WO2016195025A1

WO2016195025A1 - Composition for forming insulating protective film by offset printing

Info

Publication number: WO2016195025A1
Application number: PCT/JP2016/066433
Authority: WO
Inventors: 内田　博; 祐司伊藤; 正彦鳥羽
Original assignee: 昭和電工株式会社
Priority date: 2015-06-05
Filing date: 2016-06-02
Publication date: 2016-12-08
Also published as: JP6817199B2; TW201712078A; TWI701299B; CN107614630B; KR20170118877A; JPWO2016195025A1; CN107614630A; KR102056657B1

Abstract

[Problem] To provide an insulating protective film formation composition for forming an insulating protective film using offset printing, wherein, in a system in which a heat-curable resin is used as the insulating protective film, the curable resin is absorbed into a blanket at an insignificant level. [Solution] The composition for forming an insulating protective film by offset printing contains (A) a high-molecular-weight resin having a crosslinking reactive group and having a mass-average molecular weight of greater than 2 × 10⁴ but not greater than 40 × 10⁴, (B) a solvent having a solubility parameter of more than 8.7 and having a boiling point of 150-350°C, and (C) a solvent having a solubility parameter of 7.0-8.7 and a boiling point of 130°C or higher and less than 250°C.

Description

Composition for forming an insulating protective film by offset printing

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

The offset printing method is a printing method in which a plate on which a printing image is formed and a substrate to be printed are not contacted, and the ink paste is transferred to the surface layer of the blanket and re-transferred almost 100% from the blanket to the substrate to be printed. Printing is performed by.

In such an offset printing method, since the blanket is always in contact with the ink paste, the solvent and the binder resin contained in the ink paste are absorbed by the blanket while the printing is repeated, and the blanket deteriorates accordingly. There was a problem. However, if an appropriate amount of the solvent is not absorbed, there is a problem that the detachability of the ink from the blanket is deteriorated during transfer from the blanket to the printing medium, and the quality of the offset printing is deteriorated.

Therefore, the following Patent Document 1 includes a binder resin and a solvent having a solubility constant of 8.5 to 12.0 in order to suppress absorption of the binder resin into the blanket and absorb the solvent appropriately. 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 ball tack value of the coating film obtained by drying the ink composition is Ink compositions that are 10 to 28 are disclosed.

JP 2010-159350 A

However, in the case of ink containing a metal or solid content filler, the amount of binder resin used in the ink is low, and solid content particles may be interposed, and adsorption of the binder resin to the blanket is not a big problem. There are many. On the other hand, when an insulating protective film is formed by offset printing, the thermosetting resin itself that forms the insulating protective film is the main component, and a curable resin (UV) is used to improve the insulating performance of the protective film. Curable or thermosetting resins), and examples of such resins include polyfunctional (meth) acrylates, epoxies, and oxetane compounds having a relatively low molecular weight. When the ink also contains a thermosetting resin, the monomer and oligomer components before curing contained in the thermosetting resin are absorbed by the blanket together with the solvent, and these monomers and oligomers (including reactive diluents) ) Has a very high boiling point (it is difficult to volatilize), curing modification starts when the blanket dries, and the blanket is permanently deteriorated. For this reason, there is a problem that a system having a high content of the thermosetting resin component cannot be applied to offset printing.

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

In order to achieve the above object, one embodiment of the present invention is a composition for forming an insulating protective film by offset printing, comprising (A) a crosslinking reactive group and a weight average molecular weight of 2 × 10 ⁴ A high molecular weight resin having a large value of 40 × 10 ⁴ or less; (B) a solvent having a solubility parameter greater than 8.7 and a boiling point of 150 ° C. or higher and 350 ° C. or lower; and (C) a solubility parameter of 7.0 or higher and 8.7. And a solvent having a boiling point of 130 ° C. or higher and lower than 250 ° C.

The above-mentioned (A) high molecular weight resin having a crosslinking reactive group preferably has an average number of crosslinking reactive groups per molecule of 3 or more obtained by calculation from the number of crosslinking reactive groups per mass and the number average molecular weight.

