JP4189756B2 - Process for producing alkoxysilyl group-containing silane-modified phenylene ether resin, alkoxysilyl group-containing silane-modified phenylene ether resin, alkoxysilyl group-containing silane-modified phenylene ether resin composition, and phenylene ether resin-silica hybrid cured product - Google Patents

Description

  The present invention relates to a method for producing an alkoxysilyl group-containing silane-modified phenylene ether resin, an alkoxysilyl group-containing silane-modified phenylene ether resin obtained by the method, a composition containing the alkoxysilyl group-containing silane-modified phenylene ether resin, and the The present invention relates to a phenylene ether resin-silica hybrid cured product obtained from the composition.

  Polyphenylene ether resin is excellent in heat resistance, electrical characteristics, low water absorption, etc., so as modified PPE compounded with polystyrene, etc., it can be used in information communication equipment, housing and internal parts of home appliances, interior and exterior parts of automobiles, It is used in various fields such as parts inside vending machines. However, there are drawbacks such as poor compatibility with thermosetting resins such as epoxy resins and the fact that the solvent to be dissolved is limited to aromatic hydrocarbons and halogen hydrocarbons.

  Various methods have been studied to improve these drawbacks, and as one of them, a bifunctional phenylene ether oligomer having hydroxyl groups at both ends has been proposed (see Patent Documents 1 and 2). The bifunctional phenylene ether oligomer obtained by this method is highly compatible with the thermosetting resin and is soluble in ketone solvents. Further, the cured product obtained by modifying the hydroxyl groups at both ends to be derived into a thermosetting resin (for example, see Patent Documents 3 and 4) or a photocurable resin (for example, see Patent Documents 5 and 6). Inherited the characteristics of polyphenylene ether resin such as electrical characteristics and low water absorption. However, defects such as low chemical resistance and insufficient heat resistance still remain.

  On the other hand, so-called organic-inorganic hybrid technology, in which an organic material is combined with an inorganic material, has recently attracted attention as means for further improving the characteristics of the organic material. The present applicant also has a dealcoholization reaction of an alkoxysilane partial condensate and an epoxy resin by a dealcoholization reaction of a silane-modified epoxy resin (see Patent Document 7) obtained by reacting an alkoxysilane partial condensate and an epoxy resin. The resulting silane-modified phenolic resin (see Patent Document 8) is proposed. In addition, as a material for hybridization, a dealcoholization reaction product of an epoxy group-containing alcohol and an alkoxysilane partial condensate has already been proposed, and a technique for modifying a polyimide resin or the like using the reaction product has been found. (See Patent Document 9).

JP 2003-012796 A Japanese Patent Laid-Open No. 2004-059642 JP 2003-155340 A JP 2003-221990 A JP 2003-183350 A JP 2003-238653 A Japanese Patent No. 3077695 Japanese Patent No. 3395744 WO 01/005862 pamphlet

  The present invention relates to a method for producing an alkoxysilyl group-containing silane-modified phenylene ether resin capable of providing a cured product having improved heat resistance, chemical resistance, etc., while maintaining the excellent properties inherent in polyphenylene ether resin, and the modified resin It is an object of the present invention to provide a curable composition containing a modified resin and a phenylene ether resin-silica hybrid cured product obtained from the resin composition.

  As a result of diligent studies to solve the above problems, the present inventors have found that a composition or a cured product that can solve the above problems can be obtained by using a specific silane-modified product of a bifunctional phenylene ether resin. The present invention has been completed.

  That is, in the present invention, a bifunctional phenylene ether resin (1) (hereinafter referred to as component (1)) and an alkoxysilane silane partial condensate (2) (hereinafter referred to as component (2)) are subjected to a dealcoholization reaction. The present invention relates to a method for producing an alkoxysilyl group-containing silane-modified phenylene ether resin. The present invention also relates to an alkoxysilyl group-containing silane-modified phenylene ether resin obtained by the production method. The present invention also relates to a curable composition comprising the alkoxysilyl group-containing silane-modified phenylene ether resin. Furthermore, this invention relates to the phenylene ether resin-silica hybrid hardened | cured material formed by hardening | curing the said composition.

  According to the present invention, the excellent performance of the polyphenylene ether resin, ie, excellent electrical characteristics, low water absorption, high heat resistance, and good adhesion to various substrates, etc. Can provide an alkoxysilyl group-containing silane-modified phenylene ether resin and the organic-inorganic hybrid cured product, which can provide a cured product with improved chemical resistance and the like. Therefore, the hybrid cured product is useful as a paint, an adhesive, a sealing agent, a printed wiring board material, an IC sealing material, an insulating sealing agent, and the like.

