JPH1180169A - New polysiloxane and resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a modifier for e.g. acrylic resins used as coating materials and adhesives. SOLUTION: This new compound is shown by formula I [ R is a 1-4C alkyl; X is a group of formula II (R<1> is H or a 1-5C alkyl) or the like; A is a group of formula II (R<3> and R<4> are each a 1-18C alkyl, aryl or aralkyl; Y is a 1-8C alkoxy; (a) is 0 or 1; (b) is 0-6; (c) is 0 or 1) or the like], and is obtained by reaction between a compound of formula IV and a compound of formula V ((n) is 3-8) in the presence of an acidic or alkaline compound. Copolymerization of this compound with a polymerizable monomer such as acrylic or methacrylic monomer affords the corresponding (meth)acrylic resin improved as a moisture- curable resin which is excellent in flex resistance, contamination resistance, solvent resistance, pigment dispersibility, adhesion to substrates, weatherability and storage stability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polysiloxane and a resin composition using the same. More specifically, a novel polysiloxane compound useful as a modifier for acrylic resins and the like used in paints and adhesives, and acrylic polymers by copolymerizing the polysiloxanes with polymerizable monomers such as acrylic and methacrylic resins. The present invention relates to a resin composition which is obtained by modifying a base resin or the like, has good scratch resistance, adhesion to a substrate, tensile strength, solvent resistance, etc., and has excellent weather resistance and storage stability.

[0002]

2. Description of the Related Art Silane coupling agents and polysiloxane compounds having an unsaturated group have been widely used in the fields of paints and adhesives as modifiers for acrylic resins and the like. In this case, these compounds modify an acrylic resin or the like into a moisture-curable resin, and have weather resistance, scratch resistance,
It is useful for improving the adhesion to the substrate, tensile strength, solvent resistance and the like.

However, in recent years, there is a strong demand for weather resistance of paints for buildings and building materials, and the current situation is that conventional paints cannot sufficiently meet the demand. Furthermore, in the field of water-based paints, when modified with a silane coupling agent, the modification rate must be increased in order to obtain a sufficient effect, and as a result, the number of hydrolyzable groups in the molecule becomes too large, There is a problem that storage stability deteriorates. Moreover,
Those modified with a polysiloxane compound also have the problem of poor adhesion to the substrate.

For example, JP-B-62-56889 and JP-A-60-181173 disclose coating compositions modified with a known silane coupling agent. In each case, the stability was poor and the weather resistance was insufficient. In addition, Japanese Patent Publication 5-605
No. 03 and Japanese Patent Publication No. 7-108958,
Although an antifouling coating agent containing one-terminal methacryl-modified silicone is shown, all of these one-terminal methacryl-modified silicones have no alkoxy groups in the molecule, and therefore have poor adhesion to a substrate, and furthermore, silicone Since the components were not uniformly dispersed in the coating film, the weather resistance was insufficient. Further, Japanese Patent Application Laid-Open No. 6-99139 discloses a coating material containing a silicone modified with an unsaturated group at one end, but this coating material has a large number of alkoxy groups in the molecule, and therefore has a problem such as preservation stability and coating film. Was insufficient in workability.

Under these circumstances, in order to solve the problems caused by conventional silane coupling agents and polysiloxanes used for modifying acrylic resins in the field of paints and adhesives, acrylic resins and the like are used. When modified, it is effective in improving scratch resistance, adhesion to the substrate, tensile strength, solvent resistance, dispersibility of pigments, etc., and is a new poly-polymer with excellent weather resistance and storage stability. The appearance of siloxane and a resin composition using the same has been desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to improve the scratch resistance, adhesion to a substrate, tensile strength, solvent resistance, and pigment resistance when an acrylic resin or the like is modified into a moisture-curable resin. It is an object of the present invention to provide a novel polysiloxane which is effective in improving the dispersibility of the polysiloxane, and is excellent in weather resistance and storage stability, and a resin composition using the same.

The present inventors have conducted intensive studies to solve the problems caused by the conventional silane coupling agent and polysiloxane used for modifying the acrylic resin and the like, and as a result, the following novel polysiloxane was obtained. It has been found that the above-mentioned problems can be solved by manufacturing and using a resin composition using this polysiloxane. The present invention has been completed based on these findings.

[0008]

That is, according to the present invention, there is provided a novel polysiloxane represented by the following general formula (I). (Wherein, R represents an alkyl group having 1 to 4 carbon atoms;
Is R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; In this case, R ³ and R ⁴ each have 1 to 18 carbon atoms.
Represents a group selected from an alkyl group, a monovalent aryl group and an aralkyl group, and Y represents an alkoxy group having 1 to 8 carbon atoms. a is 0 or 1, b is 0 or an integer of 1 to 6, and c is 0 or an integer of 1 or more. Where c
Is 0, the molecule of formula (I) contains at least one A. )

Further, according to the present invention, there is provided a resin composition characterized by containing a copolymer of the novel polysiloxane and a polymerizable monomer.

Further, according to the present invention, there is provided a composite material such as a coating composition, an adhesive composition, and a coating composition produced by using the above resin composition.

As described above, the present invention relates to a novel polysiloxane and a resin composition using the same. Preferred embodiments thereof include the following. (1) A novel polysiloxane represented by the general formula (I). (2) a compound represented by the following formula (II) and a compound represented by the formula (III):
Wherein the compound represented by the formula (1) is reacted in the presence of an acidic compound or an alkaline compound. (In the formula, X, Y, R, a and b are the same as described above.)

[0012]

Embedded image (In the formula, R ³ and R ⁴ are the same as above. N is an integer of 3 to 8.) (3) A copolymer of the novel polysiloxane described in (I) and a polymerizable monomer is used. A resin composition characterized by containing: (4) The resin composition according to (2), wherein the polymerizable monomer is an acrylic monomer and / or a methacrylic monomer. (5) A composite material comprising the resin composition according to (3) or (4). (6) A coating composition comprising the resin composition according to (3) or (4). (7) An adhesive composition comprising the resin composition according to (3) or (4). (8) A coating composition comprising the resin composition according to (3) or (4).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the novel polysiloxane of the present invention and a resin composition using the same will be described in detail.

1. Polysiloxane The novel polysiloxane of the present invention is a compound represented by the following formula (I). (Wherein, R represents an alkyl group having 1 to 4 carbon atoms;
Is R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; In this case, R ³ and R ⁴ each have 1 to 18 carbon atoms.
Represents a group selected from an alkyl group, a monovalent aryl group and an aralkyl group, and Y represents an alkoxy group having 1 to 8 carbon atoms. a is 0 or 1, b is 0 or an integer of 1 to 6, and c is 0 or an integer of 1 or more. Where c
Is 0, the molecule of formula (I) contains at least one A. )

The novel polysiloxane represented by the above formula (I) can be produced by various production methods, and the production method is not particularly limited. To a compound represented by the formula (III) in the presence of an acidic compound or an alkaline compound. (In the formula, X, Y, R, a and b are the same as described above.)

[0016]

Embedded image (Wherein, R ³ and R ⁴ are the same as described above, and n is an integer of 3 to 8.) The compound represented by the formula (II) as a raw material for the above reaction is
It is a known compound. Specific examples of such compounds include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltris (n-butoxy) silane, and vinyltris (n). -Pentoxy) silane, vinyltris (n-hexoxy) silane, vinylbis (n-butoxy) methylsilane, vinylbis (n-pentoxy), methylsilane, vinyl-bis (n-hexoxy) methylsilane, γ-methacryloxypropyltrimethoxysilane, γ -Methacryloxypropyltriethoxysilane,
γ-methacryloxypropylmethyldimethoxysilane,
γ-methacryloxypropyltris (2-methoxyethoxy) silane, γ-acryloxypropyltrimethoxysilane, and the like. On the other hand, the compound represented by the formula (III), which is another raw material, is a cyclic polysiloxane having a degree of polymerization of 3 to 8, and is a known compound like the above compound. In the formula, R ³ and R ⁴ may be the same or different, and specific substituents include methyl, ethyl, propyl, isopropyl, butyl, secondary C 1-2 carbon atoms such as butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group and octadecyl group
A linear or branched alkyl group of 0; an aryl group such as a phenyl group, a tolyl group and a xylyl group; an aralkyl group such as a benzyl group and a phenethyl group.

Further, specific examples of the acidic compound used in the equilibrium reaction between the compound represented by the formula (II) and the compound represented by the formula (III) include sulfuric acid, hydrochloric acid, phosphoric acid, and active compounds. White clay, iron chloride, and the like. The reaction conditions at this time are not particularly limited as long as they are generally employed. For example, when sulfuric acid is used, the reaction temperature is 0 to 4
0 ° C. and a reaction time of 30 minutes to 12 hours are desirable. On the other hand, specific examples of the alkaline compound used when the compound represented by the formula (II) and the compound represented by the formula (III) are subjected to an equilibrium reaction include sodium hydroxide, potassium hydroxide, sodium alkoxide, Tetramethylammonium hydroxide, tetra-n-butylphosphonium hydroxide and the like can be mentioned. The reaction conditions at this time include:
As in the case of the above-mentioned acidic compound, any condition may be used as long as it is generally employed. For example, when potassium hydroxide is used, the reaction temperature is 90 to 150 ° C, and the reaction time is 3 to 2 hours.
4 hours is desirable. The acidic compound or the alkaline compound requires a certain amount to promote the above-mentioned equilibrium reaction. The amount of the acidic compound or the alkaline compound used depends on the compound represented by the formula (II) and the compound represented by the formula (III). Is preferably about 0.01 to 10% by weight based on the total amount of

The compound represented by the formula (II) and the compound represented by the formula (II)
The ratio of the compound represented by I) is preferably such that the latter compound is stoichiometrically used more than the former compound in promoting the above equilibrium reaction, and specifically, based on the total amount of both compounds. And the compound represented by the formula (II) is 1 to
50 mol%, the compound represented by the formula (III) is 99 to 5
A range of 0 mol% is desirable.

After completion of the reaction, the reaction product is purified according to a conventional method. That is, the residue of the acidic compound or the alkaline compound is filtered by neutralizing the salt generated,
Alternatively, it is removed by any method of heat decomposition and stripping of the decomposition product. Unreacted raw materials are removed by stripping as necessary.

As described above, the polysiloxane of the formula (I) thus obtained has a value of c of 0 or 1 as described above.
Is an integer greater than or equal to. However, considering the physical properties of the obtained polysiloxane, the value of c is preferably 1 to 50, and more preferably 1 to 10. If c is too large, the adhesion between the resin composition obtained using this and the substrate will be poor, while if c is too small, the storage stability of this resin composition and the flexibility of the coating film will be insufficient. And the effect of improving weather resistance cannot be obtained sufficiently, which is not desirable. Further, the polysiloxane of the formula (I) has at least two alkoxy groups. However, when the amount of the alkoxy groups is small, the adhesion to the base material becomes poor and the weather resistance becomes insufficient. This is considered to be because the polysiloxane was not uniformly present in the coating film.

The novel polysiloxane is represented by the above-mentioned general formula (I). Examples of the above-mentioned polysiloxane include compounds having the following structural formulas.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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2. Resin composition The resin composition of the present invention contains a copolymer of the novel polysiloxane represented by the above formula (I) and a polymerizable monomer.

The polymerizable monomer may be any one which is generally called a vinyl monomer, such as aromatic vinyl,
Vinyl halides, vinylidene halides, olefinic hydrocarbons, aliphatic vinyl esters, unsaturated amides, acrylates, methacrylates, or monomers having other functional groups derived therefrom, etc. It is appropriately selected according to the use of the resin composition of the present invention containing the copolymer of the monomer and polysiloxane. Typical polymerizable monomers include styrene,
Vinyl chloride, vinylidene chloride, ethylene, vinyl acetate,
Acrylamide, methacrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxy Examples include cyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, allyl acrylate, allyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, aminoethyl acrylate, aminoethyl methacrylate, and the like. Agent, coating agent, etc. Of these, the monomers of acrylic and / or methacrylic are particularly useful. These polymerizable monomers may be used alone or in combination of two or more.

