JP2018002595A - Organosilicon compound and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organosilicon compound realizing excellent hydrolysis resistance of a silane coupling agent layer when used as a silane coupling agent for surface treatment of an inorganic filler added to a resin.SOLUTION: The organosilicon compound is represented by the general formula (I). (In the formula, Rto Reach independently represent a chlorine atom, methoxy group, or ethoxy group; Rrepresents a C1-10 alkyl group; and Rrepresents a C1-10 alkylene group.)SELECTED DRAWING: None

Description

  The present invention relates to a novel organosilicon compound and a resin composition. More specifically, the present invention relates to a resin composition containing an organosilicon compound having an alkyl group at the β-position of a silyl group, and an inorganic filler surface-treated with the organosilicon compound.

  In order to improve the dimensional stability, mechanical strength, heat resistance, and the like of the resin molded body, inorganic fillers such as glass fibers are widely added to the resin. However, the inorganic filler does not necessarily have sufficient adhesion to the resin, and surface treatment of the inorganic filler with a silane coupling agent has been proposed.

  A silane coupling agent is typically a compound in which a hydrolytic group such as a methoxy group or an ethoxy group and an organic functional group such as an amino group or an epoxy group are bonded to a silicon atom, such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-ureidopropyltrimethoxy Examples thereof include silane, bis (triethoxysilylpropyl) tetrasulfide, γ-isocyanatopropyltrimethoxysilane, and tris- (trimethoxysilylpropyl) isocyanurate.

  The hydrolyzable group of the silane coupling agent is hydrolyzed by water in the solution or in the air, adsorbed water on the surface of the inorganic filler, etc. to be converted into a hydroxyl group, and an oligomer is produced by intermolecular dehydration condensation. Excess hydroxyl groups in the oligomer form hydrogen bonds with hydroxyl groups on the surface of the inorganic material, and the oligomer bonds with the inorganic material. Thereafter, dehydration / condensation occurs by heat drying treatment or the like, and an inorganic filler in which the silane coupling agent oligomer is strongly chemically bonded to the surface is obtained. The inorganic filler thus surface-treated is widely used as a reinforcing material for thermosetting resins such as epoxy resins, and thermoplastic resins such as polyamide resins, polyester resins, and polypropylene resins.

  However, under high-temperature and high-humidity conditions, the inorganic filler and resin are peeled off due to hydrolysis of the silane coupling agent layer, and the strength of the molded product is lowered. Silane coupling agents have been proposed. Examples include a long-chain spacer type silane coupling agent (Patent Literatures 1 to 3), a perfluoroalkylene group-containing silane coupling agent (Patent Literature 4), and an aromatic ring type silane coupling agent (Patent Literature 5).

Japanese Patent Application Laid-Open No. 64-50887 Japanese Patent Laid-Open No. 4-217689 US Pat. No. 3,170,891 JP 2000-248114 A Japanese Patent Laid-Open No. 50-93835

  When the linear alkyl long-chain spacer type silane coupling agent described in Patent Documents 1 to 3 and the perfluoroalkylene group-containing type silane coupling agent described in Patent Document 4 are used, the hydrolysis resistance of the silane coupling agent layer However, there is a problem that the terminal olefin alcohols and perfluorodiiodoalkanes that are raw materials are expensive and difficult to obtain. In addition, in the aromatic ring type silane coupling agent described in Patent Document 5, the hydrolysis resistance of the silane coupling agent layer and the mechanical strength of the molded body are improved. There was a problem that smooth introduction to the system was hindered.

  Accordingly, an object of the present invention is to provide an organosilicon compound which is excellent in hydrolysis resistance of a silane coupling agent layer to be formed.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by an organosilicon compound having an alkyl group at the β-position of the silyl group, and have completed the present invention.

That is, the present invention provides the following [1] to [2].
[1] An organosilicon compound represented by the following general formula (I).

(In the formula, R ^{1 to} R ³ each independently represents a chlorine atom, a methoxy group or an ethoxy group, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an alkylene group having 1 to 10 carbon atoms. Represents.)
[2] A resin composition comprising an inorganic filler surface-treated with the organosilicon compound of [1].

  By adding an inorganic filler surface-treated with the organosilicon compound of the present invention to the resin and molding it, a molded article having excellent hydrolysis resistance of the silane coupling agent layer can be provided.

[Organic silicon compound]
Hereinafter, the organosilicon compound represented by the general formula (I) of the present invention (hereinafter referred to as compound (I)) will be described.

