Liquid spray head and two-part adhesive

Abstract

To provide a liquid spray head having a cured adhesive product that has a low environmental impact, is fast-curing, and acid-resistant. [Solution] The liquid spray head is a liquid spray head that sprays liquid from a nozzle and comprises a first member, a second member, and a cured product of a two-component mixed adhesive that adheres the first member and the second member. The two-component mixed adhesive comprises liquid A, which contains a main component including an epoxy resin that does not contain bisphenol; liquid B, which contains at least one of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane and an alkylphenol; and a polymer of an aromatic amine contained in liquid A or liquid B. The alkylphenol is (a) an alkylphenol having at least one ethyl group, or (b) an alkylphenol having 1 to 3 carbon atoms in the alkyl group and at least one methyl group and one isopropyl group.

Description

Technical Field

[0001] The present disclosure relates to a liquid ejection head and a two-component mixed adhesive.

Background Art

[0002] Conventionally, resin materials have been used in the manufacture of liquid ejection heads. For example, in Patent Document 1, in order to seal an electrical connection portion between a recording element substrate including a discharge energy generation element that discharges a liquid and an electrical wiring member for transmitting a signal to the recording element substrate, a sealing agent, which is a resin material, is used. In Patent Document 1, it is described that a bisphenol type epoxy resin can be used as the main component and an aliphatic amine can be used as the curing agent for this sealing agent. Although Patent Document 1 shows a specific example in which a resin material is used as a sealing agent, the use of such a resin material is not limited to a sealing agent and can also be used as, for example, an adhesive.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] By the way, in the adhesive used for a liquid ejection head, it is required to have high liquid resistance such as acid resistance with respect to the liquid to be ejected, and to cure quickly so that the adhesive applied to bond the members constituting the liquid ejection head does not move from the applied position during high-temperature curing.

[0005] However, conventional epoxy adhesives use highly reactive bisphenol-type epoxy resins as the main component and highly reactive aliphatic amines as the curing agent. While these adhesives exhibit rapid curing properties, their acid resistance is insufficient. Furthermore, the use of bisphenol is undesirable from an environmental perspective.

[0006] As described above, there is a need for an adhesive that reduces environmental impact, has high acid resistance, and cures quickly so that the adhesive applied to bond the components of a liquid spray head does not move from its applied position during high-temperature curing. Of course, similar challenges exist for components other than liquid spray heads that need to meet the aforementioned requirements. [Means for solving the problem]

[0007] According to one embodiment of the present disclosure, a liquid spray head is provided for spraying a liquid from a nozzle. The liquid spray head comprises a first member, a second member, and a cured product of a two-component mixed adhesive for bonding the first member and the second member, wherein the two-component mixed adhesive comprises: a liquid A containing a main component including an epoxy resin that does not contain bisphenol; a liquid B containing at least one of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane and an alkylphenol; and a polymer of an aromatic amine contained in the liquid A or the liquid B, wherein the alkylphenol is (a) an alkylphenol having at least one ethyl group, or (b) an alkylphenol having 1 to 3 carbon atoms in the alkyl group and at least one methyl group and one isopropyl group. [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic diagram showing the general configuration of the liquid injection device in the embodiment. [Figure 2] This is a perspective view of the head module. [Figure 3] This is a disassembled perspective view of the liquid spray head. [Figure 4] It is a sectional view taken along line IV-IV of FIG. 3. [Figure 5] It is a sectional view of the injection unit. [Figure 6] It is a diagram showing a list of components used in the experiment. [Figure 7] It is a diagram showing chemical formulas (f1) to (f3). [Figure 8] It is a diagram for explaining Evaluation A. [Figure 9] It is a diagram for explaining Evaluation B. [Figure 10] It is a diagram showing the equivalence ratio and mass ratio of Experiment 1. [Figure 11] It is a diagram summarizing the evaluation results of each of Experiments 1 to 3. [Figure 12] It is a diagram showing the equivalence ratio and mass ratio of Experiment 2. [Figure 13] It is a diagram showing the equivalence ratio and mass ratio of Experiment 3. [Figure 14] It is a diagram showing the equivalence ratio and mass ratio of Experiment 4. [Figure 15] It is a diagram summarizing the evaluation results of Experiments 4 to 7. [Figure 16] It is a diagram showing the equivalence ratio and mass ratio of Experiment 5. [Figure 17] It is a diagram showing the equivalence ratio and mass ratio of Experiment 6. [Figure 18] It is a diagram showing the equivalence ratio and mass ratio of Experiment 7. [Figure 19] It is a diagram showing the equivalence ratio and mass ratio of Experiment 8. [Figure 20] It is a diagram summarizing the evaluation results of Experiments 8 to 11. [Figure 21] It is a diagram showing the equivalence ratio and mass ratio of Experiment 9. [Figure 22] It is a diagram showing the equivalence ratio and mass ratio of Experiment 10. [Figure 23] It is a diagram showing the equivalence ratio and mass ratio of Experiment 11. [Figure 24] It is a diagram showing the equivalence ratio and mass ratio of Experiment 12. [Figure 25]It is a diagram showing the evaluation results of Experiment 12 and Experiment 13 together. [Figure 26] It is a diagram showing the equivalence ratio and mass ratio of Experiment 13.

Mode for Carrying Out the Invention

[0009] A. Embodiment: A1. Overall Configuration of Liquid Injection Device: FIG. 1 is a schematic diagram showing the schematic configuration of a liquid injection device 100 in an embodiment. The liquid injection device 100 is an inkjet printing device that performs printing by injecting droplets of ink as a liquid onto a medium 12. The medium 12 can adopt a printing target of any material such as resin film or cloth in addition to printing paper. In the following description, the X direction, Y direction, and Z direction that are orthogonal to each other are used. Also, when specifying the direction, the positive direction is denoted as "+", the negative direction is denoted as "-", and the positive and negative signs are used together in the direction notation. In the present embodiment, the X direction is the main scanning direction which is the moving direction of the liquid injection head 30. The Y direction is the sub-scanning direction which is the medium feeding direction orthogonal to the main scanning direction. The -Z direction is the ink injection direction. In the following description, the +Z direction may be referred to as up and the -Z direction may be referred to as down.

[0010] The liquid injection device 100 includes a head module 3, a head moving mechanism 20, a plurality of liquid storage parts 14, a plurality of sub-tanks 15, a conveying mechanism 16, and a control part 80. The head module 3 has a plurality of liquid injection heads 30.

[0011] Each liquid storage part 14 stores the ink supplied to the head module 3. As the liquid storage part 14, a bag-shaped liquid pack formed of a flexible film, an ink tank capable of ink replenishment, a detachable ink cartridge, etc. can be used.

[0012] Water-based pigment inks, solvent inks, and UV-curing inks can be used as inks. Furthermore, when using cloth as the medium 12, acidic pre-treatment inks containing organic acids such as citric acid, malic acid, and malonic acid may be used. When this pre-treatment ink is dispensed onto the cloth, it reacts with the subsequent colorant ink, specifically causing the dyes and pigments to agglomerate. Therefore, the pre-treatment ink has the effect of suppressing the penetration of the colorant ink and preventing the colorant from bleeding.

[0013] Each sub-tank 15 is connected to the liquid storage unit 14 by a tube through which ink flows. Each sub-tank 15 is also connected to the head module 3 by a first tube for supplying ink to the head module 3 and a second tube for returning ink from the liquid spray head 30 to the sub-tank 15. Ink is supplied to each sub-tank 15 from the liquid storage unit 14 and returned from the head module 3. Thus, ink circulates between the sub-tank 15 and the head module 3.

[0014] The following description illustrates a case where the liquid injection device 100 comprises two liquid storage sections 14 and two sub-tanks 15. In this embodiment, each of the two liquid storage sections 14 contains ink of a different color. To distinguish between these two inks, the ink contained in one liquid storage section 14 is called the first ink, and the ink contained in the other liquid storage section 14 is called the second ink. The liquid injection device 100 may have one liquid storage section 14 or three or more. Furthermore, the inks contained in each of the two liquid storage sections 14 may be the same color.

[0015] The head module 3 has a plurality of nozzles N, which will be described later, for ejecting ink. The head module 3 ejects ink supplied from the liquid storage unit 14 from the plurality of nozzles N toward the medium 12.

[0016] The head movement mechanism 20 comprises a conveyor belt 21 and a carriage 22 that houses the head module 3. The carriage 22 is connected to the conveyor belt 21 and reciprocates in the X direction as the conveyor belt 21 is driven. The conveying mechanism 16 conveys the medium 12 in the +Y direction.

[0017] The control unit 80 includes processing circuits such as one or more CPUs (Central Processing Units) and FPGAs (Field Programmable Gate Arrays), and storage circuits such as semiconductor memory, and controls the operation of the entire liquid injection device 100. The control unit 80 is electrically connected to the transport mechanism 16, the head movement mechanism 20, and the liquid injection head 30, and controls each part. An image is printed on the medium 12 when liquid from the nozzle N is injected onto the medium 12 transported by the transport mechanism 16.

[0018] Figure 2 is a perspective view of the head module 3. As shown in Figure 2, the head module 3 has a support 301 and a plurality of liquid injection heads 30. In this embodiment, the head module 3 has eight liquid injection heads 30. However, the number of liquid injection heads 30 in the head module 3 is not limited to eight; for example, it may be one.

[0019] The support 301 is a plate-shaped member that supports multiple liquid spray heads 30. The support 301 has multiple mounting holes 302. Each liquid spray head 30 is supported by the support 301 while fitted into a mounting hole 302. The multiple liquid spray heads 30 are arranged in a matrix.

[0020] A2. Configuration of the liquid spray head: Figure 3 is an exploded perspective view of the liquid injection head 30. Figure 4 is a cross-sectional view taken along line IV-IV in Figure 3. Line IV-IV passes through the center of the first through-hole 322 of the holder, which will be described later. As shown in Figure 3, the liquid injection head 30 includes a cover member 31, a holder member 32, a flow path structure 33, a fixing plate 36, a reinforcing plate 37, a plurality of injection units 26, a wiring board 381, a wiring member 382, ​​a first circuit board 383u, and a second circuit board 383v. In this embodiment, the liquid injection head 30 has four injection units 26.

[0021] The fixing plate 36 is a plate member for fixing a plurality of injection units 26 to the holder member 32. In this embodiment, the material of the fixing plate 36 is stainless steel. The fixing plate 36 has a plurality of openings 361 for exposing the nozzles N formed on the lower surface of each injection unit 26.

[0022] The reinforcing plate 37 is a plate member for reinforcing the fixing plate 36. In this embodiment, the material of the reinforcing plate 37 is stainless steel. The reinforcing plate 37 is fixed to the fixing plate 36 by a cured adhesive GL, which will be described later. Similar to the fixing plate 36, the reinforcing plate 37 has a plurality of openings 371 for exposing the nozzles N formed on the lower surface of each injection unit 26.

[0023] The injection unit 26 includes the nozzle N described above, a case first supply pipe 336a, a case first discharge pipe 337a, a case second supply pipe 336b, and a case second discharge pipe 337b. Details of the injection unit 26 will be described later.

