KR101211083B1 - One-component self-adhesive polysiloxane composition - Google Patents

Abstract

PURPOSE: An one-component type self-adhesive polysiloxane composition is provided to have excellent insulative properties and excellent moisture-absorption, and to have excellent adhesion with a substrate than existing epoxy compound. CONSTITUTION: An one-component type self-adhesive polysiloxane composition comprises 55-90 weight% of an organic polysiloxane, 2-8 weight% of an organic polyhydrogensiloxane which has two or more Si-H functional groups in one molecule; 0.1-1 weight% of a precious metal hydrosilation catalyst, and 5-40 weight% of one or more fillers selected from polyorganosiloxane, polystyrene, polyacrylate, natural silica, synthetic silica, aluminum oxide, titanium dioxide, and feldspar as an organic or inorganic filler.

Description

One-Component Self-adhesive Polysiloxane Composition

The present invention relates to a one-component self-adhesive polysiloxane composition.

The present invention relates to a curable polyorganosiloxane composition used in the manufacturing process of a semiconductor device, characterized by having heat resistance, low hygroscopicity, excellent adhesion and low elastic modulus. Semiconductor manufacturing processes are largely classified into pre-process and post-process. The former process consists of an exposure and etching process to form a pattern, and the post process consists of a packaging process that prevents the semiconductor chip from being influenced by the environment. The curable polyorganosiloxane composition provided by the present invention is an adhesive material used to attach a semiconductor chip and a substrate in a packaging process. The semiconductor chip is surface-treated with polyimide or an inorganic insulating film for wiring protection, and the substrate is hardened with an epoxy composition. Until recently, an epoxy compound having excellent adhesive strength was used as a composition for attaching a semiconductor chip and a substrate, but according to high integration of semiconductor chips, a composition having better insulating properties and hygroscopicity than an epoxy compound is required. In order to satisfy these requirements, interest in polyorganosiloxane compounds is increasing. However, the polyorganosiloxane compound is excellent in hygroscopicity resistance but has a disadvantage in that the adhesion to the substrate is poor. Adhesive supplements are used to compensate for this, but they do not meet the required adhesion performance.

Numerous papers and patent documents are referenced and cited throughout this specification. The disclosures of the cited papers and patent documents are incorporated herein by reference in their entirety to better understand the state of the art to which the present invention pertains and the content of the present invention.

The present inventors earnestly researched to develop a novel polyorganosiloxane compound having heat resistance, low hygroscopicity, excellent adhesion and low elastic modulus and a composition for hardening die bonding using the same. As a result, an adhesive composition having improved storage stability and adhesion was developed by reacting a coupling agent having poor compatibility with the silicone composition with polyorganosilicon resin, and confirming that the composition has excellent hygroscopic resistance, storage stability and adhesion of the product. The present invention has been completed.

Accordingly, an object of the present invention is to provide a one-component self-adhesive polysiloxane composition.

Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.

According to one aspect of the present invention, the present invention provides a one-part self-adhesive polysiloxane composition comprising the following components:

(a) a polyorganosiloxane having two or more alkenyl groups in a molecule and a coupling agent reacted, or (ii) a poly having two or more alkenyl groups in a molecule with the component (iii) As a mixture of organosiloxanes, 55-90% by weight of polyorganosiloxanes relative to the total composition;

(b) 2-8% by weight of polyorganohydrogensiloxane, based on the total composition, having at least two Si-H functional groups in the molecule;

(c) 0.1-1% by weight of a noble metal silicon hydride catalyst based on the total composition; And

(d) 5-40% by weight of organic or inorganic fillers based on the total composition.

The present inventors earnestly researched to develop a novel polyorganosiloxane compound having heat resistance, low hygroscopicity, excellent adhesion and low elastic modulus, and a composition for curing die bonding using the same, and as a result, a coupling agent having poor compatibility with a silicone composition By reacting with the polyorganosilicon resin was developed an adhesive composition with improved storage stability and adhesion, it was confirmed that the hygroscopic resistance of the composition, storage stability and adhesion of the product is excellent.