  The component (1) used in the present invention is not particularly limited, and a conventionally known bifunctional phenylene ether resin can be appropriately selected and used. Specific examples of the component (1) include a method of redistributing a high molecular weight polyphenylene ether resin and a dihydric phenol described in JP-A-9-291148 with a radical catalyst, JP-B-8-11747, JP2003 Examples thereof include bifunctional phenylene ether oligomers obtained by oxidative polymerization of dihydric phenol and monohydric phenol described in JP-A-0127996 and JP-A-2004-059642. Among these, the general formula (1) described in JP-A-2004-059642:

(In the formula, R ¹ and R ² may be the same or different and each represents a halogen atom, an alkyl group having 6 or more carbon atoms, or a phenyl group. R ³ and R ⁴ may be the same or different and represent a hydrogen atom. Represents a halogen atom, an alkyl group having 6 or more carbon atoms, or a phenyl group, and m and n each represents an integer of 0 to 25, at least one of which is not 0.) The body is preferable because it can be synthesized with a desired molecular weight and does not contain a high molecular weight substance having low compatibility with the component (2).

  In order to produce the alkoxysilyl group-containing silane-modified phenylene ether resin of the present invention, it is obtained by subjecting the phenolic hydroxyl group at both ends of the component (1) and the alkoxysilyl group of the component (2) to a dealcoholization reaction. The component (1) has a crosslinked structure of an inorganic substance via silica produced by sol-gel curing (dealcohol condensation reaction of alkoxysilyl group) of the alkoxysilyl moiety of the component (2) bonded with the hydroxyl group, This is because the effects of the present invention, such as heat resistance and chemical resistance, can be obtained.

  The component (1) used in the present invention preferably has a hydroxyl group equivalent of 200 to 3000, and more preferably 300 to 2000. When the hydroxyl equivalent is less than 200, the abundance ratio of the component (2) in the alkoxysilyl group-containing silane-modified phenylene ether resin is increased, and the hydroxyl equivalent is generated from the component (2) contained in the finally obtained hybrid cured product. The cured product obtained by increasing the amount of silica tends to be brittle. If it exceeds 3000, the abundance ratio of the component (2) in the alkoxysilyl group-containing silane-modified phenylene ether resin is reduced, and the amount of silica produced is reduced, resulting in the heat resistance and chemical resistance characteristic of the present invention. It may be difficult to obtain such effects.

As the alkoxysilane partial condensate (2) used in the present invention, an oligomer obtained by partially hydrolyzing and condensing an alkoxysilane generally used in a sol-gel method, for example, a general formula (2): R ⁵ _p Si (OR ⁶ ) _4-p

(In the formula, p represents 0 or 1. R ⁵ represents a lower (1 to 4 carbon atoms) alkyl group, aryl group or unsaturated aliphatic residue which may have a hydroxyl group directly bonded to a carbon atom. R ⁶ represents a methyl group or an ethyl group, and R ⁶ may be the same or different from each other. In addition, when p is 2-4, since three-dimensional crosslinking does not occur, it becomes difficult to impart desired high heat resistance to the finally obtained cured product.

  Examples of the hydrolyzable alkoxysilane compound which is a constituent raw material of the component (2) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n- Examples thereof include propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane, and component (2) is condensed by mixing them alone or in combination. Can be used.

  Among these, when a partial condensate of tetramethoxysilane and methyltrimethoxysilane is used as a hydrolyzable alkoxysilane compound that is a constituent raw material of component (2), it has a high reactivity with component (1), and is a cured product. It is preferable because it imparts a high degree of heat resistance and has a high sol-gel curing rate.

  The number average molecular weight of the component (2) is usually about 230 to 2000, and the general formula (3):

Or general formula (4):

In the above, those having an average repeating unit number q of 2 to 11 are preferred. When the value of q exceeds 11, the compatibility with the component (1) decreases, and the reactivity with the component tends to decrease. When q is less than 2, it tends to be distilled out of the system together with the alcohol produced as a by-product in the reaction, and the productivity tends to deteriorate.

  The alkoxysilyl group-containing silane-modified phenylene ether resin of the present invention can be obtained by subjecting component (1) and component (2) to a dealcoholization condensation reaction in the presence or absence of a solvent. The amount of component (1) and component (2) used is not particularly limited, and the ratio of component (1) and component (2) used is not particularly limited, but the number of moles of component (2) / component (1). It is preferable that the number of moles (molar ratio) of the hydroxyl group is about 0.3 to 2.0, more preferably 0.5 to 1.5.

