KR20130109747A - New carbamate compound and curable polyorganosiloxane composition comprising the same - Google Patents

Abstract

PURPOSE: A curable polyorganosiloxane composition is provided to have superior adhesion and durability (wet and heat resistance) on heat resistant plastic substrates such as polyphthalamide (PPA) as well as metal substrates. CONSTITUTION: A carbamate-based compound is denoted by chemical formula 1. A curable polyorganosiloxane composition contains polyorganosiloxane with alkenyl groups, polyorganohydrogen siloxane, a platinum-based catalyst, and the carbamate-based compound. The composition contains 0.05-5 parts by weight of the carbamate-based compound based on 100 parts by weight of polyorganosiloxane. Polyorganosiloxane has 0.1-4 mol of hydrogen atoms with respect to 1 mol of alkenyl groups of polyorganosiloxane.

Description

Novel carbamate compound and curable polyorganosiloxane composition containing same {NEW CARBAMATE COMPOUND AND CURABLE POLYORGANOSILOXANE COMPOSITION COMPRISING THE SAME}

The present invention relates to a novel carbamate compound compound and a curable polyorganosiloxane composition having excellent adhesion and adhesion durability.

The optically clear curable polyorganosiloxane composition is cured by hydrosilation in the presence of a platinum catalyst to form an elastomer, commonly referred to as silicone rubber.

Silicone elastomers are excellent in their physical and chemical properties, such as heat resistance, durability, light resistance, weather resistance, water solubility, moisture resistance, strength, solubility, etc., under various circumstances, as well as resistance to degradation. Such silicone elastomers are used in various applications including substrate protective coatings, such as semiconductor devices, which are susceptible to damage by physical external forces, moisture, and contaminants.

However, silicone elastomers include not only metals such as Ag, Au, Rh, Pb, Al, etc., which are used as frames or electrode materials for semiconductor devices, but also polyphthalamide (PPA) and liquid crystal polymers (PPAs), which have recently been expanded in use. Adhesion to heat-resistant plastics, such as liquid crystral polymer (LCP), is insufficient, resulting in deterioration in durability, such as peeling at the interface to which the silicone elastomer is applied.

In view of this point, a method of improving the adhesion between the substrate and the silicone elastomer by forming a primer layer on the substrate has been proposed, but this method requires a separate process.

In addition, a method of adding a silane compound has also been proposed, but this method is difficult to secure sufficient adhesion to both the metal and the heat-resistant plastic as well as to cause discoloration or deterioration of transparency, which makes it difficult to apply to optical applications.

An object of the present invention is to provide a curable polyorganosiloxane composition that can improve durability by maintaining excellent light transmittance and excellent adhesion to both metals and heat-resistant plastics.

In order to achieve the above object, the present invention provides a carbamate compound represented by the following formula (1).

이고, R₃ 및 R₄는 각각 독립적으로 에폭시기 또는 알칸디올기이며, n은 1 내지 15의 정수임).(Wherein R ₁ and R ₂ are each independently an alkoxysilyl group, a vinyl group or

And R ₃ And R ₄ are each independently an epoxy group or an alkanediol group, n is an integer of 1 to 15).

Preferably n may be an integer of 1 to 6.

The present invention also provides a curable polyorganosiloxane composition comprising a polyorganosiloxane having an alkenyl group, a polyorganohydrogensiloxane, a platinum catalyst, and a carbamate compound represented by Formula 1.

The carbamate compound may include 0.05 to 5 parts by weight based on 100 parts by weight of polyorganosiloxane.

The carbamate compound preferably contains 0.1 to 3 parts by weight based on 100 parts by weight of polyorganosiloxane.

The polyorganohydrogensiloxane may include 1 to 4 mol of hydrogen atoms of the polyorganohydrogensiloxane relative to 1 mol of the alkenyl group of the polyorganosiloxane.

The platinum-based catalyst may include 0.1 to 1,000 ppm in terms of platinum element relative to the content of polyorganosiloxane and polyorganohydrogensiloxane.

Curable polyorganosiloxane composition according to the present invention is excellent in adhesion to the heat-resistant plastic substrate, such as polyphthalamide (PPA) as well as metal substrates (adhesive heat resistance).