[0024] The holder member 32 has a plurality of housing sections 321, a plurality of first holder through holes 322, and a plurality of second holder through holes 323. The material of the holder member 32 is a metal, such as stainless steel. Each housing section 321 is formed to protrude downward from the plate-shaped flange 324 of the holder member 32. The lower side of each housing section 321 is open. An injection unit 26 is housed in each housing section 321. Each first holder through hole 322 is a through hole for inserting one of the case first supply pipe 336a, case first discharge pipe 337a, case second supply pipe 336b, or case second discharge pipe 337b of the injection unit 26. Each second holder through hole 323 is a through hole for inserting a flexible substrate 51a, which will be described later.

[0025] The flow channel structure 33 includes a laminate 333, a first supply upper connection 331a, a first discharge upper connection 332a, a second supply upper connection 331b, and a second discharge upper connection 332b. The laminate 333 is composed of multiple flow channel members Su stacked together. Each flow channel member Su communicates with the nozzle and defines a structural flow channel Sn, which will be described later, through which liquid flows.

[0026] As shown in Figure 4, the laminate 333 is constructed by bonding two adjacent flow channel members Su together with a cured adhesive GL. In this embodiment, the material of each flow channel member Su is resin.

[0027] The laminate 333 has a structural flow path Sn formed therein for circulating ink between the sub-tank 15 and the injection unit 26. The structural flow path Sn includes a first supply flow path S1a, a first discharge flow path S2a, a second supply flow path S1b, and a second discharge flow path S2b. The first supply flow path S1a and the first discharge flow path S2a are flow paths for circulating the first ink. The second supply flow path S1b and the second discharge flow path S2b are flow paths for circulating the second ink. The first supply flow path S1a and the second supply flow path S1b are flow paths for circulating ink from the sub-tank 15 towards the injection unit 26. The first discharge flow path S2a and the second discharge flow path S2b are flow paths for circulating ink from the injection unit 26 towards the sub-tank 15.

[0028] Each structural channel Sn is composed of a groove formed on the upper or lower surface of each channel member Su and a through hole that penetrates in the thickness direction of each channel member Su. Note that in Figure 4, the structural channel Sn is shown in a simplified form.

[0029] As shown in Figure 3, the first supply upper connection 331a, the first discharge upper connection 332a, the second supply upper connection 331b, and the second discharge upper connection 332b are provided on the upper surface of the laminate 333. Each of the first supply upper connection 331a, the first discharge upper connection 332a, the second supply upper connection 331b, and the second discharge upper connection 332b is connected to the first supply channel S1a, the first discharge channel S2a, the second supply channel S1b, and the second discharge channel S2b of the laminate, respectively.

[0030] The wiring board 381 and wiring member 382 are mounting components for electrically connecting the control unit 80 and the injection unit 26. Wiring and other connections are formed on the wiring board 381. The wiring member 382 is a connector to which a signal cable (not shown) is connected. Electronic circuits are formed on the first circuit board 383u and the second circuit board 383v. The first circuit board 383u and the second circuit board 383v are electrically connected to the wiring board 381.

[0031] The cover member 31 houses the laminate 333, the wiring board 381, the wiring member 382, ​​the first circuit board 383u, and the second circuit board 383. For the material of the cover member 31, for example, resin or metal can be used. The cover member 31 has two first connection holes 311, two second connection holes 312, and a first hole 313. The first hole 313 is for inserting the wiring member 382. A first supply upper connection 331a or a second supply upper connection 331b is inserted through each of the two first connection holes 311. A first discharge upper connection 332a or a second discharge upper connection 332b is inserted through each of the two second connection holes 312.

[0032] The materials for the cover member 31 and the holder member 32 are not limited to those described above. For example, the material for the holder member 32 may be resin. Also, the materials for the cover member 31 and the holder member 32 may be, for example, carbon steel or a material that combines resin and metal.

[0033] As shown in Figure 4, the laminate 333, the wiring member 382, ​​the first circuit board 383u, and the second circuit board 383v are housed inside the cover member 31. The spray unit 26 is housed inside the holder member 32. A fixing plate 36 and a reinforcing plate 37 are placed below the holder member 32. The reinforcing plate 37, the fixing plate 36, and the holder member 32 are bonded together with the cured adhesive GL. The spray unit 26 is fixed to the holder member 32 by bonding the fixing plate 36, which supports the spray unit 26 from below, to the holder member 32. The cover member 31, which houses the above-mentioned components, and the holder member 32, which houses the above-mentioned components, are connected to assemble the liquid spray head 30.

[0034] The flow channel structure 33 further includes a first supply lower connection (not shown), a first discharge lower connection 342a, a second supply lower connection (not shown), and a second discharge lower connection 342b. The first supply lower connection, the first discharge lower connection 342a, the second supply lower connection, and the second discharge lower connection 342b are tubes having flow channels for ink and are formed protruding from the lower surface of the lowest flow channel member Su of the laminate 333. Each of the flow channels of the first supply lower connection, the first discharge lower connection 342a, the second supply lower connection, and the second discharge lower connection 342b communicates with the first supply flow channel S1a, the first discharge flow channel S2a, the second supply flow channel S1b, and the second discharge flow channel S2b of the laminate, respectively.

[0035] As shown in an enlarged view in Figure 4, the flow channel member Su of the lowest layer of the laminate 333 and the upper surface of the holder member 32 are bonded together by the cured adhesive GL. Also, the second discharge lower connection part 342b and the case second discharge pipe 337b are bonded together by the cured adhesive GL. The other connection parts, the first supply lower connection part (not shown), the first discharge lower connection part 342a, and the second supply lower connection part (not shown), are similarly bonded together by the cured adhesive GL to the case first supply pipe 336a, the case first discharge pipe 337a, and the case second discharge pipe 337b, respectively.

[0036] A3. Configuration of the injection unit: Figure 5 is a cross-sectional view of the injection unit 26. As shown in Figure 5, the injection unit 26 includes a nozzle plate 62, two flow path sealing members 64, a flow path substrate 53, a pressure chamber substrate 34, a diaphragm 54, a sealant 46, a housing portion 48, and a flexible substrate 51a. The nozzle plate 62, flow path sealing members 64, flow path substrate 53, pressure chamber substrate 34, diaphragm 54, and sealant 46 are elongated plate-shaped members in the Y direction. Each of the nozzle plate 62, flow path substrate 53, pressure chamber substrate 34, diaphragm 54, and sealant 46 has a structure that is substantially symmetrical with respect to the center line in the X direction. The planar shapes of the pressure chamber substrate 34, diaphragm 54, and sealant 46 are smaller than the planar shapes of the flow path substrate 53 and the housing portion 48. During assembly, the nozzle plate 62, the two flow path sealing members 64, the flow path substrate 53, the pressure chamber substrate 34, the diaphragm 54, the sealing body 46, and the housing portion 48 are stacked in this order and bonded to each other with a cured adhesive GL (not shown).

[0037] The nozzle plate 62 is a plate-shaped member on which multiple nozzles N are formed. Each nozzle N is a through-hole with a substantially circular planar shape. The multiple nozzles N are arranged along the Y direction. There are two rows of nozzles N, and these two rows are aligned in the X direction. The two flow path sealing members 64 are positioned in the X direction, flanking the nozzle plate 62.

[0038] The flow channel substrate 53 has two first openings 32a, a plurality of second openings 32b, and a plurality of third openings 32c. The planar shape of the first openings 32a is a rectangle that is elongated in the Y direction. The first openings 32a are formed along the side of the flow channel substrate 53 that is parallel to the Y direction. The plurality of second openings 32b are arranged in the Y direction. Similarly, the plurality of third openings 32c are arranged in the Y direction. There are two rows of second openings 32b and two rows of third openings 32c. In the X direction, the first openings 32a, a row of one second opening 32b, a row of one third opening 32c, a row of one third opening 32c, a row of one second opening 32b, and the first opening 32a are formed in this order. Furthermore, adjacent second openings 32b and third openings 32c in the X direction are formed so that their positions in the Y direction are approximately identical.

[0039] Multiple openings 34a are formed in the pressure chamber substrate 34. The planar shape of the openings 34a is a rectangle that is elongated in the X direction. The multiple openings 34a are arranged in the Y direction. There are two rows in which the multiple openings 34a are arranged, and these two rows are formed side by side in the X direction. The openings 34a are formed in a position that overlaps with the adjacent second opening 32b and third opening 32c formed in the flow channel substrate 53 when viewed from the Z direction.

[0040] A piezoelectric element 44 is formed on the diaphragm 54 at a position that overlaps with an opening 34a formed in the pressure chamber substrate 34 when viewed from the Z direction. The seal 46 reinforces the strength of the pressure chamber substrate 34 and the diaphragm 54 and protects the piezoelectric element 44. The seal 46 has a seal opening 46a. The planar shape of the seal opening 46a is a rectangle that is elongated in the Y direction.

[0041] The first circuit board 383u or the second circuit board 383v and the piezoelectric element 44 are electrically connected via the flexible substrate 51a.

[0042] The housing portion 48 is a case for storing ink and has a frame shape. The material of the housing portion 48 is resin. When laminated, the pressure chamber substrate 34, the diaphragm 54, and the sealing body 46 are arranged in the internal space of the housing portion 48. Through holes 48a are formed at each of the ends of the housing portion 48 in the X direction.

[0043] A space Rb extending in the Y direction is formed at each end of the housing portion 48 in the X direction. Space Rb communicates with the through hole 48a. Space Ra, the supply liquid chamber 26a, and the supply flow path 26b are formed by connecting the flow path substrate 53 and the flow path sealing member 64. Space Ra is the internal space of the first opening 32a. The supply liquid chamber 26a is the space enclosed by the partition wall 32d separating the first opening 32a and the second opening 32b, and the flow path sealing member 64. The supply flow path 26b is the internal space of the second opening 32b. Space Ra communicates with space Rb and the supply liquid chamber 26a, and the supply liquid chamber 26a communicates with the supply flow path 26b. A pressure chamber C is formed by connecting the pressure chamber substrate 34 and the diaphragm 54. The pressure chamber C is the space enclosed by the opening 34a and the diaphragm 54. The pressure chamber C is in communication with the supply channel 26b. The communication channel 26c is formed by the connection between the channel substrate 53 and the nozzle plate 62. The communication channel 26c is the internal space of the third opening 32c. The communication channel 26c is in communication with the pressure chamber C and the nozzle N.

[0044] Spaces Ra and Rb function as liquid storage chambers for storing ink supplied to the pressure chamber C. Space Rb communicates with multiple spaces Ra aligned in the Y direction, and the ink supplied through the through-hole 48a is stored in the multiple spaces Ra via space Rb. The ink stored in space Ra flows through the supply liquid chamber 26a and the supply channel 26b and is supplied to the pressure chamber C.

[0045] Each of the four through-holes 48a formed in the injection unit 26 defines one of the following: the flow path of the case first supply pipe 336a, the flow path of the case first discharge pipe 337a, the flow path of the case second supply pipe 336b, or the flow path of the case second discharge pipe 337b. As a result, the first ink is stored in one of the two spaces Rb formed in the injection unit 26. The second ink is stored in the other space Rb formed in the injection unit 26.

