JP5331004B2 - Ink composition - Google Patents

Abstract

Disclosed is an ink composition for printing, which has both low-temperature workability of epoxy resins and excellent physical properties of polyimide resins. Also disclosed is a multilayer printed wiring board having an insulating layer formed by using such an ink composition for printing. Specifically disclosed is an ink composition for printing, which contains (i) a thermosetting imide oligomer represented by the general formula (1) below and (ii) water, a water-soluble organic solvent or a mixture of them. (1) (In the formula, n, Ar1, Ar2, R1 and R2 are as defined in the description.)

Description

  The present invention relates to a printing ink composition, a method for producing a thermosetting imide oligomer film, and a multilayer printed wiring board.

  In recent years, in order to achieve higher density and smaller size of multilayer printed wiring boards, multilayer printed wiring boards having a conductive layer and an insulating layer having a finer pattern shape are required. As a method for forming such a conductive layer or insulating layer, for example, an inkjet printing method, a screen printing method, a spray printing method, or the like is known (see, for example, Patent Documents 1 and 2). The ink composition used in these printing methods is one that mainly uses an epoxy resin as an insulating material (see, for example, Patent Document 3), and is cured at a relatively low temperature, so that it can be easily processed. is there.

In addition, an ink composition using a silicon-modified polyimide resin as an insulating material has been proposed with the aim of further improving physical properties and electrical characteristics (see, for example, Patent Document 4).
JP 2006-147202 A JP-A-5-178950 JP 2000-143939 A Japanese National Patent Publication No. 10-502869

  However, with recent technological innovations, ink compositions using epoxy resins such as the prior art described above can sufficiently meet the demands for physical properties such as high heat resistance, moisture resistance, flame retardancy and flexibility. It is gone. Silicon modified polyimide resin is excellent in mechanical properties as compared with epoxy resin, but has a problem in heat resistance because its glass transition temperature is similar to that of epoxy resin. On the other hand, when a general polyimide resin not modified with silicon is used, the substrate needs to be processed at a high temperature of 300 ° C. or higher, which causes a problem that the substrate is damaged during film formation.

  The present invention has been made in view of such circumstances, and includes a printing ink composition that combines low-temperature processability of an epoxy resin and excellent physical properties of a polyimide resin, and an insulating layer formed using the same. An object is to provide a multilayer printed wiring board.

  As a result of repeated research to solve the above-mentioned problems, the present inventors have (i) a thermosetting imide oligomer which has been previously closed, represented by the general formula (1), and (ii) water and a water-soluble organic solvent. Alternatively, by using a mixture thereof, it is possible to provide a printing ink composition having low-temperature processability and excellent physical properties that could not be achieved conventionally, and a multilayer printed wiring board including an insulating layer formed using the same. I found.

That is, the present invention (1) comprises (i) the general formula (1):

Where
n is a number from 1 to 10,
Ar ¹ is a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or a polycyclic compound in which two or more of the same or different aromatic compounds are connected to each other directly or by a bridging member. A tetravalent group,
Ar ² is a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or a polycyclic compound in which two or more of the same or different aromatic compounds are connected to each other directly or by a bridging member. a divalent group, and wherein a bridge member, -O -, - CO -, - COO -, - OCO -, - SO 2 -, - S -, - CH 2 -, - C (CH 3) ₂ represents a divalent group selected from the group consisting of — and —C (CF ₃ ) ₂ —, and R ¹ and R ² each independently represents a hydrogen or phenyl group, and represents a thermosetting A printing ink composition comprising a water-soluble imide oligomer and (ii) water, a water-soluble organic solvent or a mixture thereof.

  The present invention (2) is the printing ink composition according to the invention (1), wherein the water-soluble organic solvent is water, alcohols or a mixture thereof.

  The present invention (3) is the printing ink composition of the invention (1) or (2), wherein the thermosetting imide oligomer has an average particle size of 10 μm or less.

  The present invention (4) is characterized in that the printing ink composition according to any one of the above inventions (1) to (3) is applied onto a substrate by an ink jet printing method, a screen printing method or a spray printing method. And a method for producing a thermosetting imide oligomer film.

  In the invention (5), the printing ink composition according to any one of the inventions (1) to (3) is applied on a substrate by an ink jet printing method, a screen printing method or a spray printing method, and further heated. A multilayer printed wiring board having a cured insulating layer.

  The ink composition for printing of the present invention can be cured at 250 ° C. or lower during film formation, and can be formed in a short time, so that an insulating film can be formed without damaging the substrate. Further, this insulating film exhibits excellent physical properties in terms of flexibility and heat resistance.

  The thermosetting imide oligomer contained in the printing ink composition of the present invention is a compound represented by the following general formula (1).

In the formula, n is a number of 1 to 10, and Ar ¹ is a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or two or more of the same or different aromatic compounds are directly or bridged It is a tetravalent group of a polycyclic compound connected to each other by members. Ar ² is a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or a polycyclic compound 2 in which two or more of the same or different aromatic compounds are connected to each other directly or by a bridging member. Is a valent group. Here, the term “crosslinking member” refers to —O—, —CO—, —COO—, —OCO—, —SO ₂ —, —S—, —CH ₂ —, —C (CH ₃ ) ₂ — and —C (CF ₃₎ 2 _- represents a divalent radical selected from the group consisting of. R ¹ and R ² each independently represent hydrogen or a phenyl group.

The “monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms” in Ar ¹ and Ar ² is preferably 6 to 18 carbon atoms, more preferably 6 to 12 monocyclic or condensed polycyclic compounds. Examples of cyclic aromatic compounds include benzene, toluene, xylene, naphthalene, anthracene, and phenanthrene. Therefore, the “tetravalent group of a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms” in Ar ¹ is preferably a tetravalent group derived from benzene, naphthalene, anthracene, phenanthrene and the like. In Ar ^2, the “divalent group of a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms” is preferably 2 derived from benzene, toluene, xylene, naphthalene, anthracene, phenanthrene and the like. A valent group, most preferably o-, m- or p-phenylene. The “monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms” in Ar ² has 1 substituent such as an alkyl group having 1 to 4 carbon atoms and a trifluoromethyl group on the aromatic ring. You may have one or more, preferably one or two.

In Ar ¹ and Ar ² , “a polycyclic compound in which two or more of the same or different aromatic compounds are directly or mutually linked by a bridging member” refers to the monocyclic or condensed polycyclic compounds mentioned in the preceding paragraph. cyclic aromatic compounds, from direct or bridge member (here a bridge member, -O -, - CO -, - COO -, - OCO -, - SO 2 -, - S -, - CH 2 -, - Means a polycyclic compound interconnected by C (CH ₃ ) ₂ — and —C (CF ₃ ) ₂ —. Therefore, as the tetravalent group of the polycyclic compound in Ar ¹ , two or more monocyclic aromatic compounds listed in the above paragraph, particularly o-, m-, or p-phenylene are directly or a cross-linking member. Tetravalent groups of polycyclic compounds linked together by, for example, biphenyl, diphenyl ether, benzophenone, phenyl benzoate, 2,2-diphenylpropane, 2,2-diphenyl-1,1,1,3,3 , 3-hexafluoropropane, tetravalent groups derived from 2,2-bis [4- (phenoxy) phenyl] propane and the like. As the divalent group of the polycyclic compound in Ar ² , two or more monocyclic aromatic compounds, particularly o-, m-, or p-phenylene mentioned in the above paragraph may be directly or by a bridging member. Examples thereof include divalent groups of polycyclic compounds linked to each other, for example, divalent groups derived from biphenyl, diphenyl ether, 2,2-diphenylpropane, and the like. The polycyclic compound in Ar ² may have one or more substituents such as an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group, preferably 1 or 2 on the aromatic ring. .

  There is no restriction | limiting in particular as a manufacturing method of the thermosetting imide oligomer which has a crosslinkable group represented by General formula (1), A well-known method may be sufficient. In the present invention, the thermosetting imide oligomer was obtained by the following steps. First, an aromatic tetracarboxylic dianhydride and an aromatic dicarboxylic anhydride having a crosslinkable group are heated and reacted in an esterification solvent to obtain a uniform solution.

