JP6922162B2 - Polyamide-imide resin and its manufacturing method - Google Patents

Description

The present invention relates to a polyamide-imide resin, a curable resin composition containing the polyamide-imide resin, and a cured product thereof. Specifically, the present invention relates to fields in which transparency is required in addition to heat resistance, for example, fields for optical materials, solder resist materials for printed wiring substrates, protective materials and insulation for household electrical 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, etc. Polyamideimide resins that can be suitably used in the fields of adhesives, reflective materials, liquid crystal alignment films, protective films for color filters, etc., curable resin compositions containing the polyamideimide resins, and It is about the cured product.

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

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

WO2010 / 107045 Pamphlet WO2015 / 068744 Pamphlet

Therefore, an object of the present invention is a curable resin composition that contains a polyamide-imide resin that is soluble in a general-purpose solvent and has excellent solvent dilatability, and has long storage stability and a long pot life even when blended with a curable resin. Another object of the present invention is to provide a cured product (cured coating film) having excellent developability.

As a result of diligent studies, the present inventors reacted the tricarboxylic acid anhydride (a1) with the isocyanurate-type polyisocyanate (a2) synthesized from the isocyanate having the aliphatic structure in the step of producing the polyamideimide resin. It was found that a polyamideimide resin having a sharp molecular weight distribution could be obtained by dividing and adding the isocyanurate-type polyisocyanate to the tricarboxylic acid anhydride and reacting the mixture, and further curing the polyamideimide resin. We have found that by blending with a sex resin, a curable resin composition having long storage stability and a long pot life can be obtained, and further, a cured product (cured coating film) having excellent developability can be obtained. It came to be completed.

That is, the present invention is a method for producing a polyamide-imide resin, which comprises a step (1) of reacting a tricarboxylic acid anhydride (a1) with an isocyanurate-type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure. There,
In the step (1), the isocyanurate-type polyisocyanate (a2) is added to the tricarboxylic acid anhydride (a1) in at least two portions to obtain the tricarboxylic acid anhydride (a1) and the isocyanurate. A method for producing a polyamide-imide resin, which comprises a step (1a) of reacting the type polyisocyanate (a2) and then further reacting the obtained reactant with the isocyanurate type polyisocyanate (a2). Regarding.

Further, the present invention is a polyamide-imide resin in which a tricarboxylic acid anhydride (a1) and an isocyanurate-type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure are bonded to each other by forming an amide or an imide. The present invention relates to a polyamide-imide resin (A) containing A) and having a molecular weight distribution in the range of 2.0 or less.

The present invention also relates to a curable resin composition containing the polyamide-imide resin (A) and the curable resin (B).

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

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

The method for producing the polyamide-imide resin (A) of the present invention involves reacting a tricarboxylic acid anhydride (a1) with an isocyanurate-type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure (1). Have.

First, the step (1) for producing the polyamide-imide resin (A) will be described.

In the present invention, by using the tricarboxylic acid anhydride (a1) as a raw material for the polyamide-imide, the transparency of the cured coating film of the obtained polyamide-imide resin is improved. Examples of such a tricarboxylic acid anhydride include a tricarboxylic acid anhydride having an aromatic structure in the molecule and a tricarboxylic acid having an aliphatic structure in the molecule. Of these, a tricarboxylic acid having an aliphatic structure in the molecule is preferable because the curable resin composition has excellent storage stability, has a long pot life, and tends to have an excellent thermosetting decomposition temperature of the cured product.

Examples of the tricarboxylic acid anhydride having an aromatic structure in the molecule include trimellitic anhydride, naphthalene-1,2,4-tricarboxylic acid anhydride and the like. 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 propanetricarboxylic acid anhydride and the like. Examples of the tricarboxylic acid anhydride having a cyclic aliphatic structure include cyclohexanetricarboxylic acid anhydride, methylcyclohexanetricarboxylic acid anhydride, cyclohexene tricarboxylic acid anhydride, methylcyclohexene tricarboxylic acid anhydride and the like.

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

Examples of the cyclohexane tricarboxylic acid anhydride include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, and 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 polyamide-imide resin having excellent solvent solubility in addition to transparency and a cured coating film having high Tg and excellent thermal physical characteristics can be obtained. Is preferable.

Here, the cyclohexane tricarboxylic acid anhydride described above is represented by the structure of the following general formula (1), and is used as a raw material for production of cyclohexane-1,2,3-tricarboxylic acid and cyclohexane-1,3,4. -If impurities such as tricarboxylic acid do not impair the curing of the present invention, for example, 10% by mass or less, preferably 5% by mass or less, they may be mixed.

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

Examples of the isocyanurate-type polyisocyanate synthesized from an isocyanate having a linear aliphatic structure include HDI3N (isocyanurate-type triisocyanate synthesized from hexamethylene diisocyanate (including a polymer such as a pentamer)) and HTMDI3N. (Isocyanurate type triisocyanate synthesized from trimethylhexamethylene diisocyanate (including a polymer such as a pentamer)) and the like can be mentioned. These may be used together or alone.

Examples of the isocyanurate-type polyisocyanate synthesized from an isocyanate having a cyclic aliphatic structure include IPDI3N (isocyanurate-type triisocyanate synthesized from isophorone diisocyanate (including a polymer such as a pentamer)) and HTDI3N (. Isocyanurate-type triisocyanate synthesized from hydrogenated tolylene diisocyanate (including a polymer such as pentamer)), HXDI3N (isocyanurate-type triisocyanate synthesized from hydrogenated xylene diisocyanate (polymer such as pentamer)) )), NBDI3N (isocyanurate-type triisocyanate synthesized from norbornenan diisocyanate (including a polymer such as pentamer)), HMDI3N (isocyanurate-type triisocyanate synthesized from hydrogenated diphenylmethane diisocyanate (pentameric)). Etc.)) and the like.

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

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

Further, an adduct body obtained by a urethanization reaction between the isocyanate compound and various polyols can also be used as long as the solvent solubility of the polyamide-imide resin of the present invention is not impaired.

The carboxy-containing polyamide-imide resin (A1) used in the present invention has problems in stability and the like by forming an imide bond directly from the above-mentioned tricarboxylic acid anhydride (a1) and the above-mentioned isocyanate compound (a2). It is possible to synthesize a polyamide-imide resin which can obtain a cured coating film having good reproducibility, good solubility, and excellent transparency without passing through a certain polyamic acid intermediate.

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

When the tricarboxylic acid anhydride (a1) is reacted with an isocyanurate-type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure to obtain the polyamide-imide resin (A1) used in the present invention, nitrogen is used. It is preferable to react in a polar solvent containing neither an atom nor a sulfur atom. The presence of a polar solvent containing nitrogen or sulfur atoms is likely to cause environmental problems, and molecular growth in the reaction of isocyanurate-type polyisocyanate (a2) with tricarboxylic acid anhydride (a1). Is easily disturbed. When such a molecule is cleaved, the physical properties of the composition are likely to deteriorate, and coating film defects such as "repellency" are likely to occur.

In the present invention, the polar solvent containing neither nitrogen atom nor sulfur atom is more preferably an aprotic solvent. For example, a cresol-based solvent is a phenolic solvent having a proton, but it is somewhat unfavorable in terms of the environment and easily reacts with an isocyanate compound to inhibit molecular growth. In addition, the cresol solvent easily reacts with the isocyanate group and becomes a blocking agent. Therefore, it is difficult to obtain good physical properties by reacting with other curing components (for example, epoxy resin) at the time of curing. Furthermore, if the blocking agent comes off, it is likely to contaminate the equipment used and other materials. Further, the alcohol solvent is not preferable because it reacts with isocyanate or acid anhydride. 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 the ester-based solvent having no hydroxyl group include ethyl acetate, propyl acetate, butyl acetate and the like. Examples of the ketone solvent having no hydroxyl group include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like. Of these, an ether solvent having no hydroxyl group is particularly preferable.

In the present invention, the ether solvent having no hydroxyl group has a weak polarity and is excellent in the reaction between the isocyanurate-type polyisocyanate (a2) of the isocyanate having the above-mentioned aliphatic structure and the tricarboxylic acid anhydride (a1). Provides a reaction field. As such ether-based solvent, known and commonly used ones can be used, and for example, ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. , Polyethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether, triethylene glycol diethyl ether and triethylene glycol dibutyl ether; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate. 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, and triethylene glycol monobutyl ether acetate; Propropylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether and propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tri Polypropylene glycol dialkyl ethers such as propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate; dipropylene glycol monomethyl ether acetate and dipropylene glycol Monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene 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 alkyl esters of polyether glycols; monoalkyl esters of polyether glycols, monoalkyl ethers, and the like.

In the step (1), the isocyanurate type polyisocyanate (a2) is added to the tricarboxylic acid anhydride (a1) in at least two portions to form the tricarboxylic acid anhydride (a1) and the isocyanurate type. The step (1a) of reacting the obtained product with the polyisocyanate (a2) and then further reacting the isocyanurate-type polyisocyanate (a2) with the obtained product is included.

In the present invention, in producing the polyamide-imide resin (A), the isocyanurate-type polyisocyanate (a2) is divided into at least 2 times, more preferably 3 to 5 times, with respect to the tricarboxylic acid anhydride (a1). By adding it, a polyamide-imide resin having excellent solvent dilatability can be obtained, which is preferable.

In the step (1a), first, one or more of the tricarboxylic acid anhydride (a1) and one or more of the isocyanurate-type polyisocyanate (a2) are mixed and stirred in a solvent or no solvent. The temperature is raised while performing the (amide) imidization reaction. At that time, the ratio of the isocyanurate-type polyisocyanate (a2) to the tricarboxylic acid anhydride (a1) is tricarboxylic with respect to the number of moles of isocyanate groups of the isocyanurate-type polyisocyanate (a2). The ratio may be such that the total number of moles of the carboxy group and the number of moles of the acid anhydride group of the acid anhydride (a1) is an excess amount.

While confirming the progress of the (amide) imidization reaction, the reaction is preferably carried out until the isocyanate group of the isocyanurate-type polyisocyanate (a2) disappears, and then the (amide) imidization reaction is further preferably carried out. It is preferable that the reaction product is further reacted with the isocyanurate-type polyisocyanate (a2) by stirring while maintaining the reaction temperature. When the isocyanurate-type polyisocyanate (a2) is added to the tricarboxylic acid anhydride (a1) in three or more portions, the isocyanurate-type polyisocyanate (a2) is further added to the obtained reaction product. ) Is added and reacted, that is, the step (a1) may be repeated.

When the isocyanurate-type polyisocyanate (a2) (hereinafter, may be simply abbreviated as the (a2) component) is added separately, the amount of the (a2) component added each time may be evenly distributed or biased. May be. As a method of biasing, for example, the amount of the component (a2) added at the first time is the largest and the balance is equalized, or the amount of the component added at the first time is less than the amount of the component (a2) added at the first time. There are various methods such as making the amount of the component the smallest and equalizing the balance, or increasing the amount of the balance added later. However, the amount of the component (a2) added at the first time is the largest and the balance is added later. The method of adding less 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 added first, then 40 to 15% by mass is added the second time, and finally. Can be added in an amount of 20 to 5% by mass.

The reaction temperature of the (amide) imidization 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 the reaction temperature to such a level, the reaction rate is increased, and side reactions and decompositions are unlikely to occur.

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

The ratio of the amount of the isocyanurate-type polyisocyanate (a2) subjected to the (amide) imidization reaction in the step (1) to the amount of the tricarboxylic acid anhydride (a1) is the isocyanurate-type polyisocyanate (a2). ) To the total number of moles of isocyanate groups (N) and the total number of moles of carboxy groups (M1) and acid anhydride groups (M2) of tricarboxylic acid anhydride (a1) [(() Reacting so that M1) + (M2)) / (N)] becomes 1.1 to 1 is obtained because the polarity in the reaction system becomes high and the reaction proceeds to lubrication without residual isocyanate groups. It is preferable because the stability of the polyamide imide resin to be obtained is good, the residual amount of the tricarboxylic acid anhydride (a1) is small, and the problem of separation such as recrystallization is unlikely to occur. Of these, 1.2 to 2 is more preferable. In the present invention, the acid anhydride group refers to a -CO-O-CO- group obtained by intramolecular dehydration condensation of two carboxylic acid molecules.

Examples of the polyamide-imide resin (A) used in the present invention include imide resins represented by the following (formula 2).

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

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

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

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

Ra represents, for example, residues of divalent aliphatic diisocyanates.

In the polyamide-imide resin (A) obtained by the above production method, at least an isocyanurate-type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure and a tricarboxylic acid anhydride (a1) form an amide or an imide. It contains a polyamide-imide resin (A) that is formed and bonded.

Further, the polyamide-imide resin (A) obtained by the production method of the present invention has a molecular weight distribution in the range of 2.0 or less, preferably in the range of 1.5 to 2.0, and further 1. It is particularly preferably in the range of 7 to 1.9.

Therefore, the polyamide-imide resin of the present invention is not only soluble in general-purpose solvents and excellent in solvent dilatability, but also has a curable resin having long storage stability and a long pot life even when blended with a curable resin described later. A composition and a cured product (cured coating film) having excellent developability can be obtained.

The number average molecular weight is preferably 800 to 20000, more preferably 850 to 8000, and particularly preferably 900 to 2500, from the viewpoint of obtaining a cured product having good solubility in a solvent and excellent mechanical strength. On the other hand, the mass average molecular weight is not particularly limited as long as it satisfies the above range of molecular weight distribution with respect to the above number average molecular weight, but from the viewpoint of good solubility in a solvent, 1600 to 40,000 is preferable. 1650 to 10000 is more preferable, and a range of 1700 to 5000 is particularly preferable.

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

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

The polyamide-imide resin (A) of the present invention has a carboxy group and an acid anhydride group at the terminals, and the acid value thereof is not particularly limited as long as the cured product exhibits excellent properties, but is 20 to 20 to 20. The range is preferably 220 KOH mg / g, more preferably 50 to 210 KOH mg / g, and particularly preferably 160 to 200 KOH mg / g. Within this range, it exhibits excellent performance as a cured physical property.
Further, among the polyamide-imide resin (A) of the present invention, the polyamide-imide resin dissolved in the polar solvent containing neither nitrogen atom nor sulfur atom is preferable. Examples of such a polyamide-imide resin include a branched polyamide-imide resin having a branched structure and having an acid value of 130 KOHmg / g or more.

The curable resin composition of the present invention contains the polyamide-imide resin (A) of the present invention, the curable resin (B) and / or the organic solvent (C).

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

In addition to the cured product of the polyamide-imide resin of the present invention and the component that reacts with the cured product, the meanings of the cured physical properties described above and described later in the present invention are the polyamide-imide resin of the present invention alone or the polyamide-imide resin of the present invention. It is intended to include a coating film or a molded product that is simply solvent-dried and contains other resins, additives, inorganic material components, etc. that do not react with. Furthermore, the polyamide-imide resin of the present invention is mixed with a curing agent that reacts with heat or light, and / or the additive component itself that does not react with the polyamide-imide resin of the present invention is cured by heat, light, or the like. The cured physical properties are also included in the meaning.

Examples of the epoxy resin (B1) include bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene and various phenols. Epoxy of various dicyclopentadiene-modified phenolic resins, epoxies of 2,2', 6,6'-tetramethylbiphenol, epoxies of 4,4'-methylenebis (2,6-dimethylphenol), Examples thereof include epoxy derived from a naphthalene skeleton such as naphthol and binaphthol or novolak modification of naphthol and binaphthol, and aromatic epoxy resins such as epoxy resins obtained by epoxidizing a phenol resin having a fluorene skeleton.

In addition, 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, and 3,4-epoxycyclohexylmethyl- 3,4-Epoxycyclohexanecarboxylate, bis- (3,4-epoxybicyclohexyl) adipate, 1,2-epoxy-4- (2-oxylanyl) cyclohexane of 2,2-bis (hydroxymethyl) -1-butanol Ring-type aliphatic epoxy resin such as additives, epoxy resin containing polyalkylene glycol chain in the main chain such as polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether, epoxy resin containing heterocycle such as triglycidyl isocyanurate. Can also be used.

Further, 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 the (meth) acryloyl group and the epoxy group include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate glycidyl ether, hydroxypropyl (meth) acrylate glycidyl ether, and 4-hydroxidibutyl (meth) acrylate glycidyl ether. , 6-Hydroxyhexyl (meth) acrylate glycidyl ether, 5-hydroxy-3-methylpentyl (meth) acrylate glycidyl ether, (meth) acrylic acid-3,4-epoxide cyclohexyl, lactone-modified (meth) acrylic acid-3, Examples thereof include 4-epoxide cyclohexyl and vinylcyclohexene oxide.

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

Such a cyclic aliphatic epoxy resin is also available on the market, and examples thereof include Denacol EX-252 (manufactured by Nagase ChemteX Corporation), EHPE3150, and EHPE3150CE (manufactured by Daicel Chemical Industry Co., Ltd.).

The polyamideimide resin (A) and the epoxy resin (B1) having two or more epoxy groups in the molecule can be freely blended according to various desired physical properties, but heat such as Tg can be freely blended. An epoxy resin having two or more epoxy groups in the molecule and the number of moles n (COOH) of the carboxy group of the polyamideimide resin (A) in terms of the balance between the physical properties, mechanical properties, etc. and the transparency of the cured coating film (A). The ratio [n (EPOXY) / n (COOH)] of B1) to the number of moles n (EPOXY) of the epoxy group is in the range of 0.3 to 4, preferably 0.8 to 1.2. By blending the polyamideimide resin (A) and the epoxy resin (B1) in a wide range, it is easy to obtain Tg as a characteristic of the cured product, a cured product having excellent mechanical properties and the like can be obtained, and the transparency of the cured product is also good. It is preferable because it becomes.

An epoxy-carboxylic acid-based curing catalyst or the like may be mixed with the curable resin composition of the present invention. Examples of such an epoxy-carboxylic acid-based curing catalyst include primary to tertiary amines for promoting the reaction, quaternary ammonium salts, dicyandiamide, nitrogen-based compounds such as imidazole compounds, and TPP (triphenylphosphine). ), Alkyl-substituted phosphin compounds such as trialkylphonylphosphine and derivatives thereof, phosphonium salts thereof, or known epoxy curing accelerators such as dialkylureas, carboxylic acids, phenols, or methylol group-containing compounds. Etc., and these can be used in combination 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 N-cyclohexylmaleimide, N-methylmaleimide, and Nn-butylmaleimide. N-aliphatic maleimides such as N-hexyl maleimide, N-tert-butyl maleimide; N-aromatic maleimides such as N-phenylmaleimide, N- (P-methylphenyl) maleimide, N-benzylmaleimide; 4,4' -Diphenylmethane bismaleimide, 4,4'-diphenylsulfone bismaleimide, m-phenylene bismaleimide, bis (3-methyl-4-maleimidephenyl) methane, bis (3-ethyl-4-maleimidephenyl) methane, bis (3) , 5-Dimethyl-4-maleimidephenyl) methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane and other bismaleimides. Be done. Among these, bismaleimide is particularly preferable from the viewpoint of improving the heat resistance of the cured product, and particularly 4,4'-diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidephenyl) methane, and bis (3). -Ethyl-5-methyl-4-maleimidephenyl) methane and bis (3,5-diethyl-4-maleimidephenyl) methane are preferred. When the maleimide compound (B2) is used in the curable resin composition of the present invention, a curing accelerator can be used, if necessary. Examples of the curing accelerator that can be used here include amine compounds, phenol compounds, acid anhydrides, imidazoles, and organometallic salts.

The curable resin composition of the present invention may further contain an organic solvent (C), if necessary. When the curable resin composition of the present invention contains the organic solvent (C), the same organic solvent as the one prepared with the alcohol-modified polyamide-imide resin (A2) can be used.

When the curable resin composition of the present invention is further cured by irradiating it with energy rays, particularly ultraviolet rays, a photopolymerization initiator (D) and, if necessary, a reactive diluent (E) are added. Can be used. The photopolymerization initiator (D) is not particularly limited, and a known and commonly used polymerizable photoinitiator can be used. Examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Benzophenones 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-tershaributyl anthraquinone, 1-chloroanthraquinone, 2-aluminum anthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4- Thioxanthones such as diisopropylthioxanthone, bis (2,6 dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, trimethylbenzoylalkylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, There are acetophenone dimethyl ketal, ketals such as benzyl dimethyl ketal, benzophenones such as benzophenone, xanthones and the like. These can be used alone or in combination of two or more.

The amount of the photopolymerization initiator (D) used is not particularly limited as long as it does not impair the effects of the present invention, but is usually 0.1 to 30 parts by mass with respect to 100 parts by mass of the polyamide-imide resin (A). The range is preferably in the range, and more preferably in the range of 0.5 to 10 parts by mass. Such a photopolymerization initiator can also be used in combination with one or more of known and commonly used photopolymerization accelerators.

As the reactive diluent (E) used in the present invention, a known and commonly used photopolymerizable vinyl monomer can be used, and typical examples thereof include dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and ethylene glycol diacrylate. Diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, trimethylol propane diacrylate, trimethylol propane triacrylate, penta Elythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, acryloylmorpholine, vinylpyrrolidone, styrene or tris (2-acryloyloxyethyl) isocyanurate, and alkyl (meth) acrylates such as methylmethacrylate and ethylacrylate. Or, each methacrylate for the above acrylate, mono-, di-, tri- or higher polyester of polybasic acid and hydroxyalkyl (meth) acrylate, or bisphenol A type epoxy acrylate, novolak type epoxy acrylate or urethane acrylate. Examples thereof include monomers and oligomers having an ethylenically unsaturated double bond. One or more of these can be used.

The polyamideimide resin (A) and the reactive diluent (E) can be freely blended according to various desired physical characteristics, but are cured with thermal and mechanical properties such as Tg. In terms of the balance with the transparency of the film, the ratio [A / E] of the polyamideimide resin (A) to the photopolymerizable group of the reactive diluent (E) is 0.2 to 5.0 on a mass basis. By blending the polyamideimide resin (A) and the reactive diluent (C) in such a range, Tg can be easily obtained as a characteristic of the cured product, a cured product having excellent mechanical characteristics and the like can be obtained, and further, the cured product can be obtained. It is preferable because the transparency becomes good.

The curable resin composition of the present invention is basically cured by appropriately selecting and adjusting the types and blending ratios of the polyamide-imide resin (A), the curable resin (B), and other components, and the curing conditions. can.

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

When curing with active energy rays, ultraviolet rays and electron beams can be used. As ultraviolet rays, ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, black light lamps, metal halide lamps and the like can be used. As the ultraviolet wavelength, a wavelength of 1900 to 3800 angstroms is mainly used. Further, in the case of curing with an electron beam, a device equipped with an irradiation source such as various electron beam accelerators can be used, and electrons having an energy of 100 to 1000 KeV are irradiated.

In the case of heat curing, the curing temperature is in the range of 80 ° C. to 300 ° C., preferably 120 ° C. to 250 ° C. in the presence of a catalyst for initiating thermal polymerization and additives. For example, after painting, casting, etc. on the object to be painted, it can be cured by heating. Further, step curing may be performed at various temperatures. Further, a sheet-like or coating film-like composition semi-cured at a temperature of about 50 ° C. to 170 ° C. may be stored and treated at the above-mentioned curing temperature when necessary.
Of course, there are no restrictions on the use of the combined use of active energy rays and heat for curing.

If necessary, other solvents, various leveling agents, antifoaming agents, antioxidants, antioxidants, ultraviolet absorbers, antisettling agents, rheology control agents, etc. are added to the curable resin composition of the present invention. 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, and Kevlar fiber, etc. Alternatively, known and commonly used coloring pigments such as phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black, and silica, and other adhesion-imparting agents may be blended. Further, if necessary, a polymer such as an acrylic resin, a cellulosic resin, a polyvinyl resin, a polyphenylene ether, or a polyether sulfone can be blended.

In order to make the cured product exhibit flame retardancy, the curable resin composition of the present invention contains a non-halogen flame retardant that does not substantially contain halogen atoms as long as the effects of the present invention are not impaired. You may. Examples of the non-halogen flame retardant include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, and the like, and their use is also restricted. However, they may be used alone, a plurality of flame retardants of the same system may be used, or different flame retardants may be used in combination.

As the phosphorus-based flame retardant, either an inorganic type or an organic type can be used. Examples of the inorganic compound include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .. The red phosphorus is preferably surface-treated for the purpose of preventing hydrolysis and the like, and examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, and water. A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof, (ii) inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide and titanium hydroxide, and Method of coating with a mixture of thermosetting resins such as phenol resin, (iii) Thermocurability of phenol resin or the like on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide Examples thereof include a method of double coating with a resin. Examples of the organic phosphorus compound include general-purpose organic phosphorus compounds such as phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphoran compounds, and organic nitrogen-containing phosphorus compounds, as well as 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 the cyclic organophosphorus compounds 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, other components of the curable resin composition, and the desired degree of flame retardancy. For example, the polyamide-imide resin (A), Red phosphorus is not contained in 100 parts by mass of the curable resin composition containing all of the curable resin (B) and / or the organic solvent (C), the curing agent, the non-halogen flame retardant and other fillers and additives. When used as a halogen-based flame retardant, it is preferably blended in the range of 0.1 to 2.0 parts by mass, and when using an organic phosphorus compound, it is similarly blended in the range of 0.1 to 10.0 parts by mass. In particular, it is preferable to blend in the range of 0.5 to 6.0 parts by mass. When the phosphorus-based flame retardant is used, hydrotalcite, magnesium hydroxide, boring compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated charcoal, etc. may be used in combination with the phosphorus-based flame retardant. good.

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable. Examples of the triazine compound include, for example, melamine, acetoguanamine, benzoguanamine, melon, melamine, succinoguanamine, ethylenedimelamine, polyphosphate melamine, triguanamine and the like, and for example, (i) guanyl melamine sulfate, melem sulfate, sulfuric acid. A cocondensate of aminotriazine sulfate compounds such as melam, (ii) phenols, cresols, xylenol, butylphenols, nonylphenols and other phenols with melamines such as melamine, benzoguanamine, acetguanamine and formguanamine and formaldehyde, (iii). Examples thereof include a mixture of the cocondensate of (ii) and a phenolic resin such as a phenol formaldehyde condensate, and (iv) the above (ii) and (iii) further modified with tung oil, isomerized melamine oil and the like. .. Specific examples of the cyanuric acid compound include cyanuric acid and melamine cyanuric acid. The blending amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the curable resin composition, and the desired degree of flame retardancy. For example, a polyamideimide resin. In 100 parts by mass of a curable resin composition containing all of (A), curable resin (B) and / or organic solvent (C), hardener, non-halogen flame retardant and other fillers and additives, It is preferably blended in the range of 0.05 to 10 parts by mass, and particularly preferably in the range of 0.1 to 5 parts by mass. When using the nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

The silicone-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin. The blending amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, other components of the curable resin composition, and the desired degree of flame retardancy. For example, a polyamide imide resin. In 100 parts by mass of a curable resin composition containing all of (A), curable resin (B) and / or organic solvent (C), hardener, non-halogen flame retardant and other fillers and additives, It is preferable to blend in the range of 0.05 to 20 parts by mass. Further, when using the silicone flame retardant, a molybdenum compound, alumina or the like may be used in combination.

Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low melting point glass. Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydride and the like. Specific examples of the metal oxide include zinc molybdenate, molybdenum trioxide, zinc tinate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. , Vismus 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, titanium carbonate and the like. Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin and the like. Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, borax and the like. Specific examples of the low melting point glass include, for example, Shipley (Boxy Brown Co., Ltd.), hydrated glass SiO ₂ -MgO-H ₂ O, PbO-B ₂ O ₃ system, ZnO-P ₂ O _5- MgO system, and the like. P ₂ O _5- B ₂ O _3- PbO-MgO system, P-Sn-OF system, PbO-V ₂ O _5- TeO ₂ system, Al ₂ O _3- H ₂ O system, lead borosilicate, etc. Glassy compounds of. The blending amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, other components of the curable resin composition, and the desired degree of flame retardancy. For example, a polyamide imide resin. In 100 parts by mass of a curable resin composition containing all of (A), curable resin (B) and / or organic solvent (C), hardener, non-halogen flame retardant and other fillers and additives, It is preferably blended in the range of 0.05 to 20 parts by mass, and particularly preferably in the range of 0.5 to 15 parts by mass. Examples of the organometallic salt-based flame retardant include ferrocene, an acetylacetonate metal complex, an organometallic carbonyl compound, an organocobalt salt compound, an organosulfonic acid metal salt, an ionic bond between a metal atom and an aromatic compound or a heterocyclic compound. Examples thereof include a coordination-bonded compound. The blending amount of the organic metal salt-based flame retardant is appropriately selected depending on the type of the organic metal salt-based flame retardant, other components of the curable resin composition, and the desired degree of flame retardancy. , Polyamideimide resin (A), curable resin (B) and / or organic solvent (C), curing agent, non-halogen flame retardant and other fillers, additives and the like. It is preferable to blend in the range of 0.005 to 10 parts by mass in the mass part.

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

Naturally, fields where transparency of cured products is not required, for example, various heat-resistant coating materials, heat-resistant adhesives; electrical / electronic component encapsulation materials, insulating varnishes, laminated boards, insulating powder coatings, semiconductor passivation. Electrical insulation materials such as films and gate insulation films; Conductive materials such as conductive films and conductive adhesives; Adhesives for structural materials such as laminated boards for printed wiring substrates, Libreg and honeycomb panels; Glass fibers, carbon fibers , Fiber reinforced plastics using various reinforcing fibers such as aramid fibers and their prepregs; Patterning materials such as resist ink; Also used as gaskets for non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries. Can be done.

Since the curable resin composition of the present invention can obtain a cured coating film that is soluble in a general-purpose solvent and has excellent heat resistance and light transmission, a white prepreg, a white laminated plate, and the white laminated plate are provided. It can be suitably used for chip LEDs. The details will be described below.
The white prepreg of the present invention is characterized in that a mixture containing the curable resin composition of the present invention and a white pigment is impregnated or applied to a sheet-shaped glass fiber base material and then dried. Specifically, a mixture containing the curable resin composition of the present invention and a white pigment is impregnated or coated on a sheet-shaped glass fiber base material, and then in a dryer in the range of 100 to 200 ° C. for 1 to 60 minutes. It is characterized by being semi-cured within the range of. The white prepreg and its manufacturing method will be specifically described below.

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

The crystal structure of titanium dioxide includes anatase type and rutile type. As for the characteristics of both, the anatase type has good reflectance in the short wavelength region of visible light, and the rutile type has excellent long-term durability and discoloration resistance. The white pigment added to the curable resin composition of the present invention may be either, and is not particularly limited. Of course, it is also possible to mix and use both.

The content of the white pigment contained in the mixture is preferably in the range of 10 to 75% by mass in the formulation. If it is 10% by mass or more, sufficient whiteness and reflectance can be obtained, and if it is 75% by mass or less, the impregnation property into the sheet-shaped glass fiber base material is lowered and the adhesive strength with the metal foil is lowered. There is no such problem as a problem.

When titanium dioxide is used as the white pigment, the titanium dioxide may be treated with alumina, silica or the like as a surface treatment. Further, it is also possible to treat a silane-based coupling agent or a titanate-based coupling agent.

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

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

The sheet-shaped glass fiber base material used for the white prepreg of the present invention may be either a glass cloth or a non-woven fabric, and the glass cloth and the non-woven fabric may be used in combination. In the case of glass cloth, a plain weave structure is basically used, but a woven structure such as a satin weave, a satin weave, or a twill weave may be used, and is not particularly limited. It is preferable to use a woven structure in which the gap between the warp and the weft is small so as not to impair the appearance and workability. The thickness of the glass cloth is not particularly limited, but a glass cloth in the range of 0.02 to 0.3 mm is preferable because it is easy to handle.

Further, the sheet-shaped glass fiber base material may be surface-treated with a silane coupling agent or the like. Further, the sheet-shaped glass fiber base material itself may be colored white.

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

A combination of the obtained white prepreg and copper foil or aluminum foil is heat-press molded to produce a white laminated plate. The number of white prepregs to be stacked is not particularly limited, but one white prepreg or 2 to 10 white prepregs are stacked as a single-layer substrate, and in the case of a metal foil-covered white laminated board, metal is placed on or above and below. It is common to stack the foils. The multilayer substrate is manufactured by laminating a plurality of the above-mentioned single-layer substrates, but the number of stacked substrates is not particularly limited. As the metal foil, copper foil, aluminum foil and the like are used. The thickness of the metal foil is generally 1 μm to 105 μm, and is particularly preferably in the range of 1.5 μm to 35 μm. It is also possible to use the white prepreg only for the surface layer on which the white prepreg is laminated, and to use the prepreg according to the prior art for the intermediate layer. The white laminated board and the white laminated board covered with metal foil thus obtained have high reflectance in the visible light region, are significantly less discolored by heating or ultraviolet rays, and have high heat resistance and excellent plate thickness accuracy. A white laminated board for a wiring board and a white laminated board covered with metal foil. As the laminating molding condition of the metal foil-clad laminate, the usual laminating plate method for printed wiring boards can be applied. For example, a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc. are used, and the temperature: 100 to 100 to Generally, the range of 300 ° C., pressure: ^{2 to} 100 kgf / cm 2, and heating time: 0.1 to 5 hours are common. It is preferable to carry out under a vacuum of 70 mmHg or less.

A conductor pattern is formed on the obtained white laminated board by an additive method to obtain a printed wiring board. Further, a circuit pattern is printed on the metal foil of the obtained metal foil-covered white laminated board and etched to obtain a printed wiring board. To mount the chip LED on the printed wiring board, first apply solder on the printed wiring board, place the chip LED on it, and then pass it through reflow or the like to melt the solder. Is fixed to the printed circuit board. By integrating chip LEDs at high density, it can be used as a surface light source, and such a surface light source is suitably used for a backlight for a liquid crystal display, which is required to be particularly thin. In addition, as a surface-emitting type lighting device, it is applied to guidance display lighting, evacuation exit lighting, advertising light, and the like.

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

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

First, a photosensitive film including a support and a photosensitive resin composition layer made of the curable resin composition of the present invention formed on the support is produced. A protective film for coating the photosensitive resin composition layer may be further provided on the photosensitive resin composition layer.

The photosensitive resin composition layer is formed by dissolving the curable resin composition of the present invention in a solvent or a mixed solvent to prepare a solution having a solid content of about 30 to 70% by mass, and then applying such a solution on a support. It is preferable to do so. The thickness of the photosensitive resin composition layer varies depending on the application, but is preferably 10 to 100 μm, more preferably 20 to 60 μm, after drying after removing the solvent by heating and / or blowing hot air. .. If the thickness is less than 10 μm, coating tends to be industrially difficult, and if it exceeds 100 μm, the above-mentioned effect produced by the present invention tends to be small, and in particular, physical characteristics and resolution tend to be lowered.

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

When the curable resin composition of the present invention is used as a photosensitive resin composition or a photosensitive film, the method for forming a resist pattern is as follows: first, a step of applying by a known screen printing, a roll coater, or protection, respectively. By the step of removing the film and pasting it by laminating or the like, it is laminated on the substrate on which the resist is formed. Then, if necessary, a removal step of removing the support film from the above-mentioned photosensitive film is performed, or active light is applied to a predetermined portion of the photosensitive resin composition layer through a mask pattern without removing the support film. An exposure step is performed in which the photosensitive resin composition layer of the irradiated portion is photocured by irradiation. The photosensitive resin composition layer other than the irradiated portion is removed by the next developing step by removing the support film, if any. The substrate on which the resist is formed refers to a printed wiring board, a substrate for a semiconductor package, and a flexible wiring board.

As the light source of the active light, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet rays is used. In addition, those that effectively radiate visible light such as photographic flood bulbs and solar lamps are also used. Further, a direct laser exposure of a direct drawing method may be used. An excellent pattern can be formed by using a photopolymerization initiator (D) corresponding to each laser light source and exposure method.

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

After the development step is completed, it is preferable to irradiate with ultraviolet rays or heat with a high-pressure mercury lamp for the purpose of improving solder heat resistance, chemical resistance and the like. When irradiating with ultraviolet rays, the irradiation amount can be adjusted as needed, and for example, irradiation can be performed with an irradiation amount of about ^{0.2 to 10 J / cm 2.} When the resist pattern is heated, it is preferably carried out in the range of about 100 to 170 ° C. for about 15 to 90 minutes. Further, ultraviolet irradiation and heating can be performed at the same time, and one of them can be performed and then the other can be performed. When irradiating with ultraviolet rays and heating at the same time, it is more preferable to heat at 60 to 150 ° C. from the viewpoint of effectively imparting solder heat resistance, chemical resistance and the like.

This photosensitive resin composition layer also serves as a protective film for wiring after soldering to a substrate, and has excellent crack resistance, HAST resistance, and gold plating property. Therefore, it is used for printed wiring boards and semiconductor package substrates. , Useful as a solder resist for flexible wiring boards.

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

Next, the present invention will be described in more detail with reference to Examples. Unless otherwise specified, "parts" and "%" are based on mass.

Example 1
[Preparation of Polyamide-imide Resin (A1)]
PGMAc (propylene glycol monomethyl ether acetate) 1102.8 g, IPDI3N (isocyanurate-type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 197.6 g (0) in a flask equipped with a stirrer, a thermometer, and a condenser. .27 mol) and 506.9 g (2.56 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 2 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 2 hours. The inside of the system became a pale yellow liquid, and as a result of measuring the characteristic absorption by the infrared spectrum, it was confirmed that ^{the characteristic absorption of the isocyanate group, 2270 cm-1, completely disappeared.} Further, 197.6 g (0.27 mol) of IPDI3N was added to continue the reaction. After measuring the characteristic absorption with an infrared spectrum and confirming that the characteristic absorption of the isocyanate group, 2270 cm- ^1, was completely eliminated, 197.6 g (0.27 mol) of IPDI3N was further added to continue the reaction. .. The characteristic absorption was measured by infrared spectrum, and the characteristic absorption of the isocyanate group, 2270 cm ^-1, was completely eliminated, and the absorption of the imide group was confirmed at ^{1780 cm -1} and 1720 cm ^-1. The acid value was 191 KOHmg / g in terms of solid content. The solution of this resin is abbreviated as the solution of the imide resin (A1).

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

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

Example 4
[Preparation of polyamide-imide resin (A4)]
PGMAc (propylene glycol monomethyl ether acetate) 331.9 g, IPDI3N (isocyanurate-type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 29.3 g (0) in a flask equipped with a stirrer, a thermometer, and a condenser. .04 mol) and 150.3 g (0.76 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 2 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 2 hours. The inside of the system became a pale yellow liquid, and as a result of measuring the characteristic absorption by the infrared spectrum, it was confirmed that ^{the characteristic absorption of the isocyanate group, 2270 cm-1, completely disappeared.} Further, 58.6 g (0.08 mol) of IPDI3N was added to continue the reaction. After measuring the characteristic absorption with an infrared spectrum and confirming that the characteristic absorption of the isocyanate group, 2270 cm- ^1, had completely disappeared, 87.8 g (0.12 mol) of IPDI3N was further added to continue the reaction. .. The characteristic absorption was measured by infrared spectrum, and the characteristic absorption of the isocyanate group, 2270 cm ^-1, was completely eliminated, and the absorption of the imide group was confirmed at ^{1780 cm -1} and 1720 cm ^-1. The acid value was 190 KOH mg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A4) solution.

Comparative Example 1 [Preparation of Polyamide-imide Resin (A5)]
PGMAc (propylene glycol monomethyl ether acetate) 276.4 g, IPDI3N (isocyanurate-type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 146.4 g (0) in a flask equipped with a stirrer, a thermometer, and a condenser. .20 mol) and 125.1 g (0.63 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 2 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 4 hours. The inside of the system became a pale yellow liquid, and as a result of measuring the characteristic absorption in the infrared spectrum, the characteristic absorption of isocyanate groups of 2270 cm ^-1 disappeared completely, and the absorption of imide groups was absorbed in ^{1780 cm -1} and 1720 cm ^-1. confirmed. The acid value was 189 KOHmg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A5) solution.

Comparative Example 2 [Preparation of Polyamide-imide Resin (A6)]
PGMAc (propylene glycol monomethyl ether acetate) 276.4 g, IPDI3N (isocyanurate-type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 146.4 g (0) in a flask equipped with a stirrer, a thermometer, and a condenser. .20 mol) and 125.1 g (0.63 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 4 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 4 hours. The inside of the system became a pale yellow liquid, and as a result of measuring the characteristic absorption in the infrared spectrum, the characteristic absorption of isocyanate groups of 2270 cm ^-1 disappeared completely, and the absorption of imide groups was absorbed in ^{1780 cm -1} and 1720 cm ^-1. confirmed. The acid value was 195 KOHmg / g in terms of solid content. The solution of this resin is abbreviated as the solution of imide resin (A6).

(Examples 1 to 4, Comparative Examples 1 to 2)
Using the polyamide-imide resin obtained above, curable resin compositions 1 to 6 were produced under the compounding conditions shown in Table 1.

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

Footnote EHPE3150 in Table 1: Cyclic aliphatic epoxy resin manufactured by Daicel Chemical Industry Co., Ltd. (1,2-epoxy-4- (2-oxylanyl) cyclohexane of 2,2-bis (hydroxymethyl) -1-butanol Additives). The epoxy equivalent is 177. The concentration of the resin content is 100% by mass.

<Measurement of storage stability>
The curable resin compositions 1 to 6 were heated on a hot plate heated to 160 ° C., and the time until the stringiness disappeared was measured. The obtained results are shown in Table 2 as "160 ° C. gel time".

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

-PGMAc tolerance evaluation After adding 10 g of resin to the flask, PGMAc at 25 ° C. was added, and the place where turbidity was confirmed was set as the dilution limit. It is shown in Table 3.

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

表中、「’」は分を、「”」は秒を表す。

In the table, "'" represents minutes and """represents seconds.

Claims (11)

A method for producing a polyamide-imide resin, which comprises a step (1) of reacting a tricarboxylic acid anhydride (a1) with an isocyanurate-type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure.
In the step (1), the isocyanurate-type polyisocyanate (a2) is added to the tricarboxylic acid anhydride (a1) in at least three portions to obtain the tricarboxylic acid anhydride (a1) and the isocyanurate. After reacting with the type polyisocyanate (a2), the obtained reactant further comprises a step (1a) of reacting the isocyanurate type polyisocyanate (a2).
In the step (1a), the isocyanurate-type polyisocyanate (a2) is reacted with a tricarboxylic acid anhydride (a1), and the reaction is carried out ^{until 2270 cm -1,} which is the characteristic absorption of the isocyanate group, disappears in the infrared absorption spectrum measurement. A method for producing a polyamide-imide resin, which is a step of further reacting the obtained reactant with the isocyanurate-type polyisocyanate (a2). In the step (1a), the total number of moles of the carboxy group and the number of moles of the acid anhydride group of the tricarboxylic acid anhydride (a1) is excessive with respect to the number of moles of the isocyanate group of the isocyanurate type polyisocyanate (a2). After reacting the isocyanurate type polyisocyanate (a2) with the tricarboxylic acid anhydride (a1) at a ratio of the amount, the obtained reaction product is further reacted with the isocyanurate type polyisocyanate (a2). The method for producing a polyamideimide resin according to claim 1, which is a step. The total number of moles (N) of isocyanate groups of the isocyanurate-type polyisocyanate (a2), the total number of moles of carboxy groups (M1) and the number of moles of acid anhydride groups (M2) of tricarboxylic acid anhydride (a1). The method for producing a polyamide imide resin according to claim 1 or 2, wherein the ratio [(M1) + (M2)) / (N)] to the number of moles is 1.1 to 3. The method for producing a polyamide-imide resin according to any one of claims 1 to 3, which has a carboxy group or an acid anhydride group at the end. A process according to any one of claims 1 to 4, a manufacturing method of the molecular weight distribution of 2.0 or less in the range der Lupo Riamidoimido resin. A method according to any one of claims 1 to 5, the number-average molecular weight is in the range of 800 to 20,000, a manufacturing method in the range der Lupo Riamidoimido resin with a weight average molecular weight of 1,600 to 40,000. Be any production method according to one of claims 1 to 6, a manufacturing method of reportage Riamidoimido resin having a acid anhydride group at the end. A method according to any one of claims 1 to 7, the manufacturing method of the acid value 20~220KOHmg / g der Lupo Riamidoimido resin. Curability characterized by containing the polyamide-imide resin (A) obtained by the production method according to any one of claims 1 to 8 and a curable resin (B) and / or an organic solvent (C). A method for producing a resin composition. The manufacturing method of claim 9, further method of manufacturing to that hardening resin composition containing a photopolymerization initiator (D). Method for producing a cured product, characterized in that formed by curing the claims 9 or 10 curable resin composition obtained by the production method according.