KR20200047181A - Silicone pressure sensitive adhesive composition for electrostatic dissipative - Google Patents

Abstract

The present invention relates to a silicone pressure-sensitive adhesive composition which is excellent in antistatic performance and, more specifically, to a silicone pressure-sensitive adhesive composition comprising: a silicone composition; and an antistatic agent, wherein the silicone composition comprises: organopolysiloxane; an organohydrogenpolysiloxane; and a metal hydrosilylation catalyst, and the antistatic agent includes at least one first antistatic agent selected from the group consisting of graphene oxide and carbon nanotubes, and polyether-modified siloxane.

Description

Antistatic silicone pressure-sensitive adhesive composition {SILICONE PRESSURE SENSITIVE ADHESIVE COMPOSITION FOR ELECTROSTATIC DISSIPATIVE}

The present invention relates to a silicone pressure-sensitive adhesive composition excellent in antistatic performance.

Pressure Sensitive Adhesive (PSA) is a material that applies an object to the adherend by applying pressure. It is also called a pressure sensitive adhesive, and can be easily removed when peeled off the adherend. It can be re-attached to the adherend. In particular, silicone pressure sensitive adhesives have excellent properties such as low surface tension, nonionic and nonpolar, hydrophobic and water repellent, heat resistance and oxidation stability, low temperature stability, gas permeability, chemical inertness, flame retardancy, environmental friendliness, and non-toxicity. The utilization is very high throughout. In particular, silicone has stability, heat resistance, oxidation resistance and low surface tension, which is advantageous for micro-part packing due to device miniaturization and is very effective as a sealing agent for materials sensitive to external environments such as moisture. However, the silicone pressure-sensitive adhesive has a disadvantage that when the surface tension of the surface to be adhered is lower, the adhesive strength is lower than that of the epoxy or acrylic pressure-sensitive adhesive.

As an alternative to this, Korean Patent Publication No. 2018-0054608 (Patent Document 1) includes a reactive polydimethylsiloxane polymer; Reactive silicone resins; Acid or base catalysts; (Meth) acrylate functionalized polydimethylsiloxane polymer or oligomer; Silicone resins, polydimethylsiloxane polymers or oligomers; And a radical initiator; a curable silicone pressure-sensitive adhesive composition is disclosed. However, the silicone pressure-sensitive adhesive disclosed in Patent Literature 1 is easily charged by contact with various substances and contains a lot of static electricity, so that foreign substances are easily introduced during manufacturing, and an electric shock caused by static electricity occurs, which causes product defects. There are disadvantages. In addition, the pressure-sensitive adhesive containing silicon, which is a non-conductive material, has a disadvantage in that it is not easy to remove static electricity charged by friction or an electric field.

Accordingly, a silicone pressure-sensitive adhesive having a polyether resin or carbon black added as an antistatic agent has been proposed. However, when a polyether resin is added to the silicone pressure-sensitive adhesive, the polyether resin is decomposed during high-temperature molding, so that an antistatic effect cannot be exhibited, and there is a problem in that the pressure-sensitive adhesive properties are also deteriorated. In addition, when carbon black is added to the silicone pressure-sensitive adhesive, there is a problem that it is difficult to maintain the electrical insulating properties of the pressure-sensitive adhesive.

Therefore, there is no need for research and development of a silicone pressure-sensitive adhesive having no deterioration in tackiness and curability of the pressure-sensitive adhesive composition and excellent antistatic performance.

Korea Patent Publication No. 2018-0054608 (Publication date: May 24, 2018)

Accordingly, the present invention is to provide a silicone pressure-sensitive adhesive excellent in curability, adhesiveness and antistatic ability.

The present invention includes a silicone composition and an antistatic agent, wherein the silicone composition comprises an organopolysiloxane, an organohydrogenpolysiloxane and a metal hydrosilylation catalyst, and the antistatic agent is from a group consisting of graphene oxide and carbon nanotubes. Provided is a silicone pressure sensitive adhesive composition comprising at least one selected first antistatic agent and a polyether modified siloxane.

