JP2009179697A - Polyimide resin, polyimide resin composition, and method for producing polyimide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide resin, a polyimide resin composition containing it, and a method for producing the polyimide resin, which has excellent shelf life, exhibits high solubility to a solvent even after prolonged storage, and forms a coating film excellent in toughness, heat resistance, and dimensional stability. <P>SOLUTION: The polyimide resin has a structure represented by general formula (1). The polyimide resin composition contains the polyimide resin and an organic solvent. In the method for producing the polyimide resin, a diisocyanate compound and a cyclohexane tricarboxylic acid anhydride are brought into reaction with each other. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyimide resin, a polyimide resin composition containing the polyimide resin, and a method for producing the polyimide resin.

  Storage stability of resin compositions used in the electrical and electronic industries such as heat-resistant coating materials, electrical insulation materials such as printed wiring board interlayer insulation materials and semiconductor insulation materials, build-up materials, prepreg resins, and heat-resistant adhesives At the same time, it has been desired to improve the toughness and heat resistance of the resulting cured product. In particular, there is a strong demand for downsizing such as ultra-thin flexible film substrates and rigid substrates in the field of electronic equipment industries such as computers. In order to respond to this demand, mechanical strength in the protective layer, adhesive layer and insulating layer of the substrate (Toughness), heat resistance, and dimensional stability must be improved.

  For example, trimellitic anhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid dianhydride as a polyimide resin having excellent resin stability and excellent toughness, heat resistance, and dimensional stability of the resulting cured product An aromatic polyamideimide resin obtained by reacting 3,3′-dimethyl-4,4′-biphenyl diisocyanate and triethylenediamine is disclosed (for example, see Patent Document 1).

  However, since the polyamide-imide resin disclosed in Patent Document 1 is soluble only in a nitrogen-containing polar solvent such as NMP (N-methylpyrrolidone), there is a problem such as whitening due to hygroscopicity due to the influence of this solvent. Stability is insufficient. For this reason, the problem that the coating film (film) obtained using this resin cannot obtain the tough coating film and excellent electrical properties of the original imide resin arises.

  In addition, a block copolymerized polyimide resin is disclosed as a resin that improves such a hygroscopic problem by not using a nitrogen-containing polar solvent such as NMP (see, for example, Patent Document 2). Direct imidization is performed by dehydration reaction between an acid anhydride compound and a diamine compound, and a multistage reaction is performed for block copolymerization. Therefore, the manufacturing process of the polyimide resin is complicated, and there is an influence of residual moisture due to the dehydration reaction.

  Furthermore, a polyimide resin composition containing N-vinyl-2pyrrolidone as an organic solvent is disclosed (for example, see Patent Document 3). In the coating film obtained using the polyimide resin composition of Patent Document 3, the whitening phenomenon due to moisture absorption is reduced. However, N-vinyl-2pyrrolidone remains in the coating film, and N-vinyl-2pyrrolidone, which is also a polymerizable monomer, is polymerized during synthesis or drying, and the same physical properties are adversely affected. The problem remains.

Furthermore, a polyimide resin having a carboxyl group, a linear hydrocarbon structure, a urethane bond, and an isocyanurate structure is disclosed as a general-purpose organic solvent-soluble polyimide resin (see, for example, Patent Document 4). Although the polyimide resin disclosed in Patent Document 4 is soluble in a solvent other than NMP, the polyimide resin alone has poor film-forming properties and needs to be cured with an epoxy resin. Although a cured coating film obtained by using an epoxy resin in combination has excellent heat resistance, mechanical properties such as dimensional stability and toughness are not sufficient.

International Publication No. 2003/072639 Pamphlet International Publication No. 2003/06010 Pamphlet JP 2003-292779 A JP 2003-292575 A

  The present invention provides a polyimide resin having excellent storage stability, good solubility in a solvent even after long-term storage, and excellent toughness, heat resistance and dimensional stability when formed into a coating film, the polyimide A polyimide resin composition containing a resin and a method for producing the polyimide resin are provided.

As a result of intensive studies, the present inventors have found the following findings (1) to (4).
(1) A polyimide resin having a structure in which a cyclohexane ring is directly linked to an imide ring is excellent in storage stability and has good solubility in a solvent even after long-term storage.

  (2) A cured product such as a coating film obtained using the polyimide resin is excellent in toughness, heat resistance, and dimensional stability.

  (3) A cured product obtained using the resin composition containing the polyimide resin is also excellent in toughness, heat resistance, and dimensional stability.

(4) The polyimide resin can be easily produced by a production method in which a diisocyanate compound and cyclohexanetricarboxylic acid anhydride are reacted.
The present invention has been completed based on the above findings.

  That is, this invention provides the polyimide resin characterized by having the structure represented by General formula (1).

  Moreover, this invention provides the polyimide resin composition characterized by including the polyimide resin and organic solvent of any one of Claims 1-10.

  Furthermore, this invention provides the manufacturing method of the polyimide resin characterized by making a diisocyanate compound and a cyclohexane tricarboxylic acid anhydride react.

  The polyimide resin of the present invention is excellent in storage stability and has good solubility in a solvent even after long-term storage. Moreover, when the polyimide resin of the present invention or the polyimide resin composition of the present invention is formed into a coating film, for example, the coating film is excellent in toughness, heat resistance, and dimensional stability, and a coating agent, a wiring interlayer insulating film, Useful for adhesives and the like. Moreover, the polyimide resin from which the hardened | cured material excellent in storage stability and excellent in toughness, heat resistance, and dimensional stability can be easily manufactured with the manufacturing method of this invention.

  The polyimide resin of the present invention has a structure represented by the general formula (1). The polyimide resin of the present invention has a structure having an imide bond directly connected to a cyclohexane ring as represented by the general formula (1). By having such a structure, the polyimide resin of the present invention has a remarkable effect excellent in the balance of physical properties such as solvent solubility, toughness and heat resistance.

  Examples of the structure represented by the general formula (1) include structures represented by the general formula (2) to the general formula (2-1).

And as a polyimide resin which has a structure represented by the said General formula (1), the polyimide resin etc. which have a structure represented by General formula (5)-General formula (5-1) etc. are mentioned, for example.

  As the polyimide resin of the present invention, a polyimide resin having a structure represented by the general formula (2) is preferable because a coating film having excellent mechanical properties such as tensile strength and elongation can be obtained.

  The content of the structure of the general formula (1) such as the structure represented by the general formula (2) and the structure represented by the general formula (2-1) of the polyimide resin of the present invention is the polyimide of the present invention. 1 to 50% by weight based on the weight of the resin is preferably a polyimide resin having excellent solvent solubility, and a cured product having excellent mechanical properties such as heat resistance, tensile strength and elongation, and dimensional stability can be obtained. 2 to 40% by weight is more preferable, and 5 to 30% by weight is still more preferable.

  The content of the structure of the general formula (1) such as the structure represented by the general formula (2) and the structure represented by the general formula (2-1) of the polyimide resin of the present invention is the polyimide of the present invention. Based on the weight of the resin (in the polyimide resin), 1 to 50 mol% is a polyimide resin excellent in solvent solubility, and has excellent mechanical properties such as heat resistance, tensile strength and elongation, and dimensional stability. It is preferable from a thing obtained, 2-40 mol% is more preferable, and 5-30 mol% is still more preferable.

  Among the polyimide resins having the structure represented by the general formula (2), the polyimide resin having the structure represented by the general formula (5) is excellent in mechanical properties such as tensile strength and elongation and dimensional stability. It is preferable for such reasons.

  The polyimide resin of the present invention is preferably a polyimide resin containing the structure of the general formula (5) in an amount of 10 to 100% by weight based on the weight of the polyimide resin of the present invention for reasons of solubility and mechanical properties. 80% by weight is more preferred.

  The polyimide resin of the present invention is preferably a polyimide resin containing 5 to 100 mol% of the structure of the general formula (5) in the polyimide resin of the present invention for reasons of solubility and mechanical properties, more preferably 5 to 98 mol%. 10 to 98 mol% is more preferable, and 20 to 80 mol% is particularly preferable.

  In addition, the content of the structure of the general formula (5) in the polyimide resin of the present invention is such that the polyimide resin containing 5 to 100 mol% based on the monomer component constituting the polyimide resin of the present invention has solubility and mechanical properties. For reasons, it is preferably 5 to 98 mol%, more preferably 10 to 98 mol%, and particularly preferably 20 to 80 mol%.

