JP6439601B2 - Flame retardant room temperature curable organopolysiloxane composition, method for producing the same, and electric / electronic component - Google Patents

Description

The present invention relates to a flame retardant room temperature curable organopolysiloxane composition useful as a silicone-based sealing agent or adhesive. In particular, excellent storage stability, and heat resistance temperature is high, the flame retardant room temperature curable organopolysiloxane composition Mono及 beauty method for producing the same, and the sealing with a cured product of the composition, fixed or bonded electrical electronic components About.

  Organopolysiloxane compositions are used for electrical and electronic parts because of their excellent heat resistance, electrical properties, and adhesiveness. Further, the composition is often required to have flame retardancy in consideration of safety. In order to impart flame retardancy to the organopolysiloxane composition, it is known to add a platinum compound and an inorganic filler (Patent Documents 1 to 3: JP-A-4-18451, JP-A-5-125285). No., JP-A-5-230376).

  Among the inorganic fillers, aluminum hydroxide is particularly useful because it has a high endothermic effect of crystal water. However, aluminum hydroxide causes a problem in terms of heat resistance because crystal water is gradually lost even at a temperature lower than 200 ° C. That is, when the organopolysiloxane cured product is used at a high temperature, water (water vapor) is generated from aluminum hydroxide added to the organopolysiloxane cured product, and bubbles are generated in the organopolysiloxane cured product. . When bubbles are generated in the cured organopolysiloxane, not only the appearance is deteriorated, but also there is a possibility that the waterproof / moisture-proof property is lowered and the electrical insulation property is lowered.

  Therefore, a method has been proposed in which magnesium hydroxide having a decomposition temperature around 350 ° C. or boehmite (aluminum hydroxide oxide) having a decomposition temperature around 500 ° C. is used as a flame retardant filler (Patent Documents 4 and 5: Patents). No. 3,297,014 and JP 2010-132865). Although these have a lower flame retardant effect than aluminum hydroxide, they can solve the above heat resistance problem. In order to obtain flame retardancy by a conventional method, it is necessary to add a large amount of these flame retardant fillers. However, these compounds have surface activity and may have a high water content, and there is a concern that the curability decreases with time.

Japanese Patent Laid-Open No. 4-18451 JP-A-5-125285 Japanese Patent Laid-Open No. 5-230376 Japanese Patent No. 3297014 JP 2010-132865 A

The present invention has been made in view of the above circumstances, and particularly when exposed to a high temperature, since no bubbles are generated from the cured product, the reliability is high, and the storage stability in which the curability does not deteriorate with time. and an object to a manufacturing method excellent flame retardancy room temperature curing organopolysiloxane compositions Mono及 beauty, and sealing with a cured product of the composition, to provide a fixed or glued electric and electronic parts.

  As a result of intensive studies to achieve the above object, the present inventors have used magnesium hydroxide having a specific average particle size and water content as a flame retardant filler, and when exposed to high temperatures. However, it has been found that a flame-retardant room temperature curable organopolysiloxane composition can be obtained in which bubbles are not generated from the cured product and the curability does not deteriorate with time, and the present invention has been made.