  Here, when the ratio is 1.0, it is theoretically possible to obtain an alkoxysilyl group-containing silane-modified phenylene ether resin in which one molecule of component (2) is bonded to both ends of component (1). Therefore, when the ratio exceeds 1.0, the component (2) remains after the reaction. When the ratio is less than 1.0, the hydroxyl group of the component (1) remains or the component (2) A plurality of hydroxyl groups of component (1) react with one molecule. As long as the effect of the present invention is not lost, the component (2) may remain or the hydroxyl group of the component (1) may remain, but when the ratio exceeds 2.0, the remaining component ( Since 2) increases too much, the cured product may become cloudy or brittle. On the other hand, if it is less than 0.3, a hydroxyl group of a plurality of components (1) reacts with one molecule of component (2) to form a three-dimensional crosslinked structure, and gelation is likely to occur as the dealcoholization reaction proceeds. This is not preferable, and the amount of component (2) introduced is too small, so that it is difficult to obtain effects such as heat resistance and chemical resistance, which are the characteristics of the present invention.

  The reaction between component (1) and component (2) is carried out, for example, while these components are charged and heated to distill off the by-produced alcohol. This reaction is preferably carried out under substantially anhydrous conditions in order to prevent the polycondensation reaction of component (2) itself. The reaction temperature is usually about 50 to 150 ° C, preferably 70 to 110 ° C. If the dealcoholization reaction is carried out at a temperature exceeding 150 ° C., the molecular weight of the reaction product tends to increase too much with the condensation of the component (2) in the reaction system, and the viscosity tends to increase or gel. In such a case, the increase in viscosity and gelation can be prevented by a method such as stopping the dealcoholization reaction during the reaction. In addition, even when the number of moles of component (2) / the number of moles of hydroxyl groups (molar ratio) in component (1) is less than 1, component (2) contains a plurality of components (1) per molecule as component (2) progresses. Since hydroxyl groups react to form a three-dimensional cross-linked structure, and high viscosity and gelation are likely to occur, the dealcoholization reaction is stopped in the middle of the reaction, leaving some of the hydroxyl groups of component (1) unreacted, etc. It is better to adopt this method. The remaining hydroxyl group of component (1) is bonded to the alkoxysilyl group of component (2) at the time of sol-gel curing, so there is no problem.

  In the dealcoholization reaction, a conventionally known catalyst can be used for promoting the reaction. Examples of the catalyst include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, cadmium, and manganese. Metals: These metal oxides, organic acid salts, halides, alkoxides and the like. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin laurate, tin octylate and the like are preferable.

  The above reaction can usually be carried out in a solvent. The solvent is not particularly limited as long as it has a boiling point equal to or higher than the reaction temperature of the dealcoholization reaction and dissolves both the component (1) and the component (2). Examples of such organic solvents include methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, and the like. Can be illustrated. Among these, toluene and xylene that hardly affect the electrical properties of the cured product even if a small amount remains in the hybrid cured product obtained by finally curing the alkoxysilyl group-containing silane-modified phenylene ether resin. Is preferred.

  Moreover, when the compatibility of a component (1) and a component (2) is high, it can also react in absence of a solvent. The alkoxysilyl group-containing silane-modified phenylene ether resin produced in the absence of a solvent has an advantage that it can be used as it is as a material for use in the absence of a solvent, for example, an adhesive, a molded product, a sealing material and the like. Such a solvent-free alkoxysilyl group-containing silane-modified phenylene ether resin can also be obtained by depressurizing an organic solvent solution of the alkoxysilyl group-containing silane-modified phenylene ether resin produced in the presence of a solvent. be able to.

  The curable composition of the present invention contains the alkoxysilyl group-containing silane-modified phenylene ether resin obtained as described above as an essential constituent, and the resin contains component (2) in the molecule. It has an alkoxysilyl group derived from it. This alkoxysilyl group undergoes a sol-gel reaction by heat treatment or reaction with moisture (humidity) to form a hybrid cured product bonded to each other. Such a cured product has fine gelled silica sites (high-order network structure of siloxane bonds). For this reason, it is usually preferable to keep about 40 to 95 mol%, preferably 50 to 90 mol% of the alkoxysilyl group of the component (2) as a raw material unreacted.

