JP2018177929A - Ink for inkjet, cured article, substrate and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink for inkjet capable of forming a film usable as an encapsulation agent of electronic components on a substrate, and containing a thermosetting resin having a silsesquioxane structure.SOLUTION: In an ink for inkjet containing a thermosetting resin having a silsesquioxane structure and a solvent for dissolving the thermosetting resin, viscosity is adjusted to low suitable for inkjet printing, repellent phenomena or fluidization on the substrate is suppressed, and a film good in adhesiveness with the substrate can be formed by using one having a hydroxyl group and/or a methoxy group and boiling point of 143°C or less as the solvent.SELECTED DRAWING: None

Description

  The present invention can be obtained, for example, from an inkjet ink containing a thermosetting resin having a silsesquioxane structure, a solvent capable of dissolving the thermosetting resin, and an inkjet ink that can be used as a sealing agent when producing an electronic component. A cured film, a substrate on which the cured film is formed, and an electronic component having the substrate.

  An epoxy resin, an acrylic resin, etc. are used as a sealing agent of electronic components. However, when these resins are used for LEDs (light emitting diodes), they often yellow due to the problem of light resistance. Therefore, in order to suppress yellowing, silicone resins have come to be used.

  Patent Document 1 reports an ink jet recording liquid containing a ladder-type silsesquioxane as a binder component, which is used for marking ceramic or the like. However, the ink jet recording liquid of the same document is for marking, and there is no description about the stability of discharge or the adhesion between a print pattern formed by the ink jet recording liquid and a substrate (substrate).

  Patent Document 2 reports a composition (silicone resin) of a thermosetting resin having a silsesquioxane structure. However, since the composition of the thermosetting resin of the same document has a viscosity of 600 mPa · s or more, it can be used for dispenser applications, but can not be used as an inkjet ink that needs to have a low viscosity. As described above, the document does not disclose that a thermosetting resin composition having a silsesquioxane structure is diluted in a solvent and used as an inkjet ink.

  Patent Document 3 reports a composition (silicone resin) of a thermosetting resin having good adhesion having a silsesquioxane structure. The document describes using an ink jet to form a coating film with the composition of the thermosetting resin and describing using a solvent. However, making the above composition into an inkjet ink has not been specifically studied, nor has it described any problems when it is applied to a substrate.

  Patent Document 4 reports a composition (silicone resin) of a thermosetting resin having a silsesquioxane structure having heat resistance, UV resistance, and high adhesion. However, the same document does not describe forming a coating of the composition using an inkjet.

Japanese Patent Application Laid-Open No. 62-250081 WO 2011/145638 A1 WO 2013/005633 A1 WO2014 / 077216A1 gazette

Since thermosetting resins having a silsesquioxane structure have high viscosity, it is necessary to dissolve in a solvent to lower the viscosity to be used as an inkjet ink, but the above thermosetting resin is dissolved in a solvent. It has not been studied to use it as an ink jet ink.
Although Patent Document 3 exemplifies toluene as a solvent for ink jet ink, the ink jet ink using toluene as a solvent can not form a film on a substrate because the ink is strongly repelled with respect to the substrate.
As described above, an ink jet ink containing a thermosetting resin having a silsesquioxane structure capable of forming a film on a substrate has not been realized yet.
Then, this invention aims at providing the ink for inkjets containing the thermosetting resin which has a silsesquioxane structure which can form a film | membrane on a board | substrate.

  The inventors of the present invention have studied to solve the above problems, and as a result, the thermosetting resin having a silsesquioxane structure has a hydroxy group and / or a methoxy group and has a boiling point of 143 ° C. or less It has been found that by dissolving in a solvent of the above, it is possible to suppress the repelling on the substrate, and to obtain an ink jet ink capable of forming a film having good adhesion to the substrate. The outline of the present invention based on the knowledge is as follows.

[1] In an inkjet ink containing a thermosetting resin having a silsesquioxane structure, and a solvent for dissolving the thermosetting resin, the solvent has a hydroxy group and / or a methoxy group. An inkjet ink having a boiling point of 143 ° C. or less.

[2] The thermosetting resin is
(A) A reaction product of a silsesquioxane having an SiH group and an organopolysiloxane having two alkenyl groups, the thermosetting resin A containing an SiH group and an alkenyl group, and (B) an SiH group A thermosetting resin B having a SiH group, which is a reaction product with silsesquioxane having an alkenyl group, an organopolysiloxane having two alkenyl groups, an epoxy compound having an alkenyl group and a silyl compound having an alkenyl group, It contains, The ink for inkjets as described in [1] characterized by the above-mentioned.

[3] The inkjet ink according to [2], wherein the silsesquioxane in the thermosetting resins A and B is a double decker silsesquioxane.

[4] The inkjet ink according to [3], wherein the thermosetting resin A is a compound represented by the following formula (1).
In Formula (1), each X independently
A compound represented by the following formula (X-I), formula (X-II) or formula (X-III), and one compound represented by the formula (1) [wherein the compound is a formula (X-I) When it is a mixture of compounds in which the proportions of the group represented by and the group represented by the formula (X-II) and the group represented by the formula (X-III) are different, per compound average of the compound]
The number of groups represented by formula (X-I) is a,
The number of groups represented by formula (X-II) is b,
When the number of groups represented by formula (X-III) is c, a + 2b + c = 4, 0 <a ≦ 3, 0 ≦ b ≦ 1, and 0 <c ≦ 3.
R ¹ is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and m is an average value of the number of repetitions and satisfies 1 to 100.
In formula (X-II), R ² and R ³ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is -OSi (R ³ ) _2- The average value of the number of repetitions of, and satisfies 2 to 20.
In formula (X-III), R ⁴ and R ⁵ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and s is —OSi (R ⁵ ) ₂ — The average value of the number of repetitions of, and satisfies 2 to 20.