In addition, the curable polyorganosiloxane composition according to the present invention has a low haze value and excellent light transmittance, and thus is used in the fields of adhesives, binders, protective agents, coatings, sealants and undercoats in electronic and electrical devices (LEDs, etc.). This is suitable.

The present invention relates to a novel carbamate compound and a curable polyorganosiloxane composition having excellent adhesion and adhesion durability.

Hereinafter, the present invention will be described in detail.

The present invention is characterized by a carbamate-based compound represented by the following formula (1).

[Formula 1]

이고, R₃ 및 R₄는 각각 독립적으로 에폭시기 또는 알칸디올기이며, n은 1 내지 15의 정수임).(Wherein R ₁ and R ₂ are each independently an alkoxysilyl group, a vinyl group or

And R ₃ And R ₄ are each independently an epoxy group or an alkanediol group, n is an integer of 1 to 15).

Preferably n may be an integer of 1 to 6.

Of these, the epoxy group is more preferably a glycidoxypropyl group or a 3,4-epoxycyclohexylethyl group.

The compound may be prepared by a method generally used in the art, and for example, the present invention may be synthesized by heating a predetermined amount of alkoxysilane, glycidyl ether, and alkylamine, and then heating to 30 to 40 ° C.

In addition, the present invention curable polyorganosiloxane composition comprises a carbamate compound represented by the formula (1). Specifically, it may include a polyorganosiloxane having an alkenyl group, a polyorganohydrogensiloxane, a platinum catalyst, and a carbamate compound represented by Chemical Formula 1.

The polyorganosiloxane is a base resin of the polyorganosiloxane curable polyorganosiloxane composition, and preferably contains at least two alkenyl groups bonded to silicon atoms in one molecule containing silicon-bonded alkenyl groups.

The molecular structure of the polyorganosiloxane may be linear or cyclic, and they may have molecular branches. It is preferable that the main structure in which diorganosiloxane units are repeated is a straight chain type molecular structure in which both ends of the molecular chain are blocked with triosanosiloxy groups. When the molecular structure is a straight-chain type, the alkenyl group may be bonded to the silicon atom only at either the end of the molecular chain or the middle, preferably the silicon atom at both the end of the molecular chain and the middle.

Examples of the alkenyl group bonded to the silicon atom in the polyorganosiloxane include those having 2 to 10 carbon atoms, and preferably 2 to 6 carbon atoms. Examples include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group and an octenyl group. Of these, the vinyl group is preferable.

A substituent other than an alkenyl group may be bonded to the silicon atom in the polyorganosiloxane. For example, methyl group, ethyl group, propyl group, 1-methylethyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group , 3-methylbutyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, heptyl group, octyl group Alkyl groups having 1 to 10 carbon atoms such as nonyl and decyl groups; An allyl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like; An aralkyl group such as benzyl group, phenethyl group and the like; Chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, chlorophenyl group, dichlorophenyl group, 2,2,2, -trifluoroethyl group, 2,2,3,3-tetrafluoro Propyl group, and 2,2,3,3,4,4,5,5-octafluoropentyl group. Of these, a methyl group or a phenyl group is preferable.

The polyorganosiloxane preferably has a viscosity of usually 100 to 100,000 mPa · S at 25 ° C, and more preferably 500 to 10,000 mPa · S. When the viscosity is within this range, not only the workability is good but also the physical properties of the cured product obtained by the curing are good.

The polyorganosiloxane may have a number average molecular weight (Mn) of 500 to 50,000. At this time, the number average molecular weight can be measured by gel permeation chromatography using a low angle laser light scattering detector, a refractive index detector or a standard sample of polyorganosiloxane resin.