The silicone pressure-sensitive adhesive according to the present invention maintains excellent properties of the silicone pressure-sensitive adhesive such as flexibility, moisture resistance, heat resistance, and cold resistance, and has excellent curability, adhesion, and antistatic ability. Due to this, the silicone pressure-sensitive adhesive according to the present invention can be applied to various fields that require antistatic performance, such as semiconductors, electric electronics, and displays.

Hereinafter, the present invention will be described in detail.

The present invention provides a silicone pressure-sensitive adhesive composition.

The silicone pressure-sensitive adhesive composition according to the present invention includes a silicone composition and an antistatic agent.

Silicone composition

The silicone composition includes an organopolysiloxane, an organohydrogenpolysiloxane and a metal hydrosilylation catalyst.

<Organopolysiloxane>

The organopolysiloxane contained in the silicone composition of the present invention serves to impart smoothness, curability, tackiness and adhesion to the composition, and is not particularly limited as long as it is a polysiloxane resin or polysiloxane polymer that can be used in a pressure-sensitive adhesive.

The organopolysiloxane may be an organopolysiloxane containing at least one alkenyl group in a molecule, and specifically, an organopolysiloxane represented by Formula 2 below.

 [Formula 2]

(R ¹ ₃ SiO _1/2 ) ₂ (R ² R ³ SiO) _a (R ³ ₂ SiO) _b

In Chemical Formula 2, R ¹ is each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and at least one or more is an alkenyl group having 2 to 10 carbon atoms, and R ² Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and R ³ each independently represents an alkyl group having 1 to 10 carbon atoms, Or it may be an alkenyl group having 2 to 10 carbon atoms.

In this case, the alkyl group may be, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, or the like, specifically, a methyl group, an ethyl group or a propyl group.

The alkenyl group may be, for example, a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like, specifically, a vinyl group or a butenyl group.

The allyl group may be, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenylene group, or the like, specifically, a phenyl group.

In Formula 2, a and b are each independently an integer of 0 or 1 or more, a + b is an integer of 5 to 10,000, and a / (a + b) is 0 to 0.1. When the a + b is within the above range, the void phenomenon in the cured product is remarkably reduced, workability is improved, and when a / (a + b) is within the above range, curing reactivity is excellent, and cracks in the cured product are excellent. There is an effect that the occurrence is significantly reduced.

The content of the vinyl group in the organopolysiloxane may be 0.01 to 0.1 mmol / g. Specifically, the organopolysiloxane may have a vinyl group content of 0.02 to 0.08 mmol / g, or 0.02 to 0.06 mmol / g. When the vinyl group content of the organopolysiloxane is within the above range, it is possible to easily control the spreadability and adhesion of the pressure-sensitive adhesive through adjusting the crosslinking density.

The organopolysiloxane has a viscosity of 10,000 to 300,000 cp (centi-poise) at 25 ° C, and a weight average molecular weight of 62,000 to 120,000 g / mol. Specifically, the organopolysiloxane has a viscosity at 25 ° C of 30,000 to 200,000 cp, 50,000 to 180,000 cp, or 60,000 to 150,000 cp, and a weight average molecular weight of 70,000 to 115,000 g / mol, 80,000 to 110,000 g / mol, or 90,000 To 110,000 g / mol. When the viscosity and the weight average molecular weight of the organopolysiloxane are within the above range, the composition containing the composition has excellent processability, easy thickness control, and excellent leveling properties.

The organopolysiloxane may further include an MQ resin including at least one alkenyl group and at least one SiO _4/2 unit (Q unit) in one molecule.

<Organohydrogen polysiloxane>

The organohydrogenpolysiloxane is crosslinked with the organopolysiloxane to form a cured product, and the physical properties and content of the organohydrogenpolysiloxane can be controlled to control the crosslink density of the silicone composition.

The organohydrogenpolysiloxane may include two or more hydrogen groups directly bonded to at least a silicon atom in one molecule, and specifically, an organohydrogenpolysiloxane represented by Formula 3 below.

[Formula 3]

H _c R ⁴ _d SiO _{(4-cd) / 2}

In Chemical Formula 3, R ⁴ may be each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, c is 0.001 to 2, d is 0.5 to 2, and c + d is 0.6 to 3.

In order to improve miscibility in the silicone composition, R ⁴ may be an alkyl group having 1 to 10 carbon atoms.

In this case, the alkyl group may be, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, and specifically, a methyl group.

