CN107614630B

CN107614630B - Composition for forming insulating protective film by offset printing

Info

Publication number: CN107614630B
Application number: CN201680026475.5A
Authority: CN
Inventors: 内田博; 伊藤祐司; 鸟羽正彦
Original assignee: Showa Denko KK
Current assignee: Resonac Holdings Corp; Resonac Corp
Priority date: 2015-06-05
Filing date: 2016-06-02
Publication date: 2021-03-30
Anticipated expiration: 2036-06-02
Also published as: WO2016195025A1; KR102056657B1; TW201712078A; CN107614630A; KR20170118877A; JP6817199B2; JPWO2016195025A1; TWI701299B

Abstract

本发明的课题在于提供在使用可用作绝缘性保护膜的热固性树脂的体系下，固化性树脂向橡皮布中的吸收不成为问题的水平的、用于利用胶版印刷形成绝缘性保护膜的绝缘性保护膜形成用组合物。本发明的用于利用胶版印刷形成绝缘性保护膜的绝缘性保护膜形成用组合物包含(A)具有交联反应基团的高分子量树脂，其重均分子量大于2×10⁴且为40×10⁴以下；(B)溶解度参数大于8.7、沸点为150℃以上350℃以下的溶剂；和(C)溶解度参数为7.0以上8.7以下、沸点为130℃以上且小于250℃的溶剂。An object of the present invention is to provide an insulating film for forming an insulating protective film by offset printing at a level where the absorption of the curable resin into the blanket does not become a problem in a system using a thermosetting resin that can be used as an insulating protective film A composition for forming a protective film. The composition for forming an insulating protective film of the present invention for forming an insulating protective film by offset printing comprises (A) a high molecular weight resin having a crosslinking reactive group, the weight average molecular weight of which is more than 2×10 ⁴ and 40× 10 ⁴ or less; (B) a solvent with a solubility parameter of more than 8.7 and a boiling point of 150°C or more and 350°C or less; and (C) a solvent with 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.

Description

Composition for forming insulating protective film by offset printing

Technical Field

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

Background

The offset printing method is a printing method in which a plate on which a print image is formed is not brought into contact with a printing object, and performs printing by transferring an ink paste (ink paste) to a surface layer of a blanket and then transferring the ink paste from the blanket to the printing object at substantially 100%.

Such an offset printing method has the following problems: 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 during repeated printing, resulting in deterioration of the blanket. However, if the solvent is not absorbed in an appropriate amount, there is a problem as follows: when transferring from the blanket to the object to be printed, the ink releasability from the blanket is deteriorated, and the quality of offset printing is deteriorated.

Accordingly, patent document 1 discloses an ink composition containing a binder resin having solubility constants of 8.5 to 12.0 and a solvent, wherein the absolute value of the difference between the solubility constants is 2.0 or less, the boiling point of the solvent is 50 to 200 ℃, the viscosity of the ink composition is 5 to 50Pa · s, and the initial viscosity value (ボールタック value) of a coating film obtained by drying the ink composition is 10 to 28, in order to suppress the absorption of the binder resin into the blanket and to absorb the solvent appropriately.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2010-159350

Disclosure of Invention

Problems to be solved by the invention

However, in the case of an ink containing a metal or a solid filler, the amount of binder resin used in the ink is low, and sometimes solid particles are interposed therebetween, and adsorption of the binder resin into the blanket is often not a great problem. On the other hand, in the case of forming an insulating protective film by offset printing, a thermosetting resin itself forming the insulating protective film is a main component, and in order to improve the insulating performance of the protective film, it is necessary to use a curable resin (UV-curable or thermosetting resin), and examples of such a resin include a polyfunctional (meth) acrylate, an epoxy resin, and an oxetane compound having a relatively low molecular weight. When the ink further contains a thermosetting resin, monomers and oligomer components before curing contained in the thermosetting resin are absorbed into the blanket together with the solvent, and since these monomers and oligomers (including the reactive diluent) have a very high boiling point (are difficult to volatilize), the curing modification starts to occur when the blanket is dried, and the blanket is permanently deteriorated. Therefore, there is a problem that a system having a high content of the thermosetting resin component cannot be applied to offset printing.

The purpose of the present invention is to provide a composition for forming an insulating protective film, which is used for forming an insulating protective film by offset printing, wherein the composition is at a level such that the absorption of a curable resin into a blanket does not become a problem in a system using a thermosetting resin which can be used as an insulating protective film.