Specific examples of the polyorganosiloxane include a dimethylsiloxane-methylvinylsiloxane copolymer in which both terminals of the molecular chain are blocked with a trimethylsiloxy group; Methylvinylpolysiloxane wherein both ends of the molecular chain are blocked with trimethylsiloxy groups; A dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer in which both terminals of the molecular chain are blocked with trimethylsiloxy groups; Dimethylpolysiloxanes wherein both ends of the molecular chain are blocked with a dimethylvinylsiloxy group; Methylvinylpolysiloxanes wherein both ends of the molecular chain are blocked with a dimethylvinylsiloxy group; A dimethylsiloxane-methylvinylsiloxane copolymer in which both ends of the molecular chain are blocked with a dimethylvinylsiloxy group; A dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer in which both terminals of the molecular chain are blocked with a dimethylvinylsiloxy group; Dimethylpolysiloxanes wherein both ends of the molecular chain are blocked with a trivinylsiloxy group; (R ₄ ) ₃ SiO _{0 .5} , a siloxy group unit represented by (R ₄ ) ₂ R ₅ SiO _0.5 , a siloxy group unit represented by R ₄ SiO, and a siloxy group represented by SiO ₂ A polyorganosiloxane copolymer; (R ₄ ) ₃ SiO _{0 .5} , a siloxy group unit represented by (R ₄ ) ₂ R ₅ SiO _{0 .5} , and a siloxane unit represented by SiO ₂ ; A polyorganosiloxane copolymer comprising a siloxane unit represented by (R ₄ ) ₂ R ₅ SiO _{0 .5} , a unit represented by R ₄ SiO, and a siloxane unit represented by SiO ₂ ; A polyorganosiloxane copolymer comprising a siloxane unit represented by R ₄ R ₅ SiO, a siloxane unit represented by R ₄ SiO _{1 .5} , or a siloxane unit represented by R ₅ SiO _{1 .5} . These may be used alone or in combination of two or more. Wherein R ₄ may be the same as other substituents other than the alkenyl group bonded to the silicon atom in the polyorganosiloxane component as another substituent other than the alkenyl group, and R ₅ is the silicon atom in the polyorganosiloxane component as the alkenyl group. It may be the same as the alkenyl group bonded to.

The polyorganohydrogen siloxane may be one containing a silicon-bonded hydrogen atom as a crosslinking component which reacts with the polyorganosiloxane.

The molecular structure of polyorganohydrogensiloxane is not specifically limited, For example, it may have a structure of linear, cyclic, branched, three-dimensional network type.

The polyorganohydrogensiloxane has a hydrosilyl group [Si-H] in which two or more, preferably three or more silicon atoms are bonded to a hydrogen atom in the molecule. When the polyorganosiloxane siloxane is in the form of a straight chain, the hydrosilyl group may be located at either or both of the molecular chain terminal and the middle.

The polyorganohydrogensiloxane may have a number of silicon atoms in one molecule, that is, a polymerization degree of 2 to 1,000, and preferably 3 to 100.

Examples of the polyorganohydrogen siloxane include polyorganohydrogen siloxane represented by (R ₆ ) _a H _b SiO _{(4-ab) / 2} . Herein, R ₆ is a hydrocarbon group having 1-14 carbon atoms, preferably 1-10 carbon atoms, excluding aliphatic unsaturated groups, and specifically methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl Alkyl groups such as groups, pentyl groups, neopentyl groups, hexyl groups, cyclohexyl groups, octyl groups, nonyl groups and decyl groups; Allyl groups such as phenyl, tolyl, xylyl and naphthyl; An aralkyl group such as a benzyl group, a phenylethyl group or a phenylpropyl group; And hydrocarbon groups in which some or all of the hydrogen atoms in the gastric hydrocarbon group are substituted with halogen atoms such as chloromethyl, 3-chloropropyl, bromoethyl and 3,3,3-trifluoropropyl groups. Among these, an alkyl group or an aryl group is preferable, and a methyl group or a phenyl group is more preferable. Also, a and b are rational numbers in the range of 0.7? A? 2.1, 0.001 b? 1.0, 0.8? A + b? 3.0, and more preferably 1.0? A + b? 2.5.

