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

Abstract

To provide a (meth)acryloyl group-containing polyimide, a photosensitive composition, a cured product, and an article.SOLUTION: A (meth)acryloyl group-containing polyimide includes: a fluorine atom-containing acid anhydride unit; and a fluorine atom- and biphenyl structure-containing diamine unit.SELECTED DRAWING: None

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 technology]

[0002] The applicant is conducting research and development of polyimides produced using dimer diamine (dimer diamine-containing polyimides) (Patent Document 1). Dimer diamine-containing polyimides have low relative dielectric constants and dielectric loss tangents. Therefore, dimer diamine-containing polyimides are used as adhesives for flexible copper-clad laminates that use high-frequency electrical signals. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2013-199645 A Summary of the Invention [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 modulus, lithographic properties and linear expansion coefficient. [Means for solving the problem]

[0005] The present disclosure provides the following: (Item 1) A (meth)acryloyl group-containing polyimide, The (meth)acryloyl group-containing polyimide contains a fluorine atom-containing acid anhydride unit and a fluorine atom- and biphenyl structure-containing diamine unit. (Meth)acryloyl group-containing polyimide. (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 relative to 100% by mass of the photosensitive compound. (Item 4) A cured product of the photosensitive composition according to any one of the preceding items. (Item 5) An article comprising the cured product described above.

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

[0007] By using the (meth)acryloyl group-containing polyimide of the present disclosure, it is possible to produce a cured product having good storage modulus, lithographic properties, and linear expansion coefficient. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Throughout this disclosure, the range of the values ​​of the physical properties, contents, etc. may be set as appropriate (for example, by selecting from the values ​​described in each item below). Specifically, when the value α includes A3, A2, A1 (where A3>A2>A1), the range of the value α may include 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 ...2, 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, and the like.

[0009] As long as the problem to be solved by the present invention is solved, the components, conditions, values, etc. are not particularly limited.

[0010] "αβ content (A / B)" means the β content (α) of A relative to 100α of B. α can be, for example, mass %, mol %, or parts by mass. β content can be, for example, the content or amount used. "% by mass content (A / B)" means the content (% by mass) of A relative to 100% by mass of B.

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

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

[0013] "(Meth)acrylic" means "acrylic and / or methacrylic". "(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 group-containing polyimide, which contains a fluorine atom-containing acid anhydride unit and a fluorine atom- and biphenyl structure-containing diamine unit.

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

[0016] Examples of fluorine atom-containing acid anhydrides include 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,4-difluoropyromellitic dianhydride, and 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorobenzene dianhydride.

[0017] Examples of the mass % content (fluorine atom-containing acid anhydride unit / polyimide) include 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] Examples of the mol % content (fluorine atom-containing acid anhydride unit / polyimide) include 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 fluorine atom- and biphenyl structure-containing diamines may be used alone or in combination of two or more kinds.

[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, 2,2'-diamino-3,3'-difluorobiphenyl, 4,4'-diamino-2,2'-difluorobiphenyl, 3,3'-diamino-2,2'-difluorobiphenyl, 2,2'-diamino-3,3'-difluorobiphenyl, ,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, and the like.

[0021] Examples of the mass% content (fluorine atom-containing diamine unit / polyimide) include 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 mass% to 40 mass%.

[0022] Examples of the mol % content (fluorine atom-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 mol % to 40 mol %.

[0023] <(Meth)acryloyl Group-Containing Unit> Examples of the (meth)acryloyl group-containing unit include a reaction product of a carboxyl group-containing diamine unit and an isocyanate group-containing (poly)(meth)acrylate, a reaction product of a carboxyl group-containing diamine unit and a glycidyl group-containing (poly)(meth)acrylate, a reaction product of a carboxyl group-containing diamine unit and an acid anhydride group-containing (poly)(meth)acrylate, and a reaction product of a carboxyl group-containing diamine unit and a hydroxyl group-containing (poly)(meth)acrylate. In one embodiment, the (meth)acryloyl group-containing unit is preferably a reaction product of a carboxyl group-containing diamine unit and an isocyanate group-containing (poly)(meth)acrylate. Reasons for the preference include, for example, an improvement in the storage modulus of the cured product, a decrease in the linear expansion coefficient of the cured product, an improvement in the amount of (meth)acryloyl groups introduced, and a decrease in dielectric properties (dielectric constant, dielectric loss tangent).

[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 diaminobenzoic acids 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 bis(aminophenoxy)benzoic acids include 3,5-bis(3-aminophenoxy)benzoic acid and 3,5-bis(4-aminophenoxy)benzoic acid.

[0029] Examples of diaminocarboxydiphenylalkanes include 3,3'-diamino-4,4'-dicarboxydiphenylmethane and 3,3'-dicarboxy-4,4'-diaminodiphenylmethane.

[0030] An example of the diaminodicarboxydiphenyl ether is 3,3'-diamino-4,4'-dicarboxydiphenyl ether.

[0031] Examples of the molar 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 mol% to 50 mol%.

[0032] The mass % content (carboxyl group-containing diamine unit / diamine unit) can be, for example, 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 mass % 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] The mass % content (carboxyl group-containing diamine unit / (meth)acryloyl group-containing polyimide) is, for example, 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)acrylates 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. [ka] (In the formula, R i1 R represents a hydrogen atom or a methyl group. i2 R 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 is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group.

[0039] 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.

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

[0041] Examples of the mol % content ((meth)acryloyl group-containing unit / (meth)acryloyl group-containing polyimide) 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 %, and 0.1 mol %. In one embodiment, the content is preferably 0.1 mol % to 5 mol %.

[0042] The mass % content ((meth)acryloyl group-containing unit / (meth)acryloyl group-containing polyimide) can be, 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 building blocks> In one embodiment, the (meth)acryloyl group-containing polyimide may optionally contain structural units (other structural units) other than those described above. The other structural units may be contained alone or in combination of two or more kinds.

[0044] Examples of the other constituent units include tricarboxylic acid 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 %, 0 mass %, and the like.

[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 %, 0 mol %, or the like.

[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] The measurement conditions (weight average molecular weight, number average molecular weight) are, for example, as follows: Model: Product name "HLC-8320GPC" (manufactured by Tosoh Corporation) Column: Product name "TSKgel guardcolum SuperHZ-L + TSKgel SuperHZM-M" (manufactured by Tosoh Corporation) Developing solvent: Tetrahydrofuran Flow rate: 0.35mL / min Measurement temperature: 40℃ Detector: RI Standard: Polystyrene Polymer concentration: 0.2wt%

[0050] Examples of the (meth)acrylic equivalent ((meth)acryloyl group-containing polyimide) include 10,000g / eq, 9500g / eq, 9000g / eq, 8500g / eq, 8000g / eq, 7500g / eq, 7000g / eq, 6500g / eq, 6000g / eq, 5500g / eq, 5000g / eq, 4500g / eq, 4000g / eq, 3500g / eq, 3000g / eq, 2500g / eq, 2000g / eq, 1500g / eq, 1000g / eq, and 500g / eq. In one embodiment, the (meth)acrylic equivalent is preferably 500g / eq to 10,000g / 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] The reaction conditions (polyamic acid synthesis step) are, for example, the following conditions. Reaction temperature: 20℃~100℃ Reaction time: 1 to 10 hours

[0053] The reaction conditions (polyimide synthesis step) are, for example, 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] The phosphine may, for example, be triphenylphosphine.

[0058] The dehydrating agent may, for example, be an acid anhydride.

[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 group-containing polyimide.

[0062] <(Meth)acryloyl group-containing polyimide> Examples of the mass % content ((meth)acryloyl group-containing polyimide / non-volatile content of photosensitive composition) include 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 compound> In one embodiment, the photosensitive composition may optionally contain a photosensitive compound. The photosensitive compounds may be used alone or in combination of two or more.

[0064] The photosensitive compound may, for example, be poly(meth)acrylate.

[0065] "Poly(meth)acrylate" means 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)glycerin poly(meth)acrylate, and urethane poly(meth)acrylate.

[0067] Examples of (poly)pentaerythritol poly(meth)acrylates 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, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate.

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

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

[0071] <Hydroxyl group-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)glycerin poly(meth)acrylate.

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

[0073] "Polyisocyanate" means a compound having two or more isocyanate groups (-N=C=O).

[0074] Examples of the polyisocyanate include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and biuret forms, isocyanurate forms, allophanate forms, adduct forms, and the like 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 polyisocyanates, crosslinked cyclic alicyclic polyisocyanates, and condensed cyclic alicyclic polyisocyanates.

[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 crosslinked alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0080] An example of the condensed ring alicyclic polyisocyanate is bicyclodecylene diisocyanate.

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

[0082] Examples of the monocyclic aromatic polyisocyanate include dialkyl diphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

[0083] An example of the condensed ring aromatic polyisocyanate is 1,5-naphthylene diisocyanate.

[0084] In one embodiment, the photosensitive compound is preferably (poly)pentaerythritol poly(meth)acrylate, more preferably dipentaerythritol poly(meth)acrylate. The reason why it is preferable is, for example, a decrease in the linear expansion coefficient of the cured product.

[0085] Examples of the mass % content (photosensitive compound / non-volatile content of photosensitive composition) include 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 mass % to 75 mass %.

[0087] <Photopolymerization initiator> In one embodiment, the photosensitive composition may optionally contain 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-hydroxycycloalkylphenone, α-aminoalkylphenone, benzyl dimethyl ketal, unsubstituted or substituted alkylphenone, unsubstituted or substituted benzyl, unsubstituted or substituted benzophenone, acylphosphine oxide, substituted thioxanthone, and oxime ester.

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

[0090] Examples of α-hydroxycycloalkylphenones include 1-hydroxycyclohexyl phenyl ketone.

[0091] Examples of α-aminoalkylphenones include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0092] An example of the benzyl dimethyl ketal is 2,2-dimethoxy-1,2-diphenylethan-1-one.

[0093] Examples of unsubstituted or substituted alkylphenones 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'-morpholinobutyrophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-isonitrosopropiophenone, and 2,2-dimethoxy-1,2-diphenylethan-1-one.

[0094] Examples of unsubstituted or substituted benzyl include benzyl and p-anisyl.

[0095] Examples of unsubstituted or substituted benzophenones 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, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.

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

[0098] Oxime esters include, for example, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one); Examples include ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (i.e., 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidene)amino)oxy)ethan-1-one).

[0099] In one embodiment, the photopolymerization initiator is preferably an oxime ester. The reason why it is preferable is, for example, that it reduces the linear expansion coefficient of the cured product.

[0100] Examples of the mass % content (photopolymerization initiator / non-volatile content of photosensitive composition) 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 agents may be used alone or in combination of two or more.

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

[0103] Examples of thiol group-containing chain transfer agents 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 hexakis(3-mercaptopropionate).

[0104] Examples of the mass % content (chain transfer agent / non-volatile content of the photosensitive composition) include 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 solvent> 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 kinds.

[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, dimethylsulfoxide, 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] The aromatic solvent may, for example, be toluene.

[0111] Examples of the mass % content (organic solvent / photosensitive composition) include 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 (additive) that does not fall into any of the above categories.

[0113] Examples of the additives include crosslinking agents, flame retardants, dehydrating agents, plasticizers, weather resistance agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brightening agents, colorants, conductive agents, release agents, surface treatment agents, viscosity adjusters, inorganic fillers, and organic fillers.

[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 %, 0 mass %, and the like.

[0115] In one embodiment, the content by weight (additive / any one 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 weight, less than 0.1 part by weight, less than 0.01 part by weight, 0 part by weight, etc.

[0116] A photosensitive composition can be produced by dispersing and mixing the above agents.

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

[0118] Examples of uses (photosensitive compositions) 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 microchannels, 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 product] The present disclosure relates to a cured product of the above-mentioned photosensitive composition.

[0120] Examples of the cured product include an active energy ray cured product and a heat cured product.

[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, blade coater coating, and curtain coater coating.

[0123] (drying process) Examples of the drying device include a circulating dryer, a hot plate, a thermostatic bath, etc. The drying temperature is, for example, 40° C. to 150° C. The drying time is, for example, 1 minute to 30 minutes.

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

[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 kinds.

[0126] The heat curing conditions are, for example, as follows: Temperature: 200℃~350℃ Time: 1 hour to 10 hours

[0127] [Goods] The present disclosure relates to an article comprising the cured product.

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

[0129] The present invention will be described in detail below through examples and comparative examples. However, the above description and the following examples are not intended to limit the present invention. The present invention is limited only by the claims. Unless otherwise specified below, numerical values ​​such as parts and % are based on mass.

[0130] Example 1 (1) Production ((meth)acryloyl group-containing polyimide) In a reaction vessel equipped with an agitator, a water divider, a thermometer, and a nitrogen gas inlet tube, 29.0 g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (trade name "6FDA", manufactured by Daikin Industries, Ltd.; hereinafter abbreviated as 6FDA), 16.5 g of methylcyclohexane, and 82.7 g of cyclohexanone were charged and heated to 60°C. Next, 3.8 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (trade name: "TFMB", manufactured by Seika Co., Ltd.; hereinafter abbreviated as TFMB) was gradually added, and then 12.0 g of 3,5-diaminobenzoic acid (trade name: "3,5-DABA", manufactured by Nippon Junryo Pharmaceutical Co., Ltd.; hereinafter abbreviated as DABA) was added dropwise, and the mixture was subjected to an imidization reaction at 140°C for 12 hours to obtain a polyimide solution. A reaction vessel containing 100 g of this polyimide solution was charged with 1.7 g of 2-isocyanatoethyl acrylate (product name: Karenz AOI, manufactured by Showa Denko K.K.) and 18.0 g of cyclohexanone, and the mixture was heated to 80°C. 1.0 g of triphenylphosphine was then added and reacted for 7 hours to obtain a (meth)acryloyl group-containing polyimide solution (non-volatile content 30%). (2) Manufacture (photosensitive composition) 23.3 g (70 parts by mass) of the (meth)acryloyl group-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-benzoyloxime)] (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one) (product name "Omnirad OXE01", manufactured by IGM Resins), and 8.2 g of cyclohexanone were mixed and thoroughly stirred to obtain a photosensitive composition with a non-volatile content of 30%.

[0131] Unless otherwise stated, the following examples were carried out in the same manner as above, except for the changes shown in the table.

[0132] [Table 1]

[0133] <Description> The numbers in the table for acid anhydrides and diamines are in mole percent. BISDA: 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride (product name "BisDA-1000", manufactured by SABIC Innovative Plastics Japan, LLC) DABPAF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Seika Co., Ltd.) Tolidine: m-Tolidine (Seika Co., Ltd.)

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

[0135] <Lithography evaluation sample> The 10 μm-thick dry film was exposed to 300 mJ / cm 2 through a mask with a Φ30 μm-sized light-shielding area. 2 The coated film was then cured with UV light (with a ghI-line parallel exposure device, UV-A region) to obtain a cured product. This cured product was used as a sample for evaluating lithographic properties.

[0136] Lithographic The cured film prepared and exposed under the conditions described in <Sample for evaluating lithographic properties> was developed by immersing it in cyclopentanone for 60 seconds. The cured film after development was observed with a confocal laser microscope to confirm whether or not depressions of Φ30μm in size were formed, and evaluated according to the following criteria. <Evaluation criteria> ○: No residue △: The exposed area was dissolved. ×: No image

[0137] <Sample for evaluating storage modulus and linear expansion coefficient> For the above 20μm dry film, a ghI line parallel exposure device was used, and the curing dose in the UV-A region was 300mJ / cm 2 The resin was irradiated with UV light for UV curing. After that, the resin was baked at 200°C for 60 minutes to obtain a cured product. The cured product was cut into a 1 cm wide piece and peeled off from the glass substrate to obtain a test piece for measuring the storage modulus. The resin was also cut into a 0.4 cm wide piece for evaluating the linear expansion coefficient.

[0138] Storage Modulus The test piece obtained in <Sample for evaluating storage modulus> was measured using a dynamic viscoelasticity measuring device (DMA7100, manufactured by Hitachi High-Tech Science Corporation) under the following measurement conditions. Measurement conditions: Nitrogen atmosphere, tension mode, frequency 1.0Hz, chuck distance 10mm

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

Claims

1. A (meth)acryloyl group-containing polyimide, The (meth)acryloyl group-containing polyimide contains a fluorine atom-containing acid anhydride unit and a fluorine atom- and biphenyl structure-containing diamine unit. (Meth)acryloyl group-containing polyimides.

2. A photosensitive composition comprising the (meth)acryloyl group-containing polyimide according to claim 1 .

3. 3. The photosensitive composition according to claim 2, 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.

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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