KR101690544B1 - Siloxane-containing polyimide resin - Google Patents

Abstract

A polyimide resin having a hexafluoroisopropanol group and a siloxane structure is a polyimide resin having a small temperature change in the modulus of elasticity, excellent heat resistance, and good reactivity with other thermosetting resins.

Description

[0001] Siloxane-containing polyimide resin [0002]

The present invention relates to a polyimide resin having a hexafluoroisopropanol group and a siloxane structure.

Polyimide resins having excellent heat resistance are widely used in the fields of electronics and aerospace. On the other hand, a material having both heat resistance and low elasticity has been developed by introducing a siloxane structure into the polyimide resin. For example, a polyimide resin having a siloxane structure in which a phenolic hydroxyl group is introduced to impart reactivity with an epoxy resin is known (Patent Document 1).

Patent Document 1: JP-A-2004-051794

According to the studies of the present inventors, it has been found that the polyimide resin containing the siloxane structure incorporating the phenolic hydroxyl group has a large change in the modulus of elasticity with the change in temperature, thereby deteriorating the heat resistance. On the other hand, when the epoxy resin does not have a phenolic hydroxyl group, the reactivity with other thermosetting resins such as an epoxy resin is lowered.

DISCLOSURE OF THE INVENTION As a result of intensive studies for solving the above problems, the inventors of the present invention have found that a polyimide resin containing a hexafluoroisopropanol group has a small change in modulus of elasticity as a function of temperature and excellent heat resistance, And the present invention has been completed.

That is, the present invention includes the following contents.

(1) A polyimide resin having a hexafluoroisopropanol group and a siloxane structure.

(2) The polyimide resin according to the above (1), which has repeating units represented by the following formulas (1) and (2).

In the above Formulas 1 and 2,

R1 is a tetravalent organic group,

R2 is a divalent diamine residue having a hexafluoroisopropanol group,

R3 is a divalent siloxane diamine residue,

The repeating number M in one molecule of the repeating unit represented by the formula (1) is an integer of 1 or more and 100 or less,

The repeating number N in one molecule of the repeating unit represented by the formula (2) is an integer of 1 or more and 100 or less.

(3) The polyimide resin according to the above (1) or (2), which is produced by reacting a tetra-basic acid dianhydride of the formula (3) with a diamine compound of the formulas (4) and (5).

In the above formulas (3), (4) and (5)

R1 is a tetravalent organic group,

R2 is a divalent diamine residue having a hexafluoroisopropanol group,

R3 is a divalent siloxane diamine residue.

(4) The polyimide resin according to (2) or (3), wherein the tetravalent organic group represented by R 1 has a structure of any one of the following formulas.

In the above formulas,

A is an oxygen atom, sulfur atom, CO, SO, SO _2, and _{CH 2, CH (CH 3)} , C (CH 3) 2, C (CF 3) 2, or C (CCl _{3) 2,}

The hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms.

(5) The polyimide resin according to any one of (2) to (4), wherein the divalent diamine residue having a hexafluoroisopropanol group represented by R 2 has a structure represented by any one of the following formulas:

In the above formulas,

A is the same as defined above,

J is an integer of 1 to 4,

K is an integer of 1 to 6,

P and Q are each independently an integer of 0 to 2, 1? (P + Q)? 4,

The hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms.

(6) The polyimide resin according to any one of (2) to (5), wherein the divalent siloxane diamine residue represented by R 3 has a structure represented by the following formula:

In the above formulas,

R4 and R5 each independently represent an alkylene group, a phenylene group or an oxyalkylene group having 1 to 5 carbon atoms,

R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenoxy group,

a, b and c each independently represents 0 or an integer of 1 or more, b + c? 1, a + b + c? 60,

The hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms.

(7) When the number of the functional group equivalent of the acid anhydride group of the tetrabasic acid dianhydride of the formula (3) is X and the number of functional groups equivalent of the amino group of all the diamine compounds in which the diamine compound is present in the reaction system is Y 0.3. ≪ RTI ID = 0.0 > (3) < / RTI >

(8) The polyimide resin according to any one of (1) to (7), wherein the proportion of the siloxane structure contained in the polyimide resin is 40 to 90% by weight.

(9) The polyimide resin according to any one of (1) to (8), wherein the functional group equivalent of the hexafluoroisopropanol group contained in the polyimide resin is 1000 to 5000 g / mol.

(10) The polyimide resin according to any one of (1) to (9), which has a number average molecular weight of 9000 to 50,000.

(11) A resin composition containing the polyimide resin and the thermosetting resin according to any one of (1) to (10).

According to the present invention, there is provided a polyimide resin containing a siloxane structure having both heat resistance and low elasticity, the polyimide resin having a small temperature change in the modulus of elasticity, excellent heat resistance and good reactivity with other thermosetting resins, and a resin composition thereof do.

Hereinafter, the present invention will be described on the basis of a preferred embodiment.

The polyimide resin of the present invention has a hexafluoroisopropanol group and a siloxane structure. It is preferable that the polyimide resin has repeating units represented by the following formulas (1) and (2).

Formula 1

(2)

In the above Formulas 1 and 2,

R1 is a tetravalent organic group,

R2 is a divalent diamine residue having a hexafluoroisopropanol group,

R3 is a divalent siloxane diamine residue,

The repeating number M in one molecule of the repeating unit represented by the formula (1) is preferably an integer of 1 or more and 100 or less (1? M? 100)

The repeating number N in one molecule of the repeating unit represented by the formula (2) is preferably an integer of 1 or more and 100 or less (1? N? 100).

Examples of the tetravalent organic group represented by R 1 include those having the following structures.

In the above formulas,

A is an oxygen atom, sulfur atom, CO, SO, SO _2, and _{CH 2, CH (CH 3)} , C (CH 3) 2, C (CF 3) 2, or C (CCl _{3) 2,}

The hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

As the divalent diamine residue having a hexafluoroisopropanol group represented by R 2, those having the following structures are exemplified.

In the above formulas,

A is the same as defined above,

J is an integer of 1 to 4,

K is an integer of 1 to 6,

P and Q are each independently an integer of 0 to 2, 1? (P + Q)? 4,

The hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

Examples of the divalent siloxane diamine residue represented by R 3 include those having the following structures.