Means for solving the problems

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, comprising (a) a high molecular weight resin having a crosslinking reactive group, wherein the high molecular weight resin has a weight average molecular weight of more than 2 × 10⁴And is 40X 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 ℃.

Preferably, the average number of crosslinking reactive groups per 1 molecule of the high molecular weight resin (a) having crosslinking reactive groups, which is determined by calculation from the number of crosslinking reactive groups per unit mass and the number average molecular weight, is 3 or more.

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

Preferably, the solubility parameter of the high molecular weight resin having a crosslinking reactive group (a) is not less than 11 and not more than 15, and the composition contains 10 to 80 mass% of the high molecular weight resin having a crosslinking reactive group (a).

Preferably, the solubility parameter of the solvent (B) having a solubility parameter of more than 8.7 and a boiling point of 150 to 350 ℃ is +1 or less of the solubility parameter of the high molecular weight resin (a) having a crosslinking reactive group.

Preferably, the composition contains 10 to 50 mass% of the solvent (C) having a solubility parameter of 7.0 to 8.7 inclusive and a boiling point of 130 ℃ to less than 250 ℃.

More preferably, the composition contains 20 to 50 mass% of the solvent (C) having a solubility parameter of 7.0 to 8.7 inclusive and a boiling point of 130 ℃ to less than 250 ℃.

Preferably, the difference in solubility parameter between the polymer resin (A) having a crosslinking reactive group and the solvent (C) having a solubility parameter of 7.0 to 8.7 inclusive and a boiling point of 130 ℃ to less than 250 ℃ is greater than 2.

Preferably, the solvent (B) having a solubility parameter of more than 8.7 and a boiling point of 150 to 350 ℃ is any one selected from the group consisting of diethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether, γ -butyrolactone, and 1, 3-dimethyl-2-imidazolidinone.

Preferably, the solvent (C) having a solubility parameter of 7.0 to 8.7 inclusive and a boiling point of 130 to less than 250 ℃ is any one selected from the group consisting of propylene glycol monomethyl ether acetate and diethylene glycol dimethyl ether.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention provides a composition for forming an insulating protective film, which is used for forming an insulating protective film by offset printing, wherein a curable resin is not easily absorbed by a blanket.

Detailed Description

Hereinafter, specific embodiments (hereinafter, referred to as embodiments) of the present invention 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) a high molecular weight resin having a weight average molecular weight of more than 2X 10 and having a crosslinking reactive group⁴And is 40X 10⁴The following; (B) a solvent having a solubility parameter of more than 8.7 and a boiling point of 150 ℃ to 350 ℃ inclusive, preferably a boiling point of more than 200 ℃ to 300 ℃ inclusive; and (C) a solvent having a solubility parameter of 7.0 to 8.7 inclusive, a boiling point of 130 to less than 250 ℃, preferably a boiling point of 130 to less than 200 ℃.

The high molecular weight resin (A) having a crosslinking reactive group has a weight average molecular weight of more than 2X 10⁴And is 40X 10⁴The following high molecular weight resins. By makingThe binder resin is a high molecular weight material having a weight average molecular weight in the above range, so that absorption into a transfer body (blanket) for offset printing can be reduced. As the weight average molecular weight is smaller than the above range, the absorption into the blanket tends to increase, and when the weight average molecular weight is larger than the above range, the solubility in the solvent tends to decrease. More preferably, the weight average molecular weight is greater than 3X 10⁴And is 35X 10⁴The following. Further, by using a curable resin which undergoes a crosslinking reaction by a crosslinking reactive group, high insulating performance and heat resistance can be achieved. In the present specification, the term "crosslinking reactive group" refers to a functional group capable of forming a crosslinked bond between the same molecule and/or different molecules. The crosslinking reactive group may be selected from known functional groups. For example, the functional group is a functional group which reacts with a crosslinking agent (D) described later to form a crosslinked structure, and the functional group reacts with a crosslinking reactive group. Examples thereof include groups having active hydrogen such as a carboxyl group, a hydroxyl group, a mercapto group and an amino group, groups having unsaturated bonds such as a vinyl group, a (meth) allyl group and a (meth) acryloyl group, cyclic ether groups such as a glycidyl group and an oxetanyl group, and isocyanate groups. In the present specification, "(meth) allyl" means allyl or methallyl, and "(meth) acryloyl" means acryloyl or methacryloyl.