That is, the present invention provides the following flame retardant room temperature curable organopolysiloxane composition, a method for producing the same, and an electric / electronic component sealed, fixed, or bonded with a cured product (silicone rubber) of the composition. To do.
[1]
(A) 100 parts by mass of a diorganopolysiloxane blocked with hydroxyl groups and / or hydrolyzable siloxy groups bonded to silicon atoms at both ends of the molecular chain,
(B) 5 to 500 parts by mass of magnesium hydroxide having an average particle diameter of 0.6 to 5 μm and a moisture content measured by an infrared moisture meter at 150 ° C. of 1.0% by mass or less;
(C) Curing catalyst 0.001 to 30 parts by mass,
(D) The following general formula (1):
R ¹ _a SiX ¹ _4-a (1)
(Wherein R ¹ is a 3-methacryloxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-glycidoxypropyl group, N-2 (aminoethyl) -3-aminopropyl group, 3 - aminopropyl group, 3-mercaptopropyl group, 3-acryloxypropyl indicates a propyl group, and a substituted monovalent hydrocarbon group or unsubstituted monovalent hydrocarbon group selected from N- phenyl-3-aminopropyl group, X ¹ Represents the same or different hydrolyzable groups, a is 1 or 2, provided that when a = 1, R ¹ is the above substituted monovalent hydrocarbon group, and when a = 2, R ¹ is They may be the same or different, but at least one R ¹ is the above substituted monovalent hydrocarbon group.)
A flame retardant room temperature curable organopolysiloxane composition comprising 0.05 to 20 parts by mass of a hydrolyzable organosilicon compound and / or a partially hydrolyzed condensate thereof.
[2]
Furthermore, (E) the following general formula (2):
R ² _b SiX ² _4-b (2)
(Wherein R ² represents an unsubstituted or substituted monovalent hydrocarbon group, X ² represents the same or different hydrolyzable group, b is 0, 1 or 2, provided that b = 2 R ² may be the same or different.
The hydrolyzable organosilicon compound other than the component (D) and / or its partial hydrolysis condensate represented by the formula (A) is contained in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A). [1] The flame-retardant room temperature curable organopolysiloxane composition according to [1].
[3]
The flame retardant room temperature curable organopolysiloxane composition according to [1] or [2], wherein the average particle size of the component (B) magnesium hydroxide is 0.6 to 3 μm .
[4 ]
A method for producing a two-component flame retardant room temperature curable organopolysiloxane composition obtained by mixing the following first composition and second composition in a mass ratio of 100: 10 to 100: 100, respectively. In addition, (C) the curing catalyst in an amount corresponding to 0.001 to 30 parts by mass with respect to 100 parts by mass in total of the component (A) of the first composition and the second composition, A method for producing a flame retardant room temperature curable organopolysiloxane composition obtained by blending with any of the second compositions.
100 parts by mass of diorganopolysiloxane blocked with a hydroxyl group and / or a hydrolyzable siloxy group in which both ends of the first composition (A) molecular chain are bonded to silicon atoms,
(B) 5 to 500 parts by mass of magnesium hydroxide having an average particle diameter of 0.6 to 5 μm and a moisture content measured by an infrared moisture meter at 150 ° C. of 1.0% by mass or less;
(D) The following general formula (1):
R ¹ _a SiX ¹ _4-a (1)
(Wherein R ¹ is a 3-methacryloxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-glycidoxypropyl group, N-2 (aminoethyl) -3-aminopropyl group, 3 - aminopropyl group, 3-mercaptopropyl group, 3-acryloxypropyl indicates a propyl group, and a substituted monovalent hydrocarbon group or unsubstituted monovalent hydrocarbon group selected from N- phenyl-3-aminopropyl group, X ¹ Represents the same or different hydrolyzable groups, a is 1 or 2, provided that when a = 1, R ¹ is the above substituted monovalent hydrocarbon group, and when a = 2, R ¹ is They may be the same or different, but at least one R ¹ is the above substituted monovalent hydrocarbon group.)
Corresponding to 0.05 to 20 parts by mass with respect to 100 parts by mass in total of the component (A) of the first composition and the second composition Amount to do,
(E) The following general formula (2):
R ² _b SiX ² _4-b (2)
(Wherein R ² represents an unsubstituted or substituted monovalent hydrocarbon group, X ² represents the same or different hydrolyzable group, b is 0, 1 or 2, provided that b = 2 R ² may be the same or different.
The hydrolyzable organosilicon compound and / or its partially hydrolyzed condensate other than the component (D) represented by 0 to 0 in total with respect to 100 parts by mass of the component (A) of the first composition and the second composition A composition comprising an amount corresponding to 30 parts by mass.
Second composition (A) 100 parts by mass of diorganopolysiloxane capped with hydroxyl groups and / or hydrolyzable siloxy groups bonded to silicon atoms at both ends of the molecular chain
(B) It contains 5-500 parts by mass of magnesium hydroxide having an average particle size of 0.6-5 μm and a moisture content measured by an infrared moisture meter at 150 ° C. of 1.0% by mass or less. Composition.
[ 5 ]
Electrical and electronic parts sealed, fixed, or bonded with a cured product of the flame-retardant room temperature curable organopolysiloxane composition according to any one of [1] to [ 3 ].

According to the present invention, a flame-retardant room temperature curable organopolysiloxane composition excellent in storage stability, which does not generate bubbles even when exposed to high temperatures, and a cured product of the composition (silicone rubber) Thus, it is possible to obtain an electric / electronic component or the like that is sealed, fixed or bonded.
In the present invention, room temperature means 23 ° C. ± 10 ° C.

Hereinafter, the present invention will be described in more detail.
[(A) component]
The diorganopolysiloxane of the component (A) is a hydroxyl group (that is, silanol group) and / or hydrolyzable siloxy group (for example, diorganohydroxysiloxy group and / or 1 to 3) having both molecular chain ends bonded to silicon atoms. Is a linear diorganopolysiloxane basically composed of repeating diorganosiloxane units, which is blocked with a siloxy group having one hydrolyzable group. It is a base polymer (main agent) component constituting the polysiloxane composition, and hydroxyl groups and / or hydrolyzable groups are bonded to silicon atoms at both ends of the molecular chain.

  Examples of the hydrolyzable group include an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a ketoxime group having 3 to 8 carbon atoms such as a methylethyl ketoxime group; an acyloxy group having 2 to 6 carbon atoms such as an acetoxy group. An aminooxy group and the like are exemplified.