[5] The inkjet ink according to any one of [2] to [4], wherein the thermosetting resin B is a compound represented by the following formula (B1).
In Formula (B1), X's are each independently the following Formula (a), Formula (b), Formula (c-i), Formula (c-ii), Formula (c-iii), Formula (d) -I) a compound represented by the formula (d-ii) or the formula (d-iii), and one molecule of the compound represented by the formula (1) [wherein the compound is represented by the group represented by the formula (a) When it is a mixture of compounds in which the proportions of groups represented by formulas (b) to (d-iii) are different, the average per molecule of the compound]
The number of groups represented by the following formula (a) is A,
The number of groups represented by the following formula (b) is B,
The number of groups represented by the following formula (ci), formula (c-ii) or formula (c-iii) is C,
When the number of groups represented by the following formula (d-i), formula (d-ii) or formula (d-iii) is D, A + 2B + C + D = 4, and 0.5 ≦ A ≦ 3. 0, 0.5 ≦ 2B ≦ 2.0, 0.1 ≦ C ≦ 2.0, and 0 ≦ D ≦ 1.0.
In formula (B1), R ¹ is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and m ′ is an average value of the number of repetitions, and satisfies 1 to 100.
In formula (b), R ^{2 ′} and R ^{3 ′} are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and t is —OSi (having 1 to 20) R3 ^' ) It is an average value of the number of repetition of _2- .
In formulas (di) to (d-iii), R ⁴ , R ^{4 ′} and R ^{4 ′ ′} are each independently a group selected from methyl, ethyl, butyl and isopropyl. x is an average value of the number of repetitions of -OSi (R ^{4 '} ) _2- satisfying 1 to 20. y is an average value of the number of repetitions of -OSi (R ^{4 "} ) _2- and satisfies 1 to 10.

[6] The inkjet ink according to any one of [2] to [4], wherein the thermosetting resin B is a compound represented by the following formula (B2).
In formula (B2), Me is a methyl group, and R ′ ′ each independently is a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is an integer of 0 to 100 It is. aii is 0.1 ≦ aii ≦ 3.5, Xii is 0 ≦ 2Xii ≦ 2.0, Yii is 0 ≦ Yii ≦ 3.0, and Zii is 0.1 ≦ Zii ≦ 3.5.

[7] One or more selected from the group consisting of methyl 2-hydroxyisobutyrate, propylene glycol monomethyl ether, cyclopentyl methyl ether, t-amyl alcohol, 1-propanol, 2-propanol and 2-butanol The inkjet ink according to any one of the above [1] to [6].

[8] The inkjet ink according to any one of [1] to [7], wherein the boiling point of the solvent is 80 ° C. or more and 140 ° C. or less.

[9] The inkjet ink according to any one of [1] to [8], which contains a Pt catalyst.

[10] The inkjet ink according to any one of [1] to [9], which contains one or more of the following groups (C), (E) and (F).
(C) A linear organopolysiloxane compound C having an SiH group only at one end
(E) Organopolysiloxane compound E having two or more alkenyl groups
(F) Silane coupling agent having an epoxy group

[11] The inkjet ink according to [10], wherein the organopolysiloxane compound C is a compound represented by the following formula (2).
R ⁶ and R ⁷ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and m is an average value of the number of repeating -Si (R ⁷ ) ₂ O- , Meet 1-20.

[12] The inkjet ink according to [10] or [11], wherein the organopolysiloxane compound E is a compound represented by the following formula (3).
In formula (3), R ⁸ and R ⁹ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and n is a repeat of —OSi (R ⁹ ) ₂ — The average value of the number of and satisfies 1 to 50.

[13] The inkjet ink according to any one of [10] to [12], wherein the silane coupling agent having an epoxy group is a compound represented by the following formula (4).
In formula (4), each R ¹⁰ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl or cyclohexyl.

[14] A cured film obtained by printing the inkjet ink according to any one of [1] to [13] by an inkjet printing method.
[15] A substrate on which the cured film according to [14] is formed.
[16] An electronic component comprising the substrate according to [15].

  The inkjet ink of the present invention is suitable for inkjet printing by dissolving a thermosetting resin having a silsesquioxane structure in a solvent having a hydroxy group and / or a methoxy group and having a boiling point of 143 ° C. or less. While adjusting to a suitable low viscosity, the repelling and flow on a board | substrate can be suppressed and the film | membrane of the adhesiveness with a board | substrate with favorable adhesiveness can be formed. Therefore, according to the present invention, for example, when using a thermosetting resin having a silsesquioxane structure as a sealing agent, it can be efficiently performed using an inkjet method.

  In the production of an electronic component, a process of forming an electronic circuit, a sealant and the like in a predetermined pattern is performed. In the process of forming a pattern film having a predetermined pattern, an etching method of etching a part of the film, a method of imparting photosensitivity to the film, and photocuring a predetermined site are used. In recent years, in order to simplify the manufacturing process of an electronic component, using inkjet printing for the formation process of a pattern film is examined. In order to form a pattern film using inkjet printing, it is necessary to optimize parameters such as the viscosity of the inkjet ink and the boiling point of the solvent to make the ejection property, the printability, etc. good.

  Regarding the viscosity, it is required that the inkjet ink have a low viscosity at the ejection temperature (ink temperature at the time of ejection). In particular, since the piezoelectric ink jet printing has a low discharge pressure, the ink may not be discharged if the viscosity of the ink for ink jet recording is high. Therefore, in general, the viscosity of the inkjet ink is preferably about 1 to 20 mPa · s at the ejection temperature.

  With regard to the solvent, when using a solvent having a too low boiling point, the ink jet head may be easily dried and the ejection stability may be deteriorated. In addition, when a solvent having a too high boiling point is used, when a silicone resin or the like having high fluidity before curing is contained, the film of the inkjet ink is fluidized at the time of drying and heat curing, and the printability is lowered. There is. Therefore, in general, the boiling point of the solvent used for the inkjet ink is preferably 80 to 250 ° C.