The high molecular weight resin (a) 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 property and heat resistance of the insulating protective film to be formed can be further improved. The number of crosslinking reactive groups per 1 molecule as calculated from the number average molecular weight is preferably at least 3, and more preferably 7 or more functional groups.

The number of crosslinking reactive groups per 1 molecule is an average number of functional groups per 1 molecule, which is determined by calculation from the number of crosslinking reactive groups per unit mass and the number average molecular weight of the high molecular weight resin.

The method for calculating the number of crosslinking reactive groups per unit mass is not particularly limited, and a known method can be used. For example, an epoxy equivalent can be used in the case of a glycidyl group, an acid value can be used in the case of a carboxyl group, a hydroxyl value can be used in the case of a hydroxyl group, and an iodine value and the like can be used in the case of an unsaturated bond group such as a vinyl group, a (meth) allyl group and the like. By using these measured values, the number of crosslinking reactive groups per unit mass of the high molecular weight resin can be calculated.

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

The solubility parameter (SP value, unit: (cal/cm) of the high molecular weight resin having a crosslinking reactive group (A) is³)^1/2) Preferably 11 to 15, more preferably 11.5 to 15, and preferably 10 to 80 mass% of the high molecular weight resin (A) having a crosslinking reactive group is contained in the composition, and more preferably 15 to 70 mass% of the high molecular weight resin (A) having a crosslinking reactive group is contained in the composition. Below 10 mass%, the amount of the low molecular weight compound increases, and the amount of the substance absorbed to the blanket may increase. When the amount is more than 80% by mass, the viscosity of the composition becomes too high, and transfer from the plate to the blanket may become poor. Therefore, the concentration of the high molecular weight resin is preferably in the above range. As the blanket used in offset printing, a silicone blanket having at least a surface formed of a silicone rubber is widely used, and the SP value thereof is 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 between the SP values of 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 degree of freedom of the solvent capable of dissolving the high molecular weight resin often decreases, and in a serious case, the transfer to the blanket itself becomes difficult, and the quality of offset printing may deteriorate. Therefore, the SP value of the high molecular weight resin is preferably in the above range. The SP value can be referred to R.F.Fedors: Polym.Eng.Sci.,14[2]]147-.

The high molecular weight resin (a) having a crosslinking reactive group may be used as long as it contains a crosslinking reactive group and can be dissolved or dispersed in the composition. Examples thereof include a high molecular weight resin having active hydrogen such as a carboxyl group-containing polyurethane (SP value 11.5 to 12), a diallyl phthalate prepolymer (for example, ダイソーダップ manufactured by ダイソー Kabushiki Kaisha (SP value 11.7. calculated on the basis of the product obtained by polymerizing only 1 allyl group in diallyl phthalate; the same applies to other diallyl phthalate prepolymers), and a diallyl isophthalate prepolymer (for example, ダイソーイソダップ manufactured by ダイソー Kabushiki Kaisha (SP value 11.7)), a high molecular weight resin having an unsaturated bond such as a diallyl terephthalate prepolymer (SP value 11.7) and a triallyl isocyanurate prepolymer (for example, タイクプレポリマー (SP value 14.9, calculated from a product obtained by polymerizing 1 allyl group in triallyl isocyanurate).

(B) The solvent having a solubility parameter (SP value) of more than 8.7 and a boiling point of 150 ℃ to 350 ℃ is a solvent having low affinity with a transfer body (blanket) for offset printing, that is, a solvent which is hardly absorbed by the transfer body (blanket). The solvent or reactive diluent preferably has an SP value of more than 8.7 and is not more than +1, the SP value of the high molecular weight resin (A) having a crosslinking reactive group. When the SP value is 8.7 or less, the difference between the SP value and the SP value of the blanket becomes small, and the difference is easily absorbed by the blanket, and therefore, the solvent concentration in the ink composition transferred from the plate to the blanket decreases, and it becomes difficult to perform retransfer to a printing object (work). On the other hand, if the SP value is greater than the SP value of the polymer resin having a crosslinking reactive group (a) +1, the affinity between the solvent and the polymer resin is reduced, the polymer resin becomes less soluble in the solvent, and a uniform ink composition cannot be formed, which may hinder retransfer to a product.

In addition, when the boiling point of a solvent having low affinity with a transfer body (blanket) for offset printing is low, the following problems are likely to occur: before the transfer from the transfer body to the substrate, the solvent is dried, and it becomes difficult to perform the retransfer. However, if the boiling point is too high, it takes a long time and a high temperature to remove the solvent by distillation, and therefore, the boiling point is 150 ℃ to 350 ℃ inclusive, preferably 200 ℃ to 300 ℃ inclusive.