Specific examples of the polyorganohydrogensiloxane include methylhydrogenpolysiloxanes in which both ends of the molecular chain are sealed with trimethylsiloxy groups; A dimethylsiloxane-methylhydrogensiloxane copolymer in which both terminals of the molecular chain are blocked with trimethylsiloxy groups; A dimethylsiloxane-methylhydrogensiloxane-methylphenylsiloxane copolymer in which both ends of the molecular chain are blocked with trimethylsiloxy groups; Dimethylpolysiloxanes wherein both ends of the molecular chain are blocked with a dimethylhydrogensiloxy group; A dimethylpolysiloxane-methylhydrogensiloxane copolymer in which both ends of the molecular chain are blocked with a dimethylhydrogensiloxy group; A dimethylsiloxane-methylphenylsiloxane copolymer in which both terminals of the molecular chain are blocked with a dimethylhydrogensiloxy group; Methylphenyl polysiloxane in which both terminals of the molecular chain are blocked with a dimethylhydrogensiloxy group; (R ₄ ) ₃ SiO _{0 .5} , a siloxy group unit represented by (R ₄ ) ₂ HSiO _{0 .5} , and a siloxane unit represented by SiO ₂ . (R ₄₎ polyorganosiloxane copolymer comprising a siloxy unit represented by siloxy units and SiO ₂ represented by ₂ HSiO _{0 .5;} A polyorganosiloxane copolymer comprising a siloxy group unit represented by R ₄ HSiO, a siloxy group unit represented by R ₄ SiO _{1 .5} , or a siloxy group unit represented by HSiO _{1 .5} . These may be used alone or in combination of two or more.

The polyorganohydrogen siloxane preferably has a viscosity of usually 1 to 500 mPa · S at 25 ° C, and more preferably 1 to 100 mPa · S.

The polyorganohydrogensiloxane may be included in an amount such that the hydrogen atom per mol of the alkenyl group of the polyorganosiloxane containing the alkenyl group is 0.1 to 4 mol, preferably 1 to 3 mol. If the content is less than 0.1 mol, the curing reaction does not proceed sufficiently and it may be difficult to obtain a cured product. If the content exceeds 4 mol, a large amount of unreacted hydrosilyl group remains in the cured product, have.

Platinum-based catalysts are catalysts for promoting hydrosilation of alkenyl groups contained in polyorganosiloxanes with hydrosilyl groups contained in polyorganohydrogensiloxanes.

Examples of the platinum-based catalyst include platinum-based metals such as platinum, rhodium, ruthenium, palladium, osmium, indium, or organometallic compounds thereof. Further, there may be mentioned chloroplatinic acid, chloroplatinic acid hexahydrate, platinum dichloride, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefinic compounds, coordination compounds of vinylsiloxane compounds or acetylene compounds.

The platinum-based catalyst may be contained in an amount of 0.1 to 1,000 ppm, preferably 1 to 500 ppm, more preferably 1 to 20 ppm, based on the platinum element, based on the total content of the polyorganosiloxane and the polyorganohydrogen siloxane. If the content is in this range, the silicon hydride addition reaction may be promoted to allow sufficient curing to proceed.

The present invention serves to impart adhesion by containing a carbamate compound represented by the following formula (1) in the curable polyorganosiloxane composition.

[Formula 1]

이고, R₃ 및 R₄는 각각 독립적으로 에폭시기 또는 알칸디올기이며, n은 1 내지 15의 정수임).(Wherein R ₁ and R ₂ are each independently an alkoxysilyl group, a vinyl group or

And R ₃ And R ₄ are each independently an epoxy group or an alkanediol group, n is an integer of 1 to 15).

Preferably n may be an integer of 1 to 6.

Of these, the epoxy group is more preferably a glycidoxypropyl group or a 3,4-epoxycyclohexylethyl group.

The compound includes a vinyl group, an alkoxysilyl group which can be bonded to a siloxane structure, an epoxy group which can react with a substrate, and an alkanediol group, and is widely used as a frame or electrode material of a semiconductor device. It can play a role in improving adhesion to both metals such as Rh, Pb, and Al, as well as heat-resistant plastics such as polyphthalamide (PPA) and liquid-crystal polymers (LCP).

Specifically, the compound of Formula 2, Formula 3, and Formula 4 may be used.

The carbamate compound may include 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of polyorganosiloxane. When the content is less than 0.05 parts by weight, it is difficult to obtain sufficient adhesion to both the metal and the heat-resistant plastic, and when it is more than 5 parts by weight, the hardness is low, making it difficult to obtain sufficient strength characteristics, and the compatibility is low, making the curable silicone composition opaque and storage stability. This can be degraded.