  Further, a catalyst for promoting the sol-gel reaction can be blended in the resin composition. Examples of the sol-gel reaction catalyst include conventional catalysts such as acid or basic catalysts and metal catalysts. In particular, tin octylate and dibutyltin dilaurate are highly active and have excellent solubility. preferable. The amount of the catalyst used can be appropriately determined depending on the activity of the catalyst used and the film thickness of the target cured product. Usually, about 0.01 to 5 mol% of paratoluenesulfonic acid or tin octylate having a high catalytic ability in a molar ratio with respect to the alkoxy group of the alkoxysilyl group-containing silane-modified phenylene ether resin to be used, the catalytic ability is low. Used in 0.1 to 50 mol% with formic acid, acetic acid, etc.

  Since it is appropriate that the curable composition is usually a liquid having a curing residue of about 10 to 70% by weight, a solvent may be added as necessary. Any known solvent can be used as long as it dissolves the alkoxysilyl group-containing silane-modified phenylene ether resin. Specifically, for example, a solvent used for the production of an alkoxysilyl group-containing silane-modified phenylene ether resin, an ester solvent, an alcohol solvent, or the like can be used.

  Further, the content of the alkoxysilyl group-containing silane-modified phenylene ether resin in the curable composition is not particularly limited, but it is usually preferably 10% by weight or more in the cured residue of the composition. Here, the curing residue means a solid content obtained by applying the curable composition and then performing sol-gel curing or solvent drying to remove volatile components, and the curable composition is 100 μm or less. It is a solid after being applied and then dried and cured at 180 ° C. for 2 hours.

  In addition to the alkoxysilyl group-containing silane-modified phenylene ether resin, the curable composition of the present invention may contain a component (2) as desired. Component (2) is converted into silica by hydrolysis and polycondensation during sol-gel curing, and is combined with an alkoxysilyl group-containing silane-modified phenylene ether resin to provide effects such as heat resistance and chemical resistance that are the characteristics of the present invention. Can be further enhanced. In addition, as described above, when the alkoxysilyl group-containing silane-modified phenylene ether resin is produced, if the number of moles of component (2) / number of moles of hydroxyl groups in component (1) (molar ratio) exceeds 1.0, the component (2) will remain, but the remaining component (2) has the same effect as when component (2) is added later. The amount of component (2) used can be appropriately determined according to the intended performance such as heat resistance and chemical resistance, but is usually in a weight ratio to the alkoxysilyl group-containing silane-modified phenylene ether resin used. If it exceeds 50%, the resulting cured product becomes cloudy or brittle, which is not preferable.

  Moreover, when a hydroxyl group remains in the alkoxysilyl group-containing silane-modified phenylene ether resin, the curable composition of the present invention can be blended with a curing agent capable of reacting with the hydroxyl group, if desired. The alkoxysilyl group-containing silane-modified phenylene ether resin in which such hydroxyl groups remain can be obtained by stopping the reaction before all the hydroxyl groups in the component (1) are reacted. At this time, it is preferable that the number of moles of the component (2) / the number of moles of the hydroxyl group in the component (1) (molar ratio) is less than 1.0 and the ratio of the remaining component (2) is as small as possible. In addition, the number of hydroxyl groups involved in the reaction can be determined from the number of moles of alcohol washed away during the reaction (number of moles of alcohol = number of hydroxyl groups involved in the reaction), and the amount of remaining hydroxyl groups can be determined.

  As the curing agent, one that can react with the hydroxyl group remaining in the alkoxysilyl group-containing silane-modified phenylene ether resin can be arbitrarily used. Specifically, for example, it is preferable to use an epoxy resin as a curing agent. The epoxy resin to be used is not particularly limited. However, when the epoxy equivalent exceeds 500 g / eq, the amount of the epoxy resin necessary for curing increases, and the heat resistance of the cured product is lowered, which is not preferable. Further, the use ratio of the epoxy resin is not particularly limited, but the number of moles of epoxy group of the epoxy resin / number of moles of hydroxyl group of the silane-modified phenylene ether resin containing alkoxysilyl group (molar ratio) is preferably 1.2 or less. . If it exceeds 1.2, the remaining unreacted epoxy resin is not preferable because the heat resistance is lowered.

  In addition, the curable composition has a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, and a whitening agent as required for various applications within a range not impairing the effects of the present invention. You may mix | blend an agent, a coloring agent, a electrically conductive agent, a mold release agent, a surface treating agent, a viscosity modifier, a coupling agent, a filler, etc.

