triarylmethane chromophore represented by the following formula (1) has various resonance structures, but in the present specification, these resonance structures are equivalent to those represented by the following formula (1). And.

In equation (1),
Ar is a substituted or unsubstituted divalent aromatic hydrocarbon group.
R ^{1 to} R ⁴ are independently hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, or aryl groups.
R ^{5 to} R ¹² are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 8 carbon atoms, or −COOR ^a . ^Ra is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
Y is a hydrogen atom or a monovalent group represented by the following formula (2).

In the formula (2), R ¹³ and R ¹⁴ are independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl group.

The divalent aromatic hydrocarbon group represented by Ar may have a monocyclic aromatic hydrocarbon ring or a polycyclic aromatic hydrocarbon ring. The number of carbon atoms of the divalent aromatic hydrocarbon group is preferably 6 to 20, and more preferably 6 to 10. Specific examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, a biphenylene group, an anthrylene group and the like.

As the substituent of the divalent aromatic hydrocarbon group, an alkyl group having 1 to 6 carbon atoms is preferable. The alkyl group may be a straight chain or a branched chain. Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group and the like.

The divalent aromatic hydrocarbon group represented by Ar was substituted with a phenylene group, a naphthylene group, a phenylene group substituted with an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. A naphthylene group is preferred.

R ¹ to R ¹⁴ an alkyl group having 1 to 8 carbon atoms represented by (including ^{R a} of -COOR ^a, represented by ^R 5 ^{to R 12)} may be either linear or branched. Specific examples of the alkyl group include groups similar to those described above, heptyl groups, octyl groups and the like.

Specific examples of the cycloalkyl group having 3 to 8 carbon atoms represented by R ^{1 to} R ⁴ , R ¹³ and R ¹⁴ include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. The groups can be mentioned.

The number of carbon atoms of the aryl group represented by ^{R 1 to} R ⁴ , R ¹³ and R ^{14 can be, for example, 6 to 20.} Specific examples of the aryl group include a phenyl group, a tolyl group, a naphthyl group and the like, and among these, a phenyl group is preferable.

Specific examples of the halogen atom represented by R ^{5 to} R ¹² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among these, a fluorine atom and a chlorine atom are preferable.

The triarylmethane chromophore represented by the formula (1) is preferably represented by the following formula (1-1) or formula (1-2) from the viewpoint of heat resistance and solvent resistance.

In equations (1-1) and (1-2),
R ¹⁵ and R ¹⁶ are independently hydrogen atoms, halogen atoms, or alkyl groups having 1 to 8 carbon atoms.
R ¹ to R ^{4, R 13} and ^{R 14} have the same meanings as ^R 1 ^{to R 4, R 13} and ^{R 14} in the formula (1) and formula (2).

As R ¹ , R ² , R ¹³ and R ¹⁴ , alkyl groups having 1 to 6 carbon atoms are preferable. The R ^3, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group and a phenyl group having 3 to 6 carbon atoms preferred. The R ^4, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms are preferred. As R ¹⁵ and R ¹⁶ , hydrogen atom, halogen atom and alkyl group having 1 to 6 carbon atoms are preferable.

The xanthene chromophore is preferably represented by the following formula (4).

In equation (4),
R ³¹ , R ³² , R ³³ and R ³⁴ are independently hydrogen atoms, -R ³⁸ or monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms. However, the hydrogen atoms contained in this monovalent aromatic hydrocarbon group are halogen atoms, -R ³⁸ , -OH, -OR ³⁸ , -SO ₃ H, -SO ₃ M ¹ , -COOH, -COM ¹ , It may be substituted with ^{-COOR 38} , -SO ₃ R ³⁸ , -SO ₂ NHR ³⁹ or -SO ₂ NR ³⁹ R ^40.
R ³⁵ and R ³⁶ are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
R ³⁷ is -SO ₃ H, -SO ₃ M ¹ , -COOH, -COOR ³⁸ , -SO ₃ R ³⁸ , -SO ₂ NHR ³⁹ or -SO ₂ NR ³⁹ R ⁴⁰ .
u is an integer from 0 to 5. When u is an integer of 2 or more, the plurality of R ^37s may be the same or different.
R ³⁸ is a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. However, the hydrogen atom contained in this monovalent saturated hydrocarbon group may be substituted with a halogen atom. Further, this monovalent saturated hydrocarbon group may have -O-, -CO- or -NR ^38A- between CC bonds. R ^38A is a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms.
R ³⁹ and ^{R 40} are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or -X ^a 3 to 30 carbon atoms, or ^{R 39} and ^{R 40} are these are combined with each other It is a substituted or unsubstituted monovalent heterocyclic group having 1 to 10 carbon atoms composed of an atom or an atomic chain to be bonded. However, the hydrogen atom contained in the alkyl group and the cycloalkyl group may be substituted with ^a hydroxy group, a halogen atom, -X a, -CH = CH ₂ or -CH = CHR ^38. Further, the alkyl group and cycloalkyl groups, -O between C-C bond -, - CO- or ^{-NR 38} - may have. Further, the hydrogen atom contained in the monovalent heterocyclic group may be substituted with ^{-R 38} , -OH or -X ^a.
M ¹ is a sodium atom or a potassium atom.
X ^a is a monovalent aromatic hydrocarbon group, or a monovalent aromatic heterocyclic group having 5 to 10 carbon atoms having 6 to 10 carbon atoms. However, the hydrogen atoms contained in the monovalent aromatic hydrocarbon group and the monovalent aromatic heterocyclic group are -OH, -R ³⁸ , -OR ³⁸ , -NO ₂ , -CH = CH ₂ , -CH. = CHR ³⁸ or may be substituted with a halogen atom.

The ^{monovalent saturated hydrocarbon group represented by R 38} may be linear, branched or cyclic as long as it has 1 to 10 carbon atoms, or may have a bridging structure. Specific examples of the monovalent saturated hydrocarbon group include a monovalent saturated aliphatic hydrocarbon group and a monovalent saturated alicyclic hydrocarbon group. Examples of the monovalent saturated aliphatic hydrocarbon group include an alkyl group and the like. Examples of the monovalent saturated alicyclic hydrocarbon group include a cycloalkyl group and the like. Examples of the alkyl group and the cycloalkyl group include groups similar to those described above.

Examples of monovalent heterocyclic groups having 1 to 10 carbon atoms in which R ³⁹ and R ⁴⁰ are combined with each other and are composed of an atom or an atomic chain to which they are bonded include a pyrrolidinyl group, a pyrazolinyl group, a morpholinyl group, a theomorpholinyl group, and piperidyl. Group, piperidino group, piperazinyl group, homopiperazinyl group, tetrahydropyrimidine group, 1,3-dioxolane-2-yl group, pyridyl group, pyrazinyl group, pyrimidyl group, pyridadinyl group, quinolyl group, isoquinolyl group, phthalazinyl group, quinoxalinyl group, Examples thereof include an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, a thiazolyl group, a benzothiazolyl group, an oxazolyl group, an indolyl group, an indazolyl group, a benzoimidazolyl group and a phthalimide group. Examples of the substituent of the monovalent heterocyclic group include a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an amino group, and an alkyl group having 1 to 6 carbon atoms.

The monovalent aromatic heterocyclic group having 5 to 10 carbon atoms represented by X ^a, such as furyl group, a thienyl group, a pyridyl group, pyrrolyl group, oxazolyl group, isoxazol group, thiazolyl group, isothiazolyl group, imidazolyl group , Pyrazolyl group, pyrimidyl group and the like.

Examples of the monovalent aromatic hydrocarbon group represented by ^{R 31, R 32, R 33} , R 34 and ^{X a,} preferably aryl group having a carbon number of 6-10, specifically, for example, a phenyl group, A naphthyl group and the like can be mentioned.

Examples of the -SO ₃ R ³⁸ represented by R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁷ include a methyloxysulfonyl group, an ethyloxysulfonyl group, a hexyloxysulfonyl group and the like.

Examples of -COOR ³⁸ include methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butyloxycarbonyl group, cyclohexyloxycarbonyl group, methoxypropyloxycarbonyl group and the like.

The ^{R 39} and ^{R 40} in -SO ₂ NHR ³⁹ and _-SO 2 ^NR 39 ^{R 40,} branched alkyl groups having 6 to 8 carbon atoms, a monovalent alicyclic hydrocarbon group having 5 to 7 carbon atoms, carbon Alkyl groups having a number of 8 to 10, alkyl groups having 2 to 8 carbon atoms substituted with a hydroxy group or an alkoxy group, and aryl groups are preferable.

As ^{the alkyl group having 1 to 8 carbon atoms represented by R 35} and R ³⁶ , an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.

The coumarin chromophore is preferably represented by the following formula (Y).