The content of the solvent having a solubility parameter (SP value) of more than 8.7 and a boiling point of 150 ℃ to 350 ℃ and having low affinity with the blanket in the ink composition is the balance of the total amount of the components other than (B).

Examples of the solvent (B) having a solubility parameter (SP value) of more than 8.7 and a boiling point of 150 to 350 ℃ and having low affinity with the blanket include diethylene glycol monoethylether acetate (SP value of 9.0), triethylene glycol monobutyl ether (SP value of 10.3), γ -butyrolactone (SP value of 9.9), and 1, 3-dimethyl-2-imidazolidinone (SP value of 11.5).

The solvent having a solubility parameter (SP value) of 7.0 to 8.7 inclusive and a boiling point of 130 to less than 250 ℃ is a solvent having high affinity with a transfer body (blanket) for offset printing, that is, a solvent which is easily absorbed by the transfer body (blanket). If the SP value is less than 7.0 or more than 8.7, the difference between the SP value and the SP value of the blanket becomes large, and the absorbency into the blanket is lowered. Therefore, the ink composition is difficult to peel off from the blanket, and re-transfer to the product becomes difficult.

When the boiling point of a solvent having high affinity with a transfer body (blanket) for offset printing is high, it takes a long time to dry the blanket after the solvent is adsorbed to the blanket, even if the blanket is heated. However, if the boiling point is too low, the following problems are present: since it is easy to dry before transfer to a transfer body and the initial transfer cannot be smoothly performed, the boiling point is 130 ℃ or higher and lower than 250 ℃, preferably 130 ℃ or higher and lower than 200 ℃.

The ink composition preferably contains 10 to 50 mass% of the solvent (C) having a solubility parameter (SP value) of 7.0 to 8.7 inclusive and a boiling point of 130 ℃ to less than 250 ℃ and having high affinity for the blanket, and more preferably contains 20 to 50 mass%. (C) When the content of the solvent having a solubility parameter (SP value) of 7.0 to 8.7 inclusive and a boiling point of 130 to less than 250 ℃ and high affinity with the blanket in the ink composition is 10% by mass or more, the transfer of the ink composition from the plate to the blanket can be favorably performed. When the amount is 50% by mass or less, the solvent concentration in the ink composition does not become too high and the ink composition cannot be completely absorbed by the blanket, and the re-transfer from the blanket to the product can be performed satisfactorily.

Examples of the solvent having a solubility parameter (SP value) of 7.0 to 8.7 and a boiling point of 130 to less than 250 ℃ as the above-mentioned (C) include propylene glycol monomethyl ether acetate (SP value 8.7), diethylene glycol dimethyl ether (SP value 8.1) and the like.

The difference in the SP value between the high molecular weight resin (a) having a crosslinking reactive group and the solvent (C) having a solubility parameter (SP value) of 7.0 to 8.7 inclusive and a boiling point of 130 ℃ to less than 250 ℃ and having high affinity for the blanket is preferably 2 or more. More preferably, it is larger than 2, and still more preferably 2.3 or more. When the difference is less than 2, the solubility of the high molecular weight resin in the solvent increases, and therefore, the solvent having high affinity with the blanket cannot be selectively adsorbed to the blanket, and the retransfer property to the product may be reduced.

Further, the ink composition according to the embodiment preferably further includes (D) a crosslinking agent for promoting a crosslinking reaction of the (a) high molecular weight resin having a crosslinking reactive group. When the crosslinking agent (D) is contained, the solubility parameter (SP value) is preferably 9 to 15, more preferably 10 or more. The composition preferably contains 10% by mass or less of (D) a crosslinking agent. When the SP value is less than 9, it becomes easy to be absorbed by the blanket, and therefore, transferability may be deteriorated. (D) The crosslinking agent may contain a compound having a plurality of groups reactive with the crosslinking reactive group of the above (A), or may contain a compound having only one group reactive with the crosslinking reactive group of the above (A). For example, in the case of a carboxyl group-containing polyurethane, since the crosslinking reactive group is a carboxyl group having an active hydrogen, a compound having a plurality of groups (for example, a hydroxyl group, a glycidyl group, etc.) reactive with the carboxyl group can be used as the crosslinking agent (D). The crosslinking reaction is preferably an addition reaction in which the elimination of the low molecular compound does not occur, and in this case, epoxy compounds 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, peroxide hydroxide of bisphenol-a-diallyl ether (SP value 10.4), EHPE 3150(SP value 11.0) manufactured by ダイセル, and the like) are more preferable. In the case of an allyl polymer such as diallyl isophthalate prepolymer, the crosslinking reactive group is an allyl group, and therefore, the crosslinking reaction can be carried out by curing by radical polymerization without using a crosslinking agent, but in order to increase the crosslinking density and improve the durability, a crosslinking agent having an unsaturated group of 2 or more functions can be used, and examples thereof include: polyfunctional acrylates (e.g., dipentaerythritol hexaacrylate (SP value: 10.4), acrylic acid adducts of epoxy resins, etc.), allyl compounds such as triallyl isocyanurate (タイク manufactured by Nippon Kasei corporation) (SP value: 13.6), and maleimide compounds such as 4, 4' -diphenylmethane bismaleimide (SP value: 14.3).

In addition to the components (a) to (D), other components such as (E) a curing catalyst, (F) a reactive diluent, and (G) an additive may be contained in the insulating protective film forming composition as needed.

(E) Curing catalyst

In order to smoothly progress the crosslinking reaction of the high molecular weight resin having a crosslinking reactive group (A), a curing catalyst (E) may be added. (E) The curing catalyst may be a known compound suitable for the curing reaction. For example, in the case of curing reaction of carboxyl groups and glycidyl groups, melamine and imidazoles can be used. In the case of radical polymerization of an allyl polymer, peroxides and the like can be used. In addition, if it is ultraviolet curing of an acryloyl group or a methacryloyl group, a photopolymerization initiator may be used. The amount of addition may be a known amount, and for example, may be 1 to 5% by mass based on the total amount of the resin (A) having a crosslinking reactive group and the crosslinking agent (D) which undergo crosslinking reaction.

(F) Reactive diluents

(F) The reactive diluent is a low-molecular compound having very low volatility and containing a crosslinking reactive group, and is a compound capable of uniformly dissolving or dispersing other components, and the viscosity of the composition can be adjusted by uniformly dissolving or dispersing the above-mentioned (a) high-molecular weight resin having a crosslinking reactive group together with a solvent. In addition, since it is reactive, it becomes a solid substance after curing.

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

(F) The boiling point of the reactive diluent is preferably higher than 300 deg.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 ℃ or lower, a part of the reactive diluent (F) may be evaporated depending on the curing conditions. Examples thereof include 1, 6-hexanediol glycidyl ether (SP value: 9.5), ethoxylated isocyanuric acid triacrylate (A-93000, manufactured by Nizhonghamu chemical industry Co., Ltd., SP value: 13.3), and 1, 6-hexanediol glycidyl ether (SP value: 9.5). The amount of the crosslinking reactive group-containing polymer (A) added is 100 parts by mass or less, preferably 80 parts by mass or less, per 100 parts by mass of the high-molecular-weight resin (A).

(G) Additive agent

Additives (G) such as a surfactant, an antioxidant and a filler may be contained as long as the performance of the composition for forming an insulating protective film is not adversely affected. For adjusting the viscosity of the composition, fillers such as fumed silica can be used. In addition, a colored filler may be added for coloring, and a conductive filler is preferably not included for securing insulation.

The amount to be added may be an amount capable of expressing the target function, and is preferably 5% by mass or less of the total composition, for example.

Examples

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

< epoxy equivalent >

The epoxy equivalent was determined in accordance with JIS-K7236. 0.1 to 0.2g of a sample was weighed and placed in an Erlenmeyer flask, and then 10mL of chloroform was added thereto and dissolved. Next, 20mL of acetic acid was added, followed by 10mL of a tetraethylammonium bromide acetic acid solution (a solution prepared by dissolving 100g of tetraethylammonium bromide in 400mL of acetic acid). 4 to 6 drops of a crystal violet indicator was added to the solution, and the solution was titrated with 0.1mol/L perchloric acid acetic acid solution, and based on the results of the titration, the epoxy equivalent was determined by the following formula.

