TW201736515A - Condensation reaction-type silicone composition and cured product - Google Patents

Abstract

The objective of the present invention is to provide a condensation reaction-type silicone composition which has excellent initial curability and provides a cured product that exhibits adhesion with excellent toughness, while having good cracking resistance, void resistance and heat resistance. The present invention is a condensation reaction-type silicone composition that contains (A) a polysilsesquioxane which contains a trisiloxy unit (TA) represented by R1SiO3/2 (wherein R1 represents an alkyl group having 1-15 carbon atoms, or the like) and a hydroxyl group, and which is in a solid state at room temperature, (B) a polysilsesquioxane which contains a trisiloxy unit (TB) represented by R2SiO3/2 (wherein R2 represents an alkyl group having 1-15 carbon atoms, or the like) and an -OR2 group (wherein R2 represents an alkyl group having 1-15 carbon atoms, or the like), and which is in a liquid state at room temperature, and (C) a condensation reaction catalyst.

Description

Condensation reaction type oxoxane composition and hardened substance

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

The decane resin is generally a cured product obtained by subjecting a siloxane (polyorganosiloxane) to hardening reaction, and a condensation reaction and an addition reaction are known.

The addition reaction is a reaction in which a decane having an olefinyl group such as Si-CH=CH ₂ and a decane having a hydroquinone group (Si-H) is hydrohalogenated in the presence of a platinum-based catalyst. Even at room temperature, the addition reaction can produce a target cured product in a short period of time, and thus it is advantageous in terms of productivity. However, the addition reaction may cause a problem that the hardening is easily hindered due to deactivation of the platinum catalyst, moisture in the use environment, and the like.

The condensation reaction is such that deuteration and/or dealcoholation occurs in the presence of an organotin-based catalyst such as an organooxy group having alkoxy group (Si-OR) or a decyl group (Si-OH). Condensation reaction. The problem of hardening inhibition of 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 is insufficient in initial hardenability, and it takes a relatively high temperature and a long time to achieve complete hardening.

The condensation reaction type oxoxane composition has been conventionally used for applications such as a sealant for an optical semiconductor, an adhesive, and the like. For example, Patent Document 1 describes a decane composition containing an acrylic resin, a condensation-reactive siloxane compound, a condensation-reactive decane compound, and a curing accelerator. Further, Citation 1 also discloses that the siloxane compound can be used as a transparent sealant and an adhesive for a light-emitting diode element.

On the other hand, in the case of the cured product of the conventional condensation reaction type oxoxane composition, in general, when it is used as a sealing agent for an optical semiconductor, the adhesion to the reflective sheet or the metal electrode is insufficient. . One of the reasons is considered to be that the strength and softness of the adhesive layer (hardened material) cannot be balanced.

In order to increase the softness of the cured product, attempts have been made to introduce a dioxooxy unit represented by, for example, (CH ₃ ) ₂ SiO _2/2 into the main chain of the siloxane polymer. However, as the amount of introduction of the above-mentioned dioxanyloxy unit increases, the strength and the decrease in adhesion cannot be avoided. On the other hand, in order to increase the strength of the cured product, attempts have been made to introduce a tridecyloxy unit represented by, for example, CH ₃ SiO _3/2 . However, as the amount of introduction of the above-mentioned tridecyloxy unit increases, cracking of the cured product cannot be avoided, and in this case, the adhesion is also lowered. As such, strength and softness are usually mutually reciprocal, and there is currently no very strong adherence.

Further, the condensation-reactive type oxoxane composition releases moisture or a low-molecular alcohol during the reaction, so that the cured product generates fine voids or cracks. These defects are expected to cause a problem in that the mechanical strength of the cured product is lowered and the appearance is impaired, and thus the use of the sealant for the adhesive and the optical semiconductor is particularly problematic.

Further, when the optical semiconductor is used, a high heat resistance is required as a cured product of the sealing material due to a high temperature of the element. In this regard, the condensation reaction type oxoxane composition described in Patent Document 1 is mainly composed of an acrylic resin and has insufficient heat resistance. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2008-101093 (Patent Document 2) JP-A-2015-163661

DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION An object of the present invention is to provide a condensation reaction type oxoxane composition which is excellent in initial hardenability and has excellent toughness and is resistant to cracking, bubble resistance and heat resistance. Good hardened material. Means to solve the problem

In order to solve the above-described condensation reaction type oxoxane composition, it is necessary to reduce the amount of low molecular components such as water or alcohol generated by the condensation reaction and other volatile components of the organic solvent. On the other hand, the hardened material itself certainly needs strength. Then, the inventors and the like have considered these conditions, and as a result, found that a composition containing a predetermined polysilsesquioxane which is solid at room temperature and a predetermined polysilsesquioxane which is liquid at room temperature is produced. The above problems can be solved and the present invention has been completed. That is, the present invention relates to a condensation reaction type oxoxane composition and a cured product.