In formula (Y),
R ^Y1 to R ^Y4 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group or an aryl group having 3 to 8 carbon atoms.
R ^Y5 to R ^Y12 are each independently a hydrogen atom, a halogen atom, an alkyl group or -COOR ^Y 1 to 8 carbon atoms. ^RY is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R ^Y1 to R ^Y12 alkyl group having 1 to 8 carbon atoms represented by (including ^{R Y} of -COOR ^Y represented by ^R Y5 ^{to R Y12)} may be either linear or branched. Specific examples of the above-mentioned alkyl group include a group similar to the above-mentioned group, a heptyl group, an octyl group and the like.

As specific examples of the cycloalkyl group of R ^Y1 to R ^Y4 carbon atoms represented by 3-8, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, a cyclooctyl group, etc. it can.

R ^Y1 The number of carbon atoms of the aryl group represented by to R ^Y4, may be, for example, 6 to 20. Specific examples of the aryl group include a phenyl group, a tolyl group, a naphthyl group and the like, and among these, a phenyl group is preferable.

Specific examples of the halogen atom represented by R ^Y5 to R ^Y12, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, among these, a fluorine atom is preferable.

The anion of compound (a1) has an anionic group and a polymerizable unsaturated group. Examples of the anionic _{^{group, -SO 3 -, -CO-N}} - -CO -, - SO 2 -N - -SO 2 -, - COO - , and the like. Examples of the anionic group, ^-CO-N - -CO- and _{-SO 2} ^-N - _-SO 2 - are _preferred, -SO _² -N - -SO ² - are more preferable.

Examples of the polymerizable unsaturated group include a (meth) acryloyloxy group, a vinylaryl group, a vinyloxy group, and an allyl group. As the polymerizable unsaturated group, a (meth) acryloyloxy group and a vinylaryl group are preferable, and a vinylaryl group is more preferable.

As the anion of the compound (a1), those represented by the following formula (5) are preferable.

In formula (5), W ¹ is a monovalent polymerizable unsaturated group. X ¹ is an alkyl group or a fluorinated alkyl group. Y ¹ is a divalent hydrocarbon group.

As W ¹ , a vinyl group is preferable.

The ^{number of carbon atoms of the alkyl group represented by X 1} or the fluorinated alkyl group is preferably 1 to 10, and more preferably 1 to 3. As X ¹ , a fluorinated alkyl group is preferable, a perfluoroalkyl group is more preferable, and a trifluoromethyl group is further preferable.

Examples of the divalent hydrocarbon group represented by Y ¹ include a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, and 7 carbon atoms. Examples thereof include an arylalkylene group of ~ 20. As Y ¹ , an arylene group is preferable, and a phenylene group is more preferable.

As the structural unit (I), a structural unit derived from the compound (a1) is preferable, and a structural unit (A) represented by the following formula (I) is more preferable.

In formula (I),
V is a hydrogen atom or a methyl group.
X ¹ is an alkyl group or a fluorinated alkyl group.
Y ¹ is a divalent hydrocarbon group.
Z ⁺ is a cationic chromophore.

As V, a hydrogen atom is preferable from the viewpoint of copolymerizability of the monomer giving the structural unit (A).

Specific embodiments and preferred embodiments of X ¹ in formula (I) is the same as X ¹ in the above equation (5).

Specific embodiments and preferred embodiments of Y ¹ in the formula (I) is the same as Y ¹ in the above equation (5).

The specific form and suitable form of the cationic chromophore represented by Z ⁺ are the same as those of the cationic chromophore of the compound (a1) described above.

(Structural unit (II))
The structural unit (II) is a structural unit having no chromophore. The monomer that gives the structural unit (II) is not particularly limited as long as it is a compound that can be copolymerized with the compound (a1) and does not contain a chromophore, but has two or more crosslinkable groups. Compounds are preferred. By forming the structural unit (II) with the compound having two or more crosslinkable groups in this way, the conversion rate during the polymerization reaction can be improved, and the oxidative deterioration of the obtained polymer can be suppressed.

It is preferable that at least a part of the structural unit (II) of the polymer forms a crosslinked structure. By cross-linking the polymer in this way, oxidative deterioration can be suppressed.

Examples of the compound having two or more crosslinkable groups include 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, and 2,3-dimethyl-1,3-. Aliphatic conjugated diene compounds such as butadiene, non-conjugated divinyl compounds such as divinylbenzene, diisopropenylbenzene and trivinylbenzene, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (Meta) acrylates, 1,6-hexaneglycol di (meth) acrylates, 1,6-hexane glycol di (meth) acrylates, neopentyl glycol di (meth) acrylates, polypropylene glycol di (meth) acrylates and other alkylene glycol di Di (meth) acrylates such as (meth) acrylate compounds, 2,2-bis (4- (meth) acryloxipropyroxyphenyl) propane, 2,2-bis (4- (meth) acryloxidiethoxyphenyl) propane, etc. Compounds and the like can be mentioned.

As the compound having two or more crosslinkable groups, a non-conjugated divinyl compound and a di (meth) acrylate compound are preferable, a non-conjugated divinyl compound and an alkylene glycol di (meth) acrylate compound are more preferable, and divinylbenzene and ethylene glycol di (divinylbenzene) and ethylene glycol di ( Meta) acrylate is more preferred.

Examples of the monomer giving the structural unit (II) other than the compound having two or more crosslinkable groups include (meth) acrylic acid, maleic acid, maleic anhydride, and mono oxalic acid [2- (meth) acryloyloxyethyl]. , Ω-carboxypolycaprolactone Mono (meth) acrylate, ethylenically unsaturated monomer having a carboxy group such as p-vinylbenzoic acid, N-position substituted maleimide such as N-phenylmaleimide and N-cyclohexylmaleimide, styrene, Aromatic vinyl compounds such as α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, and acenaphthylene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glucol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polypropylene glucol (polymerization degree) 2-10) Methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2-10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2-10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) ) Acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, Ethylene oxide-modified (meth) acrylate of paramilphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxy Methyl] -3-ethyloxetane (meth) acrylic acid ester, cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether , 3- (Vinyloxymethyl) -3-ethyloxetane and other vinyl ethers, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, and other polymers at the end of the molecular chain. Has an acryloyl group Macromonomer and the like can be mentioned.

Monomers that give a structural unit (II) other than a compound having two or more crosslinkable groups include (meth) acrylic acid ester and carboxy from the viewpoint of conversion rate, mechanical strength of the obtained polymer, and solvent resistance. Ethylene unsaturated monomers having a group are preferred.

When the polymer has the structural unit (II), the lower limit of the content ratio of the structural unit (I) in all the structural units is preferably 0.5% by mass, more preferably 5% by mass, and further 10% by mass. It is preferable, and 15% by mass is particularly preferable. On the other hand, as the upper limit of the content ratio, 90% by mass is preferable, 85% by mass is more preferable, 80% by mass is further preferable, and 50% by mass, 40% by mass, or 35% by mass may be further preferable. By setting the content ratio in the above range, the conversion rate during the polymerization reaction can be further improved, and the oxidative deterioration of the obtained polymer can be further suppressed.

When the polymer contains a structural unit derived from a compound having two or more crosslinkable groups as the structural unit (II), the content ratio of the structural unit derived from the compound having two or more crosslinkable groups in the total structural unit. As the lower limit, 5% by mass is preferable, 10% by mass is more preferable, and 15% by mass is further preferable. On the other hand, the upper limit of the content ratio is preferably 50% by mass, more preferably 40% by mass. By setting the content ratio in the above range, the conversion rate during the polymerization reaction can be improved, and the oxidative deterioration of the obtained polymer can be further suppressed.

(Polymerization method)
The polymerization method for obtaining a liquid containing a particulate polymer having a chromophore is not particularly limited, but an emulsion polymerization method is preferable. Examples of the emulsion polymerization method include a method in which a monomer such as compound (a1), a chain transfer agent, a polymerization initiator, a surfactant and the like are added to an aqueous dispersion medium such as water to carry out emulsion polymerization.

The polymerization process is
A step of preparing a mixed solution containing at least water, a surfactant and a monomer and a solution containing at least a polymerization initiator (step (1)), and starting polymerization with a mixed solution containing the monomer obtained in the step (1). Step of emulsion polymerization by mixing with a solution containing an agent (step (2))
It is preferable to provide. Hereinafter, each step will be described.

(Step (1))
In step (1), a mixed solution containing at least water, a surfactant and a monomer (hereinafter, also referred to as “monomer mixed solution”) and a solution containing at least a polymerization initiator (hereinafter, also referred to as “polymerization initiator solution”). Is the process of preparing. The polymerization initiator solution may further contain water and a surfactant. The mass ratio of the polymerization initiator solution to the monomer mixed solution is, for example, 0.01 or more and 5.0 or less. First, each component will be described.

