TW201809048A - Curable composition, cured film using said composition and overcoat film - Google Patents

Abstract

To provide a thermosetting resin composition which forms a protection film for flexible wiring boards, said protection film having excellent bending resistance and being sufficiently suppressed in warping, while maintaining high electrical insulation reliability under high temperature and high humidity conditions. A curable composition according to the present invention contains: (component A) a compound which has a specific structural unit, at least one of an imide bond and an amide bond, and a functional group that is reactive with a curing agent; (component B) a curing agent; and (component C) an organic solvent. It is preferable that (component A) contains a compound which is obtained by a reaction that uses, as essential components, (starting material a) a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group, (starting material b) a polyol represented by formula (2), and (starting material c) a polyisocyanate.

Description

Curable composition, cured film and coating film using the same

The present invention relates to a method for forming a thermosetting resin composition, a protective film for a flexible wiring board, a flexible wiring board and an electronic component, and a method for manufacturing the flexible wiring board.

In recent years, in the field of electronic components, in order to respond to miniaturization, thinning, and high speed, resin compositions (for example, sealants, solder resists, etc.) used in electronic components are required to have better heat resistance, Electrical characteristics and humidity resistance. For this reason, in terms of the resin constituting the resin composition, polyimide resin, polyimide resin, and polyimide resin have been used instead of epoxy resin. However, these resins have rigid resin structures and lack flexibility in the cured film. Therefore, when it is used for a film substrate, the substrate after curing is liable to have large warpage, and also has problems such as poor flexibility.

Regarding the above-mentioned resins, in order to improve the warpage and flexibility, the resin has been modified to be flexible and have a low elastic modulus, and various modified polyamidamine / imide resins have been proposed (for example, refer to Patent Documents 1, 2 and 3).

In addition, Patent Document 4 discloses a thermosetting resin group intended to improve low warpage, flexibility, solder heat resistance, and tin plating resistance. Into something. The thermosetting resin composition of Patent Document 4 has excellent performance in maintaining the electrical insulation characteristics of high electrical characteristics under high temperature and high humidity.

However, in recent years, with the miniaturization of wiring, when a display panel connected to a flexible wiring board is mounted on a casing in other places, the problem of wiring breakage occurs during transportation, so it has a protective function against wiring breakage. A protective film (hereinafter referred to as "bending resistance") is desired.

In addition, Patent Document 5 discloses a thermosetting resin composition containing a polyamidoamine imine-modified polyurethane, a hardener, and an organic solvent. The thermosetting resin composition has low warpage, flexibility, and resistance. Bending performance. In addition, low warpage, flexibility, and electrical insulation characteristics under high temperature and high humidity were measured here.

However, even with this thermosetting resin composition, the electrical insulation protective film having higher bending resistance is not completely satisfied with the bending resistance required by the market.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 62-106960

[Patent Document 2] Japanese Unexamined Patent Publication No. 8-12763

[Patent Document 3] Japanese Unexamined Patent Publication No. 7-196798

[Patent Document 4] Japanese Patent Laid-Open No. 2006-117922

[Patent Document 5] Japanese Patent Laid-Open No. 2015-147940

However, with respect to the resin that forms the protective film of the flexible wiring board, and the conventional resin composition that has improved warpage and flexibility, water molecules are easily infiltrated under high temperature and high humidity, and it is necessary to maintain high electrical characteristics. Its difficult. In order to impart high electrical characteristics, it is considered effective to introduce a rigid component into the resin structure and make it have a high glass transition temperature. However, if this method is used, the substrate after curing is easily warped, and problems such as poor bendability may occur.

In addition, the thermosetting resin composition described in Patent Document 4 is considered to be improved to some extent in terms of low warpage, flexibility, solder heat resistance, and tin plating resistance, but it is difficult to improve it. Provides protection against breakage of wiring.

Moreover, although the thermosetting resin composition described in patent document 5 has some degree of bending resistance, it can be said that it is not enough.

Therefore, the present invention is to provide a protective film for a flexible wiring board, which can sufficiently control warpage while maintaining high electrical insulation reliability under high temperature and high humidity, and also has excellent performance in bending resistance. A thermosetting resin composition is a main purpose.

The present inventors have devoted to repeated research in order to solve the above-mentioned problems, and found that it has a specific structure, and at the same time, if a compound having at least one kind of bond of a sulfonium imine bond and a sulfonium bond is used as a necessary compound When the hardenable composition is printed on a flexible wiring board, the printed hardenable composition hardens, and the warpage of the flexible wiring board is small, and the protective film containing the hardened product of the hardenable composition is hardened. The present invention is excellent in flexibility and long-term electrical insulation characteristics. Furthermore, when the flexible wiring board covered with the protective film is shaken, the effect of suppressing the breakage of the wiring is great, and the present invention has been completed.

That is, this invention relates to the following matters.

[1] A hardening composition containing (Component A) A compound having a structural unit represented by the following formula (1), having at least one bond of a sulfonium imine bond and a sulfonium bond, and having a functional group that reacts with a hardener, (component B) Hardener and (component C) organic solvent.

(In the formula (1), R ¹ each independently represents an organic residue derived from a diol having 3 to 36 carbons, and R ² each independently represents a phenylene group or a phenylene group having a substituent.)

[2] The curable composition according to [1], wherein The functional group that reacts with the hardener is at least one of a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, a amine group, and an amine group.

[3] The curable composition according to [1] or [2], wherein (component A) contains: (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, (Raw material b) The following polyol represented by formula (2), and (raw material c) a compound obtained by reacting a polyisocyanate as an essential component.

(In formula (2), (n + 1) R ¹ each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms, and n R ² each independently represent a phenylene group or The phenyl group of the substituent, n represents an integer of 1 to 60).

In addition, (component A) in the curable composition specified in [3] is a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group in (raw material a), and (raw material b) is represented by the formula ( 2) The polyols shown in (2) and (polycarbonate of (raw material c)) are used as raw materials, and most of the compounds corresponding to (raw material a), (raw material b), and (raw material c) can react with each other. In addition, if the blending ratio or reaction conditions of various monomers are changed, the polymer obtained will also change. Therefore, the structure of the obtained component A is extremely divergent, and it is difficult to specify a specific structure, which is well known. Technical knowledge for practitioners in this field. Furthermore, if the structure cannot be specified, the characteristics cannot be specified. This means that the polymer composition specified in [3] cannot be specified by its structure or characteristics, but can only be specified by the process (manufacturing method). It is not necessary to directly specify the object by its structure or characteristics when applying. It is possible, or it may be taken into account, that there may be impractical sexual affairs.

[3 '] The curable composition according to [1] or [2], wherein (component A) contains at least a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group from (raw material a) And (raw material b) a reaction product formed by the following polyol represented by formula (2) and (raw material c) polyisocyanate.

(In formula (2), (n + 1) R ¹ each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms, and n R ² each independently represent a phenylene group or The phenyl group of the substituent, n represents an integer of 1 to 60).

[4] The curable composition according to any one of [1] to [3], wherein (ingredient A) further has a urethane bond.

[5] The curable composition according to any one of [1] to [4], wherein the (component A) is an acid value of 10 to 50 mgKOH / g.

[6] The curable composition according to any one of [1] to [5], wherein (component B) includes a compound having two or more epoxy groups per molecule.

[7] The curable composition according to any one of [1] to [6], wherein (component C) is made of an ether solvent, an ester solvent, a ketone solvent, and an aromatic hydrocarbon solvent. Group of at least one organic solvent.

[8] The curable composition according to any one of [1] to [7], further comprising (component D) at least one kind of fine particles selected from the group consisting of inorganic fine particles and organic fine particles.

[9] The curable composition according to any one of [1] to [8], wherein when the total amount of the component (A) and the component (B) is 100 parts by mass, 1 to 55 parts by mass is included. Ingredient (B).

[10] The curable composition according to any one of [1] to [9], wherein the total amount of the component (A), the component (B), the component (C), and the component (D) (excluding In the case of the component (D), when the total amount of the component (A), the component (B), and the component (C) is 100 parts by mass, 25 to 75 parts by mass of the component (C) is included.

[11] A cured product of the curable composition according to any one of [1] to [10].

[12] A coating film for a flexible wiring board, which is characterized in that a part or all of a wiring-forming surface of a flexible wiring board formed by wiring on a flexible substrate is coated as in [ The hardening composition according to any one of [1] to [10], and the hardened composition.

[13] A flexible wiring board characterized in that a part or all of the surface of the flexible wiring board formed by wiring formed on the flexible substrate is formed as described in [12] Covered by a covering film.

[14] The flexible wiring board according to [13], wherein the wiring is tin-plated copper wiring.

[15] A method for manufacturing a flexible wiring board covered with a coating film, which is characterized by including the following (step 1) and (step 3) and the necessary (step 2):

(step 1)

A step of forming a printed film on the pattern by printing the curable composition according to any one of [1] to [10] on at least a part of a wiring pattern portion of a flexible wiring board.

(Step 2)

A step of evaporating part or all of the solvent in the printed film by placing the printed film obtained in step 1 in an atmosphere of 40 to 100 ° C.

(Step 3)

The step of heating the printed film obtained in step 1 or the printed film obtained in step 2 at 100 to 170 ° C. to harden and form a coating film.

[16] An electronic component characterized by having the hardened film according to [11].

Furthermore, described in the present specification, "(n + 1) ^th, R ¹ each independently represent a" performance, the means (n + 1) th R ^1, even if all the same structure, and a portion of the same configuration The other parts are different structures, all are different structures, etc. It doesn't matter. In addition, expressions such as "n R ² are each independently displayed" described in this specification also mean that even if all of the n R ^{2 have the} same structure, some of them have the same structure and other parts are different. Structure, all for different structures, etc. It doesn't matter.

By curing the curable composition of the present invention, a protective film with low warpage, flexibility, and long-term insulation reliability can be obtained, and a flexible wiring board covered with the cured film can be provided when shaken Protective film with a large effect of suppressing wire breakage.

Further, the present invention can provide a protective film made of a cured product of the hardenable composition, and a flexible wiring board covered with the protective film, which is capable of being sufficiently suppressed while maintaining high insulation reliability. A flexible wiring board that is warped and has excellent bendability.

[Form of Implementing Invention]

Hereinafter, suitable embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The curable composition of the present invention is characterized by containing the following components: (component A) has a structural unit represented by the following formula (1), and has at least one bond of a sulfonium imine bond and a sulfonium bond A compound having a functional group that reacts with a hardener, (component B) a hardener, and (component C) an organic solvent.

(In the formula (1), R ¹ each independently represents an organic residue derived from a diol having 3 to 36 carbons, and R ² each independently represents a phenylene group or a phenylene group having a substituent.)

(Component A), which is an essential component of the curable composition of the present invention, has a structural unit represented by the formula (1), and has a fluorene imine bond and a fluorene bond (-C (= O) -NH -) At least one bonded compound.

(Component A) may further have a urethane bond (-O-C (= O) -NH-). Moreover, (component A) has a functional group which reacts with a hardener. As a preferable functional group which can react with a hardening | curing agent, the functional group of at least 1 sort (s) of a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, an amino group, and an amino group is mentioned. When having an isocyanate group, the isocyanate group is preferably protected by a blocking agent. And in other groups, it can be protected by a blocking agent, and the blocking body is detached and the reactant is regarded as a functional group. The wave line is tied to the end of the bond, indicating that it is bonded to other bonds The bonding site.

In the formula (1), R ¹ each independently represents an organic residue derived from a diol having 3 to 36 carbon atoms. In other words, the above-mentioned organic residue derived from a diol is a divalent group obtained by removing two hydroxyl groups from a diol.

Examples of diols having 3 to 36 carbons include 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, and 2-methyl-1,3-propane Diol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonane Diol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, hydrogenated dimer ( C36) Chain diols such as diols, diethylene glycol, and triethylene glycol, 1,2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol, and bis (hydroxymethyl) tricyclic [5.2.1.0] 5-membered cyclodiols such as decane, and 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2- 6-membered cyclodiols such as cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and 2,2-bis (4-hydroxycyclohexyl) -propane A diol having an alicyclic structure.

A preferred example of R ¹ is a hydrocarbon group having a chain structure of 3 to 18 carbon atoms. A more preferable example is a hydrocarbon group of 4 to 9 carbon chains having a chain structure. A particularly preferred example is a carbon group of 4 ~ 6 Hydrocarbon group with chain structure. In other words, preferred diols from which organic residues of R ¹ can be derived include, for example, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 2-methyl -1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and more preferable diols, for example Such as 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5- Pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, particularly preferred Examples of the alcohol include 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methyl -1,5-pentanediol. The best diols are 1,6-hexanediol and 3-methyl-1,5-pentanediol.

In Formula (1), R ² each independently represents a phenylene group or a phenylene group having a substituent. Examples of the phenylene include 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene. Examples of the substituent of the phenyl group having a substituent include an alkyl group having 1 to 10 carbon atoms, and specifically, 3-methyl-1,2-phenylene and 4-methyl-1 2,2-phenylene, 4-methyl-1,3-phenylene, 2-methyl-1,4-phenylene, 3-ethyl-1,2-phenylene, 4-ethyl A phenylene group having an alkyl group as a substituent, such as -1,2-phenylene, 4-ethyl-1,3-phenylene, 2-ethyl-1,4-phenylene, and the like. As for the phenylene group which further has a substituent, 3-bromo-1,2-phenylene, 4-bromo-1,2-phenylene, 4-bromo-1,3-phenylene, 2 -Bromo-1,4-phenylene, 3-chloro-1,2-phenylene, 4-chloro-1,2-phenylene, 4-chloro-1,3-phenylene, 2-chloro Benzene having halogen, such as -1,4-phenylene.

Among these, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, and a phenylene group having an alkyl group as a substituent are more preferable, and 1, 2-phenylene, 1,3-phenylene, 1,4-phenylene, and particularly preferably 1,2-phenylene and 1,3-phenylene.

The best combination of R ¹ and R ² is that when R ² is 1,2-phenylene, R ¹ is 1,6-hexanediol or 3-methyl-1,5-pentane. When diol is an organic residue derived from diol, when R ² is 1,3-phenylene, R ¹ is an organic residue derived from 3-methyl-1,5-pentane derived from diol.

Next, the synthesis method of (component A) is demonstrated.

(Component A) can be synthesized, for example, by the following method.

(Method 1) (raw material b) a polyol represented by the following formula (2)

(In formula (2), (n + 1) R ¹ each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms, and n R ² each independently represent a phenylene group or The phenyl group of the substituent, n independently represents an integer of 1 to 60).

Reacting with (raw material c) polyisocyanate to obtain a compound having a urethane bond and having an isocyanate terminal, and allowing the obtained polyisocyanate to include a compound having a urethane bond and having an isocyanate terminal It reacts with (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group (below).

(Method 2) reacting (raw material c) the polyisocyanate with (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group to obtain at least one bond having a fluorene imine bond and a fluorene bond The resulting polyisocyanate is reacted with a polyol represented by formula (2) (raw material b).

(Method 3) reacting (raw material c) the polyisocyanate with (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group to obtain at least one bond having a fluorene imine bond and a fluorene bond A compound having an acid anhydride group and / or a carboxyl group at the terminal and reacting a polyol represented by formula (2) (raw material b) therein.

(Method 1) The synthesis method first comprises reacting a polyol represented by formula (2) with (raw material b) and a polyisocyanate of (raw material c) to synthesize a urethane bond and an isocyanate group at the end. Compound (hereinafter, referred to as "(A ¹ -1) compound").

^1, and are each the same as R ² (1) of the formula R ^1, R ² of formula R (2) in the.

N in the formula (2) represents an integer of 1 to 60. The preferred n aspect is an integer of 1 to 45, particularly preferably an integer of 1 to 30. The average value of n is preferably from 3 to 11, more preferably from 5 to 10.

The number average molecular weight of the diol of formula (2) is from 500 to 5000 Better, 750 ~ 4000 is better, 1000 ~ 3000 is better.

The polyisocyanate (meaning (raw material c)) which can react with the polyol of (raw material b) is not particularly limited as long as it is a compound having two or more isocyanate groups. Specific examples of the polyisocyanate include 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate), and 1 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, norurene diisocyanate and diurea of isophorone diisocyanate, etc. Cyclic aliphatic polyisocyanate; diphenylmethane-2,4'-diisocyanate, 3,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,3'-dimethyl Diphenylmethane-2,4'-diisocyanate, 4,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 4,3'-dimethyldiphenylmethane-2,4 '-Diisocyanate, 5,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 5,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 6,2 '-Dimethyldiphenylmethane-2,4'-diisocyanate, 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'-diethyldiphenyl Methane-2,4'-diisocyanate, 3,3'-diethyldiphenylmethane-2,4'-diisocyanate, 4,2'-diethyldiphenylmethane-2,4'-di Isocyanate, 4,3'-diethyl Phenylmethane-2,4'-diisocyanate, 5,2'-diethyldiphenylmethane-2,4'-diisocyanate, 5,3'-diethyldiphenylmethane-2,4 ' -Diisocyanate, 6,2'-diethyldiphenylmethane-2,4'-diisocyanate, 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2 ' -Dimethoxydiphenylmethane-2,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, 4,2'-dimethoxydiamine Phenylmethane-2,4'-diisocyanate, 4,3'-dimethyl Oxydiphenylmethane-2,4'-diisocyanate, 5,2'-dimethoxydiphenylmethane-2,4'-diisocyanate, 5,3'-dimethoxydiphenylmethane -2,4'-diisocyanate, 6,2'-dimethoxydiphenylmethane-2,4'-diisocyanate, 6,3'-dimethoxydiphenylmethane-2,4'- Diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenylether-4,4 '-Diisocyanate, benzophenone-4,4'-diisocyanate, diphenylfluorene-4,4'-diisocyanate, 2,4-trichloroethylene diisocyanate, 2,6-trichloroethylene diisocyanate , M-dimethylene diisocyanate, p-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4 '-[2,2bis (4-phenoxyphenyl) propane] Diisocyanates and other polyisocyanates with aromatic rings; bisurea of hexamethylene diisocyanate, triisocyanate lysine, diisocyanate lymide, hexamethylene diisocyanate, 2,4,4-trimethyl Chain aliphatic polyisocyanates such as methylene diisocyanate and 2,2,4-trimethylhexane methylene diisocyanate ; Isophorone diisocyanate isotricyanate body, hexamethylene diisocyanate isotricyanate body, and other polyisocyanates with heterocycles, etc., can be used alone or in combination 2 More than one kind of use.

Considering the reaction between the synthesized compound having a urethane bond and an isocyanate group at the terminal and the (raw material a) trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group to be reacted later Among these, a polyisocyanate having an aromatic ring is preferred, and diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, and diphenyl are more preferred. Methane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, etc. The aromatic polyisocyanate is preferably diphenylmethane-4,4'-diisocyanate.

In addition, in order to prevent the polyisocyanate from changing over time, an isocyanate group can be stabilized by a blocking agent. As the capping agent, alcohols, phenols, and oximes typified by hydroxyacrylate, methanol, and 2-butanone oxime are not particularly limited.

The reaction between the polyol of (raw material b) and the polyisocyanate of (raw material c) is carried out in the presence of an organic solvent, preferably a non-nitrogen-based polar solvent, and heating and reacting them.

The non-nitrogen-containing polar solvent may be, for example, an ether solvent such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. ; Sulfur-based solvents such as dimethyl fluorene, diethyl fluorene, dimethyl fluorene, and cyclobutyl fluorene; γ-butyrolactone and acetic acid acetate solvents; cyclohexanone and methyl Ketone solvents such as ethyl ketone; and aromatic hydrocarbon solvents such as toluene and xylene. These can be used individually by 1 type or in combination of 2 or more types.

Among the above solvents, it is preferable to select and use a solvent in which the resulting resin is soluble.

Moreover, it is preferable to use it as a solvent of thermosetting resin composition directly after synthesis | combination. Among the solvents mentioned above, cyclohexanone, γ-butyrolactone, and diethylene glycol diethyl ether are particularly preferred if they are considered to be volatile and react efficiently and uniformly.

The amount of the solvent to be used is preferably 80 to 500 parts by mass based on 100 parts by mass of the total amount of the raw materials of the compound (A ¹ -1). This amount of use is 100 parts by mass relative to the total amount of the raw materials of the compound (A ¹ -1). If it is 80 to 500 parts by mass, the viscosity during synthesis will not be too high, and it will not be difficult to stir because it cannot be stirred. It is better to synthesize the situation and the reaction speed will not be extremely reduced.

The reaction temperature is preferably 60 to 210 ° C, more preferably 70 to 190 ° C, and particularly preferably 80 to 180 ° C. If the temperature is less than 60 ° C, the reaction time tends to be too long, and if it exceeds 210 ° C, colloidation tends to be easily caused during the reaction. The reaction time can be appropriately selected depending on the capacity of the reaction container and the reaction conditions used.

If necessary, the reaction can also be carried out in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a semimetal compound.

The blending ratio when the polyol of (raw material b) and the polyisocyanate of (raw material c) are reacted can be appropriately adjusted according to the number average molecular weight of the produced (A ¹ -1) compound. However, since the terminal of the produced (A ¹ -1) compound is an isocyanate group, it is necessary that the number of the hydroxyl groups of (raw material b) <the number of isocyanate groups of (raw material c).

When synthesizing an (A ¹ -1) compound having an isocyanate group at the end, it is better to adjust the ratio of the number of isocyanate groups to the number of hydroxyl groups (isocyanate number / number of hydroxyl groups) to 1.01 or more, and to 2.0 or less. good.

The number average molecular weight of the (A ¹ -1) compound having an isocyanate group at its terminal is preferably 500 to 30,000, more preferably 1,000 to 25,000, and particularly preferably 1500 to 20,000.

Reacting (A ¹ -1) a compound having an isocyanate group at its terminal with (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, so as to form a urethane bond, Compounds with amido and / or imine bonds. In addition, when (raw material a) is a trivalent polycarboxylic acid derivative having an acid anhydride group, it may have a group of acid anhydrides and one carboxyl group. When (raw material a) is a tetravalent polycarboxylic acid derivative having an acid anhydride group, it may have two groups of acid anhydrides or one group of acid anhydride groups and two carboxyl groups. The carboxyl group may form an ester bond with an alcohol to form a derivative. The polycarboxylic acid derivative herein means a polycarboxylic acid having an acid anhydride group, or a derivative thereof such as a carboxylic acid ester.

The trivalent polycarboxylic acid derivative having an acid anhydride group is not particularly limited, and examples thereof include compounds represented by the following general formula (3) or (4).

(In the formula (3), R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group).

(In formula (4), R ⁴ represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 10 carbon atoms, and Y ¹ represents -CH _2- , -CO-, -SO _2- , or -O-).

The above-mentioned aspects of R ³ and R ⁴ are preferably hydrogen atoms, and the aspect of Y 1 is -CO- or -O-.

Among them, in terms of a trivalent polycarboxylic acid derivative having an acid anhydride group, anhydrous trimellitic acid is particularly preferable in terms of cost and the like.

The tetravalent polycarboxylic acid derivative having an acid anhydride group is not particularly limited, and examples thereof include a tetracarboxylic dianhydride represented by the following general formula (5). These can be used alone or in combination of two or more.

(In the formula (5), Y ² represents a tetravalent organic group).

The tetracarboxylic dianhydride represented by formula (5) is not particularly limited, but examples thereof include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,3,2 ', 3'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'- Diphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyphenyl) fluorene dianhydride, 3,4,9,10-fluorenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5 1,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Carboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic acid Acid dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4 -Dicarboxyphenyldimethylsilyl) phthalic anhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p -Phenylbis (trimellitic acid monoester anhydride), ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, decalin-1,4,5,8-tetralin Carboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2 , 3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, bis (exo- Bicyclic [2,2,1] heptane-2,3-dicarboxylic anhydride) hydrazone, bicyclic- (2,2,2) -oct (7) -ene-2,3,5,6-tetracarboxylic acid di Anhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic acid), 5- (2, 5-Dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 1,3,3a , 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-anyl) naphtho [1,2-c] furan-1,3-dione, ethylene glycol Bis (trimellitic anhydride) (also known as "ethylene glycol didehydrotrimellitate" or "TMEG"), etc.

Tetracarboxylic dianhydride is ethylene glycol bis (trimellitic anhydride) (TMEG), 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride Anhydride (PMDA), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic dianhydride (ODPA).

These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

Method 1, also make (A ¹ -1) compound (A ¹ -1) other than the polyisocyanate compound (hereinafter referred to as (A ¹ -2) compound) simultaneously in the reaction of (raw material A), to give Compounds having a urethane bond, a hydrazine bond, and / or a fluorenimine bond. The (A ¹ -2) compound is not particularly limited as long as it is a polyisocyanate other than the (A ¹ -1) compound, and examples thereof include the aforementioned (raw material c). These can be used individually by 1 type or in combination of 2 or more types. The ^ratio of the total number of the acid anhydride groups and the carboxyl groups of the raw material a to the total number of the isocyanate groups in A ¹ -1 and the total number of isocyanate groups in A ¹ -2 is not particularly limited. It is preferable to use a range of 0.9: 1.0 to 1.1: 1.0, and more preferably a range of 0.95: 1.0 to 1.05: 1.0.

In this embodiment, an amine compound can be used together with the polyisocyanate. Examples of the amine compound include compounds in which an isocyanate group in the above-mentioned polyisocyanate is converted into an amine group. The conversion of an isocyanate group into an amine group can be performed by a known method.

50 to 100% by mass of the total amount of the (A ¹ -2) compound is preferably an aromatic polyisocyanate. This aromatic polyisocyanate is particularly preferably a diphenylmethane-4,4'-diisocyanate when considering the balance of solubility, mechanical properties, and cost.

(Method 2) The synthesis method firstly reacts (raw material c) a polyisocyanate with (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group to synthesize a fluorene imine bond and fluorene amine At least one type of bonded polyisocyanate (hereinafter referred to as "(A ² -1) compound").

The blending ratio when reacting the polyisocyanate of (raw material c) with the trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group can be generated according to the desired (A ² -1) compound The number average molecular weight is appropriately adjusted. However, since the terminal of the produced (A ² -1) compound is an isocyanate group, the sum of the number of acid anhydride groups and the number of carboxyl groups in (raw material a) must be less than the number of isocyanate groups in (raw material c). . Here, the number of carboxyl groups, and a compound represented by the formula -COOR ³ (4) as the compound of formula (3) in the formula of the -COOR ^4, R ³ and also R ⁴ comprises a carboxyl group of a hydrogen atom The number.

In addition, the (raw material a) and (raw material c) used in the synthesis method of (method 2) can be used individually as the (raw material a) and (raw material c) used in the synthesis method of (method 1).

When synthesizing an (A ² -1) compound having an isocyanate group at the end, the ratio of the number of isocyanate groups to the number of acid anhydride groups to the total number of carboxyl groups (the number of isocyanate groups / the number of acid anhydride groups and the number of carboxyl groups) The total number is preferably adjusted to 1.01 or more, and adjusted to 2.0 or less.

The number average molecular weight of the (A ² -1) compound having an isocyanate group at the terminal is preferably 500 to 15,000, more preferably 800 to 10,000, and particularly preferably 1,000 to 5,000.

Next, the (A ² -1) compound having an isocyanate group at its terminal is reacted with a polyol represented by formula (2) in (raw material b) to form a urethane bond with a amine bond and / Or a compound having an imine bond.

When the (A ² -1) compound having an isocyanate group at its terminal is reacted with a polyol represented by formula (2) (raw material b), a compound such as 2,2-dimethylolpropionic acid or Polyols having a carboxyl group of 2,2-dimethylolbutanoic acid are used together.

The total number of isocyanate groups in A ² -1, the number of hydroxyl groups in raw material b, and the polyvalent carboxyl group such as 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid There is no particular limitation on the ratio of the total number of hydroxyl groups in the alcohol to the total number of hydroxyl groups. When A ² -1 has an amidino group, it is preferably in the range of 0.9: 1.0 to 1.1: 1.0, more preferably 0.95. : 1.0 ~ 1.05: 1.0. In addition, when A ² -1 does not have a sulfonylamino group, and a polyol having a carboxyl group such as 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid is not used, it is 0.9. : 1.0 to 0.95: 1.0, or 1.0: 0.95 to 1.0: 0.9.

The (raw material b) used in the (method 2) synthesis method can be the same as the (raw material b) described in (method 1). Moreover, also The polyol may be further added, and a urethane bond may be formed by reacting a terminal isocyanate group with the additional polyol.

(Method 3) The synthesis method firstly reacts (raw material c) a polyisocyanate with (raw material a) a trivalent and / or a tetravalent polycarboxylic acid derivative having an acid anhydride group to synthesize a fluorenimine bond and fluorenamine A compound having at least one type of bond and having an acid anhydride group and / or a carboxyl group at the terminal (hereinafter, referred to as "(A ³ -1) compound").

The blending ratio when reacting the polyisocyanate of (raw material c) with the trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group can be generated according to the desired (A ³ -1) compound The number average molecular weight is appropriately adjusted. However, since the end of the compound to be produced (A ³ -1) is an acid anhydride group and / or a carboxyl group, the total number of the number of acid anhydride groups and the number of carboxyl groups in (raw material a) is> isocyanate of (raw material c). Cardinalities are necessary. Here, the compound represented by the formula -COOR ^3, and (4) the number of compounds of formula as also shown in (3) of the carboxyl group in the -COOR ^4, comprising R ³ and R ⁴ is a hydrogen atom of a carboxyl group .

The (raw material a) and (raw material c) used in the synthesis method of (method 3) can be the same as the (raw material a) and (raw material c) used in the synthesis method of (method 1), respectively.

When synthesizing (A ³ -1) compounds having acid anhydride groups and / or carboxyl groups at the end, the ratio of the total number of acid anhydride groups to the number of carboxyl groups and the number of isocyanate groups (the sum of the number of acid anhydride groups and the number of carboxyl groups The total number / isocyanate number) is preferably adjusted to 1.01 or more, and adjusted to 2.0 or less.

The number-average molecular weight of the (A ³ -1) compound having an acid anhydride group and / or a carboxyl group at the terminal is preferably 500 to 15,000, more preferably 800 to 10,000, and particularly preferably 1,000 to 5,000.

Next, the (A ³ -1) compound having an acid anhydride group and / or a carboxyl group at its terminal is reacted with a polyol represented by formula (2) (raw material b) to synthesize a compound having a sulfonium bond and / or a sulfonium imine bond. Compound. The ratio of the total number of acid anhydride groups in A ³ -1 to the number of hydroxyl groups in raw material b is not particularly limited, and it is preferably in the range of 0.9: 1.0 to 1.1: 1.0, more preferably 0.95: 1.0 to 1.05: 1.0 range.

The (raw material b) used in the synthesis method of (method 3) may be the same as the (raw material b) described in the above (method 1).

From the viewpoints of improvement of chemical resistance and electrical characteristics, and control of functional groups such as acid value, the method (that is, (Method 1) and (Method 1) and ( Method 2)) is better.

These (Method 1) to (Method 3) reactions can be carried out by heating these in the presence of an organic solvent, preferably a non-nitrogen-based polar solvent.

The non-nitrogen-containing polar solvent may be, for example, an ether solvent such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. ; Sulfur-based solvents such as dimethyl fluorene, diethyl fluorene, dimethyl fluorene, and cyclobutyl fluorene; γ-butyrolactone and acetic acid acetate solvents; cyclohexanone and methyl Ketone solvents such as ethyl ketone; and aromatic hydrocarbon solvents such as toluene and xylene are selected. These can be used individually by 1 type or in combination of 2 or more types.

Among the above solvents, it is preferable to select and use a solvent in which the resulting resin is soluble. In addition, it is suitable to use directly after synthesis as A solvent of the thermosetting composition is preferred. Among the above solvents, in order to perform the reaction more efficiently and uniformly, γ-butyrolactone or a mixed solvent containing γ-butyrolactone is preferred.

In order to synthesize (component A), the amount of the solvent used is preferably 0.8 to 5.0 times (mass ratio) relative to the total amount of (component A). If the amount used is 0.8 to 5.0, it is preferable because the viscosity during synthesis will not be too high and the reaction rate will not be reduced.

The reaction temperature is preferably 60 to 210 ° C, more preferably 70 to 190 ° C, and particularly preferably 80 to 180 ° C. If the temperature is less than 60 ° C, the reaction time tends to be too long, and if it exceeds 210 ° C, colloidation tends to be easily caused during the reaction. The reaction time can be appropriately selected depending on the capacity of the reaction container and the reaction conditions used.

Depending on the needs, the catalyst can also be reacted in the presence of catalysts such as tertiary amines, alkali metals, alkaline earth metals, metals such as tin, zinc, titanium, and cobalt, or semi-metal compounds.

In this specification, the number average molecular weight means a value measured by colloidal permeation chromatography (GPC) and converted using a calibration curve of standard polystyrene.

The number average molecular weight, the mass average molecular weight, and the degree of dispersion are defined as follows.

(a) Number average molecular weight (Mn)

Mn = Σ (N _i M _i ) / ΣN _i = ΣX _i M _i

(X _i = Mohr fraction of the molecule of molecular weight M _i = N _i / ΣN _i )

(b) Mass average molecular weight (Mw)

Mw = Σ (N _i M _i ² ) / ΣN _i M _i = ΣW _i M _i

(W _i = mass fraction of molecule of molecular weight M _i = N _i M _i / ΣN _i M _i )

(c) Molecular weight distribution (degree of dispersion)

Dispersion = Mw / Mn

In addition, in this specification, the measurement conditions of GPC are as follows without limitation.

Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation

Column: Shodex (registered trademark) column LF-804 × 3 (in-line)

Mobile phase: tetrahydrofuran

Flow rate: 1.0mL / min

Detector: RI-2031Plus, manufactured by JASCO Corporation

Temperature: 40.0 ℃

Sample volume: 100 μL of sample loop

Sample concentration: before and after adjustment to 0.1% by mass.

The acid value of (component A) is preferably 10 to 50 mgKOH / g. It is more preferably 10 to 35 mgKOH / g, and particularly preferably 15 to 30 mgKOH / g. If the acid value of (component A) is 10 to 50 mgKOH / g, the warpage will not be too large, and the hardening will be sufficient. Therefore, it is possible to suppress the deterioration of weather resistance and bendability, etc., and it is preferable.

The acid value of (component A) can be measured by the following method. First, the fine scale contains about 1 g of the solution of (component A). Thereafter, 30 g of a mixed solvent of isopropyl alcohol / toluene = 1/2 (mass ratio) was added thereto, and the mixture was uniformly dissolved. To the obtained solution, an appropriate amount of phenolphthalein was added as an indicator, and titration was performed using a 0.1N KOH solution (alcoholic). Then, the result of the titration is expressed by the following formula (α): A = 10 × Vf × 56.1 / (Wp × I) ‧ ‧ ‧ ‧ formula (α)

To calculate the acid value. In the formula (α), A represents an acid value (mgKOH / g), Vf represents a titer (mL) of a 0.1N KOH solution, Wp represents a mass (g) of a solution containing (component A), and I represents a component containing (component A) The non-volatile matter ratio (% by mass) of the solution.

The number average molecular weight of the component A obtained in this way is preferably 5,000 to 50,000, more preferably 6,000 to 40,000, and particularly preferably 7,000 to 25,000. When the number average molecular weight is 5,000 to 50,000, it is preferable to suppress deterioration of weather resistance or chemical resistance, and to maintain solubility in a non-nitrogen-based polar solvent.

Next, (component B) which is an essential component of the curable composition of this invention is demonstrated.

The curable composition according to this embodiment further contains a curing agent that can harden the aforementioned (component A). The hardener is a compound having two or more functional groups capable of reacting with the functional group of the component (A) in one molecule. When the component (A) has any of a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, a amine group, and an amine group, the hardener of the component (B) has a plurality of compounds that can react with these functional groups. An epoxy group, an isocyanate group, a hydroxyl group, or a carboxyl group is preferred.

As for the epoxy group-containing compound used as the hardener, if one or more compounds having an epoxy group in one molecule are included and at least one of them is a compound having two or more epoxy groups in one molecule, and No special restrictions.

Specific examples of the epoxy group-containing compound used as the hardener include phenol novolac-type epoxy resin and o-cresol. Novolac epoxy resins are naphthols such as phenol, cresol, xylenol, resorcinol, resorcinol, phenols and / or α-naphthol, β-naphthol, dihydroxynaphthalene, etc. Novolak epoxy resin, bisphenol with epoxy resin, bisphenol, obtained by condensation or co-condensation with aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc. under acidic catalyst A, bisphenol F, bisphenol S, alkyl-substituted or non-substituted biphenols, stilbene phenols, and other diglycidyl ethers (bisphenol A epoxy compounds, bisphenol F epoxy compounds , Bisphenol S-type epoxy compound, biphenyl-type epoxy compound, stilbene-type epoxy compound), butylene glycol, polyethylene glycol, polypropylene glycol, and other alcohol-based glycidyl ethers , Phthalic acid, isophthalic acid, tetrahydrophthalic acid and other carboxylic acid type epoxypropyl ester epoxy resin, aniline, bis (4-aminophenyl) methane, isotricyanic acid, etc. Glycidyl-type or methyl-glycidyl-type epoxy resins, p-aminophenols in which an active hydrogen bonded to a nitrogen atom is substituted with a glycidyl group, etc. Epoxy-type or methyl-epoxy-type epoxy resins, such as amine phenols, in which the active hydrogen bonded to a nitrogen atom and the active hydrogen of a phenolic hydroxyl group are substituted with a glycidyl group, etc. Vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3 , 4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxolane and other alicyclic epoxy resins, para-dimethylene Glycidyl ether of phenyl resin modified by methylene and / or meta-position, Glycidyl ether of terpene-modified phenol resin, Glycidyl ether of dicyclopentadiene-modified phenol resin , Glycidyl ether of cyclopentadiene modified phenol resin, Glycidyl ether of polycyclic aromatic ring modified phenol resin, Glycidyl ether of naphthalene ring-containing phenol resin, Halogenated benzene Novolac epoxy resin, hydroquinone epoxy resin, trimethylolpropane epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefinic bonds with peracid such as peracetic acid, diphenyl Epoxides of aralkyl phenol resins such as methane epoxy resin, phenol aralkyl resin, naphthol aralkyl resin, epoxy resin containing sulfur atom, tricyclic [5,2,1,02, 6] Glycidyl ether of decane dimethanol, 1,3-bis (1-adamantyl) -4,6-bis (glycidyl ether) benzene, 1- [2 ', 4'-bis (Glycidyl ether) phenyl] adamantane, 1,3-bis (4'-glycidyl ether phenyl) adamantane, and 1,3-bis [2 ', 4'-bis (glycidyl ether group) An epoxy resin having an adamantane structure such as phenyl] adamantane. These can be used individually by 1 type or in combination of 2 or more types.

The compound having two or more epoxy groups in one molecule is preferably a compound having two or more epoxy groups in one molecule and having an aromatic ring structure and / or an alicyclic structure.

When attaching importance to the long-term electrical insulation performance of the cured film of the present invention described below, dicyclopentadiene is modified among compounds having two or more epoxy groups in one molecule and having an aromatic ring structure and / or an alicyclic structure Glycidyl ether of phenol resin (meaning a compound having a tricyclic [5,2,1,0 ^2,6 ] decane structure and an aromatic ring structure and having two or more epoxy groups), 1,3 -Bis (1-adamantyl) -4,6-bis (glycidyl ether) benzene, 1- [2 ', 4'-bis (glycidyl ether) phenyl) adamantane, 1,3-bis (4'-glycidyl ether phenyl) adamantane and 1,3-bis [2 ', 4'-bis (glycidyl ether) phenyl] adamantane, etc. That is, a compound having a tricyclic [3,3,1,1 ^3,7 ] decane structure and an aromatic ring structure and having two or more epoxy groups) and the like having a tricyclodecane structure and an aromatic ring structure and having A compound having two or more epoxy groups is preferred because it can provide a cured product having a low water absorption rate, and particularly preferably a compound described in the following formula (6).

(M in formula (6) represents a positive integer).

In addition, when the reactivity with (component A) of the present invention is emphasized, among compounds having two or more epoxy groups in one molecule and having an aromatic ring structure and / or an alicyclic structure, aniline is used. Bis (4-aminophenyl) methane, epoxy-type or methyl-epoxy-type epoxy resins, p-amines in which the active hydrogen bonded to a nitrogen atom is substituted with a glycidyl group, etc. Glycidyl-type or methyl-glycidyl-type epoxy resins, such as aminophenols such as aminophenols, in which the active hydrogen bonded to a nitrogen atom and the active hydrogen of a phenolic hydroxyl group are replaced with an epoxypropyl group A compound such as a resin having an amine group and an aromatic ring structure and having two or more epoxy groups is preferable, and a compound described in the following formula (7) is particularly preferable.

In addition, as the polyisocyanate compound, that is, a compound having a plurality of isocyanate groups used as a curing agent, for example, a diisocyanate compound, a triisocyanate, and other isocyanates having four or more functions. In consideration of the change over time when (component A) is mixed with the hardener, it is preferable to use a polyisocyanate compound that stabilizes an isocyanate group with a blocking agent. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the end-capping agent include alcohol, phenol, and oxime, and are not particularly limited. Examples of the blocked isocyanate include, for example, the trade names "DURANATE17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T", and the trade name "KARENZ MOI-BM" manufactured by Asahi Kasei Chemicals Corporation "MOI-BP", brand names "BL-3175, BL-4165, Desmo Cup 11, Desmo Cup -12" manufactured by Sumika BAYER Urethane Co., Ltd., etc. The blocked isocyanate is preferably selected in accordance with the heat curing temperature of (component A). For low temperature curing, BL-3175 is particularly preferred.

The hydroxyl-containing compound used as the hardener is not particularly limited as long as it contains one or more compounds having a hydroxyl group in one molecule and at least one of them is a compound having two or more hydroxyl groups in one molecule. system.

Examples of the hydroxyl-containing compound used as the curing agent include polyhydric alcohols. Specific examples include ethylene glycol, glycerol, butanediol, and pentaerythritol.

The carboxyl group-containing compound used as the hardener is not particularly limited as long as it contains one or more compounds having a carboxyl group in one molecule and at least one of them is a compound having two or more carboxyl groups in one molecule.

Examples of the carboxyl group-containing compound used as the curing agent include polyvalent carboxylic acids. Specific examples include phthalic acid, succinic acid, trimellitic acid, adipic acid, and pyromellitic acid.

As for the hardener, an epoxy group-containing compound, a polyisocyanate compound, a hydroxyl group-containing compound, and a carboxyl group-containing compound can be used alone or in combination, and can be selected by blending with the reactive group of (component A). For example, when (component A) has a hydroxyl group, it is preferable to use a blocked isocyanate, and when (component A) has a carboxyl group or an amine group, it is preferable to use an epoxy group-containing compound. The hardening agent is not limited to an epoxy group-containing compound, a polyisocyanate compound, a hydroxyl group-containing compound, and a carboxyl group-containing compound as long as it can react with the reactive group of (component A).

The amount of (ingredient B) in the curable composition of the present invention is 1 to 55% by mass, preferably 2 to 45%, based on the total amount of (ingredient A) and (ingredient B) in the curable composition. Mass%, more preferably 2.5 to 30 mass%. The amount of (ingredient B) in the curable composition of the present invention is 1 to 55% by mass relative to the total mass of (ingredient A) and (ingredient B) in the curable composition. It is preferable from the viewpoint of the solvent resistance of the cured film of the present invention described below, and it is possible to obtain low warpage of a flexible wiring board coated with the cured film as a special feature and better reliability of electrical insulation. Balance with the effect of suppressing wire breakage.

The amount of (ingredient A) in the curable composition of the present invention is 45 to 99% by mass, preferably 55 to 99% by mass based on the total amount of (ingredient A) and (ingredient B) in the curable composition. 98% by mass, more preferably 70 to 97.5% by mass. The amount of (ingredient A) in the curable composition of the present invention is 45 to 99% by mass based on the total amount of (ingredient A) and (ingredient B) in the curable composition. From the viewpoint of the solvent resistance of the cured film, it is preferable, and a balance between the low warpage of the flexible wiring board covered with the cured film and the suppression effect of the breakage of the wiring can be achieved.

Next, (component C) which is an essential component of the curable composition of this invention is demonstrated.

The organic solvent used in (component C) is not particularly limited as long as it is a solvent capable of dissolving (component A) and (component B). Examples thereof include diethylene glycol dimethyl ether and diethylene glycol diethyl. Ether, diethylene glycol ethyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, Ether solvents such as triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diethylene glycol Monoethyl ether acetate, diethylene glycol monomethyl ether acetate, methoxy Ester solvents such as methyl propionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, γ-butyrolactone, hydrocarbon solvents such as decalin, Ketone solvents such as cyclohexanone and aromatic hydrocarbon solvents such as toluene and xylene may be used alone or in combination of two or more.

Among these, when considering the balance between screen printing and the volatility of organic solvents, γ-butyrolactone, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, Ethylene glycol monomethyl ether acetate is preferred, more preferably γ-butyrolactone, diethylene glycol monoethyl ether acetate, and diethylene glycol diethyl ether, and most preferably γ-butyrolactone Solvent alone, 2 mixed solvents of γ-butyrolactone and diethylene glycol monoethyl ether acetate, 2 mixed solvents of γ-butyrolactone and diethylene glycol diethyl ether, and γ -3 mixed solvents of butyrolactone, diethylene glycol monoethyl ether acetate and diethylene glycol diethyl ether.

These preferred solvent combinations are preferred because they perform well as solvents for screen printing inks.

In addition, as part of these preferable organic solvents, the solvent for synthesis used in the production of the aforementioned (component A) can be directly used as a part of the organic solvent of the curable composition of the present invention. Better.

The content of (component C) in the curable composition of the present invention is relative to (component A), (component B), (component C), and (component D) described later as the components of the curable composition of the present invention. The total amount (when (component D) is not included in the curable composition of the present invention, it is the total amount of (component A), (component B), and (component C)), preferably 25 to 75% by mass , More preferably 35 to 65% by mass. The content of (component C) is the total amount of (component A), (component B), (component C) and the filler described later with respect to the components of the curable composition of the present invention. (However, when the filler is not included in the curable composition of the present invention, it is the total amount of (component A), (component B), and (component C)). If it is in the range of 25 to 75% by mass, it is due to the hardenability. The viscosity of the composition is good in the printing by the screen printing method, and the diffusion due to the penetration of the hardening composition after the screen printing does not become so large. As a result, the desired coating hardenability is obtained. It can be seen that the position of the composition (that is, the shape of the printing plate) does not make the printing area of the actual curable composition excessively large.

Moreover, in the said curable composition, it is preferable that (component C) is 0.5-20 mass parts with respect to 100 mass parts of (component A).

The curable composition of the present invention may include at least one kind of fine particles selected from the group consisting of inorganic fine particles and organic fine particles (component D).

The inorganic fine particles include, for example, silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), titanium dioxide (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconium dioxide (ZrO ₂ ), and silicon nitride ( Si ₃ N ₄ ), barium titanate (BaO‧TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO‧TiO ₂ ), lead zirconate titanate (PZT), lead zirconate titanate (PLZT) ), Gallium oxide (Ga ₂ O ₃ ), spinel (MgO‧Al ₂ O ₃ ), mullite (3Al ₂ O ₃ ‧ 2SiO ₂ ), vermiculite (2MgO‧2Al ₂ O ₃ ‧ 5SiO ₂ ) , Talc (3MgO‧4SiO ₂ ‧H ₂ O), aluminum titanate (TiO ₂ -Al ₂ O ₃ ), yttrium oxide-containing zirconia (Y ₂ O ₃ -ZrO ₂ ), barium silicate (BaO‧8SiO ₂ ), boron nitride (BN), calcium carbonate (CaCO ₃ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO‧TiO ₂ ), barium sulfate (BaSO ₄ ), organic bentonite , Carbon (C), hydrotalcite, etc. These can be used alone or in combination of two or more.

The organic fine particles are preferably fine particles of a heat-resistant resin having a fluorene bond, a fluorene imine bond, an ester bond, or an ether bond. In terms of these resins, from the viewpoints of heat resistance and mechanical properties, polyimide resins or precursors thereof, polyimide resins or precursors thereof, or polyimide resins are preferably mentioned. These can be used individually by 1 type or in combination of 2 or more types.

Among these, it is preferable that (component D) may include at least one selected from silica fine particles and hydrotalcite fine particles.

The silicon oxide fine particles used in the curable composition of the present invention are defined as including fine particles that are physically coated with a powder or chemically surface-treated with an organic compound.

The silica particles used in the hardenable composition of the present invention are not particularly limited as long as they are dispersed in the hardenable composition of the present invention to form a paste, and examples thereof include AEROSIL® provided by Japan AEROSIL Corporation.

Since these silica particles represented by AEROSIL® are also used to impart printability during screen printing, they are also used for the purpose of imparting shake.

In addition, hydrotalcite is a layered inorganic compound that is a naturally occurring clay mineral represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ ‧ 4H ₂ O and the like. Further, the hydrotalcite may be synthetic, such hydrotalcite Mg / Al-based lamellar compound, by ion-exchange with the carbonate group located between the layer of the chloride ion (Cl ^-) and / or a sulfate ion (SO ^4- ) Anions are immobilized. With this function, the capture of copper or tin be reasons for the chloride ions (Cl ^-) or sulfate ions (SO ^4-) and improve the insulation reliability of the object can be effectively used.

As for the hydrotalcite marketed products, for example, STABIACE HT-1, STABIACE HT-7, STABIACE HT-P, or DHT-4A, DHT-4A2, DHT-4C of Kyowa Chemical Industry Co., Ltd. .

The average particle diameter of these inorganic fine particles and / or organic fine particles is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm.

The blending amount of (component D) is 0.1 to 60% by mass, and preferably 0.3 to 55% by mass with respect to the total amount of (component A), (component B), (component C), and (component D). %, More preferably 0.5 to 40% by mass. If the blending amount of (component D) is in the range of 0.1 to 60% by mass with respect to the total amount of (component A), (component B), (component C), and (component D), the amount of the hardening composition The viscosity exhibits good printing performance by the screen printing method, and the diffusion caused by the penetration of the hardening composition after the screen printing does not become so large. As a result, the position where the hardening composition is to be applied is obtained as a result. (Meaning the shape of the printing plate) It can be seen that the printing area of the actual curable composition does not become too large.

Moreover, in the said curable composition, it is preferable that (component D) contains 1-30 mass parts with respect to 100 mass parts of (component A).

In the curable composition of the present invention, in the method of dispersing organic and / or inorganic fine particles, it is generally applicable to rolling and mixer mixing performed in the field of coatings, and if it is a method capable of sufficiently dispersing, can.

In addition, the curable composition of the present invention may preferably include an antifoaming agent for the purpose of eliminating or suppressing the generation of bubbles during printing.

Specific examples of the antifoaming agent used in the curable composition of the present invention include BYK-077 (manufactured by BYK JAPAN Co., Ltd.), SN-DEFOAMER 470 (manufactured by SAN NOPCO Co., Ltd.), and TSA750S (Momentive Performance Materials) (Manufactured by the company), silicone oil SH-203 (made by Toray Dow Corning Co., Ltd.), and other polysiloxane defoamers, DAPPO SN-348 (made by SAN NOPCO), DAPPO SN-354 (SAN NOPCO Acrylic polymer-based defoamer such as DAPPO SN-368 (manufactured by SAN NOPCO), Disparlon 230HF (manufactured by Kusumoto Kasei Co., Ltd.), SURFYNOL DF-110D (manufactured by Nissin Chemical Industry Co., Ltd.) , SURFYNOL DF-37 (manufactured by Nissin Chemical Industry Co., Ltd.) and other acetylene glycol-based defoamers, FA-630 and other fluorine-containing polysiloxane-based defoamers. These can be used individually by 1 type or in combination of 2 or more types.

The content of the antifoaming agent is relative to the total amount of (ingredient A), (ingredient B), (ingredient C), and (ingredient D) (however, when (ingredient D) is not included in the curable composition of the present invention, The total amount of (ingredient A), (ingredient B) and (ingredient C)) 100 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and particularly preferably 0.1 to 3 parts by mass .

Moreover, in the said curable composition, it is preferable that it is 0.2-10 mass parts with respect to 100 mass parts of (component A) defoamer.

The curable composition of the present invention may preferably include a hardening accelerator. The hardening accelerator is not particularly limited as long as it is a compound that promotes the reaction between an epoxy group and a carboxyl group. 6-methylpropane Allyloxyethyl-S-triazine, 2,4-methacryloxyethyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine, 2, Triazine compounds such as 4-diamino-6-vinyl-s-triazine, isotricyanic acid adducts, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2- Methylimidazole, 1- (cyanoethylaminoethyl) -2-methylimidazole, N- [2- (2-methyl-1-imidazolyl) ethyl] urea, 1-cyanoethyl 2-undecylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyano Ethyl-2-ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl -S-triazine, 2,4-diamino-6- [2'-ethyl -4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, N, N'-bis (2-methyl-1-imidazolylethyl) urea, N, N'-bis (2-methyl-1-imidazolylethyl) hexanediamine, 2-phenyl-4-methyl-5 -Hydroxymethylimidazole, 2-phenyl-4.5-dihydroxymethylimidazole, 2-methylimidazole‧isocyanuric acid adduct, 2-phenylimidazole‧isocyanuric acid adduct, 2 , 4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine‧isocyanuric acid adduct, 2-methyl-4-formamidine Imidazole, 2-ethyl-4-methyl-5-methylimidazole, 2-phenyl-4-methylformimidazole, 1-benzyl-2-phenylimidazole, 1,2-di Methylimidazole, 1- (2-hydroxyethyl) imidazole, vinylimidazole, 1-methylimidazole, 1-allylimidazole, 2-ethylimidazole, 2-butylimidazole, 2-butyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-benzyl-2-phenylimidazole Imidazole compounds such as hydrogen bromide, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1,5-diazabicyclo (4.3.0) nonene-5 and its salts , 1,8-diazabicyclo (5.4.0) undecene-7 and its salts, diazabicyclic olefins and other cyclic fluorene compounds and derivatives of cyclic fluorene compounds, triethylenediamine, benzyldiamine Amine compounds such as methylamine, triethanolamine, dimethylaminoethanol, gins (dimethylaminomethyl) phenol, triphenylphosphine, diphenyl (p-tolyl) phosphine, ginsane (alkane) Phenyl) phosphine, gins (alkoxyphenyl) phosphine, gins (alkyl‧alkoxyphenyl) phosphine, gins (dialkylphenyl) phosphine, gins (trialkylphenyl) phosphine, ginseng (Tetraalkylphenyl) phosphine, gins (dialkoxyphenyl) phosphine, gins (trialkoxyphenyl) phosphine, gins (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkyl Phosphine-based compounds such as arylphosphine and alkyldiarylphosphine, cyanodiazide and the like.

These hardening accelerators may be used alone or in combination of two or more.

Among these hardening accelerators, melamine, an imidazole compound, a cyclofluorene compound, a derivative of a cyclofluorene compound, a phosphine compound, and an amine compound are more preferable in consideration of both the hardening promoting effect and the electrical insulation performance. It is melamine, 1,5-diazabicyclo (4.3.0) nonene-5 and its salt, 1,8-diazabicyclo (5.4.0) undecene-7 and its salt.

The blending amount of these hardening accelerators is not particularly limited as long as the hardening promoting effect can be achieved. However, from the viewpoint of the hardenability of the hardenable composition of the present invention and the electrical insulation properties or water resistance of the coating film obtained by hardening the hardenable composition of the present invention, it is compared with the hardening of the present invention. 100 parts by mass of the total amount of (ingredient A) and (ingredient B) in the sexual composition as an essential component of the present invention is preferably blended in a range of 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass Serving. The blending amount is based on 100 parts by mass of the total amount of (component A) and (component B), and if it is in the range of 0.05 to 5 parts by mass, it can be cured in a short time and the curable composition of the present invention can be cured. The coating film has better electrical insulation properties and water resistance.

When it is necessary to suppress deterioration of the acid value of the resin and discoloration during heating, antioxidants such as phenol-based antioxidants, phosphite-based antioxidants, and thioether-based antioxidants can be added to the curable composition of the present invention. .

Furthermore, in the hardening composition of the present invention, in order to improve workability during coating work and film characteristics before and after film formation, coloring agents such as leveling agents, dyes, pigments, flame retardants, and lubricants may be added. Agent.

The method for producing the curable composition of the present invention is not particularly limited as long as it is a method in which (component A), (component B), and (component C) and other components required can be dissolved or dispersed in an organic solvent. For example, the curable composition of the present invention can be produced by producing a main agent including at least (component A) and a hardener including at least (component B), and then mixing the main agent and the hardener.

In addition, after the hardenable composition of the present invention has good screen printing properties and the hardenable composition is printed, in order to prevent the composition from flowing and preventing it from becoming a certain film thickness, it is desirable that the shake modification index be 25 ° C. It is 1.1 or more, more preferably in the range of 1.1 to 3.0, and particularly preferably in the range of 1.1 to 2.5. In order to make the shake modification index 1.1 or more at 25 ° C, The method of adjusting the shake modification index by using the aforementioned inorganic fine particles or organic fine particles, and the method of adjusting the shake modification index by using a polymer additive, among them, the method of adjusting the shake modification index by using inorganic fine particles or organic fine particles is preferable.

In addition, the "shake modification index" described in this specification was measured using a cone-plate viscometer (manufactured by Brookfield, type: DV-II + Pro, model of spindle: CPE-52), and it was measured at 25 ° C. The ratio of the viscosity at 1 rpm and the viscosity at 10 rpm at 25 ° C of the spindle is defined.

The viscosity of the hardening composition at 25 ° C measured by a rotary viscometer is 20 Pa. s ~ 80Pa‧s is better, 30Pa. s ~ 50Pa. s is better. If the viscosity does not reach 20Pa. s, the outflow of the composition after printing becomes larger, and the film thickness tends to be thinner, if it exceeds 80Pa. s, the transferability of the composition to the substrate is reduced, and at the same time, the pores and pinholes in the printed film tend to increase.

Finally, a method for manufacturing the cured film of the present invention, the coating film of the present invention, the flexible wiring board, and the flexible wiring board will be described.

The cured film of the present invention includes a cured product obtained by curing the curable composition of the present invention. Moreover, the electronic component of this invention has the said hardened film.

In addition, the coating film of the present invention is a coating film for a flexible wiring board including a cured product of the curable composition of the present invention. More specifically, the coating film is applied by coating the curable composition of the present invention. One of the wiring-forming surfaces of a flexible wiring board in which wiring is formed on a flexible substrate A coating film for a flexible wiring board obtained by partially or completely curing.

In addition, the flexible wiring board of the present invention is a part or all of the surface of the flexible wiring board of the flexible wiring board in which wiring is formed on a flexible substrate, which is covered by the coating film. Wiring board.

In addition, if the wiring covered by this coating film considers the oxidation resistance and economic aspects of the wiring, it is better to use tin-plated copper wiring.

Furthermore, the method for manufacturing a flexible wiring board according to the present invention is a method for manufacturing a flexible wiring board covered with a coating film in the following steps 1 'and 2'.

(Step 1 ') A step of forming a printed film on the pattern by printing the curable composition of the present invention on at least a part of a wiring pattern portion of a flexible wiring board.

(Step 2 ') The printing film obtained in step 1', and the printing film obtained in step 1 'is placed in an atmosphere of 40 to 100 ° C, so that a part of the solvent in the printing film is evaporated, and a part of the solvent is removed. The printed film obtained, or the printed film obtained by placing the printed film obtained in step 1 ′ under an atmosphere of 40 to 100 ° C. and the solvent in the printed film is completely evaporated, and the entire amount of the solvent is removed. A step of heating at a temperature of ℃ to form a coating film.

For the curable composition of the present invention, for example, an ink for a coating film for insulating protection can be used, and the cured product of the present invention can be used as a coating film for insulating protection. In particular, by covering all or part of the wiring of a flexible wiring board such as a chip-on-film (COF), it can be used as a covering film for insulation protection of wiring.

The following describes the manufacturing method of the flexible wiring board of the present invention. Specific steps implemented by law. For example, a coating film for a flexible wiring board can be formed through the following steps 1 and 3 and step 2 as necessary.

(step 1)

A step of forming a printed film on the pattern by printing the curable composition of the present invention on at least a part of a wiring pattern portion of a flexible wiring board.

(Step 2)

A step of evaporating part or all of the solvent in the printed film by placing the printed film obtained in step 1 in an atmosphere of 40 to 100 ° C.

(Step 3)

The step of heating the printed film obtained in step 1 or the printed film obtained in step 2 at 100 to 170 ° C. to harden and form a coating film.

The temperature in step 2 is implemented by placing the printing film obtained in step 1 under an atmosphere of 40 ~ 100 ° C to evaporate the solvent in the printing film. If the evaporation rate of the solvent and the next operation (100 ~ 170) are considered The operation of heating at ℃ to harden it) is rapid transition, usually 40 to 100 ° C, preferably 60 to 100 ° C, and more preferably 70 to 90 ° C. The time for evaporating the solvent in the printed film by placing the printed film obtained in step 1 in an atmosphere of 40 to 100 ° C, which is carried out in step 2, is not particularly limited, but it is preferably 10 to 120 minutes, more preferably 20 to 100 minutes.

In addition, the printing film obtained in step 1 is placed at 40 ~ The operation of evaporating the solvent in the printed film under the atmosphere of 100 ° C is an operation performed according to the needs. After the operation in step 1, immediately move to step 3 and heat it at 100 ~ 170 ° C to thereby harden it. And the operation of forming a coating film can be implemented, and the hardening reaction and the removal of the solvent can also be performed at the same time. The thermal curing conditions implemented here are from the viewpoint of preventing diffusion of the plating layer and obtaining low warpage and softness as a protective film, and the thermal curing temperature is preferably 105 to 160 ° C, and more preferably 110 ~ 150 ℃. It is hardened by heating, and the heat curing time when forming a coating film is not particularly limited, but is preferably 10 to 150 minutes, and more preferably 15 to 120 minutes.

A flexible wiring board can be obtained by the above-mentioned method. The flexible wiring board is a part or all of the wiring-forming surface of a flexible wiring board formed by wiring formed on a flexible substrate. Covered by the film.

In addition, the hardenable composition of the present invention can be mixed with any of the aforementioned components as required, and can be uniformly mixed. In addition to the film-forming material, it can be used for coating inks, solder resist inks for semiconductor devices or various electronic parts, In addition to the interlayer insulating film, it can also be used as a coating material, a coating agent, an adhesive, and the like.

[Example]

Although the present invention can be further specifically explained by the following examples, the present invention is not limited to the following examples.

<Measurement of acid value>

The solution containing (component A) used in the present invention measures the acid value by the following method, and uses the formula (α) to obtain the acid value of (component A). However, the solvents used in the aforementioned solutions are those having an acid value of "0".

First, the fine scale contains about 1 g of the solution of (component A). Thereafter, 30 g of a mixed solvent of isopropyl alcohol / toluene = 1/2 (mass ratio) was added thereto, and the mixture was uniformly dissolved. To the obtained solution, an appropriate amount of phenolphthalein was added as an indicator, and titration was performed using a 0.1N KOH solution (alcoholic). Then, the result of the titration is expressed by the following formula (α): A = 10 × Vf × 56.1 / (Wp × I) ‧‧‧‧‧ Formula (α)

To calculate the acid value. In the formula (α), A represents an acid value (mgKOH / g), Vf represents a titer (mL) of a 0.1N KOH solution, Wp represents a mass (g) of a solution containing (component A), and I represents a component containing (component The ratio (% by mass) of the component (A) of the solution of A).

<Determination of hydroxyl value>

The hydroxyl value was measured in accordance with JIS K0070.

<Determination of number average molecular weight>

The number average molecular weight is a polystyrene-equivalent number average molecular weight measured by GPC, and GPC measurement conditions are as follows.

Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation

Column: Shodex (registered trademark) column LF-804 × 3 (in-line)

Mobile phase: tetrahydrofuran

Flow rate: 1.0mL / min

Detector: RI-2031Plus, manufactured by JASCO Corporation

Temperature: 40.0 ℃

Sample volume: 100 μL of sample loop

Sample concentration: before and after adjustment to 0.1% by mass.

<Determination of Shake Modification Index>

The shake modification index of the hardenable composition is measured by the following method.

Using a hardening composition of about 0.8 g, use a cone-plate viscometer (type manufactured by Brookfield; DV-II + Pro spindle model; CPE-52) at a temperature of 25.0 ° C and a number of revolutions of 10 rpm. Viscosity after 7 minutes. Thereafter, the viscosity was measured after 7 minutes from the start of the measurement under the conditions of a temperature of 25.0 ° C and a number of revolutions of 1 rpm.

The shake modification index was obtained by the following calculation.

How to get the modification index: Shaking modification index = [viscosity at 1 rpm] ÷ [viscosity at 10 rpm]

<Synthesis of Polyester Polyols> (Reference Synthesis Example 1) <Polyester diol (α)>

In a reaction vessel provided with a stirring device, a thermometer, and a capacitor with a distillation device, 983.5 g (6.74 mol) of anhydrous phthalic acid and 87.92 g (7.44 mol) of 1,6-hexanediol were added. The temperature was raised to 140 ° C using an oil bath, and stirring was continued for 4 hours. After that, continue to stir while adding Add 1.74 g of mono-n-butyltin oxide, slowly raise the internal temperature of the reaction vessel, continue the vacuum pumping, gradually reduce the pressure in the reaction vessel gradually, and remove the water from the reaction vessel by vacuum distillation. Finally, the internal temperature was raised to 220 ° C. and the pressure was reduced to 133.32 Pa. After 15 hours, it was confirmed that water was completely distilled off and the reaction was completed. The obtained polyester polyol (hereinafter, referred to as polyester diol (α)) has a structure of the aforementioned formula (2), and n = 1 to 20. As a result of measuring the hydroxyl value, the hydroxyl value was 53.1 mg-KOH / g.

<Synthesis of (component A)> (Synthesis example 1) <A-1 solution>

In a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) as a tetracarboxylic dianhydride was placed. 270.7 parts by mass and 964.4 parts by mass of γ-butyrolactone as a solvent were stirred and dissolved at 120 ° C. To this, 142.6 parts by mass of 4,4'-diphenylmethane diisocyanate (MDI) as a diisocyanate compound was added and stirred, and 1,8-diazabicyclo as a catalyst was added thereto [5.4.0] 0.1-parts of 7-undecene (DBU) was reacted at 120 ° C for 3 hours under a nitrogen stream. Thereafter, by cooling to room temperature, a sulfonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was obtained.

Next, the obtained hydrazone imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was heated to 100 ° C. and stirred, and 908.7 parts by mass of polyester diol (α) and γ-butyrolactone were added. 1018.7 parts by mass and stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. After cooling to room As a result, a solution of a compound having a fluorene imine bond and a hydroxyl group (hereinafter referred to as "compound (A-1)") having a solid content concentration of 40% by mass was obtained. The number average molecular weight of the compound (A-1) was 15,000, the degree of dispersion was 4.0, and the acid value of the solid content was 25 mgKOH / g.

(Synthesis example 2) <A-2 solution>

In a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) as a tetracarboxylic dianhydride was placed. 270.7 parts by mass and 964.4 parts by mass of γ-butyrolactone as a solvent were stirred and dissolved at 120 ° C. To this, 142.6 parts by mass of 4,4'-diphenylmethane diisocyanate (MDI) as a diisocyanate compound was added and stirred, and 1,8-diazabicyclo as a catalyst was added thereto [5.4.0] 0.1-parts of 7-undecene (DBU) was reacted at 120 ° C for 3 hours under a nitrogen stream. Thereafter, by cooling to room temperature, a sulfonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was obtained.

Next, the obtained sulfonyl imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was heated to 100 ° C. and stirred, and 3-methyl-1,5-pentanediol: isobenzene was added. 908.7 parts by mass of polyester polyol of dicarboxylic acid (trade name: KURARAY Polyol P-2030 (*) manufactured by KURARAY Corporation) and 1018.7 parts by mass of γ-butyrolactone were stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having a fluorene imine bond and a hydroxyl group (hereinafter referred to as "compound (A-2)") having a solid content concentration of 40% by mass was obtained. Of compound (A-2) The number average molecular weight was 15,000, the degree of dispersion was 4.0, and the acid value of the solid content was 25 mgKOH / g.

(※ is a polyester polyol having the structure of the aforementioned formula (2), and the average of n is 8.0 to 8.1)

(Synthesis example 3) <A-3 solution>

In a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) as a tetracarboxylic dianhydride was placed. 270.7 parts by mass and 863.2 parts by mass of γ-butyrolactone as a solvent were stirred and dissolved at 120 ° C. To this, COSMONATE T-80 (Mitsui Chemical Polyurethane) was added as a diisocyanate compound in a mixture of 2,4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20. 99.3 parts by mass (TDI) (TDI) and stirred, and 0.1 part by mass of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) as a catalyst was added thereto under a nitrogen stream It was made to react at 120 degreeC for 3 hours. Thereafter, by cooling to room temperature, a sulfonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was obtained.

Next, the obtained hydrazone imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was heated to 100 ° C. and stirred, and 908.7 parts by mass of polyester diol (α) and γ-butyrolactone were added. 1054.8 parts by mass were stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having a fluorene imine bond and a hydroxyl group (hereinafter referred to as "compound (A-3)") having a solid content concentration of 40% by mass was obtained. Compound The number average molecular weight (A-3) was 15,000, the degree of dispersion was 4.0, and the acid value of the solid content was 26 mgKOH / g.

(Synthesis example 4) <A-4 solution>

In a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) as a tetracarboxylic dianhydride was placed. 270.7 parts by mass and 863.2 parts by mass of γ-butyrolactone as a solvent were stirred and dissolved at 120 ° C. To this, COSMONATE T-80 (Mitsui Chemical Polyurethane) was added as a diisocyanate compound in a mixture of 2,4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20. 99.3 parts by mass (TDI) (TDI) and stirred, and 0.1 part by mass of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) as a catalyst was added thereto under a nitrogen stream It was made to react at 120 degreeC for 3 hours. Thereafter, by cooling to room temperature, a sulfonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was obtained.

Next, the obtained sulfonyl imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was heated to 100 ° C. and stirred, and 3-methyl-1,5-pentanediol: isobenzene was added. 908.7 parts by mass of polyester polyol of dicarboxylic acid (trade name: KURARAY Polyol P-2030, manufactured by KURARAY, Inc.) and 1054.8 parts by mass of γ-butyrolactone were stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having a fluorene imine bond and a hydroxyl group (hereinafter referred to as "compound (A-4)") having a solid content concentration of 40% by mass was obtained. Number average compound of compound (A-4) The amount was 15000, the degree of dispersion was 4.0, and the acid value of the solid content was 26 mgKOH / g.

(Synthesis example 5) <A-5 solution>

378.29 g (0.179 mol) of polyester diol (α) was placed in a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, and MILLIONATE MT (Japanese polyamine) of 4,4'-diphenylmethane diisocyanate was placed therein. COSMONATE T-80 (Made by Carbamate Industry Co., Ltd.) 53.65 g (0.214 mol) and a mixture of 2,4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20 ( Mitsui Chemicals Polyurethane Co., Ltd.) 24.89 g (0.143 mol) and γ-butyrolactone 685.3 g, all the raw materials were dissolved at 150 ° C. and allowed to react for 4 hours to produce amino methyl esters. Polyester isocyanate.

Next, the temperature of the reaction solution was reduced to 60 ° C, 63.71 g (0.332 mol) of anhydrous trimellitic acid was added to completely dissolve, and MILLIONATE MT 23.00 g (0.092 mol) and COSMONATE T-80 10.67 g (0.061 mol) were added. ) And 146.07 g of γ-butyrolactone, heated to 120 ° C. to dissolve all the raw materials, and reacted for 1 hour.

Thereafter, the temperature of the reaction solution was raised to 180 ° C, and the reaction was allowed to react at 180 ° C for 2 hours. Next, the temperature of the reaction solution was lowered to 120 ° C., 5.61 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added to complete the reaction, and the solid content concentration was 40% by mass by cooling to room temperature. A solution of a sulfonium bond and a sulfonium bond and a block isocyanate compound (hereinafter referred to as "compound (A-5)").

The number average molecular weight of the obtained compound (A-5) was 10,500, and the degree of dispersion The acid value was 3.1 and the solid content was 19 mgKOH / g.

(Synthesis example 6) <A-6 solution>

In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, 3-methyl-1,5-pentanediol: a polyester polyol of isophthalic acid (KURARAY company product name: KURARAY Polyol P -2030) 378.29 g (0.179 mol), and placed in MILLIONATE MT (manufactured by Japan Polyurethane Industry Co., Ltd.) 4,4'-diphenylmethane diisocyanate 53.65 g (0.214 mol) and 2, COSMONATE T-80 (manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) 24.89 g (0.143 mol) with a mixture of 4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20 685.3 g of γ-butyrolactone was dissolved at 150 ° C. and reacted for 4 hours to form a polyisocyanate having a urethane bond.

Next, the temperature of the reaction solution was reduced to 60 ° C, 63.71 g (0.332 mol) of anhydrous trimellitic acid was added to completely dissolve, and MILLIONATE MT 23.00 g (0.092 mol) and COSMONATE T-80 10.67 g (0.061 mol) were added. ) And 146.07 g of γ-butyrolactone, heated to 120 ° C. to dissolve all the raw materials, and reacted for 1 hour.

Thereafter, the temperature of the reaction solution was raised to 180 ° C, and the reaction was allowed to react at 180 ° C for 2 hours. Next, the temperature of the reaction solution was lowered to 120 ° C, 5.61 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added to complete the reaction, and the solid content concentration was 40% by mass by cooling to room temperature. Compounds of amidamine bond, amidine bond, and a block isocyanate group (hereinafter referred to as "Compound (A-6)").

The number average molecular weight of the obtained compound (A-6) was 10,500, the degree of dispersion was 3.1, and the acid value of the solid content was 19 mgKOH / g.

(Synthesis example 7) <A-7 solution>

In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, 369.85 g (0.175 mol) of polyester diol (α) and 4,4'-dicyclohexylmethane diisocyanate as Desmodule-W (Sumika BAYER) were placed. 91.70 g (0.350 mol) of carbamate) and 692.33 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as solvents. All the raw materials were dissolved at 150 ° C and reacted for 4 hours. It is formed into a polyisocyanate having a urethane bond.

Next, the temperature of the reaction solution was lowered to 80 ° C, and 45.85 g (0.175 mol) of Desmodule-W, 33.60 g (0.175 mol) of anhydrous trimellitic acid (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone ( 119.18 g (manufactured by Mitsubishi Chemical Corporation) was heated to 150 ° C. to dissolve all the raw materials and allowed to react for 3 hours.

The temperature of the reaction solution was lowered to 80 ° C, 16.40 g (0.158 mol) of neopentyl glycol (manufactured by Kanto Chemical Co., Ltd.) was added as a diol, and the temperature was raised to 120 ° C to dissolve all the raw materials and react them 4 hour. Thereafter, the temperature of the reaction solution was lowered to 80 ° C, and glycerin (manufactured by Kanto Chemical Co., Ltd.) 9.67 g (0.105 mol) and γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as triols were added, and the temperature was raised. After reaching 110 ° C, the reaction was allowed to proceed. The reaction was carried out while confirming the presence of an isocyanate group in the reaction solution by IR measurement. When the isocyanate group in the reaction system cannot be confirmed, the reaction is completed. By cooling to room temperature, a compound having a solid content concentration of 40% by mass and having a hydroxyl group, an amido bond, an amidine bond, and a hydroxyl group is obtained. (Hereinafter referred to as "compound (A-7)").

The number average molecular weight of the obtained compound (A-7) was 10,000, the degree of dispersion was 4.3, the acid value of the solid content was 17 mgKOH / g, and the hydroxyl value was 10 mgKOH / g.

(Comparative Synthesis Example 1) <CA-1 solution>

In a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) as a tetracarboxylic dianhydride was placed. 270.7 parts by mass and 863.2 parts by mass of γ-butyrolactone as a solvent were stirred and dissolved at 120 ° C. To this, COSMONATE T-80 (Mitsui Chemical Polyurethane) was added as a diisocyanate compound in a mixture of 2,4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20. 99.27 parts by mass of the company), and stirred, and 0.1 part by mass of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) as a catalyst was added thereto, and the mixture was mixed with nitrogen under a nitrogen stream. Reaction was performed at 120 ° C for 3 hours. Thereafter, by cooling to room temperature, a sulfonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was obtained.

Next, the obtained ammonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was heated to 100 ° C. and stirred, and a polycarbonate diol compound (trade name: DURANOL) was added as a polyol compound. T5650E: Asahi Kasei Chemicals Co., Ltd., Mn = 500) 100.0 quality 460.0 parts by mass of polyester diol of adipic acid / neopentyl glycol / 1,6-hexanediol (trade name: OD-X-688 manufactured by DIC (stock), number average molecular weight approximately 2,000) With 531.71 parts by mass of γ-butyrolactone, and stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound (hereinafter, "compound (CA-1)") having a fluorene imine bond, a carboxyl group, and a hydroxyl group with a solid content concentration of 40% by mass was obtained. The compound (CA-1) had a number average molecular weight of 13,500, a degree of dispersion of 4.0, and an acid value of the solid content of 36 mgKOH / g.

(Comparative Synthesis Example 2) <CA-2 solution>

In a reaction vessel provided with a stirring device, a thermometer, and a capacitor, a composition unit containing 1,4-cyclohexanedimethanol and a composition derived from 1,6-hexanediol at a molar ratio of 1: 1 was placed. Polycarbonate diol UM-CARB90 (1/1) (made by Ube Kosan Co., Ltd.) was 161.44 g (0.179 mol), and MILLIONATE MT (4,4'-diphenylmethane diisocyanate) was placed in the unit. COSMONATE T (manufactured by Japan Polyurethane Industry Co., Ltd.) 53.65 g (0.214 mol) and a mixture of 2,4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20 -80 (manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) 24.89 g (0.143 mol) and 159.93 g of γ-butyrolactone. All the raw materials were dissolved at 150 ° C. and reacted for 4 hours to produce Urethane-bonded polyisocyanate.

Next, the temperature of the reaction solution was lowered to 60 ° C, and then added After 63.71 g (0.332 mol) of anhydrous trimellitic acid was completely dissolved, MILLIONATE MT 23.00 g (0.092 mol) and COSMONATE T-80 10.67 g (0.061 mol) and γ-butyrolactone 342.98 g were added, and the temperature was raised to 120 ° C. All the raw materials were dissolved and reacted for 1 hour.

Thereafter, the temperature of the reaction solution was raised to 180 ° C, and the reaction was allowed to react at 180 ° C for 2 hours. Next, the temperature of the reaction solution was lowered to 120 ° C, and 3.13 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added to complete the reaction, and the mixture was cooled to room temperature to obtain a solid content concentration of 40% by mass. A solution of a compound (hereinafter, "compound (CA-2)") having an amine bond, an imine bond, and a carboxyl group.

The number average molecular weight of the obtained compound (CA-2) was 9,200, the degree of dispersion was 3.1, and the acid value of the solid content was 31 mgKOH / g.

(Comparative Synthesis Example 3) <CA-3 solution>

In a reaction vessel provided with a stirring device, a thermometer, and a capacitor, a unit containing 1,4-cyclohexanedimethanol and a structure derived from 1,6-hexanediol at a molar ratio of 3: 1 was placed. Polycarbonate diol UM-CARB90 (3/1) (made by Ube Kosan Co., Ltd., average molecular weight: about 900) 156.98 g (0.175 mol), as 4,4'-dicyclohexyl methane diisocyanate 91.70 g (0.350 mol) of Desmodule-W (Sumika BAYER Urethane Co., Ltd.) and 165.80 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as a solvent, all raw materials were dissolved at 150 ° C , And allowed to react for 4 hours to form a polyisocyanate having a urethane bond.

Next, the temperature of the reaction solution was lowered to 80 ° C, and then Desmodule-W 45.85 g (0.175 mol), anhydrous trimellitic acid (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 33.60 g (0.175 mol) and γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) 162.33 g, heated to 150 ° C, All the raw materials were dissolved and reacted for 3 hours.

The temperature of the reaction solution was lowered to 80 ° C, 16.40 g (0.158 mol) of neopentyl glycol (manufactured by Kanto Chemical Co., Ltd.) was added as a diol, and the temperature was raised to 120 ° C to dissolve all the raw materials and react them 4 hour. Thereafter, the temperature of the reaction solution was lowered to 80 ° C, and glycerol (manufactured by Kanto Chemical Co., Ltd.) 9.67 g (0.105 mol) and γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as triols were added, and the temperature was increased. After reaching 110 ° C, the reaction was allowed to proceed. The reaction was performed while confirming the existence of an isocyanate group in the reaction solution by IR measurement. When the isocyanate group in the reaction system could not be confirmed, the reaction was completed. 177.1 g of γ-butyrolactone was added to obtain a solid form. A solution of a compound (hereinafter referred to as "compound (CA-3)") having a hydroxyl group, an amido bond, and an imine bond and a hydroxyl group at a concentration of 40% by mass.

The number average molecular weight of the obtained compound (CA-3) was 8000, the degree of dispersion was 4.4, the acid value of the solid content was 27 mgKOH / g, and the hydroxyl value was 16 mgKOH / g.

<Manufacturing of main agent blend> (Base Agent Blend 1)

160.0 parts by mass of a solution of the compound (A-1), 6.3 parts by mass of silica powder (manufactured by Japan Aerosil® Co., Ltd., trade name: AEROSIL® R-974), and melamine as a hardening accelerator (Nissan Chemical Industries, Ltd. 0.72 parts by mass and 8.4 parts by mass of diethylene glycol diethyl ether, using a three-roller rolling mill (manufactured by Inoue Seisakusho Co., Ltd., type: S-4 3/4 × 11), for compound (A-1 ) Mix the silica powder and hardening accelerator. Thereafter, 2.0 parts by mass of a defoaming agent (manufactured by Momentive Performance Materials, trade name: TSA750S) was added, and mixed using a spatula. This blend was used as the main ingredient blend C1.

(Base Mixtures 2-7 and Comparison Base Mixtures 1-3)

In the same manner as the main agent blend 1, blending was performed according to the blending composition shown in Table 1. Each was used as the main agent blend 2-7, and the main agent blend ratios 1 to 3 were compared.

The values in the table represent "mass parts".

<Manufacture of hardener solution> (Mixing Example 1 of Hardener Solution) <B-1 Solution>

To a container provided with a stirrer, a thermometer, and a capacitor, 16.85 parts by mass of epoxy resin (manufactured by Mitsubishi Chemical Corporation, specification name: JER604, epoxy equivalent 120g / eqv), and diethyl ether having a structure of the following formula (7) were added. 18.25 parts by mass of glycol diethyl ether, stirring was started.

While continuing to stir, the temperature in the container was raised to 40 ° C using an oil bath. After the internal temperature was raised to 40 ° C, stirring was continued for 30 minutes. Then, after confirming that JER604 was completely dissolved, it was cooled to room temperature to obtain a solution containing JER604 at a concentration of 48% by mass. This solution was used as a hardener solution B-1.

(Blend Example 2 of Hardener Solution) <B-2 Solution>

To a container equipped with a stirrer, a thermometer, and a capacitor, an epoxy resin (manufactured by Mitsubishi Chemical Corporation, specifications, with N, N-diglycid-4- (glycidoxy) aniline) as the main component is added Name: JER630, epoxy equivalent weight 98g / eqv) 16.85 parts by mass, diethylene glycol diethyl ether 18.25 parts by mass, and stirring was started.

While continuing to stir, the temperature in the container was raised to 40 ° C using an oil bath. After the internal temperature was raised to 40 ° C, stirring was continued for 30 minutes. After that, it was confirmed that JER630 was completely dissolved, and the solution was cooled to room temperature to obtain a solution containing JER630 at a concentration of 48% by mass. This solution was used as a hardener solution B-2.

<Mix of solution containing main agent blend and hardener> (Example 1 of hardening composition)

88.71 parts by mass of the main agent blend C1 and 3.51 parts by mass of the hardener solution B-1 were placed in a plastic container. In addition, in order to match the hardening composition and viscosity of other blending examples described later and comparative blending examples, 3.0 parts by mass of diethylene glycol diethyl ether and diethylene glycol ethyl ether acetate were added as a solvent. 1.5 parts by mass. The mixing system was carried out by using a spatula and stirring at room temperature for 5 minutes to obtain a curable composition (hereinafter referred to as "curable composition F1").

(Examples 2 to 8 and Comparative Examples 1 to 3)

In the same manner as in Example 1 of the curable composition, blending was performed according to the blending composition shown in Table 2. The blends prepared by Examples 2 to 8 of the hardenable composition are referred to as hardenable compositions F2 to F8, and the blends prepared by Comparative Examples 1 to 3 of the hardenable composition are referred to as hardenable composition G1 to G3. Here, the curable compositions F8 and G3 are further blended with a blocked isocyanate "7950" manufactured by Baxenden Co., which corresponds to (component B).

The values in the table represent "mass parts".

In addition, the hardening compositions F1 to F8 and the hardening compositions G1 to G3 The blend composition is shown in Table 2. In addition, the mass fraction of each component of the said hardenable composition F1-F8 and hardenable composition G1-G3 is put together in Table 3. The numbers of epoxy groups / carboxyl groups in Tables 2 and 3 were obtained by calculation of acid value.

(Examples 1 to 8 and Comparative Examples 1 to 3)

Use hardenable composition F1 ~ F8, hardenable composition G1 ~ G3, Evaluation of flexibility, disconnection suppression, warpage and long-term reliability of electrical insulation were performed by the methods described below. The results are shown in Table 4.

<Evaluation of flexibility>

Laminated with flexible copper (made by Sumitomo Metal Mining Co., Ltd., specification name: ESPERFLEX, copper thickness: 8 μm, polyimide thickness: 38 μm) on copper to a width of 75 mm and a length of 110 mm 2. The hardening composition F1 is applied by screen printing so that the thickness of the cured coating film is 15 μm. It is held at room temperature for 10 minutes, and placed in a hot air circulation dryer at 120 ° C. for 60 minutes to make it. hardening. The protective PET film, which is the backing of the produced test piece, was peeled. After cutting a strip with a width of 10 mm with a paper cutter, it was bent about 180 degrees so that the coating film surface became the outer side, and compressed using a compressor at 0.5 ± 0.2 MPa for 3 seconds. bell. The bent portion was observed with a 30-fold microscope in a bent state to confirm the occurrence of cracks. The results are shown in Table 4.

The same evaluations were performed using the curable compositions F2 to F8 and the curable compositions G1 to G3. These results are also shown in Table 4.

<Evaluation of the disconnection suppression of wiring of wiring boards (MIT test)>

A fine comb-shaped figure as described in JPCA-ET01, manufactured by etching a laminated copper plate (manufactured by Sumitomo Metal Mining Corporation, specification name: ESPERFLEXUS, copper thickness: 8 μm, polyimide thickness: 38 μm) Substrate (copper wiring width / copper wiring width = 15μm / 15μm) is tin-plated, and the hardening composition F1 is applied to the flexible wiring board. The screen printing method is applied so that the thickness from the polyimide surface of the coating film becomes a thickness of 10 μm (after drying). The obtained coating film was formed into a wiring board and placed in a hot-air circulation type dryer at 80 ° C for 30 minutes, and then the coating film was hardened by being placed in a hot-air circulation type dryer at 120 ° C for 120 minutes.

Using this test piece, the method described in JIS C-5016 was carried out under the following test conditions.

(Test conditions)

Testing machine: MITTESTERBE202 manufactured by TESTER Industry Co., Ltd.

Bending speed: 10 times / minute

Load: 200g

Bending angle: ± 90 °

Radius of the tip of the clamp: 0.5mm

Under the above test conditions, the number of bends was increased by 10 each time, the presence or absence of cracks in the wiring was visually observed, and the number of bends when cracks occurred was recorded. The results are shown in Table 3.

The same evaluations were performed using the curable compositions F2 to F8 and the curable compositions G1 to G3. These results are collectively shown in Table 4.

<Evaluation of Warpage>

The hardening composition F1 was applied to a substrate by screen printing using a # 180 mesh polyester plate, and the substrate was placed in a hot air circulation dryer at 80 ° C for 30 minutes. Thereafter, the substrate was dried by hot air circulation at 120 ° C. The applied curable composition F1 was cured for 60 minutes. For the substrate, a 25 μm thick polyimide film [Kapton® (registered trademark) 100EN, manufactured by DU PONT-TORAY Co., Ltd.] was used.

A circular cutter was used to cut the hardened coating film on each substrate to a diameter of 50 mm. The shape of the person who is cut into a circle is warped into a convex or concave shape near the center. If the hardened film is formed on the substrate cut by the circle cutter, it will be in a convex state below 1 hour later, that is, let the vicinity of the center of the hardened film formed on the substrate contact the horizontal surface and measure. The maximum and minimum values of the warpage height from the horizontal plane are averaged. The symbol indicates the direction of warpage. When the lower part is left standing in a convex state, the copper substrate or the polyimide film is described as "+" when the cured film becomes the upper side and "-" when the cured film becomes the lower side. . Then, if the warpage does not reach +3.0 mm, a pass is given.

The results are shown in Table 4.

The same evaluations were performed using the curable compositions F2 to F8 and the curable compositions G1 to G3. These results are also shown in Table 4.

<Evaluation of long-term electrical insulation reliability>

A fine comb-shaped figure as described in JPCA-ET01, manufactured by etching a laminated copper plate (manufactured by Sumitomo Metal Mining Corporation, specification name: ESPERFLEXUS, copper thickness: 8 μm, polyurethane thickness: 38 μm) Substrate (copper wiring width / copper wiring width = 15μm / 15μm) is tin-plated, and the hardening composition F1 is printed on the flexible wiring board by screen printing. The thickness of the polyimide surface of the film becomes 15 μm thickness (after drying). The obtained coating film was formed into a wiring board, and it was placed in a hot air circulation type dryer at 80 ° C for 30 minutes. Then, it was placed in a hot air circulation type dryer at 120 ° C for 120 minutes to make the applied hardening composition F1. hardening.

Using this test piece, a bias voltage of 60 V was applied, and a temperature and humidity steady test was performed using MIGRATION TESTER MODEL MIG-8600 (manufactured by IMV) under the conditions of a temperature of 120 ° C and a humidity of 85% RH. Table 4 shows the resistance values of the substrates of the fine comb-type pattern in the initial stage of the temperature and humidity steady test and 100 hours, 250 hours, and 400 hours after the beginning of the tests.

The same evaluations were performed using the curable compositions F2 to F8 and the curable compositions G1 to G3. These results are collectively shown in Table 4.

As is clear from the results in Table 4, the hardenable composition of the present invention is excellent in flexibility, disconnection resistance, and long-term reliability of electrical insulation, and the hardened product can be used as an insulating protective film for a flexible wiring board.

[Industrial availability]

The curable composition of the present invention is suitably used for insulation protection of a flexible wiring board.

Claims (16)

A hardening composition comprising the following components: (component A) has a structural unit represented by the following formula (1), has at least one kind of bond of a sulfonium imine bond and a sulfonium bond, and has A functional group compound that reacts with a hardener, (component B) a hardener, and (component C) an organic solvent, (In the formula (1), R ¹ each independently represents an organic residue derived from a diol having 3 to 36 carbon atoms, and R ² each independently represents a phenylene group or a phenylene group having a substituent). The curable composition according to claim 1, wherein the functional group that reacts with the curing agent is at least one of a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, an amino group, and an amine group. The curable composition according to claim 1 or 2, wherein (component A) contains: (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, and (raw material b) The compound obtained by reacting a polyol represented by formula (2) and (raw material c) using polyisocyanate as an essential component, (In formula (2), (n + 1) R ¹ each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms, and n R ² each independently represent a phenylene group or The phenyl group of the substituent, n represents an integer of 1 to 60). The curable composition according to any one of claims 1 to 3, wherein (component A) further has a urethane bond. The curable composition according to any one of claims 1 to 4, wherein the acid value of (component A) is 10 to 50 mgKOH / g. The curable composition according to any one of claims 1 to 5, wherein (component B) includes a compound having two or more epoxy groups per molecule. The curable composition according to any one of claims 1 to 6, wherein (component C) is at least 1 selected from the group consisting of an ether-based solvent, an ester-based solvent, a ketone-based solvent, and an aromatic hydrocarbon-based solvent. Organic solvents. The curable composition according to any one of claims 1 to 7, further comprising (component D) at least one kind of fine particles selected from the group consisting of inorganic fine particles and organic fine particles. The curable composition according to any one of claims 1 to 8, wherein when the total amount of the component (A) and the component (B) is 100 parts by mass, 1 to 55 parts by mass of the component (B) is included. The curable composition according to any one of claims 1 to 9, wherein the total amount of the component (A), the component (B), the component (C), and the component (D) is made (when the component (D) is not included) When the total amount of the component (A), the component (B), and the component (C) is 100 parts by mass, 25 to 75 parts by mass of the component (C) is included. A cured film comprising a cured product of the curable composition according to any one of claims 1 to 10, which is characterized in that it is a cured film. A coating film for a flexible wiring board, characterized in that a part or all of a wiring-forming surface of a flexible wiring board formed by wiring formed on a flexible substrate is coated as in claim 1 ~ The hardening composition according to any one of 10, which is obtained by curing. A flexible wiring board characterized in that part or all of the wiring-forming surface of a flexible wiring board in which wiring is formed on a flexible substrate is covered with a coating film as described in claim 12 With. The flexible wiring board according to claim 13, wherein the wiring is tin-plated copper wiring. A method for manufacturing a flexible wiring board covered with a covering film, which is characterized by including the following (step 1) and (step 3) and necessary (step 2): (step 1) by requesting The step of printing the hardenable composition according to any one of items 1 to 10 on at least a part of a wiring pattern portion of a flexible wiring board, and forming a printed film on the pattern. (Step 2) The printing film obtained in 1 is placed in an atmosphere of 40 to 100 ° C, and a part or all of the solvent in the printing film is evaporated. (Step 3) The printing film obtained in Step 1 or the printing film obtained in Step 2 A step of heating at 100 to 170 ° C to harden and form a coating film. An electronic component having a cured film as described in claim 11.