JP2002088149A - Polyether resin, its production method and insulating material - Google Patents

Abstract

[PROBLEMS] To provide a polyether resin having a thermosetting functional group and a method for producing the same, and to provide an electronic insulating material having excellent chemical resistance obtained by using the same. [1] A polyether resin having a repeating unit represented by the following formula (1). (Wherein, R ^{1 to} R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a C 6 to 10 carbon atom which may have a substituent. A cycloalkyl group, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, or 6 carbon atoms which may have a substituent -10
Or a substituent having an alkoxy group having 1 to 10 carbon atoms, a carbonyl group, or a substituent having an alcohol group. In the formula, X is a single bond, having 1 to 1 carbon atoms.
20 represents any of a hydrocarbon group, -O-, and -CO-. [2] An insulating material and an insulating film using the polyether resin according to [1].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyether resin having a thermosetting functional group, a method for producing the same, and an insulating material using the polyether resin.

[0002]

2. Description of the Related Art There are several examples of resins having a thermosetting functional group as a side chain. Specific examples include JP-B 5-8932 and JP-B 5-8933.
Japanese Patent Application Laid-Open Publication No. H11-146, pp. 147-64 describes an example in which an allyl group or a propargyl group is introduced into a polyether resin obtained by oxidative polymerization. There are also known examples of resins having a vinyl group as a side chain. Specifically, an example in which a vinyl group is introduced via chloromethylated polyethersulfone or polyoxyphenylene resin is described in Macromo.
l. Chem. 185, 2319 (1984). However, each of these methods
There are problems such as that the curing reaction at low temperature is difficult or the reaction operation is relatively complicated.

[0003] Further, in an insulating film of an electronic device, the dielectric constant of the insulating film itself has been regarded as a problem due to miniaturization between wirings. In the case of a silica-based insulating film that has been used as an insulating film, it is difficult to suppress a decrease in transmission speed. As a solution to this, organic polymers have attracted attention due to their excellent electrical properties. In addition, since the insulating film is required to have not only electrical characteristics but also excellent heat resistance,
Polymers having an aromatic ring in the main chain, particularly aromatic polymers having a thermosetting functional group in the side chain having excellent chemical resistance are expected.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyether resin having a thermosetting functional group and a method for producing the same. Another object of the present invention is to provide an electronic insulating material having excellent chemical resistance obtained by using the same.

[0005]

Means for Solving the Problems The present invention relates to [1] a polyether resin having a repeating unit represented by the following formula (1). (Wherein, R ^{1 to} R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a C 6 to 10 carbon atom which may have a substituent. A cycloalkyl group, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, or 6 carbon atoms which may have a substituent -10
Or a substituent having an alkoxy group having 1 to 10 carbon atoms, a carbonyl group, or a substituent having an alcohol group. In the formula, X is a single bond, having 1 to 1 carbon atoms.
20 represents any of a hydrocarbon group, -O-, and -CO-. )

The present invention also relates to [2] a polyether resin having a repeating unit represented by the following formula (2). (In the formula, R ^{1 to} R ¹¹ and X are the same as defined in the formula (1).)

Further, the present invention relates to [3] a thermosetting polyether resin having a repeating unit represented by the following formula (3). (In the formula, R ^{1 to} R ¹¹ and X are the same as defined in the formula (1).)

Further, the present invention relates to [4] the method for producing a polyether resin according to [1], which comprises a condensation reaction step of a dihalogenated acetophenone and a bisphenol. Further, the present invention provides [5] a reduction reaction of an acetyl group of the polyether resin described in the above [1] to obtain CH ₃ C
[2] comprising a step of converting to an HOH group.
According to the method for producing a polyether resin described in (1). Also, the present invention provides the method for producing a polyether resin according to [3], which comprises a step of [6] converting the CH ₃ CHO group of the polyether resin according to [2] to a vinyl group by a dehydration reaction. It is related.

Further, the present invention provides [7] The above [1] to [1].
The present invention relates to an insulating material using the polyether resin according to any one of [3]. Further, the present invention relates to [8]
(A) A polyether resin according to any one of the above [1] to [4], and (B) a coating liquid for forming an insulating film comprising an organic solvent as an essential component. Also, the present invention

[9] An insulating film obtained by using the coating liquid for forming an insulating film according to [8].

[0010]

Next, the present invention will be described in detail.
In the formulas (1) to (3) of the present invention, R ^{1 to} R ¹¹ each independently represent a hydrogen atom or a carbon atom having 1 or less substituents.
An alkyl group having 10 to 10 carbon atoms, or a cycloalkyl group having 6 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, or a substituent. An alkynyl group having 2 to 10 carbon atoms, or an aromatic ring having 6 to 10 carbon atoms which may have a substituent,
Represents a substituent having an alkoxy group, a carbonyl group, or a substituent having an alcohol group.

Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group and a propyl group. Carbon number 6
As a cycloalkyl group of 10 to 10, a cyclohexyl group,
And a cycloheptyl group. Examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, an allyl group, and a propenyl group. Examples of the alkynyl group having 2 to 10 carbon atoms include an ethynyl group and a propargyl group. Examples of the aromatic ring having 6 to 10 carbon atoms which may have a substituent include a phenyl group and a naphthyl group. Carbon number 1-10
Examples of the alkoxy group include a methoxy group and an ethoxy group. Acetyl groups and the like as a substituent having a carbonyl group, CH ₃ as a substituent having an alcohol group
CHOH groups. Here, examples of the substituent which may have a substituent include an alkyl group, an alkenyl group, an alkynyl group, and an aromatic ring.

In the formulas (1) to (3) of the present invention, X represents a single bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, or -CO-. Carbon number 1-2
If Shimese Specific examples of the hydrocarbon group 0, -CH ₂ -, - C
_{(CH 3) 2 -, -} CH (CH 3) -, - C (CH 3) (C
_{H 2 CH 3) -, -} C (CH 3) (CH 2 CH (CH 3) 2)
-, Such as linear or branched, and And X is a single bond or the following formula (4)
Is preferred. Furthermore, they can also have substituents.

It is preferable that R ^{1 to} R ¹¹ and X are selected according to the required performance for the polyether. For example, when it is desired to lower the dielectric constant, it is preferable that R ^{1 to} R ¹¹ and X use a bulky substituent which is effective in lowering the dielectric constant. In order to increase heat resistance, it is preferable to use a substituent having high heat resistance.

[0014] The method for producing a polyether resin according to [1] of the present invention is characterized by comprising a condensation reaction step of a dihalogenated acetophenone and a bisphenol. The dihalogenated acetophenone in the production method of the present invention indicates a benzene ring in which two or more halogen atoms and one or more acetyl groups are substituted. If this example is specifically shown, difluoroacetophenone, dichloroacetophenone, dibromoacetophenone, diiodoacetophenone, difluoromethylacetophenone, dichloromethylacetophenone, dibromomethylacetophenone, diiodomethylacetophenone (each including various isomers)
And the like, but are not limited to these.

The bisphenols in the present invention are those having two phenolic OH groups in one molecule.
There is no particular limitation. Specifically, bisphenol A, bisphenol F, biphenol, cyclohexylidenebisphenol, bis (hydroxyphenyl) methanone,
Examples include (1-methyl-ethylidene) bis [2-cyclohexylphenol], cyclohexylidenebis [2-cyclohexylphenol], and the like. It is also possible to use a mixture of two or more of these bisphenols.

In the present invention, the condensation reaction between the dihalogenated acetophenone and bisphenols can be carried out under alkaline conditions. The solvent at this time is not particularly limited, but dimethylformamide, dimethylacetamide, dimethylsulfoxide, benzophenone and the like are preferably used from the viewpoint of the boiling point and the ease of the reaction.

The alkali substance used in the condensation reaction is not particularly limited.
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Potassium carbonate and the like. These can be used in the form of a solid or a solution such as an aqueous solution.

The condensation reaction is preferably carried out under an inert atmosphere such as nitrogen or argon. The reaction temperature is not particularly limited, but is preferably 50 ° C. or more and less than 300 ° C., more preferably 10 ° C. in view of the reaction rate and the like.
0 ° C or more and less than 200 ° C.

The method for producing a polyether resin according to [2] of the present invention includes a step of subjecting the acetyl group of the polyether resin according to [1] to a reduction reaction to convert the acetyl group into a CH ₃ CHOH group. It is characterized by the following. In the present invention,
The reduction reaction of the acetyl group can be performed by coexisting with a reducing agent in a solvent. The solvent at this time is not particularly limited.

The reducing agent used in the reduction reaction is not particularly limited, but specific examples include sodium borohydride,
Examples include lithium borohydride, zinc borohydride, lithium tri-butyl borohydride, lithium aluminum hydride and the like.

Further, the method for producing a polyether resin according to [3] of the present invention comprises a step of converting a CH ₃ CHO group of the polyether resin according to [2] into a vinyl group by a dehydration reaction. It is characterized by the following. In the present invention, C
The dehydration reaction of the H ₃ CHOH group is performed in a solvent. The solvent in this case is not particularly limited. The dehydration reaction can be performed more efficiently by coexisting with a dehydrating agent.

Specific examples of the dehydrating agent used in the dehydration reaction include sulfuric acid, phosphoric acid, potassium hydrogen sulfate, oxalic acid, p
-Toluene sulfonic acid, boron trifluoride etherate,
Examples thereof include iodine and anhydrous copper sulfate.

