JP6676318B2 - Insulating resin composition for thin film printing and method for producing thin film pattern - Google Patents

Description

  The present invention relates to an insulating resin composition for thin film printing and a method for producing a thin film pattern.

  When the thickness of the conductive pattern formed on the substrate is extremely small, a technique for forming an insulating thin film for protecting the conductive pattern may be required.

  For example, in Patent Document 1 below, a coating for a protective layer is applied to the entire surface of a substrate partially covered with a formed conductive layer pattern, a solvent component is dried, and a contained resin component is cured to protect the resin component. Techniques for forming layers are disclosed.

  Patent Document 2 discloses a binder polymer obtained by copolymerizing (meth) acrylic acid having a carboxyl group, having an acid value of 100 to 190 mgKOH / g, and having an alkyl group having 4 to 18 carbon atoms. A photosensitive resin composition for use as a protective film of a touch panel electrode, comprising a photopolymerizable compound having three ethylenically unsaturated groups and having an acid value of 5 mgKOH / g or less, and a photopolymerization initiator. Is disclosed.

JP 2014-116103 A JP 2014-137394 A

  However, the above-mentioned conventional technique does not disclose a technique for forming a thin film pattern having a thickness of 3 μm or less on a conductive pattern by printing.

  An object of the present invention is to provide an insulating resin composition for thin film printing, which can form an insulating resin thin film pattern by screen printing or the like, and a method for producing a thin film pattern.

  In order to achieve the above object, one embodiment of the present invention is an insulating resin composition for thin film printing, comprising an insulating resin and a solvent, wherein the solvent contains a hydrocarbon group having a bridged ring skeleton. Wherein the content of the organic compound having a hydroxyl group and a hydroxyl group is 5 to 100% by mass, the insulating resin is contained in an amount of 3 to 30% by mass, and the viscosity at 25 ° C. is 1,000 to 200,000 mPa · s.

  The organic compound having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group is preferably any one of isobornylcyclohexanol, tricyclodecanedimethanol, and hydroxydicyclopentadiene.

  In addition, the insulating resin composition for thin-film printing has a pencil hardness of H or higher, which is 1 ± 0.5 μm or less, formed on a glass substrate and has a thickness of 1 ± 0.5 μm or less. As a result of a cross-cut peel test after forming a thin film having the following thickness, it is preferable that the adhesion is 8 or more.

  The insulating resin may be an epoxy resin or a mixture of an epoxy resin and a curing agent, a blocked isocyanate urethane resin prepolymer (for example, an isocyanate derivative having a property of releasing isocyanate by heating such as a blocked isocyanate blocked by oximation, etc.). ), An epoxy acrylate resin, an acrylic resin, a urethane acrylate resin, an allyl resin, or an unsaturated alkyd resin.

  The curing agent for the epoxy resin is preferably a phenol resin, an imidazole compound, dicyandiamide, an acid anhydride, or a polyamine compound, and furthermore, an imidazole compound encapsulated in consideration of the pot life of the ink. Is preferred.

  The epoxy acrylate resin, acrylic resin, urethane acrylate resin, allyl resin, and unsaturated alkyd resin preferably contain a heat or photo radical curing agent (initiator).

  Also, the blocked isocyanate urethane resin prepolymer preferably contains a polyol.

  Preferably, the insulating resin is a halogen-free epoxy resin obtained by epoxidizing allyl ether with hydrogen peroxide.

  Another embodiment of the present invention is a method for manufacturing a thin film pattern, comprising: a step of screen-printing a pattern of an arbitrary shape on a substrate by using the insulating resin composition for thin film printing; And b. Irradiating the pattern with light at a temperature of not more than ℃. Particularly, epoxy acrylate resin, acrylic resin, urethane acrylate resin, allyl resin, and unsaturated alkyd resin are treated in an inert atmosphere to prevent curing inhibition by oxygen when using a heat or photo radical curing agent (initiator). Is preferred.

  According to the present invention, a thin film pattern of an insulating resin having a substantially uniform thickness of 3 μm or less can be formed by screen printing or the like.

It is explanatory drawing of the determination method of a crosscut peel test.

  Hereinafter, embodiments for implementing the present invention (hereinafter, referred to as embodiments) will be described.