In the above formulas,

R4 and R5 each independently represent an alkylene group, a phenylene group or an oxyalkylene group having 1 to 5 carbon atoms,

R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenoxy group,

a, b and c each independently represents 0 or an integer of 1 or more, b + c? 1, a + b + c? 60,

The hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

The polyimide resin of the present invention can be produced, for example, by reacting a tetrabasic acid dianhydride of the formula (3) with a diamine compound of the formulas (4) and (5).

(3)

Formula 4

Formula 5

In the above formulas (3), (4) and (5)

R1, R2 and R3 are the same as defined above.

The tetravalent organic group represented by R 1 in the tetrabasic acid dianhydride represented by the general formula (3) is as described above. Specific examples of the tetravalent organic group represented by R 1 include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3 ' 4,4'-biphenyltetracarboxylic dianhydride, 2,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ' , 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 4,4'- (hexafluoroisopropylene) -bis- (phthalic acid dianhydride), 4,4'-oxydiphthalic dianhydride, 4,4'- Dihydro-1, 3-dioxo-5-isobenzofurancarboxylic acid- (1- (4,4'-isopropylidene diphenoxy) (Ethylene glycol bis ananhydrotrimellitate, 3,4,9,10-perylene tetracarboxylic acid dianhydride, 9,9-bis (3,4- Dicarboxyphenyl) fluorene dianhydride, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester , 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 4- (2, Dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 5- (2,5-dioxotetrahydrofuryl) Cyclohexene-1,2-dicarboxylic acid anhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) [1,2-C] furan-1,3-dione, and the like. These tetrabasic acid dianhydrides can be used in combination of two or more.

Examples of the diamine compound having a hexafluoroisopropanol group represented by the formula (4) include the following formulas.

[Chemical Formula 4a]

(4b)

[Chemical Formula 4c]

In the above formulas (4a), (4b) and (4c)

A is an oxygen atom, sulfur atom, CO, SO, SO _2, and _{CH 2, CH (CH 3)} , C (CH 3) 2, C (CF 3) 2, or C (CCl _{3) 2,}

J is an integer of 1 to 4,

K is an integer of 1 to 6,

P and Q are each independently an integer of 0 to 2, 1? (P + Q)? 4,

The hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

In the formula (4b), the amino groups on the naphthalene ring may be bonded to the same benzene ring or may be bonded to different benzene rings. Similarly, when there are a plurality of hexafluoroisopropanol groups, they may be bonded to the same benzene ring or may be bonded to different benzene rings.

The diamine compound of formula (4a) can be prepared according to the known methods described in WO2006 / 0443501 pamphlet. The diamine compound of formula (4c) can be prepared according to a known method described in WO2006 / 041115 pamphlet. The diamine compound of the formula (4b) can be prepared by reacting the corresponding naphthalene diamine compound with hexafluoroacetone or hexafluoroacetone according to a known method described in the pamphlet of International Publication WO 2006/043501 and International Publication WO 2006/041115 pamphlet And reacting the trihydrate to introduce a hexafluoroisopropanol group onto the naphthalene ring. These diamine compounds having a hexafluoroisopropanol group can be used in combination of two or more.

As the diaminosiloxane of the formula (5), those represented by the following formulas are exemplified.

[Chemical Formula 5a]

In the above formula (5a)

R4 and R5 each independently represent an alkylene group, a phenylene group or an oxyalkylene group having 1 to 5 carbon atoms,

R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenoxy group,

a, b and c each independently represents 0 or an integer of 1 or more, b + c? 1, a + b + c? 60,

The hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

The siloxane structure in the present invention is preferably a structure represented by the following formula (5b).

[Chemical Formula 5b]

In Formula 5b,

Re and Rf are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, or a phenoxy group,

m is an integer of 60 or more, and Re or Rf may be different for each repeating unit.

Examples of the diaminosiloxane of the formula (5a) include 1,3-bis (3-aminopropyl) -1,1,2,2-tetramethyldisiloxane, 1,3-bis Tetramethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, bis (4-aminophenoxy) dimethylsilane, 1,3-bis (4-aminophenoxy) (4-aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl- , 3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl- , 3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl- , 3-bis (4-aminobutyl) disiloxane, 1,3-dimethyl-1,3-dimethoxy- 5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl- 1, 5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl- 1, 5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1, Tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetramethyl- 5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5 , 5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5-bis . These diaminosiloxanes may be used alone or in combination of two or more.

The diamine compounds other than the diamine compounds of the formulas (4) and (5) may be used alone or in combination of two or more. The diamine compound may be represented by the following formula (6).

In Formula 6,

R11 is a divalent organic group other than a divalent diamine residue having a hexafluoroisopropanol group and a divalent siloxane diamine residue.

The diamine compound is not particularly limited, and examples thereof include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4- Diamino-2,5-dimethylbenzene, and 1,4-diamino-2,5-dihalogenobenzene; diamine compounds containing one benzene ring such as 4,4'-diaminodiphenyl ether, 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 3,3'-diamine Aminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 2 Bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 1,1'- Di-, o-tridine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'- diaminobiphenyl, -Diaminobenzanilide, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 5,5'-tetramethyl-4,4'-diamino Diphenyl ether, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenyl methane, 3,3', 5,5'-tetraethyl-4,4'-diaminobiphenyl , 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 4 , 4'-methylene-bis (2,6-diisopropylaniline), 4,4'-methylene-bis (2-ethyl- Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-diethyl- , 4'-diaminodiphenyl ether, 3, 3'-dimethoxy-4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diamino Diamine compounds containing two benzene rings such as diphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene and 2,3-diaminonaphthalene, Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, Bis (3-aminophenyl) benzene,?,? '- bis (4-aminophenyl) -1,4-di Diamine compounds containing three benzene rings such as isopropylbenzene and?,? '- bis (4-aminophenyl) -1,3-diisopropylbenzene; diamine compounds containing three benzene rings such as 2,2-bis [4- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- -Bis [4- (3-aminophenoxy) phenyl] hexafluoropropane , 4,4'- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- ) Biphenyl, 4,4'- (3-aminophenoxy) biphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis Bis (4-aminophenyl) anthracene, 1,3-bis (4-amino-3-methylphenyl) fluorene, A diamine compound containing four or more benzene rings such as diaminopyrrole and 1,6-diaminopyrrene, a diamine compound containing at least 4 benzene rings such as 4,4'-methylenebis (cyclohexylamine), 4,4'- methylenebis (2-methylcyclohexyl Amines), and diamine compounds having an alicyclic structure such as 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, Diamine compounds having a linear hydrocarbon structure such as octane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane, D-2000, D-400, D-2000, D-4000, XTJ-500, XTJ-501, and the like, diamine compounds having a dimer diamine structure such as Sumin 551 (manufactured by Cognis Japan K.K.) And diamine compounds having a polyoxyalkylene diamine structure such as XTJ-502, HK-511, XTJ-504, XTJ-542, XTJ-533 and XTJ-536 (manufactured by Hantsman Corporation).

The diaminosiloxane of the formula (5) preferably has an NH ₂ equivalent of 400 to 6000 g / mol, more preferably 400 to 2500 g / mol, further preferably 400 to 1000 g / mol. When the NH ₂ equivalent is larger than this range, the hydrophobicity of the resin becomes excessively strong due to the high molecular weight of the siloxane structure, resulting in deterioration of compatibility with the thermosetting resin. In some cases, the resin itself may have a polarity difference between the imide portion and the siloxane portion Becomes too large and it becomes difficult to stably synthesize the resin. On the other hand, when the NH ₂ equivalent is smaller than this range, it is difficult to obtain sufficient flexibility because the molecular weight of the siloxane structure becomes small. Further, it is preferable to contain a phenyl group in view of good compatibility with a thermosetting resin.

The reaction ratio of the tetra-basic acid dianhydride represented by the general formula (3) to the diamine compound represented by the general formulas (4) and (5) in combination with the diamine compound represented by the general formula (6) is not particularly limited, , It is preferable that the sum of the number of functional group equivalents of all the diamine compounds used in the reaction and the sum of the number of functional groups of the quaternary acid 2 It is preferable that the number of functional group equivalents of the anhydride is almost equal. Specifically, when the number of the functional group equivalent of the acid anhydride group of the quaternary acid dianhydride to be used is X and the number of functional groups equivalent of the amino group of the entire amine compound to be used is Y, 0? | (XY) | / X? The reaction is preferably carried out under the condition of 0 < = (XY) | / X < / = 0.1.

The functional group equivalent number X (mol) of the acid anhydride group can be obtained by the formula X = B1 / A1, where A1 (g / mol) is the functional group equivalent of the acid anhydride group and B1 (g)

That is, the functional group equivalent refers to the molecular weight of the compound per functional group, and the functional group equivalent number refers to the number of functional groups per weight of the compound (injection amount).

Similarly, the functional group equivalent A2 (g / mol) of the amino group of the diamine compound containing the hexafluoroisopropanol group represented by the formula (4), B2 (g), the functional group equivalent of the amino group of the diaminosiloxane of the formula (5) (B2 / A2) + (B3 / A3) + (B4 / A4) where B3 is the injection amount, A4 is the functional group equivalent A4 of the amino group of the diamine compound of formula (6) . The diamine compound of formula (6) is an optional component, and when it is not contained, (B4 / A4) in the above formula becomes 0.

On the other hand, the injection ratio of the diamine compounds of the formulas (4) and (5) is reflected in the content of the siloxane structure in the obtained resin and the content of the hexafluoroisopropanol group (hereinafter referred to as HFA group) , The range of the injection rate of the diamine compound of the formulas (4) and (5) is necessarily determined. First, the amount of the siloxane structure contained in the resin to be obtained is preferably 40 to 90% by weight, and more preferably 50 to 80% by weight. When the ratio of the siloxane structure is larger than 90% by weight, the resulting resin becomes more sticky and difficult to handle. Conversely, when the proportion is smaller than 40% by weight, flexibility of the resin becomes insufficient.

(% By weight) = {B3 / (B1 + B2 + B3 + B4-B5)} 100 where the weight of water to be desorbed by imidization is B5, Can be obtained. Here, B5 is obtained by the formula of B5 = 18 x W, where W is the smaller of the values of X or Y described above. Further, the diamine compound of the formula (6) is an optional component, and when it is not contained, B4 in the above formula becomes 0.

The functional group equivalent of the HFA group of the obtained polyimide resin is preferably 1000 to 5000 g / mol, more preferably 1500 to 4000 g / mol. When the functional group equivalent of the HFA group is larger than 5000 g / mol, the amount of the HFA group in the resin is too small, so that the curing is insufficient when the resin composition using the resin is cured. On the other hand, when the amount is smaller than 1000 g / mol, the HFA group is included in a large amount, thereby increasing the crosslinking density when the resin composition is cured, and inevitably decreasing the content of the siloxane structure and reducing the flexibility of the cured product. The functional group equivalent V (g / mol) of the hexafluoroisopropanol group of the polyimide resin is represented by V (g / mol) = (B1 + B2 + B3 + B4- B5) / (B2 / H). The diamine compound of the formula (6) is an optional component, and when it is not contained, B4 = 0 in the above formula.

The terminal of the polyamide resin is considered to be a dicarboxylic group in which the amino group, acid anhydride group or acid anhydride group is ring-opened, although it varies depending on the reaction ratio of the tetrabasic acid dianhydride and the diamine compound.

Although the reaction operation is not particularly limited, for example, it is more preferable to conduct the heat dehydration imidization in the polymerization solution in terms of simplicity of operation. Specifically, first, in a solvent in which a diamine compound having a hexafluoroisopropanol group and a siloxane diamine are dissolved, an azeotropic solvent such as toluene or xylene is added in an inert gas atmosphere. Then, a quaternary acid dianhydride is added and reacted at 80 DEG C or less, preferably 0 to 50 DEG C for about 1 to 24 hours to obtain a polyamic acid solution. The obtained polyamic acid solution is heated to 100 to 200 ° C, preferably 150 to 200 ° C, and at this time, the polyimide solution can be obtained by ring-closing the water to be desorbed while azeotropically removing it with toluene. At this time, it is confirmed that almost the theoretical amount of water is removed by distillation and that the outflow of water does not appear. On the other hand, unlike this method, dehydration ring closure reaction of polyamic acid can also be carried out at a low temperature using a mixed acetic anhydride / pyridine solution.

The reaction solvent to be used in the reaction is not particularly limited as long as it can react with the raw material and the obtained resin, and examples thereof include tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, Butyrolactone,? -Valerolactone,? -Caprolactone,? -Caprolactone, ethylene carbonate, propylene carbonate, ethyl cellosolve acetate, butyl cell N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, and the like can be used in combination with other solvents such as benzene, toluene, xylene, , And preferably cyclohexanone, gamma -butyrolactone. These solvents may be used alone or in combination of two or more. Particularly, it is more preferable to use an aromatic hydrocarbon solvent such as petroleum naphtha in combination with a solvent such as cyclohexanone or? -Butyrolactone.

The obtained polyimide resin solution may be put into a poor solvent such as water or methanol to precipitate and precipitate the polymer, and after dried again, it may be reused in a solvent according to the application.

The number average molecular weight of the polyimide of the present invention is preferably in the range of 9000 to 50000, more preferably in the range of 10000 to 40000. The number average molecular weight is a value measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). Specifically, the number average molecular weight by the GPC method was measured by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring apparatus and Shodex K-800P / K-804L (manufactured by Showa Denko K.K. / K-804L as a mobile phase and 0.4% by weight of lithium bromide dissolved in N-methylpyrrolidone at a column temperature of 40 占 폚 and using a calibration curve of standard polystyrene.

By mixing the thermosetting resin with the siloxane-containing imide resin (A) thus obtained, it is possible to obtain a thermosetting resin composition exhibiting small curing shrinkage, high flexibility, high heat resistance and adhesiveness. At this time, it is preferable to select a thermosetting resin having a functional group capable of reacting with the HFA group contained in the resin (A) structure, and among these, an epoxy resin having two or more glycidyl groups is more preferable. It is also preferable to add an epoxy resin curing agent, a curing accelerator and the like.

The epoxy resin used in the embodiment of the present invention is not particularly limited as long as it contains two or more glycidyl groups. Examples thereof include glycidyl ethers of phenols such as bisphenol A, bisphenol F, bisphenol S, resorcinol, phenol novolak, cresol novolak, etc., glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol, Glycidyl ethers such as glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid, glycidyl ethers such as those obtained by substituting glycidyl groups for active hydrogen bonded to nitrogen atoms such as aniline and isocyanuric acid Epoxycyclohexene diepoxide obtained by epoxidizing an olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) Alicyclic epoxy resins such as cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, glycidyl ethers of paraxylene-modified phenol resins, Len A glycidyl ether of a phenol resin, a glycidyl ether of a phenol resin, a glycidyl ether of a terpene-modified phenol resin, a glycidyl ether of a dicyclopentadiene-modified phenol resin, a glycidyl ether of a cyclopentadiene- Glycidyl ether of a naphthalene ring-containing phenol resin, biphenyl-type epoxy resin, and the like. These may be used alone or in combination of two or more.

The monoepoxy compound may suitably be used in combination with an epoxy compound having at least two epoxy groups in one molecule. Examples of such monoepoxy compounds include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, Ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide, dodecene oxide, and the like. The epoxy resin to be used is not limited to one type alone, and two or more kinds of epoxy resins may be used in combination.

The epoxy resin curing agent used in the embodiment of the present invention is not particularly limited as long as it hardens the epoxy resin, and examples thereof include a phenol compound, a carboxylic acid compound, an acid anhydride compound, an amine compound, , An amine imide resin, and a cyanate ester compound. Among these curing agents, a phenol-based curing agent is more preferable.

As the phenol compound, those having two or more phenol groups are preferable. For example, there may be mentioned bisphenol A, bisphenol F, bisphenol S, resorcinol, phenol novolak resin, cresol novolac resin, paraxylylene modified phenol resin, meta-silylene paraxylene modified phenol resin, Phenolic resin, dicyclopentadiene-modified phenol resin, cyclopentadiene-modified phenol resin, polycyclic aromatic ring-modified phenol resin, naphthalene ring-containing phenol resin, biphenyl-type phenol resin and phenazine novolac resin containing triazine structure , Alone or in combination of two or more.

As the carboxylic acid compound, those having two or more carboxyl groups are preferable. Examples thereof include organic acids such as terephthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, pyromellitic acid, trimellitic acid, methylnadic acid, dodecylsuccinic acid, chloridic acid, maleic acid and adipic acid They may be used alone or in combination of two or more.

The acid anhydride compound preferably has at least one acid anhydride group. For example, there may be mentioned phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, methylnadic anhydride, dodecylsuccinic anhydride, anhydrous chloridic acid and maleic anhydride. They may be used alone or in combination of two or more.

The amine compound is used as a curing agent for causing an addition reaction with an epoxy resin or anion polymerization of the epoxy resin itself. For example, tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol and 2,4,6- (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl- Imidazoles such as imidazole, 2-undecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole and 1-cyanoethyl- IM-1000 (manufactured by Nikko Metal Industries Co., Ltd.) or IS-1000 (manufactured by Nikko Metal Industries Co., Ltd.), which is an imidazole silane compound having an imidazole moiety and a silanol moiety together, or 4,4'- Aminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4 '-Diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane , 3,3'-aminodiphenylmethane, 3,4'-diaminodiphenylmethane, and other aromatic amine-based compounds Or an aliphatic amine compound such as m-xylylenediamine, diethylenetriamine or tetraethylenepentamine, or a triazine compound such as a melamine resin or 2-vinyl-4,6-diamino-s-triazine , Dicyandiamide, and the like.

As the benzoxazine-based compound, those having two or more benzoxazine moieties are preferable, and examples thereof include Ba type benzoxazine and Bb type benzoxazine (manufactured by Shikoku Kasei Kogyo K.K.) .

As amine imide compounds, those obtained by reacting a maleimide compound with an amine compound are preferred, and those having two or more secondary amino groups are particularly preferable. For example, it is possible to use a methacrylic acid ester such as a tachymite E2020 (manufactured by Furintech Co., ] And the like.