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

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

3. The condensation reaction type oxoxane composition according to the above item 1 or 2, wherein the (B) component has a viscosity of 5 to 10000 mPa·s / 25 °C.

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

5. The cured product of the condensation reaction type oxoxane composition according to any one of the above items 1 to 4. Effect of the invention

The condensation reaction type oxoxane composition of the present invention is excellent in handleability and transparency, and is excellent in storage stability and initial hardenability. Further, since the cured product has good heat resistance and transparency, even after heating for a long period of time, the mass reduction rate is low, and the transparency is hardly lowered. Further, since the cured product is also excellent in crack resistance and bubble resistance, cracks or fine bubbles are less likely to occur even after heating for a long period of time. In addition, it is particularly worth mentioning that the cured product has strong adhesion.

The condensation-reactive type oxoxane composition of the present invention has many advantages as described above, and thus can be supplied to a wide range of applications such as an adhesive, a sealant, a coating agent, a sealant, and a paint. Specifically, an adhesive for metal used for joining the same or different metals such as bismuth, aluminum, iron, gold, silver, copper, or the like can be used. Further, the condensation reaction type siloxane composition of the present invention can also be used as an optical semiconductor element including a UV-LED, a laser and a light-receiving element, and a sealant or a barrier agent for a power module, a temperature sensor, or the like. In addition, the condensation reaction type oxoxane 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 barrier for an electronic substrate or the like. A coating material such as a coating agent or a resistor.

The condensation reaction type oxoxane composition of the present invention (hereinafter also referred to simply as "the composition of the present invention") contains a predetermined (A) solid polyalkylsesquioxane (hereinafter also referred to as "(A) component). "), (B) liquid polyalkylsesquioxanes (hereinafter also referred to as "(B) components"), and (C) condensation reaction catalysts (hereinafter also referred to as "(C) components") Composition.

The above "room temperature" means 20 ± 15 ° C, "solid" means no fluidity at all, usually a so-called solid state, and "liquid" means a state of fluidity, for example, a viscosity of 1,000,000 mPa·s/25. The state below °C. In addition, the viscosity is a value measured using an E-type viscometer.

The component (A) is a polyvalent alkoxy unit (T _A ) represented by R ¹ SiO _3/2 (wherein R ¹ is the same as defined above) and has a hydroxyl group and is solid at room temperature. Semi-oxane.

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

T _A can be subdivided into T1 structures [R ¹ O-Si(R ¹ )(OR ¹ )-O-], T2 structures [-(R ¹ )Si(OR ¹ )(O-)-O-], and T3 structures [-(R ¹ )Si(O-) ₂ -O-]. The ratio of these structures is not particularly limited, and is usually in the range of T1: T2: T3 = 0 to 5: 10 to 40: 90 to 60, and 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 T2: T3 = 20 to 30: 80 to 70. Each configuration can be identified by measuring, for example, a ²⁹ Si-NMR spectrum of the component (A).

The proportion of T _A in the component (A) is not particularly limited. Considering the balance of the desired effects of the present invention, in particular, the compatibility and hardenability of the composition of the present invention, and the balance of strength, adhesion, crack resistance and bubble resistance of the cured product, T _A is The proportion of the component (A) is usually 90 mol% or more, preferably 95 mol%, preferably 100 mol%. Further, the component (A) may contain a certain amount of other units (monodecyloxy unit (M _A ), dioxooxy unit (D _A )) while maintaining a solid state at room temperature. Or a tetradecyloxy unit (Q _A )). The ratio of the 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.

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

In the above formula, 0 < a ≦ 3, 0 < x, 0 ≦ y, and x + y = 1. It should be x=1, y=0.

The molecular terminal of the component (A) contains a hydroxyl group derived from a sterol group. The content of the hydroxyl group is not particularly limited, and is usually about 1 to 10% by weight based on the total amount of the component (A). When the content of the hydroxyl group is 1% by weight or more, the strength and adhesion of the cured product are further improved, and the cracking resistance of the cured product is lowered by the amount of the component which is desorbed by the hardening reaction at 10% by weight or less. Bubble resistance will be better. From such a viewpoint, the content of the hydroxyl group is preferably about 2 to 5 wt%.