Epoxy equivalent (g/eq) — (1000 xm)/{ (V1-V0) × c }

m: quality (g) of sample

V0: in the blank test, the amount of perchloric acid acetic acid solution consumed until the end point (mL) is titrated

V1: titration of the amount of Perchloroacetic acid solution consumed until the endpoint (mL)

c: concentration of Perchloric acid acetic acid solution (0.1mol/L)

< weight average molecular weight, number average molecular weight >

The molecular weight was determined by gel permeation chromatography (hereinafter abbreviated as GPC.) using a value converted to polystyrene (STANDARD SM-105 manufactured by Showa Denko K.K.). The measurement conditions of GPC are as follows.

Device name: HPLC UNIT HSS-2000 manufactured by Nippon spectral Co., Ltd

Column: shodex column LF-804

Mobile phase: tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

A detector: RI-2031Plus manufactured by Japan Spectroscopy (Ltd.)

Temperature: 40.0 deg.C

Sample amount: sample Ring 100. mu.L

Sample concentration: adjusted to about 0.1 mass percent

< Synthesis example of peroxide hydroxide of bisphenol-A-diallyl ether >

A2000 ml eggplant type flask was charged with 148.4g (0.650mol) of bisphenol A (manufactured by Mitsui chemical Co., Ltd.), 1.38g (0.650mmol) of 5% -Pd/C-STD type (manufactured by エヌ & イーケムキャット Co., Ltd.) with 50% water content, 1.639g (6.50mmol) of triphenylphosphine (manufactured by Beixing chemical Co., Ltd.), 189g (1.37mol) of potassium carbonate (manufactured by Nippon Kao Co., Ltd.), 143g (1.43mol) of allyl acetate (manufactured by Showa Denko K.K.) and 64.1g of isopropyl alcohol, and reacted at 85 ℃ for 8 hours in a nitrogen atmosphere. After the reaction, a part was sampled, diluted with ethyl acetate, and then analyzed by gas chromatography, and it was confirmed that the ratio of bisphenol-a-diallyl ether to monoallyl ether was 98: 2.

then, 200g of toluene was added to the reaction solution, Pd/C and precipitated solids were removed by filtration, and isopropanol and toluene were distilled off by an evaporator. In this reaction, after repeating the post-treatment operation 4 times, 493g (isolated yield 61.7%, diallyl ether 98.1%, and the remainder monoallyl ether) of a distillate and 245g (diallyl ether 96.5%) of a non-distillate were obtained by a molecular distillation apparatus (manufactured by Dakoku industries Co., Ltd.).

bisphenol-A-diallyl ether (50.05g, 162.3mmol), acetonitrile (26.63g, 648.7mmol), and ethanol (265.1g, 5754.2mmol) (acetonitrile concentration 9.9 mol%) obtained in the above-described manner were weighed out in a 1L four-necked eggplant type flask. During the reaction, a saturated aqueous potassium hydroxide solution (KOH/H) was added₂O110 mg/100mL) so that the pH was not lower than 9, 45% aqueous hydrogen peroxide (53.92g, 713.5mmol) was added dropwise over 2 hours from a 100mL dropping funnel (the acetonitrile concentration at this point in time was 8.1 mol%, pH 9.2). Saturated aqueous potassium hydroxide solution was added dropwise so that the reaction temperature did not exceed 30 ℃, the pH was brought to 10.5 over 2 hours (2 hours from the end of the addition of aqueous hydrogen peroxide solution), and stirring was further performed for 2 hours while controlling the pH to 10.5 (at this time point, the acetonitrile concentration was reduced to 6.3 mol%). Acetonitrile (13.31g, 324.2mmol) was weighed out from a 50mL dropping funnel, and was added dropwise over 2 hours (the acetonitrile concentration after additional addition was 6.1 mol%). At the same time, 45% aqueous hydrogen peroxide (53.92g, 713.5mmol) was added dropwise from a 100mL dropping funnel over 4 hours (pH was maintained at 10 to 10.5 so that the reaction temperature did not exceed 30 ℃ during the 4 hours), and the reaction was further carried out for 4 hours while controlling the pH to 10.5While stirring (the acetonitrile concentration at the end of the reaction was 3.5 mol%). Pure water (100g) was added to the reaction solution to dilute the solution, and the solvent was distilled off under reduced pressure. The residue was extracted with ethyl acetate (100g), and then pure water (100g) was added again to conduct a liquid separation operation. The ethyl acetate was distilled off by an evaporator to obtain a target epoxidation product. The epoxy equivalent of the epoxidized product was 189 g/eq.