[0046] In a plan view from the Z direction, the piezoelectric element 44 is positioned to overlap with each of the two pressure chambers C. A drive signal and a reference voltage are input to the piezoelectric element 44 via the flexible substrate 51a. When the drive signal and reference voltage are input and voltage is applied, the piezoelectric element 44 deforms, and the diaphragm 54 vibrates in conjunction with the deformation of the piezoelectric element 44, causing the pressure in the pressure chamber C to fluctuate, which in turn causes ink to be ejected from the nozzle N.

[0047] A4. Details of the adhesive: As described above, adhesives are used at multiple locations in the manufacture of the liquid injection head 30. In this embodiment, for example, a two-component mixed adhesive, described later, is used to bond a stainless steel fixing plate 36 to a stainless steel reinforcing plate 37. In this embodiment, a two-component mixed adhesive, described later, is also used to bond a first flow path member Su, which is one of several flow path members Su, to a second flow path member Su that overlaps with the first flow path member Su. The structural flow path Sn defined in the first flow path member Su and the structural flow path Sn defined in the second flow path member Su are liquid-tightly connected by the cured adhesive GL. The first flow path member Su is an example of a "first member," and the second flow path member Su is an example of a "second member."

[0048] In the bonding process between the first flow channel member Su and the second flow channel member Su, adhesive is applied to at least one of the first or second flow channel member Su, and then cured at a high temperature. If the adhesive moves during this high-temperature curing, the adhesive will harden with an uneven film thickness. If the film thickness of the cured product GL is uneven, there is a risk of liquid leakage due to deterioration in the thinner areas. For this reason, the adhesive needs to harden quickly. Furthermore, acidic pre-treated inks are sometimes used as the ink. Therefore, there is a need for an acid-resistant cured product GL of the adhesive.

[0049] Furthermore, there is a demand for adhesives with a low environmental impact. For example, bisphenol A, which is used in the synthesis of glycidyl ether type epoxy resins commonly used as adhesives, and nonylphenol, which can be used as an adhesive accelerator, are known to have a high environmental impact. The inventors have discovered an adhesive that has a low environmental impact, cures quickly, and is acid-resistant.

[0050] Specifically, in this embodiment, the two-component mixed adhesive used for bonding the flow channel members Su together and the fixing plate 36 and the reinforcing plate 37 is a two-component mixed adhesive containing liquid A and liquid B. In the following description, the two-component mixed adhesive having the features of this application will be simply referred to as "adhesive" unless otherwise specified. Also, in the following description, liquid A, liquid B, main component, and curing agent will refer to liquid A, liquid B, main component, and curing agent constituting the two-component mixed adhesive having the features of this application, unless otherwise specified.

[0051] Solution A contains a main component which includes a bisphenol-free epoxy resin. A bisphenol-free epoxy resin refers to a resin in which bisphenol is not used in the synthesis of the epoxy resin. In this embodiment, the bisphenol-free epoxy resin is a tetrafunctional glycidylamine type epoxy resin, such as N,N,N',N'-tetraglycidyl-m-xylenediamine or 4,4'-methylenebis(N,N-diglycidylaniline).

[0052] Solution B contains at least one of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane and an alkylphenol. In this embodiment, the alkylphenol is (a) an alkylphenol having at least one ethyl group, or (b) an alkylphenol having 1 to 3 carbon atoms in the alkyl group and at least one methyl group and one isopropyl group. In this embodiment, (a) is an alkylphenol represented by the following formula (1), and (b) is an alkylphenol represented by the following formula (2). [ka] (However, R1, R2, and R3 in formula (1) represent hydrogen or an ethyl group, and at least one of R1, R2, and R3 represents an ethyl group.) [ka] (However, in formula (2), R1, R2, R3, R4, and R5 represent hydrogen or an alkyl group having 1 to 3 carbon atoms, at least one of R1, R2, R3, R4, and R5 represents a methyl group, and at least one of R1, R2, R3, R4, and R5 represents an isopropyl group.) In addition, in this embodiment, the alkylphenol represented by formula (1) is 4-ethylphenol, and the alkylphenol represented by formula (2) is carvacrol.

[0053] Furthermore, the two-component adhesive contains an aromatic amine polymer. In this embodiment, the aromatic amine polymer is contained in solution B. Also, in this embodiment, the aromatic amine polymer contains a 2-ethylaniline-formaldehyde polymer. The adhesive having the above characteristics has a low environmental impact, excellent acid resistance, and excellent rapid curing properties. Note that 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane are isomers and will be collectively referred to as bis(aminomethyl)norbornane in the following description.

[0054] Solution A contains a bisphenol-free epoxy resin as its main component. Therefore, it has a lower environmental impact compared to glycidyl ether-type epoxy resins, which contain bisphenol. For this reason, this adhesive is particularly useful when printing on a medium 12 used in food packaging materials using a liquid spray device 100.

[0055] Glycidylamine-type epoxy resins are known to have lower reactivity with amines compared to commonly used glycidyl ether-type epoxy resins. The inventors have found that by including bis(aminomethyl)norbornane and the phenol described in (a) or (b) above in solution B, the reactivity between solution B and the glycidylamine-type epoxy resin can be improved. This allows the curing reaction to proceed at a relatively low temperature. The curing temperature in this embodiment is approximately 80°C. When high temperatures are required for the curing reaction, stress may be generated in dissimilar materials after bonding, especially when bonding dissimilar materials with large differences in thermal expansion coefficients. However, since this adhesive undergoes a curing reaction at a relatively low temperature, stress generation in dissimilar materials after bonding can be reduced, even when bonding dissimilar materials. It is believed that bis(aminomethyl)norbornane contributes to the improvement in reactivity.

[0056] Generally, the viscosity of the amine contained in the curing agent is lower than that of the epoxy resin contained in the main component. If the difference in viscosity between the main component and the curing agent is large, the main component and the curing agent will be difficult to mix. Furthermore, if the difference in viscosity is large, the mixture of the main component and the curing agent may react immediately and gel, or a phenomenon called "skinning" may occur, where the surface hardens first, due to the difference in viscosity. In particular, the above phenomena are likely to occur when a curing agent with high reactivity with the main component is used. The inventors have found that a chemical reaction occurs when bis(aminomethyl)norbornane is added to the phenol of (a) or the phenol of (b) above. The inventors have found that if the curing agent contains a mixture of bis(aminomethyl)norbornane and the phenol of (a) or the phenol of (b) above, the above phenomena such as gelation can be made less likely to occur even when mixed with the main component. This is thought to be because the chemical reaction produces a product in which the highly active primary amine is reduced. Furthermore, the phenols in (a) or (b) above include several highly safe phenols, such as carvacrol. In other words, this adhesive is safer because it can be made with ingredients that do not contain reproductively toxic substances such as nonylphenol.

[0057] Furthermore, the adhesive contains a polymer of aromatic amines. This improves its acid resistance. Also, in this embodiment, since the polymer of aromatic amines is contained in solution B, solidification of solution A is suppressed even when solution A is stored at room temperature, allowing it to be stored at room temperature for a relatively long period of time. For example, as will be described later, if 3,4-dihydrocoumarin is contained in solution A, the epoxy resin, the polymer of aromatic amines, and the 3,4-dihydrocoumarins react, requiring refrigeration of solution A. Here, the inventors have found that if the polymer of aromatic amines is contained in solution B instead of solution A, the chemical reaction between the epoxy resin and 3,4-dihydrocoumarins becomes less likely to occur. Therefore, by containing the polymer of aromatic amines in solution B, it is possible to provide an adhesive that improves the acid resistance of the adhesive and allows solution A to be stored at room temperature.

[0058] Furthermore, in this embodiment, solution A contains 3,4-dihydrocoumarin. This improves acid resistance and enhances rapid curing.

[0059] Furthermore, in this embodiment, solution B contains a bisphenol-free epoxy resin or tyrosol. In this embodiment, the bisphenol-free epoxy resin is a tetrafunctional glycidylamine type epoxy resin, such as N,N,N',N'-tetraglycidyl-m-xylenediamine or 4,4'-methylenebis(N,N-diglycidylaniline). This increases the viscosity of solution B, making it easier to mix solution A and solution B.

[0060] Furthermore, in this embodiment, the ratio of the phenol equivalent of carvacrol to the amine equivalent of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in solution B is 0.35 or more and 0.70 or less. This makes it possible to provide an easy-to-handle adhesive, as will be described later in the experimental examples. Here, the amine equivalent can be calculated using the following formula (e1). The phenol equivalent can be calculated using the following formula (e2). Amine equivalent = Molecular weight of amine / Number of active hydrogen atoms in the amine ... (e1) Phenol equivalent = Molecular weight of phenol / Number of hydroxyl groups ... (e2) Furthermore, the epoxy equivalent, which will be discussed later, can be calculated using the following formula (e3). Epoxy equivalent = Molecular weight of epoxy resin / Number of epoxy groups ... (e3) Here, when solution B contains multiple amines, the "ratio of phenol equivalents to amine equivalents" means that solution B is prepared such that the total equivalent amount, obtained by summing the equivalent amounts of each amine, matches the mass of the amines calculated using the ratio (phenol equivalents / amine equivalents). Further details will be explained in the experimental examples described later.

[0061] Furthermore, in this embodiment, the ratio of the epoxy equivalent of the tetrafunctional glycidylamine-type epoxy resin contained in solution B to the amine equivalent of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in solution B is 0.14 or less. As a result, as will be described later in the experimental examples, solidification of solution B can be suppressed even when the components of solution B are mixed and then subjected to adduct treatment.

[0062] Furthermore, in this embodiment, the ratio of the epoxy equivalent of the tetrafunctional glycidylamine-type epoxy resin contained in solution B to the amine equivalent of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in solution B is 0.07 or higher. This makes it possible to provide an adhesive that is easy to mix between solution A and solution B, as will be described later in the experimental examples.

[0063] Furthermore, in this embodiment, the ratio of the amine equivalents of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in solution B to the amine equivalents of all amines contained in the two-component adhesive is 0.13 or more and 0.22 or less. This makes it possible to provide an adhesive with excellent acid resistance, as will be described later in the experimental examples.

[0064] As described above, the two-component mixed adhesive having the features described in this embodiment has a low environmental impact, cures quickly, and has excellent acid resistance. Because it cures quickly, the cured product GL of the two-component mixed adhesive can make the film thickness of the cured product GL that bonds the first flow channel member Su and the second flow channel member Su uniform, thereby improving the reliability of the liquid spray head 30. Furthermore, because it has acid resistance, even when acidic ink is used as the liquid flowing through the flow channel member Su, the deterioration of the cured product GL of the two-component mixed adhesive can be suppressed, improving the reliability of the liquid spray head 30. In addition, because it has a low environmental impact, printed materials printed using the liquid spray device 100 can be used with peace of mind. Furthermore, because it is easy to handle and has excellent storage properties, it can improve work efficiency in the manufacturing process of mixing liquid A and liquid B and applying them, and reduce the effort required for storage.

