WO2017122762A1 - Condensation reaction-type silicone composition and cured product - Google Patents
Condensation reaction-type silicone composition and cured product Download PDFInfo
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- WO2017122762A1 WO2017122762A1 PCT/JP2017/000949 JP2017000949W WO2017122762A1 WO 2017122762 A1 WO2017122762 A1 WO 2017122762A1 JP 2017000949 W JP2017000949 W JP 2017000949W WO 2017122762 A1 WO2017122762 A1 WO 2017122762A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Definitions
- the present invention relates to a condensation reaction type silicone composition and a cured product.
- a silicone resin is generally a cured product obtained by curing a silicone (polyorganosiloxane), and a condensation reaction and an addition reaction are known as the curing reaction.
- the addition reaction is a reaction in which a silicone having an alkenylsilane group such as Si—CH ⁇ CH 2 and a silicone having a hydrosilane group (Si—H) are hydrosilylated in the presence of a platinum-based catalyst.
- the addition reaction is advantageous in terms of productivity because it provides the desired cured product in a relatively short time even at room temperature.
- the addition reaction has a problem that curing inhibition is likely to occur due to deactivation of the platinum catalyst, humidity in the use environment, and the like.
- the condensation reaction is a reaction in which silicones having an organoxy group such as an alkoxy group (Si—OR) or a silanol group (Si—OH) are subjected to dehydration condensation and / or dealcoholization condensation in the presence of an organotin catalyst or the like.
- the condensation reaction is less prone to curing inhibition and has a cost advantage because it does not use a platinum catalyst.
- the condensation reaction has insufficient initial curability as compared with the addition reaction, and a relatively high temperature and a long time are required for complete curing.
- Patent Document 1 describes a silicone composition containing an acrylic resin, a condensation-reactive silicone compound and / or a condensation-reactive silane compound, and a curing accelerator.
- Reference 1 also describes that the silicone compound is useful as a transparent sealant and an adhesive for a light-emitting diode element.
- Patent Document 2 it is pointed out that a cured product of a conventional condensation reaction type silicone composition generally has insufficient adhesion to a reflector material or a metal electrode when used as a sealant for an optical semiconductor. Yes.
- One reason for this is considered to be incompatibility between the strength and flexibility of the adhesive layer (cured product).
- condensation reaction type silicone composition releases moisture or low molecular alcohol during the reaction process, so that fine voids (bubbles) or cracks are generated in the cured product. Since these defects lower the mechanical strength of the cured product and impair the appearance, they are regarded as a problem particularly in applications for adhesives and optical semiconductor encapsulants.
- the condensation reaction type silicone composition described in Patent Document 1 has an acrylic resin as a main component and has insufficient heat resistance.
- An object of the present invention is to provide a condensation reaction type silicone composition that has excellent initial curability, has excellent toughness, and provides a cured product having excellent crack resistance, void resistance, and heat resistance. There is to do.
- the condensation reaction type silicone composition that solves the above-mentioned problems needs to reduce the amount of low molecular components such as water or alcohol, organic solvent, and other volatile components that are generated in the condensation reaction.
- the strength of the cured product itself is also necessary. Therefore, as a result of considering these circumstances, the inventors have obtained a composition containing a predetermined polysilsesquioxane that is solid at room temperature and a predetermined polysilsesquioxane that is liquid at room temperature.
- the present inventors have found that the problems can be solved and have completed the present invention. That is, the present invention relates to the following condensation reaction type silicone composition and cured product.
- a trisiloxy unit represented by R 1 SiO 3/2 (wherein R 1 represents one selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, a phenyl group and a benzyl group) (T A ) and a hydroxyl group-containing polysilsesquioxane that is solid at room temperature
- B R 2 SiO 3/2 (wherein R 2 is an alkyl group having 1 to 15 carbon atoms, a phenyl group)
- T B trisiloxy unit represented by the formula: -OR 2 (wherein R 2 is an alkyl group having 1 to 15 carbon atoms, a phenyl group) And a polysilsesquioxane having a liquid state at room temperature
- C a condensation reaction catalyst.
- Item 2 The condensation reaction type silicone composition according to Item 1, wherein the softening point of the component (A) is 40 to 150 ° C.
- Item 3 The condensation reaction type silicone composition according to Item 1 or 2, wherein the component (B) has a viscosity of 5 to 10,000 mPa ⁇ s / 25 ° C.
- Item 4 The condensation reaction type silicone composition according to any one of Items 1 to 3, further comprising (D) an inorganic filler.
- the condensation reaction type silicone composition of the present invention has good handling properties and transparency, and is excellent in storage stability and initial curability. Moreover, since the cured product has good heat resistance and transparency, the mass reduction rate is small even after long-time heating, and the transparency is hardly lowered. Moreover, since this hardened
- the condensation reaction type silicone composition of the present invention has such many advantages, it can be used for a wide range of applications such as adhesives, sealants, coating agents, sealants and paints. Specifically, it can be used as a metal adhesive for joining the same or different metals such as silicon, aluminum, iron, gold, silver, and copper.
- the condensation reaction type silicone composition of the present invention can also be used as a sealing agent or dam agent for UV-LEDs, optical semiconductor elements including lasers and light receiving elements, power modules, temperature sensors and the like.
- the condensation reaction type silicone composition of the present invention can be used not only as an optical adhesive for bonding a glass or plastic lens, a transparent window or the like to a support, but also as a moisture-proof coating for an electronic substrate or the like. It can also be used as a case material such as an agent and a resistor.
- the condensation reaction type silicone composition of the present invention (hereinafter also simply referred to as “the composition of the present invention”) is also referred to as a predetermined (A) solid polyalkylsilsesquioxane (hereinafter referred to as “component (A)”). ), Predetermined (B) liquid polyalkylsilsesquioxane (hereinafter also referred to as “component (B)”), and (C) a condensation reaction catalyst (hereinafter also referred to as “component (C)”). It is a composition to contain.
- component (A) solid polyalkylsilsesquioxane
- component (B) liquid polyalkylsilsesquioxane
- component (C) a condensation reaction catalyst
- room temperature means 20 ⁇ 15 ° C.
- solid means a normal so-called solid state having no fluidity
- liquid means a state having fluidity, for example, It means a state where the viscosity is 1000000 mPa ⁇ s / 25 ° C. or less.
- the viscosity is a value measured using an E-type viscometer.
- the component (A) is a polysilicate that is solid at room temperature and contains a trisiloxy unit (T A ) represented by R 1 SiO 3/2 (wherein R 1 is the same as above) and has a hydroxyl group. Sesquioxane.
- Examples of the alkyl group having 1 to 15 carbon atoms represented by R 1 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-decyl group.