In Chemical Formula 3, when the number of silicon atoms (Si) contained in the organohydrogenpolysiloxane is 1, c represents a ratio of hydrogen atoms, and d represents a ratio of R ⁴ . In the formula (3), when c is within the above range, the workability is excellent through the control of the crosslinking density, and the hardness of the cured product is excellent. In addition, when the d is within the above range, the curing reactivity is excellent, the curing speed is improved, and the voiding phenomenon of the cured product after curing may be significantly reduced. When the c + d is within the above range, workability may be improved through viscosity control, and a low molecular weight volatile content may be suppressed by controlling a curing rate to prevent voids from occurring.

The organohydrogenpolysiloxane may have a viscosity of 5 cP to 50 cP at 25 ° C and 50% relative humidity. Specifically, the organohydrogenpolysiloxane may have a viscosity of 10 cP to 40 cP at 25 ° C and 50% relative humidity. When the viscosity of the organohydrogen polysiloxane is within the above range, curing cure may be improved to increase curing speed.

In addition, the organohydrogenpolysiloxane may be included in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the organopolysiloxane. Specifically, the organohydrogenpolysiloxane may be included in an amount of 0.2 to 3.0 parts by weight, 0.4 to 2.5 parts by weight, or 0.5 to 2.0 parts by weight based on 100 parts by weight of the organopolysiloxane. When the content of the organohydrogen polysiloxane is within the above range, curing reactivity and workability may be improved through control of crosslinking density of the silicone composition.

<Hydrosilylation metal catalyst>

The hydrosilylation metal catalyst serves to promote the curing reaction between the components of the silicone composition.

The hydrosilylation metal catalyst includes, for example, platinum hydrosilylation, rhodium hydrosilylation, ruthenium hydrosilylation, palladium hydrosilylation, and lithium hydrosilylation. The hydrosilylation platinum, specifically, may be a complex compound between [{(CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2 } _p ] _q and platinum, where p is 2 or 4, and q is 2 or 3.

The hydrosilylation metal catalyst may be included in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the organopolysiloxane. Specifically, the hydrosilylation metal catalyst may be included in an amount of 0.5 to 3.0 parts by weight, or 0.5 to 2.0 parts by weight based on 100 parts by weight of the organopolysiloxane.

Antistatic agent

The antistatic agent serves to impart antistatic performance to the silicone pressure-sensitive adhesive composition. In addition, the antistatic agent includes at least one first antistatic agent selected from the group consisting of graphene oxide and carbon nanotubes, and a polyether-modified siloxane. Specifically, the antistatic agent may include polyether-modified siloxane, graphene oxide, and carbon nanotubes.

The antistatic agent may be used in an amount of 0.5 to 5.0 parts by weight based on 100 parts by weight of the silicone composition. Specifically, the antistatic agent may be used in an amount of 0.8 to 4.0 parts by weight, 1.0 to 5.0 parts by weight, 1.0 to 3.5 parts by weight, or 1.0 to 3.0 parts by weight based on 100 parts by weight of the silicone composition.

When the content of the antistatic agent is within the above range, it is possible to impart an antistatic ability to the composition, and the composition has an excellent antistatic ability according to the amount added, so it is economical, and the adhesive strength of the adhesive, adhesion to the substrate, and stability are excellent.

<Graphene oxide>

The graphene oxide serves to improve transparency, conductivity, and antistatic ability while not reducing the adhesiveness and adhesive strength of the silicone pressure-sensitive adhesive composition.

The graphene oxide may be reduced graphene oxide. Specifically, the graphene oxide may be a reduced graphene oxide having a terminal oxygen functional group removed. When the graphene oxide reduced to the graphene oxide is used, the adhesive strength and adhesive strength of the composition are not lowered by using the graphene oxide whose oxidation degree is controlled, and the antistatic ability of the composition can be effectively improved.

Preparing the graphene oxide by mixing the reduced graphene oxide with a graphite and an acidic solution and adding a strong oxidizing agent; And mixing the prepared graphene oxide and a reducing agent to prepare reduced graphene oxide.