[0065] Furthermore, the two-component adhesive used in the manufacture of the liquid spray head 30 is not limited to the above embodiments. Specifically, the epoxy resin containing bisphenol as the main component is not limited to N,N,N',N'-tetraglycidyl-m-xylenediamine or 4,4'-methylenebis(N,N-diglycidylaniline). The phenol in (a) or (b) above is not limited to 4-ethylphenol or carvacrol. For example, as the phenol in (b), 2-hydroxyp-cymene, thymol, 3-hydroxyp-cymene, orthocymen-5-ol, etc., can be used. Even when these components are used, each of these components has the same chemical properties as the corresponding components in the above embodiments, so a two-component adhesive that exhibits the same effects as in the above embodiments can be produced.

[0066] Furthermore, solution B does not necessarily have to contain either a bisphenol-free epoxy resin or tyrosol. Also, the ratio of the phenol equivalent of carvacrol to the amine equivalent of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in solution B may be less than 0.35 and greater than 0.70. Also, the ratio of the epoxy equivalent of the tetrafunctional glycidylamine type epoxy resin contained in solution B to the amine equivalent of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in solution B may be greater than 0.14. Furthermore, the ratio of the epoxy equivalent of the tetrafunctional glycidylamine-type epoxy resin contained in Solution B to the amine equivalent of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in Solution B may be less than 0.07. Also, the ratio of the amine equivalents of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in Solution B to the amine equivalent of all amines contained in the two-component adhesive may be less than 0.13 and greater than 0.22. Regardless of the above ratio values, a two-component adhesive with excellent rapid curing properties and acid resistance can be produced.

[0067] B. Experimental Examples: B1. List of ingredients: Figure 6 shows a list of the components used in the experiment. Figure 7 shows the chemical structures of chemical formulas (f1) to (f3). In this specification, each component is identified using a unique designation.

[0068] The CAS registry number for component CA-1 is 63738-22-7. As shown in the chemical formula (f1) in Figure 7, component CA-1 is N,N,N',N'-tetraglycidyl-m-xylenediamine, an epoxy resin having four functional groups. In the experiment, TETRAD-X (registered trademark / product name) manufactured by Mitsubishi Gas Chemical Company, Inc. was used as component CA-1. The CAS registry number for component CA-2 is 28768-32-3. As shown in the chemical formula (f2) in Figure 7, component CA-2 is 4,4'-methylenebis(N,N-diglycidylaniline), an epoxy resin having four functional groups. In the experiment, ELM434VL (product name) manufactured by Sumitomo Chemical Co., Ltd. was used as component CA-2.

[0069] Component CB-1 is the alicyclic amine bis(aminomethyl)norbornane, with CAS registry number 56602-77-8. Component CB-1 is an isomer mixture containing 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane. In the experiment, the product manufactured by Tokyo Chemical Industry Co., Ltd. was used as component CB-1.

[0070] Component CC-1 is carvacrol, a phenol, with CAS registry number 499-75-2. In the experiment, a product manufactured by Tokyo Chemical Industry Co., Ltd. was used as component CC-1. Component CC-2 is 4-ethylphenol, a phenol, with CAS registry number 123-07-9. In the experiment, a product manufactured by Tokyo Chemical Industry Co., Ltd. was used as component CC-2. Component CC-3 is orthocymene-5-ol, a phenol, with CAS registry number 3228-02-2. In the experiment, a product manufactured by Tokyo Chemical Industry Co., Ltd. was used as component CC-3. Component CC-4 is thymol, a phenol, with CAS registry number 89-83-8. In the experiment, a product manufactured by Tokyo Chemical Industry Co., Ltd. was used as component CC-4.

[0071] The CAS registry number for component CD-1 is 69178-41-2. As shown in chemical formula (f3) in Figure 7, component CD-1 is a polymer of aromatic amines. In chemical formula (f3), n is an integer greater than or equal to 2. In the experiment, KAYAHARD® AA (product name), manufactured by Nippon Kayaku Co., Ltd., was used as component CD-1.

[0072] Component CE-1 is the lactone 3,4-dihydrocoumarin, with CAS registry number 119-84-6. In the experiment, a product manufactured by Tokyo Chemical Industry Co., Ltd. was used as component CE-1. Component CF-1 is the phenol tyrosol, with CAS registry number 501-94-0. In the experiment, a product manufactured by Tokyo Chemical Industry Co., Ltd. was used as component CF-1.

[0073] Component CG-1 is the aliphatic amine polyoxypropylenediamine, with CAS registry number 9046-10-0. In the experiment, the product manufactured by Mitsui Chemicals Fine, Inc. was used as component CG-1. Component CG-2 is the aromatic amine 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, with CAS registry number 19900-72-2. In the experiment, the product manufactured by Tokyo Chemical Industry Co., Ltd. was used as component CG-2.

[0074] The molecular weight, reactive groups, number of reactive groups, and equivalent weights of each component are shown in Figure 6. In each experiment described later, the mass was calculated using the equivalent weights shown in Figure 6 to obtain the desired equivalent ratio.

[0075] Experiments 1 through 13 were conducted to prepare cured products by changing the constituent components of liquid A and liquid B, as well as the equivalent ratio of the components contained in each liquid, and then to evaluate the cured products. The evaluations in the experiments included two evaluations: Evaluation A, which evaluates acid resistance, and Evaluation B, which evaluates rapid curing properties. Figure 8 is a diagram illustrating Evaluation A. Figure 9 is a diagram illustrating Evaluation B. Figures 10 through 26 summarize the components, their equivalent ratios and mass ratios, and the evaluation results for each experiment. Note that the mass ratio is equal to the mass of each component that satisfies the equivalent ratio when the total mass of all components is 100g. Note that the mass ratios shown in Figures 10 through 26 are substantially the same as the equivalent ratios. In this specification, mass ratios are also listed for reference.

[0076] B2. Explanation of Grade A: B2-1. Preparation of evaluation samples: First, a dumbbell-shaped hardened material was fabricated as shown in Figure 8. This dumbbell shape is based on the Japanese Industrial Standard JIS K 7139, Plastic - Test piece type CP. In detail of the fabrication method, a dumbbell-shaped mold was first created on a 3 mm thick PTFE (polytetrafluoroethylene) sheet using cutting.

[0077] Next, a mixture of liquid A and liquid B was prepared. Here, we will explain the method for preparing the cured product using Experiment 1 as an example. In this experiment, after preparing liquid A and liquid B separately, they were stored in the refrigerator or freezer. When preparing each experimental example, a method was adopted in which liquid A and liquid B were returned to room temperature and then mixed. When the components of liquid A are mixed, the rate of change, which is the rate of change of the viscosity of liquid A with respect to time, may become large due to the chemical reaction between the components. The same applies to liquid B. Therefore, a treatment is generally performed to allow the chemical reaction to proceed until the rate of change of viscosity becomes gradual. This treatment, in which the mixture of each component is left at the reaction temperature until the chemical reaction is mostly complete, is also called adduct treatment or aging treatment. By performing adduct treatment, even when liquid A and liquid B are returned to room temperature, abrupt changes in the viscosity of each liquid are less likely to occur, which has advantages such as enabling good mixing of liquid A and liquid B and subsequent coating work. In this experiment, both solution A and solution B were treated with adducts, followed by refrigeration or freezing.

[0078] To prepare solution A, first, component CA-1, which is an epoxy resin, and component CD-1, which is an amine, were mixed in the equivalent and mass ratios shown in Figure 10. Then, component CE-1 was added to this mixture, and the mixture was left to react at 85°C for 2 hours as an adduct treatment. After that, the prepared solution A was stored in a refrigerator or freezer.

[0079] To prepare solution B, component CA-1, which is an epoxy resin, and component CB-1, which is an amine, were mixed in the equivalent and mass ratios shown in Figure 8. After 30 minutes, component CC-1 was added to this mixture, and the mixture was left to react at 95°C for 30 minutes as an adduct treatment. After that, the prepared solution A was stored in the refrigerator or freezer.

[0080] As described above, after allowing both liquid A and liquid B to return to room temperature, they were mixed together. In this experiment, a method of refrigerating or freezing after duct treatment was used for preparing liquids A and B, but this method is not required. As mentioned above, the duct treatment is intended to improve workability, such as the mixing of liquids A and B, and omitting the duct treatment does not affect the properties of the adhesive, such as acid resistance and rapid curing. Furthermore, refrigerating or freezing liquids A and B is not essential. The purpose of refrigerating or freezing liquids A and B is to inhibit the progress of the chemical reactions between them. Therefore, if the prepared liquids A and B are mixed early, or if liquid A or B has low reactivity even at room temperature, refrigeration or freezing is not necessary.

[0081] Furthermore, in Experiments 2 through 12, unless otherwise specified, the method for preparing the mixture of solution A and solution B is the same as the method used in Experiment 1. Also, the method for preparing the mixture of solution A and solution B in Evaluation B, which will be described later, is the same as the method used in Evaluation A of Experiment 1. Therefore, the explanation of the method for preparing the mixture of solution A and solution B in Experiments 2 through 12 for Evaluation A and Experiments 1 through 12 for Evaluation B, excluding the differences, will be omitted.

[0082] The mixture of liquids A and B was poured into the fabricated dumbbell-shaped mold, and the excess mixture was removed with a PTFE squeegee. The PTFE sheet containing the mixture of liquids A and B was placed in a room temperature constant temperature bath, and the temperature of the bath was raised to 80°C after 30 minutes. The mixture of liquids A and B was then cured by heating at 80°C in the constant temperature bath for 10 hours. After stopping the heating, the cured material was left in the constant temperature bath for 5 hours, and after the temperature of the constant temperature bath had dropped to about 40°C, the cured material was removed to room temperature. The PTFE sheet was then deformed to remove the cured material.

[0083] Next, the prepared cured material was immersed in the evaluation solution for 1 hour. Specifically, the cured material was placed in a 30 ml Labolan® screw-cap bottle, the evaluation solution was poured in so that the entire cured material was submerged, the bottle was sealed, and it was left in a 60°C constant temperature bath for 1 week. The evaluation solution is a liquid that mimics the acidic pretreatment ink used in the liquid spraying device 100 described above. The components of the evaluation solution and the mass ratio of each component are as follows. The lactic acid contained in the evaluation solution is an organic acid, and the pH of the evaluation solution is approximately 2. (Evaluation solution) Component: Mass ratio 3-methyl-1,5-pentanediol (MPD): 10 Orphine (registered trademark) E1010:1 Water:84 Lactic acid: 5

[0084] Next, the cured material was separated from the evaluation solution using an aspirator-type filtration device. A PTFE membrane filter with a pore size of 10 μm was used as the filtration filter. The cured material remaining on the funnel side, including the minute particles of cured material, was washed with pure water and ethanol, and then dried at 25°C for one day. The dried cured material was evaluated using the following evaluations A-1, A-2, and A-3. In the following explanation, the dried cured material may be referred to as the evaluation material.

