(METH)acryloyl group-containing polyimide precursor and cured product

Abstract

To provide a (meth)acryloyl group-containing polyimide precursor and a cured product thereof.SOLUTION: A (meth)acryloyl group-containing polyimide precursor is a reaction product of a resin with an isocyanate group-containing (poly)(meth)acrylate, the resin containing an imide structural unit derived from a reaction product of an aromatic diamine having molecular weight of 190 or more and a tetracarboxylic acid anhydride having an oxyphthalic anhydride group, and an amic acid structural unit derived from a reaction product of an aromatic diamine having molecular weight of 190 to 300 and 4,4'-oxydiphthalic anhydride and / or 3,3',4,4'-biphenyltetracarboxylic acid dianhydride.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a (meth)acryloyl group-containing polyimide precursor and a cured product thereof.

Background Art

[0002] The applicant has been researching and developing polyimides produced using diamine dimers (polyimides using diamine dimers) (Patent Document 1). Polyimides using diamine dimers have a low relative permittivity and a low dielectric loss tangent. Therefore, polyimides using diamine dimers are used as adhesives in flexible copper-clad laminates in which high-frequency electrical signals are used.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The problem to be solved by the present invention is to provide a (meth)acryloyl group-containing polyimide precursor that can be synthesized and can produce a cured product with a small degree of curing shrinkage, good chemical resistance, and good heat resistance.

Means for Solving the Problems

[0005] The following items are provided by the present disclosure. (Item 1) An imide structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 190 or more and a tetracarboxylic dianhydride containing an oxyphtalic anhydride group and A resin containing an amic acid structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 190 to 300 and 4,4'-oxydiphthalic anhydride and / or 3,3',4,4'-biphenyltetracarboxylic dianhydride A reaction product with an isocyanate group-containing (poly)(meth)acrylate, (Meth)acryloyl group-containing polyimide precursor. (Item 2) The aromatic diamine having a molecular weight of 190 to 300 is one or more selected from the group consisting of 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl thioether, 1,4-bis(4-aminophenoxy)benzene, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-diphenylmethane, and 4,4'-diamino-2,2'-dimethylbiphenyl. The (meth)acryloyl group-containing polyimide precursor according to the above item. (Item 3) A cured product of the (meth)acryloyl group-containing polyimide precursor according to any one of the above items.

[0006] In the present disclosure, one or more of the above-described features may be provided in combination in addition to the explicitly stated combinations.

Advantages of the Invention

[0007] The (meth)acryloyl group-containing polyimide precursor of the present invention can be synthesized. The cured product of the present invention has a small degree of curing shrinkage and exhibits good chemical resistance and heat resistance.

Modes for Carrying Out the Invention

[0008] Throughout the present disclosure, the ranges of numerical values such as each physical property value and content can be set as appropriate (for example, selected from the values described in each of the following items). Specifically, for the numerical value α, when A3, A2, A1 (where A3 > A2 > A1) etc. are listed, the range of the numerical value α is A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less etc.

[0009] As long as the problems to be solved by the present invention are solved, each component, condition, numerical value etc. are not particularly limited.

[0010] “(Meth)acryl” means “acryl and / or methacryl”. “(Meth)acrylate” means “acrylate and / or methacrylate”. “(Meth)acryloyl” means “acryloyl and / or methacryloyl”.

[0011] [(Meth)acryloyl group-containing polyimide precursor] The present disclosure relates to an imide structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 190 or more and a tetracarboxylic dianhydride containing an oxyphthalic anhydride group and a resin containing an amic acid structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 190 to 300 and 4,4'-oxydiphthalic dianhydride and / or 3,3',4,4'-biphenyltetracarboxylic dianhydride and a reaction product of an isocyanate group-containing (poly)(meth)acrylate relates to a (meth)acryloyl group-containing polyimide precursor.

[0012] <Aromatic diamine> The aromatic diamine can be used alone or in combination of two or more.

[0013] "Aromatic diamine" means a diamine in which both amino groups (-NH 2 ) are directly bonded to an aromatic group.

[0014] Examples of aromatic diamines include diaminodiphenyl ether, diaminodiphenyl thioether, bis(aminophenoxy)benzene, diaminodiphenyl methane, diaminodimethyl biphenyl, diaminodiphenyl sulfone, diaminobenzanilide, aminophenyl aminobenzoate, and the like.

[0015] Examples of diaminodiphenyl ether include 4,4'-diaminodiphenyl ether (molecular weight: 200), 3,3'-diaminodiphenyl ether (molecular weight: 200), 3,4'-diaminodiphenyl ether (molecular weight: 200), and the like.