As the surfactant, a known surfactant generally known in emulsion polymerization can be used. Examples of such surfactants include alkali metal salts (particularly sodium and potassium salts) of fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid, sodium lauryl sulfate, sodium lauryl sulfonate, and dodecyl. Sodium sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyldiphenyl ether sulfonate, sodium amber acid dialkyl ester sulfonate, sodium polyoxyethylene alkyl ether sulfonate, alkali metal loginate salt (especially sodium salt, potassium salt), formaldehyde condensed naphthalene Anionic surfactants such as sodium sulfonate, nonionic surfactants such as polyoxyethylene alkyl ester and polyoxyethylene alkylaryl ether, alkyl betaine type salts such as lauryl betaine and stearyl betaine salts, lauryl-β- Examples thereof include double-sided surfactants such as amino acid types such as alanine, lauryldi (aminoethyl) glycine, and octyldi (aminoethyl) glycine.

As the lower limit of the amount of the surfactant used, 0.1 part by mass is preferable, 1 part by mass is more preferable, and 10 parts by mass is further preferable with respect to 100 parts by mass of the monomer. On the other hand, as the upper limit of the amount of the surfactant used, 100 parts by mass is preferable, and 40 parts by mass is more preferable with respect to 100 parts by mass of the monomer. Here, the "usage amount" of each material used for emulsion polymerization means the total of the content contained in the monomer mixed solution and the content contained in the polymerization initiator solution.

As the polymerization initiator, a known polymerization initiator generally known in emulsion polymerization can be used. Examples of the polymerization initiator include inorganic persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, organic peroxides such as cumene hydroperoxide, benzoyl peroxide, and isopropylbenzene peroxide, and azoisobutyronitrile. Azo-based initiators and the like are used. These polymerization initiators may be used alone or in combination of two or more.

These polymerization initiators can also be used as so-called redox-based initiators in combination with a reducing agent. Examples of the reducing agent include reducing sulfoxylates such as sulfite, hydrogen sulfite, pyrosulfite, nitionate, nithionate, thiosulfate, formaldehyde sulfonate, and benzaldehyde sulfonate, and sulfate. Examples thereof include monoiron, ferrous ammonium sulfate, and ferrous naphthenate.

As the polymerization initiator, inorganic persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate are preferable from the viewpoint of polymerization stability.

As the lower limit of the amount of the polymerization initiator used, 0.1 part by mass is preferable and 0.2 part by mass is more preferable with respect to 100 parts by mass of the monomer. On the other hand, as the upper limit of the amount used, 10 parts by mass is preferable, 8 parts by mass is more preferable, 5 parts by mass is further preferable, and 2 parts by mass is particularly preferable with respect to 100 parts by mass of the monomer.

A chain transfer agent may be added to the monomer mixture and the polymerization initiator solution. As the chain transfer agent, a known chain transfer agent generally known in emulsion polymerization can be used. Examples of such a chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, and t-tetradecyl mercaptan, dimethylxanthogen disulfide, and diethyl. Xanthogen disulfides such as xanthogen disulfides and diisopropylxanthogen disulfides, thiuram disulfides such as tetramethylthiol disulfides, tetraethyl thiuram disulfides and tetrabutyl thiuram disulfides, halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide, pentaphenylethane, Hydrocarbons such as 1,1-diphenylethylene and α-methylstyrene dimer, achlorine, metachlorine, allyl alcohol, 2-ethylhexylthioglycolate, turpinolene, α-terpinene, γ-terpinene, dipentene and the like can be mentioned. .. These chain transfer agents can be used alone or in combination of two or more.

The lower limit of the amount of the chain transfer agent used is preferably 0.05 parts by mass, more preferably 0.1 parts by mass, and even more preferably 0.2 parts by mass with respect to 100 parts by mass of the monomer. On the other hand, as the upper limit of the amount used, 20 parts by mass is preferable, 15 parts by mass is more preferable, and 10 parts by mass is further preferable.

A chelating agent such as sodium ethylenediaminetetraacetate, a dispersant such as a polycarboxylic acid salt, an inorganic salt such as a phosphate salt, or the like may be added to the monomer mixed solution and the polymerization initiator solution. Further, for emulsifying polymerization, if necessary, pH adjusters such as ammonia, sodium hydroxide and potassium hydroxide, antiaging agents such as styrenated phenol, hindered phenol, imidazoles and paraphenylenediamine, acetophenone, etc. Fragrances such as cinnamon aldehyde, vanillin, lavender oil, antibacterial agents such as siabendazole, preventol, bainazine, defoamers such as silicones and higher alcohols, dimethyldithiocarbamates, N, N-dimethylhydroxyamine , Reaction terminators such as thiourea, and additives such as ethylene glycol, diethylene glycol, and antifreeze agents such as urea may be appropriately added.

The method for preparing the monomer mixed solution and the polymerization initiator solution is not particularly limited, and each component may be added individually or all the components may be added at the same time. When each component is added individually, the order of addition of each component is not particularly limited. The concentration of the monomer in the monomer mixed solution can be appropriately selected, but is preferably 1% by mass or more and 50% by mass or less. The concentration of the polymerization initiator in the polymerization initiator solution can be appropriately selected, but is preferably 0.01% by mass or more and 0.5% by mass or less. The monomer mixture and the polymerization initiator solution may be emulsified after preparation, but may be used as they are in the next step without emulsification. The emulsification method is not particularly limited, and a conventionally known method can be appropriately selected.

(Step (2))
The step (2) is a step of emulsion polymerization by mixing the monomer mixture obtained in the step (1) with the polymerization initiator solution. As a method of charging the monomer mixed solution into the reaction vessel in the step (2), a method of charging all of the monomer mixed solution at once, a method of charging the monomer mixed solution continuously or intermittently as the polymerization progresses, and a monomer. Any method may be used, such as a method in which a part of the mixed solution is charged and polymerization is started, and then the remaining monomer mixed solution is charged all at once or continuously or intermittently for polymerization. Further, as a method of charging the polymerization initiator solution into the reaction solution in the step (2), a method of charging the entire polymerization initiator solution at once, or a method of charging the polymerization initiator solution continuously or intermittently as the polymerization progresses. It may be any method such as a method in which a part of the polymerization initiator solution is charged to start the polymerization, and then the remaining polymerization initiator solution is charged in a batch or continuously or intermittently to carry out the polymerization. .. In these cases, the composition of the monomer mixture and / or the polymerization initiator solution added continuously or intermittently may be the same or changed.

As the lower limit of the polymerization temperature of emulsion polymerization, 5 ° C. is preferable, and 20 ° C. is more preferable. On the other hand, as the upper limit of the polymerization temperature, 85 ° C. is preferable, and 80 ° C. is more preferable. The polymerization time of emulsion polymerization is preferably 1 hour or more and 12 hours or less. The emulsion polymerization is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas. The final polymerization conversion rate in emulsion polymerization is preferably 90% or more.

In addition, in the above polymerization step, the monomer and polymerization method described in International Publication No. 2017/154854 can be applied.

[Filtration process]
In the filtration step, the liquid (dispersion liquid) containing the particulate polymer obtained through the polymerization step is filtered in the order of the first filter membrane and the second filter membrane. The dispersion obtained through the polymerization step is not filtered before being filtered by the first filter membrane. The filtration step can be performed using a filter having a first filter membrane and a filter having a second filter membrane. A filter having a first filter film and a second filter film may be used.

The filter membrane (filter membrane) used in the membrane separation step is a microfiltration membrane (MF), an ultrafiltration membrane (UF), a nanofiltration membrane (Nanofiltration (NF)), and a reverse osmosis membrane (Nanofiltration membrane). It can be classified into Reverse osmosis (RO)) and the like. The microfiltration step refers to a step of separating particles having a colloid size or larger that are insoluble in a solution, and the separation membrane used at that time is called a microfiltration membrane. The first filter membrane, the second filter membrane, and the third filter membrane described later may be filter membranes classified into microfiltration membranes.

(First filter membrane)
The average pore size of the first filter film is 7 μm or less, preferably 6 μm or less, 5 μm or less, or 4 μm or less. The average pore size of the first filter film may be 0.5 μm or more, and may be 1 μm or more or 2 μm or more.

The average pore size of each filter film means an average pore size determined by the removal rate of standard particles (that is, polystyrene particles), and in the case of a commercially available product, it may be a manufacturer's nominal value.

The average thickness of the first filter film may be, for example, 0.1 μm or more and 1 μm or less. The average thickness means the average value of the thickness measured at any five points. The porosity of the first filter film is preferably 60% or more and 70% or less. Further, it is preferable that the first filter film can be used under a pressure of about 50 to 200 kPa.