The polyether having a unit structure of the formula (3) in the present invention can be cured by any method. Specifically, it is possible to cure by an electron beam, light, or the like, in addition to the method using heating.

Further, the polyether having the unit structure of the formula (2) in the present invention can also undergo a dehydration reaction by heating and be cured via a vinyl group-containing polyether.

The insulating material according to the present invention comprises the above [1] to [3]
Wherein the polyether resin is used. Examples of the insulating material using a polyether resin in the present invention include semiconductors such as interlayer insulating films or insulating materials for LCDs, and printed wiring materials such as copper-clad laminates.

The coating liquid for forming an insulating film according to the present invention comprises (A) a polyether resin as described in any one of the above [1] to [3] and (B) an organic solvent as essential components. . The insulating film of the present invention is obtained using the above-mentioned coating liquid for forming an insulating film. In the present invention, the organic solvent that is an essential component in constituting the coating liquid for forming an insulating film is not particularly limited as long as it is an organic solvent. To give a concrete example,
Aliphatic hydrocarbon solvents such as hexane, heptane and cyclohexane; hydrocarbon solvents such as benzene, toluene and xylene; methanol, ethanol, isopropanol, 1-butanol, 2-ethoxymethanol, 2-ethoxyethanol and 3-methoxypropanol Alcohol solvents such as acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, 3-pentanone and 2-heptanone; ester solvents such as propyl acetate, butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, and ethyl lactate;
Ether solvents such as diisopropyl ether, dibutyl ether and anisole can be used as commercially available solvents. Further, other additives such as a surfactant and a silane coupling agent can be mixed.

According to the present invention, a polymer containing a vinyl group directly bonded to an aromatic ring can be obtained.
A polyether resin capable of performing a thermosetting reaction at a relatively low temperature can be obtained.

According to the present invention, a thermosetting polyether resin having excellent properties in terms of heat resistance, chemical resistance, insulation and the like is obtained by performing a curing reaction by a method such as heating. be able to.

Further, according to the present invention, the bisphenol to be used can be appropriately selected, and depending on the degree of freedom of the selection, the required performance in terms of heat resistance, dielectric constant, solubility in a solvent before thermosetting, and the like can be obtained. Can be obtained.

[0030]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 In a nitrogen stream, 1,1-
Bis (4-hydroxy-3-cyclohexylphenyl)
43.2 g of cyclohexylidene, 43.2 potassium carbonate
g, 2 ′, 4′-dichloroacetophenone 18.9 g,
600 g of dimethyl sulfoxide and 12 parts of toluene
0.0 g was charged and the mixture was stirred at 170 ° C. for 8 hours. The reaction product was added to a methanol / acetic acid solution to precipitate. The precipitated crystals were filtered, washed with a large amount of methanol, and dried under reduced pressure to obtain 55.5 g of a product. This is called resin A.

Example 2 Instead of 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexylidene, 4,4 '-(9
H-fluoren-9-ylidene) bisphenol 35.
55.9 g in the same manner as in Example 1 except that 0 g was charged.
Got the product. This is called resin B.

Example 3 21.3 g of resin A and N, N-dimethylformamide 3
00 g was charged into a 500 mL four-necked flask, and 5.0 g of sodium borohydride was added at room temperature. 80 ℃ / 6
The mixture was kept under stirring for an hour. The reaction product was added to water and precipitated. The precipitated crystals are filtered, washed with water, and dried under reduced pressure.
7.0 g of product were obtained. This is called resin C.

Example 4 23.3 g of resin B, N, N-dimethylformamide 3
00 g was charged into a 500 mL four-necked flask, and 3.8 g of sodium borohydride was added at room temperature. 80 ℃ / 6
The mixture was kept under stirring for an hour. The reaction product was added to methanol and precipitated. The precipitated crystals were filtered, washed with water and dried under reduced pressure to obtain 20.2 g of a product. This is called resin D.

Example 5 A 200 mL four-necked flask was charged with 5.1 g of resin C, 100 g of toluene, and 0.2 g of methylhydroquinone.
The temperature was raised to 0 ° C. 1.2 g of phosphoric acid was charged and 120 ° C /
The mixture was kept warm and stirred for 4 hours. The reaction mass was poured into methanol to precipitate crystals. The amount obtained after drying was 4.6 g. This is called resin E.

Example 6 9.4 g of resin D, 100 g of toluene, 200 g of dimethyl sulfoxide, and 0.6 g of methylhydroquinone were added to 200 m
It was charged into an L four-necked flask and heated to 120 ° C. 1.2 g of phosphoric acid was charged and the mixture was kept at 120 ° C. for 4 hours while keeping the temperature and stirring. The reaction mass was poured into methanol to precipitate crystals. The amount obtained after drying was 4.6 g. This is called resin F.

Proton NMR measurement confirmed that a polyether resin having a substituent as shown in Table 1 was obtained. The contents of each resin are summarized in the table below.

[Table 1]

Reference Example 1 In a 500 mL four-necked flask, 21.6 g of 1,1-bis (4-hydroxy-cyclohexylphenyl) cyclohexylidene, 4.0 g of sodium hydroxide, and benzophenone 7 were added.
0.0 g and 50.0 g of toluene were charged and reflux dehydration was performed. After dehydration is completed, dibromobiphenyl 1
5.6 g were added. Further, a solution in which 0.05 g of cuprous chloride was dissolved in 5 g of pyridine was added, and the mixture was reacted at an internal temperature of 185 ° C. for 6 hours. After cooling to room temperature, the reaction solution was added to a solution in which 10 g of acetic acid was mixed with 600 g of methanol to precipitate a product. The precipitated crystals were filtered and washed with a large amount of methanol to obtain a polyether resin. This resin is called resin G.

Reference Example 2 In a 300 mL four-necked flask purged with nitrogen, 100 mL of tetrahydrofuran was charged, and 4 g of the resin G was dissolved. After adding 21.5 mL of n-butyllithium (1.6 M, n-hexane solution) and stirring for 1 hour under a nitrogen stream, 4.0 g of allyl bromide was added and the mixture was further stirred for 1 hour. After completion of the reaction, 650 g of methanol and 20 g of acetic acid
The reaction solution was added to the mixed solvent of the above to precipitate a high molecular weight substance. After filtration, washing with methanol and washing with water were performed to obtain a white powdery resin. This resin is called resin H.

Examples 7 and 8 and Comparative Example 1 Resins E and F were each dissolved in 2-heptanone so that the solid content was 20% by weight. Resin G with a solid content of 20
It was dissolved in anisole to give a weight%. Each of the prepared solutions was filtered through a 0.2 μm filter, spin-coated on a 4-inch silicon wafer at a rotation speed of 2,000 rpm, and baked at 150 ° C. for 1 minute.
Heat treatment was performed at 250 ° C. for 40 minutes. Each coating film was immersed in the solvent used for the coating solution for minutes, and the solvent resistance was examined. Table 2 shows the results. ○ indicates that the film thickness did not change, and X indicates that the film thickness decreased.

[Table 2]

[0040]

According to the present invention, a polyether resin having a thermosetting functional group is provided by an easy operation, and an insulating material for an electronic device can be obtained using the polyether resin. The insulating material of the present invention has a low dielectric constant and excellent chemical resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 3/42 H01B 3/42 GF term (Reference) 4J005 AA24 BD00 4J038 DF051 KA06 NA04 NA14 NA21 5G305 AA07 AA11 AB10 AB31 AB36 BA09 BA18 CA13

Claims (10)

[Claims] 1. A polyether resin having a repeating unit represented by the following formula (1). (Wherein, R ^{1 to} R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a C 6 to 10 carbon atom which may have a substituent. A cycloalkyl group, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, or 6 carbon atoms which may have a substituent -10
Or a substituent having an alkoxy group having 1 to 10 carbon atoms, a carbonyl group, or a substituent having an alcohol group. In the formula, X is a single bond, having 1 to 1 carbon atoms.
20 represents any of a hydrocarbon group, -O-, and -CO-. ) 2. A polyether resin having a repeating unit represented by the following formula (2). (In the formula, R ^{1 to} R ¹¹ and X are the same as defined in the formula (1).) 3. A thermosetting polyether resin having a repeating unit represented by the following formula (3). (In the formula, R ^{1 to} R ¹¹ and X are the same as defined in the formula (1).) 4. The polyether resin according to claim 1, wherein X is a single bond or any of the following formulas (4). 5. The method for producing a polyether resin according to claim 1, comprising a condensation reaction step of a dihalogenated acetophenone and a bisphenol. 6. The method for producing a polyether resin according to claim 2, further comprising a step of subjecting the acetyl group of the polyether resin according to claim 1 to a reduction reaction to convert the acetyl group into a CH ₃ CHO group. 7. CH of the polyether resin according to claim 2
_The method for producing a polyether resin according to claim 3, further comprising a step of performing a dehydration reaction of ₃ CHOH groups to convert them into vinyl groups. 8. An insulating material using the polyether resin according to claim 1. 9. A coating liquid for forming an insulating film comprising (A) the polyether resin according to claim 1 and (B) an organic solvent as essential components. 10. An insulating film obtained by using the coating liquid for forming an insulating film according to claim 9.