JP6107670B2 - Novel mesogen / silicon compound copolymer and method for producing the copolymer - Google Patents

Description

  The present invention relates to a novel mesogen / silicon compound copolymer and a method for producing the copolymer.

  In recent years, the development of electronic devices has been remarkable, but the amount of heat generation has increased with the improvement of performance. Since heat adversely affects the device, it is an important issue to efficiently release the heat to the outside. As a solution to this problem, the filling of inorganic compound particles with high thermal conductivity into a resin is widely performed, and as a result, heat conduction can be performed more efficiently than a resin alone. However, since there is a limit to the filling amount of inorganic compound particles with respect to a certain amount of resin, this method has a limit in improving thermal conductivity. In addition, the inorganic compound is expensive.

  From such a background, it has been desired to improve the thermal conductivity of the resin itself. Improvement in thermal conductivity can be achieved by providing the resin with a portion where the resins called mesogenic groups tend to overlap each other. However, as the number of mesogenic groups in the resin increases, there is a drawback that handling becomes worse, such as an increase in melting point and a poor solubility of the resin in a solvent. For this reason, it has not been possible to develop a highly thermally conductive resin having utility value by simply increasing the number of mesogenic groups.

  Patent Document 1 (Japanese Patent Laid-Open No. 2011-84714) discloses a thermoplastic resin obtained by copolymerizing a mesogenic group and a spacer. It is described that the polymer compound is excellent in thermal conductivity due to mesogen stacking. However, it is known that a resin having a mesogenic group becomes hard and brittle due to stacking of the mesogenic group, and further hardly soluble in a solvent, and the above resin is no exception. Since such a resin is brittle, there are problems in that its use location is limited, and since it is difficult to dissolve in a solvent, it is limited to use without solvent such as extrusion.

JP 2011-84714 A

  The present invention has been made in view of the above circumstances. For example, a novel mesogen-silicon compound copolymer that can be suitably used as a heat dissipation material or a resin material for semiconductor devices and electronic components, and the copolymer It aims at providing the manufacturing method of unification.

  As a result of intensive studies to achieve the above object, the present inventors have a weight average molecular weight of 300 to 500,000 having a structure represented by the following average composition formula (1), which can be produced by the following method. The new mesogen-silicon compound copolymer has excellent thermal conductivity and remarkably excellent dispersibility in commonly used solvents. Therefore, it can be used as a heat dissipation material or a resin material for semiconductor devices and electronic components. It has been found that it can be suitably used, and the present invention has been made.

Accordingly, the present invention provides the following novel mesogen / silicon compound copolymer and a method for producing the copolymer.
[1]
A mesogen / silicon compound copolymer having a structure represented by the following average composition formula (1) and having a weight average molecular weight of 300 to 500,000.
(In the formula, R ¹ represents an alkylene group having 1 to 20 carbon atoms, an alkenylene group or an aralkylene group, and R ² and R ³ may be independently the same or different and have 1 to 20 carbon atoms. R ⁴ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, different from R ^1, and l and n each represent a positive number of less than 0.5, m Represents a positive number of 0.5 or less, k represents a positive number of 0 or 0.5, and l and n satisfy l + n = 0.4 to 0.6, and m and k are m + k = 0. 4 to 0.6, provided that l + n + m + k = 1 A and B each independently represent a divalent atom or molecule selected from the group of —O—, —NH—, and —S—. D and E each independently represent a divalent atom or molecule selected from the group of -O-, * -R-NH-, * -R-S-, R represents a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms, X and Y are each independently a monovalent aliphatic hydrocarbon group, (meth) acrylic. Group, CN, OCH ₃ , NO ₂ , F atom, Cl atom, Br atom, or I atom, p and q each independently represents an integer of 0 to 4, Z represents independently a silicon atom; Indicate a divalent group.)
[2]
The mesogen / silicon compound copolymer according to [1], wherein k is a positive number of 0.5 or less in the average composition formula (1).
[3]
The mesogen / silicon compound copolymer according to [1] or [2], wherein in the average composition formula (1), R ² and R ³ are each independently an alkylene group having 1 to 18 carbon atoms.
[ 4 ]
In the average composition formula (1), Z is a group represented by the following general formula (2) or (3), wherein the mesogenic silicon compound according to any one of [1] to [3] Polymer.
(Wherein, a is an integer of 0 to 300, b is an integer of 0 to 300. R ⁵ and R ⁶ are each independently monovalent carbon atoms having 1 to 10 carbon atoms which may be the same or different. Represents a hydrogen group, provided that R ⁵ and R ⁶ are not methyl groups at the same time.)
[ 5 ]
[1] A method for producing a mesogen / silicon compound copolymer according to any one of [4], wherein a compound represented by the following general formula (4) and the following general formula (5) is reacted with acetic anhydride. is, after acetylation, a compound represented by following general formula in which the following general formula (6) (6)及beauty under following general formula (7) with a compound represented by be de-acetic acid polycondensation A process for producing a mesogen-silicon compound copolymer characterized by the above.
(In the formula, A and B each represent a divalent atom or molecule selected from the group of -O-, -NH-, and -S-.)
(In the formula, D and E each independently represent a divalent atom or molecule selected from the group of —O—, * —R—NH—, * —R—S—, where * represents a phenyl group. R represents a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms, X and Y each independently represent a monovalent aliphatic hydrocarbon group, a (meth) acryl group, CN, OCH ₃ , NO ₂ , F atom, Cl atom, Br atom, or I atom, and p and q each represent an integer of 0 to 4. R ² and R ³ are each independently the same or It may be different and represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z represents a divalent group containing a silicon atom.)
(In the formula, R ¹ represents an alkylene group having 1 to 20 carbon atoms , an alkenylene group or an aralkylene group .)
(In the formula, R ⁴ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ⁴ has a structure different from R ^1. )
[ 6 ]
[1] A method for producing a mesogen / silicon compound copolymer according to any one of [4], represented by the following general formula (4) and the following general formula (5) in the presence of a dehydrochlorinating agent. the compound with the compound represented by the following general formula (8) or the following general formula (8)及beauty under following general formula (9) with a compound represented by the mesogenic-silicon compound both which comprises reacting a A method for producing a polymer.
(In the formula, A and B each represent a divalent atom or molecule selected from the group of -O-, -NH-, and -S-.)
(In the formula, D and E each independently represent a divalent atom or molecule selected from the group of —O—, * —R—NH—, * —R—S—, where * represents a phenyl group. R represents a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms, X and Y each independently represent a monovalent aliphatic hydrocarbon group, a (meth) acryl group, CN, OCH ₃ , NO ₂ , F atom, Cl atom, Br atom, or I atom, and p and q each represent an integer of 0 to 4. R ² and R ³ are each independently the same or It may be different and represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z represents a divalent group containing a silicon atom.)
(In the formula, R ¹ represents an alkylene group having 1 to 20 carbon atoms , an alkenylene group or an aralkylene group .)
(In the formula, R ⁴ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ⁴ has a structure different from R ^1. )
[ 7 ]
[1] A method for producing a mesogen-silicon compound copolymer according to any one of [4] , represented by the following general formula (4) and the following general formula (5) in the presence of an acid catalyst. that compound, the compound represented by the following general formula (6) or the following general formula (6)及beauty under following general formula (7) with a compound represented by the mesogenic-silicon compound both which comprises reacting a A method for producing a polymer.
(In the formula, A and B each represent a divalent atom or molecule selected from the group of -O-, -NH-, and -S-.)
(In the formula, D and E each independently represent a divalent atom or molecule selected from the group of —O—, * —R—NH—, * —R—S—, where * represents a phenyl group. R represents a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms, X and Y each independently represent a monovalent aliphatic hydrocarbon group, a (meth) acryl group, CN, OCH ₃ , NO ₂ , F atom, Cl atom, Br atom, or I atom, and p and q each represent an integer of 0 to 4. R ² and R ³ are each independently the same or It may be different and represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z represents a divalent group containing a silicon atom.)
(In the formula, R ¹ represents an alkylene group having 1 to 20 carbon atoms , an alkenylene group or an aralkylene group .)
(In the formula, R ⁴ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ⁴ has a structure different from R ^1. )
[ 8 ]
[ 7 ] The method for producing a mesogen / silicon compound copolymer according to [ 7 ], wherein the acid catalyst is sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.