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

The (A) high molecular weight resin having a crosslinking reactive group has a solubility parameter of 11 or more and 15 or less, and is preferably contained in the composition in an amount of 10 to 80% by mass.

In addition, the solvent having a solubility parameter (B) greater than 8.7 and a boiling point of 150 ° C. or more and 350 ° C. or less is a solvent having a solubility parameter of (A) the solubility parameter of the high molecular weight resin having a crosslinking reactive group + 1 or less. Preferably there is.

Further, it is preferable that the solvent (C) having a solubility parameter of 7.0 or more and 8.7 or less and a boiling point of 130 ° C. or more and less than 250 ° C. is contained in an amount of 10 to 50% by mass in the composition.

Further, it is more preferable that the solvent (C) having a solubility parameter of 7.0 or more and 8.7 or less and a boiling point of 130 ° C. or more and less than 250 ° C. is contained in the composition in an amount of 20 to 50% by mass.

Further, the difference in solubility parameter between the polymer resin having the (A) crosslinking reactive group and the solvent (C) having a solubility parameter of 7.0 or more and 8.7 or less and a boiling point of 130 ° C. or more and less than 250 ° C. is It is preferred that it be greater than 2.

The solvent having a solubility parameter (B) greater than 8.7 and a boiling point of 150 ° C. or higher and 350 ° C. or lower is diethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether, γ-butyrolactone, 1,3-dimethyl- It is preferably one of the group consisting of 2-imidazolidinone.

The solvent having a solubility parameter (C) of 7.0 or more and 8.7 or less and a boiling point of 130 ° C. or more and less than 250 ° C. is one of the group consisting of propylene glycol monomethyl ether acetate and diethylene glycol dimethyl ether. Is preferred.

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

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

The composition for forming an insulating protective film by offset printing according to the embodiment (hereinafter sometimes referred to as an ink composition) has (A) a crosslinking reactive group and has a weight average molecular weight of more than 2 × 10 ⁴ and 40 X10 ⁴ or less high molecular weight resin, (B) a solvent having a solubility parameter greater than 8.7, a boiling point of 150 ° C. or more and 350 ° C. or less, preferably a boiling point of more than 200 ° C. and 300 ° C. or less, and (C) solubility. A parameter is 7.0 or more and 8.7 or less, and the boiling point is 130 degreeC or more and less than 250 degreeC, Preferably it contains the solvent whose boiling point is 130 degreeC or more and less than 200 degreeC.

The (A) high molecular weight resin having a crosslinking 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 . By using a high molecular weight material having a weight average molecular weight within this range as the binder resin, absorption to a transfer body (blanket) for offset printing can be reduced. Absorption to the blanket tends to increase as the weight average molecular weight becomes smaller than this range, and solubility in the solvent tends to decrease when the weight average molecular weight becomes larger than this range. A more preferred weight average molecular weight is more than 3 × 10 ^{4 and not} more than 35 × 10 ⁴ . Moreover, high insulation performance and heat resistance can be realized by using a curable resin that undergoes a crosslinking reaction with a crosslinking reactive group. In the present specification, the “crosslinking reactive group” means a functional group capable of forming a bridging bond between the same molecule and / or other molecules. The crosslinking reactive group can be selected from known functional groups. For example, it means a functional group that forms a cross-linked structure by reacting with a cross-linking agent (D) described later, or a functional group that reacts between cross-linking reactive groups. For example, groups having active hydrogen such as carboxyl group, hydroxyl group, mercapto group, amino group, vinyl group, group having unsaturated bond such as (meth) allyl group, (meth) acryloyl group, glycidyl group, oxetane group, etc. A cyclic ether group, an isocyanate group, etc. are mentioned. In the present specification, “(meth) allyl group” means an allyl group or methallyl group, and “(meth) acryloyl group” means an acryloyl group or methacryloyl group.

The (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. It is preferable that the number of crosslinking reactive groups per molecule calculated from the number average molecular weight is at least 3, more preferably 7 or more.

The number of cross-linking reactive groups per molecule is the average number of functional groups per molecule determined by calculation from the number of cross-linking reactive groups per mass of the high molecular weight resin and the number average molecular weight.