The first filter membrane is not particularly limited as long as it does not deteriorate depending on the liquid to be permeated and the operating temperature. For example, an inorganic film using alumina, zirconia, titania or the like as a base material, a metal film using 304 or 316 stainless steel as a base material, cellulose, bleached cotton, polysulfone (PS), polypropylene (PP), polyether monkey. Examples thereof include a polymer membrane using polysulfone (PES), polyethylene terephthalate (PET), polyvinylidene fluoride (PVDF), polyvinylidene (PCTE), polytetrafluoroethylene (PTFE) and the like as a base material. Among these, inorganic membranes, polysulfone (PS) membranes, polytetrafluoroethylene (PTFE) membranes, and polyether sulfone (PES) membranes are preferable, and polyether sulfone (PES) membranes are even more preferable.

Examples of the shape of the first filter film include a tube type, a flat plate type, and a monolith type. The method for permeating the liquid may be an internal pressure filtration method or an external pressure filtration method.

(Second filter film)
The average pore size of the second filter film is 1 μm or less. The average pore size of the second filter film may be 0.1 μm or more, and may be 0.3 μm or 0.5 μm or more.

The specific form and the preferred form other than the average pore size of the second filter film are the same as those of the first filter film described above.

When the average pore size of the first filter film is A and the average pore size of the second filter film is B, it is preferable that 1 <A / B ≦ 7 is satisfied, and 2 <A / B <7 is more likely to be satisfied. preferable. When the relationship between the average pore size of the first filter film and the average pore size of the second filter film satisfies the above formula, polymer particles having a more uniform particle size can be obtained, and the fastness during washing can be further improved. , The decrease in color development after washing can be further suppressed. In addition, the first filter is preferable because it can sufficiently remove coarse particles, which leads to an improvement in productivity.

(Third filter membrane)
In the production method according to the embodiment of the present invention, it is preferable that the plurality of filter membranes further include a third filter membrane through which the liquid permeates after the second filter membrane. In this case, the liquid obtained through the polymerization step is filtered in the order of the first filter membrane, the second filter membrane, and the third filter. By performing filtration with such three filter membranes, polymer particles having a more uniform particle size can be obtained, the fastness during washing can be further enhanced, and the deterioration of color development after washing can be further suppressed. it can. The filtration step can be performed using a filter having a third filter membrane in addition to the filter having the first filter membrane and the filter having the second filter membrane. A filter having a first filter film, a second filter film and a third filter film may be used.

The average pore size of the third filter film is preferably 1 μm or less. The average pore size of the third filter film may be 0.1 μm or more, and may be 0.3 μm or 0.5 μm or more.

The specific form and the preferred form other than the average pore size of the third filter film are the same as those of the first filter film described above.

When the average pore size of the second filter film is B and the average pore size of the third filter film is C, it is preferable that 1 ≦ B / C <2 is satisfied, and 1 ≦ <B / C <1.5 is satisfied. Is more preferable. When the relationship between the average pore size of the second filter film and the average pore size of the third filter film satisfies the above formula, polymer particles having a more uniform particle size can be obtained, and the fastness during washing can be further improved. , The decrease in color development after washing can be further suppressed.

Specific examples of each filter membrane include Profile II, Nexus NXA, Nexus NXT, Polyfine XLD, Ultipleated Profile, etc. (all manufactured by Nippon Paul Co., Ltd.), Depth Cartridge Filter, Wind Cartridge Filter, etc. (All Advantech Co., Ltd.). , CP filter, BM filter, etc. (all manufactured by Chisso), Slope Pure, Dia, Microsilia, etc. (all manufactured by Loki Techno), HDCII, Polyfine II, etc. (all manufactured by Nippon Pole), PP pleats Cartridge filter (made by Advantech), Porous Fine (made by Chisso), Sirton Pore, Micropure, etc. (all made by Loki Techno), Membrane filter Cellulose mixed ester type, Omnipore membrane, Durapore membrane, Florinate membrane, etc. (All, Commercially available products such as (Merck Millipore) can be used.

The filtration temperature in the filtration step may be within the applicable range of the filter membrane to be used and within the range in which dispersion stability can be maintained, but for example, 10 to 150 ° C. is preferable, 15 to 100 ° C. is more preferable, and 20 to 60 ° C. ° C is more preferred, and 35-60 ° C is even more preferred. By raising the filtration temperature, the liquid becomes less viscous and the filtration efficiency increases.

[Other processes]
The production method may further include steps other than the polymerization step and the filtration step. The production method can include, for example, a pH adjusting step of adjusting the pH of a liquid (dispersion liquid) containing a particulate polymer obtained through a polymerization step, a liquid (dispersion liquid) obtained through a filtration step, and the like. .. The pH can be adjusted by adding an acid or an alkali to the liquid (dispersion liquid).

[Polymer particles]
In the production method, the polymer particles are usually obtained in the state of a dispersion liquid dispersed in a dispersion medium such as water. The solid content concentration in the obtained dispersion may be, for example, 5% by mass or more and 50% by mass or less, and may be 10% by mass or more and 40% by mass or less.

The polymer particles obtained by the production method are preferably spherical particles. As described above, since the polymer particles are spherical, diffused reflection on the particle surface can be suppressed, and as a result, the color development property after printing can be further improved.

The lower limit of the average particle size of the polymer particles is preferably 10 nm, more preferably 25 nm, and even more preferably 50 nm. By setting the average particle size of the polymer particles to the above lower limit or more, the polymer particles are less likely to dissolve in water, and as a result, the fastness during washing is further enhanced, and the decrease in color development can be further suppressed. The upper limit of the average particle size of the polymer particles is preferably 1,000 nm, more preferably 600 nm, and even more preferably 400 nm. By setting the average particle size of the polymer particles to the above upper limit or less, the surface area per unit volume is increased, and the color development property is likely to be improved.

Here, the "average particle size" means that when the particle size distribution is measured using a particle size distribution measuring device based on the light scattering method and the particles to be written in order from the smallest particles are accumulated, the particles are accumulated based on the number of particles. It is a value of the particle size (D50) at a frequency of 50%.

The polymer particles are preferably textile inks. When the polymer particles are used as a component of a textile ink (textile ink agent), the printed matter of this ink has excellent fastness during washing, and the color development property does not easily deteriorate even after many washings. ..

<Ink>
One embodiment of the present invention may be an ink containing the polymer particles as an ink agent. The ink can be easily inkjet printed. In addition, the ink-printed product has excellent fastness during washing, and the color development property is unlikely to deteriorate even after a large number of washings.

[Ink]
The ink agent contained in the ink contains the above-mentioned polymer particles. The lower limit of the content of the ink agent or the polymer particles in the ink is preferably 0.1% by mass, preferably 1% by mass, and more preferably 5% by mass. On the other hand, the upper limit of the content is preferably 50% by mass, more preferably 40% by mass, further preferably 30% by mass, and particularly preferably 15% by mass. By setting the content of the ink agent in the above range, the viscosity of the ink can be adjusted to an appropriate level.

[Binder resin]
The ink preferably contains a binder resin. The binder resin plays a role like glue, and makes it easier to fix the ink agent on the fibers forming the woven fabric, thereby further enhancing the fastness of the ink. As the binder resin, a water-soluble synthetic resin is preferable, a water-soluble phenol resin, a water-soluble urethane resin, and a water-soluble acrylic resin are more preferable, and a water-soluble acrylic resin is further preferable. As the water-soluble acrylic resin, a water-soluble styrene-acrylic acid copolymer can also be used. The binder resin may be used alone or in combination of two or more.

The lower limit of the content of the binder resin in the ink is preferably 0.5% by mass, more preferably 1.5% by mass. On the other hand, the upper limit of the content of the binder resin is preferably 20% by mass, more preferably 10% by mass, and even more preferably 5% by mass. By setting the content of the binder resin in the above range, the ink agent can be easily fixed by the fibers.

[Liquid medium]
The ink usually further comprises a liquid medium. The liquid medium used for the ink is not particularly limited, and examples thereof include water, a mixed solvent containing water and an organic solvent, and the like. The organic solvent may be used alone or in combination of two or more.

(water)
The water used for the ink is not particularly limited, but pure water is preferable. This pure water can be produced by, for example, ion exchange, distillation, or the like. Further, the pure water is preferably sterilized by ultraviolet rays or the like.

(Organic solvent)
The organic solvent used for the ink is not particularly limited, but is preferably alcohol from the viewpoint of adjusting the viscosity to an appropriate level and suppressing odor, and more preferably alcohol having a boiling point of 150 ° C. or higher at 1 atm. Examples of such alcohols include keto alcohols having a boiling point of 150 ° C. or higher at 1 atm and polyhydric alcohols having a boiling point of 150 ° C. or higher at 1 atm.

Examples of the keto alcohol having a boiling point of 150 ° C. or higher at 1 atm that can be used for the ink include diacetone alcohol.