The present invention provides a novel polyorganosiloxane compound having heat resistance, low hygroscopicity, excellent adhesion and low elastic modulus, and a composition for hardening die bonding using the same. The die bonding agent is a bonding material for bonding a silicon semiconductor chip to a substrate, and the die bonding composition is coated on the substrate, and then the semiconductor chip is seated, cured at high temperature, and bonded. This is characterized in that the wire bonding process and the encapsulant process.

The present invention is to provide an adhesive material for packaging having excellent adhesive strength using a polyorganosiloxane compound having excellent moisture resistance. Generally, the semiconductor chip is coated with a polyimide compound or an inorganic insulator. On the other hand, the substrate is hard-coated with an epoxy cured material. Compositions using polyorganosiloxane compounds generally have good adhesion to chips but significantly lower adhesion to substrates. To prevent this, it is advisable to remove all foreign matter from the substrate by heat drying before entering the bonding process. During this drying process, the moisture present on the surface of the substrate or foreign substances generated during the epoxy curing process may be removed. However, the adhesive strength with the polyorganosiloxane compound may vary slightly depending on the type of epoxy curing agent used for the substrate or the substrate manufacturing process.

In the present invention, a coupling agent having poor compatibility with the silicone composition is reacted with a polyorganosilicon resin having two or more alkenyl groups in a molecule to improve storage stability and adhesion. Polyorganosilicone resins can be broadly divided into low-viscosity silicone resins containing vinyl groups at the end and vinyl-functional QM (VQM) resins having vinyl groups and SiO ₂ groups. VQM resin is a solid or high viscosity resin and its physical properties depend on the content of SiO ₂ groups. In general, VQM resin is used in a solvent-dissolved state or dissolved in a low viscosity silicone resin for ease of use. VQM resins will contain hydroxyl groups that do not fully progress to SiO ₂ groups during synthesis. If the hydroxyl group is forcibly removed during the synthesis, the VQM resin has a disadvantage in that the solubility in general solvents is reduced. When the solubility in solvents is poor, solubility in general silicone resins is also lowered, making it difficult to obtain a homogeneous product in preparing the composition. In the present invention, the alkoxy silane compound is reacted with the hydroxy group present in the VQM resin to improve the storage stability and adhesion of the product. As the alkoxy silane compound, a commonly used silane coupling agent may be used, and the amount of the alkoxy silane compound may be used in an amount of 0.05-5 equivalent% based on the total monomers of the VQM resin. If the amount of the coupling agent is less than 0.05 equivalent%, the improvement of the physical properties of the composition is inadequate. If the coupling agent is used more than 5 equivalent%, there is a disadvantage inferior in miscibility and hygroscopicity.

According to a preferred embodiment of the present invention, the present invention provides a one-component self-adhesive polysiloxane composition characterized in that the polyorganosiloxane having two or more alkenyl groups is represented by the following formula (1):

Formula 1

In the above Formula _{1, R 1, R 2,} R 3, R 4, R 5 and R ₆ are each independently C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{6 -22} aryl, C _{3 -20} An allyl or hydroxy group, where l, m, n and o are numbers satisfying 1> l≥0, 1> m≥0, 1> n≥0 and 1> o≥0 (wherein l + m + n + o = 1 and n + o≥0).

The term "alkyl" in the context of the present invention refers to an aliphatic hydrocarbon group. The alkyl moiety may be a "saturated alkyl" group, meaning that it does not contain any alkenes or alkyne moieties. The alkyl moiety may be a “unsaturated alkyl” moiety, meaning that it contains at least one alkene or alkyne moiety. In saturated or unsaturated alkyl may be branched, straight chain or cyclic.

Alkyl groups may have from 1 to 20 carbon atoms. The alkyl group may be a medium sized alkyl having 1 to 10 carbon atoms, but preferably lower alkyl having 1 to 6 carbon atoms. For example, C ₁ -C ₄ alkyl is one to four carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t- It may be selected from the group consisting of butyl.

The alkyl group may be optionally substituted or unsubstituted. When substituted, the substituents are cycloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, merceto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, O- Individually from carboxy, isocyanato, thiocyanato, isothiocyanato, amino including nitro, cyryl, trihalomethanesulfonyl, mono- and di-substituted amino groups, and protective derivatives thereof And one or more groups independently selected. Typical alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. It is not limited to this.