When a copolymer of the polysiloxane and the polymerizable monomer constituting the resin composition of the present invention is produced, the amount of each monomer can be appropriately selected. 0.1 to 98% by weight, polymerizable monomer 9
A range of 9.9 to 2% by weight is desirable. If the content of the novel polysiloxane is less than 0.1% by weight, the adhesion to the substrate and the weather resistance will be poor. On the other hand, if the content of the polysiloxane exceeds 98% by weight, the flexibility and storage stability will be poor. The above copolymerization is carried out by a known polymerization method usually carried out in this field. As this method, for example, a radical polymerization method in a solution of a novel polysiloxane and a polymerizable monomer, a novel polysiloxane, a polymerizable monomer,
The mixture comprising water, a polymerization catalyst and a surfactant is
An aqueous emulsion polymerization method in which polymerization is performed at a temperature of 80 ° C. is exemplified.

The resin composition of the present invention may contain, in addition to a copolymer of polysiloxane and a polymerizable monomer, pigments generally used in the fields of paints, adhesives, coating agents, etc., depending on the application. A catalyst, a crosslinking agent, a solvent, a filler and the like may be added as an additive. Examples of pigments include inorganic pigments such as titanium oxide, iron oxide, graphite, cadmium oxide, carbon black, calcium carbonate, kaolin, talc, aluminum silicate, and aluminum flakes; azo, azo lake, phthalocyanine, quinacridone, Organic pigments such as isoindolinone type; rust preventive pigments such as strontium chromate and basic lead silicate; and the like, but are not limited thereto. As the crosslinking agent, a compound capable of reacting with the functional group of the coating resin is used.

3. Applications The resin composition containing the copolymer of the novel polysiloxane and the polymerizable monomer of the present invention is mainly used for paints, adhesives, coating agents and the like. When the resin composition of the present invention is used for these applications, the resin composition of the present invention can be further prepared by a known preparation method performed in each field. For example, in the case of a paint composition, a pigment, a paint, etc. may be blended and dispersed in the copolymer composition as needed, and then mixed with an aluminum chelate compound, a titanium chelate compound, a zirconium chelate compound, a vanadium chelate compound, or the like. Is prepared by mixing and stirring the metal chelate curing agent of the formula (1). At that time, the compounding amount of the metal chelate curing agent is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the copolymer composition.

The coating composition prepared by the above method has good bending resistance, stain resistance, solvent resistance, pigment dispersibility, adhesion to a substrate, etc., as well as weather resistance and storage stability. Also excellent in nature. Therefore, the paint composition of the present invention is suitable as a paint for building and building materials that require particularly high weather resistance, and is also suitable as a water-based paint that is regarded as important in terms of environmental protection.

[0040]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

[Synthesis Example of Polysiloxane] Synthesis Example 1 60.3 g of γ-methacryloxypropyltrimethoxysilane was placed in a 1 l four-neck separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. 161.4 g of methylcyclotetrasiloxane and 6.7 of sulfuric acid
g was added and stirred at room temperature for 7 hours. Next, 33.3 g of sodium hydrogencarbonate was added and the mixture was stirred, and unreacted substances were removed under reduced pressure, followed by filtration. When the physical properties of the obtained product were measured, the viscosity at 25 ° C. was 14 mm ² / s, and the refractive index was 1.4111. Also, this product was converted to ¹ H-N
When analyzed by MR, the following spectrum was observed. δ (ppm); 0.3 (54H, Si-C
_{H 3), 0.7 (2H,} Si-CH 2), 2.0 (5H,
_{Si-CCH 2, C = CCH} 3 -CO), 3.5 (9
_{H, Si-OCH 3),} 4.2 (2H, COO-CH 2 -
C), 5.6 (1H, CH ₂ ＣC), 6.2 (1H, C
H ₂ = C) Further analysis of the product by GPC showed that the number average molecular weight was 647 and the weight average molecular weight was 18 in terms of styrene.
823 peaks. From the above, it was confirmed that the obtained product was a methacryl macromer having the following average structure (hereinafter, referred to as methacryl macromer A).

