WO2017221922A1 - Alcohol-modified polyamide-imide resin and process for producing same - Google Patents
Alcohol-modified polyamide-imide resin and process for producing same Download PDFInfo
- Publication number
- WO2017221922A1 WO2017221922A1 PCT/JP2017/022653 JP2017022653W WO2017221922A1 WO 2017221922 A1 WO2017221922 A1 WO 2017221922A1 JP 2017022653 W JP2017022653 W JP 2017022653W WO 2017221922 A1 WO2017221922 A1 WO 2017221922A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alcohol
- polyamideimide resin
- acid anhydride
- resin
- type polyisocyanate
- Prior art date
Links
- 0 C*([N+](*1[N+](*(C)=C)[O-])[O-])[N+]1[O-] Chemical compound C*([N+](*1[N+](*(C)=C)[O-])[O-])[N+]1[O-] 0.000 description 3
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a polyamideimide resin, a curable resin composition containing the polyamideimide resin, and a cured product thereof.
- 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.
- 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 electric and electronic industries. Recently, PGMAc (propylene glycol-1-monomethyl ether-2- The ability to be dissolved in general-purpose solvents such as acetate and EDGA (diethylene glycol monoethyl ether acetate) has been demanded.
- 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.
- 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).
- 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. .
- the acid anhydride group of the terminal group of the polyamideimide resin obtained by reacting the isocyanurate type polyisocyanate (a2) synthesized from the isocyanate having an aliphatic structure with the tricarboxylic acid anhydride (a1) is an alcohol compound. It is known that by modifying, a polyamideimide resin having a long storage stability and a long usable time when blended with a curable resin or a reaction diluent and excellent in handleability can be obtained (see Patent Document 2). . However, the polyamide-imide resin has room for improvement in solvent dilutability and developability of a cured coating film obtained by blending with a curable resin or a reactive diluent.
- the problem of the present invention includes a polyamideimide resin that is soluble in a general-purpose solvent and excellent in solvent dilutability, and is a curable resin composition that has a long storage stability and pot life even when blended with a curable resin. And it is providing the hardened
- the present inventors have reacted a tricarboxylic acid anhydride (a1) with an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure in the step of producing a polyamideimide resin.
- a1 a tricarboxylic acid anhydride
- a2 an isocyanurate type polyisocyanate synthesized from an isocyanate having an aliphatic structure
- a polyamide-imide resin that is soluble in a general-purpose solvent and excellent in solvent dilutability can be obtained by modifying with alcohol, and further, by blending the polyamide-imide resin with a curable resin, storage stability and goodness can be obtained.
- a curable resin composition having a long working time is obtained, and further, developability is excellent. It found that the product (cured film) is obtained, and have completed the present invention.
- the present invention is a process for producing a polyamideimide resin (A1) by reacting a tricarboxylic acid anhydride (a1) with an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure ( 1), Alcohol-modified polyamide having a step (2) of producing an alcohol-modified polyamideimide resin (A2) by further adding an alcohol compound (a3) to the polyamideimide resin (A1) obtained in the step (1) and reacting with the polyamide-imide resin (A1) A method for producing an imide resin, In the step (1), the isocyanurate type polyisocyanate (a2) and the tricarboxylic acid are added to the tricarboxylic acid anhydride (a1) by adding the isocyanurate type polyisocyanate (a2) at least twice.
- An alcohol-modified polyamideimide resin characterized by comprising a step (1a) of reacting the isocyanurate type polyisocyanate (a2) with the obtained reactant after reacting with the anhydride (a1). It relates to a manufacturing method.
- the present invention relates to a polyamide-imide resin in which a tricarboxylic acid anhydride (a1) and an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure are bonded together by forming an amide or imide.
- Alcohol-modified comprising an alcohol-modified polyamideimide in which the alcohol compound (a3) is bonded to the acid anhydride group of A1) by forming an ester bond, and the molecular weight distribution is in the range of 2.0 or less It relates to the polyamide-imide resin (A).
- the present invention also relates to a curable resin composition containing the alcohol-modified polyamideimide resin (A) and the curable resin (B).
- this invention relates to the hardened
- a curable resin composition that includes a polyamide-imide resin that is soluble in a general-purpose solvent and has excellent solvent dilutability, and has long storage stability and pot life even when blended with a curable resin, and developability It is possible to provide a cured product (cured coating film) excellent in.
- the method for producing the alcohol-modified polyamideimide resin (A2) of the present invention is obtained by reacting a tricarboxylic anhydride (a1) with an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure.
- Step (1) for producing an imide resin (A1) The step (2) of producing an alcohol-modified polyamideimide resin (A2) by further reacting the alcohol compound (a3) with the polyamideimide resin (A1) obtained in the step (1),
- the isocyanurate type polyisocyanate (a2) is added to the tricarboxylic acid anhydride (a1) in at least two portions, whereby the tricarboxylic acid anhydride (a1) and the isocyanurate are added.
- the product obtained further comprises a step (1a) of reacting the isocyanurate type polyisocyanate (a2).
- the transparency of the cured coating film of the resulting polyamideimide resin is improved.
- tricarboxylic acid anhydrides include tricarboxylic acid anhydrides having an aromatic structure in the molecule and tricarboxylic acids having an aliphatic structure in the molecule.
- a tricarboxylic acid having an aliphatic structure in the molecule is preferable because the storage stability of the curable resin composition is excellent, the pot life is long, and the thermal decomposition temperature of the cured product tends to be excellent.
- Examples of the tricarboxylic acid anhydride having an aromatic structure in the molecule include trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride.
- Examples of the tricarboxylic acid anhydride having an aliphatic structure include a tricarboxylic acid anhydride having a linear aliphatic structure and a tricarboxylic acid anhydride having a cyclic aliphatic structure.
- Examples of the tricarboxylic acid anhydride having a linear aliphatic structure include propane tricarboxylic acid anhydride.
- Examples of the tricarboxylic acid anhydride having a cycloaliphatic structure include cyclohexanetricarboxylic acid anhydride, methylcyclohexanetricarboxylic acid anhydride, cyclohexentricarboxylic acid anhydride, methylcyclohexentricarboxylic acid anhydride, and the like.
- a tricarboxylic acid anhydride having a cyclic aliphatic structure is preferable because a cured coating film having high Tg and excellent thermal properties can be obtained in addition to transparency.
- the isocyanurate type polyisocyanate (a2) is an isocyanurate type polyisocyanate synthesized from an isocyanate having a cycloaliphatic structure
- the tricarboxylic acid anhydride (a1) has a cycloaliphatic structure. More preferably, it is a tricarboxylic acid anhydride.
- tricarboxylic acid anhydride having a cycloaliphatic structure examples include cyclohexane tricarboxylic acid anhydride. One or more of these can be used. In some cases, bifunctional dicarboxylic acid compounds such as adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid and acid anhydrides thereof may be used in combination.
- cyclohexanetricarboxylic acid anhydride examples 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.
- 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.
- cyclohexanetricarboxylic acid anhydride is represented by the structure of the following general formula (1), and cyclohexane-1,2,3-tricarboxylic acid, cyclohexane-1,3,4, which is used as a production raw material.
- impurities such as tricarboxylic acid do not impair the curing of the present invention, for example, 10 mass% or less, preferably 5 mass% or less, they may be mixed.
- 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 of the isocyanurate type polyisocyanate synthesized from an isocyanate having a linear aliphatic structure include HDI3N (isocyanurate type triisocyanate synthesized from hexamethylene diisocyanate (including polymers such as pentamers)), HTMDI3N, and the like. (Isocyanurate-type triisocyanate synthesized from trimethylhexamethylene diisocyanate (including polymers such as pentamers)) and the like. These may be used in combination or alone.
- Examples of the isocyanurate type polyisocyanate synthesized from an isocyanate having a cycloaliphatic structure include IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate (including polymers such as pentamers)), HTDI3N ( Isocyanurate type triisocyanate (including polymer such as pentamer) synthesized from hydrogenated tolylene diisocyanate, HXDI3N (Isocyanurate type triisocyanate synthesized from hydrogenated xylene diisocyanate (polymer such as pentamer) ), NBDI3N (isocyanurate-type triisocyanate synthesized from norbornane diisocyanate (including polymers such as pentamers)), HMDI3N (isocyanur synthesized from hydrogenated diphenylmethane diisocyanate) Chromatography (including 5-mers, etc. of the polymer)
- the isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure used in the present invention has a cycloaliphatic structure since a cured coating film having a high Tg and excellent thermal properties can be obtained.
- Isocyanurate type polyisocyanate synthesized from isocyanate is preferable, and isocyanurate type triisocyanate synthesized from isophorone diisocyanate is particularly preferable.
- the isocyanurate type triisocyanate synthesized from isophorone diisocyanate may contain a polymer such as a pentamer.
- the isocyanurate type polyisocyanate synthesized from the isocyanate having a cyclic aliphatic structure in the isocyanurate type polyisocyanate (a2) synthesized from the isocyanate having an aliphatic structure is based on the mass of the compound (a2). 50 to 80% by mass is preferable because a cured coating film having a high Tg and excellent thermal properties can be obtained, more preferably 80 to 100% by mass, and most preferably 100% by mass.
- an adduct obtained by urethanization reaction of the above isocyanate compound and various polyols can be used as long as the solvent solubility of the polyamideimide resin of the present invention is not impaired.
- the polyamide-imide resin (A1) containing a carboxy group used in the present invention has a problem in stability or the like by directly forming an imide bond from the above-mentioned tricarboxylic acid anhydride (a1) and the above-mentioned isocyanate compound (a2). Without passing through a certain polyamic acid intermediate, it is possible to synthesize a polyamide-imide resin that provides a cured coating film with good reproducibility, good solubility, and excellent transparency.
- the carboxylic acid component of the tricarboxylic acid anhydride (a1) reacts with the isocyanate component in the polyisocyanate (a2), an imide and an amide are formed, and the resin of the present invention becomes an amide-imide resin.
- the polyisocyanate (a2) is reacted with the tricarboxylic acid anhydride (a1), the tricarboxylic acid anhydride (a1) and the polyisocyanate (a1) are left in such a ratio that the carboxylic acid component of the tricarboxylic acid anhydride (a1) remains.
- the resulting polyamideimide resin has a carboxy group.
- This carboxy group reacts with a polymerizable group such as an epoxy group of an epoxy resin contained in the curable resin composition of the present invention described later to form a crosslinked structure of the cured product. Since the reaction rate is fast imidization, even in the reaction of tricarboxylic acid and triisocyanate, tricarboxylic acid selectively forms an imide at the acid anhydride.
- the tricarboxylic acid anhydride (a1) and the isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure are reacted to obtain the polyamideimide resin (A1) used in the present invention, nitrogen is used. It is preferable to make it react in the polar solvent which does not contain both an atom and a sulfur atom. In the presence of a polar solvent containing nitrogen or sulfur atoms, environmental problems are likely to occur, and in the reaction of tricarboxylic acid anhydride (a1) with isocyanurate type polyisocyanate (a2), Growth is likely to be hindered. When such a molecule is cut, the physical properties of the composition are likely to deteriorate, and film defects such as “repellency” tend to occur.
- the polar solvent containing neither a nitrogen atom nor a sulfur atom is more preferably an aprotic solvent.
- 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.
- 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.
- other curing components for example, epoxy resin
- alcohol solvents are not preferred because they react with isocyanates or acid anhydrides.
- Examples of the aprotic solvent include ether solvents having no hydroxyl groups, ester solvents having no hydroxyl groups, and ketone solvents having no hydroxyl groups.
- Examples of ester solvents that do not have a hydroxyl group include ethyl acetate, propyl acetate, and butyl acetate.
- Examples of the ketone solvent having no hydroxyl group include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Of these, an ether solvent having no hydroxyl group is particularly preferred.
- the ether solvent having no hydroxyl group has weak polarity and is excellent in the reaction of the isocyanate having the aliphatic structure described above with the isocyanurate type polyisocyanate (a2) and the tricarboxylic acid anhydride (a1).
- ether solvents known and commonly used solvents can be used.
- 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 monoeth
- step (1) the isocyanurate type polyisocyanate (a2) and the tricarboxylic acid anhydride are added to the tricarboxylic acid anhydride (a1) by adding the isocyanurate type polyisocyanate (a2) at least twice.
- step (1) the product obtained further comprises a step (1a) of reacting the isocyanurate type polyisocyanate (a2).
- the isocyanurate type polyisocyanate (a2) is divided into at least two times, more preferably 3 to 5 times, with respect to the tricarboxylic acid anhydride (a1). Addition is preferable because a polyamideimide resin having excellent solvent dilutability can be obtained.
- step (1a) first, one or more types of tricarboxylic acid anhydride (a1) and one or more types of the isocyanurate type polyisocyanate (a2) are mixed in a solvent or in the absence of a solvent and stirred. (Amide) imidization reaction is carried out while heating. At that time, the ratio of the isocyanurate type polyisocyanate (a2) added to the tricarboxylic acid anhydride (a1) at each time was determined based on the number of moles of isocyanate groups of the isocyanurate type polyisocyanate (a2). What is necessary is just the ratio by which the sum total of the number of moles of the carboxy group of acid anhydride (a1) and the number of moles of acid anhydride group becomes an excess amount.
- the reaction While confirming the progress of the (amide) imidization reaction, preferably, after the reaction is allowed to proceed until the isocyanate group of the isocyanurate type polyisocyanate (a2) disappears, more preferably, the (amide) imidization reaction It is preferable to stir while maintaining the reaction temperature, and to add the isocyanurate-type polyisocyanate (a2) to the resulting reaction product for reaction.
- the isocyanurate type polyisocyanate (a2) is added to the tricarboxylic acid anhydride (a1) in three or more times, the isocyanurate type polyisocyanate (a2) is further added to the reaction product obtained above. ) To be reacted, that is, the step (a1) may be repeated.
- the amount of the component (a2) to be added may be evenly allocated or biased. May be.
- 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 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 thereof can be added.
- the reaction temperature of the (amide) imidation reaction is preferably in the range of 50 ° C to 250 ° C, particularly preferably in the range of 70 ° C to 180 ° C. By setting such a reaction temperature, the reaction rate is increased, and the side reaction and decomposition are less likely to occur.
- the progress of the (amide) imidization reaction can be traced by an analytical means such as an infrared vector, acid value, or quantitative determination of an isocyanate group.
- an analytical means such as an infrared vector, acid value, or quantitative determination of an isocyanate group.
- 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.
- the absorption of imide groups increases at 1780 cm ⁇ 1 and 1720 cm ⁇ 1 .
- the reaction may be terminated by lowering the temperature while confirming the target acid value, viscosity, molecular weight and the like. However, it is more preferable to continue the reaction until the isocyanate group disappears from the standpoint of stability over time.
- a catalyst, an antioxidant, a surfactant, other solvents, and the like may be added as long as the physical properties of the synthesized resin are not impaired.
- the ratio of the total amount of the isocyanurate type polyisocyanate (a2) subjected to the (amide) imidization reaction in the step (1) and the amount of the tricarboxylic acid anhydride (a1) is determined by the isocyanurate type polyisocyanate ( Ratio of the total number of moles (N) of isocyanate groups in a2) to the total number of moles of carboxy groups (M1) and acid anhydride groups (M2) in tricarboxylic acid anhydride (a1) [ The reaction is carried out so that (M1) + (M2)) / (N)] is 1.1 to 3, since the polarity in the reaction system becomes high and the reaction proceeds to lubrication, the isocyanate group does not remain, It is preferable because the stability of the resulting polyamideimide resin is good, the residual amount of the tricarboxylic acid anhydride (a1) is small, and separation problems such as recrystallization hardly occur. Among these, 1.2 to 2 is more prefer
- Examples of the polyamideimide resin (A1) used in the present invention include imide resins represented by the following (formula 2).
- N is a repeating unit of 0-30.
- Rb is, for example, a structural unit represented by the following structural formula (Formula 3) or (Formula 4).
- R 2 is, for example, an aromatic or aliphatic tricarboxylic acid residue that may have a substituent having 6 to 20 carbon atoms.
- Rc is represented by the following structural formula (formula 5), for example. A structural unit.
- Rd is, for example, a trivalent organic group represented by the following (formula 6):
- Ra represents, for example, a residue of a divalent aliphatic diisocyanate.
- step (2) for producing the alcohol-modified polyamideimide resin (A2) of the present invention will be described.
- the alcohol-modified polyamideimide resin (A2) of the present invention is obtained by producing the polyamideimide resin (A1) by the above method and subsequently reacting with the alcohol compound (a3).
- 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.
- the reaction can be performed by the following esterification reaction.
- the polyamideimide resin (A1) used as a raw material the one produced by the above method can be used.
- the side reaction of urethanization can be suppressed during the reaction with the alcohol compound (a3), the isocyanate group is completely It is preferable to use those that have disappeared.
- the disappearance of the isocyanate group can be confirmed by the disappearance of 2270 cm ⁇ 1, which is the characteristic absorption of the isocyanate group in the infrared spectrum, for example.
- the reaction between the polyamideimide resin (A1) and the alcohol compound (a3) is carried out by the number of moles of acid anhydride groups (M3) in the polyamideimide resin (A1) and the number of moles of hydroxyl groups (L) of the alcohol compound (a3).
- M3 acid anhydride groups
- L hydroxyl groups
- 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.
- 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.
- the polyamide-imide resin (A1) is diluted with a solvent or the like, an excess amount of n-butanol is reacted with the acid anhydride group, and then the acid value (b) is obtained by titration with an aqueous KOH solution.
- 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.
- Alcohols 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- An alcohol having 10 or less carbon atoms containing an ether bond such as isopropoxyethyl alcohol; an alcohol having 10 or less carbon atoms containing a ketone group such as 3-hydroxy-2-butanone; Number of carbon atoms including ester groups such as methyl acid 10 ppm alcohol are exemplified.
- monohydric alcohols having 5 or less carbon atoms are preferred.
- the dehydration esterification reaction is preferably carried out by mixing the polyamideimide resin (A1) and one or more alcohol compounds (a3) in a solvent or without a solvent and raising the temperature while stirring.
- the reaction temperature is preferably in the range of 50 ° C. to 150 ° C., particularly preferably in the range of 70 ° C. to 130 ° C. By setting such a reaction temperature, the reaction rate is increased, and the side reaction and decomposition are less likely to occur.
- the reaction forms an ester bond with a dehydration reaction.
- the progress of the reaction can be traced by an analytical means such as an infrared vector, acid value, or ester bond quantification.
- the infrared spectrum, 1860 cm -1 and 850 cm -1 which is the characteristic absorption of an acid anhydride group decreases with the reaction.
- the reaction may be terminated by lowering the temperature while confirming the target acid value, viscosity, molecular weight and the like. However, it is more preferable to continue the reaction until the acid anhydride group disappears from the viewpoint of stability over time.
- the solvent used for the dehydration esterification reaction can be the same as the solvent used for the (amide) imidization reaction.
- a catalyst, an antioxidant, a surfactant, other solvents, and the like may be added as long as the physical properties of the synthesized resin are not impaired.
- the alcohol-modified polyamide-imide resin (A2) obtained by the above production method includes at least an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure and a tricarboxylic acid anhydride (a1).
- the alcohol-modified polyamideimide resin (A2) obtained by the production method of the present invention has a molecular weight distribution of 2.0 or less, preferably 1.5 to 2.0, A range of 1.7 to 1.9 is particularly preferable.
- the alcohol-modified polyamideimide resin of the present invention is not only soluble in a general-purpose solvent and excellent in solvent dilutability, but also has long storage stability and a long working life even when blended with a curable resin described later. Resin composition and cured product (cured coating film) excellent in developability are obtained.
- the number average molecular weight is preferably 800 to 20000, more preferably 850 to 8000, and particularly preferably in the range of 900 to 2500 in terms of good solubility in a solvent and a cured product having excellent mechanical strength.
- 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 is preferably 1600 to 40000 in view of good solubility in a solvent. 1650 to 10000 is more preferable, and a range of 1700 to 5000 is particularly preferable.
- the molecular weight can be measured by gel permeation chromatography (GPC) or quantitative analysis of the terminal functional group amount.
- the number average molecular weight and the mass average molecular weight were measured using GPC under the following conditions.
- Measuring device Tosoh Corporation HLC-8120GPC, UV8020
- Measurement conditions Column temperature 40 ° C Solvent THF Flux 1.0ml / min Standard: Calibration curve prepared with polystyrene standard sample Sample: 0.1% by mass THF solution in terms of resin solids filtered through microfilter (injection amount: 200 ⁇ l)
- the acid value of the alcohol-modified polyamideimide resin (A2) of the present invention is preferably 70 to 210 KOHmg / g, and particularly preferably 90 to 190 KOHmg / g. When it is 70 to 210 KOHmg / g, it exhibits excellent performance as a cured material.
- polyamideimide resins (A2) of the present invention polyamideimide resins that are soluble in polar solvents that do not contain any of the nitrogen and sulfur atoms are preferred.
- examples of such polyamideimide resins include branched polyamideimide resins having a branched structure and an acid value of the resin of 60 KOHmg / g or more.
- Examples of components contained in the alcohol-modified polyamideimide resin (A2) used in the present invention include imide resins represented by the following (formula 7).
- Ra represents, for example, a residue of a divalent aliphatic diisocyanate.
- Rb represents, for example, the above structural formula (Formula 3) or (Formula 4).
- Rd is, for example, a trivalent organic group represented by the above (formula 6), and Rc ′ is, for example, a structure represented by the following structural formula (formula 8) Unit.
- R 2 is, for example, the same as described above.
- R 3 represents a residue obtained by removing a hydroxyl group from an alcohol compound.
- the curable resin composition of the present invention contains the alcohol-modified polyamideimide resin (A2) of the present invention, the curable resin (B) and / or the organic solvent (C).
- the curable resin (B) examples include an epoxy compound (B1) having two or more epoxy groups in the molecule, a compound having two or more maleimide groups in the molecule, a benzoxazine resin, and a cyanate ester resin. Is mentioned.
- 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.
- 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
- Examples of the epoxy resin (B1) include reaction of bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene and various phenols. Epoxidized products of various dicyclopentadiene-modified phenolic resins, 2,2 ′, 6,6′-tetramethylbiphenol epoxidized product, 4,4′-methylenebis (2,6-dimethylphenol) epoxidized product, Epoxy derived from naphthalene skeleton, such as naphthol, binaphthol or novolak modification of naphthol or binaphthol, aromatic epoxy resin such as epoxy resin obtained by epoxidizing phenol resin of fluorene skeleton, etc. It is.
- 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
- a cycloaliphatic epoxy resin such as an adduct, an epoxy resin containing a polyalkylene glycol chain in the main chain, such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and triglycidyl isocyanurate Heterocycle-containing epoxy resins can be used.
- 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.
- the epoxy resin (B1) component having two or more epoxy groups in the molecule is particularly preferably a cycloaliphatic epoxy resin. If it is a cycloaliphatic epoxy resin, a cured coating film having a high Tg and excellent thermal properties can be obtained, and a cured product having a high light transmittance in the ultraviolet region (around 300 nm) can be obtained.
- cycloaliphatic epoxy resins hydrogenated bisphenol A type epoxy resin, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like are preferable. .
- Such cycloaliphatic epoxy resins can be obtained on the market, and examples thereof include Denacol EX-252 (manufactured by Nagase ChemteX Corporation), EHPE3150, EHPE3150CE (manufactured by Daicel Chemical Industries, Ltd.), and the like.
- the alcohol-modified polyamideimide resin (A2) and the epoxy resin (B1) having two or more epoxy groups in the molecule can be freely blended according to various desired physical properties, such as Tg.
- the number of moles of carboxy groups (COOH) of the alcohol-modified polyamideimide resin (A2) and two or more epoxy groups in the molecule The epoxy resin (B1) having a ratio [n (EPOXY) / n (COOH)] to the number of moles of epoxy groups n (EPOXY) of the epoxy resin (B1) is 0.3 to 4, preferably 0.8 to 1.
- the blend of the alcohol-modified polyamideimide resin (A2) and the epoxy resin (B1) within the range of .2 makes it easy to obtain Tg as a property of the cured product, and a cured product having excellent mechanical properties and the like. Is preferred because the transparency of the further cured product is improved.
- the curable resin composition of the present invention may be mixed with an epoxy-carboxylic acid-based curing catalyst or the like.
- epoxy-carboxylic acid-based curing catalysts include primary to tertiary amines for promoting the reaction, quaternary ammonium salts, nitrogen compounds such as dicyandiamide and imidazole compounds, TPP (triphenylphosphine). ),
- TPP triphenylphosphine
- Known epoxy curing accelerators such as phosphine compounds such as alkyl-substituted trialkyl phonylphosphine and derivatives thereof, phosphophonium salts thereof, dialkylureas, carboxylic acids, phenols, or methylol group-containing compounds. Etc., and a small amount of these can be used in combination.
- maleimide compound (B2) examples 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 3-eth
- bismaleimide is particularly preferable because the cured product has good heat resistance, 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.
- a curing accelerator can be used as necessary.
- the curing accelerator that can be used here include amine compounds, phenol compounds, acid anhydrides, imidazoles, and organic metal salts.
- the curable resin composition of the present invention may further contain an organic solvent (C) as necessary.
- organic solvent (C) the same organic solvent as that used to prepare the alcohol-modified polyamideimide resin (A2) can be used.
- the curable resin composition of the present invention further comprises a photopolymerization initiator (D) and, if necessary, a reactive diluent (E) when curing by irradiating with energy rays, particularly ultraviolet rays.
- a 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 ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone, 2-aluminumanthraquinone, 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-tri
- 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 usually 0.1 to 30 masses per 100 mass parts of the alcohol-modified polyamideimide resin (A2). Part range, more preferably 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 reactive diluent (E) used in the present invention known and commonly used photopolymerizable vinyl monomers can be used. Typical examples include dimethylaminoethyl acrylate, diethylaminoethyl acrylate, ethylene glycol diacrylate, Diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, penta Erythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Polyhexaacrylate, acryloylmorpholine, vinylpyrrolidone, styrene, tris (2-acryloyloxyethyl) isocyanurate, alkyl (meth
- the alcohol-modified polyamideimide resin (A2) and the reactive diluent (E) can be freely blended in accordance with various desired physical properties, such as thermal properties such as Tg, mechanical properties, etc.
- the ratio [A2 / E] of the alcohol-modified polyamideimide resin (A2) to the photopolymerizable group of the reactive diluent (E) is 0.2 to Mixing the alcohol-modified polyamideimide resin (A2) and the reactive diluent (E) within a range of 5.0 makes it easy to obtain Tg as a property of the cured product, and a cured product having excellent mechanical properties and the like is obtained. Further, it is preferable because the transparency of the cured product is improved.
- Curing of the curable resin composition of the present invention is basically performed while appropriately selecting and adjusting the type and blending ratio of the alcohol-modified polyamideimide resin (A2), curable resin (B), other components, and curing conditions. be able to.
- 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.
- ultraviolet rays and electron beams can be used.
- 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.
- an apparatus having an irradiation source such as various electron beam accelerators can be used, and electrons having an energy of 100 to 1000 KeV are irradiated.
- the curing is carried out in the range of a curing temperature of 80 ° C. to 300 ° C., preferably in the range of 120 ° C. to 250 ° C. in the presence of a catalyst for starting thermal polymerization and additives.
- 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.
- the active energy ray and heat there is no limitation in using the active energy ray and heat in combination.
- curable resin composition of the present invention if necessary, other solvents than the above, various leveling agents, antifoaming agents, antioxidants, anti-aging agents, ultraviolet absorbers, anti-settling agents, rheology control agents
- Various known additives such as barium sulfate, silicon oxide, talc, clay, calcium carbonate, silica, colloidal silica, glass and the like, various metal powders, glass fibers, carbon fibers, fiber shapes such as Kevlar fibers, etc. You may mix
- blend polymers such as an acrylic resin, a cellulose resin, a polyvinyl resin, polyphenylene ether, and polyether sulfone, as needed.
- 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.
- 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.
- the phosphorus flame retardant either inorganic or organic can be used.
- 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
- a method of double coating with a resin may be used.
- general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, organic nitrogen-containing phosphorus compounds,
- 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.
- the polyamide-imide resin (A2) In 100 parts by mass of the curable resin composition containing all of the curable resin (B) and / or the organic solvent (C), the curing agent, the non-halogen flame retardant, and other fillers and additives, red phosphorus is not contained.
- a halogen-based flame retardant it is preferably blended in the range of 0.1 to 2.0 parts by mass.
- an organophosphorus compound is used, it is similarly blended in the range of 0.1 to 10.0 parts by mass.
- 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.
- nitrogen-based flame retardant examples include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazines, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.
- triazine compound examples include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenolic resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) and (iii) with paulownia oil, isomerized linseed oil
- the cyanuric acid compound examples include cyanuric acid and cyanuric acid melamine.
- the amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardant. In 100 parts by mass of curable resin composition (A2), curable resin (B) and / or organic solvent (C), curing agent, non-halogen flame retardant and other fillers and additives, etc. It is 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. Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.
- the silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.
- the amount of the silicone flame retardant is appropriately selected depending on the type of the silicone flame retardant, the other components of the curable resin composition, and the desired degree of flame retardant. In 100 parts by mass of curable resin composition (A2), curable resin (B) and / or organic solvent (C), curing agent, non-halogen flame retardant and other fillers and additives, etc. It is preferable to blend in the range of 0.05 to 20 parts by mass.
- 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.
- the metal carbonate compound examples include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.
- the metal powder examples 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.
- the low-melting-point glass include, for example, Shipley (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 system, P—Sn—O—F system, PbO—V 2 O 5 —TeO 2 system, Al 2 O 3 —H 2 O system, lead borosilicate system, 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.
- curable resin composition (A2) 100 parts by mass of curable resin composition (A2), curable resin (B) and / or organic solvent (C), curing agent, non-halogen flame retardant and other fillers and additives, etc. It is 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.
- 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.
- the curable resin composition of the present invention provides a cured coating film that is soluble in a general-purpose solvent and is excellent in heat resistance and light transmittance. For this reason, in particular, in the field where the transparency of the cured product is required, for example, the field for optical materials, solder resist materials for printed wiring boards, protective materials and insulating materials for household appliances such as refrigerators and rice cookers, liquid crystal displays, Protective materials used for liquid crystal display elements, organic and inorganic electroluminescence displays, organic and inorganic electroluminescence elements, LED displays, light emitting diodes, electronic paper, solar cells, through silicon electrodes (Through Silicon Via: TSV), optical fibers, optical waveguides, etc. It can be suitably used in fields such as insulating materials, adhesives and reflective materials, and display device fields such as liquid crystal alignment films and color filter protective films.
- the field where the transparency of the cured product is not required, for example, various heat-resistant coating materials, heat-resistant adhesives; sealing materials for electric and electronic parts, insulating varnishes, laminates, insulating powder coatings, semiconductor passivation Electrical insulating materials such as films and gate insulating films; Conductive materials such as conductive films and conductive adhesives; Adhesives for structural materials such as laminates for printed wiring boards, prepregs and honeycomb panels; glass fibers and carbon fibers , Fiber reinforced plastics using various reinforcing fibers such as aramid fibers and prepregs thereof; patterning materials such as resist inks; gaskets for non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries Can do.
- the curable resin composition of the present invention includes a white prepreg, a white laminate, and the white laminate because a cured coating film that is soluble in a general-purpose solvent and has excellent heat resistance and light transmittance is obtained. It can be suitably used for a chip LED. Details will be described below.
- the white prepreg of the present invention is characterized in that a mixture containing the curable resin composition of the present invention and a white pigment is impregnated or applied to a sheet-like glass fiber substrate and then dried. Specifically, the mixture containing the curable resin composition of the present invention and a white pigment is impregnated or applied to a sheet-like 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.
- the white prepreg and the production method thereof will be specifically described below.
- the white pigment examples include zinc oxide, calcium carbonate, titanium dioxide, alumina, and synthetic smectite.
- the white pigment is not particularly limited as long as it is a white inorganic powder, but is not limited to visible light reflectance, whiteness, or electricity. It is most preferable to use titanium dioxide from the viewpoint of characteristics.
- the crystal structure of titanium dioxide includes anatase type and rutile type.
- the anatase type has good reflectance in the visible light short wavelength region
- the rutile type has excellent long-term durability and discoloration resistance. Either may be sufficient as a white pigment added to the curable resin composition of this invention, and it does not specifically limit. It is of course possible to use a mixture of both.
- the content of the white pigment contained in the mixture is preferably in the range of 10 to 75% by mass in the 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 to the sheet-like glass fiber substrate is lowered or the adhesive strength to the metal foil is lowered. There will be no problems.
- the titanium dioxide When titanium dioxide is used as the white pigment, the titanium dioxide may be subjected to alumina or silica treatment as a surface treatment. Moreover, a silane coupling agent or titanate coupling agent treatment is also possible.
- the mixture impregnated into the sheet-like glass fiber base material may contain an inorganic filler such as silica, if necessary.
- the inorganic filler that can be contained include silica, aluminum hydroxide, magnesium hydroxide, E glass powder, magnesium oxide, potassium titanate, calcium silicate, clay, and talc. Two or more types may be used in combination.
- the blending amount is not particularly limited, but is preferably 50% by mass or less with respect to the mixture. If it is 50 mass% or less, there is almost no possibility that the impregnation property to a sheet-like glass fiber base material will fall or the adhesive strength with metal foil will generate
- Fluorescent agent can be blended in the mixture impregnated into the sheet-like glass fiber substrate, if necessary, in addition to the white pigment and the inorganic filler.
- the fluorescent agent is a compound that has the property of absorbing light energy such as light, radiation, and ultraviolet light and emitting it by changing to light of other wavelengths.
- diaminostilbene derivatives, anthracene, sodium salicylate , Diaminostilbene disulfonic acid derivatives, imidazole derivatives, coumarin derivatives, pyrazoline derivatives, decalylamine derivatives, and the like are examples of organic substances.
- the fluorescent agent preferably has a radiation wavelength in the visible light short wavelength region (380 to 470 nm) in which the reflectance is remarkably lowered.
- the fluorescent agent is generally called a fluorescent whitening agent.
- Diaminostilbene disulfonic acid derivatives, imidazole derivatives, coumarin derivatives, pyrazoline derivatives and the like are suitable.
- the addition amount is not limited, but in the case of a pyrazoline derivative, the effect is exhibited from the addition of about 0.1% by mass with respect to the mixture, and the effect is increased as the addition amount is increased. Further, it is desirable that the optical brightener to be added is soluble in a solvent.
- the sheet-like glass fiber substrate used for the white prepreg of the present invention may be either a glass cloth or a nonwoven fabric, and a glass cloth and a nonwoven fabric may be used in combination.
- a plain weave structure is basically used, but a woven structure such as Nanako weave, satin weave or twill weave may be used, and is not particularly limited.
- a woven structure such as Nanako weave, satin weave or twill weave may be used, and is not particularly limited.
- the thickness of the glass cloth is not particularly limited, but is preferably in the range of 0.02 to 0.3 mm because it is easy to handle.
- the sheet-like glass fiber base material may be subjected to a surface treatment with a silane coupling agent or the like. Furthermore, the sheet-like glass fiber base material itself may be colored white.
- a solvent such as methyl ethyl ketone is added to the mixture described above to prepare a resin varnish, impregnated into a sheet-like glass fiber substrate made of glass cloth or the like, and dried to produce a white prepreg.
- the method for impregnating and drying the resin varnish on the sheet glass fiber substrate is not particularly limited. For example, after impregnating the resin varnish by immersing the sheet glass fiber substrate in the resin varnish, 100 ° C. to A method of removing the solvent and semi-curing the curable resin by heating at a temperature of about 200 ° C. for 1 to 60 minutes can be employed.
- the impregnation amount of the curable resin composition of the white prepreg produced by impregnating and drying the sheet-like glass fiber substrate is not particularly limited, but is preferably in the range of 30 to 60% by mass.
- drying conditions for the prepreg for example, it is preferable to previously measure the gel time of the resin varnish with a gel time tester (manufactured by Yasuda Seiki Seisakusho).
- the gel time measurement conditions the gel time at 160 ° C. (curing time: the time required for the rotor torque to reach about 3.3 kg ⁇ cm) is measured by the above-mentioned apparatus, and the gel time of the varnish resin is 5 minutes or more.
- the range of ⁇ 15 minutes is preferable, and the gel time is more preferably 5 minutes to less than 10 minutes. If the gel time of the resin varnish is short, the semi-cured state cannot be maintained, and it becomes difficult to produce a uniform prepreg. Further, when the half-curing cannot be maintained and the curing is reached, it becomes difficult to bond with a metal foil described later. Therefore, it is preferable to semi-cure under conditions suitable for the process by varnish gel time measurement.
- a combination of the obtained white prepreg and copper foil or aluminum foil is heated and pressed to produce a white laminate.
- the number of white prepregs to be overlaid is not particularly limited, but as a single-layer substrate, one or two to ten white prepregs are stacked. In general, the foils are laminated.
- the multilayer substrate is manufactured by laminating a plurality of the single-layer substrates, but there is no particular limitation on the number of the stacked substrates.
- the metal foil copper foil, aluminum foil or the like is used as the metal foil. Further, the thickness of the metal foil is generally 1 ⁇ m to 105 ⁇ m, and particularly preferably in the range of 1.5 ⁇ m to 35 ⁇ m.
- the white laminates and metal foil-clad white laminates obtained in this way have high reflectivity in the visible light region, remarkably little discoloration due to heating and ultraviolet rays, and high heat resistance and excellent thickness accuracy. It becomes the white laminated board for wiring boards, and a metal foil clad white laminated board.
- the lamination molding conditions for the metal foil-clad laminate the usual method for laminates for printed wiring boards can be applied. For example, a multistage press, a multistage vacuum press, a continuous molding, an autoclave molding machine, etc.
- a temperature 100- A range of 300 ° C.
- pressure 2 to 100 kgf / cm 2
- heating time range of 0.1 to 5 hours is general, but in terms of uniform insulation layer thickness, removal of bubbles, etc., lamination molding is It is preferable to carry out under a vacuum of 70 mmHg or less.
- a conductive pattern is formed on the obtained white laminate by an additive method to obtain a printed wiring board.
- a circuit pattern is printed on the metal foil of the obtained metal foil-clad white laminate and etched to obtain a printed wiring board.
- solder is applied on the printed wiring board, and the chip LED is placed on the printed wiring board, and then the chip LED is melted by passing it through reflow or the like. Is fixed to the printed circuit board.
- chip LEDs By integrating chip LEDs with high density, it can be used as a surface light source, and such a surface light source is suitably used for a backlight for a liquid crystal display that is particularly required to be thin.
- it is applied to induction display illumination lamps, evacuation exit illumination lamps, advertisement lights, etc. as surface emitting illumination devices.
- the thickness accuracy of the chip LED mounting substrate is extremely important when the elements mounted on the substrate are sealed by transfer molding.
- transfer molding refers to a method of press-fitting a resin into a clamped mold.
- the thickness of the substrate used for the chip LED is generally 0.06 mm to 1.0 mm.
- the required accuracy of the substrate thickness in such transfer molding is, for example, a tolerance of ⁇ 0.05 mm or less (range is 0.1 mm), preferably a tolerance of ⁇ 0.03 mm or less for a substrate having a thickness of 1.0 mm. (The range is 0.06 mm). Therefore, if there is a substrate with high thickness accuracy, the defect rate can be greatly reduced in the manufacturing process of the chip LED, which is extremely significant in the industry.
- the curable resin composition of the present invention is used as a patterning material
- the curable resin composition of the present invention is applied onto a substrate, the solvent is dried, and then energy is passed through a mask having a pattern.
- a pattern can be formed by irradiating a line and developing with an alkaline aqueous solution or a solvent. Furthermore, a stronger pattern can be formed by heat treatment at 80 ° C. or higher. Details will be described below.
- a photosensitive film comprising a support and a photosensitive resin composition layer made of the curable resin composition of the present invention formed on the support is produced.
- the photosensitive resin composition layer is formed by dissolving the curable resin composition of the present invention in a solvent or mixed solvent to obtain a solution having a solid content of about 30 to 70% by mass, and then applying the solution onto a support. It is preferable to do.
- the thickness of the photosensitive resin composition layer varies depending on the use, but it is preferably 10 to 100 ⁇ m, more preferably 20 to 60 ⁇ m, after drying after removing the solvent by heating and / or hot air blowing. . If the thickness is less than 10 ⁇ m, there is a tendency that it is difficult to apply industrially, and if it exceeds 100 ⁇ m, the above-described effects produced by the present invention tend to be reduced, and in particular, physical properties and resolution tend to be reduced.
- the support provided in the photosensitive film examples include polyesters such as polyethylene terephthalate, polymer films having heat resistance and solvent resistance such as polypropylene and polyethylene.
- the thickness of the support is preferably 5 to 100 ⁇ m, and more preferably 10 to 30 ⁇ m. If the thickness is less than 5 ⁇ m, the support tends to be broken when the support is peeled off before development, and if it exceeds 100 ⁇ m, the resolution and flexibility tend to decrease.
- the photosensitive film consisting of two layers of the support and the photosensitive resin composition layer as described above or the photosensitive film consisting of three layers of the support, the photosensitive resin composition layer, and the protective film, for example, is stored as it is. Alternatively, the protective film may be interposed and wound around the core in a roll shape and stored.
- the method for forming a resist pattern when the curable resin composition of the present invention is used as a photosensitive resin composition or a photosensitive film is firstly applied to a known screen printing or roll coater, or protection, respectively.
- the film is laminated on the substrate on which the resist is formed.
- a removal step of removing the support film from the photosensitive film described above is performed, or actinic rays are passed through the mask pattern without removing the support film to a predetermined portion of the photosensitive resin composition layer. Irradiation is performed to perform an exposure process for photocuring the photosensitive resin composition layer of the irradiated portion.
- the photosensitive resin composition layer other than the irradiated part is removed by the next development step after removing the support film.
- substrate which forms a resist points out a printed wiring board, a board
- a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, or a xenon lamp is used.
- a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, or a xenon lamp is used.
- what emits visible light effectively such as a photographic flood light bulb and a solar lamp, is also used.
- direct drawing direct laser exposure may be used.
- An excellent pattern can be formed by using a photopolymerization initiator (D) corresponding to each laser light source and exposure method.
- an alkaline developer such as a dilute solution of sodium carbonate (1 to 5% by mass aqueous solution) at 20 to 50 ° C. is used as the developer, and known spraying, rocking immersion, brushing, scraping, etc. Develop by the method of.
- the irradiation amount can be adjusted as necessary.
- irradiation can be performed at an irradiation amount of about 0.2 to 10 J / cm 2 .
- the resist pattern is heated, it is preferably performed in the range of about 100 to 170 ° C. for about 15 to 90 minutes.
- ultraviolet irradiation and heating can be performed at the same time, and after either one is performed, the other can be performed. When ultraviolet irradiation and heating are performed simultaneously, heating to 60 to 150 ° C. is more preferable from the viewpoint of effectively imparting solder heat resistance, chemical resistance, and the like.
- This photosensitive resin composition layer also serves as a protective film for wiring after soldering to the substrate, and has excellent crack resistance, HAST resistance, and gold plating properties, so for printed wiring boards and semiconductor package substrates It is useful as a solder resist for flexible wiring boards.
- the substrate provided with the resist pattern in this manner is then mounted with a semiconductor element or the like (for example, wire bonding, solder connection), and then mounted on an electronic device such as a personal computer.
- a semiconductor element or the like for example, wire bonding, solder connection
- Example 1 [Preparation of polyamideimide resin (A1-1)]
- PGMAc propylene glycol monomethyl ether acetate
- 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 characteristic absorption was measured in the infrared spectrum, and the characteristic absorption of the isocyanate group, 2270 cm ⁇ 1 , completely disappeared, and the absorption of the imide group was confirmed at 1780 cm ⁇ 1 and 1720 cm ⁇ 1 .
- the acid value was 190 KOHmg / g in terms of solid content.
- This resin solution is abbreviated as an imide resin (A1-1) solution.
- PGMAc propylene glycol monomethyl ether acetate
- Characteristic absorption was measured in the infrared spectrum, and after confirming that 2270 cm ⁇ 1, which is the characteristic absorption of the isocyanate group, was completely extinguished, 35.1 g (0.05 mol) of IPDI3N was further added to continue the reaction. . Characteristic absorption was measured in the infrared spectrum, and after confirming that 2270 cm ⁇ 1, which is the characteristic absorption of the isocyanate group, was completely extinguished, 35.1 g (0.05 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 , disappeared completely, and the absorption of the imide group was confirmed at 1780 cm ⁇ 1 and 1720 cm ⁇ 1 .