The term “alkenyl” refers to a straight or branched unsubstituted or substituted unsaturated hydrocarbon group having the specified carbon number, for example ethenyl, vinyl, propenyl, isopropenyl, butenyl, isobutenyl, n -pentenyl and n -Hexenyl. C _{2 -20} alkenyl group is not included in the carbon number of a substituent when the means alkenyl group having an alkenyl unit having 1 to 20 carbon atoms, the alkenyl-substituted C _{2 -20} Al.

As used herein, the term “aryl” refers to a substituted or unsubstituted monocyclic or polycyclic carbon ring which is wholly or partially unsaturated. C _{6 -22} aryl means an aryl group having 6 to 22 carbon ring atoms, and when C _{6 -22} aryl is substituted, carbon atoms of the substituent are not included. By aryl is meant an aryl group having at least one ring having a shared pi electron field and comprising a carboxylic aryl (eg phenyl) and a heterocyclic aryl group (eg pyridine). The aryl includes monocyclic or fused ring polycyclic (ie rings that divide adjacent pairs of carbon atoms) groups.

To have the term "allyl (Allyl)" molecular structure _{H 2 C = CH-CH 2} R in the context of the present invention, a methylene group (-CH ₂ -) attached to the vinyl group (-CH = CH ₂₎ to Allyl positions include, but are not limited to, all of the functional groups mentioned above, such as alkyl, aryl, heteroaryl, hydroxyl, amine, carbonyl group and derivatives thereof.

In the present specification, the term “hydroxyl” has a molecular formula of R—OH and means a functional group including a hydrogen atom covalently linked to an oxygen atom. The neutral form of the hydroxyl group is a radical, The anionic form of the hydroxyl group is called hydroxide.

If the alkenyl group is located at both ends, the elasticity is good after curing but the hardness and adhesive strength are lowered. If the alkenyl group is too large, the surface crack of the cured product may occur by reducing the elasticity after curing. Suitable amounts of alkenyl groups in formula (1) are preferably in the range of 0.05 to 0.5 moles per 100 g of component. In particular, in the case of the component (a), a polyorganosiloxane may be used by mixing a compound having n + o = 0 and a compound having n + o> 0 in the formula (1). In the case of polyorganosiloxane having a repeating unit of n + o = 0, the compound has a low viscosity and serves to relieve stress after curing. In order to relieve stress, it is advantageous to have an alkenyl group located at the end of the molecule. The polyorganosiloxane having a repeating unit of n + o> 0 plays a role of improving reinforcement like the inorganic filler after curing. In the case where a compound having a repeating unit of n + o = 0 and a compound having n + o> 0 are used in combination, the ratio may be different depending on the use. If a lot of compounds with n + o = 0, the stress after curing is relaxed, but the hardness is poor.

In the composition of the present invention, component (a) is 55-90% by weight of polyorganosiloxane, preferably 60-85% by weight, more preferably 70-80% by weight, based on the total composition.

According to a preferred embodiment of the present invention, the polyorganosiloxane produced by reacting a polyorganosiloxane having two or more alkenyl groups (eg, VQM resin) and a coupling agent in the molecule of component (a) is represented by the following formula (2) It provides a one-part self-adhesive polysiloxane composition characterized by:

(2)

In Chemical Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ And R ₇ each independently represent a C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{6 -22} aryl, C _{3 -20} and allyl, or a hydroxy group, R ₈ and R ₉ is a glycidyl group, a vinyl siloxane group or hydro A functional group containing a gen siloxane group, wherein l, m, n, o, p, and q represent 1> l≥0, 1> m≥0, 1> n≥0, 1> o≥0, 1> p≥0 And 1> q≥0, provided they are l + m + n + o + p + q = 1 and l + m + n + o> 0 and p + q> 0. .

The monomer (p + q) containing these functional groups is 0.05-5 equivalent% with respect to the total equivalent of polyorganosiloxane. If the amount is too small, the original adhesive properties cannot be obtained, and if the amount is too large, there is a disadvantage in that miscibility and hygroscopicity are poor. The compound represented by the formula (2) may be used in admixture with the compound represented by the formula (1) in preparing a curable silicone composition, or may be used alone without using the compound represented by the formula (1). If used alone may be difficult to adjust the viscosity.