  Furthermore, the polyimide resin of the present invention is preferable because the polyimide resin having the structure represented by the general formula (3) can provide a coating film having a low linear expansion coefficient and excellent dimensional stability.

  Examples of the structure represented by the general formula (3) include structures represented by the general formula (4) to the general formula (4-1).

  Among the polyimide resins of the present invention, the polyimide having the structure of the general formula (4) in the polyimide resin of the present invention is preferably 2 to 50 mol% for reasons of solvent solubility and linear expansion coefficient, and 10 to 40 mol%. More preferred.

  In addition, the content of the structure represented by the general formula (4) of the polyimide resin of the present invention is 2 to 50 mol% based on the molar amount of the monomer component constituting the polyimide resin of the present invention. It is preferable from the reason of a rate, and 10-40 mol% is more preferable.

  Among the polyimide resins having the structure represented by the general formula (4), the polyimide resin having the structure represented by the general formula (6) further provides a cured product having excellent mechanical properties such as tensile strength and elongation. This is preferable.

  Among the polyimide resins of the present invention, a polyimide resin containing 2 to 95 mol% of the structure of the general formula (6) in the polyimide resin of the present invention is preferable because it exhibits good mechanical properties, and 10 to 80 mol%. Is more preferable.

  In addition, the content of the structure of the general formula (6) of the polyimide resin of the present invention is 2 to 95 mol% based on the molar amount of the monomer component constituting the polyimide resin of the present invention, and exhibits good mechanical properties. Therefore, it is preferable, and 10 to 80 mol% is more preferable.

（式中ｎ、ｍはそれぞれ１〜１０００である。） Furthermore, the polyimide resin of the present invention is such that the polyimide resin represented by the general formula (7) becomes a polyimide resin having excellent solvent solubility, and a coating film having a low linear expansion coefficient and excellent mechanical properties can be obtained. To preferred.

(Where n and m are each 1 to 1000)

  The n and m are each preferably 10 to 100 because a polyimide resin having better solvent solubility and a lower linear expansion coefficient and a more excellent mechanical property can be obtained. In addition, in the structure represented by General formula (7), each imide unit which comprises a copolymer was represented as a composition unit for convenience. The arrangement of each imide unit may or may not have specific regularity and regularity. Therefore, the imide unit (n or m) of each copolymer may appear multiple times in the polyimide resin. In that case, n and m in the general formula (7) are the total of the imide units of the respective copolymers.

  Furthermore, the polyimide resin of the present invention is preferable because a polyimide resin having a structure represented by the general formula (8) and / or the general formula (9) can provide a coating film having excellent toughness. The polyimide resin having the structure represented by 9) is more preferable.

  Among the polyimide resins of the present invention, the polyimide resin containing 2-50 mol% of the structure represented by the general formula (8) and the structure represented by the general formula (9) in the polyimide resin of the present invention is dissolved in a solvent. It is preferable from the reason of expressing property and high strength, and 5 to 20 mol% is more preferable.

  The content of the structure represented by the general formula (8) and the structure represented by the general formula (9) in the polyimide resin of the present invention is 2 based on the molar amount of the monomer component constituting the polyimide resin of the present invention. -50 mol% is preferable for the reason of expressing solvent solubility and high strength, and 5-20 mol% is more preferable.

  Furthermore, among the structures represented by the general formula (8) and / or the general formula (9), a polyimide resin having a structure represented by the general formula (10) and / or the general formula (11) is low in linear expansion. In particular, a polyimide resin having a structure represented by the general formula (10) is more preferable.

  Among the polyimide resins of the present invention, the polyimide resin containing 2-50 mol% of the structure represented by the general formula (10) and the structure represented by the general formula (11) in the polyimide resin is solvent soluble. It is preferable for the reason of exhibiting good mechanical properties, and more preferably 5 to 20 mol%.

  Among the polyimide resins of the present invention, the content of the structure represented by the general formula (10) and the structure represented by the general formula (11) is 2 based on the molar amount of the monomer component constituting the polyimide resin of the present invention. ˜50 mol% is preferable for the reason that solvent solubility and good mechanical properties are expressed, and 5 to 20 mol% is more preferable.

  Furthermore, the polyimide resin of the present invention is preferable because the polyimide resin having the structure represented by the general formula (12) provides a cured coating film having excellent mechanical properties such as toughness and dimensional stability.

（ｎ、ｍおよびｐはそれぞれ１〜１０００である。）

(N, m, and p are each 1-1000.)

  The n, m, and p are each preferably a polyimide resin having excellent solvent solubility, and preferably have a low linear expansion coefficient and a coating film having excellent mechanical properties. In addition, in the structure represented by General formula (12), each imide unit which comprises a copolymer was represented as a composition unit for convenience. The arrangement of each imide unit may or may not have specific regularity and regularity. Therefore, the imide unit (n, m or p) of each copolymer may appear multiple times in the polyimide resin. In that case, n, m, and p in the general formula (12) are respectively the sum of the imide units of each copolymer.

  Although the polyimide resin of the present invention is a resin having excellent storage stability, it tends to have the property of being easily dissolved in an organic solvent. As the organic solvent using the polyimide resin of the present invention, a conventionally used polar solvent organic solvent having a large dissolving power such as N-methylpyrrolidone and dimethylformamide can be used, but gamma-butyrolactone (γ An organic solvent having a relatively weak dissolving power such as (butyrolactone) can also be used.

  In the present invention, whether or not the polyimide resin of the present invention is dissolved in an organic solvent is determined by adding the polyimide resin concentration of the present invention to 10% by weight in the organic solvent and allowing to stand at 25 ° C. for 7 days. Then, the appearance was visually observed.

  The polyimide resin of the present invention is preferable because the polyimide resin dissolved in gamma butyrolactone is a polyimide resin having excellent storage stability, and is soluble in gamma butyrolactone when dissolved in gamma butyrolactone at 10% by weight at 25 ° C. Certain polyimide resins are preferred. In order to obtain a polyimide resin that is soluble in gamma butyrolactone, it can be obtained, for example, by the method for producing a polyimide resin of the present invention.

  The polyimide resin of the present invention may be a polyimide resin having a linear structure or a polyimide resin having a branched structure. Further, the copolymer component may have a polyester-modified polyesterimide or urethane-modified polyurethaneimide structure.

  Examples of the terminal structure of the polyimide resin of the present invention include structures such as carboxylic acid, carboxylic acid anhydride, isocyanate group, and amine group. As the terminal structure, the structure of the carboxylic acid or its anhydride is preferable because the stability of the polyimide resin itself of the present invention and the stability after blending with an organic solvent or another resin are good. When the terminal structure is a carboxylic acid or its anhydride structure, the acid value should be a polyimide resin with a solid content acid value of 5 to 50, and a film or molded product with excellent mechanical strength and dimensional stability can be obtained. To preferred.

  The molecular weight of the polyimide resin of the present invention is preferably 1000 to 50000, more preferably 2000 to 30000, since it becomes a polyimide resin that is easy to handle, and a film or molded product having excellent mechanical strength and dimensional stability is obtained. The molecular weight can be measured by GPC or quantitative determination of the terminal functional group. In the present invention, the molecular weight was determined from the acid value as a quantitative determination of the carboxylic acid group present at the terminal.

The polyimide resin used in the present invention can be produced, for example, by the following method.
Production method 1: A method of directly imidizing using a polyisocyanate compound and cyclohexanetricarboxylic acid anhydride (isocyanate method).
Production method 2: A method in which cyclohexanetricarboxylic acid anhydride and a diamine compound are reacted to synthesize an amic acid, followed by a dehydration reaction of the amic acid to cause imide ring closure.

  In order to produce the polyimide resin of the present invention, the amount of remaining water can be reduced and the physical properties can be kept good, the reaction can be easily controlled, and the polyimide resin subjected to various modifications can be easily prepared. The isocyanate method (a method for producing a polyimide resin in which a diisocyanate compound and cyclohexanetricarboxylic acid anhydride are reacted) is preferable. Hereinafter, Production Method 1 will be described in detail. Production method 1 includes, for example, a method of directly imidizing using a diisocyanate compound and cyclohexanetricarboxylic acid anhydride.

  Examples of the polyisocyanate include aromatic polyisocyanates and aliphatic polyisocyanates.

  Examples of the aromatic polyisocyanate compound include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4. '-Diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,3-bis (Α, α-dimethylisocyanatomethyl) benzene, tetramethylxylylene diisocyanate, diphenylene ether-4,4′-diisocyanate, naphthalene diisocyanate and the like.

  Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylenemethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, and norbornylene diisocyanate.

  As the polyisocyanate compound, it is also possible to use an isocyanate prepolymer obtained by reacting the polyisocyanate compound and various polyol components in advance with an excess of isocyanate groups.

  The polyimide resin of the present invention may have a branched structure in order to improve solvent solubility and compatibility with other resins. As the branching method, as the polyisocyanate compound, for example, a tri- or higher functional polyisocyanate compound having an isocyanurate ring that is an isocyanurate body such as the diisocyanate compound, a burette body, an adduct body, an allohanate body of the diisocyanate, or Polymethylene polyphenyl polyisocyanate (crude MDI) or the like may be used.

  As the polyisocyanate compound, an aromatic diisocyanate is preferably used since mechanical properties such as mechanical strength and elongation at break and heat resistance of the obtained cured product are improved, and among the aromatic diisocyanates, 4, 4 are preferable. '-Diphenylmethane diisocyanate is more preferred.

  A polyisocyanate compound may be used independently and may use 2 or more types together. By using 2 or more types together, it can be expected to easily obtain a polyimide resin having improved solubility and compatibility with various resins. Even when used together, when 4,4'-diphenylmethane diisocyanate is used in an amount of 50% by weight or more based on the weight of the polyisocyanate compound, a cured product having excellent mechanical properties such as mechanical strength and elongation at break and heat resistance can be obtained. This is preferable.

  As a usage-amount of a polyisocyanate compound, 10-70 mol% is preferable on the basis of the molar amount of all the raw materials which comprise a polyimide resin, 10-60 mol% is more preferable, 30-60 mol% is still more preferable.

  Examples of the cyclohexane tricarboxylic acid anhydride include, for example, cyclohexane-1,3,4-tricarboxylic acid anhydride-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid anhydride-3,5-anhydride. , Cyclohexane-1,2,3-tricarboxylic acid anhydride-2,3-anhydride and the like. Among them, cyclohexane-1,3,4-tricarboxylic acid anhydride-3,4-anhydride is obtained because a cured product having excellent solvent solubility and mechanical properties such as mechanical strength and elongation at break and heat resistance is obtained. preferable.

  Here, the above-mentioned cyclohexanetricarboxylic acid anhydride is represented by the structure of the following general formula (13), and cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,2,4 used as production raw materials. -In the range which impurities, such as a tricarboxylic acid, do not impair the hardening of this invention, for example, 10 weight% or less, Preferably it may be mixed if it is 5 weight% or less.

  In the production method of the present invention, polycarboxylic acid anhydrides other than the cyclohexanetricarboxylic acid anhydride can be used in combination as long as the effects of the present invention are not impaired. Examples of other polycarboxylic acid anhydrides include polycarboxylic acid anhydrides having one acid anhydride group and polycarboxylic acid anhydrides having two acid anhydride groups. Examples of the polycarboxylic acid anhydride having one acid anhydride group include aromatic tricarboxylic acid anhydrides such as trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride.

  Examples of the polycarboxylic acid anhydride having two acid anhydride groups include pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenyl ether-3, 3 ', 4,4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic dianhydride , Biphenyl-2,2 ', 3,3'-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic acid Dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2, 3,5,6,7-hexahydro Phthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4 5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,3,9,10-tetracarboxylic Acid dianhydride, berylene-3,4,9,10-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3- Dicarboxyphenyl) propane Anhydride, 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride object,

Ethylene glycol bisanhydro trimellitate, propylene glycol bis anhydro trimellitate, butanediol bis anhydro trimellitate, hexamethylene glycol bis anhydro trimellitate, polyethylene glycol bis anhydro trimellitate, polypropylene lenglycol bis Anhydro trimellitate, other alkylene glycol bisan hydroxy trimellitate, etc. are mentioned.

  Among the polycarboxylic acid anhydrides, trimellitic anhydride, pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenyl ether-3,3', 4, 4'-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl-2,2', 3,3'-tetracarboxylic dianhydride, and ethylene Glycol bisanhydro trimellitate is preferred, and trimellitic anhydride is more preferred.

  In addition, the above-mentioned cyclohexanetricarboxylic acid anhydride and trimellitic anhydride are used in combination in terms of the balance between solvent solubility, mechanical properties, and heat resistance, and cyclohexanetricarboxylic acid anhydride and benzophenone-3,3 ', 4,4'- More preferred is a combined use of tetracarboxylic dianhydride, a combined use of cyclohexanetricarboxylic anhydride and pyromellitic dianhydride, and more preferred is cyclohexanetricarboxylic anhydride, trimellitic anhydride, benzophenone-3,3 ', More preferred is a combination of two or more selected from the group consisting of 4,4'-tetracarboxylic dianhydride and pyromellitic dianhydride, and cyclohexanetricarboxylic anhydride, trimellitic anhydride, benzophenone-3,3. Three types of combination of ', 4,4'-tetracarboxylic dianhydride are more preferable.

  The use amount of the cyclohexanetricarboxylic acid anhydride is 5-100 mol% in the total acid anhydride compound constituting the imide resin becomes a polyimide resin excellent in solvent solubility, and a cured product excellent in mechanical properties and heat resistance. Is preferable, and 10 to 80 mol% is more preferable. The amount of cyclohexanetricarboxylic acid anhydride used is preferably 2 to 60 mol%, more preferably 5 to 50 mol%, based on the molar amount of all raw materials constituting the polyimide resin.

  The amount used when trimellitic anhydride is used in combination with cyclohexanetricarboxylic acid anhydride as the acid anhydride is similarly 5 to 90 mol% cyclohexanetricarboxylic acid anhydride based on the molar amount of the total acid anhydride compound, trimellitic anhydride. The acid is preferably 20 to 90 mol%, more preferably 10 to 50 mol% of cyclohexanetricarboxylic anhydride and 40 to 90 mol% of trimellitic anhydride. Moreover, the usage-amounts of the said cyclohexanetricarboxylic acid anhydride and trimellitic anhydride are 2-60 mol% and 2-60 mol% respectively on the basis of the molar amount of all the raw materials which comprise a polyimide resin.

  When trimellitic anhydride and benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride are used in combination with cyclohexanetricarboxylic acid anhydride as the acid anhydride, the moles of all acid anhydrides constituting the imide resin Preferred is 5 to 90 mol% cyclohexanetricarboxylic anhydride, 2 to 80 mol% trimellitic anhydride, 3 to 50 mol% benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride based on the amount. More preferred are 10 to 80 mol% of cyclohexanetricarboxylic anhydride, 10 to 80 mol% of trimellitic anhydride, and 5 to 30 mol% of benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride. The amount of cyclohexanetricarboxylic anhydride, trimellitic anhydride, and benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride used is based on the molar amount of all raw materials constituting the polyimide resin. Are preferably 2 to 60 mol%, 2 to 60 mol% and 2 to 60 mol%, respectively.

  In the method for producing the polyimide resin, the polyisocyanate compound and cyclohexanetricarboxylic acid anhydride react. The ratio (ma) / (mb) of the total number of moles (mb) of the isocyanate groups in the polyisocyanate compound (ma) and the total number of moles of hydroxyl groups and carboxyl groups in the cyclohexanetricarboxylic acid anhydride (ma) / (mb) is a high molecular weight polyimide. A ratio of 0.7 to 1.2 is preferable, and a ratio of 0.8 to 1.1 is more preferable because a resin is easily obtained and a cured resin having excellent mechanical properties can be obtained. Moreover, since it is easy to obtain the polyimide resin excellent in storage stability, the range of (ma) / (mb) is more preferably in the range of 0.8 to 1.0. When other carboxylic acid anhydride is used in combination with cyclohexanetricarboxylic acid anhydride, the above (mb) is the total number of moles of hydroxyl-free and carboxyl groups in all carboxylic acid anhydrides. .

  In the case of producing in a one-step reaction in the production method 1, for example, a polyisocyanate compound and cyclohexanetricarboxylic acid anhydride are charged in a reaction vessel, and the reaction is allowed to proceed while decarboxylation by raising the temperature while stirring.

  The reaction temperature can be in the range of 50 ° C. to 250 ° C., and is preferably performed at a temperature of 70 ° C. to 180 ° C. in terms of reaction rate and prevention of side reactions.

  The reaction is preferable because the stability of the resulting polyimide resin is improved when the reaction is performed until almost all isocyanate groups have reacted. Moreover, you may make it react by adding an alcohol and a phenol compound with respect to the isocyanate group which remains a little.

  In the method for producing a polyimide resin of the present invention, it is preferable to use an organic solvent because a uniform reaction can proceed. Here, the organic solvent may be present after being present in the system in advance or may be introduced in the middle. In order to maintain an appropriate reaction rate, the proportion of the organic solvent in the system is preferably 98% by weight or less, more preferably 10 to 90% by weight of the reaction system. As such an organic solvent, since a compound containing an isocyanate group is used as a raw material component, an aprotic polar organic solvent having no active proton such as a hydroxyl group or an amino group is preferable.

  As the aprotic polar organic solvent, for example, polar organic solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and γ-butyrolactone can be used. In addition to the above solvents, ether solvents, ester solvents, ketone solvents, petroleum solvents and the like may be used as long as they are soluble. Various solvents may be mixed and used.

  In particular, the use of γ-butyrolactone is preferred from the viewpoints of the odor and toxicity of the solvent, the reduction of the residual solvent amount upon drying and curing of the coating film, and the reduction of the moisture absorption amount of the solvent of the coating film. Moreover, the structure which melt | dissolves in (gamma) -butyrolactone also in the polyimide resin obtained is preferable. As a polyimide resin which is dissolved in such γ-butyrolactone and has good performance in various physical properties (heat resistance, low linear expansion coefficient, mechanical properties), an isocyanate component containing 4,4′-diphenylmethane diisocyanate is used. It can be obtained by reacting 1,3,4-tricarboxylic acid-3,4-anhydride with trimellitic anhydride. The proportion of 4,4-diphenylmethane diisocyanate, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and trimellitic anhydride used here is the moles of all raw materials constituting the polyimide resin. 10-60 mol%, 2-60 mol% and 2-60 mol% are preferred, respectively, based on the amount.

  Furthermore, a polyimide resin which is dissolved in such γ-butyrolactone and has good performance in various physical properties (heat resistance, low linear expansion coefficient, mechanical properties) is 4,4-diphenylmethane diisocyanate and cyclohexane-1,3,5- It can preferably be obtained by reacting tricarboxylic acid-3,4-anhydride, trimellitic anhydride, and benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride. 4,4-diphenylmethane diisocyanate, cyclohexane-1,3,5-tricarboxylic acid-3,4-anhydride, trimellitic anhydride, and benzophenone-3,3 ', 4,4'-tetracarboxylic The use ratio of the acid dianhydride is preferably 10 to 60 mol%, 2 to 60 mol%, 2 to 60, and 2 to 60 mol% based on the molar amount of all raw materials constituting the polyimide resin.

  Examples of the ether solvent that can be used in the method for producing a polyimide resin of the present invention include ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol. Polyethylene glycol dialkyl ethers such as dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether; ethylene such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate Recall monoalkyl ether acetates; polyethylene glycol monoalkyl such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate Ether acetates;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol Polypropylene glycol dialkyl ethers such as propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; Polypropylene glycol monoalkyl ether acetate such as triglycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate Dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymers; monoacetate monoalkyl ethers of copolymerized polyether glycols; alkyl esters of copolymerized polyether glycols; Examples include ether glycol monoalkyl esters and monoalkyl ethers. It is.

  Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the ketone solvent include acetone, methyl ethyl ketone, and cyclohexanone. In addition, as the petroleum solvent, it is also possible to use toluene, xylene, other high-boiling aromatic solvents, and aliphatic and alicyclic solvents such as hexane and cyclohexane.

  The ratio of the organic solvent in the system when the organic solvent is used when producing the polyimide resin (A) used in the present invention is preferably 98% by weight or less of the reaction system, and preferably 40 to 90% by weight. More preferred.

  A thermosetting resin component can be further added to the polyimide resin of the present invention. Specifically, an epoxy resin, an isocyanate compound, a silicate, an alkoxysilane compound, etc. are mentioned, for example.

  The epoxy resin preferably has two or more epoxy groups in the molecule. Examples of such epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin; novolak types such as phenol novolac epoxy resin, cresol novolac type epoxy resin, and bisphenol type novolak. Epoxy resins; epoxidized products of various dicyclopentadiene-modified phenol resins obtained by reacting dicyclopentadiene with various phenols; biphenyl type epoxy resins such as epoxidized products of 2,2 ', 6,6'-tetramethylbiphenol; Epoxy resin having naphthalene skeleton; aromatic epoxy resin such as epoxy resin having fluorene skeleton and hydrogenated product of these aromatic epoxy resins; neopentyl glycol diglycidyl Aliphatic epoxy resins such as ether and 1,6-hexanediol diglycidyl ether; fats such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate Cyclic epoxy resins; and heterocyclic ring-containing epoxy resins such as triglycidyl isocyanurate. Among these, an aromatic epoxy resin is preferable because a thermosetting polyimide resin composition excellent in opportunity physical properties of a cured coating film is obtained, and a novolac type epoxy resin is more preferable.

  The blending amount of the polyimide resin (A) and the epoxy resin (D) can be used in a ratio of (A) / (D) of 1/100 to 50/1 as a weight ratio of the resin, and more preferably. Is from 1/10 to 20/1.

  Examples of the isocyanate compound include aromatic isocyanate compounds, aliphatic isocyanate compounds, and alicyclic isocyanate compounds. Preferably, a polyisocyanate compound having two or more isocyanate groups in one molecule is preferable. A blocked isocyanate compound can also be used.

  Examples of the alkylalkoxysilane include alkyltrialkoxysilane and dialkyldialkoxysilane.

  Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, Examples thereof include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, and phenyltributoxysilane.

  Examples of the dialkyl dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, and diphenyldimethoxy. Silane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldibutoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldipropoxysilane, methylethyldibutoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane , Methylphenyldipropoxysilane, methylphenyldibutoxysilane, trimethylmethoxysilane, trimethyl ether Kishishiran, triethyl silane, triethyl silane, triphenyl methoxy silane, triphenyl ethoxy silane, and the like.

  In addition, condensates of alkylalkoxysilanes are also used, and examples thereof include the above-mentioned alkyltrialkoxysilane condensates and dialkyldialkoxysilane condensates.

Further, the resin of the present invention includes polyester, phenoxy resin, PPS resin, PPE resin, polyarylene resin and other binder resins, phenolic resin, melamine resin, alkoxysilane-based curing agent, polybasic acid anhydride, cyanate compound and other curing agents, Reactive compounds, melamine, dicyandiamide, guanamine and derivatives thereof, imidazoles, amines, phenols having one hydroxyl group, organic phosphines, phosphonium salts, quaternary ammonium salts, photocationic catalysts, and other curing catalysts and accelerators Further, as a filler and other additives, an antifoaming material, a leveling agent, a slip agent, a wetting improver, an anti-settling agent, a flame retardant, an antioxidant, an ultraviolet absorber and the like can be added.

  Moreover, the resin composition of this invention can add a various filler, an organic pigment, an inorganic pigment, an extender, a rust preventive agent, etc. further as needed. These may be used alone or in combination of two or more.

Examples of the filler include barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, and alumina. Is mentioned.
As the filler, those having various particle sizes are used, and it is possible to add the filler to such an extent that the physical properties of the resin and its composition are not impaired. Such an appropriate amount is in the range of about 5 to 80% by weight, and is preferably used after being uniformly dispersed. As a dispersion method, it is possible to carry out dispersion by a known roll, bead mill, high-speed dispersion or the like, and the surface of the particles may be modified in advance with a dispersion treatment agent.

  Examples of the organic pigment include azo pigments; copper phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, and quinacridone pigments.

  Examples of the inorganic pigment include chromates such as chrome lead, zinc chromate and molybdate orange; ferrocyanides such as bitumen, titanium oxide, zinc white, bengara, iron oxide; metal oxides such as chromium carbide green, Cadmium yellow, cadmium red; metal sulfides such as mercury sulfide; selenides; sulfates such as lead sulfate; silicates such as ultramarine; carbonates, cobalt biored; phosphates such as manganese purple; aluminum powder, zinc dust Metal powders such as brass powder, magnesium powder, iron powder, copper powder and nickel powder; carbon black and the like.

  In addition, any of other coloring, rust prevention, and extender pigments can be used. These may be used alone or in combination of two or more.

  The resin treatment method of the present invention can be dried or cured by heating at 100 to 300 ° C. after preparing the resin of the present invention alone or its composition to form a coating or molding.

  The substrate used in the method for forming the coating film can be used without any particular limitation. Examples of the substrate include plastic, metal, wood, glass, inorganic material, and composite materials thereof.

  In addition, the resin and the composition of the present invention are in a form suitable for the production of a flexible circuit board, and a film (adhesive film) comprising a resin and a composition layer (A layer) and a support film (B layer). It can also be used as a form.

  The adhesive film is prepared according to various methods, for example, by preparing a resin varnish obtained by dissolving the resin of the present invention and its composition in an organic solvent, applying the resin varnish to a support film, and heating or blowing hot air to the organic film. It can manufacture by drying a solvent and forming a resin composition layer.

  The support film (B layer) serves as a support when the adhesive film is produced, and is finally peeled off or removed in the production of the flexible circuit board. Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, and release paper and copper foil. The metal foil etc. can be mentioned. In addition, when using copper foil as a support body film, it can remove by etching with etching liquid, such as ferric chloride and cupric chloride. The support film may be subjected to a release treatment in addition to a mat treatment and a corona treatment, but it is more preferable that the release treatment is performed in consideration of releasability. Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers.

  Organic solvents for preparing the varnish include, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, cellosolve, butyl Examples thereof include carbitols such as carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and gamma butyrolactone. Two or more organic solvents may be used in combination.

  The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition is usually 5% by mass or less, preferably 3% by mass or less. The specific drying conditions vary depending on the curability of the resin composition and the amount of the organic solvent in the varnish. For example, in a varnish containing 30 to 60% by mass of an organic solvent, it is usually 3 to 13 minutes at 80 to 120 ° C. It can be dried to some extent. Those skilled in the art can appropriately set suitable drying conditions by simple experiments.

  The thickness of the resin and its composition layer (A layer) can usually be in the range of 5 to 500 μm. The preferred range of the thickness of the A layer varies depending on the use of the adhesive film, and when used for manufacturing a multilayer flexible circuit board by the build-up method, the thickness of the conductor layer forming the circuit is usually 5 to 70 μm. The thickness of the A layer corresponding to the layer is preferably in the range of 10 to 100 μm.

  The A layer may be protected with a protective film. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The protective film is peeled off during lamination. As the protective film, the same material as the support film can be used. Although the thickness of a protective film is not specifically limited, Preferably it is the range of 1-40 micrometers.

  Especially the adhesive film of this invention can be used conveniently for manufacture of a multilayer flexible circuit board. Below, the method to manufacture a multilayer flexible circuit board is demonstrated. The adhesive film of the present invention can be suitably laminated on a flexible circuit board with a vacuum laminator. The flexible circuit board used here is mainly composed of a conductive layer (circuit) patterned on one or both sides of a substrate such as a polyester substrate, a polyimide substrate, a polyamideimide substrate, or a liquid crystal polymer substrate, as well as alternating circuits and insulating layers. It is also possible to use a multilayer flexible circuit board that is layered and has a circuit formed on one or both sides for further multilayering. In addition, from the viewpoint of adhesion of the insulating layer to the circuit board, the surface of the circuit should have been previously roughened with a surface treatment agent such as hydrogen peroxide / sulfuric acid or MEC Etch Bond (MEC Co., Ltd.). preferable.

  Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo Morton, a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Techno Engineering Co., Ltd., Hitachi AIC ( A vacuum laminator manufactured by Co., Ltd. can be mentioned.

In the lamination, when the adhesive film has a protective film, the protective film is removed, and then the adhesive film is pressure-bonded to the circuit board while being pressurized and heated. The laminating conditions include pre-heating the adhesive film and the circuit board as required, laminating at a pressure of preferably 70 to 140 ° C., a pressure of pressure of preferably 1 to 11 kgf / cm ² and laminating under a reduced pressure of an air pressure of 20 mmHg or less. preferable. The laminating method may be a batch method or a continuous method using a roll.

  After laminating the adhesive film on the circuit board, it is cooled to around room temperature and the support film is peeled off. Next, the thermosetting polyimide resin composition laminated on the circuit board is cured by heating. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes. In addition, when a support body film has a peeling process or peeling layers, such as a silicon | silicone, a support body film can also be peeled after heat-hardening of a thermosetting polyimide resin composition, or after heat-hardening and punching.

  After the insulating layer, which is a cured product of the thermosetting polyimide resin composition, is formed, the circuit board is drilled by a method such as drilling, laser, plasma, or a combination thereof to form via holes and through holes as necessary. It may be formed. In particular, drilling with a laser such as a carbon dioxide laser or a YAG laser is generally used.

  Next, surface treatment of the insulating layer (cured product of the thermosetting polyimide resin composition) is performed. The surface treatment can employ a method used in a desmear process, and can be performed in a form that also serves as a desmear process. As a chemical used in the desmear process, an oxidizing agent is generally used. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, and the like. Preferably, an alkaline permanganate solution (for example, potassium permanganate, sodium hydroxide aqueous solution of sodium permanganate), which is an oxidizer widely used for roughening the insulating layer in the production of multilayer printed wiring boards by the build-up method. It is preferable to carry out the treatment using A treatment with a swelling agent can also be performed before the treatment with the oxidizing agent. Further, after the treatment with an oxidizing agent, neutralization treatment with a reducing agent is usually performed.

  After the surface treatment, a conductor layer is formed by plating on the surface of the insulating layer. The conductor layer can be formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. After the conductor layer is formed, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.

  As a method for forming a circuit by patterning the conductor layer, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. In the case of the subtractive method, the thickness of the electroless copper plating layer is 0.1 to 3 μm, preferably 0.3 to 2 μm. An electroplating layer (panel plating layer) is formed thereon with a thickness of 3 to 35 μm, preferably 5 to 20 μm, an etching resist is formed, and etching is performed with an etching solution such as ferric chloride or cupric chloride. After forming a conductor pattern by this, a circuit board can be obtained by peeling an etching resist. In the case of the semi-additive method, after forming the electroless copper plating layer with an electroless copper plating layer thickness of 0.1 to 3 μm, preferably 0.3 to 2 μm, a pattern resist is formed, and then the electrolytic copper A circuit board can be obtained by peeling after plating.

  A film in which the support film is replaced with a heat-resistant resin layer (heat-resistant resin film), that is, a film composed of a polyimide resin and its composition layer (A layer) and a heat-resistant resin layer (C layer) is used for a flexible circuit board. Can be used as a base film. A film made of a resin and its composition layer (A layer), a heat resistant resin layer (C layer) and a copper foil (D layer) can also be used as a base film of a flexible circuit board. In this case, the base film has a layer structure in the order of A layer, C layer, and D layer. In the base film as described above, the heat-resistant resin layer is not peeled off and constitutes a part of the flexible circuit board.

  A film in which an insulating layer (A ′ layer) made of a cured product of the resin composition of the present invention is formed on a heat-resistant resin layer (C layer) can be used as a base film for a single-sided flexible circuit board. Moreover, it consists of the film which has a layer structure of the order of A 'layer, C layer, and A' layer, and A 'layer, C layer, and copper foil (D layer), A' layer, the order of C layer, and D layer Similarly, a film having a layer structure can be used as a base film for a double-sided flexible circuit board.

  Examples of the heat-resistant resin used for the heat-resistant resin layer include a polyimide resin, an aramid resin, a polyamideimide resin, and a liquid crystal polymer. In particular, a polyimide resin and a polyamideimide resin are preferable. Moreover, on the characteristic used for a flexible circuit board, the breaking strength is 100 MPa or more, the breaking elongation is 5% or more, the thermal expansion coefficient between 20 and 150 ° C. is 40 ppm or less, and the glass transition temperature is 200 ° C. or more or the decomposition temperature is 300 ° C. It is preferable to use the above heat resistant resin.

  As the heat-resistant resin satisfying such characteristics, a heat-resistant resin that is commercially available in the form of a film can be suitably used. For example, a polyimide film “Upilex-S” manufactured by Ube Industries, Ltd., Toray DuPont Co., Ltd. ) Polyimide film "Kapton", Kaneka Chemical Co., Ltd. polyimide film "Apical", Teijin Advanced Films Ltd. "Aramika", Kuraray Co., Ltd. liquid crystal polymer film "Bexstar", Sumitomo Bakelite Co., Ltd. A polyether ether ketone film “Sumilite FS-1100C” and the like are known.

  The thickness of the heat-resistant resin layer is usually 2 to 150 μm, preferably 10 to 50 μm. As the heat-resistant resin layer (C layer), a surface-treated layer may be used. Examples of the surface treatment include dry treatment such as mat treatment, corona discharge treatment and plasma treatment, chemical treatment such as solvent treatment, acid treatment and alkali treatment, sand blast treatment and mechanical polishing treatment. In particular, from the viewpoint of adhesion to the A layer, it is preferable that plasma treatment is performed.

  A base film for a single-sided flexible circuit board composed of an insulating layer (A ′) and a heat-resistant resin layer (C) can be produced as follows. First, similarly to the adhesive film described above, a resin varnish prepared by dissolving the resin composition of the present invention in an organic solvent is prepared, this resin varnish is applied on a heat-resistant resin film, and the organic solvent is removed by heating or hot air blowing. It is made to dry and a thermosetting polyimide resin composition layer is formed. Conditions such as the organic solvent and drying conditions are the same as those for the adhesive film. The thickness of the resin composition layer is preferably in the range of 5 to 15 μm.

  Next, the resin composition layer is heated and dried to form an insulating layer of the thermosetting polyimide resin composition. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes.

  The production of a base film of a double-sided flexible circuit board film comprising three layers of an insulating layer (A ′ layer), a heat resistant resin layer (C) layer and a copper foil (D layer) A resin composition may be formed on a copper-clad laminated film made of (D layer) and manufactured in the same manner as described above. Examples of the copper clad laminated film include a cast method two-layer CCL (Copper-clad laminate), a sputtering method two-layer CCL, a laminate method two-layer CCL, and a three-layer CCL. The thickness of the copper foil is preferably 12 μm or 18 μm.

  Commercially available two-layer CCL includes Espanex SC (manufactured by Nippon Steel Chemical Co., Ltd.), Neoprex I <CM>, Neoprex I <LM> (Mitsui Chemicals), S'PERFLEX (Sumitomo Metal Mining Co., Ltd.) Nikaflex F-50VC1 (manufactured by Nikkan Kogyo Co., Ltd.) and the like are mentioned as the commercially available three-layer CCL.

  The production of a base film of a double-sided flexible circuit board film comprising three layers of an insulating layer (A ′ layer), a heat resistant resin layer (C layer) and an insulating layer (A ′ layer) can be carried out as follows. First, in the same manner as the adhesive film described above, a resin varnish prepared by dissolving the resin composition of the present invention in an organic solvent is prepared, this resin varnish is applied on a support film, and the organic solvent is dried by heating or hot air blowing. To form a resin composition layer. Conditions such as the organic solvent and drying conditions are the same as those for the adhesive film. The thickness of the resin composition layer is preferably in the range of 5 to 15 μm.

  Next, this adhesive film is laminated on both surfaces of the heat resistant resin film. Lamination conditions are the same as described above. Moreover, if the resin composition layer is previously provided on one side of the heat-resistant film, the lamination may be only on one side. Next, the resin composition layer is cured by heating to form an insulating layer that is a layer of the resin composition. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes.

  A method for producing a flexible circuit board from the base film for the flexible circuit board will be described. In the case of a base film comprising an A ′ layer, a C layer, and an A ′ layer, first, after heat-curing, a circuit board is drilled by a method such as drilling, laser, or plasma to form a through hole for conduction on both sides. . In the case of a base film composed of an A ′ layer, a C layer, and a D layer, holes are formed by the same method to form via holes. In particular, drilling with a laser such as a carbon dioxide laser or a YAG laser is generally used.

  Next, a surface treatment of the insulating layer (resin composition layer) is performed. About surface treatment, it is the same as that of the case of the adhesive film mentioned above. After the surface treatment, a conductor layer is formed by plating on the surface of the insulating layer. The formation of the conductor layer by plating is the same as in the case of the adhesive film described above. After the conductor layer is formed, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.

  Next, the conductor layer is patterned to form a circuit to obtain a flexible circuit board. When a base film composed of an A layer, a C layer, and a D layer is used, a circuit is also formed on the copper foil that is the D layer. As a circuit formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. Details are the same as in the case of the adhesive film described above.

  The single-sided or double-sided flexible circuit board obtained in this way can be produced as a multilayer flexible circuit board by using the adhesive film of the present invention, for example, as described above.

  The resin composition of the present invention is also useful as a material for forming a stress relaxation layer between a semiconductor and a substrate substrate. For example, in the same manner as described above, all or part of the uppermost insulating layer of the substrate substrate is formed by the adhesive film obtained by using the resin composition of the present invention, and the resin is connected by connecting the semiconductor. A semiconductor device in which a semiconductor and a substrate substrate are bonded via a cured product of the composition can be manufactured. In this case, the thickness of the resin composition layer of the adhesive film is appropriately selected within a range of 10 to 1000 μm. The resin composition of the present invention can form a conductor layer by plating, and a circuit pattern can also be produced by simply forming a conductor layer by plating on an insulating layer for stress relaxation provided on a substrate substrate. Is possible.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following, all parts and “%” are “% by weight” unless otherwise specified.

Example 1
In a flask equipped with a stirrer, a thermometer and a condenser, 1422.8 g of GBL (gamma-butyrolactone), 250 g (1.0 mol) of MDI (diphenylmethane diisocyanate) and 134.3 (0.7 mol of trimellitic anhydride) were added. ) And 59.4 g (0.3 mol) of TMA-H (cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride), and the temperature was raised to 80 ° C. while stirring while taking care of heat generation. The mixture was heated, dissolved and reacted at this temperature for 1 hour, further heated to 160 ° C. over 2 hours, and then reacted at this temperature for 5 hours. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown transparent liquid. A solution of a polyimide resin (A-1) having a resin solid content of 20% with a viscosity of 10 Pa · s at 25 ° C. and a solution acid value of 1.8 (KOHmg / g) (a resin composition in which the polyimide resin is dissolved in γ-butyrolactone) Product). It was concluded from the resin acid value [1.8 (KOHmg / g)] that the average molecular weight was 12500.

  The obtained polyimide resin (A-1) solution was coated on a KBr plate and the infrared absorption spectrum (FIG. 1) of the sample in which the solvent was volatilized was measured. As a result, 2270 cm-1 which is the characteristic absorption of the isocyanate group was completely obtained. The characteristic absorption of the imide ring was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1. The amount of carbon dioxide generated was 88 g (2 moles), which was monitored by the change in the weight charged to the flask. From this, it is concluded that the total amount of 2 moles, which is the total amount of isocyanate groups, has been converted to imide bonds and amide bonds. Furthermore, as a result of analysis by C13-NMR (FIG. 2), it was confirmed that the raw material was a polyimide resin represented by the following structure having a composition ratio of MDI: TMA: TMA-H of 52:35:15 mol%. It was done.

但しｎ：ｍ＝３：７

However, n: m = 3: 7

  The storage stability, coating workability, film-forming property, heat resistance, mechanical properties, electrical properties and dimensional stability of the obtained polyimide resin (A-1) were evaluated according to the following methods. The results are shown in Table 1.

(1) Storage stability The storage stability test was performed by evaluating the solvent solubility of the polyimide resin (A-1) immediately after preparation and the solvent solubility after standing for a long time. Immediately after preparation, the polyimide resin (A-1) was adjusted to a solution having a resin concentration of 10% with gamma butyrolactone, placed in a glass bottle with a lid, the appearance was observed, and the following evaluation criteria were used. This was defined as the solvent solubility of the polyimide resin (A-1) immediately after preparation. Thereafter, the lidded glass bottle containing the polyimide resin (A-1) was allowed to stand at 25 ° C. for 7 days, and then the appearance was observed and evaluated according to the following evaluation criteria.

○: The resin solution is transparent and fluid.
Δ: Fluidity but turbidity occurs.
X: There is no transparency and fluidity.

(2) Evaluation of coating workability Polyimide resin (A-1) was coated on a tin plate at room temperature with a 0.152 mil applicator. The appearance of the coating was evaluated according to the following evaluation criteria. In addition, when solid content was mixed in the resin solutions prepared in the following Examples and Comparative Examples, the temperature of the resin solution was raised to 120 ° C. and the solid content was once dissolved before coating.

○: Transparent, glossy and flat surface.
Δ: Opaque but flat surface.
X: Opaque and not a flat surface.

(3) Evaluation of film-forming property After applying polyimide resin (A-1) to the tin plate with an applicator so that the film thickness after drying is 30 μm, it is dried at 110 ° C. for 30 minutes to prepare a test piece. did. This test piece was allowed to stand at 25 ° C. for 24 hours, and the appearance of the coating film was evaluated according to the following evaluation criteria.

○: No abnormalities such as cracks are observed in the coating film.
Δ: Some cracks are observed in the coating film.
X: Cracks occurred on the entire surface of the coating film.

(4) Evaluation of heat resistance The polyimide resin (A-1) was coated on a glass epoxy substrate laminated with copper so that the film thickness after curing was 30 μm, and dried for 60 minutes with a 200 ° C. drier. Then, it cooled to room temperature and created the test piece. This test piece was immersed in a molten solder bath at 260 ° C. for 30 seconds and cooled to room temperature. This solder bath immersion operation was performed three times in total, and the appearance of the cured coating film was evaluated according to the following evaluation criteria.

○: Appearance abnormality is not observed in the coating film.
Δ: Abnormalities such as swelling and peeling are slightly observed in the coating film.
X: Abnormalities such as swelling and peeling are observed on the entire surface of the coating film.

(5) Evaluation of mechanical properties Mechanical properties were evaluated by conducting a tensile test of a coating film (film) and obtaining elastic modulus, breaking strength and breaking elongation.
<Preparation of test piece>
It coated on the tinplate board | substrate so that the film thickness of the coating film which can obtain a polyimide resin (A-1) might be set to 30 micrometers. Next, this coated plate was dried with a dryer at 50 ° C. for 30 minutes, with a dryer at 100 ° C. for 30 minutes, and with a dryer at 200 ° C. for 60 minutes to form a coating film (film). After cooling to room temperature, the coating film (film) was cut into a predetermined size, isolated from the substrate, and used as a measurement sample.

<Tensile test measurement method>
Five samples for measurement were prepared and subjected to a tensile test under the following conditions to determine the elastic modulus, breaking strength, and breaking elongation. It represents that it is a coating film which is excellent in a softness | flexibility, so that the value of an elasticity modulus is low. It represents that it is a coating film which is excellent in a softness | flexibility, so that the value of breaking elongation is high. And it shows that it is a tough coating film, so that the value of breaking strength is high.
Measuring instrument: Tensilon manufactured by Toyo Baldwin, Inc. Sample shape: 10 mm x 70 mm
Between chucks: 20 mm
Tensile speed: 10 mm / min
Measurement atmosphere: 22 ° C., 45% RH

(6) Measurement of TG and linear expansion coefficient
<Preparation of test specimen>
The polyimide resin (A-1) was coated on a tin plate so that the film thickness after curing was 50 μm, dried for 20 minutes with a 70 ° C. dryer, then cured at 200 ° C. for 1 hour, cooled, and then peeled off. The cured coating film was cut into a width of 5 mm and a length of 30 mm to obtain a measurement sample.

<TG and linear expansion coefficient measurement method>
Using a thermal analysis system TMA-SS6000 manufactured by Seiko Electronics Co., Ltd., measurement was performed by the TMA (Thermal Mechanical Analysis) method under the conditions of a sample length of 10 mm, a heating rate of 10 ° C./min, and a load of 30 mN. In addition, TG calculated | required the inflection point from the temperature-dimension change curve by TMA measurement, and made the temperature TG. Furthermore, the temperature range used for the linear expansion coefficient was determined from the displacement of the sample length at 50 to 60 ° C and 110 to 120 ° C. The higher the TG, the better the heat resistance, and the smaller the linear expansion coefficient, the better the dimensional stability.

Example 2
In a flask equipped with a stirrer, a thermometer and a condenser, 1420.5 g of GBL, 240 g (0.96 mol) of MDI, 134.3 (0.7 mol) of TMA and 39.6 g (0.2 mol) of TMA-H And 32.2 g (0.1 mol) of BTDA (benzophenone tetracarboxylic acid anhydride) were added, and the temperature was raised to 170 ° C. over 2 hours with careful attention to heat generation while stirring, followed by reaction at this temperature for 5 hours. I let you. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown transparent liquid. A solution of a polyimide resin (A-2) having a resin solid content of 20% with a viscosity of 8 Pa · s at 25 ° C. and a solution acid value of 2.48 (KOHmg / g) (resin composition in which the polyimide resin is dissolved in γ-butyrolactone) Product). In addition, it is concluded from the resin solution acid value [2.48 (KOHmg / g)] that the average molecular weight is 9050.

  The obtained polyimide resin (A-2) solution was coated on a KBr plate and the infrared absorption spectrum (FIG. 3) of the sample in which the solvent was volatilized was measured. As a result, 2270 cm-1 which is the characteristic absorption of the isocyanate group was completely obtained. The characteristic absorption of the imide ring was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1. The amount of carbon dioxide gas generated was 84.5 g (1.92 mol), which was monitored by the change in the weight charged to the flask. From this, it is concluded that the total amount of isocyanate groups is converted to imide bonds and amide bonds. Further, as a result of analysis by C13-NMR (FIG. 4), the composition ratio of MDI: TMA: BTDA: TMA-H which is a raw material is a polyimide resin represented by the following structure having a composition ratio of 50: 35: 5: 10 mol%. It was confirmed that there was.

ｎ：ｍ：ｐ＝２：７：１

n: m: p = 2: 7: 1

  The polyimide resin (A-2) was evaluated in the same manner as in Example 1 except that the obtained polyimide resin (A-2) solution was used. The results are shown in Table 1.

Comparative Example 1
A flask equipped with a stirrer, a thermometer and a condenser was charged with 337.8 g of GBL, 225 g of MDI (0.9 mol) and TMA 192 (1 mol). After heating up to 160 degreeC, it was made to react at this temperature for 5 hours. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown transparent liquid. An attempt was made to measure the viscosity at 25 ° C., but crystallization occurred and the viscosity could not be measured. The resin solid content was 50%. This is abbreviated as a solution of polyimide resin (a-1) (resin composition in which polyimide resin is dissolved in γ-butyrolactone). The resin solution acid value [16.6 (KOHmg / g)] concludes that the average molecular weight is 3400.

  As a result of coating the obtained polyimide resin (a-1) solution on a KBr plate and measuring the infrared absorption spectrum of the sample in which the solvent was volatilized, 2270 cm-1 which is the characteristic absorption of the isocyanate group completely disappeared, Characteristic absorption of the imide ring was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1. The amount of carbon dioxide generated was 79.2 g (1.8 mol), which was monitored by the change in the weight charged to the flask. From this, it is concluded that the total amount of 1.8 moles, which is the total amount of isocyanate groups, is converted to imide bonds and amide bonds.

  The polyimide resin (a-1) was evaluated in the same manner as in Example 1 except that the obtained polyimide resin (a-1) solution was used. The results are shown in Table 2.

Comparative Example 2
A flask equipped with a stirrer, a thermometer and a condenser was charged with 345.9 g of GBL, 237.5 g (0.95 mol) of MDI and 192 (1 mol) of TMA, and stirred for 2 hours while paying attention to heat generation. The temperature was raised to 160 ° C over a period of time, and the reaction was carried out at this temperature for 5 hours. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown transparent liquid. An attempt was made to measure the viscosity at 25 ° C., but crystallization occurred and the viscosity could not be measured. The resin solid content was 50%. This is abbreviated as a solution of polyimide resin (a-2) (resin composition in which polyimide resin is dissolved in γ-butyrolactone). The resin solution acid value [8.1 (KOHmg / g)] concludes that the average molecular weight is 6900.

  As a result of coating the obtained polyimide resin (a-2) solution on a KBr plate and measuring the infrared absorption spectrum of the sample in which the solvent was volatilized, 2270 cm-1 which is the characteristic absorption of the isocyanate group completely disappeared, Characteristic absorption of the imide ring was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1. The amount of carbon dioxide generated was 83.6 g (1.9 mol), which was monitored by the change in the weight charged to the flask. From this, it is concluded that the total amount of 1.9 mol, which is the total amount of isocyanate groups, has been converted to imide bonds and amide bonds.

  The polyimide resin (a-2) was evaluated in the same manner as in Example 1 except that the obtained polyimide resin (a-2) solution was used. The results are shown in Table 2.

Comparative Example 3
GBL 292.32 g, MDI 190 g (0.76 mol), TMA 130.56 (0.68 mol) and BTDA 38.64 g (0.12 mol) were added to a flask equipped with a stirrer, a thermometer and a condenser. While charging and stirring, paying attention to heat generation, the temperature was raised to 160 ° C. over 2 hours, and then reacted at this temperature for 5 hours. The reaction proceeded with the foaming of carbon dioxide gas, and the system was turbid from a brown transparent liquid. An attempt was made to measure the viscosity at 25 ° C., but crystallization occurred and the viscosity could not be measured. The resin solid content was 50%. This is abbreviated as a solution of polyimide resin (a-3) (resin composition in which polyimide resin was not dissolved in γ-butyrolactone). From the resin solution acid value [7.7 (KOHmg / g)], it is concluded that the average molecular weight is 7300.

  As a result of coating the obtained polyimide resin (a-3) solution on a KBr plate and measuring the infrared absorption spectrum of the sample in which the solvent was volatilized, 2270 cm-1 which is the characteristic absorption of the isocyanate group completely disappeared, Characteristic absorption of the imide ring was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1. The amount of carbon dioxide generated was 66.88 g (1.52 mol), which was monitored by the change in the weight of the flask charged. From this, it is concluded that the total amount of 1.52 mol, which is the total amount of isocyanate groups, is converted to imide bonds and amide bonds.

  The polyimide resin (a-3) was evaluated in the same manner as in Example 1 except that the obtained polyimide resin (a-3) solution was used. The results are shown in Table 2.

Comparative Example 4
In a flask equipped with a stirrer, thermometer and condenser, 4951 g of EDGA (ethyl diglycol acetate) and a polyisocyanate having an isocyanurate ring derived from isophorone diisocyanate (isocyanate group content: 18.2%, containing isocyanurate ring) Triisocyanate content 85%) 2760 g (12 moles as isocyanate group) and polytail HA [Mitsubishi Chemical Co., Ltd., hydrogenated liquid polybutadiene having hydroxyl groups at both ends, number average molecular weight 2,100, hydroxyl value 51.2 mgKOH / G] 2191 g (2 moles as a hydroxyl group) was charged, and the temperature was raised to 80 ° C. while stirring while paying attention to heat generation. The urethanization reaction was carried out at this temperature for 3 hours. Next, 1536 g of EDGA and 1536 g (8 mol) of EDGA were further added, and the temperature was raised to 160 ° C. and reacted for 4 hours to obtain a light brown polyimide resin (a-4) solution (resin composition in which the polyimide resin was dissolved in EDGA). Obtained. The resin solid content was 48.2%. In addition, it was resin solution acid value [38.1 (KOHmg / g)], and the number average molecular weight was 5,900 and the weight average molecular weight was 24,000 from GPC.

  As a result of coating a solution of the obtained polyimide resin for comparison (a-4) on a KBr plate and measuring the infrared absorption spectrum of the sample in which the solvent was volatilized, 2270 cm-1 which is the characteristic absorption of the isocyanate group was completely obtained. It disappeared, and absorption of the imide ring was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1, characteristic absorption of the isocyanurate ring was observed at 1690 cm −1 and 1460 cm −1, and characteristic absorption of the urethane bond was confirmed at 1550 cm −1. The acid value of the polyimide resin was 79 mgKOH / g in terms of solid content, and the concentration of the isocyanurate ring was 0.66 mmol / g (in terms of resin solid content).

  The polyimide resin (a-4) was evaluated in the same manner as in Example 1 except that the obtained polyimide resin (a-4) solution was used. The results are shown in Table 2.

Comparative Example 5
80 parts of polyimide resin (a-4), N680 (Dainippon Ink & Chemicals, Inc., cresol novolac type epoxy resin, epoxy equivalent 214, softening point 81 ° C.) 20 parts and 0.5 part of triphenylphosphine are mixed for comparison. Polyimide resin composition (a-5) for use was prepared.

  Except having used the obtained polyimide resin composition (a-5), it carried out similarly to Example 1, and evaluated the polyimide resin composition (a-5). The results are shown in Table 2.

2 is an infrared absorption spectrum of the polyimide resin of the present invention obtained in Example 1. 2 is a nuclear magnetic resonance absorption spectrum of the polyimide resin of the present invention obtained in Example 1. 2 is an infrared absorption spectrum of the polyimide resin of the present invention obtained in Example 2. 2 is a nuclear magnetic resonance absorption spectrum of the polyimide resin of the present invention obtained in Example 2.

Claims (21)

A polyimide resin characterized by having a structure represented by the general formula (1).

The polyimide resin according to claim 1, wherein the structure represented by the general formula (1) is a structure represented by the general formula (2).

Furthermore, the polyimide resin of Claim 1 which has a structure represented by General formula (3).

The polyimide resin according to claim 1, wherein the structure represented by the general formula (3) is a structure represented by the general formula (4).

The polyimide resin according to claim 2, wherein the structure represented by the general formula (2) is a structure represented by the general formula (5).

The polyimide resin according to claim 4, wherein the structure represented by the general formula (4) is a structure represented by the general formula (6).

The polyimide resin of Claim 1 which has a structure shown by General formula (7).

(Where n and m are each 1 to 1000) The polyimide resin of Claim 1 which has a structure shown by General formula (8) and / or General formula (9).

The polyimide resin of Claim 1 which has a structure shown by General formula (10) and / or General formula (11).

The polyimide resin containing the structure represented by the general formula (2), the general formula (4), and the general formula (9), and the general formula (2), the general formula (4), and the general formula (9). The polyimide resin according to claim 1, which is contained in the polyimide resin in an amount of 2 to 40 mol%, 2 to 50 mol%, and 2 to 50 mol%, respectively. The polyimide resin containing the structure represented by the general formula (5), the general formula (6), and the general formula (10), and the general formula (5), the general formula (6), and the general formula (10). The polyimide resin according to claim 1, which is contained in the polyimide resin in an amount of 5 to 98 mol%, 2 to 95 mol%, and 2 to 50 mol%, respectively. The polyimide resin of Claim 1 represented by following General formula (12).

(N, m, and p are each 1-1000.) 2. The polyimide resin according to claim 1, which is soluble in gamma butyrolactone when dissolved in gamma butyrolactone at 25 ° C. so as to be 10% by weight. A polyimide resin composition comprising the polyimide resin according to any one of claims 1 to 10 and an organic solvent. The polyimide resin composition according to claim 11, wherein the organic solvent is gamma butyrolactone. A method for producing a polyimide resin, comprising reacting a diisocyanate compound and cyclohexanetricarboxylic acid anhydride. The method for producing a polyimide resin according to claim 16, wherein the cyclohexanetricarboxylic acid anhydride is cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. The method for producing a polyimide resin according to claim 11, wherein a diisocyanate compound, cyclohexanetricarboxylic anhydride and trimellitic anhydride are reacted. The method for producing a polyimide resin according to claim 16, wherein the diisocyanate compound is 4,4-diphenylmethane diisocyanate. The polyimide according to claim 16, which is obtained by using 10 to 60 mol%, 2 to 60 mol%, and 2 to 60 mol% of 4,4-diphenylmethane diisocyanate, cyclohexanetricarboxylic anhydride, and trimellitic anhydride, respectively. Production method. 4,4-diphenylmethane diisocyanate, cyclohexane-1,3,5-tricarboxylic acid-3,4-anhydride, trimellitic anhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, The manufacturing method of the polyimide of Claim 16 obtained by using 10-60 mol%, 2-60 mol%, 2-60, and 2-60 mol%, respectively.

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