A thermosetting resin having a silsesquioxane structure has good adhesion to metals and the like, and ink jet printing is useful for simplifying the manufacturing process of electronic components. However, a thermosetting resin having a silsesquioxane structure can not be used as it is as an inkjet ink because of its high viscosity. For this reason, in order to use as an inkjet ink, it is necessary to dissolve in a solvent. However, an ink jet ink containing a thermosetting resin having a silsesquioxane structure has not been studied so far, and it is possible to form a film on a substrate while having various properties suitable for ink jet printing in a well-balanced manner. Ink jet inks have not been realized yet.
In the present invention, a solvent having a hydroxyl group and / or a methoxy group and having a boiling point of 143 ° C. or less is used as a solvent for dissolving a thermosetting resin having a silsesquioxane structure on a substrate. It is based on the new finding that it becomes an ink jet ink capable of forming a film on a substrate by suppressing the repelling and flowability.

  In the following description, the compound (1) represented by the formula (1) described in the section of the means for solving the problems may be abbreviated as the compound (1). The same applies to compounds and groups represented by other formulas.

The inkjet ink of the present example (hereinafter, appropriately referred to as “ink”) contains a thermosetting resin having a silsesquioxane structure, and a solvent for dissolving the thermosetting resin.
<Thermosetting resin>
The thermosetting resin having a silsesquioxane structure (hereinafter, also simply referred to as "thermosetting resin") contained in the inkjet ink will be described below.
Silsesquioxane is a generic term for polysiloxane whose basic constituent unit is the following T unit. The structure of the Si-O-Si skeleton of silsesquioxane includes a random structure, a ladder structure, a cage structure and a double decker structure.

  The content of the thermosetting resin contained in 100 parts by weight of the inkjet ink is preferably 80 parts by weight or less, and is 60 parts by weight or less, from the viewpoint of easy adjustment to the viscosity suitable for the ink jet Is more preferable, and 40 parts by weight or less is more preferable. Further, from the viewpoint of reducing the number of printings required to form a film having a predetermined thickness, it is preferably 20 parts by weight or more, more preferably 30 parts by weight or more, and 40 parts by weight or more. Is more preferred.

The thermosetting resin preferably contains the following thermosetting resins A and B.
(A) A thermosetting resin A which is a reaction product of a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups, and which comprises an SiH group and an alkenyl group.
(B) A reaction product of a silsesquioxane having an SiH group, an organopolysiloxane having two alkenyl groups, an epoxy compound having an alkenyl group and a silyl compound having an alkenyl group, wherein the thermosetting is carried out having an SiH group Resin B

  The weight ratio of the thermosetting resin A to the thermosetting resin B is preferably such that A / B is 100/0 to 95/5, and more preferably 99/1 to 96/4, 99 It is further preferable that the ratio is from 1 to 97/3.

<Thermosetting resin A>
As thermosetting resin A, the compound shown by Formula (1) is mentioned.
In the group represented by formula (X-III), the number s of -OSi (R ⁵ ) _2- repetitions is an average value satisfying 2 to 20, preferably 2 to 10, more preferably 2 to 4 preferable.
In the compound (1), when the number a of the group represented by the formula (X-I) is larger than the number c of the group represented by the formula (X-III) (a> c), the compound (1) Can be defined as a so-called thermosetting resin of the SiH group type, on average having more SiH than a vinyl group.
As the thermosetting resin A, it is preferable to use a SiH group thermosetting resin in which H is bonded to Si. The number a of the group represented by the formula (X-I) is preferably 1.0 or more and 3.0 or less, and preferably 1.5 or more, from the viewpoint of making the excellent properties of the cured product remarkable. More preferably, it is 2.5 or less.

  In the ink of the present embodiment, the content of the thermosetting resin A is preferably 50 to 99 parts by weight, based on 100 parts by weight of the total amount of the composition obtained by removing the solvent from the ink. The amount is more preferably 70 to 95 parts by weight, further preferably 80 to 90 parts by weight.

<Thermosetting resin B>
As thermosetting resin B, the compound (B1) represented by Formula (B1) and the compound (B2) shown by Formula (B2) are mentioned.

  In the compound (B1), the group represented by the formula (a) is a group derived from silsesquioxane having an SiH group, and a compound corresponding to the group represented by the formula (b), and a compound represented by the formula (c- Si) residue after reaction with an epoxy derivative represented by i) to (c-iii), and a compound corresponding to a group represented by formulas (di) to (d-iii) optionally used It is a group.

  The group (a) can react with the thermosetting resin B which is the reaction product of silsesquioxane and organopolysiloxane. For this reason, the group (a) has a role of strengthening the function of the thermosetting resin B as an adhesion imparting agent for imparting adhesion to the inkjet ink of this example.

  The (b) group is a crosslinking component of silsesquioxane and can impart flexibility to the thermosetting resin B. If the value of B which is the number of groups represented by Formula (b) becomes large, the crosslinking component of molecules will increase and the molecular weight of thermosetting resin B will become large. If B = 0, the thermosetting resin B is in a state having no crosslinking component. In the range of 0 <B <1 (0 <2B <2), the molecular weight increases as the value of B increases. In the range of B> 1 (2B> 2), since crosslinking between molecules is in a very advanced state, gelation occurs and the use as a thermosetting resin becomes difficult. Therefore, it is preferable to adjust the molecular weight of the thermosetting resin B by changing the value of B within the range of 0 <B ≦ 1 (0 <2B ≦ 2).

  The (c-i) to (c-iii) groups are epoxy groups bonded to SiH groups in a crosslinked product of silsesquioxane and organopolysiloxane, and a base material such as a substrate and a thermosetting resin B Plays a role in improving the adhesion of

The (d-i) to (d-iii) groups are alkoxysilyl groups bonded to SiH groups in a crosslinked product of silsesquioxane and organopolysiloxane.
The (di) group has a role of improving the adhesion of the thermosetting resin B to metals and inorganic substrates.
The (d-ii) group is a group derived from the (b) group and is an optional component. In the (d-ii) group, those in which R ^{4 ′} is methyl are preferred. Although x which is the number of repetition of -OSi (R ^{4 '} ) _2- is an average value that satisfies 1 to 20, it is preferable that it is an average value that satisfies 1 to 10. The (d-ii) group is used for the purpose of adjusting the viscosity of the thermosetting resin B and adjusting the hardness of a cured product obtained by curing the inkjet ink (composition of the thermosetting resin).
The (d-iii) group is preferably such that R ^{4 ′ ′} is methyl.

