JP3983935B2 - Method for producing episulfide resin - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to epitaxial sulfide resins manufacturing how. In particular, the present invention provides a cured product having a low viscosity and excellent electrical properties and weatherability, so that it is useful as a resin for semiconductor encapsulation, a resin for laminates, an electrical insulating material, a weather resistant paint, an optical material, and the like. a method for producing a certain epi sulfide resins.
[0002]
[Prior art]
Epoxy resins are excellent in heat resistance, adhesiveness, water resistance, mechanical strength, electrical properties, and the like, and are therefore used in various fields such as paints, adhesives, and electrical / electronic applications. On the other hand, as described in British Patent 968,424, episulfide resin is obtained by reacting an epoxy resin and a sulfiding agent, and has excellent curability, heat resistance, water resistance, etc. Although it is known, it has not been put into practical use yet. This is because a liquid episulfide resin which is excellent in storage stability and easy to handle is not obtained.
[0003]
An episulfide resin obtained from a typical epoxy resin of bisphenol A is liquid after production, but crystallizes during storage and becomes a solid having a melting point of about 80 ° C., so it is inferior in handleability. Furthermore, episulfide resin is very difficult to produce industrially because it causes gelation or thickens in the reactor during production. .
However, in recent years, materials used in the paint, civil engineering, and electrical / electronic fields have been required to have low-temperature curability, moisture resistance, and heat resistance. Resin is starting to attract attention again.
[0004]
Therefore, JPBell et al. Used a mixture of epoxy resin and episulfide resin as described in “Synthesis and Properties of Epoxy-Episulfide Resin” Makromolekulare Chemie 240 (1996) 67-81 (4229). I am trying to modify the epoxy resin. However, this method is uniform at the beginning of mixing, but the fundamental problem that the episulfide resin crystallizes and precipitates during storage has not been solved.
[0005]
[Problems to be solved by the invention]
The present invention has solved the above problems, an epi sulfide resin having a low viscosity without the conventional, electrical characteristics, moisture resistance, the epitaxial sulfide resins which can give a cured product excellent in balance between weather resistance prepared it is intended to provide mETHODS.
[0006]
[Means for Solving the Problems]
This invention is invention regarding the manufacturing method of episulfide resin among each following invention.
[0007]
General formula (1) obtained by reacting a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin with a sulfurizing agent.
[Chemical 3]
[Wherein, R _{1 to} R ₆ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents a number of 0 to 20, Z ₁ and Z ₂ represent a sulfur atom or an oxygen atom, and One of them is a sulfur atom. ] Episulfide resin shown by this.
[0008]
Hydrogenation of aromatic epoxy resin gives general formula (2)
[Formula 4]
_Wherein, R 1 to R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is the number of 0 to 20. ]
A hydrogenated epoxy resin represented by the general formula (1) is produced, and the hydrogenated epoxy resin is reacted with a sulfurizing agent.
[Chemical formula 5]
[Wherein, R _{1 to} R ₆ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents a number of 0 to 20, Z ₁ and Z ₂ represent a sulfur atom or an oxygen atom, and One of them is a sulfur atom. ]
The manufacturing method of episulfide resin shown by these.
[0009]
General formula (1) obtained by reacting a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin with a sulfurizing agent.
[Chemical 6]
[Wherein, R _{1 to} R ₆ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents a number of 0 to 20, Z ₁ and Z ₂ represent a sulfur atom or an oxygen atom, and One of them is a sulfur atom. ]
A curable resin composition comprising a curing agent in a proportion of 0.01 to 200 parts by weight with respect to 100 parts by weight of the episulfide resin represented by formula (1).
[0010]
DETAILED DESCRIPTION OF THE INVENTION
(Episulfide compounds)
The episulfide compound of the present invention is a diepisulfide compound represented by the following general formula (3) and a monoepisulfide compound represented by the general formula (4).
[0011]
[Chemical 7]
[Wherein R _{1 to} R ₆ and n are the same as above]
[0012]
[Chemical 8]
[Wherein R _{1 to} R ₆ and n are the same as above]
[0013]
In the episulfide resin of the present invention, the ratio of sulfur atoms in Z ₁ and Z ₂ in the general formula (1) is 5 to 95% with respect to the sum of sulfur atoms and oxygen atoms in Z ₁ and Z ₂ . It is preferable that it is within the range from the viewpoint that the resulting episulfide resin can have a low viscosity and a fast curing property and can exhibit the electrical properties of the cured product.