  The novel mesogen-silicon compound copolymer of the present invention is excellent in thermal conductivity, and further has excellent dispersibility in commonly used solvents. Therefore, a heat dissipation material, or a resin for semiconductor devices and electronic components It can be suitably used as a material.

1 is a ¹ H-NMR spectrum of a resin (1) obtained in Example 1.

The mesogen-silicon compound copolymer of the present invention has a structure represented by the following average composition formula (1), and has a weight average molecular weight of 300 to 500,000, preferably 1,000 to 30,000. is there.
(In the formula, R ^{1 to} R ³ may be the same or different and each represents a divalent hydrocarbon group having 1 to 20 carbon atoms. R ⁴ is different from R ¹ and has 1 carbon atom. Represents a divalent hydrocarbon group of ˜20, and l and n each represent a positive number of less than 0.5, m and k each represent a positive number of 0 or less than 0.5, and l and n represent l + n = 0.4 to 0.6, m and k satisfy m + k = 0.4 to 0.6, where l + n + m + k = 1, A and B are each independently -O-,- A divalent atom or molecule selected from the group of NH- and -S-, wherein D and E are each independently selected from the group of -O-, * -R-NH-, * -R-S-; Wherein * represents the direction of bonding to the phenyl group, R represents a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms, and X and Y are independent of each other. Shi Monovalent aliphatic hydrocarbon group, (meth) acryl _{group, CN, OCH 3, NO 2} , F atom, Cl atom, a Br atom, or an I atom. The p, q are each independently 0-4 of Represents an integer, Z independently represents a divalent group containing a silicon atom.

In the above average composition formula (1), R ^{1 to} R ⁴ may each independently be the same or different and are linear, branched or cyclic, alkylene group, alkenylene group, alkynylene group, arylene group, It is a C1-C20 divalent hydrocarbon group such as an aralkylene group or a group in which two or more of these are bonded.