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

The starting material of the component (A), a trialkoxy decane (a1) (hereinafter also referred to as "(a1) component"), is a general formula: X ¹ Si(OX ¹ ) ₃ (wherein, X ^{1 is the} same Or different, which means 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. The alkyl group having 1 to 15 carbon atoms is exemplified by the above alkyl group. Further, X ¹ does not contain the aforementioned reactive functional group.

Specific examples of the component (a1) include methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, n-propyltrimethoxydecane, and positive Propyltriethoxydecane, n-hexyltrimethoxydecane, n-hexyltriethoxydecane, n-octyltriethoxydecane, n-decyltrimethoxydecane,phenyltrimethoxydecane,phenyl three Ethoxy decane, 3-hydroxypropyltriethoxy decane, trichloromethoxy decane, trichloroethoxy decane, (3,3,3-trifluoropropyl)trimethoxydecane, and the like. In particular, methyltrimethoxydecane is preferably used, by using methyltrimethoxydecane, (A) component and (B) a condensation-reactive type oxoxane composition containing: (A) solid at room temperature a 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 trioxooxy unit (T _A ) having a hydroxyl group; (B) a polysilsesquioxane which is liquid at room temperature and which contains R ² SiO _3/2 (wherein R ² represents a trioxooxy unit (T _B ) selected from one selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, a phenyl group and a benzyl group, and having -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 component is good, and the balance of the desired effect of the present invention, the balance of heat resistance, transparency, and bubble 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 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 usually [the number of moles of water/the number of moles of the OX ¹ group contained in the component (a1)) is in the range of about 0.3 to 1.

In the case of the hydrolysis reaction, various well-known catalysts can be used. 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 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 Alkaline catalyst. The amount of the catalyst to be used is not particularly limited, and 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 well-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; and ethylene glycol dimethyl ether; An ether solvent such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran or 1,4-dioxane; An ester solvent such as ester, ethyl acetate or butyl acetate; a ketone solvent such as acetone, 2-butanone or methyl-isobutyl ketone; acetonitrile, dimethyl hydrazine, N,N-dimethylmethyl Indoleamine, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like.

The hydrolyzate obtained by the hydrolysis reaction can be subjected to a condensation reaction to produce a siloxane coupling between the hydroxyl groups or the hydroxyl group and the remaining -OX ¹ group to produce the target component (A). 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 carried out in the aforementioned solvent. Further, the composition of the present invention is preferably a solventless type, and therefore it is desirable to remove the solvent from the component (A) by various well-known means after the hydrolysis and condensation reaction.

The physical properties of the component (A) are not particularly limited. In consideration of the balance of the desired effect of the present invention, the softening point (the softening point measured under the conditions specified in JIS K5903, the same applies to the softening point hereinafter) is usually about 40 to 150 ° C, preferably It is 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 cured product associated with the present invention are further improved. The weight average molecular weight is not particularly limited, but is usually about 2,000 to 10,000, preferably about 3,000 to 7,000. When the weight average molecular weight of the component (A) is 2,000 or more, when the composition to which the present invention is applied is heat-cured, 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 wire drawing can be suppressed, and the workability is further improved.

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

The component (B) is 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). a trioxooxy unit (T _B ) having -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), A liquid sesquioxane 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 having 1 to 15 carbon atoms and the phenyl group and the 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 can be subdivided into T1 structure [R ² O-Si(R ² )(OR ² )-O-], T2 structure [-(R ² )Si(OR ² )(O-), similarly to T _A described above. -O-] and T3 structure [-(R ² )Si(O-) ₂ -O-], and the ratio of these structures is also not particularly limited. Each configuration can be identified by measuring, for example, a ²⁹ Si-NMR spectrum of the component (B).

The proportion of T _B in the component (B) is not particularly limited. Considering the balance of the effects desired by the present invention, in particular, the compatibility, workability, hardenability, and the like of the composition of the present invention, and the balance of strength, adhesion, crack resistance, and bubble resistance of the cured product, etc. The proportion of T _B in the component (B) is usually about 65 to 100 mol%, preferably 95 to 100 mol%.

The component (B) may contain other units (monodecyloxy unit (M _B ), dioxooxy unit (D _B ), or tetradecyloxy) while maintaining a liquid state at room temperature. Base unit (Q _B )). The ratio of these other units is usually from 0 to 35 mol%, preferably from 0 to 5 mol%.

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 above formula, 0<b≦3, 0<x', 0≦y', and x'+y'=1. It should be x'=1, y'=0.

