WO2019031890A1 - Composition for coating silicone - Google Patents

Abstract

Provided in the present invention is a composition for coating silicone, containing, in predetermined amounts: organopolysiloxane comprising an alkenyl group coupled to at least two silicon atoms in a molecule; organohydrogenpolysiloxane comprising a hydrogen atom coupled to at least two silicon atoms in a molecule; a filler comprising polysilsesquioxane; a volatile silicone oil; and a hydrosilylation reaction catalyst.

Description

Composition for silicone coating

The present invention relates to a silicone coating composition.

Silicone exhibits excellent weather-resistant and heat-resistant properties and excellent rubber-like properties such as hardness and elongation, and as a result can form the cured product used in all types of applications.

Silicon is also known as an environmentally friendly material that is not harmful to human body as compared to other materials. As regulations for chemical substances are strengthened worldwide, materials used in various fields are being changed to silicon. Particularly, the proportion of silicon as a material to be directly exposed to human bodies such as kitchen appliances and textile coatings is increasing.

However, according to other characteristics of silicon, it is possible to have stickiness on the surface of the silicon formed, such as tackiness. Therefore, foreign substances such as dust are liable to adhere to each other, and when friction occurs, it may cause wear and scratches on the surface.

The present invention provides a silicone coating composition.

Another object of the present invention is to provide a silicone containing a coating layer formed of a cured product of the silicone coating composition.

One aspect of the present invention relates to an organohydrogenpolysiloxane containing a hydrogen atom bonded to at least two silicon atoms in a molecule, based on 100 parts by weight of an organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in the molecule, 1 to 10 parts by weight of a polysiloxane, 10 to 150 parts by weight of a filler comprising polysilsesquioxane, 50 to 2,000 parts by weight of a volatile silicone oil, and 0.01 to 10 parts by weight of a hydrosilylation reaction catalyst do.

Another aspect of the present invention provides a coating film formed using the silicone coating composition.

The silicone coating composition according to one embodiment of the present invention is coated on the surface of the silicon substrate to reduce the contact area of the silicon substrate surface and reduce the friction coefficient. Therefore, the slip property can be improved and a volatile organic solvent It is possible to provide a composition which is not harmful to the health of the operator or the user.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

An aspect of the present invention provides a composition for silicone coating.

The silicone coating composition of the present invention comprises an organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in a molecule, an organohydrogenpolysiloxane containing a hydrogen atom bonded to at least two silicon atoms in the molecule, Fillers comprising polysilsesquioxane, volatile silicone oils, and hydrosilylation catalysts and other additives.

Hereinafter, the individual components will be described in more detail.

<Organopolysiloxane>

The organopolysiloxane contained in the composition for silicone coating of the present invention is a component that becomes a main agent of the silicone coating composition and serves to connect the silicon substrate and the filler. The organopolysiloxane includes at least two silicon atoms And an organopolysiloxane containing an alkenyl group. That is, it may be an organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms in the molecule of the organopolysiloxane.

The organopolysiloxane may be represented by the following formula (1).

[Chemical Formula 1]

(R ¹ R ² ₂ SiO _1/2 ) ₂ (R ¹ R ² SiO) _a (R ² ₂ SiO) _b

Wherein R ¹ is independently an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, R ² is independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, Is 0 or an integer of 1 or more, and a + b = 10 to 10,000.

In the present invention, the alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group or a cyclohexyl group, and the alkenyl group may be a vinyl group, an allyl group, a butenyl group, Or a hexenyl group, and the aryl group may be a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a biphenylyl group.

Specifically, the organopolysiloxane is a vinyldimethyl-terminated dimethylpolymer (ViMe ₂ SiO _1/2 ) (Me ₂ SiO) _n (ViMe ₂ SiO _1/2 ), a vinyldimethyl-terminated methylvinyldimethylblock polymer (ViMe _{2 SiO 1/2) (Me 2 SiO)} n (ViMeSiO) m (ViMe 2 SiO 1/2)), trimethyl terminated dimethyl methylvinylsiloxane block polymer _{((Me 3 SiO 1/2) (} Me 2 SiO) n (ViMeSiO) may be used, such as the _{m (Me 3 SiO 1/2))} ( wherein, the m + n = 10 to 10,000).