For example, the acidic solution may be a mixture of sulfuric acid and hydrochloric acid, and the strong oxidizing agent may include KMnO ₄ and H ₂ O ₂ . Further, the reducing agent may include hydrazine (NH ₂ NH ₂ ), NaBH ₄ , and the like, and acetone, which is easy to disperse the silicone adhesive composition, may be used as a solvent used in the preparation method.

The graphene oxide may have an electrical conductivity of 0.1 to 0.5 μS / cm at 20 ° C., and a resistivity of 2.0 to 5.0 μΩ · cm. Specifically, the graphene oxide has an electrical conductivity of 0.1 to 0.4 μS / cm, or 0.2 to 0.35 μS / cm at 20 ° C., and a resistivity of 2.0 to 4.5 μΩ · cm, 2.5 to 4.0 μΩ · cm, or 3.0 to 4.0. μΩ · cm. When the electrical conductivity and resistivity of the graphene oxide are within the above ranges, the antistatic performance of the pressure-sensitive adhesive is effectively improved, and the transparency, adhesion and adhesion of the composition may not be lowered.

The graphene oxide may be included in an amount of 0.0005 to 0.05 parts by weight based on 100 parts by weight of the silicone composition. Specifically, the graphene oxide may be included in an amount of 0.001 to 0.03 parts by weight and 0.005 to 0.01 parts by weight based on 1 part by weight of the silicone composition. When the content of the graphene oxide is within the above range, it is possible to impart an antistatic ability to the composition, and it is economical because the antistatic ability of the composition according to the amount added is excellent.

The graphene oxide may be used in the form of a graphene oxide dispersion, which is a form dispersed in a solvent.

Examples of the solvent include hydrocarbon-based organic solvents, alcohols, esters, ketones, and mixtures thereof. The hydrocarbon-based organic solvent is, for example, toluene, xylene, heptane, etc., and the alcohol is, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, and the like. In addition, the ester is, for example, methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, etc., and the ketone is, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. have.

For example, the graphene oxide dispersion may include 0.01% to 1.0% by weight of graphene oxide based on the total weight of the dispersion. Specifically, the graphene oxide dispersion may include 0.03% to 0.8% by weight, or 0.05% to 0.5% by weight of graphene oxide based on the total weight of the dispersion.

<Carbon nanotube>

Carbon nanotubes have a 3D structure and have conductivity, thereby improving the antistatic ability of the composition.

The carbon nanotubes may have an average diameter of 1 nm to 200 nm, and an average length of 0.1 μm to 200 μm. Specifically, the carbon nanotubes have an average diameter of 3 nm to 110 nm, 3 nm to 80 nm, 5 nm to 50 nm, or 5 nm to 30 nm, and an average length of 0.3 μm to 150 μm, 0.5 μm to 120 μm, 1 μm to 100 μm, It may be 5 μm to 80 μm, or 10 μm to 75 μm.

The carbon nanotube may be included in an amount of 0.0005 to 0.05 parts by weight based on 100 parts by weight of the silicone composition. Specifically, the carbon nanotubes may be included in an amount of 0.001 to 0.03 parts by weight and 0.005 to 0.01 parts by weight based on 100 parts by weight of the silicone composition. When the content of the carbon nanotube is within the above range, it is possible to impart an antistatic ability to the composition, and it is economical because the antistatic ability of the composition according to the amount added is excellent.

The carbon nanotubes may be used in the form of a carbon nanotube dispersion liquid dispersed in a solvent.

Examples of the solvent include hydrocarbon-based organic solvents, alcohols, esters, ketones, and mixtures thereof. The hydrocarbon-based organic solvent is, for example, toluene, xylene, heptane, etc., and the alcohol is, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, and the like. In addition, the ester is, for example, methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, etc., and the ketone is, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. have.

The carbon nanotube dispersion may include 0.01 to 5.0% by weight of carbon nanotubes based on the total weight of the dispersion. Specifically, the carbon nanotube dispersion may include 0.05% to 3.0% by weight, 0.05% to 1.0% by weight, or 0.05% to 0.5% by weight of carbon nanotubes based on the total weight of the dispersion.

<Polyether modified siloxane>

The polyether-modified siloxane forms a conductive layer on the surface of the cured film upon curing of the silicone pressure-sensitive adhesive composition, thereby leaking electric charges to impart an antistatic ability to the silicone pressure-sensitive adhesive composition, and improving dispersibility of the antistatic agent described below. It serves to improve the antistatic ability in the pressure-sensitive adhesive composition.

