JP2003137980A - Phenoxy resin, epoxy resin, method for producing the same and resin composition for semiconductor sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenol resin or an epoxy resin useful as a resin for semiconductor sealing materials and capable of providing a composition excellent in a balance of heat resistance, moisture resistance, crack resistance and moldability after curing. SOLUTION: This phenol resin is obtained by reacting phenols with unsaturated hydrocarbon compounds having two or more carbon-carbon double bonds in the presence of an acid catalyst. In the phenol resin, the average molecular weight expressed in terms of polystyrene is <=320 and the content of a monofunctional component containing only one phenolic hydroxy group in one molecule is >2 wt.% but <=20 wt.% based on the resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a phenolic resin having a good balance of heat resistance, moisture resistance, crack resistance and moldability, which is useful as an electric insulating material, particularly as a resin for semiconductor encapsulating materials and resin for laminated boards. The present invention relates to an epoxy resin and a composition for semiconductor encapsulant.

[0002]

2. Description of the Related Art In recent years, semiconductor-related technologies have been rapidly advancing, and the required characteristics of each component and its raw material have become severe. In particular, the miniaturization of wiring and the increase in chip size are advancing along with the improvement in the integration density of semiconductor memories, and the mounting method is also shifting from through-hole mounting to surface mounting. However, in the surface mounting automation line, the semiconductor package undergoes a rapid temperature change during soldering of the lead wire, cracks occur in the resin molding part for the semiconductor encapsulant, and the interface between the lead wire resins deteriorates. Then, there is a problem that the moisture resistance is lowered.
As the phenol resin used in the resin composition for semiconductor encapsulant, a phenol resin such as a phenol novolac resin or a cresol novolac resin is conventionally used as a curing agent, or an epoxy resin having a cresol novolac skeleton is used as a main component. Has been done. However, when these resins are used, there is a problem in that the moisture absorption characteristics of the semiconductor package are poor and, as a result, the occurrence of cracks during immersion in the solder bath as described above cannot be avoided.

Therefore, recently, in order to improve the moisture resistance and heat resistance of the resin composition for semiconductor encapsulant, studies have been made to improve the epoxy resin raw material and the phenol resin as a curing agent for the epoxy resin, For example, JP-A-6
In JP-A 1-291615, an epoxy resin having an excellent balance of moisture resistance, heat resistance and internal plasticity, which contains an epoxy resin derived from phenols and dicyclopentadiene (hereinafter sometimes referred to as DCPD) as an essential component. Compositions have been proposed. However, the moldability is not always sufficient. In addition, JP-A-9-488
In JP-A 39-39, in DCPD / phenol-modified epoxy resin, the epoxy resin or the phenolic resin as a raw material thereof is distilled or reprecipitated to adjust the amount of low molecular weight components, so that heat resistance is not impaired and good flow is achieved. It is disclosed that sex is obtained. However,
Adjustment by distillation is difficult, and there are problems that the amount of residual phenol in the resin increases. Further, since adjustment by reprecipitation uses a solvent, there is a problem that it is necessary to remove the solvent from the resin again.

[0004]

The problem to be solved by the present invention is to provide a phenolic resin, an epoxy resin, which has excellent heat resistance after curing, excellent fluidity, and excellent moldability when sealing a semiconductor. An object of the present invention is to provide an efficient production method thereof and an epoxy resin composition using the resin.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an unsaturated ring having two or more phenols and carbon-carbon double bonds in the presence of an acid catalyst. A polystyrene-converted number average molecular weight is 320 in a phenol resin obtained by addition reaction with a hydrocarbon (hereinafter sometimes simply referred to as “unsaturated cyclic hydrocarbon”).
Monofunctional component having the following and containing only one phenolic hydroxyl group in one molecule (hereinafter, may be simply referred to as "monofunctional component"), particularly ether type compound and phenols and unsaturated It has been found that when a proper amount of a 1: 1 addition product with a cyclic hydrocarbon is contained, the balance between heat resistance after curing and fluidity during molding is excellent. Further, in the production of a phenol resin, by devising a reaction method between a phenol and an unsaturated cyclic hydrocarbon or a method for concentrating a reaction product, the content of the monofunctional component is controlled within an appropriate range. We have completed an efficient manufacturing method.

That is, the present invention provides a phenol resin obtained by reacting a phenol with an unsaturated cyclic hydrocarbon compound having two or more carbon-carbon double bonds,
The polystyrene reduced number average molecular weight is 320 or less, and the content of the monofunctional component containing only one phenolic hydroxyl group in one molecule is more than 2% by mass and 20% by mass or less of the resin. The present invention relates to a characteristic phenol resin. Further, the method includes a reaction step of bringing the phenols into contact with an unsaturated cyclic hydrocarbon compound having two or more carbon-carbon double bonds in the presence of an acid catalyst, and a concentration step of mainly removing unreacted phenols. In the method for producing a phenolic resin, the catalyst concentration in the reaction system is adjusted to a predetermined concentration in the reaction step, and the reaction product is concentrated under predetermined conditions in the concentration step, so that the polystyrene reduced number average molecular weight is 320 or less, And 1 phenolic hydroxyl group
The present invention relates to a method for producing a phenol resin, wherein the content of the monofunctional component contained in the resin is more than 2% by mass and 20% by mass or less. The present invention also relates to an epoxy resin obtained by reacting the phenol resin obtained by the above production method with an epihalohydrin. Furthermore, an epoxy resin composition for a semiconductor encapsulant containing an epoxy resin, a curing agent composed of a phenol resin obtained by the above production method, a curing accelerator and an inorganic filler as essential components, or an epoxy obtained by the above production method. The present invention relates to an epoxy resin composition for a semiconductor encapsulating material, which contains a resin, a curing agent, a curing accelerator and an inorganic filler as essential components.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The phenol resin of the present invention, in the presence of an acid catalyst, phenols having a phenolic hydroxyl group and carbon-
It is produced by reacting with an unsaturated cyclic hydrocarbon compound having two or more carbon double bonds. Examples of unsaturated cyclic hydrocarbon compounds having two or more carbon-carbon double bonds include dicyclopentadiene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, 3a, 4,7,7.
Examples include a-tetrahydroindene, α-pinene, limonene and the like. These can be used alone or in combination. In particular, dicyclopentadiene is preferable because the resulting resin is excellent in heat resistance, moisture resistance and mechanical properties.