  The thermosetting resin B functions as an adhesion imparting agent which imparts adhesiveness to the composition of the thermosetting resin. When the thermosetting resin B is the compound (B1), the values of A to D indicating the proportions of the respective groups constituting the compound (B1) are in accordance with the properties of the thermosetting resin B, within the above-mentioned range It can be changed arbitrarily.

  In addition, the values of aii, Xii, Yii and Zii, which indicate the proportions of the respective groups constituting the compound (B2), are also arbitrarily changed within the above-mentioned range in accordance with the properties of the thermosetting resin B. Can.

  The content of the thermosetting resin B is preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total composition of the thermosetting resin obtained by removing the solvent from the ink (100 parts by weight). The amount is more preferably 0.5 to 6 parts by weight, and still more preferably 0.8 to 4 parts by weight.

  As silsesquioxane which has a SiH group in thermosetting resin A and B, double decker type silsesquioxane and cage type silsesquioxane of T8 structure are mentioned. The caged silsesquioxane having a T8 structure has eight functional groups, whereas the double decker silsesquioxane has four functional groups. Has the advantage that the structure is easy to control. Also, unlike fully condensed cage silsesquioxane, double decker silsesquioxane is incompletely condensed, has a high degree of molecular freedom, and is excellent in flexibility. From such a viewpoint, the silsesquioxane having an SiH group is preferably a double decker silsesquioxane.

<Solvent>
The ink-jet ink of the present embodiment contains a solvent that dissolves a thermosetting resin having a silsesquioxane structure. The viscosity of the inkjet ink can be adjusted by changing the amount of the thermosetting resin to be dissolved.

  The solvent is a polar solvent having a hydroxy group (hydroxyl group) and / or a methoxy group. By using a polar solvent, the solubility of the thermosetting resin having a silsesquioxane structure and the printability (coatability) of the ink are improved. The solvent may have other functional groups in addition to the hydroxy group and / or the methoxy group. Other functional groups include alkoxy groups other than methoxy groups, carbonyl groups, ether groups and the like.

  A thermosetting resin (silicone resin) having a silsesquioxane structure dissolved in a solvent has high fluidity before curing. For this reason, the ink according to the present embodiment uses a solvent having a low boiling point that can be removed in a short time from the viewpoint of improving the printability (applicability) of the ink by preventing flow when the film is dried. ing. The boiling point of the solvent is preferably 143 ° C. or less, more preferably 140 ° C. or less, and still more preferably 138 ° C. or less.

  On the other hand, the solvent of the inkjet ink also has the function of preventing the drying of the head. Therefore, the boiling point of the solvent is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and still more preferably 100 ° C. or higher, from the viewpoint of preventing the head from drying.

  From the viewpoint of preventing the head from drying while achieving good printability, the boiling point of the solvent is preferably 80 ° C. or more and 143 ° C. or less. As preferable solvents, hydroxybutyric acid esters, alcohols, ethers and the like having a boiling point of 80 ° C. or more and 143 ° C. or less can be mentioned. Among these, methyl 2-hydroxyisobutyrate, 1-methoxy-2-propanol, cyclopentyl methyl ether, t-amyl alcohol, 1-propanol, 2-propanol and 2-butanol are preferable. These preferred solvents may be used alone or in combination of two or more. By mixing two or more solvents, the polarity and the boiling point of the solvent (mixed solvent) can be finely adjusted.

  By using a solvent having polarity, the wettability of the ink to a substrate such as a glass substrate is improved. On the other hand, when the polarity of the solvent is too large, the solubility of the thermosetting resin is reduced, and the ink tends to be clouded. For this reason, it is preferable to use a solvent having a dielectric constant of 25 or less from the viewpoint of appropriately adjusting the wettability of the ink and the solubility of the thermosetting resin. Examples of the solvent having a dielectric constant of 25 or less include alcohols having 3 or more carbon atoms. Further, alcohols having 3 or more carbon atoms are preferred in the order of tertiary alcohol, secondary alcohol and primary alcohol.

  When mixing 2 or more types of solvents, it is preferable to use the mixed solvent which mixed the solvent whose boiling point is 100 degreeC or more, and the solvent (boiling-point solvent) whose boiling point is 100 degrees C or less. By using a mixed solvent containing a low boiling point solvent, the film formed by the inkjet ink can be made better. Low boiling solvents include alcohols such as 1-propanol, 2-propanol and 2-butanol.

  A film can be formed on a substrate even if an ink using only a low boiling point solvent as the solvent is used. However, when only a low boiling point solvent is used, the evaporation rate of the solvent with respect to the time required for forming a film may be too fast, and the uniformity of the formed film may be degraded. Therefore, in order to form a uniform film by the inkjet ink, it is preferable to adjust the evaporation rate of the solvent using a mixed solvent in which a solvent having a boiling point of 100 ° C. or more and a low boiling point solvent are mixed.

  The viscosity of the inkjet ink of the present embodiment is preferably in the range of 1 mPas to 50 mPas, and more preferably in the range of 1.5 mPas to 20 mPas, from the viewpoint of coating accuracy and ejection stability.

  The content of the solvent is preferably 30 parts by weight or more, and 40 parts by weight or more, based on 100 parts by weight of the total amount of the ink for ink jet, from the viewpoint of making the ink jet ink excellent in dischargeability. And more preferably 60 parts by weight or more. The upper limit of the content of the solvent is preferably 70 parts by weight or less from the viewpoint of reducing the number of printings required to form a film having a predetermined thickness.

<Pt catalyst>
The ink-jet ink of the present embodiment may contain a Pt catalyst. The Pt catalyst is a catalyst containing platinum, and may be either platinum oxidized or platinum not oxidized. Platinum oxide is mentioned as what platinum was oxidized. Partially oxidized platinum includes, for example, Adams' catalyst.

  As Pt catalyst, Spear's catalyst (Speier's Catalyst), Karstedt's catalyst (Karstedt's Catalyst), etc. may be mentioned, but Karstedt's catalyst is preferably used.

  The content of the Pt catalyst is preferably 0.0001 ppm to 10 ppm, more preferably 0.1 to 3 ppm, in the composition of the thermosetting resin contained in the inkjet ink (the ink obtained by removing the solvent from the ink). Is more preferred.

The ink-jet ink may further contain one or more of the following groups (C), (E) and (F).
(C) A linear organopolysiloxane compound C having an SiH group only at one end
(E) Organopolysiloxane compound E having two or more alkenyl groups
(F) Silane coupling agent having an epoxy group

As organopolysiloxane compound C, a compound (2) is mentioned.
The organopolysiloxane compound E includes a compound (3).
The silane coupling agent F includes a compound (4).
The silane coupling agent (F) has the function of improving the adhesion of the composition of the thermosetting resin to silicon, SiO ₂ and glass.

  The ink-jet ink of this embodiment may contain components other than the above-described components. When other components are contained, the content thereof may be in a range that does not inhibit the inkjet ink of the present invention from exhibiting a function according to the purpose.

<Cured film, substrate, electronic parts>
The present invention can be carried out as a cured film obtained by printing the above-described inkjet ink by an inkjet printing method. As a use of the said cured film, a sealing agent, an adhesive agent, an insulating film etc. are mentioned, for example. Further, the present invention can be implemented as a substrate on which a cured film is formed and an electronic component having the substrate. As the substrate, a silicon wafer, a Si / SiO ₂ substrate, a glass substrate or the like can be used.

  Hereinafter, the present invention will be described by showing Examples and Comparative Examples, but the present invention is not limited to the specific examples.

Synthesis Example
The reagents and the like used in the synthesis examples are as follows.
DD-4H: Double-Decker type silsesquioxane derivative DVTS (1, 5-divinylhexamethyltrisiloxane): FM-2205 manufactured by JNC Co., Ltd. (polydimethylsiloxane having a number average molecular weight of 700 having a vinyl group at both ends) : MA-DGIC (monoallyl diglycidyl isoanurate) manufactured by JNC Co., Ltd .: S-210 (vinyltrimethoxysilane) manufactured by Shikoku Kasei Kogyo Co., Ltd .: S510 manufactured by JNC Co., Ltd. (3-glycidoxypropyltrimethoxysilane) : Made by JNC Corporation

<Thermosetting resin A>
As the thermosetting resin A, in the compound (1), a [(X-I) group] = 1.5, b [(X-II) group] = 0, d [(X-III) group] = 1 The following compounds, which are .5, were prepared using the methods described below.

A double-decker silsesquioxane derivative (DD-4H) prepared by the method disclosed in WO 2004/024741 was placed in a 200 mL reaction vessel equipped with a thermometer, a reflux condenser, and a stirrer. 50 g (0.0384 mol), 51.3 g (0.197 mol) of DVTS (5 times mol to DD-4H), and 37.5 g of toluene as a solvent were added. Heating and stirring were started under a nitrogen atmosphere. After the contents reached 115 ° C., a Karstedt catalyst was added to a Pt concentration of 0.004 ppm relative to DD-4H, and heating and stirring were performed. The reaction was traced by GPC, and after 7 hours, the reaction was stopped by stopping heating. The reaction solution was transferred to an eggplant flask and toluene and excess DVTS were distilled off under reduced pressure of 70 ° C. and 1 mmHg with an evaporator to obtain 58 g of a colorless and transparent liquid having a viscosity of 95 Pa · s at 25 ° C. The molecular weight was analyzed by GPC, and the number average molecular weight was Mn = 1200 and the weight average molecular weight was Mw = 1400. It is judged that the obtained colorless and transparent liquid has the following structure from the following analysis result.
(result of analysis)
1 H-NMR (solvent: CDCl ₃ ): δ (ppm); 0.0-0.6 (m, 50.8 H), 5.0 (s, 2.4 H), 5.8-6.4 ( m, 3.2H), 7.05 to 7.50 (m, 40H)
(Construction)
a = 2.5, SiH equivalent is 670 g / mol, vinyl group equivalent is 1500 g / mol

<Thermosetting resin B>
As a thermosetting resin B, in the compound (B1), A [(a) group] = 1.32, C [(ci) group] = 0.65, B [(b)] = 0. The following compound, which is 69 (2B = 1.38), D [(di) group] = 0.65, was prepared using the method described below.

  50 g of silsesquioxane derivative (DD-4H) and 18.6 g (0.0266 mol) of vinyl silicone (FM-2205) in a 300 mL reaction vessel equipped with a thermometer, a reflux condenser, and a stirrer 7.47 g (0.0252 mol) of monoallyl diepoxyisocyanurate (MA-DGIC), 3.7 g (0.0252 mol) of S210, and 50 g of toluene as a solvent were added.

  Heating and stirring were started under a nitrogen atmosphere. After the contents reached 90 ° C., Karstedt's Catalyst was added in an amount such that the Pt concentration became 1 ppm with respect to DD-4H, and heating and stirring were performed for 5 hours as it was. The reaction was terminated after confirming the disappearance of MA-DGIC by GC. After cooling to room temperature, 1.6 g of activated carbon was added and stirred for 3 hours or more, and then the activated carbon was removed by filtration. The filtrate was evaporated under a reduced pressure condition of 1 mmHg at 90 ° C. using an evaporator to distill off the solvent toluene. 74 g of a water-colored, colorless, transparent liquid were obtained.

