(meth) acryloyl group-containing polyimide, photosensitive composition, cured product, and article

Abstract

[Problem] To provide a (meth) acryloyl group-containing polyimide, a photosensitive composition, a cured product, and an article. [Technical means] A polyimide containing a (meth) acryloyl group, said polyimide containing an acid anhydride unit containing a fluorine atom, and a diamine unit containing a fluorine atom and a biphenyl structure.

Description

Technical Field

[0001] The present disclosure relates to a (meth)acryloyl group-containing polyimide, a photosensitive composition, a cured product, and an article. Background Art

[0002] The applicant has conducted research and development of polyimide manufactured using dimer diamine (polyimide using dimer diamine) (Patent Document 1). The relative dielectric constant and dielectric loss tangent of the polyimide using dimer diamine are low. Therefore, the polyimide using dimer diamine is used as an adhesive for flexible copper-clad laminates using high-frequency electrical signals. [Prior art literature] [Patent Document]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2013-199645 Summary of the invention [Technical problem 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 for producing a cured product having good storage elastic modulus, lithographic properties, and linear expansion coefficient. [Technical means to solve technical problems]

[0005] According to the present disclosure, the following items are provided. (Item 1) A polyimide containing a (meth)acryloyl group, The (meth)acryloyl group-containing polyimide includes an acid anhydride unit containing a fluorine atom and a diamine unit containing a fluorine atom and a biphenyl structure. (Item 2) A photosensitive composition comprising the (meth)acryloyl group-containing polyimide described in the above item. (Item 3) The photosensitive composition according to the above item, wherein the content of the (meth)acryloyl group-containing polyimide is 40% by mass to 75% by mass based on 100% by mass of the photosensitive compound. (Item 4) A cured product of the photosensitive composition according to any one of the above items. (Item 5) An article comprising the solidified material described in the above item.

[0006] In the present disclosure, one or more features may be provided in further combinations than those explicitly shown. [Beneficial Effects]

[0007] The (meth)acryloyl group-containing polyimide of the present disclosure can produce a cured product having excellent storage elastic modulus, lithography properties, and linear expansion coefficient. DETAILED DESCRIPTION

[0008] In the whole of the present disclosure, the range of the numerical values ​​of each physical property value, content, etc. can be set appropriately (for example, selected from the values ​​described in the following items). Specifically, with respect to the numerical value α, when A3, A2, A1 (set as A3>A2>A1) and the like are cited, the range of the numerical value α can be listed as less than A3, less than A2, less than A3, less than A2, more than A1, more than A2, greater than A1, greater than A2, A1-A2 (more than A1 and less than A2), A1-A3, A2-A3, more than A1 and less than A3, more than A1 and less than A2, more than A2 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 less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 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 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 less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A3 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, etc.

[0009] As long as the problems to be solved by the present invention are solved, the components, conditions, numerical values ​​and the like are not particularly limited.

[0010] "αβ amount (A / B)" refers to the β amount (α) of A relative to B100α. Examples of α include mass %, mole %, and mass parts. Examples of β amount include content and usage amount. "Mass % content (A / B)" refers to the content (mass %) of A relative to B100 mass %.

[0011] "γ ratio (A / B)" refers to the γ ratio calculated by the formula "A÷B". Examples of the γ ratio include mass ratio and molar ratio.

[0012] The "non-volatile content" refers to the total mass of components other than the organic solvent and water. In one embodiment, the "non-volatile content of A" refers to the total mass of components remaining when 1 g of A is heated at 180°C to a constant weight.

[0013] “(Meth)acrylic acid” means “acrylic acid and / or methacrylic acid”. “(Meth)acrylate” means “acrylate and / or methacrylate”. “(Meth)acryloyl” means “acryloyl and / or methacryloyl”.

[0014] [(Meth)acryloyl group-containing polyimide: polyimide] The present disclosure relates to a (meth)acryloyl-containing polyimide, which comprises an acid anhydride unit containing a fluorine atom and a diamine unit containing a fluorine atom and a biphenyl structure.

[0015] <Fluorine-containing anhydride unit> The fluorine atom-containing acid anhydride may be used alone or in combination of two or more.

[0016] Examples of the fluorine-containing acid anhydride include 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,4-difluoropyromellitic acid dianhydride, and 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorophthalic dianhydride.