- R 1 does not include a reactive functional group such as an isocyanate group, a thiol group, an amino group, an epoxy group, an acid anhydride group, and a vinyl group.
- T A includes a T1 structure [R 1 O—Si (R 1 ) (OR 1 ) —O—], a T2 structure [— (R 1 ) Si (OR 1 ) (O —) — O—], and a T3 structure [ -(R 1 ) Si (O-) 2 -O-].
- Each structure can be identified, for example, by measuring a 29 Si-NMR spectrum of the component (A).
- (A) percentage of T A occupying the components is not particularly limited. Considering the balance of the desired effect of the present invention, particularly the compatibility and curability of the composition of the present invention, and the balance of the strength, adhesiveness, crack resistance and void resistance of the cured product, (A) ratio of T a occupying the component is generally 90 mol% or more, preferably 95 mol%, more preferably 100 mol%. Further, as long as the component (A) is kept solid at room temperature, it may contain some other units (monosiloxy unit (M A ), disiloxy unit (D A ), or tetrasiloxy unit (Q A )). The ratio of such other units is not particularly limited, and is usually less than 10 mol%, preferably less than 5 mol%.
- the structure of the component (A) can be specifically expressed by the following average unit formula.
- Component (A) contains a hydroxyl group derived from a silanol group at the molecular end.
- the content of the hydroxyl group is not particularly limited, and is usually about 1 to 10 wt% with respect to the total amount of component (A).
- the content of the hydroxyl group is 1 wt% or more, the strength and adhesiveness of the cured product are further improved, and when it is 10 wt% or less, the amount of desorbed components associated with the curing reaction is reduced, and curing is performed.
- the crack resistance and void resistance of the product are further improved. From this viewpoint, the hydroxyl group content is preferably about 2 to 5 wt%.
- a component can be manufactured by various well-known methods. Hereinafter, an example of a production example of the component (A) is shown below.
- the trialkoxysilane (a1) (hereinafter also referred to as “component (a1)”), which is the starting material of the component (A), has a general formula: X 1 Si (OX 1 ) 3 (wherein X 1 is the same or Differently, it represents an alkyl group having 1 to 15 carbon atoms, a phenyl group, a benzyl group, a hydroxyl group or a halogen atom. Examples of the halogen atom include a fluorine atom and a chlorine atom. Examples of the alkyl group having 1 to 15 carbon atoms include those described above. X 1 does not contain the reactive functional group.
- component (a1) examples include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-hexyltri.
- methyltrimethoxysilane is preferable, and by using methyltrimethoxysilane, the reactivity between the component (A) and the component (B) is improved, and the desired balance of effects of the present invention, heat resistance, transparency, and The balance of void resistance is particularly good.
- the component (A) can be obtained by subjecting the component (a1) to a hydrolysis reaction and a condensation reaction.
- the conditions for the hydrolysis reaction are not particularly limited, and the reaction temperature is usually about 25 to 90 ° C., and the reaction time is usually about 30 minutes to 10 hours.
- the amount of water added to the reaction system is not particularly limited, and is usually in a range where [number of moles of water / number of moles of OX 1 group contained in component (a1)] is about 0.3 to 1.
- catalysts can be used in the hydrolysis reaction.
- specific examples of the catalyst include acidic catalysts such as formic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, phosphoric acid and cation exchange resin; sodium hydroxide, potassium hydroxide, calcium hydroxide, 1, Such as 8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, pyridine, etc.
- a basic catalyst is mentioned.
- the amount of the catalyst used is not particularly limited, and is usually about 0.001 to 1 part by mass with respect to 100 parts by mass of component (a1).
- solvents include hydrocarbon solvents such as benzene, toluene, xylene, n-hexane and n-heptane; alcohol solvents such as methanol, ethanol, n-propanol and iso-propanol; ethylene glycol dimethyl ether and diethylene glycol.
- hydrocarbon solvents such as benzene, toluene, xylene, n-hexane and n-heptane
- alcohol solvents such as methanol, ethanol, n-propanol and iso-propanol
- ethylene glycol dimethyl ether diethylene glycol.
- Ether solvents such as dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1,4-dioxane; ester solvents such as methyl acetate, ethyl acetate, butyl acetate; acetone, 2-butanone, methyl -Ketone solvents such as iso-butyl ketone; acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl 2-pyrrolidone, and the like.
- the hydrolyzate obtained by the hydrolysis reaction is further subjected to a condensation reaction, whereby a siloxane bond is generated between the hydroxyl groups or between the hydroxyl group and the remaining —OX 1 group, and the desired component (A) is obtained.
- the condensation reaction conditions are not particularly limited, and the reaction temperature is usually about 40 to 150 ° C., and the reaction time is usually about 1 to 12 hours.
- the condensation reaction can be carried out in the solvent.
- the composition of this invention is a solventless type, it is desirable to remove the said solvent from (A) component by various well-known means after a hydrolysis and a condensation reaction.
- the physical properties of the component (A) are not particularly limited.
- the softening point (softening point measured under the conditions defined in JIS K5903; hereinafter, the same applies when referred to as the softening point) is usually about 40 to 150 ° C.
- the temperature is preferably about 50 to 130 ° C, more preferably about 60 to 120 ° C.
- the weight average molecular weight is not particularly limited, and is usually about 2000 to 10000, preferably about 3000 to 7000.
- the weight average molecular weight of the component (A) is 2000 or more, volatilization or bleed out of the low molecular weight component when the composition according to the present invention is heat-cured is further suppressed.
- the weight average molecular weight of the component (A) is 10,000 or less, the compatibility of the composition of the present invention is further improved, and workability is further improved such that stringing is suppressed.
- the shape of the component (A) is not particularly limited, and may be a flake shape, a powder shape, a semi-solid shape, or the like.
- Examples of the commercially available component (A) include KR-220L and KR-220LP manufactured by Shin-Etsu Chemical Co., Ltd., YR3370 manufactured by Momentive Performance Materials Japan, and the like.
- Component (B) is trisiloxy represented by R 2 SiO 3/2 (wherein R 2 represents one selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, a phenyl group, and a benzyl group).
- the alkyl group having 1 to 15 carbon atoms, phenyl group and benzyl group constituting each R 2 are the same as those constituting R 1 , and none of them contains the reactive functional group.
- T B is similar to T A in that T1 structure [R 2 O—Si (R 2 ) (OR 2 ) —O—], T2 structure [— (R 2 ) Si (OR 2 ) (O —) — O-] and T3 structure [— (R 2 ) Si (O—) 2 —O—] can be subdivided, and the ratio thereof is not particularly limited. Each structure can be identified, for example, by measuring a 29 Si-NMR spectrum of the component (B).
- the proportion of T B occupying the components is not particularly limited. Considering the balance of the desired effect of the present invention, in particular, the compatibility of the composition of the present invention, handling properties and curability, and the balance of the strength, adhesion, crack resistance and void resistance of the cured product, (B) the proportion of T B occupying the components, usually about 65-100 mol%, preferably 95-100 mol%.
- the component (B) may contain other units (monosiloxy unit (M B ), disiloxy unit (D B ), or tetrasiloxy unit (Q B )) as long as it remains liquid at room temperature.
- the ratio of these other units is usually about 0 to 35 mol%, preferably 0 to 5 mol%.
- the structure of the component (B) can also be expressed by the following average unit formula.
- 0 ⁇ b ⁇ 3, 0 ⁇ x ′, 0 ⁇ y ′, and x ′ + y ′ 1.
- content of the hydroxyl group in (B) component is 0 wt% substantially.
- the content of —OR 2 can be determined based on, for example, 1 H-NMR spectrum, and is usually about 15 to 45 wt% with respect to the total amount of component (B).
- a component can be manufactured by various well-known methods. Hereafter, an example of the manufacture example of (B) component is shown below.
- the trialkoxysilane (b1) (hereinafter also referred to as “component (b1)”), which is one of the starting materials for the component (B), has a general formula: X 2 Si (OX 2 ) 3 (wherein X 2 Are the same or different and each represents an alkyl group having 1 to 15 carbon atoms, a phenyl group, a benzyl group, a hydroxyl group or a halogen atom. Examples of the halogen atom and the alkyl group having 1 to 15 carbon atoms include those described above.
- component (b1) As a component, what was mentioned as said (a1) component can be illustrated.
- methyltrimethoxysilane is preferable. By using methyltrimethoxysilane as the component (b1), the reactivity between the component (A) and the component (B) is further improved, and the desired effect balance of the present invention is maintained. Heat resistance, transparency and void resistance are further improved.
- component (b2) The starting material of the component (B), other features, as long as maintaining the liquid at room temperature (B) component (hereinafter also referred to as "component (b2)”.)
- component (b3) component M B units
- (b4) component Q tetraalkoxysilane giving the B units
- the component (b2) is represented by the general formula: (X 2 ) 2 Si (OX 2 ) 2 (wherein X 2 is the same as described above and may be the same or different). Specific examples thereof include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, and phenylmethylmethoxyethoxysilane.
- the component (b3) is represented by the general formula: (X 2 ) 3 SiOX 2 (wherein X 2 is the same as above and may be the same or different). Specific examples thereof include, for example, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, tri (n-propyl) methoxysilane, tri (isopropyl) methoxysilane, tri (n-propyl) ethoxysilane, tri (N-butyl) methoxysilane, tri (isobutyl) methoxysilane, tri (isobutyl) ethoxysilane, dimethyl tert-butylmethoxysilane, dimethylisobutylmethoxysilane, dimethylcyclopentylmethoxysilane, dimethylcyclohexylethoxysilane and the like.
- the component (b4) is represented by the general formula: Si (OX 2 ) 4 (wherein X 2 is the same as above and may be the same or different). Specific examples thereof include tetraalkoxysilanes such as tetraethoxysilane, tetraisopropoxysilane, tetra n-propoxysilane, tetra n-butoxysilane, tetramethoxysilane, and dimethoxydiethoxysilane.
- Component (B) is obtained by subjecting component (b1) and, if necessary, at least one selected from the group consisting of component (b2), component (b3) and component (b4) to a hydrolysis reaction and a condensation reaction. Can do.
- the conditions for the hydrolysis reaction are not particularly limited, the reaction temperature is usually about 25 to 90 ° C., and the reaction time is usually about 30 minutes to 10 hours.
- the amount of water to be added to the reaction system is not particularly limited, and [number of moles of water / [total number of moles of —OX 2 contained in components (b1) to (b4)] is about 0.1 to 1. It is a range.
- both the catalyst and the solvent used in the hydrolysis reaction of the component (a1) can be used.
- condensation reaction conditions are not particularly limited, and the reaction temperature is usually about 40 to 150 ° C., and the reaction time is usually about 1 to 12 hours.
- the condensation reaction can be carried out in the solvent.
- the condensation reaction type silicone composition of this invention is a solventless type, it is desirable to remove the said solvent from (B) component by various well-known means after a hydrolysis and a condensation reaction.
- the physical properties of the component (B) are not particularly limited.
- the viscosity is usually about 5 to 10000 mPa ⁇ s / 25 ° C., preferably about 5 to 5000 mPa ⁇ s / 25 ° C., more preferably 5 to 2000 mPa ⁇ s / 25 ° C. It is good to make it about.
- the composition of this invention is a thermosetting type, about a room temperature curable silicone composition, a viscosity may be measured at 23 degreeC. In that case, in one embodiment, it is preferably 501 to 10,000 mPa ⁇ s / 23 ° C. or higher.
- the weight average molecular weight of the component (B) is usually about 500 to 9000, preferably about 700 to 8000.
- the weight average molecular weight of the component (B) is 500 or more, volatilization or bleed out of the low molecular weight component when the composition of the present invention is heat-cured is further suppressed.
- the number average molecular weight of (B) component is 9000 or less, the compatibility of the composition of this invention becomes more favorable, and workability
- Examples of commercially available components (B) include MSE100 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., KC-89S and KR-500 manufactured by Shin-Etsu Chemical Co., Ltd., and MTMS-A manufactured by Tama Chemical Industry Co., Ltd. It is done.
- the blending ratio of the component (A) and the component (B) is not particularly limited. From the viewpoints of handling properties of the composition of the present invention, hardness, toughness and void resistance of the cured product of the present invention, the number of moles of hydroxyl groups (M OH ) contained in the component (A) and the component (A)
- the ratio (M OR / M OH ) to the total number of moles (M OR ) of —OR 1 contained and —OR 2 contained in component (B) is usually about 0.1 to 20, preferably about 5 to 20 More preferably, the component (A) and the component (B) are blended so as to be in the range of about 8 to 15.
- the ratio is 0.1 or more, the defoaming property at the time of curing the composition of the present invention is further improved, and the workability is further improved such that the stringing is less likely to occur when the composition is applied. It becomes good. Further, when the ratio is 20 or less, the adhesiveness of the composition of the present invention is further improved, and cracks or voids are hardly generated in the cured product.
- the mass ratio of the solid content of the component (A) and the component (B) is not particularly limited. From the viewpoints of handling properties of the composition of the present invention, compatibility and coating workability of the composition of the present invention, and hardness, toughness, and void resistance of the cured product, the solid content mass ratio is the component (A).