[0085] B2-2. Evaluation A-1 (Weight change rate): When the weight of the cured material before immersion in the evaluation solution is W1 and the weight of the evaluation material is W2, the swelling rate was calculated using the following formula (e4). Swelling rate [%] = (W2 - W1) / W1 × 100 ... (e4) In the case of cured materials with poor acid resistance, that is, those whose chemical structure is easily altered by acids, they swell and increase in mass when immersed in the evaluation solution. Therefore, using the determined swelling rate, the acid resistance was evaluated using three ranks: A, B, and C, as described below. The ranks C, B, and A indicate the order of acid resistance, from best to worst. Note that cured materials with poor acid resistance typically lose their shape and break into multiple small pieces when immersed in the evaluation solution. Therefore, evaluation A-2, described later, was performed on cured materials that maintained their dumbbell shape. A: Swelling rate is less than 10% B: Swelling rate of 10% or more but less than 20% C: Swelling rate of 20% or more

[0086] B2-3. Evaluation A-2 (Tensile breaking strength): The tensile strength of the evaluated material was measured using a tensile testing apparatus. The tensile testing apparatus used was the STB-1225S manufactured by A&D Corporation. Specifically, parallel clamping jaws were attached to each of the wide ends of a dumbbell-shaped hardened material, and the evaluation material was pulled at a speed of 0.5 mm / min until it fractured. The tensile load at the time of fracture was measured. The area of ​​the fracture surface was measured and obtained using a digital microscope VHX-6000 manufactured by Keyence Corporation. Using the obtained tensile load and the area of ​​the fracture surface, the fracture strength was calculated using the following formula (e5). Breaking strength [MPa] = Tensile load [N] / Area of ​​the fracture [mm²] 2 ] ···(e5)

[0087] The greater the acid resistance of the cured material, the greater its tensile strength. Therefore, the tensile strength was evaluated using three ranks, A, B, and C, as shown below. The ranks C, B, and A indicate the order of acid resistance, from best to worst. A: Breaking strength of 40 MPa or more B: Breaking strength between 20 MPa and less than 40 MPa C: Breaking strength less than 20 MPa

[0088] B2-4. Evaluation A-3 (Visual Observation): The acid resistance of the evaluated samples was assessed by visual inspection. Hardened materials with poor acid resistance undergo a change in chemical structure due to acid, resulting in cracks. Furthermore, this change in chemical structure causes a brownish discoloration. Cracks and discoloration are more likely to occur at the edges of the dumbbell-shaped samples. Therefore, the appearance was evaluated using four ranks: A, B, C, and D, as shown below. The ranks indicate acid resistance in the order of D, C, B, and A. A: There is no discoloration or cracks on the edges. B: There is discoloration on the edges, but no cracks. C: Discoloration and cracks on the edges. D: Cracks are present in areas other than the edges, and the shape is not maintained.

[0089] B3. Explanation of Rating B (Fast Curing): A mixture of solution A and solution B was applied to an evaluation test plate using a dispenser. The dispenser used was the ML-808FX manufactured by Musashi Engineering Co., Ltd. Specifically, the mixture was filled into a dispenser syringe with a plastic needle with an inner diameter of 0.66 mm, and 5 mg was applied to the center of the evaluation test plate.

[0090] The evaluation test plate used was a SUS430 plate measuring 20 mm in length, 20 mm in width, and 0.2 mm in thickness, to which N-(3-trimethoxysilylpropyl)ethylenediamine, with CAS number 1760-24-3, was applied by a known method. This evaluation test plate is modeled after, for example, the fixing plate 36 in the liquid injection device 100. N-(3-trimethoxysilylpropyl)ethylenediamine is a commonly used silane coupling agent. Silane coupling agents are known to improve the adhesion between metals and organic materials. In other words, this evaluation B is intended to evaluate the case where, when bonding metal components, a manufacturing method is employed in which an adhesive is applied to a metal component that has been pre-coated with a silane coupling agent.

[0091] Using a silane coupling agent has the advantage of improving the adhesion between inorganic materials like metal and organic materials like adhesives. On the other hand, when a silane coupling agent is applied, the applied adhesive tends to move more easily from its application site. Therefore, evaluations using silane coupling agents can be considered as evaluations of positional movement under worse conditions.

[0092] The evaluation test plate was placed on a table so that its 20mm x 20mm flat surface (shown in Figure 9) was parallel to the plane perpendicular to the direction of gravity. The mixture of liquid A and liquid B, which had been returned to room temperature, was applied to the center of this flat surface of the evaluation test plate, and then left at room temperature for 5 hours. The evaluation test plate was then placed upright in a room temperature constant temperature bath and the temperature was raised to 80°C after 30 minutes. After that, the mixture of liquid A and liquid B was cured at 80°C for 10 hours. After that, the heating was stopped, and the cured material was left in the constant temperature bath for 5 hours. After the temperature of the constant temperature bath had dropped to about 40°C, the evaluation test plate with the cured material attached was removed and returned to room temperature.

[0093] The jig used to hold the evaluation test plate vertically comprises a base, a vertical plate fixed to the base in a position perpendicular to the base, and a permanent magnet. The permanent magnet is attached to the back surface of the vertical plate. When the evaluation test plate is placed on the surface of the vertical plate, the evaluation test plate, being a magnetic material, is attracted to the permanent magnet by magnetic force, and the evaluation test plate is held in contact with the surface of the vertical plate.

[0094] In the manufacturing of the liquid spray head 30, for example, when bonding a fixed plate 36 and a reinforcing plate 37, the mixture of liquid A and liquid B is applied to at least one of the bonding surfaces of the fixed plate 36 and the reinforcing plate 37, and then left at a set curing temperature for a set curing time until the mixture hardens. If the mixture of liquid A and liquid B moves from its initial position before hardening, the film thickness of the hardened adhesive becomes uneven. When the adhesive, which is a mixture of liquid A and liquid B, is placed in a high-temperature environment for curing, the viscosity of the mixture decreases as the temperature rises, and the curing reaction proceeds. If the hardening is fast, movement due to viscosity decrease is less likely to occur. Therefore, the rapid curing properties can be evaluated by the distance of movement.

[0095] When the evaluation test plate is positioned vertically, the mixture of liquid A and liquid B moves downward due to its own weight. Therefore, as shown in Figure 9, the shorter the distance between the initial position where the mixture of liquid A and liquid B is applied and the position of the cured product, the better the rapid curing performance can be evaluated. Specifically, the rapid curing performance was evaluated using the evaluation distance De, which is the center of the evaluation test plate (the center of the initial position) and the upper edge of the cured product, in three ranks: A, B, and C. The ranks C, B, and A indicate the order of rapid curing performance, with C being the order of best rapid curing performance. A: The upper edge of the cured material is above the center of the evaluation test plate. B: Evaluation distance De is between 0mm and 5mm. C: Evaluation distance De is longer than 5mm

[0096] B4. Experiment 1: As described above, the inventors found that the reactivity between solution B and the glycidylamine-type epoxy resin can be improved by including bis(aminomethyl)norbornane and the phenol described in (a) or (b) above in solution B. It is believed that bis(aminomethyl)norbornane contributes to the improvement in reactivity. In Experiment 1, the content ratio of bis(aminomethyl)norbornane to the amine in the entire adhesive was evaluated.

[0097] Figure 10 shows the equivalent ratios and mass ratios for Experimental Examples 1 to 7 of Experiment 1. Figure 10 shows the value of the ratio (CB-1 / amine). The ratio (CB-1 / amine) is the ratio of the amine equivalent of bis(aminomethyl)norbornane contained in Solution B to the amine equivalent of all amines contained in the adhesive. In Experiment 1, there are two amines contained in the adhesive: component CD-1 and component CB-1. If the amine equivalent of component CD-1 is Ae(CD-1) and the amine equivalent of component CB-1 is Ae(CB-1), then the ratio (CB-1 / amine) can be calculated using the following formula (e6). Ratio (CB-1 / amine) = Ae(CD-1) / (Ae(CD-1)+Ae(CB-1)) ···(e6) In Experiment 1, the ratio (CB-1 / amine) was varied within the range of 0.1 to 0.63.

[0098] Figure 11 summarizes the evaluation results for each experiment from Experiment 1 to Experiment 3. As shown in the evaluation results for Experiment 1 in Figure 11, for evaluation A, Experiments 1 to 3 are ranked B, while Experiments 4 to 7 are ranked A. Therefore, it can be seen that a ratio (CB-1 / amine) of 0.22 or less is preferable. This is thought to be because acid resistance decreases as the amount of bis(aminomethyl)norbornane (component CB-1) increases, and acid resistance improves as the amount of aromatic amine polymer (component CD-1) increases.

[0099] Furthermore, in Experimental Example 7, evaluation B is ranked B. This is thought to be because the amount of bis(aminomethyl)norbornane (component CB-1) in solution A is small compared to the main agent, thus reducing the effect of bis(aminomethyl)norbornane in accelerating the reactivity during the curing reaction between solution A and solution B. From the above, it can be seen that a ratio of (CB-1 / amine) of 0.22 or less is preferable. Moreover, it can be seen that a ratio of (CB-1 / amine) greater than 0.10 is preferable, and 0.13 or more is even preferable.

[0100] B5. Experiment 2: Figure 12 shows the equivalent ratio and mass ratio for Experimental Examples 8 to 14 of Experiment 2. Experiment 2 differs from Experiment 1 in that Solution A does not contain component CE-1. As shown in the evaluation results of Experiment 2 in Figure 11, for example, focusing on Experimental Examples 11 to 14 where the ratio (CB-1 / amine) is 0.22 or less, the evaluation A-3 for cracks is rank B. In contrast, for Experimental Examples 4 to 7 in Experiment 1 where the ratio (CB-1 / amine) is 0.22 or less, the result for evaluation A-3 is rank A. In other words, when comparing the experimental examples with a ratio (CB-1 / amine) of 0.22 or less in Experiment 1 and Experiment 2, the rank of evaluation A-3 for Experimental Examples 11 to 14 in Experiment 2 is lower than the rank A in Experiment 1. This is thought to be because the crack suppression effect of 3,4-dihydrocoumarin (component CE-1) was not obtained.

[0101] Furthermore, focusing on evaluation B, the results of Experimental Examples 4 to 6 in Experiment 1 are rank A, but the results of Experimental Examples 11 to 13 in Experiment 2 are rank B, a decrease from rank A in Experiment 1. This is thought to be because, when 3,4-dihydrocoumarin (component CE-1) is included, the curing properties are improved due to the reaction between 3,4-dihydrocoumarin (component CE-1) and bis(aminomethyl)norbornane (component CB-1). From the above, it can be seen that it is preferable to include 3,4-dihydrocoumarin (component CE-1) in the adhesive.

[0102] Furthermore, since component CE-1 (3,4-dihydrocoumarin) has an odor, it is not desirable to increase its equivalent ratio. Also, if the equivalent ratio of component CE-1 is high, the viscosity of the adhesive will decrease. In addition, since component CE-1 promotes the curing reaction, including a large amount in the adhesive will cause it to cure quickly. Therefore, it is preferable that the equivalent amount of component CE-1 be between 0.1 and 0.5 equivalents relative to the amine equivalent.

[0103] B6. Experiment 3: Figure 13 shows the equivalent ratios and mass ratios for Experimental Examples 15 to 24 of Experiment 3. Based on the evaluation results of Experiments 1 and 2, the component composition of Solution A in Experimental Example 5, which showed good evaluation results, was used as the basis for evaluating the components of Solution B in Experiment 3. Specifically, the ratio (CA-1 / CB-1), which is the equivalent ratio of component CA-1 to bis(aminomethyl)norbornane (component CB-1) in Solution B, was varied from 0.05 to 0.17. Note that component CA-1 is included in Solution B to increase its viscosity. In addition, the ratio (CC-1 / CB-1), which is the equivalent ratio of component CC-1 to component CB-1, was varied from 0.10 to 0.95.