  When the molecular weight of the obtained product was analyzed by GPC, it was number average molecular weight: Mn = 3900 and weight average molecular weight: Mw = 18,200.

^{According to 1} H-NMR measurement, Compound B was found to have an epoxy group, an isocyanuric ring skeleton, an alkoxysilyl group (methoxysilyl group), and an SiH group.

<Organopolysiloxane compound C>
The following compounds were used as a linear organopolysiloxane compound C having an SiH group only at one end.

<Pt catalyst>
A Karstedt catalyst was used as a Pt catalyst.

<Organopolysiloxane compound E>
As the organopolysiloxane compound E having two or more alkenyl groups, the following DVTS (1,5-divinylhexamethyltrisiloxane, manufactured by JNC Corporation) or FM-2205 (having a vinyl group at both ends) has a number average molecular weight of 700 Polydimethylsiloxane, manufactured by JNC Corporation).

<Silane coupling agent>
The following S510 (3-glycidoxypropyltrimethoxysilane, manufactured by JNC Corporation) was used as a silane coupling agent having an epoxy group.

Each component mentioned above was mixed by the composition shown in following Table 1 and Table 2, and the composition PSQ1 and PSQ2 of the thermosetting resin which has a silsesquioxane structure were prepared. The compositional ratio shown in the table indicates the weight ratio (parts by weight) of each component.

Abbreviations of solvents used in the following Examples and Comparative Examples are as follows.
HBM: methyl 2-hydroxyisobutyrate PGM: 1-methoxy-2-propanol CPME: cyclopentyl methyl ether t-amylOH: t-amyl alcohol NPA: 1-propanol IPA: 2-propanol MTM: triethylene glycol dimethyl ether HBE: 2- Ethyl hydroxyisobutyrate ML: Methyl lactate EL: Ethyl lactate 14BG: 1,4-butanediol PGMEA: Propylene glycol 1-monomethyl ether 2-acetate

〔Example〕
<Evaluation method>
Preparation of Ink
The composition of the thermosetting resin and the solvent were mixed at room temperature (25 ° C.), and it was evaluated whether or not the composition of the thermosetting resin was dissolved in the solvent to be usable as an inkjet ink.
<Ink viscosity>
The viscosity of the ink (room temperature) prepared to be usable as an inkjet ink was measured using an E-type viscometer TV-22. The rotational speed in viscosity measurement was 50 (rpm).

<Spin coat application>
Using an ink prepared to be usable as an inkjet ink, a film was produced on a 0.7 um thick glass substrate by spin coating at 500 rpm for 10 seconds. The produced film was dried on a hot plate at 80 ° / 5 for 5 minutes and baked at 160 ° for 1 hour to produce a cured film. If the cured film could be obtained, it was evaluated as ○, otherwise it was evaluated as x.

<Inkjet (IJ) printing>
With regard to the ink whose cured film has been produced by the spin coating method, a film of ink of a pattern of 3 cm × 3 cm is set at a dot pitch of 20 microns on a 0.7 um thick glass substrate by an inkjet coater DMP-2831 manufactured by FUJIFILM Dimatix. Was produced. After ink jet printing, the film was dried at 80 ° / 5 for 5 minutes and baked at 160 ° for 1 hour to produce a cured film. If a cured film could be produced, it was rated ○, otherwise it was rated x.

<Ink jet (IJ) ejection performance>
After 1 minute of discharging by the ink jet and then stopping for 10 minutes, the dischargeability of the ink discharged from the nozzle at the time of discharging again was evaluated.
If ink can be ejected from all (16) nozzles without cleaning the head ◎, if ink can be ejected from all the nozzles after cleaning ○, one or more nozzles that can not eject ink after cleaning If there is, it is considered as x.

<Adhesiveness>
A square (3 cm × 3 cm) cured film was formed on each of the glass substrate, the Si substrate, and the SiO ₂ substrate, and the adhesion of the cured film to each substrate was evaluated using the cross cut method.
In the cross-cut method, 11 lines of 1 mm intervals are drawn by a cutter with a cutter to make 100 grids, and then the ratio of the cured film peeled from the substrate surface is obtained by sticking and peeling a tape based on ASTM D3359. It evaluated.
The peeling tape is NITTO TAPE No. 31B: 7.5 N / 19 mm was used.
The evaluation criteria based on ASTMD3359 are as follows.
0B: 65% or more 1B: 35% or more, 65% or less 2B: 15% or more, 35% or less 3B: 5% or more, 15% or less 4B: 5% or less 5B: no peeling

Example 1
The thermosetting resin composition PSQ1 (hereinafter referred to as "PSQ1") was dissolved in solvent: methyl 2-hydroxyisobutyrate (HBM) at a weight ratio shown in the following table. The viscosity of the obtained ink 1 was 8.3 mPa · s.
Whether or not the film formation by spin coating application and ink jet printing was possible, the ink jettability, and the adhesion of the cured film to the substrate were evaluated using the test method described above.

Example 2
PSQ1 was dissolved in solvent: 1-methoxy-2-propanol (PGM) in the weight ratio indicated in the table below. The viscosity of the obtained ink 2 was 5.7 mPa · s.
The same evaluation was performed under the same conditions as in Example 1 except that Ink 2 was used.

[Example 3]
PSQ1 was dissolved in solvent: cyclopentyl methyl ether (CPME) in the weight ratio indicated in the table below. The viscosity of the obtained ink 3 was 2.0 mPa · s.
The same evaluation was performed under the same conditions as in Example 1 except that the ink 3 was used.

Example 4
PSQ1 was dissolved in solvent: t-amyl alcohol (t-Amyl OH) in the weight ratio shown in the following table. The viscosity of the obtained ink 4 was 10.3 mPa · s.
The same evaluation was performed under the same conditions as in Example 1 except that the ink 4 was used.

[Example 5]
The thermosetting resin composition PSQ2 (hereinafter referred to as "PSQ2") was dissolved in solvent: methyl 2-hydroxyisobutyrate (HBM) at a weight ratio shown in the following table. The viscosity of the obtained ink 5 was 8.9 mPa · s.
The same evaluation was performed under the same conditions as in Example 1 except that the ink 5 was used.

[Example 6]
PSQ2 was dissolved in solvent: 1-methoxy-2-propanol (PGM) in the weight ratio indicated in the table below. The viscosity of the obtained ink 6 was 6.2 mPa · s.
The same evaluation was performed under the same conditions as in Example 1 except that the ink 6 was used.

[Example 7]
PSQ2 was dissolved in solvent: cyclopentyl methyl ether (CPME) in the weight ratio indicated in the table below. The viscosity of the obtained ink 7 was 2.3 mPa · s.
The same evaluation was performed under the same conditions as in Example 1 except that the ink 7 was used.

Example 8
PSQ1 was dissolved in a mixed solvent consisting of methyl 2-hydroxyisobutyrate (HBM) and 1-propanol (NPA) at the weight ratios shown in the following table. The viscosity of the obtained ink 15 was 6.1 mPa · s.
The same evaluation was performed under the same conditions as in Example 1 except that the ink 15 was used.

[Example 9]
PSQ1 was dissolved in a mixed solvent consisting of methyl 2-hydroxyisobutyrate (HBM) and 2-propanol (IPA) at the weight ratios shown in the following table. The viscosity of the obtained ink 16 was 6.0 mPa · s.
The same evaluation was performed under the same conditions as in Example 1 except that the ink 16 was used.

Comparative Example 1
PSQ1 was dissolved in solvent: triethylene glycol dimethyl ether (MTM) in the weight ratio indicated in the table below. The viscosity of the obtained ink 8 was 6.1 mPa · s.
A pattern of 3 cm × 3 m was produced under the same conditions as in Example 1 except that the ink 8 was used, and the evaluation was performed. In both the spin coating method and the inkjet printing, the ink 8 flowed and was repelled from the glass substrate surface during drying at 80 ° C., and a film could not be formed after drying.

Comparative Example 2
PSQ1 was dissolved in solvent: ethyl 2-hydroxybutyrate (HBE) in the weight ratio indicated in the table below. The viscosity of the obtained ink 9 was 6.8 mPa · s.
The film was produced by spin coating using the ink 9. However, the ink 9 flowed and was repelled from the surface of the glass substrate during drying at 80 ° C. after coating, and the film could not be formed after drying. The application by the ink jet method was not considered.

Comparative Example 3
PSQ1 was mixed with solvent: methyl lactate (ML) in the weight ratio shown in the table below. However, PSQ1 did not dissolve in methyl lactate. The ink 10 became cloudy and was not ready for use as an inkjet ink.

Comparative Example 4
PSQ1 was mixed with solvent: ethyl lactate (EL) in the weight ratio shown in the table below. However, PSQ1 did not dissolve in ethyl lactate. The ink 11 became cloudy and was not ready for use as an inkjet ink.

Comparative Example 5
PSQ1 was mixed with solvent: 1,4-butanediol (14BG) in the weight ratio shown in the table below. PSQ1 did not dissolve in 1,4-butanediol. The ink 12 was phase separated, and was not ready for use as an inkjet ink.

Comparative Example 6
PSQ1 was dissolved in solvent: toluene at the weight ratio shown in the table below. The viscosity of the obtained ink 13 was 2 mPa · s.
The film was produced by spin coating using the ink 13. However, at the time of application, the ink 13 was repelled from the substrate surface, and a film could not be formed. Therefore, the application of the ink 13 by inkjet printing was not considered.

Comparative Example 7
PSQ1 was dissolved in solvent: propylene glycol 1-monomethyl ether 2-acetate (PGMEA) in the weight ratio shown in the following table. The viscosity of the obtained ink 14 was 3.7 mPa · s.
Ink 14 was used to make a film by spin coating, but during drying at 80 ° C., the ink 14 flowed and was repelled from the substrate surface, and the film could not be formed after drying. Application of the ink 14 by inkjet printing was not considered.

The evaluation results of the example and the comparative example are shown in the following table.

  A thermosetting resin composition containing a thermosetting resin having a polysilsesquioxane structure has a high viscosity and can not be used as it is for an ink jet ink. Therefore, the solvent was used for dilution to prepare an inkjet ink. However, depending on the solvent to be used, clouding or phase separation occurs, and it can not be used as an inkjet ink. In addition, the ink 13 of Comparative Example 6 using toluene as a dilution solvent caused repulsion when applied to a substrate, and could not form a film. Note that "repelling" means that the film on the substrate flows to form an island. In the inks 8, 9 and 14 of Comparative Examples 1, 2 and 7, when the film formed by the inkjet is dried at 80 ° C., after the film flows, repulsion occurs and it can not be made a dry film The

In any of the inkjet inks of Examples 1 to 9, the films formed by the inkjet printing did not cause repulsion or fluidization, and the films were cured to form a cured film. From this result, it can be said that using a polar solvent having a polar group such as a hydroxy group or a methoxy group is effective for forming a cured film.
The ink 1 of Example 1 (HBM: methyl 2-hydroxyisobutyrate) could form a cured film, while the ink 9 of Comparative Example 2 (HBE: ethyl 2-hydroxyisobutyrate) could form a cured film. It was not. From this result, it is understood that the difference in the polarity and the boiling point of the solvent affects the possibility of the formation of the cured film.

  From the measurement results of the contact angles of the inks of Examples and Comparative Examples shown in Table 19 with respect to the glass substrate, in order to stably form a cured film by inkjet printing, the contact to the surface of the object forming the cured film It is preferable to use an ink having a corner of 15 degrees or more.

The inkjet ink of the present invention can form a cured film on a substrate, and the cured film can be used as a sealant for electronic components.

Claims (16)

In an inkjet ink comprising a thermosetting resin having a silsesquioxane structure, and a solvent for dissolving the thermosetting resin,
The said solvent has a hydroxyl group and / or a methoxy group, and the boiling point is 143 degrees C or less, The inkjet ink characterized by the above-mentioned. The thermosetting resin is
(A) A reaction product of a silsesquioxane having an SiH group and an organopolysiloxane having two alkenyl groups, the thermosetting resin A containing an SiH group and an alkenyl group, and (B) an SiH group A thermosetting resin B having a SiH group, which is a reaction product of a silsesquioxane having one or two organopolysiloxanes having two alkenyl groups, an epoxy compound having one or more alkenyl groups, and a silyl compound having one or more alkenyl groups; The ink according to claim 1, wherein the ink is contained.   The inkjet ink according to claim 2, wherein the silsesquioxane in the thermosetting resins A and B is a double decker silsesquioxane. The ink according to claim 3, wherein the thermosetting resin A is a compound represented by the following formula (1).
In Formula (1), each X independently
A compound represented by the following formula (X-I), formula (X-II) or formula (X-III), and one compound represented by the formula (1) [wherein the compound is a formula (X-I) When it is a mixture of compounds in which the proportions of the group represented by and the group represented by the formula (X-II) and the group represented by the formula (X-III) are different, per compound average of the compound]
The number of groups represented by formula (X-I) is a,
The number of groups represented by formula (X-II) is b,
When the number of groups represented by formula (X-III) is c, a + 2b + c = 4, 0 <a ≦ 3, 0 ≦ b ≦ 1, and 0 <c ≦ 3.
R ¹ is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and m is an average value of the number of repetitions and satisfies 1 to 100.
In formula (X-II), R ² and R ³ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is -OSi (R ³ ) _2- The average value of the number of repetitions of, and satisfies 2 to 20.

In formula (X-III), R ⁴ and R ⁵ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and s is —OSi (R ⁵ ) ₂ — The average value of the number of repetitions of, and satisfies 2 to 20. The ink for ink jet recording according to any one of claims 2 to 4, wherein the thermosetting resin B is a compound represented by the following formula (B1).
In Formula (B1), X's are each independently the following Formula (a), Formula (b), Formula (c-i), Formula (c-ii), Formula (c-iii), Formula (d) -I) a compound represented by the formula (d-ii) or the formula (d-iii), and one compound represented by the formula (1) [wherein the compound is represented by the group represented by the formula (a) When it is a mixture of compounds in which the proportions of groups represented by formulas (b) to (d-iii) are different, the average per molecule of the compound]
The number of groups represented by the following formula (a) is A,
The number of groups represented by the following formula (b) is B,
The number of groups represented by the following formula (ci), formula (c-ii) or formula (c-iii) is C,
When the number of groups represented by the following formula (d-i), formula (d-ii) or formula (d-iii) is D, A + 2B + C + D = 4, and 0.5 ≦ A ≦ 3. 0, 0.5 ≦ 2B ≦ 2.0, 0.1 ≦ C ≦ 2.0, and 0 ≦ D ≦ 1.0.
In formula (B1), R ¹ is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and m ′ is an average value of the number of repetitions, and satisfies 1 to 100.

In formula (b), R ^{2 ′} and R ^{3 ′} are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and t is —OSi (having 1 to 20) R3 ^' ) It is an average value of the number of repetition of _2- .
In formulas (di) to (d-iii), R ⁴ , R ^{4 ′} and R ^{4 ′ ′} are each independently a group selected from methyl, ethyl, butyl and isopropyl. x is an average value of the number of repetitions of -OSi (R ^{4 '} ) _2- satisfying 1 to 20. y is an average value of the number of repetitions of -OSi (R ^{4 "} ) _2- and satisfies 1 to 10. The ink for ink jet recording according to any one of claims 2 to 4, wherein the thermosetting resin B is a compound represented by the following formula (B2).
In formula (B2), Me is a methyl group, and R ′ ′ each independently is a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is an integer of 0 to 100 It is. aii is 0.1 ≦ aii ≦ 3.5, Xii is 0 ≦ 2Xii ≦ 2.0, Yii is 0 ≦ Yii ≦ 3.0, and Zii is 0.1 ≦ Zii ≦ 3.5.   The solvent contains one or more selected from the group consisting of methyl 2-hydroxyisobutyrate, propylene glycol monomethyl ether, cyclopentyl methyl ether, t-amyl alcohol, 1-propanol, 2-propanol and 2-butanol The ink for inkjet according to any one of claims 1 to 6.   The boiling point of the said solvent is 80 degreeC or more and 140 degrees C or less, The ink for inkjet as described in any one of Claims 1-7.   The ink for inkjet according to any one of claims 1 to 8, which contains a Pt catalyst. The ink for ink jet recording according to any one of claims 1 to 9, which contains one or more of the following groups (C), (E) and (F).
(C) A linear organopolysiloxane compound C having an SiH group only at one end
(E) Organopolysiloxane compound E having two or more alkenyl groups
(F) Silane coupling agent having an epoxy group The ink for inkjet according to claim 10, wherein the organopolysiloxane compound C is a compound represented by the following formula (2).
R ⁶ and R ⁷ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and m is an average value of the number of repeating -Si (R ⁷ ) ₂ O- , Meet 1-20. The inkjet ink according to claim 10, wherein the organopolysiloxane compound E is a compound represented by the following formula (3).
In formula (3), R ⁸ and R ⁹ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and n is a repeat of —OSi (R ⁹ ) ₂ — The average value of the number of and satisfies 1 to 50. The ink for ink jet recording according to any one of claims 10 to 12, wherein the silane coupling agent having an epoxy group is a compound represented by the following formula (4).
In formula (4), each R ¹⁰ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl or cyclohexyl.   The cured film obtained by printing the ink for inkjets as described in any one of Claims 1-13 by the inkjet printing method.   A substrate on which the cured film according to claim 14 is formed. An electronic component comprising the substrate according to claim 15.