[0016] Examples of diaminodiphenyl thioether include 4,4'-diaminodiphenyl thioether (molecular weight: 216), 3,3'-diaminodiphenyl thioether (molecular weight: 216), 3,4'-diaminodiphenyl thioether (molecular weight: 216), and the like.

[0017] Examples of bis(aminophenoxy)benzene include 1,4-bis(4-aminophenoxy)benzene (molecular weight: 292), 1,3-bis(4-aminophenoxy)benzene (molecular weight: 292), and the like.

[0018] Examples of diaminodiphenyl methane include 4,4'-diamino-diphenyl methane (molecular weight: 198), 3,3'-diamino-diphenyl methane (molecular weight: 198), 3,4'-diamino-diphenyl methane (molecular weight: 198), 4,4'-diamino-3,3'-dimethyl diphenyl methane (molecular weight: 226), 4,4'-diamino-3,3'-dimethyl diphenyl methane (molecular weight: 226), and the like.

[0019] Diaminodimethylbiphenyl includes, for example, 4,4'-diamino-3,3'-dimethylbiphenyl (o-tolidine, molecular weight: 212), 4,4'-diamino-2,2'-dimethylbiphenyl (m-tolidine, molecular weight: 212), and the like.

[0020] Diaminodiphenylsulfone includes, for example, 4,4'-diaminodiphenylsulfone (molecular weight: 248), 3,3'-diaminodiphenylsulfone (molecular weight: 248), 3,4'-diaminodiphenylsulfone (molecular weight: 248), and the like.

[0021] Diaminobenzanilide includes, for example, 3,3'-diaminobenzanilide (molecular weight: 227), 4,4'-diaminobenzanilide (molecular weight: 227), and the like.

[0022] Aminophenylaminobenzoate includes, for example, 3-aminophenyl-3'-aminobenzoate (molecular weight: 228), 4-aminophenyl-4'-aminobenzoate (molecular weight: 228), and the like.

[0023] In one embodiment, the aromatic diamine preferably includes a compound represented by the following structural formula. [Chemical formula] (In the formula, R a1 ~R a8 each independently represents a hydrogen atom or an alkyl group (preferably a methyl group). Y represents a single bond, an amide bond, an ester bond, an oxygen atom, a sulfur atom, -SO 2 -, an alkylene group (preferably a methylene group), or an oxyphenyleneoxy group (-O-Ph-O-: Ph represents a phenylene group).)

[0024] In one embodiment, the molecular weight of the aromatic diamine constituting the imide structural unit is, for example, 500, 475, 450, 425, 415, 410, 400, 375, 350, 325, 300, 295, 292, 290, 275, 250, 230, 226, 225, 220, 216, 215, 212, 210, 205, 201, 200, 198, 195, 190, etc. In one embodiment, the above molecular weight is preferably 190 or more, more preferably 201 or more, still more preferably 190 to 500, and even more preferably 201 to 500.

[0025] In one embodiment, the aromatic diamine having a molecular weight of 190 or more is preferably 4,4'-diaminodiphenyl thioether (molecular weight: 216), 1,4-bis(4-aminophenoxy)benzene (molecular weight: 292), 4,4'-diamino-3,3'-dimethyl diphenylmethane (molecular weight: 226), 4,4'-diamino-2,2'-dimethyl biphenyl (m-tridine, molecular weight: 212), 4,4'-diamino-diphenylmethane (molecular weight: 198), etc.

[0026] The molecular weight of the aromatic diamine constituting the amic acid structural unit is, for example, 300, 295, 292, 290, 275, 250, 230, 226, 225, 220, 216, 215, 212, 210, 205, 200, 198, 195, 190, etc. In one embodiment, the above molecular weight is preferably 190 to 300.

[0027] In one embodiment, the aromatic diamine having a molecular weight of 190 to 300 is preferably 4,4'-diaminodiphenyl ether (molecular weight: 200), 3,4'-diaminodiphenyl ether (molecular weight: 200), 4,4'-diaminodiphenyl thioether (molecular weight: 216), 1,4-bis(4-aminophenoxy)benzene (molecular weight: 292), 4,4'-diamino-3,3'-dimethyldiphenylmethane (molecular weight: 226), 4,4'-diamino-diphenylmethane (molecular weight: 198), 4,4'-diamino-2,2'-dimethylbiphenyl (m-tridine, molecular weight: 212), and the like.

[0028] <Tetracarboxylic dianhydride containing an oxophthalic anhydride group> The tetracarboxylic dianhydride containing an oxophthalic anhydride group can be used alone or in combination of two or more.

[0029] "Tetracarboxylic dianhydride containing an oxophthalic anhydride group" means a tetracarboxylic dianhydride having the following oxophthalic anhydride group. [Chemical formula]

[0030] The tetracarboxylic dianhydride constituting the imide structural unit and the tetracarboxylic dianhydride constituting the amic acid structural unit may be the same or different.

[0031] Examples of the tetracarboxylic dianhydride containing an oxophthalic anhydride group include 4,4'-oxydiphthalic dianhydride, 3,4'-oxydiphthalic dianhydride, 3,3'-oxydiphthalic dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanedioic dianhydride, 4,4'-(p-phenylenedioxy)diphthalic dianhydride, and the like.

[0032] <(Poly)(meth)acrylate containing an isocyanate group> The (poly)(meth)acrylate containing an isocyanate group can be used alone or in combination of two or more.

[0033] In one embodiment, the isocyanate group-containing (poly)(meth)acrylate has 1 to 2 (meth)acryloyl groups.

[0034] The isocyanate group-containing (poly)(meth)acrylate is represented by the following structural formula. [Chemical formula] (In the formula, R i1 is a hydrogen atom or a methyl group, R i2 is a substituted or unsubstituted alkylene group, R i3 is a substituted or unsubstituted alkylene group, and Z is a single bond or an oxygen atom.)

[0035] The alkylene group is preferably an alkylene group having 1 to 4 carbon atoms, more preferably a methylene group.

[0036] The substituent of the alkylene group is preferably an alkyl group or a methyloxy(meth)acryloyl group, more preferably a methyl group or a methyloxy(meth)acryloyl group.

[0037] Examples of the isocyanate group-containing (poly)(meth)acrylate include 2-isocyanatoethyl (meth)acrylate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, 2-(2-(meth)acryloyloxyethoxy)ethyl isocyanate, and the like.

[0038] <Content of each structural unit, etc.> In the present disclosure, unless otherwise specified, "resin" means a polymer (polyamic acid) containing imide structural units derived from a reaction product of an aromatic diamine having a molecular weight of 190 or more and a tetracarboxylic dianhydride containing an oxyphthalic anhydride group, and amic acid structural units derived from a reaction product of an aromatic diamine having a molecular weight of 190 to 300 and 4,4'-oxydiphthalic dianhydride and / or 3,3',4,4'-biphenyltetracarboxylic dianhydride, and in which an isocyanate group-containing (poly)(meth)acrylate has not reacted.

[0039] Examples of the content of the imide structural units in 100% by mass of the resin include 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25% by mass, etc. In one embodiment, the above content is preferably 25 to 80% by mass, more preferably 30 to 75% by mass.

[0040] Examples of the content of the imide structural units in 100 mol% of the resin include 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25 mol%, etc. In one embodiment, the above content is preferably 25 to 80 mol%, more preferably 30 to 75 mol%.

[0041] Examples of the content of the amic acid structural units in 100% by mass of the resin include 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20% by mass, etc. In one embodiment, the above content is preferably 20 to 75% by mass, more preferably 25 to 70% by mass.

[0042] Examples of the content of the amic acid structural units in 100 mol% of the resin include 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 mol%, etc. In one embodiment, the above content is preferably 20 to 75 mol%, more preferably 25 to 70 mol%.

[0043] The content of imide structural units in 100% by mass of the (meth)acryloyl group-containing polyimide precursor may be, for example, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20% by mass, etc. In one embodiment, the above content is preferably 20 to 75% by mass, more preferably 25 to 70% by mass.

[0044] The content of imide structural units in 100% by mole of the (meth)acryloyl group-containing polyimide precursor may be, for example, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20% by mole, etc. In one embodiment, the above content is preferably 20 to 75% by mole, more preferably 25 to 70% by mole.

[0045] The content of amic acid structural units in 100% by mass of the (meth)acryloyl group-containing polyimide precursor may be, for example, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15% by mass, etc. In one embodiment, the above content is preferably 15 to 70% by mass, more preferably 20 to 65% by mass.

[0046] The content of amic acid structural units in 100% by mole of the (meth)acryloyl group-containing polyimide precursor may be, for example, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15% by mole, etc. In one embodiment, the above content is preferably 15 to 70% by mole, more preferably 20 to 65% by mole.