Although the calculation method of the number of cross-linking reactive groups per mass is not particularly specified, a known method can be used. For example, an epoxy equivalent can be used for a glycidyl group, an acid value for a carboxyl group, a hydroxyl value for a hydroxyl group, and an iodine value for an unsaturated bond group such as a vinyl group or a (meth) allyl group. . By using these measured values, the number of crosslinking reactive groups per mass of the high molecular weight resin can be calculated.

The method for measuring the number average molecular weight is not particularly defined, but a known method can be used. For example, a GPC (gel permeation chromatography) method can be used.

The (A) high molecular weight resin having a crosslinking reactive group preferably has a solubility parameter (SP value, unit: (cal / cm ³ ) ^1/2 ) of 11 or more and 15 or less, more preferably 11. 5 to 15 and preferably 10 to 80% by mass, more preferably 15 to 70% by mass in the composition. If it is less than 10% by mass, the amount of the low molecular weight compound increases, and the amount of the substance absorbed into the blanket may increase. If it exceeds 80% by mass, the composition viscosity becomes too high and transfer from the plate to the blanket may be poor. For this reason, the concentration of the high molecular weight resin is preferably within the above range. As a blanket used for offset printing, a silicone blanket having at least a surface formed of silicone rubber is widely used, and its SP value is 7.3 to 7.6. For this reason, absorption to the blanket of high molecular weight resin can be suppressed more by making SP value of the said high molecular weight resin 11 or more and widening the difference with SP value of blanket. On the other hand, if the difference in SP value between the high molecular weight resin and the blanket becomes too large, the high molecular weight resin in the ink composition is difficult to absorb into the blanket, but the degree of freedom of the solvent that can dissolve the high molecular weight resin is low. In many cases, it is difficult to transfer to the blanket itself, and the quality of offset printing may be deteriorated. Therefore, the SP value of the high molecular weight resin is preferably in the above range. The SP value can be calculated with reference to RFFedors: Polym.Eng.Sci., 14 [2], 147-154 (1974).

The (A) high molecular weight resin having a crosslinking reactive group can be used as long as it contains a crosslinking reactive group and can be dissolved or dispersed in the composition. For example, a high molecular weight resin having active hydrogen such as a carboxyl group-containing polyurethane (SP value 11.5 to 12) or a prepolymer of diallyl phthalate (for example, Daiso Dup (SP value 11.7, diallyl phthalate 1 manufactured by Daiso Corporation) The calculation was based on the polymerization of only two allyl groups, the same applies to other diallyl phthalate prepolymers)), diallyl isophthalate prepolymers (for example, Daiso Isodap (SP value 11.7) manufactured by Daiso Corporation), diallyl A terephthalate prepolymer (SP value 11.7), a prepolymer of triallyl isocyanurate (for example, Tyke prepolymer manufactured by Nippon Kasei Co., Ltd. (SP value 14.9. As a result of polymerization of one allyl group of triallyl isocyanurate) Calculated high) with unsaturated bonds such as)) Molecular weight resins.

(B) A solvent having a solubility parameter (SP value) larger than 8.7 and a boiling point of 150 ° C. or higher and 350 ° C. or lower is a solvent having a low affinity with a transfer body (blanket) for offset printing, that is, a transfer body (blanket). ) Is a solvent that is difficult to absorb. A solvent or reactive diluent having an SP value of greater than 8.7 and an SP value of +1 or less of the above-mentioned (A) high molecular weight resin having a crosslinking reactive group is preferred. When the SP value is 8.7 or less, the difference from the SP value of the blanket becomes small and is easily absorbed by the blanket, so that the solvent concentration in the ink composition transferred from the plate onto the blanket becomes low, and It is difficult to re-transfer to the printed body (work). On the other hand, when the SP value is larger than the SP value + 1 of the polymer resin having (A) a crosslinking reactive group, the affinity between the solvent and the high molecular weight resin is lowered, and the high molecular weight resin is dissolved in the solvent. Since it becomes difficult and a uniform ink composition cannot be formed, retransfer to a workpiece may be hindered.

In addition, when the boiling point of the solvent having low affinity with the transfer body (blanket) for offset printing is low, the solvent is dried before further transfer from the transfer body to the substrate, which makes it difficult to retransfer. It becomes easy to get up. However, if the boiling point is too high, a high temperature and a long time are required to finally distill off the solvent. Therefore, the boiling point is 150 ° C. or higher and 350 ° C. or lower, preferably 200 ° C. or higher and 300 ° C. or lower.

The content in the ink composition of the solvent (B) having a solubility parameter (SP value) greater than 8.7 and a low boiling point with a boiling point of 150 ° C. or higher and 350 ° C. or lower is other than (B). The balance of the total amount of ingredients.

Examples of the solvent (B) having a solubility parameter (SP value) larger than 8.7 and a low affinity with a blanket having a boiling point of 150 ° C. or higher and 350 ° C. or lower include 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-imidazolidinone (SP value 11.5), and the like.

The solvent having a solubility parameter (SP value) of 7.0 or more and 8.7 or less and a boiling point of 130 ° C. or more and less than 250 ° C. is a solvent having a high affinity for a transfer body (blanket) for offset printing. That is, it is a solvent that is easily absorbed by the transfer body (blanket). If the SP value is less than 7.0 or exceeds 8.7, the difference from the SP value of the blanket increases, and the absorbability to the blanket decreases. For this reason, the ink composition is difficult to peel off from the blanket, and retransfer to the workpiece is difficult.

When the boiling point of the solvent having a high affinity with the transfer material (blanket) for offset printing is high, it takes a long time to heat the blanket after it is adsorbed to the blanket. However, if the boiling point is too low, drying tends to occur before transfer to the transfer body, and there is a problem that the initial transfer is not successful. Therefore, the boiling point is 130 ° C. or higher and lower than 250 ° C., and 130 ° C. or higher and lower than 200 ° C. It is preferable.

The solvent (C) having a solubility parameter (SP value) of 7.0 or more and 8.7 or less and having a high affinity with a blanket having a boiling point of 130 ° C. or more and less than 250 ° C. is 10 in the ink composition. It is preferably contained in an amount of ˜50 mass%, more preferably 20-50 mass%. (C) The content of the solvent in the ink composition having a solubility parameter (SP value) of 7.0 or more and 8.7 or less and a high boiling point of 130 ° C. or more and less than 250 ° C. in the ink composition is 10% by mass. If it is above, the transfer of the ink composition from a plate to a blanket can be performed satisfactorily. On the other hand, when the amount is 50% by mass or less, there is no problem that the solvent concentration in the ink composition becomes too high to be completely absorbed by the blanket, and retransfer from the blanket to the work can be performed satisfactorily.

Examples of the solvent (C) having a solubility parameter (SP value) of 7.0 or more and 8.7 or less and a boiling point of 130 ° C. or more and less than 250 ° C. include propylene glycol monomethyl ether acetate (SP value 8.7), diethylene glycol, and the like. Dimethyl ether (SP value 8.1) etc. are mentioned.

Also, the affinity between the (A) high molecular weight resin having a crosslinking reactive group and the blanket having the (C) solubility parameter (SP value) of 7.0 or more and 8.7 or less and a boiling point of 130 ° C. or more and less than 250 ° C. It is preferable that the difference in SP value with a solvent having high properties is 2 or more. More preferably, it is more than 2, more preferably 2.3 or more. If this difference is less than 2, the solubility of the solvent in the high molecular weight resin increases, so that the solvent having high affinity to the blanket cannot be selectively adsorbed to the blanket, and the retransferability to the workpiece is reduced. There are things to do.

In addition, it is preferable that the ink composition according to the embodiment further includes (A) a crosslinking agent for accelerating the crosslinking reaction of the high molecular weight resin having a crosslinking reaction group (A). (D) When a crosslinking agent is included, the solubility parameter (SP value) is preferably 9 or more and 15 or less, more preferably 10 or more. It is preferable that 10% by mass or less is contained in the composition. If the SP value is less than 9, it will be easily absorbed by the blanket, and the transferability may be deteriorated. (D) The crosslinking agent may include a compound having a plurality of groups reactive with the crosslinking reactive group of (A), and a compound having only one group reactive with the crosslinking reactive group of (A). Good. For example, in the case of a carboxyl group-containing polyurethane, since the crosslinking reaction group is a carboxyl group having active hydrogen, a compound having a plurality of groups that react with the carboxyl group (for example, a hydroxyl group or a glycidyl group) is used as the (D) crosslinking agent. I can do it. The cross-linking reaction is preferably an addition reaction without elimination of a low molecular compound, and in this case, an epoxy compound having a glycidyl group is more preferable (for example, bisphenol-A-diglycidyl ether (SP value 10.4), bisphenol-F -Diglycidyl ether, glycidyl ether of novolak phenol resin, hydrogen peroxide oxide of bisphenol-A-diallyl ether (SP value 10.4), EHPE 3150 (SP value 11.0) manufactured by Daicel Corporation). In the case of an allylic polymer such as a diallyl isophthalate prepolymer, the crosslinking reaction group is an allyl group, so that a crosslinking reaction can be carried out without using a crosslinking agent by curing by radical polymerization. In order to improve durability, a polyfunctional acrylate (for example, dipentaerythritol hexaacrylate (SP value 10.4), addition of acrylic acid to an epoxy resin) may be used. And allyl compounds such as triallyl isocyanurate (Nippon Kasei Co., Ltd.) (SP value 13.6), and maleimide compounds such as 4,4′-diphenylmethane bismaleimide (SP value 14.3). .

In addition to the above components (A) to (D), if necessary, other components such as (E) a curing catalyst, (F) a reactive diluent and (G) an additive are contained in the insulating protective film forming composition. can do.

(E) Curing catalyst (A) In order to smoothly perform the crosslinking reaction of the high molecular weight resin having a crosslinking reactive group, (E) a curing catalyst may be added. (E) As the curing catalyst, a known compound suitable for the curing reaction can be used. For example, melamine and imidazoles can be used in the case of a curing reaction between a carboxyl group and a glycidyl group. In the case of radical polymerization of an allylic polymer, a peroxide or the like can be used. In addition, a photopolymerization initiator can be used in the case of ultraviolet curing of an acryloyl group or a methacryloyl group. The addition amount may be a known addition amount. For example, the addition amount may be 1 to 5% by mass with respect to the total amount of the resin ((A) high molecular weight resin having a crosslinking reactive group) and (D) a crosslinking agent. Can be added.

(F) Reactive Diluent (F) Reactive Diluent is a low-molecular compound that has very low volatility and contains a crosslinking reactive group, and is a compound that can uniformly dissolve or disperse other components. (A) The viscosity of the composition can be adjusted by uniformly dissolving or dispersing the high molecular weight resin having a crosslinking reactive group together with a solvent. Moreover, since it has reactivity, it becomes a solid after curing.

Also, since it is difficult to volatilize, it is selected from compounds that have low affinity for the blanket and are difficult to absorb. When the SP value is used as an affinity index, 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 the (A) crosslinking reactive group. Preferably it is 9 or more, More preferably, it is 10 or more.

(F) The boiling point of the reactive diluent is preferably above 300 ° C., and the upper limit of the boiling point of the reactive diluent is not particularly limited. It is preferable that the reactive diluent is not substantially distilled off. If the boiling point is 300 ° C. or lower, depending on the curing conditions, there is a possibility that a part of the (F) reactive diluent may be evaporated. For example, 1.6 hexanediol glycidyl ether (SP value 9.5), ethoxylated isocyanuric acid triacrylate (A-93000 Shin-Nakamura Chemical Co., Ltd., SP value 13.3), 1.6 hexanediol glycidyl ether (SP value) 9.5). The addition amount 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 (A) having a crosslinking reactive group.

(G) Additives (G) Additives such as surfactants, antioxidants, and fillers may be included as long as the performance of the composition for forming an insulating protective film is not adversely affected. In order to adjust the viscosity of the composition, a filler such as fumed silica can be used. Moreover, although a colored filler may be added in order to color, in order to ensure insulation, it is preferable not to contain a conductive filler.

The addition amount may be an amount that can express the target function, and is preferably 5% by mass or less of the entire composition, for example.

Hereinafter, embodiments of the present invention will be specifically described. In addition, the following examples are for facilitating understanding of the present invention, and the present invention is not limited to these examples.

<Epoxy equivalent>
The epoxy equivalent was determined according to JIS-K7236. Weigh 0.1 to 0.2 g of the sample, put it in an Erlenmeyer flask, and add 10 mL of chloroform to dissolve. Next, 20 mL of acetic acid is added, followed by 10 mL of tetraethylammonium bromide solution (100 g of tetraethylammonium bromide dissolved in 400 mL of acetic acid). 4 to 6 drops of crystal violet indicator was added to this solution, and titrated with a 0.1 mol / L perchloric acid acetic acid solution. Based on the titration result, the epoxy equivalent was determined according to the following formula.
Epoxy equivalent (g / eq) = (1000 × m) / {(V1−V0) × c}
m: Mass of the sample (g)
V0: Amount of perchloric acid acetic acid solution consumed for titration to the end point in the blank test (mL)
V1: Amount of perchloric acid acetic acid solution consumed for titration to the end point (mL)
c: Concentration of perchloric acid acetic acid solution (0.1 mol / L)

<Weight average molecular weight, number average molecular weight>
Using gel permeation chromatography (hereinafter abbreviated as GPC), the value was calculated as a value converted to polystyrene (using standard sample STANDARD SM-105 manufactured by Showa Denko KK). The measurement conditions for GPC are as follows.
Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation
Column: Shodex column LF-804
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: manufactured by JASCO Corporation RI-2031Plus
Temperature: 40.0 ° C
Sample amount: 100 μl of sample loop Sample concentration: prepared around 0.1% by mass

<Example of synthesis of hydrogen peroxide oxide of bisphenol-A-diallyl ether>
In a 2000 ml eggplant type flask, 148.4 g (0.650 mol) of bisphenol-A (manufactured by Mitsui Chemicals), 5% water content 5% -Pd / C-STD type (manufactured by N.E. Chemcat Co., Ltd.) 1.38 g (0.650 mmol), triphenylphosphine (Hokuko Chemical Co., Ltd.) 1.639 g (6.50 mmol), potassium carbonate (Nihon Soda Co., Ltd.) 189 g (1.37 mol), allyl acetate (Showa Denko Co., Ltd.) 143 g (1.43 mol) 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 part 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 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. This reaction and post-treatment operation were repeated four times, and then 493 g of a distillate (isolation yield 61.7%, diallyl ether 98.1%, the rest was mono) by using a molecular distillation apparatus (manufactured by Otsuka Kogyo Co., Ltd.). Allyl ether), 245 g of non-distilled product (96.5% diallyl ether).

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

<Synthesis example of carboxyl group-containing polyurethane>
[Synthesis Example 1]
C-1015N as a polyol compound (manufactured by Kuraray Co., Ltd., polycarbonate diol, raw material diol molar ratio: 1,9-nonanediol: 2-methyl-1,8-octane) was added to a 2 L three-necked flask equipped with a stirrer, a thermometer, and a condenser. Diol = 15: 85, molecular weight 964) 143.6 g, 2,2-dimethylolbutanoic acid (made by Nippon Kasei Co., Ltd.) 27.32 g as a dihydroxyl compound having a carboxyl group, and propylene glycol monomethyl ether acetate (product) (Name: methoxypropyl acetate, manufactured by Daicel Corporation) 259 g was charged, and the 2,2-dimethylolbutanoic acid was dissolved at 90 ° C.

The temperature of the reaction solution was lowered to 70 ° C., and 87.5 g of Desmodur (registered trademark) -W (methylenebis (4-cyclohexylisocyanate), manufactured by Sumika Bayer Urethane Co., Ltd.) was added as polyisocyanate over 30 minutes with a dropping funnel. It was dripped. After completion of the dropwise addition, the temperature was raised to 120 ° C., and the reaction was carried out at 120 ° C. for 6 hours. After confirming that the isocyanate almost disappeared by IR, 0.5 g of isobutanol was added, and the reaction was further carried out at 120 ° C. for 6 hours. went. The obtained carboxyl group-containing polyurethane had a weight average molecular weight of 32,300, a number average molecular weight of 17,900, and an acid value of the resin of 40 mgKOH / g. The number of cross-linking groups calculated from the number average molecular weight and acid value was 12.8 [pieces / one resin].

[Synthesis Example 2]
C-1015N (manufactured by Kuraray Co., Ltd.) 77.2 g, 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) 50.00 g, and 237 g of propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation) as a solvent, Desmodur A carboxyl group-containing polyurethane was obtained in the same manner as in Synthesis Example 1 except that 109.54 g of (Registered Trademark) -W (manufactured by Sumika Bayer Urethane Co., Ltd.) was used. The weight average molecular weight of the obtained carboxyl group-containing polyurethane was 43200, the number average molecular weight was 21,700, and the acid value of the resin was 80 mgKOH / g. The number of crosslinking reactive groups calculated from the number average molecular weight and the acid value was 30.9 [pieces / one resin].

[Example 1]
23 parts by mass of carboxyl group-containing polyurethane (acid value 40 [KOHmg / resin g]) as resin (high molecular weight), hydrogen peroxide oxide of bisphenol-A-diallyl ether (epoxy equivalent 189 [g / eq]) as crosslinking agent 3 parts by mass, 26 parts by mass of triethylene glycol monobutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) as a solvent having a low affinity with a blanket, and 28.4 parts by mass of propylene glycol monomethyl ether acetate as a solvent having a high affinity with a blanket Parts (manufactured by Wako Pure Chemical Industries, Ltd.) and 19 parts by mass of diethylene glycol dimethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.6 parts by mass of melamine (manufactured by Nissan Chemical Industries, Ltd.) as a curing catalyst were charged in a glass container at room temperature. The ink composition was prepared by stirring and mixing.

[Examples 2 to 7, Comparative Examples 1 to 4]
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 were changed as shown in Table 1 The same operation as in No. 1 was performed to prepare an ink composition.

(* 1) Calculated using the Fedors estimation method (RFFedors: Polym.Eng.Sci., 14 [2], 147-154 (1974)). The resin (high molecular weight) was calculated from the SP value of the repeating unit and the molar fraction (in the case of a copolymer, the molar ratio).
(* 2) Weight average molecular weight Polystyrene equivalent (measured by GPC).
(* 3) Number average molecular weight 9400, iodine value 78 [g / 100g] (manufacturer measured value), number of cross-linking reactive groups calculated from number average molecular weight and iodine value is 28.9 [piece / resin 1 molecule], weight average molecular weight Is the catalog value.
(* 4) Calculated from the chemical formula C ₁₂₆ H ₁₉₄ O ₃₃ (described in Daicel SDS).
(* 5) Calculated with 2,2-bis (4-glycidyloxyphenyl) propane as the main component.
(* 6) Measured with an E-type viscometer (VISCONIC EHD rotation speed 10rpm manufactured by Tokimec Co., Ltd.).
(* 7) Could not be evaluated due to transfer failure from intaglio to blanket.

[Printing test]
(Silicone blanket cylinder)
A commercially available silicone blanket (manufactured by Kinyo Co., Ltd.) used for intaglio offset printing is affixed to the surface of a rubber roller (manufactured by Nippon Nippon Zokei Co., Ltd., SN-print rubber roller No. 3) using a double-sided tape (ST-416P manufactured by 3M). Use the same thing.

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

(printing)
Each ink composition shown in Table 1 is placed on the concave portion of the intaglio with a spatula, and the ink composition is filled into the concave portion by scraping with a squeegee, and the ink composition in other portions is removed.

Next, the silicone blanket cylinder is rolled on the recess filled with the ink composition to transfer the ink composition to the silicone blanket cylinder.

The silicone blanket cylinder onto which the ink composition has been transferred is rolled on a glass substrate, and the ink composition is retransferred to the glass substrate.

[Transferability evaluation]
The silicone blanket cylinder onto which the ink composition has been transferred is rolled on a glass substrate, and after the ink composition is retransferred to the glass substrate, the amount of the ink composition remaining on the silicone blanket is visually observed.
A: Almost no ink composition remains (ink composition remaining area ratio is less than 1%).
○: A slight amount of the ink composition remains (ink composition remaining area ratio of 1 to less than 5%).
X: Remaining ink composition is large (ink composition remaining area ratio is over 5%).
In this evaluation, the smaller the remaining ink, the better the result.

[Evaluation results]
The results are shown in Table 1. Although the transferability of the ink compositions of Examples 1 to 7 using a high molecular weight resin was good, a low molecular weight resin was used as in Comparative Examples 1 and 2 ((A) without using a high molecular weight resin (F) When the reactive diluent was used alone, or when the solvent (B) or (C) was used alone as in Comparative Examples 3 and 4, the transferability was poor.

Claims

(A) a high molecular weight resin having a crosslinking reactive group and a weight average molecular weight of greater than 2 × 10 4 and less than or equal to 40 × 10 4 ; and (B) a solubility parameter greater than 8.7 and a boiling point of 150 ° C. or higher and 350 ° C. A composition for forming an insulating protective film by offset printing, comprising a solvent having a temperature of not more than ° C and (C) a solvent having a solubility parameter of 7.0 to 8.7 and a boiling point of 130 ° C to less than 250 ° C.
The high molecular weight resin having the cross-linking reactive group (A) has an average number of cross-linking reactive groups per molecule of 3 or more determined by calculation from the number of cross-linking reactive groups per mass and the number average molecular weight. A composition for forming an insulating protective film by offset printing.
(D) The composition for insulating protective film formation by offset printing of Claim 1 or 2 which further contains a crosslinking agent.
The offset according to any one of claims 1 to 3, wherein the high molecular weight resin (A) having a crosslinking reactive group has a solubility parameter of 11 or more and 15 or less and is contained in the composition at 10 to 80% by mass. A composition for forming an insulating protective film by printing.
The solvent (B) having a solubility parameter greater than 8.7 and a boiling point of 150 ° C. or higher and 350 ° C. or lower has a solubility parameter equal to or lower than the solubility parameter +1 of the high molecular weight resin having the (A) crosslinking reactive group. The composition for insulating protective film formation by offset printing as described in any one of 1-4.
6. The solvent according to claim 1, wherein the solvent (C) has a solubility parameter of 7.0 or more and 8.7 or less and a boiling point of 130 ° C. or more and less than 250 ° C. is contained in the composition at 10 to 50% by mass. The composition for forming an insulating protective film by offset printing according to one item.
The offset printing according to claim 6, wherein (C) the solubility parameter is 7.0 or more and 8.7 or less and the solvent has a boiling point of 130 ° C or more and less than 250 ° C in the composition of 20 to 50% by mass. Composition for forming an insulating protective film.
The difference in solubility parameter between the (A) high molecular weight resin having a crosslinking reactive group and the solvent (C) having a solubility parameter of 7.0 or more and 8.7 or less and a boiling point of 130 ° C. or more and less than 250 ° C. is 2 The composition for forming an insulating protective film by offset printing according to claim 6 or 7, which is large.
The solvent having a solubility parameter (B) greater than 8.7 and a boiling point of 150 ° C. or higher and 350 ° C. or lower is diethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether, γ-butyrolactone, 1,3-dimethyl-2- The composition for forming an insulating protective film by offset printing according to any one of claims 1 to 8, which is one of the group consisting of imidazolidinone.
2. The solvent (C) having a solubility parameter of 7.0 or more and 8.7 or less and a boiling point of 130 ° C. or more and less than 250 ° C. is one of the group consisting of propylene glycol monomethyl ether acetate and diethylene glycol dimethyl ether. The composition for insulating protective film formation by offset printing as described in any one of Claims 9.