JP6432814B2 - Alcohol-modified polyamideimide resin and method for producing the same - Google Patents

Description

  The present invention relates to a polyamideimide resin, a curable resin composition containing the polyamideimide resin, and a cured product thereof. Specifically, the present invention is a field that requires transparency in addition to heat resistance, for example, a field for optical materials, a solder resist material for printed wiring boards, a protective material and insulation for household appliances such as refrigerators and rice cookers. Materials, liquid crystal displays and liquid crystal display elements, organic and inorganic electroluminescence displays, organic and inorganic electroluminescence elements, LED displays, light emitting diodes, electronic paper, solar cells, TSVs, protective materials used for optical fibers and optical waveguides, insulating materials, Polyamideimide resin that can be suitably used in fields such as adhesives, reflective materials, and display device fields such as liquid crystal alignment films and protective films for color filters, and curable resin compositions containing the polyamideimide resin and It relates to the cured product.

  Polyamideimide resins are excellent in heat resistance and mechanical properties, and have been used in various fields mainly in the electrical and electronic industries. Recently, PGMAc (propylene glycol-1-monomethyl ether-2-phenyl ester) is used for the purpose of reducing the burden on the environment. The ability to be dissolved in general-purpose solvents such as acetate and EDGA (diethylene glycol monoethyl ether acetate) has been demanded. For example, a polyamide-imide resin obtained by reacting an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure with a tricarboxylic acid anhydride (a1) having an aliphatic structure is soluble in general-purpose solvents. It is known that a cured product (cured coating film) having excellent transparency can be provided by blending with a curable resin and further curing while maintaining the above (see Patent Document 1). However, the curable resin composition obtained by blending the polyamide-imide resin with a curable resin or a reaction diluent tends to have insufficient storage stability and pot life and insufficient handleability. .

  Therefore, the acid anhydride group of the terminal group of the polyamideimide resin obtained by reacting the isocyanurate type polyisocyanate (a2) synthesized from the isocyanate having an aliphatic structure with the tricarboxylic acid anhydride (a1) is an alcohol compound. It is known that by modifying, a polyamideimide resin having a long storage stability and a long usable time when blended with a curable resin or a reaction diluent and excellent in handleability can be obtained (see Patent Document 2). . However, the polyamide-imide resin has room for improvement in solvent dilutability and developability of a cured coating film obtained by blending with a curable resin or a reactive diluent.

WO2010 / 107045 pamphlet WO2015 / 068744 pamphlet

  Therefore, the problem of the present invention includes a polyamideimide resin that is soluble in a general-purpose solvent and excellent in solvent dilutability, and is a curable resin composition that has a long storage stability and pot life even when blended with a curable resin. And it is providing the hardened | cured material (cured coating film) excellent in developability.

  As a result of intensive studies, the present inventors have reacted a tricarboxylic acid anhydride (a1) with an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure in the step of producing a polyamideimide resin. At that time, by adding the isocyanurate type polyisocyanate to the tricarboxylic acid anhydride and reacting it, it was found that a polyamideimide resin having a sharp molecular weight distribution was obtained. Furthermore, it was found that a polyamide-imide resin that is soluble in a general-purpose solvent and excellent in solvent dilutability can be obtained by modifying with alcohol, and further, by blending the polyamide-imide resin with a curable resin, storage stability and goodness can be obtained. A curable resin composition having a long service life is obtained, and furthermore, a hard resin having excellent developability. It found that the object (cured film) is obtained, and have completed the present invention.

That is, the present invention is a process for producing a polyamideimide resin (A1) by reacting a tricarboxylic acid anhydride (a1) with an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure ( 1),
Alcohol-modified polyamide having a step (2) of producing an alcohol-modified polyamideimide resin (A2) by further adding an alcohol compound (a3) to the polyamideimide resin (A1) obtained in the step (1) and reacting with the polyamide-imide resin (A1) A method for producing an imide resin,
In the step (1), the isocyanurate type polyisocyanate (a2) and the tricarboxylic acid are added to the tricarboxylic acid anhydride (a1) by adding the isocyanurate type polyisocyanate (a2) at least twice. An alcohol-modified polyamideimide resin characterized by comprising a step (1a) of reacting the isocyanurate type polyisocyanate (a2) with the obtained reactant after reacting with the anhydride (a1). It relates to a manufacturing method.

  Further, the present invention relates to a polyamide-imide resin in which a tricarboxylic acid anhydride (a1) and an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure are bonded together by forming an amide or imide. Alcohol-modified, comprising an alcohol-modified polyamideimide in which the alcohol compound (a3) is bonded to the acid anhydride group of A1) by forming an ester bond, and the molecular weight distribution is in the range of 2.0 or less It relates to the polyamide-imide resin (A).

  The present invention also relates to a curable resin composition containing the alcohol-modified polyamideimide resin (A) and the curable resin (B).

  Furthermore, the present invention relates to a cured product obtained by curing the curable resin composition.

  According to the present invention, a curable resin composition that includes a polyamide-imide resin that is soluble in a general-purpose solvent and has excellent solvent dilutability, and has long storage stability and pot life even when blended with a curable resin, and developability It is possible to provide a cured product (cured coating film) excellent in.

The method for producing the alcohol-modified polyamideimide resin (A2) of the present invention is obtained by reacting a tricarboxylic anhydride (a1) with an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure. Step (1) for producing an imide resin (A1),
The step (2) of producing an alcohol-modified polyamideimide resin (A2) by further reacting the alcohol compound (a3) with the polyamideimide resin (A1) obtained in the step (1),
In the step (1), the isocyanurate type polyisocyanate (a2) is added to the tricarboxylic acid anhydride (a1) in at least two portions, whereby the tricarboxylic acid anhydride (a1) and the isocyanurate are added. After reacting with the polyisocyanate type (a2), the product obtained further comprises a step (1a) of reacting the isocyanurate type polyisocyanate (a2).

  First, the step (1) for producing the polyamideimide resin (A1) will be described.

  In this invention, the transparency of the cured coating film of the polyamideimide resin obtained improves by using tricarboxylic acid anhydride (a1) as a raw material of a polyamideimide. Examples of such tricarboxylic acid anhydrides include tricarboxylic acid anhydrides having an aromatic structure in the molecule and tricarboxylic acids having an aliphatic structure in the molecule. Among these, a tricarboxylic acid having an aliphatic structure in the molecule is preferable because the storage stability of the curable resin composition is excellent, the pot life is long, and the thermal decomposition temperature of the cured product tends to be excellent.

  Examples of the tricarboxylic acid anhydride having an aromatic structure in the molecule include trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride. Examples of the tricarboxylic acid anhydride having an aliphatic structure include a tricarboxylic acid anhydride having a linear aliphatic structure and a tricarboxylic acid anhydride having a cyclic aliphatic structure. Examples of the tricarboxylic acid anhydride having a linear aliphatic structure include propane tricarboxylic acid anhydride. Examples of the tricarboxylic acid anhydride having a cycloaliphatic structure include cyclohexanetricarboxylic acid anhydride, methylcyclohexanetricarboxylic acid anhydride, cyclohexentricarboxylic acid anhydride, methylcyclohexentricarboxylic acid anhydride, and the like.

  Among the tricarboxylic acid anhydrides having an aliphatic structure used in the present invention, a tricarboxylic acid anhydride having a cyclic aliphatic structure is preferable because a cured coating film having high Tg and excellent thermal properties can be obtained in addition to transparency. Further, when the isocyanurate type polyisocyanate (a2) is an isocyanurate type polyisocyanate synthesized from an isocyanate having a cycloaliphatic structure, the tricarboxylic acid anhydride (a1) has a cycloaliphatic structure. More preferably, it is a tricarboxylic acid anhydride. Examples of the tricarboxylic acid anhydride having a cycloaliphatic structure include cyclohexane tricarboxylic acid anhydride. One or more of these can be used. In some cases, bifunctional dicarboxylic acid compounds such as adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid and acid anhydrides thereof may be used in combination.

  Examples of the cyclohexanetricarboxylic acid anhydride include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1 2,3-tricarboxylic acid-2,3-anhydride and the like. Among them, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is obtained because it becomes a polyamideimide resin excellent in solvent solubility in addition to transparency, and a cured coating film having high Tg and excellent thermal properties can be obtained. Is preferred.

  Here, the above-mentioned cyclohexanetricarboxylic acid anhydride is represented by the structure of the following general formula (1), and cyclohexane-1,2,3-tricarboxylic acid, cyclohexane-1,3,4, which are used as production raw materials. -In the range which impurities, such as a tricarboxylic acid, do not impair the hardening of this invention, for example, 10 mass% or less, Preferably it is 5 mass% or less, and may mix.

  On the other hand, the isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure used in the present invention includes an isocyanurate type polyisocyanate synthesized from an isocyanate having a linear aliphatic structure, and a cyclic aliphatic. An isocyanurate type polyisocyanate synthesized from an isocyanate having a structure.