- the component (B) is usually in the range of about 30 to 120 parts by mass, preferably about 40 to 110 parts by mass with respect to 100 parts by mass.
- condensation reaction catalysts include compounds of metals such as magnesium, aluminum, tin, zinc, iron, cobalt, nickel, zirconium, cerium, and titanium.
- the color tone or transparency of the cured product of the present invention one selected from the group consisting of a titanium compound, a tin compound, a zinc compound and a zirconium compound is preferable. Particularly preferred are tin compounds and / or zirconium compounds.
- titanium compound examples include titanium diisopropoxy bis (ethyl acetoacetate), tetraethoxy titanium, tetra n-propoxy titanium, tetra n-butoxy titanium, diisopropoxy bis (ethyl acetoacetate) titanium, diisopropoxy.
- -Bis methyl acetoacetate) titanium, diisopropoxy-bis (acetylacetone) titanium, di-n-butoxy-bis (ethyl acetoacetate) titanium, dimethoxy-bis (ethyl acetoacetate) titanium and the like.
- tin compound examples include di-n-butyltin methoxide, di-n-butyltin diacetate, di-n-butyltin dioctate, di-n-butyltin dilaurate, di-n-octyltin diacetate, and di-n-octyltin maleate.
- di-n-butyltin oxyacetate, di-n-butyltin oxyoctylate, di-n-butyltin oxylaurate, di-n-butyltin bismethylmalate, di-n-butyltin oxyoleate, or n-dibutyltin malate polymer examples thereof include di-n-octyltin maleate polymer, mono-n-butyltin tris (2-ethylhexanoate), and di-n-butyltin bis (acetylacetonato).
- Examples of the zinc compound include zinc acetate, zinc acetyl acetate, zinc 2-ethylhexanoate, zinc octylate, zinc neodecanoate, zinc laurate, zinc stearate, zinc naphthenate, zinc benzoate, p-tert- Examples include zinc butylbenzoate, zinc salicylate, zinc (meth) acrylate, zinc acetylacetonate, and 2,2,6,6-tetramethyl-3,5-heptanedionate zinc.
- zirconium compound examples include tetraalkyl zirconate, zirconium trialkoxy mononaphthate, zirconium trialkoxy monocyclopropane carboxylate, zirconium trialkoxy cyclobutane carboxylate, zirconium trialkoxy monocyclopentane carboxylate, zirconium trialkoxy monocyclohexane.
- examples thereof include carboxylate and zirconium trialkoxymonoadamantanecarboxylate.
- alkyl examples include linear or branched alkyl having 1 to 18 carbon atoms
- preferred examples of alkoxy include linear or branched alkyloxy having 1 to 18 carbon atoms. Is mentioned.
- the amount of component (C) used is not particularly limited. From the viewpoints of storage stability and curability of the composition of the present invention, and yellowing resistance of the cured product, the amount of component (C) used is based on a total of 100 parts by weight of component (A) and component (B). The range is usually about 0.001 to 10 parts by mass, preferably about 0.01 to 5 parts by mass, and more preferably about 0.1 to 1 part by mass. In the composition of the present invention, the desired effect can be achieved even when the amount of component (C) used is less than 0.1 parts by mass, that is, 0.001 to 0.099 parts by mass. it can.
- the composition of the present invention can contain various known (D) inorganic fillers (hereinafter also referred to as “component (D)”), for example, for the purpose of improving the crack resistance of the cured product of the present invention.
- component (D) include silica (colloidal silica, fumed silica, etc.), barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, yttrium oxide, and the like. Among these, silica is preferable, and fumed silica is particularly preferable.
- the average primary particle diameter of (D) component is not specifically limited.
- the average primary particle size of component (D) is Usually, it is 100 ⁇ m or less, preferably about 5 to 100 nm, more preferably about 5 to 30 nm.
- the amount of component (D) used is not particularly limited. From the viewpoints of coating workability and thixotropy of the composition of the present invention, transparency of the cured product, crack resistance, and the like, the amount of component (D) used is a total of 100 masses of component (A) and component (B). The amount is usually in the range of about 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to parts.
- the composition of the present invention may further include a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive polymer, a conductive filler, a release agent, if necessary.
- Additives such as molds, surface treatment agents, viscosity modifiers, and silane coupling agents can be blended.
- the composition of this invention is a solvent-free type, in one embodiment, the composition of this invention does not contain a solvent.
- the method for producing the composition of the present invention is not particularly limited. Usually, the solid component (A) and component (C) are added to the liquid component (B), and if necessary, the component (D) and additives are further blended, and then they are homogenized.
- the composition of the present invention can be obtained by mixing up to. Mixing can be performed by a known means.
- the physical properties of the composition thus obtained are not particularly limited.
- the viscosity is usually about 5 to 1000000 mPa ⁇ s / 25 ° C., preferably about 500 to 500000 mPa ⁇ s / 25 ° C., more preferably 1000 to 200000 mPa -It is about s / 25 degreeC.
- the cured product of the present invention is a condensation reaction product of the composition of the present invention.
- the curing conditions are not particularly limited, and may be set as appropriate according to the application.
- the curing temperature is usually about 25 to 200 ° C., and the curing time is usually about 30 minutes to 5 hours.
- the weight average molecular weight is a conversion value of polystyrene standard substance by gel permeation chromatography method (use apparatus: HLC-8220 manufactured by Totoso Co., Ltd., column: TSKgel ⁇ -M manufactured by Tosoh Corporation, developing solvent: tetrahydrofuran). It is.
- the shift value of 1 H-NMR is a measured value obtained by using 400-MR (400 MHz, CDCl 3 ) manufactured by VARIAN.
- the viscosity is a measured value obtained using an E-type viscometer (product name “RE-80U”, manufactured by Toki Sangyo Co., Ltd., rotor No. 1 ° 34 ′ ⁇ R24, rotor rotational speed 5 rpm). .
- Component (B-1) had a viscosity of 20 mPa ⁇ s / 25 ° C. and a weight average molecular weight of 900.
- the content calculated from the peak intensity of the residual methoxy group ( ⁇ 3.2-3.8) measured by 1 H-NMR (hereinafter abbreviated as “residual methoxy group content”) was about 32 wt%. It was.
- Example 2 A homogeneous and transparent condensation reaction type silicone composition 2 (8000 mPa ⁇ s / 25 ° C.) was obtained in the same manner as in Example 1 except that 50 parts of the component (B-2) were used as the component (B).
- Example 3 A homogeneous and transparent condensation reaction type silicone composition 3 (5000 mPa ⁇ s / 25 ° C.) was obtained in the same manner as in Example 1 except that 50 parts of the component (B-3) were used as the component (B).