An example of using the curable composition of the present invention as a cured product is illustrated. The cured composition is poured into a Teflon (registered trademark) coated container and heated to perform solvent drying and sol-gel curing. Subsequently, the desired hybrid cured product is obtained by further raising the temperature and completely curing and drying. The drying / curing step is preferably performed in two or more stages as described above in order to control foaming and curing shrinkage due to rapid scattering of volatile components such as solvents. Therefore, the curing temperature and the heating time are determined based on the amount of alcohol produced as a by-product during the dealcoholization condensation reaction of the alkoxysilyl group, and the type of solvent, the thickness of the cured product, etc. It is determined as appropriate in consideration. Since the first stage is partially cured and dried to such an extent that the surface tack of the cured product is eliminated, it is usually preferable to set the conditions at about 20 to 150 ° C. for about 1 minute to 2 hours. Next, heating is performed at about 130 ° C. to 280 ° C., preferably 200 ° C. or more and less than 250 ° C. for about 1 minute to 6 hours, thereby completely removing the residual solvent and completing the dealcoholization condensation reaction of the alkoxysilyl group. The cured film thus obtained has a silica (SiO ₂ ) site derived from the alkoxysilyl group in the alkoxysilyl group-containing silane-modified phenylene ether resin, and the cured product has heat resistance, It has the feature of excellent chemical resistance.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In each example, “%” is based on weight unless otherwise specified.

Example 1 (Production of alkoxysilyl group-containing silane-modified phenylene ether resin)
A bifunctional phenylene ether resin (trade name “OPE-1000” manufactured by Mitsubishi Gas Chemical Co., Ltd., hydroxyl equivalent 520 g / eq) is added to a reactor equipped with a stirrer, a condenser, a water separator, a thermometer, and a nitrogen inlet. 500 g and 447 g of poly (tetramethoxysilane) (manufactured by Tama Chemical Co., Ltd., trade name “M silicate 51”, average number of Si of 4.0 per molecule) are melted and mixed at 90 ° C. under solvent-free conditions. Solution. 0.22 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name “Neostan U-100”) was added as a catalyst, and methanol was reacted at 90 ° C. for 15 hours to distill off 32 g of methanol, resulting in an alkoxysilyl group. A silane-modified phenylene ether resin (hereinafter referred to as resin (A-1)) was obtained.
Number of moles of component (2) / number of moles of hydroxyl group in component (1) = 1.0.

Example 2
In the same reactor as in Example 1, 71.8 g of bifunctional phenylene ether resin (Mitsubishi Gas Chemical Co., Ltd., trade name “OPE-1000”, hydroxyl equivalent 520 g / eq) and poly (methyltrimethoxysilane) ( 45.3 g of Tama Chemical Co., Ltd., trade name “MTMS-A”, average number of Si per molecule 3.2) was charged and melt-mixed at 90 ° C. without solvent to obtain a uniform solution. 0.023 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name “Neostan U-100”) was added as a catalyst, and methanol was reacted at 90 ° C. for 15 hours to distill off 6.0 g of methanol. A silyl group-containing silane-modified phenylene ether resin (hereinafter referred to as resin (A-2)) was obtained.
Number of moles of component (2) / number of moles of hydroxyl group in component (1) = 1.0.

Example 3
In the same reactor as in Example 1, 100 g of bifunctional phenylene ether resin (trade name “OPE-1500”, hydroxyl equivalent 840 g / eq, manufactured by Mitsubishi Gas Chemical Co., Ltd.), poly (tetramethoxysilane) (Tama Chemical Co., Ltd.) Product name “M silicate 51”, 56.4 g of Si average number per molecule (4.0) and 56.4 g of toluene were charged and dissolved at 90 ° C. to obtain a uniform solution. 0.028 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name “Neostan U-100”) was added as a catalyst, and 3.8 g of methanol was distilled off at 90 ° C. for 5 hours. A silyl group-containing silane-modified phenylene ether resin (hereinafter referred to as resin (A-3)) was obtained.
Number of moles of component (2) / number of moles of hydroxyl group in component (1) = 1.0.

Example 4
Bifunctional phenylene ether resin (trade name “OPE-1500”, manufactured by Mitsubishi Gas Chemical Co., Ltd., hydroxyl equivalent 840 g / eq) 100 g, poly (methyltrimethoxysilane) (Tama Chemical) Product name “MTMS-A” manufactured by Co., Ltd., 39.8 g of average number of Si per molecule 3.2) and 89.3 g of toluene were charged and dissolved at 90 ° C. to obtain a uniform solution. 0.020 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name “Neostan U-100”) was added as a catalyst, and 3.8 g of methanol was distilled off at 90 ° C. for 5 hours. A silyl group-containing silane-modified phenylene ether resin (hereinafter referred to as resin (A-4)) was obtained.
Number of moles of component (2) / number of moles of hydroxyl group in component (1) = 1.0.