The curable polyorganosiloxane composition of the present invention may further include at least one filler such as fumed silica, calcium carbonate, titanium dioxide, ferric oxide, carbon black, zinc oxide and the like.

In addition, the curable polyorganosiloxane composition may further include one or more additives commonly used in curable silicone compositions such as pigments, dyes, stabilizers, flame retardants and the like.

The curable polyorganosiloxane composition preferably has a viscosity of 100 to 10,000 mPa · S as measured by a rotary viscometer at 25 ° C., more preferably 300 to 5,000 mPa · S, in view of workability.

The curable polyorganosiloxane composition can be prepared in a one-part form by mixing the components in a batch process or a continuous process using known methods such as milling, blending or stirring. In addition, a curing inhibitor such as acetylene alcohol can be added to adjust the curing arbitrarily. Two curing liquids can be mixed and cured when they are stored in two liquids so as not to proceed curing.

The curable polyorganosiloxane composition of the present invention configured as described above has low haze and maintains high light transmittance while providing good adhesion to both heat-resistant plastics as well as metals, thereby improving durability without peeling at the interface to which the composition is applied. You can.

The curable polyorganosiloxane composition of the present invention can be cured to produce a cured product (silicone elastomer).

The curing conditions of the curable polyorganosiloxane composition are not particularly limited and are, for example, usually from 40 to 250 ° C, preferably from 40 to 200 ° C, more preferably from 60 to 170 ° C for 1 minute to 10 hours, Min to 6 hours.

The cured product produced by the curing of the curable polyorganosiloxane composition includes a light emitting diode (LED), a photo diode, a charge coupled device (CCD), and a complementary metal oxide semiconductor. semiconductor, such as CMOS) can be widely used. For example, as protective coatings for transistors, integrated circuits as well as electronic devices.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Compound synthesis

Synthetic example  One

15 g (1 eq) of 3-isocyanatepropyltriethoxysilane (KBE-9007, Shin-Etsu), 19.35 g (1.5 eq) of glycerol diglycidyl ether (Aldrich) and N, N-diisopropyl in a 1000 ml round bottom flask Ethylamine (DIPEA) 35ml (3eq) was added and warmed to 30 to 40 ℃. In order to remove DIPEA, ethylacetate (EA) was concentrated under reduced pressure several times, and the following Chemical Formula 2 was synthesized.

 (2)

¹ H-NMR (CDCl ₃ , ppm): 0.58 (t, 2H), 1.21 (t, 9H), 1.62 (m, 2H), 2.61 (q, 2H), 2.81 (q, 2H), 3.16 (m, 2H), 3.19 (t, 2H), 3.38 (m, 3H) 3.63 (m, 3H) 3.76 (m, 1H), 3.83 (t, 6H), 4.34 (d, 2H)

Synthetic example  2

In the same manner as in Synthesis example 1, but instead of the -isocyanatepropyltriethoxysilane 5-isocyatetopent-1-ene (Uniplus) 7.02g (1eq) to synthesize the following formula (3).

(3)

¹ H-NMR (CDCl ₃ , ppm): 1.69 (m, 2H), 2.18 (q, 2H), 2.61 (q, 2H), 2.81 (q, 2H), 3.16 (m, 2H), 3.19 (t, 2H), 3.38 (m, 3H) 3.63 (m, 3H) 3.76 (m, 1H), 4.34 (d, 2H) 4.96 (d, 1H), 5.01 (d, 1H), 5.80 (m, 1H)

Synthetic example  3

13.44 g (42.67 mmol) of Chemical Formula 3 synthesized in Synthesis Example 2, 36 ml of 1,4-dioxane and 24 ml of H ₂ O were mixed and then dissolved by stirring for 30 minutes. Thereafter, 0.3 ml (4.267 mmol) of trifluoroacetic acid was added thereto, and the mixture was refluxed for 1 hour. Thereafter, after confirming the termination of the reaction by using TLC ( thin - layer chromatography) , the solvent was removed by distillation under reduced pressure to synthesize Formula 4 below.