[0104] Furthermore, if component CA-1 is not included in solution B, the viscosity of solution B is very low. In this case, when mixing solution A and solution B, stirring at a slow speed is necessary. For example, when using a mixing machine, the amount of liquid and rotation speed are limited to prevent splashing. Alternatively, manual mixing beforehand is required. In other words, the manufacturing process can be made more efficient by creating a solution B with a viscosity high enough to facilitate mixing with solution A.

[0105] The ratio (CA-1 / CB-1) is the ratio of the epoxy equivalent of the tetrafunctional glycidylamine-type epoxy resin contained in solution B to the amine equivalent of bis(aminomethyl)norbornane contained in solution B. In Experiment 3, the only tetrafunctional glycidylamine-type epoxy resin contained in solution B is component CA-1. Therefore, if the epoxy equivalent of component CA-1 is Ae(CA-1) and the amine equivalent of component CB-1 is Ae(CB-1), the ratio (CA-1 / CB-1) can be calculated using the following formula (e7). Ratio (CA-1 / CB-1)=Ae(CA-1) / Ae(CB-1) ·(e7) In the table showing the equivalent ratios in Figure 14, the equivalent ratio of component CB-1 is "1.0". Therefore, the equivalent ratio of component CA-1 listed in the table in Figure 14 is the same as the ratio (CA-1 / CB-1). For this reason, the ratio (CA-1 / CB-1) is omitted in Figure 14.

[0106] As shown in the evaluation results for Experiment 3 in Figure 11, all of Experiment Examples 15 through 24 received a rank A for both Evaluation A and Evaluation B. This is likely because the equivalent ratio of component CA-1 in Solution B is small, ranging from 0.05 to 0.17, and therefore, changes within this small range do not significantly affect the evaluation.

[0107] However, regarding viscosity other than that of evaluations A and B, it was found that there is a preferred range for the ratio (CA-1 / CB-1). The viscosity of solution B increases as the equivalent ratio of component CA-1 included in solution B increases. Experimental examples 15 and 16, where the ratio (CA-1 / CB-1) is 0.05, have low viscosity and are difficult to handle. Also, in experimental examples 21 and 22, where the ratio (CA-1 / CB-1) is 0.17, solution B becomes a high-viscosity liquid after adduct treatment. Comparing experimental examples 21 and 22, experimental example 22 has a higher ratio of component CB-1 to component CC-1 than experimental example 21, and the exothermic reaction when components CC-1 and CB-1 are mixed results in a higher temperature. Therefore, careful handling of solution B is required, making it difficult to handle. In addition, the viscosity of experimental example 21 is higher than that of experimental example 22. While it does not make it impossible to use as an adhesive, it does become difficult to handle, so the ratio (CA-1 / CB-1) is preferably 0.07 or higher, more preferably less than 0.17, and even more preferably 0.14 or lower.

[0108] The ratio (CC-1 / CB-1) is the ratio of the phenol equivalent of carvacrol to the amine equivalent of bis(aminomethyl)norbornane contained in solution B. If the phenol equivalent of component CC-1 is Ae(CC-1) and the amine equivalent of component CB-1 is Ae(CB-1), the ratio (CC-1 / CB-1) can be calculated using the following formula (e8). Ratio (CC-1 / CB-1)=Ae(CC-1) / Ae(CB-1) ···(e8) In the table showing the equivalent ratios in Figure 13, the equivalent ratio of component CB-1 is "1.0". Therefore, the equivalent ratio of component CC-1 listed in the table in Figure 13 is the same as the ratio (CC-1 / CB-1). For this reason, the ratio (CC-1 / CB-1) is omitted in Figure 14.

[0109] Regarding the ratio (CC-1 / CB-1), it was found that there is a preferred range in terms of viscosity other than evaluations A and B. In experimental example 24, where the ratio (CC-1 / CB-1) is 0.95, the temperature rises due to the exothermic reaction when components CC-1 and CB-1 are mixed. Therefore, it was found that caution is required when handling solution B, making it difficult to handle.

[0110] Furthermore, in Experimental Example 23, where the ratio (CC-1 / CB-1) is 0.01, there is less carvacrol (component CC-1) compared to bis(aminomethyl)norbornane (component CB-1), so the chemical reaction between component CB-1 and component CC-1 is minimal. As described above, the chemical reaction between component CB-1 and component CC-1 results in an effect that makes phenomena such as gelation less likely to occur even when mixed with the main agent. Therefore, if the chemical reaction between component CB-1 and component CC-1 is minimal, when mixed with solution A, the component CB-1 remaining in solution B will rapidly react with the epoxy resin, making phenomena such as gelation more likely. As the curing temperature increases, the curing reaction progresses, so phenomena such as gelation are more likely to occur at higher curing temperatures.

[0111] Furthermore, in Experimental Example 24, where the ratio (CC-1 / CB-1) is 0.95, there is a higher amount of carvacrol (component CC-1) compared to bis(aminomethyl)norbornane (component CB-1). As a result, component CC-1 that does not react with component CB-1 and remains in solution B also remains in the cured product, and there is a risk that it will dissolve in an acidic liquid and deform the cured product. Therefore, it can be seen that a ratio (CC-1 / CB-1) of 0.35 or more and 0.70 or less is preferable.

[0112] B7. Experiment 4: Figure 14 shows the equivalent ratio and mass ratio for Experimental Examples 25 to 28 of Experiment 4. Figure 15 summarizes the evaluation results for Experiments 4 to 7. In Experiment 3 described above, the ratio (CA-1 / CB-1) was varied within the range of 0.05 to 0.17. As shown in Figure 14, Experimental Examples 25 and 26 of Experiment 4 differ from Experimental Examples 21 and 22 of Experiment 3 in that the ratio (CA-1 / CB-1) was further increased to 0.33. Experimental Examples 25 and 26 solidify when Solution B is heated or left to stand. In other words, they solidify before they can be applied as an adhesive and therefore cannot be used as an adhesive. For this reason, evaluations A and B could not be performed. From the above, it can be seen that the ratio (CA-1 / CB-1) in Solution B needs to be smaller than 0.33.

[0113] In Experimental Examples 27 and 28 of Experiment 4, tyrosol (component CF-1) was added to solution B. The purpose of adding component CF-1 to solution B is to increase its viscosity. In Experiments 1 through 3 described above, component CA-1 was added to solution B to increase its viscosity. In Experimental Examples 27 and 28, the sum of the equivalent ratios of component CA-1 and component CF-1 was set to "0.33".

[0114] In Experimental Example 28, where Solution B does not contain epoxy resin (component CA-1), when preparing Solution B, tyrosol (component CF-1) and bis(aminomethyl)norbornane (component CB-1) were mixed, and then carvacrol (component CC-1) was mixed into the prepared mixture. After 30 minutes, the mixture was left at 95°C for 30 minutes as an adduct treatment to allow it to react. When component CC-1 and component CB-1 are mixed, a byproduct is produced. As described above, in each experimental example where Solution B contains epoxy resin (component CA-1), Solution B was prepared by first mixing component CA-1 and component CB-1, and then mixing component CC-1 into the mixture. If component CB-1 and component CC-1 are mixed first, a greenish byproduct is produced. Furthermore, even when component CA-1 is mixed into the mixture containing this byproduct, the byproduct remains. From these results, it can be seen that when solution B contains component CA-1, the generation of by-products can be avoided by first mixing component CA-1 and component CB-1, and then mixing component CC-1 into the mixture. Also, as mentioned above, by-products are generated when component CC-1 and component CB-1 are mixed. The generation of by-products cannot be avoided even if component CF-1 and component CB-1 are mixed first, and then component CC-1 into the mixture. Therefore, if you want to include component CF-1 in solution B while avoiding the generation of by-products, it is best to use a component composition that includes component CA-1 in solution B.

[0115] As shown in the evaluation results for Experiment 4 in Figure 15, in both Experiment 27 and Experiment 28, the results for both Evaluation A and Evaluation B were all rank A. Therefore, it can be seen that when at least one of component CA-1 and component CF-1 is included, a cured product with excellent rapid curing properties and acid resistance can be produced.

[0116] Furthermore, it was found that if the equivalent ratio of tyrosol (component CF-1) included in solution B is in the range of at least 0.33 or less, the mixture of solution A and solution B will not solidify when mixed. Specifically, it was found that if the ratio (CF-1 / CB-1), which is the ratio of the phenol equivalent of tyrosol to the amine equivalent of bis(aminomethyl)norbornane contained in solution B, is in the range of at least 0.33 or less, an adhesive can be produced that does not solidify when solution A and solution B are mixed, while increasing the viscosity of solution B. Note that the phenol equivalent of tyrosol refers to the equivalent amount of tyrosol shown in Figure 6. From the above, it can be seen that including component CA-1 or component CF-1 in solution B is preferable because it can increase the viscosity of solution B.

[0117] B8. Experiment 5: Figure 16 shows the equivalent ratios and mass ratios for Experimental Examples 29 to 32 of Experiment 5. In Experiments 1 to 4 above, the phenol (a) or (b) included in solution B is carvacrol (component CC-1). In Experimental Examples 29 to 31 of Experiment 5, one of components CC-2, CC-3, and CC-4 was included in solution B instead of component CC-1. In Experimental Example 32 of Experiment 5, neither the phenol (a) nor the phenol (b) was included in solution B.

[0118] As shown in the evaluation results of Experiment 5 in Figure 15, in Experimental Examples 29 to 27, in which one of components CC-2, CC-3, and CC-4 was included in Solution B, both Evaluation A and Evaluation B results were rank A. In addition, in Experimental Example 32, in which neither the phenol of (a) nor the phenol of (b) above was included, the evaluation results for Evaluation A and Evaluation B were rank C or rank D. From these results, it can be seen that by including the phenol of (a) or the phenol of (b) above in Solution B, an adhesive with rapid curing properties and acid resistance can be produced. Furthermore, it can be seen that carvacrol (component CC-1), 4-ethylphenol (component CC-2), orthocymen-5-ol (component CC-3), and thymol (component CC-4) can be used as the phenol of (a) or the phenol of (b) above.

[0119] Furthermore, from perspectives other than evaluations A and B, it was found that there are preferred components to be included in solution B as the phenol of (a) or (b) above. Of components CC-1 to CC-4, only components CC-1 and CC-2 reacted exothermically with bis(aminomethyl)norbornane (component CB-1) when mixed. Therefore, components CC-1 and CC-2 are preferred because they eliminate the need for heat treatment to promote the reaction with component CB-1. As for component CC-2, which is a solid powder at room temperature, the reaction was carried out by melting and dissolving it in component CB-1, which is a liquid at room temperature, and stirring by hand.

[0120] Components CC-3 and CC-4, which are solids at room temperature, did not react exothermally with component CB-1 when mixed. Therefore, components CC-3 and CC-4 were reacted by mixing them with component CB-1 and then heat-treating them.