The coupling agent that reacts with the polyorganosiloxane having two or more alkenyl groups is vinyl trialkoxysilane, allyl trialkoxysilane, 3-glycidoxypropyl trialkoxysilane, 3-methacryloxypropyl trialkoxysilane, or To compounds having Formula 11 can be used:

Formula 5

6

Formula 7

Formula 8

Formula 9

Formula 10

Formula 11

In Formulas 5 to 11, a and b are integers of 1-30.

Coupling agents that react with polyorganosiloxanes (eg, VQM resins) having two or more alkenyl groups in the molecule are preferably vinyl trialkoxysilanes, allyl trialkoxysilanes, 3-glycidoxypropyl trialkoxysilanes or 3- Methacryloxypropyl trialkoxysilane, more preferably vinyl trialkoxysilane or 3-glycidoxypropyl trialkoxysilane, still more preferably vinyl trimethoxysilane, vinyl triethoxysilane, 3-glyci Doxypropyl trimethoxysilane or 3-glycidoxypropyl triethoxysilane.

In the composition of the present invention the coupling agent is 0.5-15% by weight, preferably 1-10% by weight, more preferably 1-4% by weight, based on the total composition.

The said coupling agent can also be used in mixture of 1 or more types. The compound containing an epoxy group and the alkoxysilane group shows the favorable effect on adhesive force. The chemical reaction of the polyorganosiloxane (VQM resin) having two or more alkenyl groups with the coupling agent may be represented by, for example, Scheme 1 below.

Scheme 1

R ₁ and R ₂ in the above Scheme 1 each independently represents a C _{1 -20} alkoxy group or C _{1 -20} alkyl, R ₃ represents a group of functions including a glycidyl group, a vinyl group is a siloxane or hydrogen siloxane. The term "alkoxy" refers to the group -O, and, for example, methoxy, ethoxy and the like, it is not the number of carbon atoms of the C _1-20 alkoxy when the substituted substituent includes.

Synthesis of the novel resin using the VQM resin (polyorganosiloxane having two or more alkenyl groups) can be easily synthesized by mixing with alkoxysilane, but it is necessary to shorten the reaction time by raising the reactor temperature to 80 ° C. Byproduct methanol is removed under reduced pressure. In general, since the VQM resin is a solid or high viscosity resin, it is advantageous to proceed with the reaction after dissolving in a solvent or a low viscosity silicone resin. Examples of the solvent include benzene, toluene or xylene which are aromatic compounds. The low viscosity silicone resin may be a resin having 500-6,000 cPS containing vinyl groups at both ends. The viscosity of the low viscosity resin can be selected and used depending on the application. If a solvent is used, it must be removed under reduced pressure after completion of the reaction. If possible, distillation under reduced pressure below 100 ° C. is advantageous. If the temperature is higher than this, side reactions proceed to change color or increase viscosity. The reaction time is appropriate for 5 hours at 80 ℃. As the reaction proceeds, the viscosity increases, and when the viscosity stops, the reaction may be terminated.

According to a preferred embodiment of the invention, the present invention is a one-component self-adhesive, characterized in that the polyorganohydrogensiloxane having at least two Si-H functional groups in the molecule of the component (b) is represented by the following formula (3) Polysiloxane compositions are provided:

(3)

In Formula 3, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a C _1-20 alkyl group, C _6-22 aryl group, hydrogen or a hydroxy group, and R ₈ And R ₉ is hydrogen or methyl group, l ', m', n ', o', p 'and q' are 1>l'≥0,1>m'≥0,1>n'≥0,1>o'≥0,1>p'≥0 and 1>q'≥0, provided they are l '+ m' + n '+ o' + p '+ q' = 1 and l '+ m '+ n' + o '> 0 and p' + q '≧ 0).