[0014]
(Method for producing episulfide resin)
The production of the episulfide resin of the present invention can be obtained by reacting the epoxy resin represented by the general formula (2) with a sulfiding agent. It is preferable to make it react within the range of 5 mol.
That is, when the episulfide resin of the present invention is produced, if the amount of the sulfurizing agent used is less than 0.05 mol with respect to 1 equivalent of the hydrogenated epoxy resin, the ratio of sulfur atoms in the resulting episulfide resin is , Because it becomes less than 5% with respect to the sum of sulfur atom and oxygen atom. On the other hand, when the amount exceeds 5 mol, a large amount of unnecessary sulfiding agent is used, which is uneconomical.
[0015]
The reaction is carried out in the presence of an appropriate solvent at the charging ratio as described above within a range of a reaction temperature of -15 to 100 ° C, preferably 0 to 50 ° C, and a reaction time of 0.5 to 30 hours.
The sulfurizing agent used is thiocyanates such as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, thioureas such as thiourea, N-methylthiourea, 1,3-diethylthiourea, phosphine sulfide, dimethylthioformamide, N-methylbenzothiazole-2-thione and the like can be mentioned. Of these, thiocyanates and thioureas are preferable from the viewpoint of easy availability of raw materials.
[0016]
Examples of the solvent used include water, alcohols such as methanol, ethanol and propanol, ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, acetone, methyl ethyl ketone and Ketones such as methyl isobutyl ketone, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane and chlorobenzene, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, aprotic such as dimethylformamide, dimethylacetamide and dimethylsulfoxide Examples include polar solvents. These can be used alone or in admixture of two or more.
[0017]
After completion of the reaction, the desired episulfide resin can be obtained by separating and purifying the reaction product by a method such as extraction, washing with water, and concentration.
Moreover, the epoxy resin represented by the general formula (2), which is a raw material of the episulfide resin of the present invention, is a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin, and the purity of the resulting episulfide resin is improved. Therefore, it is preferable. Further, the hydrogenated epoxy resin used is a resin having an aromatic ring hydrogenation rate of 85% or more, an epoxy group loss rate of 20% or less, and a total chlorine content of 0.3% by weight or less. Particularly preferred is a cured product of episulfide resin excellent in weather resistance, heat resistance and electrical properties.
[0018]
In addition, an epoxy resin in which R _{1 to} R _{2 of the} epoxy resin represented by the general formula (2) is a hydrogen atom or a methyl group, R _{3 to} R ₆ are hydrogen atoms, and n is 0 to 5, It is preferable at the point that the purity of the obtained episulfide resin improves.
Furthermore, when manufacturing the episulfide resin of this invention, you may add a polyfunctional alicyclic epoxy resin in the epoxy resin shown by General formula (2) for the purpose of heat resistance improvement. Examples of polyfunctional epoxy resins that can be used include hydrogenated epoxy resins obtained from phenol novolac, hydrogenated epoxy resins obtained from cresol novolac, hydrogenated bisphenol A novolac epoxy resins, and hydrogen obtained from phenols and hydroxybenzaldehydes. A novolac epoxy resin.
[0019]
In addition, as an example of producing a hydrogenated epoxy resin, an aromatic ring is selectively hydrogenated in the presence of a catalyst using a solvent-free organic ether solvent such as tetrahydrofuran or dioxane. It can be suitably performed. A particularly preferable catalyst is a catalyst in which rhodium or ruthenium is supported on graphite (hexagonal crystal graphite). In addition, it is preferable to use a support having a surface area of 10 m ² / g or more and 400 m ² / g or less for the graphite. The reaction is preferably performed within a range of pressure, 1 to 30 MPa, temperature 30 to 150 ° C., and time 1 to 20 hours. After completion of the reaction, the catalyst is removed by filtration, and when an ether organic solvent is used, the organic solvent is distilled off under reduced pressure until it substantially disappears to obtain a hydrogenated epoxy resin.
[0020]
(Curing resin composition)
The episulfide resin of the present invention can be cured using a curing agent. As the curing agent used, a general curing agent for epoxy resins is used. For example:
[0021]
Amines; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-aminoethylpiperazine, isophoronediamine, bis (4-aminocyclohexyl) methane, bis (aminomethyl) cyclohexane, m-xylylenediamine, 3,9-bis (3-Aminopropyl) -2,4,8,10-tetraspiro [5,5] undecane and other aliphatic and alicyclic amines, polyamides, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and other aromatics Amines, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0) nonene Tertiary amines such as -7 and salts thereof;
[0022]
Acid anhydrides: aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride Cyclic aliphatic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, and trialkyltetrahydrophthalic anhydride.
[0023]
Polyphenols: catechol, resorcin, hydroquinone, bisphenol F, bisphenol A, bisphenol S, biphenol, phenol novolacs, cresol novolacs, bisphenol A and other dihydric phenol novolacs, trishydroxyphenylmethanes, aralkyl polyphenols And dicyclopentadiene polyphenols.
[0024]
Other: Bronsted acid salts such as 2-methylimidazole, 2-ethyl-4-imidazole and 2-phenylimidazole and the like, and salts thereof, BF ₃ complex compounds of amines, aliphatic sulfonium salts and aromatic sulfonium salts Organic hydrazides such as dicyandiamides, adipic acid dihydrazide and phthalic acid dihydrazide, organic phosphine compounds such as polymercaptans and triphenylphosphine, and the like.
[0025]
These epoxy resin curing agents may be used singly or in combination of two or more.
The use ratio of the curing agent described above is blended so that the curing agent is 0.01 to 200 parts by weight with respect to 100 parts by weight of the episulfide resin of the present invention. Outside this range, the heat resistance of the cured product is lowered and the moisture resistance is deteriorated, which is not preferable.
[0026]
(Optional component)
In the curable resin composition of the present invention, the following components can be added and blended as necessary.
Powdery reinforcing agents and fillers, such as metal oxides such as aluminum oxide and magnesium oxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, basic magnesium silicate, calcined clay, fine powder silica, molten Silicon compounds such as silica and crystalline silica, metal hydroxides such as aluminum hydroxide, kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc., and fibrous reinforcing agents and fillers such as glass fibers and ceramics Examples thereof include fibers, carbon fibers, alumina fibers, silicon carbide fibers, boron fibers, polyester fibers, and polyamide fibers.
These are blended in an amount of 10 to 900 parts by weight per 100 parts by weight of the curable resin composition of the present invention.
[0027]
Colorants, pigments, flame retardants such as titanium dioxide, iron black, molybdenum red, bitumen, ultramarine, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, bromine compounds and triphenyl phosphate.
These are blended in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the curable resin composition.
[0028]
Furthermore, various curable monomers, oligomers and synthetic resins can be blended for the purpose of improving the properties of the resin in the final coating film, adhesive layer, molded article and the like. For example, diluent for epoxy resin such as monoepoxy, general aromatic and alicyclic epoxy resin, phenol resin, alkyd resin, melamine resin, fluorine resin, vinyl chloride resin, acrylic resin, silicone resin, polyester resin, etc. One type or a combination of two or more types can be mentioned. The blending ratio of these resins is preferably 50 parts by weight or less with respect to an amount within a range not impairing the original properties of the resin composition of the present invention, that is, 100 parts by weight of the curable resin composition.
[0029]
Examples of the blending means of the episulfide resin, the curing agent and the optional component of the present invention include heat melt mixing, roll, melt kneading with a kneader, wet mixing using an appropriate organic solvent, and dry mixing.
[0030]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
Example 1
In a 1 liter glass flask equipped with a stirrer, a cooler and a thermometer, a liquid hydrogenated epoxy resin (epoxy equivalent) obtained by hydrogenating Epicoat 807 (trade name of Yuka Shell Epoxy; diglycidyl ether of bisphenol F) is used. 181 g / eq., Hydrogenation rate: almost 100%, epoxy group loss rate: 2.8%, total chlorine content: 0.23% by weight, also referred to as “hydrogenation E807”) 100 g (0.552 equivalents) and 100 g of tetrahydrofuran was charged and stirred at room temperature to dissolve the epoxy compound. After dissolution, 63 g (0.829 mol) of thiourea and 150 g of methanol were added, and the reaction was performed at a temperature of 30 to 35 ° C. with stirring for 5 hours. After completion of the reaction, 300 g of methyl isobutyl ketone was added and then washed 5 times with 500 g of pure water. After washing with water, methyl isobutyl ketone was distilled off at 100 ° C. under reduced pressure using a rotary evaporator to obtain 105.5 g of a colorless transparent liquid episulfide resin. Table 1 shows the properties of the obtained episulfide resin.
[0031]
Whether or not the obtained compound was the target product was confirmed by infrared absorption spectrum (FIG. 1) and GC-mass spectrum.
Infrared absorption spectrum: Epoxy groups at 910 cm ⁻¹ almost disappeared, and absorption of episulfide groups at 610 cm ⁻¹ newly appeared. (See Figure 1)
GC-mass spectrum: After determining the attribution of each peak, the proportion of diepisulfide, monoepisulfide and unreacted epoxy was determined from the weight percentage of the total ion chromatograph.
[0032]
Example 2
Except changing the amount of thiourea charged to 42 g (0.552 mol), the same operation as in Example 1 was carried out to obtain 103.5 g of a colorless transparent liquid episulfide resin. Table 1 shows the properties of the obtained episulfide resin.
[0033]
Example 3
Liquid hydrogenated epoxy resin (epoxy equivalent; 200 g / eq., Hydrogenation rate) obtained by hydrogenating raw material hydrogenated epoxy resin Epicoat 828EL (trade name of Yuka Shell Epoxy; diglycidyl ether of bisphenol A); almost 100% Loss rate of epoxy group: 4.0%, total chlorine amount: 0.11% by weight, also referred to as “hydrogenated E828”) to 100 g (0.500 equivalent), 38.0 g (0.500 mol) of thiourea Except for the above, the same operation as in Example 1 was performed to obtain 103.1 g of a colorless transparent liquid episulfide resin. Table 1 shows the properties of the obtained episulfide resin.
[0034]
Example 4
100 parts of episulfide resin obtained in Example 1, 40 parts of MH-700 (trade name of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride), and 1 part of 2-ethyl-4-methylimidazole at 60 ° C. After stirring and mixing and defoaming to obtain a uniform solution, a curable resin composition was obtained.
Next, the composition was poured into a mold and cured in an oven at 100 ° C. for 4 hours and further at 150 ° C. for 6 hours to obtain a cured product. The physical properties of the cured product are shown in Table 2.
[0035]
Examples 5-6
A composition was obtained by performing the same operation as in Example 4 except that the episulfide resin was changed to the resin obtained in Example 2 or Example 3, and a cured product was obtained. The physical properties of the cured product are shown in Table 2.
[0036]
Comparative Example 1
Except for changing the episulfide resin to a liquid hydrogenated epoxy resin “hydrogenated E807” obtained by hydrogenating the same Epicoat 807 as in Example 1, a composition was obtained by performing the same operation as in Example 4 to obtain a cured product. It was. The physical properties of the cured product are shown in Table 2.
[0037]
[Table 1]
[0038]
[Table 2]
[0039]
【The invention's effect】
By carrying out the present invention, an unprecedented low chlorine episulfide resin having an alicyclic structure can be easily obtained. In addition, a cured resin cured with a curing agent is expected to have high heat resistance, good moisture resistance, and high refractive index, and can be applied to a wide range of applications. In particular, it can be advantageously used in applications such as electrical materials such as semiconductor sealing materials and electrical insulation materials, and optical materials such as lens resins.
[Brief description of the drawings]
1 is an infrared absorption spectrum of the episulfide resin synthesized in Example 1. FIG.

Claims (5)

Hydrogenation of aromatic epoxy resin gives general formula (2)
[In the formula, R ₁ ~ R ₆ Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is a number from 0 to 20. ]
A hydrogenated epoxy resin represented by the general formula (1) is produced, and the hydrogenated epoxy resin is reacted with a sulfurizing agent.
[In the formula, R ₁ ~ R ₆ Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents a number of 0 to 20, and Z ₁ And Z ₂ Represents a sulfur atom or an oxygen atom, and at least one of them is a sulfur atom. ]
The manufacturing method of episulfide resin shown by these. The epoxy resin of the general formula (2) is obtained by hydrogenating an aromatic epoxy resin, the hydrogenation rate of the aromatic ring is 85% or more, the loss rate of the epoxy group is 20% or less, and the total chlorine content 2. The method for producing an episulfide resin according to claim 1, wherein the amount is an epoxy resin having an amount of 0.3% by weight or less. R in the epoxy resin of the general formula (2) ₁ ~ R ₂ Is a hydrogen atom or a methyl group, R ₃ ~ R ₆ Is a hydrogen atom, and n is 0-5, The manufacturing method of the episulfide resin of Claim 1 or 2 characterized by the above-mentioned.   The sulfurating agent is added within a range of 0.05 to 5 mol and reacted with 1 equivalent of epoxy group of the epoxy resin of the general formula (2). The manufacturing method of episulfide resin as described in claim | item.   The method for producing an episulfide resin according to any one of claims 1 to 4, wherein the sulfurizing agent is thiocyanate or thiourea.