R ^{1 to} R ³ each independently represents a chlorine atom, a methoxy group or an ethoxy group. Of these, a methoxy group or an ethoxy group is preferable.

R ⁴ represents an alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ⁴ is not limited to a straight chain, and may be branched or cyclic, or may be a structure in which a linear and / or branched structure and a cyclic structure are bonded.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptanyl group, cyclooctanyl group Etc. Among these, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, a methyl group or an ethyl group is further preferable, and a methyl group is most preferable.

R ⁵ represents an alkylene group having 1 to 10 carbon atoms. The alkylene group represented by R ⁵ is not limited to a straight chain, and may be branched or cyclic, or may be a structure in which a linear and / or branched structure and a cyclic structure are bonded.

Examples of the alkylene group having 1 to 10 carbon atoms represented by R ⁵ include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, and a propane-1 2, 2-diyl group, propane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, cyclohexane-1,4-diyl group and the like. From the viewpoint of improving the mechanical strength of the molded article, an alkylene group having 1 to 5 carbon atoms is preferable, an alkylene group having 1 to 3 carbon atoms is more preferable, a methylene group or an ethylene group is further preferable, and a methylene group is most preferable.

In compound (I), R ⁵ has a role as a spacer between a site related to dehydration condensation accompanying the bond with the inorganic filler and an epoxy group which is a site related to the reaction with the resin. By the presence of R ⁵ as a spacer, the site involved in dehydration condensation and the epoxy group that reacts with the resin are kept at an appropriate distance, and smooth dehydration condensation is performed.

In the compound (I), the α-position carbon of the silyl group has two hydrogen atoms, and the β-position carbon has an alkyl group R ⁴ . When compound (I) acts as a silane coupling agent, R ^{1 to} R ³ become hydroxyl groups by hydrolysis, and at least one of the hydroxyl groups undergoes dehydration condensation with a hydroxyl group on the surface of the inorganic material.
At this time, if an alkyl group is present in the vicinity of the silyl group, the alkyl group becomes an obstacle to the access of water to the dehydration condensation part, and hydrolysis of the silane coupling agent layer is suppressed.
On the other hand, such alkyl groups, for which can also suppress the generation of hydroxyl by hydrolysis R ¹ to R ^3, which may hinder smooth coupling to the inorganic filler surface.

Detailed investigation of the present inventors, if the carbon of the α-position of the silyl group having an alkyl group, interfere excess access of water to the R ¹ to R ^3, the hydrolysis of the R ¹ to R ³ It was found to suppress and prevent smooth bonding to the inorganic filler surface. On the other hand, when the α-position and β-position carbon of the silyl group each have two hydrogen atoms and the γ-position carbon has an alkyl group, the effect of preventing the water from approaching the dehydration condensation portion is small. It was found that the effect of suppressing hydrolysis of the silane coupling agent layer was small.

However, when the α-position carbon has two hydrogen atoms and the β-position carbon has an alkyl group with respect to the silyl group, it is inorganic without inhibiting the generation of hydroxyl groups by hydrolysis of R ^{1 to} R ^3. The silane coupling agent layer can be smoothly introduced to the surface of the filler, and after the silane coupling agent layer is formed, water access to the dehydration condensation part is appropriately prevented and hydrolysis is effectively suppressed. I found out that

  Specific examples of compound (I) include, but are not limited to, the following compounds.

  There is no restriction | limiting in particular in the manufacturing method of compound (I), It can manufacture by combining a well-known method. As an example, first, an epoxy compound (IV) is obtained from alcohol (II) and epihalohydrin (III) in the presence of a base (this step is referred to as Step 1), and then hydrosilanes ( There is a method of producing organosilicon compound (I) by hydrosilylation using V) (this step is referred to as step 2).

(In the formula, R ^{1 to} R ⁵ are as defined above. X represents a chlorine atom, a bromine atom or an iodine atom.)
Hereafter, the manufacturing method of compound (I) is demonstrated in detail.

(Process 1)
Although there is no restriction | limiting in particular in the usage-amount of epihalohydrin (III), it is preferable that it is 0.8-10 mol with respect to 1 mol of alcohol (II) of a raw material, and 1-5 mol from a viewpoint of a yield and volumetric efficiency. It is more preferable that

Step 1 can be performed in the presence or absence of a solvent.
Such a solvent is not particularly limited as long as it does not adversely influence the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane; chlorobenzene And halogenated aromatic hydrocarbons such as fluorobenzene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran. These may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the usage-amount in the case of using a solvent, it is preferable that it is 0.5-20 mass parts with respect to 1 mass part of alcohol (II) of a raw material, and 1-5 mass from a viewpoint of volume efficiency. Part.