It is preferable that the quantity of the silicon atom which has the said Si-H functional group is 2-30 mol% with respect to the quantity of all the silicon atoms. If the amount is larger than this, the elasticity, which is an inherent characteristic of the cured silicone, is lowered. If the amount is smaller than this, the alkenyl group and the curing reaction do not sufficiently occur and the hardness is lowered. It is common to mix the Si—H functional groups in an amount of 0.5 to 4.0 equivalents relative to the total alkenyl groups in preparing the compositions. The most common ratio uses about 1.5 times Si-H equivalents relative to alkenyl. However, it may be used in a wider range depending on the purpose of the final cured product.

In the composition of the present invention, component (b) is 2-8% by weight of polyorganohydrogensiloxane, preferably 3-6% by weight based on the total composition.

In the composition of the present invention, the noble metal hydride catalyst (component c) is a catalyst in which an alkenyl group and a Si-H functional group promote an addition curing reaction. Preferably, the noble metal hydrosilation catalyst is a platinum-containing catalyst, the platinum-containing catalyst, for example 1, platinum black, (2) Halon halogenated platinum _{(PtCl 4, H 2 PtCl 4} . 6 H 2 O, NaPtCl. 4 H ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ ), (3) complexes between platinum and olefins, alcohols, ethers, aldehydes, ketones or vinylsiloxanes, (4) bis (gamma-picolin) -platinum dichloride, (5 ) Trimethylenedipyridine-platinum dichloride, (6) dicyclopentadiene-platinum dichloride, (7) cyclooctadiene-platinum dichloride, (8) cyclopentadiene-platinum dichloride, (9) bis (alky) Nil) bis (triphenylphosphine) -platinum complex or (10) bis (alkynyl) (cyclooctadiene) -platinum complex. The platinum catalyst may be used alone or in a mixture of two or more thereof. The amount of the platinum catalyst is generally 1 to 1000 ppm, more preferably 5 to 500 ppm, as a metal equivalent to the total polyorganosiloxane compound.

In the composition of the present invention, component (c) is 0.1-1% by weight of the noble metal hydride catalyst based on the total composition, preferably 0.1-0.5% by weight.

Organic or inorganic fillers that can be used in the compositions of the present invention are not particularly limited as long as the average particle size is 0.01 to 100 μm. Typically, fillers having a particle size of 0.1 to 30 μm are used. More fillers have the advantage of reducing the coefficient of thermal expansion of the cured product, while increasing the viscosity or the filler is not evenly distributed in the cured product. It is common to use filler after drying at 110 degreeC or more before use. When 1% or more of moisture is contained, the curing rate or degree of curing of the composition may be reduced. The organic filler is for example polyorganosiloxane, polystyrene or polyacrylate, and the inorganic filler is for example natural silica, synthetic silica, aluminum oxide, titanium dioxide or feldspar. Silica is usually advantageously treated with an organosilicon compound. Examples of the organosilicon compound include methyltrichlorosilane, trimethyl monochlorosilane, hexamethyldisilazane and the like. The use of spherical inorganic fillers is advantageous for viscosity and dispersion stabilization. Fumed silica may also be used to control the thixotropy of the composition. Fumed silica refers to fillers that are more lipophilic than hydrophilic and have a surface area of 50-400 m ² / g. When the filler is less than this, the inherent properties of the filler are lowered, and when the filler is used more than this, the dispersion and adhesion are lowered. The amount of the organic or inorganic filler used may be 5 to 40% by weight, preferably 5-30% by weight, more preferably 10-20% by weight, based on 100 parts by weight of the total composition.

The composition of the present invention may further include an additive in addition to the components (a) to (d) to supplement the physical properties after curing, for example, a cyclic siloxane having an alkenyl group in the molecule, and a cyclic siloxane having a Si-H functional group in the molecule. It may include a coupling agent or a curable pot life adjusting agent, and may include 0.1-3% by weight based on the total composition. Additives may not be used in some cases.

According to a preferred embodiment of the present invention, the additive is a low molecular cyclic organosiloxane represented by the following formula (4).

Formula 4

In the above Formula 4, R ₁ and R ₂ are each independently C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{6 -22} aryl or represents hydrogen, n = an integer of 1-8. In the case of the compound represented by the formula (4), an equivalent of an alkenyl group, an aryl group, or a hydro group is easy, and may be used as a viscosity modifier.