- Example 4 A homogeneous and transparent condensation reaction type silicone composition 4 (6000 mPa ⁇ s / 25 ° C.) was obtained in the same manner as in Example 1 except that 0.1 part of di-n-octyltin was used as the component (C).
- Example 5 As in Example 1, except that 0.1 part of titanium chelate (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-710 63% solution of titanium diisopropoxybis (ethyl acetoacetate) was used, A transparent condensation reaction type silicone composition 5 (6000 mPa ⁇ s / 25 ° C.) was obtained.
- Example 6 A homogeneous and transparent condensation reaction type silicone composition 6 (1000 mPa ⁇ s / 25 ° C.) was obtained in the same manner as in Example 1 except that the component (D) was not used.
- Example 9 60 parts of Z-6018 as component (A) and 40 parts of X-40-9227 as component (B) were mixed well at 130 ° C. to obtain a homogeneous colorless and transparent liquid. Next, 3.0 parts of ZC-700 as component (C) was added thereto and mixed well at room temperature to obtain a homogeneous and transparent die bonding agent 9 (4100 mPa ⁇ s / 25 ° C.).
- Comparative Example 2 100 parts of component, 0.3 part of zirconium chelate, and 5.5 parts of AEROSIL RX200 are mixed well at room temperature to obtain a homogeneous and transparent condensation reaction type silicone composition (4000 mPa ⁇ s / 25 ° C.). Obtained.
- Comparative Example 3 (A) 50 parts of KR220L as component, (B) component (B-1) 50 parts, and (D) component AEROSIL RX200 5.5 parts are mixed well at room temperature, and homogeneous and transparent condensation reaction Type silicone composition C (6000 mPa ⁇ s / 25 ° C.) was obtained.
- Mass reduction rate after heating (%) 100 ⁇ (mass of cured product 1 / mass of condensation reaction type silicone composition 1) ⁇ 100
- Mass reduction rate after heating (%) 100 ⁇ (mass of cured product 2 / mass of cured product 1) ⁇ 100
- Shear strength A silicon chip (2 mm ⁇ 2 mm ⁇ 1 mm) was mounted on an aluminum plate using the condensation reaction type silicone composition 1 obtained in Example 1, and heated in a drying furnace at 120 ° C. for 1 hour. Then, it was further heated at 150 ° C. for 3 hours. Next, the shear strength of the adhesive layer (cured product) was measured at room temperature (25 ° C.) using a commercially available bond tester (product name “DAGE-SERIES-4000PXY”, manufactured by Dage), and evaluated according to the following criteria. .
- the condensation reaction type silicone composition of the present invention is excellent in storage stability and initial curability, and the obtained cured product has heat resistance, transparency, crack resistance, and void resistance. It was found that the film was excellent in bending strength and shear strength.
- the composition is a condensation reaction type composition, and it should be noted that the void resistance of the cured product is good even though water or a low molecular alcohol is by-produced in the reaction process. .
- condensation reaction type silicone composition of the present invention has such many advantages, it can be used for a wide range of applications such as adhesives, sealants, coating agents, sealants and paints.
- the composition joins the same or different metals such as silicon, aluminum, iron, gold, silver, and copper. It can be used as a case material for metal adhesives and resistors.
- the composition is also used as a moisture-proof coating agent for power module and temperature sensor sealants, electronic substrates and the like. be able to.
- the composition is bonded to a support such as a glass or plastic lens or a transparent window. It can also be used as an optical adhesive, a packaging material for optical elements such as LEDs, a sealant for optical semiconductor elements including UV-LEDs, lasers, and light receiving elements, or a dam material.
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Abstract
Description
製造例1
撹拌機、冷却管、温度計及び窒素導入管を備える反応装置に、メチルトリメトキシシラン136.2部及び水10.8部を仕込み、反応系を40℃に昇温した。次いでギ酸0.14部を仕込み、加水分解反応を開始した。反応開始後、反応熱により反応系の温度は62℃に達したが、その後40℃に降温したため、同温度で30分間保持した。その後、副生するメタノールを系外に除去しながら3時間かけて反応系を120℃に昇温した。次いで、同温度で1時間、縮合反応を行うことにより、CH3SiO3/2で示されるトリシロキシ単位(x=1、y=0)を有する液状のポリシルセスキオキサン(B-1)を得た。(B-1)成分の粘度は20mPa・s/25℃、重量平均分子量は900であった。また、1H-NMRで測定された残存メトキシ基(δ3.2-3.8)のピーク強度より算出した含有量(以下、「残存メトキシ基含有量」と略す。)は約32wt%であった。 <Production of component (B)>
Production Example 1
A reaction apparatus equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen introduction pipe was charged with 136.2 parts of methyltrimethoxysilane and 10.8 parts of water, and the reaction system was heated to 40 ° C. Next, 0.14 part of formic acid was charged to start the hydrolysis reaction. After the start of the reaction, the temperature of the reaction system reached 62 ° C. due to the heat of reaction. Thereafter, the reaction system was heated to 120 ° C. over 3 hours while removing by-produced methanol out of the system. Next, by performing a condensation reaction at the same temperature for 1 hour, liquid polysilsesquioxane (B-1) having a trisiloxy unit (x = 1, y = 0) represented by CH 3 SiO 3/2 is obtained. Obtained. Component (B-1) had a viscosity of 20 mPa · s / 25 ° C. and a weight average molecular weight of 900. The content calculated from the peak intensity of the residual methoxy group (δ3.2-3.8) measured by 1 H-NMR (hereinafter abbreviated as “residual methoxy group content”) was about 32 wt%. It was.
水の仕込み量を16.2部にした以外は製造例1と同様にして、CH3SiO3/2で示されるトリシロキシ単位(x=1、y=0)を有する液状のポリシルセスキオキサン(B-2)を得た。(B-2)成分の粘度は350mPa・s/25℃、重量平均分子量2500、残存メトキシ基含有量は約24wt%であり、残存水酸基のピークは認められなかった。 Production Example 2
A liquid polysilsesquioxane having a trisiloxy unit (x = 1, y = 0) represented by CH 3 SiO 3/2 in the same manner as in Production Example 1 except that the amount of water charged was 16.2 parts. (B-2) was obtained. Component (B-2) had a viscosity of 350 mPa · s / 25 ° C., a weight average molecular weight of 2500, a residual methoxy group content of about 24 wt%, and no residual hydroxyl peak was observed.
メチルトリメトキシシラン136.2部、ジメチルジメトキシシラン51.5部、及び水27.8部にした以外は製造例1と同様にして、(CH3)1.3SiO1.35を平均シロキシ単位(x’=0.7、y’=0.3、b=2)として有するポリシルセスキオキサン(B-3)を得た。(B-3)成分の粘度は1600mPa・s/25℃、重量平均分子量7000、残存メトキシ基含有量は約19wt%であり、残存水酸基のピークは認められなかった。 Production Example 3
In the same manner as in Production Example 1 except that 136.2 parts of methyltrimethoxysilane, 51.5 parts of dimethyldimethoxysilane and 27.8 parts of water were used, (CH 3 ) 1.3 SiO 1.35 was converted into an average siloxy unit. Polysilsesquioxane (B-3) having (x ′ = 0.7, y ′ = 0.3, b = 2) was obtained. Component (B-3) had a viscosity of 1600 mPa · s / 25 ° C., a weight average molecular weight of 7000, a residual methoxy group content of about 19 wt%, and no residual hydroxyl peak was observed.
実施例1
(A)成分として室温で固体状のポリシルセスキオキサン(商品名「KR220L」、信越化学工業(株)製、フレーク状、R1=メチル基、シラノール基由来水酸基含有量3wt%、TA単位100モル%、軟化点67℃)50部と、(B)成分として(B-1)成分50部と、(C)成分としてジルコニウムキレート(マツモトファインケミカル株式会社製、ZC-700(ジルコニウムテトラアセチルアセトネート20%溶液))0.3部と、(D)成分として市販のヒュームドシリカ(商品名「AEROSIL RX200」、日本アエロジル(株)製、平均一次粒子径12nm)5.5部とを室温でよく混合し、均質で透明な縮合反応型シリコーン組成物1(6000mPa・s/25℃)を得た。 <Production of condensation reaction type silicone composition>
Example 1
Solid polysilsesquioxane at room temperature as the component (A) (trade name "KR220L", manufactured by Shin-Etsu Chemical Co., Ltd., flaky, R 1 = methyl group, a silanol group derived from the hydroxyl group content of 3 wt%, T A Unit: 100 mol%, softening point 67 ° C.) 50 parts, (B) component (B-1) component 50 parts, (C) component zirconium chelate (manufactured by Matsumoto Fine Chemical Co., Ltd., ZC-700 (zirconium tetraacetyl) Acetonate 20% solution)) 0.3 parts and (D) component commercially available fumed silica (trade name “AEROSIL RX200”, Nippon Aerosil Co., Ltd., average primary particle size 12 nm) 5.5 parts The mixture was thoroughly mixed at room temperature to obtain a homogeneous and transparent condensation reaction type silicone composition 1 (6000 mPa · s / 25 ° C.).
(B)成分として前記(B-2)成分50部を使用した以外は実施例1と同様にして、均質で透明な縮合反応型シリコーン組成物2(8000mPa・s/25℃)を得た。 Example 2
A homogeneous and transparent condensation reaction type silicone composition 2 (8000 mPa · s / 25 ° C.) was obtained in the same manner as in Example 1 except that 50 parts of the component (B-2) were used as the component (B).
(B)成分として前記(B-3)成分50部を使用した以外は実施例1と同様にして、均質で透明な縮合反応型シリコーン組成物3(5000mPa・s/25℃)を得た。 Example 3
A homogeneous and transparent condensation reaction type silicone composition 3 (5000 mPa · s / 25 ° C.) was obtained in the same manner as in Example 1 except that 50 parts of the component (B-3) were used as the component (B).
(C)成分としてジn-オクチル錫0.1部を使用した以外は実施例1と同様にして、均質で透明な縮合反応型シリコーン組成物4(6000mPa・s/25℃)を得た。 Example 4
A homogeneous and transparent condensation reaction type silicone composition 4 (6000 mPa · s / 25 ° C.) was obtained in the same manner as in Example 1 except that 0.1 part of di-n-octyltin was used as the component (C).
(C)成分としてチタンキレート(マツモトファインケミカル株式会社製、TC-710 チタンジイソプロポキシビス(エチルアセトアセテート)63%溶液)0.1部を使用した以外は実施例1と同様にして、均質で透明な縮合反応型シリコーン組成物5(6000mPa・s/25℃)を得た。 Example 5
As in Example 1, except that 0.1 part of titanium chelate (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-710 63% solution of titanium diisopropoxybis (ethyl acetoacetate)) was used, A transparent condensation reaction type silicone composition 5 (6000 mPa · s / 25 ° C.) was obtained.
(D)成分を使用しなかった以外は実施例1と同様にして、均質で透明な縮合反応型シリコーン組成物6(1000mPa・s/25℃)を得た。 Example 6
A homogeneous and transparent condensation reaction type silicone composition 6 (1000 mPa · s / 25 ° C.) was obtained in the same manner as in Example 1 except that the component (D) was not used.
(A)成分として室温で固体状のポリシルセスキオキサン(商品名「Z-6018」、Dow Corning Corp.製、フレーク状、R1=フェニル基およびn-プロピル基、シラノール基由来水酸基含有量6wt%、TA単位100モル%、軟化点40℃)40部と、(B)成分として室温で液体状のポリシルセスキオキサン(商品名「MSE-100」、Wacker Chemie AG製、R1=メチル基、粘度30mPa・s/25℃、アルコキシ基含有量32wt%)60部とを130℃でよく混合し、均質な無色透明の液体を得た。次いでそこへ(C)成分としてZC-700を0.3部加えて、室温でよく混合し、均質で透明なダイボンディング剤7(2300mPa・s/25℃)を得た。 Example 7
Polysilsesquioxane (trade name “Z-6018”, manufactured by Dow Corning Corp., flake form, R 1 = phenyl group and n-propyl group, silanol group-derived hydroxyl group content as a component (A) solid at room temperature 6 wt%, T a unit 100 mol%, and the softening point 40 ° C.) 40 parts, (B) liquid polysilsesquioxane at room temperature as the component (trade name "MSE-100", Wacker Chemie AG made, R 1 = Methyl group, viscosity 30 mPa · s / 25 ° C., alkoxy group content 32 wt%) 60 parts were mixed well at 130 ° C. to obtain a homogeneous colorless and transparent liquid. Next, 0.3 part of ZC-700 as component (C) was added thereto and mixed well at room temperature to obtain a homogeneous and transparent die bonding agent 7 (2300 mPa · s / 25 ° C.).
(A)成分としてKR-220Lを50部と、(B)成分として室温で液体状のポリシルセスキオキサン(商品名「X-40-9227」、信越化学工業(株)製、R1=メチル基およびフェニル基、粘度20mPa・s/25℃、アルコキシ基含有量15wt%)50部とを130℃でよく混合し、均質な無色透明の液体を得た。次いでそこへ、(C)成分としてZC-700を0.8部、及び(D)成分としてAEROSIL RX200を3.0部加えて、室温でよく混合し、均質で透明なダイボンディング剤8(8000mPa・s/25℃)を得た。 Example 8
50 parts of KR-220L as component (A) and polysilsesquioxane (trade name “X-40-9227”, manufactured by Shin-Etsu Chemical Co., Ltd.), R 1 = 50 parts of methyl group and phenyl group, viscosity 20 mPa · s / 25 ° C., alkoxy group content 15 wt%) were thoroughly mixed at 130 ° C. to obtain a homogeneous colorless and transparent liquid. Next, 0.8 parts of ZC-700 as the component (C) and 3.0 parts of AEROSIL RX200 as the component (D) are added thereto and mixed well at room temperature to obtain a homogeneous and transparent die bonding agent 8 (8000 mPa -S / 25 degreeC) was obtained.
(A)成分としてZ-6018を60部と、(B)成分としてX-40-9227を40部とを130℃でよく混合し、均質な無色透明の液体を得た。次いでそこへ、(C)成分としてZC-700を3.0部加えて、室温でよく混合し、均質で透明なダイボンディング剤9(4100mPa・s/25℃)を得た。 Example 9
60 parts of Z-6018 as component (A) and 40 parts of X-40-9227 as component (B) were mixed well at 130 ° C. to obtain a homogeneous colorless and transparent liquid. Next, 3.0 parts of ZC-700 as component (C) was added thereto and mixed well at room temperature to obtain a homogeneous and transparent die bonding agent 9 (4100 mPa · s / 25 ° C.).
(A)成分として室温で固体状のポリシルセスキオキサン(商品名「SILRES MK」、旭化成ワッカーシリコーン(株)製、R1=メチル基、シラノール基由来水酸基含有量0wt%)50部と、前記(B-1)成分50部と、ジルコニウムキレート(マツモトファインケミカル株式会社製、ZC-700(ジルコニウムテトラアセチルアセトネート20%溶液))0.3部と、AEROSIL RX200 5.5部とを室温でよく混合し、均質で透明な縮合反応型シリコーン組成物イ(5000mPa・s/25℃)を得た。 Comparative Example 1
(A) 50 parts of polysilsesquioxane (trade name “SILRES MK” manufactured by Asahi Kasei Wacker Silicone Co., Ltd., R 1 = methyl group, silanol group-derived hydroxyl group content 0 wt%) solid at room temperature, 50 parts of the component (B-1), 0.3 part of zirconium chelate (manufactured by Matsumoto Fine Chemical Co., Ltd., ZC-700 (zirconium tetraacetylacetonate 20% solution)) and 5.5 parts of AEROSIL RX200 at room temperature The resulting mixture was mixed well to obtain a homogeneous and transparent condensation reaction type silicone composition (5000 mPa · s / 25 ° C.).
(B-1)成分100部、ジルコニウムキレート0.3部、及びAEROSIL RX200 5.5部を室温でよく混合し、均質で透明な縮合反応型シリコーン組成物ロ(4000mPa・s/25℃)を得た。 Comparative Example 2
(B-1) 100 parts of component, 0.3 part of zirconium chelate, and 5.5 parts of AEROSIL RX200 are mixed well at room temperature to obtain a homogeneous and transparent condensation reaction type silicone composition (4000 mPa · s / 25 ° C.). Obtained.
(A)成分としてKR220L 50部と、(B)成分として(B-1)成分50部と、(D)成分としてAEROSIL RX200 5.5部とを室温でよく混合し、均質で透明な縮合反応型シリコーン組成物ハ(6000mPa・s/25℃)を得た。 Comparative Example 3
(A) 50 parts of KR220L as component, (B) component (B-1) 50 parts, and (D) component AEROSIL RX200 5.5 parts are mixed well at room temperature, and homogeneous and transparent condensation reaction Type silicone composition C (6000 mPa · s / 25 ° C.) was obtained.
実施例1で得られた縮合反応型シリコーン組成物1を、テフロン(登録商標)コーティングされた円形金属枠(直径5cm、高さ2mm)に注入し、120℃の乾燥炉で1時間硬化させたのち、150℃の乾燥炉で3時間硬化させることにより、硬化物1(試験片)を作製した。 <Production 1 of cured product>
The condensation reaction type silicone composition 1 obtained in Example 1 was poured into a Teflon (registered trademark) -coated circular metal frame (diameter: 5 cm, height: 2 mm) and cured in a drying furnace at 120 ° C. for 1 hour. After that, the cured product 1 (test piece) was produced by curing in a drying furnace at 150 ° C. for 3 hours.
上記縮合反応型シリコーン組成物1を、25±1℃、50±10%RHの条件で静置し、以下の基準でポットライフを評価した。
5:粘度が初期値の125%以上になるまでの時間が48時間以上
3:粘度が初期値の125%以上になるまでの時間が12時間以上48時間未満
1:粘度が初期値の125%以上になるまでの時間が12時間未満 (1) Storage stability The said condensation reaction type silicone composition 1 was left still on 25 +/- 1 degreeC and 50 +/- 10% RH conditions, and pot life was evaluated on the following references | standards.
5: Time until viscosity reaches 125% or more of initial value is 48 hours or more 3: Time until viscosity becomes 125% or more of initial value is 12 hours or more and less than 48 hours 1: Viscosity is 125% of initial value Less than 12 hours
上記硬化物1の硬度を、高分子計器(株)製のショア硬度計D型を用いて測定することにより、実施例1に係る縮合反応型シリコーン組成物1の初期硬化性を以下の基準で評価した。 (2) Initial Curability Initial hardness of the condensation reaction type silicone composition 1 according to Example 1 by measuring the hardness of the cured product 1 using a Shore hardness meter D type manufactured by Kobunshi Keiki Co., Ltd. Sex was evaluated according to the following criteria.
3:20以上40未満
1:20未満 5:40 or more, 3:20 or more, but less than 40, but less than 1:20
<初期耐熱性>
上記硬化物1の質量減少率を下記計算式に基づいて計算し、その以下に示す基準で初期耐熱性を再評価した。 (3) Heat resistance <Initial heat resistance>
The mass reduction rate of the cured product 1 was calculated based on the following formula, and the initial heat resistance was re-evaluated based on the criteria shown below.
3:15%以上25%未満
1:25%以上 5: Less than 15% 3: 15% or more and less than 25% 1: 25% or more
上記硬化物1を、更に200℃の乾燥炉で1000時間加熱することにより硬化物2を得た。次いで、その質量減少率を下記計算式に基づいて計算し、以下の基準で耐熱性を再評価した。 <Heat resistance after heating>
The cured product 1 was further heated in a drying furnace at 200 ° C. for 1000 hours to obtain a cured product 2. Subsequently, the mass reduction rate was calculated based on the following formula, and the heat resistance was re-evaluated according to the following criteria.
3:5%以上7.5%未満
1:7.5%以上 5: Less than 5% 3: 5% or more Less than 7.5% 1: 7.5% or more
上記硬化物1の波長400nmにおける平行線透過率を、(株)島津製作所製分光光度計 UV-MINI-1240を用いて測定し、以下の基準で透明性を評価した。 (4) Transparency The parallel line transmittance at a wavelength of 400 nm of the cured product 1 was measured using a spectrophotometer UV-MINI-1240 manufactured by Shimadzu Corporation, and the transparency was evaluated according to the following criteria.
3:65%以上75%未満
1:65%未満 5: 75% or more 3: 65% or more and less than 75% 1: less than 65%
上記硬化物1について、耐クラック性を以下の基準で目視評価した。 (5) Crack resistance About the said hardened | cured material 1, the crack resistance was visually evaluated on the following references | standards.
1:クラックあり 5: No crack 1: Crack present
上記硬化物1について、耐ボイド性を以下の基準で目視評価した。
5:気泡なし
1:気泡あり (6) Void resistance About the said hardened | cured material 1, the void resistance was visually evaluated on the following references | standards.
5: No air bubbles 1: Air bubbles
上記硬化物1の曲げ強度を、(株)島津製作所製のオートグラフAGS-10kNDを用いて測定し、柔軟性と強度とのバランスを以下の基準で評価した。 (7) Bending strength The bending strength of the cured product 1 was measured using an autograph AGS-10kND manufactured by Shimadzu Corporation, and the balance between flexibility and strength was evaluated according to the following criteria.
3:10MPa以上20MPa未満
1:10MPa未満 5: 20 MPa or more 3: 10 MPa or more and less than 20 MPa 1: less than 10 MPa
実施例1で得られた縮合反応型シリコーン組成物1を用いてシリコンチップ(2mm×2mm×1mm)をアルミニウム板にマウントし、乾燥炉で120℃、1時間の条件で加熱した後、更に150℃、3時間の条件で加熱した。次いで、接着層(硬化物)のせん断強度を、市販のボンドテスター(製品名「DAGE-SERIES-4000PXY)、Dage社製)を用いて室温(25℃)で測定し、以下の基準で評価した。 (8) Shear strength A silicon chip (2 mm × 2 mm × 1 mm) was mounted on an aluminum plate using the condensation reaction type silicone composition 1 obtained in Example 1, and heated in a drying furnace at 120 ° C. for 1 hour. Then, it was further heated at 150 ° C. for 3 hours. Next, the shear strength of the adhesive layer (cured product) was measured at room temperature (25 ° C.) using a commercially available bond tester (product name “DAGE-SERIES-4000PXY”, manufactured by Dage), and evaluated according to the following criteria. .
3:15N以上30N未満
1:15N未満 5: 30N or more 3: 15N or more and less than 30N 1: 15N or less
表2で示すように、本発明の縮合反応型シリコーン組成物は、保存安定性及び初期硬化性に優れており、得られた硬化物は、耐熱性、透明性、耐クラック性、耐ボイド性、曲げ強度及びせん断強度において優れることが判った。特に、該組成物は、縮合反応型組成物であって反応過程で水又は低分子アルコールが副生するにも関わらず、その硬化物の耐ボイド性が良好である点は特筆すべきである。 (Industrial applicability)
As shown in Table 2, the condensation reaction type silicone composition of the present invention is excellent in storage stability and initial curability, and the obtained cured product has heat resistance, transparency, crack resistance, and void resistance. It was found that the film was excellent in bending strength and shear strength. In particular, the composition is a condensation reaction type composition, and it should be noted that the void resistance of the cured product is good even though water or a low molecular alcohol is by-produced in the reaction process. .
Claims (5)
- (A)R1SiO3/2(式中、R1は、炭素数1~15のアルキル基、フェニル基及びベンジル基からなる群より選ばれる一種を示す。)で表されるトリシロキシ単位(TA)を含み、かつ水酸基を有する、室温で固体状のポリシルセスキオキサンと、
(B)R2SiO3/2(式中、R2は、炭素数1~15のアルキル基、フェニル基及びベンジル基からなる群より選ばれる一種を示す。)で表されるトリシロキシ単位(TB)を含み、かつ-OR2(式中、R2は、炭素数1~15のアルキル基、フェニル基及びベンジル基からなる群より選ばれる一種を示す。)を有する、室温で液状のポリシルセスキオキサンと、
(C)縮合反応触媒と、
を含有する、縮合反応型シリコーン組成物。 (A) A trisiloxy unit represented by R 1 SiO 3/2 (wherein R 1 represents one selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, a phenyl group and a benzyl group) (T A ) and a polysilsesquioxane solid at room temperature having a hydroxyl group,
(B) a trisiloxy unit represented by R 2 SiO 3/2 (wherein R 2 is one selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, a phenyl group and a benzyl group) B )) and a —OR 2 (wherein R 2 represents one selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, a phenyl group and a benzyl group) With Rusesquioxane,
(C) a condensation reaction catalyst;
Condensation reaction type silicone composition containing - (A)成分の軟化点が40~150℃である、請求項1に記載の縮合反応型シリコーン組成物。 The condensation reaction type silicone composition according to claim 1, wherein the softening point of the component (A) is 40 to 150 ° C.
- (B)成分の粘度が5~10000mPa・s/25℃である、請求項1又は2に記載の縮合反応型シリコーン組成物。 The condensation reaction type silicone composition according to claim 1 or 2, wherein the component (B) has a viscosity of 5 to 10,000 mPa · s / 25 ° C.
- 更に(D)無機フィラーを含有する、請求項1~3のいずれか1項に記載の縮合反応型シリコーン組成物。 The condensation reaction type silicone composition according to any one of claims 1 to 3, further comprising (D) an inorganic filler.
- 請求項1~4のいずれか1項に記載の縮合反応型シリコーン組成物の硬化物。
The cured product of the condensation reaction type silicone composition according to any one of claims 1 to 4.
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JP2020045387A (en) * | 2018-09-14 | 2020-03-26 | スリーエム イノベイティブ プロパティズ カンパニー | Curable composition, cured product, and optical member |
JP2021172707A (en) * | 2020-04-22 | 2021-11-01 | 信越化学工業株式会社 | Organopolysiloxane, composition containing the organopolysiloxane, production method therefor, coating agent, and coated article |
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