TWI663215B - Condensation reaction type siloxane composition and hardened material - Google Patents

Abstract

An object of the present invention is to provide a condensation-reactive siloxane composition which can provide a hardened product which is excellent in initial hardening properties, has good adhesion, and has excellent crack resistance, bubble resistance, and heat resistance. The present invention is a condensation reaction type silicone composition containing: (A) a polysilsesquioxane which is solid at room temperature, and contains polysilsesquioxane selected from R ¹ SiO _3/2 (where R ¹ It is a trisilyloxy unit (T _A ) represented by one of the group consisting of an alkyl group having 1 to 15 carbon atoms, a phenyl group, and a benzyl group, and has a hydroxyl group; (B) at room temperature is Liquid polysilsesquioxane containing R ² SiO _3/2 (where R ² represents a group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, a phenyl group, and a benzyl group. (One) is a trisilyloxy unit (T _B ), and has -OR ² (wherein R ² is selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, a phenyl group, and a benzyl group One); and (C) a condensation reaction catalyst.

Description

Condensation reaction type siloxane composition and hardened material

The invention relates to a condensation reaction type siloxane composition and a cured product.

The silicone resin is generally a hardened product obtained by subjecting the silicone (polyorganosiloxane) to a curing reaction, and the curing reaction is known as a condensation reaction and an addition reaction.

The addition reaction is a reaction in which a silanol having an alkoxysilyl group such as Si-CH = CH ₂ and a silanol having a hydrosilyl group (Si-H) undergo hydrogen silylation in the presence of a platinum-based catalyst. Even at room temperature, the addition reaction can produce a target hardened product in a short period of time, which is advantageous in terms of productivity. However, the addition reaction has a problem that the hardening is likely to be hindered due to the deactivation of the platinum catalyst and the humidity of the use environment.

The condensation reaction is a dehydration condensation and / or dealcoholization of an organic oxy group such as an alkoxy group (Si-OR) or a silanol group (Si-OH) in the presence of an organic tin-based catalyst or the like. Condensation reaction. The problem of hardening hindering the condensation reaction is small, and since platinum catalyst is not used, there is also a cost advantage. However, compared with the addition reaction, the condensation reaction has less initial hardenability and requires higher temperature and time to achieve full hardening.

Condensation reaction type siloxane compositions have been conventionally supplied to applications such as sealants and adhesives for optical semiconductors. For example, Patent Document 1 describes a silicone composition containing an acrylic resin, a condensation-reactive silicone compound and / or a condensation-reactive silicone compound, and a hardening accelerator. In addition, Cited Document 1 describes that the siloxane compound can be used as a transparent sealant and an adhesive for a light emitting diode device.

On the other hand, in Patent Document 2, it is pointed out that, in the case of a conventional condensation-reactive siloxane composition hardened product, when it is used as an optical semiconductor sealant, the adhesion to a reflective plate or a metal electrode is insufficient. . One reason is considered to be that the strength and flexibility of the adhesive layer (hardened material) cannot be balanced.

In order to improve the flexibility of the cured product, there have been attempts to introduce a disiloxy unit represented by (CH ₃ ) ₂ SiO _2/2 into the main chain of the siloxane polymer. However, as the introduction amount of the above-mentioned disiloxy unit increases, it is unavoidable that the strength and the adhesiveness are lowered. On the other hand, in order to increase the strength of the cured product, there have been attempts to introduce a _trisiloxy unit represented by, for example, CH ₃ SiO _3/2 . However, as the amount of the trisiloxyoxy unit introduced increases, cracks in the hardened material cannot be avoided, and in this case, the adhesiveness is also reduced. As such, strength and flexibility are usually mutually compensated, and very strong adhesion has not yet been achieved.

In addition, the condensation reaction type siloxane composition releases moisture or a low-molecular-weight alcohol during the reaction. Therefore, the cured product may generate fine voids or cracks. These defects reduce the mechanical strength of the cured product and also impair the appearance. Therefore, it is considered to be a problem especially for the use of adhesives and sealants for optical semiconductors.

In addition, when an optical semiconductor is used, a high temperature resistance is also required for a cured product as a sealing material due to a relationship between an increased element temperature. In this regard, the condensation reaction type siloxane composition described in Patent Document 1 contains an acrylic resin as a main component and has insufficient heat resistance. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-101093 [Patent Document 2] Japanese Patent Laid-Open No. 2015-163661

Problem to be Solved by the Invention The object of the present invention is to provide a condensation-reactive siloxane composition which can produce excellent initial hardening properties, has very strong adhesion, and has crack resistance, bubble resistance, and heat resistance. Good hardened material. Means to solve the problem

The condensation reaction type siloxane composition that solves the aforementioned problems must reduce the amount of low-molecular components such as water, alcohol, and the like and other volatile components of the organic solvent accompanying the condensation reaction. On the other hand, the hardened material itself naturally requires strength. Then, the inventors have considered these conditions, and as a result, found that a composition containing a predetermined polysilsesquioxane that is solid at room temperature and a predetermined polysilsesquioxane that is liquid at room temperature is produced. Can solve the aforementioned problems, and completed the present invention. That is, this invention relates to the following condensation reaction type siloxane composition and hardened | cured material.

1. A condensation reaction type siloxane composition, comprising: a condensation reaction type siloxane composition, containing: (A) a polysilsesquioxane which is solid at room temperature, and which contains R ¹ SiO _3/2 (wherein R ¹ represents a trisilyloxy unit (T _A ) selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, a phenyl group, and a benzyl group), and (B) polysilsesquioxane which is liquid at room temperature and contains R ² SiO _3/2 (wherein R ² represents an alkyl group selected from the group consisting of 1 to 15 carbon atoms, Trisilyloxy unit (T _B ) represented by one of the group consisting of phenyl and benzyl, and has -OR ² (wherein R ² represents a group selected from alkyl groups having 1 to 15 carbon atoms) (C), one of the group consisting of phenyl and benzyl); and (C) a condensation reaction catalyst.

2. The condensation reaction type siloxane composition according to item 1 above, wherein the softening point of the component (A) is 40 to 150 ° C.

3. The condensation reaction type siloxane composition according to item 1 or 2 above, wherein the viscosity of the component (B) is 5 to 10,000 mPa ･ s / 25 ° C.

4. The condensation reaction type siloxane composition according to any one of items 1 to 3 above, further containing (D) an inorganic filler.

5. The cured product of the condensation reaction type siloxane composition according to any one of items 1 to 4 above. Invention effect

The condensation-reactive siloxane composition of the present invention has good operability and transparency, and is excellent in storage stability and initial hardenability. In addition, since the cured product has good heat resistance and transparency, even after heating for a long time, the mass reduction rate is low, and the transparency is hardly reduced. Moreover, this hardened | cured material is also excellent in crack resistance and bubble resistance, Therefore, even after heating for a long time, it is hard to generate | occur | produce a crack or a fine bubble. In addition, it is particularly worth mentioning that the hardened material has strong adhesion.

Since the condensation reaction type siloxane composition of the present invention has many advantages as described above, it can be supplied to a wide range of applications such as adhesives, sealants, coating agents, sealants, and coatings. Specifically, it can be used as a metal adhesive for bonding the same or dissimilar metals such as silicon, aluminum, iron, gold, silver, and copper to each other. In addition, the condensation reaction type siloxane composition of the present invention can also be used as an optical semiconductor device containing UV-LEDs, lasers, and light-receiving elements, as well as a sealant or a barrier agent for power modules, temperature sensors, and the like. In addition, the condensation reaction type siloxane composition of the present invention can be used not only as an optical adhesive for bonding a lens made of glass or plastic, a transparent window, or the like to a support, but also as a moisture-proof material for an electronic substrate or the like. Housing materials such as coating agents and resistors.

The condensation reaction type silicone composition of the present invention (hereinafter also simply referred to as "the composition of the present invention") contains a predetermined (A) solid polyalkylsilsesquioxane (hereinafter also referred to as "(A) component "), A predetermined (B) liquid polyalkylsilsesquioxane (hereinafter also referred to as" (B) component "), and (C) a condensation reaction catalyst (hereinafter also referred to as" (C) component ") Composition.

The above "room temperature" means 20 ± 15 ℃, "solid" means no fluidity at all, usually the so-called solid state, and "liquid" means fluidity, for example, the viscosity is 1000000mPa ･ s / 25 State below ℃. The viscosity is a value measured using an E-type viscometer.

(A) The component is a polysilicone containing a trisilyloxy unit (T _A ) represented by R ¹ SiO _3/2 (wherein R ¹ is the same as above), and has a hydroxyl group, and is a solid at room temperature. Siloxane.

Examples of the alkyl group having 1 to 15 carbon atoms represented by R ¹ include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-decyl; Branched alkyl groups such as isopropyl, isobutyl, isopentyl, isohexyl, and isodecyl, and cyclic alkyl groups such as cyclohexyl. A phenyl group and a benzyl group represented by R ¹ , and at least one hydrogen on each ring of the cyclic alkyl group such as the cyclohexyl group may be substituted by the alkyl group having 1 to 15 carbon atoms. However, R ¹ does not contain reactive functional groups such as isocyanate group, thiol group, amine group, epoxy group, acid anhydride group, and vinyl group.

T _A can be subdivided into T1 structure [R ¹ O-Si (R ¹ ) (OR ¹ ) -O-], T2 structure [-(R ¹ ) Si (OR ¹ ) (O-)-O-], and T3 structure [-(R ¹ ) Si (O-) ₂ -O-]. The ratios of these structures are not particularly limited. In terms of mole ratios, T1: T2: T3 = 0 to 5:10 to 40:90 to 60 are usually used. It is preferable to include only the T2 structure and the T3 structure. In this case, the ratio of the T2 structure to the T3 structure is about T2: T3 = 20 to 30:80 to 70. Each structure can be identified by measuring, for example, a ²⁹ Si-NMR spectrum of the component (A).

The proportion of T _A in the (A) component is not particularly limited. Considering the balance of the desired effects of the present invention, especially the compatibility and hardenability of the composition of the present invention, and the balance of the strength, adhesion, crack resistance, and bubble resistance of the hardened product, T _A is The proportion of the component (A) is usually 90 mol% or more, preferably 95 mol%, and more preferably 100 mol%. In addition, the component (A) may contain a certain amount of other units (monosilyloxy unit (M _A ), disilanooxy unit (D _A )), provided that it is solid at room temperature. , Or a tetrasilyloxy unit (Q _A )). The ratio of the other units is not particularly limited, but is usually less than 10 mole%, and preferably less than 5 mole%.

The structure of the component (A) can be specifically expressed by the following average unit formula.

(R ¹ SiO _3/2 ) _x [R ¹ _a SiO _{(4-a) / 2} ] _y

In the foregoing formula, 0 <a ≦ 3, 0 <x, 0 ≦ y, and x + y = 1. Should be x = 1 and y = 0.

The molecular end of the component (A) contains a hydroxyl group derived from a silanol group. The content of the hydroxyl group is not particularly limited, but is usually about 1 to 10% by weight based on the total amount of the (A) component. When the content of the hydroxyl group is 1% by weight or more, the strength and adhesiveness of the hardened material will be better. In addition, when the content of the detached component decreases with the hardening reaction when the content is 10% or less, the crack resistance and Bubble resistance will be better. From such a viewpoint, the content of the hydroxyl group is preferably about 2 to 5 wt%.

(A) A component can be manufactured by various well-known methods. An example of a production example of the (A) component is disclosed below.

The starting material of the component (A), trialkoxysilane (a1) (hereinafter also referred to as "(a1) component"), has a general formula: X ¹ Si (OX ¹ ) ₃ (where X ^{1 is the} same Or different, and 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 the aforementioned alkyl groups. X ¹ does not contain the aforementioned reactive functional group.

Specific examples of the component (a1) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, and Propyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane Ethoxysilane, 3-hydroxypropyltriethoxysilane, trichloromethoxysilane, trichloroethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, etc. Particularly preferred is methyltrimethoxysilane. By using methyltrimethoxysilane, (A) component and (B) a condensation reaction type siloxane composition containing: (A) solid at room temperature Polysilsesquioxane containing 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. ( _A ) The trisilyloxy unit (T _A ) shown in the figure has a hydroxyl group; (B) is a polysilsesquioxane at room temperature which contains R ² SiO _3/2 (wherein R ² represents a trisilyloxy unit (T _B ) selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, a phenyl group, and a benzyl group, and has -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; and (C) a condensation reaction catalyst. The reactivity of the components is good, and the balance of the effects desired by the present invention, the balance of heat resistance, transparency, and bubble resistance are particularly good.

The component (A) can be obtained by subjecting the component (a1) to a hydrolysis reaction and a condensation reaction.

The conditions of 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 to be added to the reaction system is not particularly limited, and the [mole number of water / mole number of OX ¹ group contained in the (a1) component] is usually in the range of about 0.3 to 1.

In the hydrolysis reaction, various known catalysts can be used. Specific examples of the catalyst include acid catalysts such as formic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, phosphoric acid, and cation exchange resins; sodium hydroxide, potassium hydroxide, calcium hydroxide, 1,8- Diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, pyridine And other alkaline catalysts. The use amount of the catalyst is not particularly limited, but is usually about 0.001 to 1 part by mass based on 100 parts by mass of the component (a1).

In the hydrolysis reaction, various known solvents can be used. Specific examples of the solvent include hydrocarbon solvents such as benzene, toluene, xylene, n-hexane, and n-heptane; alcohol solvents such as methanol, ethanol, n-propanol, and isopropanol; ethylene glycol dimethyl ether, Ether solvents such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1,4-dioxane; methyl acetate Ester solvents such as esters, ethyl acetate, butyl acetate; ketone solvents such as acetone, 2-butanone, and methyl-isobutyl ketone; acetonitrile, dimethyl sulfoxide, and N, N-dimethylformamide Amidoamine, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

The hydrolysate obtained by the hydrolysis reaction can be further subjected to a condensation reaction to generate a siloxane bond between the hydroxyl groups or between the hydroxyl groups and the remaining -OX ¹ group, thereby producing the target (A) component. 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. This condensation reaction can be performed in the aforementioned solvent. In addition, since the composition of the present invention is preferably a solventless type, it is desirable to remove the solvent from the component (A) by various known means after the hydrolysis and condensation reaction.

(A) The physical property of a component is not specifically limited. Considering the balance of the desired effect of the present invention, the softening point (the softening point measured under the conditions prescribed by JIS K5903, and the same applies to the softening point below) is usually about 40 to 150 ° C, and is preferably About 50 to 130 ° C, preferably about 60 to 120 ° C. When the softening point of the component (A) is in such a range, the mechanical properties of the hardened product related to the present invention are more favorable. The weight average molecular weight is also not particularly limited, but is usually about 2000 to 10,000, and preferably about 3000 to 7,000. When the weight-average molecular weight of the component (A) is 2,000 or more, when the composition related to the present invention is heat-hardened, volatilization or bleeding of the low-molecular-weight component can be further suppressed. In addition, when 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 the phenomenon such as drawing is suppressed, and workability is also improved.

The shape of the component (A) is not particularly limited, and may be a chip shape, a powder shape, a semi-solid shape, or the like. (A) As a commercial item of a component, KR-220L and KR-220LP by Shin-Etsu Chemical Industry Co., Ltd., YR3370 by Momentive Performance Materials Japan, etc. are mentioned, for example.

The component (B) contains 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). A trisilyloxy unit (T _B ) and -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), It is a liquid polysilsesquioxane at room temperature. In addition, the R R ² SiO _3/2 and R ² is -OR ^{2 2} may be the same or different.

The alkyl group, phenyl group, and benzyl group having 1 to 15 carbon atoms constituting each R ^{2 are} the same as these groups constituting R ¹ , and none of the reactive functional groups is included.

T _B T _A the same manner as the aforementioned, can be subdivided into T1 structure ^{[R 2 O-Si (R} 2) (OR 2) -O -], T2 configuration ^{[- (R 2) Si (} OR 2) (O-) -O-] and T3 structures [-(R ² ) Si (O-) ₂ -O-], and the ratio of these structures are not particularly limited. Each structure can be identified by measuring, for example, a ²⁹ Si-NMR spectrum of the component (B).

The proportion of T _B in the (B) component is not particularly limited. Considering the balance of the desired effects of the present invention, especially the compatibility of the composition of the present invention, the operability, and the hardenability, and the balance of the strength, adhesion, crack resistance, and bubble resistance of the hardened material, The proportion of T _B in the component (B) is usually about 65 to 100 mole%, and preferably 95 to 100 mole%.

The component (B) may contain other units (monosilyloxy unit (M _B ), disilyloxy unit (D _B ), or tetrasilyloxy) provided that it is kept liquid at room temperature. Base unit (Q _B )). The ratio of these other units is usually about 0 to 35 mole%, preferably 0 to 5 mole%.

The structure of the component (B) can be specifically expressed by the following average unit formula.

(R ² SiO _3/2 ) _{x '} [R ² _b SiO _{(4-b) / 2} ] _y'

In the foregoing formula, 0 <b ≦ 3, 0 <x ', 0 ≦ y', and x '+ y' = 1. Should be x '= 1, y' = 0.

The content of the hydroxyl group in the component (B) was substantially 0% by weight. The content of -OR ² can be obtained by, for example, ¹ H-NMR spectrum, and is usually about 15 to 45 wt% based on the total amount of the (B) component.

The component (B) can be produced by various known methods. An example of a production example of the (B) component is disclosed below.

(B) One of the starting materials of the component, trialkoxysilane (b1) (hereinafter also referred to as "(b1) component"), is a general formula: X ² Si (OX ² ) ₃ (where X ^{2 is the} same or different and 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 the aforementioned alkyl groups. (b1) As a component, the thing mentioned by the said (a1) component can be illustrated. (b1) The component is preferably methyltrimethoxysilane. By using methyltrimethoxysilane as the (b1) component, the reactivity between the (A) component and the (B) component is better, and the desired effect balance of the present invention can be maintained, especially heat resistance, transparency, and bubble resistance. Sex is better.

Starting material (B) component in the holding component (B) is a liquid under the premise, and the other may be used to generate the dialkoxy silane-D _B cells at room temperature (hereinafter also referred to as "(b2 ”Component”), a monoalkoxysilane (hereinafter also referred to as “(b3) component”) that generates the aforementioned M _B unit, or a tetraalkoxysilane (hereinafter also referred to as “(b4)” that generates the aforementioned Q _B unit ingredient").

The component (b2) is represented by a general formula: (X ² ) ₂ Si (OX ² ) ₂ (wherein X ² may be the same as or different from the above). Specific examples thereof include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethylmethoxyethoxysilane, and the like. The use amount of the component (b2) relative to the component (b1) is not particularly limited, and it is usually in the range of (b1): (b2) = 65 to 95: 5 to 35 in terms of mole ratio.

The component (b3) is represented by a general formula: (X ² ) ₃ SiOX ² (wherein X ² may be the same as or different from the above). Specific examples thereof include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, tri (n-propyl) methoxysilane, and trimethylethoxysilane. (Isopropyl) methoxysilane, tri (n-propyl) ethoxysilane, tri (n-butyl) methoxysilane, tri (isobutyl) methoxysilane, tri (isobutyl) ethyl Oxysilane, dimethyl tert-butylmethoxysilane, dimethylisobutylmethoxysilane, dimethylcyclopentylmethoxysilane, dimethylcyclohexylethoxysilane, and the like. The use amount of the component (b3) with respect to the component (b1) is not particularly limited, and is usually in the range of (b1): (b3) = 65 to 95: 5 to 35 in terms of mole ratio.

The component (b4) is represented by a general formula: Si (OX ² ) ₄ (wherein X ² may be the same as or different from the above). Specific examples thereof include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetramethoxysilane, dimethoxydiethoxysilane, and the like. Tetraalkoxysilanes, etc. The use amount of the (b4) component with respect to the (b1) component is not particularly limited, and it is usually in the range of (b1): (b4) = 65 to 95: 5 to 35 in terms of mole ratio.

The component (B) can be obtained by subjecting (b1) component and at least one selected from the group consisting of (b2) component, (b3) component, and (b4) component to a hydrolysis reaction and a condensation reaction as necessary.

The conditions of 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 to be added to the reaction system is not particularly limited either, [the mole number of water / [the total mole number of -OX ² contained in the (b1) component to (b4) component] is 0.1 to 1 Left and right range.

In the hydrolysis reaction, any of the catalyst and the solvent used in the hydrolysis reaction of the component (a1) may be used.

The hydrolyzate obtained by the hydrolysis reaction can be further condensed to generate a siloxane bond between the hydroxyl group in the decomposed product and the remaining -OX ² group to produce the target (B) component. 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. This condensation reaction can be performed in the aforementioned solvent. In addition, since the condensation reaction type siloxane composition of the present invention is preferably a solventless type, it is desirable to remove the solvent from the component (B) by various well-known means after the hydrolysis and condensation reaction.

(B) The physical property of a component is not specifically limited. In order to exert the desired effect of the present invention, the viscosity is usually about 5 to 10,000 mPa ･ s / 25 ° C, preferably 5 to 5000 mPa ･ s / 25 ° C, and preferably 5 to 2000 mPa ･ s / 25 ° C. . In addition, although the composition of the present invention is a heat-curable type, the viscosity of a room-temperature-curable silicone composition may be measured at 23 ° C. In this case, in one embodiment, the viscosity is preferably 501 to 10,000 mPa ･ s / 23 ° C or higher. When the viscosity of the component (B) is within this range, the balance between the coating workability and the shape maintenance property of the composition of the present invention is better. The weight average molecular weight is not particularly limited. From the same viewpoints as described above, the weight average molecular weight of the component (B) is usually about 500 to 9,000, and preferably about 700 to 8,000. When the weight-average molecular weight of the component (B) is 500 or more, when the composition of the present invention is heat-hardened, volatilization or bleeding of the low-molecular-weight component can be further suppressed. In addition, by making the number average molecular weight of the (B) component be 9,000 or less, the composition of the present invention has better compatibility, and can suppress the phenomenon of drawing, etc., and also has better workability.

(B) The commercially available component includes, for example, MSE100 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., KC-89S and KR-500 manufactured by Shin-Etsu Chemical Industry Co., Ltd., and MTMS-A manufactured by Tama Chemical Industry Co., Ltd. .

The blending ratio of the component (A) and the component (B) is not particularly limited. From the viewpoints of the operability of the composition of the present invention, the hardness, toughness, and bubble resistance of the cured product of the present invention, the component (A) and the component (B) are usually blended into the component (A) The ratio of the molar number of hydroxyl groups (M _OH ) to the total molar number (M _OR ) of -OR ¹ contained in (A) component and -OR ² contained in (B) component is (M _OR / M _OH ) The range is about 0.1 to 20, preferably about 5 to 20, and more preferably about 8 to 15. If this ratio is 0.1 or more, the defoaming property at the time of hardening the composition of this invention will be more favorable, and a phenomenon such as drawing will not occur easily when coating it, and workability | operativity will also become more favorable. In addition, if the ratio is 20 or less, the adhesiveness of the composition of the present invention will be better, and the hardened product will be less likely to crack or bubble.

The solid content mass ratio of (A) component and (B) component is also not specifically limited. From the viewpoints of the operability of the composition of the present invention, the compatibility of the composition of the present invention, the coating workability, etc., and the hardness, toughness, and bubble resistance of the cured product, the mass ratio of the solid content is relative to The component (A) is 100 parts by mass, and the component (B) is usually in a range of about 30 to 120 parts by mass, preferably about 40 to 110 parts by mass.

As the component (C), various well-known condensation reaction catalysts can be used. Specific examples of the condensation reaction catalyst include compounds of metals such as magnesium, aluminum, tin, zinc, iron, cobalt, nickel, zirconium, cerium, and titanium. Considering the life of the composition of the present invention, the color tone and transparency of the hardened product of the present invention, the compound is preferably one selected from the group consisting of a titanium compound, a tin compound, a zinc compound, and a zirconium compound. In particular, tin compounds and / or zirconium compounds are preferred.

Examples of the titanium compound include diisopropoxy bis (ethylacetamidineacetate) titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, and diisopropoxy-bis ( Ethyl Acetate) Titanium, Diisopropoxy-bis (Ethyl Acetyl Acetate) Titanium, Diisopropoxy-bis (Ethyl Acetyl Acetate) Titanium, Di-n-butoxy-bis (Ethyl Acetate) (Ester) titanium, dimethoxy-bis (ethyl ethyl acetate) titanium, and the like.

Examples of the tin compound include di-n-butyltinmethoxylate, di-n-butyltindiacetate, di-n-butyltindioctoate, di-n-butyltindilaurate, di-n-octyltindiacetate, and di-n-octyl Tin maleate, tin di-n-butyloxy tin acetate, tin di-n-butyloxy caprylate, tin di-n-butyloxy laurate, tin di-n-butyl dimethyl malate, di-n-butyloxy Tin base oleate, or n-dibutyl tin malate polymer, di-n-octyl tin malate polymer, mono-n-butyl ginseng (ethyl 2-hexanoate) tin, and di-n-butyl bis (acetamidine) Tin etc.

Examples of the zinc compound include zinc acetate, zinc ethylacetate, zinc 2-ethylhexanoate, zinc octoate, zinc neodecanoate, zinc laurate, zinc stearate, zinc naphthenate, zinc benzoate, To the third butyl zinc benzoate, zinc salicylate, zinc (meth) acrylate, zinc acetoacetone and zinc 2,2,6,6-tetramethyl-3,5-heptanedione.

Examples of the zirconium compound include tetraalkyl zirconate, trialkoxy mononaphthoate, zirconium trialkoxy monocyclopropanecarboxylate, zirconium trialkoxy cyclobutanecarboxylate, and trialkoxy mono Zirconium cyclopentanecarboxylate, zirconyl trialkoxymonocyclohexane and zirconium trialkoxymonoadamantanecarboxylate. Here, examples of a suitable alkyl group include a linear or branched alkyl group having 1 to 18 carbon atoms, and examples of a suitable alkoxy group include a linear or branched alkyl group having 1 to 18 carbon atoms. Aryloxy.

(C) The usage-amount of a component is not specifically limited. From the viewpoints of storage stability and hardenability of the composition of the present invention, and yellowing resistance of the hardened material, the amount of the component (C) used is 100 parts by mass relative to the total of the components (A) and (B). It is usually in the range of 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. Moreover, in the composition of this invention, even if the usage-amount of (C) component is less than 0.1 mass part, ie, 0.001-0.099 mass part, a desired effect can be achieved.

The composition of the present invention may contain, for example, various known (D) inorganic fillers (hereinafter also referred to as "(D) component") in order to improve the crack resistance of the cured product of the present invention. The component (D) includes, for example, silicon dioxide (colloidal silica, fumed silica, etc.), barium titanate, titanium oxide, zirconia, niobium oxide, aluminum oxide, cerium oxide, and yttrium oxide. Particularly preferred is silicon dioxide, and particularly fuming silica. (D) The average primary particle diameter of a component is not specifically limited. From the viewpoints of dispersion stability, coating workability, shake resistance (drip resistance after coating) of the composition of the present invention, and crack resistance and transparency of a cured product, the component (D) The average primary particle diameter is usually 100 μm or less, preferably about 5 to 100 nm, and more preferably about 5 to 30 nm.

(D) The usage-amount of a component is not specifically limited. From the viewpoints of the coating workability and shake properties of the composition of the present invention, and the transparency and crack resistance of the cured product, the amount of the (D) component used is higher than that of the (A) component and (B) The total amount of the ingredients is 100 parts by mass, usually in the range of about 0.1 to 20 parts by mass, and preferably 0.5 to 10 parts by mass.

Plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive polymers, conductive fillers, Additives such as mold agents, surface treatment agents, viscosity modifiers, and silane coupling agents. In addition, since the composition of the present invention is preferably a solvent-free type, in one embodiment, the composition of the present invention contains no solvent.

The manufacturing method of the composition of this invention is not specifically limited. Generally, by adding the solid component (A) and the component (C) to the liquid component (B), the component (D) and the additive may be further blended as necessary, and the components may be mixed until homogeneous. So far, the composition of the present invention is obtained. Mixing can be performed by well-known means.

The physical properties of the composition obtained in this way are not particularly limited. In consideration of operability and moldability when used as a sealant, the viscosity is usually about 5 to 1,000,000 mPa ･ s / 25 ° C, preferably s is about 500 to 500,000 mPa ･ s / 25 ° C, and preferably 1,000 to 200000 mPa ･. s / 25 ℃.

The hardened | cured material of this invention is a condensation reaction product of the composition of this invention. The curing conditions are not particularly limited as long as they are appropriately set 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. Examples

Hereinafter, the present invention will be described in detail through examples and comparative examples. However, the scope of the present invention is not limited by these examples. In each case, parts are based on mass unless otherwise specified.

In the production examples, the weight-average molecular weight was obtained by gel permeation chromatography (using apparatus: HLC-8220 manufactured by Tosoh Corporation, column: TSKgel α-M manufactured by Tosoh Corporation, and developing solvent: tetrahydrofuran). Conversion value of polystyrene standard material.

In the production example, the ¹ H-NMR shift value is a measurement value obtained by using 400-MR (400 MHz, CDCl ₃ ) manufactured by VARIAN.

In the examples, the viscosity is a measurement value obtained using an E-type viscometer (product name "RE-80U", manufactured by Toki Sangyo Co., Ltd., rotor No. 1 ° 34 ′ × R24, rotor rotation speed 5 rpm).

<Production of (B) component> Production Example 1 A reaction device including a stirrer, a condenser tube, a thermometer, and a nitrogen introduction tube 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 parts of formic acid was charged to start the hydrolysis reaction. After the reaction started, the temperature of the reaction system reached 62 ° C due to the heat of reaction, and then the temperature was lowered to 40 ° C, so it was kept at the same temperature for 30 minutes. Then, the by-produced methanol was removed from the system, and it took 3 hours to raise the temperature of the reaction system to 120 ° C. Next, a condensation reaction was performed at the same temperature for 1 hour to obtain a liquid polysilsesquioxane (B having a trisiloxy unit (x = 1, y = 0) represented by CH ₃ SiO _3/2 . -1). (B-1) The viscosity of the component was 20 mPa ･ s / 25 ° C, and the weight average molecular weight was 900. The content (hereinafter abbreviated as "residual methoxy content") calculated from the peak intensity of the residual methoxy group (δ 3.2-3.8) measured by ¹ H-NMR was about 32% by weight.

Production Example 2 Except that the charged amount of water was 16.2 parts, in the same manner as in Production Example 1, a _trisilyloxy unit represented by CH ₃ SiO _3/2 (x = 1, y = 0) Liquid polysilsesquioxane (B-2). (B-2) The viscosity of the component was 350 mPa ･ s / 25 ° C, the weight average molecular weight was 2500, and the residual methoxyl content was about 24% by weight. No peak of the residual hydroxyl group was observed.

Production Example 3 An average silaneoxy group was obtained in the same manner as in Production Example 1 except that the methyltrimethoxysilane was determined to be 136.2 parts, the dimethyldimethoxysilane was determined to be 51.5 parts, and 27.8 parts of water. The unit is (CH ₃ ) _1.3 SiO _1.35 (x '= 0.7, y' = 0.3, b = 2) polysilsesquioxane (B-3). (B-3) The viscosity of the component was 1600 mPa ･ s / 25 ° C, the weight average molecular weight was 7000, and the residual methoxyl content was about 19% by weight. No peak of the residual hydroxyl group was observed.

<Production of Condensation-Responsive Siloxane Composition> Example 1 50 parts of polysilsesquioxane as a component (A) and solid at room temperature (trade name "KR220L", Shin-Etsu Chemical Co., Ltd. Made by the company, in the form of chips, R ¹ = methyl, content of hydroxyl group derived from silanol group is 3% by weight, 100 mole% of T _A unit, and softening point of 67 ° C.); 50 parts of (B-1) (B-1 ) Component; 0.3 part of zirconium chelate (Matsumoto Fine Chemical Co., Ltd., manufactured by Matsumoto Fine Chemical Co., Ltd., ZC-700 (tetraacetamidine, zirconium acetone 20% solution)); 5.5 parts of commercially available hair as (D) component Smoke silicon dioxide (trade name "AEROSIL RX200", manufactured by Japan Aerosil Co., Ltd., with an average primary particle diameter of 12 nm) was thoroughly mixed at room temperature to obtain a homogeneous and transparent condensation reaction type siloxane composition 1 (6000 mPa ･ s / 25 ° C).

Example 2 A homogeneous and transparent condensation reaction type siloxane composition 2 (8000 mPa ･ s /) was obtained in the same manner as in Example 1 except that 50 parts of the component (B-2) was used as the component (B). 25 ° C).

Example 3 A homogeneous and transparent condensation reaction type siloxane composition 3 (5000 mPa ， s /) was obtained in the same manner as in Example 1 except that 50 parts of the component (B-3) was used as the component (B). 25 ° C).

Example 4 A homogeneous and transparent condensation-reaction type siloxane 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 a component (C), 0.1 part of titanium chelate (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-710 diisopropoxybis (ethylacetamidineacetate) titanium 63% solution) was used. Example 1 Similarly, a homogeneous and transparent condensation reaction type siloxane composition 5 (6000 mPa.s / 25 ° C) was obtained.

Example 6

A homogeneous and transparent condensation reaction type siloxane 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 7

40 parts of polysilsesquioxane (trade name "Z-6018", manufactured by Dow Corning Corp., as a component (A)) and solid at room temperature, chipped, R ¹ = phenyl and n-propyl the content of silanol groups from the hydroxyl groups of 6wt%, 100 mole% T _a units, a softening point of 40 ℃); 60 parts as the component (B) at room temperature and liquid poly-silicon siloxane sesquioleate (trade The name "MSE-100", manufactured by Wacker Chemie AG, R ¹ = methyl, viscosity 30 mPa · s / 25 ° C, alkoxy content 32% by weight) was thoroughly mixed at 130 ° C to obtain a homogeneous, colorless and transparent liquid. Next, 0.5 part of ZC-700 as a component (C) was added thereto, and the mixture was sufficiently mixed at room temperature to obtain a homogeneous and transparent grain adhesive 7 (2300 mPa · s / 25 ° C).

Example 8

50 parts of KR-220L as component (A) and 50 parts of polysilsesquioxane as component (B) at room temperature (trade name "X-40-9227", Shin-Etsu Chemical Industry Co., Ltd. Made by the company, R ¹ = methyl and phenyl, viscosity 20 mPa.s / 25 ° C, alkoxy content 15% by weight) are thoroughly mixed at 130 ° C to obtain a homogeneous, colorless and transparent liquid. Next, 1.5 parts of ZC-700 as component (C) and 3.0 parts of AEROSIL RX200 as component (D) were added thereto, and they were thoroughly mixed at room temperature to obtain a homogeneous and transparent grain adhesive 8 (8000 mPa.s). / 25 ° C).

Example 9

60 parts of Z-6018 as the component (A) and 40 parts of X-40-9227 as the component (B) were thoroughly mixed at 130 ° C to obtain a homogeneous, colorless and transparent liquid. Next, 6.0 parts of ZC-700 as a component (C) was added thereto, and they were thoroughly mixed at room temperature to obtain a homogeneous and transparent crystal grain adhesive 9 (4100 mPa.s / 25 ° C).

Comparative Example 1

Polysilsesquioxane (trade name "SILRES MK", manufactured by Asahi Kasei Wacker Silicone Co., Ltd., 50 parts as component (A) and solid at room temperature, R ¹ = methyl, derived from silanol group The content of the hydroxyl group is 0% by weight), 50 parts of the aforementioned (B-1) component, and 0.3 part of a zirconium chelate (manufactured by Matsumoto Fine Chemical Co., Ltd., ZC-700 (20% solution of zirconium acetone zirconium tetraacetonate)) Mix well at temperature to obtain a homogeneous and transparent condensation reaction type siloxane composition A (5000 mPa.s / 25 ° C).

Comparative Example 2

100 parts (B-1), 0.3 parts of zirconium chelate, and 5.5 parts of AEROSIL RX200 were thoroughly mixed at room temperature to obtain a homogeneous and transparent condensation reaction type siloxane composition B (4000 mPa.s / 25 ° C) ).

Comparative Example 3

50 parts of KR220L as component (A) and 50 parts of component (B-1) as component (B) and 5.5 parts of AEROSIL RX200 as component (D) were thoroughly mixed at room temperature to obtain a homogeneous and transparent condensation reaction Type Siloxane Composition C (6000 mPa.s / 25 ° C).

<Creation of hardened matter 1>

The condensation reaction type siloxane composition 1 obtained in Example 1 was poured into a circular metal frame (5 cm in diameter and 2 mm in height) coated with Teflon (registered trademark), and was cured in a 120 ° C drying furnace. After 1 hour, it was hardened in a drying oven at 150 ° C for 3 hours to produce a cured product 1 (test piece).

(1) Preservation stability

The condensation reaction type siloxane composition 1 was allowed to stand under the conditions of 25 ± 1 ° C and 50 ± 10% RH, and the useful life was evaluated according to the following criteria.

5: The time when the viscosity reaches 125% or more of the initial value is 48 hours or more

3: The time when the viscosity reaches 125% or more of the initial value is 12 hours or more and less than 48 hours

1: The time when the viscosity reaches 125% or more of the initial value is less than 12 hours

(2) Initial hardenability The hardness of the above-mentioned hardened product 1 was measured using a Schole Hardness Tester Type D manufactured by Polymer Meter Co., Ltd., and the condensation reaction type silicone composition 1 related to Example 1 was evaluated according to the following criteria. Initial hardening.

5:40 or more 3:20 or more and less than 40 1: 1 or less

(3) Heat resistance <Initial heat resistance> The mass reduction rate of the cured product 1 was calculated by the following calculation formula, and the initial heat resistance was evaluated again in accordance with the criteria disclosed below.

(Formula) Mass reduction rate after heating (%) = 100- (mass of hardened product 1 / mass of condensation reaction type siloxane composition 1) × 100

5: below 15% 3: above 15% below 25% 1: above 25%

<The heat resistance after heating> The said hardened | cured material 1 was heated further in the 200 degreeC drying furnace for 1000 hours, and the hardened | cured material 2 was obtained. Next, the mass reduction rate was calculated by the following calculation formula, and the heat resistance was evaluated again according to the following criteria.

(Formula) Mass reduction rate after heating (%) = 100- (mass of hardened product 2 / mass of hardened product 1) × 100

5: less than 5% 3: more than 5% less than 7.5% 1: more than 7.5%

(4) Transparency Using a UV-MINI-1240 spectrophotometer manufactured by Shimadzu Corporation, the parallel light transmittance of the cured product 1 at a wavelength of 400 nm was measured, and the transparency was evaluated according to the following criteria.

5: 75% or more 3: 65% or more and less than 75% 1: 65% or less

(5) Crack resistance With respect to the above-mentioned hardened material 1, the crack resistance was evaluated visually in accordance with the following criteria.

5: No cracking 1: Cracking

(6) Bubble resistance The above-mentioned cured product 1 was evaluated for bubble resistance visually in accordance with the following criteria. 5: No bubbles 1: With bubbles

(7) Flexural strength Using Autograph AGS-10kND manufactured by Shimadzu Corporation, the flexural strength of the hardened body 1 was measured, and the balance between flexibility and strength was evaluated according to the following criteria.

5: above 20MPa 3: above 10MPa below 20MPa 1: below 10MPa

(8) Shear strength Using the condensation reaction type siloxane composition 1 obtained in Example 1, a silicon wafer (2 mm × 2 mm × 1 mm) was adhered to an aluminum plate, and the conditions were 120 ° C. and 1 hour in a drying furnace. After heating, it was further heated under the conditions of 150 ° C and 3 hours. Next, using a commercially available bond strength tester (product name "DAGE-SERIES-4000PXY", manufactured by Dage), the shear strength of the adhesive layer (hardened material) was measured at room temperature (25 ° C), and the The following benchmarks were evaluated.

5: 30N or more 3: 15N or more and less than 30N 1: less than 15N

The above-mentioned test was performed similarly about each condensation reaction type siloxane composition or its hardened | cured material of the other Example and the comparative example.

[Table 2]

(Industrial Applicability) As shown in Table 2, it was found that the condensation reaction type siloxane composition of the present invention is excellent in storage stability and initial hardening property, and the obtained hardened product has heat resistance, transparency, and resistance to heat. Excellent cracking resistance, bubble resistance, flexural strength and shear strength. In particular, the composition is a condensation reaction type composition. Although water or a low-molecular-weight alcohol is formed as a by-product during the reaction, the hardened product has good bubble resistance, which is worth mentioning in particular.

Since the condensation reaction type siloxane composition of the present invention has many advantages as described above, it can be supplied to a wide range of applications such as adhesives, sealants, coating agents, sealants, and coatings.

Specifically, from the results of the above-mentioned initial hardening, crack resistance, flexural strength, and shear strength, the composition can be used as a homogeneous or silicon compound for silicon, aluminum, iron, gold, silver, and copper. Adhesives for metals where dissimilar metals are bonded to each other, and case materials such as resistors.

In addition, from the results of the above-mentioned initial hardening, heat resistance, transparency, crack resistance, and bubble resistance, the composition can also be used as a sealant for power modules and temperature sensors, electronic substrates, and the like. Anti-moisture coating.

In addition, from the results of the above-mentioned initial hardening, heat resistance, transparency, crack resistance, bubble resistance, bending strength, and shear strength, the composition can also be used as a lens made of glass or plastic. , Transparent window and other optical adhesives bonded to the support, packaging materials for optical elements such as LEDs, sealants or barrier materials for optical semiconductor elements containing UV-LEDs, lasers, and light-receiving elements.

Claims (5)

A condensation reaction type siloxane composition comprising: (A) a polysilsesquioxane which is solid at room temperature, and which contains R ¹ SiO _3/2 (where R ¹ One of the group consisting of an alkyl group having 1 to 15 carbon atoms, a phenyl group, and a benzyl group) is a trisilyloxy unit (T _A ) and has a hydroxyl group; (B) is liquid at room temperature Polysilsesquioxane containing 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 trisilyloxy unit (T _B ) shown and has -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. ); And (C) a condensation reaction catalyst. For example, the condensation reaction type siloxane composition of claim 1, wherein the softening point of the component (A) is 40 to 150 ° C. For example, the condensation reaction type siloxane composition of claim 1, wherein the viscosity of the component (B) is 5 to 10,000 mPa. s / 25 ° C. The condensation reaction type siloxane composition according to any one of claims 1 to 3, further comprising (D) an inorganic filler. A hardened product of a condensation reaction type siloxane composition according to any one of claims 1 to 4.