[0121] Furthermore, since component CC-1 is liquid at room temperature, it mixes easily with component CB-1, which is also liquid at room temperature, making it suitable for reaction with component CB-1. In addition, as component CC-1 is known to be an essential oil component extracted from the plant oregano, it emits an odor that is easily liked by people, making it preferable for use in the manufacturing process of adhesives.

[0122] As mentioned above, it is possible to omit the heat treatment to promote the reaction between components CC-1 and CC-2 and component CB-1, but an additional experiment was conducted in which this heat treatment was performed. As a result, for evaluation A-2, the result for component CC-1 was better than the result for component CC-2. Component CC-1 is a dialkylphenol in which two hydrogens of the benzene ring are substituted with alkyl groups. Component CC-2 is a monoalkylphenol in which one hydrogen of the benzene ring is substituted with an alkyl group. From the above, it was found that the phenol in (a) or the phenol in (b) above is preferably carvacrol and 4-ethylphenol, and carvacrol is more preferably carvacrol.

[0123] B9. Experiment 6: Figure 17 shows the equivalent ratio and mass ratio for Experimental Examples 29 to 32 of Experiment 6. As mentioned in Experiment 2 above, the inclusion of 3,4-dihydrocoumarin (component CE-1) can suppress the occurrence of cracks in the cured product. On the other hand, component CE-1 has the property of promoting chemical reactions. Therefore, when component CE-1 is included in solution A, it reacts with the polymer of aromatic amine (component CD-1), and solidifies in about several months at room temperature. Therefore, we investigated a component composition that would allow solution A to be stored at room temperature for a long period of time. As a result of preliminary experiments in which component CE-1 was included in solution B, it was found that mixing component CE-1 and component CB-1 caused solidification. Furthermore, it was found that mixing component CD-1 after mixing component CB-1 and component CC-1 caused early solidification.

[0124] Therefore, in Experiment 6, instead of component CE-1, an aromatic amine polymer (component CD-1) was added to solution B. To prepare solution B, each component except component CD-1 was mixed, and after 30 minutes, the mixture was left to react at 95°C for 30 minutes as an adduct treatment. After that, component CD-1 was mixed into this mixture. It was found that solution B prepared in this way could be stored for a long period of time at room temperature. It was also found that solution A could be stored for a long period of time at room temperature.

[0125] As shown in Experiment 6 in Figure 15, for all of Experimental Examples 33 to 36, both Evaluation A and Evaluation B results were rank A. In Experiment 6, the component composition of the adhesive itself was the same as in Experimental Examples 15, 16, 27, and 28, and therefore the same evaluation results were obtained. From the above, it was found that by including the aromatic amine polymer (component CD-1) in solution B instead of solution A, both solution A and solution B can be stored at room temperature for a long period of time.

[0126] B10. Experiment 7: Figure 18 shows the equivalent ratios and mass ratios for Experimental Examples 37 to 41 of Experiment 7. Experimental Example 37, like Experiment 6 above, is a configuration in which an aromatic amine polymer (component CD-1) is included in solution B, and the equivalent ratio of component CA-1 in solution B is set to "0.1". The method for preparing solution B is the same as in Experiment 6 above. As shown in the evaluation results of Experimental Example 7 in Figure 15, the evaluation results for Experimental Example 37 were rank A for both evaluation A and evaluation B. Experimental Example 37 is the best mode from the viewpoint of rapid curing, acid resistance, and storage properties.

[0127] As shown in Figure 18, in Experimental Examples 38 and 39, Solution B contains either an aliphatic amine (Component CG-2) or an aromatic amine (Component CG-1) instead of the aromatic amine polymer (Component CD-1) in Solution B. Furthermore, in Experimental Examples 38 and 39, Solution B does not contain bis(aminomethyl)norbornane (Component CB-1) and carvacrol (Component CC-1), which are characteristic of the present invention. Also, in Experimental Examples 38 and 39, Solution A does not contain 3,4-dihydrocoumarin (Component CE-1). When preparing Solution B, each component except for Components CG-1 and CG-2 was mixed, and then the mixture was left to react at 95°C for 30 minutes as an adduct treatment after 30 minutes. After that, Component CG-1 or Component CG-2 was mixed into this mixture.

[0128] As shown in the evaluation results for Experiment 7 in Figure 15, Experimental Examples 38 and 39 did not receive good evaluations, neither A nor B. Comparing Experimental Examples 38 and 39 with Experimental Example 37, it can be seen that by including components CB-1, CC-1, and CD-1 in Solution B, an adhesive with excellent rapid curing properties and acid resistance can be produced.

[0129] As shown in Figure 18, Experimental Examples 40 and 41 differ from Experimental Examples 38 and 39 in that components CG-1 and CG-2, which were contained in solution B in Experimental Examples 38 and 39, were included in solution A. As shown in the evaluation results of Experiment 7 in Figure 15, the evaluation results of Experimental Examples 40 and 41 were the same as those of Experimental Examples 38 and 39. Component CG-2, which is an aromatic amine and not a polymer, has a melting point of approximately 85°C and is solid at room temperature. Therefore, in Experimental Examples 40 and 41, component CG-2 was melted by heating solution B at 95°C for 2 hours, and then it was mixed with solution A and cured. The poor evaluation results of Experimental Examples 40 and 41 are thought to be because the activity of component CG-2 was low at a curing temperature of 80°C, and the same curing reaction as with component CD-1 did not occur, resulting in the cured product not being given acid resistance.

[0130] B11. Experiment 8: Figure 19 shows the equivalent ratios and mass ratios for Experimental Examples 42 to 45 of Experiment 8. Experiment 8 differs from Experimental Examples 25 to 28 of Experiment 4 in that component CA-1 in solution A is changed to component CA-2.

[0131] Figure 20 summarizes the evaluation results from Experiments 8 to 11. As shown in the evaluation results for Experiment 8 in Figure 20, all evaluation results for Experiments 42 to 45, both A and B, were rank A. From the above, it can be seen that the same results as in each of the above experiments can be obtained even when component CA-1 is replaced with CA-2 as the epoxy resin included in Solution A.

[0132] B12. Experiment 9: Figure 21 shows the equivalent ratios and mass ratios for Experimental Examples 46 to 49 of Experiment 9. Experiment 9 differs from Experimental Examples 25 to 28 of Experiment 4 in that component CA-1 in solution B is changed to component CA-2.

[0133] As shown in the evaluation results for Experiment 9 in Figure 20, all evaluation results for both Evaluation A and Evaluation B in Experiments 46 to 49 were rank A. From the above, it can be seen that the same results as in each of the above experiments can be obtained even when component CA-1 is replaced with CA-2 as the epoxy resin included in Solution B.

[0134] B13. Experiment 10: Figure 22 shows the equivalent ratios and mass ratios for Experimental Examples 50 to 53 of Experiment 10. Experiment 10 differs from Experimental Examples 25 to 28 of Experiment 4 in that component CA-1 in solution A is changed to component CA-2, and component CA-1 in solution B is also changed to component CA-2.

[0135] As shown in the evaluation results for Experiment 10 in Figure 20, all evaluation results for both Evaluation A and Evaluation B in Experiments 50 to 53 were rank A. From the above, it can be seen that, for both Solution A and Solution B, the same results as in the above experiments can be obtained even when component CA-1 in the epoxy resin contained in each solution is replaced with CA-2.

[0136] B14. Experiment 11: Figure 23 shows the equivalent ratio and mass ratio for Experimental Examples 54 and 55 of Experiment 11. As shown in Figure 23, Experimental Example 54 differs from Example 5 of Experiment 1 in that, for both Solution A and Solution B, component CA-1 is replaced with component CB-1. Experimental Example 55 differs from Example 12 of Experiment 2 in that, for both Solution A and Solution B, component CA-1 is replaced with component CB-1.

[0137] As shown in the evaluation results of Experiment 11 in Figure 20, the evaluation results of Experimental Example 54 were the same as those of Example 5. Furthermore, the evaluation results of Experimental Example 55 were the same as those of Example 12. From the above, it can be seen that, in both cases with and without 3,4-dihydrocoumarin (component CE-1), a good evaluation result can be obtained when component CB-1 is used, with a ratio (CB-1 / amine) of 0.18.

[0138] B15. Experiment 12: Figure 24 shows the equivalent ratios and mass ratios for Experimental Examples 56 to 59 of Experiment 12. Figure 25 is a summary of the evaluation results for Experiment 12 and Experiment 13. As shown in Figure 24, Experimental Example 56 differs from Experimental Example 44 of Experiment 8 in that the equivalent ratio of 3,4-dihydrocoumarin (component CE-1) is set to "0.5". Experimental Example 57 differs from Example 56 in that component CA-1 is changed to component CB-1 for both Solution A and Solution B. Experimental Examples 58 and 59 differ from Example 56 in that both Solution A and Solution B are modified to include both component CA-1 and component CB-1 as epoxy resins in each solution.

[0139] As shown in the evaluation results for Experiment 12 in Figure 25, for all of Experiment Examples 56 to 59, both Evaluation A and Evaluation B results were ranked A. From the above, it was found that even when the equivalent ratio of 3,4-dihydrocoumarin (component CE-1) is increased to "0.5", it is possible to produce adhesives with excellent rapid curing properties and acid resistance.

[0140] B16. Experiment 13: Figure 26 shows the equivalent ratios and mass ratios for Experimental Examples 60 to 63 of Experiment 13. As shown in Figure 26, Experimental Example 60 differs from Example 5 of Experiment 1 in that it includes component CA-2 in addition to component CA-1 in solution A, making the total equivalent ratio of these two components "0.5", the equivalent ratio of the aromatic amine polymer (component CD-1) is "4.5", and component CA-1 is not included in solution B. Example 61 differs from Example 12 of Experiment 2 in that it includes component CA-2 in addition to component CA-1 in solution A, making the total equivalent ratio of these two components "0.5", the equivalent ratio of the aromatic amine polymer (component CD-1) is "4.5", and component CA-1 is not included in solution B.

[0141] As shown in the results of Experiment 13 in Figure 25, the evaluation results for Experiment Example 60 are the same as those for Experiment Example 5. The evaluation results for Experiment Example 61 are the same as those for Experiment Example 12. Therefore, it was found that the evaluation results when component CA-1 is not included in Solution B are the same as the evaluation results when component CA-1 is included in Solution B. However, as mentioned above, when epoxy resin is not included in Solution B, the viscosity of Solution B is low, which may reduce the efficiency in the manufacturing process. Also, in Example 60, the equivalent ratio of component CE-1 contained in Solution A is large at "0.5", so the viscosity of Solution A is high. Therefore, the heating time for the adduct treatment of Solution A may be shortened.

[0142] As shown in Figure 26, Example 62 differs from Example 60 in that the aromatic amine polymer (component CD-1) is included in solution B instead of solution A. Example 63 differs from Example 61 in that the aromatic amine polymer (component CD-1) is included in solution B instead of solution A.