Examples of the polyhydric alcohol having a boiling point of 150 ° C. or higher at 1 atm that can be used for the ink include ethylene glycol-based polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, glycerin, and propylene glycol. Dipropylene glycol, tripropylene glycol, polyethylene glycol with a molecular weight of 2,000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-pentane Diol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2,6-hexanetriol, 1,8-octanediol, 1,2-octanediol, mesoerythritol, penta Examples thereof include erythritol and 2-mercaptoethanol. As the polyhydric alcohol, ethylene glycol-based polyhydric alcohol and glycerin are preferable, and diethylene glycol and glycerin are more preferable.

As the liquid medium, a mixed solvent containing water and an organic solvent is preferable, a mixed solvent containing water, ketoalcohol and polyhydric alcohol is more preferable, and a mixed solvent containing water, diacetone alcohol, diethylene glycol and glycerin is further preferable.

When the ink contains a liquid medium, the lower limit of the content of the liquid medium in the ink is preferably 10% by mass, more preferably 20% by mass, still more preferably 50% by mass. On the other hand, the upper limit of the content of the liquid medium is preferably 95% by mass, more preferably 80% by mass. By setting the content of the liquid medium in the above range, the viscosity of the ink can be adjusted to a more appropriate level.

When the ink contains water, the lower limit of the water content in the ink is not particularly limited, but is preferably 5% by mass, more preferably 10% by mass. On the other hand, the upper limit of the water content is not particularly limited, but is preferably 90% by mass, more preferably 85% by mass, further preferably 80% by mass, particularly preferably 70% by mass, and even more particularly preferably 60% by mass. It is preferable, and 30% by mass is most preferable. By setting the water content in the above range, the viscosity of the ink can be adjusted to a more appropriate level.

When the ink contains ketoalcohol, the lower limit of the content of ketoalcohol in the ink is not particularly limited, but is preferably 5% by mass, more preferably 20% by mass. On the other hand, the upper limit of the content of the ketoalcohol is not particularly limited, but is preferably 80% by mass, more preferably 60% by mass. By setting the content of the keto alcohol in the above range, the viscosity of the ink can be adjusted to a more appropriate level.

When the ink contains a polyhydric alcohol, the lower limit of the content of the polyhydric alcohol in the ink is not particularly limited, but is preferably 1% by mass, more preferably 5% by mass. On the other hand, the upper limit of the content of the polyhydric alcohol is not particularly limited, but is preferably 40% by mass, more preferably 20% by mass. By setting the content of the polyhydric alcohol in the above range, the viscosity of the ink can be adjusted to a more appropriate level.

[Additive]
The ink may further contain other additives in addition to the above-mentioned components. Examples of the other additives include hydrotropy agents, alkylene glycol monoalkyl ethers, surfactants, preservatives, defoamers (antifoaming agents), chelating agents, light stabilizers and the like.

The hydrotropy agent used for the ink improves the affinity between the ink agent and the liquid medium by breaking the hydrogen bond of the liquid medium or the like. Examples of the hydrotropy agent include urea, dimethylurea, thiourea, monomethylthiourea, dimethylthiourea and the like, and urea is preferable.

When the ink contains a hydrotropy agent, the lower limit of the content of the hydrotropy agent in the ink is preferably 1% by mass, more preferably 5% by mass. On the other hand, the upper limit of the content is preferably 40% by mass, more preferably 25% by mass. By setting the content in the above range, the affinity between the ink agent and the liquid medium can be further improved.

The alkylene glycol monoalkyl ether and the surfactant improve the stability when ejecting the ink with an inkjet printer, particularly the stability when ejecting with an inkjet printer using a piezo head. Examples of the alkylene glycol monoalkyl ether include triethylene glycol mono-n-butyl ether and the like. Examples of the surfactant include acetylene glycol-based surfactants, compounds listed as surfactants used in the step (1) during the polymerization step, and the like.

The lower limit of the content of each of the alkylene glycol monoalkyl ether and the surfactant in the ink is preferably 0.1% by mass, more preferably 0.3% by mass, still more preferably 0.5% by mass. On the other hand, the upper limit of the content is preferably 20% by mass, more preferably 18% by mass, and may be 15% by mass, 10% by mass, or 5% by mass.

Examples of the preservative used in the ink include "Proxel CRL", "Proxel BDN", "Proxel GXL", "Proxel XL2", "Proxel IB", and "Proxel TN" manufactured by Avecia.

When the ink contains a preservative, the lower limit of the content of the preservative in the ink is preferably 0.01% by mass, more preferably 0.1% by mass, and even more preferably 0.3% by mass. On the other hand, the upper limit of the content of the preservative is preferably 2% by mass, more preferably 1% by mass, and even more preferably 0.8% by mass. By setting the content of the preservative in the above range, the preservative property can be sufficiently exhibited without deteriorating the color development property and the like.

Examples of the defoaming agent (defoaming agent) used in the ink include mineral oil-based defoaming agents, silicone-based defoaming agents, and polymer-based defoaming agents.

When the ink contains a defoaming agent (foaming agent), the lower limit of the content of the defoaming agent in the ink is preferably 0.005% by mass, more preferably 0.01% by mass, and 0. 02% by mass is more preferable. On the other hand, the upper limit of the content of the defoaming agent is preferably 0.2% by mass, more preferably 0.15% by mass, and even more preferably 0.1% by mass. By setting the content of the defoaming agent in the above range, it is possible to sufficiently exert the defoaming / suppressing effect without deteriorating the color-developing property and the like.

The chelating agent used for the ink improves the reliability of the ink by trapping the metal in the ink, and prevents dyeing spots by trapping the heavy metal of the woven fabric. As the chelating agent, ethylenediaminetetraacetic acid salt, nitrilotriacetate salt, hexametaphosphate, pyrophosphate and metaphosphate are preferable. As commercially available products of the chelating agent, BASF's "TRILON TA" and "DEKOL SN" and Benkiesed's "Calgon T" are preferable. Since the commercially available products of these chelating agents are excellent in biodegradability, the environmental load can be reduced. The upper limit of the content of the chelating agent in the ink is not particularly limited, but is, for example, 5% by mass.

The light stabilizer used in the ink can further enhance the fastness during washing and further suppress the deterioration of the color development property after washing. Examples of the light stabilizer include hindered phenol-based antioxidants, hindered phenol-based ultraviolet absorbers, organic sulfur-based antioxidants, organic phosphorus-based antioxidants, hindered amine-based light stabilizers, and benzotriazole-based ultraviolet absorbers. Examples thereof include benzophenol-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, organic nickel-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. Among these, hindered phenol-based antioxidants and hindered amine-based light stabilizers are preferable, and hindered amine-based light stabilizers are more preferable. Further, the light stabilizer may be used alone or in combination of two or more.

Examples of the hindered phenol-based antioxidant include 2,6-di-tert-butyl-4-phenylmethyl-phenol, 2,6-di-tert-butyl-4-phenylphenol, and 2,6-di-tert. -Butyl-P-cresol, 4,4'-thiobis- (6-tert-butyl-3-methylphenol), 4,4'-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2 '-Methylenebis- (4-methyl-6-tert-butylphenol), 2,2'-methylenebis- (4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-ethylphenol, 1,1,3-Tris (2-methyl-4hydroxy-5-tert-butylphenyl) butane, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [ Methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, triethylene glycolbis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], Tris (3,5-di-tert-butyl-4, hydroxybenzyl) isocyanurate, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1, 6-Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5) -Di-t-butylanilino) -1,3,5-triazine, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Adecastab AO-50 (Adecastab AO-50) ADEKA)), N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxybenzylphos Phonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl) -4-Hi Ethyl droxybenzylphosphonate) calcium, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, diphenylamine octylated, 2,4-bis [(octylthio) methyl] -O -Cresol, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4-thiobis- (2-tert-butyl-5-methylphenol), pentaerythritol tetrakis- (3) , 5-Di-t-Butyl-4-hydroxyhydrocinnamate, Tris (4-t-Butyl-2,6-Dimethyl-3-hydroxybenzyl) -1,3,5-Triazine-2,4,6 ( 1H, 3H, 5H) (Adecastab AO-20 (manufactured by ADEKA)), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate butylated hydroxyanisole, 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, bis [3,3'-bis (4'-hydroxy-) 3'-t-butylphenyl) butyric acid] glycol ester, tocopherols and the like can be mentioned.

Examples of the hindered phenol-based ultraviolet absorber include 2', 4'-di-tert-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate and the like.

Examples of the organic sulfur-based antioxidant include dilaurylthiodipropionate, distearylthiodipropionate, dimyristylthiodipropionate, ditridecylthiodipropionate, and pentaerythritol tetrakis- (3-dodecylthiopropionate). ), Etc. can be mentioned.

