JP2019189757A - Alcohol modified polyamideimide resin, curable resin composition, and cured article thereof - Google Patents

Abstract

To provide: a curable resin composition containing a polyamideimide resin soluble in a general purpose solvent, and excellent in solvent dilution property and development property, high in storage stability even when blended with a curable resin, and further excellent in adsorptivity; and a cured article capable of producing a cured coated film excellent in adhesiveness by curing the curable resin composition.SOLUTION: There are provided: a manufacturing method of an alcohol modified polyamideimide resin including a step of adding an isocyanurate type polyisocyanate to a tricarboxylic acid anhydride having an aromatic structure in at least two portions and reacting the isocyanurate type polyisocyanate and the tricarboxylic acid anhydride to obtain a polyamideimide resin, and a step of reacting an alcohol compound with the polyamideimide resin; a curable resin composition; and a cured article capable of producing a cured coated film excellent in adhesiveness by curing the curable resin composition.SELECTED DRAWING: Figure 1

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 resin is excellent in heat resistance and mechanical properties, and has been used in various fields mainly in the electrical and electronic industries. In recent years, general-purpose solvents such as EDGA (diethylene glycol monoethyl ether acetate) have been used to reduce the burden on the environment. There is a demand for the ability to dissolve in water. In addition, the polyamide-imide resin is expected to be used in fields where transparency of cured products such as the above-mentioned liquid crystal display and LED display is required in view of heat resistance and mechanical properties. In these fields, for example, light transmittance from the visible to the ultraviolet region (around 300 nm) is required.

  As the polyamide-imide resin soluble in a general-purpose solvent, for example, a polyamide-imide resin obtained by reacting an isocyanurate-type polyisocyanate (a2) of an isocyanate having an aliphatic structure with trimellitic anhydride is disclosed (for example, (See Patent Document 1). However, the cured product obtained by using the polyamideimide resin disclosed in Patent Document 1 has insufficient transparency. For example, in the measurement of light transmittance, light transmission particularly in the ultraviolet region (around 300 nm). Sex was not enough.

  Thus, 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 2). 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. .

  Accordingly, an acid anhydride of a terminal group of a polyamideimide 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. By modifying the group with an alcohol compound, it is soluble in general-purpose solvents and has a long storage stability and pot life even when blended with a curable resin. Further, it is obtained by curing the resin composition. It discovered that a thing was excellent also in heat resistance and transparency (refer patent document 3). However, the obtained polyamide-imide resin has room for improvement in adsorptivity and adhesion with inorganic materials (fillers, pigments, etc.).

JP 2001-316469 A WO2010 / 107045 pamphlet

  Therefore, the problem to be solved by the present invention is that it is soluble in a general-purpose solvent and has excellent solvent dilutability and developability, but also storage stability and adsorbability with an inorganic material even when blended with a curable resin. An object of the present invention is to provide a polyamide-imide resin capable of obtaining an excellent curable resin composition and a method for producing the same. In addition, it contains a polyamide-imide resin that is soluble in general-purpose solvents and has excellent solvent dilutability and developability, and even when blended with a curable resin, it has excellent storage stability and adsorbability with inorganic materials. Another object of the present invention is to provide a cured product capable of producing a cured coating film having excellent adhesion to a substrate by curing the curable resin composition and a method for producing the same.

  As a result of intensive studies, the inventors of the present invention divided and added the isocyanurate type polyisocyanate (a2) synthesized from the isocyanate having the aliphatic structure to the tricarboxylic acid anhydride (a1) having the aromatic structure. By modifying the acid anhydride group of the terminal group of the polyamideimide resin obtained by the reaction with an alcohol compound, an alcohol-modified polyamideimide resin that is soluble in general-purpose solvents and that has excellent solvent dilutability and developability is obtained. The curable resin containing the resin is found to be capable of providing a curable resin composition having excellent storage stability and excellent adsorptivity, and further curing the curable resin composition. As a result, it was found that a cured product capable of producing a cured coating film having excellent adhesion was obtained, and the present invention was completed.

That is, the present invention is a method for producing an alcohol-modified polyamideimide resin in which the ratio (Mw / Mn) of the mass average molecular weight (Mw) and the number average molecular weight (Mn) is in the range of 1.0 to 1.5,
The isocyanurate type polyisocyanate (a2) and the tricarboxylic acid anhydride are added to the tricarboxylic acid anhydride (a1) having an aromatic structure by adding the isocyanurate type polyisocyanate (a2) at least twice. A step (1) of obtaining a polyamide-imide resin (A1) by reacting the product (a1) until 2270 cm ^−1, which is a characteristic absorption of an isocyanate group, disappears in an infrared absorption spectrum measurement;
The present invention relates to a method for producing an alcohol-modified polyamideimide resin, comprising a step (2) of reacting an alcohol compound (a3) with a polyamideimide (A1).

The present invention also relates to an alcohol-modified polyamideimide resin having a ratio (Mw / Mn) of a mass average molecular weight (Mw) to a number average molecular weight (Mn) in the range of 1.0 to 1.5,
Obtained by reacting the alcohol compound (a3) with the polyamideimide resin (A1) obtained by reacting the tricarboxylic acid anhydride (a1) having an aromatic structure with the isocyanurate type polyisocyanate (a2). The present invention relates to an alcohol-modified polyamideimide resin.