- the acid value was 196 KOH mg / g in terms of solid content.
- This resin solution is abbreviated as an imide resin (A2-1) solution.
- PGMAc propylene glycol monomethyl ether acetate
- the characteristic absorption was measured in the infrared spectrum, and the characteristic absorption of the isocyanate group, 2270 cm ⁇ 1 , completely disappeared, 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 (A3-1) solution.
- PGMAc propylene glycol monomethyl ether acetate
- the characteristic absorption was measured in the infrared spectrum, and the characteristic absorption of the isocyanate group, 2270 cm ⁇ 1 , completely disappeared, and the absorption of the imide group was confirmed at 1780 cm ⁇ 1 and 1720 cm ⁇ 1 .
- the acid value was 190 KOHmg / g in terms of solid content.
- This resin solution is abbreviated as an imide resin (A4-1) solution.
- curable resin compositions 1 to 6 were produced under the blending conditions shown in Table 1.
- Footnote EHPE3150 in Table 1 Cycloaliphatic epoxy resin manufactured by Daicel Chemical Industries, Ltd. (1,2-epoxy-4- (2-oxiranyl) cyclohexane of 2,2-bis (hydroxymethyl) -1-butanol Adduct). Epoxy equivalent is 177. The resin content is 100% by mass.
- the resin was coated on a glass substrate so as to have a film thickness of 17 ⁇ m after drying.
- the coated plate was dried with a dryer at 90 ° C. for 15 minutes to obtain a coating film.
- the coated plate was immersed in a 1% Na 2 CO 3 aqueous solution at 25 ° C., and the time until the coating film disappeared was measured. It is shown in Table 3.
Abstract
Description
工程(1)で得られたポリアミドイミド樹脂(A1)に、さらにアルコール化合物(a3)を加えて反応させることによりアルコール変性ポリアミドイミド樹脂(A2)を生成する工程(2)、を有するアルコール変性ポリアミドイミド樹脂の製造方法であって、
前記工程(1)は、トリカルボン酸無水物(a1)に対して、前記イソシアヌレート型ポリイソシアネート(a2)を少なくとも2回に分けて加えることにより、前記イソシアヌレート型ポリイソシアネート(a2)とトリカルボン酸無水物(a1)とを反応させた後、得られた反応物に、さらに、前記イソシアヌレート型ポリイソシアネート(a2)を反応させる工程(1a)を含むことを特徴とするアルコール変性ポリアミドイミド樹脂の製造方法に関する。 That is, the present invention is a process for producing a polyamideimide resin (A1) by reacting a tricarboxylic acid anhydride (a1) with an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure ( 1),
Alcohol-modified polyamide having a step (2) of producing an alcohol-modified polyamideimide resin (A2) by further adding an alcohol compound (a3) to the polyamideimide resin (A1) obtained in the step (1) and reacting with the polyamide-imide resin (A1) A method for producing an imide resin,
In the step (1), the isocyanurate type polyisocyanate (a2) and the tricarboxylic acid are added to the tricarboxylic acid anhydride (a1) by adding the isocyanurate type polyisocyanate (a2) at least twice. An alcohol-modified polyamideimide resin characterized by comprising a step (1a) of reacting the isocyanurate type polyisocyanate (a2) with the obtained reactant after reacting with the anhydride (a1). It relates to a manufacturing method.
工程(1)で得られたポリアミドイミド樹脂(A1)に、さらにアルコール化合物(a3)を反応させることによりアルコール変性ポリアミドイミド樹脂(A2)を生成する工程(2)を有し、
前記工程(1)は、トリカルボン酸無水物(a1)に対して、前記イソシアヌレート型ポリイソシアネート(a2)を少なくとも2回に分けて加えることにより、トリカルボン酸無水物(a1)と、前記イソシアヌレート型ポリイソシアネート(a2)とを反応させた後、得られた生成物に、さらに前記イソシアヌレート型ポリイソシアネート(a2)を反応させる工程(1a)を含むことを特徴とする。 The method for producing the alcohol-modified polyamideimide resin (A2) of the present invention is obtained by reacting a tricarboxylic anhydride (a1) with an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure. Step (1) for producing an imide resin (A1),
The step (2) of producing an alcohol-modified polyamideimide resin (A2) by further reacting the alcohol compound (a3) with the polyamideimide resin (A1) obtained in the step (1),
In the step (1), the isocyanurate type polyisocyanate (a2) is added to the tricarboxylic acid anhydride (a1) in at least two portions, whereby the tricarboxylic acid anhydride (a1) and the isocyanurate are added. After reacting with the polyisocyanate type (a2), the product obtained further comprises a step (1a) of reacting the isocyanurate type polyisocyanate (a2).
(1)ポリアミドイミド樹脂(A1)を、溶剤等で希釈し、KOH水溶液の滴定により酸価(a)を求める。
(2)ポリアミドイミド樹脂(A1)を溶剤等で希釈し、酸無水物基に過剰量のn-ブタノールを反応させた後、KOH水溶液の滴定により酸価(b)を求める。なお、(2)において、酸無水物基とn-ブタノールの反応は、117℃にて行うものとする。酸無水物の消失は赤外スペクトルにて、酸無水物基の特性吸収である1860cm-1が完全に消滅したことで確認する。
(3)上記酸価(a)と酸価(b)の差より、本発明のポリアミドイミド樹脂(A1)中の酸無水物基の濃度を算出し、モル数(M3)に換算する。 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, an excess amount of n-butanol is reacted with the acid anhydride group, and then the acid value (b) is obtained 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).
測定装置:東ソー株式会社製 HLC-8120GPC、UV8020
カラム :東ソー株式会社製 TFKguardcolumnhxl-L、TFKgel(G1000HXL、G2000HXL、G3000HXL、G4000HXL)
検出器 :RI(示差屈折計)及びUV(254nm)
測定条件:カラム温度 40℃
溶媒 THF
流束 1.0ml/min
標準 :ポリスチレン標準試料にて検量線作成
試料 :樹脂固形分換算で0.1質量%のTHF溶液をマイクロフィルターでろ過したもの(注入量:200μl) In the present invention, the number average molecular weight and the mass average molecular weight were measured using GPC under the following conditions.
Measuring device: Tosoh Corporation HLC-8120GPC, UV8020
Column: TFKguardcolumnhxl-L, TFKgel (G1000HXL, G2000HXL, G3000HXL, G4000HXL) manufactured by Tosoh Corporation
Detector: RI (differential refractometer) and UV (254 nm)
Measurement conditions: Column temperature 40 ° C
Solvent THF
Flux 1.0ml / min
Standard: Calibration curve prepared with polystyrene standard sample Sample: 0.1% by mass THF solution in terms of resin solids filtered through microfilter (injection amount: 200 μl)
もちろん、活性エネルギー線と熱とを併用して硬化させることについてもその使用にあたっては、何ら限定がない。 In the case of curing with heat, the curing is carried out in the range of a curing temperature of 80 ° C. to 300 ° C., preferably in the range of 120 ° C. to 250 ° C. in the presence of a catalyst for starting thermal polymerization and additives. 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.
本発明の白色プリプレグは、本発明の硬化性樹脂組成物と白色顔料を含む混合物を、シート状ガラス繊維基材に含浸または塗布させた後、乾燥させてなることを特徴とする。具体的には、本発明の硬化性樹脂組成物と白色顔料を含む混合物を、シート状ガラス繊維基材に含浸または塗布させた後、100~200℃の範囲の乾燥機中で1~60分間の範囲にて半硬化させることを特徴とする。以下に白色プリプレグ、その製造方法を具体的に説明する。 The curable resin composition of the present invention includes a white prepreg, a white laminate, and the white laminate because a cured coating film that is soluble in a general-purpose solvent and has excellent heat resistance and light transmittance is obtained. It can be suitably used for a chip LED. Details will be described below.
The white prepreg of the present invention is characterized in that a mixture containing the curable resin composition of the present invention and a white pigment is impregnated or applied to a sheet-like glass fiber substrate and then dried. Specifically, the mixture containing the curable resin composition of the present invention and a white pigment is impregnated or applied to a sheet-like 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. The white prepreg and the production method thereof will be specifically described below.
〔ポリアミドイミド樹脂(A1-1)の調製〕
撹拌装置、温度計、コンデンサーを付けたフラスコにPGMAc(プロピレングリコールモノメチルエーテルアセテート)1102.8g、IPDI3N(イソホロンジイソシアネートから合成されたイソシアヌレート型トリイソシアネート:NCO%=17.2)197.6g(0.27mol)及びシクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物506.9g(2.56mol)を加え、140℃まで2時間掛けて昇温した。反応は、発泡とともに進行した。この温度で2時間反応させた。系内は淡黄色の液体となり、赤外スペクトルにて特性吸収を測定した結果、イソシアネート基の特性吸収である2270cm-1が完全に消滅したことが確認された。更に、IPDI3Nを197.6g(0.27mol)加え、反応を継続させた。赤外スペクトルにて特性吸収を測定し、イソシアネート基の特性吸収である2270cm-1が完全に消滅したことを確認した後、更にIPDI3Nを197.6g(0.27mol)加え、反応を継続させた。赤外スペクトルにて特性吸収を測定し、イソシアネート基の特性吸収である2270cm-1が完全に消滅し、1780cm-1、1720cm-1にイミド基の吸収が確認された。酸価は、固形分換算で190KOHmg/gであった。この樹脂の溶液をイミド樹脂(A1-1)の溶液と略記する。 Example 1
[Preparation of polyamideimide resin (A1-1)]
In a flask equipped with a stirrer, a thermometer and a condenser, 1102.8 g of PGMAc (propylene glycol monomethyl ether acetate), IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 197.6 g (0 .27 mol) and 506.9 g (2.56 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added and heated to 140 ° C. over 2 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 2 hours. The inside of the system became a pale yellow liquid, and the characteristic absorption was measured by infrared spectrum. As a result, 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, and the reaction was continued. . The characteristic absorption was measured in the infrared spectrum, and the characteristic absorption of the isocyanate group, 2270 cm −1 , completely disappeared, and the absorption of the imide group was confirmed at 1780 cm −1 and 1720 cm −1 . The acid value was 190 KOHmg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A1-1) solution.
続いて、得られたイミド樹脂(A1-1)の溶液にn-ブタノール99.8g(1.35mol)を加え、120℃にて2時間反応させた。赤外スペクトルにて特性吸収を測定した結果、酸無水物基の特性吸収である1860cm-1の吸収が完全に消失した。酸価は、固形分換算で、162KOHmg/gで、分子量はポリスチレン換算で数平均分子量1180、質量平均分子量2054、分散度は1.74であった。この樹脂の溶液をアルコール変性ポリアミドイミド樹脂(A1-2)と略記する。 [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, disappeared completely. 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 (A1-2).
〔ポリアミドイミド樹脂(A2-1)の調製〕
撹拌装置、温度計、コンデンサーを付けたフラスコにPGMAc(プロピレングリコールモノメチルエーテルアセテート)331.9g、IPDI3N(イソホロンジイソシアネートから合成されたイソシアヌレート型トリイソシアネート:NCO%=17.2)35.1g(0.05mol)及びシクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物150.3g(0.76mol)を加え、140℃まで2時間掛けて昇温した。反応は、発泡とともに進行した。この温度で2時間反応させた。系内は淡黄色の液体となり、赤外スペクトルにて特性吸収を測定した結果、イソシアネート基の特性吸収である2270cm-1が完全に消滅したことが確認された。更に、IPDI3Nを35.1g(0.05mol)加え、反応を継続させた。赤外スペクトルにて特性吸収を測定し、イソシアネート基の特性吸収である2270cm-1が完全に消滅したことを確認した後、更にIPDI3Nを35.1g(0.05mol)加え、反応を継続させた。赤外スペクトルにて特性吸収を測定し、イソシアネート基の特性吸収である2270cm-1が完全に消滅したことを確認した後、更にIPDI3Nを35.1g(0.05mol)加え、反応を継続させた。赤外スペクトルにて特性吸収を測定し、イソシアネート基の特性吸収である2270cm-1が完全に消滅したことを確認した後、更にIPDI3Nを35.1g(0.05mol)加え、反応を継続させた。赤外スペクトルで特性吸収を測定し、イソシアネート基の特性吸収である2270cm-1が完全に消滅し、1780cm-1、1720cm-1にイミド基の吸収が確認された。酸価は、固形分換算で196KOHmg/gであった。この樹脂の溶液をイミド樹脂(A2-1)の溶液と略記する。 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 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 the characteristic absorption was measured by infrared spectrum. As a result, 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. Characteristic absorption was measured in the infrared spectrum, and after confirming that 2270 cm −1, which is the characteristic absorption of the isocyanate group, was completely extinguished, 35.1 g (0.05 mol) of IPDI3N was further added to continue the reaction. . Characteristic absorption was measured in the infrared spectrum, and after confirming that 2270 cm −1, which is the characteristic absorption of the isocyanate group, was completely extinguished, 35.1 g (0.05 mol) of IPDI3N was further added to continue the reaction. . Characteristic absorption was measured in the infrared spectrum, and after confirming that 2270 cm −1, which is the characteristic absorption of the isocyanate group, was completely extinguished, 35.1 g (0.05 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 , disappeared completely, and the absorption of the imide group was confirmed at 1780 cm −1 and 1720 cm −1 . The acid value was 196 KOH mg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A2-1) solution.
続いて、得られたイミド樹脂(A2-1)の溶液にn-ブタノール29.4g(0.40mol)を加え、120℃にて2時間反応させた。赤外スペクトルにて特性吸収を測定した結果、酸無水物基の特性吸収である1860cm-1の吸収が完全に消失した。酸価は、固形分換算で、161KOHmg/gで、分子量はポリスチレン換算で数平均分子量990、質量平均分子量1822、分散度は1.84であった。この樹脂の溶液をアルコール変性ポリアミドイミド樹脂(A1-2)と略記する。 [Production of alcohol-modified polyamideimide resin (A2-2)]
Subsequently, 29.4 g (0.40 mol) of n-butanol was added to the resulting solution of the 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, disappeared completely. The acid value was 161 KOHmg / g in terms of solid content, the molecular weight was number average molecular weight 990, mass average molecular weight 1822 in terms of polystyrene, and the degree of dispersion was 1.84. This resin solution is abbreviated as alcohol-modified polyamideimide resin (A1-2).
〔ポリアミドイミド樹脂(A3-1)の調製〕
撹拌装置、温度計、コンデンサーを付けたフラスコにPGMAc(プロピレングリコールモノメチルエーテルアセテート)331.9g、IPDI3N(イソホロンジイソシアネートから合成されたイソシアヌレート型トリイソシアネート:NCO%=17.2)87.8g(0.12mol)及びシクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物150.3g(0.76mol)を加え、140℃まで2時間掛けて昇温した。反応は、発泡とともに進行した。この温度で2時間反応させた。系内は淡黄色の液体となり、赤外スペクトルにて特性吸収を測定した結果、イソシアネート基の特性吸収である2270cm-1が完全に消滅したことが確認された。更に、IPDI3Nを58.6g(0.08mol)加え、反応を継続させた。赤外スペクトルにて特性吸収を測定し、イソシアネート基の特性吸収である2270cm-1が完全に消滅したことを確認した後、更にIPDI3Nを29.3g(0.04mol)加え、反応を継続させた。赤外スペクトルにて特性吸収を測定し、イソシアネート基の特性吸収である2270cm-1が完全に消滅し、1780cm-1、1720cm-1にイミド基の吸収が確認された。酸価は、固形分換算で185KOHmg/gであった。この樹脂の溶液をイミド樹脂(A3-1)の溶液と略記する。 Example 3
[Preparation of polyamideimide resin (A3-1)]
In a flask equipped with a stirrer, a thermometer, and a condenser, 331.9 g of PGMAc (propylene glycol monomethyl ether acetate), IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 87.8 g (0 .12 mol) and 150.3 g (0.76 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 2 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 2 hours. The inside of the system became a pale yellow liquid, and the characteristic absorption was measured by infrared spectrum. As a result, 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. . The characteristic absorption was measured in the infrared spectrum, and the characteristic absorption of the isocyanate group, 2270 cm −1 , completely disappeared, 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 (A3-1) solution.
続いて、得られたイミド樹脂(A3-1)の溶液にn-ブタノール29.4g(0.40mol)を加え、120℃にて2時間反応させた。赤外スペクトルにて特性吸収を測定した結果、酸無水物基の特性吸収である1860cm-1の吸収が完全に消失した。酸価は、固形分換算で、157KOHmg/gで、分子量はポリスチレン換算で数平均分子量1007、質量平均分子量1762、分散度は1.75であった。この樹脂の溶液をアルコール変性ポリアミドイミド樹脂(A3-2)と略記する。 [Production of alcohol-modified polyamideimide resin (A3-2)]
Subsequently, 29.4 g (0.40 mol) of n-butanol was added to the resulting solution of the 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, disappeared completely. The acid value in terms of solid content was 157 KOH mg / g, the molecular weight in terms of polystyrene was a number average molecular weight of 1007, a mass average molecular weight of 1762, and the degree of dispersion was 1.75. This resin solution is abbreviated as alcohol-modified polyamideimide resin (A3-2).
〔ポリアミドイミド樹脂(A4-1)の調製〕
撹拌装置、温度計、コンデンサーを付けたフラスコにPGMAc(プロピレングリコールモノメチルエーテルアセテート)331.9g、IPDI3N(イソホロンジイソシアネートから合成されたイソシアヌレート型トリイソシアネート:NCO%=17.2)29.3g(0.04mol)及びシクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物150.3g(0.76mol)を加え、140℃まで2時間掛けて昇温した。反応は、発泡とともに進行した。この温度で2時間反応させた。系内は淡黄色の液体となり、赤外スペクトルにて特性吸収を測定した結果、イソシアネート基の特性吸収である2270cm-1が完全に消滅したことが確認された。更に、IPDI3Nを58.6g(0.08mol)加え、反応を継続させた。赤外スペクトルにて特性吸収を測定し、イソシアネート基の特性吸収である2270cm-1が完全に消滅したことを確認した後、更にIPDI3Nを87.8g(0.12mol)加え、反応を継続させた。赤外スペクトルにて特性吸収を測定し、イソシアネート基の特性吸収である2270cm-1が完全に消滅し、1780cm-1、1720cm-1にイミド基の吸収が確認された。酸価は、固形分換算で190KOHmg/gであった。この樹脂の溶液をイミド樹脂(A4-1)の溶液と略記する。 Example 4
[Preparation of polyamideimide resin (A4-1)]
331.9 g of PGMAc (propylene glycol monomethyl ether acetate) and IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 29.3 g (0 0.04 mol) and 150.3 g (0.76 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 2 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 2 hours. The inside of the system became a pale yellow liquid, and the characteristic absorption was measured by infrared spectrum. As a result, 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. Measuring the characteristic absorption at the infrared spectrum, after 2270 cm -1 which is the characteristic absorption of an isocyanate group was confirmed that completely disappeared, was further IPDI3N the 87.8 g (0.12 mol) was added, and the reaction continued . The characteristic absorption was measured in the infrared spectrum, and the characteristic absorption of the isocyanate group, 2270 cm −1 , completely disappeared, and the absorption of the imide group was confirmed at 1780 cm −1 and 1720 cm −1 . The acid value was 190 KOHmg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A4-1) solution.
続いて、得られたイミド樹脂(A4-1)の溶液にn-ブタノール29.4g(0.40mol)を加え、120℃にて2時間反応させた。赤外スペクトルにて特性吸収を測定した結果、酸無水物基の特性吸収である1860cm-1の吸収が完全に消失した。酸価は、固形分換算で、161KOHmg/gで、分子量はポリスチレン換算で数平均分子量1022、質量平均分子量1931、分散度は1.89であった。この樹脂の溶液をアルコール変性ポリアミドイミド樹脂(A4-2)と略記する。 [Production of alcohol-modified polyamideimide resin (A4-2)]
Subsequently, 29.4 g (0.40 mol) of n-butanol was added to the resulting solution of the 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, disappeared completely. The acid value in terms of solid content was 161 KOH mg / g, the molecular weight in terms of polystyrene was a number average molecular weight 1022, a mass average molecular weight 1931, and the degree of dispersion was 1.89. This resin solution is abbreviated as alcohol-modified polyamideimide resin (A4-2).
撹拌装置、温度計、コンデンサーを付けたフラスコにPGMAc(プロピレングリコールモノメチルエーテルアセテート)276.4g、IPDI3N(イソホロンジイソシアネートから合成されたイソシアヌレート型トリイソシアネート:NCO%=17.2)146.4g(0.20mol)及びシクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物125.1g(0.63mol)を加え、140℃まで2時間掛けて昇温した。反応は、発泡とともに進行した。この温度で4時間反応させた。系内は淡黄色の液体となり、赤外スペクトルにて特性吸収を測定した結果、イソシアネート基の特性吸収である2270cm-1が完全に消滅し、1780cm-1、1720cm-1にイミド基の吸収が確認された。酸価は、固形分換算で212KOHmg/gであった。この樹脂の溶液をイミド樹脂(A5-1)の溶液と略記する。 Comparative Example 1 [Preparation of polyamideimide resin (A5-1)]
In a flask equipped with a stirrer, a thermometer and a condenser, 276.4 g of PGMAc (propylene glycol monomethyl ether acetate), IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 146.4 g (0 .20 mol) and 125.1 g (0.63 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 2 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 4 hours. As a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm −1, which is the characteristic absorption of the isocyanate group, disappeared completely, and imide group absorption was observed at 1780 cm −1 and 1720 cm −1. confirmed. The acid value was 212 KOHmg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A5-1) solution.
続いて、得られたイミド樹脂(A5-1)の溶液にn-ブタノール24.5g(0.33mol)を加え、120℃にて2時間反応させた。赤外スペクトルにて特性吸収を測定した結果、酸無水物基の特性吸収である1860cm-1の吸収が完全に消失した。酸価は、固形分換算で、162KOHmg/gで、分子量はポリスチレン換算で数平均分子量1289、質量平均分子量3152、分散度は2.45であった。この樹脂の溶液をアルコール変性ポリアミドイミド樹脂(A5-2)と略記する。 [Production of alcohol-modified polyamideimide resin (A5-2)]
Subsequently, 24.5 g (0.33 mol) of n-butanol was added to the resulting solution of the imide resin (A5-1) and reacted at 120 ° C. for 2 hours. As a result of measuring the characteristic absorption in the infrared spectrum, the absorption at 1860 cm −1 which is the characteristic absorption of the acid anhydride group completely disappeared. The acid value in terms of solid content was 162 KOH mg / g, the molecular weight in terms of polystyrene was a number average molecular weight 1289, a mass average molecular weight 3152, and the degree of dispersion was 2.45. This resin solution is abbreviated as alcohol-modified polyamideimide resin (A5-2).
撹拌装置、温度計、コンデンサーを付けたフラスコにPGMAc(プロピレングリコールモノメチルエーテルアセテート)276.4g、IPDI3N(イソホロンジイソシアネートから合成されたイソシアヌレート型トリイソシアネート:NCO%=17.2)146.4g(0.20mol)及びシクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物125.1g(0.63mol)を加え、140℃まで4時間掛けて昇温した。反応は、発泡とともに進行した。この温度で4時間反応させた。系内は淡黄色の液体となり、赤外スペクトルにて特性吸収を測定した結果、イソシアネート基の特性吸収である2270cm-1が完全に消滅し、1780cm-1 、1720cm-1にイミド基の吸収が確認された。酸価は、固形分換算で184KOHmg/gであった。この樹脂の溶液をイミド樹脂(A6-1)の溶液と略記する。 Comparative Example 2 [Preparation of polyamideimide resin (A6-1)]
In a flask equipped with a stirrer, a thermometer and a condenser, 276.4 g of PGMAc (propylene glycol monomethyl ether acetate), IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 146.4 g (0 .20 mol) and 125.1 g (0.63 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. over 4 hours. The reaction proceeded with foaming. The reaction was carried out at this temperature for 4 hours. As a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm −1, which is the characteristic absorption of the isocyanate group, disappeared completely, and imide group absorption was observed at 1780 cm −1 and 1720 cm −1. confirmed. The acid value was 184 KOH mg / g in terms of solid content. This resin solution is abbreviated as an imide resin (A6-1) solution.
続いて、得られたイミド樹脂(A6-1)の溶液にn-ブタノール24.5g(0.33mol)を加え、120℃にて2時間反応させた。赤外スペクトルにて特性吸収を測定した結果、酸無水物基の特性吸収である1860cm-1の吸収が完全に消失した。酸価は、固形分換算で、163KOHmg/gで、分子量はポリスチレン換算で数平均分子量1216、質量平均分子量2528、分散度は2.08であった。この樹脂の溶液をアルコール変性ポリアミドイミド樹脂(A6-2)と略記する。 [Production of alcohol-modified polyamideimide resin (A6-2)]
Subsequently, 24.5 g (0.33 mol) of n-butanol was added to the resulting solution of the imide resin (A6-1) and reacted at 120 ° C. for 2 hours. As a result of measuring the characteristic absorption in the infrared spectrum, the absorption at 1860 cm −1 which is the characteristic absorption of the acid anhydride group completely disappeared. The acid value was 163 KOH mg / g in terms of solid content, the molecular weight was number average molecular weight 1216, mass average molecular weight 2528, and dispersity was 2.08 in terms of polystyrene. This resin solution is abbreviated as alcohol-modified polyamideimide resin (A6-2).
上記で得られたアルコール変性ポリアミドイミド樹脂を用いて、表1に記載した配合条件で、硬化性樹脂組成物1~6を製造した。 (Examples 1 to 4, Comparative Examples 1 and 2)
Using the alcohol-modified polyamideimide resin obtained above, curable resin compositions 1 to 6 were produced under the blending conditions shown in Table 1.
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%。
160℃に加熱したホットプレート上で加熱し、当該硬化性樹脂組成物1~6の糸引きがなくなるまでの時間をそれぞれ測定した。得られた結果を表2に「160℃ゲルタイム」として示した。 <Measurement of storage stability>
Heating was performed on a hot plate heated to 160 ° C., and the time until stringing of the curable resin compositions 1 to 6 disappeared was measured. The obtained results are shown in Table 2 as “160 ° C. gel time”.
樹脂をガラス基板上に乾燥後に膜厚17μmになるように塗装を行った。塗装板を90℃の乾燥機で15分乾燥させて、塗膜を得た。次いで、塗装板を25℃の1%Na2CO3水溶液に浸漬し、塗膜が消失するまでの時間を測定した。表3に示した。 -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 with a dryer at 90 ° C. for 15 minutes to obtain a coating film. Next, the coated plate was immersed in a 1% Na 2 CO 3 aqueous solution at 25 ° C., and the time until the coating film disappeared was measured. It is shown in Table 3.
フラスコに樹脂を10g加えた後、25℃のPGMAcを加えていき、濁りが確認されたところを希釈限界とした。表3に示した。 -PGMac tolerance evaluation After adding 10g of resin to a flask, 25 degreeC PGMac was added and the place where turbidity was confirmed was made into the dilution limit. It is shown in Table 3.
ポリスチレン換算の数平均分子量と質量平均分子量の比から算出した。表3に示した。 ・ Dispersity (molecular weight distribution)
It was calculated from the ratio of the number average molecular weight and the mass average molecular weight in terms of polystyrene. It is shown in Table 3.
Claims (12)
- トリカルボン酸無水物(a1)と、脂肪族構造を有するイソシアネートから合成されたイソシアヌレート型ポリイソシアネート(a2)とを反応させることによりポリアミドイミド樹脂(A1)を生成する工程(1)、
工程(1)で得られたポリアミドイミド樹脂(A1)に、さらにアルコール化合物(a3)を反応させることによりアルコール変性ポリアミドイミド樹脂(A2)を生成する工程(2)、を有するアルコール変性ポリアミドイミド樹脂の製造方法であって、
前記工程(1)は、トリカルボン酸無水物(a1)に対して、前記イソシアヌレート型ポリイソシアネート(a2)を少なくとも2回に分けて加えることにより、前記イソシアヌレート型ポリイソシアネート(a2)とトリカルボン酸無水物(a1)とを反応させた後、得られた反応物に、さらに前記イソシアヌレート型ポリイソシアネート(a2)を反応させる工程(1a)を含むことを特徴とするアルコール変性ポリアミドイミド樹脂の製造方法。 A step (1) of producing a polyamideimide resin (A1) by reacting a tricarboxylic acid anhydride (a1) with an isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure;
Alcohol-modified polyamideimide resin comprising the step (2) of further producing an alcohol-modified polyamideimide resin (A2) by reacting the polyamideimide resin (A1) obtained in the step (1) with an alcohol compound (a3). A manufacturing method of
In the step (1), the isocyanurate type polyisocyanate (a2) and the tricarboxylic acid are added to the tricarboxylic acid anhydride (a1) by adding the isocyanurate type polyisocyanate (a2) at least twice. Production of an alcohol-modified polyamideimide resin characterized by comprising a step (1a) of reacting the isocyanurate type polyisocyanate (a2) with the obtained reactant after reacting with the anhydride (a1) Method. - 前記工程(1a)は、前記イソシアヌレート型ポリイソシアネート(a2)のイソシアネート基のモル数に対して、トリカルボン酸無水物(a1)のカルボキシ基のモル数及び酸無水物基モル数の合計が過剰量となる割合で、トリカルボン酸無水物(a1)と、前記イソシアヌレート型ポリイソシアネート(a2)とを反応させた後、得られた反応物に、さらに前記イソシアヌレート型ポリイソシアネート(a2)を反応させる工程である、請求項1記載のアルコール変性ポリアミドイミド樹脂の製造方法。 In the step (1a), the sum of the number of moles of carboxy groups and the number of moles of acid anhydride groups of the tricarboxylic acid anhydride (a1) is excessive with respect to the number of moles of isocyanate groups of the isocyanurate type polyisocyanate (a2). After reacting the tricarboxylic acid anhydride (a1) with the isocyanurate type polyisocyanate (a2) in a proportion to be an amount, the reaction product obtained is further reacted with the isocyanurate type polyisocyanate (a2). The method for producing an alcohol-modified polyamideimide resin according to claim 1, wherein the method is a step of causing the reaction to occur.
- 前記工程(1a)は、トリカルボン酸無水物(a1)と前記イソシアヌレート型ポリイソシアネート(a2)とを反応させ、赤外吸収スペクトル測定においてイソシアネート基の特性吸収である2270cm-1が消滅するまで反応を進行させた後に、得られた反応物に、さらに前記イソシアヌレート型ポリイソシアネート(a2)を反応させる工程である請求項1又は2記載のアルコール変性ポリアミドイミド樹脂の製造方法。 In the step (1a), the tricarboxylic acid anhydride (a1) and the isocyanurate type polyisocyanate (a2) are reacted, and the reaction is continued until 2270 cm −1, which is the characteristic absorption of the isocyanate group in the infrared absorption spectrum measurement, disappears. The method for producing an alcohol-modified polyamideimide resin according to claim 1, wherein the isocyanurate-type polyisocyanate (a2) is further reacted with the obtained reaction product after proceeding.
- 前記イソシアヌレート型ポリイソシアネート(a2)のイソシアネート基の合計のモル数(N)に対する、トリカルボン酸無水物(a1)のカルボキシ基のモル数(M1)及び酸無水物基モル数(M2)の合計のモル数の比〔(M1)+(M2))/(N)〕が1.1~3である請求項1~3の何れか一項記載のアルコール変性ポリアミドイミド樹脂の製造方法。 Sum of the number of moles of carboxy groups (M1) and the number of moles of acid anhydride groups (M2) of the tricarboxylic acid anhydride (a1) with respect to the total number of moles (N) of isocyanate groups of the isocyanurate type polyisocyanate (a2). The method for producing an alcohol-modified polyamideimide resin according to any one of claims 1 to 3, wherein the molar ratio [(M1) + (M2)) / (N)] is 1.1 to 3.
- 前記工程(2)において、赤外吸収スペクトル測定においてイソシアネート基の特性吸収である2270cm-1が消滅したポリアミドイミド樹脂(A1)に対して、アルコール化合物(a3)を反応させる、請求項1~4の何れか一項記載のアルコール変性ポリアミドイミド樹脂の製造方法。 In the step (2), the alcohol compound (a3) is reacted with the polyamideimide resin (A1) from which 2270 cm −1, which is the characteristic absorption of the isocyanate group in infrared absorption spectrum measurement, has disappeared. A method for producing an alcohol-modified polyamideimide resin according to any one of the above.
- 前記工程(2)において、前記ポリアミドイミド樹脂(A1)とアルコール化合物(a3)との反応は、該ポリアミドイミド樹脂(A1)中の酸無水物基モル数(M3)と、アルコール化合物(a3)の水酸基のモル数(L)との比が、M3/L=1~5の範囲である請求項1~5の何れか一項記載のアルコール変性ポリアミドイミド樹脂の製造方法。 In the step (2), the reaction between the polyamideimide resin (A1) and the alcohol compound (a3) is performed by reacting the number of moles of acid anhydride groups (M3) in the polyamideimide resin (A1) with the alcohol compound (a3). The method for producing an alcohol-modified polyamideimide resin according to any one of claims 1 to 5, wherein the ratio of the number of moles to the number of moles (L) of hydroxyl groups is in the range of M3 / L = 1 to 5.
- トリカルボン酸無水物(a1)と、脂肪族構造を有するイソシアネートから合成されたイソシアヌレート型ポリイソシアネート(a2)とがアミドまたはイミドを形成して結合しているポリアミドイミド樹脂(A1)の酸無水物基に、アルコール化合物(a3)がエステル結合を形成して結合しているアルコール変性ポリアミドイミドを含み、分子量分布が2.0以下の範囲であることを特徴とするアルコール変性ポリアミドイミド樹脂。 Acid anhydride of polyamideimide resin (A1) in which tricarboxylic acid anhydride (a1) and isocyanurate type polyisocyanate (a2) synthesized from an isocyanate having an aliphatic structure are bonded together by forming an amide or imide An alcohol-modified polyamideimide resin comprising an alcohol-modified polyamideimide in which an alcohol compound (a3) forms an ester bond, and has a molecular weight distribution of 2.0 or less.
- 数平均分子量が800~20000の範囲であり、質量平均分子量が1600~40000の範囲である請求項7記載のアルコール変性ポリアミドイミド樹脂。 The alcohol-modified polyamideimide resin according to claim 7, wherein the number average molecular weight is in the range of 800 to 20,000 and the mass average molecular weight is in the range of 1600 to 40,000.
- 酸価が70~210KOHmg/gである請求項8記載のアルコール変性ポリアミドイミド樹脂。 The alcohol-modified polyamideimide resin according to claim 8, which has an acid value of 70 to 210 KOHmg / g.
- 請求項7~9のいずれか1項記載のアルコール変性ポリアミドイミド樹脂(A2)と、硬化性樹脂(B)及び/又は有機溶剤(C)とを含有することを特徴とする硬化性樹脂組成物。 A curable resin composition comprising the alcohol-modified polyamideimide resin (A2) according to any one of claims 7 to 9, and a curable resin (B) and / or an organic solvent (C). .
- さらに、光重合開始剤(D)を含有する請求項10項記載の硬化性樹脂組成物。 Furthermore, the curable resin composition of Claim 10 containing a photoinitiator (D).
- 請求項10または11記載の硬化性樹脂組成物を硬化させてなることを特徴とする硬化物。 A cured product obtained by curing the curable resin composition according to claim 10 or 11.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018521670A JP6432814B2 (en) | 2016-06-21 | 2017-06-20 | Alcohol-modified polyamideimide resin and method for producing the same |
KR1020187035118A KR102351942B1 (en) | 2016-06-21 | 2017-06-20 | Alcohol-modified polyamideimide resin and manufacturing method thereof |
CN201780039072.9A CN109312045B (en) | 2016-06-21 | 2017-06-20 | Alcohol-modified polyamideimide resin and method for producing same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016122621 | 2016-06-21 | ||
JP2016-122621 | 2016-06-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017221922A1 true WO2017221922A1 (en) | 2017-12-28 |
Family
ID=60783338
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/022653 WO2017221922A1 (en) | 2016-06-21 | 2017-06-20 | Alcohol-modified polyamide-imide resin and process for producing same |
Country Status (5)
Country | Link |
---|---|
JP (2) | JP6432814B2 (en) |
KR (1) | KR102351942B1 (en) |
CN (1) | CN109312045B (en) |
TW (1) | TWI745383B (en) |
WO (1) | WO2017221922A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019189757A (en) * | 2018-04-25 | 2019-10-31 | Dic株式会社 | Alcohol modified polyamideimide resin, curable resin composition, and cured article thereof |
WO2021045085A1 (en) * | 2019-09-06 | 2021-03-11 | 太陽インキ製造株式会社 | Curable resin composition, dry film and cured product of same, and electronic component containing said cured product |
WO2021044984A1 (en) * | 2019-09-06 | 2021-03-11 | 太陽インキ製造株式会社 | Curable resin composition, dry film and cured article comprising same, and electronic component equipped with said cured article |
JP7443000B2 (en) | 2019-09-06 | 2024-03-05 | 太陽ホールディングス株式会社 | Curable resin composition |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7310253B2 (en) | 2019-04-19 | 2023-07-19 | Dic株式会社 | Amideimide resin composition, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55123617A (en) * | 1979-03-14 | 1980-09-24 | Hitachi Chem Co Ltd | Polyamide-imide resin composition soluble in cresol-type solvent |
JPS55123649A (en) * | 1979-03-14 | 1980-09-24 | Hitachi Chem Co Ltd | Polyamide-imide resin composition |
JPS5964633A (en) * | 1982-10-05 | 1984-04-12 | Hitachi Chem Co Ltd | Production of heat-resistant resin |
JPS6036521A (en) * | 1983-08-10 | 1985-02-25 | Hitachi Chem Co Ltd | Manufacture of granular polymer |
JPH08193181A (en) * | 1994-09-09 | 1996-07-30 | Re Hart Labs Inc | Water-based solvent-free or low volatile organic compound content two-pack poly-urethane coating material |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5124428A (en) * | 1991-05-31 | 1992-06-23 | Amoco Corporation | Amide-imide resin for production of heat-resistant fiber |
JPH05140309A (en) * | 1991-11-25 | 1993-06-08 | Mitsui Toatsu Chem Inc | Polyamideimide resin and its production |
JP4061531B2 (en) * | 2001-06-28 | 2008-03-19 | 大日本インキ化学工業株式会社 | Active energy ray-curable polyimide resin composition |
JPWO2010107045A1 (en) | 2009-03-18 | 2012-09-20 | Dic株式会社 | Polyimide resin, curable resin composition and cured product thereof |
JP2011236384A (en) * | 2010-05-13 | 2011-11-24 | Hitachi Chem Co Ltd | Heat-resistant resin composition, coating material, and enameled wire using the same |
CN105408394B (en) * | 2013-07-18 | 2017-09-22 | Dic株式会社 | Polyamide-imide resin, hardening resin composition and its solidfied material |
CN103450832B (en) * | 2013-08-14 | 2015-08-05 | 广西南宁绿园北林木业有限公司 | Modified urea-formaldehyde resin glue sticks agent and production method thereof |
RU2673084C2 (en) | 2013-11-08 | 2018-11-22 | Киссеи Фармасьютикал Ко., Лтд. | Carboxymethyl piperidine derivative |
JP2015155500A (en) * | 2014-02-20 | 2015-08-27 | Dic株式会社 | Curable amide-imide resin and method for producing amide-imide resin |
CN105295047B (en) * | 2015-11-30 | 2017-12-22 | 苏州太湖电工新材料股份有限公司 | A kind of preparation method of polyimides high polymer |
JP6922162B2 (en) * | 2016-06-21 | 2021-08-18 | Dic株式会社 | Polyamide-imide resin and its manufacturing method |
-
2017
- 2017-06-20 KR KR1020187035118A patent/KR102351942B1/en active IP Right Grant
- 2017-06-20 WO PCT/JP2017/022653 patent/WO2017221922A1/en active Application Filing
- 2017-06-20 TW TW106120511A patent/TWI745383B/en active
- 2017-06-20 CN CN201780039072.9A patent/CN109312045B/en active Active
- 2017-06-20 JP JP2018521670A patent/JP6432814B2/en active Active
-
2018
- 2018-09-25 JP JP2018178784A patent/JP6886596B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55123617A (en) * | 1979-03-14 | 1980-09-24 | Hitachi Chem Co Ltd | Polyamide-imide resin composition soluble in cresol-type solvent |
JPS55123649A (en) * | 1979-03-14 | 1980-09-24 | Hitachi Chem Co Ltd | Polyamide-imide resin composition |
JPS5964633A (en) * | 1982-10-05 | 1984-04-12 | Hitachi Chem Co Ltd | Production of heat-resistant resin |
JPS6036521A (en) * | 1983-08-10 | 1985-02-25 | Hitachi Chem Co Ltd | Manufacture of granular polymer |
JPH08193181A (en) * | 1994-09-09 | 1996-07-30 | Re Hart Labs Inc | Water-based solvent-free or low volatile organic compound content two-pack poly-urethane coating material |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019189757A (en) * | 2018-04-25 | 2019-10-31 | Dic株式会社 | Alcohol modified polyamideimide resin, curable resin composition, and cured article thereof |
WO2021045085A1 (en) * | 2019-09-06 | 2021-03-11 | 太陽インキ製造株式会社 | Curable resin composition, dry film and cured product of same, and electronic component containing said cured product |
WO2021044984A1 (en) * | 2019-09-06 | 2021-03-11 | 太陽インキ製造株式会社 | Curable resin composition, dry film and cured article comprising same, and electronic component equipped with said cured article |
JP7443000B2 (en) | 2019-09-06 | 2024-03-05 | 太陽ホールディングス株式会社 | Curable resin composition |
Also Published As
Publication number | Publication date |
---|---|
JPWO2017221922A1 (en) | 2018-07-26 |
JP6432814B2 (en) | 2018-12-05 |
CN109312045A (en) | 2019-02-05 |
TW201811872A (en) | 2018-04-01 |
KR20190020295A (en) | 2019-02-28 |
TWI745383B (en) | 2021-11-11 |
JP2018197359A (en) | 2018-12-13 |
JP6886596B2 (en) | 2021-06-16 |
CN109312045B (en) | 2021-08-24 |
KR102351942B1 (en) | 2022-01-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5839149B2 (en) | Polyamideimide resin, curable resin composition and cured product thereof | |
JP6432814B2 (en) | Alcohol-modified polyamideimide resin and method for producing the same | |
JP6922162B2 (en) | Polyamide-imide resin and its manufacturing method | |
KR101252731B1 (en) | Epoxy Resin and Epoxy Resin Composition | |
JP6240069B2 (en) | Epoxy resin composition, cured product thereof, and curable resin composition | |
WO2008053985A1 (en) | Photosensitive resin composition, cured product thereof, and method for producing photosensitive resin | |
TWI734251B (en) | Manufactuaring method of film and printed wiring board | |
WO2011083554A1 (en) | Polyamide or polyimide resin compositions that contain phosphine oxide, and cured products thereof | |
JP2019189757A (en) | Alcohol modified polyamideimide resin, curable resin composition, and cured article thereof | |
JP2002148799A (en) | Resist composition with excellent flame resistance | |
JP7277126B2 (en) | A phenoxy resin, a resin composition thereof, a cured product thereof, and a method for producing the same. | |
JP5087638B2 (en) | Flame-retardant photosensitive resin composition and circuit board using the same | |
WO2015119188A1 (en) | Epoxy resin, curable resin composition, and cured product thereof | |
KR20140115988A (en) | Epoxy acrylate resins, acid anhydride adduct of epoxy acrylate resins, curable resin composition, alkali-developable photosensitive resin composition and cured object each containing | |
JP2007204604A (en) | Liquid epoxy resin, epoxy resin composition and cured product | |
US20220325047A1 (en) | Curable resin composition, dry film and cured product of same, and electronic component containing said cured product | |
KR20220144318A (en) | Novel reactive epoxy carboxylate compound, derivative thereof, photosensitive resin composition containing them, and cured product thereof | |
TW202104334A (en) | Resin composition, semiconductor sealing material, prepreg, circuit board, build-up film, solder resist, dry film, and printed wiring board | |
JP2020052362A (en) | Production method of cured product, photosensitive resin composition used for the same, dry film, cured product and electronic component | |
KR20160044937A (en) | Multifunctional compound, photo-curable and thermo-curable resin composition and dry film solder resist |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2018521670 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17815390 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20187035118 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17815390 Country of ref document: EP Kind code of ref document: A1 |