  The insulating resin composition for thin film printing according to the embodiment includes an insulating resin and a solvent. The solvent contains 5 to 100% by mass of an organic compound having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group. Further, the insulating resin composition for thin film printing contains 3 to 30% by mass of the insulating resin, and has a viscosity at 25 ° C. of 1,000 to 200,000 mPa · s.

  Even if the concentration of the insulating resin in the insulating resin composition for thin film printing is low, the viscosity is so high that screen printing is possible, and the solvent is removed by heat treatment and / or light irradiation. It has become possible to reduce the film thickness after the treatment.

  The use of the insulating resin composition for thin film printing (hereinafter, sometimes referred to as ink for thin film) facilitates formation of a thin film of an insulating resin by screen printing, particularly formation of a thin film pattern of an insulating resin. It can be carried out. In the present specification, the “thin film” means a film having a thickness of 3 μm or less.

  The insulating resin used in the insulating resin composition for thin film printing according to the present embodiment is a component having a function of protecting the conductive pattern and a binder function for the thin film printing pattern to develop good adhesion to the substrate. There is no particular limitation as long as it is an insulating resin that has these functions under the conditions of use of the substrate and is soluble in a solvent described below, and any of a thermosetting resin, a photocurable resin, and a thermoplastic resin can be used. However, a low viscosity is suitable for thin film printing.Before light irradiation or heating, a curable resin prepolymer that is not three-dimensionally cross-linked is a resin that has a three-dimensional cross-linked structure by light irradiation or heating. Preferably, it is used. As such a curable resin, for example, an epoxy resin or a mixture of an epoxy resin and a curing agent, a blocked isocyanate urethane resin prepolymer (for example, a blocked isocyanate blocked by oximation, etc.) Used isocyanate derivative), epoxy acrylate resin, acrylic resin (polyfunctional acrylate), urethane acrylate resin, allyl resin (DAP (diallyl phthalate), allyl ester), unsaturated alkyd resin and the like. When a curable resin is used in combination with a curing agent as the insulating resin, the resin concentration means the total content of the curable resin and the curing agent in the resin composition.

  Examples of the epoxy resin include bisphenol-A-type epoxy resin, bisphenol-F-type epoxy resin, novolak type epoxy resin, aliphatic polyvalent epoxy resin, alicyclic glycidyl type polyvalent epoxy resin, and the like. Further, an epoxy acrylate resin obtained by adding acrylic acid to the above epoxy resin may be used.

  Here, the curing agent for the epoxy resin is preferably any one of a phenol resin, an imidazole compound, dicyandiamide, an acid anhydride, and a polyamine compound. Preferred is an imidazole compound, specifically, NOVACURE (registered trademark) manufactured by Asahi Kasei E-Materials Co., Ltd. Further, as a curing agent, an acid anhydride, a phenol resin (novolak), dicyandiamide, or a polyamine may be used.

  Further, as the epoxy resin, a halogen-free epoxy resin obtained by epoxidizing allyl ether with hydrogen peroxide may be used. Here, as the allyl ether, for example, bisphenol-A diallyl ether, bisphenol-F diallyl ether, 2,6,2 ′, 6′-tetramethylbisphenol-A diallyl ether, 2,2′-diallylbisphenol-A diallyl Ether, 2,2′-di-t-butylbisphenol-A diallyl ether, 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diallyl ether, 2,2′-diisopropylbiphenol diallyl ether, 4,4'-ethylidenebisphenol diallyl ether, 4,4'-cyclohexylidene bisphenol diallyl ether, 4,4 '-(1-α-methylbenzylidene) bisphenol diallyl ether, 4,4'-(3,3,3 5-trimethylcyclohexylidene) bis E Nord diallyl ether, 4,4 '- (1-methyl - benzylidene) bisphenol diallyl ether.

  Further, the epoxy acrylate resin is obtained by adding (meth) acrylic acid to the epoxy resin, and in this case, a curing agent (initiator) can use a normal heat or photo radical polymerization initiator. . When using an acrylic resin, a urethane acrylate resin, an allyl-based resin, or an unsaturated alkyd resin as the curable resin, it is preferable to use a heat or photo radical curing agent (initiator). The heat or photo radical curing agent (initiator) will be described later.

  In addition, the blocked isocyanate-based urethane resin prepolymer is generally a reaction product of a compound having a hydroxyl group and an isocyanate group, and a preferred example of the compound having a hydroxyl group has a number average molecular weight of 500 to 2,000, more preferably 800 to 1500 polyether polyols (such as polyethylene glycol and polypropylene glycol), at least one polyol selected from polycarbonate polyols and polyester polyols, or pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, and glycerin. And ethylene oxide and / or propylene oxide adducts of at least one polyol or paratoluenesulfonic acid. Examples of compounds having an isocyanate group dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene-1,6-diisocyanate, and at least one diisocyanate selected from tolylene diisocyanate. In the present embodiment, as described above, these isocyanate groups are blocked by oximation or the like. Since such a blocked isocyanate releases a blocking agent by heating to produce an isocyanate, it can be cured by containing (present) a polyol.

  As a solvent used in the insulating resin composition for thin film printing (ink for thin film) according to the present embodiment, an organic compound having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group is used as a solvent for adjusting viscosity. Is done. Examples of the organic compound having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group include, for example, isobornylcyclohexanol, tricyclodecanedimethanol or hydroxydicyclopentadiene. These compounds impart appropriate adhesiveness to the ink for thin films due to the hydrogen bond of the hydroxyl group in addition to the complicated three-dimensional structure of the hydrocarbon group having a bridged ring skeleton. Further, the compound having an isobornyl group and a hydroxyl group has a high viscosity, despite the fact that the volatilization temperature is not so high, so that the viscosity of the thin film ink can be increased. In addition, since the ink solvent has an appropriate boiling point, the residue can be reduced by appropriate heat treatment and / or light irradiation after printing and drying.

  The content of an organic compound having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group (such as isobornylcyclohexanol, tricyclodecane dimethanol or hydroxydicyclopentadiene) in the solvent may be adjusted according to the necessity of another solvent. Although it depends on (diluting solvent), it is in the range of 5 to 100% by mass, more preferably 20 to 100% by mass, and still more preferably 50 to 100% by mass. When the content of the organic compound is less than 5% by mass, the insulating resin composition for thin film printing (ink for thin film) cannot have an appropriate viscosity and cannot maintain the shape of a printed pattern. .

  The solvent may be adjusted to a desired viscosity by mixing the above organic compound such as isobornylcyclohexanol, tricyclodecanedimethanol or hydroxydicyclopentadiene with another appropriate solvent (diluting solvent).

  Examples of other solvents include alcohols, ketones, esters, ethers, aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. From the viewpoint of favorably dispersing each component in the insulating resin composition for thin film printing (ink for thin film), ethanol, isopropyl alcohol, 1-methoxy-2-propanol (PGME), ethylene glycol, diethylene glycol, triethylene glycol, Dipropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monopropyl ether, diethylene glycol Monobutyl ether, tripropylene glycol, triethylene glycol monoethylene Ether, terpineol, dihydroterpineol, dihydroterpinyl monoacetate, methyl ethyl ketone, cyclohexanone, ethyl lactate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, dibutyl ether , Octane and toluene are preferred, and terpineol and dihydroterpineol are particularly preferred. These solvents may be used alone or as a mixture of two or more.

  In the insulating resin composition for thin film printing according to the present embodiment, various additives can be used as needed as long as the properties are not impaired. Examples of the additives used include a thixotropic agent for improving printability and an antifoaming agent for suppressing foaming during the preparation of the resin composition and defoaming after the preparation. As thixotropic agents, BYK (registered trademark) -405, BYK (registered trademark) -410 (manufactured by BYK Japan KK), Aerosil (registered trademark) 200, 380, R106 (manufactured by Nippon Aerosil Co., Ltd.), defoaming Examples of the agent include BYK (registered trademark) -051 and BYK (registered trademark) -054 (manufactured by BYK Japan KK).

  The insulating resin described above is contained in the insulating resin composition for thin film printing in an amount of 3 to 30% by mass, the solvent is contained in an amount of 70% by mass or more, and the additive is contained in an amount of 5% by mass or less.

  The insulating resin composition for thin film printing (ink for thin film) according to the present embodiment is produced by appropriately selecting the above-mentioned components by stirring, mixing, heating, cooling, dissolving, dispersing, and the like by a known method. it can.

  In the case of screen printing, the viscosity of the insulating resin composition for thin film printing (ink for a thin film) according to the present embodiment is from 1,000 to 200,000 mPa · s at 25 ° C., and more preferably from 3,000 to 100,000 mPa · s. It is.

  The method for forming an insulating thin film pattern according to the present embodiment is to screen-print a pattern of an arbitrary shape on a substrate using the insulating resin composition for thin film printing (ink for thin film) prepared as described above. And a step of irradiating the pattern with a heat treatment at a temperature of 300 ° C. or less and / or light.

Printing is performed by screen printing. The “pattern” in this specification includes a solid pattern applied to the entire surface of the substrate. It is needless to say that the screen mesh to be used has a smaller transmission volume, which is advantageous, and is preferably 25 cm ³ / cm ² or less, more preferably 20 cm ³ / cm ² or less. If it is larger than 25 cm ³ / cm ² , the film thickness becomes large. Also, if the screen is too fine, the strength of the screen is insufficient because it is necessary to reduce the wire diameter, and in the case of including an additive such as a thixotropic agent blended with an inorganic filler or the like in the thin film ink. It becomes easy to be clogged. Also, if it is too rough, pattern printing cannot be performed. Therefore, the mesh count (the number of lines (wires) constituting the mesh in one inch) is 100 to 800, more preferably 200 to 700. The wire diameter also depends on the mesh count, but if it is too thick, the transmission volume will be small, and if it is too thin, the strength will be low and it will be easy to break. Therefore, when the mesh count is 500, the wire diameter is preferably 10 to 30 μm, more preferably 15 to 25 μm.

  The screen plate is preferably made of stainless steel in terms of printing accuracy, and may be subjected to calendering or the like, if necessary.

  As for the emulsion thickness for forming a pattern on the screen plate, a thinner one is better for thin film printing, but if it is too thin, traces of the screen will be transferred, so it is preferably 1 to 30 μm, more preferably 2 to 20 μm. It is.

  The substrate on which pattern printing is performed may be rigid (rigid) or bendable (flexible). Moreover, it may be colored. As the substrate, for example, a rigid substrate such as a glass substrate, an alumina substrate, a glass epoxy substrate, a paper phenol substrate, an insulating resin-coated metal substrate, a polyimide film, a polycarbonate film, a polyethersulfone film, an acrylic film, a polyester (polyethylene terephthalate, Materials such as a flexible substrate such as a polyethylene naphthalate film, a polyolefin film, a cycloolefin polymer film, and a cycloolefin copolymer film. These may be opaque, but those having high light transmittance and low haze value are more preferable because they can be applied to a wide range of uses. On the substrate, a circuit pattern may be further formed. In this case, a resin thin film is formed by the thin film ink according to the present embodiment so as to cover the circuit pattern with a pattern having substantially the same shape as the circuit pattern. It can be printed as a solid film so as to cover the whole. Also, a large number of substrates may be stacked.

  The amount of the insulating resin composition for thin film printing (ink for thin film) applied to the substrate is determined in consideration of the thickness of the resin thin film required for the application. The film thickness is selected based on the application. The desired film thickness can be obtained by adjusting the application amount of the ink for thin film and the conditions of the application method. The thickness is preferably thicker from the viewpoint of the strength of the protective layer, and thinner in order to reduce the thickness of the member. Therefore, considering these factors comprehensively, a thickness of 0.05 μm or more and 3 μm or less is preferable. The film thickness is preferably 0.1 μm or more and 1 μm or less, and more preferably 0.2 μm or more and 0.8 μm or less. If the thickness is less than 0.05 μm, it becomes impossible to secure insulation.

  The printed (coated) ink layer for a thin film can be dried by heating if necessary. As used herein, "dry" means evaporating and removing the solvent. The heating temperature for drying varies depending on the solvent used. However, if the drying temperature is too high, foaming occurs when the solvent evaporates and pores are generated, which is not preferable. Therefore, the drying temperature is 120 ° C or lower, more preferably 100 ° C or lower. Since the initial drying temperature is particularly important, it is particularly preferable to start drying from about 40 to 80 ° C. and to raise the temperature stepwise within a range not exceeding 120 ° C. as necessary. Organic compounds having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group (such as isobornylcyclohexanol, tricyclodecanedimethanol or hydroxydicyclopentadiene), which are viscous liquids, have a high boiling point, and When a diluting solvent having a lower boiling point coexists, the diluting solvent having a lower boiling point is preferentially evaporated and removed. Therefore, the viscosity of the dispersion medium is increased by drying, and the collapse of the conductive pattern during drying is suppressed.

  To form a pattern of a resin thin film using the insulating resin composition for thin film printing (ink for thin film), a pattern is printed in an arbitrary shape on a substrate by screen printing or the like using the ink for thin film, and the pattern is formed. Is irradiated with light to a heat treatment of 300 ° C. or less and / or a pattern.

  The heat treatment is preferably performed at a temperature in the range of 80 ° C to 300 ° C, more preferably 100 ° C to 200 ° C. If the temperature is lower than 80 ° C., it takes too long to evaporate and remove the organic compound having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group. If the temperature is higher than 300 ° C., usable substrates are restricted, and members and the like may be damaged. Needless to say, lower temperatures are preferable in terms of the degree of freedom and energy of the used substrates and members. Although the required time varies depending on the processing temperature, it goes without saying that a shorter time is advantageous in terms of damage to members and the like and energy.

  In particular, in the case of a curable resin system which is cured by radical polymerization, the treatment is preferably performed in an inert atmosphere such as a nitrogen gas or an argon gas because it is inhibited by oxygen.

  When a thermosetting resin is used, a thermopolymerization initiator is used in combination. As the thermal polymerization initiator, an ordinary thermal radical polymerization initiator can be preferably used. Specific examples of the thermal polymerization initiator are not particularly limited, and known ones can be widely used. Specific examples include azo-based compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis- (2,4-dimethylvaleronitrile), benzoyl peroxide, diisopropyl peroxycarbonate, and t-butyl. Peroxy-2-ethylhexanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t -Butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, dilauroyl peroxide, diisopropylperoxydica-carbonate, di (4-t-butyl Cyclohexyl) peroxydicarbonate and 2,2-di (4,4-di- ( - butylperoxy) cyclohexyl) propane, 1,1-di (t-hexyl peroxy) -3,3,5 peroxide such as trimethyl cyclohexane. These can be used alone or in combination. The polymerization initiator is preferably one having low volatility and sublimability, and is preferably blended in a range of 0.1 mol% to 30 mol% based on the total number of moles of the monomer.

  As the heating device, a hot plate, a hot-air circulating thermostat, an IR furnace, or the like can be used, and the atmosphere can be changed from air to an inert gas atmosphere or a reducing gas atmosphere as needed. It is to be noted that the temperature profile can be controlled and implemented simultaneously or continuously without distinction between the above-mentioned drying step and heating step.

  In the case of an epoxy acrylate resin, an acrylic resin, a urethane acrylate resin, an allyl-based resin, or an unsaturated alkyd resin, curing may be performed by irradiation with light using an electron beam or a photopolymerization initiator instead of the above heat treatment. As the photopolymerization initiator, generally, a photopolymerization initiator that generates a radical by UV light to visible light can be selected. Specific examples of the photopolymerization initiator are not particularly limited, and widely known photopolymerization initiators can be used. Preferred specific examples include 1-hydroxycyclohexylphenyl ketone, 2,2′-dimethoxy-2-phenylacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy -2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine Oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methylpropane- Polymerization initiators such as 1-one, hexaarylbiimidazole compounds, triazine compounds, amino Examples include an acetophenone-based compound, a combination of a sensitizing dye and an organic boron salt-based compound, a quinone-based compound, a titanocene-based compound, an oxadiazole-based compound, a glyoxyester-based compound, and a bisacylphosphine oxide-based compound. These can be used alone or in combination. The mixing ratio of the polymerization initiator is 0.2 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, based on 100 parts by mass of the resin component (total of the resin and the curing agent). Preferably it is 1 to 5 parts by mass. If the proportion is less than 0.2 parts by mass, the curability tends to decrease, and if it exceeds 10 parts by mass, the physical properties of the cured product tend to decrease.

The UV light or visible light to be irradiated varies depending on the initiator used, but generally ranges from 250 to 450 nm, more preferably 300 to 400 nm, and the intensity ranges from 10 to 2000 mJ / cm ² , more preferably from 30 to 1000 mJ / cm ² . It is desirable to select from.

  It is preferable that the resin thin film obtained as described above has a thickness of 1 ± 0.5 μm on a glass substrate according to JIS K5600-5-4 and has a pencil hardness of H or higher after curing. Further, the adhesion measured by a cross-cut peel test after forming on a glass substrate according to the old JIS K5400 is preferably 8 or more, more preferably 9 or more, according to the judging method shown in the figure. More preferably, it is a point.

  Hereinafter, examples of the present invention will be specifically described. The following examples are provided to facilitate understanding of the present invention, and the present invention is not limited to these examples.

<Reference example>
Synthesis of bisphenol-A-glycidyl ether In a 2000 ml eggplant-shaped flask, 148.4 g (0.650 mol) of bisphenol-A (manufactured by Mitsui Chemicals, Inc.), 50% water-containing 5% -Pd / C-STD type (N. 1.38 g (0.650 mmol) of Echemcat Co., Ltd., 1.639 g (6.50 mmol) of triphenylphosphine (Hokuko Chemical Co., Ltd.), 189 g (1.37 mol) of potassium carbonate (Nippon Soda Co., Ltd.), 143 g (1.43 mol) of allyl acetate (manufactured by Showa Denko KK) and 64.1 g of isopropanol were added and reacted at 85 ° C. for 8 hours in a nitrogen gas atmosphere. After the reaction, a portion was sampled, diluted with ethyl acetate, and analyzed by gas chromatography to confirm that the ratio of bisphenol-A-diallyl ether to monoallyl ether was up to 98: 2.

  Thereafter, 200 g of toluene was added to the reaction solution, Pd / C and the precipitated solid were removed by filtration, and isopropanol and toluene were distilled off by an evaporator. After repeating this reaction and post-treatment operation four times, 493 g of a distillate (61.7% of isolated yield, 98.1% of diallyl ether, and the rest of mono Allyl ether) and 245 g of non-distilled product (diallyl ether 96.5%) were obtained.

Bisphenol-A-diallyl ether (50.05 g, 162.3 mmol), acetonitrile (26.63 g, 648.7 mmol), and ethanol (265.1 g, 5754.2 mmol) obtained by the above operation were placed in a 1 L 4-diameter eggplant-shaped flask. It was weighed (acetonitrile concentration 9.9 mol%, pH = 8.2). A 45% aqueous hydrogen peroxide solution (53.92 g, 713.5 mmol) was added to a 100 mL dropping funnel over 2 hours while adding a saturated aqueous potassium hydroxide solution (KOH / H ₂ O = 110 mg / 100 mL) so that the pH did not fall below 9. And dropped. A saturated aqueous potassium hydroxide solution was added dropwise so that the reaction temperature did not exceed 30 ° C., and the pH was reached to 10.5 over 2 hours (2 hours from the end of the dropping of the hydrogen peroxide solution), and the pH was controlled at 10.5. While stirring for another 2 hours. Acetonitrile (13.31 g, 324.2 mmol) was weighed into a 50 mL dropping funnel and added dropwise over 2 hours. At the same time, 45% aqueous hydrogen peroxide (53.92 g, 713.5 mmol) was added dropwise using a 100 mL dropping funnel over 4 hours (during this period, the pH was adjusted to 10 to 10 so that the reaction temperature did not exceed 30 ° C). 10.5) and further stirred for 4 hours while controlling the pH at 10.5. Pure water (100 g) was added to the reaction solution for dilution, and the solvent was distilled off under reduced pressure. After the residue was extracted with ethyl acetate (100 g), pure water (100 g) was added again to carry out a liquid separation operation. When the obtained solution was measured by gas chromatography, the conversion of bisphenol A type diallyl ether as a raw material was 100%, bisphenol A type diglycidyl ether as a diepoxy monomer was 87.7%, and monoglycidyl was used. It was confirmed that ether was 5.1%.

  Ethyl acetate was distilled off by an evaporator to obtain the desired epoxidation product. It has a chlorine atom concentration of 6 mass ppm, a total bromine atom concentration of less than 1 mass ppm, and an epoxy equivalent of 178 g / eq. there were.

<Example 1>
As shown in Table 1, 5.80 g of bisphenol-A-glycidyl ether synthesized in Reference Example 1, 44.0 g of Tersolve MTPH (manufactured by Nippon Terpen Chemical Co., Ltd., isobornylcyclohexanol), and Aerosil 380 (Japan) 1.03 g of Aerosil Co., Ltd. and 1.93 g of Novacure (registered trademark) HX-3722 (epoxy resin curing agent manufactured by Asahi Kasei E-Materials Co., Ltd.) were added, and a planetary vacuum stirrer (ARV-310, manufactured by Shinky Corporation) was added. )), Mixing at a maximum stirring speed of 2000 rpm for about 30 minutes to prepare an insulating resin composition sample having a resin concentration (the ratio of the total of the resin and the curing agent in Table 1 to the entire resin composition) of about 15% by mass. did.

<Comparative Example 1>
As shown in Table 1, 25.60 g of bisphenol-A-glycidyl ether synthesized in Reference Example 1, 10.3 g of diethylene glycol monobutyl ether acetate as a solvent, 1.33 g of Aerosil 380 (produced by Nippon Aerosil Co., Ltd.), Novacure (registered) 8.53 g of HX-3722 (trademark) (an epoxy resin curing agent manufactured by Asahi Kasei E-material Co., Ltd.) was added and mixed in the same manner as in Example 1 to prepare an insulating resin composition sample.

<Examples 2 and 3>
As shown in Table 1, the resin concentration (the ratio of the sum of the resin and the curing agent in Table 1 to the entire resin composition) was about 20% by mass (Example 2), except that the composition was changed. And about 10% by mass (Example 3) of an insulating resin composition sample were prepared.

<Comparative Example 2>
As shown in Table 1, an insulating resin composition having a resin concentration (a ratio of the sum of the resin and the curing agent in Table 1 to the entire resin composition) of about 2% by mass as in Example 1 except that the composition was changed. Sample was prepared.

<Example 4>
As shown in Table 1, instead of epoxy resin (bisphenol-A-glycidyl ether and NOVACURE (registered trademark) HX-3722), epoxy acrylate resin Lipoxy (registered trademark) SP-1509 (manufactured by Showa Denko KK) Was used to prepare an insulating resin composition sample having a resin concentration (the ratio of the total of the resin and the curing agent in Table 1 to the entire resin composition) of about 15% by mass.

<Examples 5 and 6>
As shown in Table 1, as in Example 3, except that the solvent composition was changed, the resin concentration (the ratio of the sum of the resin and the curing agent in Table 1 to the entire resin composition) was about 10% by mass. Each product sample was prepared.

<Viscosity measurement>
The viscosity of the insulating resin composition (ink) was measured at 25 ° C. using a Brookfield B-type viscometer DV-II + Pro. In addition, the rotor number 52 was used when the viscosity exceeded 10,000 mPa · s, and the rotor number 40 was used when the viscosity was 10,000 mPa · s or less. Table 2 shows the results.

<Printing of insulating resin composition (ink)>
A screen plate having a 2 cm square pattern prepared by hardening a film having a thickness of 5 μm using an emulsion IC-10000 (manufactured by Murakami) using a mesh of a calendered product with a mesh count of 640 and a mesh diameter of 640 as a screen plate. Printed using. The substrate used was a 15 cm square glass plate. After the insulating composition (ink) prepared as described above was printed on the surface of the base material in a 2 cm square pattern using the screen plate, heating was performed in a hot air drying oven at 140 ° C. for 60 minutes without preliminary drying. This was processed to form a thin film insulating pattern.

<Thickness measurement of thin film insulating pattern>
Three points were measured by FE-SEM S-5200 manufactured by Hitachi High-Tech Co., Ltd., and the average value was obtained. Table 2 shows the results.

