JP4028672B2 - Method for producing reaction product - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a specific reaction product. The reaction product obtained by the present invention is used in various applications such as IC sealing materials, epoxy resin laminates, paints, adhesives, and coating materials for electrical / electronic materials.
[0002]
[Prior art]
In recent years, with the development of science and technology, high performance has been required for materials used in various fields. For example, improvement in heat resistance is desired for cured epoxy resins that have been used in electrical and electronic materials.
[0003]
As a method for improving the heat resistance of the cured epoxy resin, for example, there is a method in which a curing agent and, if necessary, a filler such as glass fiber, glass particles, and mica are mixed with the epoxy resin. However, this method cannot provide sufficient heat resistance. Further, in this method, the transparency of the cured epoxy resin is lost, and the adhesive property at the interface between the filler and the resin is inferior, so that the mechanical properties are also insufficient.
[0004]
Moreover, as a method of improving the heat resistance of the cured epoxy resin, there is a method of using an epoxy resin reacted with a silane coupling agent. However, in general, since the silane portion of the silane coupling agent is small and the organic part is often an alkyl chain, the glass transition point (Tg) is hardly lowered by the introduction of the silane coupling agent. Absent. In addition, in order to introduce a large amount of glass component into the cured epoxy resin, the amount of the silane coupling agent is inevitably increased. However, since the silane coupling agent is generally expensive, the use of the silane coupling agent results in High cost.
[0005]
Further, as a method for improving the heat resistance of the cured epoxy resin, a method using a composite of an epoxy resin and a metal oxide has been proposed (Japanese Patent Laid-Open No. 8-100107). The composite is obtained by adding a metal alkoxide to a solution obtained by partially curing an epoxy resin to obtain a homogeneous sol solution, and then polycondensing the metal alkoxide. However, although such a composite has heat resistance improved to some extent as compared with a cured product of a simple epoxy resin, voids (bubbles) are generated in the cured product due to water in the composite, water generated during curing, or alcohol. . In addition, for further improvement in heat resistance, when the amount of metal alkoxide is increased, the generated silica cannot be dispersed, the transparency of the cured product is lost and whitening occurs. Since water is required, warping of the cured product and cracks are caused.
[0006]
In addition to attempts to compound epoxy resins, silica is also used to improve the heat resistance, toughness, gas barrier properties, etc. by utilizing the sol-gel curing reaction of alkoxysilanes for various polymer compounds. Many studies have been made to hybridize (Japanese Patent Laid-Open Nos. 11-92623, 6-192454, 10-168386, 10-152646, and 7-118543). Such). However, the hybrid obtained by the sol-gel curing reaction is produced by using a hydrogen bond between a silanol group generated mainly by hydrolysis of alkoxysilane and a hydrogen bonding functional group in the polymer compound. Is dispersed in the polymer compound, the reaction cannot be applied to a polymer compound having no hydrogen bonding functional group or a high Tg polymer compound having a cohesive force.
[0007]
[Problems to be solved by the invention]
The present invention aims to provide a reaction product and a manufacturing method thereof capable of improving the heat resistance such as e epoxy resin or a cured product thereof.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have caused an epoxy ring-opening reaction between a specific epoxy-modified alkoxysilane condensate and a polymer compound having a functional group capable of reacting with the epoxy group. As a result, it was found that a reaction product meeting the above purpose could be produced, and the present invention was completed.
[0009]
That is, the present invention relates to glycidol and general formula (1): R ^a _m Si (OR ^b ) _4-m (wherein m represents an integer of 0 or 1 and R ^a is alkyl having 1 to 8 carbon atoms. It represents a group or an aryl group, R ^b is Si hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) represented by hydrolyzable alkoxy hydrolysable obtained from silane alkoxysilane condensate (condensate The average number of the glycidol is equivalent to the equivalent of the epoxy group of glycidol / the equivalent of the alkoxy group contained in the hydrolyzable alkoxysilane condensate = 0.05 / 1 to 3/1. An epoxy-modified alkoxysilane condensate (a) (hereinafter referred to as (a) component) obtained by alcohol reaction and polyamic acid (c) (hereinafter referred to as (c) component) in the condensate (a) Alkoxysil The present invention relates to a method for producing a reaction product, characterized in that an epoxy ring-opening reaction is carried out at a temperature lower than the temperature at which a ru group is condensed .
[0023]
As described above, the component (a) used in the present invention is glycidol and general formula (1): R ^a _m Si (OR ^b ) _4-m (wherein m represents an integer of 0 or 1, R ^a represents a C 1-8 alkyl group or aryl group, and R ^b represents a hydrogen atom or a C 1-3 alkyl group.) A condensate (condensation) obtained from a hydrolyzable alkoxysilane represented by The average number of Si in the product is 2 to 300). In the formula, when R ^b is an alkyl group having 1 to 3 carbon atoms, examples of OR ^b include a methoxy group, an ethoxy group, and an n-propoxy group. The number of carbon atoms of the alkoxy group has a great influence on the physical properties of the reaction product finally obtained, for example, the condensation rate of the glass part. Therefore, when curing at low temperatures or when increasing the curing rate, methoxy is required. Groups are preferred. In R ^a , examples of the alkyl group or aryl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, cyclohexyl group, n -An octyl group, a phenyl group, a phenesyl group, etc. are mention | raise | lifted. When ^Ra is a long-chain alkyl group, it contributes to improving the flexibility (stretch rate) of the reaction product finally obtained and its cured product, but it can lower the glass transition point of the cured product. Since there are many, a methyl group is preferable from a heat resistant point.
[0025]
In addition, the glycidyl ether group does not necessarily need to exist in the above-mentioned proportion in each molecule of the component (a), and may exist in the above-mentioned proportion in the whole component (a) .
[0026]
Moreover, the average number of Si in the component (a) is 2 to 300 . Usually, when the average number of Si is large, the component (a) obtained tends to have a branched chain, but when the average number of Si is about 2 to 8, there is little or no branching structure, Easy to handle.
[0031]
(A) in the manufacture of components, the proportion of the hydrolyzable alkoxysilane condensate and glycidol, alkoxy group equivalent / the alkoxysilane condensate of epoxy groups grayed Rishidoru eq = 0.05-3 / 1 It is charging ratio. The ratio of the alkoxysilane condensate which is not epoxy-modified when the charging ratio is less increases, the charging ratio, compared alkoxy group 1 equivalent of the alkoxysilane condensate, 0 equivalents of epoxy groups of the glycidol. It is preferable to set it to 1 or more. Also, the when the charging ratio is increased, there is a tendency that heat resistance becomes poor of the cured product by unreacted glycidol remaining, the charging ratio, compared alkoxy group 1 equivalent of the alkoxysilane condensate, epoxy group glycidol The equivalent of is preferably 1 or less.
[0032]
In the reaction of the alkoxysilane condensate and glycidol, for example, the above components are charged and the ester exchange reaction is performed while distilling off the alcohol produced by heating. The reaction temperature is about 50 to 150 ° C., preferably 70 to 110 ° C., and the total reaction time is about 1 to 15 hours.
[0033]
If the dealcoholization reaction is carried out at a temperature exceeding 150 ° C., the reaction product increases in molecular weight with the condensation of alkoxysilane, which is not preferable because the viscosity tends to increase and gel. If the reaction temperature is less than about 50 ° C., the alcohol cannot be removed from the reaction system and the reaction does not proceed.
[0034]
In the transesterification reaction, a conventionally known ester-hydroxyl transesterification catalyst that does not open an epoxy ring can be used to promote the reaction. For example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, , These oxides, organic acid salts, halides, alkoxides and the like. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate is effective.
[0035]
Moreover, the said reaction can also be performed in a solvent. The solvent is not particularly limited as long as it is an organic solvent that dissolves the alkoxysilane condensate and glycidol. As such an organic solvent, it is preferable to use an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, toluene, and xylene.
[0036]
As described above, the component (a) thus obtained does not require that all the molecules have a glycidyl ether group, and may contain an unreacted alkoxysilane condensate.
[0048]
The reaction product according to the present invention, the (a) component and (c) component may be granulated steel Ri by the fact to epoxy ring-opening reaction.
[0050]
The production method of the present invention is extremely effective for producing a polymer compound having no hydrogen bonding functional group or a high Tg polymer compound having strong cohesive force, which has been difficult to hybridize by the sol-gel method. is there. That is, polyamic acid is used as the component (c) of the present invention.
[0051]
Wherein component (c) and (a) the reaction ratios of the components, the reaction temperature, For the reaction conditions time, taking into account the equivalent of functional group of the equivalent weight and the component (c) epoxy groups of component (a) And it adjusts suitably so that the reaction product obtained may not gelatinize . Below (110 ° C. in trimethoxysilyl group) temperature A alkoxysilyl group is condensed, preferably to carry out the reaction.
[0052]
In addition, the resulting reaction product thus, depending on the nature of the reaction product, within no phase separation, optionally further general formula _{^{(2): R c r Si}} (OR d) 4 _{-r (wherein,} r is an integer of 0 to 2, R ^c is an alkyl group having 1 to 3 carbon atoms which may have a functional group directly bonded to a carbon atom, an aryl group or an unsaturated aliphatic residue R ^d represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each may be the same or different, and a hydrolyzable alkoxysilane represented by the following formula: / Or its condensate (b) (hereinafter referred to as component (b)) can also be blended. Specific examples of the hydrolyzable alkoxysilane corresponding to the component (b) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, and methyltriethoxysilane. , Methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, trialkoxysilanes such as 3,4-epoxycyclohexylethyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyl And dialkoxysilanes such as dimethoxysilane and diethyldiethoxysilane. Among these, tetraalkoxysilanes and / or condensates of trialkoxysilanes are preferable. Furthermore, the reaction product may contain a solvent, a filler, a mold release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a plasticizer, an antibacterial agent, an antibacterial agent, as necessary, as long as the effects of the present invention are not impaired. A glaze, a leveling agent, an antifoaming agent, a coloring agent, a stabilizer, a coupling agent and the like may be blended.
[0053]
【The invention's effect】
The production method of the present invention can be applied to a polymer compound that has conventionally been difficult to form a silica hybrid, and the reaction product of interest can be easily produced. In addition, the reaction product obtained by the production method of the present invention can provide a cured product excellent in heat resistance by heating and curing, for example, an IC sealing material, an epoxy resin-based laminate, a paint, an adhesive, It can be used for various applications such as coating agents for electrical and electronic materials.
[0054]
【Example】
Hereinafter, the present invention will be specifically described with reference to production examples, examples and comparative examples. In each example, “%” is based on weight unless otherwise specified.
[0055]
Production Example 1 Into a 1-liter four-necked flask equipped with a stirrer, a water separator, a thermometer, and a nitrogen blowing port, 350 g of glycidol (manufactured by NOF Corporation, trade name Epiol OH) and a tetramethoxysilane condensate ( Tama Chemical Co., Ltd., trade name: Methyl silicate 51: In general formula (1), OR ^b is a methoxy group and the average number of Si is 4 ) 671.8 g is charged, and stirred at 80 ° C. under a nitrogen stream. After raising the temperature, 1 g of dibutyltin dilaurate was added as a catalyst and reacted at 80 ° C. During the reaction, methanol was distilled off from the reaction system using a water separator, and when the amount reached about 130 g, it was cooled. The time required for cooling after raising the temperature was 6 hours. After cooling to 50 ° C., the nitrogen blowing stopper and the water separator were removed, and the pressure reduction line was connected, and methanol remaining in the system was removed under reduced pressure at 1 kPa for about 15 minutes. During this time, about 25 g of methanol was removed by vacuum. Thereafter, the flask was cooled to room temperature to obtain 869.7 g of component (a). In addition, the equivalent of the epoxy group of glycidol / the equivalent of the alkoxy group of the alkoxysilane condensate at the time of preparation = 0.33 / 1.
[0056]
¹ H-NMR (acetone-d ₆ solution) of glycidol (FIG. 1) and the reaction product of Production Example 1 (FIG. 2) are shown. FIG. 2 shows that the methylene peak a (around 2.56 ppm, around 2.68 ppm) and methine peak b (around 3.02 ppm) of the oxirane ring of glycidol in FIG. 1 are retained without participating in the reaction. In FIG. 2, it is recognized that the peak d (approximately 3.86 ppm) of the hydroxyl group in glycidol in FIG. Further, (near 3.47Ppm, around 3.75 ppm) methylene peak c adjacent to the hydroxyl group of glycidol in Figure 1, by a hydroxyl group to react with the alkoxysilane, the component (a) in FIG. 2, c '(3 .78 ppm vicinity, 4.08 ppm vicinity). Moreover, in FIG. 2, the peak (near 3.6 ppm) of the methoxy group newly derived from the alkoxysilane condensate was seen. From these, it was determined that the component (a) obtained in Production Example 1 was mainly composed of a compound as shown in FIG.
[0057]
Production Example 2
In the same reaction apparatus as in Production Example 1, 350 g of glycidol (manufactured by NOF Corporation, trade name Epiol OH) and methyltrimethoxysilane condensate (manufactured by Tama Chemical Co., Ltd., prototype MTMS-A: general formula ( 1 ) in OR ^b is methoxy, ^{R a} is a methyl group, the average number of Si is 4.5) were charged 626.2G, under nitrogen flow, while stirring, temperature was raised to 80 ° C., the catalyst as dibutyl tin dilaurate 1g And reacted at 80 ° C. During the reaction, methanol was distilled off from the reaction system using a water separator, and when the amount reached about 130 g, it was cooled. It took 8 hours to cool after raising the temperature. After cooling to 50 ° C., the nitrogen blowing stopper and the water separator were removed, and the pressure reduction line was connected, and methanol remaining in the system was removed under reduced pressure at 1 kPa for about 15 minutes. During this time, about 22 g of methanol was removed by vacuum. Thereafter, the flask was cooled to room temperature to obtain 825.0 g of component (a) . In addition, the equivalent of the epoxy group of glycidol / the equivalent of the alkoxy group of the alkoxysilane condensate at the time of preparation = 0.5 / 1.
[0058]
In the same manner as in Production Example 1, glycidol and ¹ H-NMR (acetone-d ₆ solution) of component (a) obtained in Production Example 2 were compared. In the reaction product, the methylene peak (around 2.56 ppm, around 2.68 ppm) and the methine peak (around 3.02 ppm) of the oxirane ring were retained without being involved in the reaction. On the other hand, the hydroxyl group peak d (around 3.86 ppm) in glycidol disappeared. Further, the methylene peak c adjacent to the hydroxyl group of glycidol (around 3.47 ppm, around 3.75 ppm) was shifted to (around 3.78 ppm, around 4.08 ppm) due to the reaction of the hydroxyl group with alkoxysilane. . Further, a methoxy group peak (around 3.6 ppm) and a methyl group peak (0.15 ppm) derived from the alkoxysilane condensate were observed. From these, it was judged that the component (a) obtained in Production Example 2 was a compound in which a predetermined amount of the methoxy group of the methyltrimethoxysilane condensate was a glycidyl ether group.
[0059]
Production Example 3
In the same reactor as in Production Example 1, 350 g of glycidol (manufactured by NOF Corporation, trade name Epiol OH) and tetramethoxysilane condensate (manufactured by Tama Chemical Co., Ltd., prototype MS-56: general formula ( 1 )) OR ^b is a methoxy group and Si has an average number of 18) of 636.4 g. While stirring under a nitrogen stream, the temperature is raised to 80 ° C., 1 g of dibutyltin dilaurate is added as a catalyst, and the reaction is carried out at 80 ° C. I let you. During the reaction, methanol was distilled off from the reaction system using a water separator, and when the amount reached about 130 g, it was cooled. The time required for cooling after raising the temperature was 7.5 hours. After cooling to 50 ° C., the nitrogen blowing stopper and the water separator were removed, and the pressure reduction line was connected, and methanol remaining in the system was removed under reduced pressure at 1 kPa for about 15 minutes. During this time, about 20 g of methanol was removed by vacuum. Thereafter, the flask was cooled to room temperature to obtain 835.4 g of component (a) . In addition, the equivalent of the epoxy group of glycidol / the equivalent of the alkoxy group of the alkoxysilane condensate at the time of preparation = 0.42 / 1.
[0060]
As in the case of Production Example 1, ¹ H-NMR (acetone-d ₆ solution) of glycidol and the reaction product of Production Example 3 was compared, and the same results as in the chart of Production Example 1 were obtained. From these, it was judged that the component (a) obtained in Production Example 3 was a compound in which a predetermined amount of the methoxy group of the tetramethoxysilane condensate was a glycidyl ether group.
[0067]
Production Example 4
In the same reactor as in Example 1, glycidol (manufactured by NOF Corp., trade name EPIOL OH) 178.7G and tetramethoxysilane condensate (Tama Chemicals Co., Ltd., the prototype MS-5 6) 892 .6 g was charged, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. Then, 1 g of dibutyltin dilaurate was added as a catalyst and reacted at 80 ° C. During the reaction, methanol was distilled off from the reaction system using a water separator, and when the amount reached about 73 g, the reaction system was cooled. The time required for cooling after raising the temperature was 4 hours. After cooling to 50 ° C., the nitrogen blowing stopper and the water separator were removed, and the pressure reduction line was connected, and methanol remaining in the system was removed under reduced pressure at 1 kPa for about 15 minutes. During this time, about 10 g of methanol was removed by vacuum. Thereafter, the flask was cooled to room temperature, and 989.4 g of a reaction product was obtained. In addition, the equivalent of the epoxy group of glycidol / the equivalent of the alkoxy group of the alkoxysilane condensate at the time of preparation = 0.14 / 1.
[0068]
As in the case of Production Example 1, glycidol and ¹ H-NMR (acetone-d ₆ solution) of the reaction product of Production Example 4 were compared, and the same results as the chart of Production Example 1 were obtained. From these, it was judged that the reaction product was a compound in which a predetermined amount of methoxy groups of the tetramethoxysilane condensate became glycidyl ether groups.
[0069]
Example 1
100 g of bis- (4-aminophenyl) ether and 879.6 g of dimethylacetamide were added to a 1.5-liter four-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen blowing port, and the mixture was stirred while stirring. 9 g of pyromellitic acid was added slowly at room temperature with stirring. The mixture was stirred as it was for 1 hour to obtain a polyamic acid having an acid anhydride group at the terminal. Furthermore, 61.5 g of component (a) obtained in Production Example 4 was added and reacted at 95 ° C. for 3 hours to obtain the desired reaction product (equivalent of glycidyl ether group / equivalent of acid anhydride group = 1.5). Further, this solution was poured on a glass plate, heated at 100 ° C. for 1 hour to remove dimethylacetamide, and further heated at 300 ° C. to obtain a light yellow and transparent cured film (silica / polyimide = 0.14 (weight) ratio)).
[0070]
Comparative Example 2
To the same reactor as in Example 1 , 100 g of bis- (4-aminophenyl) ether and 836 g of dimethylacetamide were added, and 109 g of pyromellitic acid was slowly added at room temperature while stirring. The mixture was stirred as it was for 1 hour to obtain a polyamic acid having an acid anhydride group at the terminal. Furthermore, tetramethoxysilane condensate (Tama Chemicals Co., Ltd., the trade name Methyl Silicate 5 1) was stirred at room temperature for 1 hour added 54.9g of water 5.2 g. Furthermore, this solution was poured on a glass plate and heated at 100 ° C. for 1 hour to remove dimethylacetamide and further heated at 300 ° C., but the silica phase-separated from the polyimide and became a cloudy film (silica / polyimide = 0.14 (weight ratio)).
[Brief description of the drawings]
FIG. 1 is a ¹ H-NMR chart of glycidol.
2 is a ¹ H-NMR chart of component (a) obtained in Production Example 1. FIG.

Claims (1)

Glycidol and general formula (1): R ^a _m Si (OR ^b ) _4-m (wherein m represents an integer of 0 or 1, R ^a represents an alkyl group or aryl group having 1 to 8 carbon atoms) , R ^b represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) A hydrolyzable alkoxysilane condensate obtained from a hydrolyzable alkoxysilane represented by (the average number of Si in the condensate is 2 to 2). 300) is obtained by a dealcoholization reaction at a ratio of equivalent of epoxy group of glycidol / equivalent of alkoxy group contained in hydrolyzable alkoxysilane condensate = 0.05 / 1 to 3/1. and epoxy-modified alkoxysilane condensate (a), the reaction product alkoxysilyl groups in the polyamic acid (c) and the condensate (a) is characterized in that to an epoxy ring-opening reaction at a temperature below the condensation Manufacturing method.

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