(Meth)acryloyl group-containing polyimides, photosensitive compositions, cured products and articles

Abstract

The present invention provides (meth)acryloyl group-containing polyimides, photosensitive compositions, cured products, and articles for producing cured products with good storage modulus, lithographic properties, and coefficient of thermal expansion. [Solution] A (meth)acryloyl group-containing polyimide, wherein the (meth)acryloyl group-containing polyimide contains a fluorine atom-containing acid anhydride unit and a fluorine atom and a biphenyl structure-containing diamine unit.

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 been researching and developing a polyimide produced using a dimer diamine (a polyimide using a dimer diamine) (Patent Document 1). The polyimide using a dimer diamine has a low relative permittivity and a low dielectric loss tangent. Therefore, the polyimide using a dimer diamine is used as an adhesive for a flexible copper-clad laminate in which a high-frequency electrical signal is 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 for producing a cured product having good storage elastic modulus, lithography properties, and linear expansion coefficient.

Means for Solving the Problems

[0005] The following items are provided by the present disclosure. (Item 1) A (meth)acryloyl group-containing polyimide, wherein the (meth)acryloyl group-containing polyimide contains a fluorine atom-containing acid anhydride unit and a diamine unit containing a fluorine atom and a biphenyl structure. (Meth)acryloyl group-containing polyimide. (Item 2) A photosensitive composition containing the (meth)acryloyl group-containing polyimide according to 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% to 75% by mass with respect to 100% by mass of the photosensitive compound. (Item 4) A cured product of any one of the above items of the photosensitive composition. (Item 5) Articles containing the cured material described in the above items.

[0006] In this disclosure, one or more of the features described above may be provided in combinations other than those explicitly stated. [Effects of the Invention]

[0007] By using the (meth)acryloyl group-containing polyimide of this disclosure, it is possible to produce a cured product with good storage modulus, lithographic properties, and coefficient of thermal expansion. [Modes for carrying out the invention]

[0008] Throughout this disclosure, the ranges of numerical values ​​such as physical properties and content may be set as appropriate (for example, by selecting from the values ​​listed in each of the items below). Specifically, if the numerical value α is such as A3, A2, A1 (A3 > A2 > A1), then the range of the numerical value α may be 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 A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less.

[0009] The components, conditions, numerical values, etc., are not particularly limited, as long as the problems that this invention aims to solve are resolved.

[0010] "αβ quantity (A / B)" means the β quantity (α) of A with respect to B100α. α includes, for example, mass %, mole %, parts by mass, etc. The β quantity includes, for example, content, usage amount, etc. "Mass % content (A / B)" means the content (% by mass) of A with respect to B100 mass %.

[0011] "γ ratio (A / B)" means the γ ratio calculated by the formula "A÷B". The γ ratio includes, for example, mass ratio, mole ratio, etc.

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

[0013] "(Meth)acryl" means "acryl and / or methacryl". "(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, wherein the (meth)acryloyl group-containing polyimide contains a fluorine atom-containing acid anhydride unit and a diamine unit containing a fluorine atom and a biphenyl structure.

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

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

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

[0018] The molar percentage content (fluorine atom-containing acid anhydride unit / polyimide) is, 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 above 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 can 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, 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] Examples of mass% content (fluorine atom-containing diamine units / polyimide) include 40% by mass, 39% by mass, 37% by mass, 35% by mass, 33% by mass, 31% by mass, 30% by mass, 29% by mass, 27% by mass, 25% by mass, 23% by mass, 21% by mass, and 20% by mass. In one embodiment, the above content is preferably 20% by mass to 40% by mass.

[0022] Examples of molar content (fluorine atom-containing diamine units / 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%, and 20 mol%. In one embodiment, the above content is preferably 20 mol% to 40 mol%.

[0023] <(meth)acryloyl group-containing unit> Examples of (meth)acryloyl group-containing units include reaction products of carboxyl group-containing diamine units and isocyanate group-containing (poly)(meth)acrylate, reaction products of carboxyl group-containing diamine units and glycidyl group-containing (poly)(meth)acrylate, reaction products of carboxyl group-containing diamine units and acid anhydride group-containing (poly)(meth)acrylate, and reaction products of carboxyl group-containing diamine units and hydroxyl group-containing (poly)(meth)acrylate. In one embodiment, the (meth)acryloyl group-containing unit is preferably a reaction product of carboxyl group-containing diamine units and isocyanate group-containing (poly)(meth)acrylate. The reasons for this preference include, for example, improved storage modulus of the cured product, reduced coefficient of thermal expansion of the cured product, increased amount of (meth)acryloyl group introduced, and reduced dielectric properties (dielectric constant, dielectric loss tangent).

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

[0025] Examples of carboxyl group-containing diamines include diaminobenzoic acid, alkylene bis(2-aminobenzoic acid), bis(aminophenoxy)benzoic acid, diaminocarboxydiphenylalkanes, and diaminodicarboxydiphenyl ethers.

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

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

[0028] Examples of bis(aminophenoxy)benzoic acid 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] Examples of diaminodicarboxydiphenyl ethers include 3,3'-diamino-4,4'-dicarboxydiphenyl ether.

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

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

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

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

[0035] (Isocyanate group-containing (poly)(meth)acrylate) (Poly)(meth)acrylates containing isocyanate groups can 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] (Poly)(meth)acrylates containing isocyanate groups are 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 (where represents a substituted or unsubstituted alkylene group, and Z represents a single bond or 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 substituents of the alkylene group are preferably alkyl groups and methyloxy(meth)acryloyl groups, and more preferably methyl groups and methyloxy(meth)acryloyl groups.

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

[0041] Examples of molar content ((meth)acryloyl group-containing units / (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%, 0.1 mol%, etc. In one embodiment, the above content is preferably 0.1 mol% to 5 mol%.

[0042] Examples of mass% content ((meth)acryloyl group-containing units / (meth)acryloyl group-containing polyimide) include 20% by mass, 19% by mass, 17% by mass, 15% by mass, 13% by mass, 11% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass, 3% by mass, and 1% by mass. In one embodiment, the above content is preferably 1% by mass to 20% by mass.

[0043] <Other constituent units> In one embodiment, the (meth)acryloyl group-containing polyimide may optionally contain other constituent units (other constituent units). These other constituent units may be included individually or in combination of two or more types.

[0044] Other constituent units include, for example, tricarboxylic acid anhydride units.

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

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

[0047] <Physical properties ((meth)acryloyl group-containing polyimide)> Examples of weight-average molecular weights ((meth)acryloyl group-containing polyimides) 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 above weight-average molecular weight is preferably 10,000 to 100,000.

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

[0049] Measurement conditions (weight-average molecular weight, number-average molecular weight) can include, for example, the following conditions. 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: 0.2 wt%

[0050] Examples of (meth)acrylic equivalents ((meth)acryloyl group-containing polyimide) include 10,000 g / eq, 9,500 g / eq, 9,000 g / eq, 8,500 g / eq, 8,000 g / eq, 7,500 g / eq, 7,000 g / eq, 6,500 g / eq, 6,000 g / eq, 5,500 g / eq, 5,000 g / eq, 4,500 g / eq, 4,000 g / eq, 3,500 g / eq, 3,000 g / eq, 2,500 g / eq, 2,000 g / eq, 1,500 g / eq, 1,000 g / eq, 500 g / eq, etc. In one embodiment, the above (meth)acrylic equivalent is preferably 500 g / eq to 10,000 g / eq.

[0051] <Manufacturing method ((meth)acryloyl group-containing polyimide)> (Meth)acryloyl group-containing polyimides can be produced by a manufacturing method that includes the following steps. (1) Polyamic acid synthesis process (2) Polyimide synthesis process (3) (meth)acryloyl group introduction process

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

[0053] Reaction conditions (polyimide synthesis process) include, for example, the following conditions. Reaction temperature: 100℃~200℃ Reaction time: 1 hour to 20 hours

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

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

[0056] Examples of tertiary amines include triethylamine and dimethylaniline.

[0057] Examples of phosphines include triphenylphosphine.

[0058] Examples of dehydrating agents include acid anhydrides.

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

[0060] Examples of reaction solvents include organic solvents, as described later.

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

[0062] <(meth)acryloyl group-containing polyimide> Examples of mass percentage content ((meth)acryloyl group-containing polyimide / non-volatile content of photosensitive composition) include 100% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, and so on. In one embodiment, the above content is preferably 40% by mass to 100% by mass.

[0063] <Photosensitive compound> 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 photosensitive compounds include poly(meth)acrylates.

[0065] "Poly(meth)acrylate" refers to a compound having two or more (meth)acryloyl groups.

[0066] Examples of poly(meth)acrylates 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)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, tripentaerythritol octa(meth)acrylate, and so on.

[0068] Examples of (poly)trimethylolpropane poly(meth)acrylate include trimethylolpropanedi(meth)acrylate, trimethylolpropanetri(meth)acrylate, ditrimethylolpropanedi(meth)acrylate, ditrimethylolpropanetri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, and the like.

[0069] Examples of (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 urethane poly(meth)acrylates include reaction products of compounds containing hydroxyl group-containing poly(meth)acrylates and polyisocyanates.

[0071] <Hydroxygroup-containing poly(meth)acrylate> Examples of hydroxyl group-containing poly(meth)acrylates include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, and (poly)glycerin poly(meth)acrylate.