Example 5
Bifunctional phenylene ether resin (trade name “OPE-1000”, hydroxyl group equivalent 520 g / eq) 100 g, poly (tetramethoxysilane) (Tama Chemical Co., Ltd., manufactured by Mitsubishi Gas Chemical Co., Ltd.) The product name “M silicate 51”, 44.7 g of Si average number per molecule 4.0) and 57.1 g of toluene were charged and dissolved at 90 ° C. to obtain a uniform solution. 0.022 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name “Neostan U-100”) is added as a catalyst, and methanol is removed at 90 ° C. for 5 hours to distill off 3.0 g of methanol. A silyl group-containing silane-modified phenylene ether resin (hereinafter referred to as resin (A-5)) was obtained.
Since the residual amount of hydroxyl groups in component (1) is calculated as 50% from the outflow amount of methanol, the hydroxyl equivalent of the resin (A-5) is 1750 g / eq.
Number of moles of component (2) / number of moles of hydroxyl group in component (1) = 0.50.

Example 6
Bifunctional phenylene ether resin (trade name “OPE-1000”, hydroxyl group equivalent 520 g / eq) 100 g, poly (tetramethoxysilane) (Tama Chemical Co., Ltd., manufactured by Mitsubishi Gas Chemical Co., Ltd.) A product name “M silicate 51” manufactured by the company, 134.1 g of an average number of Si per molecule 4.0) was charged and melt-mixed at 90 ° C. in the absence of a solvent to obtain a uniform solution. Here, 0.067 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name “Neostan U-100”) is added as a catalyst and subjected to a methanol removal reaction at 90 ° C. for 12 hours, whereby an alkoxysilyl group-containing silane-modified phenylene ether resin is obtained. (Hereinafter referred to as resin (A-6)).
Number of moles of component (2) / number of moles of hydroxyl group in component (1) = 1.5.

Comparative Example 1
Bifunctional phenylene ether resin (Mitsubishi Gas Chemical Co., Ltd., trade name “OPE-1000”, hydroxyl equivalent 520 g / eq) 52 g and bisphenol A type liquid epoxy resin (Japan Epoxy Resin, trade name “Epicoat 828”, epoxy Equivalent 190 g / eq) To 107 g of toluene was added 107 g of toluene and dissolved. Hereinafter, this resin composition is called resin (a-1).

Comparative Example 2
Bifunctional phenylene ether resin (Mitsubishi Gas Chemical Co., Ltd., trade name “OPE-1500”, hydroxyl group equivalent 840 g / eq) 100 g, poly (tetramethoxysilane) (Tama Chemical Co., Ltd., trade name “M silicate 51” An average number of Si per molecule (4.0) of 56.4 g and toluene of 56.4 g were charged and dissolved at 90 ° C. to obtain a uniform solution. Hereinafter, this resin composition is called resin (a-2).

Examples 7 to 12 (Preparation of alkoxysilyl group-containing silane-modified phenylene ether resin composition)
The resins (A-1) to (A-6) obtained in Examples 1 to 6 were each diluted with toluene so that the curing residue was 40%, and then tin octylate (manufactured by API Corporation, trade name “STANOCTO”). )) Was added in an amount of 0.3% per cured residue to obtain alkoxysilyl group-containing silane-modified phenylene ether resin compositions (B-1) to (B-6).

Example 13 (Preparation of alkoxysilyl group-containing silane-modified phenylene ether resin composition)
20 g of the resin (A-5) obtained in Example 5 and 2.2 g of an epoxy resin (manufactured by Japan Epoxy Resin, trade name “Epicoat 828”, epoxy equivalent 190 g / eq) were diluted with 13.8 g of toluene, and octylic acid 0.043 g of tin (manufactured by API Corporation, trade name “STANOCTO”) was added to obtain an alkoxysilyl group-containing silane-modified phenylene ether resin composition (B-7).

Comparative Example 3 (Preparation of phenylene ether resin composition)
To the resin composition a-1 obtained in Comparative Example 1, 0.5% of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “Cureazole 2E4MZ”) is added per solid content, and phenylene It was set as the ether resin composition (b-1).