<Cleaning test>
The cross-cut peel test after curing of the thin film insulating patterns of Examples 1 to 6 formed on a glass substrate with a thickness of 1 ± 0.5 μm was performed. Using a cutter knife with a new blade, 11 cuts were made in the thin-film insulating pattern at intervals of 1 mm, and after changing the 90 ° direction, 11 more cuts were formed to form 100 1-mm squares. A cellophane adhesive tape was adhered so as to adhere to the cut print surface, and the cellophane adhesive tape was rubbed with an eraser to adhere the tape to the coating film. One to two minutes after the tape was applied, the edge of the tape was held at a right angle to the printing surface, peeled off instantaneously, and judged according to the standard shown in FIG. 1 according to the old JIS K5400. Table 2 shows the results. In Comparative Example 1, since a thin film having a thickness of 1 ± 0.5 μm could not be formed, the test result at a thickness of 12 μm was shown as a reference value.
<Pencil hardness>
According to JIS K5600-5-4, the pencil hardness after curing of the thin film insulating patterns of Examples 1 to 6 formed on a glass substrate with a thickness of 1 ± 0.5 μm was measured. Table 2 shows the results. In Comparative Example 1, since a thin film having a thickness of 1 ± 0.5 μm could not be formed, the measurement result at a thickness of 12 μm was shown as a reference value.

  As shown in Table 2, in Examples 1 to 6, the viscosity of the insulating resin composition was within the range of the present invention (1000 to 200000 mPa · s), and the film thickness of the thin film insulating pattern was 0.1 mm. It could be 6 to 1.3 μm (3 μm or less). In addition, the result of the crosscut peel test is 10 points. The pencil hardness was H or higher (2H).

  In contrast, in Comparative Example 1, since diethylene glycol monobutyl ether acetate was used as the solvent, the resin concentration was set to about 75% by mass in order to make the viscosity suitable for screen printing (4600 mPa · s) as an example. As a result, the result of the cross-cut peel test was 10 points, and the pencil hardness was 2H. However, the thickness of the thin film insulating pattern was 12 μm, and it was difficult to form a thin film.

Further, in Comparative Example 2, the resin concentration was about 2% by mass and less than 3% by mass, which is the lower limit of the present invention. It was difficult.

Claims (10)

Including an insulating resin and a solvent, the content of the organic compound having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group in the solvent is 5 to 100% by mass, and the insulating resin is 3 to 30% by mass. %, Containing 70 to 97% by mass of the solvent, and having a viscosity at 25 ° C. of 1,000 to 200,000 mPa · s.   The insulating material for thin film printing according to claim 1, wherein the organic compound having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group is any one of isobornylcyclohexanol, tricyclodecanedimethanol, and hydroxydicyclopentadiene. Resin composition.   Pencil hardness of a thin film formed on a glass substrate with a thickness of 1 ± 0.5 μm is H or higher, and results of a cross-cut peel test after forming a thin film of 1 ± 0.5 μm on a glass substrate 3. The insulating resin composition for thin-film printing according to claim 1, wherein the adhesiveness is 8 points or more in a cross-cut peeling test.   The insulating resin is an epoxy resin or a mixture of an epoxy resin and a curing agent, a blocked isocyanate urethane resin prepolymer, an epoxy acrylate resin, an acrylic resin, a urethane acrylate resin, an allyl resin, or an unsaturated alkyd resin. The insulating resin composition for thin-film printing according to claim 1.   The insulating resin composition for thin film printing according to claim 4, wherein the curing agent for the epoxy resin is any one of a phenol resin, an imidazole compound, dicyandiamide, an acid anhydride, and a polyamine compound.   The insulating resin composition according to claim 5, wherein the imidazole compound is an encapsulated imidazole compound.   The insulating resin composition for thin film printing according to claim 4, wherein the epoxy acrylate resin, the acrylic resin, the urethane acrylate resin, the allyl-based resin, and the unsaturated alkyd resin include a heat or photo-radical curing agent.   The insulating resin composition for thin-film printing according to claim 4, wherein the blocked isocyanate-based urethane resin prepolymer contains a polyol.   The insulating resin composition for thin film printing according to any one of claims 1 to 3, wherein the insulating resin is a halogen-free epoxy resin obtained by epoxidizing allyl ether with hydrogen peroxide. A step of screen-printing a pattern of an arbitrary shape on a substrate with the insulating resin composition for thin-film printing according to any one of claims 1 to 9,
A step of irradiating the pattern with a heat treatment of 300 ° C. or less and / or light,
A method for producing a thin film pattern, comprising: