CN107614630A - Composition for forming insulating protective film by offset printing - Google Patents

Abstract

The present invention provides an insulating protective film-forming composition for forming an insulating protective film by offset printing, which comprises (A) a high-molecular-weight resin having a crosslinking reactive group and a weight-average molecular weight of more than 2 × 10, wherein the high-molecular-weight resin has a crosslinking reactive group⁴And is 40 × 10⁴The following; (B) a solvent having a solubility parameter of greater than 8.7 and a boiling point of 150 ℃ to 350 ℃; and (C) a solvent having a solubility parameter of 7.0 to 8.7 inclusive and a boiling point of 130 ℃ to less than 250 ℃.

Description

For forming an insulating protective film for forming an insulating protective film by offset printing combination

technical field

The present invention relates to a composition for forming an insulating protective film for forming an insulating protective film by offset printing.

Background technique

The offset printing method is a printing method in which the plate forming the printed image does not come into contact with the printed object, and the ink paste is transferred to the surface layer of the blanket, and then transferred from the blanket to the printed object at approximately 100%. body for printing.

In such an offset printing method, there is a problem that since the blanket is always in contact with the ink paste, the solvent and binder resin contained in the ink paste are absorbed by the blanket during repeated printing, resulting in deterioration of the blanket. . However, if an appropriate amount of solvent is not absorbed, there is also a problem that the release property of the ink from the blanket deteriorates during transfer from the blanket to the printed object, and the quality of offset printing deteriorates.

Therefore, in the following Patent Document 1, in order to moderately absorb the solvent while suppressing the absorption of the binder resin into the blanket, an ink composition is disclosed. 12.0 binder resin and solvent, the absolute value of the difference between the solubility constants of the two is 2.0 or less, the boiling point of the solvent is 50 to 200 ° C, the viscosity of the ink composition is 5 to 50 Pa·s, and the ink composition is dried. The initial tack value (Japanese text: Boltack value) of the obtained coating film was 10-28.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2010-159350

Contents of the invention

The problem to be solved by the invention

However, in the case of inks containing metal or solid fillers, the amount of binder resin used in the ink is low, and sometimes solid particles are interposed, and the adsorption of the binder resin into the blanket often does not become very large. The problem. On the other hand, in the case of forming an insulating protective film by offset printing, the thermosetting resin itself forming the insulating protective film becomes the main component, and in order to improve the insulating performance of the protective film, it is necessary to use a curable resin (UV curing system or thermosetting resin). system resin), and examples of such resins include polyfunctional (meth)acrylates, epoxy resins, and oxetane compounds having relatively low molecular weights. When the ink also contains a thermosetting resin, the uncured monomer and oligomer components contained in the thermosetting resin are absorbed into the blanket together with the solvent. Since these monomers and oligomers (including reactive diluents) The boiling point of the blanket is very high (hard to volatilize), so when the blanket dries, curing modification begins to occur, resulting in permanent degradation of the blanket. Therefore, there is a problem that a system with a high content of a thermosetting resin component cannot be applied to offset printing.

An object of the present invention is to provide an insulating film for forming an insulating protective film by offset printing at a level at which the absorption of the curable resin into the blanket does not become a problem in a system using a thermosetting resin usable as an insulating protective film. A composition for forming a protective film.

means to solve the problem

In order to achieve the above object, one embodiment of the present invention is an insulating protective film forming composition for forming an insulating protective film by offset printing, which is characterized in that it contains (A) a high Molecular weight resins, the weight average molecular weight of which is greater than 2×10 ⁴ and less than 40×10 ⁴ ; (B) a solvent with a solubility parameter greater than 8.7 and a boiling point of 150°C to 350°C; and (C) a solubility parameter of 7.0 to 8.7 , Solvents with a boiling point of not less than 130°C and less than 250°C.

Preferably, the average number of crosslinking reactive groups per molecule of (A) the high molecular weight resin having crosslinking reactive groups is calculated from the number of crosslinking reactive groups per unit mass and the number average molecular weight. The number of groups is 3 or more.

Moreover, it is preferable that the composition for forming an insulating protective film for forming an insulating protective film by offset printing further contains (D) a crosslinking agent.

In addition, it is preferable that the above-mentioned (A) high molecular weight resin having a crosslinking reactive group has a solubility parameter of 11 to 15 and the composition contains 10 to 80% by mass of the (A) crosslinking reactive group. Group of high molecular weight resins.

In addition, it is preferable that the solubility parameter of the above-mentioned (B) solvent with a solubility parameter greater than 8.7 and a boiling point of 150° C. to 350° C. is the solubility parameter of the above-mentioned (A) high molecular weight resin having a crosslinking reactive group + 1 or less.

