JPH11349668A - Phenylene group-containing polymer and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable polymer excellent in heat resistance, low dielectric constant and solvent resistance by substituting a phenylene group-containing polymer comprising a specific recurring unit by allyl groups to a specific degree. SOLUTION: The objective curable phenylene group-containing polymer comprises a specific recurring unit represented by the formula and has a substitution ratio by allyl groups, defined by the following equation, of 0.1-400 mole % and a wt. average mol.wt., in terms of polystyrene, of 1,000-1,000,000. [The substitution ratio by allyl group] is (the total mole number of allyl groups in the phenylene group-containing polymer)/(the total mole number of phenylene groups in the phenylene group-containing polymer)×100(%). In the formula, X is S, -SO2 , O(CH2 )O, fluorenylene group or the like; R<1> -R<12> are the same or different and are each an aryl, H, a halogen, an alkyl or a haloalkyl; (r) is a number of 1-10; (n) is 0.1-100 mole %; and (m) is 0-99.9 mole %.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable phenylene group-containing polymer and a method for producing the same.

[0002]

2. Description of the Related Art Large-scale integrated circuits (LSIs) have become highly integrated, multifunctional, and high-performance, reflecting the progress of fine processing technology. As a result, the circuit resistance and the capacitance between the wirings (hereinafter, also referred to as “parasitic resistance” and “parasitic capacitance”, respectively) increase, which not only increases the power consumption, but also increases the delay time. This is a major factor in lowering the signal speed. Therefore, it is required to reduce the parasitic resistance and the parasitic capacitance. One of the solutions is to cover the periphery of the wiring with an interlayer insulating film to reduce the parasitic capacitance and respond to the speeding up of the device. I have. However, the interlayer insulating film needs to have excellent heat resistance that can withstand post-processes such as a thin-film forming process at the time of manufacturing a mounting board and chip connection and pinning. Polyimide is widely known as the organic material having high heat resistance, however, since it contains a highly polar imide group, no satisfactory material is obtained in terms of low dielectric property and low water absorption. On the other hand, polyphenylene is known as a high heat-resistant organic material containing no polar group. In order to impart solubility to this polyphenylene, a side chain is generally introduced.However, by introducing a side chain, problems such as reduced heat resistance and complicated production of raw materials are caused. is there.

Further, a polymer is disclosed which imparts solubility by introducing a bending group into the main chain and is excellent in high heat resistance, low dielectric constant, processability, and transparency. Because it is soluble, it is susceptible to solvent attack. For polyimides, it has been proposed to improve solvent resistance by curing with a acetylene, maleimide, or vinyl-terminated curing agent, but such cured polyimides have an increased dielectric constant. There's a problem. In addition, it has been proposed to improve the heat resistance and chemical resistance by introducing and curing a crosslinking group in polyphenylene ether, but it is not more satisfactory than polyphenylene because it contains an ether bond in terms of dielectric constant. .

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made based on these conventional techniques as problems, and has a heat resistance, a low dielectric constant,
An object of the present invention is to provide a curable phenylene group-containing polymer having excellent solvent resistance and a method for producing the same.

[0005]

The present invention comprises a repeating unit represented by the following general formula (1), wherein the substitution rate of an allyl group defined by the following formula is 0.1 mol% to 400 mol% or less. A curable phenylene group-containing polymer (hereinafter, referred to as “phenylene group-containing polymer of the present invention”), and a phenylene group-containing polymer represented by the following general formula (2), An object of the present invention is to provide a method for producing a curable phenylene group-containing polymer, which is characterized by substitution with an allyl halide.

Allyl group substitution rate = (total number of moles of allyl group in phenylene group-containing polymer / total number of moles of phenylene group in phenylene group-containing polymer) × 100 (%) General formula (1)

Embedded image [Wherein, X is a sulfur atom, -SO2-,-(CH) 2-,
_{-O (CH2) r O -,} - (CYY ') p- group represented by (wherein, Y and Y' are the same or different, a hydrogen atom, an aryl group, an alkyl group, a halogenated alkyl group) Or a fluorenylene group, wherein R ^{1 to} R ¹² are
Same or different, allyl group, hydrogen atom, halogen atom, alkyl group, halogenated alkyl group, and p is 0
Or, the number of 1 is shown, r shows the number of 1-10, n shows 0.1-100 mol%, and m shows 0-99.9 mol%. ]

General formula (2)

Embedded image [Wherein, X is a sulfur atom, -SO2-,-(CH) 2-,
_{-O (CH2) r O -,} - (CYY ') p- group represented by (wherein, Y and Y' are the same or different, a hydrogen atom, an aryl group, an alkyl group, a halogenated alkyl group) Or a fluorenylene group, wherein R ^{13 to} R ²⁴ are
The same or different, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, p represents a number of 0 or 1, r represents a number of 1 to 10, and n represents a number of 0.1 to 100.
Mol% and m represent 0 to 99.9 mol%. ]

In the present invention, the above general formulas (1) and (2)
In Y and Y ′, the alkyl group includes a methyl group, an ethyl group, a propyl group, and a butyl group, the halogenated alkyl group includes a trifluoromethyl group and a pentafluoroethyl group, and the aryl group includes Phenyl group, biphenyl group, tolyl group, pentafluorophenyl group and the like. Further, among R ^{1 to} R ^12, a halogen atom is a fluorine atom, an alkyl group is a methyl group or an ethyl group, and a halogenated alkyl group is a trifluoromethyl group or a pentafluoroethyl group. Examples of the allyl group include a propenyl group, and examples of the aryl group include a phenyl group and a pentafluorophenyl group. In the present invention, the phenylene group-containing polymer represented by the general formula (1) generally has a weight average molecular weight in terms of polystyrene of 1,000 to 1,000.
000, preferably 1,500-200,000.

The method for producing the curable phenylene group-containing polymer of the present invention comprises a step of metallizing the phenylene group-containing polymer represented by the general formula (2) with an organic alkali metal and subjecting the polymer to a substitution reaction with allyl halide. Become. General formula (2)
As a specific example of the phenylene group-containing polymer represented by,
Poly (1,4-phenylenemethylene-1,4-phenylene), poly (1,4-phenylene-9,9-fluorenylene-1,4-phenylene), poly (1,4-phenylene-2,2-hexene) Fluoropropylene-1,4-phenylene), poly (1,4-phenylene-2,2-
Propylene-1,4-phenylene) and the like. In particular, poly (1,4-phenylene-2,2-hexafluoropropylene-
1,4-phenylene) is preferred in terms of heat resistance and low dielectric constant.

As the organic alkali metal, it is preferable that an organic lithium compound, particularly an alkyl lithium having 1 to 10 carbon atoms, can facilitate the metalation reaction.
Specific examples of organic alkali metals include methyl lithium,
n-butyllithium, sec-butyllithium, tert-butyllithium and the like. Preferred are n-butyllithium, sec-butyllithium and tert-butyllithium. The amount of the organic alkali metal used is preferably 0.001 to 5 mol per 1 mol of the phenylene group of the phenylene group-containing polymer represented by the general formula (2). Allyl halides include allyl chloride, allyl bromide, and allyl iodide. Particularly, allyl bromide and allyl iodide are preferred from the viewpoint of reactivity. The amount of the allyl halide to be used is 0.001 to 1 mol per phenylene group of the phenylene group-containing polymer represented by the general formula (2).
5 moles are preferred.

In the present invention, the reaction of the phenylene group-containing polymer represented by the general formula (2) with an organic alkali metal and allyl halide is carried out in tetrahydrofuran (hereinafter THF).
), 1,4-dioxane, dimethoxyethane, diethyl ether and the like. Alternatively, the reaction can be performed using a hydrocarbon solvent such as benzene, toluene, xylene, and cyclohexane in the presence of N, N, N, N-tetramethylethylenediamine. In the actual reaction, these solvents are preferably subjected to pretreatments such as purification and dehydration.These solvents may be mixed at an appropriate ratio, and other solvents may be used as long as they do not inhibit the reaction. You may mix. The reaction is preferably performed under an inert gas such as nitrogen or argon.

The temperature and time for the reaction of the phenylene group-containing polymer represented by the general formula (2) with the organic alkali metal and the subsequent reaction with the allyl halide are not particularly limited. For example, in the case of a reaction with an organic alkali metal,
The reaction is carried out at -78 ° C to the boiling point of the solvent (between the freezing point and the boiling point when the system solidifies), preferably at 0 ° C to the boiling point of the solvent used, and the reaction time is usually 1 second to 48 hours. In the present invention, factors that control the substitution rate of the allyl group include a reaction temperature, a reaction time, a solvent type, an amount of an organic alkali metal to be reacted, an amount of an allyl halide, and the like.
Although the substitution rate can be controlled by any factor, it is preferable to change the amount of the organic alkali metal and apply an allyl halide in an amount equal to or more than this, or use an excess amount of the organic alkali metal to reduce the amount of the allyl halide. A method of adjusting is preferred.

The substitution rate of the allyl group in the present invention is generally
Phenylene of phenylene group-containing polymer represented by formula (1)
Defined by the ratio of the total number of allyl groups to the total number of allyl groups
And at most 400 mol%, usually from 0.1 to 100%.
Mol%, preferably 1 to 50 mol%. Departure
Allyl introduced into bright curable phenylene group-containing polymer
The group has a nuclear magnetic resonance spectrum (hereinafter abbreviated as NMR).
Can be confirmed by infrared absorption spectrum, ¹H-NM
The substitution rate can be determined from the peak area of the R spectrum.
it can.

The curable phenylene group-containing polymer of the present invention can be cured by the addition reaction of an allyl group by heating. The curable phenylene group-containing polymer of the present invention is used after being dissolved in a solvent. The concentration at which the curable phenylene group-containing polymer is dissolved in the solvent is usually 1 to 60% by weight, preferably 5 to 40% by weight. If the concentration of the specific polymer is less than 1% by weight, a coating film having a sufficient thickness cannot be obtained,
On the other hand, if it exceeds 60% by weight, it may not be sufficiently cast and a uniform coating film may not be obtained. The curable phenylene group-containing polymer of the present invention may be mixed with an adhesion aid or the like in order to increase the adhesion of the film to the substrate. The curable phenylene group-containing polymer of the present invention can be cured by an addition reaction of an allyl group by heating.

The cured molded product is prepared by applying the curable phenylene group-containing polymer of the present invention to a substrate by spraying, spin coating, or casting, preferably spin coating, and the like.
The film can be formed as a film by heating at 0 ° C., preferably 300 to 350 ° C. to perform crosslinking. The curable phenylene group-containing polymer of the present invention has low dielectric constant, high heat resistance,
As an insulating film for electronic components that has solvent resistance, for example, as an interlayer insulating film, a protective film, a printed circuit board material, a sealing material,
Further, it can be suitably used for optical applications.

[0016]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. In Examples,% and parts are by weight unless otherwise specified. Various measurement items in the examples were obtained as follows. Weight average molecular weight (Mw) and number average molecular weight (Mn ) were determined by gel permeation chromatography (GPC) measurement in terms of polystyrene. 5% weight loss temperature (Td5 ) The temperature was measured by a TG method in a nitrogen atmosphere at a heating rate of 10 ° C./min. Relative Dielectric Constant (ε ) A polymer film was formed on a SUS substrate in the same manner as described above, and then a gold electrode was formed by mask evaporation to obtain a sample for relative dielectric constant measurement. The capacitance of this sample was measured with an LCR meter, and the relative dielectric constant was determined from the following equation. ε = C · d / ε ₀ · S Here, ε is a relative permittivity, C is a capacitance, ε ₀ is a permittivity in a vacuum, and S is an upper electrode area. Volume resistivity (ρ _v ) Measured according to JIS K6911, except that the obtained polymer was applied to a SUS substrate as a test piece. The appearance of the coating film was visually observed. ○ No change, △ Devitrification or crack, × shows dissolution.

Examples 1 to 3 Inner volume 100 ml equipped with an argon gas inlet tube and a thermometer
Poly (1,4-phenylene-2,2-hexafluoroisopropylene-1,4-phenylene) (Mn: 1
(5800 Mw: 31200) 3.0 g was added, and the inside of the three-necked flask was replaced with argon gas. 50m anhydrous THF
Then, 12.5 ml, 25.0 ml and 37.5 ml of an n-butyllithium hexane solution (1.6 M) were added at room temperature, and the mixture was stirred at room temperature for 1 hour under an argon atmosphere. 3.7 ml of allyl bromide was added to the resulting deep blue solution.
(Example 1), 7.4 ml (Example 2) and 11.1 ml (Example 3) were added, and the mixture was stirred at room temperature for 1 hour, and then methanol was added under ice cooling to terminate the reaction. After adding 200 ml of diethyl ether to the obtained reaction mixture and extracting and washing with 2N hydrochloric acid, diethyl ether was distilled off, the residue was poured into methanol, and the precipitate was collected and dried to obtain a white powdery polymer. Was. The substitution rates of allyl groups were determined by ¹ H-NMR to be 5%, 10% and 21%, respectively. 20 parts of the obtained polymer is dissolved in 80 parts of propylene glycol-1-monomethyl ether-2-acetate (hereinafter abbreviated as PGMEA), applied to a glass substrate by a spin coating method, and heated at 80 ° C. and 130 ° C. for 3 minutes each. Thirteen
Baking was performed at 0 ° C. and 300 ° C. for 30 minutes each to obtain a uniform coating film. The obtained coating film was colorless and transparent. This coating film was immersed in PGMEA for 10 minutes, and the state of the thin film was visually observed. Table 1 shows the relative dielectric constant and the 5% weight loss temperature.

Example 4 Inner volume 100 ml equipped with an argon gas inlet tube and a thermometer
Poly (1,4-phenylene-2,2-hexafluoroisopropylene-1,4-phenylene) (Mn: 1
(5800 Mw: 31200) 3.0 g was added, and the inside of the three-necked flask was replaced with argon gas. 50m anhydrous THF
Then, 30 ml of an n-butyllithium hexane solution (1.6 M) was added at room temperature, and the mixture was stirred at room temperature for 24 hours under an argon atmosphere. After adding 8.9 ml of allyl bromide to the resulting deep blue solution and stirring at room temperature for 1 hour,
Under ice cooling, methanol was added to terminate the reaction. After adding 200 ml of diethyl ether to the obtained reaction mixture and performing extraction and washing with 2N hydrochloric acid, diethyl ether was distilled off.
The residue was poured into methanol, and the precipitate was collected and dried to obtain a white powdery polymer. The substitution rate of the allyl group was determined by ¹ H-NMR to be 33%. 20 parts of the obtained polymer is dissolved in 80 parts of propylene glycol-1-monomethyl ether-2-acetate (hereinafter abbreviated as PGMEA) and applied to a glass substrate by a spin coating method.
80 ° C, 130 ° C for 3 minutes, 130 ° C, 300
Each was baked at 30 ° C. for 30 minutes to obtain a uniform coating film. The obtained coating film was colorless and transparent. PG
Table 1 shows the relative permittivity and 5% weight loss temperature of the thin film after immersion in MEA for 10 minutes.

[Table 1]

[0019]

The phenylene group-containing polymer of the present invention is excellent in heat resistance, low dielectric constant and solvent resistance, and according to the present invention, the phenylene group-containing polymer of the present invention can be easily produced. Can be.

[0020]

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum (CDCl ₃ ) of a polymer obtained in Example 4.

FIG. 2 is an IR spectrum of a polymer obtained in Example 4.

Claims (2)

[Claims] 1. It comprises a repeating unit represented by the following general formula (1), and has an allyl group substitution rate defined by the following formula of 0.1.
A phenylene group-containing polymer, which has a weight average molecular weight of 1,000 to 1,000,000 in terms of polystyrene in an amount of from mol% to 400 mol% or less. Allyl group substitution rate = (total number of moles of allyl group in phenylene group-containing polymer / total number of moles of phenylene group in phenylene group-containing polymer) × 100 (%) General formula (1) [Wherein, X is a sulfur atom, -SO2-,-(CH) 2-,
_{-O (CH2) r O -,} - (CYY ') p- group represented by (wherein, Y and Y' are the same or different, a hydrogen atom, an aryl group, an alkyl group, a halogenated alkyl group) Or a fluorenylene group, wherein R ^{1 to} R ¹² are
Same or different, allyl group, hydrogen atom, halogen atom, alkyl group, halogenated alkyl group, and p is 0
Or, the number of 1 is shown, r shows the number of 1-10, n shows 0.1-100 mol%, and m shows 0-99.9 mol%. ] 2. The curable composition according to claim 1, wherein an organic alkali metal is allowed to act on a phenylene group-containing polymer comprising a repeating unit represented by the following general formula (2), and the polymer is substituted with an allyl halide. A method for producing a phenylene group-containing polymer. General formula (2) [Wherein, X is a sulfur atom, -SO2-,-(CH) 2-,
_{-O (CH2) r O -,} - (CYY ') p- group represented by (wherein, Y and Y' are the same or different, a hydrogen atom, an aryl group, an alkyl group, a halogenated alkyl group) Or a fluorenylene group, wherein R ^{13 to} R ²⁴ are
The same or different, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, p represents a number of 0 or 1, r represents a number of 1 to 10, and n represents a number of 0.1 to 100.
Mol% and m represent 0 to 99.9 mol%. ]