JPH04372675A - Covering resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition excellent in pigment dispersion, the extensibility of a coating film, water repellency, weatherability, etc., by mixing a specified vinyl/silicone block copolymer and an organic solvent. CONSTITUTION:An azoic polysiloxane compound is prepared which has repeating units of the formula [wherein R1 is H, lower alkyl or nitrile; R2 is H or lower alkyl; R3 is H, halogen, etc.; p is 0 or 1 to 6; m is 0 or 1 to 200; A is-NH or-O; B is (CH2)q, etc., (wherein q is 0 or 1 to 6)], at least one azo bond in the molecule, and a number-average molecular weight of 1,500 to 100,000. 98-10wt.% polymerizable unsaturated monomer mixture composed mainly of a (meth) acrylic ester and containing 1-10wt.% polymerizable unsaturated carboxylic acid is polymerized in the presence of 2-90wt.% of the prepared compound. The obtained vinyl/silicone block copolymer is mixed with an organic solvent to produce the composition.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a resin composition for coating, and more particularly, the present invention relates to a resin composition for coating, and more particularly, the present invention relates to a coating resin composition in which a polymerizable unsaturated monomer is The present invention relates to a coating resin composition that can be used in fields such as weather-resistant and water-repellent coatings, which contains a vinyl-silicone block copolymer obtained by polymerizing a silicone-based block copolymer and an organic solvent.

0002

[Prior Art] Conventionally, when attempts were made to modify vinyl resins using silicone resins with good water repellency and weather resistance, these two resins were not compatible at all, so composites obtained by polymer blending were used. has poor uniformity, and the silicone resin contained in the film cannot exist as a stable domain or matrix. As a result, the silicone resin that migrates to the surface layer is removed by friction or solvent, making it an efficient and practical solution. It did not become a suitable modifier for vinyl resin. As a solution to this drawback, vinyl
Silicone-based block copolymers have been proposed. As a method for producing this vinyl-silicone block copolymer, a living anionic polymerization method (for example, M. Morton
et al., J. Appl. Polym. Sci. ,8,270
7 (1964)), hydrosilylation methods (e.g. P.C.
haumont et al., Polymer, 22[5], 66
3 (1981)), but both require strict control of polymerization conditions and have drawbacks such as limited applicable vinyl monomers.

0003

OBJECTS OF THE INVENTION The object of the present invention is to provide a composite material obtained by the above-mentioned conventional polymer blend,
The object of the present invention is to overcome the drawbacks of conventional methods for producing vinyl-silicone block copolymers and to provide a resin composition for coating that has excellent weather resistance, water repellency, etc.

0004

Means for Solving the Problems The present invention provides a coating resin composition that can achieve the above objects.

That is, the present invention provides general formula (I)

00
06]

[In the formula, each R1 is the same or different and is a hydrogen atom,
It represents a lower alkyl group or a nitrile group, and each R2 is
The same or different R3's represent a hydrogen atom or a lower alkyl group, and each R3 is the same or different and represents a hydrogen atom, a halogen atom-substituted or unsubstituted alkyl group, or a phenyl group. p is the same or different, 0 or 1
represents an integer of ~6, m represents 0 or an integer of 1 to 200, A represents -NH or -O, B represents (CH2)q
(However, q is the same or different and represents 0 or an integer from 1 to 6.) or -(CH2)3OCH2CH
2 indicates -. ]

In the presence of 2 to 90% by weight of an azo group-containing polysiloxane compound having a repeating unit represented by the following and having at least one azo bond in one molecule and a number average molecular weight of 1,500 to 100,000, The main component is (meth)acrylic acid ester, and 1 to 1 polymerizable unsaturated carboxylic acid.
10 to 9 of the polymerizable unsaturated monomer mixture containing 0% by weight
The present invention relates to a coating resin composition comprising a vinyl-silicone block copolymer obtained by polymerizing 8% by weight and an organic solvent.

[0008] The present invention also provides a repeating unit represented by the above general formula (I) and a repeating unit represented by the general formula (II).

[0009]

embedded image [In the formula, Y represents a dibasic acid residue. R2, R3, A
, B and m are the same as above. ]

In the presence of 2 to 90% by weight of an azo group-containing polysiloxane compound having a repeating unit represented by: and having at least one azo bond in one molecule and a number average molecular weight of 1,500 to 100,000 The main component is (meth)acrylic acid ester, and 1 to 1 polymerizable unsaturated carboxylic acid.
10 to 9 of the polymerizable unsaturated monomer mixture containing 0% by weight
The present invention relates to a coating resin composition comprising a vinyl-silicone block copolymer obtained by polymerizing 8% by weight and an organic solvent.

The general formula (I) used in the present invention
The azo group-containing polysiloxane compound having a repeating unit represented by ) has at least one azo bond in one molecule, has a number average molecular weight of 1,500 to 100,000, and is a type of polymeric azo initiator. It is.

In the general formula (I) and general formula (II), the lower alkyl group is a group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl group, etc. Mention may be made of straight-chain or branched alkyl groups. In addition to the above-mentioned lower alkyl groups, examples of the alkyl group include straight-chain or branched alkyl groups having 7 to 12 carbon atoms, such as heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups. Further, as the alkyl group substituted with a halogen atom, the above-mentioned alkyl group is halogenated, such as chloromethyl, bromomethyl, trifluoromethyl, 2-chloroethyl, 3-chloropropyl, 3
Examples include -bromopropyl, 3,3,3,-trifluoropropyl, and 1,1,2,2,-tetrahydroperfluorooctyl groups. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As the azo group-containing polysiloxane compound having a repeating unit represented by general formula (I), general formula (III)

[0014]

[C5] [In the formula, R1 and p are the same as above. ]

[0015]
Constituent components and general formula (IV) represented by

[0016]

embedded image [In the formula, R2, R3, A, B and m are the same as above. ]

It goes without saying that the constituent components represented by the formula (III) are alternately bonded to each other, and some of the constituent components represented by the general formula (III) are bonded to the general formula (V).

[0018]

[Chemical 7]-CO-Y-CO-
(V) [Wherein, Y represents a dibasic acid residue. ]

It also includes those substituted with the constituent components represented by the following. The amount that can be replaced with the component represented by the general formula (V) is limited to an amount that does not eliminate the radical polymerization activity of the azo group-containing polysiloxane compound.

Examples of dibasic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid,
Examples include azelaic acid, sebacic acid, fumaric acid, itaconic acid, terephthalic acid, isophthalic acid, and phthalic acid.

The azo group-containing polysiloxane compound represented by the general formula (I) is, for example, a compound represented by the general formula (VI).

00
22]

[In the formula, B is (CH2)q or -(CH2)3
OCH2 CH2 -, D represents NH2 or OH, and R2, R3, q and m are the same as above. ]

A diamine or dihydroxy compound containing a polysiloxane (including disiloxane) segment represented by the formula (VII);

[0024]

embedded image [In the formula, R1 and p are the same as above. X represents a halogen atom. ]

It can be produced in high yield by reacting with a dibasic acid dihalide containing an azo group represented by the following formula. In addition, when producing an azo group-containing polysiloxane compound having a component represented by the above general formula (V), a part of the azo group-containing dibasic acid dihalide of the above general formula (VII) is prepared. A mixture in which the dibasic acid dihalide is replaced with the corresponding dibasic acid dihalide may be used.

Preferably, the azo group-containing polysiloxane compound is produced in the presence of a basic catalyst. Examples of the base catalyst include triethylamine, tributylamine,
N,N-dimethylaniline, piperidine, pyridine, 1
,5-diazabicyclo[4,3,0]nonene-5,1,
8-diazabicyclo[5,4,0]undecene-7, tri-n-butylamine, sodium hydride, n-
Examples include butyllithium, and can be appropriately selected from these.

Further, the azo group-containing polysiloxane compound is usually produced in a solvent. Examples of the solvent include ethers such as tetrahydrofuran, diethyl ether, dimethoxyethane, and dioxane; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and trichlene; hydrocarbons such as n-hexane, benzene, and xylene; Examples include acetonitrile, N,N-dimethylformamide, etc., and one or more of these may be used.

The ratio of the diamine or dihydroxy compound represented by the general formula (VI) to the azo group-containing dibasic acid dihalide represented by the general formula (VII) is as follows:
Although not particularly limited and determined as appropriate, in order to obtain a high molecular weight, it is preferable to use approximately equimolar ratios of both. When a base catalyst is used, the amount used is based on the raw material compound (V
It is preferable to use about 0.5 to 1.5 times the mole of II).

The reaction temperature is not particularly limited, but in order to prevent the decomposition of the azo group and make the product have a high molecular weight, -
10-80 degreeC is preferable. The reaction time is not particularly limited, but is preferably 0.5 to 24 hours. The reaction temperature may be raised stepwise from low temperature to room temperature.

[0030] The target product is separated from the raw materials used, the base catalyst,
This is carried out as appropriate depending on the type of solvent and the like. For example, this is carried out by diluting a viscous reaction solution with a solvent, washing the by-produced quaternary ammonium salt with water to remove it, and then drying and removing the solvent.

The azo group-containing polysiloxane compound thus obtained is, as described above, components (III) and (IV), or an oligomer or polymer consisting of components (III), (IV) and (V). Its properties vary depending on the molecular weight and content of polysiloxane segments, but it is usually a colorless or yellowish powder, viscous oil, or rubber-like substance. Also, the solubility in solvents varies depending on the molecular weight and content of polysiloxane segments as mentioned above, but ethers such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane, etc.; carbon tetrachloride, chloroform, methylene chloride, trichlene, etc. halogenated hydrocarbons such as; aromatic hydrocarbons such as toluene, benzene, xylene, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; methyl acetate, ethyl acetate, propyl acetate, acetic acid-n- butyl,
Dissolves in acetic acid esters such as amyl acetate.

If the number average molecular weight of the azo group-containing polysiloxane compound is less than 1500, there will be a large number of molecules that do not substantially have an azo bond, so the efficiency of block polymerization will decrease and the compound will not exhibit its original function. In addition, when the number average molecular weight exceeds 100,000, the solubility decreases and the solution viscosity increases, so block copolymerization must be carried out at a low concentration. Since the polymerization rate of the sexually unsaturated monomer decreases, there are drawbacks such as a long reaction time being forced.

Production of a vinyl-silicone block copolymer using the azo group-containing polysiloxane compound is as follows:
A polymerizable unsaturated monomer containing (meth)acrylic acid ester as a main component and 1 to 10% by weight of a polymerizable unsaturated carboxylic acid in the presence of 2 to 90% by weight of an azo group-containing polysiloxane compound. This is carried out by polymerizing 10 to 98% by weight of the body mixture.

Examples of (meth)acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. , lauryl (meth)acrylate, stearyl (meth)acrylate, and the like. These (meth)acrylic esters are used in an amount of at least 50% by weight in the polymerizable unsaturated monomer mixture.

The polymerizable unsaturated carboxylic acid in the polymerizable unsaturated monomer mixture is used to improve the adhesion of the film formed from the coating resin composition to the coated object. A typical example of a polymerizable unsaturated carboxylic acid is (meth)
Examples include unsaturated acids such as acrylic acid, crotonic acid, itaconic acid, maleic acid (anhydride), fumaric acid, and the like.

The amount of the polymerizable unsaturated carboxylic acid used is 1 to 10% by weight, preferably 3% by weight in the polymerizable unsaturated monomer mixture.
~6% by weight. If the amount of the polymerizable unsaturated carboxylic acid used is less than 1% by weight, the adhesion to the adherend will be extremely reduced, which is not preferable. Moreover, if the amount of the polymerizable unsaturated carboxylic acid used exceeds 10% by weight, there is a fear that the water resistance will decrease, which is not preferable.

The polymerizable unsaturated monomer mixture may contain other unsaturated monomers in addition to the (meth)acrylic acid ester and the polymerizable unsaturated carboxylic acid. Such other unsaturated monomers include aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, etc.; aliphatic compounds such as (meth)acrylonitrile, vinyl acetate, vinyl propionate, vinyl versatate, etc. Typical examples include vinyl esters. Also usable are diesters of maleic acid or fumaric acid and C1 to C18 monohydric alcohols; or fluorine-containing vinyl monomers such as hexafluoropropylene or tetrafluoroethylene. Furthermore, as functional unsaturated monomers, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N
- alkoxymethyl (meth)acrylamides such as ethoxymethyl (meth)acrylamide, N-(iso)butoxymethyl (meth)acrylamide, etc.; acrolene;
Active carbonyl group-containing unsaturated compounds such as crotonaldehyde, vinyl methyl ketone, diacetone acrylamide, etc.; 2-hydroxyethyl (meth)acrylate;
Hydroxyl group-containing unsaturated compounds such as hydroxypropyl (meth)acrylate and hydroxybutyl (meth)acrylate, epoxy group-containing unsaturated compounds such as glycidyl (meth)acrylate, 2-vinyloxazoline, and the like can also be used.

The ratio of the azo group-containing polysiloxane compound and the polymerizable unsaturated monomer mixture is 10 to 98% by weight of the polymerizable unsaturated monomer mixture to 2 to 90% by weight of the azo group-containing polysiloxane compound. %. If the proportion of the azo group-containing polysiloxane compound used is less than 2% by weight, there will be disadvantages such as a decrease in the polymerization rate due to a decrease in the azo group concentration, and unreacted unsaturated monomers will remain. When the amount of the siloxane compound used exceeds 90% by weight, there are disadvantages such as a decrease in film strength and a failure to exhibit the characteristics of a vinyl-silicone block copolymer.

The polymerization reaction between the azo group-containing polysiloxane compound and the polymerizable unsaturated monomer mixture is usually carried out in the presence of an organic solvent. Examples of organic solvents include hydrocarbons such as toluene, xylene, cyclohexane, n-hexane, and n-octane; esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and amyl acetate; acetone; , methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; N
- Nitrogen-containing substances such as methylpyrrolidone; methyl alcohol, ethyl alcohol, (iso)propyl alcohol, (
t) Alcohols such as butyl alcohol and the like can be mentioned.

In addition, in the polymerization reaction, lauryl mercaptan, octyl mercaptan, 2-mercaptoethyl alcohol, 2-mercaptoethyl alcohol, 2-mercaptoethyl alcohol,
- Chain transfer agents such as mercaptopropionic acid, octyl thioglycolate, etc. can be added.

[0041] The temperature for the reaction between the azo group-containing polysiloxane compound and the polymerizable unsaturated monomer mixture is usually 30 to 180°C, and the temperature may be changed as the polymerization progresses. The reaction time is usually 1 to 48 hours.

Thus, by using an azo group-containing polysiloxane compound, a vinyl-silicone block copolymer can be produced extremely easily. The vinyl obtained
The content of the polysiloxane segment in the silicone block copolymer can be arbitrarily varied by changing the ratio of the azo group-containing polysiloxane compound to the polymerizable unsaturated monomer mixture, etc.
Specifically, vinyl-silicone block copolymer 1
．． It is about 8 to 90% by weight.

The coating resin composition of the present invention contains the vinyl-silicone block copolymer obtained as described above and an organic solvent. As the organic solvent used to prepare the coating resin composition of the present invention, the above-mentioned organic solvent used in the reaction of the azo group-containing polysiloxane compound and the polymerizable unsaturated monomer mixture is used. be able to. The organic solvent may be blended during or after the reaction of the azo group-containing polysiloxane compound and the polymerizable unsaturated monomer mixture. The amount of organic solvent used is selected appropriately.

The coating resin composition of the present invention may contain pigments, fillers, aggregates, antifoaming agents, plasticizers, film forming aids,
Rust inhibitors and other additives can be added.

The thus obtained coating resin composition of the present invention has excellent pigment dispersibility and provides a film with excellent elongation, water repellency and weather resistance, and is therefore useful for interior and exterior coatings of buildings, metal coatings, and the like.

[0046]

[Examples] The present invention will be explained in more detail below with reference to Examples and Comparative Examples.

Reference Example 1 In a four-necked flask equipped with a thermometer, stirrer, reflux condenser and calcium chloride tube, α,ω-
100 g (21.7 mM) of diaminopropylpolydimethylsiloxane (of the general formula (VI) in which R2 and R3 are methyl groups, D is an amino group, B is (CH2)3, and m is 58 on average), triethylamine 4.
38g (43.4mM) and 86.8g chloroform
and stirred thoroughly. While cooling the flask with ice water, a solution consisting of 6.88 g (21.7 mM) of 4,4'-azobis(-4-cyanopentanoic acid chloride) and 86.8 g of chloroform was added dropwise over 40 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, diluted by adding 50 g of chloroform, transferred to a separatory funnel, and washed with water by adding water. The chloroform layer was then separated, dried over sodium sulfate, and concentrated to dryness at room temperature under reduced pressure to yield the product 98.
9g was obtained. It was confirmed from the 1H-NMR spectrum and infrared absorption spectrum that this product was an azo group-containing polysiloxane amide having polysiloxane segments. The number average molecular weight of the azo group-containing polysiloxane amide was found to be 92,000 by GPC analysis. Further, the average number of azo group bonds was 23. Hereinafter, this will be abbreviated as a polymer azo initiator (1-1).

Reference Example 2 15g (17.0mM) of α,ω-diaminopropylpolydimethylsiloxane having a molecular weight of 880, 3.43g (34.0mM) of triethylamine, and 100g of chloroform.
Reference Example 1 except that a solution consisting of 5.39 g (17.0 mM) of 4,4'-azobis(-4-cyanopentanoic acid chloride) and 100 g of chloroform was added dropwise.
In the same manner as above, 121.3 g of the desired azo group-containing polysiloxane amide was obtained. This azo group-containing polysiloxane amide had a number average molecular weight of 21,000 and an average number of azo group bonds of 18. Hereinafter, this will be abbreviated as a polymer azo initiator (1-2).

Example 1 The polymeric azo initiator (1-1) obtained in Reference Example 1 was placed in a four-necked flask equipped with a thermometer, stirrer, and reflux condenser.
2.5g, methyl methacrylate 22.8g, 2-ethylhexyl acrylate 22.8g, methacrylic acid 1
．． 9g and 75g of methyl isobutyl ketone,
The reaction was carried out at 0°C for 1 hour. Next, 2.5 g of polymer azo initiator (1-1) and 22.5 g of methyl methacrylate were added.
8g of acrylic acid, 22.8g of 2-ethylhexyl acrylate, and 1.9g of methacrylic acid were added dropwise over 2 hours, and after the dropwise addition was completed, the same temperature was maintained for 5 hours to obtain a solution of the desired vinyl-silicone block copolymer. I got it. The target product was confirmed by 1H-NMR spectrum and infrared absorption spectrum. The polysiloxane segment content of this block copolymer according to 1H-NMR spectrum was 5.1% by weight. In order to prevent an abnormal increase in viscosity due to an increase in the polymerization rate, 75 g of methyl isobutyl ketone was appropriately added at the end of the polymerization and/or after the polymerization. The block copolymer solution thus obtained had a nonvolatile content of 38.7% and a BM
The viscosity at 30°C measured by a type viscometer was 4,700 cps.

Examples 2 to 5 The procedure was the same as in Example 1, except that the polymerization solvent, polymer azo initiator, and polymerizable unsaturated monomer shown in Table 1 were changed to be used in the predetermined ratios. A solution of the desired vinyl-silicone block copolymer was obtained.

Comparative Example 1 The polymerization solvent and polymerizable unsaturated monomer shown in Table 1 were used, and the low molecular weight initiator azobisisobutylene was used instead of the high molecular weight azo initiator (1-1). Lonitrile (AIB
A solution of a vinyl copolymer resin as a control resin was obtained in the same manner as in Example 1 except that 0.1 g (0.6 mM) of N) was used.

Comparative Examples 2 to 3 The same procedure as in Example 1 was carried out except that the polymerization solvent, low-molecular initiator, and polymerizable unsaturated monomer shown in Table 1 were used in the prescribed proportions. A solution of a vinyl copolymer resin as a control resin was obtained.

[0053]

[Table 1]

The respective resin solutions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were mixed into "Dipake R-820" (rutile manufactured by Ishihara Sangyo Co., Ltd.) at the compounding ratio shown in Table 2. [type titanium oxide] and methyl isobutyl ketone or xylene were ground together in a homomixer and made into a paint. Next, each of the obtained paints was applied to a polished steel plate and a slate plate using air spray at 3 atm, then dried at room temperature for 1 day, at 50°C for 2 days, and then left at room temperature for 1 day. This was subjected to various coating film performance tests.

Regarding elongation, tensile strength, and tensile product,
Each resin solution was adjusted so that the film thickness was approximately 0.2 mm, poured onto a smooth glass plate overlayed with a PE sheet, and dried at room temperature for 7 days and under reduced pressure for 1 day. provided to.

Tests on each coated board were conducted in the following manner.