[0017] The mass % content (fluorine-containing anhydride unit / polyimide) includes, for example, 70 mass %, 69 mass %, 67 mass %, 65 mass %, 63 mass %, 61 mass %, 60 mass %, 59 mass %, 57 mass %, 55 mass %, 53 mass %, 51 mass %, 50 mass %, etc. In one embodiment, the content is preferably 50 mass % to 70 mass %.

[0018] The mole % content (fluorine-containing anhydride unit / polyimide) includes, for example, 70 mol%, 69 mol%, 67 mol%, 65 mol%, 63 mol%, 61 mol%, 60 mol%, 59 mol%, 57 mol%, 55 mol%, 53 mol%, 51 mol%, 50 mol%, etc. In one embodiment, the content is preferably 50 mol% to 70 mol%.

[0019] <Diamine unit containing fluorine atom and biphenyl structure> The diamine containing a fluorine atom and a biphenyl structure may be used alone or in combination of two or more.

[0020] Examples of the diamine containing a fluorine atom and a biphenyl structure include 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diamino-2,2'-difluorobiphenyl, 3,3'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 3,3'-diamino-2,2'-difluorobiphenyl, 2,2'-diamino-3,3'-bis(trifluoromethyl)biphenyl, and 2,2'-diamino-3,3'-difluorobiphenyl. , 4,4'-diamino-3,3'-bis(trifluoromethyl)biphenyl, 4,4'-diamino-3,3'-difluorobiphenyl, 2,2'-diamino-4,4'-bis(trifluoromethyl)biphenyl, 2,2'-diamino-4,4'-difluorobiphenyl, 3,3'-diamino-4,4'-bis(trifluoromethyl)biphenyl, 3,3'-diamino-4,4'-difluorobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc.

[0021] The mass % content (fluorine atom-containing diamine unit / polyimide) is, for example, 40 mass %, 39 mass %, 37 mass %, 35 mass %, 33 mass %, 31 mass %, 30 mass %, 29 mass %, 27 mass %, 25 mass %, 23 mass %, 21 mass %, 20 mass %, etc. In one embodiment, the content is preferably 20 to 40 mass %.

[0022] Examples of the mole % content (fluorine-containing diamine unit / polyimide) include 40 mol %, 39 mol %, 37 mol %, 35 mol %, 33 mol %, 31 mol %, 30 mol %, 29 mol %, 27 mol %, 25 mol %, 23 mol %, 21 mol %, 20 mol %, etc. In one embodiment, the content is preferably 20 to 40 mol %.

[0023] <Unit containing a (meth)acryloyl group> The unit containing (meth) acryloyl group includes, for example, the reaction product of the diamine unit containing carboxyl group and the (multi) (meth) acrylate containing isocyanate group, the reaction product of the diamine unit containing carboxyl group and the (multi) (meth) acrylate containing glycidyl group, the reaction product of the diamine unit containing carboxyl group and the (multi) (meth) acrylate containing anhydride group, the reaction product of the diamine unit containing carboxyl group and the (multi) (meth) acrylate containing hydroxyl group, etc. In one embodiment, the unit containing (meth) acryloyl group preferably includes the reaction product of the diamine unit containing carboxyl group and the (multi) (meth) acrylate containing isocyanate group, etc. Preferred reasons include, for example, the storage elastic modulus of the cured product is increased, the linear expansion coefficient of the cured product is decreased, the (meth) acryloyl group introduction amount is increased, and the dielectric properties (dielectric constant, dielectric loss tangent) are decreased.

[0024] (Carboxyl-containing diamine) The carboxyl group-containing diamines may be used alone or in combination of two or more.

[0025] Examples of the carboxyl group-containing diamine include diaminobenzoic acid, alkylenebis(2-aminobenzoic acid), bis(aminophenoxy)benzoic acid, diaminocarboxydiphenylalkane, and diaminodicarboxydiphenyl ether.

[0026] Examples of the diaminobenzoic acid include 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, and 3,4-diaminobenzoic acid.

[0027] Examples of the alkylenebis(2-aminobenzoic acid) include 5,5′-methylenebis(2-aminobenzoic acid) and 5,5′-methylenebis(3-aminobenzoic acid).

[0028] Examples of the bis(aminophenoxy)benzoic acid include 3,5-bis(3-aminophenoxy)benzoic acid and 3,5-bis(4-aminophenoxy)benzoic acid.

[0029] Examples of the diaminocarboxydiphenylalkane include 3,3′-diamino-4,4′-dicarboxydiphenylmethane and 3,3′-dicarboxy-4,4′-diaminodiphenylmethane.

[0030] Examples of the diaminodicarboxy diphenyl ether include 3,3′-diamino-4,4′-dicarboxy diphenyl ether.

[0031] Examples of the mol% content (carboxyl group-containing diamine unit / diamine unit) include 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, etc. In one embodiment, the content is preferably 20 to 50 mol%.

[0032] Examples of the mass % content (carboxyl group-containing diamine unit / diamine unit) include 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, etc. In one embodiment, the content is preferably 10 to 50 mass %.

[0033] Examples of the mol% content (carboxyl group-containing diamine unit / (meth)acryloyl group-containing polyimide) include 16 mol%, 15 mol%, 13 mol%, 11 mol%, 10 mol%, 9 mol%, 7 mol%, 5 mol%, etc. In one embodiment, the content is preferably 5 mol% to 16 mol%.

[0034] Examples of the mass % content (carboxyl group-containing diamine unit / (meth)acryloyl group-containing polyimide) include 12 mass %, 10 mass %, 9 mass %, 7 mass %, 5 mass %, 4 mass %, etc. In one embodiment, the content is preferably 4 mass % to 12 mass %.

[0035] (isocyanate group-containing (poly) (meth) acrylate) The isocyanate group-containing (poly)(meth)acrylate may be used alone or in combination of two or more.

[0036] In one embodiment, the isocyanate group-containing (poly) (meth)acrylate has 1 to 2 (meth) acryloyl groups.

[0037] The isocyanate group-containing (poly)(meth)acrylate is represented by the following formula. [Chemistry 1] (Where R i1 represents a hydrogen atom or a methyl group. i2 represents a substituted or unsubstituted alkylene group. i3 represents a substituted or unsubstituted alkylene group. Z represents a single bond or an oxygen atom. )

[0038] The alkylene group preferably includes an alkylene group having 1 to 4 carbon atoms, and more preferably includes a methylene group.

[0039] As the substituent of the alkylene group, preferably an alkyl group and a methoxy(meth)acryloyl group are mentioned, and more preferably a methyl group and a methoxy(meth)acryloyl group are mentioned.

[0040] Examples of the isocyanate group-containing (poly) (meth)acrylate include 2-isocyanateethyl (meth)acrylate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, and 2-(2-(meth)acryloyloxyethoxy)ethyl isocyanate.

[0041] Examples of the mole % content (unit containing a (meth)acryloyl group / polyimide containing a (meth)acryloyl group) include 5 mol%, 4.5 mol%, 4 mol%, 3.5 mol%, 3 mol%, 2.5 mol%, 2 mol%, 1.5 mol%, 1 mol%, 0.5 mol%, 0.1 mol%, etc. In one embodiment, the content is preferably 0.1 mol% to 5 mol%.

[0042] The mass % content (unit containing (meth) acryloyl group / polyimide containing (meth) acryloyl group) includes, for example, 20 mass %, 19 mass %, 17 mass %, 15 mass %, 13 mass %, 11 mass %, 10 mass %, 9 mass %, 7 mass %, 5 mass %, 3 mass %, 1 mass %, etc. In one embodiment, the content is preferably 1 mass % to 20 mass %.

[0043] <Other structural units> In one embodiment, the (meth)acryloyl group-containing polyimide may optionally include structural units other than those described above (other structural units). Other structural units may be included alone or in combination of two or more.

[0044] Examples of other structural units include tricarboxylic anhydride units.

[0045] In one embodiment, the mass % content (other structural units / (meth)acryloyl group-containing polyimide) is preferably less than 1 mass %, less than 0.1 mass %, less than 0.01 mass %, or 0 mass %.

[0046] In one embodiment, the mol% content (other structural units / (meth)acryloyl group-containing polyimide) is preferably less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, or 0 mol%.

[0047] <Physical properties ((meth)acryloyl group-containing polyimide)> Examples of the weight average molecular weight ((meth)acryloyl group-containing polyimide) include 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, and 10,000. In one embodiment, the weight average molecular weight is preferably 10,000 to 100,000.

[0048] Examples of the number average molecular weight ((meth)acryloyl group-containing polyimide) include 50,000, 40,000, 30,000, 20,000, 10,000, and 5,000. In one embodiment, the number average molecular weight is preferably 5,000 to 50,000.