[0042]

Embedded image Synthesis Example 2 In a 1 l four-neck separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, 70.7 g of vinyltrimethoxysilane, 317.7 g of octamethylcyclotetrasiloxane, and 0.1 ml of potassium hydroxide were placed. Add 5g and add 10
The mixture was stirred under reflux at 0 ° C. for 6 hours. Next, after cooling the reaction solution, 1.5 g of acetic acid was added and stirred, and unreacted substances were removed under reduced pressure, followed by filtration. When the physical properties of the obtained product were measured, the viscosity at 25 ° C. was 11 mm ² / s, and the refractive index was 1.3990. Also, this product was converted to ¹ H-
When analyzed by NMR, the following spectrum was observed. δ (ppm); 0.3 (54H, Si-C
_{H 3), 3.5 (9H,} Si-OCH 3), 6.1 (3
H, CH ₂ ＣＨCH—Si) Further, when this product was analyzed by GPC, the number average molecular weight was 586 and the weight average molecular weight was 16 in terms of styrene.
It showed 450 peaks. Further, when this product was analyzed by IR, absorption at 1600 cm ^-1 was attributed to a vinyl group. From the above, it was confirmed that the obtained product was a vinyl macromer having the following average structure (hereinafter, referred to as vinyl macromer B).

[0043]

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[Synthesis Example of Resin Composition (Silylated Acrylic Resin)] Synthesis Example 3 Xylene 350 was placed in a 1.5-liter four-neck separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel.
g, and 75 g of isobutyl acetate were added and heated to 120 ° C., and then 50 g of methacrylic macromer A, 100 g of 3,4-epoxycyclohexylmethyl methacrylate,
100 g of n-butyl methacrylate, 150 g of 2-ethylhexyl methacrylate, 100 g of FM-3X monomer (manufactured by Daicel Chemical Industries, Ltd., 100 g of a ring-opening polymer of ε-caprolactone having a polymerizable unsaturated group and a hydroxyl group), and 2,2 ′ -A mixed solution consisting of 10 g of azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, stirring was continued at the same temperature for another 3 hours to complete the polymerization reaction. Finally, 75 g of isobutanol was added to obtain silylated acryl A having a solid content of about 50% and a number average molecular weight of about 19000. Synthesis Example 4 A synthesis was performed in the same manner as in Synthesis Example 3 except that 50 g of methacrylic macromer A used in Synthesis Example 3 was replaced with 50 g of vinyl macromer B. The solid content was about 50% and the number average molecular weight was about 1
8,000 silylated acryl B were obtained. Synthesis Example 5 50 g of methacrylic macromer A used in Synthesis Example 3 was converted to γ
When the same procedure was performed as in Synthesis Example 3 except that 50 g of methacryloxypropyltrimethoxysilane was used, silylated acryl C having a solid content of about 50% and a number average molecular weight of about 16,000 was obtained. Synthesis Example 6 Xylene 350 was placed in a 1.5-liter four-neck separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel.
g and isobutyl acetate (75 g), and heated to 120 ° C., followed by 3,4-epoxycyclohexylmethyl methacrylate (114 g) and n-butyl methacrylate (114).
g, 2-ethylhexyl methacrylate 172 g, FM
A mixed solution comprising 100 g of -3X monomer (a product of Daicel Chemical Industries, Ltd., ring-opening polymer of ε-caprolactone having a polymerizable unsaturated group and a hydroxyl group) and 10 g of 2,2′-azobisisobutyronitrile It was dropped in 2 hours. After completion of the dropwise addition, stirring was continued at the same temperature for another 3 hours to complete the polymerization reaction. Finally, 75 g of isobutanol was added to obtain Acrylic D having a solid content of about 50% and a number average molecular weight of about 14,000.

[Preparation Example of Paint] Production Example 1 After mixing and dispersing 270 g of rutile-type titanium white in 600 g of silylated acryl A obtained in Synthesis Example 3, tris (n-propylacetoacetate) was used as a metal chelate curing agent. 3) 3 g of aluminum was blended and uniformly stirred to obtain a paint. Production Example 2 A coating material was obtained in the same manner as in Production Example 1, except that 600 g of silylated acryl A used in Production Example 1 was replaced with 600 g of silylated acryl B obtained in Synthesis Example 4. Production Example 3 A coating material was obtained in the same manner as in Production Example 1, except that 600 g of silylated acryl A used in Production Example 1 was replaced with 600 g of silylated acryl C obtained in Synthesis Example 5. Production Example 4 A coating material was obtained in the same manner as in Production Example 1, except that 600 g of the silylated acryl A used in Production Example 1 was replaced with 600 g of the acrylic D obtained in Synthesis Example 6.

[Coating Examples / Comparative Examples] Example 1 KP color 84 was applied to an electrogalvanized steel plate having a thickness of 0.5 mm.
16 primers (Epoxy resin primer for pre-coated metal, manufactured by Kansai Paint Co., Ltd.) with a dry film thickness of about 4 μm
And baked for 30 seconds under the condition that the maximum temperature of the material reached 200 ° C. to obtain a primer-coated plate.
The paint obtained in Production Example 1 was applied to this primer-coated plate so as to have a dry film thickness of about 18 μm.
It was baked for 30 seconds under the condition of 50 ° C. to obtain an overcoated plate.

Example 2 The procedure of Example 1 was repeated, except that the paint used in Example 1 was replaced with the paint obtained in Production Example 2, to obtain a top-coated plate.

Comparative Example 1 An overcoated plate was obtained in the same manner as in Example 1 except that the paint used in Example 1 was replaced with the paint obtained in Production Example 3.

Comparative Example 2 An overcoated plate was obtained in the same manner as in Example 1 except that the paint used in Example 1 was replaced with the paint obtained in Production Example 4.

When the following evaluation was performed on the obtained coated plate, the results shown in Table 1 were obtained. Workability: In a room at 20 ° C., the test plate was bent 180 ° with the painted surface facing outward, and the T number at which no crack was generated in the bent portion was determined. The T number is 0T when 180 ° bending is performed without sandwiching anything inside the bent portion.
When one sheet of the same thickness as the test plate is sandwiched and bent,
T, similarly, 2T for 2 sheets, 3T for 3 sheets, and nT for n sheets. Solvent resistance: In a room at 20 ° C., a load of 1 kg / cm ² was applied to the coated surface with gauze impregnated with methyl ethyl ketone, and the coated surface was reciprocated for a length of 5 cm, and the number of reciprocations until the primer coated portion was visible was measured. . When the primer coating was not visible after 50 reciprocations, the number was 50 or more. Carbon contamination resistance: carbon black / water = 2/98
(Weight ratio) 1 cc of the solution was placed on the painted surface,
After being left in a constant temperature room at 0 ° C. for 8 hours, it was washed with water and the trace of the solution was visually judged. The judgment was made based on the following criteria. A: No trace is observed. ：: Slight traces are observed. Δ: Significant marks remain. ×: The trace remains dark. Accelerated weather resistance: 3000 with sunshine weatherometer
The gloss retention (%) of the surface of the coating film after the irradiation was measured for hours.

[0051]

[Table 1]

From the above evaluation results, in the examples using the paint produced using the polysiloxane of the present invention, all the evaluations were excellent, but the paint produced using the compound other than the present invention was excellent. The comparative example used is inferior. That is, Comparative Example 1 is significantly inferior in workability and carbon contamination resistance, and is also inferior in accelerated weather resistance. Also,
Comparative Example 2 is significantly inferior in carbon stain resistance and accelerated weather resistance.

[Examples and Comparative Examples of Silylated Acrylic Emulsion] Example 3 80 parts of n-butyl methacrylate, 20 parts of methacrylic macromer A, 2.5 parts of acrylamide, 1 part of polyoxyethylene nonyl phenyl ether, sodium dodecylbenzenesulfonate An emulsion monomer composition having a composition of 1.4 parts and 55 parts of water was prepared, while a polymerization comprising 10 parts of a 3.5% aqueous solution of t-butylhydrobaroxide and 10 parts of a 3.5% aqueous solution of Rongalite. A catalyst was prepared. Next, 90% of the emulsified monomer composition was added to an emulsion polymerization apparatus charged with 40 parts of water, 0.3 part of ammonium acetate, 1.3 parts of polyoxyethylene nonylphenyl ether, and 0.7 part of sodium dodecylbenzenesulfonate. 70% of the above polymerization catalyst was added dropwise for about 3 hours to carry out emulsion polymerization. During the emulsion polymerization, the polymerization temperature was maintained at about 50 ° C., and the pH of the polymerization reaction solution was maintained at pH 7 by dropwise addition of an aqueous ammonia solution. After dropping, the mixture was aged for about 1 hour, and after cooling, the concentration was adjusted with an appropriate amount of water to obtain a silylated acrylic emulsion having a solid content of 45% and a pH of 7.

Example 4 A silylated acrylic emulsion was obtained in the same manner as in Example 3, except that 20 parts of methacrylic macromer A used in Example 3 was replaced with 20 parts of vinyl macromer B.

Comparative Example 3 20 parts of methacrylic macromer A used in Example 3
-A silylated acrylic emulsion was obtained in the same manner as in Example 3, except that 20 parts of methacryloxypropyltrimethoxysilane was used.

Comparative Example 4 A silylated acrylic emulsion was obtained in the same manner as in Example 3 except that 20 parts of methacrylic macromer A used in Example 3 was replaced with 20 parts of the following compound (methacrylic modified silicone at one end).

[0057]

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The following evaluation was performed for the obtained silylated acrylic emulsion, and the results shown in Table 2 were obtained. Stability: The obtained silylated acrylic emulsion was placed in a closed container, allowed to stand at room temperature for 6 months, and then measured by the change in the minimum film forming temperature that occurred compared to the initial one.
The measurement was performed according to the following criteria. ：: Change in minimum film formation temperature less than 10 ° C. ×: Change in minimum film formation temperature not less than 10 ° C. Adhesion: The obtained silylated acrylic emulsion was applied to a glass plate with an applicator so as to have a coating film of 20 μm, and then 120 After drying for 1 hour at 50 ° C, the test piece was
Was immersed in warm water for 4 days, and the change of the coating film was visually determined.
The judgment was made based on the following criteria. ：: No change. X: The coating film has deteriorated or peeled.

[0059]

[Table 2]

From the above evaluation results, the examples using the silylated acrylic emulsion produced using the polysiloxane of the present invention are excellent in all the evaluations, but the examples using the compounds other than the present invention are excellent. The comparative example using the silylated acrylic emulsion has inferior points. That is, Comparative Example 3 is inferior in storage stability, and Comparative Example 4 is inferior in adhesion.

[0061]

According to the novel polysiloxane of the present invention, an acrylic resin or the like is modified into a moisture-curable resin by copolymerization with a polymerizable monomer such as an acrylic monomer or a methacrylic monomer. The cured resin has good bending resistance, stain resistance, solvent resistance, pigment dispersibility, adhesion to the substrate, etc., and is also excellent in weather resistance and storage stability. Useful for Further, the paint of the present invention is suitable as a paint for architectural and building materials particularly requiring weather resistance, and is also suitable as a water-based paint which is regarded as important from the viewpoint of environmental protection.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G77 / 20 C08G77 / 20 C08L 55/00 C08L 55/00 83/07 83/07

Claims (3)

[Claims] 1. A novel polysiloxane represented by the following general formula (I). (Wherein, R represents an alkyl group having 1 to 4 carbon atoms;
Is R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; In this case, R ³ and R ⁴ each have 1 to 18 carbon atoms.
Represents a group selected from an alkyl group, a monovalent aryl group and an aralkyl group, and Y represents an alkoxy group having 1 to 8 carbon atoms. a is 0 or 1, b is 0 or an integer of 1 to 6, and c is 0 or an integer of 1 or more. However, even when c is 0, the molecule of formula (I) contains at least one A. ) 2. A resin composition containing the copolymer of the novel polysiloxane according to claim 1 and a polymerizable monomer. 3. The resin composition according to claim 2, wherein the polymerizable monomer is an acrylic monomer and / or a methacrylic monomer.