JP2019104902A - Aqueous (co)polymer composition - Google Patents

Abstract

To provide an aqueous (co)polymer composition excellent in adhesiveness to various materials.SOLUTION: An aqueous (co)polymer composition (X) contains: a (co)polymer (A) containing acrylic acid (a1) and 2-carboxyethyl acrylate (a3) as constituent monomers; and water. The weight ratio [(a1)/(a3)] of (a1) to (a3) is 95/5-99.99/0.01. The (co)polymer (A) may further contain a (meth)acrylic acid alkyl (C1-24 alkyl) ester (a2) as a constituent unit in order to enhance dispersibility and adhesiveness.SELECTED DRAWING: None

Description

  The present invention relates to aqueous (co) polymer compositions.

  Heretofore, aqueous (co) polymer compositions have been used for various applications. For example, acrylic polymers have been developed as dispersants, detergent builders, adhesives and the like. (See, for example, Patent Document 1).

JP, 2014-208765, A

The polyacrylic acid-based polymer of Patent Document 1 aims at color stability at the time of heating by introducing a specific group.
However, for example, with regard to adhesion and dispersibility, the above-mentioned techniques can not be said to be sufficiently satisfactory, and development of an excellent aqueous (co) polymer composition is desired.
An object of the present invention is to provide an aqueous (co) polymer composition which is excellent in the adhesiveness of various materials.

  The present inventors arrived at the present invention as a result of earnestly examining in order to solve the above-mentioned subject. That is, the present invention is an aqueous (co) polymer comprising (co) polymer (A) containing acrylic acid (a1) and 2-carboxyethyl acrylate (a3) as constituent monomers, and water. A composition composition, wherein an aqueous (co) polymer composition wherein the weight ratio of the (a1) to (a3) [(a1) / (a3)] is 95/5 to 99.99 / 0.01 It is thing (X).

The aqueous (co) polymer composition (X) of the present invention exhibits the following effects.
(1) Excellent adhesion of various materials.
(2) It is excellent in the dispersibility of various materials.

<(Co) polymer (A)>
The (co) polymer (A) in the present invention contains acrylic acid (a1) and 2-carboxyethyl acrylate (a3) as constituent monomers [hereinafter, may be abbreviated as constituent units].
The weight ratio [(a1) / (a3)] between (a1) and (a3) is 95/5 to 99.99 / 0.01, preferably 97/3 to 99.98 / 0.02, Particularly preferred is 99/1 to 99.97 / 0.03. When this weight ratio [(a1) / (a3)] is less than 95/5, the dispersibility and adhesion become insufficient, and when it exceeds 99.99 / 0.01, the dispersibility and adhesion become insufficient. Tend.

  The (co) polymer (A) may further contain an alkyl (C1-C24 alkyl) ester (a2) of (meth) acrylic acid as a structural unit in order to enhance dispersibility and adhesion.

Examples of the (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, and (meth) acrylate Isodecyl, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, (meth) acrylic acid 2 -Decyl tetradecyl and (meth) acrylic acid tetracosyl] etc. are mentioned.
Among the above-mentioned (a2), from the viewpoint of dispersibility and adhesiveness, the alkyl is preferably one having 2 to 18 carbon atoms [hereinafter, may be abbreviated as C], more preferably the alkyl is C3 to 12 Linear or branched alkyl esters, particularly preferred are those wherein the alkyl is C4-10 linear or branched alkyl esters.

  The weight ratio of the monomers constituting (A) [(a1) / (a2)] is preferably from 40/60 to 99.9 / 0.1, more preferably from 60/40, from the viewpoint of adhesiveness and dispersibility. To 99.5 / 0.5, particularly preferably 80/20 to 99/1.

In addition, (A) is also a copolymer having an unsaturated monomer (x) other than the monomers of (a1), (a2) and (a3) as a structural unit within the range not inhibiting the effects of the present invention. Good.
Examples of the unsaturated monomer (x) include methacrylic acid, maleic acid, hydroxyalkyl (C1-5) (meth) acrylate, (meth) acrylamide, styrene and (meth) acrylonitrile.
The above (x) is preferably at most 20 wt%, more preferably at most 5 wt%, particularly preferably at most 1 wt%, based on the weight of (a1).