  Furthermore, the present invention relates to a curable resin composition comprising the alcohol-modified polyamideimide resin (A2), a curable resin (B) and / or a reactive diluent (C).

  Furthermore, the present invention relates to a curable resin composition comprising the alcohol-modified polyamideimide resin (A2), a curable resin (B) and / or a reactive diluent (C).

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

  Furthermore, the present invention is characterized in that the alcohol-modified polyamideimide resin (A2) produced by the method for producing the polyamideimide resin is mixed with a curable resin (B) and / or a reactive diluent (C). It relates to a method for producing a curable resin composition.

Furthermore, this invention relates to the manufacturing method of hardened | cured material which hardens the curable resin composition manufactured by the manufacturing method of the said curable resin composition.

  According to the present invention, a curable resin composition that is soluble in a general-purpose solvent, excellent in solvent dilution and developability, and excellent in storage stability and adsorbability with an inorganic material even when blended with a curable resin. Can be provided, and a method for producing the same. In addition, it contains a polyamide-imide resin that is soluble in general-purpose solvents and has excellent solvent dilutability and developability, and even when blended with a curable resin, it has excellent storage stability and adsorbability with inorganic materials. And the hardened | cured material which can harden the said curable resin composition and can manufacture the cured coating film excellent in adhesiveness with a base material, and those manufacturing methods can be provided.

2 is a GPC chart of a resin component obtained in Synthesis Example 1. In the figure, the peak given A is a component having a mass average molecular weight of 1000 or less. 6 is a GPC chart of a resin component obtained in Synthesis Example 2. In the figure, the peak given A is a component having a mass average molecular weight of 1000 or less. 7 is a GPC chart of a resin component obtained in Synthesis Example 3. In the figure, the peak given A is a component having a mass average molecular weight of 1000 or less. 7 is a GPC chart of a resin component obtained in Synthesis Example 4. In the figure, the peak given A is a component having a mass average molecular weight of 1000 or less. 3 is a GPC chart of resin components obtained in Comparative Synthesis Example 1. In the figure, the peak given A is a component having a mass average molecular weight of 1000 or less. 6 is a GPC chart of resin components obtained in Comparative Synthesis Example 2. In the figure, the peak given A is a component having a mass average molecular weight of 1000 or less.

The method for producing the alcohol-modified polyamideimide resin of the present invention comprises:
The isocyanurate type polyisocyanate (a2) and the tricarboxylic acid anhydride are added to the tricarboxylic acid anhydride (a1) having an aromatic structure by adding the isocyanurate type polyisocyanate (a2) at least twice. The product (a1) is reacted until 2270 cm ^−1, which is the characteristic absorption of the isocyanate group in the infrared absorption spectrum measurement, disappears (hereinafter sometimes referred to as “amidimide reaction”), and the polyamideimide resin (A1 (1) to obtain
A step (2) of reacting the alcohol compound (a3) with the polyamideimide (A1) is included.

  The present invention is obtained by using a tricarboxylic acid anhydride (a1) having an aromatic structure in the molecule (hereinafter sometimes referred to as “aromatic tricarboxylic acid anhydride (a1)”) as a raw material for polyamideimide. The adsorptivity and adhesion of the alcohol-modified polyamideimide resin can be improved.

  Examples of the aromatic tricarboxylic acid anhydride (a1) include trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride. Moreover, although it is not an essential component, it has excellent storage stability of the curable resin composition, has a long pot life, and tends to be superior to the heat-resistant decomposition temperature of the cured product, and thus has an aliphatic structure in the molecule. Tricarboxylic acid or its anhydride can also be used in combination. Since the tricarboxylic acid having an aliphatic structure is not an essential component, the tricarboxylic acid having an aromatic structure and the tricarboxylic acid having an aliphatic structure should be used in a molar ratio of 30% or less. Is preferable, and it is more preferable to use in 10% or less of range.

  Examples of the tricarboxylic acid anhydride having an aliphatic structure include a tricarboxylic acid anhydride having a linear aliphatic structure, a tricarboxylic acid anhydride having a cyclic aliphatic structure, and the like. 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.

  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.

  On the other hand, an isocyanurate type polyisocyanate (a2) synthesized from a diisocyanate having an aliphatic structure (hereinafter sometimes referred to as “isocyanurate type polyisocyanate (a2)”) includes a diisocyanate having a linear aliphatic structure. And isocyanurate type polyisocyanate synthesized from a diisocyanate having a cycloaliphatic structure.

  Examples of the isocyanurate type polyisocyanate synthesized from a diisocyanate 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 a diisocyanate having a cycloaliphatic structure include IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate (including a pentamer polymer)), HTDI3N (water Isocyanurate type triisocyanate (including pentamer polymer) synthesized from hydrogenated tolylene diisocyanate, HXDI3N (isocyanurate type triisocyanate synthesized from hydrogenated xylene diisocyanate (including pentamer polymer)) ), NBDI3N (isocyanurate type triisocyanate synthesized from norbornane diisocyanate (including pentamer polymer)), HMDI3N (isocyanurate type synthesized from hydrogenated diphenylmethane diisocyanate) (Including polymer pentamer) polyisocyanate), and the like.

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

  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 is 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.

  When the carboxylic acid component of the aromatic tricarboxylic acid anhydride (a1) reacts with the isocyanate component in the isocyanurate type polyisocyanate (a2), an imide and an amide are formed to form an amide-imide resin. Further, when the isocyanurate type polyisocyanate (a2) is reacted with the tricarboxylic acid anhydride (a1), the raw material aromatic tricarboxylic acid anhydride is left in such a ratio that the carboxylic acid component of the tricarboxylic acid anhydride (a1) remains. The polyamideimide resin obtained by reacting (a1) with polyisocyanate (a2) has a carboxy group and an acid anhydride group. The polyamidoimide resin (A1) used in the present invention forms a imide bond directly from the above isocyanurate type polyisocyanate (a2) and the aromatic tricarboxylic acid anhydride (a1). A polyamideimide resin having good reproducibility and good solubility can be synthesized without going through an intermediate.

  When the aromatic tricarboxylic acid anhydride (a1) and the isocyanurate type polyisocyanate (a2) are reacted to obtain the polyamideimide resin (A1) used in the present invention, neither a nitrogen atom nor a sulfur atom is contained. It is preferable to react in a polar solvent. In the presence of a polar solvent containing nitrogen or sulfur atoms, environmental problems are likely to occur, and in the reaction of aromatic tricarboxylic acid anhydride (a1) with isocyanurate type polyisocyanate (a2), molecules 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 ketone solvents having no hydroxyl group include acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, methoxypropanol, methyl cellosolve, 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 a weak polarity and provides an excellent reaction field in the reaction between the aromatic tricarboxylic acid anhydride (a1) and the isocyanurate type polyisocyanate (a2). 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 the step (1), the isocyanurate type polyisocyanate (a2) is added at least twice, preferably 3 to the tricarboxylic acid anhydride (a1) having the aromatic structure in a solvent or in the absence of a solvent. It is preferable to perform the amidimidization reaction by adding in 6 portions and raising the temperature while stirring.

  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 amidimide 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. In the amidimidization reaction, a hydroxyl-free group and an isocyanate group form an imide group with decarboxylation. The progress of the amidimidation reaction can be traced by an analytical means such as an infrared vector, an acid value, or an isocyanate group. 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 . For this reason, in the amidimidization reaction, the isocyanurate type polyisocyanate (a2) and the tricarboxylic acid anhydride (a1) are reacted, and 2270 cm ⁻¹ which is the characteristic absorption of the isocyanate group disappears in the infrared absorption spectrum measurement. It is preferable that the isocyanurate type polyisocyanate (a2) is further added to the obtained reaction product to cause an amidimidization reaction.

  The amidimidation 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 terminate the reaction after continuing the reaction until the isocyanate group disappears from the viewpoint 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.

  Further, in the amidimidization reaction, the aromatic tricarboxylic acid anhydride (a1) and the isocyanurate type polyisocyanate (a2) are finally added in respective amounts of the isocyanate groups of the isocyanurate type polyisocyanate (a2). The ratio of the number (N) and the total number of moles of carboxy groups (M1) and acid anhydride groups (M2) of the aromatic tricarboxylic acid anhydride (a1) [((M1) + (M2 )) / (N)] is made to undergo amidimidation reaction in the range of 1.1 to 3, the polarity in the reaction system becomes high, the reaction proceeds to lubrication, and the isocyanate group does not remain and can be obtained. This is preferable because the stability of the 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, the range of 1.2 to 2.5 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.

  The amidoimide resin (A1) may have only one of an acid group or an acid anhydride group, or may have both. Especially, it is preferable to have an acid anhydride group from a viewpoint of the reactivity with alcohol compound (a3) and reaction control, and it is preferable to have both an acid group and an acid anhydride group. Although the acid value of the said amide imide resin (A1) is not specifically limited, It is preferable that it is the range of 16 mgKOH / g or more and 210 KOHmg / g or less. The acid value is a value measured by “3.1 neutralization titration method” of JIS K 0070 (1992).

  The polyamideimide resin (A1) used in the present invention thus obtained has an imide bond and an amide bond represented by the following structural formula (1), and at the molecular end, the following structural formula ( It has a structure represented by at least one selected from the group consisting of 2) to (4).

（ただし、式中、Ｒ_１は前記トリカルボン酸無水物（ａ１）から酸無水物基とカルボキシ基を除いた残基である。）

(In the formula, R ₁ is a residue obtained by removing the acid anhydride group and the carboxy group from the tricarboxylic acid anhydride (a1).)

  As an example of the polyamideimide resin of the present invention, the following structural formula

（式中、ｎは、繰り返し単位で０〜３０である。また、Ｒｂは、上記の構造式（１）で示されるアミド結合およびイミド結合である。Ｒｃは、上記の構造式（２）〜（４）のいずれかである。Ｒｄは、前記ポリイソシアネート（ａ２）からイソシアナト基を除いた残基である。）で表されるものが挙げられるが、これに限定されるものではない。

(In the formula, n is a repeating unit of 0 to 30. Rb is an amide bond and an imide bond represented by the structural formula (1). Rc is the structural formula (2) to (4) Rd is a residue obtained by removing the isocyanato group from the polyisocyanate (a2), but is not limited thereto.

  Rd is, for example, the following structural formula (6)

  (However, Ra represents a residue obtained by removing an isocyanato group from the diisocyanate, for example).

  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 mixing ratio when the amideimide resin (A1) and the alcohol compound (a3) are reacted is such that the alcohol compound (a3) is added to the total of acid groups and acid anhydride groups in the amideimide resin (1A). It is preferably used in the range of 0.9 to 1.1 mol. Further, 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 of the alcohol compound (a3) (L ), L / M3 = 1 to 5 is preferable because the storage stability of the obtained polyamideimide resin is increased, and it is more preferable that L / M3 = 1 to 2 It is more preferable from the viewpoint of reducing the alcohol and obtaining a cured coating film excellent in thermal decomposition resistance.

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 dehydration esterification reaction temperature is preferably in the range of 50 ° C. to 150 ° C., and 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.

  The solvent used for the dehydration esterification reaction can be the same as the solvent used for the imidization 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 acid value of the alcohol-modified polyamideimide resin (A2) of the present invention is preferably in the range of 70 KOH mg / g or more, more preferably 90 KOH mg / g or more, preferably 210 KOH mg / g or less, more preferably 190 KOH mg / g or less. . If it is the said range, the performance outstanding as cured | curing material property will be exhibited. The acid value is a value measured by “3.1 neutralization titration method” of JIS K 0070 (1992).

  The number average molecular weight (Mw) of the alcohol-modified polyamideimide resin (A2) of the present invention is preferably 1000 or more, more preferably from the viewpoint of obtaining a cured product having excellent solubility in a solvent and excellent mechanical strength. Is in the range of 2000 or more, preferably 20000 or less, more preferably 8000 or less. Further, according to the production method of the present invention, it is possible to obtain an alcohol-modified polyamideimide resin (A2) having a sharp ratio between the mass average molecular weight and the number average molecular weight (Mw / Mn) (hereinafter, sometimes referred to as dispersity). Is possible. Since the degree of dispersion required depending on the purpose, application, etc. is different, it cannot be specified unconditionally, but is preferably in the range of 1.5 or less, more preferably 1.0 or more, more preferably 1.2 or more. , 1.5 or less.

In the present invention, the number average molecular weight and the mass average molecular weight were measured under the following conditions using GPC (gel permeation chromatography).
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
Flow rate 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 alcohol-modified polyamideimide resin (A2) of the present invention thus obtained has an imide bond and an amide bond represented by the following structural formula (1), and at the molecular end, the following structural formula ( It has a structure represented by at least one selected from the group consisting of 2), (3), (4), (2 ′), (3 ′) and (3 ″).

（ただし、式中、Ｒ_１は前記トリカルボン酸酸無水物（ａ１）から酸無水物基とカルボキシ基を除いた残基である。Ｒ_２は、前記アルコール化合物（ａ３）からヒドロキシ基を除いた残基である。）

(In the formula, R ₁ is a residue obtained by removing an acid anhydride group and a carboxy group from the tricarboxylic acid anhydride (a1). R ₂ is a residue obtained by removing a hydroxy group from the alcohol compound (a3). Residue.)

  As an example of the acid group-containing (meth) acrylate resin of the present invention, the following structural formula (7)

（式中、ｎは、繰り返し単位で０〜３０である。また、Ｒｂは、上記の構造式（１）で示されるアミド結合とイミド結合である。Ｒｃ’は、下記の構造式（２）、（３）、（４）、（２’）、（３’）および（３”）からなる群から選ばれる少なくとも１種で表される構造である。Ｒｄは、前記と同様の定義である。）で表されるものが挙げられるが、これに限定されるものではない。

(In the formula, n is a repeating unit of 0 to 30. Rb is an amide bond and an imide bond represented by the above structural formula (1). Rc ′ is the following structural formula (2). , (3), (4), (2 ′), (3 ′) and (3 ″). The structure is represented by at least one selected from the group consisting of (3 ″). Rd is as defined above. )), But is not limited thereto.

  Moreover, according to the manufacturing method of this invention, it is possible to reduce the component of the mass mean molecular weight 1000 or less produced | generated other than alcohol-modified polyamideimide resin. The proportion of the component having a mass average molecular weight of 1000 or less relative to the total amount of the alcohol-modified polyamideimide resin containing a component having a mass average molecular weight of 1000 or less is preferably 15% or less in terms of the area ratio in GPC measurement. Is in the range of 0.1 or more, more preferably 1% or more, 15% or less, preferably 14% or less, more preferably 13% or less, still more preferably 12% or less, and particularly preferably 10% or less. The main components having a mass average molecular weight of 1000 or less include unreacted monomers and oligomers. Specific examples include the tricarboxylic acid anhydride (a1), the polyisocyanate (a2), and the alcohol compound (a3). The oligomer component mainly includes a component obtained by reacting the tricarboxylic acid anhydride (a1) and the alcohol compound (a3) or a component obtained by reacting the polyisocyanate (a2) and the alcohol compound (a3).

  Furthermore, as a component which this tricarboxylic acid anhydride (a1) and alcohol compound (a3) reacted, the following general formula (8-1) and (8-2)

（式中、Ｒ_１は、炭素原子数６〜２０の置換基を有しても良い芳香族トリカルボン酸から酸無水物基およびカルボキシ基を除いた残基である。Ｘは、それぞれ独立に、水素原子またはＲ_２であり、Ｒ_２はアルコール化合物から水酸基を除いた残基を表す。）で表される化合物からなる群から選ばれる少なくとも１つの化合物（８）が挙げられ、かつ、当該化合物（８）の含有率はＧＰＣ測定における面積比率で１５％以下の範囲であるが、好ましくは０．１以上、より好ましくは１％以上から、１５％以下、好ましくは１４％以下、より好ましくは１３％以下、さらに好ましくは１２％以下、特に好ましくは１０％以下の範囲である。

(In the formula, R ₁ is a residue obtained by removing an acid anhydride group and a carboxy group from an aromatic tricarboxylic acid which may have a substituent having 6 to 20 carbon atoms. X is independently And at least one compound (8) selected from the group consisting of compounds represented by: a hydrogen atom or R ₂ , wherein R ₂ represents a residue obtained by removing a hydroxyl group from an alcohol compound, and the compound The content ratio of (8) is in the range of 15% or less in terms of area ratio in GPC measurement, preferably 0.1 or more, more preferably 1% or more, and 15% or less, preferably 14% or less, more preferably It is 13% or less, more preferably 12% or less, and particularly preferably 10% or less.