Examples of the organophosphorus antioxidant include tris (2,4-di-tert-butylphenyl) phosphine, triphenylphosphine, tri (nonylphenyl) phosphine, tri (dynonylphenyl) phosphine, and tricresylphosphine. Examples thereof include tri (2,4-dibutylphenoxy) phosphine.

Examples of the hindered amine-based light stabilizer include bis- [2,2,6,6-tetramethyl-4-piperidinyl] sebacate (Sanol LS-770 (manufactured by Sankyo Co., Ltd.), Adecaster LA-77 (manufactured by ADEKA)). Bis- [N-methyl-2,2,6,6-tetramethyl-4-piperidinyl] sebacate (TINUVIN 765 (manufactured by BASF), SANOL LS 765 (manufactured by Sankyo)), Bis- (1,2,2) , 6,6-Pentamethyl-4-piperidinyl) -2- (3,5-di-tetra-butyl-4-hydroxybenzyl) -2-n-butylmalonate (TINUVIN 144 (manufactured by BASF)), Tetrax (manufactured by BASF) 2,2,6,6-Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (Adecastab LA-57 (manufactured by ADEKA)), Tetrakiss (1,2,2,6) 6-Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (Adecastab LA-52 (manufactured by ADEKA)), 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butantetracarboxylate (Adecastab LA-67 (manufactured by ADEKA), 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4 -Butan tetracarboxylate (ADECASTAB LA-62 (manufactured by ADEKA)) and the like can be mentioned.

Examples of the benzotriazole-based ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-. Benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2 -(3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2' -Hydroxy-5'-t-octylphenyl) benzotriazole, 5-chloro-2- (3,5-di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3-t-butyl) -2-Hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5) -Di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2H-benzotriazole-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidine) Methyl) phenol, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, 2- (2-hydroxy- 5-octylphenyl) -benzotriazole and the like can be mentioned.

Examples of the benzophenone-based ultraviolet absorber include 2,4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, and the like. 4-Dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 1 , 4-Bis (4-benzoyl-3-hydroxyphenoxy) -butane and the like.

Examples of the salicylate-based ultraviolet absorber include phenylsalicylate and 4-t-butylphenylsalicylate.

Examples of the cyanoacrylate-based ultraviolet absorber include ethyl2-cyano-3,3-diphenylacrylate, 2'-ethylhexyl 2-cyano-3,3-diphenylacrylate and the like.

Examples of the organic nickel-based ultraviolet absorber include [2,2'-thiobis (4-t-octylphenolate)] -2-ethylhexylamine nickel (II) and 2,2-thiobis (4-t-octylphenolate). ) -N-Butylamine nickel (II) and the like.

Examples of the triazine-based ultraviolet absorber include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- (octyloxy) phenol, and the like. Can be mentioned.

The lower limit of the content of the light stabilizer in the ink is preferably 0.01% by mass, more preferably 0.1% by mass, and even more preferably 0.3% by mass. On the other hand, the upper limit of the content of the light stabilizer is preferably 10% by mass, more preferably 8% by mass, and even more preferably 6% by mass. By setting the content of the light stabilizer in the above range, the ink agent (polymer particles) can be easily fixed by the fibers.

In the ink, the mass ratio (Mc / Ma) of the content (Mc) of the light stabilizer to the content (Ma) of the polymer particles is preferably in the range of 0.001 to 1, and preferably 0.05 to 1. It is more preferably in the range of 0.8, and even more preferably in the range of 0.01 to 0.8. When the mass ratio (Mc / Ma) is in the above range, the contour of the printed material is less likely to bleed, the fastness during washing becomes better, and the deterioration of color development is less likely to occur. The reason for this is not clear, but the polymer particles having a color-developing group and the light stabilizer are appropriately compatible with each other, so that the polymer particles are well dispersed in a state where the light stabilizer surrounds the polymer particles. It is presumed that it is fixed to the fibers.

The method for producing the ink is not particularly limited, and the ink can be obtained by mixing the above-mentioned components by a conventionally known method.

<Printing method>
Next, a printing method using the ink will be described. This printing method includes a step of ejecting ink droplets and adhering the droplets to the woven fabric (ejection step) and a step of heating the woven fabric after the ejection step (heating step). The printing method may further include a step (pretreatment step) of pretreating the woven fabric before the discharge step. According to the printing method, the obtained printed material has excellent fastness during washing, and it is possible to suppress a decrease in color development even after a large number of washings.

The woven fabric used in the above printing method is not particularly limited, but is formed of, for example, natural fibers such as cotton, linen, wool and silk, synthetic fibers such as polyester, nylon and polyurethane, and semi-synthetic fibers such as acetate fibers. Textiles can be mentioned.

[Pretreatment process]
In this step, in order to improve the fixability of the ink contained in the ink to the woven fabric, the woven fabric is pretreated before the ejection step. Examples of the pretreatment method include a method of applying a pretreatment agent to a woven fabric.

As the pretreatment agent, for example, those containing a hydrotropy agent, an aqueous metal salt, a pH adjuster, a pH buffer, an aqueous polymer and the like can be used. The pretreatment agent may further contain additives such as a water repellent and a surfactant.

Examples of the hydrotropy agent include urea, dimethylurea, thiourea, monomethylthiourea, dimethylthiourea and the like.

Examples of the aqueous metal salt include alkali metal salts and alkaline earth metal salts.

Examples of the pH adjuster include ammonium acid salts such as ammonium sulfate and ammonium tartrate.

Examples of the aqueous polymer include starch substances such as corn and wheat, cellulosic polymers such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, and polysaccharide-based polymers such as sodium alginate, arabia rubber, locust bean gum, tranth gum, guar gum and tamarind seeds. Natural aqueous polymers such as molecules, protein substances such as gelatin and casein, tannin-based substances and lignin-based substances, and synthetic aqueous polymers such as polyvinyl alcohol, polyethylene oxide, acrylic acid-based polymers and maleic anhydride-based polymers. Can be mentioned.

[Discharge process]
In this step, droplets of the ink are ejected and the droplets are attached to the fabric. An inkjet method is preferable as a method for ejecting ink droplets. The inkjet printer used in the inkjet method is not particularly limited, and a commercially available printer can be used.

[Heating process]
In this step, the woven fabric after the ejection step is heated to remove volatile components such as a liquid medium in the ink. The heating temperature at this time is, for example, 70 ° C. or higher and 140 ° C. or lower. The heating time is, for example, 30 seconds or more and 20 minutes or less, preferably 30 seconds or more and 5 minutes or less. By setting the heating temperature and the heating time within the above ranges, volatile components can be reliably removed while suppressing thermal decomposition of the ink agent.

[Other processes]
The printing method may further include other steps. However, the printing method does not have to include a step (cleaning step) of cleaning the woven fabric after the discharge step. By not performing the cleaning treatment in the printing method, a printed product having particularly little bleeding and excellent color development can be obtained.

The present invention is not limited to the above embodiment, and various modifications are possible. The present invention includes a configuration substantially the same as the configuration described in the embodiment (for example, a configuration having the same function, method and result, or a configuration having the same purpose and effect). The present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration. Furthermore, the present invention also includes a configuration that exhibits the same effects as the configuration described in the above embodiment or a configuration that can achieve the same object. Further, the present invention also includes a configuration in which a known technique is added to the configuration described in the above embodiment.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

[Average particle size and shape of polymer particles, and ratio based on the number of spherical particles in the polymer particles]
The average particle size of the polymer particles is measured by measuring the particle size distribution using a particle size distribution measuring device based on the light scattering method, and the cumulative frequency of the number of particles when the particles are accumulated from small particles is 50%. It is a value of (D50). As such a particle size distribution measuring device, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was used.
The shape and the number ratio of spherical particles were measured by the following methods. That is, the shape of the particles was visually confirmed with a transmission electron microscope (“H-7650” manufactured by Hitachi High-Technologies Corporation), and the ratio of spherical particles to 100 particles existing in the observation field of view was calculated.

[Manufacturing of polymer particles]
[Example 1]
A colored particle dispersion was obtained according to Synthesis Example 1 of JP2015-214682A. Specifically, 20.0 g of methyl methacrylate, 5.0 g of ethylene glycol dimethacrylate, and 6.5 g of the monomer (1) represented by the following formula were mixed so as to be uniform. 6.3 g of sodium dodecylsulfonate and 56.9 g of ion-exchanged water were added to this mixed solution to prepare a monomer mixed solution.

Separately from the above monomer mixed solution, 0.6 g of sodium dodecylsulfonate, 1.5 g of a 5 mass% aqueous solution of sodium persulfate, and 110.5 g of ion-exchanged water were mixed to prepare a polymerization initiator solution. This polymerization initiator solution was heated to 80 ° C. under a nitrogen flow. The above-mentioned monomer mixture was added dropwise to the heated polymerization initiator solution over 3 hours. After completion of the dropping, the reaction solution was maintained at an internal temperature of 80 ° C. for 1 hour. Subsequently, an aqueous solution obtained by mixing 1.3 g of a 2% by mass aqueous solution of sodium persulfate and 0.5 g of ion-exchanged water was added to the above reaction solution. The reaction solution was maintained at 80 ° C. for another 2 hours and then allowed to cool to room temperature. Ammonia water having a concentration of 11.5% was added to the obtained reaction solution until the pH reached 8.2, and then 0.015 g of a silicone emulsion-based defoaming agent (SN Deformer 381 manufactured by San Nopco Co., Ltd.) was added. Then, this reaction solution was permeated through a filter having a first filter membrane having an average pore size of 5 μm (manufactured by Nippon Pole Co., Ltd., product name “5EC488389050J”). Next, a filter having a second filter membrane having an average pore diameter of 1 μm (manufactured by Nippon Pole Co., Ltd., product name “5EC488389010J”) and a filter having a third filter membrane having an average pore diameter of 0.7 μm (Nippon Pole Co., Ltd.). The product name "5EC4888389007J") was transmitted in this order. This was used as a dispersion liquid (A-1) containing a textile ink containing polymer particles. In addition, 90% or more of the polymer particles in the dispersion liquid (A-1) were spherical particles on a number basis. The solid content concentration of the dispersion liquid (A-1) was 30% by mass, and the average particle size of the polymer particles determined by observation with a transmission electron microscope in the dispersion liquid (A-1) was 246 nm.

[Example 2]
71.5 g of methyl methacrylate, 19.0 g of ethylene glycol dimethacrylate, 3.0 g of methacrylic acid and 6.5 g of the above-mentioned monomer (1) were mixed so as to be uniform. 2. 1.1 g of a surfactant (Kao Corporation's "Latemuru E-118B", concentration 26% by mass) and a surfactant (New Japan Chemical Co., Ltd. "Ricasurf M-30", concentration 70% by mass). A monomer mixture was prepared by adding to a container containing 7 g and 40.4 g of ion-exchanged water and stirring for 20 minutes.

Separately from the above monomer mixture, 1.12 g of a surfactant (Kao Corporation's "Latemuru E-118B", concentration 26% by mass), 5.8 g of a 5% by mass aqueous solution of ammonium persulfate, and 157.7 g of ion-exchanged water were added. Mixing was used to prepare a polymerization initiator solution. This polymerization initiator solution was heated to 80 ° C. under a nitrogen flow. The above-mentioned monomer mixture was added dropwise to the heated polymerization initiator solution over 3 hours. After completion of the dropping, the reaction solution was maintained at an internal temperature of 80 ° C. for 1 hour. Subsequently, 7.14 g of a 1.4% by mass aqueous solution of ammonium persulfate was added to the above reaction solution. The reaction solution was maintained at 80 ° C. for another 2 hours and then allowed to cool to room temperature. Ammonia water having a concentration of 11.5% was added to the obtained reaction solution until the pH reached 8.2, and then 0.015 g of a silicone emulsion-based defoaming agent (SN Deformer 381 manufactured by San Nopco Co., Ltd.) was added. Then, this reaction solution was permeated through a filter having a first filter membrane having an average pore size of 3 μm (manufactured by Advantech Co., Ltd., product name “MCP-FX-C10S”). Next, it has a filter having a second filter film having an average pore size of 0.8 μm (manufactured by Advantech, product name “MCP-LX-C10S”), and a third filter film having an average pore size of 0.8 μm. A filter (manufactured by Advantech, product name "MCP-LX-C10S") was transmitted in this order. This was used as a dispersion liquid (A-2) containing a textile ink containing polymer particles. The solid content concentration of the dispersion liquid (A-2) was 30% by mass, and the average particle size of the polymer particles was 103 nm.

[Example 3]
In Example 2, the monomer composition of the monomer mixed solution was 70.0 g of methyl methacrylate, 17.0 g of ethylene glycol dimethacrylate, 3.0 g of methacrylic acid and 10.0 g of the above-mentioned monomer (1), and the filters were shown in Table 1. The dispersion liquid (A-3) was obtained in the same manner as in Example 2 except that the dispersion was prepared. The solid content concentration of the dispersion liquid (A-3) was 30% by mass, and the average particle size of the polymer particles was 107 nm.

[Example 4]
In Example 3, as the monomer having a chromophore, the same amount of the monomer (2) represented by the following formula was used instead of the above-mentioned monomer (1), and the filter was as shown in Table 1. The dispersion liquid (A-4) was obtained in the same manner except for the above. The solid content concentration of the dispersion liquid (A-4) was 30% by mass, and the average particle size of the polymer particles was 94 nm.

[Example 5]
61.0 g of methyl methacrylate, 16.0 g of ethylene glycol dimethacrylate, 3.0 g of methacrylic acid and 20.0 g of the monomer (3) represented by the following formula were mixed so as to be uniform. 2. 5.3 g of a surfactant (Kao's "Latemuru E-118B", concentration 26% by mass) and a surfactant (New Japan Chemical Co., Ltd. "Ricasurf M-30", concentration 70% by mass) of this mixed solution. A monomer mixture was prepared by adding to a container containing 3 g and 46.2 g of ion-exchanged water and stirring for 20 minutes.

Separately from the above monomer mixture, 6.1 g of a surfactant (Kao Corporation's "Latemuru E-118B", concentration 26% by mass), 4.8 g of a 5% by mass aqueous solution of ammonium persulfate, and 311.9 g of ion-exchanged water were added. Mixing was used to prepare a polymerization initiator solution. This polymerization initiator solution was heated to 80 ° C. under a nitrogen flow. The above-mentioned monomer mixture was added dropwise to the heated polymerization initiator solution over 3 hours. After completion of the dropping, the reaction solution was maintained at an internal temperature of 80 ° C. for 1 hour. Subsequently, 7.14 g of a 1.4% by mass aqueous solution of ammonium persulfate was added to the above reaction solution. The reaction solution was maintained at 80 ° C. for another 2 hours and then allowed to cool to room temperature. Ammonia water having a concentration of 11.5% was added to the obtained reaction solution until the pH reached 8.2, and then 0.015 g of a silicone emulsion-based defoaming agent (SN Deformer 381 manufactured by San Nopco Co., Ltd.) was added. Then, this reaction solution was permeated through a filter having a first filter membrane having an average pore size of 5 μm (manufactured by Nippon Pole Co., Ltd., product name “5EC488389050J”). Then, a filter having a second filter film having an average pore diameter of 1 μm (manufactured by Nippon Pole Co., Ltd., product name “5EC488389010J”) was allowed to pass through. This was used as a dispersion liquid (A-5) containing a textile ink containing polymer particles. The solid content concentration of the dispersion liquid (A-5) was 20% by mass, and the average particle size of the polymer particles was 68 nm.

[Example 6]
In Example 5, as the monomer having a chromophore, the same amount of the monomer (4) represented by the following formula was used instead of the above-mentioned monomer (3), and the filter was as shown in Table 1. A dispersion (A-6) was obtained in the same manner except for the above. The solid content concentration of the dispersion liquid (A-6) was 20% by mass, and the average particle size of the polymer particles was 71 nm.

[Example 7]
In Example 5, as the monomer having a chromophore, the same amount of the monomer (5) represented by the following formula was used instead of the above-mentioned monomer (3), and the filter was as shown in Table 1. A dispersion (A-7) was obtained in the same manner except for the above. The solid content concentration of the dispersion liquid (A-7) was 20% by mass, and the average particle size of the polymer particles was 67 nm.

[Example 8]
In Example 5, as the monomer having a chromophore, the same amount of the monomer (6) represented by the following formula was used instead of the above-mentioned monomer (3), and the filter was as shown in Table 1. A dispersion liquid (A-8) was obtained in the same manner except for the above. The solid content concentration of the dispersion liquid (A-8) was 20% by mass, and the average particle size of the polymer particles was 68 nm.

[Comparative Example 1]
In Example 3, the dispersion liquid (a-1) was obtained in the same manner except that the filters were as shown in Table 1. The average particle size of the polymer particles of the dispersion liquid (a-1) was 106 nm.

[Comparative Example 2]
In Example 5, the dispersion liquid (a-2) was obtained in the same manner except that the filters were as shown in Table 1. The average particle size of the polymer particles of the dispersion liquid (a-2) was 70 nm.

[Comparative Example 3]
In Example 6, the dispersion liquid (a-3) was obtained in the same manner except that the filters were as shown in Table 1. The average particle size of the polymer particles of the dispersion liquid (a-3) was 71 nm.