  Weight average molecular weight of (A) [hereinafter referred to as Mw. The measurement is carried out by gel permeation chromatography (GPC) method described later. ] Is preferably 2,000 to 100,000, more preferably 4,000 to 70,000, and particularly preferably 6,000 to 40,000, from the viewpoint of adhesion and dispersibility.

The GPC measurement conditions of Mw and number average molecular weight (Mn) in the present invention are as follows.
<GPC measurement conditions>
[1] Equipment: Gel Permeation Chromatography
[Model number "HLC-8120GPC", manufactured by Tosoh Corporation]
[2] Column: "TSKgel G6000PWxl", "TSKgel
G3000PWxl "(all manufactured by Tosoh Corp.) connected in series.
[3] Eluent: Methanol / water = 30/70 (volume ratio)
A solution of 0.5% by weight of sodium acetate.
[4] Reference substance: polyethylene glycol (hereinafter abbreviated as PEG)
[5] Injection conditions: sample concentration 0.25% by weight, column temperature 40 ° C.

<Aqueous (co) polymer composition (X)>
The aqueous (co) polymer composition (X) of the present invention comprises the (co) polymer (A) and water.
The aqueous (co) polymer composition (X) is useful for dispersants, detergent builders and adhesives, and can be suitably used as dispersants and adhesives, among others.
Moreover, it is preferable to contain this amine compound (B) mentioned later in this (X), in order to improve dispersibility and adhesiveness.

The (co) polymer (A) can be produced, for example, by a known solution polymerization method, and a solution polymerization method containing water is preferable from the viewpoint of productivity. As content of water, it is preferable to use 40 mass% or more of water with respect to the total amount of solvent to be used, and it is preferable to make the whole quantity of the solvent to be used into water.
When an organic solvent is used, it may be removed after polymerization and dissolved in water, or may be used as it is without removing the solvent. As an organic solvent which can be used alone or together with water, an aqueous solvent (solubility in water at 25 ° C. is 10 g or more / 100 g water), such as ketone (acetone, methyl ethyl ketone (hereinafter abbreviated as MEK), diethyl ketone etc.), Alcohols (methanol, ethanol, isopropanol and the like) and the like are mentioned, and acetone, MEK and isopropanol are preferable from the viewpoint of productivity. The organic solvent can be used alone or in combination of two or more.
The (A) is obtained, for example, as a solution (preferably an aqueous solution from the industrial viewpoint), and the content (% by weight) of (A) in the solution is preferably 5 to 80% from the viewpoint of productivity. More preferably, it is 10 to 70%, and particularly preferably 20 to 60%.

The polymerization temperature during production (A) is preferably 0 to 200 ° C., more preferably 40 to 150 ° C. from the viewpoint of productivity and control of the molecular weight of (A).
The polymerization time is preferably 1 to 10 hours, more preferably 2 to 8 hours, from the viewpoint of the reduction of the residual monomer content in the product and the productivity.
The end point of the polymerization reaction can be confirmed by the amount of residual monomer. The amount of the residual monomer is preferably 5% or less, more preferably 3% or less, based on the weight of (A), from the viewpoint of adhesion and dispersibility. The amount of residual monomer can be measured by gas chromatography.

  The content of (A) in the aqueous (co) polymer composition (X) of the present invention is preferably 2 to 80% by weight, more preferably 4 to 70% by weight, particularly preferably from the viewpoint of productivity and handling. Is 6 to 50% by weight.

<Amine compound (B)>
Examples of the amine compound (B) include an amine compound (B1) having one hydroxyl group, an amine compound (B2) having two or more hydroxyl groups, an amine compound (B3) having no hydroxyl group, and the like.

  Examples of the amine compound (B1) having one hydroxyl group include those having 2 or more carbon atoms (hereinafter sometimes abbreviated as C) and Mn 1,000 or less, the following (B11) to (B13) and the like.