R ¹ and R ⁴ are preferably a divalent hydrocarbon group having 2 to 16 carbon atoms, more preferably a divalent hydrocarbon group having 4 to 14 carbon atoms, and particularly a divalent carbon group having 6 to 12 carbon atoms. A hydrogen group is particularly preferred. R ⁴ is different from R ¹ .
Specific examples of R ¹ and R ⁴ include —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — _{(CH 2) 6 -, -} (CH 2) 8 -, - (CH 2) 10 -, - (CH 2) 12 -, - (CH 2) 15 -, - (CH 2) 20 -, - CH = CH—, —C≡C—, —CH═CH—CH═CH—, —CH═CH—C≡C—, — (CH ₂ ) ₁₂ CH (C ₆ H ₅ ) —, —CH (CH ₃ ) _{-, - C (CH 3)} (CH 3) -, - C (CH 3) 2 (CH 2) 3 C (CH 3) 2 -, - CH 2 -CH (CH 3) -, - CH 2 -CH (CH ₃ ) —CH (CH ₃ ) —, —CH ₂ —CH (CH ₂ CH ₂ CH ₃ ) —, —CH ₂ —C (CH ₂ CH ₂ CH ₃ ) (CH ₂ CH ₂ CH ₃ ) —, _{-CH 2 -C (CH 2 CH (} CH 3) CH 3) (CH 2 CH 2 CH 3 _{) -, - CH 2 -C (} CH 2 CH (CH 3) CH 3) (CH 2 C (CH 3) (CH 3) CH 3) - and the like.

In addition, the bivalent hydrocarbon group which has a cyclic structure as shown below, and the bivalent hydrocarbon group which has an aromatic ring can be illustrated.
(In the formula, a wavy line indicates a bond.)

R ² and R ³ are preferably divalent hydrocarbon groups such as alkylene groups having 1 to 18 carbon atoms, more preferably divalent hydrocarbon groups having 1 to 15 carbon atoms, and 3 to 4 carbon atoms. A divalent hydrocarbon group is particularly preferred. As R ² and R ³ , specifically, —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₂ —CH ( CH ₃ ) — and the like can be exemplified. Among them _{- (CH 2) 2 -,} - (CH 2) 3 -, - (CH 2) 2 -CH (CH 3) - are preferred.

  L and n each represent a positive number less than 0.5, and m and k each represent a positive number of 0 or 0.5 or less. Furthermore, l and n satisfy l + n = 0.4 to 0.6, and m and k satisfy m + k = 0.4 to 0.6. In particular, it is preferable that l + n = 0.5 and m + k = 0.5. However, l + n + m + k = 1.

  A and B each independently represent a divalent atom or molecule selected from the group of -O-, -NH-, and -S-. D and E each independently represent a divalent atom or molecule selected from the group of —O—, * —R—NH—, and * —R—S—. However, * shows the coupling | bonding direction with a phenyl group, R is a C1-C3 bivalent hydrocarbon group, such as a single bond or a methylene group, ethylene group, a propylene group (trimethylene group, methylethylene group). Show.

X and Y each independently represent a monovalent aliphatic hydrocarbon group, (meth) acryl group, CN, OCH ₃ , NO ₂ , F atom, Cl atom, Br atom, or I atom. Specific examples of monovalent aliphatic hydrocarbon groups include linear, branched or cyclic alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and cyclohexyl groups, and vinyl groups. And those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms such as an alkenyl group such as an allyl group. X and Y are preferably Cl, OCH ₃ , an allyl group, and a methacryl group.
P and q are each independently an integer of 0 to 4, preferably 0 or 1.

Z is not limited as long as it is a divalent group containing a silicon atom. However, when Z is a group having a structure represented by the following general formula (2) or the following general formula (3), the effect of the present invention appears remarkably. .
(Wherein, a is an integer of 0 to 300, b is an integer of 0 to 300. R ⁵ and R ⁶ are each independently monovalent carbon atoms having 1 to 10 carbon atoms which may be the same or different. Represents a hydrogen group, provided that R ⁵ and R ⁶ are not methyl groups at the same time.)

In the above formula (3), R ⁵ and R ⁶ may each independently be the same or different and are monovalent having 1 to 10 carbon atoms, preferably 1 to 6 linear, branched or cyclic carbon atoms. It is a hydrocarbon group. Specific examples of the monovalent hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and an octyl group. Cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group, propenyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group, phenylpropyl group, etc. Aralkyl group etc. are mentioned, Among these, a methyl group, a phenyl group, and a vinyl group are preferable. However, R ⁵ and R ⁶ are not methyl groups at the same time.
a is an integer of 0 to 300, preferably an integer of 5 to 20, and b is an integer of 0 to 300, preferably an integer of 0 to 20.

Examples of the group represented by the formula (3) include the following.
(In the formula, Me is a methyl group.)

  The mesogen / silicon compound copolymer of the present invention has a polystyrene-reduced weight average molecular weight of 300 to 500,000, preferably measured by high temperature GPC (gel permeation chromatography) using 1,2,4-trichlorobenzene as an elution solvent. Is a copolymer of 1,000 to 300,000, more preferably 1,000 to 200,000. If the weight average molecular weight is too small, the thermal conductivity decreases, and if it is too large, the solubility or dispersibility in the solvent deteriorates.

In the mesogen / silicon compound copolymer containing the repeating unit represented by the above formula (1), each unit may be bonded at random or may be bonded as a block polymer.
Examples of such mesogen / silicon compound copolymers include the following.

  Next, although the manufacturing method of the mesogen silicon compound copolymer of this invention is shown, it is not this limitation.

[Production Method 1]
The first production method of the mesogen / silicon compound copolymer of the present invention will be described.
The mesogen / silicon compound copolymer of the present invention comprises a compound selected from compounds represented by the following general formula (4), the following general formula (5), the following general formula (6), and the following general formula (7). It can be manufactured by the method shown below. In addition, in the said Formula (1), when either m and k are 0, it manufactures without using the compound represented by following formula (6) or (7).

  After the compounds represented by the following general formula (4) and the following general formula (5) are reacted with acetic anhydride and acetylated, they are represented by the following general formula (6) and / or the following general formula (7). The mesogen-silicon compound copolymer of the present invention can be produced by performing a deacetic acid polycondensation reaction with the compound. These reactions are preferably carried out in the absence of a solvent.

(In the formula, A and B are the same as above.)

Examples of such a compound represented by the formula (4) include the following.

(In the formula, D, E, X, Y, p, q, R ² , R ³ and Z are the same as above.)

Examples of the compound represented by the formula (5) include the following.

(In the formula, Me is a methyl group and Ph is a phenyl group.)

(Wherein R ¹ is the same as above)

(In the formula, R ⁴ is the same as described above, provided that R ⁴ has a structure different from R ^1. )

Examples of the compound represented by the formulas (6) and (7) include the following structures.
(In the formula, Me is a methyl group.)

The method for producing the mesogen / silicon compound copolymer of the present invention is obtained by separately converting the compounds represented by the formulas (4) and (5) into acetic acid esters using acetic anhydride, respectively, or separately. And a method in which a deacetic acid polycondensation reaction is carried out with the compound represented by the formula (6) and / or (7) in the same reaction tank.
In addition, the compound represented by the formula (6) and / or the formula (7) may be added before the compound represented by the formula (4) and the formula (5) is reacted with acetic anhydride. .

  Acetic anhydride used when the compounds represented by the above formulas (4) and (5) are reacted is a phenolic hydroxy group or an aniline amino group in the compounds represented by the above formulas (4) or (5). It is preferable to add 1 equivalent or more, more preferably 1.05 equivalent or more, and even more preferably 1.10 to 1.50 equivalent to 1 equivalent of the group or thiophenolic thiol group.

  The reaction between the compounds represented by the above formulas (4) and (5) and acetic anhydride is usually 120 to 220 ° C., more preferably 130 to 200 ° C., particularly 140 to 180 ° C., and 0.5 to It is preferably performed for 15 hours, particularly 1 to 5 hours. If the reaction temperature is too high, decomposition or an unintended reaction may proceed, and if it is too low, the progress of the reaction may be delayed.

  The deacetic acid polycondensation reaction is preferably carried out at a temperature of usually 120 to 300 ° C., further 140 to 280 ° C., particularly 150 to 260 ° C., for 30 minutes to 24 hours, particularly 1 to 10 hours. Depending on the progress of the reaction, the temperature can be raised and the reaction rate can be increased. However, if the reaction temperature is too high, side reactions such as decomposition tend to occur, and if it is too low, the progress of the reaction may be slow.

[Production Method 2]
A second method for producing the mesogen / silicon compound copolymer of the present invention will be described.
The compound represented by the general formula (4) and the general formula (5) and the compound represented by the following general formula (8) and / or the following general formula (9) in the presence of a dehydrochlorinating agent in a solvent. And the mesogen / silicon compound copolymer of the present invention can also be produced. In addition, in the said Formula (1), when either m or k is 0, it manufactures without using the compound represented by following formula (8) or (9).

(Wherein R ¹ is the same as above)

(In the formula, R ⁴ is the same as described above, provided that R ⁴ has a structure different from R ^1. )

Examples of such a compound include the following structures.
(In the formula, Me is a methyl group.)

The solvent can be widely used as long as it does not have a hydroxy group, a carboxy group, or a halogen. For example, specifically, toluene, xylene, hexane, cyclohexane, ethylcyclohexane, isododecane, isononane, tetrahydrofuran, 1,4- Examples include dioxane, cyclopentanone, ethyl acetate, and acetone.
The amount of the solvent used is 0.1 to 10 mol / L, preferably 0.1 to 3 mol / L, based on the total amount of the compounds of formula (4) and formula (5).

  The dehydrochlorinating agent can be widely used, and examples thereof include trimethylamine, diethylamine, triethylamine, potassium carbonate, calcium carbonate, sodium hydroxide, magnesium hydroxide, potassium hydroxide, and calcium hydroxide. The dehydrochlorinating agent may be added in an amount of 1.8 to 20 equivalents, preferably 2 to 10 equivalents, more preferably 2 to 6 equivalents, relative to the total amount of the compounds of formulas (8) and (9). desirable.

  The reaction temperature is preferably 0 to 150 ° C., more preferably 0 to 100 ° C., and particularly preferably 5 to 50 ° C. for 30 minutes to 24 hours, particularly 1 to 10 hours during the desalting reaction. Sometimes, it is usually carried out at a temperature of 20 to 150 ° C., further 20 to 120 ° C., particularly 60 to 80 ° C., for 30 minutes to 24 hours, particularly 1 to 10 hours.

[Production Method 3]
A third method for producing the mesogen / silicon compound copolymer of the present invention will be described.
In the presence of an acid catalyst in a solvent, the compound represented by the general formula (4) and the general formula (5) and the compound represented by the general formula (6) and / or the general formula (7) The mesogen / silicon compound copolymer of the present invention can also be produced by subjecting to a dehydration condensation reaction. In addition, in the said Formula (1), when either m and k are 0, it manufactures without using the compound represented by following formula (6) or (7).

  As the solvent, the same amount of the solvent described in the above production method 2 can be used.

As the acid catalyst, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and the like can be used.
The addition amount of the acid catalyst is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, still more preferably 0.10 to 5% by mass, and 0.20 to 3% by mass with respect to the solvent. Is particularly preferred.

  As reaction temperature, 90-160 degreeC is preferable, 100-150 degreeC is more preferable, 120-140 degreeC is still more preferable. If the reaction temperature is too high, side reactions such as decomposition tend to occur, and if it is too low, the progress of the reaction may be slow. The reaction time is 0.5 to 48 hours, preferably 2 to 15 hours.