The polyether-modified siloxane may have a hydrophile-lipophile balance (HLB) of 5 to 20, and a viscosity at 25 ° C of 10cP to 5,000cP. Specifically, the polyether-modified siloxane has an HLB of 7 to 20, 7 to 18, 8 to 18, 10 to 18, or 10 to 16, and a viscosity at 25 ° C of 30cP to 2,000cP, 50cP to 2,000cP, or It may be 100cP to 1,000cP. When the HLB of the polyether-modified siloxane is within the above range, due to the hydrophilicity of the polyether-modified siloxane, moisture can be attracted from the surface of the cured film to improve the antistatic ability of the silicone pressure-sensitive adhesive composition. In addition, when the viscosity at 25 ° C. of the polyether-modified siloxane is within the above range, the slipping property of the pressure-sensitive adhesive coating film containing the same is prevented, and the curing speed of the composition is uniformly maintained, so that the stability of the prepared coating film is excellent. have.

The polyether-modified siloxane may be represented by Formula 1 below.

In Formula 1,

R is -CH ₂ CH ₂ CH ₂ O (C ₂ H ₄ O) _n CH ₃ ,

a and b are each an integer from 1 to 10,

n is an integer from 1 to 20.

The polyether-modified siloxane may have an electrical conductivity of 0.01 to 0.2 μS / cm at 20 ° C., and a resistivity of 5 to 80 μΩ · cm. Preferably, the polyether-modified siloxane has an electrical conductivity of 0.02 to 0.1 μS / cm, 0.02 to 0.08 μS / cm, or 0.02 to 0.05 μS / cm at 20 ° C., and a resistivity of 8 to 70 μΩ · cm, 10 to 10 60 μΩ · cm, or 10 to 55 μΩ · cm. When the electrical conductivity and resistivity of the polyether-modified siloxane are within the above ranges, the low conductivity and high resistance inherent in siloxanes are canceled out, and the contact potential of moisture on the surface is high, so that the discharge of the electrostatic charge of the prepared coating film becomes smooth.

The polyether-modified siloxane may be included in an amount of 0.4 to 4.999 parts by weight based on 100 parts by weight of the silicone composition. Specifically, the polyether-modified siloxane may be included in an amount of 0.5 to 3.0 parts by weight, or 0.8 to 2.0 parts by weight based on 100 parts by weight of the silicone composition. When the content of the polyether-modified siloxane is within the above range, a peeling force and an adhesive force (adhesive force) of the composition are appropriate, and an antistatic ability is excellent, thereby forming a cured film having a low surface resistance.

additive

The silicone pressure-sensitive adhesive composition may further include at least one additive selected from the group consisting of retarders, solvents, plasticizers, heat stabilizers and pigments.

The retarder serves to prevent the adhesive composition from curing below a predetermined temperature and excessive curing. The retarder delays curing of the silicone pressure-sensitive adhesive composition at room temperature, but does not interfere with curing after elevated temperature. In addition, when the silicone pressure-sensitive adhesive composition contains a retarder, it is preferable to heat and cure at 70 ° C. or higher for effective curing of the composition.

Examples of the retarding agent include acetylene alcohol, maleate and fumarate. In addition, the acetylene alcohol, for example, 2-methyl-3-butyn-2-ol, 3-methyl-3-pentin-1 phosphorus, 3,5-dimethyl-3-hexene-1-yne or 3 And 5-dimethyl-1-hexyn-3-ol.

The retarder may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the silicone composition. Specifically, the retarder may be included in an amount of 0.1 to 3 parts by weight, or 0.5 to 2 parts by weight based on 100 parts by weight of the silicone composition.

The solvent serves to lower the viscosity of the silicone pressure-sensitive adhesive composition and improve the ease of manufacture, handling and application.

The solvent may include, for example, a hydrocarbon-based organic solvent, alcohol, ester, ketone, and mixtures thereof. The hydrocarbon-based organic solvent is, for example, toluene, xylene, heptane, etc., and the alcohol is, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, and the like. In addition, the ester is, for example, methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, etc., and the ketone is, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. have.

The plasticizer serves to increase the plasticity of the silicone composition.

The plasticizer includes, for example, phthalic acid ester systems such as di-2-ethylhexyl phthalate, dioctyl phthalate, diisononyl phthalate, and dibutyl phthalate; Phosphoric acid ester systems such as tricresyl phosphate, trixylyl phosphate, and triphenyl phosphate; Fatty acid ester systems such as di-2-ethylhexyl adipate and di-2-ethylhexyl sebacate; Epoxy systems such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, and epoxidized polybutadiene; Or mixtures thereof.

The heat stabilizer serves to increase the heat stability of the silicone composition.

Examples of the heat stabilizer include hydrotalcite-based compounds, calcium-zinc-based compounds, organophosphite-based compounds, zeolite-based compounds, and barium-zinc-based compounds.

The pigment may be an organic pigment or an inorganic pigment. Examples of the organic pigment include azo-based compounds, phthalocyanine-based compounds, and dye lake-based compounds. Further, examples of the inorganic pigments include oxide-based compounds, molybdenum chromate-based compounds, or ferrocyanide-based compounds.

The specimen prepared by applying and curing the silicone pressure-sensitive adhesive composition may have a surface resistance of 5 × 10 ¹¹ Ω / sq or less. Specifically, the specimen prepared by applying and curing the silicone pressure-sensitive adhesive composition may have a surface resistance of 3 × 10 ¹¹ Ω / sq or less, or 1 × 10 ¹¹ Ω / sq or less.

The silicone pressure-sensitive adhesive as described above maintains excellent properties of the silicone pressure-sensitive adhesive such as flexibility, moisture resistance, heat resistance, and cold resistance, and has excellent curability, adhesion, and antistatic ability. Due to this, the silicone pressure-sensitive adhesive can be applied to various fields that require antistatic performance, such as semiconductors, electric electronics, and displays.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the description by the following examples is only intended to describe and describe specific embodiments of the present invention, and is not intended to limit or limit the scope of the present invention to the contents described in these examples.

 [Example]

The components and product names of each component used in the following Examples and Comparative Examples are shown in Table 1 below.

division ingredient Organo
Polysiloxane Polydimethylsiloxane with a vinyl group content of 0.05 mmol / g, a viscosity of 60,000 cP at 25 ° C, and a terminal having a weight average molecular weight of 90,000 g / mol, blocked with a vinyl group Organohydrogenpolysiloxane The silicon-bonded hydrogen group is 0.25 mol% in the molecule and has a viscosity of 20 cP at 25 ° C.
Polydimethylsiloxane blocked at the terminal with a methylhydrogensiloxy group Hydrosilylation metal catalyst 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane containing 0.5% by weight of platinum
Platinum complex Retardant 2-methyl-3-butyn-2-ol, Cas.No 115-19-5 Polyether modified siloxane-A At 25 ° C, the viscosity is 250 to 450cP, the HLB is 13, the electrical conductivity at 20 ° C is 0.027 μS / cm, and the resistivity at 20 ° C is 37 μΩ · cm. Polyether modified siloxane-B Viscosity is 260 ~ 360 cP at 25 ℃, HLB is 2.3, electrical conductivity at 20 ℃ is 0.020μS / cm, and resistivity at 20 ℃ is 50μΩ · cm. Polyether modified siloxane-C The viscosity at 25 ° C is 600 to 1,100cP, the HLB is 4.5, the electrical conductivity at 20 ° C is 0.085 μS / cm, and the resistivity at 20 ° C is 12 μΩ · cm. Reduced graphene
Oxide The electrical conductivity at 20 ℃ is 0.29μS / cm, and the resistivity at 20 ℃ is 3.6μΩ · cm.
Reduced graphene oxide Carbon nanotube Carbon nanotubes with an average diameter of 10 nm and an average length of 50 μm

Example 1. Preparation of silicone pressure-sensitive adhesive composition

A resin composition was prepared by mixing 99 g organopolysiloxane and 1 g retarder. Thereafter, 1 g of polyether-modified siloxane and 0.001 g of reduced graphene oxide were added to the resin composition to prepare a mixture.

Then, 1 g of organohydrogen polysiloxane and 1 g of a hydrosilylation metal catalyst were added to the mixture, and stirred to prepare a silicone pressure-sensitive adhesive composition.

Example 2.

A silicone pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 0.001 g of carbon nanotubes instead of reduced graphene oxide were added to 100 g of a resin composition composed of an organopolysiloxane and a retarder.

Example 3.

A silicone pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 0.001 g of carbon nanotubes was additionally added to the resin composition of Example 1.

Comparative Example 1.

A silicone pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that the reduced graphene oxide and polyether-modified siloxane-A were not added to the resin composition of Example 1.

Comparative Example 2.

A silicone pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that only 0.001 g of reduced graphene oxide was added to the resin composition of Example 1.

Comparative Example 3.

A silicone pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that only 1 g of polyether-modified siloxane-A was added to the resin composition of Example 1.

Comparative Example 4.

A silicone pressure-sensitive adhesive composition was prepared in the same manner as in Comparative Example 3, except that polyether-modified siloxane-B was used as an antistatic agent.

Comparative Example 5.

A silicone pressure-sensitive adhesive composition was prepared in the same manner as in Comparative Example 3, except that polyether-modified siloxane-C was used as an antistatic agent.

Comparative Example 6.

A silicone pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 0.06 g of graphene oxide reduced with an antistatic agent and 0.001 g of carbon nanotubes were added to the resin composition.

Comparative Example 7.

A silicone pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 0.001 g of graphene oxide reduced by an antistatic agent and 0.06 g of carbon nanotubes were added to the resin composition.

The reduced graphene oxide contained in Examples 1 to 3 and Comparative Examples 1 to 7 mentioned above was dissolved in acetone at 0.1% by weight, and then added in the form of a reduced graphene oxide dispersion sonicated for 1 hour, The carbon nanotube was dissolved in xylene at 0.1% by weight, and then a silicone pressure-sensitive adhesive composition was prepared by using a carbon nanotube dispersion form that was sonicated for 1 hour.

Silicone composition (g) Antistatic agent (g) Organo
Poly
Siloxane Retardant Origano
Hydrogen
Polysiloxane Hydro
Metal silylation catalyst Polyether
Modified siloxane Reduced graphene
Oxide Carbon nanotube A B C Example 1 99 One One One One - - 0.001 - Example 2 99 One One One One - - - 0.001 Example 3 99 One One One One - - 0.001 0.001 Comparative Example 1 99 One One One - - - - - Comparative Example 2 99 One One One - - - 0.001 - Comparative Example 3 99 One One One One - - - - Comparative Example 4 99 One One One - One - - - Comparative Example 5 99 One One One - - One - - Comparative Example 6 99 One One One One - - 0.06 0.001 Comparative Example 7 99 One One One One - - 0.001 0.06

Test Example: Measurement of adhesive strength, peel strength and surface resistance of the molded product

The physical properties of the silicone pressure-sensitive adhesive compositions of Examples 1 to 3 and Comparative Examples 1 to 5 were measured in the following manner, and the results are shown in Table 3.

(1) Adhesion

A silicone pressure-sensitive adhesive composition was applied to an A4 sized PET film to have a dry thickness of 10 μm, followed by heat curing in a 140 ° C. oven for 2 minutes to prepare a cured product. Thereafter, the cured product was cut into a size of 1 inch x 1 inch (width x length), and then attached to a stainless steel panel having a clean surface by pushing twice with a 2 kgf rubber coating roller. Thereafter, the force required to peel the cured product from the stainless steel panel at a rate of 300 mm / min at a peel angle of 180 ° was measured using a universal tensile tester (UTM).

(2) Peeling force

A silicone pressure-sensitive adhesive composition was applied to an A4 sized PET film to have a dry thickness of 10 μm, followed by heat curing in a 140 ° C. oven for 2 minutes to prepare a cured product. Thereafter, the cured product was cut into 1 inch × 1 inch (horizontal × vertical) size, and then attached using a PET film having a clean surface as a substrate and pushed twice with a 2 kgf rubber coating roller. Then, the force required to peel the cured product from the substrate at a rate of 300 mm / min at a peel angle of 180 ° was measured using a universal tensile tester (UTM).

(3) Surface resistance

A silicone pressure-sensitive adhesive composition was applied to the PET film to have a dry thickness of 10 μm, followed by heating and curing in an oven at 140 ° C. for 2 minutes to prepare a cured product. Then, the surface resistance of the cured product was measured using a surface resistor.

Surface resistance (Ω / sq) Peeling force (gf / in) Adhesion (gf / in) Example 1 1x10 ¹¹ 0.9 0.5 Example 2 1x10 ¹⁰ 0.8 0.8 Example 3 1x10 ¹⁰ 0.6 0.8 Comparative Example 1 1.6x10 ¹⁴ 1.6 1.1 Comparative Example 2 1x10 ¹⁴ 1.0 0.6 Comparative Example 3 1x10 ¹³ 1.1 0.4 Comparative Example 4 5x10 ¹³ - - Comparative Example 5 2x10 ¹³ - - Comparative Example 6 1x10 ⁹ <0.1 <0.1 Comparative Example 7 1x10 ⁹ <0.1 <0.1

As shown in Table 3, the cured products prepared from the compositions of Examples 1 to 3 have a low surface resistance of 1 × 10 ¹¹ Ω / sq or less, and are excellent in antistatic performance, and have good peeling force and adhesion, so that they are suitable for semiconductor and electrical / electronic applications. And it was confirmed that it can be applied as a pressure-sensitive adhesive in a variety of fields that require antistatic ability such as display.

On the other hand, it was confirmed that the cured products prepared from the compositions of Comparative Examples 1 to 5 had a high surface resistance of 1 × 10 ¹³ Ω / sq or higher, and insufficient antistatic ability. In addition, the cured product prepared from the compositions of Comparative Examples 2 and 3 and 5 using only graphene oxide as an antistatic agent and polyether-modified siloxane also had a high surface resistance of 1 × 10 ¹³ Ω / sq or higher, so that antistatic performance was insufficient. Was found. In particular, the cured products prepared with the compositions of Comparative Examples 6 to 7 have a surface resistance of 1 × 10 ⁹ Ω / sq, which has excellent antistatic properties, but the transparency of the adhesive is lowered, and the peeling force and adhesive force are due to the delayed curing of the adhesive, poor adhesion, etc. It was found that this was not enough.

Claims (6)

It contains a silicone composition and an antistatic agent,
The silicone composition comprises an organopolysiloxane, an organohydrogenpolysiloxane and a metal hydrosilylation catalyst,
The antistatic agent comprises at least one first antistatic agent selected from the group consisting of graphene oxide and carbon nanotubes, and a polyether-modified siloxane, silicone pressure-sensitive adhesive composition. The method according to claim 1,
The silicone pressure-sensitive adhesive composition contains 0.5 to 5.0 parts by weight of an antistatic agent with respect to 100 parts by weight of the silicone composition,
The silicone composition comprises 0.1 to 5.0 parts by weight of an organohydrogenpolysiloxane and 0.1 to 5.0 parts by weight of a hydrosilylation metal catalyst with respect to 100 parts by weight of an organopolysiloxane, a silicone pressure sensitive adhesive composition. The method according to claim 1,
The silicone pressure-sensitive adhesive composition is an antistatic agent containing 0.0005 to 0.05 parts by weight of graphene oxide, 0.0005 to 0.05 parts by weight of carbon nanotubes, and 0.4 to 4.999 parts by weight of polyether-modified siloxane based on 100 parts by weight of the silicone composition. Composition. The method according to claim 1,
The polyether-modified siloxane has a hydrophile-lipophile balance (HLB) of 5 to 20, a viscosity at 25 ° C of 10cP to 5,000cP, and a silicone pressure-sensitive adhesive composition represented by Formula 1 below:
[Formula 1]

In Formula 1,
R is -CH ₂ CH ₂ CH ₂ O (C ₂ H ₄ O) _n CH ₃ ,
a and b are each an integer from 1 to 10,
n is an integer from 1 to 20. The method according to claim 1,
The carbon nanotubes have an average diameter of 1 nm to 200 nm, and an average length of 0.1 μm to 200 μm, a silicone pressure-sensitive adhesive composition. The method according to claim 1,
The cured product prepared by applying and curing the silicone pressure-sensitive adhesive composition has a surface resistance of 5 × 10 ¹¹ Ω / sq or less, and a silicone pressure-sensitive adhesive composition.