Moreover, it is preferable to contain 10-50 mass % of the said (C) solvent whose solubility parameter is 7.0-8.7, and a boiling point of 130-250 degreeC in a composition.

Moreover, it is more preferable to contain 20-50 mass % of said (C) solvents whose solubility parameter is 7.0-8.7, and whose boiling point is 130-250 degreeC in a composition.

In addition, it is preferable that the difference between the solubility parameters of the above-mentioned (A) polymer resin having a cross-linking reactive group and the above-mentioned (C) solvent whose solubility parameter is 7.0 to 8.7 and has a boiling point of 130° C. to less than 250° C. is greater than 2.

In addition, it is preferable that the above-mentioned (B) solvent whose solubility parameter is greater than 8.7 and whose boiling point is not less than 150°C and not more than 350°C is selected from diethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether, γ - Any one of butyrolactone and 1,3-dimethyl-2-imidazolidinone.

In addition, it is preferable that the solvent (C) having a solubility parameter of 7.0 to 8.7 and a boiling point of 130° C. to less than 250° C. is selected from propylene glycol monomethyl ether acetate and diethylene glycol dimethyl ether. of any kind.

The effect of the invention

According to the present invention, it is possible to realize a composition for forming an insulating protective film for forming an insulating protective film by offset printing in which curable resin is hardly absorbed by a blanket.

detailed description

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

The composition for forming an insulating protective film (hereinafter, sometimes referred to as an ink composition) for forming an insulating protective film by offset printing according to the embodiment is characterized by comprising (A) an ink having a crosslinking reactive group. High molecular weight resin, the weight average molecular weight is greater than 2×10 ⁴ and less than 40×10 ⁴ ; (B) the solubility parameter is greater than 8.7, the boiling point is between 150°C and 350°C, preferably the boiling point is higher than 200°C and less than 300°C solvent; and (C) a solvent having a solubility parameter of 7.0 to 8.7, a boiling point of 130°C to 250°C, preferably a boiling point of 130°C to 200°C.

The above-mentioned (A) high-molecular-weight resin having a cross-linking reactive group is a high-molecular-weight resin having a weight-average molecular weight of more than 2×10 ⁴ and not more than 40×10 ⁴ . Absorption into a transfer body (blanket) for offset printing can be reduced by using a high molecular weight material having a weight average molecular weight within the above range as the binder resin. As the weight average molecular weight becomes smaller than the above range, the absorption into the blanket tends to increase, and when the weight average molecular weight becomes larger than the above range, the solubility in solvents tends to decrease. A more preferable weight average molecular weight is greater than 3×10 ⁴ and not more than 35×10 ⁴ . In addition, high insulation performance and heat resistance can be achieved by using a curable resin that undergoes a crosslinking reaction using a crosslinking reactive group. In this specification, the so-called "cross-linking reactive group" refers to a functional group that can form a cross-linking connection between the same molecule and/or different molecules. The crosslinking reactive group can be selected from known functional groups. For example, it refers to a functional group that forms a crosslinked structure by reacting with a (D) crosslinking agent described later, and a functional group that reacts between crosslinking reactive groups. Examples include groups having active hydrogen such as carboxyl, hydroxyl, mercapto, and amino groups, groups having unsaturated bonds such as vinyl, (meth)allyl, and (meth)acryloyl, glycidyl, oxygen, etc. Cyclic ether groups such as heterocyclobutane groups, isocyanate groups, and the like. In the present specification, "(meth)allyl" means allyl or methallyl, and "(meth)acryloyl" means acryloyl or methacryloyl.

In addition, the above (A) high molecular weight resin having a crosslinking reactive group preferably has a plurality of crosslinking reactive groups. By having a plurality of crosslinking reactive groups, the crosslinking density can be increased, and the insulating performance and heat resistance of the formed insulating protective film can be further improved. The number of crosslinking reactive groups per molecule calculated from the number average molecular weight is preferably at least 3, more preferably 7 or more functional groups.

The number of crosslinking reactive groups per molecule is the average number of functional groups per molecule calculated from the number of crosslinking reactive groups per unit mass of the high molecular weight resin and the number average molecular weight.

The method of calculating the number of crosslinking reactive groups per unit mass is not particularly defined, and a known method can be used. For example, if it is a glycidyl group, the epoxy equivalent can be used; if it is a carboxyl group, the acid value can be used; if it is a hydroxyl group, the hydroxyl value can be used; As for the bonding group, the iodine value and the like can be used. By using these measured values, the number of crosslinking reactive groups per unit mass of the high molecular weight resin can be calculated.

The measuring method of the number average molecular weight is not specifically defined, A well-known method can be utilized. For example, GPC (Gel Permeation Chromatography) method can be utilized.

