JP5365024B2 - Silicone graft copolymer and process for producing the same - Google Patents

Abstract

Disclosed are: a silicone graft copolymer having a silicone polymer moiety as a hydrophobic branch part and a polymer derived from a hydrophilic polymerizable monomer as a stem part; and a method for producing the silicone graft copolymer. Specifically disclosed are: a silicone graft copolymer produced by the copolymerization of a (meth)acrylic acid ester represented by the following formula: CH2=C(R1)-COO-(R2-O)n-R3 [wherein R1 represents H or a methyl; R2 represents an ethylene or propylene group; R3 represents H or a C1-6 hydrocarbon group; and n represents a number of 1 to 25, provided that R3 represents a univalent C1-6 hydrocarbon group when n is 1], an ethylenically unsaturated carboxylic acid (salt), a silicone macromonomer having Mw of 5000 to 35000, and optionally other monomer; an aqueous coating polymer composition comprising the graft copolymer; and a method for producing the graft copolymer by the copolymerization in a mixed solvent composed of an organic solvent selected from the members of group (A) (a ketone, an ether, an ester, an aromatic hydrocarbon, and others) and an organic solvent selected from the members of group (B) (a monohydric or polyhydric alcohol, and a glycol ester).

Description

  The present invention relates to a silicone-based graft copolymer and a method for producing the same.

In recent years, a structurally controlled graft copolymer obtained by copolymerizing a macromonomer having a polymerizable group at the end of a molecule and another polymerizable monomer has attracted attention as a high-performance polymer material, It is used for adhesives, polymer additives, molding materials, sealants, etc.
Among the above graft copolymers, a silicone-based polymer obtained by copolymerizing a silicone-based macromonomer having a radical polymerizable group at one end of a silicone-based polymer such as polydimethylsiloxane with another polymerizable monomer In the graft copolymer, the silicone polymer constituting the branch part has properties such as water repellency, lubricity, mold release, weather resistance, and stain resistance. It is suitably used as a material coating agent, paint additive, sealing agent, molding material and the like (see Patent Documents 1 and 2).
When these silicone-based graft copolymers are used as a coating agent or the like, they are generally used in the form of an organic solvent solution. However, the use of an organic solvent has problems in terms of safety and environmental pollution. Therefore, there is a demand for an aqueous silicone graft copolymer that can be used in the form of an aqueous solution that is safe and environmentally friendly.

  On the other hand, after producing a silicone graft copolymer by copolymerizing a silicone-based macromonomer with a polymerizable monomer such as an ethylenically unsaturated carboxylic acid or (meth) acrylic acid ester in an organic solvent, A method has been proposed in which a graft copolymer is reacted with a base to make it water-soluble, and then an organic solvent is removed to obtain a silicone-based graft copolymer (see Patent Documents 3 and 4). Yes.

  For example, in the field of coatings for metal cans, a polymer composition containing an aqueous silicone graft copolymer by a combination of a silicone graft copolymer and an amino resin is used to improve the transport speed in the transport of the can manufacturing process, It is known that it can be suitably used as a coating agent that satisfies the required performance such as reduction of scratches on the can surface and is excellent in lubricity, scratch resistance, and adhesion (see Patent Document 5).

  In the field of backside coating for thermal recording media, an aqueous silicone polymer composition containing an organic amine neutralized product of a silicone graft copolymer having a carboxyl group has water resistance, printability, and running property during recording. It is known that it can be suitably used as an excellent coating agent (see Patent Document 6).

  In addition, a graft copolymer having a hydrophilic polymer segment and a hydrophobic polymer segment derived from a silicone-based macromonomer, a block copolymer having a vinyl polymer segment and a silicone polymer segment, or a graft copolymer may be used for inkjet, etc. It has been proposed to improve the water resistance and printing characteristics of printed matter by using it as an additive / dispersant for ink (see Patent Documents 7 and 8).

  However, the silicone-based graft copolymer and the aqueous silicone-based block copolymer described in these documents are still insufficient in stability, oil resistance, weather resistance and the like when made into an aqueous solution. When used as an additive for paints and inks containing pigments such as the above, the lubricity, scratch resistance, gloss, etc. of the film deteriorated and the required performance may not be satisfied.

JP 60-123518 A JP-A 63-227670 JP-A-4-175309 JP 2000-80135 A JP-A-8-231925 JP-A-9-86047 JP-A-9-188732 Special Table 2000-506198

The object of the present invention is to provide hydrophobicity derived from a silicone-based polymer that is stably present in the polymerization system during the polymerization, and forms a stable aqueous solution by adding a base after the polymerization to neutralize and dissolve in water. A silicone-based graft copolymer having as its trunk a polymer having a structural unit derived from a branching unit of water and a hydrophilic polymerizable monomer is used as an additive, whereby a paint / ink containing a pigment is provided. For example, a film having sufficient lubricity, scratch resistance and gloss is formed.
Furthermore, the objective of this invention is providing the method of manufacturing the said silicone type graft copolymer smoothly with a high polymerization rate and a high yield.

  The present inventors have intensively studied to achieve the above-described object. As a result, a specific (meth) acrylic acid ester, an ethylenically unsaturated carboxylic acid, and a silicone-based macromonomer having a predetermined molecular weight, and optionally other polymerizable monomers such as (meth) acrylic acid alkyl ester A new silicone-based graft copolymer having a specific structure, which is copolymerized with a base, forms a stable aqueous solution when neutralized with a base to make it water-soluble. When a polymer composition for aqueous coating is prepared using a copolymer, water repellency, lubricity, scratch resistance, mold release, weather resistance, stain resistance, gloss, etc. are obtained from the aqueous coating polymer composition. It is found that a film with excellent properties is formed, and even when the composition is added to a paint or ink containing a pigment such as a coloring material, the performance is maintained at a high rate. It was found to be.

  In addition, in the production of the silicone-based graft copolymer, the present inventors perform copolymerization in a mixed solvent obtained by mixing two or more kinds of specific organic solvents, thereby producing monomer components and polymerization. In a state where both of the produced polymer components are stably dissolved in the mixed solvent, almost all of the monomers used for the polymerization are copolymerized to form hydrophobic branches and hydrophilicity derived from the silicone polymer. A novel silicone-based graft copolymer with a copolymer composition and a narrow molecular weight distribution, which is based on a polymer having a structural unit derived from a polymerizable monomer, can be obtained smoothly with a high polymerization rate and high yield. I found out.

  Furthermore, the present inventors changed the mixed composition of the mixed solvent during the polymerization step for producing the silicone-based graft copolymer, and maintained the solubility in the mixed solvent of the components present in the polymerization system. It has been found that a silicone-based graft copolymer having a narrower molecular weight distribution can be produced in a higher yield by polymerization, and the present invention has been completed based on these findings.

That is, the present invention
(1) the following general formula (I);

^{_{CH 2 = C (R 1)}} -COO- (R 2 -O) n -R 3 (I)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an ethylene group or a propylene group, R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is a number from 1 to 25. (However, when n = 1, R ³ is a monovalent hydrocarbon group of 1 to 6.)
A structural unit derived from (meth) acrylic acid ester (I), a structural unit derived from ethylenically unsaturated carboxylic acid (II) and / or a salt thereof, and a silicone macro having a weight average molecular weight of 5000 to 35000 A silicone-based graft copolymer having a structural unit derived from a monomer (III), wherein a silicone-based polymer portion derived from the silicone-based macromonomer constitutes a branch.

And this invention,
(2) The silicone-based graft copolymer of (1) further having a structural unit derived from a (meth) acrylic acid ester other than the (meth) acrylic acid ester (I);
(3) Based on the total mass of all structural units constituting the silicone-based graft copolymer, the content of structural units derived from (meth) acrylic acid ester (I) is 10 to 70% by mass, ethylenically unsaturated. The content ratio of structural units derived from carboxylic acid (II) and / or a salt thereof is 5 to 30% by mass, the content ratio of structural units derived from silicone-based macromonomer (III) is 10 to 50% by mass, and (meth) The silicone-based graft copolymer of (1) or (2) above, wherein the content of structural units derived from (meth) acrylic acid esters other than acrylic acid ester (I) is 0 to 70% by mass;
(4) The silicone-based graft copolymer according to any one of (1) to (3), which has a weight average molecular weight of 6,000 to 40,000 and an acid value of 40 to 200 mgKOH / g;
It is.

Furthermore, the present invention provides
(5) the following general formula (I);

^{_{CH 2 = C (R 1)}} -COO- (R 2 -O) n -R 3 (I)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an ethylene group or a propylene group, R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is a number from 1 to 25. (However, when n = 1, R ³ is a monovalent hydrocarbon group of 1 to 6.)
(Meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (II) and / or salt thereof, and silicone macromonomer (III) having a weight average molecular weight of 5000 to 35000, ketones, ethers 1 type, or 2 or more types of organic solvents selected from the group, esters, aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons and alicyclic hydrocarbons ( A) is copolymerized in a mixed solvent obtained by mixing one or two or more organic solvents (B) selected from monohydric alcohols, polyhydric alcohols, and glycol ethers. 1) A method for producing a silicone-based graft copolymer.

And this invention,
(6) The method for producing a silicone-based graft copolymer according to the above (5), wherein another (meth) acrylic ester other than (meth) acrylic ester (I) is further copolymerized;
(7) The method for producing a silicone-based graft copolymer according to the above (5) or (6), wherein the copolymerization is performed while changing the mixed composition of the mixed solvent during the polymerization; and
(8) After copolymerization in a mixed solvent, the concentration of the polymer is reduced to 40% by mass or less, and then a base is added to neutralize part or all of the carboxyl groups in the silicone-based graft copolymer to form a salt And then distilling off the mixed solvent and replacing it with water to make an aqueous solution. The method for producing a silicone-based graft copolymer according to any one of the above (5) to (7);
It is.

The silicone graft copolymer of the present invention has a silicone polymer portion derived from a silicone macromonomer as a hydrophobic branch, and a polymer having a structural unit derived from a hydrophilic polymerizable monomer as a trunk. Because of its graft structure, it exhibits excellent lubrication performance, mold release performance, water repellency performance, scratch resistance performance, stain resistance performance, weather resistance performance, and gloss performance due to the branching silicone polymer. . These performances are not significantly impaired even in paints and inks containing pigments.
Moreover, the silicone-based graft copolymer of the present invention has a hydrophilic structural unit, particularly a structural unit in which a part or all of the carboxyl group is neutralized with a base to form a salt at the trunk. The solubility in water is excellent, and the structural unit derived from the (meth) acrylic acid ester (I) generates insoluble components even in an aqueous solution mixed with a low pH or a large amount of a hydrophilic organic solvent. It is difficult to add to water-based paints and water-based inks mixed with a large amount of low pH or hydrophilic organic solvents.
In addition, because of the hydrophilic structural unit, the aqueous polymer solution obtained by dissolving the silicone-based graft copolymer of the present invention in water is excellent in storage stability and does not aggregate or precipitate during storage.

The silicone-based graft copolymer of the present invention, in which a part or all of the carboxyl groups in the silicone-based graft copolymer is neutralized with a base to be water-solubilized, is a polymer composition for aqueous coating, a sealing agent It can be effectively used for various applications such as molding materials.
In particular, an aqueous coating polymer composition in which the water-soluble silicone-based graft copolymer of the present invention is dissolved in an aqueous medium has various bases as a coating material excellent in safety and environmentally friendly using water as a medium. It can be used effectively for coating of materials, additives for paints and inks, etc., and by drying after coating, such as lubricity, releasability, water repellency, scratch resistance, stain resistance, weather resistance, gloss, etc. A film or film having excellent characteristics is formed.

(Meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (II), silicone-based macromonomer (III) having a weight average molecular weight of 5000 to 35000, and optionally other polysynthetic monomers, (A ) Group of organic solvents (ketones, ethers, esters, aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons and alicyclic hydrocarbons) Silicone graft by copolymerization in a mixed solvent obtained by mixing seeds or two or more and one or more organic solvents (monohydric alcohol, polyhydric alcohol and glycol ethers) of group (B). In the case of the production method of the present invention for producing a copolymer, the monomer used for the polymerization in a state where both the monomer component and the polymer component produced by the polymerization are stably dissolved in the mixed solvent. Almost all copolymerized without residual can be obtained molecular weight distribution, a narrow silicone-based graft copolymer of composition distribution in high yield.
In the production method of the present invention, particularly when the above-described copolymerization is performed while changing the mixed composition of the mixed solvent during the polymerization, both the monomer component and the polymer component produced by the polymerization are contained in the mixed solvent. The silicone-based graft copolymer of the present invention can be produced more smoothly while being more stably dissolved.

The present invention is described in detail below.
The silicone-based graft copolymer of the present invention has the following general formula (I):

^{_{CH 2 = C (R 1)}} -COO- (R 2 -O) n -R 3 (I)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an ethylene group or a propylene group, R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is a number from 1 to 25. (However, when n = 1, R ³ is a monovalent hydrocarbon group of 1 to 6.)
Derived from a structural unit derived from (meth) acrylic acid ester (I) represented by the formula [hereinafter sometimes referred to as “structural unit (I)”], ethylenically unsaturated carboxylic acid (II) and / or a salt thereof. A structural unit [hereinafter sometimes referred to as “structural unit (II)”] and a structural unit derived from the silicone-based macromonomer (III) [hereinafter sometimes referred to as “structural unit (III)”] are included as essential units. In some cases, it further has structural units derived from other polymerizable monomers.

  In the silicone-based graft copolymer of the present invention, the trunk has structural units (I), structural units (II) and units derived from a polymerizable unsaturated group at one end of the silicone-based macromonomer. Furthermore, it has a structural unit derived from another polymerizable monomer, and a silicone-based polymer that forms the main body of the silicone-based macromonomer is bonded to the trunk as a branch. The branching silicone polymer is bonded to the trunk in a branching manner at the site of copolymerization of the silicone macromonomer (that is, the portion of the silicone macromonomer copolymerized by the polymerizable unsaturated group at one end). Yes.

In the (meth) acrylate ester (I) represented by the above general formula (I) that forms the structural unit (I) in the trunk of the silicone-based graft copolymer of the present invention, R ¹ is a hydrogen atom or a methyl group It is. R ¹ is preferably a methyl group, that is, a methacrylic terminal, from the viewpoint of high scratch resistance and good weather resistance.
In the (meth) acrylic acid ester (I), R ² is an ethylene group or a propylene group. R ² is preferably an ethylene group from the viewpoint of excellent oil resistance and gloss of the coating.
In (meth) acrylic acid ester (I), R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. Among them, R ³ is an alkyl group having 1 to 6 carbon atoms, particularly a methyl group or an ethyl group, so that the solubility of the (meth) acrylic acid ester (I) in the mixed solvent during polymerization is improved. Thus, the copolymerization with the silicone-based macromonomer is more smoothly performed, and the viscosity of the resulting aqueous solution of the silicone-based graft copolymer is preferable.
Moreover, in (meth) acrylic acid ester (I), n is a number of 1-25. Among these, n is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 2 to 5. When n is small, the stability of the aqueous polymer solution tends to be poor when the aqueous polymer solution has a low pH or a large amount of hydrophilic organic solvent is mixed. When n is larger than 25, The copolymerizability of the polymer deteriorates, and a uniform copolymer cannot be obtained.

Specific examples of (meth) acrylic acid ester (I) include methoxy (poly) ethylene glycol (meth) acrylate and ethoxy (poly) ethylene, wherein n is any number from 1 to 10 in general formula (I). Glycol (meth) acrylate, propoxy (poly) ethylene glycol (meth) acrylate, butoxy (poly) ethylene glycol (meth) acrylate, pentoxy (poly) ethylene glycol (meth) acrylate, hexoxy (poly) ethylene glycol (meth) acrylate, Methoxy (poly) propylene glycol (meth) acrylate, ethoxy (poly) propylene glycol (meth) acrylate, propoxy (poly) propylene glycol (meth) acrylate, butoxy (poly) propylene glycol (meth) Acrylate, pentoxy (poly) propylene glycol (meth) acrylate, and the like can be illustrated hexoxy (poly) propylene glycol (meth) acrylate, can be used alone or in combination of two or more thereof.
Among them, methoxy (poly) ethylene glycol (meth) acrylate and / or ethoxy (poly) ethylene in which n is any number of 1 to 10, particularly 2 to 5, in general formula (I) Glycol (meth) acrylate is preferably used from the viewpoint of easy availability and excellent stain resistance of the coating, and those having a methacrylic end are preferred from the viewpoint of scratch resistance and weather resistance of the coating.
Commercial products of (meth) acrylic acid ester (I) include “NK Ester M Series” and “NK Ester AM Series” (trade name) manufactured by Shin-Nakamura Chemical Co., Ltd., “Blemmer PME Series” manufactured by Nippon Oil & Fats Co., Ltd. ”And“ Blemmer AME Series ”(trade name),“ Light Ester MC ”and“ Light Ester 130MA ”manufactured by Kyoeisha Chemical Co., Ltd. are known, and one or more of these commercially available products are used. Also good.

  The ethylenically unsaturated carboxylic acid forming the structural unit (II) in the trunk portion of the silicone-based graft copolymer of the present invention can be copolymerized with (meth) acrylic acid ester (I) and a silicone-based macromonomer. Any ethylenically unsaturated carboxylic acid having one or more carboxyl groups can be used. Specific examples of the ethylenically unsaturated carboxylic acid that can be used in the present invention include (meth) acrylic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, crotonic acid, itaconic acid, fumaric acid, citraconic acid, maleic acid, And maleic anhydride, ω-carboxypolycaprolactone mono (meth) acrylate, ω-carboxypolyalkylene glycol mono (meth) acrylate, various acid anhydride adducts of ω-hydroxymono (meth) acrylate, and the like. These 1 type (s) or 2 or more types can be used. Among them, the ethylenically unsaturated carboxylic acid is preferably acrylic acid and / or methacrylic acid from the viewpoints of availability, copolymerization with a silicone-based macromonomer, efficiency of introduction of carboxylic acid, and the like. From the viewpoint of water resistance, methacrylic acid is particularly preferably used.

The silicone-based macromonomer (III) for introducing a branch made of a silicone-based polymer into the silicone-based graft copolymer of the present invention has a polymerizable unsaturated group at one end and a weight average molecular weight of 5000-35000. This is a silicone polymer.
Silicone macromonomer (III) is a linear silicone polymer with lubricity, releasability, water repellency, scratch resistance, stain resistance, weather resistance, and gloss, and is polymerized at one end. Any silicone-based macromonomer having a polymerizable unsaturated group (particularly a polymerizable double bond) may be used. Among them, as the silicone-based macromonomer (III), the following general formula (IIIa):

D—O— [Si (R ⁴ ) (R ⁵ ) —O] _p —X (IIIa)

[Wherein, D is a group having a polymerizable unsaturated bond at the terminal (polymerizable unsaturated group), R ⁴ and R ⁵ are each independently a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon. Group or monovalent halogenated hydrocarbon group, X represents a substituent having no radical polymerizability, and p represents the degree of polymerization. ]
A silicone macromonomer represented by the formula is preferably used.

The silicone-based macromonomer represented by the above general formula (IIIa), that is, the silicone-based macromonomer having a polymerizable unsaturated group at one end of the silicone-based polymer composed of diorganopolysiloxane has lubricity and releasability. Excellent in terms of chemical stability.
In the general formula (IIIa), R ⁴ and R ⁵ are preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, and particularly preferably a methyl group from the viewpoint of lubricity.

The silicone macromonomer (III) is a dimethylpolysiloxane macromonomer in which R ⁴ and R ⁵ are both methyl groups and a polymerizable unsaturated group is bonded to one end in the above general formula (IIIa). A diorganopolysiloxane macromonomer in which a part of R ⁴ and / or R ^{5 in} the dimethylpolysiloxane macromonomer is replaced with an ethyl group or other alkyl group and / or a phenyl group is more preferably used. A dimethylpolysiloxane-based macromonomer in which all of R ⁴ and R ⁵ are methyl groups is more preferably used.

The polymerizable unsaturated group at one end of the silicone-based macromonomer (III) [for example, D in the above general formula (IIIa)] represents (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (II), Any polymerizable unsaturated group copolymerizable with other polymerizable monomers may be used, but (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (II), other polymerizable monomers A polymerizable unsaturated group having a (meth) acryloyl group at the end is preferable from the viewpoint of copolymerization with a monomer and ease of production of a silicone-based macromonomer.
Preferable examples of the polymerizable unsaturated group D at one end of the silicone macromonomer include, for example, those represented by the following general formula (IIId).

^{_{CH 2 = C (R 6)}} -COO- (CH 2) q - (O) r - (CH 2) 3 -Si (R 7) (R 8) - (IIId)

(Wherein R ⁶ is a hydrogen atom or methyl group, R ⁷ and R ⁸ are alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, acetoxy group, q is 0 to 0 when r is 0) 2. When r is 1, it is 2, and r is 0 or 1.)

The other end of the silicone-based macromonomer (III) [X in the general formula (IIIa)] is a chemical group such as a trialkylsilyl group (for example, trimethylsilyl group, dimethylethylsilyl group, dimethylbutylsilyl group). It is preferable that a stable group is bonded from the viewpoint of the chemical stability of the silicone-based macromonomer and the graft copolymer.
If an active group such as a silanol group, hydroxyl group, epoxy group, amino group, or alkoxy group is bonded to the other end of the silicone macromonomer (III), the chemical stability of the silicone macromonomer is improved. It tends to decrease.

The weight average molecular weight of the silicone-based macromonomer (III) constituting the silicone-based graft copolymer of the present invention is 5,000 to 35,000, preferably 8,000 to 30,000, and particularly preferably 10,000 to 20,000. When the weight average molecular weight of the silicone-based macromonomer is smaller than the above range, when the silicone-based graft copolymer produced using the silicone-based macromonomer is used as a coating agent, lubricity, releasability, water repellency, A film excellent in scratch resistance, stain resistance and weather resistance is not formed. On the other hand, if the weight average molecular weight of the silicone macromonomer is larger than the above range, the copolymerizability with other monomers deteriorates and unreacted monomers (silicone macromonomer and / or other monomers). The polymer) remains, or it is difficult to make the resulting silicone-based graft copolymer water-soluble. Moreover, when the silicone-based graft copolymer is used as a coating agent or the like, the adhesion to the base material is lowered, and problems such as repellency occur.
In addition, the weight average molecular weight in this specification (the weight average molecular weight of the silicone-based macromonomer and the silicone-based graft copolymer) refers to the weight average molecular weight determined by gel permeation chromatography using polystyrene as a reference substance.

In the present invention, as the silicone macromonomer (III), only one silicone macromonomer may be used, or two or more silicone macromonomers may be used.
Examples of silicone macromonomers that can be used in the present invention include “AK-5”, “AK-30” and “AK-32” (trade name) manufactured by Toagosei Co., Ltd., “Shin-Etsu Chemical Co., Ltd.” It is sold as “X-22-174DK”, “X-24-8201”, “X-22-2426” (trade name), etc., and these commercially available products may be used.

  The method for producing the silicone macromonomer is not particularly limited. The silicone macromonomer can be produced by a known method. For example, (1) a living polymer is produced by anionic polymerization of cyclic siloxane using lithium trialkylsilanolate as an initiator, and γ-methacryloxypropyldimethylmono It can be produced by a method in which chlorosilane is reacted (see Patent Document 6), a method in which a terminal silanol group-containing silicone and an organic silicon compound such as γ-methacryloxypropyldimethylmonochlorosilane are subjected to a condensation reaction (Patent Document 1).

The silicone-based graft copolymer of the present invention uses only the above-mentioned (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (salt) (II), and silicone-based macromonomer (III). It may be formed, or (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (II) and silicone-based macromonomer (III) together with other polymerizable monomers [hereinafter "others" It may be formed using a polymerizable monomer (IV) ”.
When the silicone-based graft copolymer of the present invention is formed by further using another polymerizable monomer (IV), the structural unit derived from the other polymerizable monomer (IV) is generally It constitutes the structural unit of the polymer constituting the trunk.

  When the silicone-based graft copolymer of the present invention has a structural unit derived from another polymerizable monomer (IV), examples of the other polymerizable monomer (IV) include (meta ) Alkyl ester of acrylic acid, alicyclic hydrocarbon ester of (meth) acrylic acid, hydroxyalkyl ester of (meth) acrylic acid, (meth) acrylamide vinyl, (meth) acrylonitrile, aromatic vinyl compound, sulfonic acid group-containing Monomer, vinyl acetate, N-vinylpyrrolidone and the like can be mentioned. The silicone-based graft copolymer of the present invention can have a structural unit derived from one or more of these other polymerizable monomers.

  Specific examples of alkyl esters of (meth) acrylic acid that can be used as other polymerizable monomers (IV) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth Butyl acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like.

  Specific examples of alicyclic hydrocarbon esters of (meth) acrylic acid that can be used as other polymerizable monomer (IV) include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) acrylic acid. Cyclooctyl, cyclononyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Examples thereof include pentenyloxyalkyl and adamantyl (meth) acrylate.

  Specific examples of hydroxyalkyl esters of (meth) acrylic acid that can be used as other polymerizable monomer (IV) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth ) 4-hydroxybutyl acrylate, (meth) acrylic acid ω-hydroxypolyalkylene glycol (n = 2 to 25), (meth) acrylic acid ω-hydroxypolycaprolactone, and the like.

  Specific examples of the aromatic vinyl compound that can be used as the other polymerizable monomer (IV) include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, o-methylstyrene, p-tert-butyl. Examples include styrene.

  Specific examples of the sulfonic acid group-containing monomer that can be used as the other polymerizable monomer (IV) include (meth) acrylic acid 2-ethyl sulfonate, styrene sulfonic acid, α-methyl styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, (meth) allylsulfonic acid, isoprenesulfonic acid, vinyltoluenesulfonic acid, (meth) allyloxybenzenesulfonic acid, (meth) allyloxy-2-hydroxypropylsulfonic acid , (Meth) acrylic acid 3-sulfopropyl, itaconate bis (3-sulfopropyl) and the like.

The silicone-based graft copolymer of the present invention is a small amount (generally 2 mol% or less, particularly 0.5 mol% or less based on the total number of moles of all monomers constituting the silicone-based graft copolymer). If present, a structural unit derived from a monomer having two or more vinyl groups in one molecule may be included as a structural unit derived from another polymerizable monomer (IV).
Specific examples of the monomer having two or more vinyl groups at that time include methylene bisacrylamide, methylene bismethacrylamide, butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, di (meth) acryloxyethylene phosphate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl maleate, poly Examples thereof include crosslinkable monomers such as allyl saccharose.

When the silicone-based graft copolymer of the present invention has a structural unit derived from another polymerizable monomer (IV), among the polymerizable monomers described above, an alkyl ester of (meth) acrylic acid Particularly, having a structural unit derived from an alkyl ester of methacrylic acid has good copolymerizability with (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid and silicone-based macromonomer, and is obtained. The silicone-based graft copolymer film is preferable from the viewpoint of more excellent scratch resistance and weather resistance.
Preferred examples of the alkyl ester of (meth) acrylic acid in that case include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. In particular, methyl methacrylate is preferred from the viewpoint of excellent scratch resistance of the coating film.
In particular, a book formed using (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (II) and silicone-based macromonomer (III) together with alkyl ester of (meth) acrylic acid, particularly methyl methacrylate. The silicone-based graft copolymer of the invention is excellent in molecular weight distribution, stability of aqueous polymer solution, lubricity of film, release property, water repellency, scratch resistance, stain resistance, weather resistance, etc. It is.

The silicone-based graft copolymer of the present invention has 10 to 10 structural units (I) derived from (meth) acrylic acid ester (I) based on the total mass of all structural units constituting the silicone-based graft copolymer. 70% by mass, 10-30% by mass of structural unit (II) derived from ethylenically unsaturated carboxylic acid (II) and / or salt thereof, and 10% of structural unit (III) derived from silicone-based macromonomer (III) It is preferable to have structural units derived from ˜50 mass% and other polymerizable monomer (IV) in a proportion of from 0 to 70 mass%, and structural units derived from (meth) acrylic acid ester (I) (I 20 to 60% by mass, 10 to 20% by mass of the structural unit (II) derived from the ethylenically unsaturated carboxylic acid and / or its salt, and 1 structural unit derived from the silicone macromonomer (III). The structural units derived from 40 wt% and the other polymerizable monomer (IV) and more preferably has a ratio of 20 to 60 wt%.
When the amount of (meth) acrylic acid ester (I) is less than 10% by mass, the stability of the aqueous polymer solution is poor when a low pH or a large amount of hydrophilic organic solvent is mixed. Poor property, scratch resistance and weather resistance. When the ethylenically unsaturated carboxylic acid (II) is less than 5% by mass, it is difficult to make the silicone-based graft copolymer water-soluble, and when it is more than 35% by mass, the water resistance of the coating is inferior. When the silicone macromonomer (III) is less than 10% by mass, the film is inferior in lubricity, releasability, water repellency, scratch resistance, stain resistance, and weather resistance. Stable production of the graft copolymer becomes difficult. When the amount of the other polymerizable monomer (IV) is small, there is a tendency for the scratch resistance of the film to be insufficient, and when it exceeds 70% by mass, it is difficult to balance various physical properties.
By having each structural unit in the above-mentioned range, the stability of the silicone-based graft copolymer in the aqueous medium after polymerization during the production of the silicone-based graft copolymer is improved. The lubricity, releasability, water repellency, scratch resistance, stain resistance, weather resistance, and gloss of the coating film of the graft copolymer are further improved.

In the silicone-based graft copolymer of the present invention, the acid value of the silicone-based graft copolymer (the acid value before neutralizing the carboxyl group in the silicone-based graft copolymer with a base) is in the range of 40 to 200 mgKOH / g. Furthermore, it is preferable to adjust the content ratio of the structural unit (II) derived from the ethylenically unsaturated carboxylic acid so as to be in the range of 60 to 150 mgKOH / g, particularly 80 to 120 mgKOH / g.
If the acid value of the silicone-based graft copolymer before neutralization with a base is too low, it will be difficult to make the silicone-based graft copolymer water-soluble even if neutralized with a base. If the acid value of the coalescence is too high, the water resistance of the silicone-based graft copolymer film is lowered.

Further, in the silicone-based graft copolymer of the present invention, each polymerizable monomer constituting the trunk other than the silicone-based macromonomer (III) [(meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid] (II), a combination of other polymerizable monomer (IV)], a glass transition temperature (Tg) determined according to the following formula (1) based on the glass transition temperature of a homopolymer of each polymerizable monomer When the trunk portion is formed so that the temperature is 0 ° C. or higher, particularly 20 ° C. or higher, the silicone graft copolymer of the present invention has an appropriate hardness without being too soft when used as a coating composition. A film can be formed.

1 / Tg = (W ₁ / Tg ₁ + W ₂ / Tg ₂ + W ₃ / Tg ₃ +... + W _n / Tg _n ) (1)

Where
Tg = Glass transition temperature of trunk (K)
Tg ₁ , Tg ₂ , Tg ₃ ,..., Tg _n = Glass transition temperature (K) of the homopolymer of each polymerizable monomer constituting the trunk portion
W ₁ , W ₂ , W ₃ ,..., W _n = mass ratio of each polymerizable monomer constituting the trunk portion The glass transition temperature of the homopolymer is a value described in POLYMER HANDBOOK It was adopted.

The weight average molecular weight of the silicone-based graft copolymer of the present invention is preferably 6,000 to 40,000, more preferably 8,000 to 30,000, and particularly preferably 10,000 to 20,000. If the weight average molecular weight of the silicone-based graft copolymer is too low, the characteristics of the silicone-based polymer will not be sufficiently exerted, and the film lubricity, releasability, water repellency, scratch resistance, stain resistance, weather resistance Gets worse. Moreover, when the weight average molecular weight of a silicone type graft copolymer is too high, water-solubilization will become difficult, or the viscosity of aqueous solution will become high and handling will become difficult.
The molecular weight distribution (Mw / Mn) of the silicone-based graft copolymer is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.5 or less. The deterioration of physical properties when the molecular weight distribution is large varies depending on the composition, but the stability of the aqueous polymer solution and the scratch resistance of the coating are often reduced. In addition, when polymerization is unstable (progresses in a state where it is not uniformly dissolved), the molecular weight distribution tends to be high.
In addition, the number average molecular weight and the weight average molecular weight of the silicone-based graft copolymer in the present specification are the weight average molecular weight determined by gel permeation chromatography using polystyrene as a reference substance, like the silicone-based macromonomer.

The present invention relates to a silicone-based graft copolymer in which all of the carboxyl groups are not neutralized, and a silicone-based graft copolymer in which a part or all of the carboxyl groups are neutralized with a base to form a salt. Include.
The silicone-based graft copolymer of the present invention in which some or all of the carboxyl groups are neutralized with a base is excellent in solubility in water.
In the case where some or all of the carboxyl groups of the silicone-based graft copolymer are neutralized with a base to form a salt, 50 mol% or more of all the carboxyl groups of the silicone-based graft copolymer, particularly 75 It is preferable from the viewpoint of the stability of the polymer aqueous solution that the mol% or more is in the form of salt.
As the base used for neutralization, inorganic alkali agents such as alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and organic amines such as diethanolamine and triethanolamine can be used. It is desirable to use an alkali metal hydroxide when the water solubility of the polymer and the storage stability of the water-soluble product are strongly required, and when the water resistance of the coating is strongly demanded, use ammonia or a low boiling point organic amine. .

As a method for producing a silicone-based graft copolymer, a macromonomer method, an ionic polymerization method, a method by introducing a side chain by a polymer reaction, and the like are known. The silicone-based graft copolymer of the present invention is produced by adopting a macromonomer method because adjustment is easy and branch portions can be easily connected (bonded) to the trunk portion.
That is, (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (II), silicone-based macromonomer (III) having a weight average molecular weight of 5000 to 35000, and optionally other polymerizable monomer (IV). The silicone-based graft copolymer of the present invention is produced by copolymerization in an organic solvent.
The polymerization is generally preferably performed in a state where the carboxyl group of the ethylenically unsaturated carboxylic acid (II) is not neutralized in order to perform uniform polymerization.

In producing the silicone-based graft copolymer of the present invention by the macromonomer method, as the organic solvent, one or more organic solvents selected from the following group (A) and the following group (B) are used. Solution polymerization using a mixed solvent in which one or two or more selected organic solvents are mixed can stabilize both the monomer component used for polymerization and the polymer component generated by the polymerization in the mixed solvent. A silicone graft copolymer having a narrow molecular weight distribution and narrow composition distribution in a dissolved state is preferable because it can be smoothly produced in a high yield.
Group (A) organic solvents: ketones, ethers, esters, aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, alicyclic hydrocarbons.
(B) Group organic solvents: monohydric alcohols, polyhydric alcohols, glycol ethers.

The boiling point of the mixed solvent of the group (A) organic solvent and the group (B) organic solvent used for the polymerization is 100 from the viewpoints of handling at the time of copolymerization, ease of separation and removal of the solvent after polymerization, and the like. It is preferable that it is below ° C, and it is more preferable that it is 60-95 ° C.
Before the polymerization, the monomer component may be dissolved in a single organic solvent selected from the group (A) organic solvent or the group (B) organic solvent. It is preferable to use a mixed solvent composed of at least one organic solvent of group (A) and at least one organic solvent of group (B).

Specific examples of the above-mentioned ketones used as the organic solvent of group (A) include acetone and methyl ethyl ketone. Specific examples of the ethers include diethyl ether and tetrahydrofuran. Specific examples of the esters Examples include methyl acetate, ethyl acetate, propyl acetate, cellosolve acetate, etc. Specific examples of aromatic hydrocarbons include benzene, toluene, etc. Examples of chlorinated aromatic hydrocarbons Examples of the aliphatic hydrocarbons include hexane, heptane, and various paraffin oils. Specific examples of the chlorinated aliphatic hydrocarbons include methylene chloride, dichloroethane, and chloroform. , Carbon tetrachloride and the like, and alicyclic carbonization Specific examples of Motorui can include cyclohexane, etc. cycloheptane.
Among them, one or two of methyl ethyl ketone and tetrahydrofuran are preferably used as the organic solvent of the group (A) from the viewpoint of the solubility and ease of handling of the silicone-based macromonomer and the generated silicone-based graft copolymer. .

Specific examples of the above-described monohydric alcohol used as the organic solvent of group (B) include methanol, ethanol, propanol, butanol, isopropyl alcohol and the like. Specific examples of the polyhydric alcohol include ethylene glycol and propylene. Examples of the glycol ether include methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, and diethylene glycol dimethyl ether.
Among them, one or two kinds of ethanol and isopropyl alcohol are preferably used as the organic solvent of the group (B) from the viewpoint of the dissolving power and ease of handling of the silicone-based macromonomer and the generated silicone-based graft copolymer. .

  In particular, in the production of the silicone-based graft copolymer of the present invention, each monomer component used for the polymerization and the polymer component produced by the polymerization are more stably dissolved in the mixed solvent, and each monomer. Mixing methyl ethyl ketone and isopropyl alcohol from the viewpoints of higher component polymerization rate and higher yield of silicone graft copolymer, easier removal later when making the polymer aqueous solution, availability, price, etc. Polymerization is preferably carried out using a solvent, a mixed solvent of methyl ethyl ketone and ethanol, a mixed solvent of tetrahydrane and isopropyl alcohol, or a mixed solvent of tetrahydrfuran and ethanol. Among them, methyl ethyl ketone and isopropyl are preferred due to solvent odor and toxicity problems. Mixed solvent of alcohol or mixed of methyl ethyl ketone and ethanol It is more preferable to carry out the polymerization using a solvent.

(Meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (II), silicone-based macromonomer (III) having a weight average molecular weight of 5,000 to 35,000 and optionally other polymerizable monomers In the production of the silicone graft copolymer by polymerizing the body (IV), the mixed composition of the mixed solvent [mixed solvent] is used so that the solubility of the components present in the polymerization system in the mixed solvent is maintained well. The content ratio of the organic solvent of the group (A) and the organic solvent of the group (B) in the inside is changed with the progress of the polymerization, so that the silicone-based graft copolymer having a uniform composition distribution is higher. It is preferable from the point of being able to manufacture more smoothly with a polymerization rate and a yield.
At that time, the content ratio of the organic solvent of group (A) and the organic solvent of group (B) in the mixed solvent during the polymerization reaction is more preferably continuously changed as the polymerization proceeds.
The organic solvent that is optimal for dissolving the monomer components before polymerization and the organic solvent that is optimal for dissolving the silicone-based graft copolymer produced by polymerization are generally different. By suitably changing the composition of a suitable mixed solvent as the polymerization reaction proceeds, the polymerization reaction proceeds efficiently.

In changing the mixing ratio (content ratio) of the organic solvent of the group (A) and the organic solvent of the group (B) with the progress of the polymerization, from the start of the polymerization to the end of the polymerization, [the organic of the group (A) Solvent]: [Organic solvent of group (B)] is preferably continuously changed by mass ratio within a range of 1: 5 to 5: 1, and within a range of 1: 3 to 3: 1. It is more preferable to change continuously. In addition, when the mixing ratio of [(A) group organic solvent]: [(B) group organic solvent] exceeds the above range, the productivity of the silicone-based graft copolymer may be lowered.
In general, it is preferable to perform the polymerization while gradually increasing the content ratio of the organic solvent of group (B) in the mixed solvent as the polymerization proceeds.

  For example, when a mixed solvent of methyl ethyl ketone and isopropyl alcohol is used, or when the silicone-based graft copolymer of the present invention is produced using a mixed solvent of methyl ethyl ketone and ethanol, the mass ratio of methyl ethyl ketone to isopropyl alcohol at the start of the polymerization Alternatively, the mass ratio of methyl ethyl ketone to ethanol is in the range of 2: 1 to 1: 2, and the mass ratio of methyl ethyl ketone: isopropyl alcohol or the mass ratio of methyl ethyl ketone to ethanol at the end of the polymerization is in the range of 1: 1 to 1: 3. As described above, when polymerization is performed while continuously changing the mixed composition of the mixed solvent, a silicone-based graft copolymer having a well-distributed composition can be produced more smoothly with a higher polymerization rate and yield. it can.

In the production of the silicone-based graft copolymer of the present invention, radical polymerization using a radical polymerization initiator is preferably employed because it can be applied to a wide variety of monomers and the adjustment of the polymerization operation and molecular weight is easy. .
The type of radical polymerization initiator is not particularly limited, but it is easy to control the molecular weight of the silicone-based graft copolymer, has a low decomposition temperature, and is easy to handle. A polymerization initiator is preferably used, and an azo polymerization initiator is particularly preferably used. Specific examples of the azo polymerization initiator preferably used in the present invention include cyano azobisisobutyronitrile, azobis (2-methylbutyronitrile), and non-cyano dimethyl-2,2′-azobis. Examples include isobutyrate. Specific examples of the organic peroxide polymerization initiator preferably used in the present invention include peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and the like. Can do.
The amount of radical polymerization initiator used is preferably 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, based on the total mass of all monomers used in the polymerization. .

It is also possible to use one or more azo macroazo initiators having a polymer skeleton of polyethylene oxide and / or polydimethylsiloxane. Specifically, examples of the macroazo initiator having a polyethylene oxide unit include VPE-0201, VPE-0401, and VPE-0601 (manufactured by Wako Pure Chemical Industries, Ltd.), and a macroazo initiator having a polydimethylsiloxane unit. Examples thereof include VPS-0501 and VPS-1001 (manufactured by Wako Pure Chemical Industries, Ltd.).
When these initiators are used, block copolymers having polyethylene oxide and polydimethylsiloxane skeleton can be obtained, respectively. Since these block units can exhibit the same effects as the (meth) acrylic acid ester (I) and the silicone-based macromonomer (III) used in the present invention, respectively, these macroazo initiators and (meth) are used in accordance with the spirit of the present invention. What is necessary is just to adjust the usage-amount of acrylic ester (I) and silicone type macromonomer (III).

  Moreover, in this invention, in order to adjust the molecular weight of a silicone type graft copolymer, you may superpose | polymerize by adding a suitable amount of chain transfer agents as needed. Specific examples of the chain transfer agent that can be used in the present invention include mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 2-mercaptanethanol, thiophenol, dodecyl mercaptan, thioglycerol and the like. Species or two or more can be used.

40-180 degreeC is preferable and, as for the polymerization temperature at the time of manufacturing a silicone type graft copolymer, 50-150 degreeC is more preferable. If the polymerization temperature is too low, the copolymerization rate is decreased and the polymerization initiator is likely to remain. On the other hand, if the polymerization temperature is too high, the (meth) acrylate (I) is thermally decomposed and the produced silicone graft copolymer. There is a risk of thermal decomposition of the coalescence.
In general, the polymerization time is preferably about 3 to 25 hours, more preferably about 3 to 12 hours.

The silicone-based graft copolymer of the present invention having a weight average molecular weight generally in the range of 6000 to 40000 can be obtained by the above production process.
In the silicone-based graft copolymer obtained by the above production method, the carboxyl group present in the silicone-based graft copolymer is in a state in which it is not neutralized.

Water-solubilization can be achieved by neutralizing a part or all of the carboxyl groups present in the silicone-based graft copolymer obtained above with a base.
As described above, the degree of neutralization when the silicone graft copolymer is water-solubilized by neutralizing the carboxyl group in the silicone graft copolymer with a base is as follows. By setting the degree of neutralization so that 50 mol% or more, particularly 70 mol% or more of the compound is in a salt form, the silicone-based graft copolymer can be stably water-solubilized.
Examples of the base used for neutralization include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, and organic amines such as aqueous ammonia, diethanolamine, and triethanolamine. However, when sodium hydroxide and / or potassium hydroxide is used, the stability of the aqueous polymer solution is excellent, and when ammonia or an organic amine having a low boiling point is used, the water resistance of the film after drying is excellent.

Neutralization and water-solubilization of the silicone-based graft copolymer with a base may be performed while the produced silicone-based graft copolymer is present in the organic solvent used for the polymerization, or from the polymerization system. After the silicone-based graft copolymer is separated and recovered, the recovered silicone-based graft copolymer may be put into water, and a base may be added thereto for neutralization and water-solubilization.
Generally, all or part of the organic solvent is distilled, vacuum distilled, dried, etc. after neutralization and water-solubilization by adding base and water to the organic solvent solution containing the silicone-based graft copolymer produced by polymerization The method of distilling off by an appropriate method is preferably employed because an aqueous solution in which a water-soluble silicone-based graft copolymer is dissolved can be easily obtained, and a uniform and stable aqueous polymer solution can be obtained. The

  The aqueous polymer solution obtained by dissolving the water-soluble silicone graft copolymer obtained by converting a part or all of the carboxyl groups of the silicone graft copolymer into a salt form with a base to be water-solubilized is obtained as described above. It is particularly useful as a combined composition (including use as an additive in water-based paints and water-based inks). Accordingly, the present invention includes the aqueous coating polymer composition. From the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention, a coating excellent in properties such as lubricity, mold release, water repellency, scratch resistance, stain resistance, weather resistance, and gloss Is formed.

In the aqueous coating polymer composition that contains the water-soluble silicone-based graft copolymer, the medium water is deionized water or distilled water from which ionic components have been removed by ion exchange or other treatments. However, it is preferable in that it can be stably stored for a long time by preventing aggregation of the aqueous coating polymer composition.
The aqueous coating polymer composition containing the water-solubilized silicone-based graft copolymer dissolved therein may contain a water-soluble organic solvent together with water, if necessary. By containing a water-soluble organic solvent, it is possible to prevent drying during storage of the aqueous coating polymer composition and improve adhesion to the substrate.

Examples of the water-soluble organic solvent that can be contained in the aqueous coating polymer composition include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert- C1-14 alkyl alcohols such as butyl alcohol, amides such as dimethylformamide and dimethylacetamide, ketones or ketoalcohols such as acetone and diacetone alcohol, ethers such as tetrahydrofuran and dioxane, polyethylene glycol, polypropylene glycol Polyalkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2-hexanediol, 1,2,6-hex Alkylene glycols having 2 to 6 carbon atoms in the alkylene group such as Ntriol, thiodiglycol, hexylene glycol, diethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether , Lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. One or two or more of these can be contained in the aqueous coating polymer composition.
Among these, lower alkyl ethers of polyhydric alcohols such as diethylene glycol, other polyhydric alcohols, and triethylene glycol monomethyl ether are preferably used.

  The obtained water-soluble polymer can be used as it is for various paints, coatings, inks, or additives thereof, but it is not suitable for use in precision materials such as high weather resistance and inkjet. In order to remove the adverse effects of trace impurities, those purified by liquid-liquid separation washing, reprecipitation purification method or the like can be applied.

An aqueous coating polymer composition containing a water-soluble silicone-based graft copolymer dissolved therein has been conventionally used in various known and commonly used additives added to aqueous pigment inks and silicone-based aqueous coating polymer compositions. Various additives can be contained as required.
Examples of such additives include surfactants, antifoaming agents, preservatives, antisettling agents, chelating agents, thickeners, antioxidants, dyes and pigments, and one or more of these Two or more kinds can be contained.

  Specific examples of the surfactant that can be contained in the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention include fatty acid salts, higher alcohol sulfate esters, liquid fatty oil sulfate esters, Anionic surfactants such as alkyl allyl sulfonates, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, acetylene alcohol, acetylene glycol, Examples thereof include cationic surfactants such as alkylamines and quaternary ammonium salts, and amphoteric surfactants such as alkylbetaines and alkylamine oxides.

The aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention is an aqueous coating from the viewpoint of the stability of the aqueous coating polymer composition, the handleability during coating, the leveling properties of the liquid, and the like. It is preferable to contain the water-solubilized silicone-based graft copolymer of the present invention in a proportion of 0.1 to 50% by mass, based on the total mass of the polymer composition for use, and a proportion of 0.5 to 30% by mass It is more preferable to contain.
If the water-soluble silicone-based graft copolymer content in the aqueous coating polymer composition is too low, the water repellency, lubricity, release properties, weather resistance, scratch resistance, and stain resistance are excellent and the strength is high. It is difficult to form a film having excellent durability and, on the other hand, if the content ratio of the water-soluble silicone-based graft copolymer is too high, the viscosity of the aqueous coating polymer composition becomes too high, and the coating is not effective. Handling properties and leveling properties (uniform coating properties) are likely to deteriorate.

In the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention, the content of water is in the range of 10 to 97% by mass based on the total mass of the aqueous coating polymer composition. The range is preferably 25 to 90% by mass, and more preferably 40 to 80% by mass.
In the case where a water-soluble organic solvent is contained together with water in the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention, the content of the water-soluble organic solvent is determined based on the weight of the water-based coating weight. Based on the total mass of the combined composition, the range is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

The pH of the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention is preferably in the range of 4 to 11, and more preferably in the range of 5 to 10. If the pH of the aqueous coating polymer composition is 5 or less, the ionization rate of the carboxyl group in the polymer (ratio of being a salt) is insufficient to maintain water solubility, and if the pH exceeds 10, the polymer Alkaline hydrolysis is promoted.
The pH of the aqueous coating polymer composition is adjusted by alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and other inorganic alkali agents, organic amines such as dimethylethanolamine, diethanolamine and triethanolamine, It can be performed using an organic acid such as acid and tartaric acid, or an inorganic acid such as hydrochloric acid and phosphoric acid.

  The aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention can be used in combination with various water-based crosslinking agents. Although it does not restrict | limit especially as a crosslinking agent which can be used, Generally a melamine type crosslinking agent, an oxazoline type crosslinking agent, a block isocyanate crosslinking agent, an epoxy crosslinking agent, a polyvalent metal crosslinking agent etc. are used.

  The aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention has excellent film lubricity, releasability, water repellency, scratch resistance, stain resistance, weather resistance, gloss, etc. Utilizing characteristics, various products such as fabrics, papers, synthetic resins, rubber, wood, metals, ceramics, various products and semi-finished products formed using one or two of the above-mentioned materials For example, it can be effectively used as a coating composition for coating clothing, coated paper, and the like.

A coating method and a coating apparatus for coating with an aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention are not particularly limited, and a coating technique using the aqueous coating polymer composition Can be carried out using a coating method and a coating apparatus conventionally employed. For example, a coating method such as roller coating, spray coating, casting coating, blade coating, brush coating, dipping, and inkjet coating using the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention. (Coating method) can be used for coating.
The aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention exhibits sufficient characteristics even after drying at room temperature after coating various materials, products, semi-finished products, etc. By removing the water and water-soluble organic solvent in the aqueous coating polymer composition by heat drying at 100 ° C. or higher, particularly 100 ° C. or higher, lubricity, releasability, water repellency, scratch resistance, scratch resistance, A film excellent in properties such as contamination, weather resistance, and gloss can be formed.
The thickness of the coating is not particularly limited and can be adjusted according to the type, application, shape, etc. of the material for coating the aqueous coating polymer composition.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
[1] Production of silicone-based graft copolymer and aqueous coating polymer composition containing the same:
The aqueous coating polymer compositions shown in the Examples and Comparative Examples were produced according to the following procedures.

Example 1
(1) Production of silicone graft copolymer:
To a glass flask equipped with a stirrer, dropping funnel, reflux condenser, nitrogen gas inlet tube and thermometer, methoxydiethylene glycol methacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd. “NK Ester M-20G” (trade name) ), Equivalent to (meth) acrylic acid ester (I)] 35 g, methacrylic acid 15 g, silicone macromonomer (A) [“X-22-2426” manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight = 12,000 , 1-terminal methacryloyl-modified polydimethylsiloxane], 25 g of methyl methacrylate, 1.8 g of dodecyl mercaptan as a chain transfer agent, 80 g of methyl ethyl ketone as a polymerization solvent and 80 g of isopropyl alcohol, and heated to 80 ° C. 80 g of alcohol with azobis-2-methyllob Runitoriru (ABN-E) was added over 3 hours the polymerization initiator solution prepared by dissolving a 1.5g, by a total of 7 hours the polymerization as it 80 ° C., to produce the silicone-based graft copolymer solution. In this polymerization step, the content ratio (mass ratio) of methyl ethyl ketone: isopropyl alcohol in the mixed solvent was changed from 50:50 (80: 80 = 1: 1) at the start of polymerization to 33.3: 66. It was gradually changed to 7 (80: 160 = 1: 2).
The solid content of the organic solvent solution of the silicone graft copolymer thus obtained was 30% by mass.
In addition, the appearance of an organic solvent solution of the silicone graft copolymer thus obtained is evaluated by the following method, and the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer is evaluated. When the acid value, molecular weight (weight average molecular weight and number average molecular weight), and molecular weight distribution were determined by the method, they were as shown in Table 1 below.

(2) Preparation of polymer composition for aqueous coating:
To 100 g of the organic graft copolymer solution of the silicone graft copolymer obtained in (1) above, 90 mol% equivalent of potassium hydroxide as a neutralizing base with respect to the carboxyl group in the silicone graft copolymer (Example 1) 2.7 g) was neutralized by adding an aqueous solution diluted to 5% with ion-exchanged water (51.3 g in Example 1) (solid content concentration at the time of neutralization 30% by mass), and then under reduced pressure. The organic solvent used in the polymerization was distilled off. After adjusting this to pH 8.0 with the above-described neutralizing agent, the concentration is adjusted by adding ion-exchanged water, and a silicone-based graft copolymer aqueous solution having a silicone graft copolymer content of 25% by mass Manufactured. This aqueous solution filtered with a membrane filter having a pore size of 5.0 μm was used as an aqueous coating polymer composition (potassium hydroxide neutralized product) containing a silicone-based graft copolymer, and the performance was as follows. Evaluation was performed (general performance evaluation of a polymer composition for aqueous coating and performance evaluation of an ink jet type coating agent).
In addition, dimethylethanolamine (4.3 g in Example 1) was used instead of potassium hydroxide, and an aqueous coating polymer composition (dimethylethanolamine neutralized product) was prepared in the same manner as described above. The performance was evaluated by the following method (performance evaluation of the coating agent for metal cans).

<< Examples 2 to 5 >>
(1) In the polymerization step of the silicone-based graft copolymer of (1) of Example 1, Example 1 was used except that the monomers listed in Table 1 below were used in the proportions described in Table 1. In the same manner as in (1), an organic solvent solution of the silicone-based graft copolymer was produced. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated. When the value, molecular weight (weight average molecular weight and number average molecular weight) and molecular weight distribution were determined by the method, they were as shown in Table 1 below.
(2) An aqueous coating polymer containing a silicone graft copolymer in the same manner as (2) of Example 1 using the organic solvent solution of the silicone graft copolymer obtained in (1) above. A composition (solid content 25% by mass, pH 8.0) was produced, and its performance was evaluated by the following method. The results are shown in Table 1 below.

Example 6
(1) In the polymerization step of the silicone-based graft copolymer of (1) of Example 1, azobis-2-methylobutylnitrile (ABN-E) was added to a mixed solvent of 40 g of methyl ethyl ketone and 40 g of isopropyl alcohol as a polymerization initiator solution. An organic solvent solution of the silicone-based graft copolymer was produced in the same manner as (1) of Example 1 except that 1.5 g dissolved was used. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated. When the value, molecular weight (weight average molecular weight and number average molecular weight) and molecular weight distribution were determined by the method, they were as shown in Table 1 below.
(2) An aqueous coating polymer containing a silicone graft copolymer in the same manner as (2) of Example 1 using the organic solvent solution of the silicone graft copolymer obtained in (1) above. A composition (solid content 25% by mass, pH 8.0) was produced, and its performance was evaluated by the following method. The results are shown in Table 1 below.

Example 7
(1) In the polymerization step of the silicone-based graft copolymer of (1) of Example 1, 1.5 g of azobis-2-methylobutylnitrile (ABN-E) was dissolved in 80 g of methyl ethyl ketone as a polymerization initiator solution. An organic solvent solution of a silicone-based graft copolymer was produced in the same manner as (1) of Example 1 except that the above was used. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated. When the value, molecular weight (weight average molecular weight and number average molecular weight) and molecular weight distribution were determined by the method, they were as shown in Table 1 below.
(2) An aqueous coating polymer containing a silicone graft copolymer in the same manner as (2) of Example 1 using the organic solvent solution of the silicone graft copolymer obtained in (1) above. A composition (solid content 25% by mass, pH 8.0) was produced, and its performance was evaluated by the following method. The results are shown in Table 1 below.

<< Examples 8 to 14 >>
(1) Example 1 except that the monomers described in Table 2 below were used as monomers in the polymerization step of the silicone-based graft copolymer of Example 1 (1) in the proportions described in Table 2. In the same manner as in (1), an organic solvent solution of the silicone-based graft copolymer was produced. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated. When the value, molecular weight (weight average molecular weight and number average molecular weight) and molecular weight distribution were determined by the method, they were as shown in Table 2 below.
(2) An aqueous coating polymer containing a silicone graft copolymer in the same manner as (2) of Example 1 using the organic solvent solution of the silicone graft copolymer obtained in (1) above. A composition (solid content 25% by mass, pH 8.0) was produced, and its performance was evaluated by the following method. The results are shown in Table 2 below.

<< Examples 15 to 20 >>
(1) Example 1 except that in the polymerization step of the silicone-based graft copolymer of Example 1 (1), the monomers listed in Table 3 below were used in the proportions described in Table 3. In the same manner as in (1), an organic solvent solution of the silicone-based graft copolymer was produced. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated. When the value, molecular weight (weight average molecular weight and number average molecular weight) and molecular weight distribution were determined by the method, they were as shown in Table 3 below.
(2) An aqueous coating polymer containing a silicone graft copolymer in the same manner as (2) of Example 1 using the organic solvent solution of the silicone graft copolymer obtained in (1) above. A composition (solid content 25% by mass, pH 8.0) was produced, and its performance was evaluated by the following method. The results are shown in Table 3 below.

<< Examples 21 to 23 >>
(1) In the polymerization step of the silicone-based graft copolymer of (1) of Example 1, 0.2 g of dodecyl mercaptan (Example 21), dodecyl mercaptan 3 instead of 1.8 g of dodecyl mercaptan as a chain transfer agent An organic solvent solution of a silicone-based graft copolymer was produced in the same manner as in (1) of Example 1 except that 0.0 g (Example 22) or 0.9 g of 3-mercaptopropionic acid (Example 23) was used. did. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated. When the value, molecular weight (weight average molecular weight and number average molecular weight) and molecular weight distribution were determined by the method, they were as shown in Table 4 below.
(2) An aqueous coating polymer containing a silicone graft copolymer in the same manner as (2) of Example 1 using the organic solvent solution of the silicone graft copolymer obtained in (1) above. A composition (solid content 25% by mass, pH 8.0) was produced, and its performance was evaluated by the following method. The results are shown in Table 4 below.

Example 24
(1) In the polymerization step of the silicone graft copolymer of Example 1 (1), the silicone graft copolymer was used in the same manner as in Example 1 (1) except that 160 g of isopropyl alcohol was used alone as a polymerization solvent. An organic solvent solution of the polymer was prepared. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated. When the value, molecular weight (weight average molecular weight and number average molecular weight) and molecular weight distribution were determined by the method, they were as shown in Table 4 below.
(2) An aqueous coating polymer containing a silicone graft copolymer in the same manner as (2) of Example 1 using the organic solvent solution of the silicone graft copolymer obtained in (1) above. A composition (solid content 25% by mass, pH 8.0) was produced, and its performance was evaluated by the following method. The results are shown in Table 4 below.

Example 25
(1) In the polymerization step of the silicone-based graft copolymer of (1) in Example 1, 160 g of methyl ethyl ketone was used alone as a polymerization solvent, and 80 g of methyl ethyl ketone as a polymerization initiator solution was added to azobis-2-methylobutylnitrile ( An organic solvent solution of a silicone-based graft copolymer was produced in the same manner as (1) of Example 1 except that 1.5 g of ABN-E was used. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated. When the value, molecular weight (weight average molecular weight and number average molecular weight) and molecular weight distribution were determined by the method, they were as shown in Table 4 below.
(2) An aqueous coating polymer containing a silicone graft copolymer in the same manner as (2) of Example 1 using the organic solvent solution of the silicone graft copolymer obtained in (1) above. A composition (solid content 25% by mass, pH 8.0) was produced, and its performance was evaluated by the following method. The results are shown in Table 4 below.

Example 26
In the preparation step of the aqueous coating polymer composition of Example 1 (2), 33 g (33 g) of the organic solvent used in the polymerization was added before adding the neutralizing base to the organic solvent solution of the silicone-based graft copolymer. 47% by mass of the total amount of the solvent was distilled off under reduced pressure, and then neutralized base was added in the same manner as (2) of Example 1 except that a neutralizing base was added (solid content concentration at the time of neutralization 45% by mass). An aqueous coating polymer composition (solid content 25% by mass, pH 8.0) containing a system graft copolymer was produced, and its performance was evaluated by the following method. The results are shown in Table 4 below.

<< Comparative Examples 1-6 >>
(1) In the polymerization step of the silicone-based graft copolymer of (1) of Example 1, Example 1 was used except that the monomers listed in Table 5 below were used in the proportions described in Table 5 as monomers. In the same manner as in (1), an organic solvent solution of the silicone-based graft copolymer was produced. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated. When the value, molecular weight (weight average molecular weight and number average molecular weight) and molecular weight distribution were determined by the method, they were as shown in Table 5 below.
(2) An aqueous coating polymer containing a silicone graft copolymer in the same manner as (2) of Example 1 using the organic solvent solution of the silicone graft copolymer obtained in (1) above. A composition (solid content 25% by mass, pH 8.0) was produced, and its performance was evaluated by the following method. The results are shown in Table 5 below.

<< Comparative Examples 7 to 10 >>
(1) In the polymerization step of the silicone-based graft copolymer of (1) of Example 1, the monomers and chain transfer agents described in Table 6 below are described in Table 6 without using a silicone-based macromonomer. In this case, 160 g of isopropyl alcohol was used alone as a polymerization solvent, and 1.5 g of azobis-2-methylobutyronitrile (ABN-E) was dissolved in 80 g of isopropyl alcohol as a polymerization initiator solution. Then, an organic solvent solution of a non-silicone copolymer was produced in the same manner as in Example 1 (1). The appearance of the organic solvent solution of the non-silicone copolymer thus obtained was evaluated by the following method, and the acid value and molecular weight (weight average) of the copolymer contained in the organic solvent solution of the copolymer. The molecular weight and number average molecular weight) and molecular weight distribution were determined by the method, and the results were as shown in Table 6 below.
(2) An aqueous coating polymer composition containing a copolymer in the same manner as in (2) of Example 1 using the organic solvent solution of the non-silicone copolymer obtained in (1) above ( A solid content of 25% by mass, pH 8.0) was produced, and its performance was evaluated by the following method. The results are shown in Table 6 below.

  The appearance of the organic solvent solution of the silicone-based graft copolymer obtained in Examples 1 to 26 and Comparative Examples 1 to 6 and the organic solvent solution of the non-silicone copolymer obtained in Comparative Examples 7 to 10 Evaluation, measurement of acid value and molecular weight of silicone-based graft copolymer or non-silicone copolymer contained in the organic solvent solution, aqueous solutions obtained in Examples 1 to 26 and Comparative Examples 1 to 10 above The appearance and stability of the coating polymer composition and the performance when the aqueous coating composition was used as a coating agent were evaluated by the following methods.

(1) Evaluation of appearance of organic solvent solution of silicone-based graft copolymer or non-silicone copolymer:
The appearance of the organic solvent solution of the silicone-based graft copolymer or the non-silicone-based copolymer was determined visually according to the following criteria, and used as an index of polymerization stability.
-Transparent: The organic solvent solution of the copolymer is transparent.
-White: The organic solvent solution of the copolymer has a transparent white color.
-White turbidity: The organic solvent solution of the copolymer is white with no transparency (white turbidity).
Precipitate generation: Precipitates are confirmed in the organic solvent solution of the copolymer.

(2) Acid value of silicone-based graft copolymer or non-silicone copolymer:
An organic solvent solution of a silicone-based graft copolymer or a non-silicone copolymer is titrated with a 0.05 M KOH / ethanol solution, and the acid value per copolymer solid content [mg KOH / g (polymer solid content) ] Was calculated.

(3) Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the silicone-based graft copolymer or non-silicone-based copolymer:
A silicone macromonomer used in the following examples, a silicone graft copolymer or a non-silicone copolymer obtained in Examples and Comparative Examples, dissolved in tetrahydrofuran (THF) to a concentration of 0.2% by mass Then, 100 μL of the solution is injected into a column [“TSK-GEL MULTIPLEORE HXL-M” (four) manufactured by Tosoh Corporation], and the eluent (THF) is supplied at a flow rate of 1 at a column temperature of 40 ° C. A gel permeation chromatograph (GPC) method was employed in which the components adsorbed on the column were eluted by passing through the column at 0.0 mL / min.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated from a calibration curve prepared in advance using polystyrene having a known molecular weight as a reference substance. The molecular weight distribution (Mw / Mn) was determined by dividing the weight average molecular weight (Mw) obtained above by the number average molecular weight (Mn).

(4) Appearance of aqueous coating composition (neutralized potassium hydroxide) (silicone graft copolymer or non-silicone copolymer aqueous solution):
The appearance of the aqueous coating composition (silicone graft copolymer or non-silicone copolymer aqueous solution) was visually determined according to the following criteria.
Transparent: The aqueous coating composition (aqueous solution) is transparent.
White: The aqueous coating composition (aqueous solution) has a transparent white color.
-White turbidity: The aqueous coating composition (aqueous solution) has a white color without transparency (white turbidity).
Precipitate generation: Precipitates are confirmed in the aqueous coating composition (aqueous solution).

(5) Storage stability of aqueous coating composition (potassium hydroxide neutralized product) (aqueous solution of silicone-based graft copolymer or non-silicone copolymer):
The aqueous coating compositions (silicone graft copolymer or non-silicone copolymer aqueous solution) prepared in the following examples and comparative examples were stored at a temperature of 60 ° C. for 3 months, and then visually in a liquid state. The storage stability was evaluated according to the following evaluation criteria.
A: Transparency and color of the aqueous coating composition (aqueous solution) before and after the test were hardly changed, and no two-layer separation or agglomeration of the liquid occurred, and the storage stability was very good.
○: Transparency and / or coloration of the aqueous coating composition (aqueous solution) is slightly confirmed before and after the test, but no two-layer separation or agglomeration of the liquid occurs, and the storage stability is quite good. is there.
Δ: In the aqueous coating composition (aqueous solution), generation of fine aggregates or two-layer separation of the liquid was slightly confirmed, and the storage stability was slightly inferior.
X: In the aqueous coating composition (aqueous solution), generation of many aggregates and / or intense two-layer separation of the liquid was confirmed, and the storage stability was greatly inferior.

[2] Performance Evaluation of Polymer Composition for Aqueous Coating Polymer compositions for aqueous coating (silicone graft copolymer or non-silicone copolymer obtained in Examples 1 to 26 and Comparative Examples 1 to 10) The performance of the polymer composition for aqueous coating was evaluated by preparing a coating agent for a metal can and an inkjet discharge type coating agent using an aqueous solution, and evaluating the performance by the following method.

(1) Preparation of coating agent for metal can and performance evaluation:
(I) Preparation of coating agent for metal can and coating on metal can:
(A) 10 g of methyl methacrylate, 10 g of ethyl acrylate, 40 g of butyl acrylate, 20 g of styrene, 20 g of styrene, 2-hydroxy methacrylate in a glass flask equipped with a stirrer, a dropping funnel, a reflux condenser, a nitrogen gas inlet tube and a thermometer 10 g of ethyl, 10 g of acrylic acid, 50 g of isopropyl alcohol and 50 g of butyl cellosolve are added and heated to 80 ° C., 0.5 g of 2,2-azobisisobutyronitrile is added thereto and polymerized at 80 ° C. for a total of 4 hours. A copolymer solution of an acid value of 80 mg KOH / g resin was produced. To the obtained copolymer solution, 100 g of a 6% aqueous solution of dimethylethanolamine was added while gradually stirring, and then isopropanol was distilled off at a temperature of 50 ° C. under reduced pressure to obtain a solid content of 40% by mass and pH 7.8. An aqueous acrylic resin solution was prepared.
(B) Each aqueous solution obtained in Examples 1 to 26 and Comparative Examples 1 to 10 with respect to 100 parts by mass of the aqueous acrylic resin solution (solid content 40% by mass, pH 7.8) obtained in (a) above. 3 parts by mass of a coating polymer composition (neutralized dimethylethanolamine) (silicone graft copolymer or non-silicone copolymer aqueous solution, solid content 25% by mass, pH 8.0) was added, and further dimethyl 20 parts by weight of an imino-type benzoguanamine resin [“My Coat 106” manufactured by Mitsui Cytec Co., Ltd.] is added, and ion-exchanged water is further added to adjust the solid content to 30% by weight. Got.
(C) The aqueous coating agent for metal cans obtained in (b) above was applied on an aluminum plate with a bar coater so as to have a film pressure of 5 to 6 μm, and heat-cured at a temperature of 200 ° C. for 10 minutes for coating. An aluminum plate (test piece) was prepared, and various performances of the coating film were evaluated by the following methods using the test piece.

(Ii) Leveling properties of the coating film:
The coating film surface of the test piece (painted aluminum plate) prepared in (c) of (i) above was visually observed, and the leveling property of the coating film was evaluated according to the following criteria.
○: No coating lines on the bar coater were confirmed, and the leveling property was excellent.
Δ: A slight coating line of the bar coater is confirmed, and the leveling property is slightly inferior.
X: The coating line of the bar coater is clearly confirmed, and the leveling property is inferior.

(Iii) Coefficient of surface dynamic friction of coating film:
Using the surface property measuring instrument ["HEIDON-14" manufactured by Shin-Toyo Kagaku Co., Ltd.] for the surface dynamic friction coefficient of the coated cotton of the test piece (painted aluminum plate) prepared in (c) of (i) above Then, the measurement was performed under the conditions of a load of 50 g and a moving speed of 1000 mm / min. A value with a surface dynamic friction coefficient smaller than 0.1 is set to “0.1 or less” because the reproducibility of measured values is poor.

(Iv) Scratch resistance of the coating film:
Using two test pieces (painted aluminum plate) prepared in (c) above (i), the coating film surfaces in the test pieces are brought into contact with each other and subjected to rubbing under a load of 5 kg, The degree of scratching of the coating film at that time was visually observed and evaluated according to the following criteria.
○: No scratches are observed on the coating film surface.
Δ: Some scratches are observed on the surface of the coating film ×: There is a part where the coating film is peeled off.

(V) Oil resistance of coating film:
After dropping 1 drop of soybean oil with a dropper on the coating surface on the test piece (painted aluminum plate) prepared in (i) (c) above, leaving it for 1 hour, wiping off, and coating after wiping off The uneven gloss of the film was visually observed and evaluated according to the following criteria.
○: Uneven gloss is not confirmed.
Δ: Gloss unevenness is confirmed to some extent.
X: Uneven gloss is clearly confirmed.

(2) Preparation and performance evaluation of inkjet discharge type coating agent:
(I) Inkjet discharge type coating agent and printing on paper:
(A) Polymer compositions for aqueous coating obtained in Examples 1 to 26 and Comparative Examples 1 to 10 with respect to 100 parts by mass of a commercially available pigment ink for inkjet [BCI-9BK manufactured by Canon Inc.] 20 parts by weight of a product (neutralized potassium hydroxide) (silicone graft copolymer or non-silicone copolymer aqueous solution, solid content 25% by mass, pH 8.0), It filtered using the membrane filter and prepared the inkjet discharge type coating agent (ink for printing).
(B) The inkjet discharge type coating agent (printing ink) obtained in the above (a) is filled in an ink cartridge of a commercially available printer [“PIXUS iP4200” manufactured by Canon Inc.], and commercially available glossy paper [Canon “Photo Glossy Paper GP-301” manufactured by Co., Ltd.] was printed solidly to evaluate ink jet discharge suitability during printing, and various physical properties of the printed matter were obtained by drying the printed matter at room temperature for 24 hours. Evaluation was performed.

(Ii) Inkjet ejection suitability:
Using the inkjet discharge coating agent (printing ink) prepared in (a) of (i) above, 10 sheets of solid paper are continuously printed on glossy paper by the method of (i) (b) above. The print defects were visually observed and evaluated according to the following criteria.
(Double-circle): There is no blur of printing in all 10 printed matter, and it is excellent in the discharge property of an inkjet.
○: Less than 3 out of 10 printed materials, there is a slight blur of printing, which is slightly inferior in ink jet discharge.
(Triangle | delta): All the 10 printed matter has a printing blur considerably, and it is inferior to the discharge property of an inkjet.
X: Inkjet ejection is not possible.

(Iii) Coefficient of surface dynamic friction of printed matter:
The surface dynamic friction coefficient of the printed part of the printed matter obtained in (b) of (i) above is measured using a surface property measuring instrument [“HEIDON-14” manufactured by Shin-Toyo Kagaku Co., Ltd.] The measurement was performed at a speed of 1000 mm / min.

(Iv) Scratch resistance of printed matter:
The printed part of the printed matter obtained in the above (i) and (b) was rubbed strongly with a finger, and scratch resistance was evaluated according to the following criteria.
A: There is almost no peeling of the print, and the scratch resistance is extremely excellent.
○: Peeling of printing is slight and excellent in scratch resistance.
Δ: Peeling of printing is recognized to some extent, and the scratch resistance is slightly inferior.
X: Peeling off of printing is severe, paper as a base material is exposed, and scratch resistance is poor.

(V) Gloss of printed matter:
Using as a control a printed matter printed using the same printer as described above using a normal pigment ink [Canon Inc. “BCI-9BK”] to which no aqueous coating polymer composition was added, The gloss was evaluated according to the following criteria.
○: Gloss equivalent to or higher than that of the control is maintained.
(Triangle | delta): The glossiness has fallen a little compared with the control | contrast.
X: The gloss is greatly reduced as compared with the control.

(Vi) Water resistance of printed matter:
On the printed part of the printed matter obtained in (b) of (i) above, water or an aqueous mixed solution (mixed solution having a mass ratio of water: glycerin: diethylene glycol: 2-pyrrolidone = 78: 5: 15: 2) ) Was dropped with a dropper and allowed to stand for 3 minutes, and then wiped off. The ink bleeding (color unevenness) after wiping was evaluated based on the following criteria.
A: There is no bleeding in either water or an aqueous mixed solution, and the water resistance is extremely excellent.
○: Slight bleeding in aqueous mixed solution, but no bleeding in water and excellent water resistance.
(Triangle | delta): There exists a certain amount of bleeding in both water and an aqueous mixed solution, and water resistance is somewhat inferior.
X: There is clear bleeding in both water and aqueous mixed solution, and the water resistance is poor.

(Vii) Weather resistance of printed matter:
The printed matter obtained in (b) of (i) above was measured using a metering weather meter [Daipura Wintes Co., Ltd. “DAIPLA METAL WEATHER KU-R5NCI-A”] without using water. After the 100-hour weather resistance test, the printed material was subjected to a scratch resistance test in the same manner as in the above (iv), and the scratch resistance test performed in the above (iv) (on a metering weather meter). The weather resistance was evaluated according to the following criteria in comparison with the results of the scratch resistance test before exposure).
○: There is almost no difference in scratch resistance after the weather resistance test, and the weather resistance is excellent.
Δ: Scratch resistance is slightly deteriorated after the weather resistance test, and weather resistance is slightly inferior.
X: The scratch resistance is greatly deteriorated after the weather resistance test, and the weather resistance is poor.

  Here, the types and abbreviations of the monomers, chain transfer agents and organic solvents used in Examples 1 to 26 and Comparative Examples 1 to 10 are as follows.

○ (Meth) acrylic acid ester (I) :
(Meth) acrylic acid ester (Ia):
Methacrylic acid ester represented by the above general formula (I), wherein R ¹ = methyl group, R ² = ethylene group, n = 2, R ³ = methyl group [“Blemmer PME-100” manufactured by NOF Corporation]
(Meth) acrylic acid ester (Ib):
In the above general formula (I), R ¹ = methyl group, R ² = ethylene group, n = 2, R ³ = hydrogen methacrylate ester [“Blemmer PE-90” manufactured by NOF Corporation]
(Meth) acrylic acid ester (Ic):
A methacrylic acid ester represented by the above general formula (I), wherein R ¹ = methyl group, R ² = propylene group, n≈4 to 6, and R ³ = hydrogen [“Blemmer PP-400” manufactured by NOF Corporation]
(Meth) acrylic acid ester (Id):
A methacrylic acid ester in which R ¹ = methyl group, R ² = ethylene group, n≈23, R ³ = methyl group in the above general formula (I) [“Blemmer PME-1000” manufactured by NOF Corporation]
(Meth) acrylic acid ester (Ie):
Methacrylic acid ester represented by general formula (I), wherein R ¹ = methyl group, R ² = ethylene group, n = 1, R ³ = methyl group [“Acryester MT” manufactured by Mitsubishi Rayon Co., Ltd.]
(Meth) acrylic acid ester (If):
Methacrylic compounds in which R ¹ = methyl group, R ² = ethylene group and propylene group, ethylene oxide unit repeat number n≈5, propylene oxide unit repeat number n≈2, R ³ = hydrogen Acid ester [Nippon Yushi Co., Ltd. "Blemmer 50PEP-300"]
(Meth) acrylic acid ester (Ig):
In the above general formula (I), R ¹ = methyl group, R ² = propylene group and butylene group, propylene oxide unit repeat number n≈4, butylene oxide unit repeat number n≈8, R ³ = hydrogen Methacrylic acid ester [Nippon Yushi Co., Ltd. "Blemmer 30PPT-800"]
(Meth) acrylic acid ester (Ih):
A methacrylic acid ester represented by the above general formula (I), wherein R ¹ = methyl group, R ² = ethylene group, n≈90, R ³ = methyl group [“Blemmer PME-4000” manufactured by NOF Corporation]
(Meth) acrylic acid ester (I-i):
Methacrylic acid ester in the above general formula (I), wherein R ¹ = methyl group, R ² = ethylene group, n≈4, R ³ = lauryl group [“Blemmer PLE-200” manufactured by NOF Corporation]

○ Ethylenically unsaturated carboxylic acid (II) :
・ MAA: Methacrylic acid

○ Silicone macromonomer (III) :
Silicone macromonomer (III _A ):
“X22-2426” manufactured by Shin-Etsu Chemical Co., Ltd. (Mw = 12000)
Silicone macromonomer (III _B ):
A dimethylsiloxane-based macromonomer / silicone-based macromonomer (III _C ) having an Mw of 20000 having a methacryloyl machine at one end and an alkyl group at the other end:
“AK-32” manufactured by Toagosei Co., Ltd. (Mw = 33000)
Silicone macromonomer (III _D ):
“X22-174DX” manufactured by Shin-Etsu Chemical Co., Ltd. (Mw = 5000)
Silicone macromonomer (III _E ):
“X24-8201” manufactured by Shin-Etsu Chemical Co., Ltd. (Mw = 2300)

○ Other monomers :
MMA: methyl methacrylate BMA: butyl methacrylate M-5300: “Aronix M-5300” (ω-carboxypolycaprolactone monoacrylate) manufactured by Toagosei Co., Ltd.
・ HEMA: 2-hydroxymethyl methacrylate ・ St: Styrene

○ Chain transfer agent :
DM: Dodecyl mercaptan MP: 3-mercaptopropionic acid

○ Organic solvent :
・ MEK: Methyl ethyl ketone ・ iPA: Isopropyl alcohol

The silicone-based graft copolymer of the present invention has a silicone-based polymer portion derived from a silicone-based macromonomer as a hydrophobic branch, and a polymer having a structural unit derived from a hydrophilic polymerizable monomer as a trunk. Therefore, the silicone-based polymer forming the branches exhibits excellent water repellency performance, lubrication performance, mold release performance, weather resistance performance, and contamination resistance performance. And the water-soluble polymer composition for dissolution containing the water-soluble silicone-based graft copolymer is excellent in storage stability, water repellency, lubricity, release properties, weather resistance, stain resistance, Since the coating film having excellent gloss is formed, the silicone-based graft copolymer of the present invention and the aqueous coating polymer composition containing the same should be effectively used as an aqueous coating polymer composition for other applications. Can do.
Furthermore, the above-described silicone-based graft copolymer can be produced smoothly with good productivity by the production method of the present invention using a mixed solvent of a specific organic solvent of group (A) and organic solvent of group (B). Therefore, the method of the present invention is also useful as a method for producing a silicone-based graft copolymer.

Claims (10)

A silicone-based graft copolymer;
The following general formula (I);

^{_{CH 2 = C (R 1)}} -COO- (R 2 -O) n -R 3 (I)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an ethylene group or a propylene group, R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is a number from 1 to 25. (However, when n = 1, R ³ is a monovalent hydrocarbon group of 1 to 6.)
A structural unit derived from (meth) acrylic acid ester (I) represented by the formula (I) in a proportion of 10 to 70% by mass based on the total mass of all structural units constituting the silicone-based graft copolymer;
Containing structural units derived from the ethylenically unsaturated carboxylic acid (II) in a ratio that the acid value of the silicone-based graft copolymer is 40 to 200 mgKOH / g;
A structural unit derived from a silicone macromonomer (III) having a weight average molecular weight of 5000 to 35000 is contained in a proportion of 10 to 50% by mass based on the total mass of all the structural units constituting the silicone graft copolymer. ;
A structural unit derived from a (meth) acrylic acid ester other than (meth) acrylic acid ester (I), based on the total mass of all structural units constituting the silicone-based graft copolymer, a proportion of 0 to 70% by mass. Containing; and
A silicone polymer portion derived from the silicone macromonomer (III) constitutes a branch;
A silicone-based graft copolymer.   The silicone-based graft copolymer according to claim 1, having a weight average molecular weight of 6,000 to 40,000. The structural unit derived from ethylenically unsaturated carboxylic acid (II) is contained in a proportion of 5 to 30% by mass based on the total mass of all structural units constituting the silicone-based graft copolymer. The silicone-based graft copolymer described in 1. The silicone-based graft copolymer according to claim 3, wherein the structural unit derived from the ethylenically unsaturated carboxylic acid (II) is a structural unit derived from acrylic acid and / or methacrylic acid . A part or all of the carboxyl groups in the structural unit derived from the ethylenically unsaturated carboxylic acid (II) in the silicone-based graft copolymer according to any one of claims 1 to 4 is neutralized with a base. A silicone-based graft copolymer in the form of a salt. A method for producing a silicone-based graft copolymer according to claim 1;
10 to 70% by mass of the following general formula (I) based on the total mass of all monomers used for the production of the silicone-based graft copolymer;

^{_{CH 2 = C (R 1)}} -COO- (R 2 -O) n -R 3 (I)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an ethylene group or a propylene group, R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is a number from 1 to 25. (However, when n = 1, R ³ is a monovalent hydrocarbon group of 1 to 6.)
(Meth) acrylic acid ester (I) represented by:
An ethylenically unsaturated carboxylic acid (II ) in an amount such that the acid value of the resulting silicone-based graft copolymer is 40 to 200 mg KOH / g;
10 to 50% by weight, based on the total weight of all monomers used in the production of the silicone graft copolymer, a silicone macromonomer (III) having a weight average molecular weight of 5000 to 35000;
(Meth) acrylic acid ester other than (meth) acrylic acid ester (I) based on 0 to 70% by mass based on the total mass of all monomers used for the production of the silicone-based graft copolymer;
1 or 2 selected from ketones, ethers, esters, aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons and alicyclic hydrocarbons Copolymerization in a mixed solvent obtained by mixing one or more organic solvents (A) with one or more organic solvents (B) selected from monohydric alcohols, polyhydric alcohols and glycol ethers; The method for producing a silicone-based graft copolymer according to claim 1, wherein: The silicone-based graft according to claim 6 , wherein the ethylenically unsaturated carboxylic acid (II) is used in a proportion of 5 to 30% by mass based on the total mass of all monomers used for the production of the silicone-based graft copolymer. A method for producing a copolymer. The method for producing a silicone-based graft copolymer according to claim 7 , wherein the ethylenically unsaturated carboxylic acid (II) is acrylic acid and / or methacrylic acid . The method for producing a silicone-based graft copolymer according to any one of claims 6 to 8 , wherein the copolymerization is carried out while changing a mixed composition of the mixed solvent during the polymerization. After manufacturing a silicone type graft copolymer by the manufacturing method of any one of Claims 6-9, the density | concentration of the silicone type graft copolymer in a mixed solvent shall be 40 mass% or less, and it is a base after that. Is added to neutralize some or all of the carboxyl groups in the structural unit derived from the ethylenically unsaturated carboxylic acid (II) in the silicone-based graft copolymer to form a salt, and then the mixed solvent is distilled off. A part or all of the carboxyl groups in the structural unit derived from ethylenically unsaturated carboxylic acid (II) in the silicone-based graft copolymer is neutralized with a base. A method for producing a silicone-based graft copolymer in the form of a salt .