The phenols are not particularly limited as long as they are aromatic compounds having a phenolic hydroxyl group in which the hydroxyl group is directly substituted on the aromatic ring.
For example, phenol, o-cresol, m-cresol,
p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-isopropylphenol, m-propylphenol, p-propylphenol, p-sec-butylphenol, p-tert.
-Butylphenol, p-cyclohexylphenol,
Monohydric phenols such as p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, α-naphthol, β-naphthol; resorcin, catechol, hydroquinone, 2,2-bis (4 ′)
-Hydroxyphenyl) propane, 1,1'-bis (dihydroxyphenyl) methane, 1,1'-bis (dihydroxynaphthyl) methane, tetramethylbiphenol,
Examples thereof include dihydric phenols such as biphenol; trihydric phenols such as trishydroxyphenylmethane. Particularly, phenol, o-cresol, m-cresol, α-naphthol, β-naphthol, 2,2-bis (4′-hydroxyphenyl) propane and the like are preferable from the viewpoints of economy and ease of production. These can be used alone or in combination.

The molar ratio of unsaturated cyclic hydrocarbon and phenols used in the reaction is appropriately adjusted depending on the molecular weight and melt viscosity of the desired phenol resin. Normally,
The range of phenols / unsaturated cyclic hydrocarbon = 1 to 20 (molar ratio) is preferable. Especially to lower the melt viscosity,
The range of phenols / unsaturated cyclic hydrocarbon = 2 to 15 (molar ratio) is preferable. Incidentally, a low melt viscosity phenolic resin, and a low melt viscosity epoxy resin obtained by epoxidizing the same, both of which can be highly filled with a filler when used as a semiconductor encapsulating material, resulting in a small linear expansion coefficient, In addition, the moisture resistance is improved, which is preferable.

As the acid catalyst, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid and organic acids such as formic acid, acetic acid and oxalic acid, boron trifluoride, boron trifluoride / ether complex, boron trifluoride / phenol complex, A Friedel-Crafts medium such as a boron trifluoride / water complex, a boron trifluoride / alcohol complex, a boron trifluoride / amine complex, or a mixture thereof is used. Among these, boron trifluoride, from the viewpoint of catalytic activity and ease of catalyst removal,
Boron trifluoride / phenol complex and boron trifluoride / ether complex are preferably used.

In the present invention, a monofunctional component having a polystyrene reduced number average molecular weight of 320 or less and containing only one phenolic hydroxyl group in one molecule, particularly an ether type compound, phenols and unsaturated cyclic hydrocarbons. 1: 1
The content of the adduct in the phenol resin is controlled to exceed 2% by mass and 20% by mass or less. If the content is 2% by mass or less, the fluidity becomes low, and if it exceeds 20% by mass, the heat resistance decreases, which is not preferable. The polystyrene-equivalent number average molecular weight is, in GPC measurement,
It is the number average molecular weight calculated from the molecular weight converted into the molecular weight of polystyrene having an equivalent retention time.

The method for producing a phenolic resin of the present invention includes a reaction step and a concentration step, both of which affect the amount of the monofunctional component. The monofunctional component and its control method will be described in detail below. First, the reaction step will be described. The concentration of the catalyst used in the reaction affects the reaction mechanism and addition position of the phenols and the unsaturated cyclic hydrocarbons, so that the concentration is 0.01 to 0 with respect to the total mass of the phenols, the unsaturated cyclic hydrocarbons and the catalyst. The amount is preferably 0.5% by mass, more preferably 0.03 to 0.3% by mass. For example, when phenol and dicyclopentadiene are reacted in the presence of boron trifluoride / phenol complex, boron trifluoride is added to the total mass of phenol, dicyclopentadiene and boron trifluoride / phenol complex. Make it within the above range. Catalyst concentration is 0.5% by mass
If it is more than the above, the reaction proceeds too fast, and the rate is less than 0.
If the amount is less than 01% by mass, the progress of the reaction is remarkably slowed, and it becomes difficult to control the amount of the monofunctional component in both cases, which is not preferable. It should be noted that the catalyst concentration must be maintained throughout the reaction. Therefore, when the phenols and the catalyst are charged in the reactor first and the reaction is carried out by adding the unsaturated cyclic hydrocarbon dropwise, the catalyst concentration at the start of the reaction is actually the concentration for the phenols,
The above catalyst concentration range is maintained from the start to the end of the reaction.

Further, in the above catalyst concentration range, water affects the catalytic activity and the composition of the reaction product. When the water content is large, the catalytic activity is lowered and the reaction progresses slowly, so that it becomes difficult to control the resin composition. Therefore, it is preferable to set the water concentration in the phenols and unsaturated cyclic hydrocarbons before the addition of the catalyst before the start of the reaction to 500 ppm or less. Especially, since phenols easily contain water,
It is preferable to appropriately perform dehydration operation to control the water content. Examples of the dehydration method include a method of azeotropically diluting phenols with an organic solvent in a nitrogen stream, if necessary. The amount of the catalyst used and the amount of water in the raw material are not limited to the above range, and it is preferable to appropriately adjust the balance within a range in which the resin composition can be controlled. During the reaction, the inside of the reactor is usually replaced with an inert gas such as nitrogen or argon. The reaction is preferably carried out in a closed system replaced with an inert gas, but it is also possible to carry out the reaction in an open system while supplying the inert gas into the reactor. In the reaction, it is preferable that the amount of water in the reaction system is 500 ppm or less so that water does not enter the system.