[Formula 4]

¹ H-NMR (CDCl ₃ , ppm): 1.29 (m, 8H), 1.53 (m, 4H), 1.62 (m, 4H), 1.71 (m, 2H), 2.18 (q, 2H), 3.19 (m, 4H), 3.38 (m, 3H) 3.6 (m, 4H) 3.76 (m, 6H), 4.11 (m, 6H), 4.34 (d, 2H), 4.96 (d, 1H), 5.01 (d, 1H), 5.80 (m, 1 H)

Hardenability Polyorganosiloxane  Composition

Example  1 to 6 and Comparative Example  1 to 6

Were mixed in the compositions shown in Table 1 below to prepare a curable polyorganosiloxane composition.

division
(Parts by weight) Polyorgano
Siloxane
Polyorgano
Hydrogen
Siloxane Platinum-based catalyst
(ppm) Carbamate Compound Adhesion Enhancer A-1 A-2 A-3 B-1 B-2 B-3 B-4 Example 1 100 5.5 10 0.5 - - - - - - Example 2 100 5.5 10 One - - - - - - Example 3 100 5.5 10 3 - - - - - - Example 4 100 5.5 10 5 - - - - - - Example 5 100 5.5 10 - One - - - - - Example 6 100 5.5 10 - - One - - - - Comparative Example 1 100 5.5 10 - - - - - - - Comparative Example 2 100 5.5 10 - - - One - - - Comparative Example 3 100 5.5 10 - - - - One - - Comparative Example 4 100 5.5 10 - - - - - One - Comparative Example 5 100 5.5 10 - - - - - - One _{Polyorganosiloxane: (CH 3) 3 SiO 0} .5 / (CH 3) 2 (CH 2 = CH) SiO 0 .5 / SiO 2 And a dimethylpolysiloxane having both ends of the molecular chain blocked with a dimethylvinylsiloxy group
(Gelest, DMS-V31, viscosity 1,000mPaS at 25 ℃)
Polyorganohydrogensiloxane: Methylhydrogenpolysiloxane whose both ends of the molecular chain are sealed with trimethylsiloxy group (Gelest, HMS-071 product, viscosity 20 mPa * S, Si-H group content 7mmol (equivalent / g) at 25 degreeC), Molar ratio of SiH groups to vinyl groups in the polyorganosiloxane mixture 1.5)
Platinum-based catalyst: Complexing of chloroplatinic acid and divinyl tetramethyldisiloxane (Damipolychem, CP101)
A-1: Carbamate Compound of Synthesis Example 1
A-2: Carbamate Compound of Synthesis Example 2
A-3: Carbamate Compound of Synthesis Example 3
B-1: vinyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
B-2: 3-glycidoxypropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
B-3: glycidyl methacrylate (aldrich)
B-4: triethoxysilylpropylethyl carbamate (Gelest)

Experimental Example

The physical properties of the curable polyorganosiloxane composition and the cured product (sample) thereof prepared in Examples and Comparative Examples were measured by the following method and the results are shown in Table 2 below.

The cured product was prepared by pouring the curable polyorganosiloxane composition prepared in Examples and Comparative Examples into a metal mold having an area of 100 mm × 100 mm and a thickness of 2 mm and curing at a temperature of 150 ° C. for 1 hour.

One. Hayes (%)

The prepared cured product (sample) was measured using a haze meter (HZ-1, manufactured by Suga Test Instrument Co., Ltd.) in accordance with JIS K 7361-1.

2. Permeability (%)

The transmittance (400-750 nm region) of the produced cured product (sample) was measured using a UV spectrometer (UV-Vis spectrometer, Shimadzu).

3. Adhesion

1) adhesion to metal

The curable polyorganosiloxane composition thus prepared was applied to one surface of an Al substrate of 25 mm × 25 mm × 1 mm to have a thickness of 1 mm, and then the same Al substrate was laminated. The laminate was cured at a temperature of 150 ° C. for 1 hour to prepare a cured body (sample).

2) adhesion to heat-resistant plastics

The curable polyorganosiloxane composition was applied to one surface of a polyphthalamide (PPA) substrate having a thickness of 25 mm x 25 mm x 1 mm, and then laminated on the same PPA substrate. This laminated body was hardened at the temperature of 150 degreeC for 1 hour, and the hardened | cured material (sample) was produced.

Each prepared specimen was left at room temperature for 12 hours, and then both ends of the specimen were pulled using a tensile tester to measure the agglomerated fracture ratio of the cured layer, and evaluated based on the following criteria.

<Evaluation Criteria>

○: 60% <percentage of agglomerated fractures

Δ: 50% <agglomerated fracture ratio ≤ 60%

×: coagulated fracture ratio ≤ 50%

4. Moisture and Heat Resistance

The curable polyorganosiloxane composition was applied to a LED device having a polyphthalamide (PPA) substrate and an Ag electrode, and then cured at 80 ° C. for 1 hour and 150 ° C. for 2 hours. The cured LED device was stored in an oven for 24 hours at 125 ° C. and a moist heat condition (temperature: 60 ° C./relative humidity: 90%) for 168 hours, followed by three reflow processes. After that, the device was observed under a microscope to confirm that the device was peeled from the PPA and Ag electrodes.

It described as the total number of LED elements (n) / number of silicon encapsulant and the number of elements peeled (NG).

division Hayes
(%) Permeability
(%) Adhesion Moisture Resistance Test
(N total number / NG number) Al PPA Example 1 3.0 99.42 ○ ○ 20/1 Example 2 3.0 99.30 ○ ○ 20/0 Example 3 3.3 98.12 ○ ○ 20/0 Example 4 3.6 95.98 ○ ○ 20/0 Example 5 3.0 99.40 ○ ○ 20/4 Example 6 3.1 99.35 ○ ○ 20/2 Comparative Example 1 2.8 99.78 × × 20/20 Comparative Example 2 3.0 99.48 ○ × 20/19 Comparative Example 3 3.2 98.51 × × 20/17 Comparative Example 4 3.1 99.42 × × 20/20 Comparative Example 5 3.1 99.52 △ △ 20/15

As shown in Table 2, the curable polyorganosiloxane composition of Examples 1 to 6 according to the present invention has a low haze value equivalent to or higher than that of the compositions of Comparative Examples 1 to 5, while having a high light transmittance and at the same time for both metals as well as heat resistant plastics. It was confirmed that the adhesion and adhesion durability (humidity heat resistance) were excellent.

Claims (8)

Carbamate compound represented by the formula (1):
[Formula 1]

(Wherein R ₁ and R ₂ are each independently an alkoxysilyl group, a vinyl group or

And R ₃ And R ₄ are each independently an epoxy group or an alkanediol group, n is an integer of 1 to 15).
The carbamate compound of claim 1, wherein n is an integer of 1 to 6.
A curable polyorganosiloxane composition comprising a polyorganosiloxane having an alkenyl group, a polyorganohydrogensiloxane, a platinum catalyst, and a carbamate compound represented by Formula 1 below:
[Formula 1]

(Wherein R ₁ and R ₂ are each independently an alkoxysilyl group, a vinyl group or

And R ₃ And R ₄ are each independently an epoxy group or an alkanediol group, n is an integer of 1 to 15).
4. The curable polyorganosiloxane composition of claim 3, wherein n is an integer from 1 to 6.
The curable polyorganosiloxane composition according to claim 3, wherein the carbamate compound comprises 0.05 to 5 parts by weight based on 100 parts by weight of polyorganosiloxane.
The curable polyorganosiloxane composition according to claim 5, wherein the carbamate compound comprises 0.1 to 3 parts by weight based on 100 parts by weight of polyorganosiloxane.
The curable polyorganosiloxane composition according to claim 3, wherein the polyorganohydrogensiloxane comprises 0.1 to 4 mol of hydrogen atoms of the polyorganohydrogensiloxane relative to 1 mol of the alkenyl group of the polyorganosiloxane.
The curable polyorganosiloxane composition according to claim 3, wherein the platinum-based catalyst comprises 0.1 to 1,000 ppm in terms of platinum element relative to the content of polyorganosiloxane and polyorganohydrogensiloxane.