[0049] Examples of measurement conditions (weight average molecular weight, number average molecular weight) include the following conditions. Model: Product name "HLC-8320GPC" (manufactured by Tosoh Corporation) Column: Product name "TSKgel guardcolum SuperHZ-L + TSKgelSuperHZM-M" (manufactured by Tosoh Corporation) Developing solvent: tetrahydrofuran Flow rate: 0.35mL / min Measurement temperature: 40℃ Detector: refractive index (RI) Standard: Polystyrene Polymer concentration: 0.2wt%

[0050] Examples of the (meth)acrylic acid equivalent (polyimide containing a (meth)acryloyl group) include 10,000 g / eq, 9500 g / eq, 9000 g / eq, 8500 g / eq, 8000 g / eq, 7500 g / eq, 7000 g / eq, 6500 g / eq, 6000 g / eq, 5500 g / eq, 5000 g / eq, 4500 g / eq, 4000 g / eq, 3500 g / eq, 3000 g / eq, 2500 g / eq, 2000 g / eq, 1500 g / eq, 1000 g / eq, 500 g / eq, etc. In one embodiment, the (meth)acrylic acid equivalent is preferably 500 g / eq to 10,000 g / eq.

[0051] <Production method ((meth)acryloyl group-containing polyimide)> The (meth)acryloyl group-containing polyimide can be produced by a production method including the following steps. (1) Polyamic acid synthesis process (2) Polyimide synthesis process (3) (Meth)acryloyl group introduction step

[0052] As reaction conditions (polyamic acid synthesis step), the following conditions are mentioned, for example. Reaction temperature: 20℃~100℃ Reaction time: 1 hour to 10 hours

[0053] Examples of the reaction conditions (polyimide synthesis step) include the following conditions. Reaction temperature: 100℃~200℃ Reaction time: 1 hour to 20 hours

[0054] Examples of the reaction conditions ((meth)acryloyl group introduction step) include the following conditions. Reaction temperature: 70℃~100℃ Reaction time: 1 hour to 20 hours

[0055] Examples of the reaction catalyst include tertiary amines and phosphines.

[0056] Examples of the tertiary amine include triethylamine and dimethylaniline.

[0057] Examples of the phosphine include triphenylphosphine and the like.

[0058] Examples of the dehydrating agent include acid anhydride and the like.

[0059] Examples of the acid anhydride include acetic anhydride and benzoic anhydride.

[0060] Examples of the reaction solvent include the organic solvents described below.

[0061] [Photosensitive composition: composition] The present disclosure relates to a photosensitive composition, comprising the above-mentioned (meth)acryloyl-containing polyimide.

[0062] <(Meth)acryloyl group-containing polyimide> The mass % content (non-volatile component of the (meth)acryloyl-containing polyimide / photosensitive composition) includes, for example, 100 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, etc. In one embodiment, the content is preferably 40 mass % to 100 mass %.

[0063] <Photosensitive compounds> In one embodiment, the photosensitive composition may optionally include a photosensitive compound. The photosensitive compound may be used alone or in combination of two or more.

[0064] Examples of the photosensitive compound include poly(meth)acrylate and the like.

[0065] “Multi (meth)acrylate” refers to a compound having two or more (meth)acryloyl groups.

[0066] Examples of the poly(meth)acrylate include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, (poly)glycerol poly(meth)acrylate, and urethane poly(meth)acrylate.

[0067] Examples of the (poly)pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate and tripentaerythritol octa(meth)acrylate.

[0068] Examples of the (poly)trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane di(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, and di-trimethylolpropane tetra(meth)acrylate.

[0069] Examples of the (poly)glycerol poly(meth)acrylate include glycerol di(meth)acrylate, glycerol tri(meth)acrylate, diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, and diglycerol tetra(meth)acrylate.

[0070] (Urethane poly(meth)acrylate) Examples of the urethane poly(meth)acrylate include a reaction product of a compound group consisting of a hydroxyl group-containing poly(meth)acrylate and a polyisocyanate.

[0071] <Hydryl-containing poly(meth)acrylate> Examples of the hydroxyl group-containing poly(meth)acrylate include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, and (poly)glycerol poly(meth)acrylate.

[0072] <Polyisocyanate> The polyisocyanate may be used alone or in combination of two or more.

[0073] “Polyisocyanate” refers to a compound having two or more isocyanate groups (—N═C═O).