< example of Synthesis of carboxyl group-containing polyurethane >

[ Synthesis example 1]

A2L three-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 143.6g of C-1015N (manufactured by Kokai クラレ Co., Ltd., polycarbonate diol, raw material diol molar ratio: 1, 9-nonanediol: 2-methyl-1, 8-octanediol ═ 15: 85, molecular weight 964) as a polyol compound, 27.32g of 2, 2-dimethylolbutyric acid (manufactured by Kokai Co., Ltd., Japan) as a dihydroxy compound having a carboxyl group, and 259g of propylene glycol monomethyl ether acetate (trade name: methoxypropyl acetate, manufactured by ダイセル Co., Ltd.) as a solvent, and the 2, 2-dimethylolbutyric acid was dissolved at 90 ℃.

The temperature of the reaction solution was lowered to 70 ℃ and 87.5g of デスモジュール (registered trademark) -W (methylene bis (4-cyclohexyl isocyanate, manufactured by Kyowa バイエルウレタン Co., Ltd.) was added dropwise to the reaction solution over 30 minutes from a dropping funnel. After completion of the dropwise addition, the temperature was raised to 120 ℃ to conduct a reaction at 120 ℃ for 6 hours, and after confirming that isocyanate had substantially disappeared by IR, 0.5g of isobutanol was added to conduct a reaction at 120 ℃ for 6 hours. The resulting carboxyl group-containing polyurethane had a weight average molecular weight of 32300, a number average molecular weight of 17900, and an acid value of 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 molecular resin ].

[ Synthesis example 2]

A carboxyl group-containing polyurethane was obtained in the same manner as in Synthesis example 1, except that 77.2g of C-1015N (manufactured by Kabushiki Kaisha クラレ), 50.00g of 2, 2-dimethylolbutyric acid (manufactured by Nippon Kaisha), 237g of propylene glycol monomethyl ether acetate (manufactured by ダイセル Kabushiki Kaisha), and 109.54g of デスモジュール (registered trademark) -W (manufactured by Kyoki Kaisha バイエルウレタン Co., Ltd.) were used as solvents. The resulting carboxyl group-containing polyurethane had a weight-average molecular weight of 43200, a number-average molecular weight of 21700, and an acid value of 80 mgKOH/g. The number of crosslinking reactive groups calculated from the number average molecular weight and the acid value was 30.9[ number/1 molecular resin ].

[ example 1]

An ink composition was prepared by charging 23 parts by mass of a carboxyl group-containing polyurethane (acid value 40[ KOHmg/resin g ]) as a resin (high molecular weight), 3 parts by mass of a peroxide hydroxide (epoxy equivalent 189[ g/eq ]) of bisphenol-A-diallyl ether as a crosslinking agent, 26 parts by mass of triethylene glycol monobutyl ether (Tokyo chemical Co., Ltd.) as a solvent having low affinity with a blanket, 28.4 parts by mass of propylene glycol monomethyl ether acetate (Wako pure chemical industries, Ltd.) as a solvent having high affinity with a blanket, 19 parts by mass of diethylene glycol dimethyl ether (Wako pure chemical industries, Ltd.) and 0.6 part by mass of melamine (Nissan chemical industries, Ltd.) as a curing catalyst into a glass container and mixing them under stirring at room temperature.

Examples 2 to 7 and comparative examples 1 to 4

Ink compositions were prepared in the same manner as in example 1 except that the resin (high molecular weight, examples 2 to 7, comparative examples 3 and 4), the resin (low molecular weight, comparative examples 1 and 2), the crosslinking agent, the solvent, the filler and the curing catalyst were changed as shown in table 1.

[ Table 1]

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

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

(. about.3) number average molecular weight was 9400, iodine value was 78[ g/100g ] (measured by manufacturer), number of crosslinking reactive groups calculated from number average molecular weight and iodine value was 28.9[ pieces/1 molecule resin ], and weight average molecular weight was a product catalog value.

(. 4) is represented by the formula C₁₂₆H₁₉₄O₃₃Calculation (described in SDS (manufactured by Kabushiki Kaisha ダイセル)).

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

(. 6) measured by using an E-type viscometer (VISCONIC EHD rotation speed 10rpm, manufactured by トキメック Co., Ltd.).

(. 7) was not evaluated because transfer from the gravure plate to the blanket was poor.

[ printing test ]

(Silicone blanket cylinders)

A commercially available silicone blanket (manufactured by Kagaku corporation, Kimura, Ltd.) for gravure offset printing was bonded to the surface of a rubber roll (SN-plate rubber roll No. 3, Nissan modeling Co., Ltd.) with a double-sided tape (ST-416P, 3M).

(intaglio)

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

(printing)

The ink compositions described in table 1 were placed on the recessed portions of the intaglio plate with a spatula, and the ink compositions were filled in the recessed portions by scraping with a squeegee (squeegee), and the ink compositions in the other portions were removed.

Next, a silicone blanket cylinder was rolled over the recesses filled with the ink composition, and the ink composition was transferred to the silicone blanket cylinder.

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

[ evaluation of transferability ]

The silicone blanket cylinder to which the ink composition was transferred was rolled on a glass substrate, the ink composition was transferred to the glass substrate again, and the amount of the ink composition remaining on the silicone blanket was visually observed.

Excellent … … ink composition was almost free from residue (ink composition residual area ratio less than 1%).

Slightly residual ink composition (residual ink composition area ratio of 1 to less than 5%) was observed in the sample of … ….

The x … … ink composition remained much (the ink composition area remaining ratio was more than 5%).

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

[ evaluation results ]

The results are shown in Table 1. The ink compositions of examples 1 to 7 using a high molecular weight resin had good transferability, but had poor transferability when a low molecular weight resin was used (the high molecular weight resin (A) was not used, and the reactive diluent (F) was used alone) as in comparative examples 1 and 2, and when the solvent (B) or (C) was used alone as in comparative examples 3 and 4.

Claims

1. An insulating protective film forming composition for forming an insulating protective film by offset printing, comprising:

(A) a high molecular weight resin having a weight average molecular weight of more than 2X 10 and having a crosslinking reactive group⁴And is 40X 10⁴The following;

(B) a solvent having a solubility parameter greater than 8.7, a boiling point greater than 200 ℃ and less than 300 ℃; 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 ℃,

the solubility parameter of the solvent (B) having a solubility parameter of more than 8.7 and a boiling point of more than 200 ℃ and 300 ℃ or less is +1 or less of the solubility parameter of the high molecular weight resin (A) having a crosslinking reactive group.

2. The insulating protective film forming composition for forming an insulating protective film by offset printing according to claim 1, wherein the average number of crosslinking reactive groups per 1 molecule of the (a) high molecular weight resin having a crosslinking reactive group, which is determined by calculation from the number of crosslinking reactive groups per unit mass and the number average molecular weight, is 3 or more.

3. The insulating protective film forming composition for forming an insulating protective film by offset printing according to claim 1 or 2, further comprising (D) a crosslinking agent.

4. The insulating protective film forming composition for forming an insulating protective film by offset printing as claimed in claim 1 or 2, wherein the solubility parameter of the (a) high molecular weight resin having a crosslinking reactive group is 11 or more and 15 or less, and the (a) high molecular weight resin having a crosslinking reactive group is contained in the composition in an amount of 10 to 80 mass%.

5. The composition for forming an insulating protective film according to claim 1 or 2, wherein the solvent (C) having a solubility parameter of 7.0 to 8.7 inclusive and a boiling point of 130 ℃ to less than 250 ℃ is contained in an amount of 10 to 50 mass%.

6. The composition for forming an insulating protective film according to claim 5, wherein the solvent (C) having a solubility parameter of 7.0 to 8.7 inclusive and a boiling point of 130 ℃ to less than 250 ℃ is contained in an amount of 20 to 50 mass%.

7. The insulating protective film forming composition for forming an insulating protective film by offset printing according to claim 5, wherein a difference between solubility parameters of said (A) high molecular weight resin having a crosslinking reactive group and said (C) solvent having a solubility parameter of 7.0 or more and 8.7 or less and a boiling point of 130 ℃ or more and less than 250 ℃ is more than 2.

8. The insulating protective film forming composition for forming an insulating protective film by offset printing according to claim 1 or 2, wherein the solvent (B) having a solubility parameter of more than 8.7 and a boiling point of more than 200 ℃ and 300 ℃ or less is any one selected from the group consisting of diethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether, γ -butyrolactone, and 1, 3-dimethyl-2-imidazolidinone.

9. The insulating protective film forming composition for forming an insulating protective film by offset printing according to claim 1 or 2, wherein the solvent (C) having a solubility parameter of 7.0 to 8.7 inclusive and a boiling point of 130 ℃ to less than 250 ℃ is any one selected from propylene glycol monomethyl ether acetate and diethylene glycol dimethyl ether.