  Furthermore, as a component which the said polyisocyanate (a2) and alcohol compound (a3) reacted, following General formula (9)

（式中、Ｒａは、それぞれ独立に２価の脂肪族ジイソシアネート類のイソシアナト基を除いた残基である。Ｙは、それぞれ独立に、水素原子またはＲ_２であり、Ｒ_２はアルコール化合物から水酸基を除いた残基を表す。）で表される化合物（９）が挙げられ、かつ、当該化合物（９）の含有率はＧＰＣ測定における面積比率で１％未満の範囲であることが好ましく、０．５％以下の範囲であることがより好ましく、かつ、０．１％以下の範囲であることが好ましく、最も好ましくは０％（検出限界以下）である。

(In the formula, each Ra is a residue obtained by removing an isocyanato group from divalent aliphatic diisocyanates independently. Y is each independently a hydrogen atom or R ₂ , and R ₂ is a hydroxyl group from an alcohol compound.) And the content of the compound (9) is preferably in the range of less than 1% in terms of area ratio in GPC measurement. More preferably, it is in the range of 0.5% or less, more preferably in the range of 0.1% or less, and most preferably 0% (below the detection limit).

  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 reactive diluent (C).

  Examples of the curable resin (B) include an epoxy compound (B1) having two or more epoxy groups in the molecule, a compound (B2) having two or more maleimide groups in the molecule, a benzoxazine resin, and a cyanate. Examples include ester resins. 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 bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol S type epoxy resins, and bisphenol F type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, and biphenyl type epoxies. Resin, triphenylmethane type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolak type Epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl 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, Preferable examples include epoxides derived from a naphthalene skeleton such as naphthol, binaphthol or novolak modification of naphthol or binaphthol, and aromatic epoxy resins such as an epoxy resin obtained by epoxidizing a phenol resin having a fluorene skeleton.

  Further, 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 an aromatic epoxy resin. If it is an aromatic epoxy resin, a cured coating film having a high Tg and excellent thermal properties can be obtained, and a cured product having excellent adhesion can be obtained. Among aromatic epoxy resins, bisphenol A type epoxy resins and the like are preferable.

  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 Alcohol-modified polyamideimide resin (A2) in a range such that the ratio [n (EPOXY) / n (COOH)] of the epoxy group (B1) to the number of moles n (EPOXY) of the epoxy group is 0.3 to 4 And the epoxy resin (B1) are blended, it is easy to obtain Tg as a property of the cured product, a cured product having excellent mechanical properties and the like is obtained, and the transparency of the cured product is further improved. Masui.

  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). ), Phosphine compounds such as alkyl-substituted trialkylphenylphosphine and derivatives thereof, phosphophonium salts thereof, or known epoxy curing accelerators such as dialkylureas, carboxylic acids, phenols, or methylol group-containing compounds. These can be used in small amounts.

  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.

  As the reactive diluent (C) 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 polyamide-imide resin (A2) and the reactive diluent (C) can be freely blended in accordance with various target 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 / C] of the alcohol-modified polyamideimide resin (A2) and the photopolymerizable group of the reactive diluent (C) is 0.2 to Mixing the alcohol-modified polyamideimide resin (A2) and the reactive diluent (C) 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.

  When the curable resin composition of the present invention is further cured by irradiation with energy rays, particularly ultraviolet rays, a photopolymerization initiator (D) 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.

  Examples of commercially available photopolymerization initiators include “IRGACURE127”, “IRGACURE184”, “IRGACURE250”, “IRGACURE270”, “IRGACURE290”, “IRGACURE369E”, “IRGACURE379EG”, “IRGACURE500” manufactured by BASF. “IRGACURE 651”, “IRGACURE 754”, “IRGACURE 819”, “IRGACURE 907”, “IRGACURE 1173”, “IRGACURE 2959”, “IRGACURE MBF”, “IRGACURE TPO”, “IRGACURE OXE 02”, “IRGACURE OXE 02” OMIRAD184, OMIRAD250, MNIRAD369 "," OMNIRAD369E "," OMNIRAD651 "," OMNIRAD907FF "," OMNIRAD1173 ", and the like.

  Although the addition 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, 0.05-30 mass with respect to 100 mass parts of alcohol modified polyamideimide resin (A2). Is preferably in the range of 0.1 to 15 parts by mass, and more preferably in the range of 0.5 to 10 parts by mass. Such photopolymerization initiators can also be used in combination with one or more known and commonly used photopolymerization accelerators.

  The curable resin composition of the present invention may further contain an organic solvent (E) as necessary. When the curable resin composition of the present invention contains the organic solvent (E), the same organic solvent as that used to prepare the alcohol-modified polyamideimide resin (A2) can be used. The kind and addition amount are appropriately adjusted according to the desired performance. Generally, it is used in the range of 10 to 90% by mass with respect to the total of the curable resin composition. The effective resin composition of the present invention is

  Moreover, other hardening | curing agents and thermosetting accelerators can be used as needed. Furthermore, additives such as a polymerization inhibitor, a thixotropic agent, an antifoaming agent, a leveling agent, and a coupling agent can also be used.

  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 which starts thermal polymerization, and an additive. 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.

  Various additives such as other solvents, various leveling agents, antifoaming agents, antioxidants, anti-aging agents, ultraviolet absorbers, anti-settling agents, rheology control agents and the like are added to the curable resin composition of the present invention as necessary. Agents, known and conventional fillers such as barium sulfate, silicon oxide, talc, clay, calcium carbonate, silica, colloidal silica, glass, various metal powders, fibrous fillers such as glass fiber, carbon fiber, Kevlar fiber, etc. Or you may mix | blend well-known and usual coloring pigments, such as phthalocyanine blue, phthalocyanine green, a titanium oxide, carbon black, a silica, and other adhesive provision agents. 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 curable resin composition containing all of curable resin (B) and / or reactive diluent (C), curing agent, non-halogen flame retardant, and other fillers and additives, red phosphorus Is preferably blended in the range of 0.1 to 2.0 parts by weight when used as a non-halogen flame retardant, and similarly in the range of 0.1 to 10.0 parts by weight when using an organophosphorus compound. It is preferable to mix | blend in especially 0.5-6.0 mass parts. 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, nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, 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 tung 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. 100 parts by mass of a curable resin composition containing all of (A2), curable resin (B) and / or reactive diluent (C), curing agent, non-halogen flame retardant, and other fillers and additives It is preferable to mix | blend in the range of 0.05-10 mass parts in particular, 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. 100 parts by mass of a curable resin composition containing all of (A2), curable resin (B) and / or reactive diluent (C), curing agent, non-halogen flame retardant, and other fillers and additives 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. 100 parts by mass of a curable resin composition containing all of (A2), curable resin (B) and / or reactive diluent (C), curing agent, non-halogen flame retardant, and other fillers and additives In particular, 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 polyamide-imide resin (A2), a curable resin (B) and / or a reactive diluent (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 100 mass parts of things.

  The curable resin composition containing the alcohol-modified polyamideimide resin (A1) of the present invention is excellent in adsorptivity to pigments such as phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black, and silica. Moreover, it has the characteristics which are excellent in the developability evaluated by a photosensitivity, a dry management width | variety, etc., the heat resistance in a hardened | cured material, and heat-resistant decomposition property. In addition, it also has excellent characteristics such as solvent solubility, substrate adhesion in a cured product, and non-adhesiveness after temporary drying. As applications in which various characteristics of the curable resin composition containing the alcohol-modified polyamideimide resin (A1) of the present invention are utilized, for example, as a semiconductor device-related application, a solder resist, an interlayer insulating material, a packaging material, an undercoat It can be used as a package adhesive layer such as a fill material or a circuit element, or an adhesive layer between an integrated circuit element and a circuit board. In addition, thin film display applications such as LCD and OELD can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, color filter pigment resists, black matrix resists, spacers, and the like. Among these, it can use suitably especially for a soldering resist use.

  The method for obtaining a resist member using the resin material for solder resist of the present invention is, for example, by applying the curable resin composition of the present invention on a substrate and evaporating and drying an organic solvent in a temperature range of about 60 to 100 ° C. Then, it is exposed to ultraviolet rays or electron beams through a photomask on which a desired pattern is formed, an unexposed portion is developed with an alkaline aqueous solution, and further heated and cured in a temperature range of about 140 to 180 ° C. Can be mentioned.

  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.

Synthesis 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 trimellitic anhydride 491.5 g (2.56 mol) 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, 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 176 KOH mg / 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 is 155 KOH mg / g in terms of solid content, the molecular weight is the number average molecular weight 1120 in terms of polystyrene, the mass average molecular weight 1869, the degree of dispersion calculated from the ratio of the number average molecular weight in terms of polystyrene and the weight average molecular weight (hereinafter the same) Was 1.39. This resin solution is abbreviated as an alcohol-modified polyamideimide resin (A1-2). FIG. 1 shows a GPC chart of the resin component obtained. From the GPC chart, the content of the component represented by compound (8) (A in the figure) was 12%, and the content of the component represented by compound (9) was not detected.

Synthesis 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 145.9 g (0.76 mol) of trimellitic 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 180 KOHmg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A2-1) solution.

[Preparation 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 in terms of solid content was 158 KOH mg / g, the molecular weight in terms of polystyrene was a number average molecular weight 1109, a mass average molecular weight 1903, and the degree of dispersion was 1.46. This resin solution is abbreviated as an alcohol-modified polyamideimide resin (A2-2). FIG. 2 shows a GPC chart of the resin component obtained. From the GPC chart, the content of the component represented by compound (8) (A in the figure) was 13%, and the content of the component represented by compound (9) was not detected.

Synthesis 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 trimellitic anhydride 145.9 g (0.76 mol) 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 177 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 was 154 KOH mg / g in terms of solid content, the molecular weight was number average molecular weight 1126, mass average molecular weight 2048 in terms of polystyrene, and the degree of dispersion was 1.47. This resin solution is abbreviated as alcohol-modified polyamideimide resin (A3-2). FIG. 3 shows a GPC chart of the resin component obtained. From the GPC chart, the content of the component represented by the compound (8) (A in the figure) was 14%, and the content of the component represented by the compound (9) was not detected.

Synthesis example 4
[Preparation of polyamideimide resin (A4-1)]
In a flask equipped with a stirrer, a thermometer and a condenser, 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 trimellitic anhydride 145.9 g (0.76 mol) 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 178 KOHmg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A4-1) solution.

[Preparation 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 was 157 KOH mg / g in terms of solid content, the molecular weight was number average molecular weight 1126, mass average molecular weight 2227 in terms of polystyrene, and the degree of dispersion was 1.48. This resin solution is abbreviated as alcohol-modified polyamideimide resin (A4-2). FIG. 4 shows a GPC chart of the resin component obtained. From the GPC chart, the content of the component represented by the compound (8) (A in the figure) was 14%, and the content of the component represented by the compound (9) was not detected.

Comparative Synthesis Example 1 [Preparation of polyamideimide resin (c.A1-1)]
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 trimellitic anhydride 121 g (0.63 mol) 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 178 KOHmg / g in terms of solid content. This resin solution is abbreviated as an imide resin (c.A1-1) solution.

[Production of alcohol-modified polyamideimide resin (c.A1-2)]
Subsequently, 24.5 g (0.33 mol) of n-butanol was added to the solution of the obtained imide resin (c.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 150 KOH mg / g in terms of solid content, the molecular weight was number average molecular weight 1158, mass average molecular weight 2363 in terms of polystyrene, and the degree of dispersion was 1.67. This resin solution is abbreviated as alcohol-modified polyamideimide resin (c.A1-2). FIG. 5 shows a GPC chart of the resin component obtained. From the GPC chart, the content of the component represented by the compound (8) (A in the figure) was 16%, and the content of the component represented by the compound (9) was not detected.

Comparative Synthesis Example 2 [Preparation of polyamideimide resin (c.A2-1)] (aliphatic polyamideimide)
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 (c.A2-1) solution.

[Production of alcohol-modified polyamideimide resin (c.A2-2)]
Subsequently, 99.8 g (1.35 mol) of n-butanol was added to the solution of the obtained imide resin (c.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 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 alcohol-modified polyamideimide resin (c.A2-2).
FIG. 6 shows a GPC chart of the resin component obtained. From the GPC chart, the content of the component represented by the compound (8) (A in the figure) was 11%, and the content of the component represented by the compound (9) was not detected.

(Measurement example Tolerance evaluation by PGMAc)
In order to evaluate the dilution stability, the polyamideimide resins (A1-2) to (A4-2), (c.A1-2) and (c.A1-2) obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2 were used in flasks. c) After adding 10 g of A2-2), 25 ° C. PGMAc was added, and the total amount added when turbidity was confirmed was taken as the dilution limit. The total amount of PGMAc relative to the polyamide-imide resin was expressed as a magnification (percentage) (Table 1). The higher the magnification, the better the dilution stability (tolerance).

(Measurement example Development evaluation)
The polyamideimide resins (A1-2) to (A4-2), (c.A1-2), and (c.A2-2) obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2 are placed on a glass substrate. The coating was performed so that the film thickness was in the range of 19 μm 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 (sec) until the coating film disappeared was measured. Table 1 shows the results. The shorter the disappearance time, the better the developability.

(Measurement example Adsorption evaluation)
Polyamideimide resins (A1-2) to (A4-2), (c.A1-2), and (c.A2-2) obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2 were replaced with carbon black. The time period until mixing and precipitation occurred was measured. Table 1 shows the results. The longer the period until precipitation occurs, the better the adsorptivity.

(Examples 1-4, Comparative Examples 1 and 2)
The alcohol-modified polyamideimide resins (A1-2) to (A4-2), (c.A1-2), and (c.A2-2) obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2 were used. The curable resin compositions (1) to (4), (c.1) and (c.2) were produced using the blending conditions described in Table 1.

(Measurement example Storage stability)
It heated on the hotplate heated at 160 degreeC, and each time until the stringing of the said curable resin composition (1)-(4), (c.1) and (c.2) was lose | eliminated was measured. The obtained results are shown in Table 2 as “160 ° C. gel time”.

(Measurement example DMA-Tg)
The curable resin compositions (1) to (4), (c.1) and (c.2) were applied to a mirror aluminum plate with an applicator and cured at 170 ° C. for 1 hour after preheating at 100 ° C. for 30 minutes. A membrane was created. The obtained cured film was isolated from an aluminum plate to prepare a test piece having a thickness of 35 μm, a width of 5 mm, and a length of 54 mm. Using a “solid viscoelasticity measuring device RSAII” manufactured by Rheometric Co., Ltd., the temperature at which the change in the elastic modulus of the test piece becomes the maximum (the tan δ change rate is the highest) is measured by the DMA (dynamic viscoelasticity) measurement by the rectangular tension method. The transition temperature was measured. The measurement conditions were a frequency of 1 Hz and a heating rate of 3 ° C./min.

(Measurement example Adhesion)
The curable resin compositions (1) to (4), (c.1) and (c.2) were applied to a copper foil (shine surface, mud surface) with an applicator, and after preheating at 100 ° C. for 30 minutes. A cured film was prepared at 170 ° C. for 1 hour. The resulting cured film was cut into a grid of 100 squares, and the amount of the cured film remaining when the cellophane tape was applied and then peeled off is shown in the table.

エピクロン８５０：ＤＩＣ株式会社製のビスフェノールA型エポキシ樹脂。エポキシ当量は１８８。樹脂分の濃度は１００質量％。
銅箔：ＪＸ金属株式会社製「ＢＨＹ−Ｔ」

Epicron 850: bisphenol A type epoxy resin manufactured by DIC Corporation. Epoxy equivalent is 188. The resin content is 100% by mass.
Copper foil: “BHY-T” manufactured by JX Metals, Ltd.

Claims (19)

A method for producing an alcohol-modified polyamideimide resin in which a ratio (Mw / Mn) of a mass average molecular weight (Mw) and a number average molecular weight (Mn) is in a range of 1.0 to 1.5,
The isocyanurate type polyisocyanate (a2) and the tricarboxylic acid anhydride are added to the tricarboxylic acid anhydride (a1) having an aromatic structure by adding the isocyanurate type polyisocyanate (a2) at least twice. (A1) is reacted until 2270 cm ^−1, which is a characteristic absorption of an isocyanate group, disappears in infrared absorption spectrum measurement to obtain a polyamideimide resin (A1) (1),
A method for producing an alcohol-modified polyamideimide resin, comprising a step (2) of reacting an alcohol compound (a3) with a polyamideimide (A1). The method for producing an alcohol-modified polyamideimide resin according to claim 1, wherein the component having a mass average molecular weight of 1000 or less is in a range of 15% or less in terms of area ratio in GPC measurement. The method for producing an alcohol-modified polyamideimide resin according to claim 1 or 2, wherein the acid value of the alcohol-modified polyamideimide resin is in the range of 70 to 210 [KOHmg / g]. 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 the isocyanurate type polyisocyanate (a2) and the tricarboxylic acid anhydride (a1) are reacted at a ratio that makes up the amount, the resulting isocyanurate type polyisocyanate (a2) is further reacted. The manufacturing method of the polyamide-imide resin as described in any one of Claims 1-3 which is a process. In the step (1a), the isocyanurate-type polyisocyanate (a2) is reacted with the tricarboxylic acid anhydride (a1), 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 a polyamide-imide resin according to any one of claims 1 to 4, which is a step of allowing the isocyanurate type polyisocyanate (a2) to further react with the obtained reaction product after proceeding. Isocyanurate type polyisocyanate (a2) synthesized from the isocyanate having the aliphatic structure (N2), the number of moles of carboxy group (M1) and acid anhydride of the tricarboxylic acid anhydride (a1) The ratio [((M1) + (M2)) / (N)] of the number of moles of the group (M2) to the total number of moles is 1.1 to 3. The alcohol according to any one of claims 1 to 5. A method for producing a modified polyamideimide resin. 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 number of moles of hydroxyl groups of the alcohol compound (a3) (L ), L / M3 = 1-5, The method for producing an alcohol-modified polyamideimide resin according to any one of claims 1-6. A ratio (Mw / Mn) of mass average molecular weight (Mw) and number average molecular weight (Mn) is an alcohol-modified polyamideimide resin having a range of 1.0 to 1.5,
Obtained by reacting the alcohol compound (a3) with the polyamideimide resin (A1) obtained by reacting the tricarboxylic acid anhydride (a1) having an aromatic structure with the isocyanurate type polyisocyanate (a2). Alcohol-modified polyamideimide resin. The alcohol-modified polyamideimide resin is
It has an imide bond and an amide bond represented by the following structural formula (1), and the following structural formulas (2), (3), (4), (2 '), (3' The alcohol-modified polyamideimide resin according to claim 8, which has a structure represented by at least one selected from the group consisting of:

(In the formula, R ₁ is a residue obtained by removing an acid anhydride group and a carboxy group from the tricarboxylic acid anhydride (a1). R ₂ is a residue obtained by removing a hydroxy group from the alcohol compound (a3). Residue.) The alcohol-modified polyamideimide resin according to claim 8 or 9, wherein the component having a mass average molecular weight of 1000 or less is in a range of 15% or less in terms of area ratio in GPC measurement. A curable resin comprising the alcohol-modified polyamideimide resin (A2) according to any one of claims 8 to 10, a curable resin (B) and / or a reactive diluent (C). Composition. Furthermore, the curable resin composition of Claim 11 containing a photoinitiator (D). The curable resin composition according to claim 11 or 12, wherein the curable resin (B) is an epoxy compound (B1) having two or more epoxy groups in a molecule. The curable resin composition according to claim 13, wherein the epoxy compound (B1) is an epoxy resin having an aromatic skeleton. The curable resin composition according to any one of claims 11 to 14, wherein the curable resin (B) further contains a pigment. It is a soldering resist material, The curable resin composition as described in any one of Claims 11-15. Hardened | cured material formed by hardening | curing curable resin composition as described in any one of Claims 11-16. Mixing the alcohol-modified polyamideimide resin (A2) produced by the production method according to any one of claims 1 to 10, and the curable resin (B) and / or the reactive diluent (C). A method for producing a curable resin composition. The manufacturing method of hardened | cured material which hardens the curable resin composition manufactured by the manufacturing method of Claim 18.

Images