  In a solvent, the compound represented by the general formula (4) and the formula (5), the compound represented by the general formula (6) and / or the formula (7), and an acid catalyst are added, and the temperature is 90 to 160 ° C. The mesogen / silicon compound copolymer of the present invention can be produced by performing reaction until water reaches 90% or more of the theoretical production amount, washing the reaction mixture with water, and performing distillation under reduced pressure.

  In addition, in the said manufacturing methods 1-3, the introduction amount of the compound represented by the said Formula (5) is 10-50 mol% among the total addition amount of the compound represented by the said Formula (4) and (5). It is preferable that it is, More preferably, it is 20-35 mol%. When the introduction amount of the compound represented by the formula (5) is small, the thermal conductivity may be lowered. When the introduction amount of the compound represented by the formula (5) is large, the dispersibility or solubility in the solvent is increased. May decrease.

  The amount of the compound represented by the above formula (6) and / or the formula (7) or the compound represented by the above formula (8) and / or the formula (9) may be introduced by the above formula (6) and / or Or it is represented by the said Formula (4) and Formula (5) with respect to the total number of moles of the carboxy group which the compound represented by Formula (7) or the said Formula (8) and / or Formula (9) has. The total number of moles of reactive functional groups possessed by the compound is 0.67 to 1.67, preferably 0.83 to 1.25. When the amount of the compound represented by formula (6) and / or formula (7), or the compound represented by formula (8) and / or formula (9) is large or too small, the molecular weight does not increase. There is a tendency.

  The production method of the mesogen / silicon compound copolymer of the present invention is not limited to the above method, and a known method can be used.

  In general, a resin having a large amount of mesogen exhibits a poor solubility in a solvent due to mesogen stacking, particularly by taking a random structure. However, the mesogen / silicon compound copolymer of the present invention is remarkably excellent in dispersibility in commonly used solvents. Specific examples of solvents that can be used include toluene, benzene, xylene, styrene, phenol, chloroform, carbon tetrachloride, hexane, cyclohexane, ethylcyclohexane, isododecane, isononane, tetrahydrofuran, 1,4-dioxane, and cyclopentanone. , Diethylamine, triethylamine, ethyl acetate, acetone and the like.

  The mesogen / silicon compound copolymer of the present invention can be suitably used as, for example, a heat dissipation material or a resin material for semiconductor devices and electronic components. Examples of the usage as a resin material include: a sealant or an adhesive used in the manufacture of a semiconductor device; a protective film material on the surface of an electronic component such as a diode, transistor, IC, and LSI; Coating film, passivation film and buffer coating film; α-ray shielding film such as LSI; Interlayer insulating film of multilayer wiring; Conformal coating of printed circuit board; Ion implantation mask;

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, Me represents a methyl group and Ph represents a phenyl group.

The compounds used in the examples are shown below.

[Example 1]
In a 500 mL flask equipped with a stirrer, a thermometer, a nitrogen displacement device, a Dean-Stark device and a reflux condenser, 60.00 g (0.322 mol) of the compound represented by the above formula (S-1) and the above formula ( 21.30 g (0.046 mol) of the compound represented by S-2), 85.66 g (0.372 mol) of the compound represented by the above formula (S-3), and 82.71 g (0.810 mol) of acetic anhydride. Then, the mixture was heated to 150 ° C. in a nitrogen gas atmosphere and stirred for 1 hour. Thereafter, the mixture was heated to 240 ° C., and further stirred for 2 hours to distill off about 90% of the theoretical acetic acid production amount, and then reduced in pressure at 240 ° C., and melt polymerization was carried out for 1.5 hours. . As a result, the obtained resin was designated as resin (1). This resin was subjected to high temperature GPC TSKgel GMH _HR- H (20) HT (7.8 mm ID x 30 cm, manufactured by Tosoh Corporation), flow rate 0.3 ml / min, eluent 1,2,4-trichlorobenzene, column The weight average molecular weight of the resin (1) was 1,800 as measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions at a temperature of 140 ° C. This was subjected to ¹ H-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis). As a result, it was found to be a compound represented by the following average structural formula. ^{The 1} H-NMR spectrum is shown in FIG.

[Example 2]
In a 500 mL flask equipped with a stirrer, a thermometer, a nitrogen displacement device, a Dean-Stark device and a reflux condenser, 33.16 g (0.180 mol) of the compound represented by the above formula (S-4) and the above formula ( 118.13 g (0.220 mol) of the compound represented by S-5), 21.10 g (0.182 mol) of the compound represented by the above formula (S-6), and a compound represented by the above formula (S-7). After adding 29.36 g (0.222 mol) and acetic anhydride 89.84 g (0.880 mol), the mixture was heated to 150 ° C. in a nitrogen gas atmosphere and stirred for 1 hour. Thereafter, the mixture was heated to 240 ° C., and further stirred for 2 hours to distill off about 90% of the theoretical acetic acid production amount, and then reduced in pressure at 240 ° C., and melt polymerization was carried out for 1.5 hours. . As a result, the obtained resin was named Resin (2). Gel permeation chromatography using GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a standard and monodisperse polystyrene as a standard under analysis conditions of flow rate 0.6 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. The weight average molecular weight of the resin (2) was 3,400 as measured by chromatography (GPC). This was subjected to ¹ H-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis). As a result, it was found to be a compound represented by the following average structural formula.

[Example 3]
In a 500 mL flask equipped with a stirrer, thermometer, nitrogen displacement device, Dean-Stark device and reflux condenser, 22.11 g (0.120 mol) of the compound represented by the above formula (S-1), 216.93 g (0.404 mol) of the compound represented by S-3), 32.50 g (0.280 mol) of the compound represented by the above formula (S-8), and 89.84 g (0.880 mol) of acetic anhydride. Then, the mixture was heated to 150 ° C. in a nitrogen gas atmosphere and stirred for 1 hour. Thereafter, the mixture was heated to 240 ° C., and further stirred for 2 hours to distill off about 90% of the theoretical acetic acid production amount, and then reduced in pressure at 240 ° C., and melt polymerization was carried out for 1.5 hours. . As a result, the obtained resin was designated as resin (3). Gel permeation chromatography using GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a standard and monodisperse polystyrene as a standard under analysis conditions of flow rate 0.6 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. The weight average molecular weight of the resin (3) was 3,690 as measured by chromatography (GPC). This was subjected to ¹ H-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis). As a result, it was found to be a compound represented by the following average structural formula.

[Example 4]
In a 2 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device, a Dean-Stark device and a reflux condenser, 578.46 g (1.25 mol) of the compound represented by the above formula (S-2), 230.30 g (1.25 mol) of the compound represented by S-9), 290.18 g (2.50 mol) of the compound represented by the above formula (S-6), and 561.50 g (5.50 mol) of acetic anhydride. Then, the mixture was heated to 150 ° C. in a nitrogen gas atmosphere and stirred for 3 hours. Thereafter, the mixture was heated to 260 ° C., and further stirred for 6 hours to distill off about 90% of the theoretical acetic acid production amount, and then the pressure was reduced at 260 ° C., and melt polymerization was carried out for 5 hours. As a result, the obtained resin was designated as resin (4). Gel permeation chromatography using GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a standard and monodisperse polystyrene as a standard under analysis conditions of flow rate 0.6 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. The weight average molecular weight of the resin (4) was 22,720 as measured by chromatography (GPC). This was subjected to ¹ H-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis). As a result, it was found to be a compound represented by the following average structural formula.

[Example 5]
In a 2 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux condenser, the compound represented by the above formula (S-9) 76.42 g (0.350 mol), the above formula (S-10). After adding 180.64 g (0.150 mol) of the compound represented by the formula, 200 g (1.98 mol) of triethylamine, and 1,000 g of toluene, the above formula was maintained while maintaining the solution at 5 to 15 ° C. in a nitrogen gas atmosphere. A solution in which 71.46 g (0.352 mol) of the compound represented by (S-11) and 32.09 g (0.152 mol) of the compound represented by the above formula (S-12) were uniformly mixed was added to the system. It was dripped. After dropping, the mixture was stirred for 3 hours, then heated to 60 ° C. and further stirred for 2 hours. The reaction mixture was filtered, washed with water, and unreacted products and by-products were removed under reduced pressure to obtain the resin of the present invention. The obtained resin was shown in the following formula, and this was designated as resin (5). Gel permeation chromatography using GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a standard and monodisperse polystyrene as a standard under analysis conditions of flow rate 0.6 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. The weight average molecular weight of the resin (5) was 3,200 as measured by chromatography (GPC). This was subjected to ¹ H-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis). As a result, it was found to be a compound represented by the following average structural formula.

[Example 6]
In a 2 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device, and a reflux condenser, 62.85 g (0.338 mol) of the compound represented by the above formula (S-1), and the above formula (S-13). After adding 61.08 g (0.113 mol) of the compound represented by the formula, 200 g (1.98 mol) of triethylamine, and 1,000 g of toluene, the above formula was maintained while maintaining the solution at 5 to 15 ° C. in a nitrogen gas atmosphere. A solution in which 101.00 g (0.378 mol) of the compound represented by (S-14) and 14.45 g (0.095 mol) of the compound represented by the above formula (S-15) were uniformly mixed was added to the system. It was dripped. After dropping, the mixture was stirred for 3 hours, then heated to 60 ° C. and further stirred for 2 hours. The reaction mixture was filtered, washed with water, and unreacted products and by-products were removed under reduced pressure to obtain the resin of the present invention. The obtained resin was shown in the following formula, and this was designated as resin (6). Gel permeation chromatography using GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a standard and monodisperse polystyrene as a standard under analysis conditions of flow rate 0.6 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. The weight average molecular weight of the resin (6) was 2,420 as measured by chromatography (GPC). This was subjected to ¹ H-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis). As a result, it was found to be a compound represented by the following average structural formula.

[Example 7]
In a 2 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux condenser, 138.18 g (0.75 mol) of the compound represented by the above formula (S-4), and the above formula (S-8). After adding 710.68 g (0.75 mol) of a compound represented by the formula, 516.07 g (5.10 mol) of triethylamine and 1,000 g of toluene, the solution was kept at 5 to 15 ° C. under a nitrogen gas atmosphere. A solution in which 229.44 g (1.50 mol) of the compound represented by the above formula (S-15) was uniformly mixed was dropped into the system. After dropping, the mixture was stirred for 3 hours, then heated to 80 ° C. and further stirred for 5 hours. The reaction mixture was filtered, washed with water, and unreacted products and by-products were removed under reduced pressure to obtain the resin of the present invention. The obtained resin was shown in the following formula, and this was designated as resin (7). Gel permeation chromatography using GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a standard and monodisperse polystyrene as a standard under analysis conditions of flow rate 0.6 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. The weight average molecular weight of the resin (7) was 20,120 as measured by chromatography (GPC). This was subjected to ¹ H-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis). As a result, it was found to be a compound represented by the following average structural formula.

[Example 8]
In a 2 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device, a Dean-Stark device and a reflux condenser, 73.70 g (0.400 mol) of the compound represented by the above formula (S-4), 45.68 g (0.100 mol) of the compound represented by S-16), 87.44 g (0.502 mol) of the compound represented by the above formula (S-17), 1,000 g of toluene, and 10 g of concentrated sulfuric acid were added. Then, it heated at 120 degreeC by nitrogen gas atmosphere, and stirred for 5 hours. After confirming distillation of 90% or more of the theoretical production amount, the reaction mixture was washed with water, and the low boiling point compound was distilled off under reduced pressure to obtain the resin of the present invention. The structure is shown in the following formula, and this is resin (8). Gel permeation chromatography using GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a standard and monodisperse polystyrene as a standard under analysis conditions of flow rate 0.6 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. The weight average molecular weight of the resin (8) was 2,000 as measured by chromatography (GPC). This was subjected to ¹ H-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis). As a result, it was found to be a compound represented by the following average structural formula.

[Example 9]
In a 2 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device, a Dean-Stark device and a reflux condenser, 48.88 g (0.263 mol) of the compound represented by the above formula (S-1), 47.50 g (0.088 mol) of a compound represented by S-13), 30.79 g (0.177 mol) of a compound represented by the above formula (S-17), and a compound represented by the above formula (S-18). After 29.36 g (0.177 mol), 1,000 g of toluene, and 10 g of concentrated sulfuric acid were added, the mixture was heated to 120 ° C. in a nitrogen gas atmosphere and stirred for 5 hours. After confirming distillation of 90% or more of the theoretical production amount, the reaction mixture was washed with water, and the low boiling point compound was distilled off under reduced pressure to obtain the resin of the present invention. The structure is shown in the following formula, and this is resin (9). This resin was subjected to high temperature GPC TSKgel GMH _HR- H (20) HT (7.8 mm ID x 30 cm, manufactured by Tosoh Corporation), flow rate 0.3 ml / min, eluent 1,2,4-trichlorobenzene, column The weight average molecular weight of the resin (9) was 3,550 as measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions at a temperature of 140 ° C. This was subjected to ¹ H-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis). As a result, it was found to be a compound represented by the following average structural formula.

[Example 10]
In a 2 L flask equipped with a stirrer, thermometer, nitrogen displacement apparatus, Dean-Stark apparatus and reflux condenser, 404.92 g (0.88 mol) of the compound represented by the above formula (S-2), 161.21 g (0.88 mol) of the compound represented by S-9), 231.21 g (1.75 mol) of the compound represented by the above formula (S-7), 1,000 g of toluene, and 25 g of concentrated nitric acid were added. Then, the mixture was heated to 150 ° C. in a nitrogen gas atmosphere and stirred for 10 hours. After confirming distillation of 90% or more of the theoretical production amount, the reaction mixture was washed with water, and the low boiling point compound was distilled off under reduced pressure to obtain the resin of the present invention. The structure is shown in the following formula, and this is resin (10). This resin was subjected to high temperature GPC TSKgel GMH _HR- H (20) HT (7.8 mm ID x 30 cm, manufactured by Tosoh Corporation), flow rate 0.3 ml / min, eluent 1,2,4-trichlorobenzene, column The weight average molecular weight of the resin (10) was 16,110 as measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions at a temperature of 140 ° C. This was subjected to ¹ H-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis). As a result, it was found to be a compound represented by the following average structural formula.

[Comparative Example 1]
In a 1 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device, a Dean-Stark device, and a reflux condenser, 186.21 g (1.00 mol) of the compound represented by the above formula (S-1), After adding 232.60 g (1.01 mol) of the compound represented by S-3) and 224.60 g (2.20 mol) of acetic anhydride, the mixture was heated to 150 ° C. in a nitrogen gas atmosphere and stirred for 1 hour. went. Thereafter, the mixture was heated to 240 ° C., and further stirred for 2 hours to distill off about 90% of the theoretical acetic acid production amount, and then reduced in pressure at 240 ° C., and melt polymerization was carried out for 1.5 hours. . As a result, the obtained resin was designated as a resin (11). This resin was subjected to high temperature GPC TSKgel GMH _HR- H (20) HT (7.8 mm ID x 30 cm, manufactured by Tosoh Corporation), flow rate 0.3 ml / min, eluent 1,2,4-trichlorobenzene, column The weight average molecular weight of the resin (11) was 3,740 as measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions at a temperature of 140 ° C. As a result of performing infrared absorption spectrum analysis (IR analysis) on this product, it was found to be a compound represented by the following average structural formula.

[Solubility test]
Each of the resins (1) to (11) obtained in Examples 1 to 10 and Comparative Example 1 was finely crushed, and 50 parts by mass were added to 100 parts by mass of each solvent shown in Tables 1 and 2, and a stirrer ( The mixture was stirred at 2,000 rpm for 20 minutes at room temperature (23 ° C.) with a rotation / revolution supermixer (ARE-250) manufactured by Shinky Co., Ltd., and the solubility was visually examined. The results are shown in Tables 1 and 2.

Claims (8)

A mesogen / silicon compound copolymer having a structure represented by the following average composition formula (1) and having a weight average molecular weight of 300 to 500,000.
(In the formula, R ¹ represents an alkylene group having 1 to 20 carbon atoms, an alkenylene group or an aralkylene group, and R ² and R ³ may be independently the same or different and have 1 to 20 carbon atoms. R ⁴ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, different from R ^1, and l and n each represent a positive number of less than 0.5, m Represents a positive number of 0.5 or less, k represents a positive number of 0 or 0.5, and l and n satisfy l + n = 0.4 to 0.6, and m and k are m + k = 0. 4 to 0.6, provided that l + n + m + k = 1 A and B each independently represent a divalent atom or molecule selected from the group of —O—, —NH—, and —S—. D and E each independently represent a divalent atom or molecule selected from the group of -O-, * -R-NH-, * -R-S-, R represents a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms, X and Y are each independently a monovalent aliphatic hydrocarbon group, (meth) acrylic. Group, CN, OCH ₃ , NO ₂ , F atom, Cl atom, Br atom, or I atom, p and q each independently represents an integer of 0 to 4, Z represents independently a silicon atom; Indicate a divalent group.)   The mesogen / silicon compound copolymer according to claim 1, wherein k is a positive number of 0.5 or less in the average composition formula (1).   In the average composition formula (1), R ² , R ^Three The mesogen / silicon compound copolymer according to claim 1 or 2, wherein each independently represents an alkylene group having 1 to 18 carbon atoms. In the average composition formula (1), Z is a group represented by the following general formula (2) or (3), The mesogenic silicon compound according to any one of claims 1 to 3, Polymer.
(Wherein, a is an integer of 0 to 300, b is an integer of 0 to 300. R ⁵ and R ⁶ are each independently monovalent carbon atoms having 1 to 10 carbon atoms which may be the same or different. Represents a hydrogen group, provided that R ⁵ and R ⁶ are not methyl groups at the same time.) It is a manufacturing method of the mesogen silicon compound copolymer of any one of Claims 1-4, Comprising: The compound represented by following General formula (4) and following General formula (5) is reacted with acetic anhydride. is, after acetylation, a compound represented by following general formula in which the following general formula (6) (6)及beauty under following general formula (7) with a compound represented by be de-acetic acid polycondensation A process for producing a mesogen-silicon compound copolymer characterized by the above.
(In the formula, A and B each represent a divalent atom or molecule selected from the group of -O-, -NH-, and -S-.)
(In the formula, D and E each independently represent a divalent atom or molecule selected from the group of —O—, * —R—NH—, * —R—S—, where * represents a phenyl group. R represents a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms, X and Y each independently represent a monovalent aliphatic hydrocarbon group, a (meth) acryl group, CN, OCH ₃ , NO ₂ , F atom, Cl atom, Br atom, or I atom, and p and q each represent an integer of 0 to 4. R ² and R ³ are each independently the same or It may be different and represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z represents a divalent group containing a silicon atom.)
(In the formula, R ¹ represents an alkylene group having 1 to 20 carbon atoms , an alkenylene group or an aralkylene group .)
(In the formula, R ⁴ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ⁴ has a structure different from R ^1. ) It is a manufacturing method of the mesogen and silicon compound copolymer of any one of Claims 1-4, Comprising: It represents with following General formula (4) and following General formula (5) in the presence of a dehydrochlorination agent. the compound with the compound represented by the following general formula (8) or the following general formula (8)及beauty under following general formula (9) with a compound represented by the mesogenic-silicon compound both which comprises reacting a A method for producing a polymer.
(In the formula, A and B each represent a divalent atom or molecule selected from the group of -O-, -NH-, and -S-.)
(In the formula, D and E each independently represent a divalent atom or molecule selected from the group of —O—, * —R—NH—, * —R—S—, where * represents a phenyl group. R represents a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms, X and Y each independently represent a monovalent aliphatic hydrocarbon group, a (meth) acryl group, CN, OCH ₃ , NO ₂ , F atom, Cl atom, Br atom, or I atom, and p and q each represent an integer of 0 to 4. R ² and R ³ are each independently the same or It may be different and represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z represents a divalent group containing a silicon atom.)
(In the formula, R ¹ represents an alkylene group having 1 to 20 carbon atoms , an alkenylene group or an aralkylene group .)
(In the formula, R ⁴ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ⁴ has a structure different from R ^1. ) It is a manufacturing method of the mesogen * silicon compound copolymer of any one of Claims 1-4, Comprising: It represents with following General formula (4) and following General formula (5) in presence of an acid catalyst. that compound, the compound represented by the following general formula (6) or the following general formula (6)及beauty under following general formula (7) with a compound represented by the mesogenic-silicon compound both which comprises reacting a A method for producing a polymer.
(In the formula, A and B each represent a divalent atom or molecule selected from the group of -O-, -NH-, and -S-.)
(In the formula, D and E each independently represent a divalent atom or molecule selected from the group of —O—, * —R—NH—, * —R—S—, where * represents a phenyl group. R represents a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms, X and Y each independently represent a monovalent aliphatic hydrocarbon group, a (meth) acryl group, CN, OCH ₃ , NO ₂ , F atom, Cl atom, Br atom, or I atom, and p and q each represent an integer of 0 to 4. R ² and R ³ are each independently the same or It may be different and represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z represents a divalent group containing a silicon atom.)
(In the formula, R ¹ represents an alkylene group having 1 to 20 carbon atoms , an alkenylene group or an aralkylene group .)
(In the formula, R ⁴ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ⁴ has a structure different from R ^1. ) The method for producing a mesogen / silicon compound copolymer according to claim 7 , wherein the acid catalyst is sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.