0057] Elongation……“Shimadzu Autograph AG
-2000A” [manufactured by Shimadzu Corporation] for 100 m.
m/min crosshead speed, temperature 20℃, 6
Measurement was performed under the condition of 5% (RH).

[0058] Tensile strength... Same as above

[0059] Tensile product……Same as above

Pencil hardness: Based on JIS K-5400, the hardness was expressed as the hardness at which the paint film was scratched using "Mitsubishi Uni" (manufactured by Mitsubishi Pencil Co., Ltd.).

[0061] Flexibility: A test was conducted based on JIS K-5400 by bending the film 180 degrees using a bending tester. In the evaluation, when the thickness of the mandrel is 2 mm, if there is no crack at all on the painted surface even when bent, it is marked as "good", and if there is a crack, it is marked as "crack", and the thickness of the mandrel at that time is evaluated. It was also displayed.

[0062] Adhesion...Based on JIS K-5400, a grid (10 x 10) is placed on the coated surface of the test plate.
This was then peeled off using cellophane tape. The evaluation method is as follows. 10...Cut 1
Each book is thin and smooth on both sides, and there is no peeling at the intersection of the cuts or at the first glance of the square. 8... There is slight peeling at the intersection of the cuts, but there is no peeling at the first glance of the square.
The area of the missing part is within 5% of the total square area. 6... There is peeling on both sides and the intersection of the cut, and the area of the defective part is 5% to 15% of the total square area. 4... The width of the peeling due to the cut is wide, and the area of the defective part is 15 to 35% of the total square area. 2...
...The width of the peeling caused by the cut is wider than the four points, and the area of the defective part is 35 to 65% of the total square area. 0...Peeling area is 65% or more of the total square area.

[0063] Gloss……“Digital variable angle gloss meter UGV
-5D" (manufactured by Suga Test Instruments Co., Ltd.), the 60 degree specular gloss was measured.

[0064] Weather resistance... "Sunshine Super Long Life Weather Meter WEL-SUN-H
An accelerated weathering test was carried out for 800 hours using "Type C" (manufactured by Suga Test Instruments Co., Ltd.), and the gloss retention rate before and after the test was expressed.

Pigment dispersibility: Based on JIS K-5400, using a grain gauge, those with grains of 20 μm or less were considered "good", and those with grains of 20 μm or more were classified as "agglomerated".

Drying property: After each paint was applied by air spray, the time required for no trace to be left when pressing the painted surface with a finger was expressed as the time required.

Water contact angle: A resin or paint was applied onto a glass plate, water droplets were dropped on the test plate, and the surface contact angle was measured.

[0068]

[Table 2]

[0069]

Effects of the Invention As is clear from the results shown in Table 2, the coating composition using the vinyl-silicone block copolymer obtained by the present invention has higher water repellency than conventional vinyl resins. , exhibits weather resistance, and is useful in fields where these performances are required.

Claims (2)

[Claims] [Claim 1] General formula (1) [In the formula, each R1 is the same or different, a hydrogen atom,
It represents a lower alkyl group or a nitrile group, and each R2 is
The same or different R3's represent a hydrogen atom or a lower alkyl group, and each R3 is the same or different and represents a hydrogen atom, a halogen atom-substituted or unsubstituted alkyl group, or a phenyl group. p is the same or different, 0 or 1
represents an integer of ~6, m represents 0 or an integer of 1 to 200, A represents -NH or -O, B represents (CH2)q
(However, q is the same or different and represents 0 or an integer from 1 to 6.) or -(CH2)3OCH2C
Indicates H2-. ] has a repeating unit represented by
In the presence of 2 to 90% by weight of an azo group-containing polysiloxane compound having at least one azo bond in one molecule and having a number average molecular weight of 1,500 to 100,000, the main component is a (meth)acrylic acid ester, and 1 of a polymerizable unsaturated monomer mixture containing 1 to 10% by weight of a polymerizable unsaturated carboxylic acid
A coating resin composition comprising a vinyl-silicone block copolymer obtained by polymerizing 0 to 98% by weight and an organic solvent. Claim 2: The azo group-containing polysiloxane compound comprises a repeating unit represented by the general formula (1) according to claim 1 and the general formula (II) [In the formula, Y represents a dibasic acid residue] . R2, R3, A
, B and m are the same as above. The coating resin composition according to claim 1, which comprises a repeating unit represented by the following.