  Next, the obtained uniform solution and aromatic diamine are mixed to obtain a mixed solution. The solute concentration of the mixed solution at this time is preferably 50% by weight or less.

  An imidation catalyst such as 1,2-dimethylimidazole, benzimidazole, isoquinoline, or substituted pyridine may be added to this mixed solution. Moreover, you may add a well-known additive, for example, an inorganic filler, an organic filler, an inorganic pigment, or an organic pigment.

  Next, the mixed solution is evaporated to dryness and further heated to imidize. About heating, it is desirable to heat for 5 to 180 minutes, preferably 30 to 90 minutes within the temperature range from the vicinity of the glass transition temperature of the resulting imide oligomer to a temperature lower than the temperature at which thermosetting by the crosslinkable group starts.

  Examples of the esterification solvent used here include lower primary alcohols such as methanol, ethanol, n-propanol and n-butanol, preferably methanol or ethanol. These can be used alone or in combination of two or more.

  Examples of the aromatic tetracarboxylic dianhydride used include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′- Biphenyltetracarboxylic dianhydride, 2,2,3 ′, 3′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,4′-oxydiphthalic dianhydride, 3, 3'-oxydiphthalic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-di Carboxyphenyl) hex Fluoro propane dianhydride, and the like 1,2,7,8-naphthalene tetracarboxylic dianhydride. These can be used alone or in combination of two or more.

  The aromatic dicarboxylic anhydride having a crosslinkable group to be used is 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride or a mixture thereof.

  The printing ink composition of the present invention may contain an imide oligomer having another crosslinkable terminal group in addition to the thermosetting imide oligomer represented by the general formula (1). Such an imide oligomer can be produced by the same method as described above, but as an aromatic dicarboxylic acid anhydride having a crosslinkable group, instead of the one in the above paragraph, 3-phenylethynylphthalic acid anhydride, Ethynylnaphthalenedicarboxylic acid anhydride, phenylethynylnaphthalenedicarboxylic acid anhydride, ethynylanthracene dicarboxylic acid anhydride, phenylethynylanthracene dicarboxylic acid anhydride, 4-naphthylethynylphthalic acid anhydride, 3-naphthylethynylphthalic acid anhydride, 4- Anthracenylethynylphthalic anhydride, 3-anthracenylethynylphthalic anhydride, anthracenylethynylnaphthalenedicarboxylic anhydride, anthracenylethynylanthracene dicarboxylic anhydride, and the like can be used. In addition, the hydrogen atom on the aromatic ring of these aromatic dicarboxylic acid anhydrides may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkynyl group or an alkoxyl group, or a halogen atom. These anhydrides can be used alone or in combination of two or more.

As aromatic diamines to be used, p-phenylenediamine, m-phenylenediamine, p-aminobenzylamine, m-aminobenzylamine, diaminotoluenes, diaminoxylenes, diaminonaphthalenes, diaminoanthracenes, 4,4 ′ -Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, o-tolidine, m-tolidine, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diamino Diphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diamino Diphenyl sulfone, 4,4'-di Aminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone, 2,2-bis (4-aminophenoxy) propane, 2,2-bis (3-aminophenoxy) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,3- bis (4-aminobenzoyl ) benzene, 1,3-bis (3-aminobenzoyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) pheny ] Propane, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- ( 3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 4,4′-bis (4-aminophenoxy) benzophenone 4,4′-bis (3-aminophenoxy) benzophenone, 1,4-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (2- , 3- or 4-aminophenoxy) benzoyl] benzene, 1,4-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl Benzene, 1,3-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] benzene, 4,4′-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] diphenyl ether 4,4′-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] biphenyl 4,4′-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] biphenyl, 4,4′-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] diphenyl And sulfone and 4,4′-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] diphenyl sulfone. These can be used alone or in combination of two or more.

  The above-mentioned thermosetting imide oligomer has a glass transition after thermosetting in order to improve the processability (heat meltability) before curing and to cope with the heating process and lead-free soldering at the time of mounting. An aromatic tetracarboxylic dianhydride having a repeating number n = 1 to 10 and preferably a repeating number n = 1 to 5 so that the temperature is 200 ° C. or more, preferably 250 ° C. or more, The composition of the aromatic dicarboxylic acid anhydride and aromatic diamine having a crosslinkable group is appropriately selected. When the number n of repetitions exceeds 10, the relative content of the crosslinkable group in the composition decreases, so that the heat resistance of the cured film tends to decrease or the formation of the film tends to be difficult. Therefore, it is not preferable.

  The obtained imide oligomer is crushed to an average particle size of 100 μm or less by using a mortar or the like at the laboratory level, for example, to form a coarse powder.

  The method for producing the printing ink composition in which the thermosetting imide oligomer powder is dissolved or dispersed is not particularly limited, but the above-mentioned thermosetting imide oligomer coarse powder is prepared by using water, a water-soluble organic solvent, or their It is preferable to further wet pulverize in the mixture. The liquid material in which the thermosetting imide oligomer thus obtained is dispersed may be used as an ink composition as it is, or filtered to separate the thermosetting imide oligomer, and another water or water-soluble organic solvent. Alternatively, in addition to the mixture thereof, the printing ink composition of the present invention may be used. The thermosetting imide oligomer is dissolved or dispersed in the printing ink composition depending on the type, amount, mixing ratio, additive described later, and the like of water, water-soluble organic solvent or a mixture thereof added at this time.

  Examples of the water-soluble organic solvent in the printing ink composition of the present invention include alcohols, glycols, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethyl. Examples include formamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, and acetone. From this point of view, it is desirable to use alcohols and glycols.

  Alcohols and glycols used are, for example, lower alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, monoethylene glycol, diethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether Glycols such as glycerin and polyethylene glycol, but are not limited thereto. Moreover, it is preferable to use a low boiling point methanol, ethanol, n-propanol, isopropanol, or a mixed solvent thereof with water.

  The solid content concentration of the thermosetting imide oligomer in the printing ink composition of the present invention may be appropriately adjusted so as to have a desired viscosity in various coating methods, but is preferably 70% by weight or less.

  As an apparatus used for wet pulverization, conventionally used apparatuses such as a ball mill and a rod mill can be used.

  Further, the average particle size of the pulverized thermosetting imide oligomer is preferably 10 μm or less, and more preferably 1 μm or less, in order to improve dispersibility when formed into an ink.

  As a method for dispersing the thermosetting imide oligomer, conventionally used dispersion methods such as ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint A shaker or the like can be used. However, in the case of a dispersion method using media such as beads, it is possible to mix impurities from the media, so it is necessary to take measures such as cleaning the media or using media that does not precipitate harmful impurities.

  In order to achieve good dispersion, it is also possible to add a dispersant within a range that does not impair desired physical properties such as insulation of the thermosetting imide oligomer after curing. As a dispersant, an anionic, nonionic surfactant, or a polymeric dispersant can be used. For example, an ethylenically unsaturated monomer such as acrylic acid, methacrylic acid, maleic acid, and salts thereof, acrylic esters, styrene or derivatives thereof, vinyl ethers, vinyl esters, etc. What was mixed and polymerized can be used as a polymeric dispersant. Furthermore, in order to improve the dispersion state, a conventionally known surface tension adjusting agent, water, a lipophilic organic solvent, and the like that have been conventionally used can be added as necessary.

  The printing ink composition obtained as described above is applied to a substrate such as a silicon-based wafer or metal foil by an inkjet printing method, a screen printing method, a spray method, etc., and a thermosetting imide oligomer is applied to the surface. By attaching and drying, a thermosetting imide oligomer film can be obtained. When this is heated, the thermosetting imide oligomer is softened (melted) and then cured, a film (insulating film) can be obtained. Here, heating is performed at 60 ° C. to 450 ° C., but may be a constant temperature over the entire processing time, or may be performed while gradually raising the temperature. In order to soften and then cure the thermosetting imide oligomer, 150 ° C to 300 ° C is preferable. More preferably, it is 150 to 250 degreeC. The heating time at this time is preferably 5 to 60 minutes.

  Moreover, in order to improve the adhesiveness between the base material and the insulating film, it is desirable to perform a silane coupling process on the base material such as a silicon-based wafer or a metal foil. Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and N-2- (aminoethyl). -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 2- (2-amino Ethylthioethyl) triethoxysilane, p-aminophenyltrimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltri Metoki Silane, N- phenyl-3-aminopropyl triethoxysilane and the like, it can also be used as hydrolysis with these acids or alkali compound. Moreover, it is not limited to these, The 1 or more types of silane coupling agent chosen from these is preferable. 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane are more preferable because of the large adhesive effect.

  The method for producing an insulating film on a substrate such as a silicon-based wafer or metal foil subjected to the silane coupling treatment is the same as described above.

  Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to the following examples. In the following synthesis examples, comparative synthesis examples, examples, and comparative examples, those obtained were evaluated as follows.

(1) Glass transition temperature Using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-60), measurement was carried out under a temperature increase of 10 ° C./min in a nitrogen atmosphere.
(2) Average particle diameter The sample was ultrasonically dispersed for 3 minutes, and measured with a wet flow cell using a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.). The average particle size was taken.
(3) Decrease in thermogravity Using a differential thermogravimetric simultaneous measurement device (DTG-60, manufactured by Shimadzu Corporation), measurement is started from 100 ° C under a nitrogen atmosphere, and measurement is performed at a temperature increase rate of 10 ° C / min. (Unit:%).
(4) Volume resistivity The measurement was performed according to ASTM D257 using a digital ultrahigh resistance / microammeter (manufactured by Advantest, R8340A type).

Synthesis example 1
A 500 ml four-necked flask was charged with 9.9269 g (32 mmol) of 4,4′-oxydiphthalic dianhydride, 5.5084 g (32 mmol) of 4-ethynylphthalic anhydride, and 100 ml of methanol, and an oil bath at 80 ° C. The mixture was heated and stirred for 3 hours while refluxing to obtain a homogeneous solution. Next, this solution was cooled to 50 ° C., and 9.6114 g (48 mmol) of 3,4′-diaminodiphenyl ether and 40 ml of methanol were added to obtain a homogeneous solution. This solution is concentrated with an evaporator, and the temperature is further increased to 160 ° C., and the pressure is reduced and heated for 1 hour. The imide oligomer of the general formula (1) (Ar ¹ = diphenyl ether, Ar ² = diphenyl ether, R ¹ = R ² = Hydrogen, n = 2) was obtained as a solid. Furthermore, this solid was pulverized in a mortar and then dried at 150 ° C. for 5 hours. The glass transition temperature of this oligomer was 154 ° C.

Synthesis example 2
According to the same method as in Synthesis Example 1, except that the amount of 4-ethynylphthalic anhydride used was changed to 2.7542 g (16 mmol) and the amount of 3,4'-diaminodiphenyl ether used was changed to 8.0095 g (40 mmol). The imide oligomer (n = 4) of the general formula (1) was obtained as a solid. The glass transition temperature of this oligomer was 170 ° C.

Synthesis example 3
In a 500 ml four-necked flask, 10.4097 g (20 mmol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 6.8855 g (40 mmol) of 4-ethynylphthalic anhydride ) And 100 ml of methanol, and heated and stirred for 3 hours while refluxing in an oil bath at 80 ° C. to obtain a uniform solution. Next, after this solution was cooled to 50 ° C., 8.0095 g (40 mmol) of 4,4′-diaminodiphenyl ether and 40 ml of methanol were added to obtain a uniform solution. The solution is concentrated with an evaporator, and further heated to 160 ° C., heated under reduced pressure for 1 hour to give an imide oligomer of general formula (1) (Ar ¹ = 2,2-bis [4- (phenoxy) phenyl]). Propane, Ar ² = diphenyl ether, R ¹ = R ² = hydrogen, n = 1) was obtained as a solid. Furthermore, this solid was pulverized in a mortar and then dried at 150 ° C. for 5 hours. The glass transition temperature of this oligomer was 152 ° C.

Synthesis example 4
The amount of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride used was 15.6146 g (30 mmol), and the amount of 4-ethynylphthalic anhydride used was 3.4427 g ( An imide oligomer (n = 3) of the general formula (1) was obtained as a solid in the same manner as in Synthesis Example 3 except that the amount was changed to 20 mmol). The glass transition temperature of this oligomer was 165 ° C.

Example 1
The powdered imide oligomer obtained in Synthesis Example 1 was added to a mixed solution of ion-exchanged water: methanol (50:50), zirconia beads having a diameter of 200 μm were further added, and wet pulverization was performed using a ball mill. After pulverization, first, zirconia beads were separated, then filtered to perform solid-liquid separation, and a thermosetting imide oligomer fine powder was isolated. The average particle size of this powder was 1 μm.

  Next, 2 g of the obtained imide oligomer fine powder was added to 18 g of a distilled water: methanol (60:40) mixed solution and dispersed using an ultrasonic homogenizer to obtain a printing ink composition.

Example 2
A printing ink composition [imide] was obtained in the same manner as in Example 1 except that the powdery imide oligomer obtained in Synthesis Example 2 was used instead of the powdery imide oligomer obtained in Synthesis Example 1. 2 g of oligomer fine powder (average particle size 1 μm) was dispersed in 18 g of distilled water: methanol (60:40) mixed solution].

Example 3
A printing ink composition [imide] was obtained in the same manner as in Example 1 except that the powdery imide oligomer obtained in Synthesis Example 3 was used instead of the powdery imide oligomer obtained in Synthesis Example 1. 2 g of oligomer fine powder (average particle size 1 μm) was dispersed in 18 g of distilled water: methanol (60:40) mixed solution].

Example 4
A printing ink composition [imide] was obtained in the same manner as in Example 1 except that the powdery imide oligomer obtained in Synthesis Example 4 was used instead of the powdery imide oligomer obtained in Synthesis Example 1. 2 g of oligomer fine powder (average particle size 1 μm) was dispersed in 18 g of distilled water: methanol (60:40) mixed solution].

Production Example 1
The printing ink composition obtained in Example 1 was uniformly applied to the entire surface of the glass plate by a spray method to form a thermosetting imide oligomer film. This was heated at 130 ° C. for 2 minutes and then at 250 ° C. for 10 minutes. This was cooled to room temperature and peeled off from the glass plate to obtain a cured film having a thickness of 10 μm. The obtained cured film had a glass transition temperature of 290 ° C., and no thermogravimetric decrease up to 350 ° C. was confirmed. Further, the volume resistivity of the cured film was 2.6 × 10 ¹⁷ (Ω · cm).

Production Example 2
The printing ink composition obtained in Example 2 was uniformly applied to the entire surface by a spray method on a glass plate to form a thermosetting imide oligomer film. This was heated at 130 ° C. for 2 minutes and then at 250 ° C. for 10 minutes. This was cooled to room temperature and peeled off from the glass plate to obtain a cured film having a thickness of 10 μm. The obtained cured film had a glass transition temperature of 259 ° C., and no thermogravimetric reduction up to 350 ° C. was confirmed.

Production Example 3
The printing ink composition obtained in Example 3 was uniformly applied to the entire surface of the glass plate by a spray method to form a thermosetting imide oligomer film. This was heated at 130 ° C. for 2 minutes and then at 250 ° C. for 10 minutes. This was cooled to room temperature and peeled off from the glass plate to obtain a cured film having a thickness of 10 μm. The obtained cured film had a glass transition temperature of 277 ° C., and no decrease in thermal weight up to 350 ° C. was confirmed.

Production Example 4
The printing ink composition obtained in Example 4 was uniformly applied to the entire surface of the glass plate by a spray method to form a thermosetting imide oligomer film. This was heated at 130 ° C. for 2 minutes and then at 250 ° C. for 10 minutes. This was cooled to room temperature and peeled off from the glass plate to obtain a cured film having a thickness of 10 μm. The obtained cured film had a glass transition temperature of 255 ° C., and no thermogravimetric decrease up to 350 ° C. was confirmed.

Production Example 5
A mixture of 1 g of 3-aminopropyltriethoxysilane, 4.5 g of ethanol, 4 g of distilled water and 0.5 g of 10% hydrochloric acid and stirred for 1 hour was used as a silane coupling agent on a 6-inch silicon wafer (thickness 500 μm). Applied. This was dried at 100 ° C. for 5 minutes.
Next, the ink composition for printing obtained in Example 1 was uniformly applied to the entire surface of the wafer by a spray method to form a thermosetting imide oligomer film. This was heated at 130 ° C. for 2 minutes and then heated at 250 ° C. for 10 minutes to obtain a silicon wafer having an insulating film having a thickness of about 4 to 6 μm. The adhesion was evaluated by a cross-cut tape method JIS-K5400 (interval 1 mm, number of squares 100). As a result, all of the 100 pieces remained without peeling.

Production Example 6
A copper foil having an insulating film was obtained in the same manner as in Production Example 5 except that the base material was changed from a silicon wafer to a copper foil (3EC-VLP thickness 18 μm, manufactured by Mitsui Kinzoku Co., Ltd.). The adhesion was evaluated by a cross-cut tape method JIS-K5400 (interval 1 mm, number of squares 100). As a result, all of the 100 pieces remained without peeling. For flexibility, the test piece was bent 180 ° on a wire with a diameter of 1 mm, and the subsequent cracks, cracks and peeling were visually determined. As a result, no cracks, cracks, or peeling were confirmed.

Comparative Example 1
First, 30 ml of N-methyl-2-pyrrolidone was placed in a 100 ml four-necked flask equipped with a Dimroth condenser, a nitrogen inlet tube, and a stirring blade under a nitrogen atmosphere, and 4,0047 g (20 mmol) of 3,4'-diaminodiphenyl ether. Then, 4,2043 g (20 mmol) of 4,4′-oxydiphthalic dianhydride was added. The polymerization of the polyamic acid was advanced by stirring for 8 hours. The obtained polyamic acid varnish was diluted with N-methyl-2-pyrrolidone to 10 wt%, and this was used as a printing ink composition.

Production Comparative Example 1
The printing ink composition of Comparative Example 1 was uniformly applied to the entire surface of the glass plate by a spray method to form a polyamic acid film. This was heated at 130 ° C. for 2 minutes and then at 250 ° C. for 10 minutes. This was cooled to room temperature and peeled from the glass plate to obtain a polyimide film having a thickness of 10 μm. The glass transition temperature of the obtained film was 217 ° C., and the thermogravimetric decrease up to 350 ° C. was 1.0%. The volume resistivity of the film was 8.3 × 10 ¹⁵ (Ω · cm).

Production Comparative Example 2
Except for changing the heating conditions to 130 ° C. for 2 minutes, 180 ° C. for 2 minutes, and 350 ° C. for 10 minutes, the same examination as in Production Comparative Example 1 was performed. The glass transition temperature of the obtained film was 238 ° C., and no thermogravimetric decrease up to 350 ° C. was confirmed. The volume resistivity of the film was 6.4 × 10 ¹⁶ (Ω · cm).

Comparative Example 2
A 500 ml four-necked flask is charged with 12.4086 g (40 mmol) of 4,4′-oxydiphthalic dianhydride, 0.6885 g (4 mmol) of 4-ethynylphthalic anhydride, and 100 ml of methanol, and an oil bath at 80 ° C. The mixture was heated and stirred for 3 hours while refluxing to obtain a homogeneous solution. Next, after this solution was cooled to 50 ° C., 8.499 g (42 mmol) of 3,4′-diaminodiphenyl ether and 40 ml of methanol were added to obtain a homogeneous solution. This solution is concentrated by an evaporator, and further heated to 170 ° C., heated under reduced pressure for 1 hour, and imide oligomer of general formula (1) (Ar ¹ = diphenyl ether, Ar ² = diphenyl ether, R ¹ = R ² = Hydrogen, n = 20) was obtained as a solid. Furthermore, this solid was pulverized in a mortar and then dried at 150 ° C. for 5 hours. The glass transition temperature of this oligomer was 177 ° C.

  The ink composition for printing [imide oligomer fine powder] was prepared in the same manner as in Example 1 except that the powdered imide oligomer obtained above was used instead of the powdered imide oligomer obtained in Synthesis Example 1. 2 g of powder (average particle size 1 μm) was dispersed in 18 g of a mixed solution of distilled water: methanol (60:40)].

Comparative Example 3
In a 500 ml four-necked flask, 20.8194 g (40 mmol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 0.6885 g (4 mmol) of 4-ethynylphthalic anhydride ) And 100 ml of methanol, and heated and stirred for 3 hours while refluxing in an oil bath at 80 ° C. to obtain a uniform solution. Next, this solution was cooled to 50 ° C., and then 8.499 g (42 mmol) of 4,4′-diaminodiphenyl ether and 40 ml of methanol were added to obtain a homogeneous solution. This solution is concentrated with an evaporator, and the temperature is raised to 170 ° C., followed by heating under reduced pressure for 1 hour, and the imide oligomer of general formula (1) (Ar ¹ = 2,2-bis [4- (phenoxy) phenyl]). Propane, Ar ² = diphenyl ether, R ¹ = R ² = hydrogen, n = 20) was obtained as a solid. Furthermore, this solid was pulverized in a mortar and then dried at 150 ° C. for 5 hours. The glass transition temperature of this oligomer was 173 ° C.

  The ink composition for printing [imide oligomer fine powder] was prepared in the same manner as in Example 1 except that the powdered imide oligomer obtained above was used instead of the powdered imide oligomer obtained in Synthesis Example 1. 2 g of powder (average particle size 1 μm) was dispersed in 18 g of a mixed solution of distilled water: methanol (60:40)].

Production Comparative Example 3
The printing ink composition obtained in Comparative Example 2 was uniformly applied to the entire surface of the glass plate by a spray method to form a thermosetting imide oligomer film. This was heated at 130 ° C. for 2 minutes and then at 250 ° C. for 10 minutes, but no film was obtained. In addition, the glass transition temperature of the obtained powdery cured product was 239 ° C.

Production Comparative Example 4
The printing ink composition obtained in Comparative Example 3 was uniformly applied to the entire surface of the glass plate by a spray method to form a thermosetting imide oligomer film. This was heated at 130 ° C. for 2 minutes and then at 250 ° C. for 10 minutes, but no film was obtained. In addition, the glass transition temperature of the obtained powdery hardened | cured material was 216 degreeC.

Claims (5)

(I) General formula (1):

Where
n is a number from 1 to 5 ,
Ar ¹ is a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or a polycyclic compound in which two or more of the same or different aromatic compounds are connected to each other directly or by a bridging member. A tetravalent group,
Ar ² is a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or a polycyclic compound in which two or more of the same or different aromatic compounds are connected to each other directly or by a bridging member. a divalent group, and wherein a bridge member, -O -, - CO -, - COO -, - OCO -, - SO 2 -, - S -, - CH 2 -, - C (CH 3) ₂ represents a divalent group selected from the group consisting of — and —C (CF ₃ ) ₂ —, and R ¹ and R ² each independently represents a hydrogen or phenyl group, and represents a thermosetting A printing ink composition comprising a water-soluble imide oligomer and (ii) water, a water-soluble organic solvent or a mixture thereof.   The printing ink composition according to claim 1, wherein the water-soluble organic solvent is an alcohol.   The printing ink composition according to claim 1 or 2, wherein an average particle size of the thermosetting imide oligomer is 10 µm or less.   The thermosetting imide oligomer film | membrane characterized by apply | coating the ink composition for printing of any one of Claims 1-3 on a base material by the inkjet printing method, the screen printing method, or the spray printing method. Manufacturing method.   Multi-layer printing which has the insulating layer which apply | coated the ink composition for printing of any one of Claims 1-3 on the base material by the inkjet printing method, the screen printing method, or the spray printing method, and also heat-hardened it Wiring board.