(B11) Monoalkanolamines C2-15, such as ethanolamine, n-propanolamine, isopropanolamine, 6-amino-1-hexanol and the like.

(B12) The alkylene oxide of (B3) described below (hereinafter abbreviated as AO) (C2 to 4) 1 mole adduct C4 or more and Mn 1,000 or less, for example, 1 mole adduct of ethylene oxide propylene oxide, 1,4-phenylene The ethylene oxide 1-mole adduct of diamine, 2- (2-aminoethylamino) ethanol, etc. are mentioned.

(B13) Other than the above (B11) and (B12) C3 to 20, for example, N-methylethanolamine, N-ethylethanolamine, N-pentylhexanolamine.

  As an amine compound (B2) which has 2 or 3 or more hydroxyl groups, the thing of C4 or more and Mn1,000 or less, the following (B21)-(B23), etc. are mentioned.

(B21) Dialkanolamine C4-10, for example, diethanolamine, diisopropanolamine and the like.
Among the above (B21), diethanolamine is preferable from the viewpoint of adhesion and dispersibility.

(B22) trialkanolamine C6-15, for example, triethanolamine, triisopropanolamine etc. are mentioned.
Among the above (B22), preferred is triethanolamine from the viewpoint of adhesiveness and dispersibility.

(B23) AO adduct of (B3) described later (additional mole number is 2 to 20 moles)
C6 or more and Mn1,000 or less, for example, 2 to 20 mole AO adduct of diethylenetriamine, 2 to 20 mole AO adduct of tetramethylene pentamine, etc. may be mentioned.

  The amine compound (B3) having no hydroxyl group is a poly (di- to hexavalent or higher) amine of C2 or more and Mn 2,000 or less, aliphatic polyamine (B31), alicyclic polyamine (B32), heterocyclic ring The polyamines of the formula (B33), aromatic polyamines (B34) and polyamidepolyamines (B35) can be mentioned.

  As the aliphatic polyamine (B31), aliphatic polyamine [C2-6 alkylene diamine (C2-10, for example, ethylene diamine, propylene diamine, hexamethylene diamine (1,6-hexane diamine)), polyalkylene (C2-6 ) Polyamines [C4 to 10, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, iminobispropylamine, bis (hexamethylene) triamine]] etc. and their alkyl (C1 to 4) substituted products [C4 to 10 For example, dialkyl (C1-3) aminopropylamine, trimethylhexamethylenediamine, methyliminobispropylamine etc., alicyclic or heterocycle-containing aliphatic polyamine [C5-20, for example, 3,9-bis (3-aminopro) Aromatic ring-containing aliphatic amines [C6-14, for example, xylylenediamine, tetrachloro-p-xylylenediamine], etc. It can be mentioned.

  Examples of alicyclic polyamines (B32) include C6 to 20, for example, 1,3-diaminocyclohexane, isophorone diamine, mensene diamine, and 4,4'-methylenedicyclohexane diamine (hydrogenated methylene dianiline).

  Heterocyclic polyamines (B33) include C4-20, such as piperazine, N-aminoethyl piperazine, 1,4-diaminoethyl piperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine .

  As the aromatic polyamines (B34), unsubstituted aromatic polyamines [C6 to 30, for example, 1,2-, 1,3- and 1,4-phenylenediamines, 2,4′- and / or 4,4 ′ Aromatic polyamines having a core-substituted alkyl group [a C1-C4 alkyl group such as methyl, ethyl, n- and i-propyl, butyl, etc.] [C7-C4-diphenylmethane diamine, crude diphenyl methane diamine (polyphenyl polymethylene polyamine)] 30, for example, 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o -Toluidine), dianisidine], an aromatic polyamine having an imino group [C7 to 30, for example, 4,4'- (Methylamino) diphenylmethane, and 1-methyl-2-methylamino-4-aminobenzene] and the like.