In addition, the solubility parameter (SP value, unit: (cal/cm ³ ) ^1/2 ) of the above (A) high molecular weight resin having a crosslinking reactive group is preferably 11 to 15, more preferably 11.5 to 15, Preferably, 10 to 80% by mass of the (A) high molecular weight resin having a crosslinking reactive group is included in the composition, and more preferably 15 to 70% by mass of (A) the high molecular weight resin having a crosslinking reactive group is included in the composition. high molecular weight resins. When it is less than 10% by mass, the amount of low-molecular-weight compounds increases, and the amount of substances absorbed into the blanket may increase. When it exceeds 80% by mass, the viscosity of the composition becomes too high, and the transfer from the plate to the blanket may become poor. Therefore, the concentration of the high molecular weight resin is preferably within the aforementioned range. For blankets used in offset printing, silicone blankets at least the surface of which are formed of silicone rubber are widely used, and their SP values are 7.3 to 7.6. Therefore, by setting the SP value of the high molecular weight resin to 11 or more and increasing the difference from the SP value of the blanket, the absorption of the high molecular weight resin into the blanket can be further suppressed. On the other hand, if the difference in SP value between the high molecular weight resin and the blanket becomes too large, the absorption of the high molecular weight resin in the ink composition into the blanket becomes difficult, but the solvent capable of dissolving the high molecular weight resin is free. The degree of printing often decreases, and in severe cases, the transfer to the blanket itself becomes difficult, and the quality of offset printing may decrease. Therefore, the SP value of the high molecular weight resin is preferably within the above range. The SP value can be calculated with reference to RF Fedors: Polym. Eng. Sci., 14[2], 147-154 (1974).

As the above (A) high molecular weight resin having a crosslinking reactive group, any resin may be used as long as it contains a crosslinking reactive group and can be dissolved or dispersed in the composition. Examples thereof include high-molecular-weight resins having active hydrogen such as carboxyl group-containing polyurethane (SP value 11.5 to 12), and diallyl phthalate prepolymers (for example, Daisor Co., Ltd. Daisor Dapp (SP value 11.7). The calculation is based on the product obtained by polymerizing only one allyl group in diallyl phthalate. The same applies to other diallyl phthalate prepolymers)) and diene isophthalate Propyl ester prepolymer (for example, Daiso Isodapp (SP value 11.7) manufactured by Daiso Corporation), diallyl terephthalate prepolymer (SP value 11.7), prepolymer of triallyl isocyanurate Polymers (for example, Nippon Kasei Co., Ltd. タイクプレラリマー (SP value 14.9. Calculated as a product obtained by polymerizing one allyl group in triallyl isocyanurate.)) etc. have unsaturated bonds high molecular weight resins.

(B) A solvent having a solubility parameter (SP value) greater than 8.7 and a boiling point of 150° C. to 350° C. is a solvent with low affinity with a transfer body (blanket) for offset printing, that is, a body that is difficult to be transferred ( Blanket) absorbs the solvent. Preferably, the solvent or reactive diluent has an SP value greater than 8.7 and is equal to or less than the SP value+1 of the above-mentioned (A) high molecular weight resin having a crosslinking reactive group. When the above-mentioned SP value is 8.7 or less, the difference with the SP value of the blanket becomes smaller, and it becomes easier to be absorbed by the blanket. Therefore, the solvent concentration in the ink composition transferred from the plate to the blanket is reduced, and it becomes difficult to Retransfer to a printed body (work) is performed. On the other hand, when the above-mentioned SP value becomes a value greater than (A) the SP value of the polymer resin having a crosslinking reactive group+1, the affinity between the solvent and the high-molecular-weight resin decreases, and the high-molecular-weight resin becomes less soluble in In a solvent, a uniform ink composition cannot be formed, and therefore, retransfer to a product may be hindered.

In addition, when the boiling point of the solvent with low affinity with the transfer body (blanket) for offset printing is low, the following problem is likely to occur: the solvent dries before further transfer from the transfer body to the substrate. , it becomes difficult to perform retransfer. However, if the boiling point is too high, high temperature and long time are required for the final distillation to remove the solvent. Therefore, the boiling point is 150°C to 350°C, preferably higher than 200°C and 300°C.

It should be noted that (B) the content of the solvent in the ink composition that has a solubility parameter (SP value) greater than 8.7 and a boiling point of 150°C to 350°C and has low affinity with the blanket is in addition to (B) The balance of the total amount of ingredients.

Examples of solvents with low affinity for blankets having a solubility parameter (SP value) of (B) greater than 8.7 and a boiling point of 150° C. to 350° C. include, for example, diethylene glycol monoethyl ether acetate ( SP value 9.0), triethylene glycol monobutyl ether (SP value 10.3), γ-butyrolactone (SP value 9.9), 1,3-dimethyl-2-imidazolinone (SP value 11.5), etc.

The above (C) solvent having a solubility parameter (SP value) of 7.0 to 8.7 and a boiling point of 130°C to less than 250°C is a solvent having a high affinity with the transfer body (blanket) for offset printing, that is, A solvent that is easily absorbed by the transfer body (blanket). When the said SP value is less than 7.0 or more than 8.7, the difference with the SP value of a blanket will become large, and the absorbency in a blanket will fall. Therefore, the ink composition becomes difficult to peel off from the blanket, and retransfer to a product becomes difficult.

When the boiling point of the solvent with high affinity with the transfer body (blanket) for offset printing is high, it takes a long time to dry the blanket after absorbing the solvent in the blanket, even if it is heated. However, if the boiling point is too low, there is also the following problem: it is easy to dry before transferring to the transfer body, and the initial transfer cannot be performed smoothly. Therefore, the boiling point is 130°C or higher and lower than 250°C, preferably 130°C or higher. And lower than 200°C.

In addition, it is preferable that 10 to 50% by mass of the above-mentioned (C) affinity with blankets having a solubility parameter (SP value) of 7.0 to 8.7 and a boiling point of 130°C to less than 250°C be contained in the above-mentioned ink composition. The high solvent is more preferably contained in an amount of 20 to 50% by mass. (C) When the solubility parameter (SP value) is 7.0 to 8.7 and the boiling point is 130° C. to 250° C. The content of the solvent with high affinity with the blanket is 10% by mass or more in the ink composition, The transfer of the ink composition from the plate to the blanket was performed well. In addition, when it is 50% by mass or less, there is no problem that the solvent concentration in the ink composition becomes too high and cannot be completely absorbed by the blanket, and retransfer from the blanket to the product can be performed satisfactorily.

Examples of the (C) solvent having a solubility parameter (SP value) of 7.0 to 8.7 and a boiling point of 130°C to less than 250°C include, for example, propylene glycol monomethyl ether acetate (SP value 8.7), diethyl Glycol dimethyl ether (SP value 8.1), etc.

In addition, the above-mentioned (A) high molecular weight resin having a crosslinking reactive group and the above-mentioned (C) affinity with a blanket having a solubility parameter (SP value) of 7.0 to 8.7 and a boiling point of 130°C to less than 250°C It is preferable that the difference in the SP value of the solvent with high property is 2 or more. It is more preferably greater than 2, and still more preferably 2.3 or greater. When the difference is less than 2, the solubility of the high-molecular-weight resin in the solvent becomes large, so that the solvent with high affinity to the blanket cannot be selectively adsorbed to the blanket, and the retransferability to the product may decrease.

In addition, it is preferable that the ink composition according to the embodiment further contains (D) a crosslinking agent for accelerating the crosslinking reaction of (A) the high molecular weight resin having a crosslinking reactive group. When the (D) crosslinking agent is included, its solubility parameter (SP value) is preferably 9 or more and 15 or less, and more preferably 10 or more. It is preferable to contain 10 mass % or less of (D) crosslinking agents in a composition. When the SP value is less than 9, it becomes easy to be absorbed by the blanket, so the transferability may be deteriorated. (D) The crosslinking agent may contain a compound having a plurality of groups that can react with the crosslinking reactive group of the aforementioned (A), or may contain a compound having only one crosslinking reactive group with the aforementioned (A). A compound that undergoes a reactive group. For example, in the case of carboxyl group-containing polyurethane, since the crosslinking reactive group is a carboxyl group having active hydrogen, a compound having a plurality of groups (such as hydroxyl group, glycidyl group, etc.) capable of reacting with carboxyl group can be used as (D) Cross-linking agent. The crosslinking reaction is preferably an addition reaction in which there is no detachment of a low-molecular compound. Therefore, in this case, an epoxy compound having a glycidyl group (for example, bisphenol-A-diglycidyl ether (SP value 10.4), bisphenol-F-diglycidyl ether, glycidyl ether of novolac (Novolac) phenol resin, peroxyhydroxide of bisphenol-A-diallyl ether (SP value 10.4), Co., Ltd. EHPE 3150 (SP value 11.0) manufactured by Daicel Co., Ltd., etc.). In the case of an allyl-based polymer such as a prepolymer of diallyl isophthalate, the crosslinking reactive group is an allyl group, so curing occurs by free radical polymerization, so that even without using crosslinking It can also carry out crosslinking reaction, but in order to increase the crosslinking density and improve durability, a crosslinking agent with more than two functional unsaturated groups can be used, such as: multifunctional acrylate (for example, dipentaerythritol hexaacrylate esters (SP value 10.4), acrylic acid adducts of epoxy resins, etc.), allyl compounds such as triallyl isocyanurate (Taiku manufactured by Nippon Kasei Co., Ltd.) (SP value 13.6), 4,4'- Maleimide compounds such as diphenylmethane bismaleimide (SP value 14.3).

In addition to the above-mentioned components (A) to (D), other components such as (E) curing catalyst, (F) reactive diluent, (G) additives may be contained in the composition for forming an insulating protective film as needed. .

(E) Curing catalyst

In order to make the crosslinking reaction of (A) the high molecular weight resin having a crosslinking reactive group proceed smoothly, (E) a curing catalyst may be added. (E) As a curing catalyst, known compounds suitable for curing reaction can be used. For example, melamine and imidazoles can be used for curing reaction of carboxyl group and glycidyl group. In the case of radical polymerization of an allyl polymer, a peroxide or the like can be used. In addition, a photopolymerization initiator can be used for ultraviolet curing of acryloyl or methacryloyl groups. The addition amount can be a known addition amount, for example, with respect to the total amount of the resin ((A) high molecular weight resin having a crosslinking reaction group) and (D) crosslinking agent that undergoes crosslinking reaction, 1 to 5 quality%.

(F) Reactive diluent

(F) The reactive diluent is a low-molecular compound that has very low volatility and contains a cross-linking reactive group, and is a compound that can dissolve or disperse other components uniformly. By making the aforementioned (A) have a cross-linking reactive group The high-molecular-weight resin is uniformly dissolved or dispersed with the solvent, and the viscosity of the composition can be adjusted. In addition, due to its reactivity, it becomes a solid substance after curing.

In addition, since it is difficult to volatilize, it can be selected from compounds that have low affinity with blankets and are difficult to be absorbed. When the SP value is used as an index of affinity, the SP value is greater than 8.7, and is equal to or less than the SP value+1 of the high molecular weight resin having a crosslinking reactive group (A). Preferably it is 9 or more, More preferably, it is 10 or more.

(F) The boiling point of the reactive diluent is preferably higher than 300° C., and the upper limit of the boiling point of the reactive diluent is not particularly limited. Preferably, the reactive diluent is not substantially distilled off. When the boiling point is 300° C. or lower, a part of the (F) reactive diluent may be evaporated and distilled off depending on curing conditions. For example, 1,6-hexanediol glycidyl ether (SP value 9.5), ethoxylated isocyanurate triacrylate (A-93000 manufactured by Shin-Nakamura Chemical Industry, SP value 13.3), 1, 6-Hexanediol glycidyl ether (SP value 9.5). The amount added is 100 parts by mass or less, preferably 80 parts by mass or less, with respect to 100 parts by mass of the high molecular weight resin having (A) a crosslinking reactive group.

(G) Additives

(G) additives, such as a surfactant, an antioxidant, a filler, may be contained, as long as the performance of the insulating protective film forming composition is not adversely affected. In order to adjust the viscosity of the composition, fillers such as fumed silica may be used. In addition, a colored filler may be added for coloring, but it is preferable not to contain a conductive filler in order to ensure insulation.

The addition amount should just be the amount which can express the objective function, for example, it is preferable that it is 5 mass % or less of the whole composition.

Example

Hereinafter, examples of the present invention will be specifically described. It should be noted that the following examples are for easy understanding of the present invention, and the present invention is not limited by these examples.

＜Epoxy Equivalent＞

The epoxy equivalent was determined in accordance with JIS-K7236. Weigh 0.1 to 0.2 g of the sample, put it in the Erlenmeyer flask, and then add 10 mL of chloroform to dissolve it. Next, 20 mL of acetic acid was added, and then 10 mL of a tetraethylammonium bromide acetic acid solution (a solution obtained by dissolving 100 g of tetraethylammonium bromide in 400 mL of acetic acid) was added. Add 4-6 drops of crystal violet indicator to this solution, titrate with 0.1 mol/L perchloric acid acetic acid solution, based on the titration result, obtain the epoxy equivalent according to the following formula.

Epoxy equivalent (g/eq)=(1000×m)/{(V1-V0)×c}

m: Mass of sample (g)

V0: In the blank test, the amount of perchloric acid acetic acid solution consumed until the end point of titration (mL)

V1: The amount of perchloric acid acetic acid solution consumed until the end point of titration (mL)

c: Concentration of perchloric acid acetic acid solution (0.1mol/L)

＜Weight average molecular weight, number average molecular weight＞

Gel permeation chromatography (hereinafter, abbreviated as GPC) was used to obtain a value converted to polystyrene (the standard sample used is Standard SM-105 manufactured by Showa Denko Co., Ltd.). In addition, the measurement conditions of GPC are as follows.

Apparatus name: HPLC unit HSS-2000 manufactured by JASCO Co., Ltd.

Column: Shodex column LF-804

Mobile phase: tetrahydrofuran

Flow rate: 1.0mL/min

Detector: RI-2031Plus manufactured by JASCO Co., Ltd.

Temperature: 40.0°C

Sample volume: sample loop 100μL

Sample concentration: adjusted to about 0.1% by mass

<Synthesis example of hydrogen peroxide of bisphenol-A-diallylether>

148.4 g (0.650 mol) of bisphenol-A (manufactured by Mitsui Chemicals Co., Ltd.) and 1.38 g of 50% water-containing 5%-Pd/C-STD type (manufactured by エヌイームムィット Co., Ltd.) (0.650mmol), triphenylphosphine (manufactured by Hokko Chemical Co., Ltd.) 1.639g (6.50mmol), potassium carbonate (manufactured by Nippon Soda Co., Ltd.) 189g (1.37mol), allyl acetate (manufactured by Showa Denko Co., Ltd. ) 143 g (1.43 mol) and 64.1 g of isopropanol were reacted at 85° C. for 8 hours in a nitrogen atmosphere. After the reaction, a part of the sample was sampled, diluted with ethyl acetate, and analyzed by gas chromatography, and it was confirmed that the ratio of bisphenol-A-diallyl ether to monoallyl ether was 98:2.

Then, 200 g of toluene was added to the reaction liquid, Pd/C and the precipitated solid were removed by filtration, and isopropanol and toluene were distilled off using an evaporator. For this reaction, the post-treatment operation was repeated 4 times, and then, using a molecular distillation device (manufactured by Dake Industry Co., Ltd.), 493 g of distillate (isolation yield 61.7%, diallyl ether 98.1%, and the rest It is monoallyl ether), non-distillate 245g (diallyl ether 96.5%).

Measure bisphenol-A-diallyl ether (50.05g, 162.3mmol), acetonitrile (26.63g, 648.7mmol), ethanol (265.1g, 5754.2mmol) obtained by the above operations in a 1L four-neck eggplant-type flask ) (acetonitrile concentration 9.9 mol%). During the reaction, while adding saturated potassium hydroxide aqueous solution (KOH/H ₂ O = 110mg/100mL) so that the pH was not lower than 9, 45% hydrogen peroxide aqueous solution (53.92g , 713.5 mmol) (the concentration of acetonitrile at this time point was 8.1 mol%, pH=9.2). Saturated potassium hydroxide aqueous solution was added dropwise so that the reaction temperature did not exceed 30°C, and the pH was adjusted to 10.5 over 2 hours (2 hours from the completion of the hydrogen peroxide aqueous solution dropwise addition), and the pH was controlled to 10.5 while further proceeding for 2 hours. Stirring (at this point the acetonitrile concentration was reduced to 6.3 mol%). Acetonitrile (13.31 g, 324.2 mmol) was weighed in a 50 mL dropping funnel, and added dropwise over 2 hours (after the additional addition, the acetonitrile concentration was 6.1 mol%). At the same time, 45% aqueous hydrogen peroxide (53.92 g, 713.5 mmol) was added dropwise over 4 hours using a 100 mL dropping funnel (during these 4 hours, the pH was kept at 10 to 10.5 so that the reaction temperature did not exceed 30° C. ), and further stirred for 4 hours while controlling the pH to 10.5 (the acetonitrile concentration at the end of the reaction was 3.5 mol%). Pure water (100g) was added and diluted to the reaction liquid, and the solvent was distilled off under reduced pressure. After extracting the residue with ethyl acetate (100 g), pure water (100 g) was added again, and liquid separation operation was performed. Ethyl acetate was distilled off with an evaporator to obtain the target epoxidation product. The epoxy equivalent of this epoxidation product was 189 g/eq.

<Synthesis example of carboxyl group-containing polyurethane>

[Synthesis Example 1]

In a 2L three-neck flask equipped with a stirring device, a thermometer, and a condenser, C-1015N (manufactured by Kuraray Co., Ltd., polycarbonate diol, raw material diol molar ratio: 1,9-nonanediol) was charged as a polyol compound Alcohol: 2-methyl-1,8-octanediol=15:85, molecular weight 964) 143.6 g, 2,2-dimethylol butyric acid (manufactured by Nippon Chemicals Co., Ltd.) which is a dihydroxy compound having a carboxyl group 27.32 g and 259 g of propylene glycol monomethyl ether acetate (trade name: methoxypropyl acetate, manufactured by Daicel Corporation) as a solvent were dissolved at 90°C.

The temperature of the reaction liquid was lowered to 70° C., and using a dropping funnel, Desmodul (registered trademark)-W (methylene bis(4-cyclohexyl isocyanate), Sumika Bioleuretan) was added dropwise as a polyisocyanate over 30 minutes. Co., Ltd.) 87.5 g. After completion of the dropwise addition, the temperature was raised to 120°C, and the reaction was performed at 120°C for 6 hours. After confirming that the isocyanate had almost disappeared by IR, 0.5 g of isobutanol was added, and the reaction was further performed at 120°C for 6 hours. The weight average molecular weight of the obtained carboxyl group-containing polyurethane was 32300, the number average molecular weight was 17900, and the acid value of this resin was 40 mgKOH/g. The number of crosslinking reactive groups calculated from the number average molecular weight and the acid value was 12.8 [pieces/1 molecule of resin].

[Synthesis Example 2]

In addition to using 77.2 g of C-1015N (manufactured by Kuraray Co., Ltd.), 50.00 g of 2,2-dimethylolbutyric acid (manufactured by Nippon Chemicals Co., Ltd.), and propylene glycol monomethyl ether acetate as a solvent (Daisel Co., Ltd. 237 g of Desmogul (registered trademark)-W (manufactured by Sumika Bayer Uletan Co., Ltd.) and 109.54 g of Synthesis Example 1 were carried out to obtain a carboxyl group-containing polyurethane. The weight average molecular weight of the obtained carboxyl group-containing polyurethane was 43200, the number average molecular weight was 21700, and the acid value of the resin was 80 mgKOH/g. The number of crosslinking reaction groups calculated from the number average molecular weight and the acid value was 30.9 [pieces/1 molecule of resin].

[Example 1]

23 parts by mass of carboxyl group-containing polyurethane (acid value 40 [KOHmg/resin g]) as a resin (high molecular weight), and bisphenol-A-diallyl ether peroxide hydroxide (ring Oxygen equivalent 189 [g/eq]) 3 parts by mass, 26 parts by mass of triethylene glycol monobutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) as a solvent with low affinity with the blanket, 28.4 parts by mass of propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and 19 parts by mass of diethylene glycol dimethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) of high-affinity solvents, as 0.6 parts by mass of melamine (manufactured by Nissan Chemical Industries, Ltd.) as a curing catalyst was charged into a glass container, and stirred and mixed at room temperature to prepare an ink composition.

[Examples 2-7, Comparative Examples 1-4]

Change the resin (high molecular weight, Examples 2 to 7, Comparative Examples 3 and 4), resin (low molecular weight, Comparative Examples 1 and 2), crosslinking agent, solvent, filler, and curing catalyst as shown in Table 1. Other than that, the same operation as in Example 1 was carried out to prepare an ink composition.

[Table 1]

(*1) Calculated using Fedors' estimation method (R.F.Fedors: Polym.Eng.Sci., 14[2], 147-154(1974)). The resin (high molecular weight) is calculated from the SP value of the repeating unit and the mole fraction (in the case of a copolymer, its molar ratio).

(*2) Weight average molecular weight in terms of polystyrene (measured value by GPC).

(*3) The number average molecular weight is 9400, the iodine value is 78 [g/100g] (measured value by the manufacturer), and the number of crosslinking reaction groups calculated from the number average molecular weight and iodine value is 28.9 [pieces/1 molecule of resin] , the weight-average molecular weight is the catalog value.

(*4) Calculated from the chemical formula C ₁₂₆ H ₁₉₄ O ₃₃ (described in Daicel SDS Co., Ltd.).

(*5) Calculated using 2,2-bis(4-glycidyloxyphenyl)propane as the main component.

(*6) Measured value with an E-type viscometer (VISCONIC EHD, manufactured by Tokimec Co., Ltd., rotational speed: 10 rpm).

(*7) Evaluation was not possible due to poor transfer from the gravure plate to the blanket.

[print test]

(polysiloxane rubber roller)

A commercially available polysiloxane blanket (manufactured by Kinyo Co., Ltd.) for gravure offset printing was bonded to a rubber roller (New Nippon Modeling Co., Ltd. SN-print rubber) using a double-sided tape (ST-416P manufactured by 3M Co., Ltd.) The material obtained on the surface of roll No. 3).

(gravure)

An etching plate having a linear groove pattern with a line width of 100 μm and a recess depth of 20 μm was used.

(print)

Each of the ink compositions listed in Table 1 was placed on the concave portion of the gravure with a spatula, and the ink composition was filled in the concave portion by scraping with a squeegee, and the inks of the other parts were combined. Things removed.

Next, on the concave portion filled with the ink composition, a silicone blanket was rolled to transfer the ink composition to the silicone blanket.

The silicone blanket on which the ink composition was transferred was rolled on a glass substrate, and the ink composition was transferred to the glass substrate again.

[Transfer Evaluation]

Roll the silicone blanket on which the ink composition was transferred on the glass substrate, transfer the ink composition to the glass substrate again, and then visually observe the amount of the ink composition remaining on the silicone blanket .

◎...The ink composition hardly remains (the ink composition remaining area ratio is less than 1%).

○...The ink composition remains slightly (the ink composition remaining area ratio is 1 to less than 5%).

×... Residue of the ink composition is large (area ratio of the ink composition remaining is more than 5%).

In this evaluation, it can be said that the less ink remains, the better the result.

[Evaluation results]

The results are shown in Table 1. The transferability of the ink compositions of Examples 1 to 7 using high molecular weight resins was good, but low molecular weight resins were used as in Comparative Examples 1 and 2 (without using (A) high molecular weight resins and using (F) alone ) Reactive diluent) and when the solvent of (B) or (C) was used alone like Comparative Examples 3 and 4, the transferability was poor.

Claims (10)

1. a kind of insulating properties diaphragm formation composition for being used to form insulating properties diaphragm using hectographic printing, it is included：

(A) there is the high molecular weight resin of cross-linking reaction group, its weight average molecular weight is more than 2 × 10⁴And it is 40 × 10⁴Below；

(B) solubility parameter is more than the solvent that 8.7, boiling point is less than more than 150 DEG C 350 DEG C；With

(C) solubility parameter be less than more than 7.0 8.7, boiling point be 130 DEG C less than 250 DEG C of solvent.

2. the insulating properties diaphragm according to claim 1 for being used to be formed insulating properties diaphragm using hectographic printing forms use Composition, wherein, (A) have cross-linking reaction group it is high molecular weight resin, pass through the cross-linking reaction by unit mass Group number and number-average molecular weight are calculated and obtained, the average cross-linking reaction group number of every 1 molecule is more than 3.

3. the insulating properties diaphragm shape according to claim 1 or 2 for being used to form insulating properties diaphragm using hectographic printing Into with composition, it also includes (D) crosslinking agent.

4. according to the insulating properties according to any one of claims 1 to 3 for being used to form insulating properties diaphragm using hectographic printing Diaphragm formation composition, wherein, it is 11 that (A), which has the solubility parameter of the high molecular weight resin of cross-linking reaction group, Below the above 15, there is the high molecular weight resin of cross-linking reaction group comprising (A) described in 10~80 mass % in the composition.

5. according to the insulating properties according to any one of claims 1 to 4 for being used to form insulating properties diaphragm using hectographic printing Diaphragm formation composition, wherein, it is less than more than 150 DEG C 350 DEG C molten that (B) solubility parameter, which is more than 8.7, boiling point, The solubility parameter of agent is the solubility parameter for the high molecular weight resin that (A) has cross-linking reaction group below+1.

6. according to the insulating properties according to any one of claims 1 to 5 for being used to form insulating properties diaphragm using hectographic printing Diaphragm formation composition, wherein, (C) solubility parameter comprising 10~50 mass % is more than 7.0 in composition Less than 8.7, boiling point is 130 DEG C less than 250 DEG C of solvent.

7. the insulating properties diaphragm according to claim 6 for being used to be formed insulating properties diaphragm using hectographic printing forms use Composition, wherein, (C) solubility parameter comprising 20~50 mass % is less than more than 7.0 8.7, boiling point in composition For 130 DEG C less than 250 DEG C of solvent.

8. the insulating properties diaphragm shape for being used to be formed insulating properties diaphragm using hectographic printing according to claim 6 or 7 Into with composition, wherein, it is 7.0 that (A), which has high molecular weight resin of cross-linking reaction group and (C) solubility parameter, The above is below 8.7, boiling point is more than 2 for the difference of 130 DEG C of solubility parameters less than 250 DEG C of solvent.

9. according to the insulating properties according to any one of claims 1 to 8 for being used to form insulating properties diaphragm using hectographic printing Diaphragm formation composition, wherein, it is less than more than 150 DEG C 350 DEG C molten that (B) solubility parameter, which is more than 8.7, boiling point, Agent is selected from TC acetic acid esters, triethylene glycol monobutyl base ether, gamma-butyrolacton, 1,3- dimethyl -2- imidazolines It is any number of in ketone.

10. according to the insulating properties according to any one of claims 1 to 9 for being used to form insulating properties diaphragm using hectographic printing Diaphragm formation composition, wherein, (C) solubility parameter is less than more than 7.0 8.7, boiling point is more than 130 DEG C and small It is any number of in propylene glycol monomethyl ether, diethylene glycol dimethyl ether in 250 DEG C of solvents.