JPWO2010053186A1 - Siloxane-containing polyimide resin - Google Patents

Abstract

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

Description

  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 electronics field, aerospace field, and the like. 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).

JP 2004-051794 A

  According to the study by the present inventors, it has been found that the siloxane structure-containing polyimide resin into which the phenolic hydroxyl group has been introduced has a large change in elastic modulus with a change in temperature, resulting in a decrease in heat resistance. On the other hand, when it does not have a phenolic hydroxyl group, the reactivity with other thermosetting resins such as epoxy resins decreases.

  As a result of diligent research to solve the above problems, the present inventors have found that a siloxane structure-containing polyimide resin into which a hexafluoroisopropanol group is introduced has a small change in elastic modulus with a change in temperature and is excellent in heat resistance and other heat resistance. The inventors have found that the reactivity with the curable resin is also good and completed the present invention.

That is, the present invention includes the following contents.
(1) A polyimide resin having a hexafluoroisopropanol group and a siloxane structure.
(2) The following formulas (1) and (2);

(Wherein R1 represents a tetravalent organic group, R2 represents a divalent diamine residue having a hexafluoroisopropanol group, R3 represents a divalent siloxane diamine residue, and is represented by the formula (1)). The repeating number M in one molecule of the unit is an integer of 1 to 100, and the repeating number N in one molecule of the repeating unit represented by the formula (2) is an integer of 1 to 100.)
The polyimide resin as described in said (1) which has a repeating unit represented by these.
(3) The above (1) or (2) produced by reacting a tetrabasic dianhydride represented by the formula (3) with a diamine compound represented by the formulas (4) and (5) ) The polyimide resin described.

(In the formula, R1 represents a tetravalent organic group, R2 represents a divalent diamine residue having a hexafluoroisopropanol group, and R3 represents a divalent siloxane diamine residue.)
(4) The tetravalent organic group represented by R1 is represented by the following formula:

(In the formula, A represents an oxygen atom, a sulfur atom, CO, SO, SO ₂ , 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 the above (2) or (3), which has any structure represented by:
(5) A divalent diamine residue having a hexafluoroisopropanol group represented by R2 is represented by the following formula:

(In the formula, A represents the same as above, J represents an integer of 1 to 4, K represents an integer of 1 to 6, P and Q each independently represents an integer of 0 to 2, and 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.
Polyimide resin in any one of said (2)-(4) which has either structure represented by these.
(6) The divalent siloxane diamine residue represented by R3 is represented by the following formula:

(Wherein R4 and R5 each independently represents an alkylene group having 1 to 5 carbon atoms, a phenylene group or an oxyalkylene group, and R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms, carbon An alkoxy group of 1 to 5 or a phenoxy group, a, b and c each independently represent 0 or an integer of 1 or more, and b + c ≧ 1, a + b + c ≧ 60. The hydrogen atom may be substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms.)
The polyimide resin according to the above (2) to (5) having a structure represented by:
(7) X represents the functional group equivalent number of the acid anhydride group of the tetrabasic acid dianhydride represented by the formula (3), and Y represents the functional group equivalent number of the amino group of all diamine compounds present in the reaction system. The polyimide resin according to the above (3), which is reacted so as to satisfy the relationship of 0 ≦ (X−Y) /X≦0.3.
(8) The polyimide resin according to any one of the above (1) to (7), wherein the proportion of the siloxane structure contained in the polyamide resin is 40 to 90% by weight.
(9) The polyimide resin according to any one of the above (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 50000.
(11) A resin composition containing the polyimide resin and thermosetting resin according to any one of (1) to (10) above.

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

  Hereinafter, the present invention will be described with reference to preferred embodiments.

  The polyimide resin of the present invention has a hexafluoroisopropanol group and a siloxane structure. The polyimide resin preferably has a repeating unit represented by the following formulas (1) and (2).

  In the formula, R1 represents a tetravalent organic group, R2 represents a divalent diamine residue having a hexafluoroisopropanol group, and R3 represents a divalent siloxane diamine residue. The number M of repeating units in one molecule of the repeating unit represented by the formula (1) is preferably an integer of 1 to 100 (1 ≦ M ≦ 100). Moreover, it is preferable that the repeating number N in 1 molecule of the repeating unit represented by Formula (2) is an integer of 1 or more and 100 or less (1 ≦ N ≦ 100).

  Examples of the tetravalent organic group represented by R1 include those having the following structures.

In the formula, A represents an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH (CH ₃ ), C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , or C (CCl ₃ ) ₂ . To express.
In the formula, a 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 diamine residue having a hexafluoroisopropanol group represented by R2 include those having the following structure.

  In the formula, A has the same meaning as described above. J shows the integer of 1-4. K represents an integer of 1 to 6. P and Q each independently represent an integer of 0 to 2, and 1 ≦ (P + Q) ≦ 4. In the formula, a 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 R3 include those having the following structures.

  In the formula, R4 and R5 each independently represent an alkylene group having 1 to 5 carbon atoms, a phenylene group or an oxyalkylene group, and R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms or a carbon number. An alkoxy group of 1 to 5 or a phenoxy group; a, b and c each independently represents 0 or an integer of 1 or more, and b + c ≧ 1 and a + b + c ≧ 60. In the formula, a 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 this invention can be manufactured by making the tetrabasic dianhydride represented by Formula (3) react with the diamine compound represented by Formula (4) and (5), for example.

  In the formula, R1, R2 and R3 have the same meaning as described above.

  The tetravalent organic group represented by R1 of the tetrabasic acid dianhydride represented by the formula (3) is as described above. Specific examples of the tetravalent organic group represented by R1 include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid. Dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- Benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) -bis- (phthalic dianhydride), 4 , 4′-oxydiphthalic dianhydride, 4,4 ′-(4,4′-isopropylidenediphenoxy) -bis- (phthalic dianhydride), 1,3-dihydro-1,3-dioxo-5 -Isobenzofurancarboxylic acid (1-methylethylidene) -di-4,1-phenylene ester, ethylene glycol bisanhydro trimellitate, 3,4,9,10-perylenetetracarboxylic 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 Anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclo Xene-1,2-dicarboxylic anhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan -1,3-dione and the like. These tetrabasic 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 those represented by the following formula.

In the formula, A represents an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH (CH ₃ ), C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , or C (CCl ₃ ) ₂ . To express. J shows the integer of 1-4. K represents an integer of 1 to 6. P and Q each independently represent an integer of 0 to 2, where 1 ≦ (P + Q) ≦ 4.
In the formula, a 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 formula (4-b), 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, each may be bonded to the same benzene ring, or may be bonded to different benzene rings.
The diamine compound represented by the formula (4-a) can be produced according to a known method described in International Publication No. 2006/043501. The diamine compound represented by the formula (4-c) can be produced according to a known method described in International Publication No. 2006/041115. The diamine compound represented by the formula (4-b) is prepared by reacting a corresponding naphthalenediamine compound with a hexagonal compound according to a known method described in International Publication No. 2006/043501 and International Publication No. 2006/041115. It can be produced by reacting fluoroacetone or hexafluoroacetone trihydrate and introducing a hexafluoroisopropanol group onto the naphthalene ring. These diamine compounds having a hexafluoroisopropanol group can be used in combination of two or more.

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

  In the formula, R4 and R5 each independently represent an alkylene group having 1 to 5 carbon atoms, a phenylene group or an oxyalkylene group, and R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms or a carbon number. An alkoxy group of 1 to 5 or a phenoxy group; a, b and c each independently represents 0 or an integer of 1 or more, and b + c ≧ 1 and a + b + c ≧ 60. In the formula, a 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).

  In the formula, Re and Rf each independently represent 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, For each, Re or Rf may be different.

  Examples of the diaminosiloxane represented by the formula (5a) include 1,3-bis (3-aminopropyl) -1,1,2,2-tetramethyldisiloxane, 1,3-bis (3-aminobutyl). ) -1,1,2,2-tetramethyldisiloxane, bis (4-aminophenoxy) dimethylsilane, 1,3-bis (4-aminophenoxy) tetramethyldisiloxane, 1,1,3,3-tetra Methyl-1,3-bis (4-aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetra Phenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetra Methyl-1,3- (2-aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3- Bis (4-aminobutyl) disiloxane, 1,3-dimethyl-1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane, 1,1,3,3,5,5-hexamethyl- 1,5-bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5 , 5-Tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5 -Aminopentyl) trisiloxane, , 1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5 -Bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-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, 1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane and the like. These diaminosiloxanes may be used alone or in combination of two or more.

  You may use together diamine compounds other than the diamine compound represented by Formula (4) and (5), combining 1 type (s) or 2 or more types. The diamine compound can be represented by the following formula (6).

  In the formula, R11 represents 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. For example, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diamino-2,5- Diamine compounds containing one benzene ring such as dimethylbenzene and 1,4-diamino-2,5-dihalogenobenzene, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3, , 4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 3,3'-aminodi Phenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 2,2′-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis (3-aminophenyl) hexafluoropropane, 2,2′- Bis (3-amino-4-methylphenyl) hexafluoropropane, 1,1′-bis (4-aminophenyl) cyclohexane, o-dianisidine, o-tolidine, 2,2′-dimethyl-4,4′-diamino Biphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 4,4′-di Minobenzanilide, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminobiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenyl ether, 3,3 ′ , 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 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-6-methylaniline), 3,3'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-di Methyl-4,4′-diaminodiphenyl ether, 3,3′-diethyl-4,4′-diaminodiphenyl ether, 3,3′-dimethoxy-4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4 '-Diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,3-diaminonaphthalene, etc. Diamine compounds containing two benzene rings, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4- (3-aminophenyl) benzene, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, α, α′-bis (4-aminophenyl) -1,3-diisopropylbenzene, etc. Diamine compound containing three benzene rings, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4 ′-(4-aminophenoxy) biphenyl, 4,4 ′ -(3-aminophenoxy) biphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) Benzene rings such as fluorene, 9,9-bis (4-amino-3-fluorophenyl) fluorene, 5,10-bis (4-aminophenyl) anthracene, 1,3-diaminopyrene, 1,6-diaminopyrene, etc. Diamine compounds containing 4 or more, diamine compounds having an alicyclic structure such as 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine), 1,4-diaminobutane, , 5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9 Diamino amines such as diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, diamine compounds having a linear hydrocarbon structure such as 1,12-diaminododecane, and trade name Versamine 551 (manufactured by Cognis Japan Co., Ltd.) Diamine compound having a structure, trade name Jeffamine D-230, D-400, D-2000, D-4000, XTJ-500, XTJ-501, XTJ-502, HK-511, XTJ-504, XTJ-542, Examples thereof include diamine compounds having a polyoxyalkylene diamine structure such as XTJ-533 and XTJ-536 (manufactured by Huntsman Corporation).

The diaminosiloxane represented by the formula (5) preferably has an NH ₂ equivalent in the range of 400 to 6000 g / mol, more preferably in the range of 400 to 2500 g / mol, and further in the range of 400 to 1000 g / mol. Are more preferred. When the NH ₂ equivalent is larger than this range, the hydrophobicity of the resin becomes too strong due to the large molecular weight of the siloxane structure and the compatibility with the thermosetting resin deteriorates. The difference in polarity of the siloxane part becomes too large, making it difficult to stably synthesize the resin. On the other hand, when the NH ₂ equivalent is smaller than this range, the molecular weight of the siloxane structure is small, and it is difficult to obtain sufficient flexibility. Moreover, the thing containing a phenyl group is preferable at the point with good miscibility with a thermosetting resin.

When the tetrabasic acid dianhydride represented by the formula (3) and the diamine compound represented by the formulas (4) and (5) are used together (the diamine compound represented by the formula (6) is used in combination, the formula (4) To the total of the diamine compounds represented by formula (6) is not particularly limited, and either one may be excessive, but preferably the molecular weight of the resulting resin is increased. From the viewpoint of improving mechanical properties, it is preferable that the total number of functional group equivalents of all diamine compounds used in the reaction is substantially equal to the number of functional group equivalents of tetrabasic acid dianhydride. Specifically, when the number of functional group equivalents of the acid anhydride group of the tetrabasic acid dianhydride used is X, and the number of functional group equivalents of the amino group of all amine compounds used is Y, 0 ≦ | (XY) The reaction is preferably performed under the condition of | /X≦0.3, and more preferably the reaction is performed under the condition of 0 ≦ | (XY) | /X≦0.1.
In addition, the functional group equivalent number X (mol) of the acid anhydride group is expressed by the formula X = B1 / A1, where A1 (g / mol) is the functional group equivalent of the acid anhydride group and B1 (g) is charged. Can be sought.
That is, the functional group equivalent represents the molecular weight of the compound per functional group, and the functional group equivalent number represents the number of functional groups per compound weight (charge 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), the charge amount is represented by B2 (g), and the formula (5). Functional group equivalent A3 (g / mol) of amino group of diaminosiloxane, charge amount B3, functional group equivalent A4 (g / mol) of amino group of diamine compound represented by formula (6), charge amount B4 ( g), Y = (B2 / A2) + (B3 / A3) + (B4 / A4). The diamine compound represented by the formula (6) is an optional component, and when it is not contained, (B4 / A4) = 0 in the above formula.

  On the other hand, the charging ratio of the diamine compounds of the formulas (4) and (5) is reflected in the content of the siloxane structure and the content of hexafluoroisopropanol groups (hereinafter referred to as HFA groups) in the obtained resin. Therefore, by arbitrarily setting these two values, the range of the charging ratio of the diamine compounds of formulas (4) and (5) is inevitably determined. First, the amount of the siloxane structure contained in the obtained resin is preferably 40 to 90% by weight, and more preferably 50 to 80% by weight. When the proportion of the siloxane structure is larger than 90% by weight, the resulting resin has high adhesiveness and is difficult to handle, and conversely when it is smaller than 40% by weight, the flexibility of the resin becomes poor.

  The content Z (% by weight) of the siloxane structure can be determined by the following formula: Z (% by weight) = {B3 / (B1 + B2 + B3 + B4-B5)} × 100, where B5 is the weight of water removed by imidization. . Here, B5 can be obtained by the equation B5 = 18 × W, where W is the smaller of the above X or Y values. Moreover, the diamine compound represented by Formula (6) is an arbitrary component, and when it is not contained, B4 = 0 in the above formula.

  Moreover, about the functional group equivalent of the HFA group of the polyimide resin obtained, it is preferable to become 1000-5000 g / mol, and it is more preferable to become 1500-4000 g / mol. Here, 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 when the resin composition using this resin is cured, the curing is insufficient. Become. On the other hand, if it is less than 1000 g / mol, the amount of HFA groups contained increases the crosslinking density when the resin composition is cured, and the content of the siloxane structure inevitably decreases. The flexibility of the cured product is reduced. The functional group equivalent V (g / mol) of the hexafluoroisopropanol group of the polyimide resin is V (g / mol) = (B1 + B2 + B3 + B4-B5) ÷ (B2 / H) where the HFA group equivalent of the HFA group-containing diamine compound is H. ). The diamine compound represented by 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 dicarboxyl group in which an amino group, an acid anhydride group or an acid anhydride group is ring-opened, although it varies depending on the reaction ratio of the tetrabasic acid dianhydride and the diamine compound.

  Although reaction operation is not specifically limited, For example, performing heat | fever dehydration imidation in a polymerization solution is more preferable from the simplicity of work. Specifically, first, under an inert gas atmosphere, a solvent azeotropic with water such as toluene or xylene is added to a solvent in which a diamine compound having a hexafluoroisopropanol group and a siloxane diamine are dissolved. Next, tetrabasic acid dianhydride is added and reacted at 80 ° C. or lower, preferably 0 to 50 ° C. for about 1 to 24 hours to obtain a polyamic acid solution. The obtained polyamic acid solution is heated at 100 to 200 ° C., preferably 150 to 200 ° C., and the polyimide solution can be obtained by ring-closing while removing water azeotropically with toluene. At this time, the reaction was completed when it was confirmed that almost the theoretical amount of water was distilled off and that no outflow of water was observed. On the other hand, apart from this method, the polyamic acid dehydration ring closure reaction can also be carried out at a low temperature using an acetic anhydride / pyridine mixed solution.

  The reaction solvent used in the reaction is not particularly limited as long as it does not react with the raw material and the obtained resin. For example, tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, α-methyl- γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, ethylene carbonate, propylene carbonate, ethyl cellosolve acetate, butyl cellosolve acetate, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl isobutyl ketone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide and the like can be mentioned, preferably cyclohexanone, γ-butyrolac Tons. These solvents may be used alone or in combination of two or more. In particular, it is more preferable to use an aromatic hydrocarbon solvent such as petroleum naphtha in combination with a solvent such as cyclohexanone or γ-butyrolactone.

  Further, the obtained polyimide resin solution can be put into a poor solvent such as water or methanol to precipitate the polymer, and further dried, and then re-dissolved in a solvent suitable for the use.

  The number average molecular weight of the polyimide of the present invention is preferably in the range of 9000 to 50000, and 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 (polystyrene conversion). Specifically, the number average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L is measured at a column temperature of 40 ° C. using a solution of 0.4% by weight of lithium bromide dissolved in N-methylpyrrolidone as a mobile phase, and can be calculated using a standard polystyrene calibration curve. .

  By mixing a thermosetting resin with the siloxane-containing imide resin (A) thus obtained, a thermosetting resin composition having a small curing shrinkage, high flexibility, high heat resistance, and adhesiveness is obtained. Obtainable. 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 an epoxy resin having two or more glycidyl groups is more preferable. Furthermore, you may add the hardening | curing agent, hardening accelerator, etc. of an epoxy resin.

  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. For example, 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, polypropylene glycol, phthalic acid, isophthalic acid, tetrahydrophthal Glycidyl type (including methyl glycidyl type) epoxy resins such as glycidyl groups substituted with active hydrogen bonded to nitrogen atoms such as glycidyl ethers of carboxylic acids such as acids, aniline and isocyanuric acid, epoxy olefin bonds in the molecule Vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-ethylene Xy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane and other alicyclic epoxy resins, glycidyl ethers of paraxylylene-modified phenol resins, glycidyl ethers of metaxylylene and paraxylylene-modified phenol resins, terpene-modified phenols Resin glycidyl ether, dicyclopentadiene modified phenolic resin glycidyl ether, cyclopentadiene modified phenolic resin glycidyl ether, polycyclic aromatic ring modified phenolic resin glycidyl ether, naphthalene ring-containing phenolic resin glycidyl ether, biphenyl type epoxy resin, etc. These may be used alone or in combination of two or more.

  It should be noted that a monoepoxy compound may be appropriately used in combination with an epoxy compound having at least two epoxy groups in one molecule. Examples of the monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, Examples include ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide, dodecene oxide and the like. Moreover, the epoxy resin to be used is not necessarily limited to only one type, and two or more types can 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 cures an epoxy resin. For example, a phenol compound, a carboxylic acid compound, an acid anhydride compound, an amine compound, Examples include benzoxazine resins, amine imide resins, and cyanate ester compounds. Among these curing agents, phenolic curing agents are particularly preferable.

  As a phenol type compound, what has a 2 or more phenol group is preferable. For example, bisphenol A, bisphenol F, bisphenol S, resorcinol, phenol novolac resin, cresol novolac resin, paraxylylene modified phenol resin, metaxylylene / paraxylylene modified phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, cyclopentadiene modified phenol resin , Polycyclic aromatic ring-modified phenol resin, naphthalene ring-containing phenol resin, biphenyl type phenol resin, triazine structure-containing phenol novolak resin, and the like, and these can be used alone or in admixture of two or more.

  As the carboxylic acid compound, those having two or more carboxyl groups are preferred. Examples include organic acids such as terephthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, pyromellitic acid, trimellitic acid, methyl nadic acid, dodecyl succinic acid, chlorendic acid, maleic acid, and adipic acid. It can be used alone or in combination of two or more.

  As the acid anhydride compound, those having one or more acid anhydride groups are preferable. Examples include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, maleic anhydride, etc. These can be used alone or in admixture of two or more.

  The amine compound is used as a curing agent for causing an addition reaction with the epoxy resin or anionic polymerization of the epoxy resin itself. For example, tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6- (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2 -IM- which is an imidazole silane compound having both imidazole and silanol moieties, and imidazoles such as undecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, etc. 1000 (Nikko Metal Co., Ltd.) and IS-1000 (Nikko Metal Co., Ltd.), or 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4 ′ -Diaminodiphenyl ether, 4,4'-diaminobenzophenone, , 3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylmethane, Aromatic amine compounds such as 3,3′-aminodiphenylmethane and 3,4′-diaminodiphenylmethane; aliphatic amine compounds such as m-xylylenediamine, diethylenetriamine and tetraethylenepentamine; and melamine resins, 2 -Triazine compounds such as 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 Chemicals Co., Ltd.).

  The amine imide compound is obtained by reacting a maleimide compound and an amine compound, and in particular, one having two or more secondary amino groups is preferable. For example, Techmite E2020 (manufactured by Printec Co., Ltd.), etc. Is mentioned.

  As the cyanate ester-based 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 Co., Ltd.

  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, tetraphenylphosphonium tetraphenylborate, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6- (dimethylaminomethyl) ) Tertiary amines such as phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole And imidazoles such as dicyandiamide.

  The compounding amount of the thermosetting resin in the resin composition varies depending on its specific type, but generally (A) 100 parts by mass of the polyimide resin (B) the thermosetting resin is It is preferable that it is 1-200 mass parts, More preferably, it is 5-100 mass parts. If the blending amount of the thermosetting resin is too small, curing may be insufficient and chemical resistance and heat resistance may be inferior, and if too large, flexibility may be insufficient. Moreover, the chemical equivalent ratio of the total of the epoxy resin curing agent and the siloxane-containing polyimide having an HFA group in the structure with respect to the epoxy resin is not particularly limited, but is preferably set in the range of 0.7 to 1.3. Is more preferably 0.8 to 1.2. By limiting to this range, the unreacted content of each functional group can be suppressed, and chemical resistance, electrical characteristics, etc. can be improved.

  If necessary, a filler can be further added to the resin composition of the present invention. The filler may be either an organic filler or an inorganic filler. Any two or more kinds of fillers can be mixed and used. Although the compounding quantity of an inorganic filler is not specifically limited, Preferably, it can add in 60 weight% or less in a thermosetting resin composition. If it exceeds 60% by weight, the flexibility of the cured product of the resin composition tends to be impaired and fragile.

  Inorganic fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, titanate Examples include strontium, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Silica is particularly preferable. The inorganic filler preferably has an average particle size of 5 μm or less, and more preferably has an average particle size of 1 μm or less. Examples of the organic filler include acrylic rubber particles and silicone particles. The organic filler preferably has an average particle size of 5 μm or less, and more preferably has an average particle size of 1 μm or less. The average particle diameter can be measured with a laser diffraction / scattering particle size distribution measuring apparatus LA-500 (manufactured by Horiba, Ltd.).

  In the resin composition of the present invention, various resin additives, resin components other than the components (A) and (B), and the like can be blended as long as the effects of the present invention are exhibited. Examples of resin additives include thickeners such as Orben (manufactured by Shiraishi Kogyo Co., Ltd.) and Benton (manufactured by Leox), silicone-based, fluorine-based or acrylic antifoaming agents, leveling agents, imidazole-based, thiazole. -Based, triazole-based adhesion promoters, silane coupling agents and other surface treatment agents, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black and other colorants, phosphorus-containing compounds, bromine-containing compounds, hydroxylation Examples thereof include flame retardants such as aluminum and magnesium hydroxide, and antioxidants such as phosphorus antioxidants and phenolic antioxidants.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

(Synthesis of polyimide resin)
[Synthesis Example 1]
In a 500 mL separable flask equipped with a water content receiver connected with a reflux condenser, a nitrogen inlet tube, and a stirrer, 4,4 ′-(hexafluoroisopropylidene) -bis- (phthalic dianhydride) , 6FDA) 25 parts by mass, γ-butyrolactone 69.9 parts by mass, toluene 7 parts by mass, diaminosiloxane X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) 55.7 parts by mass (amine equivalent) 665), 2,6-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -1,5-naphthalenediamine (hereinafter referred to as HFA-NAP) 6.7 parts by mass In addition, the reaction was carried out by stirring at 45 ° C. for 2 hours under a nitrogen stream. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by weight of a polyimide resin (A1) having an HFA group (hexafluoroisopropanol group) was produced. In this case, the content of the siloxane structure in the resin is 65.2% by weight, and the HFA group equivalent is 3313 g / mol.

The obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. As a result, absorption of a hydroxyl group derived from an HFA group was confirmed at 3300-3500 cm ⁻¹ . In addition, 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, and the whole was adjusted to 5 g. When GPC measurement was performed using this adjustment solution, Mn = 11064 and Mw = 18769.

[Synthesis Example 2]
In a 500-mL separable flask equipped with a moisture receiver connected with a reflux condenser, a nitrogen inlet tube, and a stirrer, 32 parts by mass of 6FDA, 28.6 parts by mass of γ-butyrolactone, and 28.6 parts by mass of ipzol 150 Parts, 7 parts by mass of toluene, 50.1 parts by mass (amine equivalent 430) of diaminosiloxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.), 6.3 parts by mass of HFA-NAP, and 45 under nitrogen flow. The reaction was carried out with stirring at 2 ° C. for 2 hours. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by weight of a polyimide resin (A2) having an HFA group was produced. Note that ipzol is an aromatic high-boiling 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 applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. As a result, absorption of a hydroxyl group derived from an HFA group was confirmed at 3300-3500 cm ⁻¹ . In addition, 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, and the whole was adjusted to 5 g. When the GPC measurement was performed using this adjustment solution, it was Mn = 23086 and Mw = 35970.

[Synthesis Example 3]
In a 500 mL separable flask equipped with a moisture receiver connected with a reflux condenser, a nitrogen inlet tube, and a stirrer, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (hereinafter referred to as BTDA) 23 parts by mass, 30.9 parts by mass of γ-butyrolactone, 30.9 parts by mass of Ipsol 150, 7 parts by mass of toluene, 49.0 parts by mass of diaminosiloxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.) (Amine equivalent 430) was charged, and the reaction was carried out by stirring at 45 ° C. for 1 hour under a nitrogen stream, followed by 3,3′-bis (1-hydroxy-1-trifluoromethyl-2,2,2). -Trifluoroethyl) -4,4'-methylenedianiline (hereinafter referred to as HFA-MDA) was added in an amount of 6.1 parts by mass, and the reaction was performed by stirring at 45 ° C for 2 hours. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by weight of a polyimide resin (A3) having an HFA group was produced. 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, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. As a result, absorption of a hydroxyl group derived from an HFA group was confirmed at 3300-3500 cm ⁻¹ . In addition, 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, and the whole was adjusted to 5 g. When the GPC measurement was performed using this adjustment solution, it was Mn = 18914 and Mw = 38256.

[Synthesis Example 4]
In a 500 mL separable flask equipped with a moisture receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer, 20 parts by mass of BTDA, 70.9 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, diamino 61.5 parts by mass of siloxane X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) (amine equivalent 665) and 7.4 parts by mass of HFA-NAP were added and stirred at 45 ° C. for 2 hours under a nitrogen stream. The reaction was performed. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by weight of a polyimide resin (A4) having an HFA group was produced. 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 applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. As a result, absorption of a hydroxyl group derived from an HFA group was confirmed at 3300-3500 cm ⁻¹ . In addition, 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, and the whole was adjusted to 5 g. When GPC measurement was performed using this adjustment solution, Mn = 13135 and Mw = 35245.

[Synthesis Example 5]
In a 500 mL separable flask equipped with a moisture receiver connected with a reflux condenser, a nitrogen inlet tube, and a stirrer, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (hereinafter referred to as DSDA). ) 19 mass parts, γ-butyrolactone 22.7 mass parts, Ipsol 150 22.7 mass parts, toluene 7 mass parts, diaminosiloxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.) 30.9 mass Parts (amine equivalent 430), and stirred for 1 hour at 45 ° C. under a nitrogen stream. Then, 7.5 parts by mass of HFA-NAP was added and stirred for 2 hours at 45 ° C. to react. Went. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by weight of a polyimide resin (A5) having an HFA group was produced. 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 applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. As a result, absorption of a hydroxyl group derived from an HFA group was confirmed at 3300-3500 cm ⁻¹ . In addition, 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, and the whole was adjusted to 5 g. When GPC measurement was performed using this adjustment solution, Mn = 27337 and Mw = 50713.

[Synthesis Example 6]
In a 500 mL separable flask equipped with a moisture receiver connected with a reflux condenser, a nitrogen inlet tube, and a stirrer, 25 parts by mass of 6FDA, 68.1 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, diamino Add 58.4 parts by mass of siloxane X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) (amine equivalent 665), 1.8 parts by mass of 1,5-diaminonaphthalene (hereinafter referred to as NDA), and under nitrogen flow The reaction was carried out with stirring at 45 ° C. for 2 hours. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by weight of a polyimide resin (B1) having no phenol group and HFA group was produced. In this case, the content of the siloxane structure in the resin is 70.2% by weight.

The obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. confirmed. In addition, 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, and the whole was adjusted to 5 g. When GPC measurement was performed using this adjustment solution, Mn = 15974 and Mw = 30002.

[Synthesis Example 7]
In a 500 mL separable flask equipped with a moisture meter, a nitrogen inlet tube and a stirrer connected to a reflux condenser, 36 parts by mass of 6FDA, 19.6 parts by mass of γ-butyrolactone, and 29.3 parts by mass of ipzol 150 Part, 7 parts by mass of toluene, 51.5 parts by mass (amine equivalent 430) of diaminosiloxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.), and stirred for 1 hour at 45 ° C. under a nitrogen stream. Subsequently, 3.2 parts by mass of NDA, 16.4 parts by mass of γ-butyrolactone, and 6.7 parts by mass of ipsol 150 were added, and the reaction was performed by stirring at 45 ° C. for 2 hours. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by weight of a polyimide resin (B2) having no phenol group and HFA group was produced. In this case, the content of the siloxane structure in the resin is 58.6% by weight.

The obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. confirmed. In addition, 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, and the whole was adjusted to 5 g. When GPC measurement was performed using this adjustment solution, Mn = 33046 and Mw = 67573 were obtained.

[Synthesis Example 8]
In a 500 mL separable flask equipped with a moisture meter, a nitrogen inlet tube, and a stirrer connected to a reflux condenser, 23 parts by mass of BTDA, 29.5 parts by mass of γ-butyrolactone, and 29.5 parts by mass of ipsol 150 Part, 7 parts by mass of toluene, 49.1 parts by mass (amine equivalent 430) of diaminosiloxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.), and stirred for 1 hour at 45 ° C. under a nitrogen stream. Subsequently, 2.6 parts by mass of 4,4′-diamino-3,3′-dimethyldiphenylmethane (hereinafter referred to as C-100) was added, and the reaction was performed by stirring at 45 ° C. for 2 hours. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 50% by weight of a polyimide resin (B3) having no phenol group and HFA group was produced. In this case, the content of the siloxane structure in the resin is 68.0% by weight.

The obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. confirmed. In addition, 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, and the whole was adjusted to 5 g. When GPC measurement was performed using this adjustment solution, Mn = 38052 and Mw = 110120.

[Synthesis Example 9]
In a 500 mL separable flask equipped with a moisture receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer, 19 parts by mass of DSDA, 55.2 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, diamino 44.1 parts by mass (amine equivalent 665) of siloxane X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) was charged, and the reaction was performed by stirring at 45 ° C. for 1 hour under a nitrogen stream. , 3-bis (4-amino-3-hydroxyphenoxy) benzene (hereinafter referred to as AHPB) was added in an amount of 6.3 parts by mass, and the reaction was carried out at 45 ° C. for 2 hours. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by weight of a polyimide resin (B4) having a phenol group but not having an 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 1744 g / mol.

The obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. As a result, absorption derived from a phenolic hydroxyl group was confirmed at 3300 to 3500 cm ⁻¹ . In addition, 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, and the whole was adjusted to 5 g. When the GPC measurement was performed using this adjustment solution, it was Mn = 14430 and Mw = 28630.

[Synthesis Example 10]
In a 500 mL separable flask equipped with a moisture receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer, 19 parts by mass of DSDA, 54.5 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, diamino 44.1 parts by mass (amine equivalent: 665) of siloxane X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) was charged, and the reaction was performed by stirring at 45 ° C. for 1 hour under a nitrogen stream. , 3′-diamino-4,4′-dihydroxydiphenylsulfone (hereinafter referred to as DABS) was added in an amount of 5.4 parts by mass, and the reaction was carried out at 45 ° C. for 2 hours. Next, the reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by weight of a polyimide resin (B5) having a phenol group but no HFA group was prepared. In this case, the content of siloxane structure in the resin is 66.2% by weight; the OH equivalent is 1722 g / mol.

The obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried. When the infrared absorption spectrum of this coating film was measured by a reflection method, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ^−1. As a result, absorption derived from a phenolic hydroxyl group was confirmed at 3300 to 3500 cm ⁻¹ . In addition, 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, and the whole was adjusted to 5 g. When GPC measurement was carried out using this adjustment solution, Mn = 16631 and Mw = 30691.

(Preparation of resin composition)
An epoxy resin, a curing accelerator, a curing agent, and a siloxane-containing polyimide resin synthesized according to the above synthesis examples 1 to 10 are mixed in the blending amounts shown in Table 2 (indicated by parts by weight of solid content), and a centrifugal defoaming mixer (Product name “Nentaro Awatori”, manufactured by Shinky Co., Ltd.) was used for stirring and mixing to obtain a resin composition. In addition, phenol novolac type epoxy resin EP157 (manufactured by Japan Epoxy Resin Co., Ltd.) was used as the epoxy resin. Moreover, dicyclopentadiene modified phenolic resin DPP6115L (manufactured by Nippon Oil Co., Ltd.) was used as a curing agent, and imidazole P200 (manufactured by Japan Epoxy Resin Co., Ltd.) was used as a curing accelerator. In addition, a solvent was mixed and used as necessary.

(Cure cured film)
Next, after apply | coating the obtained resin composition on the PET film which gave the mold release process, and heating for 12 minutes at 75-120 degreeC, it heated at 180 degreeC for 90 minutes, and also became a 40 micrometers thick cured film. Obtained.

(Solvent resistance test)
The surface of the cured film was rubbed 5 times with a weight of 10 g using a cotton swab containing acetone, and the presence or absence of surface change was confirmed.
(Results) In Examples 6 to 10 and Comparative Examples 9 and 10, no surface change was observed (indicated by ◯ in Table 2). In Comparative Examples 6 to 8, color fading 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 in the same manner as described above were applied to a copper foil glossy surface so that the thickness upon drying was in the range of 40 to 100 μm. After heating at ˜120 ° C. for 12 minutes, it was further heated at 180 ° C. for 90 minutes to produce a cured film on the copper foil. The copper foil on which the cured film was formed was immersed in a ferric chloride solution and etched away, and then dried at 100 ° C. for 10 minutes to produce a cured film from which the copper foil was removed. The cured film from which the copper foil has been removed is subjected to a tensile test using a Tensilon universal testing machine (manufactured by A & D Co., Ltd.) in accordance with Japanese Industrial Standard (JIS K7127), and the elastic modulus before heat treatment is measured. did.

  On the other hand, the cured film with copper foil obtained by the above method was (1) 220 ° C in air for 30 minutes, (2) 250 ° C in air for 30 minutes, (3) 270 ° C in air for 30 minutes, respectively. Heat treatment was performed. The cured film with copper foil after the heat treatment was immersed in a ferric chloride solution, the copper foil was removed by etching, and then dried at 100 ° C. for 10 minutes to prepare a cured film from which the copper foil was removed. The cured film from which the copper foil has been removed is subjected to a tensile test with a Tensilon universal testing machine (manufactured by A & D Co., Ltd.) in accordance with Japanese Industrial Standard (JIS K7127), and cured after heat treatment under each condition. The elastic modulus of the film was measured.

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

  Hereinafter, the results of Tables 1 and 2 will be described. In the composition containing the siloxane structure-containing polyimide resin having neither hexafluoroisopropanol group (HFA group) nor phenol group, as shown in Comparative Examples 6 to 8 in Table 2, the solvent resistance is inferior. became. This is considered due to the low reactivity between the polyimide resin and the epoxy resin. On the other hand, in a siloxane structure-containing polyimide resin having a phenol group (Comparative Examples 4 and 5 in Table 1) and a composition containing the polyimide resin (Comparative Examples 9 and 10 in Table 2), the fluctuation range of the elastic modulus with temperature. Was large and the heat resistance was inferior. On the other hand, in the siloxane structure-containing polyimide resin of the present invention having an HFA group (Examples 1 to 5 in Table 1) and a composition containing the polyimide resin (Examples 6 to 10 in Table 2), the elastic modulus The fluctuation range due to temperature was small, and excellent heat resistance was exhibited. The result was excellent in solvent resistance.

  This application is based on Japanese Patent Application No. 2008-288151 filed in Japan, the contents of which are incorporated in full herein.

Claims (11)

  A polyimide resin having a hexafluoroisopropanol group and a siloxane structure. The following formulas (1) and (2);

(Wherein R1 represents a tetravalent organic group, R2 represents a divalent diamine residue having a hexafluoroisopropanol group, R3 represents a divalent siloxane diamine residue, and is represented by the formula (1)). The repeating number M in one molecule of the unit is an integer of 1 to 100, and the repeating number N in one molecule of the repeating unit represented by the formula (2) is an integer of 1 to 100.)
The polyimide resin of Claim 1 which has a repeating unit represented by these. The polyimide resin according to claim 1 or 2, which is produced by reacting a tetrabasic acid dianhydride represented by the formula (3) with a diamine compound represented by the formulas (4) and (5).

(In the formula, R1 represents a tetravalent organic group, R2 represents a divalent diamine residue having a hexafluoroisopropanol group, and R3 represents a divalent siloxane diamine residue.) The tetravalent organic group represented by R1 is represented by the following formula:

(In the formula, A represents an oxygen atom, a sulfur atom, CO, SO, SO ₂ , 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 of Claim 2 or 3 which has either structure represented by these. A divalent diamine residue having a hexafluoroisopropanol group represented by R2 is represented by the following formula:

(In the formula, A represents the same as above, J represents an integer of 1 to 4, K represents an integer of 1 to 6, P and Q each independently represents an integer of 0 to 2, and 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.
The polyimide resin of any one of Claims 2-4 which has either structure represented by these. The divalent siloxane diamine residue represented by R3 has the following formula:

(Wherein R4 and R5 each independently represents an alkylene group having 1 to 5 carbon atoms, a phenylene group or an oxyalkylene group, and R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms, carbon An alkoxy group of 1 to 5 or a phenoxy group, a, b and c each independently represent 0 or an integer of 1 or more, and b + c ≧ 1, a + b + c ≧ 60. The hydrogen atom 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 2 to 5, which has a structure represented by:   When the functional group equivalent number of the acid anhydride group of the tetrabasic acid dianhydride represented by the formula (3) is X, and the functional group equivalent number of amino groups of all diamine compounds present in the reaction system is Y The polyimide resin according to claim 3, wherein the reaction is performed so as to satisfy a relationship of 0 ≦ (X−Y) /X≦0.3.   The ratio of the siloxane structure contained in a polyamide resin is 40 to 90 weight%, The polyimide resin of any one of Claims 1-7.   The polyimide resin according to any one of claims 1 to 8, wherein a functional group equivalent of a hexafluoroisopropanol group contained in the polyimide resin is 1000 to 5000 g / mol.   The polyimide resin according to any one of claims 1 to 9, having a number average molecular weight of 9000 to 50,000.   The resin composition containing the polyimide resin and thermosetting resin of any one of Claims 1-10.