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

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

One of the starting materials of the component (B), a trialkoxy decane (b1) (hereinafter also referred to as "(b1) component"), is a general formula: X ² Si(OX ² ) ₃ (wherein, 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). The halogen atom and the alkyl group having 1 to 15 carbon atoms include the above-mentioned alkyl group. The component (b1) can be exemplified by the above-mentioned (a1) component. The component (b1) is preferably methyltrimethoxydecane. By using methyltrimethoxydecane as the component (b1), the reactivity of the component (A) and the component (B) is further improved, and the balance of the desired effect of the present invention can be maintained, particularly heat resistance, transparency, and bubble resistance. Sex is better.

The starting material of the component (B) can be used in combination with the dialkoxy decane which produces the aforementioned D _B unit (hereinafter also referred to as "(b2)", while maintaining the component (B) in a liquid state at room temperature. "Component"), a monoalkoxy decane (hereinafter also referred to as "(b3) component)) of the above M _B unit, or a tetraalkoxy decane which produces the Q _B unit (hereinafter also referred to as "(b4) ingredient").

The component (b2) is represented by the general formula: (X ² ) ₂ Si(OX ² ) ₂ (wherein X ² may be the same or different in the same manner as described above). Specific examples thereof include dimethyl dimethoxy decane, phenylmethyl dimethoxy decane, dimethyl diethoxy decane, and phenyl methyl methoxy ethoxy decane. The amount of the component (b2) to be used in the component (b1) is not particularly limited, and is usually in the range of (b1):(b2)=65 to 95:5 to 35 in terms of a molar ratio.

The component (b3) is represented by the general formula: (X ² ) ₃ SiOX ² (wherein X ² may be the same or different in the same manner as described above). Specific examples thereof include trimethyl methoxy decane, trimethyl ethoxy decane, triethyl methoxy decane, triethyl ethoxy decane, tri(n-propyl) methoxy decane, and three. (isopropyl)methoxy decane, tri(n-propyl)ethoxy decane, tri(n-butyl)methoxydecane, tris(isobutyl)methoxydecane, tris(isobutyl)B Oxydecane, dimethyl tert-butyl methoxy decane, dimethyl isobutyl methoxy decane, dimethyl cyclopentyl methoxy decane, dimethyl cyclohexyl ethoxy decane, and the like. The amount of the component (b3) to be used in 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 the molar ratio.

The component (b4) is represented by a general formula: Si(OX ² ) ₄ (wherein X ² may be the same or different in the same manner as described above). Specific examples thereof include tetraethoxysilane, tetraisopropoxy decane, tetra-n-propoxy decane, tetra-n-butoxy decane, tetramethoxy decane, dimethoxydiethoxy decane, and the like. Tetraalkoxydecane, and the like. The amount of the component (b4) to be used in the component (b1) is not particularly limited, and is usually in the range of (b1):(b4)=65 to 95:5 to 35 in terms of a molar ratio.

The component (B) can be obtained by subjecting the component (b1) and at least one selected from the group consisting of the component (b2), the component (b3) and the component (b4) 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 number of moles of water / the total number of moles of -OX ² contained in the components (b1) to (b4)] is 0.1 to 1 The range around.

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

By further condensing the hydrolyzate obtained by the hydrolysis reaction, a siloxane coupling can be generated between the hydroxyl group in the decomposition product and the remaining -OX ² group to produce the target component (B). 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 carried out in the aforementioned solvent. Further, the condensation reaction type oxoxane composition of the present invention is preferably a solventless type, and therefore it is desirable to remove the solvent from the component (B) by various well-known means after the hydrolysis and condensation reaction.

The physical properties of the component (B) are not particularly limited. In order to exhibit the desired effect of the present invention, the viscosity is usually about 5 to 10,000 mPa·s / 25 ° C, preferably about 5 to 5,000 mPa·s / 25 ° C, preferably about 5 to 2,000 mPa·s / 25 ° C. . Further, the composition of the present invention is a heat curing type, but the room temperature curing type siloxane composition also measures the viscosity at 23 °C. In this case, in one embodiment, the viscosity is preferably 501 to 10000 mPa·s / 23 ° C or more. When the viscosity of the component (B) is in this range, the balance between the coating workability and the shape maintainability of the composition of the present invention is further improved. Further, the weight average molecular weight thereof is also not particularly limited. From the same viewpoint as described above, the weight average molecular weight of the component (B) is usually from about 500 to 9,000, preferably from 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-cured, volatilization or bleeding of the low molecular weight component can be further suppressed. In addition, when the number average molecular weight of the component (B) is 9000 or less, the compatibility of the composition of the present invention is further improved, and the phenomenon such as the drawing can be suppressed, and the workability is further improved.

The commercially available product of the component (B), for example, 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., etc. .

The blending ratio of the component (A) and the component (B) is not particularly limited. From the viewpoints of the workability of the composition of the present invention, the hardness, toughness, and bubble resistance of the cured product of the present invention, the components (A) and (B) are usually blended into the component (A). The ratio of the molar number of the hydroxyl group (M _OH ) to the total number of moles (M _OR ) of the -OR ² contained in the -OR ¹ and (B) components of the component (A) is (M _OR /M _OH ) The range of about 0.1 to 20 is preferably about 5 to 20, preferably about 8 to 15. When 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 phenomenon such as wire drawing is less likely to occur during coating, and the workability is further improved. Further, when the ratio is 20 or less, the composition of the present invention is more excellent in adhesion, and the cured product is less likely to be cracked or bubbled.

The solid content mass ratio of the component (A) and the component (B) is also not particularly limited. From the viewpoints of the workability of the composition of the present invention, the compatibility of the composition of the present invention, the coating workability, and the hardness, toughness, and bubble resistance of the cured product, the mass ratio of the solid component is relative to The component (A) is 100 parts by mass, and the component (B) is usually in the 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, hafnium, and titanium. When considering the lifespan of the composition of the present invention, the color tone or transparency of the cured product of the present invention, etc., the compound is preferably 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.

The titanium compound may, for example, be diisopropoxy bis(ethylacetamidineacetic acid) titanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, diisopropoxy-bis ( Ethyl acetate ethyl acetate) titanium, diisopropoxy-bis(ethyl acetoxyacetate) titanium, diisopropoxy-bis(acetoxime) titanium, di-n-butoxy-bis(acetonitrile acetate B Ester) titanium, dimethoxy-bis(acetic acid ethyl acetate) titanium, and the like.

Examples of the tin compound include di-n-butyl methoxy tin, di-n-butyl diacetate, tin di-n-butyl dioctoate, di-n-butyl dilaurate, di-n-octyl diacetate, and di-n-octane. Tin methinate, tin di-n-butyloxyacetate, tin di-n-butyloxyoctanoate, tin di-n-butyloxylaurate, tin di-n-butyl dimethyl malate, di-n-butyloxy Tin oleate, or n-dibutyl malate polymer, di-n-octyltin malate polymer, mono-n-butyl succinate (2-ethylhexanoate) tin and di-n-butyl bis(acetonitrile) Tin and so on.

Examples of the zinc compound include zinc acetate, zinc acetylacetate, zinc 2-ethylhexanoate, zinc octoate, zinc neodecanoate, zinc laurate, zinc stearate, zinc naphthenate, and zinc benzoate. Zirconium tert-butyl benzoate, zinc salicylate, zinc (meth)acrylate, zinc acetylacetonate, and zinc 2,2,6,6-tetramethyl-3,5-heptanedionate.

The zirconium compound may, for example, be a tetraalkyl zirconate, a trialkoxy zirconium mononaphthalate, a trialkoxy monocyclopropanecarboxylate, a trialkoxycyclobutanecarboxylate or a trialkoxy group. Zirconium cyclopentanecarboxylate, zirconium dialkoxy monocyclohexanecarboxylate, zirconium trialkoxymonoadamantanecarboxylate, and the like. Here, a suitable example of the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms, and a suitable alkoxy group is a linear or branched alkane having 1 to 18 carbon atoms. Baseoxy.

The amount of the component (C) used is not particularly limited. The storage stability and the curability of the composition of the present invention, and the yellowing resistance of the cured product, etc., the amount of the component (C) used is 100 parts by mass based on the total of the components (A) and (B). The amount is usually in the range of about 0.001 to 10 parts by mass, preferably about 0.01 to 5 parts by mass, preferably about 0.1 to 1 part by mass. Further, among the compositions of the present invention, even when the amount of the component (C) used is less than 0.1 part by mass, that is, 0.001 to 0.099 parts by mass, the desired effect can be achieved.

In the composition of the present invention, for example, in order to improve the crack resistance of the cured product of the present invention, various well-known (D) inorganic fillers (hereinafter also referred to as "(D) component") may be contained. Examples of the component (D) include cerium oxide (colloidal cerium oxide, fumed cerium oxide, etc.), barium titanate, titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, cerium oxide, and cerium oxide. In particular, cerium oxide is preferred, especially fuming cerium oxide. The average primary particle diameter of the component (D) is not particularly limited. (D) component from the viewpoints of dispersion stability, coating workability, shaking property (anti-dripping property after coating), crack resistance and transparency of a cured product, and the like The average primary particle diameter is usually 100 μm or less, preferably about 5 to 100 nm, preferably about 5 to 30 nm.

The amount of the component (D) used is not particularly limited. The amount of the component (D) used is relative to the component (A) and (B) from the viewpoints of the coating workability and the shakeability of the composition of the present invention, and the transparency and crack resistance of the cured product. The total amount of the components is usually from 0.1 to 20 parts by mass, preferably from 0.5 to 10 parts by mass, based on 100 parts by mass.

In the composition of the present invention, a plasticizer, a weathering agent, an antioxidant, a thermal stabilizer, a lubricant, an antistatic agent, a whitening agent, a coloring agent, a conductive polymer, a conductive filler, and a stripping agent may be further blended as necessary. Additives such as a molding agent, a surface treatment agent, a viscosity modifier, and a decane coupling agent. Further, the composition of the present invention is preferably a solventless type, and therefore, in one embodiment, the composition of the present invention contains no solvent.

The method for producing the composition of the present invention is not particularly limited. Usually, the solid component (A) and the component (C) are added to the liquid component (B), and the component (D) and the additive are further blended as necessary, and the mixture is mixed to homogeneity. The composition of the present invention has been obtained up to now. Mixing can be carried out by well-known means.

The physical properties of the composition obtained in such a manner are not particularly limited. When considering the operability, the moldability when used as a sealant, etc., the viscosity is usually about 5 to 1,000,000 mPa·s / 25 ° C, and preferably s is about 500 to 500,000 mPa·s / 25 ° C, preferably about 1,000 to 200,000 mPa. s / 25 ° C or so.

The cured product of the present invention is a condensation reactant of the composition of the present invention. The curing conditions are not particularly limited as long as they are appropriately set depending on the intended use. The hardening temperature is usually about 25 to 200 ° C, and the hardening time is usually about 30 minutes to 5 hours. Example

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, however, the scope of the present invention is not limited by these examples. In addition, in each case, unless otherwise indicated, a part is based on mass.

In the production example, the weight average molecular weight is obtained by gel permeation chromatography (using apparatus: HLC-8220 manufactured by Tosoh Corporation, TSKgel α-M manufactured by Tosoh Corporation, developing solvent: tetrahydrofuran). The converted value of the polystyrene standard substance.

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

In the examples, the viscosity was measured 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 component (B)> Production Example 1 In a reaction apparatus equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas introduction tube, 136.2 parts of methyltrimethoxydecane and 10.8 parts of water were placed, 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 start of the reaction, 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 that it was kept at the same temperature for 30 minutes. Then, the by-produced methanol was removed to the outside of the system while taking 3 hours to raise the temperature of the reaction system to 120 °C. Next, the condensation reaction was carried out at the same temperature for 1 hour to obtain a liquid polysesquioxane having a trioxomethoxy unit (x = 1, y = 0) represented by CH ₃ SiO _3/2 (B) -1). The (B-1) component had a viscosity of 20 mPa·s / 25 ° C and a weight average molecular weight of 900. Further, the content (hereinafter abbreviated as "residual methoxy group 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 A tridecyloxy unit represented by CH ₃ SiO _3/2 was obtained in the same manner as in Production Example 1 except that the amount of water charged was 16.2 parts (x=1, y=). 0) Liquid polysesquioxane (B-2). The (B-2) component had a viscosity of 350 mPa·s/25 ° C, a weight average molecular weight of 2,500, and a residual methoxy group content of about 24% by weight, and no peak of residual hydroxyl groups was observed.

Production Example 3 An average decyloxy group was obtained in the same manner as in Production Example 1 except that the methyltrimethoxy decane was determined to be 136.2 parts, and the dimethyldimethoxy decane was determined to be 51.5 parts of water 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). The (B-3) component had a viscosity of 1600 mPa·s/25 ° C, a weight average molecular weight of 7,000, and a residual methoxy group content of about 19% by weight, and no peak of residual hydroxyl groups was observed.

<Production of Condensation-Reactive Type Oxetane Composition> Example 1 50 parts of polysilsesquioxane which is a component (A) and is solid at room temperature (trade name "KR220L", Shin-Etsu Chemical Co., Ltd. Company made, fragmented, R ¹ = methyl, content of hydroxyl group derived from sterol group is 3 wt%, T _A unit 100 mol %, softening point 67 ° C); 50 parts as component (B) (B-1) ) Component: 0.3 part of a zirconium chelate compound (C) (Zatsuki Fine Chemical Co., Ltd., ZC-700 (tetrazincacetone zirconium 20% solution)); 5.5 parts of a commercially available product as component (D) Tobacco dioxide (trade name "AEROSIL RX200", manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter: 12 nm) was sufficiently 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 oxoxane composition 2 (8000 mPa·s/) was obtained in the same manner as in Example 1 except that the component (B-2) was used as the component (B). 25 ° C).

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

Example 4 A homogenous and transparent condensation reaction type oxoxane 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 0.1 part of a titanium chelate compound (manufactured by Matsumoto Fine Chemical Co., Ltd., TC-710 diisopropoxy bis(ethylacetonitrile acetate) titanium 63% solution) was used as the component (C), and In the same manner as in Example 1, a homogeneous and transparent condensation reaction type oxoxane composition 5 (6000 mPa·s / 25 ° C) was obtained.

Example 6 A homogeneous and transparent condensation reaction type oxoxane 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 (product name "Z-6018", manufactured by Dow Corning Corp., which is a component (A) and which is solid at room temperature, has a fragment shape, R ¹ = phenyl group and N-propyl, content of hydroxyl group derived from sterol group is 6 wt%, unit of T _A 100 mol%, softening point 40 ° C); 60 parts as component (B) and liquid at room temperature Alkane (trade name "MSE-100", manufactured by Wacker Chemie AG, R ¹ = methyl group, viscosity 30 mPa·s / 25 ° C, alkoxy group content 32 wt%) was thoroughly mixed at 130 ° C to obtain a homogeneous and colorless transparent liquid. . Next, 0.3 part of ZC-700 as the component (C) was added thereto, and the mixture was sufficiently mixed at room temperature to obtain a homogeneous and transparent crystal grain adhesive 7 (2300 mPa·s / 25 ° C).

Example 8 50 parts of KR-220L as component (A) and 50 parts of liquid polysesquioxane as a component (B) at room temperature (trade name "X-40-9227", Shin-Etsu Chemical Co., Ltd. Industrial Co., Ltd., R ¹ = methyl and phenyl, viscosity 20 mPa·s / 25 ° C, alkoxy group content 15 wt%) was thoroughly mixed at 130 ° C to obtain a homogeneous and colorless transparent liquid. Next, 0.8 part of ZC-700 as the component (C); and 3.0 parts of AEROSIL RX200 as the component (D) were added thereto, and sufficiently mixed at room temperature to obtain a homogeneous and transparent die attaching agent 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 sufficiently mixed at 130 ° C to obtain a homogeneous and colorless transparent liquid. Next, 3.0 parts of ZC-700 as the component (C) was added thereto, and the mixture was thoroughly mixed at room temperature to obtain a homogeneous and transparent die attaching agent 9 (4100 mPa·s / 25 ° C).

Comparative Example 1 50 parts of polysilsesquioxane which is a component (A) and which is solid at room temperature (trade name "SILRES MK", manufactured by Asahi Kasei Wacker Silicone Co., Ltd., R ¹ = methyl group, from 矽The content of the hydroxyl group of the alcohol group is 0% by weight), 50 parts of the above (B-1) component, and 0.3 part of the zirconium chelate compound (manufactured by Matsumoto Fine Chemical Co., Ltd., ZC-700 (tetraethylguanidinium zirconium 20% solution)) And 5.5 parts of AEROSIL RX200 were thoroughly mixed at room temperature to obtain a homogeneous and transparent condensation reaction type azide composition A (5000 mPa·s / 25 ° C).

Comparative Example 2 100 parts of the component (B-1), 0.3 part of the zirconium chelate compound, and 5.5 parts of AEROSIL RX200 were thoroughly mixed at room temperature to obtain a homogeneous and transparent condensation reaction type oxoxane composition B (4000 mPa·s). /25 ° C).

Comparative Example 3 50 parts of KR220L as the component (A) and 50 parts of the component (B-1) as the component (B) and 5.5 parts of the AEROSIL RX200 as the component (D) were sufficiently mixed at room temperature to obtain a homogeneous and transparent Condensation-reactive type oxoxane composition C (6000 mPa·s / 25 ° C).

<Preparation 1 of cured product> The condensation reaction type azide composition 1 obtained in Example 1 was poured into a circular metal frame (diameter: 5 cm, height: 2 mm) coated with Teflon (registered trademark) to make it It was hardened in a drying oven at 120 ° C for 1 hour, and then hardened in a drying oven at 150 ° C for 3 hours to prepare a cured product 1 (test piece).

[Table 1]

(1) Preservation stability The above condensation reaction type azide composition 1 was allowed to stand at 25 ± 1 ° C and 50 ± 10% RH, and the service life was evaluated according to the following criteria. 5: The time when the viscosity reaches 125% 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 lower than the time. 12 hours

(2) Initial hardening property The hardness of the cured product 1 was measured using a Durometer D model manufactured by Kobunshi Co., Ltd., and the condensation reaction type siloxane composition 1 related to Example 1 was evaluated according to the following criteria. Initial hardenability.

5:40 or more 3:20 or more is lower than 40 1: lower than 20

(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 basis disclosed below.

(Formula) Mass reduction rate after heating (%) = 100 - (mass of hardened material 1 / mass of condensation-reactive type helium oxide composition 1) × 100

5: less than 15% 3:15% or more is less than 25% 1:25% or more

<Heat resistance after heating> The cured product 1 was further heated in a drying oven at 200 ° C for 1,000 hours to obtain a cured product 2 . Next, the mass reduction rate was calculated by the following calculation formula, and the heat resistance was evaluated again in accordance with the following criteria.

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

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

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

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

(5) Crack resistance The crack resistance was visually evaluated on the cured product 1 in accordance with the following criteria.

5: no cracks 1: cracked

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

(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 softness and strength was evaluated in accordance with the following criteria.

5: 20 MPa or more 3: 10 MPa or more and less than 20 MPa 1: less than 10 MPa

(8) Shear strength Using the condensation reaction type azide composition 1 obtained in Example 1, a tantalum wafer (2 mm × 2 mm × 1 mm) was bonded to an aluminum plate at 120 ° C for 1 hour in a drying furnace. It was heated and then further heated at 150 ° C for 3 hours. Next, using a commercially available bond strength tester (product name "DAGE-SERIES-4000PXY", manufactured by Dage Co., Ltd.), the shear strength of the adhesive layer (cured material) was measured at room temperature (25 ° C), and The following benchmarks are evaluated.

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

The above test was carried out in the same manner for each of the condensation reaction type oxoxane compositions of the other examples and the comparative examples or the cured products thereof.

[Table 2]

(Industrial Applicability) As shown in Table 2, it is understood that the condensation-reactive type azide composition of the present invention is excellent in storage stability and initial hardenability, and heat resistance, transparency, and resistance of the obtained cured product. Excellent in cracking, bubble resistance, bending strength and shear strength. In particular, the composition is a condensation-reactive composition, and although the water-repellent or low-molecular-weight alcohol is formed by the by-product during the reaction, the bubble resistance of the cured product is still good, which is particularly worth mentioning.

The condensation reaction type oxoxane composition of the present invention has many advantages as described above, and thus can be supplied to a wide range of applications such as an adhesive, a sealant, a coating agent, a sealant, and a coating material.

Specifically, from the results of the initial hardenability, crack resistance, flexural strength, and shear strength, the composition can be used as the same species for bismuth, aluminum, iron, gold, silver, copper, or the like. Adhesives for metals in which dissimilar metals are bonded to each other, and outer casing materials such as resistors.

Moreover, from the results of the initial hardenability, heat resistance, transparency, crack resistance, and bubble resistance, the composition can also be used as a sealing agent for a power module and a temperature sensor, an electronic substrate, or the like. Moisture-proof paint.

Further, from the results of the initial hardenability, heat resistance, transparency, crack resistance, bubble resistance, bending strength, and shear strength, the composition can also be used as a lens for glass or plastic. A transparent adhesive or the like, an optical adhesive bonded to a support, an encapsulant of an optical element such as an LED, or a sealant or a barrier material of an optical semiconductor element including a UV-LED, a laser, and a light-receiving element.

no

Claims (5)

A condensation reaction type oxoxane composition comprising: (A) a polysesquioxane which is solid at room temperature, which contains R ¹ SiO _3/2 (wherein R ¹ is selected from the group consisting of a trioxooxy unit (T _A ) having one carbon group of 1 to 15 carbon atoms, one of a group consisting of a phenyl group and a benzyl group, and having a hydroxyl group; (B) being liquid at room temperature a polysesquioxane 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) a trioxooxy unit (T _B ), and having -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) condensation reaction catalyst. The condensation reaction type oxoxane composition of claim 1, wherein the component (A) has a softening point of 40 to 150 °C. The condensation reaction type oxoxane composition of claim 1 or 2, wherein the (B) component has a viscosity of 5 to 10000 mPa·s / 25 °C. The condensation reaction type oxoxane composition according to any one of claims 1 to 3, which further contains (D) an inorganic filler. A cured product of the condensation reaction type oxoxane composition according to any one of claims 1 to 4.