The above-mentioned coupling agent may be used to improve the adhesive force. In the case of a coupling agent, the main feature is that it contains at least one epoxy group, alkenyl group, hydro group or alkoxy group. Common coupling agents are, for example, vinyl trialkoxysilanes, allyl trialkoxysilanes, 3-glycidoxypropyl trialkoxysilanes and 3-methacryloxypropyl trialkoxysilanes.

Examples of the additive used to control the pot life in the curing process include acetylene alcohol, cycloalkenylsiloxane, triazole phosphine, mercaptans, amines, hydrazines, fumarates, and malates. Among these, ethynyl cyclohexanol, methyl butynol, and dimethyl hexinol are excellent, and can be used 1 type or in mixture of 2 or more types. The amount used may vary depending on the amount of catalyst and the desired pot life.

The composition of the present invention may have different physical properties depending on the composition of the polyorganosiloxane. According to a preferred embodiment of the present invention, the one-component self-adhesive polysiloxane composition of the present invention has a detach mode (Detach Mode) of 50% or more, adhesive strength 8-25 kg / cm ² , moisture absorption 0.05-0.3%, hardness (Shore A) 50-70, tensile strength is 600-950 psi and elongation is 80-250%.

The composition prepared using the above-described materials should minimize contamination by metallic foreign particles and particulate foreign materials in order to be used as a die bonding material. The composition preparation is placed in each stirrer and stirred until the mixture is uniformly mixed and there is no change in viscosity. If the viscosity remains constant, the composition is filtered and then packaged in a suitable container and stored at low temperature.

The features and advantages of the present invention are summarized as follows:

(a) The one-component self-adhesive polysiloxane composition of the present invention can be used as an adhesive material used to attach a semiconductor chip and a substrate in a packaging process.

(b) The composition of the present invention is excellent in excellent insulating properties and hygroscopic resistance, and has a very excellent adhesive force with a substrate than when using a conventional epoxy compound.

(c) In the case of using the composition of the present invention, regardless of the type of epoxy cured product or the manufacturing process, it has excellent adhesion, and overcomes the disadvantages of storage stability and viscosity control of the product when using a conventional excessive coupling reagent is not easy. can do.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

Example

Experimental Method

① Detach Mode

Print the adhesive with a 250 mesh stencil and apply it to the plastic substrate, and then place a 6.13 x 6.13 mm ² size silicon mirror chip on the applied paste and place the head and stage at a temperature of 195 ° C. The chips were attached by thermal compression with a force of 4 kg for a second, and then the degree of dropping of the SR (solder resistor) ink of the substrate was measured.

② high temperature adhesion

After printing the adhesive with a 250 mesh stencil and applying it to the plastic substrate, place a 6.13 x 6.13 mm ² silicon mirror chip on the applied paste and 4 kg for 1 second on a thermocompressor fixed at 195 ° C. The chip was attached by thermal pressing with force, and then cured at 175 ° C. for 1 hour, and then measured at 260 ° C. using a Dage 4000 Die shear tester (Dage).

③ moisture absorption rate

In order to evaluate the reliability by the high temperature absorption, a specimen having a thickness of 1 mm was placed in an 85 ° C./85 RH% chamber, and the moisture absorption in the saturated state was measured.

④ hardness

After thermocompression bonding at 150 ° C. for 5 minutes, a sheet having a thickness of 2 mm was prepared and cured at 175 ° C. for 1 hour. Two sheets of cured 2 mm thickness were stacked and measured using a Shore A durometer (Techra).

⑤ Tensile strength and elongation

After thermocompression bonding at 150 ° C. for 5 minutes to prepare a sheet having a thickness of 2 mm, the sheet was cured at 175 ° C. for 1 hour. The specimens were prepared by cutting the cured 2 mm thickness to 10 mm length and 5 mm width, and then pulling at a speed of 500 mm / min with UTM equipment (hardness precision) to measure tensile strength and elongation.

Synthetic example

 VQM resin (polyorganosiloxane having two or more alkenyl groups) and a silane compound (coupling agent) were added to a reactor equipped with a stirrer and a distillation apparatus, followed by stirring for 1 hour. After confirming that both compounds were well dissolved, the temperature inside the reactor was raised to 80 ° C. and stirred for 5 hours. After the reaction was completed, the pressure was reduced to 10 mmHg at the same temperature to completely remove the by-product methanol and the unreacted silane compound. Then, the reactor temperature was lowered to room temperature and the vacuum was released to measure the viscosity of the resin.

Viscosity Measurement of New Resin Resin No. VQM Resin Silane compound New Resin
Viscosity (cPs) S1 usage
(g) Viscosity (cPs) Compound name usage
(g) 9,800 S2 100 6,000 3-glycidoxypropyl
Trimethoxysilane 5 7,500 S3 100 6,000 3-glycidoxypropyl
Trimethoxysilane 2 8,200 S4 100 6,000 Vinyl trimethoxysilane 5 6,900 S5 100 6,000 Vinyl trimethoxysilane 2 9,500 S6 100 6,000 3-glycidoxypropyl
Triethoxysilane 5 7,100 S7 100 6,000 3-glycidoxypropyl
Triethoxysilane 2 8,000 S8 100 6,000 Vinyl triethoxysilane 5 6,700

Example  1-7

The synthesized siloxane polymer was put in a plannerary mixer (Daehwa Tech) and stirred sufficiently so that the two polymers (100 g) could be mixed. 5 g of polyhydrogendimethylsiloxane (hydrogen content: 0.7 mol / 100 g, viscosity: 40 cPs), 20 g of spherical silica (average diameter: 1 µm), ethynyl cyclohexanol (TCI) as a pot life regulator ) 1.5 g, 1,3-dimethyl-1,1,3,3-tetramethyldisiloxane platinum complex (Aldrich) to 1,3-diethenyl-1,1,3,3-tetramethylsiloxane (Aldrich) 0.35 g of a diluted platinum catalyst (Gelest) (platinum content 4% by weight) and 1 g of 3-glycidyloxypropyltrimethoxysilane (Gelest) as an adhesion aid were added thereto, followed by stirring for 5 hours. The composition was removed from the filter and stored in a container at low temperature. The stored composition was used after stabilizing the viscosity for a sufficient time at room temperature before use.

Resin Composition and Physical Properties of Each Composition (1) Resin No. Example 1 Example 2 Example 3 Example 4 Example 5 S1 70 g 70 - - - S2 - - 70 g 70 g - S3 30 g - 30 g - 70 g S4 - 30 - 30 g - S5 - - - - 30 g S6 - - - - - S7 - - - - - S8 - - - - - Detach Mode [%] 70 70 60 55 55 High Temperature Adhesion [kg / cm ² ] 17.5 17.4 15.3 13.5 13.2 Moisture absorption rate [%] 0.15 0.15 0,16 0.16 0.16 Shore A 58 56 60 58 65 Tensile strength [psi] 720 700 780 720 850 Elongation [%] 180 200 160 180 120

Resin Composition and Physical Properties of Each Composition (2) Resin No. Example 6 Example 7 Comparative Example Resin Comparative Example 1 S1 - - VQM Resin 100 S2 - - - - S3 - - - - S4 70 g 30 g - - S5 - 70 g - - S6 30 g - - - S7 - - - - S8 - - - - Detach Mode [%] 50 70 - 10 High Temperature Adhesion [kg / cm ² ] 10.2 16.5 - 6.5 Moisture absorption rate [%] 0.15 0.15 - 0.15 Shore A 62 60 - 52 Tensile strength [psi] 810 750 - 760 Elongation [%] 140 175 - 160

Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that the specific technology is merely a preferred embodiment, and the scope of the present invention is not limited thereto. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (12)

One-component self-adhesive polysiloxane compositions comprising:
(a) a polyorganosiloxane having two or more alkenyl groups in the molecule (iii), vinyl trialkoxysilane, allyl trialkoxysilane, 3-glycidoxypropyl trialkoxysilane, 3-methacryloxypropyl trialkoxysilane, and A polyorganosiloxane produced by the reaction of a coupling agent selected from the group consisting of the following formulas (5) to (11), polyorganosiloxanes characterized by the following formula (2), or (ii) two of the above components (iii) and molecules 55-90% by weight of polyorganosiloxanes, based on the total composition, as a mixture of polyorganosiloxanes having alkenyl groups or more;
(b) 2-8% by weight of polyorganohydrogensiloxane, based on the total composition, having at least two Si-H functional groups in the molecule;
(c) 0.1-1% by weight of a noble metal silicon hydride catalyst based on the total composition; And
(d) 5-40% by weight of organic or inorganic fillers, based on the total composition, polyorganosiloxanes, polystyrenes, polyacrylates. At least one filler selected from the group consisting of natural silica, synthetic silica, aluminum oxide, titanium dioxide and feldspar;
(2)

Formula 5

6

Formula 7

Formula 8

Formula 9

Formula 10

Formula 11

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-22 aryl, C _{3 -20} allyl or hydroxy group; R ₈ and R ₉ are functional groups comprising a glycidyl group, a vinyl siloxane group or a hydrogen siloxane group; l, m, n, o, p and q satisfy 1> l≥0, 1> m≥0, 1> n≥0, 1> o≥0, 1> p≥0 and 1> q≥0 Number; Provided that they are l + m + n + o + p + q = 1 and are satisfying l + m + n + o> 0 and p + q>0; In Formulas 7 to 8, a and b are integers of 1-30.
delete delete The one-component self-adhesive polysiloxane composition according to claim 1, wherein the polyorganosiloxane having two or more Si-H functional groups in the molecule of component (b) is represented by the following general formula (3):
(3)

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently C _1-20 alkyl, C _6-22 aryl, hydrogen or hydroxy group; R ₈ and R ₉ are hydrogen or a methyl group; l ', m', n ', o', p 'and q' are 1>l'≥0,1>m'≥0,1>n'≥0,1>o'≥0,1> p ' A number satisfying ≧ 0 and 1> q ′ ≧ 0; However, these are the numbers satisfying l '+ m' + n '+ o' + p '+ q' = 1 and l '+ m' + n '+ o'> 0 and p '+ q'≥0.
According to claim 1, wherein the noble metal hydride catalyst (1) Platinum Black, (2) Halogenated platinum (PtCl ₄ , H ₂ PtCl ₄ 6H ₂ O, NaPtCl ₄ H ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ ), (3) complexes between platinum and olefins, alcohols, ethers, aldehydes, ketones or vinylsiloxanes, (4) bis (gamma-picolin) -platinum dichloride, (5) trimethylenedipyridine-platinum dichloride, (6) Dicyclopentadiene-platinum dichloride, (7) cyclooctadiene-platinum dichloride, (8) cyclopentadiene-platinum dichloride, (9) bis (alkynyl) bis (triphenylphosphine) -platinum complex or (10) A one-component self-adhesive polysiloxane composition, which is a bis (alkynyl) (cyclooctadiene) -platinum complex.
6. The one-component self-adhesive polysiloxane composition according to claim 5, wherein the amount of the noble metal silicon hydride catalyst of component (c) is 1 to 1000 ppm by weight of metal relative to the total polyorganosiloxane compound.
delete The method of claim 1, wherein the one-component self-adhesive polysiloxane composition further comprises an additive, wherein the additive is a cyclic siloxane, a cyclic siloxane having a Si-H functional group in the molecule, a coupling agent or a curable pot life regulator. One-component self-adhesive polysiloxane composition.
The one-component self-adhesive polysiloxane composition according to claim 8, wherein the cyclic siloxane is represented by the following Chemical Formula 4:
Formula 4

Wherein R ₁ and R ₂ are each independently C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{6 -22} aryl group or hydrogen, n = an integer of 1-8.
delete 9. The one-component type according to claim 8, wherein the curable pot life regulator is an acetylenic alcohol, a cycloalkenylsiloxane, a triazole phosphine, a mercapto derivative, an amine derivative, a hydrazine derivative, a fumarate derivative, a maleate derivative. Self-adhesive polysiloxane composition.
The composition of claim 1, wherein the composition has a detachable mode of 50% or more, an adhesion of 8-25 kg / cm ² , a moisture absorption of 0.05-0.3%, a hardness of 50-70, and a tensile strength of 600-950. One-component self-adhesive polysiloxane composition, characterized in that psi and elongation of 80-250%.