[0072] <Polyisocyanate> Polyisocyanates can be used alone or in combination of two or more types.

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

[0074] Examples of polyisocyanates include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and their biuret, isocyanurate, allophanate, and adduct derivatives.

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

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

[0077] Examples of alicyclic polyisocyanates include monocyclic alicyclic polyisocyanates, crosslinked alicyclic polyisocyanates, and condensed alicyclic polyisocyanates.

[0078] Examples of monocyclic alicyclic polyisocyanates 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 cross-linked alicyclic polyisocyanates include tricyclodecile diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0080] Examples of condensed alicyclic polyisocyanates include bicyclodecile diisocyanate.

[0081] Examples of aromatic polyisocyanates include monocyclic aromatic polyisocyanates and fused-ring aromatic polyisocyanates.

[0082] Examples of monocyclic aromatic polyisocyanates 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-phenylenediisocyanate, 1,4-phenylenediisocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

[0083] Examples of condensed ring aromatic polyisocyanates include 1,5-naphthylene diisocyanate.

[0084] In one embodiment, the photosensitive compound is preferably (poly)pentaerythritol poly(meth)acrylate, and more preferably dipentaerythritol poly(meth)acrylate. The reasons for this preference include, for example, a reduction in the coefficient of thermal expansion of the cured product.

[0085] Examples of mass % content (photosensitive compound / non-volatile content of photosensitive composition) include 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 60% by mass.

[0086] Examples of mass percentage content ((meth)acryloyl group-containing polyimide / photosensitive compound) include 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, and so on. In one embodiment, the above content is preferably 40% by mass to 75% by 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 photopolymerization initiators include α-hydroxydimethylacetophenone group-containing photopolymerization initiators, α-hydroxycycloalkylphenone, α-aminoalkylphenone, benzyldimethylketal, unsubstituted or substituted alkylphenone, unsubstituted or substituted benzyl, unsubstituted or substituted benzophenone, acylphosphine oxide, substituted thioxanthone, oxime ester, and the like.

[0089] Examples of α-hydroxydimethylacetophenone group-containing photopolymerization initiators 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-hydroxycyclohexylphenyl ketone.

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

[0092] Examples of benzyldimethyl ketals include 2,2-dimethoxy-1,2-diphenylethane-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'-morpholinobylophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-isonitrosopropiophenone, and 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0094] Examples of unsubstituted or substituted benzyls include benzyl, p-anisyl, and the like.

[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 acylphosphine oxides include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0097] Examples of substituted thioxanthones 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-carbazole-3-yl]-, 1-(O-acetyloxime) (i.e., 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl)ethylidene)amino)oxy)ethane-1-one).

[0099] In one embodiment, the photopolymerization initiator is preferably an oxime ester. The reasons for this preference include, for example, a reduction in the coefficient of thermal expansion of the cured product.

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

[0101] <Chain movement 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 chain transfer agents include thiol group-containing chain transfer agents.

[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 mass% content (chain transfer agent / non-volatile content of photosensitive composition) include 20% by mass, 18% by mass, 16% by mass, 15% by mass, 14% by mass, 12% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 20% by mass.

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

[0106] Examples of organic solvents include aprotic polar solvents, alicyclic solvents, alcoholic solvents, and aromatic solvents.

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

[0108] Examples of alicyclic solvents include cyclohexanone and methylcyclohexane.

[0109] Examples of alcoholic solvents include methanol, ethanol, propanol, benzyl alcohol, and cresol.

[0110] Examples of aromatic solvents include toluene.

[0111] Examples of mass% content (organic solvent / photosensitive composition) include 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 90% by mass.

[0112] <Additives> The above photosensitive composition may optionally contain agents (additives) that do not fall under any of the above categories.

[0113] Examples of additives include crosslinking agents, flame retardants, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold 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% by mass, less than 0.1% by mass, less than 0.01% by mass, 0% by mass, etc.

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

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

[0117] Dispersion and mixing means include, for example, emulsifiers, dispersers, ultrasonic dispersers, and the like.

[0118] Applications (photosensitive compositions) include, for example, photosensitive resist compositions, photosensitive compositions for dry film resists, photosensitive encapsulation compositions, photosensitive resist compositions for hollow packages, photosensitive encapsulation compositions for hollow packages, photosensitive compositions for microfluidics, photosensitive compositions for forming MEMS (Micro Electro Mechanical Systems) structures, photosensitive compositions for forming waveguides, photosensitive compositions for screen printing plates, and photosensitive adhesive compositions.

[0119] [Cured product] This disclosure relates to a cured product of the above-mentioned photosensitive composition.

[0120] Examples of the cured products mentioned above include activated energy ray cured products and thermoset products.

[0121] The cured product can be manufactured by a manufacturing method that includes the following steps. (1) Coating process (2) Drying process (3) Exposure / Development Process

[0122] (Coating process) Coating methods include, for example, spin coater coating, bar coater coating, blade coater coating, and curtain coater coating.

[0123] (drying process) Drying equipment can include, for example, a circulating air dryer, a hot plate, or a constant temperature bath. Drying temperatures can range from 40°C to 150°C. Drying times can range from 1 minute to 30 minutes.

[0124] (Exposure / Development Process) Examples of exposure light sources include ultraviolet light, excimer laser light, and active energy rays such as semiconductor lasers. The irradiation dose is, for example, 30 mJ / cm². 2 ~3,500 mJ / cm² 2 These are some examples.

[0125] Development methods include, for example, immersion and spray methods. Examples of developers include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Developers can be used individually or in combination of two or more.

[0126] Examples of thermosetting conditions include the following: Temperature: 200℃~350℃ Duration: 1 to 10 hours

[0127] [Goods] This disclosure relates to an article containing the above-mentioned cured product.

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

[0129] The present invention will be specifically described 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 to the claims. Unless otherwise specified below, numerical values ​​such as parts and percentages are based on mass.

[0130] Example 1 (1) Manufacturing ((meth)acryloyl group-containing polyimide) In a reaction vessel equipped with a stirrer, water divider, thermometer, and 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. Then, 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, followed by the dropwise addition of 12.0 g of 3,5-diaminobenzoic acid (trade name: "3,5-DABA", manufactured by Nippon Junryo Yakuhin Co., Ltd.; hereinafter abbreviated as DABA). The mixture was then imidized at 140°C for 12 hours to obtain a polyimide solution. 100 g of this polyimide solution was placed in a reaction vessel, and 1.7 g of 2-isocyanatoethyl acrylate (product name: "Karenz AOI", manufactured by Showa Denko Corporation) and 18.0 g of cyclohexanone were added. The mixture was heated to 80°C, 1.0 g of triphenylphosphine was added, and the mixture was 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 a (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 specified, the examples below were carried out in the same manner as above, except for the changes shown in the table.

[0132] [Table 1]

[0133] <Explanation> The figures for acid anhydrides and diamines in the table are in mole percent. BISDA: 4,4'-[propane-2,2-diirbis(1,4-phenyleneoxy)]diphthalic acid 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 (manufactured by Seika Co., Ltd.)

[0134] The prepared photosensitive composition was coated onto a 0.7 mm thick glass substrate using a bar coater and dried at 120°C for 5 minutes to obtain dried films with thicknesses of 10 μm and 20 μm.

[0135] <Sample for lithographic evaluation> For the above 10 μm thick dried film, 300 mJ / cm² was applied through a mask having a light-shielding area of ​​Φ30 μm size. 2 The cured material was obtained by UV curing using a parallel ghI exposure system (UV-A range). This cured material was used as a sample for lithographic evaluation.

[0136] Lithographic properties The cured film, prepared and exposed under the conditions described in <Sample for Lithographic Evaluation>, was developed by immersion in cyclopentanone for 60 seconds. The developed cured film was observed with a confocal laser microscope to confirm the formation of a Φ30 μm size depression, and evaluated according to the following criteria. <Evaluation Criteria> ○: No residue △: The exposed area melted. ×: No image

[0137] <Sample for evaluating storage modulus and coefficient of thermal expansion> For the above 20 μm dried film, a ghI-ray parallel exposure apparatus was used to cure it with a UV-A dose of 300 mJ / cm². 2 The material was irradiated and UV-cured. Afterward, it was exposed to light at 200°C for 60 minutes and then baked to obtain a cured product. This cured product was cut into 1 cm wide strips, peeled from the glass substrate, and used to obtain test pieces for measuring the storage modulus. For evaluating the coefficient of thermal expansion, a 0.4 cm wide strip was also used.

[0138] Storage modulus The test specimens obtained from the <Sample for Storage Modulus Evaluation> were measured using a dynamic viscoelasticity measuring device (Hitachi High-Tech Science Corporation, DMA7100) under the following measurement conditions. Measurement conditions: Nitrogen atmosphere, tensile mode, frequency 1.0 Hz, chuck distance 10 mm

[0139] Measurement (coefficient of linear expansion) The test specimens obtained from the <Sample for Evaluation of Linear Expansion Coefficient> were measured using a thermomechanical analyzer (TMA7100, Hitachi High-Tech Science Corporation) under the following measurement conditions. Measurement conditions: Under nitrogen atmosphere, chuck distance 10 mm

Claims

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

2. A photosensitive composition comprising the (meth)acryloyl group-containing polyimide described in 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 with respect to 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 described in claim 4.

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