  As the polyamide polyamine (B35), low molecular weight obtained by condensation of dicarboxylic acid (such as dimer acid) and excess (equivalent ratio of amino group / carboxyl group is 2 or more) of polyamine (the above-mentioned alkylene diamine, polyalkylene polyamine etc) (Mn 100 to 1,000) polyamide polyamines.

Among the above-mentioned (B), from the viewpoint of adhesiveness and dispersibility, preferred is (B2), and more preferred is diethanolamine.
The weight ratio [(A) / (B)] of the (co) polymer (A) to the amino compound (B) is preferably 50/50 to 99/1 from the viewpoint of adhesion and dispersibility. More preferably, it is 60/40 to 97/3, and particularly preferably 70/30 to 95/5.

When the aqueous (co) polymer composition (X) of the present invention contains the above (B), for example, a solution of (co) polymer (A) and a solution of (B) or (B) It can be mixed and manufactured.
In that case, the total content (% by weight) of (A) and (B) in the composition (X) is preferably 5 to 80%, more preferably 10 to 70%, from the viewpoint of productivity. Particularly preferably, it is 20 to 60%.

The aqueous (co) polymer composition (X) of the present invention is dispersible (eg, inorganic pigments such as clay, calcium carbonate, titanium oxide), adhesive (inorganic materials such as glass, organic materials such as polyethylene terephthalate) Being excellent, it is useful for various industrial applications.
When used as a dispersant for an inorganic pigment, the dispersant differs depending on the form of the dispersion, but the weight of (A) is preferably 1 to 25% by weight, and more preferably, based on the weight of the inorganic pigment. It is 3 to 15% by weight.
Moreover, when using it as an adhesive agent, it can adhere | attach, for example by heating for 2 to 60 minutes at 100-300 degreeC, for example, adhering or apply | coating to a to-be-adhered body.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In the following, parts and% indicate parts by weight and% by weight, respectively.

[Production of (Co) polymer (A)]
<Production Example 1>
In an autoclave, 260 parts of water as a solvent and 23.1 parts of sodium hypophosphite [chain transfer agent] were charged, and nitrogen was purged under stirring to carry out nitrogen substitution in the autoclave (gas phase oxygen concentration of 300 ppm or less). An aqueous solution [initiator] in which 12.1 parts of hydrogen peroxide water (30% by weight aqueous solution) are dissolved in 60 parts of water after raising the temperature to 100 ° C. while blowing in nitrogen, and acrylic acid (a1-1) 279. A mixed solution of 8 parts and 0.3 part of 2-carboxyethyl acrylate (a3-1) [monomer solution] is separately dropped simultaneously and over 3 hours, and the mixture is further stirred for 2 hours at 100 ° C. to polymerize, Water was added so that the nonvolatile component was 40%, to obtain an aqueous solution of (co) polymer (A-1). (A-1) was Mw 11,000.

<Production Examples 2 to 5, Comparative Production Examples 1 to 2>
In Production Example 1, the same procedure as in Production Example 1 is carried out except that the procedure in Table 1 is followed, and an aqueous solution of (co) polymers (A-2) to (A-5), (co) polymer (ratio A-1) An aqueous solution of ̃ (ratio A-2) was obtained.

<Production Example 6>
The autoclave was charged with 300 parts of water as a solvent and 300 parts of isopropanol, and nitrogen was purged while stirring to carry out nitrogen substitution in the autoclave (gas phase oxygen concentration of 300 ppm or less). A solution in which 17.6 parts of sodium persulfate is dissolved in 45 parts of water [initiator], 255.1 parts of acrylic acid (a1-1) and acrylic acid A mixed solution of 0.2 parts of carboxyethyl (a3-1) and 11 parts of butyl acrylate (a2-1) [monomer solution] is simultaneously added dropwise over 2 hours, and the mixture is further stirred at 82 ° C. for 2 hours for polymerization reaction. Did. Thereafter, isopropanol in the solution was removed from the solvent, and water was added so that the nonvolatile content was 40%, to obtain an aqueous solution of (co) polymer (A-6). (A-6) was Mw 14,000.