Although the reaction method is not particularly limited, for example, a reactor is charged with a predetermined amount of phenols and an acid catalyst, and then unsaturated cyclic hydrocarbons are added dropwise to carry out the reaction. The reaction temperature may be appropriately adjusted according to the progress of the reaction and is not particularly limited, but in the present invention, it is usually 30 to 150 ° C., preferably 50 to 1
By carrying out the reaction in the range of 20 ° C, the progress of the reaction can be preferably controlled. The reaction time may be stopped when the amount of the monofunctional component in the resin reaches a desired amount and is not particularly limited, but is usually 10 minutes to 6 minutes.
0 hours, preferably 1 to 20 hours, more preferably 2
By performing the reaction within the range of 10 hours, the reaction can be efficiently performed. The end point of the reaction is determined by confirming the resin composition in the reaction solution.

The reaction is terminated by deactivating the catalyst. At that time, it is important to surely stop the reaction. The deactivation means is not particularly limited, but it is preferable to use a means such that the residual amount of ionic impurities such as boron and fluorine in the finally obtained phenol resin is 100 ppm or less. As a deactivator, alkali metals, alkaline earth metals or their oxides, hydroxides, carbonates, ammonium hydroxide, inorganic bases such as ammonia gas, etc. can be used, but fast and simple processing is possible. It is preferable to use hydrotalcites as a deactivator because the amount of ionic impurities remaining after the treatment is small.

When the phenol resin of the present invention is used as a resin for encapsulant, it exhibits excellent curability, moldability and the like, and in order to impart excellent heat resistance and moisture resistance after curing, the phenol resin is used. It is important to control the physical properties of the resin as described below. The content of a compound containing two phenolic hydroxyl groups (hereinafter sometimes referred to as a binuclear component) in which two molecules of phenol are added to one molecule of unsaturated cyclic hydrocarbon in the resin is the viscosity of the resin. Since it has a great influence on fluidity, curability, etc., it is important to adjust it appropriately. The content of the binuclear component in the phenol resin is preferably 30 to 90% by mass, and particularly preferably 40 to 80% by mass, which shows preferable curing characteristics. When the content of the binuclear component is less than 30% by mass, the fluidity of the resin is lowered and the moldability is deteriorated.
If the amount is larger, the fluidity is good but the crosslinking density after curing is lowered, which is not preferable. The amount of binuclear components is
It can be controlled mainly by the reaction molar ratio of the phenol and the unsaturated cyclic hydrocarbon, and it is preferable to control the amount of the binuclear component by appropriately adjusting the molar ratio. Further, the resin viscosity has a great influence on the flow characteristics at the time of molding, so it is necessary to appropriately adjust the viscosity. The viscosity is not particularly limited, but it is effective to grasp the solution viscosity of a 50% resin solution of n-butanol by the Canon-Fenske kinematic viscosity tube method. preferably to fall in the range of 10mm ² / sec~200mm ² / sec, especially 30mm ² / sec~1
Resins controlled in the range of 80 mm ² / sec exhibit favorable flow properties. Further, the content of the phenolic hydroxyl group in the resin affects the curing characteristics and the like, and therefore needs to be appropriately adjusted. The phenolic hydroxyl group content is not particularly limited, but for example, 165 g / eq to 300 g is equivalent to the hydroxyl group in the resin measured by the alkaline back titration method of the acetylated product in a pyridine-acetic anhydride solution.
/ Eq range is preferred, especially 170 g / eq-250
The resin adjusted to g / eq not only exhibits favorable curing characteristics, but also has a good balance with fluidity and very good handling during molding. According to the production method described in the present specification, it is possible to produce a phenol resin satisfying the above-mentioned resin physical properties.

Next, the concentration step will be described. The above reaction liquid is treated in the concentration step after removing the deactivating agent and the like by filtration. In the concentration step, unreacted phenols are recovered and the amount of monofunctional component is controlled to obtain a phenol resin. Concentration conditions are not defined as constant conditions based on the relationship between the temperature and pressure in the concentration system and the vapor pressure, but the most efficient concentration can be achieved under the following conditions. That is, the temperature in the system is not particularly limited as long as it does not cause decomposition of the resin, but is preferably 250 ° C. or lower, and more preferably 180 to 220 ° C. The system pressure may be normal pressure, reduced pressure, or increased pressure, but the system may be under reduced pressure in order to smoothly and quickly concentrate in the above temperature range. preferable. Specifically, the range is preferably 66.5 kPa (500 torr) or less, and particularly preferably 40 kPa (300 torr) or less. Further, in order to efficiently remove unreacted phenols in the resin, it is preferable to blow nitrogen or high-pressure steam into the system under reduced pressure. The pressure of steam or nitrogen introduced into the system is not particularly limited, but specifically, it is 0.
The range of 3 to 2.0 MPa is preferable, and more preferably 0.0.
Impurities can be efficiently removed when the blowing operation is performed in the range of 5 to 1.5 MPa.

The concentration method is not particularly limited, but the following examples are mentioned as preferable concentration methods. After the filtered reaction liquid (filtrate) is transferred to a pot for concentration, heating is started and at the same time, the pressure in the system is continuously reduced. When the temperature in the system reaches 200 ° C., the pressure in the system is fully reduced to 13 kPa (100 torr) or less. After concentrating in this state for an arbitrary time, high-pressure steam is blown into the system under reduced pressure, and finally nitrogen is blown so that the steam does not remain to complete the concentration. The end point of the concentration is determined by confirming the amount of the unreacted phenols and the amount of the monofunctional component detected in the region having a polystyrene reduced number average molecular weight of 320 or less by GPC analysis. It is necessary that the content of the monofunctional component in the phenol resin is more than 2% by mass and 20% by mass or less. Further, the content of unreacted phenols is preferably small from the viewpoint of the environment when using the product, but from the viewpoint of production efficiency and quality, the residual amount in the resin should be 500 ppm or less. Is sufficient, preferably 200 ppm or less, more preferably 100 ppm or less.
It is below ppm. That is, when it is more than 500 ppm, it is not preferable from the viewpoint of the performance of the resin and the influence on the environment. On the other hand, when trying to reduce it, there is a problem that the concentration time becomes long, so it is important to consider their balance. Is. As described above, the phenol resin of the present invention can be obtained by controlling the amount of the monofunctional component in the reaction step and the concentration step.