As the cyanate ester compound, those having two or more cyanate groups are preferable, and examples thereof include Primaset BADCY, Primaset BA230S and Primaset LECY manufactured by Lonza Japan K.K.

The epoxy resin curing accelerator used in the embodiment of the present invention is not particularly limited. For example, phosphorus compounds such as triphenylphosphine, triphenylphosphonium triphenylborate, and tetraphenylphosphonium tetraphenylborate, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6- Dimethylaminomethyl) phenol, and other tertiary amines such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, Imidazoles such as methylimidazole and 1-cyanoethyl-2-methylimidazole, and dicyandiamide.

The blending amount of the thermosetting resin in the resin composition differs depending on the specific type, but generally, the thermosetting resin (B) is added in an amount of 1 to 200 parts by mass, preferably 100 to 200 parts by mass, per 100 parts by mass of the polyamide resin (A) Is preferably 5 to 100 parts by mass. If the blending amount of the thermosetting resin is too small, the curing will be insufficient and the chemical resistance and heat resistance may be lowered. If too much, the flexibility may be insufficient. The chemical equivalent ratio of the sum of the epoxy resin curing agent to the epoxy resin and the siloxane-containing polyimide having the HFA group in the structure is not particularly limited, but is preferably set in the range of 0.7 to 1.3, more preferably 0.8 to 1.2 desirable. By controlling the content in this range, it is possible to control the unreacted contents of each of the functional groups to a smaller extent and to make the chemical resistance, electric characteristics and the like better.

In the resin composition of the present invention, a filler may be added as required. The filler may be either an organic filler or an inorganic filler. Any two or more kinds of fillers may be used in combination. The blending amount of the inorganic filler is not particularly limited, but it can be preferably added in the range of 60 wt% or less in the thermosetting resin composition. If it exceeds 60% by weight, the flexibility of the cured product of the resin composition is impaired and tends to be broken.

As the inorganic filler, inorganic fillers such as silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, strontium titanate, calcium titanate, magnesium titanate , Bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Particularly, silica is preferable. The inorganic filler preferably has an average particle diameter of 5 mu m or less and more preferably 1 mu m or less. Examples of the organic filler include acrylic rubber particles and silicone particles. The average particle diameter of the organic filler is preferably 5 占 퐉 or less, more preferably 1 占 퐉 or less. The average particle diameter can be measured by a laser diffraction / scattering type particle size distribution analyzer LA-500 (trade name, manufactured by Horiba Seisakusho Co., Ltd.).

In the resin composition of the present invention, various resin additives, resin components other than the components (A) and (B), and the like may be blended to the extent that the effects of the present invention are exerted. Examples of the resin additive include thickeners such as allene (manufactured by Shiraishi Kogyo K.K.) and benton (manufactured by REOX), silicone-based, fluorine- or acrylic-based antifoaming agents, leveling agents, imidazole-based, thiazole- A surface treating agent such as a silane coupling agent, a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow or carbon black, a phosphorus containing compound, a bromine containing compound, a flame retardant such as aluminum hydroxide or magnesium hydroxide , Phosphorus-based antioxidants, and phenol-based antioxidants.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(Synthesis of polyimide resin)

[Synthesis Example 1]

(Hexafluoroisopropylene) -bis- (phthalic acid dianhydride) (hereinafter, referred to as 6FDA) was added to a 500 mL separable flask equipped with a reflux condenser, a nitrogen introducing tube and a stirrer, , 69.9 parts by mass of? -Butyrolactone, 7 parts by mass of toluene, 55.7 parts by mass of diaminosiloxane X-22-9409 (Shin-Etsu Chemical Industries, Ltd.) (Hereinafter referred to as " HFA-NAP ") was used in place of 2,6-bis (1-hydroxy-1 -trifluoromethyl-2,2,2- 6.7 parts by mass was added, and the mixture was reacted at 45 DEG C for 2 hours under a stream of nitrogen. Then, the reaction solution was heated to maintain the temperature at about 160 ° C, and the condensed water was azeotropically removed with toluene under a nitrogen stream. At the time when it was confirmed that a predetermined amount of water was accumulated in the water determination machine and no outflow of water was confirmed, the temperature was further raised and the mixture was stirred at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (A1) having an HFA group (hexafluoroisopropanol group) was prepared. In this case, the content of the siloxane structure in the resin was 65.2 wt%, and the HFA group equivalent was 3313 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 占 폚 to 120 占 폚 over 12 minutes, heated again at 180 占 폚 for 90 minutes, and dried. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption of the hydroxyl group derived from the HFA group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to adjust the total weight to 5 g. GPC measurement was carried out using this adjusting solution. As a result, Mn = 11064 and Mw = 18769 were obtained.

[Synthesis Example 2]

32.0 parts by mass of 6FDA, 28.6 parts by mass of? -Butyrolactone, 28.6 parts by mass of Ipzol 150, and 10.0 parts by mass of toluene were placed in a 500 ml separable flask equipped with a water content determining machine connected to a reflux condenser, , 50.1 parts by mass (amine equivalent: 430) of diaminosiloxane KF-8010 (Shin-Etsu Chemical Co., Ltd.) (amine equivalent: 430) and 6.3 parts by mass of HFA-NAP were added, and the mixture was stirred at 45 ° C for 2 hours Lt; / RTI > and the reaction was carried out. Then, the reaction solution was heated to maintain the temperature at about 160 ° C, and the condensed water was azeotropically removed with toluene under a nitrogen stream. At the time when it was confirmed that a predetermined amount of water was accumulated in the water determination machine and no outflow of water was confirmed, the temperature was further raised and the mixture was stirred at 200 ° C for 1 hour. Thereafter, the reaction mixture was cooled to completion, and a varnish containing 55 wt% of polyamide resin (A2) having HFA group was prepared. Ip sol is an aromatic high boiling point solvent manufactured by Idemitsu Kosan Co., Ltd. In this case, the content of the siloxane structure in the resin is 58.4% by weight and the HFA group equivalent is 3316 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 占 폚 to 120 占 폚 over 12 minutes, heated again at 180 占 폚 for 90 minutes, and dried. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption of the hydroxyl group derived from the HFA group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to adjust the total weight to 5 g. GPC measurement was carried out using this adjusting solution. As a result, Mn = 23086 and Mw = 35970 were obtained.

[Synthesis Example 3]

3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride (hereinafter referred to as BTDA) was added in a mass of 23 mass% to a 500 ml separable flask equipped with a reflux condenser, a nitrogen introduction pipe and a stirrer , 30.9 parts by mass of? -Butyrolactone, 30.9 parts by mass of Ipzol 150, 7 parts by mass of toluene, 49.0 parts by mass of diaminosiloxane KF-8010 (Shin-Etsu Chemical Industries, Ltd.) And the reaction was carried out at 45 DEG C for 1 hour under a nitrogen stream. Then, 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2 -Trifluoroethyl) -4,4'-methylene dianiline (hereinafter referred to as HFA-MDA) was added in an amount of 6.1 parts by weight, and the mixture was stirred at 45 ° C for 2 hours to carry out the reaction. Then, the reaction solution was heated to maintain the temperature at about 160 ° C, and the condensed water was azeotropically removed with toluene under a nitrogen stream. At the time when it was confirmed that a predetermined amount of water was accumulated in the water determination machine and no outflow of water was confirmed, the temperature was further raised and the mixture was stirred at 200 ° C for 1 hour. Thereafter, the resultant mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (A3) having an HFA group was prepared. In this case, the content of the siloxane structure in the resin is 64.9% by weight and the HFA group equivalent is 3271 g / mol.

The obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C to 120 ° C over 12 minutes, heated again at 180 ° C for 90 minutes, and dried. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption of the hydroxyl group derived from the HFA group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to adjust the total weight to 5 g. As a result of GPC measurement using this adjusting solution, Mn = 18914 and Mw = 38256.

[Synthesis Example 4]

A 500 mL separable flask equipped with a reflux condenser, a nitrogen inlet tube, and a stirrer was charged with 20 parts by mass of BTDA, 70.9 parts by mass of? -Butyrolactone, 7 parts by mass of toluene, 10 parts by mass of diaminosiloxane X (Amine equivalent 665) and 7.4 parts by mass of HFA-NAP were added and stirred at 45 占 폚 for 2 hours under a nitrogen stream to carry out the reaction . Then, the reaction solution was heated to maintain the temperature at about 160 ° C, and the condensed water was azeotropically removed with toluene under a nitrogen stream. At the time when it was confirmed that a predetermined amount of water was accumulated in the water determination machine and no outflow of water was confirmed, the temperature was further raised and the mixture was stirred at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (A4) having an HFA group was prepared. In this case, the content of the siloxane structure in the resin is 70.9% by weight and the HFA group equivalent is 2881 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 占 폚 to 120 占 폚 over 12 minutes, heated again at 180 占 폚 for 90 minutes, and dried. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption of the hydroxyl group derived from the HFA group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to adjust the total weight to 5 g. As a result of GPC measurement using this adjusting solution, Mn = 13135 and Mw = 35245.

[Synthesis Example 5]

3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride (hereinafter referred to as DSDA) was added to a 500 mL separable flask equipped with a reflux condenser, a nitrogen introduction pipe, and a stirrer, 19 22.7 parts by mass of? -Butyrolactone, 22.7 parts by mass of Ipzol 150, 7 parts by mass of toluene, 30.9 parts by mass of diaminosiloxane KF-8010 (Shin-Etsu Chemical Co., Ltd.) Amine equivalent: 430), and the mixture was stirred at 45 DEG C for 1 hour under a nitrogen stream to carry out the reaction. Subsequently, 7.5 parts by mass of HFA-NAP was added and the mixture was stirred at 45 DEG C for 2 hours. Then, the reaction solution was heated to maintain the temperature at about 160 ° C, and the condensed water was azeotropically removed with toluene under a nitrogen stream. At the time when it was confirmed that a predetermined amount of water was accumulated in the water determination machine and no outflow of water was confirmed, the temperature was further raised and the mixture was stirred at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (A5) having an HFA group was prepared. In this case, the content of the siloxane structure in the resin is 55.7% by weight, and the HFA group equivalent is 1810 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 占 폚 to 120 占 폚 over 12 minutes, heated again at 180 占 폚 for 90 minutes, and dried. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption of the hydroxyl group derived from the HFA group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to adjust the total weight to 5 g. As a result of GPC measurement using this adjusting solution, Mn = 27337 and Mw = 50713 were obtained.

[Synthesis Example 6]

To a 500 mL separable flask equipped with a water quantitative flow meter connected to a reflux condenser, a nitrogen introduction tube and a stirrer, 25 parts by mass of 6FDA, 68.1 parts by mass of? -Butyrolactone, 7 parts by mass of toluene, diaminosiloxane X , 1.8 parts by mass of 1,5-diaminonaphthalene (hereinafter referred to as NDA) was added in an amount of 58.4 parts by mass (amine equivalent 665), and 45 parts by mass of N, N'- RTI ID = 0.0 > C < / RTI > for 2 hours. Then, the reaction solution was heated to maintain the temperature at about 160 ° C, and the condensed water was azeotropically removed with toluene under a nitrogen stream. At the time when it was confirmed that a predetermined amount of water was accumulated in the water determination machine and no outflow of water was confirmed, the temperature was further raised and the mixture was stirred at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (B1) having no phenol group and HFA group was prepared. In this case, the content of the siloxane structure in the resin is 70.2% by weight.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 占 폚 to 120 占 폚 over 12 minutes, heated again at 180 占 폚 for 90 minutes, and dried. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 Respectively. Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to adjust the total weight to 5 g. As a result of GPC measurement using this adjusting solution, Mn = 15974 and Mw = 30002.

[Synthesis Example 7]

36.0 parts by mass of 6FDA, 19.6 parts by mass of? -Butyrolactone, 29.3 parts by mass of Ipzol 150, and 30.0 parts by mass of toluene were placed in a 500 ml separable flask equipped with a reflux condenser, , 51.5 parts by mass (amine equivalent: 430) of diaminosiloxane KF-8010 [Shin-Etsu Chemical Co., Ltd.] (amine equivalent: 430) were charged and reacted at 45 ° C for 1 hour under a nitrogen stream, Subsequently, 3.2 parts by mass of NDA, 16.4 parts by mass of? -Butyrolactone and 6.7 parts by mass of Ip sol 150 were added and stirred at 45 占 폚 for 2 hours to carry out the reaction. Then, the reaction solution was heated to maintain the temperature at about 160 ° C, and the condensed water was azeotropically removed with toluene under a nitrogen stream. At the time when it was confirmed that a predetermined amount of water was accumulated in the water determination machine and no outflow of water was confirmed, the temperature was further raised and the mixture was stirred at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (B2) having no phenol group and HFA group was prepared. In this case, the content of the siloxane structure in the resin is 58.6% by weight.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 占 폚 to 120 占 폚 over 12 minutes, heated again at 180 占 폚 for 90 minutes, and dried. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 Respectively. Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to adjust the total weight to 5 g. As a result of GPC measurement using this adjusting solution, Mn = 33046 and Mw = 67573.

[Synthesis Example 8]

23 parts by mass of BTDA, 29.5 parts by mass of? -Butyrolactone, 29.5 parts by mass of Ip sol 150, and toluene were added to a 500 ml separable flask equipped with a reflux condenser, a nitrogen introduction pipe and a stirrer, And 49.1 parts by mass (amine equivalent: 430) of diaminosiloxane KF-8010 (Shin-Etsu Chemical Co., Ltd.) were charged and stirred at 45 占 폚 for 1 hour under a nitrogen stream to carry out the reaction. Subsequently, 2.6 parts by mass of 4,4'-diamino-3,3'-dimethyldiphenylmethane (hereinafter referred to as C-100) was added, and the mixture was stirred at 45 ° C for 2 hours to carry out the reaction. Then, the reaction solution was heated to maintain the temperature at about 160 ° C, and the condensed water was azeotropically removed with toluene under a nitrogen stream. At the time when it was confirmed that a predetermined amount of water was accumulated in the water determination machine and no outflow of water was confirmed, the temperature was further raised and the mixture was stirred at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 50 wt% of a polyimide resin (B3) having no phenol group and HFA group was prepared. In this case, the content of the siloxane structure in the resin is 68.0% by weight.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 占 폚 to 120 占 폚 over 12 minutes, heated again at 180 占 폚 for 90 minutes, and dried. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 Respectively. Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to adjust the total weight to 5 g. GPC measurement was carried out using this adjusting solution. As a result, Mn = 38052 and Mw = 110120.

[Synthesis Example 9]

To a 500 mL separable flask equipped with a reflux condenser, a nitrogen introducing tube and a stirrer, 19 parts by mass of DSDA, 55.2 parts by mass of? -Butyrolactone, 7 parts by mass of toluene, 10 parts by mass of diaminosiloxane X -22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) (44.1 parts by mass, amine equivalent: 665) was charged and stirred at 45 ° C for 1 hour under a nitrogen stream. 6.3 parts by mass of bis (4-amino-3-hydroxyphenoxy) benzene (hereinafter referred to as AHPB) was added, and the mixture was stirred at 45 DEG C for 2 hours to carry out the reaction. Then, the reaction solution was heated to maintain the temperature at about 160 ° C, and the condensed water was azeotropically removed with toluene under a nitrogen stream. At the time when it was confirmed that a predetermined amount of water was accumulated in the water determination machine and no outflow of water was confirmed, the temperature was further raised and the mixture was stirred at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (B4) having a phenol group but no HFA group was prepared. In this case, the content of the siloxane structure in the resin is 65.3% by weight, and the OH equivalent is 1,744 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 占 폚 to 120 占 폚 over 12 minutes, heated again at 180 占 폚 for 90 minutes, and dried. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption from the phenolic hydroxyl group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to adjust the total weight to 5 g. As a result of GPC measurement using this adjusting solution, Mn = 14430 and Mw = 28630 were obtained.

[Synthesis Example 10]

19 parts by mass of DSDA, 54.5 parts by mass of? -Butyrolactone, 7 parts by mass of toluene, and 10 parts by mass of diaminosiloxane X (trade name, manufactured by Nippon Aerosil Co., Ltd.) were added to a 500 ml separable flask equipped with a water- -22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) (44.1 parts by mass, amine equivalent: 665) was charged and stirred at 45 ° C for 1 hour under a nitrogen stream to carry out the reaction. Diamino-4,4'-dihydroxydiphenyl sulfone (hereinafter referred to as DABS) was added in an amount of 5.4 parts by mass, and the mixture was stirred at 45 ° C for 2 hours to carry out the reaction. Then, the reaction solution was heated to maintain the temperature at about 160 ° C, and the condensed water was azeotropically removed with toluene under a nitrogen stream. At the time when it was confirmed that a predetermined amount of water was accumulated in the water determination machine and no outflow of water was confirmed, the temperature was further raised and the mixture was stirred at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (B5) having a phenol group but no HFA group was prepared. In this case, the content of the siloxane structure in the resin is 66.2 wt%, and the OH equivalent is 1722 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 占 폚 to 120 占 폚 over 12 minutes, heated again at 180 占 폚 for 90 minutes, and dried. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption from the phenolic hydroxyl group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to adjust the total weight to 5 g. GPC measurement was carried out using this adjusting solution. As a result, Mn = 16631 and Mw = 30691.

(Preparation of resin composition)

The epoxy resin, the curing accelerator, the curing agent, and the siloxane-containing polyimide resin synthesized according to Synthesis Examples 1 to 10 were mixed in the amounts shown in Table 2 (expressed in parts by weight of solid content) Manufactured by Shinki Kogyo Co., Ltd.), and the mixture was stirred to obtain a resin composition. As the epoxy resin, phenol novolak type epoxy resin EP157 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) was used. As the curing agent, a dicyclopentadiene-modified phenol resin DPP6115L (Shin-Nippon Sekiyu K.K.) was used, and an imidazole-based P200 (manufactured by Japan Epoxy Resin Co., Ltd.) was used as a curing accelerator . In addition, a solvent was mixed as needed.

(Preparation of Cured Film)

The resin composition obtained was applied onto a release-treated PET film, heated at 75 to 120 占 폚 for 12 minutes, and then heated again at 180 占 폚 for 90 minutes to obtain a 40 占 퐉 -thick cured film.

(Solvent resistance test)

The surface of the cured film was subjected to reciprocating rubbing five times with a weight of 10 g using a cotton swab containing acetone to confirm the presence or absence of surface change.

(result)

In Examples 6 to 10 and Comparative Examples 9 and 10, surface changes were not observed (indicated by o in Table 2). In Comparative Examples 6 to 8, color discontinuity occurred (indicated by X in Table 2).

(Heat resistance test)

The polyimide resin obtained in Synthesis Examples 1 to 10 and the resin composition prepared from the polyimide resin as described above were applied to a copper foil-lined surface so as to have a thickness in the range of 40 to 100 탆 at the time of drying, Lt; 0 > C for 12 minutes, and then heated again at 180 < 0 > C for 90 minutes to prepare a cured film on the copper foil. The copper foil on which the cured film was formed was immersed in a ferric chloride solution for etching removal, and then dried at 100 DEG C for 10 minutes to produce a cured film from which the copper foil was removed. The cured film from which the copper foil was removed was subjected to a tensile test in accordance with Japanese Industrial Standards (JIS K7127) using a Tenshiron universal testing machine (manufactured by Abrand Co., Ltd.), and the modulus of elasticity before heat treatment was measured.

On the other hand, the copper foil-cured film obtained by the above method was subjected to (1) heating at 220 DEG C for 30 minutes in air, (2) at 250 DEG C for 30 minutes in air, and (3) Heat treatment was performed. The copper foil-cured film after the heat treatment was immersed in a ferric chloride solution, and the copper foil was removed by etching and then dried at 100 DEG C for 10 minutes to produce a cured film from which the copper foil was removed. With respect to the cured film from which the copper foil was removed, a tensile test was conducted by a tensile all purpose tester (manufactured by Abrand Co., Ltd., Japan) according to Japanese Industrial Standards (JIS K7127) The elastic modulus of the film was measured.

Table 1 shows the results of the heat resistance test of the polyimide resin described in the table. Table 2 shows the results of the heat resistance test and the solvent resistance test of the composition of the polyimide resin and the thermosetting resin described in the table.

The results of Tables 1 and 2 will be described below. As shown in Comparative Examples 6 to 8 in Table 2, the composition containing the siloxane structure-containing polyimide resin having neither the hexafluoroisopropanol group (HFA group) nor the phenol group was poor in solvent resistance. This is thought to be due to the low reactivity of the polyimide resin and the epoxy resin. On the other hand, in the polyimide resin having a phenolic group-containing siloxane structure (Comparative Examples 4 and 5 in Table 1) and the composition containing the polyimide resin (Comparative Examples 9 and 10 in Table 2) And the heat resistance was deteriorated. On the other hand, in the polyimide resin (Examples 1 to 5 in Table 1) and the composition containing the polyimide resin (Examples 6 to 10 in Table 2) of the siloxane structure-containing polyimide resin of the present invention having an HFA group, The fluctuation width due to temperature was small and excellent heat resistance was exhibited. The results also showed excellent results.

This application is based on Japanese Patent Application No. 2008-288151, the contents of which are incorporated herein by reference.

Claims (11)

A polyimide resin having a hexafluoroisopropanol group and a siloxane structure, wherein the polyimide resin has repeating units represented by the following general formulas (1) and (2).
Formula 1

(2)

In the above Formulas 1 and 2,
R1 is a tetravalent organic group,
R2 is a divalent diamine residue having a hexafluoroisopropanol group,
R3 is a divalent siloxane diamine residue,
The number of repeating units of formula (1) in a molecule is an integer of 1 or more and 100 or less,
The number of repeating units of formula (2) in a molecule is an integer of 1 or more and 100 or less. The polyimide resin according to claim 1, which is prepared by reacting a tetrabasic acid dianhydride of the formula (3) with a diamine compound of the formulas (4) and (5).
(3)

Formula 4

Formula 5

In the above formulas (3), (4) and (5)
R1 is a tetravalent organic group,
R2 is a divalent diamine residue having a hexafluoroisopropanol group,
R3 is a divalent siloxane diamine residue. The polyimide resin according to any one of claims 1 to 3, wherein the tetravalent organic group represented by R 1 is represented by any one of the following formulas.

In the above formulas,
A is an oxygen atom, sulfur atom, CO, SO, SO _2, and _{CH 2, CH (CH 3)} , C (CH 3) 2, C (CF 3) 2, or C (CCl _{3) 2,}
The hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms. The polyimide resin according to any one of claims 1 to 3, wherein the divalent diamine residue having a hexafluoroisopropanol group represented by R 2 is represented by any of the following formulas.

In the above formulas,
A is an oxygen atom, sulfur atom, CO, SO, SO _2, and _{CH 2, CH (CH 3)} , C (CH 3) 2, C (CF 3) 2, or C (CCl _{3) 2,}
J is an integer of 1 to 4,
K is an integer of 1 to 6,
P and Q are each independently an integer of 0 to 2, 1? (P + Q)? 4,
The hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms. 3. The polyimide resin according to any one of claims 1 to 3, wherein the divalent siloxane diamine residue represented by R < 3 >

In the above formulas,
R4 and R5 each independently represent an alkylene group, a phenylene group or an oxyalkylene group having 1 to 5 carbon atoms,
R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenoxy group,
a, b and c each independently represents 0 or an integer of 1 or more, b + c? 1, a + b + c? 60,
The hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms. (XY) when the number of functional group equivalents of the acid anhydride group of the quaternary acid dianhydride of the formula (3) is X and the number of functional groups of the amino group of all the diamine compounds present in the reaction system is Y, / X < / = 0.3. The polyimide resin according to claim 1 or 2, wherein the proportion of the siloxane structure contained in the polyimide resin is 40 to 90% by weight. The polyimide resin according to claim 1 or 2, wherein the functional group equivalent of the hexafluoroisopropanol group contained in the polyimide resin is 1000 to 5000 g / mol. 3. The polyimide resin according to claim 1 or 2, wherein the polyimide resin has a number average molecular weight of 9000 to 50,000. A resin composition comprising the polyimide resin and the thermosetting resin according to claim 1 or 2. delete