Production Example 7
The autoclave was charged with 300 parts of water as a solvent and 300 parts of isopropanol, and nitrogen was purged while stirring to carry out nitrogen substitution in the autoclave (gas phase oxygen concentration of 300 ppm or less). After raising the temperature to 82 ° C. while blowing in nitrogen, 8.6 parts of 3-mercaptopropionic acid, 0.41 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2) -A solution of 1.9 parts of methyl butyronitrile dissolved in 50 parts of isopropanol, 271 parts of acrylic acid (a1-1) and 5.6 parts of 2-carboxyethyl acrylate (a3-1) [monomer solution] Were simultaneously added dropwise over 2 hours, and the mixture was further stirred at 82 ° C. for 2 hours to carry out a polymerization reaction. After that, isopropanol in the solution was removed from the solvent, water was added so that the nonvolatile content was 40%, and an aqueous solution of (co) polymer (A-7) was obtained. (A-7) was Mw 8,000.

  The results of Production Examples 1 to 7 and Comparative Production Examples 1 and 2 are shown in Table 1.

<Examples 1 to 18, Comparative Examples 1 to 2>
The respective aqueous (co) polymer compositions (X) were prepared by charging the containers according to the composition (parts) shown in Table 2 and mixing them. The obtained respective aqueous (co) polymer compositions (X) were evaluated by the method described later. The results are shown in Table 2.

<1> Evaluation of dispersibility 300 g of calcium carbonate (volume average particle diameter 10 μm), 80 g of aqueous (co) polymer composition (X), and 620 g of ion exchange water are charged in a kneader, and kneaded for 30 minutes. I got a liquid.
100 mL of this dispersion was placed in a glass bottle (bottom area 10 cm ² , height 12 cm) and allowed to stand at 35 ° C. for 3 days, and then the presence or absence of separation was visually evaluated based on the following criteria.
<Evaluation criteria>
☆: The supernatant is less than 1 mm ◎: The supernatant is more than 1 mm and less than 2 mm ○: The supernatant is more than 2 mm and less than 3 mm Δ: The supernatant is more than 3 mm and less than 5 mm ×: The supernatant is more than 5 mm

<2> Adhesive evaluation 20 g of aqueous (co) polymer composition (X) was apply | coated uniformly to the glass plate (vertical 100 mm x horizontal 100 mm x thickness 10 mm). A polyethylene terephthalate (PET) film (vertical 25 mm × horizontal 100 mm × thickness 0.5 mm) was placed on this coated surface, heated at 120 ° C. for 30 minutes, and then cooled to 25 ° C.
Next, the end of the PET film was peeled off, and using a tensile tester, adhesive strength (unit: N / 25 mm) was measured at a peeling speed of 100 mm / min and a peeling angle of 90 degrees. The adhesive strength was evaluated by the following evaluation criteria.
<Evaluation criteria>
☆: More than 25 N / 25 mm ◎: More than 20 N / 25 mm, less than 25 N / 25 mm ○: More than 15 N / 25 mm, less than 20 N / 25 mm Δ: More than 10 N / 25 mm, less than 15 N / 25 mm ×: less than 10 N / 25 mm

  From the results of Tables 1 and 2, it can be seen that the aqueous (co) polymer composition (X) of the present invention is superior in dispersibility and adhesion as compared with the comparative ones.

  The aqueous (co) polymer composition (X) of the present invention is extremely useful because it can be suitably applied to a wide range of fields such as dispersants, detergent builders, adhesives and the like. In particular, it can be suitably used as a dispersant and an adhesive.

Claims (2)

  An aqueous (co) polymer composition comprising (co) polymer (A) containing acrylic acid (a1) and 2-carboxyethyl acrylate (a3) as constituent monomers, and water, Aqueous (co) polymer composition (X) whose weight ratio [(a1) / (a3)] between (a1) and (a3) is 95/5 to 99.99 / 0.01.   The aqueous (co) polymer composition according to claim 1, further comprising an amine compound (B).