Hereinafter, the monofunctional component will be specifically described in the case where phenol is used as the phenol and dicyclopentadiene is used as the unsaturated cyclic hydrocarbon. In this case, the monofunctional component mainly includes the compound A represented by the following general formula (1) and the compound B represented by the following general formula (2).

[0020]

[Chemical 3]

[Chemical 4]

Compounds A and B are components separated by gel permeation chromatography (GPC) and isolated by nuclear magnetic resonance (NMR, magnetic frequency 4
It can be identified by analysis at 00 MHz). Compound A was calculated from the ¹ H-NMR measurement result to have an aliphatic hydrogen content in the molecule of about 60% by the following calculation formula 1, and a single peak derived from a phenolic hydroxyl group near a chemical shift of 4.9 ppm. Can be identified from the fact that is observed. Further, it can be obtained from the ¹³ C-NMR measurement result by the following calculation formula 2. Calculation Formula 1 Aliphatic Hydrogen Content in Molecule = A1 / (A1 + A2) (A1 has 0 Chemical Shift on ¹ H-NMR Measurement Chart
Peak area intensity of ~ 4.8 ppm, A2 is ¹ H-NMR
Peak area intensity at chemical shift on the measurement chart of 6.5-8.5 ppm) Calculation formula 2 Ether type product content = B3 / (B1 + B2 + B)
3) (B1 is chemical shift 1 on ¹³ C-NMR measurement chart)
Area intensity of 30 to 133 ppm, B2 is ¹³ C-NMR
Area intensity of chemical shift 137 to 140 ppm on measurement chart, B3 is area intensity of chemical shift 155 to 160 ppm on ¹³ C-NMR measurement chart) Compound B is a molecule calculated from ¹ H-NMR measurement by the following calculation formula 3. It can be identified from the fact that the content of aliphatic hydrogen in the product is calculated to be 76%. Calculation formula 3 Aliphatic hydrogen content in molecule = C1 / (C1 + C2) (C1 is 0 in the chemical shift on the ¹ H-NMR measurement chart.
Peak area intensity of ~ 6 ppm, C2 is a peak area intensity of chemical shift of 6.5-8.5 ppm on the ¹ H-NMR measurement chart)

Compound A and compound B of phenol resin
The content of can be determined by GPC analysis by measuring those amounts detected in a region corresponding to a polystyrene reduced number average molecular weight of 320 or less. In the reaction step, it is important to confirm the production amounts of the compound A and the compound B, and if the total content of the compounds A and B is more than 2% by mass and 25% by mass or less of the whole resin at the end of the reaction step. In the subsequent concentration step, the monofunctional components can be efficiently controlled, and finally it becomes possible to obtain a phenol resin in which the content thereof is controlled to an appropriate amount.

In the concentration step, the total content of the compounds A and B of the resin can be set to more than 2% by mass and 20% by mass or less by performing a high pressure steam blowing operation under reduced pressure. Furthermore, it is preferable that the total content of the compounds A and B is 3 to 18% by mass.

In the method for producing a phenol resin of the present invention, it is essential to carry out the above reaction control and concentration control,
By carrying out these simultaneously, a phenol resin having a good balance between heat resistance and fluidity can be obtained. The phenolic resin obtained as described above has excellent heat resistance, moisture resistance, crack resistance, and excellent fluidity, and therefore has good moldability. It is useful as a curing agent for epoxy resin, or as a raw material for epoxy resin.
The use is not particularly limited.

Next, the method for producing the epoxy resin of the present invention will be described. The epoxy resin of the present invention can be obtained by reacting the above-mentioned phenol resin with an epihalohydrin in the presence of a base catalyst to form a glycidyl group. The glycidylation reaction can be carried out by a conventional method. Specifically, for example, in the presence of a base such as sodium hydroxide or potassium hydroxide, a phenol resin is usually added to glycidyl such as epichlorohydrin or epibromhydrin at a temperature of 10 to 150 ° C, preferably 30 to 80 ° C. It can be obtained by reacting with an agent and then washing with water and drying. The amount of the glycidylating agent used is preferably 2 to 20 times, and particularly preferably 3 to 7 times the molar equivalent of the phenol resin. Further, during the reaction, the water can be distilled off by azeotropic distillation with a glycidylating agent under reduced pressure, so that the reaction can proceed faster. When the epoxy resin of the present invention is used in the electronic field, by-produced salts such as sodium chloride must be completely removed in the washing step. At this time, the unreacted glycidylating agent may be recovered by distillation to concentrate the reaction solution, and then the concentrate may be dissolved in a solvent and washed with water. Preferred solvents include methyl isobutyl ketone, cyclohexanone,
Examples thereof include benzene and butyl cellosolve.
The concentrate washed with water is concentrated by heating.

The epoxy resin of the present invention is used as the resin for the sealing material.
Shows excellent curability, moldability, etc.
In order to impart excellent heat resistance and moisture resistance after conversion,
It is important to control the resin properties of xy resin as follows.
Is. Two glycidyl groups are added to the binuclear component in the resin
Compound (hereinafter referred to as a binuclear epoxidized component)
The content of () exists in the resin viscosity, fluidity, and curability.
It is important to make appropriate adjustments because it will have a large impact.
It That is, of the binuclear epoxidized component in the epoxy resin
The content is preferably 30 to 90% by mass, and particularly
The range of 40-80 mass% is preferable. Less than 30% by mass
In this case, the fluidity decreases and the moldability of the cured product is greatly affected.
And if it is more than 90% by mass, good fluidity is obtained.
However, the crosslink density decreases and the curing characteristics deteriorate.
Therefore, it is not preferable. Resin viscosity has a great influence on the flow characteristics during molding
It needs to be adjusted appropriately because it will affect the situation. This stickiness
There are no particular restrictions on the degree, but examples
For example, Canon-Fenske kinematic viscosity tube method, 1,4
-To understand the solution viscosity of 50% dioxane resin solution.
And are effective, and the solution viscosity by the same method is 100
mm ^Two/ Sec or less is preferable, especially 70 mm^Two
Compounds controlled in the range of 1 / sec or less are preferable flow
Demonstrate the characteristics. Epoxy group content in epoxy resin
Is usually 200 to 500 g / eq, preferably 250 to
It is preferably 450 g / eq. Epoxy group content
When the value is 500 g / eq or more, the crosslinking density becomes low.
It is not preferable because it is too much. According to the manufacturing method described in the present invention
For example, manufacture epoxy resin that satisfies the above physical properties.
You can The epoxy resin thus obtained is
An epoxy resin having a similar structure obtained by a conventional method
By comparison, the fluidity is excellent and the moldability is good. Also Epo
Excellent in curability and heat resistance due to high concentration of xy groups.
Especially, it is semi-finished because of its excellent solder crack resistance.
It is very useful for conductor encapsulation materials. Also for laminated boards
It is also useful as a raw material for epoxy resin compositions of
Because of the excellent solubility of resin in solvents, it can be used as an electrical laminate.
It can be used as a varnish, etc. Also, the present invention
Modified epoxy resin with brominated polyphenols
Use of oligomer type epoxy resin for laminated board applications
You can also Furthermore, a multifunctional epoxy resin is added to this.
Alternatively, a material that has been modified to impart heat resistance can also be used.
In addition, in order to obtain a polymer type epoxy resin
It is also possible to use the resin as the raw resin. So
Besides, it is also useful for powder coating, brake shoes, etc.
The use is not limited to.