The viscosity of the organopolysiloxane at 25 占 폚 is preferably in the range of 50 to 300,000 mPa 占 퐏 at 25 占 폚 in order to further improve physical properties such as adhesiveness, rubber strength, Lt; / RTI &gt;

In addition, the organopolysiloxane may be used alone or in combination of two or more in the silicone coating composition.

&Lt; Organohydrogenpolysiloxane >

The organohydrogenpolysiloxane contained in the silicone coating composition of the present invention is a component which acts as a crosslinking agent in the addition curing reaction with the organopolysiloxane and also imparts adhesiveness to the cured product, And organohydrogenpolysiloxanes containing hydrogen atoms bonded to atoms. That is, it may be an organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in the molecule of the organohydrogenpolysiloxane.

Here, in the organohydrogenpolysiloxane molecule, the bonding position of the silicon atom-bonded hydrogen atom may be a terminal of a molecular chain or may be a terminal end of a molecular chain (i.e., a side chain portion of a molecular chain), or both It is possible.

The organohydrogenpolysiloxane may be represented by the following formula (2). Specifically, the organohydrogenpolysiloxane may include a repeating unit represented by the following formula (2).

(2)

H _c R ³ _d SiO _{(4-cd) / 2}

Wherein R ³ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, c is 0.6 to 2.2, d is 0.001 to 1.0 and c + d is 0.8 to 3.0, or c is 1.0 To 2.0, d is 0.01 to 1.0, and c + d is 1.5 to 2.5.

Specifically, the organohydrogenpolysiloxane may be a hydrogendimethyl terminated dimethyl polymer ((HMe ₂ SiO _1/2 ) (Me ₂ SiO) _n (HMe ₂ SiO _1/2 )), a trimethylendermethylhydrogen polymer _{3 SiO 1/2) (HMeSiO) n} (Me 3 SiO 1/2)), trimethyl terminated methylhydrogen dimethyl polymer block _{((Me 3 SiO 1/2) (} Me 2 SiO) m (HMeSiO) n (Me 3 the SiO _1/2)), dimethyl hydrogen terminated dimethyl methyl hydrogen polymer block _{((HMe 2 SiO 1/2) (} Me 2 SiO) m (HMeSiO) n (HMe 2 SiO 1/2)) , etc. may be used (Where m + n is 10 to 100).

The hydrogen content in the organohydrogenpolysiloxane may be from 1 mmol / g to 20 mmol / g. If the hydrogen content in the organohydrogenpolysiloxane is less than the above range, the reactivity with the organopolysiloxane is lowered and the crosslinking density is lowered. If the hydrogen content exceeds the above range, the hydrogen curing will occur or the hydrogen gas will be generated and the workability will be lowered.

The viscosity of the organohydrogenpolysiloxane at 25 캜 is preferably in the range of 10 to 1,000 mPa 揃 s to improve the physical properties such as adhesiveness, rubber strength, blocking resistance, and workability of the silicone coating composition to the silicon substrate, · S.

In addition, the organohydrogenpolysiloxane may be used alone or in combination of two or more in the silicone coating composition.

The organohydrogenpolysiloxane may be contained in the silicone coating composition in an amount of 1 to 10 parts by weight based on 100 parts by weight of the organopolysiloxane. If the content of the organohydrogenpolysiloxane is less than the above range, the crosslinking density of the curable organopolysiloxane is lowered and the reactivity is delayed. If the content of the organohydrogenpolysiloxane exceeds the above range, hydrogen gas is generated and workability is lowered.

<Filling agent>

The filler contained in the silicone coating composition of the present invention is a spherical particle filler capable of increasing the slipperiness of the surface by positioning the silicone coating composition on the surface of the cured coating layer and is excellent in scratch resistance, As a component capable of improving the antifouling property and the like to protect the substrate, it includes polysilsesquioxane.

Here, the polysilsesquioxane may include at least one functional group selected from the group consisting of a hydroxyl group, an alkyl group and an aryl group on the surface thereof. Specifically, the polysilsesquioxane may be polyalkylsilsesquioxane And more specifically polymethylsilsesquioxane.

The polysilsesquioxane may be in the form of spherical particles having an average particle diameter of 0.5 to 20 탆 and 4 to 10 탆. By having a particle diameter within the above range, excellent slipping properties and physical properties of the coating layer can be secured.

The content of the polysilsesquioxane-containing filler may be 10 to 150 parts by weight based on 100 parts by weight of the organopolysiloxane, and may be 10 to 100 parts by weight . If the content of the filler including polysilsesquioxane is less than the above range, the number of the filler to be expressed on the surface of the coating layer may be small and the contact area of the surface may not be small, so that low friction performance may not be obtained, If the content of the filler including oxane is in the above range, the processability for forming a coating layer with the silicone coating composition of the present invention may be deteriorated, and the appearance of the silicon substrate having the coating layer formed may be greatly impaired.

<Volatile Silicone Oil>

The volatile silicone oil contained in the silicone coating composition of the present invention not only acts as a diluent without a separate organic solvent to make the silicone coating composition of the present invention have low friction, A part of the filler component including the polysiloxane can be expressed on the surface of the coating layer of the coating layer by volatilization and the substantial contact between the coating layer formed by the silicone coating composition of the present invention and the outside By reducing the area, the friction coefficient on the surface of the coating layer can be reduced.

In order to achieve the above-mentioned effect, the volatile silicone oil may be a low-molecular substance, specifically, at least one of polydimethylsiloxane and cyclosiloxane.

The polydimethylsiloxane may be represented by the following general formula (3).

(3)

M is an integer of 0? M <4.

The cyclosiloxane may be represented by the following general formula (4).

[Chemical Formula 4]

N is an integer of 3? N <6, and each R ⁴ is independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms.

The volatile silicone oil may be used alone or in combination of two or more in the silicone coating composition.

The volatile silicone oil may be contained in the silicone coating composition in an amount of 50 to 2,000 parts by weight based on 100 parts by weight of the organopolysiloxane. If the content of the volatile silicone oil is less than the above range, the handling of the composition becomes difficult and the workability becomes poor. When the content of the volatile silicone oil exceeds the above range, the filler to be expressed on the surface of the coating layer becomes small and slipperiness can not be obtained.

&Lt; Hydrosilylation reaction catalyst >

The hydrosilylation reaction catalyst contained in the silicone coating composition of the present invention is a catalyst for promoting the hydrosilylation addition reaction between an alkenyl group bonded to silicon of the organopolysiloxane and hydrogen bonded to silicon of the organohydrogenpolysiloxane And may include a noble metal catalyst.

The noble metal catalyst includes, for example, platinum group metals such as platinum, palladium and rhodium; (Triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium and the like, or the like, or the like, or a salt compound of a chlorosulfuric acid or a chloroplatinic acid, an alcohol-modified chloroplatinic acid, a chloroplatinic acid and an olefin, a chloroplatinic acid hexahydrate, Of the platinum group metal compounds.

The content of the catalyst may be an effective amount as a catalyst in the silicone coating composition, but may be 0.01 to 10 parts by weight based on 100 parts by weight of the organopolysiloxane. Specifically, the total amount of the organopolysiloxane and the organohydrogenpolysiloxane And 0.1 to 1,000 ppm in terms of mass of the platinum group metal atom relative to the total amount of the platinum group metal atoms. The curing reaction can be more effectively promoted by being included in the silicone coating composition within the above-mentioned range.

The hydrosilylation reaction catalyst may be used alone or in combination of two or more.

<Other additives>

The silicone coating composition of the present invention may further comprise other optional ingredients such as conventional additives known in the art. Specifically, it may further include a retarder, an adhesion-imparting agent, and the like.

As the retarder, any of the compounds known as a reaction retarder can be used as a curing retarder and can include an alcohol compound, specifically 1-ethynyl-1-cyclohexanol, 2-methyl- 3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 3,5-dimethyl- , 7-tetramethylcyclotetrasiloxane.

The adhesion-imparting agent may be added to improve the adhesion of the silicone coating composition to the substrate. Methoxysilane compounds can be used. Specific examples thereof include methyltrimethoxysilane, vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Or similar silane coupling agents.

In addition, other optional components may also be added to the silicone coating composition of the present invention (provided that such addition does not impair the function or effect of the present invention). Examples of such other optional components include flame retardants, surfactants, storage stability improvers, light stabilizers, coupling agents, heat stabilizers, antistatic agents, and organic solvents. These optional ingredients may be used alone or in combination of two or more different materials.

Another aspect of the present invention provides a silicone article comprising the coating layer formed by curing the silicone coating composition. The coating layer may be formed on the silicon article to a thickness of 5 to 300 mu m. By setting the thickness of the coating layer within the above range, properties such as scratch resistance, abrasion resistance, and antifouling property can be ensured at the same time while ensuring slip property.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Examples and Comparative Examples

&Lt; Preparation of silicone coating composition >

Using the respective compositions and contents according to the following Table 1, silicone coating compositions of Examples 1 to 7 and compositions and contents according to the following Table 2 were used to prepare silicone coating compositions of Comparative Examples 1 to 6.

&Lt; Formation of Coating Layer &

The silicone coating compositions of the above Examples and Comparative Examples were coated on a silicon substrate SL7260 made by KCC Silicone Co., Ltd. to a thickness of 20 탆, and cured at 160 캜 for 6 minutes to prepare a coating layer.

Experimental Example

The physical properties of the samples obtained according to the above Examples and Comparative Examples were measured as follows, and the results are shown in Tables 1 and 2 below.

1) Kinetic friction coefficient

The sample was measured at a speed of 500 mm / min with a load of 100 g and a rubber probe for friction force measurement in a dynamic friction tester (MTT 175). The resulting measured values are listed in Tables 1 and 2 as the coefficient of dynamic friction.

2) Adhesiveness

For the sample, the surface of the coating was scratched with the fingernail to check the surface condition. The case where the filler did not come out on the fingernail was regarded as good, and the cases where the base material was exposed or the filler was released were visually confirmed, and the results are shown in Tables 1 and 2.

division	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7
Organopolysiloxane	100	100	100	100	100	100	100
Organohydrogenpolysiloxane	6	6	6	6	6	6	6
Filler	10	33	66	100	150	66	66
Hydrosilylation reaction catalyst	0.5	0.5	0.5	0.5	0.5	0.5	0.5
Volatile silicone oil	850	850	850	850	850	500	1000
Other additives 1 + Other additives 2	0.6	0.6	0.6	0.6	0.6	0.6	0.6
Coefficient of dynamic friction	0.69	0.60	0.40	0.38	0.38	0.39	0.38
Attachment	Good	Good	Good	Good	Good	Good	Good

division	Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4	Comparative Example 5	Comparative Example 6
Organopolysiloxane	100	100	100	100	100	100
Organohydrogenpolysiloxane	6	6	6	6	6	6
Filler	-	5	200	-	66	66
Silica (HMDZ treated)	-	-	-	66	-	-
Hydrosilylation reaction catalyst	0.5	0.5	0.5	0.5	0.5	0.5
Volatile silicone oil	850	850	850	850	2500	25
Other additives 1 + Other additives 2	0.6	0.6	0.6	0.6	0.6	0.6
Coefficient of dynamic friction	1.46	0.82	0.32	0.94	1.33	0.88
Attachment	Good	Good	Filler detachment	Good	Good	Good

Organopolysiloxane: polydimethylsiloxane having a vinyl-siloxane group at both ends and a vinyl content of 0.02 mmol / g and a viscosity at 150 ° C of 150 Pa · s

(Organohydrogenpolysiloxane 1) having a trimethylsiloxy group at both terminals and a hydrogen content of 4.3 mmol / g and a viscosity at 25 DEG C of 40 mPa.s, (Organohydrogenpolysiloxane 2) having a trimethylsiloxy group and a hydrogen content of 15.5 mmol / g and a viscosity of 22.5 mPa · s at 25 ° C was mixed

Filler: Polymethylsilsesquioxane (Filler 1) having a primary particle size of 1 to 5 μm and polymethylsilsesquioxane having a primary particle size of 6 to 10 μm (Filler 2) were mixed at a weight ratio of 1: 2

Hydrosilylation reaction catalyst: A solution of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane in a mixture of platinum and 1,3-diethynyl-1,1,3,3-tetramethyldisiloxane (Platinum content: 1% by weight based on 100% by weight of the solution)

Volatile silicone oil: Decamethylpentacyclosiloxane (Decamethylpentacyclosiloxane)

Other additives 1: retarding agent, 1-ethynyl-1-cyclohexanol

Other additives 2: Pressure-sensitive adhesive, (3-glycidyloxypropyl) trimethoxysilane

Claims (11)

1. Based on 100 parts by weight of an organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in the molecule,

   1 to 10 parts by weight of an organohydrogenpolysiloxane containing a hydrogen atom bonded to at least two silicon atoms in the molecule,

   10 to 150 parts by weight of a filler comprising polysilsesquioxane,

   50 to 2,000 parts by weight of a volatile silicone oil, and

   0.01 to 10 parts by weight of a hydrosilylation reaction catalyst.
2. The method according to claim 1,

   Wherein the organopolysiloxane is represented by the following formula (1).

   [Chemical Formula 1]

   (R ¹ R ² ₂ SiO _1/2 ) ₂ (R ¹ R ² SiO) _a (R ² ₂ SiO) _b

   (Wherein R ¹ is independently an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, R ² is independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, 0 or an integer of 1 or more, and a + b = 10 to 10,000).
3. The method according to claim 1,

   Wherein the organohydrogenpolysiloxane is represented by the following formula (2).

   (2)

   H _c R ³ _d SiO _{(4-cd) / 2}

   Wherein R ³ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, c is 0.6 to 2.2, d is 0.001 to 1.0, and c + d is 0.8 to 3.0.
4. The method according to claim 1,

   Wherein the polysilsesquioxane comprises at least one functional group selected from the group consisting of a hydroxyl group, an alkyl group and an aryl group on the surface thereof.
5. The method according to claim 1,

   Wherein the polysilsesquioxane is in particulate form having an average particle size of 0.5 to 20 占 퐉.
6. The method according to claim 1,

   Wherein the volatile silicone oil comprises at least one of polydimethylsiloxane and cyclosiloxane as a low molecular weight.
7. The method of claim 6,

   Wherein the polydimethylsiloxane is represented by the following formula (3).

   (3)

   

   (Wherein m is an integer of 0? M <4).
8. The method of claim 6,

   Wherein the cyclosiloxane is represented by the following formula (4).

   [Chemical Formula 4]

   

   (Wherein n is an integer of 3? N <6, and each R ⁴ is independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
9. The method according to claim 1,

   Wherein the hydrosilylation reaction catalyst comprises a noble metal catalyst.
10. The method according to claim 1,

    Wherein the hydrogen content in the organohydrogenpolysiloxane is 1 mmol / g to 20 mmol / g and the viscosity at 25 캜 is 10 to 1,000 mPa · s.
11. A silicone article comprising a coating layer formed by curing the silicone coating composition of claim 1.