[Example 9]
An ink (I-1) having the following composition was prepared. The ink was prepared through a known procedure (step). Further, in the ink (I-1), glycerin and diethylene glycol and water (including those in the dispersion liquid (A-1)) correspond to liquid media.
1) Dispersion liquid component: 50% by mass of the dispersion liquid (A-1) obtained in Example 1.
2) Hydrotropy agent: urea 15% by mass
3) Multivalent alcohol: 5% by mass of glycerin, 10% by mass of diethylene glycol
4) Water-soluble binder resin: 3% by mass of styrene-acrylic acid copolymer (BASF's "John Krill 61")
5) Preservative: Avecia's "Proxel XL2" 0.1% by mass
6) Remaining: water

Example 9 is obtained by ejecting droplets of ink (I-1) onto a pretreated silk white cloth using an inkjet printer, drying at 80 ° C. for 5 minutes, and then holding the ink (I-1) in heated steam at 170 ° C. for 7 minutes. I got the printed material. As the inkjet printer, "TX2-1600" manufactured by Mimaki Engineering Co., Ltd. was used, and the print density was set to 100%. As the pretreatment, the white silk cloth was immersed in a pretreatment agent (guar gum: ammonium sulfate: urea: water = 2: 4: 10: 84) for 1 minute. As the guar gum, "NP8" manufactured by Sansho Co., Ltd. was used.

[Examples 10 to 16, Comparative Examples 4 to 6]
In the ninth embodiment, the ink (I) is the same as in the ninth embodiment except that the dispersion liquids (A-2) to (A-8) and (a-1) to (a-3) are used as the dispersion liquid components, respectively. -2)-(I-8) and (i-1)-(i-3) were prepared respectively, and the printing products of Examples 10 to 16 and Comparative Examples 4 to 6 were printed by the same printing method as in Example 9. Was obtained respectively.

[Example 17]
In Example 9, an ink (I-9) was prepared in the same manner as in Example 9 except that 0.5% by mass of ADEKA STAB LA-77 (manufactured by ADEKA) was further added as the light stabilizer a, and Example 9 was prepared. The printed matter of Example 17 was obtained by the same printing method as in the above.

[Example 18]
In Example 9, an ink (I-10) was prepared in the same manner as in Example 9 except that 1% by mass of TINUVIN 765 (manufactured by BASF) was further added as a light stabilizer b, and printing was carried out in the same manner as in Example 9. By the method, the printed matter of Example 18 was obtained.

[Example 19]
In Example 9, an ink (I-11) was prepared in the same manner as in Example 9 except that 5% by mass of ADEKA STAB AO-50 (manufactured by ADEKA) was further added as the light stabilizer c, and the same as in Example 9. The printed material of Example 19 was obtained by the printing method of.

[Example 20]
In Example 10, the surfactant "Ramtel E-118B" was added to the ink, and the amount of the surfactant in the ink was combined with the surfactants "Ramtel E-118B" and "Ricasurf M-30" used in the synthesis. The ink (I-12) was prepared in the same manner as in Example 10 except that the ink (I-12) was adjusted to 1.5% by mass, and the printed matter of Example 20 was obtained by the same printing method as in Example 9. It was.

[Example 21]
In Example 13, the surfactant "Ramtel E-118B" was added to the ink, and the amount of the surfactant in the ink was combined with the surfactants "Ramtel E-118B" and "Ricasurf M-30" used in the synthesis. The ink (I-13) was prepared in the same manner as in Example 13 except that the ink (I-13) was adjusted to 1% by mass, and the printed matter of Example 21 was obtained by the same printing method as in Example 9.

<Evaluation>
The textiles of Examples 9 to 21 and Comparative Examples 4 to 6 were washed with water, and the fastness during washing was confirmed. Specifically, after stirring the printed material in water at 60 ° C. for 60 minutes, the printed material was squeezed and the collected waste water was observed. The printed materials of Examples 9 to 21 and Comparative Examples 4 to 6 did not generate colored wastewater when washed with water.

Next, the printed matter of Examples 9 to 21 and Comparative Examples 4 to 6 after washing with water was visually evaluated for color development. The textiles of Examples 9 to 21 and Comparative Examples 4 to 6 were clean textiles without bleeding. In addition, the printed materials of Examples 9 to 21 and Comparative Examples 4 to 6 were excellent in saturation and color intensity (color value).

The washing with water in the evaluation of the fastness at the time of washing was repeated 30 times. The printed materials of Examples 9 to 21 did not produce colored wastewater even after being washed with water 30 times repeatedly. Let this result be A. On the other hand, the printed materials of Comparative Examples 4 to 6 had lightly colored wastewater when washed with water. Let this result be B. These results are shown in Table 2.

Next, the color-developing properties of the printed materials of Examples 9 to 21 and Comparative Examples 4 to 6 after washing with water 30 times were visually evaluated. The textiles of Examples 9 to 21 were clean textiles without bleeding. In addition, the printed materials of Examples 9 to 21 were excellent in saturation and color intensity (color value). Let this result be A. On the other hand, bleeding and fading were confirmed in the printed materials of Comparative Examples 4 to 6. Let this result be B. These results are shown in Table 2.

Table 1 shows the filters used in Examples 1 to 8 and Comparative Examples 1 to 3. Table 2 shows the ink compositions and evaluation results used in Examples 9 to 21 and Comparative Examples 4 to 6.

The abbreviations of the filters in Table 1 above represent the following filters, respectively.
・ 100J: Made by Nippon Pole Co., Ltd., product name "5EC4888389100J"
Average pore size of filter membrane 10 μm
70J: Made by Nippon Pole Co., Ltd., product name "5EC488838970J"
Average pore size of filter membrane 7 μm
・ 50J: Made by Nippon Pole Co., Ltd., product name "5EC488389050J"
Average pore size of filter membrane 5 μm
・ 20J: Made by Nippon Pole Co., Ltd., product name "5EC48883889020J"
Average pore size of filter membrane 2 μm
・ 10J: Made by Nippon Pole Co., Ltd., product name "5EC4888389010J"
Average pore size of filter membrane 1 μm
07J: Made by Nippon Pole, product name "5EC4888389007J"
Average pore size of filter membrane 0.7 μm
-FX: Made by Advantech, product name "MCP-FX-C10S"
Average pore size of filter membrane 3 μm
・ HX: Made by Advantech, product name "MCP-JX-C10S"
Average pore size of filter membrane 2 μm
・ JX: Made by Advantech, product name "MCP-JX-C10S"
Average pore size of filter membrane 1 μm
-LX: Made by Advantech, product name "MCP-LX-C10S"
Average pore size of filter membrane 0.8 μm
A "-" in the column of the third filter in Table 1 indicates that the third filter is not used.

“-” In Table 2 indicates that no light stabilizer is contained. The inks (I-1) to (I-11) of Examples 9 to 19 and the inks (i-1) to (i-3) of Comparative Examples 4 to 6 also had a small amount of surface activity used during synthesis. The agent is contained.

As is clear from Tables 1 and 2, the textiles of Examples 9 to 21 using the ink containing the polymer particles obtained by the production methods of Examples 1 to 8 are excellent in fastness during washing, and 30 It had excellent color development even after washing several times. On the other hand, in the printed products of Examples 9 to 21 using the ink containing the polymer particles obtained by the production methods of Comparative Examples 1 to 3, colored drainage was generated after washing 30 times, and after washing. The printed material had bleeding and fading, and the color development was reduced. In particular, as in Comparative Example 3, even when filtration is performed using a filter membrane having an average pore diameter of 7 μm or less (second filter) and a filter membrane having an average pore diameter of 1 μm or less (third filter) in this order. When the filter film (first filter) having an average pore diameter of more than 7 μm was used first, colored drainage was generated after 30 times of washing, and the color development property was deteriorated. Although the reason is not clear, it can be seen that the average pore size of the filter membrane that is first permeated after polymerization is 7 μm, and the average pore size of the filter membrane that is continuously permeated is 1 μm or less.

The method for producing polymer particles of the present invention can be suitably used as a method for producing an ink agent for textiles.

Claims (4)

A step of obtaining a liquid containing a particulate polymer having a chromophore by polymerization and a step of filtering the liquid with a plurality of filter films are provided.
The above multiple filter films
The first filter membrane through which the liquid first permeates after polymerization and has an average pore size of 7 μm or less,
A method for producing polymer particles, which comprises a second filter film having an average pore size of 1 μm or less. The method for producing polymer particles according to claim 1, wherein when the average pore size of the first filter film is A and the average pore size of the second filter film is B, 1 <A / B ≦ 7 is satisfied. The polymer particles according to claim 1 or 2, wherein the plurality of filter membranes further include a third filter membrane through which the liquid permeates after the second filter membrane and has an average pore size of 1 μm or less. Production method. The method for producing polymer particles according to any one of claims 1 to 3, wherein the polymer particles are an ink agent for textiles.