  Examples of the isocyanurate type polyisocyanate synthesized from an isocyanate having a linear aliphatic structure include HDI3N (isocyanurate type triisocyanate synthesized from hexamethylene diisocyanate (including polymers such as pentamers)), HTMDI3N, and the like. (Isocyanurate-type triisocyanate synthesized from trimethylhexamethylene diisocyanate (including polymers such as pentamers)) and the like. These may be used in combination or alone.

  Examples of the isocyanurate type polyisocyanate synthesized from an isocyanate having a cycloaliphatic structure include IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate (including polymers such as pentamers)), HTDI3N ( Isocyanurate type triisocyanate (including polymer such as pentamer) synthesized from hydrogenated tolylene diisocyanate, HXDI3N (Isocyanurate type triisocyanate synthesized from hydrogenated xylene diisocyanate (polymer such as pentamer) ), NBDI3N (isocyanurate-type triisocyanate synthesized from norbornane diisocyanate (including polymers such as pentamers)), HMDI3N (isocyanurate synthesized from hydrogenated diphenylmethane diisocyanate) Preparative (including 5-mers, etc. of the polymer) triisocyanate), and the like.

  The isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure used in the present invention has a cycloaliphatic structure since a cured coating film having a high Tg and excellent thermal properties can be obtained. Isocyanurate type polyisocyanate synthesized from isocyanate is preferable, and isocyanurate type triisocyanate synthesized from isophorone diisocyanate is particularly preferable. The isocyanurate type triisocyanate synthesized from isophorone diisocyanate may contain a polymer such as a pentamer.

  The isocyanurate type polyisocyanate synthesized from the isocyanate having a cyclic aliphatic structure in the isocyanurate type polyisocyanate (a2) synthesized from the isocyanate having an aliphatic structure is based on the mass of the compound (a2). 50 to 80% by mass is preferable because a cured coating film having a high Tg and excellent thermal properties can be obtained, more preferably 80 to 100% by mass, and most preferably 100% by mass.

  Moreover, the adduct body obtained by the urethanation reaction of the said isocyanate compound and various polyols can also be used in the range which does not impair the solvent solubility of the polyamide-imide resin of this invention.

  The polyamide-imide resin (A1) containing a carboxy group used in the present invention has a problem in stability or the like by directly forming an imide bond from the above-mentioned tricarboxylic acid anhydride (a1) and the above-mentioned isocyanate compound (a2). Without passing through a certain polyamic acid intermediate, it is possible to synthesize a polyamide-imide resin that provides a cured coating film with good reproducibility, good solubility, and excellent transparency.

  When the carboxylic acid component of the tricarboxylic acid anhydride (a1) reacts with the isocyanate component in the polyisocyanate (a2), an imide and an amide are formed, and the resin of the present invention becomes an amide-imide resin. In addition, when the polyisocyanate (a2) is reacted with the tricarboxylic acid anhydride (a1), the tricarboxylic acid anhydride (a1) and the polyisocyanate (a1) are left in such a ratio that the carboxylic acid component of the tricarboxylic acid anhydride (a1) remains. When reacted with a2), the resulting polyamideimide resin has a carboxy group. This carboxy group reacts with a polymerizable group such as an epoxy group of an epoxy resin contained in the curable resin composition of the present invention described later to form a crosslinked structure of the cured product. Since the reaction rate is fast imidization, even in the reaction of tricarboxylic acid and triisocyanate, tricarboxylic acid selectively forms an imide at the acid anhydride.

  When the tricarboxylic acid anhydride (a1) and the isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure are reacted to obtain the polyamideimide resin (A1) used in the present invention, nitrogen is used. It is preferable to make it react in the polar solvent which does not contain both an atom and a sulfur atom. In the presence of a polar solvent containing nitrogen or sulfur atoms, environmental problems are likely to occur, and in the reaction of tricarboxylic acid anhydride (a1) with isocyanurate type polyisocyanate (a2), Growth is likely to be hindered. When such a molecule is cut, the physical properties of the composition are likely to deteriorate, and film defects such as “repellency” tend to occur.

  In the present invention, the polar solvent containing neither a nitrogen atom nor a sulfur atom is more preferably an aprotic solvent. For example, a cresol solvent is a phenolic solvent having protons, but is somewhat unfavorable in terms of the environment, and easily reacts with an isocyanate compound to hinder molecular growth. In addition, the cresol solvent easily reacts with an isocyanate group to easily become a blocking agent. Therefore, it is difficult to obtain good physical properties by reacting with other curing components (for example, epoxy resin) during curing. Furthermore, if the blocking agent is removed, it is likely to cause contamination of the equipment used and other materials. Also, alcohol solvents are not preferred because they react with isocyanates or acid anhydrides. Examples of the aprotic solvent include ether solvents having no hydroxyl groups, ester solvents having no hydroxyl groups, and ketone solvents having no hydroxyl groups. Examples of ester solvents that do not have a hydroxyl group include ethyl acetate, propyl acetate, and butyl acetate. Examples of the ketone solvent having no hydroxyl group include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Of these, an ether solvent having no hydroxyl group is particularly preferred.

  In the present invention, the ether solvent having no hydroxyl group has weak polarity and is excellent in the reaction of the isocyanate having the aliphatic structure described above with the isocyanurate type polyisocyanate (a2) and the tricarboxylic acid anhydride (a1). Provide a reaction field. As such ether solvents, known and commonly used solvents can be used. For example, ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether , Polyethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether, triethylene glycol diethyl ether and triethylene glycol dibutyl ether; ethylene glycol monomers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate Alkyl ether acetates; polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether Polypropylene glycol dialkyl ethers such as tellurium, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether; propylene glycol monoalkyl such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate Ether acetates: Dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene group Polypropylene glycol monoalkyl ether acetates such as recall monobutyl ether acetate; or dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymers; monoacetate monoalkyl ethers of copolymerized polyether glycols; or Such polyether glycol alkyl esters; polyether glycol monoalkyl esters monoalkyl ethers, and the like.

  In step (1), the isocyanurate type polyisocyanate (a2) and the tricarboxylic acid anhydride are added to the tricarboxylic acid anhydride (a1) by adding the isocyanurate type polyisocyanate (a2) at least twice. After reacting the product (a1), the product obtained further comprises a step (1a) of reacting the isocyanurate type polyisocyanate (a2).

  In the production of the polyamideimide resin (A1), the present invention divides the isocyanurate type polyisocyanate (a2) into the tricarboxylic acid anhydride (a1) at least twice, more preferably 3 to 5 times. Addition is preferable because a polyamideimide resin having excellent solvent dilutability can be obtained.

  In the step (1a), first, one or more types of tricarboxylic acid anhydride (a1) and one or more types of the isocyanurate type polyisocyanate (a2) are mixed in a solvent or in the absence of a solvent and stirred. (Amide) imidization reaction is carried out while heating. At that time, the ratio of the isocyanurate type polyisocyanate (a2) added to the tricarboxylic acid anhydride (a1) at each time was determined based on the number of moles of isocyanate groups of the isocyanurate type polyisocyanate (a2). What is necessary is just the ratio by which the sum total of the number of moles of the carboxy group of acid anhydride (a1) and the number of moles of acid anhydride group becomes an excess amount.

  While confirming the progress of the (amide) imidization reaction, preferably, after the reaction is allowed to proceed until the isocyanate group of the isocyanurate type polyisocyanate (a2) disappears, more preferably, the (amide) imidization reaction It is preferable to stir while maintaining the reaction temperature, and to add the isocyanurate-type polyisocyanate (a2) to the resulting reaction product for reaction. When the isocyanurate type polyisocyanate (a2) is added to the tricarboxylic acid anhydride (a1) in three or more times, the isocyanurate type polyisocyanate (a2) is further added to the reaction product obtained above. ) To be reacted, that is, the step (a1) may be repeated.

  When adding the isocyanurate type polyisocyanate (a2) (hereinafter sometimes simply referred to as the component (a2)) separately, the amount of the component (a2) to be added may be evenly allocated or biased. May be. As a method for imparting bias, for example, the amount of the component (a2) to be added at the first time is the largest and the balance is made equal or the amount to be added later is reduced, or the component (a2) to be added at the first time. There are various methods such as a method of making the balance the smallest and making the balance evenly, or making the balance more the amount added later, but the amount of the component (a2) added first time is the largest and the balance is added later. A method of decreasing the amount added is preferable. For example, when the component (a2) is added in three portions, 40 to 80% by mass of the component (a2) to be added is first added, and 40 to 15% by mass is added the second time. 20 to 5% by mass can be added.

  The reaction temperature of the (amide) imidation reaction is preferably in the range of 50 ° C to 250 ° C, particularly preferably in the range of 70 ° C to 180 ° C. By setting such a reaction temperature, the reaction rate is increased, and the side reaction and decomposition are less likely to occur.

The progress of the (amide) imidization reaction can be traced by an analytical means such as an infrared vector, acid value, or quantitative determination of an isocyanate group. For example, in the infrared spectrum, 2270 cm ^-1 which is the characteristic absorption of an isocyanate group was reduced as the reaction further acid anhydride group is reduced with a characteristic absorption at 1860 cm ^-1 and 850 cm ^-1. On the other hand, the absorption of imide groups increases at 1780 cm ⁻¹ and 1720 cm ⁻¹ . The reaction may be terminated by lowering the temperature while confirming the target acid value, viscosity, molecular weight and the like. However, it is more preferable to continue the reaction until the isocyanate group disappears from the standpoint of stability over time. In addition, during the reaction or after the reaction, a catalyst, an antioxidant, a surfactant, other solvents, and the like may be added as long as the physical properties of the synthesized resin are not impaired.

  The ratio of the total amount of the isocyanurate type polyisocyanate (a2) subjected to the (amide) imidization reaction in the step (1) and the amount of the tricarboxylic acid anhydride (a1) is determined by the isocyanurate type polyisocyanate ( Ratio of the total number of moles (N) of isocyanate groups in a2) to the total number of moles of carboxy groups (M1) and acid anhydride groups (M2) in tricarboxylic acid anhydride (a1) [ (M1) + (M2)) / (N)] is made to be 1.1 to 3, the polarity in the reaction system becomes high and the reaction proceeds to lubrication, the isocyanate group does not remain, It is preferable because the stability of the resulting polyamideimide resin is good, the residual amount of the tricarboxylic acid anhydride (a1) is small, and separation problems such as recrystallization hardly occur. Among these, 1.2 to 2 is more preferable. In the present invention, the acid anhydride group refers to a —CO—O—CO— group obtained by intramolecular dehydration condensation of two molecules of carboxylic acid.

  Examples of the polyamideimide resin (A1) used in the present invention include imide resins represented by the following (formula 2).

  (N is a repeating unit of 0 to 30. Moreover, Rb is a structural unit represented by the following structural formula (Formula 3) or (Formula 4), for example.

(R ₂ is, for example, an aromatic or aliphatic tricarboxylic acid residue that may have a substituent having 6 to 20 carbon atoms.) Rc is represented by the following structural formula (formula 5), for example. A structural unit.

(R ₂ is, for example, the same as described above.)

  Rd is, for example, a trivalent organic group represented by the following (formula 6),

  Ra represents, for example, a residue of a divalent aliphatic diisocyanate.

  Next, the step (2) for producing the alcohol-modified polyamideimide resin (A2) of the present invention will be described.

  The alcohol-modified polyamideimide resin (A2) of the present invention is obtained by reacting the alcohol compound (a3) subsequently after producing the polyamideimide resin (A1) by the above method. The reaction between the polyamideimide resin (A1) and the alcohol compound (a3) is not particularly limited as long as the effects of the present invention are not impaired. For example, the reaction can be performed by the following esterification reaction.

As the polyamideimide resin (A1) used as a raw material, the one produced by the above method can be used. However, since the side reaction of urethanization can be suppressed during the reaction with the alcohol compound (a3), the isocyanate group is completely It is preferable to use those that have disappeared. The disappearance of the isocyanate group can be confirmed by the disappearance of 2270 cm ^−1, which is the characteristic absorption of the isocyanate group in the infrared spectrum, for example.

  The reaction between the polyamideimide resin (A1) and the alcohol compound (a3) is carried out by the number of moles of acid anhydride groups (M3) in the polyamideimide resin (A1) and the number of moles of hydroxyl groups (L) of the alcohol compound (a3). The ratio of L / M = 1 to 5 is preferable because the storage stability of the resulting polyamideimide resin is increased, and the range of L / M3 = 1 to 2 is preferable. More preferable from the viewpoint of reduction.

The number of moles of acid anhydride groups (M3) in the polyamideimide resin (A1) is determined by the following method because the tricarboxylic acid anhydride (a1) is consumed by the reaction with the polyisocyanate (a2). Can be obtained.
(1) The polyamideimide resin (A1) is diluted with a solvent or the like, and the acid value (a) is determined by titration with an aqueous KOH solution.
(2) The polyamide-imide resin (A1) is diluted with a solvent or the like, and after an excess amount of n-butanol is reacted with the acid anhydride group, the acid value (b) is determined by titration with an aqueous KOH solution. In (2), the reaction between the acid anhydride group and n-butanol is carried out at 117 ° C. The disappearance of the acid anhydride is confirmed by the complete disappearance of 1860 cm ^−1, which is the characteristic absorption of the acid anhydride group, in the infrared spectrum.
(3) From the difference between the acid value (a) and the acid value (b), the concentration of the acid anhydride group in the polyamideimide resin (A1) of the present invention is calculated and converted to the number of moles (M3).

  Examples of the alcohol compound (a3) include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, trimethylolpropane, and benzyl alcohol. An alcohol having 10 or less carbon atoms; 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol, 1-methoxy-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 3-methoxy-1-butyl alcohol, 2- Alcohol having 10 or less carbon atoms including an ether bond such as isopropoxyethyl alcohol; Alcohol having 10 or less carbon atoms including a ketone group such as 3-hydroxy-2-butanone; Hydroxyisobutyrate Alcohols having 10 or less carbon atoms containing ester groups such as methyl and the like. In the present invention, it is preferable to use a monohydric alcohol having 10 or less carbon atoms from the physical properties of the resulting thermosetting resin. Furthermore, monohydric alcohols having 5 or less carbon atoms are preferred.

The dehydration esterification reaction is preferably carried out by mixing the polyamideimide resin (A1) and one or more alcohol compounds (a3) in a solvent or without a solvent and raising the temperature while stirring. The reaction temperature is preferably in the range of 50 ° C to 150 ° C, particularly preferably in the range of 70 ° C to 130 ° C. By setting such a reaction temperature, the reaction rate is increased, and the side reaction and decomposition are less likely to occur. The reaction forms an ester bond with a dehydration reaction. The progress of the reaction can be traced by an analytical means such as an infrared vector, acid value, or ester bond quantification. The infrared spectrum, 1860 cm ^-1 and 850 cm ^-1 which is the characteristic absorption of an acid anhydride group decreases with the reaction. The reaction may be terminated by lowering the temperature while confirming the target acid value, viscosity, molecular weight and the like. However, it is more preferable to continue the reaction until the acid anhydride group disappears from the viewpoint of stability over time.

  Moreover, the same solvent as the solvent used for the (amide) imidation reaction can be used for the solvent used for dehydration esterification reaction. In addition, during the reaction or after the reaction, a catalyst, an antioxidant, a surfactant, other solvents, and the like may be added as long as the physical properties of the synthesized resin are not impaired.

  The alcohol-modified polyamide-imide resin (A2) obtained by the above production method includes at least an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure and a tricarboxylic acid anhydride (a1). This includes an alcohol-modified polyamideimide resin in which the alcohol compound (a3) forms an ester bond and is bonded to the carboxy group or acid anhydride group of the polyamideimide resin (A1) bonded by forming an imide.

  Further, the alcohol-modified polyamideimide resin (A2) obtained by the production method of the present invention has a molecular weight distribution of 2.0 or less, preferably 1.5 to 2.0, A range of 1.7 to 1.9 is particularly preferable.

  For this reason, the alcohol-modified polyamideimide resin of the present invention is not only soluble in a general-purpose solvent and excellent in solvent dilutability, but also has long storage stability and a long working life even when blended with a curable resin described later. Resin composition and cured product (cured coating film) excellent in developability are obtained.

  The number average molecular weight is preferably 800 to 20000, more preferably 850 to 8000, and particularly preferably in the range of 900 to 2500 in terms of good solubility in a solvent and a cured product having excellent mechanical strength. preferable. On the other hand, the mass average molecular weight is not particularly limited as long as it satisfies the range of the molecular weight distribution with respect to the number average molecular weight, but is preferably 1600 to 40000 in terms of good solubility in a solvent. 1650 to 10000 is more preferable, and a range of 1700 to 5000 is particularly preferable.

  The molecular weight can be measured by gel permeation chromatography (GPC) or quantitative analysis of the terminal functional group amount.

In the present invention, the number average molecular weight and the mass average molecular weight were measured using GPC under the following conditions.
Measuring device: HLC-8120GPC, UV8020 manufactured by Tosoh Corporation
Column: TFKguardcolumnhxl-L, TFKgel (G1000HXL, G2000HXL, G3000HXL, G4000HXL) manufactured by Tosoh Corporation
Detector: RI (differential refractometer) and UV (254 nm)
Measurement conditions: Column temperature 40 ° C
Solvent THF
Flux 1.0ml / min
Standard: Calibration curve prepared with polystyrene standard sample Sample: 0.1% by mass THF solution in terms of resin solids filtered through microfilter (injection amount: 200 μl)

  The acid value of the alcohol-modified polyamideimide resin (A2) of the present invention is preferably 70 to 210 KOHmg / g, and particularly preferably 90 to 190 KOHmg / g. If it is 70-210 KOHmg / g, the performance excellent as cured | curing material property will be exhibited.

  Further, among the alcohol-modified polyamideimide resin (A2) of the present invention, a polyamideimide resin that is soluble in a polar solvent that does not contain any of the nitrogen atom and sulfur atom described above is preferable. Examples of such polyamideimide resins include branched polyamideimide resins having a branched structure and an acid value of the resin of 60 KOHmg / g or more.

  Examples of the component contained in the alcohol-modified polyamideimide resin (A2) used in the present invention include an imide resin represented by the following (formula 7).

  (N is a repeating unit of 0 to 30. Ra represents, for example, a residue of a divalent aliphatic diisocyanate. Rb represents, for example, the above structural formula (Formula 3) or (Formula 4). Rd is, for example, a trivalent organic group represented by the above (formula 6), and Rc ′ is, for example, a structure represented by the following structural formula (formula 8) Unit.

(In the formula, R ₂ is, for example, the same as described above. R ₃ represents a residue obtained by removing a hydroxyl group from an alcohol compound.)

  The curable resin composition of the present invention includes the alcohol-modified polyamideimide resin (A2) of the present invention, the curable resin (B), and / or the organic solvent (C).

  Examples of the curable resin (B) include an epoxy compound (B1) having two or more epoxy groups in the molecule, a compound having two or more maleimide groups in the molecule, a benzoxazine resin, and a cyanate ester resin. Is mentioned. As the component (B1), known and commonly used epoxy resins can be used, and two or more kinds may be mixed and used. Other examples include melamine resins, isocyanate compounds, silicates and alkoxysilane compounds, (meth) acrylic resins, etc., which are excellent in heat resistance, dimensional stability and mechanical properties (toughness, flexibility). An epoxy resin is preferable in that a cured product such as a cured coating film is obtained.

  In addition, the meaning of the hardened | cured material property mentioned above and below-mentioned described in this invention is the polyamideimide resin of this invention alone or the polyamideimide resin of this invention other than the hardened | cured material of the polyamideimide resin of this invention and the component which reacts with this. It also includes meanings including simply solvent-dried coatings and molded bodies that also contain other resins, additives, inorganic material components, etc. that do not react with the resin. Furthermore, the cured product obtained by mixing the polyamideimide resin of the present invention with a curing agent that reacts by heating or light and / or does not react with the polyamideimide resin of the present invention, but is cured by heat, light, etc. Those having cured properties are also included in the meaning.

  Examples of the epoxy resin (B1) include reaction of bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene and various phenols. Epoxidized products of various dicyclopentadiene-modified phenolic resins, 2,2 ′, 6,6′-tetramethylbiphenol epoxidized product, 4,4′-methylenebis (2,6-dimethylphenol) epoxidized product, Epoxy derived from naphthalene skeleton such as naphthol, binaphthol, or novolak modification of naphthol or binaphthol, aromatic epoxy resin such as epoxy resin obtained by epoxidizing phenol resin of fluorene skeleton, etc. That.

  Also, aliphatic epoxy resins such as neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, 3,4-epoxycyclohexylmethyl- 3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxybicyclohexyl) adipate, 1,2-epoxy-4- (2-oxiranyl) cyclohexane of 2,2-bis (hydroxymethyl) -1-butanol Cyclic aliphatic epoxy resins such as adducts, such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, epoxy resins containing a polyalkylene glycol chain in the main chain, such as triglycidyl isocyanurate Heterocycle-containing epoxy resins can be used.

  In addition, an epoxy group-containing polymerization resin obtained by polymerizing an unsaturated group of an epoxy compound having a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and other monomers having a polymerizable unsaturated bond Copolymers with can also be used.

  Examples of the compound having both (meth) acryloyl group and epoxy group include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate glycidyl ether, hydroxypropyl (meth) acrylate glycidyl ether, 4-hydroxydibutyl (meth) acrylate glycidyl ether. , 6-hydroxyhexyl (meth) acrylate glycidyl ether, 5-hydroxy-3-methylpentyl (meth) acrylate glycidyl ether, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone modified (meth) acrylic acid-3, 4-epoxycyclohexyl, vinylcyclohexene oxide and the like can be mentioned.

  The epoxy resin (B1) component having two or more epoxy groups in the molecule in the present invention is particularly preferably a cycloaliphatic epoxy resin. If it is a cycloaliphatic epoxy resin, a cured coating film having a high Tg and excellent thermal properties can be obtained, and a cured product having a high light transmittance in the ultraviolet region (around 300 nm) can be obtained. Among the cycloaliphatic epoxy resins, hydrogenated bisphenol A type epoxy resin, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like are preferable. .

  Such cycloaliphatic epoxy resins can be obtained on the market, and examples thereof include Denacol EX-252 (manufactured by Nagase ChemteX Corporation), EHPE3150, EHPE3150CE (manufactured by Daicel Chemical Industries, Ltd.), and the like.

  The alcohol-modified polyamideimide resin (A2) and the epoxy resin (B1) having two or more epoxy groups in the molecule can be freely blended according to various desired physical properties, such as Tg. In terms of the balance between the thermal properties, mechanical properties, etc. of the film and the transparency of the cured coating film, the number of moles of carboxy groups (COOH) of the alcohol-modified polyamideimide resin (A2) and two or more epoxy groups in the molecule The epoxy resin (B1) having a ratio [n (EPOXY) / n (COOH)] to the number of moles of epoxy groups n (EPOXY) of the epoxy resin (B1) is 0.3 to 4, preferably 0.8 to 1. The blend of the alcohol-modified polyamideimide resin (A2) and the epoxy resin (B1) within the range of .2 makes it easy to obtain Tg as a property of the cured product, and a cured product having excellent mechanical properties and the like is obtained. Is preferred because the transparency of the further cured product is improved.

  The curable resin composition of the present invention may be mixed with an epoxy-carboxylic acid curing catalyst or the like. Such epoxy-carboxylic acid curing catalysts include primary to tertiary amines for promoting the reaction, quaternary ammonium salts, nitrogen compounds such as dicyandiamide, imidazole compounds, and TPP (triphenylphosphine). ), Known epoxy curing accelerators such as phosphine compounds such as alkyl-substituted trialkyl phonylphosphine and derivatives thereof, phosphophonium salts thereof, dialkylureas, carboxylic acids, phenols, or methylol group-containing compounds. Etc., and a small amount of these can be used in combination.

  Examples of the compound (B2) having two or more maleimide groups in one molecule (hereinafter referred to as maleimide compound (B2)) include, for example, N-cyclohexylmaleimide, N-methylmaleimide, Nn-butylmaleimide, N-aliphatic maleimides such as N-hexylmaleimide and N-tert-butylmaleimide; N-aromatic maleimides such as N-phenylmaleimide, N- (P-methylphenyl) maleimide and N-benzylmaleimide; 4,4 ′ -Diphenylmethane bismaleimide, 4,4'-diphenylsulfone bismaleimide, m-phenylene bismaleimide, bis (3-methyl-4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, bis (3 , 5-Dimethyl-4-maleimidophenyl) methane, bis ( - ethyl-5-methyl-4-maleimide phenyl) methane, bis (3,5-diethyl-4-maleimide phenyl) bismaleimide such as methane and the like. Among these, bismaleimide is preferable from the viewpoint that the heat resistance of the cured product is particularly good, and 4,4′-diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3 Preferred examples include -ethyl-5-methyl-4-maleimidophenyl) methane and bis (3,5-diethyl-4-maleimidophenyl) methane. When the maleimide compound (B2) is used in the curable resin composition of the present invention, a curing accelerator can be used as necessary. Examples of the curing accelerator that can be used here include amine compounds, phenol compounds, acid anhydrides, imidazoles, and organic metal salts.

  The curable resin composition of the present invention may further contain an organic solvent (C) as necessary. When the organic solvent (C) is contained in the curable resin composition of the present invention, the same organic solvent as that used to prepare the alcohol-modified polyamideimide resin (A2) can be used.

  The curable resin composition of the present invention further comprises a photopolymerization initiator (D) and, if necessary, a reactive diluent (E) when curing by irradiating with energy rays, particularly ultraviolet rays. Can be used. The photopolymerization initiator (D) is not particularly limited, and a known and commonly used polymerizable photoinitiator can be used. Typical examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether. Benzoin and benzoin alkyl ethers such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, acetophenones such as 1,1-dichloroacetophenone, 2-methylanthraquinone, 2 -Anthraquinones such as ethyl anthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-aluminum anthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chloro Thioxanthones such as thioxanthone, 2,4-diisopropylthioxanthone, trimethylbenzoyl such as bis (2,6dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide Examples include alkyl phosphine oxides, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenones such as benzophenone, and xanthones. These can be used alone or in combination of two or more.

  Although the usage-amount of a photoinitiator (D) will not be specifically limited if it is a range which does not impair the effect of this invention, Usually, 0.1-30 mass with respect to 100 mass parts of alcohol modified polyamideimide resin (A2). The range of parts is preferable, and the range of 0.5 to 10 parts by mass is more preferable. Such photopolymerization initiators can also be used in combination with one or more known and commonly used photopolymerization accelerators.

  As the reactive diluent (E) used in the present invention, known and commonly used photopolymerizable vinyl monomers can be used. Typical examples include dimethylaminoethyl acrylate, diethylaminoethyl acrylate, ethylene glycol diacrylate, Diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, penta Erythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Hexaacrylate, acryloylmorpholine, vinylpyrrolidone, styrene or tris (2-acryloyloxyethyl) isocyanurate, and alkyl (meth) acrylates such as methyl methacrylate and ethyl acrylate, or the respective methacrylates and polybasic acids for the above acrylates Monomers having ethylenically unsaturated double bonds, such as mono-, di-, tri- or higher polyesters of hydroxyalkyl (meth) acrylates, or bisphenol A type epoxy acrylate, novolac type epoxy acrylate or urethane acrylate And oligomers. These 1 type (s) or 2 or more types can be used.

  The alcohol-modified polyamideimide resin (A2) and the reactive diluent (E) can be freely blended in accordance with various desired physical properties, such as thermal properties such as Tg, mechanical properties, etc. In terms of balance with the transparency of the cured coating film, the ratio [A2 / E] of the alcohol-modified polyamideimide resin (A2) and the photopolymerizable group of the reactive diluent (E) is 0.2 to Mixing the alcohol-modified polyamideimide resin (A2) and the reactive diluent (E) within a range of 5.0 makes it easy to obtain Tg as a property of the cured product, and a cured product having excellent mechanical properties and the like is obtained. Further, it is preferable because the transparency of the cured product is improved.

  Curing of the curable resin composition of the present invention is basically performed while appropriately selecting and adjusting the type and blending ratio of the alcohol-modified polyamideimide resin (A2), curable resin (B), other components, and curing conditions. be able to.

  As the curing method of the curable resin composition of the present invention, active energy ray curing, curing by heat, and both are used in combination, that is, semi-curing by active energy ray curing, then curing by heat, semi-curing by curing by heat It is also possible to carry out active energy ray curing and both at the same time.

  When curing with active energy rays, ultraviolet rays or electron beams can be used. As the ultraviolet ray, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, a metal halide lamp, or the like can be used. As the ultraviolet wavelength, a wavelength of 1900 to 3800 angstroms is mainly used. Moreover, when hardening with an electron beam, the apparatus provided with irradiation sources, such as various electron beam accelerators, can be used, and the electron with an energy of 100-1000 KeV is irradiated.

Moreover, when making it harden | cure with a heat | fever, it is carried out in the range of the curing temperature of 80 to 300 degreeC, Preferably it is the range of 120 to 250 degreeC in presence of the catalyst and additive which start thermal polymerization. For example, the material to be coated can be cured by heating after being painted or cast. Further, step curing at various temperatures may be performed. Alternatively, a sheet-like or film-like composition semi-cured at a temperature of about 50 ° C. to 170 ° C. may be stored and treated at the above-described curing temperature when necessary.
Of course, there is no limitation in using the active energy ray and heat in combination.

  In the curable resin composition of the present invention, if necessary, other solvents than the above, various leveling agents, antifoaming agents, antioxidants, anti-aging agents, ultraviolet absorbers, anti-settling agents, rheology control agents Various known additives such as barium sulfate, silicon oxide, talc, clay, calcium carbonate, silica, colloidal silica, glass and the like, various metal powders, glass fibers, carbon fibers, fiber shapes such as Kevlar fibers, etc. You may mix | blend well-known and usual pigments, such as a filler, or phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black, a silica, other adhesive imparting agents, etc. Moreover, it is also possible to mix | blend polymers, such as an acrylic resin, a cellulose resin, a polyvinyl resin, polyphenylene ether, and polyether sulfone, as needed.

  In the curable resin composition of the present invention, a non-halogen flame retardant containing substantially no halogen atom is blended so long as the effect of the present invention is not impaired so that the cured product exhibits flame retardancy. May be. Examples of the non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. The flame retardants may be used alone or in combination, and a plurality of flame retardants of the same system may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. . The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used. Examples of the organic phosphorus compound include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7- Examples thereof include cyclic organophosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins. The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, the polyamide-imide resin (A2), In 100 parts by mass of the curable resin composition containing all of the curable resin (B) and / or the organic solvent (C), the curing agent, the non-halogen flame retardant, and other fillers and additives, red phosphorus is not contained. When used as a halogen-based flame retardant, it is preferably blended in the range of 0.1 to 2.0 parts by mass. When an organophosphorus compound is used, it is similarly blended in the range of 0.1 to 10.0 parts by mass. It is preferable to mix in the range of 0.5 to 6.0 parts by mass. In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable. Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenolic resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) and (iii) with paulownia oil, isomerized linseed oil, etc. It is. Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine. The amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardant. In 100 parts by mass of curable resin composition (A2), curable resin (B) and / or organic solvent (C), curing agent, non-halogen flame retardant and other fillers and additives, etc. It is preferable to mix | blend in the range of 0.05-10 mass parts, and it is preferable to mix | blend especially in the range of 0.1-5 mass parts. Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin. The amount of the silicone flame retardant is appropriately selected depending on the type of the silicone flame retardant, the other components of the curable resin composition, and the desired degree of flame retardant. In 100 parts by mass of curable resin composition (A2), curable resin (B) and / or organic solvent (C), curing agent, non-halogen flame retardant and other fillers and additives, etc. It is preferable to mix in the range of 0.05 to 20 parts by mass. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass. Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like. Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like. Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate. Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin. Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax. Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned. The blending amount of the inorganic flame retardant is appropriately selected depending on the kind of the inorganic flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. In 100 parts by mass of curable resin composition (A2), curable resin (B) and / or organic solvent (C), curing agent, non-halogen flame retardant and other fillers and additives, etc. It is preferable to mix | blend in the range of 0.05-20 mass parts, and it is preferable to mix | blend especially in the range of 0.5-15 mass parts. Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound. The amount of the organic metal salt flame retardant is appropriately selected depending on the type of the organic metal salt flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. , A polyamideimide resin (A2), a curable resin (B) and / or an organic solvent (C), a curing agent, a non-halogen flame retardant, and other fillers and additives, etc. It is preferable to mix | blend in the range of 0.005-10 mass parts in a mass part.

  The curable resin composition of the present invention provides a cured coating film that is soluble in a general-purpose solvent and is excellent in heat resistance and light transmittance. For this reason, in particular, in the field where the transparency of the cured product is required, for example, the field for optical materials, solder resist materials for printed wiring boards, protective materials and insulating materials for household appliances such as refrigerators and rice cookers, liquid crystal displays, Protective materials used for liquid crystal display elements, organic and inorganic electroluminescent devices, organic and inorganic electroluminescent devices, LED displays, light emitting diodes, electronic paper, solar cells, through silicon electrodes (Through Silicon Via: TSV), optical fibers, optical waveguides, etc. It can be suitably used in fields such as insulating materials, adhesives and reflective materials, and display device fields such as liquid crystal alignment films and color filter protective films.

  Naturally, the field where the transparency of the cured product is not required, for example, various heat-resistant coating materials, heat-resistant adhesives; sealing materials for electric and electronic parts, insulating varnishes, laminates, insulating powder coatings, semiconductor passivation Electrical insulating materials such as films and gate insulating films; Conductive materials such as conductive films and conductive adhesives; Adhesives for structural materials such as laminates for printed wiring boards, prepregs and honeycomb panels; glass fibers and carbon fibers , Fiber reinforced plastics using various reinforcing fibers such as aramid fibers and prepregs thereof; patterning materials such as resist inks; gaskets for non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries Can do.

The curable resin composition of the present invention includes a white prepreg, a white laminate, and the white laminate because a cured coating film that is soluble in a general-purpose solvent and has excellent heat resistance and light transmittance is obtained. It can be suitably used for a chip LED. Details will be described below.
The white prepreg of the present invention is characterized in that a mixture containing the curable resin composition of the present invention and a white pigment is impregnated or applied to a sheet-like glass fiber substrate and then dried. Specifically, after impregnating or applying a mixture containing the curable resin composition of the present invention and a white pigment to a sheet-like glass fiber substrate, the mixture is dried for 1 to 60 minutes in a dryer in the range of 100 to 200 ° C. It is characterized by being semi-cured within the range. The white prepreg and the production method thereof will be specifically described below.

  Examples of the white pigment include zinc oxide, calcium carbonate, titanium dioxide, alumina, and synthetic smectite. The white pigment is not particularly limited as long as it is a white inorganic powder, but is not limited to visible light reflectance, whiteness, or electricity. It is most preferable to use titanium dioxide from the viewpoint of characteristics.

  The crystal structure of titanium dioxide includes anatase type and rutile type. When both characteristics are mentioned, the anatase type has good reflectance in the visible light short wavelength region, and the rutile type has excellent long-term durability and discoloration resistance. Either may be sufficient as a white pigment added to the curable resin composition of this invention, and it does not specifically limit. It is of course possible to use a mixture of both.

  The content of the white pigment contained in the mixture is preferably in the range of 10 to 75% by mass in the blend. If it is 10% by mass or more, sufficient whiteness and reflectance can be obtained, and if it is 75% by mass or less, the impregnation property to the sheet-like glass fiber substrate is lowered or the adhesive strength to the metal foil is lowered. There will be no problems.

  When titanium dioxide is used as the white pigment, the titanium dioxide may be subjected to alumina or silica treatment as a surface treatment. Moreover, a silane coupling agent or titanate coupling agent treatment is also possible.

  In addition to the white pigment, the mixture impregnated into the sheet-like glass fiber base material may contain an inorganic filler such as silica as necessary. Examples of the inorganic filler that can be contained include silica, aluminum hydroxide, magnesium hydroxide, E glass powder, magnesium oxide, potassium titanate, calcium silicate, clay, and talc. Two or more types may be used in combination. By containing these inorganic fillers, the rigidity of the substrate is improved. The blending amount is not particularly limited, but is preferably 50% by mass or less with respect to the mixture. If it is 50 mass% or less, there is almost no possibility that the impregnation property to a sheet-like glass fiber base material will fall or the adhesive strength with metal foil will generate | occur | produce.

  In addition to the white pigment and the inorganic filler, a fluorescent agent can be blended in the mixture impregnated into the sheet-like glass fiber base as necessary. By blending the fluorescent agent, the apparent reflectance in the visible light short wavelength region can be increased. Here, the fluorescent agent is a compound that has the property of absorbing light energy such as light, radiation, and ultraviolet light and emitting it by changing to light of other wavelengths. For example, in the case of organic substances, diaminostilbene derivatives, anthracene, sodium salicylate , Diaminostilbene disulfonic acid derivatives, imidazole derivatives, coumarin derivatives, pyrazoline derivatives, decalylamine derivatives, and the like. Examples of inorganic substances include ZnCdS: Ag, ZnS: Pb, and ZnS: Cu. The fluorescent agent preferably has a radiation wavelength in the visible light short wavelength region (380 to 470 nm) in which the reflectance is remarkably lowered, and among the above fluorescent agents, it is generally called a fluorescent whitening agent. Diaminostilbene disulfonic acid derivatives, imidazole derivatives, coumarin derivatives, pyrazoline derivatives and the like are suitable. The addition amount is not limited, but in the case of a pyrazoline derivative, the effect is exhibited from the addition of about 0.1% by mass with respect to the mixture, and the effect is increased as the addition amount is increased. Further, it is desirable that the optical brightener to be added is soluble in a solvent.

  As a sheet-like glass fiber base material used for the white prepreg of the present invention, either a glass cloth or a nonwoven fabric may be used, and a glass cloth and a nonwoven fabric may be used in combination. In the case of a glass cloth, a plain weave structure is basically used, but a woven structure such as Nanako weave, satin weave or twill weave may be used, and is not particularly limited. In order not to impair the appearance and workability, it is preferable to use a woven structure in which the gap between the intersections of the warp and the weft is small. Although there is no restriction | limiting in particular about the thickness of a glass cloth, The thing of the range of 0.02-0.3 mm is easy to handle and preferable.

  Moreover, you may perform surface treatment by a silane coupling agent etc. to a sheet-like glass fiber base material. Furthermore, the sheet-like glass fiber base material itself may be colored white.

  A solvent such as methyl ethyl ketone is added to the above-described mixture as necessary to prepare a resin varnish, impregnated into a sheet-like glass fiber substrate made of glass cloth or the like, and dried to produce a white prepreg. The method for impregnating and drying the resin varnish on the sheet-like glass fiber substrate is not particularly limited. For example, the resin varnish is impregnated by immersing the sheet-like glass fiber substrate in the resin varnish. A method of removing the solvent and semi-curing the curable resin by heating at a temperature of about 200 ° C. for 1 to 60 minutes can be employed. The impregnation amount of the curable resin composition of the white prepreg produced by impregnating and drying the sheet-like glass fiber substrate is not particularly limited, but is preferably in the range of 30 to 60% by mass. As selection of drying conditions for the prepreg, for example, it is preferable to previously measure the gel time of the resin varnish with a gel time tester (manufactured by Yasuda Seiki Seisakusho). Here, as the gel time measurement conditions, the gel time at 160 ° C. (curing time: the time required for the rotor torque to reach about 3.3 kg · cm) is measured by the above-mentioned apparatus, and the gel time of the varnish resin is 5 minutes or more. The range of less than -15 minutes is preferable, and the gel time is more preferably 5 minutes or more and less than 10 minutes. If the gel time of the resin varnish is short, the semi-cured state cannot be maintained, and it becomes difficult to produce a uniform prepreg. Further, when the half-curing cannot be maintained and the curing is reached, it becomes difficult to bond with a metal foil described later. Therefore, it is preferable to semi-cure under conditions suitable for the process by varnish gel time measurement.

A combination of the obtained white prepreg and copper foil or aluminum foil is heated and pressed to produce a white laminate. In addition, the number of white prepregs to be superimposed is not particularly limited, but as a single layer substrate, one or two to ten white prepregs are stacked. In general, the foils are laminated. The multilayer substrate is manufactured by laminating a plurality of the single-layer substrates, but there is no particular limitation on the number of the stacked substrates. As the metal foil, copper foil, aluminum foil or the like is used. The thickness of the metal foil is generally 1 μm to 105 μm, particularly preferably 1.5 μm to 35 μm. It is also possible to use only the surface layer on which the white prepreg is laminated, and use a prepreg of the prior art for the intermediate layer. The white laminates and metal foil-clad white laminates obtained in this way have high reflectivity in the visible light region, remarkably little discoloration due to heating and ultraviolet rays, and high heat resistance and excellent thickness accuracy. It becomes the white laminated board for wiring boards, and a metal foil clad white laminated board. As a lamination molding condition of a metal foil-clad laminate, a general method for a laminate for a printed wiring board can be applied. For example, a multistage press, a multistage vacuum press, a continuous molding, an autoclave molding machine, and the like are used. The range of 300 ° C., pressure: ^{2 to} 100 kgf / cm ² , heating time: range of 0.1 to 5 hours is general, but from the viewpoint of uniform insulation layer thickness, removal of bubbles, etc., lamination molding is It is preferable to carry out under a vacuum of 70 mmHg or less.

  A conductive pattern is formed on the obtained white laminate by an additive method to obtain a printed wiring board. Moreover, a circuit pattern is printed on the metal foil of the obtained metal foil-clad white laminate and etched to obtain a printed wiring board. In order to mount the chip LED on the printed wiring board, first, solder is applied on the printed wiring board, and the chip LED is placed on the printed wiring board, and then the chip LED is melted by passing it through reflow or the like. Is fixed to the printed circuit board. By integrating chip LEDs with high density, it can be used as a surface light source, and such a surface light source is suitably used for a backlight for a liquid crystal display that is particularly required to be thin. In addition, it is applied to induction display illumination lamps, evacuation exit illumination lamps, advertisement lights, etc. as surface emitting illumination devices.

  The thickness accuracy of the chip LED mounting substrate is extremely important when the elements mounted on the substrate are sealed by transfer molding. Here, transfer molding refers to a method of press-fitting a resin into a clamped mold. The thickness of the substrate used for the chip LED is generally 0.06 mm to 1.0 mm. However, if the accuracy of the plate thickness is poor, there is a gap between the substrate and the mold at the time of clamping during transfer molding. And the press-fitted resin leaks from the gap, resulting in molding defects. The required accuracy of the substrate thickness in such transfer molding is, for example, a tolerance of ± 0.05 mm or less (range is 0.1 mm), preferably a tolerance of ± 0.03 mm or less for a substrate having a thickness of 1.0 mm. (The range is 0.06 mm). Therefore, if there is a substrate with high thickness accuracy, the defect rate can be greatly reduced in the manufacturing process of the chip LED, which is extremely significant in industry.

  When the curable resin composition of the present invention is used as a patterning material, for example, the curable resin composition of the present invention is applied onto a substrate, the solvent is dried, and then energy is passed through a mask having a pattern. A pattern can be formed by irradiating a line and developing with an alkaline aqueous solution or a solvent. Furthermore, a stronger pattern can be formed by heat treatment at 80 ° C. or higher. Details will be described below.

  First, a photosensitive film comprising a support and a photosensitive resin composition layer made of the curable resin composition of the present invention formed on the support is produced. On the photosensitive resin composition layer, you may further provide the protective film which coat | covers this photosensitive resin composition layer.

  The photosensitive resin composition layer is formed by dissolving the curable resin composition of the present invention in a solvent or mixed solvent to obtain a solution having a solid content of about 30 to 70% by mass, and then applying the solution on a support. It is preferable to do. Although the thickness of the photosensitive resin composition layer varies depending on the use, it is preferably 10 to 100 μm and more preferably 20 to 60 μm in thickness after drying after removing the solvent by heating and / or hot air blowing. . If the thickness is less than 10 μm, there is a tendency that it is difficult to apply industrially, and if it exceeds 100 μm, the above-described effects produced by the present invention tend to be reduced, and in particular, physical properties and resolution tend to be reduced.

  Examples of the support provided in the photosensitive film include a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene. The thickness of the support is preferably 5 to 100 μm, and more preferably 10 to 30 μm. If the thickness is less than 5 μm, the support tends to be broken when the support is peeled off before development, and if it exceeds 100 μm, the resolution and flexibility tend to decrease. The photosensitive film consisting of two layers of the support and the photosensitive resin composition layer as described above or the photosensitive film consisting of three layers of the support, the photosensitive resin composition layer, and the protective film, for example, is stored as it is. Alternatively, the protective film may be interposed and wound around the core in a roll shape and stored.

  The method for forming a resist pattern when the curable resin composition of the present invention is used as a photosensitive resin composition or a photosensitive film is firstly applied to a known screen printing or roll coater, or protection, respectively. In the process of removing the film and attaching it by lamination or the like, the film is laminated on the substrate on which the resist is formed. Then, if necessary, a removal step of removing the support film from the photosensitive film described above is performed, or actinic rays are passed through the mask pattern without removing the support film to a predetermined portion of the photosensitive resin composition layer. Irradiation is performed to perform an exposure process for photocuring the photosensitive resin composition layer of the irradiated portion. If there is a support film, the photosensitive resin composition layer other than the irradiated part is removed by the next development step after removing the support film. In addition, the board | substrate which forms a resist points out a printed wiring board, a board | substrate for semiconductor packages, and a flexible wiring board.

  As the light source of actinic light, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp that emits ultraviolet rays effectively is used. Moreover, what emits visible light effectively, such as a photographic flood light bulb and a solar lamp, is also used. Further, direct drawing direct laser exposure may be used. An excellent pattern can be formed by using a photopolymerization initiator (D) corresponding to each laser light source and exposure method.

  In the development process, an alkaline developer such as a dilute solution of sodium carbonate (1 to 5% by mass aqueous solution) at 20 to 50 ° C. is used as the developer, and known spraying, rocking immersion, brushing, scraping, etc. Develop by the method of.

After the development step, it is preferable to perform ultraviolet irradiation or heating with a high-pressure mercury lamp for the purpose of improving solder heat resistance, chemical resistance, and the like. In the case of irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary. For example, the irradiation can be performed at an irradiation amount of about 0.2 to 10 J / cm ² . Moreover, when heating a resist pattern, it is preferable to carry out for about 15 to 90 minutes in the range of about 100-170 degreeC. Furthermore, ultraviolet irradiation and heating can be performed at the same time, and after either one is performed, the other can be performed. When performing ultraviolet irradiation and heating simultaneously, it is more preferable to heat to 60 to 150 ° C. from the viewpoint of effectively imparting solder heat resistance, chemical resistance and the like.

  This photosensitive resin composition layer also serves as a protective film for wiring after soldering to the substrate, and has excellent crack resistance, HAST resistance, and gold plating properties, so for printed wiring boards and semiconductor package substrates It is useful as a solder resist for flexible wiring boards.

  The substrate provided with the resist pattern in this manner is then mounted with a semiconductor element or the like (for example, wire bonding or solder connection), and is mounted on an electronic device such as a personal computer.

  EXAMPLES Next, an Example is shown and this invention is demonstrated further in detail. Unless otherwise specified, “part” and “%” are based on mass in the examples.

Example 1
[Preparation of polyamideimide resin (A1-1)]
In a flask equipped with a stirrer, a thermometer and a condenser, 1102.8 g of PGMAc (propylene glycol monomethyl ether acetate), IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 197.6 g (0 .27 mol) and 506.9 g (2.56 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added and heated to 140 ° C. over 2 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 2 hours. The inside of the system became a pale yellow liquid, and as a result of measuring characteristic absorption with an infrared spectrum, it was confirmed that 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared. Further, 197.6 g (0.27 mol) of IPDI3N was added and the reaction was continued. After measuring the characteristic absorption in the infrared spectrum and confirming that the characteristic absorption of the isocyanate group, 2270 cm ⁻¹ , completely disappeared, 197.6 g (0.27 mol) of IPDI3N was further added to continue the reaction. . Characteristic absorption was measured in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared, and imide group absorption was confirmed at 1780 cm ⁻¹ and 1720 cm ⁻¹ . The acid value was 190 KOHmg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A1-1) solution.

[Production of alcohol-modified polyamideimide resin (A1-2)]
Subsequently, 99.8 g (1.35 mol) of n-butanol was added to the resulting solution of the imide resin (A1-1) and reacted at 120 ° C. for 2 hours. As a result of measuring the characteristic absorption in the infrared spectrum, the absorption at 1860 cm ⁻¹ which is the characteristic absorption of the acid anhydride group completely disappeared. The acid value was 162 KOH mg / g in terms of solid content, the molecular weight was number average molecular weight 1180, mass average molecular weight 2054 in terms of polystyrene, and the degree of dispersion was 1.74. This resin solution is abbreviated as an alcohol-modified polyamideimide resin (A1-2).

Example 2
[Preparation of polyamideimide resin (A2-1)]
In a flask equipped with a stirrer, a thermometer and a condenser, 331.9 g of PGMAc (propylene glycol monomethyl ether acetate) and 35.1 g of IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) (0 .05 mol) and 150.3 g (0.76 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 2 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 2 hours. The inside of the system became a pale yellow liquid, and as a result of measuring characteristic absorption with an infrared spectrum, it was confirmed that 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared. Furthermore, 35.1 g (0.05 mol) of IPDI3N was added, and the reaction was continued. After measuring the characteristic absorption in the infrared spectrum and confirming that the characteristic absorption of the isocyanate group, 2270 cm ⁻¹ , completely disappeared, 35.1 g (0.05 mol) of IPDI3N was further added to continue the reaction. . After measuring the characteristic absorption in the infrared spectrum and confirming that the characteristic absorption of the isocyanate group, 2270 cm ⁻¹ , completely disappeared, 35.1 g (0.05 mol) of IPDI3N was further added to continue the reaction. . After measuring the characteristic absorption in the infrared spectrum and confirming that the characteristic absorption of the isocyanate group, 2270 cm ⁻¹ , completely disappeared, 35.1 g (0.05 mol) of IPDI3N was further added to continue the reaction. . Characteristic absorption was measured with an infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared, and imide group absorption was confirmed at 1780 cm ⁻¹ and 1720 cm ⁻¹ . The acid value was 196 KOH mg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A2-1) solution.

[Production of alcohol-modified polyamideimide resin (A2-2)]
Subsequently, 29.4 g (0.40 mol) of n-butanol was added to the solution of the obtained imide resin (A2-1) and reacted at 120 ° C. for 2 hours. As a result of measuring the characteristic absorption in the infrared spectrum, the absorption at 1860 cm ⁻¹ which is the characteristic absorption of the acid anhydride group completely disappeared. The acid value was 161 KOHmg / g in terms of solid content, the molecular weight was number average molecular weight 990, mass average molecular weight 1822 in terms of polystyrene, and the degree of dispersion was 1.84. This resin solution is abbreviated as an alcohol-modified polyamideimide resin (A1-2).

Example 3
[Preparation of polyamideimide resin (A3-1)]
In a flask equipped with a stirrer, a thermometer, and a condenser, 331.9 g of PGMAc (propylene glycol monomethyl ether acetate), IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 87.8 g (0 .12 mol) and 150.3 g (0.76 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 2 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 2 hours. The inside of the system became a pale yellow liquid, and as a result of measuring characteristic absorption with an infrared spectrum, it was confirmed that 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared. Further, 58.6 g (0.08 mol) of IPDI3N was added and the reaction was continued. After measuring the characteristic absorption in the infrared spectrum and confirming that the characteristic absorption of the isocyanate group, 2270 cm ⁻¹ , completely disappeared, 29.3 g (0.04 mol) of IPDI3N was further added to continue the reaction. . Characteristic absorption was measured in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared, and imide group absorption was confirmed at 1780 cm ⁻¹ and 1720 cm ⁻¹ . The acid value was 185 KOH mg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A3-1) solution.

[Production of alcohol-modified polyamideimide resin (A3-2)]
Subsequently, 29.4 g (0.40 mol) of n-butanol was added to the solution of the obtained imide resin (A3-1) and reacted at 120 ° C. for 2 hours. As a result of measuring the characteristic absorption in the infrared spectrum, the absorption at 1860 cm ⁻¹ which is the characteristic absorption of the acid anhydride group completely disappeared. The acid value in terms of solid content was 157 KOH mg / g, the molecular weight in terms of polystyrene was a number average molecular weight of 1007, a mass average molecular weight of 1762, and the degree of dispersion was 1.75. This resin solution is abbreviated as alcohol-modified polyamideimide resin (A3-2).

Example 4
[Preparation of polyamideimide resin (A4-1)]
331.9 g of PGMAc (propylene glycol monomethyl ether acetate) and IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 29.3 g (0 0.04 mol) and 150.3 g (0.76 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 2 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 2 hours. The inside of the system became a pale yellow liquid, and as a result of measuring characteristic absorption with an infrared spectrum, it was confirmed that 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared. Further, 58.6 g (0.08 mol) of IPDI3N was added and the reaction was continued. After measuring the characteristic absorption in the infrared spectrum and confirming that the characteristic absorption of the isocyanate group, 2270 cm ⁻¹ , completely disappeared, 87.8 g (0.12 mol) of IPDI3N was further added to continue the reaction. . Characteristic absorption was measured in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared, and imide group absorption was confirmed at 1780 cm ⁻¹ and 1720 cm ⁻¹ . The acid value was 190 KOHmg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A4-1) solution.

[Production of alcohol-modified polyamideimide resin (A4-2)]
Subsequently, 29.4 g (0.40 mol) of n-butanol was added to the solution of the obtained imide resin (A4-1), and reacted at 120 ° C. for 2 hours. As a result of measuring the characteristic absorption in the infrared spectrum, the absorption at 1860 cm ⁻¹ which is the characteristic absorption of the acid anhydride group completely disappeared. The acid value in terms of solid content was 161 KOH mg / g, the molecular weight in terms of polystyrene was a number average molecular weight 1022, a mass average molecular weight 1931, and the degree of dispersion was 1.89. This resin solution is abbreviated as alcohol-modified polyamideimide resin (A4-2).

Comparative Example 1 [Preparation of polyamideimide resin (A5-1)]
In a flask equipped with a stirrer, a thermometer and a condenser, 276.4 g of PGMAc (propylene glycol monomethyl ether acetate), IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 146.4 g (0 .20 mol) and 125.1 g (0.63 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 2 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 4 hours. As a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, disappeared completely, and the absorption of the imide group was observed at 1780 cm ⁻¹ and 1720 cm ^−1. confirmed. The acid value was 212 KOHmg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A5-1) solution.

[Production of alcohol-modified polyamideimide resin (A5-2)]
Subsequently, 24.5 g (0.33 mol) of n-butanol was added to the solution of the obtained imide resin (A5-1), and reacted at 120 ° C. for 2 hours. As a result of measuring the characteristic absorption in the infrared spectrum, the absorption at 1860 cm ⁻¹ which is the characteristic absorption of the acid anhydride group completely disappeared. The acid value in terms of solid content was 162 KOH mg / g, the molecular weight in terms of polystyrene was a number average molecular weight 1289, a mass average molecular weight 3152, and the degree of dispersion was 2.45. This resin solution is abbreviated as alcohol-modified polyamideimide resin (A5-2).

Comparative Example 2 [Preparation of polyamideimide resin (A6-1)]
In a flask equipped with a stirrer, a thermometer and a condenser, 276.4 g of PGMAc (propylene glycol monomethyl ether acetate), IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 146.4 g (0 .20 mol) and 125.1 g (0.63 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 4 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 4 hours. As a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, disappeared completely, and the absorption of the imide group was observed at 1780 cm ⁻¹ and 1720 cm ^−1. confirmed. The acid value was 184 KOH mg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A6-1) solution.

[Production of alcohol-modified polyamideimide resin (A6-2)]
Subsequently, 24.5 g (0.33 mol) of n-butanol was added to the solution of the obtained imide resin (A6-1) and reacted at 120 ° C. for 2 hours. As a result of measuring the characteristic absorption in the infrared spectrum, the absorption at 1860 cm ⁻¹ which is the characteristic absorption of the acid anhydride group completely disappeared. The acid value was 163 KOH mg / g in terms of solid content, the molecular weight was number average molecular weight 1216, mass average molecular weight 2528, and dispersity was 2.08 in terms of polystyrene. This resin solution is abbreviated as alcohol-modified polyamideimide resin (A6-2).

(Examples 1-4, Comparative Examples 1-2)
Using the alcohol-modified polyamideimide resin obtained above, curable resin compositions 1 to 6 were produced under the blending conditions described in Table 1.

第１表の脚注
ＥＨＰＥ３１５０：ダイセル化学工業株式会社製の環式脂肪族系エポキシ樹脂（２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロヘキサン付加物）。エポキシ当量は１７７。樹脂分の濃度は１００質量％。

Footnote EHPE3150 in Table 1: Cyclic aliphatic epoxy resin (1,2-epoxy-4- (2-oxiranyl) cyclohexane of 2,2-bis (hydroxymethyl) -1-butanol manufactured by Daicel Chemical Industries, Ltd. Adduct). Epoxy equivalent is 177. The resin content is 100% by mass.

<Measurement of storage stability>
It heated on the hotplate heated at 160 degreeC, and each time until stringing of the said curable resin compositions 1-6 was lose | eliminated was measured. The obtained results are shown in Table 2 as “160 ° C. gel time”.

-Evaluation of developability The resin was coated on a glass substrate so as to have a film thickness of 17 m after drying. The coated plate was dried with a dryer at 90 ° C. for 15 minutes to obtain a coating film. Next, the coated plate was immersed in a 1% Na ₂ CO ₃ aqueous solution at 25 ° C., and the time until the coating film disappeared was measured. It is shown in Table 3.

-PGMac tolerance evaluation After adding 10g of resin to a flask, 25 degreeC PGMac was added and the place where turbidity was confirmed was made into the dilution limit. It is shown in Table 3.

・ Dispersity (molecular weight distribution)
It was calculated from the ratio of the number average molecular weight and the mass average molecular weight in terms of polystyrene. It is shown in Table 3.

表中、「’」は分を、「”」は秒を表す。

In the table, “'” represents minutes and “” ”represents seconds.

Claims (13)

A step (1) of producing a polyamideimide resin (A1) by reacting a tricarboxylic acid anhydride (a1) with an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure;
Alcohol-modified polyamideimide resin comprising the step (2) of further producing an alcohol-modified polyamideimide resin (A2) by reacting the polyamideimide resin (A1) obtained in the step (1) with an alcohol compound (a3). A manufacturing method of
In the step (1), the isocyanurate type polyisocyanate (a2) and the tricarboxylic acid are added to the tricarboxylic acid anhydride (a1) by adding the isocyanurate type polyisocyanate (a2) at least twice. Production of an alcohol-modified polyamideimide resin characterized by comprising a step (1a) of reacting the isocyanurate type polyisocyanate (a2) with the obtained reactant after reacting with the anhydride (a1) Method.   In the step (1a), the sum of the number of moles of carboxy groups and the number of moles of acid anhydride groups of the tricarboxylic acid anhydride (a1) is excessive with respect to the number of moles of isocyanate groups of the isocyanurate type polyisocyanate (a2). After reacting the tricarboxylic acid anhydride (a1) with the isocyanurate type polyisocyanate (a2) in a proportion to be an amount, the reaction product obtained is further reacted with the isocyanurate type polyisocyanate (a2). The method for producing an alcohol-modified polyamideimide resin according to claim 1, wherein the method is a step of causing the reaction to occur. In the step (1a), the tricarboxylic acid anhydride (a1) is reacted with the isocyanurate type polyisocyanate (a2), and the reaction is continued until 2270 cm ^−1, which is the characteristic absorption of the isocyanate group in the infrared absorption spectrum measurement, disappears. The method for producing an alcohol-modified polyamideimide resin according to claim 1, wherein the isocyanurate-type polyisocyanate (a2) is further reacted with the obtained reaction product after proceeding.   Sum of the number of moles of carboxy groups (M1) and the number of moles of acid anhydride groups (M2) of the tricarboxylic acid anhydride (a1) with respect to the total number of moles (N) of isocyanate groups of the isocyanurate type polyisocyanate (a2). The method for producing an alcohol-modified polyamideimide resin according to any one of claims 1 to 3, wherein the molar ratio [(M1) + (M2)) / (N)] is 1.1 to 3. In the step (2), the alcohol compound (a3) is reacted with the polyamideimide resin (A1) in which 2270 cm ^−1, which is the characteristic absorption of the isocyanate group in the infrared absorption spectrum measurement, has disappeared. A method for producing an alcohol-modified polyamideimide resin according to any one of the above.   In the step (2), the reaction between the polyamideimide resin (A1) and the alcohol compound (a3) is performed by reacting the number of moles of acid anhydride groups (M3) in the polyamideimide resin (A1) with the alcohol compound (a3). The method for producing an alcohol-modified polyamideimide resin according to any one of claims 1 to 5, wherein the ratio of the number of moles to the number of moles (L) of hydroxyl groups is in the range of M3 / L = 1 to 5. Manufacturing method of the molecular weight distribution of 2.0 or less of any one of claims 1 to 6, wherein a range of alcohol-modified polyamideimide resin. The method for producing an alcohol-modified polyamideimide resin according to any one of claims 1 to 7 , wherein the number average molecular weight is in the range of 800 to 20000, and the mass average molecular weight is in the range of 1600 to 40000. The method for producing an alcohol-modified polyamideimide resin according to any one of claims 1 to 8, wherein the acid value is 70 to 210 KOHmg / g. The method for producing an alcohol-modified polyamideimide resin according to any one of claims 1 to 9, wherein the isocyanate having an aliphatic structure is an isocyanate having a cycloaliphatic structure. Preparation of claim 1 with an alcohol-modified polyamide-imide resins according to any one of to 10, the curable resin (B) and / or an organic solvent (C) a curable resin composition characterized by containing Way . Furthermore, the manufacturing method of the curable resin composition of Claim 11 containing a photoinitiator (D). A method for producing a cured product obtained by curing the curable resin composition according to claim 11 or 12 .