[0074] Examples of the polyisocyanate include linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and biuret forms, isocyanurate forms, allophanate forms, and adduct forms thereof.

[0075] Examples of the linear aliphatic polyisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate and decamethylene diisocyanate.

[0076] Examples of the branched aliphatic polyisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0077] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, bridged alicyclic polyisocyanate, and condensed alicyclic polyisocyanate.

[0078] Examples of the monocyclic alicyclic polyisocyanate include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane diisocyanate.

[0079] Examples of the bridged alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0080] Examples of the condensed-ring alicyclic polyisocyanate include bicyclodecylene diisocyanate and the like.

[0081] Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanate and condensed-ring aromatic polyisocyanate.

[0082] Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, and tetramethyl-m-xylylene diisocyanate.

[0083] Examples of the condensed ring aromatic polyisocyanate include 1,5-naphthalene diisocyanate and the like.

[0084] In one embodiment, the photosensitive compound is preferably (poly)pentaerythritol poly(meth)acrylate, and more preferably dipentaerythritol poly(meth)acrylate. The reason for this preference is, for example, that the linear expansion coefficient of the cured product decreases.

[0085] The mass % content (photosensitive compound / photosensitive composition non-volatile component) includes, for example, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 60 mass %.

[0086] Examples of the mass % content ((meth)acryloyl group-containing polyimide / photosensitive compound) include 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, etc. In one embodiment, the content is preferably 40 to 75 mass %.

[0087] <Photopolymerization initiator> In one embodiment, the photosensitive composition may optionally include a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more.

[0088] Examples of the photopolymerization initiator include an α-hydroxydimethylacetophenone group-containing photopolymerization initiator, α-hydroxyphenylcycloalkyl ketone, α-aminophenylalkyl ketone, benzyl dimethyl ketal, unsubstituted or substituted phenylalkyl ketone, unsubstituted or substituted benzil, unsubstituted or substituted benzophenone, acylphosphine oxide, substituted thioxanthone, and oxime ester.

[0089] Examples of the α-hydroxydimethylacetophenone group-containing photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropane-1-one.

[0090] Examples of the α-hydroxyphenylcycloalkyl ketone include 1-hydroxycyclohexyl phenyl ketone and the like.

[0091] Examples of α-aminoalkylphenone include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one and the like.

[0092] Examples of benzyl dimethyl ketal include 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0093] Examples of the unsubstituted or substituted alkyl phenone include benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4′-morpholinobutylphenone, 2-methyl-4′-(methylthio)-2-morpholinopropiophenone, 2-isonitrosopropiophenone, and 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0094] Examples of the unsubstituted or substituted benzil include benzil and anisil (p-anisil).

[0095] Examples of the unsubstituted or substituted benzophenone include benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 1,4-dibenzoylbenzene, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and methyl 2-benzoylbenzoate.

[0096] Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0097] Examples of the substituted thioxanthone include 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0098] Examples of oxime esters include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyloxime)] (1,2-oktandione, 1-[4-(fenilthio)-, 2-(O-benziloxime)]) (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one); Ethyl ketone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(ortho Acetyl oxime)(エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-, 1-(O-アセチルオキシム)) (i.e. 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylene)amino)oxy)ethane-1-one, etc.

[0099] In one embodiment, the photopolymerization initiator is preferably an oxime ester. The reason for being preferred is, for example, that the linear expansion coefficient of the cured product is reduced.

[0100] Examples of the mass % content (photopolymerization initiator / photosensitive composition non-volatile component) include 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 10 mass %.

[0101] <Chain transfer agent> In one embodiment, the photosensitive composition may optionally include a chain transfer agent. The chain transfer agent may be used alone or in combination of two or more.

[0102] Examples of the chain transfer agent include thiol group-containing chain transfer agents.

[0103] Examples of the thiol group-containing chain transfer agent include tetraethylene glycol bis(3-mercaptopropionate), tetrapropylene glycol bis(3-mercaptopropionate), polyethylene glycol bis(3-mercaptopropionate), polypropylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), and dipentaerythritol hexa(3-mercaptopropionate).

[0104] The mass % content (chain transfer agent / photosensitive composition non-volatile component) includes, for example, 20 mass %, 18 mass %, 16 mass %, 15 mass %, 14 mass %, 12 mass %, 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 20 mass %.

[0105] <Organic solvents> In one embodiment, the photosensitive composition may optionally contain an organic solvent. The organic solvent may be used alone or in combination of two or more.

[0106] Examples of the organic solvent include aprotic polar solvents, alicyclic solvents, alcohol solvents, and aromatic solvents.

[0107] Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylcaprolactam, methyl triglyme, and methyl diglyme.

[0108] Examples of the alicyclic solvent include cyclohexanone and methylcyclohexane.

[0109] Examples of the alcohol solvent include methanol, ethanol, propanol, benzyl alcohol, and cresol.

[0110] Examples of the aromatic solvent include toluene.

[0111] The mass % content (organic solvent / photosensitive composition) includes, for example, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 90 mass %.

[0112] <Additives> The photosensitive composition may optionally contain an agent other than any of the above as an additive.

[0113] Examples of the additives include crosslinking agents, flame retardants, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, release agents, surface treatment agents, viscosity modifiers, inorganic fillers, organic fillers, and the like.

[0114] In one embodiment, the mass % content (additive / photosensitive composition) is preferably less than 1 mass %, less than 0.1 mass %, less than 0.01 mass %, or 0 mass %.

[0115] In one embodiment, the content by mass (additive / any of the (meth)acryloyl group-containing polyimide, poly(meth)acrylate, photopolymerization initiator, chain transfer agent, and organic solvent) is preferably less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, or 0 part by mass.

[0116] The photosensitive composition can be produced by dispersing and mixing the above-mentioned reagents.

[0117] Examples of the dispersing and mixing means include an emulsifying disperser and an ultrasonic dispersing device.

[0118] Examples of the uses (photosensitive composition) include photosensitive resist compositions, photosensitive compositions for dry film resists, photosensitive sealing compositions, photosensitive resist compositions for hollow packages, photosensitive sealing compositions for hollow packages, photosensitive compositions for micro flow paths, photosensitive compositions for forming MEMS (Micro Electro Mechanical Systems) structures, photosensitive compositions for forming waveguides, photosensitive compositions for screen printing plates, and compositions for photosensitive adhesives.

[0119] [cured material] The present disclosure relates to a cured product of the photosensitive composition.

[0120] Examples of the cured product include active energy ray-cured products and thermally cured products.

[0121] The cured product can be produced by a production method including the following steps. (1) Coating process (2) Drying process (3) Exposure / Development Process

[0122] (Coating process) Examples of the coating method include spin coater coating, bar coater coating, knife coater coating, curtain coater coating, and the like.

[0123] (Drying process) Examples of drying equipment include circulating air dryers, hot plates, thermostatic chambers, etc. Examples of drying temperatures include 40° C. to 150° C. Examples of drying times include 1 minute to 30 minutes.

[0124] (Exposure / Development Process) Examples of the exposure light source include ultraviolet rays, excimer lasers, active energy rays such as semiconductor lasers, etc. The irradiation dose is, for example, 30 mJ / cm 2 ~3,500mJ / cm 2 wait.

[0125] Examples of the developing method include an immersion method and a spray method. Examples of the developing solution include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. The developing solution may be used alone or in combination of two or more.

[0126] Examples of the thermal curing conditions include the following conditions. Temperature: 200℃~350℃ Time: 1 hour to 10 hours

[0127] [thing] The present disclosure relates to an article comprising the above-mentioned cured product.

[0128] Examples of the articles include electronic components, filter devices, semiconductor elements, mobile terminals, servers, network switches, rigid printed circuit boards, flexible printed circuit boards, and the like. [Example]

[0129] The present invention is specifically described below by examples and comparative examples. However, the above description and the following examples are not recorded for the purpose of limiting the present invention. The present invention is limited only by the scope of the claims. Unless otherwise specified, the numerical values ​​such as parts and % are based on mass.

[0130] Example 1 (1) Production of (meth)acryloyl-containing polyimide Into a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen inlet tube, 29.0 g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (trade name "6FDA", manufactured by Daikin Industry Co., Ltd., hereinafter referred to as 6FDA), 16.5 g of methylcyclohexane, and 82.7 g of cyclohexanone were added, and heated to 60°C. Then, 3.8 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (trade name: "TFMB", manufactured by Seika Co., Ltd., hereinafter referred to as TFMB) was slowly added, and 12.0 g of 3,5-diaminobenzoic acid (trade name: "3,5-DABA", manufactured by Nippon Junryo Pharmaceutical Co., Ltd., hereinafter referred to as DABA) was added dropwise, and an imidization reaction was carried out at 140°C for 12 hours to obtain a polyimide solution. Into a reaction container containing 100 g of the polyimide solution, 1.7 g of 2-isocyanateethyl acrylate (trade name: "Karenzu AOI", manufactured by Showa Denko K.K.) and 18.0 g of cyclohexanone were added, and the mixture was heated to 80° C., and 1.0 g of triphenylphosphine was added to react for 7 hours to obtain a (meth)acryloyl-containing polyimide solution (non-volatile content 30%). (2) Production (Photosensitive Composition) 23.3 g (70 parts by mass) of a (meth)acryloyl-containing polyimide solution, 3.0 g (30 parts by mass) of dipentaerythritol polyacrylate, 0.5 g of 1.2-octanedione, 1-[4-(phenylthio)-,2-(o-benzoyl oxime)] (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octane-1-one) (product name "Omnirad OXE01", manufactured by IGM Resins), and 8.2 g of cyclohexanone are mixed and stirred thoroughly to obtain a photosensitive composition having a non-volatile component content of 30%.

[0131] Unless otherwise specified, the following examples are implemented in the same manner as above except for making changes as shown in the table.

[0132]

Table 1

[0133] <Explanation> The figures for anhydrides and diamines in the table are in mol %. BISDA: 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride (product name "BisDA-1000", manufactured by SABIC Technology Co., Ltd.) DABPAF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Seika Co., Ltd.) Tolidin: m-tolidine (manufactured by Seika Co., Ltd.)

[0134] The prepared photosensitive composition was applied on a 0.7 mm thick glass substrate using a bar coater and dried at 120° C. for 5 minutes to obtain dry films having a film thickness of 10 μm or 20 μm.

[0135] <Samples for evaluating photolithography> For the above 10 μm thick dry film, 300 mJ / cm 2 (ghI line parallel exposure device, UV-A range) UV curing was performed to obtain a cured product. This cured product was used as a sample for evaluating photolithography properties.

[0136] Lithography The cured film prepared and exposed under the conditions described in <Sample for Evaluation of Photolithography> was immersed in cyclopentanone for 60 seconds for development. The cured film after development was observed with a confocal laser microscope to confirm whether a concave portion of Φ30 μm was formed, and the evaluation was determined according to the following evaluation criteria. <Evaluation Criteria> ○: No residue △: The exposed portion was dissolved. ×: No pattern

[0137] <Samples for evaluating storage elastic modulus and linear expansion coefficient> For the above 20 μm dry film, a ghI line parallel exposure device was used with a curing radiation dose of 300 mJ / cm in the UV-A region. 2 Irradiate and UV cure. Then, expose at 200°C for 60 minutes and bake to obtain a cured product. The cured product is cut into 1 cm width and peeled off from the glass substrate to obtain a test piece for measuring the storage elastic modulus. In addition, it is cut into 0.4 cm width for evaluating the linear expansion coefficient.

[0138] Storage elastic modulus The test piece obtained in <Sample for evaluation of storage elastic modulus> was measured under the following measurement conditions using a dynamic viscoelasticity measuring apparatus (manufactured by Hitachi High-Tech Science & Technology Co., Ltd., DMA7100). Measurement conditions: nitrogen atmosphere, tensile mode, frequency 1.0 Hz, distance between chucks 10 mm.

[0139] Measurement (linear expansion coefficient) The test piece obtained in <Sample for evaluating linear expansion coefficient> was measured under the following measurement conditions using a thermomechanical analyzer (TMA7100, manufactured by Hitachi High-Tech Science & Technology Co., Ltd.). Measurement conditions: nitrogen atmosphere, distance between chucks 10 mm.

Claims

1. A polyimide containing a (meth)acryloyl group, The (meth)acryloyl group-containing polyimide includes an acid anhydride unit containing a fluorine atom and a diamine unit containing a fluorine atom and a biphenyl structure. 2 . A photosensitive composition comprising the (meth)acryloyl group-containing polyimide according to claim 1 .

3. The photosensitive composition according to claim 2, wherein The content of the (meth)acryloyl group-containing polyimide is 40% to 75% by mass based on 100% by mass of the photosensitive compound.

4. A cured product of the photosensitive composition according to claim 2 or 3.

5. An article comprising the cured product according to claim 4.

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