[0047] The content of isocyanate group-containing (poly)(meth)acrylate units in 100% by mass of the (meth)acryloyl group-containing polyimide precursor may be, for example, 23, 20, 17, 15, 13, 10, 9, 5% by mass, etc. In one embodiment, the above content is preferably 5 to 23% by mass.

[0048] The content of the isocyanate group-containing (poly)(meth)acrylate unit in 100 mol% of the (meth)acryloyl group-containing polyimide precursor is, for example, 47, 45, 40, 35, 30, 25, 20, 17 mol%, etc. In one embodiment, the above content is preferably 17 to 47 mol%.

[0049] <Polyisocyanate> In one embodiment, when reacting the above resin with the isocyanate group-containing (poly)(meth)acrylate, polyisocyanate can be reacted. By reacting polyisocyanate, the chemical resistance properties of the (meth)acryloyl group-containing polyimide precursor can be improved.

[0050] "Polyisocyanate" means a compound having two or more isocyanate groups (-N=C=O).

[0051] Polyisocyanate can be used alone or in combination of two or more.

[0052] Polyisocyanates include, for example, linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and their biuret forms, isocyanurate forms (nurate forms), allophanate forms, adduct forms, etc.

[0053] Examples of linear aliphatic polyisocyanates include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, etc.

[0054] Branched aliphatic polyisocyanates include, for example, diethylpentamethylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentamethylene diisocyanate, trimethylhexamethylene diisocyanate, and the like.

[0055] Alicyclic polyisocyanates include, for example, monocyclic alicyclic polyisocyanates, bridged alicyclic polyisocyanates, condensed alicyclic polyisocyanates, and the like.

[0056] Monocyclic alicyclic polyisocyanates include, for example, hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, and the like.

[0057] Bridged alicyclic polyisocyanates include, for example, tricyclodecylene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like.

[0058] Condensed alicyclic polyisocyanates include, for example, bicyclodecylene diisocyanate, and the like.

[0059] Aromatic polyisocyanates include, for example, monocyclic aromatic polyisocyanates, condensed ring aromatic polyisocyanates, and the like.

[0060] The monocyclic aromatic polyisocyanates include, for example, dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, and the like.

[0061] The condensed-ring aromatic polyisocyanates include, for example, 1,5-naphthylene diisocyanate and the like.

[0062] The amount of the polyisocyanate used relative to 100% by mass of the resin in the (meth)acryloyl group introduction step is, for example, 8, 7, 6, 5, 4, 3, 2, 1, 0% by mass, and the like. In one embodiment, the above amount used is preferably 0 to 8% by mass.

[0063] The molar ratio of "the number of moles of isocyanate groups / the number of polymer moles of the resin (polyamic acid)" is, for example, 3, 2.9, 2.7, 2.5, 2.3, 2.1, 2, 1.9, 1.7, 1.5, 1.3, 1.1, 1, and the like. In one embodiment, the above molar ratio is preferably 1 to 3, and more preferably 1 to 2.5. In the preferred range, gelation is prevented and the mechanical properties are more easily improved.

[0064] <Polyfunctional amine> In one embodiment, the (meth)acryloyl group-containing polyimide precursor may contain a polyfunctional amine moiety. The polyfunctional amine moiety is synthesized by Method 1 of reacting a group of compounds including a reaction product of the above resin and an isocyanate group-containing (poly)(meth)acrylate, a polyfunctional amine, and a polyfunctional acid anhydride, or Method 2 of using a polyfunctional amine as a monomer during the synthesis of an imide structural unit. The (meth)acryloyl group-containing polyimide precursor produced by Method 1 may also be referred to as a "polyfunctional amine-extended (meth)acryloyl group-containing polyimide precursor".

[0065] "Polyfunctional amine" means a compound having two or more amino groups (-NH 2 ). The polyfunctional amine may be used alone or in combination of two or more.

[0066] Examples of the polyfunctional amine include diamines, triamines, and the like.

[0067] Examples of the diamine include aromatic diamines, aliphatic diamines, and the like.

[0068] "Aliphatic diamine" means a diamine in which both amino groups (-NH 2 ) are directly bonded to an aliphatic group.

[0069] Aliphatic diamines include, for example, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 2-methylpentanediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,12-dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decalin, bis(aminomethyl)tricyclodecane, dimer diamine, and the like.

[0070] <Polyfunctional acid anhydride> "Polyfunctional acid anhydride" means a compound having two or more acid anhydride groups. The acid anhydride group is represented by the following structure. Polyfunctional acid anhydrides can be used alone or in combination of two or more. [Chemical formula]

[0071] Examples of polyfunctional acid anhydrides include tetracarboxylic acid anhydrides and the like.