Next, the epoxy resin composition for semiconductor encapsulating material of the present invention will be described. The epoxy resin composition of the present invention contains an epoxy resin, a curing agent and an inorganic filler as essential components, but the epoxy resin of the present invention is used as the epoxy resin, or the phenol resin of the present invention is used as the curing agent. Is characterized by. When the epoxy resin of the present invention is used as the epoxy resin, other epoxy resins may be used together. As the other epoxy resin, any known epoxy resin can be used, for example, bisphenol A diglycidyl ether type epoxy resin,
Phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, brominated phenol novolac type epoxy resin, naphthol novolac type epoxy resin, biphenyl type bifunctional epoxy resin, etc. However, the present invention is not limited to these. Among these, the orthocresol novolac type epoxy resin is preferable because of its excellent heat resistance, and the biphenyl type difunctional epoxy resin is preferable because of its excellent fluidity. The other known epoxy resins described above can be used as the epoxy resin even when the phenol resin of the present invention is used as the curing agent.

As the curing agent, in addition to the phenol resin of the present invention, any compound commonly used as a curing agent for epoxy resins can be used, and the curing agent is not particularly limited, and examples thereof include diethylenetriamine and triethylene. Aliphatic amines such as tetramine, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, phenol novolac resin, orthocresol novolac resin, bisphenol A novolac resin, bisphenol F novolac resin, phenols-dicyclopentadiene Polyaddition type resins, dihydroxynaphthalene novolac resins, polyhydric phenols having xylidene as a bonding group, phenol aralkyl resins, naphthol resins, polyamide resins and modified products thereof, Acid anhydride type curing agents such as water maleic acid, phthalic anhydride, hexahydrophthalic anhydride and pyromellitic anhydride, latent curing agents such as dicyandiamide, imidazole, boron trifluoride / amine complex, guanidine derivative, etc. To be Among them, for the semiconductor encapsulating material, the aromatic hydrocarbon-formaldehyde resin such as the above-mentioned phenol novolac resin is excellent in heat resistance and moldability, and the phenol aralkyl resin is preferable in view of heat resistance, moldability and low water absorption. The amount of the curing agent is not particularly limited as long as it provides sufficient heat resistance to the epoxy resin composition, but preferably the number of epoxy groups contained in one molecule of the epoxy resin and the activity in the curing agent. This is the amount at which the number of hydrogen is close to the equivalent.

Further, a curing accelerator can be used appropriately. As the curing accelerator, any known one can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acid / amine complex salts, and the like. Combinations of more than one species are also possible.

The inorganic filler can enhance the mechanical strength and hardness of the semiconductor encapsulating material, achieve a low water absorption rate and a low linear expansion coefficient, and enhance the crack prevention effect. The inorganic filler to be used is not particularly limited, and examples thereof include fused silica, crystalline silica, alumina, talc, clay and glass fiber. Of these, fused silica and crystalline silica are generally used, especially for semiconductor encapsulation materials, and fused silica is preferred because of its excellent fluidity.
Further, spherical silica, crushed silica and the like can be used. The compounding amount of the inorganic filler is not particularly limited, but it is preferably in the range of 75 to 95 mass% in the composition, and particularly in the semiconductor encapsulant application, the solder crack resistance is very excellent. Ranges are preferred. In the present invention, 75
Even if it is more than mass%, the fluidity and moldability are not impaired at all.

In addition to the above components, if necessary, a coloring agent,
Various known additives such as a flame retardant, a release agent, or a coupling agent can be appropriately added. Semiconductor encapsulating materials include tetrabromo A type epoxy resins, brominated epoxy resins such as brominated phenol novolac type epoxy resins, antimony trioxide, flame retardants such as hexabromobenzene, colorants such as carbon black and red iron oxide, and natural waxes. It is preferable to properly mix a female mold agent such as a synthetic wax and an additive such as a low stress additive such as silicone oil, synthetic rubber and silicone rubber.

Further, in order to prepare a molding material using each of the above components, an epoxy resin, a curing agent, an inorganic filler, a curing accelerator, and other additives are sufficiently uniformly mixed with a mixer or the like. After that, the mixture is further melt-kneaded with a hot roll or a kneader, injection-molded or cooled and then pulverized.

[0033]

EXAMPLES Next, the present invention will be specifically described with reference to production examples, examples and comparative examples. The characteristics of the phenol resin were measured by the following methods. 1) Content of Compound A (% by Mass) Compound A was isolated and purified from the phenol resin using preparative GPC, an open column or the like, and identified by using NMR or the like. In addition, a component (polystyrene-equivalent number average molecular weight 2) detected at the retention time corresponding to the compound A when using an analytical GPC and using no aromatic hydrocarbon solvent for the synthesis.
The amount of the substance detected in the range of 30 or more and less than 320) is measured in advance, and the measured amount is subtracted from the amount of the retention time component in the case of synthesizing using an aromatic hydrocarbon solvent,
From the measurement chart of the entire phenol resin, the content of compound A relative to the entire phenol resin was determined from the area ratio. The measurement was performed using a 1 mass% tetrahydrofuran (THF) solution of phenol resin using a high performance liquid chromatography system "Millennium" manufactured by WATERS. 2) Content of Compound B (% by Mass) Compound B was isolated and purified from the phenol resin using preparative GPC, an open column or the like, and identified by using NMR or the like. In addition, the amount of the component corresponding to Compound B (substance detected in the range of polystyrene-reduced number average molecular weight of 100 or more and less than 230) was measured using analytical GPC, and the phenol resin as a whole was determined from the area ratio of the measurement chart of the phenol resin as a whole The content of compound B relative to The measurement is performed with a 1% by mass tetrahydrofuran (THF) solution of phenol resin in W
This was performed using a high performance liquid chromatography system "Millennium" manufactured by ATERS. 3) The phenol resin obtained by OH equivalent production was heated to reflux in a pyridine-acetic anhydride mixed solution, and the solution after the reaction was determined by back titration with potassium hydroxide. 4) Softening point The softening point was measured according to the ring and ball softening point measuring method described in JIS K2207. 5) Solution viscosity of 50 mass% n-butanol solution An n-butanol solution having a solid content concentration of 50 ± 0.001% was prepared, and a constant temperature water temperature of 25
It was measured at ° C. 6) Solution viscosity of 50% by mass 1,4-dioxane solution A 1,4-dioxane solution having a solid content concentration of 50 ± 0.001% was prepared, and a constant temperature water temperature of 2 was measured by a countercurrent type Canon Fenske viscometer.
It was measured at 5 ° C. 7) Amount of dinuclear component and amount of dinuclear epoxidized component Using a 1% by mass THF solution of phenol resin, WATER
It was detected by a differential refraction detector "WATERS410" manufactured by S Co. and measured by using a high performance liquid chromatography system "Millennium" manufactured by S.

<Production Example 1> [Production of Phenol Resin (I)] To a four-necked flask equipped with a stirrer and a thermometer, 1500 g of phenol and 100 g of toluene were added to carry out azeotropic dehydration to obtain water content in phenol. Was set to 400 ppm. 1050g of this phenol
Boron trifluoride / phenol complex 1. (11.1 mol)
5 g was added and stirred well. Then, with stirring, 188 g (1.4 mol) of dicyclopentadiene was added to the system temperature of 70
The mixture was added over 2 hours while maintaining the temperature at 0 ° C. Then, the temperature in the system was raised to 100 ° C., and heating and stirring were maintained for 2 hours. After lowering the temperature in the system to 90 ° C., the resulting reaction product solution was added with hydrotalcite “KW-1000” (trade name:
8 g of Kyowa Chemical Industry Co., Ltd.) was added to inactivate the reaction. The reaction solution was filtered, and the unreacted phenol was distilled and recovered from the obtained solution, and the temperature was raised to 190 ° C. to 13 kPa.
Nitrogen bubbling was performed under a reduced pressure of (100 torr) 3
Held for hours. As a result, 411 g of reddish brown phenol resin (I) was obtained. The contents of compound A and compound B in this resin were 2.5% by mass and 3.2% by mass, respectively. The content of the binuclear component was 63% by mass.
When the physical properties of this resin were measured, the softening point was 87 ° C,
The hydroxyl equivalent was 177 g / eq. The solution viscosity of a 50% by mass solution of n-butanol at 25 ° C. is 86 mm ^2.
/ Sec.

<Production Example 2> [Production of Epoxy Resin (I)] (Glycidylation Reaction) Phenol produced in Production Example 1 was placed in a 3-liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer. After 177 g of Resin (I) and 400 g of epichlorohydrin were charged, the mixture was stirred and dissolved. Adjust the pressure in the reaction system to 20 kPa (150 torr), and
The temperature was raised to 8 ° C. While continuously adding 100 g of a sodium hydroxide aqueous solution having a concentration of 48% by mass, the reaction was carried out for 3.5 hours. The water generated by the reaction and the water of the sodium hydroxide aqueous solution were decomposed by refluxing the water-epichlorohydrin azeotrope, and continuously removed outside the reaction system. After the reaction was completed, the reaction system was returned to normal pressure and the temperature was raised to 110 ° C. to completely remove the water in the reaction system. Excessive epichlorohydrin was distilled off under normal pressure, and further 2 kPa (15
Distillation was performed at 140 ° C. under reduced pressure of (torr). (Washing) 300 g of methyl isobutyl ketone and 36 g of a 10 mass% sodium hydroxide aqueous solution were added to the resulting mixture of resin and sodium chloride, and the mixture was reacted at 85 ° C. for 1.5 hours. After completion of the reaction, methyl isobutyl ketone 7
50 g and 300 g of water were added, and the lower layer inorganic salt aqueous solution was separated and removed. Separation of oil and water layers was very good.
Next, 150 g of water was added to the methyl isobutyl ketone liquid layer for washing, neutralized with phosphoric acid, the aqueous layer was separated, and then washed with 800 g of water to separate the aqueous layer. After quantitatively recovering the inorganic salts, the methyl isobutyl ketone liquid layer was distilled under normal pressure, and then 0.67 kPa (5 torr), 140
Distillation under reduced pressure was carried out at 0 ° C. to obtain 216 g of epoxy resin (I). The obtained epoxy resin has an epoxy equivalent of 269.
The solution viscosity of g / eq and 1,4-dioxane 50% by mass was 22 mm ² / sec, and the content of the binuclear epoxidized component was 51% by mass.

<Production Comparative Example 1> [Production of Phenol Resin (II)] Phenol and toluene were charged in a reactor and heated to 160 ° C. to azeotrope with toluene and distill off toluene. Properly sampled and the water content of phenol in the system is 100 ppm
After confirming the following, 15 g of boron trifluoride / phenol complex was added to 1050 g (11.2 mol) of phenol after the dehydration to make the mixture uniform, and then the liquid temperature was set to 80 ° C.
188 g of dicyclopentadiene (1.4 g
Mol) was gradually added dropwise over 1 hour, and after the addition was completed, 14
The temperature was raised to 0 ° C., and the mixture was further stirred for 3 hours. In addition, it has been confirmed that the water content is 100 ppm or less by separately measuring dicyclopentadiene and the like. Also, the water content of the reaction system was appropriately measured, and it was confirmed that the water content was 100 ppm or less. The reaction solution was cooled to 90 ° C., 50 g of magnesium hydroxide / aluminum hydroxide / hydrotalcite (Kyoward 1000) was added to deactivate the catalyst, and then the reaction solution was filtered. The resulting filtrate is 190
The mixture was distilled and concentrated at 13 ° C under reduced pressure of 13 kPa (100 torr) for 5 hours to obtain 415 g of phenol resin (II). The obtained phenol resin had a softening point of 95.0 ° C. and a phenolic hydroxyl group equivalent of 170 g / eq. According to GPC measurement, the content of the compound A in the phenol resin was 1.1% by mass, and the content of the compound B was 0.4% by mass. The content of the binuclear component was 65% by mass, and the solution viscosity of 50% by mass of n-butanol was 90 mm ² / sec.

<Production Comparative Example 2> [Production of Epoxy Resin (II)] Production by Production Comparative Example 1
Other than using 170 g of the prepared phenolic resin (II)
Was produced in the same manner as in Production Example 2, and 216 g of epoxy
A xy resin (II) was obtained. Epoxy of the obtained epoxy resin
Equivalent weight is 263 g / eq, containing dinuclear epoxidized component
The amount is a solution of 53 mass% and 1,4-dioxane 50 mass%
Viscosity is 26 mm ^Two/ Sec.

<Production Comparative Example 3> [Production of Phenolic Resin (III)] The same reaction as in Production Example 1 was conducted except that phenol having a water content after azeotropic dehydration of 950 ppm was used, and the phenol resin (III) was produced. 408
g was obtained. The softening point of this resin is 84 ° C, and the hydroxyl equivalent is 3
It was 01 g / eq. The solution viscosity of the 50% by mass n-butanol solution at 25 ° C. was 64 mm ² / sec. In addition, this resin contains 6.3 mass% of compound A and compound B.
16.9 mass% was included. The content of the binuclear component was 51% by mass.

<Production Comparative Example 4> [Production of Epoxy Resin (III)] (Glycidylation Reaction) Phenol produced in Production Comparative Example 3 was placed in a 3-liter 4-necked flask equipped with a stirrer, a reflux condenser and a thermometer. After charging 301 g of Resin (III) and 680 g of epichlorohydrin, the mixture was stirred and dissolved. Adjust the pressure in the reaction system to 20 kPa (150 torr),
The temperature was raised to 68 ° C. While continuously adding 170 g of sodium hydroxide aqueous solution having a concentration of 48% by mass to 3.5
Reacted for hours. The water generated by the reaction and the water of the sodium hydroxide aqueous solution were decomposed by refluxing the water-epichlorohydrin azeotrope, and continuously removed outside the reaction system. After the reaction was completed, the reaction system was returned to normal pressure and the temperature was raised to 110 ° C. to completely remove the water in the reaction system. Excessive epichlorohydrin was distilled off under normal pressure, and further 2 kPa (15
Distillation was performed at 140 ° C. under reduced pressure of (torr). (Washing) To the resulting mixture of resin and sodium chloride, 500 g of methyl isobutyl ketone and 60 g of a 10 mass% sodium hydroxide aqueous solution were added, and the reaction was carried out at 85 ° C. for 1.5 hours. After the reaction, methyl isobutyl ketone 1
000 g and 300 g of water were added, and the lower layer inorganic salt aqueous solution was separated and removed. Separation of oil and water layers was very good. Next, 300 g of water was added to the methylisobutylketone liquid layer for washing, neutralized with phosphoric acid, the aqueous layer was separated, and then washed with 800 g of water to separate the aqueous layer. After quantitatively recovering the inorganic salts, the methylisobutylketone liquid layer was distilled under normal pressure, followed by 0.67 kPa (5 torr), 1
After vacuum distillation at 40 ° C, 367 g of epoxy resin (II
I) got. The obtained epoxy resin had an epoxy equivalent of 341 g / eq, 1,4-dioxane 50 mass% and a solution viscosity of 12 mm ² / sec, and the content of the binuclear epoxidized component was 42 mass%.

<Example 1 and Comparative Examples 1 and 2> Using the phenolic resins produced up to this point, the epoxy resin compositions were compared for fluidity and curability. The mixture prepared according to the formulation shown in Table 1 was heated to 1 on a hot roll.
Knead at 00 ° C for 8 minutes, and then crush it for 12 to 1
A tablet is prepared at a pressure of 4 MPa (1200 to 1400 kg / cm ² ), and a plunger pressure is 0.8 MPa (80 kg / c) at a transfer molding machine using the tablet.
m ² ), the mold temperature was 175 ° C., the molding time was 100 seconds, and a flat package having a thickness of 2 mm was prepared as a test piece for evaluation. Then, post-curing was performed at 175 ° C. for 8 hours. Gel time and a test mold are used as an index of fluidity of the epoxy resin composition at 175 ° C. and 0.7 MPa.
The spiral flow was measured under the conditions of (70 kg / cm ² ) and 120 seconds. Further, the glass transition temperature was measured by DMA as an index of curability using the test piece for evaluation. Further, the sample was allowed to stand in an atmosphere of 85 ° C. and 85% RH for 168 hours for moisture absorption treatment, and the water absorption rate was measured. In addition, the rate of crack generation when dipped in a solder bath at 260 ° C. for 10 seconds was examined. The results are shown in Table 1. Example 1 has a good balance of fluidity and heat resistance, Comparative Example 1 has poor fluidity, and Comparative Example 2 has poor heat resistance. Phenol novolac is Tamanol 758 (Arakawa Chemical Co., Ltd.).
Manufactured, softening point 83 ° C., hydroxyl group equivalent 104 g / eq) was used. Ortho-cresol novolac epoxy is ESCN-
220 L (manufactured by Sumitomo Chemical Co., Ltd., softening point 66 ° C., epoxy equivalent 212 g / eq) was used.

[0041]

[Table 1]

<Example 2 and Comparative Examples 3 and 4> The fluidity and curability of a composition using an epoxy resin made of a phenol resin as a raw material were compared. The mixture prepared according to the formulation shown in Table 2 was heated to 100 on a hot roll.
Knead at ℃ for 8 minutes, then crushed to 12-14M
A tablet is prepared at a pressure of Pa (1200 to 1400 kg / cm ² ), and a plunger pressure of 0.8 MPa (80 kg / c is obtained using a transfer molding machine using the tablet.
m ² ), the mold temperature was 175 ° C., the molding time was 100 seconds, and a flat package having a thickness of 2 mm was prepared as a test piece for evaluation. Then, post-curing was performed at 175 ° C. for 8 hours. Gel time and a test mold are used as an index of fluidity of the epoxy resin composition at 175 ° C. and 0.7 MPa.
The spiral flow was measured under the conditions of (70 kg / cm ² ) and 120 seconds. Further, the glass transition temperature was measured by DMA as an index of curability using the test piece for evaluation. Further, the sample was allowed to stand in an atmosphere of 85 ° C. and 85% RH for 168 hours for moisture absorption treatment, and the water absorption rate was measured. In addition, the rate of crack generation when dipped in a solder bath at 260 ° C. for 10 seconds was examined. The results are shown in Table 2. Example 2 has a good balance of fluidity and heat resistance, Comparative Example 3 has poor fluidity, and Comparative Example 4 has poor heat resistance. Phenol novolac is Phenolite TD-2131 (manufactured by Dainippon Ink and Chemicals, Inc., softening point 80 ° C., hydroxyl equivalent 104).
g / eq) was used.

[0043]

[Table 2]

[0044]

EFFECTS OF THE INVENTION According to the present invention, a phenol resin composition, an epoxy resin composition, and a resin composition having excellent fluidity and excellent moldability when encapsulating a semiconductor, and further having excellent heat resistance after encapsulation and curing are obtained. A semiconductor encapsulating material can be provided.

Continued front page    F-term (reference) 4J032 CA01 CA02 CA04 CA16 CA21                       CA25 CA34 CA38 CB03 CF05                       CG06 CG07                 4J036 AA01 AA02 AC00 AC01 AE05                       DC01 DC02 DC06 DC09 DC10                       DC15 DC26 DC31 DC40 DC41                       FB08 GA04 GA07 GA19 JA03                       JA07 JA08                 4M109 AA01 CA21 EA02 EB03 EB04                       EB07 EB13 EC01 EC03 EC05

Claims (14)

[Claims] 1. A phenolic compound and a carbon-carbon double bond are combined with each other.
A phenolic resin obtained by reacting with one or more unsaturated cyclic hydrocarbon compounds, having a polystyrene-equivalent number average molecular weight of 320 or less, and a monofunctional component containing only one phenolic hydroxyl group in one molecule. A phenol resin having a content of more than 2% by mass and 20% by mass or less of the resin. 2. The phenol resin according to claim 1, wherein the phenol is phenol and the unsaturated cyclic hydrocarbon compound having two or more carbon-carbon double bonds is dicyclopentadiene. 3. The phenol according to claim 2, wherein the monofunctional component contains at least a compound A represented by the following general formula (1) and a compound B represented by the following general formula (2). resin. [Chemical 1] [Chemical 2] 4. Phenols and carbon in the presence of an acid catalyst
In a method for producing a phenol resin, which comprises a reaction step of contacting an unsaturated cyclic hydrocarbon compound having two or more carbon double bonds, and a concentration step of mainly removing unreacted phenols, a reaction system in the reaction step The monofunctional compound having a polystyrene-reduced number average molecular weight of 320 or less and containing only one phenolic hydroxyl group by adjusting the catalyst concentration to a predetermined concentration and concentrating the reaction product under predetermined conditions in the concentration step. The method for producing a phenol resin, wherein the content of the components in the resin is more than 2% by mass and 20% by mass or less. 5. The acid catalyst used in the reaction step is a boron trifluoride / phenol complex.
The method for producing a phenolic resin according to 1. 6. The amount of the acid catalyst used is phenols, carbon-
The phenol according to claim 4 or 5, wherein the amount is 0.01 to 0.5 mass% with respect to the total amount of the unsaturated cyclic hydrocarbon compound having two or more carbon double bonds and the acid catalyst. Resin manufacturing method. 7. The water concentration of the phenols before the addition of the acid catalyst is 500 ppm or less.
7. The method for producing a phenol resin according to any one of 1 to 6. 8. In the concentration step, 40 kPa (300
After reducing the pressure to less than torr), the residual amount of unreacted phenols in the resin is reduced to 5 by blowing high-pressure steam.
8. The composition according to claims 4 to 7, characterized in that the content is set to 00 ppm or less.
The method for producing a phenol resin according to any one of 1. 9. The phenolic compound is phenol, and the unsaturated cyclic hydrocarbon compound having two or more carbon-carbon double bonds is dicyclopentadiene, according to any one of claims 4 to 8. Method for producing phenolic resin. 10. In the concentration step, 40 kPa (30
After reducing the pressure to 0 torr or less, by blowing high-pressure steam, the total content of the compounds A and B in the resin is more than 2% by mass and 20% by mass or less. A method for producing the phenolic resin described. 11. An epoxy resin obtained by reacting the phenolic resin according to claim 1 with an epihalohydrin. 12. A method for producing an epoxy resin, which comprises producing a phenol resin by the production method according to claim 4 and then reacting the phenol resin with epihalohydrins in the presence of a base catalyst. 13. An epoxy resin composition for a semiconductor encapsulating material, which contains an epoxy resin, a curing agent, a curing accelerator and an inorganic filler as essential components, and the curing agent is defined in any one of claims 1 to 3. An epoxy resin composition, which is a phenol resin. 14. An epoxy resin composition for a semiconductor encapsulant, comprising the epoxy resin according to claim 11, a curing agent, a curing accelerator and an inorganic filler as essential components.