  Further, as other groups (unsubstituted or substituted, preferably monovalent hydrocarbon group having 1 to 20 carbon atoms) bonded to the silicon atom of the organopolysiloxane, a methyl group, an ethyl group, a propyl group, an isopropyl group, Alkyl groups such as butyl group, 2-ethylbutyl group and octyl group; cycloalkyl groups such as cyclohexyl group and cyclopentyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, naphthyl group and biphenylyl group Aryl groups such as phenanthryl groups; aralkyl groups such as benzyl groups and phenylethyl groups; alkyl halides such as chloromethyl groups, trichloropropyl groups, trifluoropropyl groups, bromophenyl groups, and chlorocyclohexyl groups; aryl or cycloalkyl groups 2-cyanoethyl group, 3-silane Nopuropiru groups include cyanated alkyl groups such as 2-cyanobutyl group, a methyl group, a vinyl group, a phenyl group, a trifluoropropyl group are preferred, a methyl group is particularly preferred. In addition, as another group couple | bonded with a silicon atom, it is preferable that it is group which does not contain a nitrogen atom, a sulfur atom, and an oxygen atom.

The viscosity of the organopolysiloxane of component (A) at 23 ° C. is preferably in the range of 10 to 500,000 mPa · s, more preferably 100 to 100,000 mPa · s, and still more preferably 200 to 50,000 mPa · s. is there. When the viscosity is too small, sufficient mechanical properties may not be obtained in the cured product, and when the viscosity is too large, the viscosity of the composition may be increased and workability may be deteriorated. In addition, as a range in which the organopolysiloxane of component (A) can take the above viscosity, the degree of polymerization (or the number of repeating bifunctional diorganosiloxane units present in the molecule) is usually 10 to 1,500, It is preferably 30 to 1,200, more preferably 50 to 1,000, and still more preferably about 100 to 800. Here, the viscosity can be measured by a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer, etc.). The degree of polymerization (or molecular weight) can be determined, for example, as the number average degree of polymerization (or number average molecular weight) in terms of polystyrene in gel permeation chromatography (GPC) analysis using toluene or the like as a developing solvent.
The (A) component organopolysiloxane may be used alone or in combination of two or more.

[Component (B)]
(B) Magnesium hydroxide having an average particle size of 0.6 to 5 μm and a water content at 150 ° C. of 1.0% by mass or less is the composition of the present invention as a flame retardant filler. It is blended to impart flame retardancy to a cured silicone rubber obtained by curing. This magnesium hydroxide component (B) is a flame retardant filler having a thermal decomposition temperature of 300 ° C. or higher. Therefore, the composition of the present invention and its cured product (silicone rubber) have excellent heat resistance and flame resistance. Can have sex.
Examples of the flame retardant filler having a thermal decomposition temperature of 300 ° C. or higher include boehmite, zinc carbonate, calcium hydroxide and the like in addition to magnesium hydroxide. In the present invention, the cured product ( From the viewpoint of flame retardancy and heat resistance of silicone rubber), magnesium hydroxide having a specific average particle size and a specific water content is selectively used as a flame retardant filler of the component (B). is there.

That is, the magnesium hydroxide component (B) has an average particle diameter of 0.6 to 5 μm and a temperature at 150 ° C. in order to prevent deterioration of the curability of the composition with time and maintain storage stability. The water content needs to be 1.0 mass% or less. When magnesium hydroxide that does not satisfy at least one of the requirements for the average particle size and the water content is used as the flame retardant filler, the curability is lowered over time or the flame retardancy is inferior. The average particle diameter needs to be 0.6-5 μm, preferably 0.6-3 μm, more preferably 0.7-2 μm. Moreover, it is preferable that the specific surface area by BET method is 11 m < ² > / g or less. The water content at 150 ° C. needs to be 1.0% by mass or less (that is, 0 to 1.0% by mass), preferably 0 to 0.8% by mass, more preferably 0 to 0.6% by mass. is there. In addition, an average particle diameter can be calculated | required with the particle size distribution measuring apparatus by a laser beam diffraction method, and is the value measured as mass average value D50 (namely, particle diameter or median diameter when cumulative mass will be 50%). The amount of moisture can be obtained with an infrared moisture meter, and is a value measured at 150 ° C.

The component (B) magnesium hydroxide may be used as a flame retardant filler whose surface is hydrophobized with an organosilicon compound such as organochlorosilane, organoalkoxysilane, or organosilazane, a fatty acid, paraffin, or the like. Good.
(B) A component may be used individually by 1 type, or may use 2 or more types together.

  (B) The compounding quantity of a component is 5-500 mass parts with respect to 100 mass parts of organopolysiloxane of (A) component, and it is preferable that it is 10-300 mass parts. If the amount is less than 5 parts by mass, sufficient flame retardancy cannot be obtained. If the amount exceeds 500 parts by mass, the viscosity of the resulting composition is too high, and workability and dischargeability are deteriorated.

[Component (C)]
The curing catalyst which is the component (C) of the present invention is a condensation catalyst for condensation reaction which is added to accelerate the condensation reaction and accelerate rubberization.
Examples of the curing catalyst include organic titanates such as tetrabutyl titanate and tetraisopropyl titanate; organic titanium chelate compounds such as diisopropoxybis (acetylacetonato) titanium and diisopropoxybis (ethylacetoacetate) titanium; aluminum Organic aluminum compounds such as tris (acetylacetonate) and aluminum tris (ethylacetoacetate); organic zirconium compounds such as zirconium tetra (acetylacetonate) and zirconium tetrabutyrate; dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin di (2 -Ethylhexanoate), organotin compounds such as dioctyltin dineodecanoate; tin naphthenate, tin oleate, tin butyrate, cobalt naphthenate Metal salts of organic carboxylic acids such as zinc stearate; amine compounds such as hexylamine and dodecylamine phosphate; and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; lower alkali metals such as potassium acetate and lithium nitrate Fatty acid salts; Dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; and guanidyl group-containing organosilicon compounds such as tetramethylguanidinepropyltrimethoxysilane.
Component (C) can be used alone or in combination of two or more.

  The compounding amount of the curing catalyst is 0.001 to 30 parts by mass, preferably 0.002 to 20 parts by mass, more preferably 0.004 to 10 parts by mass with respect to 100 parts by mass of the component (A). Degree. If the curing catalyst is too small, curing is insufficient, and if it is too large, curing is too fast and handling is difficult.

[(D) component]
In the present invention, in order to improve adhesive strength, a specific hydrolyzable organosilicon compound and / or a partial hydrolysis condensate thereof is further blended as an adhesion-imparting component (adhesion aid) as component (D).
That is, the component (D) has the following general formula (1):
R ¹ _a SiX ¹ _4-a (1)
(Wherein R ¹ represents a substituted monovalent hydrocarbon group or an unsubstituted monovalent hydrocarbon group containing at least one atom selected from a nitrogen atom, a sulfur atom and an oxygen atom, and X ¹ is the same or A different hydrolyzable group, a being 0, 1 or 2, provided that when a = 1, R ¹ is a substituted monovalent hydrocarbon group; when a = 2, R ¹ may be the same But may be different, at least one R ¹ is a substituted monovalent hydrocarbon group.)
A hydrolyzable organosilicon compound such as hydrolyzable silane and / or a partially hydrolyzed condensate thereof (that is, a hydrolyzable siloxane oligomer). The “partially hydrolyzed condensate” means an organopolysiloxane (siloxane oligomer) having two or more residual hydrolyzable groups in a molecule formed by partially hydrolyzing the hydrolyzable silane compound. .

In the above formula (1), R ¹ is a substituted monovalent hydrocarbon group or an unsubstituted monovalent hydrocarbon group containing at least one atom selected from a nitrogen atom, a sulfur atom and an oxygen atom, and R ¹ Among them, specific examples of the substituted monovalent hydrocarbon group include 3-methacryloxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-glycidoxypropyl group, and N-2 (aminoethyl). ) A nitrogen atom or sulfur atom having 1 to 10 carbon atoms such as a 3-aminopropyl group, a 3-aminopropyl group, a 3-mercaptopropyl group, a 3-acryloxypropyl group, or an N-phenyl-3-aminopropyl group. And a substituted monovalent hydrocarbon group such as an alkyl group substituted with at least one atom selected from oxygen atoms.
Further, among R ^1, the unsubstituted monovalent hydrocarbon group includes an alkyl group such as a methyl group, an ethyl group, and a propyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, a vinyl group, and an allyl group. An unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as an aralkyl group such as an alkenyl group and a benzyl group, is preferable, and an alkyl group is preferable.

X ¹ is a hydrolyzable group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; an alkenoxy group having 2 to 6 carbon atoms such as an isopropenoxy group; 3 to 3 carbon atoms such as a methyl ethyl ketoxime group. An ketoxime group of 8; an acyloxy group having 2 to 6 carbon atoms such as an acetoxy group; an aminooxy group and the like are exemplified.
a is 0, 1 or 2, preferably 0 or 1.

  As the hydrolyzable organosilicon compound of component (D) and / or its partial hydrolysis condensate, a silane coupling agent (hydrolyzable silyl group-containing carbon functional silane) known in the art is preferably used. And a number of silane coupling agents can be exemplified, and among them, the number of carbon atoms is 1 to 10, particularly, the number of carbon atoms including at least one atom selected from a nitrogen atom, a sulfur atom and an oxygen atom. 3 to 8 substituted monovalent hydrocarbon groups are preferred, and those having an alkoxy group or alkenoxy group as the hydrolyzable group are preferred.

Specific examples of the component (D) include 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl. Methyldiethoxysilane, N-2 (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxy Propyltriisopropenoxysilane, 3-glycidoxypropylmethyldiisopropenoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and partial hydrolytic condensation of these silanes Things etc. are illustrated . In particular, the use of an amino group-containing silane coupling agent is preferred.
(D) A component may be used individually by 1 type, or 2 or more types of mixtures may be sufficient as it.

  (D) The compounding quantity of a component is 0.05-20 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.1-15 mass parts, Most preferably, it is 0.5-10 mass parts. If it is less than 0.05 parts by mass, sufficient adhesion cannot be obtained, and if it exceeds 20 parts by mass, the weather resistance and mechanical properties are inferior.

[(E) component]
In the present invention, if necessary, a specific hydrolyzable organosilicon compound other than the component (D) and / or a partial hydrolysis condensate thereof (component (E)) is optionally blended as a crosslinking agent component. May be.
That is, the component (E) has the following general formula (2):
R ² _b SiX ² _4-b (2)
(Wherein R ² represents an unsubstituted or substituted monovalent hydrocarbon group, X ² represents the same or different hydrolyzable group, b is 0, 1 or 2, provided that b = 2 R ² may be the same or different.
And a hydrolyzable organosilicon compound other than the component (D) and / or a partially hydrolyzed condensate thereof.

In the above formula (2), R ² is an unsubstituted or substituted monovalent hydrocarbon group, and the substituted monovalent hydrocarbon group in R ^{2 is} a substituted monovalent hydrocarbon group other than R ¹ (for example, A halogen-substituted or cyano-substituted monovalent hydrocarbon group, etc., and the unsubstituted or substituted monovalent hydrocarbon group of R ² includes an alkyl group such as a methyl group, an ethyl group, and a propyl group, and an alkenyl such as a vinyl group Groups, aryl groups such as phenyl groups, chloromethyl groups, 2-cyanoethyl groups, 3,3,3-trifluoropropyl groups and the like, unsubstituted or substituted monovalent hydrocarbon groups having about 1 to 8 carbon atoms, especially Is preferably an unsubstituted monovalent hydrocarbon group having about 1 to 6 carbon atoms, particularly preferably a methyl group, an ethyl group, a propyl group, a vinyl group and a phenyl group.

In addition, examples of the hydrolyzable group for X ² include carbon numbers such as alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, alkenoxy groups having 2 to 6 carbon atoms such as isopropenoxy group, and methylethylketoxime group. Examples thereof include an acyloxy group having 2 to 6 carbon atoms such as a 3-8 ketoxime group and an acetoxy group, and an alkoxy group and an isopropenoxy group are preferable.
b is 0, 1 or 2, preferably 0 or 1.

Specific examples of the component (E) include alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, and methyltriethoxysilane, methyltris (dimethylketoxime) silane, and methyltris (methylethylketoxime). ) Ketoxime silane such as silane, ethyltris (methylethylketoxime) silane, methyltris (methylisobutylketoxime) silane, vinyltris (methylethylketoxime) silane, phenyltris (methylethylketoxime) silane, methyltriisopropenoxysilane, ethyltriisopropeno Isopropenoxy group-containing silanes such as xyloxysilane and vinyltriisopropenoxysilane, methyltriacetoxysilane, Acetoxysilane, various silane such as acetoxy silanes such as vinyl triacetoxy silane, and partial hydrolytic condensates of these silanes.
(E) A component may be used individually by 1 type, or 2 or more types of mixtures may be sufficient as it.

  (E) When mix | blending a component, the compounding quantity is 0.1-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.5-20 mass parts, Most preferably, it is 1-15 mass parts. Used in the range of If the amount is less than 0.1 parts by mass, sufficient crosslinking cannot be obtained, and it may be difficult to obtain a composition having an appropriate rubber elasticity. If the amount exceeds 30 parts by mass, the obtained cured product tends to have poor mechanical properties.

[Other additives]
The flame retardant room temperature curable organopolysiloxane composition of the present invention includes reinforcing fillers such as fumed silica, wet silica, precipitated silica, calcium carbonate, pigments, dyes, antioxidants, antioxidants, electrification Inhibitors, platinum compounds, antimony oxide, flame retardants such as chlorinated paraffin, and the like can be blended. Furthermore, polyethers, fungicides, antibacterial agents and the like as thixotropy improvers can be blended. The amount of these additives is arbitrary as long as the object of the present invention is not impaired.

  The flame retardant room temperature curable organopolysiloxane composition of the present invention preferably contains the above components (A) to (E) and other various additives, preferably in a dry atmosphere (substantially free of moisture). Can be obtained by mixing uniformly.

  In addition, the flame retardant room temperature curable organopolysiloxane composition of the present invention is separately prepared and stored as a two-component mixed composition, and the two-component composition is uniformly mixed immediately before use. Flame retardant room temperature curable organopolysiloxane composition. In this case, for example, the following first composition and second composition are prepared separately, and (C) 0.0011 to 60 parts by mass of the curing catalyst (that is, the first composition and the second composition). (A) An amount corresponding to 0.001 to 30 parts by mass with respect to a total of 100 parts by mass of the component) is blended in either the first composition or the second composition, and these first composition and Immediately before using the second composition, it is preferable to uniformly mix at a mass ratio of 100: 10 to 100: 100, respectively, to obtain a flame retardant room temperature curable organopolysiloxane composition.

100 parts by weight of the first composition component (A),
5 to 500 parts by mass of the component (B),
The amount corresponding to 0.05 to 20 parts by mass with respect to a total of 100 parts by mass of the component (A) of the first component and the second composition (D),
Optionally, a composition comprising an amount corresponding to 0 to 30 parts by mass with respect to 100 parts by mass in total of the component (A) of the first component and the component (A) of the second composition as necessary. .
Second composition 100 parts by weight of component (A) above,
The composition formed by containing 5-500 mass parts of said (B) component.
In addition, when mix | blending the said (E) component and other additives, although a 1st composition and a 2nd composition can be mix | blended, the mixing | blending to either one is preferable on performance, and a 1st composition The blending into is more preferred.

  The flame retardant room temperature curable organopolysiloxane composition of the present invention is cured by moisture in the atmosphere by being applied or molded at room temperature and in the atmosphere. It may be the same as the curable organopolysiloxane composition.

  The flame-retardant room temperature curable organopolysiloxane composition of the present invention can be suitably used for sealing, fixing or bonding electric and electronic parts, and is electrically sealed, fixed or bonded with a cured product of the composition. Examples of the electronic component include a solar battery frame, a terminal box, and an electronic substrate capacitor.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the viscosity is the value measured with a rotational viscometer at 23 ° C. The average particle diameter is the cumulative mass average value D50 in the particle size distribution measurement by the laser light diffraction method, and the water content is a value measured with an infrared moisture meter at 150 ° C.

[Example 1]
100 parts by mass of polydimethylsiloxane having both ends of molecular chain having a viscosity of 30,000 mPa · s at 23 ° C. blocked with a trimethoxysiloxy group, an average particle size of 1.0 μm as a flame retardant filler, and a moisture content at 150 ° C. 60 parts by mass of 0.4% by weight magnesium hydroxide, 2 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane as a reinforcing filler, and an alcoholic solution of chloroplatinic acid as a flame retardant improver A platinum amount of 20 ppm was added to the mixture, and the mixture was thoroughly mixed under reduced pressure to obtain a mixture. Next, 2 parts by mass of a partial hydrolyzate of methyltrimethoxysilane, 1 part by mass of vinyltrimethoxysilane, 0.5 part by mass of 3-aminopropyltrimethoxysilane, diisopropoxybis (acetylacetonate) titanium Sample 1 was obtained by thoroughly mixing 3 parts by mass under reduced pressure.

[Comparative Example 1]
Sample 2 was prepared in the same manner as in Example 1 except that the flame retardant filler was changed to boehmite with an average particle size of 1.8 μm and a moisture content of 0.4 mass% at 150 ° C.

[Example 2]
Sample 3 was prepared under the same conditions as in Example 1, except that the flame-retardant filler was changed to silane-treated magnesium hydroxide having an average particle size of 1.1 μm and a moisture content of 0.4 mass% at 150 ° C. Got.

[Comparative Example 2]
Sample 4 was prepared in the same manner as in Example 1 except that the flame retardant filler was changed to magnesium hydroxide having an average particle size of 7.0 μm and a moisture content of 0.2% by mass at 150 ° C. .

[Example 3]
100 parts by mass of polydimethylsiloxane having both ends of a molecular chain having a viscosity of 5,000 mPa · s at 23 ° C. blocked with a hydroxyl group, 4 parts by mass of vinyltrimethoxysilane and 1.0 part by mass of tetramethylguanidinepropyltrimethoxysilane Thorough mixing under reduced pressure gave a mixture. This mixture was treated with 60 parts by mass of magnesium hydroxide having an average particle size of 1.0 μm as a flame retardant filler and a moisture content of 0.4% by mass at 150 ° C., and a surface treated with dimethyldichlorosilane as a reinforcing filler. 5 parts by mass of silica, and an alcohol solution of chloroplatinic acid as a flame retardant improver is added in an amount such that the platinum amount is 20 ppm with respect to the total mass of the mixture, and thoroughly mixed under reduced pressure, and then 3-aminopropyltrimethoxy 0.5 parts by mass of silane and 0.15 parts by mass of dioctyltin dineodecanoate were added and thoroughly mixed under reduced pressure to obtain Sample 5.

[Example 4]
To 100 parts by mass of polydimethylsiloxane having both molecular chain ends with a viscosity of 30,000 mPa · s at 23 ° C. blocked with a trimethoxysilyl group, an average particle size of 0.7 μm as a flame retardant filler, and a water content of 150 ° C. 60 mass parts of 0.6 mass% magnesium hydroxide, 2 mass parts of fumed silica whose surface was treated with dimethyldichlorosilane as a reinforcing filler, and an alcohol solution of chloroplatinic acid as a flame retardant improver A platinum amount of 20 ppm was added to the mixture, and the mixture was thoroughly mixed under reduced pressure to obtain a mixture. Next, 3 parts by mass of 3-aminopropyltrimethoxysilane was added to this mixture and thoroughly mixed under reduced pressure to obtain a first composition.
Further, 100 parts by mass of polydimethylsiloxane having both ends of molecular chain having a viscosity of 5,000 mPa · s at 23 ° C. blocked with silanol groups, an average particle size of 0.7 μm as a flame retardant filler, and a moisture content at 150 ° C. 60 parts by mass of 0.6% by weight magnesium hydroxide, 5 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane as a reinforcing filler, and an alcoholic solution of chloroplatinic acid as a flame retardant improver A platinum amount of 20 ppm was added to the mixture, and the mixture was thoroughly mixed under reduced pressure to obtain a mixture. Next, 0.15 parts by mass of dioctyltin dineodecanoate was added to this mixture and thoroughly mixed under reduced pressure to obtain a second composition.
The first composition and the second composition were mixed at a mass ratio of 1: 1 immediately before being used in the adhesion test described below to obtain Sample 6.

[Comparative Example 3]
Sample 7 was prepared in the same manner as in Example 1 except that the flame retardant filler was changed to magnesium hydroxide having an average particle diameter of 0.4 μm and a moisture content of 0.7 mass% at 150 ° C. .

[Comparative Example 4]
Sample 8 was prepared in the same manner as in Example 1 except that the flame retardant filler was changed to magnesium hydroxide having an average particle size of 0.8 μm and a moisture content of 1.2% by mass at 150 ° C. .

[Comparative Example 5]
A sample 9 was obtained in the same manner as in Example 1 except that the flame retardant filler was changed to boehmite having an average particle size of 0.7 μm and a moisture content of 1.4% by mass at 150 ° C.

[Comparative Example 6]
A sample 10 was obtained under the same conditions as in Example 1 except that the flame retardant filler was changed to aluminum hydroxide having an average particle size of 1.2 μm and a moisture content of 0.4 mass% at 150 ° C. .

[Evaluation]
For storage stability evaluation, tackiness time after initial and heat-promoted deterioration (left at 70 ° C for 5 days) and flame-retardant polycarbonate resin used in electrical parts (trade name: Iupilon FPR3500, manufactured by Mitsubishi Engineering Plastics) Simple adhesion was confirmed. The heat resistance and flame retardancy were also evaluated. The obtained results are shown in Tables 1 and 2.

Tack free time:
Measured by finger touch. Specifically, the sample was placed flat in an atmosphere of 23 ° C./50% RH, the surface was touched with a fingertip cleaned with ethyl alcohol, and the time until the sample did not adhere to the fingertip was measured.

Simple adhesion:
A sample was applied in a shape of 20 mm × 30 mm × 5 mm on a flame-retardant polycarbonate resin, and allowed to stand for 7 days in a 23 ° C./50% RH environment to be cured. The adhesiveness was confirmed by visual inspection. After the pulling, the case where the cured silicone rubber was adhered was evaluated as ◯, and the case where it was peeled off was evaluated as ×.

Heat-resistant:
A glass petri dish having a diameter of 25 mm and a depth of 10 mm was filled with the sample so as to have a thickness of 5 mm, and cured for one week in an atmosphere of 23 ± 2 ° C. and 50 ± 5% RH. The whole glass petri dish was allowed to stand at 200 ° C. for 2 hours.

Flame retardance:
A sample having a thickness of 3.0 mm was prepared by allowing the sample to stand for 7 days in a 23 ° C./50% RH environment, and evaluated by a method defined in UL-94.

  From the above results, it can be seen that the composition of the present invention (Samples 1, 3, 5, and 6 of Examples 1 to 4) has little change in tack-free time after heat-promoting deterioration and is excellent in storage stability. Furthermore, it turns out that it is excellent also about heat resistance and a flame retardance. On the other hand, in samples 2 and 4 of Comparative Examples 1 and 2 using a flame retardant filler outside the scope of the present invention, the cured product (silicone rubber) is inferior in flame retardancy compared to the composition of the present invention. It is. Moreover, in the samples 7 to 9 of Comparative Examples 3 to 5 using the flame retardant filler which is also outside the scope of the present invention, the tack-free time change after the accelerated heating deterioration is large, the adhesiveness is lowered, and the storage stability is also reduced. It became inferior result. Further, in the sample 10 of Comparative Example 6 using aluminum hydroxide having a thermal decomposition temperature of about 200 ° C. as a flame retardant filler, foaming is performed after heat resistance, so that reliability as a sealing agent or an adhesive is lowered. .

Claims (5)

(A) 100 parts by mass of a diorganopolysiloxane blocked with hydroxyl groups and / or hydrolyzable siloxy groups bonded to silicon atoms at both ends of the molecular chain,
(B) 5 to 500 parts by mass of magnesium hydroxide having an average particle diameter of 0.6 to 5 μm and a moisture content measured by an infrared moisture meter at 150 ° C. of 1.0% by mass or less;
(C) Curing catalyst 0.001 to 30 parts by mass,
(D) The following general formula (1):
R ¹ _a SiX ¹ _4-a (1)
(Wherein R ¹ is a 3-methacryloxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-glycidoxypropyl group, N-2 (aminoethyl) -3-aminopropyl group, 3 - aminopropyl group, 3-mercaptopropyl group, 3-acryloxypropyl indicates a propyl group, and a substituted monovalent hydrocarbon group or unsubstituted monovalent hydrocarbon group selected from N- phenyl-3-aminopropyl group, X ¹ Represents the same or different hydrolyzable groups, a is 1 or 2, provided that when a = 1, R ¹ is the above substituted monovalent hydrocarbon group, and when a = 2, R ¹ is They may be the same or different, but at least one R ¹ is the above substituted monovalent hydrocarbon group.)
A flame retardant room temperature curable organopolysiloxane composition comprising 0.05 to 20 parts by mass of a hydrolyzable organosilicon compound and / or a partially hydrolyzed condensate thereof. Furthermore, (E) the following general formula (2):
R ² _b SiX ² _4-b (2)
(Wherein R ² represents an unsubstituted or substituted monovalent hydrocarbon group, X ² represents the same or different hydrolyzable group, b is 0, 1 or 2, provided that b = 2 R ² may be the same or different.
The hydrolyzable organosilicon compound other than the component (D) and / or its partial hydrolysis condensate represented by the formula (A) is contained in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A). The flame retardant room temperature curable organopolysiloxane composition according to claim 1. The flame retardant room temperature curable organopolysiloxane composition according to claim 1 or 2, wherein the magnesium hydroxide as the component (B) has an average particle size of 0.6 to 3 µm . A method for producing a two-component flame retardant room temperature curable organopolysiloxane composition obtained by mixing the following first composition and second composition in a mass ratio of 100: 10 to 100: 100, respectively. In addition, (C) the curing catalyst in an amount corresponding to 0.001 to 30 parts by mass with respect to 100 parts by mass in total of the component (A) of the first composition and the second composition, A method for producing a flame retardant room temperature curable organopolysiloxane composition obtained by blending with any of the second compositions.
100 parts by mass of diorganopolysiloxane blocked with a hydroxyl group and / or a hydrolyzable siloxy group in which both ends of the first composition (A) molecular chain are bonded to silicon atoms,
(B) 5 to 500 parts by mass of magnesium hydroxide having an average particle diameter of 0.6 to 5 μm and a moisture content measured by an infrared moisture meter at 150 ° C. of 1.0% by mass or less;
(D) The following general formula (1):
R ¹ _a SiX ¹ _4-a (1)
(Wherein R ¹ is a 3-methacryloxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-glycidoxypropyl group, N-2 (aminoethyl) -3-aminopropyl group, 3 - aminopropyl group, 3-mercaptopropyl group, 3-acryloxypropyl indicates a propyl group, and a substituted monovalent hydrocarbon group or unsubstituted monovalent hydrocarbon group selected from N- phenyl-3-aminopropyl group, X ¹ Represents the same or different hydrolyzable groups, a is 1 or 2, provided that when a = 1, R ¹ is the above substituted monovalent hydrocarbon group, and when a = 2, R ¹ is They may be the same or different, but at least one R ¹ is the above substituted monovalent hydrocarbon group.)
Corresponding to 0.05 to 20 parts by mass with respect to 100 parts by mass in total of the component (A) of the first composition and the second composition Amount to do,
(E) The following general formula (2):
R ² _b SiX ² _4-b (2)
(Wherein R ² represents an unsubstituted or substituted monovalent hydrocarbon group, X ² represents the same or different hydrolyzable group, b is 0, 1 or 2, provided that b = 2 R ² may be the same or different.
The hydrolyzable organosilicon compound and / or its partially hydrolyzed condensate other than the component (D) represented by 0 to 0 in total with respect to 100 parts by mass of the component (A) of the first composition and the second composition A composition comprising an amount corresponding to 30 parts by mass.
Second composition (A) 100 parts by mass of diorganopolysiloxane capped with hydroxyl groups and / or hydrolyzable siloxy groups bonded to silicon atoms at both ends of the molecular chain
(B) It contains 5-500 parts by mass of magnesium hydroxide having an average particle size of 0.6-5 μm and a moisture content measured by an infrared moisture meter at 150 ° C. of 1.0% by mass or less. Composition. An electric / electronic component sealed, fixed or bonded with a cured product of the flame-retardant room temperature curable organopolysiloxane composition according to any one of claims 1 to 3 .