JP2611893B2 - Graft copolymer and coating composition using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a graft copolymer branch polymer comprising a backbone polymer composed of a vinyl polymer organopolysiloxane Tona Ru branch polymer and the polyoxyalkylene is grafted, and the graft copolymer The present invention relates to a coating composition comprising a polymer and a solvent .

[0002]

2. Description of the Related Art Silicone-based graft copolymers using radically polymerizable group-containing silicone macromonomers are:
Due to its excellent weather resistance, water repellency, antifouling properties, mold release properties and lubricity, it is of great interest as a coating material (JP-A-58-154766, JP-A-59-2036).
0, JP-A-59-126478, JP-A-61-15
1272, JP-A-62-156172). However, conventional silicone-based graft copolymers are all graft copolymers of a vinyl polymer as a backbone polymer and an organopolysiloxane as a branch polymer. There is a disadvantage that it is inferior.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silicone graft copolymer having not only excellent weather resistance, water repellency, antifouling property, release property and lubricity but also excellent antistatic performance. An object of the present invention is to provide a polymer and a coating composition using the copolymer.

[0004]

In order to solve the above problems, the present invention provides : (a) the following formula:

Embedded image (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is an oxygen atom
Divalent carbon having 1 to 11 carbon atoms which may be interrupted by
A hydride group, m represents 0, 1 or 2, and n represents an average degree of polymerization of 0.
~ 200. (B) a structural unit represented by the following formula:

Embedded image (Wherein, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrogen atom
, A monovalent hydrocarbon group having 1 to 4 carbon atoms or acetyl
Group, i is a number satisfying 2 ≦ i <3, j is an average degree of polymerization of 2 to 5
Number of 0. ), And in some cases
From (c) the following formula:

Embedded image (Wherein R ^x is a hydrogen atom, a methyl group or a —COOH group.
And when R ^x is a hydrogen atom, R ^y is —COOR ^z
Group (where R ^z is an alkyl group, a hydroxyalkyl group
Or a perfluoroalkyl group), phenyl
Group, Torimetokishishi Lil group, a cyano group, the following formula:

Embedded image A group represented by, -CONH ₂ group, -OCOCH ₃ group or
An alkyl ether group, and when R ^x is a methyl group,
Is a group in which R ^y is a —COOR ^z group (where R ^z is as ^defined above)
Means a is) or _{-COOC 3 H 6 Si (OCH 3} ) 3
A group, when ^{R x} is a -COOH group, ^{R y} represents -C
A vinyl unit comprising a structural unit represented by the formula:
A graft copolymer having a polymer chain as a trunk polymer.
And the structural units (a) and (b) account for the weight of all the structural units.
And (c) are 5 to 60% by weight,
50% by weight and the balance of the graft copolymer,
An object of the present invention is to provide a coating composition comprising a graft copolymer and a solvent .

Graft copolymer The graft copolymer of the present invention comprises the above structural units (a) to
(B) optionally a graft copolymer comprising (c)
Coalescence, i.e., those having a vinyl as branch polymer grafted to a backbone polymer composed of a polymer, a branch polymer comprising a branch polymer and a polyoxyalkylene comprising organopolysiloxane.

In the graft copolymer of the present invention, a composition containing the branched polymer comprising the organopolysiloxane
The unit (a) is

Embedded image (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent hydrocarbon group having 1 to 11 carbon atoms which may be interrupted by an oxygen atom, m is 0, 1 or 2, and n is an average. 0 representing the degree of polymerization
~ 200. ).

In the graft copolymer of the present invention, the constituent unit containing the branched polymer composed of the polyoxyalkylene is used.
Position (b) is

Embedded image (Wherein, R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 4 carbon atoms or an acetyl group, i is a number satisfying 2 ≦ i <3, and j is an average polymerization. 2-5 representing degree
Number of 0. ).