  Examples of the base used in Step 1 include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. Tertiary amines such as triethylamine, tributylamine and diazabicyclo [2.2.2] octane; nitrogen-containing heterocyclic aromatic compounds such as pyridine; Among these, alkali metal hydroxides are preferable from the viewpoints of economy and reactivity.

  Although there is no restriction | limiting in particular in the usage-amount of a base, From a viewpoint of economical efficiency and ease of post-processing, it is preferable that it is 0.8-5 mol with respect to 1 mol of alcohol (II), and 0.8-3 mol It is more preferable that

Step 1 can be carried out in the presence or absence of a phase transfer catalyst, but is preferably carried out in the presence.
The phase transfer catalyst is not particularly limited, and examples thereof include benzyltrimethylammonium chloride, trioctylmethylammonium chloride, laurylpyridium bromide, decyltrimethylammonium chloride, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide and the like. Can be mentioned. These may be used alone or in combination of two or more.

  The amount of the phase transfer catalyst used is 0.1 to 10.0% by mass, preferably 0.3 to 3.0% by mass, based on the alcohol (II). If it is less than 0.1% by mass, the reaction takes a long time, and even if it is used in an amount of 10.0% by mass or more, no improvement in the effect is expected.

  The reaction temperature in step 1 is preferably in the range of −20 ° C. to 200 ° C., more preferably in the range of 0 ° C. to 150 ° C. In addition, the reaction can be carried out in an air atmosphere or an inert gas atmosphere such as nitrogen or argon. Furthermore, the reaction may be carried out under atmospheric pressure or under reduced pressure.

  After completion of the reaction, depending on the base used, the reaction mixture is appropriately washed with water or an acidic aqueous solution such as aqueous hydrochloric acid to remove the base and then concentrated, followed by normal purification such as recrystallization, distillation, column chromatography, etc. By purifying by means, the target epoxy compound (IV) can be separated and obtained.

(Process 2)
Examples of the hydrosilanes (V) used in step 2 include trichlorosilane, trimethoxysilane, triethoxysilane, and the like.

As the platinum-based catalyst used in Step 2, a platinum chloride-based catalyst can be preferably used. Specifically, hexachloride platinum (IV) acid (H ₂ PtCl ₆ ), platinum chloride / unsaturated ketone complex, chloride Examples thereof include platinum / β-diketone complexes and platinum chloride olefin complexes. Although there is no restriction | limiting in particular in the usage-amount of a platinum type catalyst, 10 ^<-7 > ^-10 <^-3> mol is preferable with respect to 1 mol of raw material epoxy compounds (IV), and 10 ^<-6 > ^-10 <^-3> mol is more preferable.

Step 2 can be performed in the presence or absence of a solvent.
Such a solvent is not particularly limited as long as it does not adversely influence the reaction. For example, alcohols such as methanol, ethanol, n-propanol and isopropanol; aromatic hydrocarbons such as benzene, toluene and xylene, hexane, heptane and octane Aliphatic hydrocarbons such as cyclohexane and methylcyclohexane; ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran; halogenated aromatic hydrocarbons such as chlorobenzene and fluorobenzene; dichloromethane, chloroform, 1,2-dichloroethane and the like And halogenated aliphatic hydrocarbons. These may be used individually by 1 type, and may use 2 or more types together. When the solvent is used, the amount used is not particularly limited, but is preferably 0.5 to 100 parts by mass with respect to 1 part by mass of the raw material epoxy compound (IV). It is more preferable that it is 10 mass parts.

  The reaction temperature is preferably in the range of −10 to 100 ° C., more preferably in the range of 20 to 80 ° C. The reaction time is usually 0.5 hours to 48 hours.

When it is desired to obtain the compound (I) in which R ^{1 to} R ³ are a methoxy group or an ethoxy group, a method of directly synthesizing using trimethoxysilane or triethoxysilane as a hydrosilane (V), or a reaction with trichlorosilane. Later, it can also be obtained by a method of obtaining a desired alkoxy compound in methanol or ethanol. In the case of via a trichloro form, triethylamine, pyridine, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide and the like can be present together as a base in order to capture hydrogen chloride generated during alkoxylation. Although there is no restriction | limiting in particular in the usage-amount of a base, It is preferable that it is 0.8-20 mol with respect to 1 mol of hydrosilanes (V), and it is more preferable that it is 1.0-10 mol.

  The reaction can be carried out under normal pressure or under pressure, but is usually carried out under normal pressure.

  Compound (I) obtained after completion of the reaction can be isolated by a method usually used in the isolation and purification of organic compounds. For example, the target organic silicon compound (I) can be obtained by filtering the reaction mixture, concentrating it, and purifying it by distillation under reduced pressure. Moreover, it can also be used as a silane coupling agent by concentrating a reaction mixture as it is.

  The compound (I) thus produced has a function as a silane coupling agent, such as surface modification of an inorganic filler, improvement in adhesive adhesion, improvement in coating durability, cross-linking of an organic polymer, etc. For the purpose of adhesive, primer, sealant, sealant, paint, coating material, glass fiber reinforced resin, inorganic filler compounded resin, composite reinforced resin, printing ink, elastomer material, thermoplastic resin material, composite material, electrical insulation Can be widely used on the body.

[Resin composition]
The resin composition of the present invention contains an inorganic filler surface-treated with compound (I). In the present specification, “resin” is a concept including an elastomer.

  The inorganic filler surface-treated with the compound (I) is not particularly limited as long as it is made of an inorganic material that generally reacts with a silanol group to form a bond, and the shape of the inorganic filler is not particularly limited. Examples of such inorganic fillers include fillers made of silicon, titanium, zirconium, magnesium, aluminum, indium, tin, and single or composite oxides thereof; glass fiber, glass cloth, glass tape, glass mat, glass paper, etc. Glass fillers; silica-based fillers; mineral-based fillers such as clay, mica, talc and wollastonite; metal substrates such as iron and aluminum.

  There is no restriction | limiting in particular in the surface treatment method of an inorganic filler. For example, after adding the inorganic filler to the resin, a method of adding and mixing the compound (I) diluted with a stock solution or an organic solvent or water, or by adding a dry method or a wet method in advance before adding the inorganic filler to the resin. Examples thereof include a method of treating with compound (I) and a primer method in which compound (I) diluted with an organic solvent or water is directly applied to an inorganic filler.

  The surface treatment of the inorganic filler is preferably accompanied by a heat drying treatment. By performing a drying treatment with heat, dehydration condensation proceeds between the hydroxyl group of compound (I) and the hydroxyl group on the surface of the inorganic filler, and a strong bond can be formed.

  The temperature in the drying treatment is usually 60 to 180 ° C, preferably 80 to 150 ° C. The drying time is preferably 5 minutes to 4 hours.

Examples of the resin constituting the resin composition of the present invention include unsaturated polyester, silicone resin, melamine resin, polystyrene, polyethylene, polypropylene, polyether, acrylic resin, diallyl phthalate, butyl rubber, and epoxy resin.
These resins may be used alone or in combination of two or more.

  The resin composition of the present invention includes the above-described inorganic filler and resin subjected to surface treatment, a solvent, a surfactant, a preservative, a discoloration inhibitor, an antioxidant, a flame retardant, a light stabilizer, a surface depending on the application. You may contain other additives, such as an untreated inorganic filler, in the range which does not impair the meaning of this invention.

  The resin composition of this invention can be prepared by mixing each said structural component according to a well-known method. For example, a method of dry blending a resin and other components, a method of melt-kneading each component using an extruder, and the like can be mentioned.

  By molding the resin composition of the present invention, a molded product having excellent hydrolysis resistance of the silane coupling agent layer can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

<Example 1>
(Step 1) Synthesis of 3-methyl-3-butenyl glycidyl ether

  In a 1 L reactor equipped with a stirrer, a thermometer, and a dropping funnel, 280 g (3.5 mol) of 50% aqueous sodium hydroxide solution, 200 g (2.32 mol) of 3-methyl-3-buten-1-ol under a nitrogen stream, 4.4 g (0.024 mol) of benzyltrimethylammonium chloride was charged and heated to 40 ° C. Epichlorohydrin 430g (4.65mol) was dripped over 30 minutes, and it stirred at 40 degreeC for 4 hours. 400 g of distilled water was added to the reaction solution to separate the organic layer and the aqueous layer. The organic layer was washed with 400 g of distilled water and then concentrated under reduced pressure, and the residue was further distilled under reduced pressure to obtain 175.2 g (1.23 mol; yield 53%) of 3-methyl-3-butenyl glycidyl ether. .

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 4.75 (m, 1H), 4.73 (m, 1H), 3.73 (dd, J = 11.6, 3.0 Hz, 1H) 3.62 (m, 2H), 3.39 (dd, J = 11.6, 5.8 Hz, 1H), 3.13 (m, 1H), 2.77 (dd, J = 5.1) 4.2 Hz, 1H), 2.59 (dd, J = 5.1, 2.7 Hz, 1H), 2.31 (m, 2H), 1.76 (s, 3H).

(Step 2) Synthesis of 4-glycidyloxy-2-methyltrimethoxysilane

Stirrer, 25mL reactor equipped with a thermometer, under a nitrogen stream, 3-methyl-3-butenyl glycidyl ether 1.0 g (7.0 mmol) were _{charged, H 2 PtCl 6 · 6H 2} O5.0mg (9. After adding 0.3 ml of a 7 μmol) tetrahydrofuran solution, 1.22 g (10.0 mmol) of trimethoxysilane was added dropwise, followed by stirring at 25 ° C. for 20 hours. The obtained reaction solution was concentrated under reduced pressure to obtain 1.22 g (4.61 mmol; yield 66%) of 4-glycidyloxy-2-methyltrimethoxysilane.

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 3.74 (m, 1H), 3.63 (m, 2H), 3.55 (s, 9H), 3.40 (m, 1H), 3.10 (m, 1H), 2.78 (m, 1H), 2.60 (m, 1H), 1.72 (m, 2H), 1.48 (m, 1H), 1.01 (d , J = 6.4 Hz, 3H), 0.73 (m, 2H).

<Example 2>
The glass plate was immersed in a 2 mol / L ethanol-water (95/5 (v / v)) solution of 4-glycidyloxy-2-methyltrimethoxysilane obtained in Example 1 at 25 ° C. for 2 hours, and then 110 ° C. Heat treatment was performed for 3 hours. A resin obtained by mixing equimolar amounts of bisphenol A type epoxy resin (“Epicoat 828” manufactured by Mitsubishi Chemical Corporation) and diethylenetriamine was applied to this plate at a film thickness of 100 μm and cured to prepare two test pieces.
First, a cross-cut adhesion test was performed on one of the test pieces in accordance with JIS K 5600.5.6. Specifically, a 25 square grid is created by cutting a test piece with a knife until it reaches the glass plate with a gap of 3 mm, and an adhesive tape is pasted on the grid, The adhesive tape was peeled off in a direction forming an angle of 45 degrees with respect to the surface. Thereafter, the squares from which the resin was peeled were counted, and the ratio (%) of the squares that were peeled to the whole square was calculated. The numerical values scored according to the following criteria are shown in the “Initial” column of Table 1.
Evaluation score 5: 0% peeling rate of grid on grid
Evaluation score 4: Stripping rate of grid on grid is 0% more than 5% or less Evaluation score 3: Stripping rate on grid is more than 5% but not more than 15% Evaluation score 2: Stripping rate of grid on grid is more than 15% and 25% Hereinafter, evaluation score 1: peeling rate of grid of grid exceeds 25% Next, after the other test piece was immersed in boiling water for 24 hours, a grid adhesion test was performed under the same conditions as described above. The numerical values scored by the same method as above are shown in the “After boiling water treatment” column of Table 1.

<Comparative example>
In Example 2, the same operation as in Example 2 was performed except that 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 4-glycidyloxy-2-methyltrimethoxysilane. The results are shown in Table 1.

  As shown in Table 1, when the organosilicon compound of the present invention is used, performance degradation due to hydrolysis is less than when the organosilicon compound of a comparative example having a similar structure is used. That is, it turns out that the molded object which is excellent in the hydrolysis resistance of a silane coupling agent layer can be provided by using the organosilicon compound of this invention.

  By adding an inorganic filler surface-treated with the organosilicon compound of the present invention to a resin and molding it, a molded article having excellent hydrolysis resistance of the silane coupling agent layer can be provided.

Claims (2)

An organosilicon compound represented by the following general formula (I).
(In the formula, R ^{1 to} R ³ each independently represents a chlorine atom, a methoxy group or an ethoxy group, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an alkylene group having 1 to 10 carbon atoms. Represents.) The resin composition containing the inorganic filler surface-treated with the organosilicon compound of Claim 1.