Comparative Example 4 (Preparation of phenylene ether resin composition)
Each resin obtained in Comparative Example 2 was diluted with toluene so that the curing residue was 40%, and tin octylate (manufactured by API Corporation, trade name “STANOCTO”) was added at 0.3% per curing residue. The phenylene ether resin compositions (b-2) and (b-3) were used.

(Evaluation of bifunctional phenylene ether resin-silica hybrid cured product)
Resin compositions (B-1) to (B-6) obtained in Examples 7 to 12 and resin compositions (b-2) and (b-3) obtained in Comparative Examples 5 and 6, respectively, Pour into a fluororesin-coated container (length x width x depth = 10 cm x 10 cm x 1.5 cm) and heat at 120 ° C for 30 minutes and at 230 ° C for 2 hours to evaporate the solvent and cure the sol-gel. A cured product was obtained. The state (appearance, shrinkage, foaming) of the obtained cured product was evaluated according to the following criteria. The results are shown in Table 1.

(Evaluation of cured bifunctional phenylene ether resin)
The resin composition (b-1) obtained in Comparative Example 3 was poured into a fluororesin-coated container (length × width × depth = 10 cm × 10 cm × 1.5 cm), and the temperature was 120 ° C. for 30 minutes, 200 ° C. Was heated for 2 hours to evaporate the solvent and cure the sol-gel to obtain a cured product. The reason for the difference in the curing conditions is that the curing reaction is different (Examples 7 to 10, 12: sol-gel curing, Example 11: sol-gel curing + epoxy curing, Comparative Example 3: epoxy curing). This is because of consideration. The state (appearance, shrinkage, foaming) of the obtained cured product was evaluated according to the following criteria. The results are shown in Table 1.

(Appearance evaluation)
○: Transparent.
Δ: Cloudy
×: Whitened.

(Evaluation of shrinkage)
○: There is no crack or warpage in the cured product.
Δ: Warpage exists in the cured product.
X: The cured product has cracks.

(Evaluation of foaming)
○: There are no bubbles in the cured product.
Δ: Less than 5 bubbles exist in the cured product.
X: Five or more bubbles exist in hardened | cured material.

  In each of Examples 7 to 13 and Comparative Example 3, a transparent cured product was obtained. The cured product obtained in Comparative Example 4 had unevenness, foaming, and cracks due to phase separation of the phenylene ether resin and silica, and was very brittle, and thus could not be used for further evaluation.

(Heat-resistant)
The cured products obtained in Examples 7 to 13 and Comparative Example 3 were cut into 5 mm × 25 mm, and viscoelasticity measuring device (manufactured by Rheology, trade name “DVE-V4”, measurement conditions: amplitude 1.5 μm, frequency) The dynamic storage elastic modulus was measured using 10 Hz and a slope of 3 ° C./min) to evaluate the heat resistance. The measurement results are shown in FIG.

  As is clear from FIG. 1, in Examples 7 to 13, compared with Comparative Example 3, there is little decrease in the elastic modulus of the cured film even at a high temperature, and the heat resistance is excellent.

(Heat-resistant decomposition)
The thermogravimetric loss of the cured products obtained in Examples 7 to 13 and Comparative Example 3 was measured using a differential thermal / thermogravimetric simultaneous measurement device (manufactured by Seiko Instruments Inc., trade name “TG / DTA220”, measurement conditions: (Slope 10 ° C./min). The results are shown in Table 2.

  As is clear from Table 2, Examples 7 to 13 have sufficiently higher temperatures at 5% weight loss and 10% weight loss than Comparative Example 3. Further, even after the temperature is raised to 600 ° C., there is little weight loss, which indicates that the thermal decomposition resistance is excellent.

(Linear expansion coefficient)
Using the cured products obtained in Examples 7 to 10 and Comparative Example 3, the linear expansion coefficient at 50 to 100 ° C. was measured with a thermal stress strain measuring device (trade name TMA120C, manufactured by Seiko Electronics Industry Co., Ltd.). The results are shown in Table 3.

As apparent from Table 3, Examples 7 to 10 have a lower linear expansion coefficient than Comparative Example 3.

(Water absorption rate)
The cured products obtained in Examples 7 to 10 and Comparative Example 3 were immersed in a constant temperature bath maintained at 23 ° C. for 24 hours after being measured in a constant temperature bath maintained at 50 ° C. for 24 hours. The water absorption was calculated from the difference from the later measured weight. The results are shown in Table 4.

  As is apparent from Table 4, Examples 7 to 10 have a low water absorption rate comparable to that of Comparative Example 3, indicating that the low water absorption of polyphenylene ether is maintained.