Further, a structural unit containing no branch polymer
(C) is obtained by copolymerizing a radical polymerizable monomer. Examples of the radical polymerizable monomer include acrylic acid or methacrylic acid (hereinafter referred to as (meth) acrylic acid); alkyl esters such as methyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Hydroxyalkyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, acid amides such as acrylamide, perfluorodecylethyl (meth) acrylate, ( (Meth) such as perfluoroesters such as perfluorooctylethyl (meth) acrylate, perfluorohexylethyl (meth) acrylate, and perfluorobutylethyl (meth) acrylate
Various derivatives of acrylic acid; styrene or styrene derivatives; fumaric acid, maleic acid or derivatives thereof; radically polymerizable silicon compounds such as vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane; acrylonitrile, vinylpyrrolidone, vinyl acetate; And vinyl alkyl ethers. These radically polymerizable monomers can be used alone or in combination of two or more.

In the graft copolymer of the present invention, hydroxyalkyl esters such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate among the radically polymerizable monomers are used. When a copolymer is contained, solvent resistance can be improved by blending a polyfunctional isocyanate compound as a crosslinking agent when the graft copolymer is used in a coating composition. Details of this will be described later.

[0010] The graft copolymer of the present invention comprises the structural unit (a) and the structural unit (a) without the structural unit (c).
(B) . That is, the trunk polymer is
When the composition unit (c) does not exist, the composition unit (a)
(B). The ratio of the structural units (a) and (b) in the graft copolymer of the present invention is (a), (b)
And ( a) 5 to 60% by weight, (b) 2 to 50% by weight, preferably (a) 10 to 50% by weight, and (b) 5 to 5% by weight.
３０30% by weight. If (a) is less than 5% by weight , the weather resistance, water repellency, antifouling property, mold release properties and lubricity are insufficient, while if it exceeds 60% by weight, the film forming properties become insufficient. When (b) is less than 2% by weight, the antistatic property is insufficient, and when it exceeds 50% by weight , water repellency, mold release property and lubricity become insufficient.

Preparation of Graft Copolymer The graft copolymer of the present invention comprises a radically polymerizable group-containing organopolysiloxane compound and a radically polymerizable group-containing polyoxyalkylene compound, and the aforementioned radically polymerizable monomer copolymerizable therewith. Of a predetermined amount and copolymerized. The radically polymerizable group-containing organopolysiloxane compound has the general formula (A);

Embedded image (Wherein R ¹ , R ² , m and n are as described above).

The compound represented by the general formula (A) is, for example, a compound represented by the general formula (B):

Embedded image (Wherein R ¹ , R ² and m are as defined above), and a chlorosilane compound substituted with acrylate or methacrylate represented by the general formula (C):

Embedded image (Wherein, n is as defined above).
An acid group-substituted dimethylpolysiloxane, can be obtained by dehydrochlorination reaction according to a conventional method. Specific examples of the compound represented by the general formula (A) include the following.

Embedded image

Embedded image

Embedded image

Embedded image

[0013] La radical polymerizable group-containing polyoxyalkylene compounds have the general formula (D);

Embedded image (Wherein, R ³ , R ⁴ , i and j are as described above). Specific examples of the compound represented by the general formula (D) include the following.

Embedded image

Embedded image

The copolymerization is carried out in the presence of a conventional radical polymerization initiator such as peroxides such as benzoyl peroxide and dicumyl peroxide; and azo compounds such as azobisisobutyronitrile. Any of the following methods can be applied: a synthetic method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method. Among them, the solution polymerization method is particularly preferable because it is easy to adjust the molecular weight of the obtained copolymer to an optimum range. Examples of the solvent used in this case include aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and one or a mixture of two or more esters such as ethyl acetate and isobutyl acetate. Is raised. The reaction temperature is preferably in the range of 50 to 180 ° C, particularly preferably in the range of 60 to 120 ° C.
The reaction can be completed in about 10 hours.

Coating Composition The coating composition of the present invention comprises the above graft copolymer and a solvent.
Consists of For the composition, the graft copolymer solution obtained as described above may be used as it is, or the graft copolymer may be separated and dissolved in another solvent. If necessary, other solvents, crosslinking agents, resins other than the above graft copolymer, fillers, and other various additives can be added to the composition in any combination. The solvent is used for the purpose of adjusting the viscosity of the composition, adjusting the film thickness of the coating, and the like, and is not particularly limited as long as it is compatible with the graft copolymer of the present invention. For example, aromatic solvents such as benzene, toluene, and xylene Hydrocarbons; aliphatic hydrocarbons such as n-hexane, n-octane and n-decane; chlorine-based compounds such as methylene chloride, chloroform and carbon tetrachloride;
Ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; dioxane and dimethylformamide. These can be used alone or in combination of two or more.

The coating composition of the present invention only needs to dissolve the graft copolymer in a solvent, whereby an excellent air-drying paint can be obtained. When a hydroxyalkyl ester such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, or hydroxybutyl (meth) acrylate is used as a copolymer component,
Further, by blending a polyfunctional isocyanate compound as a cross-linking agent, it is also possible to obtain a room-temperature-curable paint capable of obtaining a film having excellent solvent resistance. The polyfunctional isocyanate compound is not particularly limited as long as it is bifunctional or more. For example, tolylene diisocyanate (TD
I), diphenylmethane diisocyanate (MDI),
Trizine diisocyanate (TODI), naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IP
DI), diisocyanates such as xylylene diisocyanate (XDI); trimethylolpropane (TM
P), modified TDI, isocyanurate-bound TDI, TM
Examples include polyisocyanates such as P-modified HDI, isocyanurate-bound HDI, burette-bound HDI, TMP-modified IPDI, and isocyanurate-bound IPDI. The compounding amount of the isocyanate compound is 0.5 to 2.0 equivalents to 1 equivalent of the hydroxyl group of the graft copolymer of the present invention,
In particular, it is preferably 0.8 to 1.5 equivalents. Also,
In this case, a small amount of an organotin compound such as dibutyltin dioctate or dibutyltin dilaurate may be added as a crosslinking accelerator to promote crosslinking.

[0017] The coating composition of the present invention comprises a graft copolymer and
And other solvents such as a phenol resin, an epoxy resin, a urethane resin, a urea resin, a melamine resin, and an alkyd resin. Also, for the purpose of improving the strength of the film, even if inorganic fillers such as silica, alumina, glass powder, clay, talc, calcium carbonate, mica powder, titanium dioxide, wollastonite, and magnesium hydroxide are blended, Additives, for example, antioxidants, antioxidants, antistatic agents, coloring agents and the like may be added.

The coating composition comprising the graft copolymer and solvent utility present invention, since the organopolysiloxane is one of the branch polymer is concentrated on the surface of the coating film, weather resistance, water repellency, releasing property ,
While exhibiting lubricity and antifouling properties, it has excellent antistatic performance by containing a branch polymer composed of polyoxyalkylene. Furthermore, despite having a hydrophilic polyoxyalkylene, it is more excellent in water repellency and lubricity than a conventional graft copolymer containing only a branch polymer composed of an organopolysiloxane. this is,
It is presumed that the presence of the polyoxyalkylene incompatible with the organopolysiloxane in the graft copolymer of the present invention makes it easier for the organopolysiloxane to be more concentrated on the coating film surface. Therefore, the coating composition comprising the graft copolymer and the solvent of the present invention is a thermal transfer recording ink ribbon back surface treatment agent, magnetic tape back surface treatment agent, architectural weather resistant paint, icing and snow-prevention paint, It can be used for anti-paste / graffiti paint, anti-sea organism adhesion paint, concrete waterproof paint, etc.

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Synthesis Example 1 In a glass reaction vessel, the following formula:

Embedded image 35 parts by weight of a radically polymerizable group-containing dimethylpolysiloxane compound represented by the following formula:

Embedded image 30 parts by weight of a radical polymerizable group-containing polyoxyalkylene compound represented by the formula: 28 parts by weight of methyl methacrylate, 7 parts by weight of hydroxyethyl methacrylate, 75 parts by weight of methyl ethyl ketone, 75 parts by weight of methyl isobutyl ketone, and azobisisobutyronitrile 2 parts by weight were charged and a copolymerization reaction was carried out at 80 to 85 ° C. for 5 hours while stirring in a nitrogen stream to obtain a viscous solution having a solid content of 40% by weight. Further, the hydroxyl equivalent of the solution in terms of solid content was determined according to JIS K 007.
When measured according to 0, it was 1880 g / mol. Next, an excessive amount of methanol was added to this solution, and the operation of precipitating and washing the copolymer was performed three times.
Drying under reduced pressure at 10 mmHg gave a colorless and transparent solid copolymer. The obtained copolymer was analyzed by an infrared absorption spectrum and a ¹ H NMR spectrum, and as a result, it was confirmed that the copolymer was a grafted dimethylpolysiloxane and polyoxyalkylene. G
The weight average molecular weight in terms of polystyrene by PC is about 6
It was 1,000.

Synthesis Examples 2 to 9 In each of the synthesis examples, instead of the radically polymerizable group-containing dimethylpolysiloxane compound, the radically polymerizable group-containing polyoxyalkylene compound, the radically polymerizable monomer and the solvent used in Synthesis Example 1, a compound represented by the formula (A);

Embedded image (Wherein R ¹ , R ² , m and n are shown in Table 1), a radically polymerizable group-containing dimethylpolysiloxane compound represented by the formula (D):

Embedded image (In the formula, R ³ , R ⁴ , i and j are shown in Table 1.) Except that a radical polymerizable group-containing polyoxyalkylene compound represented by the following formula, a radical polymerizable monomer shown in Table 1 and a solvent were used. A graft copolymer solution was obtained in the same manner as in Synthesis Example 1. For this solution, the concentration of the solid content and the hydroxyl equivalent were measured in the same manner as in Synthesis Example 1. Furthermore,
A solid copolymer was obtained in the same manner as in Synthesis Example 1, and the weight average molecular weight was measured. Table 2 shows the results.

In Table 1, MMA is methyl methacrylate, BMA is butyl methacrylate, ZHEA is 2-ethylhexyl acrylate, HEMA is hydroxyethyl methacrylate, PFMA is perchlorooctyl ethyl methacrylate, MEK is methyl ethyl ketone, MIBK represents methyl isobutyl ketone.

[0023]

[Table 1]

[0024]

[Table 2]

Example 1 The graft copolymer solution obtained in Synthesis Example 1 was diluted with a mixed solvent of methyl ethyl ketone / ethyl acetate (weight ratio 1: 1) so that the solid content became 20% by weight. The diluted solution was applied to an aluminum plate with a spinner and air-dried at room temperature for 24 hours to obtain a transparent film having a thickness of 10 μm. The appearance, contact angle of water, coefficient of kinetic friction, weather resistance, solvent resistance and antistatic property of this coating were examined by the following methods. Table 3 shows the results.

(1) Appearance: The presence or absence of stickiness was examined by touching with a finger. No stickiness… ○ Sticky… × (2) Contact angle of water: Drop 5 μl of pure water on the coating and contact angle meter (Contact Ang)
le Meter CA-A: manufactured by Kyowa Science Co., Ltd.) at 25 ° C. (3) Dynamic friction coefficient: Surface property measuring device (HEIDON-1)
(Type 4: manufactured by Oyato Kagaku Co., Ltd.) under the following conditions. Friction element: SUS Ball Load: 20 g Speed: 150 mm / min (4) Weather resistance: After exposure in a sunshine weather meter (manufactured by Suga Test Instruments) for 1000 hours, the gloss retention was measured. Gloss retention of 90% or more… Gloss retention of less than 90% × (5) Solvent resistance: The coating was observed after immersion in toluene for 1 hour. No change ... ○ Dissolution ... × (6) Antistatic property: STATIC HONESTOM
ETER TYPE S-4104 (SHISHID
O CO. , LTD. ) Was measured under the following conditions. Applied voltage: 10 kV x 30 seconds Electrode distance: 20 mm

Examples 2 to 8 Instead of the graft copolymer solution obtained in Synthesis Example 1,
The same operation as in Example 1 was performed except that each of the graft copolymer solutions obtained in Synthesis Examples 2 to 8 was used, and the coating performance was examined. Table 3 shows the results.

Comparative Example 1 Instead of the graft copolymer solution obtained in Synthesis Example 1,
The same operation as in Example 1 was carried out except that the graft copolymer solution obtained in Synthesis Example 9 was used, and the film performance was examined. Table 3 shows the results.

Example 9 A solution obtained by diluting the graft copolymer solution obtained in Synthesis Example 1 with a mixed solvent of methyl ethyl ketone / ethyl acetate (weight ratio 1/1) so that the solid content was 20% by weight was obtained.
0 parts by weight of 2.7 parts by weight of isocyanurate-bound HDI and 0.05 parts by weight of dibutyltin dioctate were mixed,
When applied to an aluminum plate with a spinner and air-dried at room temperature for 3 days, a transparent film having a thickness of 10 μm was obtained. The coating performance of this coating was examined in the same manner as in Example 1. Table 3 shows the results.

Example 10 Instead of the graft copolymer solution obtained in Synthesis Example 1,
A coating was formed in the same manner as in Example 9 except that the graft copolymer solution obtained in Synthesis Example 4 was used, and the coating performance of the obtained coating was examined. Table 3 shows the results.

[0031]

[Table 3]

[0032]

EFFECT OF THE INVENTION From the graft copolymer of the present invention and the solvent
Comprising coating compositions, weather resistance, water repellency, stain resistance, releasability,
Not only has excellent lubricity, but also has excellent antistatic performance. Further, the graft copolymer of the present invention has, as the branch polymer, a branch polymer composed of an organopolysiloxane and a branch polymer composed of a polyoxyalkylene. Also has excellent water repellency and lubricity. Further, when the graft copolymer of the present invention contains a copolymer of a hydroxyalkyl ester in the backbone polymer, when a polyfunctional isocyanate compound is added to a coating composition comprising the graft copolymer and a solvent , solvent resistance is also improved. Can be improved.

Claims (3)

(57) [Claims] [Claim 1] (a) the following formula: 1] (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is an oxygen atom
Divalent carbon having 1 to 11 carbon atoms which may be interrupted by
A hydride group, m represents 0, 1 or 2, and n represents an average degree of polymerization of 0.
~ 200. Structural unit represented by), (b) the following formula: 2] (Wherein, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrogen atom
, A monovalent hydrocarbon group having 1 to 4 carbon atoms or acetyl
Group, i is a number satisfying 2 ≦ i <3, j is an average degree of polymerization of 2 to 5
Number of 0. Structural units represented by), and, optionally, (c) the following formula: ## STR3 ## (Wherein R ^x is a hydrogen atom, a methyl group or a —COOH group.
And when R ^x is a hydrogen atom, R ^y is —COOR ^z
Group (where R ^z is an alkyl group, a hydroxyalkyl group
Or a perfluoroalkyl group), phenyl
Group, trimethoxysilyl group, a cyano group, the following formula: 4] A group represented by, -CONH ₂ group, -OCOCH ₃ group or
An alkyl ether group, and when R ^x is a methyl group,
Is a group in which R ^y is a —COOR ^z group (where R ^z is as ^defined above)
Means a is) or _{-COOC 3 H 6 Si (OCH 3} ) 3
A group, when ^{R x} is a -COOH group, ^{R y} represents -C
A vinyl unit comprising a structural unit represented by the formula:
A graft copolymer having a polymer chain as a trunk polymer.
And the structural units (a) and (b) account for the weight of all the structural units.
And (c) are 5 to 60% by weight,
50% by weight and the balance of the graft copolymer. 2. A graft copolymer according to claim 1 and soluble
A coating composition comprising an agent . Wherein said R ^x is a hydrogen atom or a methyl group der
R ^y is a —COOR ^z group (where R ^z is hydroxy
3. The coating composition according to claim 2, wherein the compound is an alkyl group).
0.5 to 2.0 equivalents to 1 equivalent of hydroxyl group of copolymer
A coating composition comprising: