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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/14—Polycondensates modified by chemical after-treatment

Definitions

• the problem to be solved by the present invention is a method for producing a (meth) acrylate resin which has excellent alkali developability and high photosensitivity, and has excellent elasticity, heat resistance and substrate adhesion in a cured product. It is an object of the present invention to provide a method for producing a curable resin composition contained therein, a method for producing a cured product composed of the curable resin composition, and a method for producing an insulating material and a resist member.
• the amount of the basic catalyst used is such that a (meth) acrylate resin capable of forming a cured product having excellent alkali developability and high photosensitivity and having excellent elasticity, heat resistance and substrate adhesion can be obtained. , 0.01 to 1.0 parts by mass, preferably 0.05 to 0.8 parts by mass with respect to a total of 100 parts by mass of the epoxy resin (A1) and the unsaturated monobasic acid (A2). Is more preferable.
• the gas (b1) and the inert gas (b2) may be introduced into the reaction apparatus in advance as a mixed gas, or the gas (b1) and the inert gas (b2) may be introduced. And may be introduced separately into the reactor and mixed in the reaction system.
• the total amount of the gas (b1) and the inert gas (b2) introduced can form a cured product having excellent alkali developability and high photosensitivity, and excellent elasticity, heat resistance, and substrate adhesion. Since a (meth) acrylate resin can be obtained, the range of 1 ⁇ 10 -12 to 1 ⁇ 10 -3 / min is preferable per 1 kg of the total amount of the epoxy resin (A1) and the unsaturated monobasic acid (A2). More preferably, 1 ⁇ 10 -11 to 1 ⁇ 10 -3 / min. Further, the gas (b1) and the inert gas (b2) may be introduced continuously or intermittently, and the average of the introduced amounts may be within this range.
• Pv is the stirring power per unit volume (kW / m 3 )
• Np is the stirring power number (-)
• ⁇ is the resin density (kg / m 3 )
• n is the rotation speed of the stirring blade.
• (Sec -1 ) and d indicate the diameter of the stirring blade (m)
• V indicates the reaction solution volume (m 3 ).
• the reaction temperature in the reaction between the epoxy resin (A1) and the unsaturated monobasic acid (A2) is preferably in the range of, for example, 80 to 160 ° C., and the reaction time is preferably in the range of 1 to 20 hours.
• R 1 is either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, respectively.
• R 2 is either an alkyl group having 1 to 4 carbon atoms independently, or a bond point linked to a structural site represented by the structural formula (5) via a methylene group marked with *.
• l is an integer of 0 or 1 to 3
• m is an integer of 1 to 15.
• Examples of the (meth) acrylate compound having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropanedi (meth) acrylate, and pentaerythritol (meth).
• the method for producing the epoxy resin having a polymerizable unsaturated group is not particularly limited, and any method may be used for producing the epoxy resin.
• it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.
• the same catalysts as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.
• the urethane resin having a polymerizable unsaturated group is obtained by reacting with, for example, a polyisocyanate compound, a (meth) acrylate compound having a hydroxyl group, a polyol compound if necessary, and a polybasic acid anhydride. And so on.
• the same compounds as those exemplified for the (meth) acrylate compound having a hydroxyl group can be used, and the (meth) acrylate compound having a hydroxyl group is used alone. It is also possible to use two or more types together.
• the (meth) acrylate compound ( ⁇ ) is not particularly limited as long as it can react with the reactive functional group of the (meth) acrylate compound ( ⁇ ), but the combination is as follows from the viewpoint of reactivity. Is preferable. That is, when water (meth) acrylate is used as the (meth) acrylate compound ( ⁇ ), it is preferable to use (meth) acrylate having an isocyanate group as the (meth) acrylate compound ( ⁇ ). When a (meth) acrylate having a carboxyl group is used as the (meth) acrylate compound ( ⁇ ), it is preferable to use a (meth) acrylate having a glycidyl group as the (meth) acrylate compound ( ⁇ ).
• Examples of the amideimide resin having a polymerizable unsaturated group include an amideimide resin having an acid group and / or an acid anhydride group, and a (meth) acrylate compound having a hydroxyl group and / or a (meth) acrylate compound having an epoxy group. And, if necessary, those obtained by reacting a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. ..
• the compound having a reactive functional group may or may not have a (meth) acryloyl group.
• polybasic acid anhydride the same ones as those exemplified as the above-mentioned polybasic acid anhydride (A3) can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. It can also be used together.
• the method for producing the amidoimide resin having a polymerizable unsaturated group is not particularly limited, and any method may be used for production. In the production of the amidoimide resin having a polymerizable unsaturated group, it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.
• the same catalysts as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.
• N-alkoxyalkyl (meth) acrylamide compound examples include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-methoxyethyl (meth) acrylamide. , N-ethoxyethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide and the like.
• the N-alkoxyalkyl (meth) acrylamide compound may be used alone or in combination of two or more.
• organic solvent the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.
• the amount of the resin having a polymerizable unsaturated group is preferably in the range of 10 to 900 parts by mass with respect to 100 parts by mass of the (meth) acrylate resin of the present invention.
• Mono (meth) acrylate compounds such as acrylate compounds: Polyoxy such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain in the molecular structure of the various mono (meth) acrylate monomers.
• azo compound examples include azobisisobutyronitrile.
• -Salicyloyl amino-1,2,4-triazole, N'1, N'12-bis (2-hydroxybenzoyl) dodecanedihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine , 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinone and other phenolic compounds, hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy- Quinone compounds such as 1,4-naphthoquinone, anthraquinone and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N.I.
• N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, diphenylamine, 4 , 4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly (2,2,4-trimethyl-1,2-dihydroquinoline), sylated diphenylamine, sylated diphenylamine and 2,4,4-trimethyl Penten reaction products, amine compounds such as diphenylamine and 2,4,4-trimethylpenten reaction products, phenothiazine, distearylthiodipropionate, 2,2-bis ( ⁇ [3- (dodecylthio) propionyl] oxy ⁇ Methyl) -1,3-propanediyl bis [3- (
• the pigment a known and commonly used inorganic pigment or organic pigment can be used.
• the flame retardant examples include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, and inorganic phosphorus compounds such as phosphate amide; phosphoric acid ester compounds and phosphoruses.
• the cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays.
• active energy ray include ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
• ultraviolet rays When ultraviolet rays are used as the active energy rays, they may be irradiated in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently carry out the curing reaction by the ultraviolet rays.
• acrylate resin (3) 269 parts by mass of ethyldiglycol acetate and 161 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain an acrylate resin (3).
• the non-volatile content of this acrylate resin (3) was 64% by mass, and the solid content acid value was 86 mgKOH / g.
• the number of moles of tetrahydrophthalic anhydride was 0.53 with respect to 1 mol of the epoxy group contained in the epoxy resin (1).
• the esterification reaction was carried out at 140 ° C. for 6 hours to obtain an intermediate (14).
• the viscosity of the intermediate (14) at 100 ° C. was 950 mPa ⁇ s, and the density of the intermediate (14) at 25 ° C. was 1200 kg / m 3 .
• 230 parts by mass of ethyldiglycolacetate and 137 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C.

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Citations (4)

• 2021
  • 2021-05-13 JP JP2022512802A patent/JPWO2022137591A1/ja active Pending
  • 2021-05-13 WO PCT/JP2021/018137 patent/WO2022137591A1/ja not_active Ceased

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