(chemical resistance)
The cured products obtained in Examples 7 to 10 and Comparative Example 3 were immersed in a solvent for 8 hours, and the appearance was visually observed. The degree of swelling was calculated from the difference in measured weight before and after immersion (calculation method: (weight after immersion−weight before immersion) / weight before immersion × 100, and 0% when there was no absorption). The results are shown in Table 5.

  As is clear from Table 5, Examples 7 to 10 are superior to Comparative Example 3 in solvent resistance.

(Electrical characteristics: dielectric constant)
Using the cured products obtained in Examples 7 to 10 and Comparative Example 3, the electrical characteristics were evaluated by measuring the dielectric constant and dielectric loss tangent at a frequency of 1 MHz. The results are shown in Table 6.

  As is apparent from Table 6, Examples 7 to 10 have lower dielectric constant and dielectric loss tangent than Comparative Example 3, and are excellent in electrical properties.

(Physical properties of coatings: adhesion, surface hardness)
Each resin composition obtained in Examples 7 to 10 was applied to a glass plate with a bar coater and cured by heating at 120 ° C. for 30 minutes and at 230 ° C. for 2 hours to obtain a cured product having a thickness of 20 μm. It was. Further, the resin composition obtained in Comparative Example 3 was applied to a glass plate with a bar coater and cured by heating at 120 ° C. for 30 minutes and at 200 ° C. for 2 hours to obtain a cured product having a thickness of 20 μm. . In addition, the reason for providing the difference in the curing conditions is because the difference in the curing reaction (Examples 7 to 10: sol-gel curing, Comparative Example 3: epoxy curing) was taken into consideration.

(surface hardness)
About each hardened | cured material obtained by apply | coating and hardening on the conditions same as the above, the pencil hardness test by the general test method of JISK-5401 was done. Table 7 shows the evaluation results.

(Adhesion)
About each hardened | cured material obtained by apply | coating and hardening on the conditions same as the above, the Goban eyes cellophane tape peeling test by the general test method of JISK-5400 was done. Table 7 shows the evaluation results.

  As is clear from Table 7, Examples 7 to 10 have high adhesion to glass as in Comparative Example 3. Moreover, Examples 7-10 show that surface hardness is higher than Comparative Example 3, and scratch resistance is high.

  The alkoxysilyl group-containing silane-modified phenylene ether resin obtained by the present invention is excellent in heat resistance, adhesion, electrical characteristics, low water absorption, and chemical resistance, so that it can be used for paints, adhesives, sealing agents, printed wiring board materials, It is useful as an IC sealing material, an insulating sealant and the like.

It is a measurement result of the dynamic storage elastic modulus regarding the hardened | cured material of this invention, and the hardened | cured material of a comparative example.

Claims (9)

A method for producing an alkoxysilyl group-containing silane-modified phenylene ether resin obtained by subjecting a bifunctional phenylene ether resin (1) and an alkoxysilane partial condensate (2) to a dealcoholization condensation reaction. The production method according to claim 1, wherein the hydroxyl group equivalent of the bifunctional phenylene ether resin (1) is 200 to 3,000. The production method according to claim 1 or 2, wherein the alkoxysilane partial condensate (2) is a partial condensate of tetramethoxysilane and / or methyltrimethoxysilane. The use ratio of the bifunctional phenylene ether (1) to the alkoxysilane partial condensate (2) is the number of moles of the alkoxysilane partial condensate (2) / the number of moles of hydroxyl groups in the bifunctional phenylene ether (1) ( The production method according to any one of claims 1 to 3, which is a use ratio such that the molar ratio is 0.3 to 2.0. An alkoxysilyl group-containing silane-modified phenylene ether resin obtained by the production method according to claim 1. An alkoxysilyl group-containing silane-modified phenylene ether resin composition comprising the alkoxysilyl group-containing silane-modified phenylene ether resin according to claim 5 and a solvent. An alkoxysilyl group-containing silane-modified phenylene ether resin composition comprising the alkoxysilyl group-containing silane-modified phenylene ether resin according to claim 5 and an alkoxysilane partial condensate (2). An alkoxysilyl group-containing silane-modified phenylene ether resin composition comprising the alkoxysilyl group-containing silane-modified phenylene ether resin and the epoxy resin according to claim 5. A cured phenylene ether resin-silica hybrid obtained by curing the alkoxysilyl group-containing silane-modified phenylene ether resin composition according to any one of claims 6 to 8.

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