[0072] <Content of each raw material, etc.> The content of the (meth)acryloyl group-containing polyimide precursor in 100% by mass of the polyfunctional amine-extended (meth)acryloyl group-containing polyimide precursor is, for example, 100, 95, 90, 85, 80, 75, 70, 65, 62% by mass, and the like. In one embodiment, the above content is preferably 62 to 100% by mass.

[0073] The content of the polyfunctional amine in 100% by mass of the (meth)acryloyl group-containing polyimide precursor is, for example, 16, 15, 10, 9, 7, 5, 4, 3, 2, 1, 0.5, 0.1, 0% by mass, etc. In one embodiment, the above content is preferably 0 to 16% by mass, more preferably 0.1 to 16% by mass.

[0074] The content of the polyfunctional acid anhydride in 100% by mass of the (meth)acryloyl group-containing polyimide precursor is, for example, 22, 20, 15, 10, 9, 7, 5, 4, 3, 2, 1, 0.5, 0.1, 0% by mass, etc. In one embodiment, the above content is preferably 0 to 22% by mass.

[0075] The amount of the polyfunctional acid anhydride used relative to 100% by mass of the resin (polyamic acid) is, for example, 35, 30, 25, 20, 15, 10, 9, 7, 5, 4, 2, 1, 0% by mass, etc. In one embodiment, the above usage amount is preferably 0 to 35% by mass. By setting it within a preferable range, the residue during development can be reduced.

[0076] The molar ratio of "the number of moles of the acid anhydride groups contained in the polyfunctional acid anhydride and the resin (polyamic acid) / the number of moles of the amino groups of the polyfunctional amine" is, for example, 1.10, 1.09, 1.07, 1.05, 1.04, 1.03, 1.01, 1.00, 0.99, 0.97, 0.95, etc. In one embodiment, the above molar ratio is preferably 0.95 to 1.10. By setting it within a preferable range, the mechanical properties of the (meth)acryloyl group-containing polyimide precursor can be improved.

[0077] <Other structural units> The above-mentioned (meth)acryloyl group-containing polyimide precursor may contain an imide structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 190 or more and a tetracarboxylic dianhydride containing an oxyphthalic anhydride group, an amic acid structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 190 to 300 and 4,4'-oxydiphthalic dianhydride and / or 3,3',4,4'-biphenyltetracarboxylic dianhydride, and a structural unit that does not correspond to any of the structural units derived from an isocyanate group-containing (poly)(meth)acrylate (other structural units).

[0078] Examples of the other structural units include an imide structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 189 or less and a tetracarboxylic dianhydride containing an oxyphthalic anhydride group, an amic acid structural unit derived from a reaction product of an aromatic diamine having a molecular weight of less than 190 and 4,4'-oxydiphthalic dianhydride and / or 3,3',4,4'-biphenyltetracarboxylic dianhydride, an amic acid structural unit derived from a reaction product of an aromatic diamine having a molecular weight of more than 300 and 4,4'-oxydiphthalic dianhydride and / or 3,3',4,4'-biphenyltetracarboxylic dianhydride, an amic acid structural unit derived from a reaction product of an aliphatic diamine and a tetracarboxylic dianhydride, and an imide structural unit derived from a reaction product of an aliphatic diamine and a tetracarboxylic dianhydride.

[0079] In one embodiment, the content of the other structural units is, for example, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, 0% by mass, etc. with respect to 100% by mass of the (meth)acryloyl group-containing polyimide precursor. Further, the content of the other structural units is, for example, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, 0% by mass, etc. with respect to any 100 parts by mass of the imide structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 190 or more and a tetracarboxylic dianhydride containing an oxyphthalic anhydride group, the amic acid structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 190 to 300 and 4,4'-oxydiphthalic dianhydride and / or 3,3',4,4'-biphenyltetracarboxylic dianhydride, and the structural unit derived from an isocyanate group-containing (poly)(meth)acrylate.

[0080] In one embodiment, the content of other structural units is, for example, less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, 0 mol%, etc. with respect to 100 mol% of the (meth)acryloyl group-containing polyimide precursor. Further, the content of other structural units is, for example, an imide structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 190 or more and a tetracarboxylic dianhydride containing an oxyphtalic anhydride group, an amic acid structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 190 to 300 and 4,4'-oxydiphthalic dianhydride and / or 3,3',4,4'-biphenyltetracarboxylic dianhydride, or a structural unit derived from an isocyanate group-containing (poly)(meth)acrylate, less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, 0 mol%, etc. with respect to 100 mol parts of any one of them.

[0081] <Physical properties, etc. ((meth)acryloyl group-containing polyimide precursor)> The weight average molecular weight of the (meth)acryloyl group-containing polyimide precursor is, for example, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, etc. In one embodiment, the above weight average molecular weight is preferably 5,000 to 100,000.

[0082] The number average molecular weight of the (meth)acryloyl group-containing polyimide precursor is, for example, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, etc. In one embodiment, the above number average molecular weight is preferably 2,000 to 50,000.

[0083] The weight average molecular weight and the number average molecular weight can be determined, for example, as polystyrene conversion values measured by gel permeation chromatography (GPC). Detailed conditions include the following, etc. Model: Product name "HLC-8420" (manufactured by Tosoh Corporation) Column: Product name "TSKgel α-M" (manufactured by Tosoh Corporation) Developing solvent: Dissolve 30 mM of lithium bromide and 30 mM of phosphoric acid in dimethylformamide Flow rate: 0.6 mL / min Measurement temperature: 40 °C Detector: RI Standard: Polystyrene Polymer concentration: 0.2 wt%

[0084] <Method for producing (meth)acryloyl group-containing polyimide precursor, etc.> The above (meth)acryloyl group-containing polyimide precursor can be produced by various known methods.

[0085] More specifically, the method for producing the (meth)acryloyl group-containing polyimide precursor includes the following steps. (1) Imide structural unit synthesis step (2) Amic acid structural unit synthesis step (3) (Meth)acryloyl group introduction step

[0086] The reaction conditions for the imide structural unit synthesis step include, for example, reacting a monomer group containing diamine and tetracarboxylic dianhydride at 25 °C to 100 °C for 0.5 hour to 3 hours to form an amic acid, and then reacting at 120 °C to 150 °C for 1 hour to 24 hours, etc.

[0087] The reaction conditions for the amic acid structural unit synthesis step include, for example, reacting a monomer group containing aromatic diamine and amine-terminated resin and tetracarboxylic dianhydride and / or tetracarboxylic dianhydride and acid anhydride-terminated resin and aromatic diamine at 25 °C to 60 °C for 1 hour to 24 hours, etc.

[0088] The reaction conditions for the (meth)acryloyl group introduction step include, for example, reacting resin and isocyanate group-containing (poly)(meth)acrylate at 40 °C to 120 °C for 1 hour to 24 hours, etc.

[0089] In the step of subjecting to an imidization reaction, various known reaction catalysts, dehydrating agents, and organic solvents can be used. The various known reaction catalysts, dehydrating agents, and organic solvents can be used alone or in combination of two or more.

[0090] Examples of the reaction conditions in the polyfunctional amine extension step include reacting at 10°C to 60°C for 0.5 hours to 24 hours.

[0091] Examples of the reaction catalyst include aliphatic tertiary amines, aromatic tertiary amines, heterocyclic tertiary amines, and the like.

[0092] Examples of the aliphatic tertiary amine include triethylamine and the like.

[0093] Examples of the aromatic tertiary amine include dimethylaniline and the like.

[0094] Examples of the heterocyclic tertiary amine include pyridine, picoline, isoquinoline, and the like.

[0095] Examples of the dehydrating agent include aliphatic acid anhydrides, aromatic acid anhydrides, and the like.

[0096] Examples of the aliphatic acid anhydride include acetic anhydride and the like.

[0097] Examples of the aromatic acid anhydride include benzoic anhydride and the like.

[0098] Examples of the organic solvent include aprotic polar solvents, alicyclic solvents, alcohol solvents, aromatic solvents, and the like.

[0099] Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylcaprolactam, methyl triglyme, methyl diglyme, and the like.

[0100] Examples of the alicyclic solvent include cyclohexanone, methylcyclohexane, and the like.

[0101] Examples of the alcohol solvent include methanol, ethanol, propanol, benzyl alcohol, cresol, and the like.

[0102] Examples of the aromatic solvent include toluene and the like.

[0103] Examples of the usage form of the (meth)acryloyl group-containing polyimide precursor include a (meth)acryloyl group-containing polyimide precursor solution for an interlayer insulating film, a (meth)acryloyl group-containing polyimide precursor solution for a resist, and the like.

[0104] [Cured product] The present disclosure provides a cured product of the (meth)acryloyl group-containing polyimide precursor described in the above item.

[0105] Examples of the cured product include a cured product by active energy rays, a thermoset product, and the like.

[0106] A method for producing a cured product of the (meth)acryloyl group-containing polyimide precursor includes the following steps. (1) Coating step of the (meth)acryloyl group-containing polyimide precursor (2) Drying step (3) Exposure / development step (4) Thermosetting step

[0107] [Coating step] Examples of the coating method include spin coater coating, bar coater coating, blade coater coating, curtain coater coating, and the like.

[0108] [Drying step] Examples of the drying conditions include conditions of standing still at 40°C to 130°C for 1 minute to 30 minutes using a circulating air dryer, a hot plate, a constant temperature bath, and the like.

[0109] [Exposure / development step] Exposure is performed by irradiating active energy rays such as ultraviolet rays, excimer laser light, and semiconductor laser light. The energy dose to be irradiated is, for example, 30 mJ / cm 2 ~3,500 mJ / cm 2 and the like.

[0110] Examples of the development method include a dipping method and a spraying method. Examples of the developer include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, and the like. Also, two or more of each solvent, for example, several kinds, can be used in combination.

[0111] (Thermal curing step) Examples of the thermal curing conditions include conditions of standing at 200°C to 350°C for 1 hour to 10 hours under reduced pressure or in a nitrogen atmosphere using a reduced-pressure dryer, a circulating-air dryer, or the like.

Examples

[0112] Hereinafter, the present invention will be specifically described through examples and comparative examples. However, the above description and the following examples are not described for the purpose of limiting the present invention. The present invention is limited only by the scope of the claims. Unless otherwise specifically described below, numerical values such as parts and % are based on mass.

[0113] Example 1-1: Synthesis of (meth)acryloyl group-containing polyimide precursor Into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 130.13 g (0.250 mol) of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride (product name "SD1100P", manufactured by SABIC Innovative Plastics Japan Co., Ltd.), 508.0 g of dimethylacetamide as a solvent, and 56.5 g of methylcyclohexane were charged, and the reaction vessel was heated until the temperature reached 45 to 50 °C. After the temperature reached 45 to 50 °C and SD1100P was dissolved, 39.81 g (0.188 mol) of m-tolidine (product name "m-TB HG", manufactured by Seika Corporation, hereinafter also referred to as m-TB), slurried with 50.0 g of dimethylacetamide, was charged over 15 minutes. A Dean-Stark tube / condenser was installed and filled with methylcyclohexane. Then, the temperature was gradually raised, and the water generated by imidization was collected by the Dean-Stark tube, and dehydration was carried out until a predetermined amount of water was generated or until the temperature reached 140 °C. Water and the solvent were taken out from the Dean-Stark tube, and the reaction vessel was heated to 150 °C while removing volatile substances and kept warm for 1 hour. After cooling to 60 °C, 100.82 g (0.325 mol) of 3,3'-oxydiphthalic anhydride (product name "ODPA-C", manufactured by MANAC Co., Ltd., hereinafter also referred to as ODPA), slurried with 200 g of dimethylacetamide, was charged. 72.11 g (0.360 mol) of 4,4'-diaminodiphenyl ether (product name "DPE", manufactured by Seika Corporation, hereinafter also referred to as ODA), slurried with 185.3 g of dimethylacetamide, was charged at 40 to 50 °C over 30 minutes. Then, it was kept warm at 50 °C for 1 hour. Next, it was cooled to room temperature and stirred for 12 hours. The reaction vessel was heated to 80 °C, and 67.98 g (0.438 mol) of 2-isocyanatoethyl methacrylate (product name "Karenz MOI", manufactured by Resonaak Co., Ltd.) was charged and reacted for 24 hours.

[0114] Unless otherwise specified, Example 1 and Comparative Example 1 other than Example 1-1 were carried out in the same manner as Example 1-1, except that they were changed as shown in the following table.

[0115] Example 18 was carried out in the same manner as Example 1-1, except that the type and amount of the monomer forming the amic acid structural unit, the amount of the isocyanate group-containing (poly) methacrylate used, and the polyisocyanate (Coronate HX: isocyanurate form of hexamethylene diisocyanate, manufactured by Tosoh Corporation) was used during the reaction of the resin with the isocyanate group-containing (poly) methacrylate).

[0116]

Table 1

[0117] <Explanation of Abbreviations> (Diamine)

Table 2

[0118] <Synthesis> 〇: The (meth)acryloyl group-containing polyimide precursor was obtained without problems. ×: (A (meth)acryloyl group-containing polyimide precursor could not be obtained (the reaction of the isocyanate group-containing (poly)(meth)acrylate did not proceed, or the (meth)acryloyl group-containing polyimide precursor was insoluble in the organic solvent))

[0119] <Shrinkage> (A dimethylacetamide solution (solid content: 25% by mass) containing a (meth)acryloyl group-containing polyimide precursor and Omnirad TPO at a solid content ratio of 100:5 was prepared. The prepared solution was coated on a PET film with a thickness of 50 μm using a bar coater #30 and heated at 80 °C for 20 minutes using a hot air dryer. Using a 365 nm illuminometer, UV irradiation was carried out under the condition of 1000 mJ / cm 2 and then immersed in cyclopentanone stirred by a magnetic stirrer for 1 minute and then dried at 100 °C for 5 minutes. The thickness after drying was 15 μm. It was heated at 230 °C for 4 hours under a nitrogen stream using an inert gas oven. The thickness after curing was measured, and those with a thickness of less than 13 μm were marked as ×, and those with a thickness of 13 μm or more were marked as ○.

[0120] <Chemical resistance> (A dimethylacetamide solution (solid content: 25% by mass) containing a (meth)acryloyl group-containing polyimide precursor and Omnirad TPO at a solid content ratio of 100:5 was prepared. The adjusted solution was coated on rolled copper foil using an applicator so that the thickness after curing would be 15 - 25 μm. It was heated at 80 °C for 20 minutes using a hot air dryer. Using a 365 nm illuminometer, UV irradiation was carried out under the condition of 1000 mJ / cm 2 and then immersed in cyclopentanone stirred by a magnetic stirrer for 1 minute and then heated at 230 °C for 4 hours under a nitrogen stream using an inert gas oven. The obtained copper / polyimide laminate film was immersed in an organic chemical solution (dimethyl sulfoxide: 25% TMAH aqueous solution = 92:8) at 65 °C for 60 minutes, and the change in film thickness before and after immersion was measured. Those with a film thickness change of less than 1 μm were marked as ◎, those with a film thickness change of 1 μm or more and less than 2 μm were marked as ○, and those with a film thickness change of 2 μm or more were marked as ×.

[0121] <Heat resistance> (Meta)acryloyl group-containing polyimide precursor and Omnirad TPO were used to prepare a dimethylacetamide solution (solid content: 25% by mass) with a solid content ratio of 100:5. The adjusted solution was coated onto a rolled copper foil using an applicator so that the thickness after curing would be 15 - 25 μm. It was heated at 80 °C for 20 minutes using a hot air dryer. Using a 365 nm illuminometer, it was irradiated with UV under the condition of 1000 mJ / cm 2 and then immersed in cyclopentanone being stirred with a magnetic stirrer for 1 minute. After that, it was heated at 230 °C for 4 hours under a nitrogen stream in an inert gas oven. The obtained copper / polyimide laminated film was immersed in an aqueous ferric oxide solution, and the aqueous solution was stirred until the copper dissolved. The obtained film was washed with deionized water and dried at 110 °C for 20 minutes to obtain a cured product (polyimide film).

[0122] (Coefficient of linear expansion, glass transition temperature) Measurement was carried out under the following conditions using a thermomechanical analyzer (product name: "TMA60", manufactured by Shimadzu Corporation), and the average coefficient of expansion from 100 °C to 140 °C was adopted. Also, for the glass transition temperature, the intersection temperature of the tangents before and after the slope change was adopted. Sample width: 10 mm Distance between chucks: 20 mm The temperature was raised from 40 °C to 300 °C at 10 °C / min Those with a glass transition temperature of 200 °C or higher and a coefficient of linear expansion of less than 70 ppm were marked as ○, and the others were marked as ×.

Claims

1. Imide structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 190 or more and a tetracarboxylic acid anhydride having an oxyphthalic anhydride group and a resin containing an amic acid structural unit derived from a reaction product of an aromatic diamine having a molecular weight of 190 to 300 with 4,4'-oxydiphthalic anhydride and / or 3,3',4,4'-biphenyltetracarboxylic dianhydride; A reaction product with an isocyanate group-containing (poly)(meth)acrylate. (Meth)acryloyl group-containing polyimide precursor.

2. The (meth)acryloyl group-containing polyimide precursor according to claim 1, wherein the aromatic diamine having a molecular weight of 190 to 300 is one or more selected from the group consisting of 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl thioether, 1,4-bis(4-aminophenoxy)benzene, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-diphenylmethane, and 4,4'-diamino-2,2'-dimethylbiphenyl.

3. A cured product of the (meth)acryloyl group-containing polyimide precursor according to claim 1 or 2.

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