[0143] As shown in the results of Experiment 13 in Figure 25, the evaluation results for Experiment 62 are the same as those for Experiment 60. The evaluation results for Experiment 63 are the same as those for Experiment 61. Therefore, it was found that the evaluation results when component CD-1 is included in solution B are the same as the evaluation results when component CD-1 is included in solution A. However, when the aromatic amine polymer (component CD-1) is included in solution B, the viscosity of solution B increases to about the same level as the viscosity of solution A. Therefore, by including the aromatic amine polymer (component CD-1) in solution B, an adhesive that is easy to mix between solution A and solution B can be produced.

[0144] Examples 61 and 63 do not contain 3,4-dihydrocoumarin (component CE-1), but the evaluation A-2 result is rank B, and the tensile breaking strength is 20 MPa or more, so they are practical.

[0145] C. Other embodiments: (C1) In the above embodiment, an embodiment in which a two-component mixed adhesive is applied to a liquid spray head 30 is shown, but the member to which the two-component mixed adhesive is applied is not limited to the liquid spray head 30. Also, in the above embodiment, the adhesive does not contain a filler, but it may contain a filler for viscosity adjustment.

[0146] The two-component adhesive used in the manufacture of the liquid spray head 30 is not limited to the embodiments described above. Specifically, the bisphenol-free epoxy resin is not limited to a tetrafunctional glycidylamine type epoxy resin. The tetrafunctional glycidylamine type epoxy resin is not limited to N,N,N',N'-tetraglycidyl-m-xylenediamine or 4,4'-methylenebis(N,N-diglycidylaniline). The bisphenol-free epoxy resin may contain multiple types of epoxy resins. Furthermore, the aromatic amine polymer is not limited to 2-ethylaniline-formaldehyde polymer, but may be, for example, 2-ethyl-3ethylaniline-formaldehyde polymer. Even when these components are used, each of these components has the same chemical properties as the corresponding components in the embodiments described above, so a two-component adhesive exhibiting the same effects as in the embodiments described above can be produced.

[0147] D. Other forms: This disclosure is not limited to the embodiments described above, and can be implemented in various configurations without departing from its spirit. For example, the technical features of the embodiments corresponding to the technical features in each of the embodiments described below can be replaced or combined as appropriate in order to solve some or all of the above-described problems, or to achieve some or all of the above-described effects. Furthermore, if a technical feature is not described as essential in this specification, it can be deleted as appropriate.

[0148] (1) According to a first embodiment of the present disclosure, a liquid spray head is provided which sprays a liquid from a nozzle. The liquid spray head comprises a first member, a second member, and a cured product of a two-component mixed adhesive that adheres the first member and the second member, wherein the two-component mixed adhesive comprises: liquid A containing a main component including an epoxy resin that does not contain bisphenol; liquid B containing at least one of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane and an alkylphenol; and a polymer of an aromatic amine contained in liquid A or liquid B, wherein the alkylphenol is (a) an alkylphenol having at least one ethyl group, or (b) an alkylphenol having 1 to 3 carbon atoms in the alkyl group and at least one methyl group and one isopropyl group. According to this embodiment, the environmental burden can be reduced by using an epoxy resin that does not use bisphenol as the main component. Furthermore, by including at least one of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane and the alkylphenol described in (a) or (b) above in the curing agent, phenomena such as gelation can be suppressed when mixed with the epoxy resin main component at room temperature, and rapid curing occurs at high temperatures. As a result, the adhesive applied to the gap between the first and second components does not move until it hardens, allowing for a uniform curing agent film thickness and improving reliability. Additionally, the use of aromatic amine polymers can improve the acid resistance of the cured product.

[0149] (2) In the liquid spray head of the above embodiment, the alkylphenol may include at least one of 4-ethylphenol and carvacrol. According to this embodiment, the chemical reaction between the alkylphenol and at least one of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane can be completed without heat treatment.

[0150] (3) In the liquid spray head of the above form, the alkylphenol may be carvacrol. This form is preferable from the viewpoint of use in the manufacturing process of adhesives because carvacrol emits an odor that is easily liked by people. (4) In the liquid spray head of the above form, the ratio of the phenol equivalent of carvacrol to the amine equivalent of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in liquid B may be 0.35 or more and 0.70 or less. With this form, since liquid B has an appropriate viscosity, liquid A and liquid B can be easily mixed and phenomena such as gelation can be suppressed. In addition, although heat is generated when either 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane or 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane reacts with carvacrol, the temperature of liquid B does not become too high, so an easy-to-handle adhesive can be provided. (5) In the liquid spray head of the above embodiment, liquid B may contain at least one of the bisphenol-free epoxy resin and tyrosol. In this embodiment, since liquid B has an appropriate viscosity, liquid A and liquid B can be easily mixed. (6) In the liquid spray head of the above embodiment, the bisphenol-free epoxy resin contained in liquid B may also include a tetrafunctional glycidylamine type epoxy resin. This embodiment provides an adhesive with a low environmental impact. (7) In the liquid spray head of the above form, the tetrafunctional glycidylamine type epoxy resin may contain at least one of N,N,N',N'-tetraglycidyl-m-xylenediamine and 4,4'-methylenebis(N,N-diglycidylaniline). (8) In the liquid spray head of the above embodiment, the ratio of the epoxy equivalent of the tetrafunctional glycidylamine type epoxy resin contained in the liquid B to the amine equivalent of the 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and the 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in the liquid B may be 0.14 or less. According to this embodiment, even after adduct treatment of the liquid B, the viscosity of the liquid B can be made appropriately low, and an easy-to-handle adhesive can be produced. (9) In the liquid spray head of the above embodiment, the ratio of the epoxy equivalent of the tetrafunctional glycidylamine type epoxy resin contained in the liquid B to the amine equivalents of the 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and the 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in the liquid B may be 0.07 or more. According to this embodiment, the viscosity of the liquid B can be made appropriately high, and an easy-to-handle adhesive can be produced. (10) In the liquid spray head of the above embodiment, the ratio of the amine equivalents of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in liquid B to the amine equivalents of all amines contained in the two-component mixed adhesive may be 0.22 or less. This embodiment provides an adhesive with excellent acid resistance. (11) In the liquid spray head of the above embodiment, the ratio of the amine equivalents of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in liquid B to the amine equivalents of all amines contained in the two-component mixed adhesive may be 0.13 or more. This embodiment provides an adhesive with excellent rapid curing properties. (12) In the liquid spray head of the above embodiment, liquid A may contain 3,4-dihydrocoumarin. With this embodiment, even when in contact with an acid-resistant liquid, browning of the adhesive can be prevented and cracking can be suppressed. Furthermore, an adhesive with excellent rapid curing properties can be provided. (13) In the liquid spray head of the above form, the polymer of the aromatic amine may be contained in the liquid B. In this form, the main component can be stored at room temperature. (14) In the liquid spray head of the above embodiment, the bisphenol-free epoxy resin contained in liquid A may also include a tetrafunctional glycidylamine type epoxy resin. This embodiment provides an adhesive with a low environmental impact. (15) In the liquid spray head of the above form, the tetrafunctional glycidylamine type epoxy resin may contain at least one of N,N,N',N'-tetraglycidyl-m-xylenediamine and 4,4'-methylenebis(N,N-diglycidylaniline). (16) In the liquid spray head of the above form, the polymer of the aromatic amine may include a 2-ethylaniline-formaldehyde polymer. (17) In the liquid spray head of the above embodiment, each of the first member and the second member communicates with the nozzle and defines a flow path through which the liquid flows, and the cured material may liquid-tightly connect the flow path of the first member and the flow path of the second member. With this embodiment, the cured material has excellent acid resistance and rapid curing properties, so a highly reliable liquid spray head can be provided. (18) In the liquid spray head of the above embodiment, (a) is an alkylphenol represented by formula (1) above (wherein R1, R2, and R3 of formula (1) represent hydrogen or an ethyl group, and at least one of R1, R2, and R3 represents an ethyl group), and (b) is an alkylphenol represented by formula (2) above (wherein R1, R2, R3, R4, and R5 of formula (2) represent hydrogen or an alkyl group having 1 to 3 carbon atoms, at least one of R1, R2, R3, R4, and R5 represents a methyl group, and at least one of R1, R2, R3, R4, and R5 represents an isopropyl group). (19) A second embodiment of the present disclosure provides a two-component adhesive. This two-component adhesive comprises: a main component A containing an epoxy resin that does not contain bisphenol; a B component B containing at least one of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane and an alkylphenol; and a polymer of an aromatic amine contained in the A or B component, wherein the alkylphenol is (a) an alkylphenol having at least one ethyl group, or (b) an alkylphenol having 1 to 3 carbon atoms in the alkyl group and at least one methyl group and one isopropyl group. (20) In the above-described two-component adhesive, (a) is an alkylphenol represented by formula (1) above (wherein R1, R2, and R3 of formula (1) represent hydrogen or an ethyl group, and at least one of R1, R2, and R3 represents an ethyl group), and (b) is an alkylphenol represented by formula (2) above (wherein R1, R2, R3, R4, and R5 of formula (2) represent hydrogen or an alkyl group having 1 to 3 carbon atoms, at least one of R1, R2, R3, R4, and R5 represents a methyl group, and at least one of R1, R2, R3, R4, and R5 represents an isopropyl group). (21) In the above-described two-component adhesive, the A liquid may contain 3,4-dihydrocoumarin. This configuration prevents the adhesive from turning brown even when in contact with an acid-resistant liquid, and suppresses cracking. [Explanation of Symbols]

[0151] C…Pressure chamber, GL…Cured material, N…Nozzle, Ra…Space, Rb…Space, S1a…Laminate first supply channel, S1b…Laminate second supply channel, S2a…Laminate first discharge channel, S2b…Laminate second discharge channel, Sn…Structural channel, Su…Channel member, 3…Head module, 12…Media, 14…Liquid container, 15…Sub-tank, 16…Conveying mechanism, 20…Head moving mechanism, 21…Conveyor belt, 22…Carriage, 26…Injection unit 26a...supply liquid chamber, 26b...supply channel, 26c...communication channel, 30...liquid injection head, 31...cover member, 32...holder member, 32a...first opening, 32b...second opening, 32c...third opening, 32d...partition wall, 33...channel structure, 34...pressure chamber substrate, 34a...opening, 36...fixing plate, 37...reinforcement plate, 44...piezoelectric element, 46...sealing body, 46a...sealing body opening, 48...housing part, 48a...through hole, 51a...flexible 53...channel substrate, 54...diaphragm, 62...nozzle plate, 64...channel sealing member, 80...control unit, 100...liquid injection device, 301...support, 302...mounting hole, 311...hole for first connection part, 312...hole for second connection part, 313...first hole, 321...housing part, 322...first through hole for holder, 323...second through hole for holder, 324...flange, 331a...first upper connection part for supply, 331b...second upper connection part for supply, 332a...first Upper discharge connector, 332b...Second upper discharge connector, 333...Laminate, 336a...Case first supply pipe, 337a...Case first discharge pipe, 336b...Case second supply pipe, 337b...Case second discharge pipe, 342a...First lower discharge connector, 342b...Second lower discharge connector, 361...Opening, 371...Opening, 381...Wiring board, 382...Wiring member, 383v...Second circuit board, 383...Second circuit board, 383u...First circuit board

Claims

1. A liquid spray head that sprays liquid from a nozzle, The device comprises a first member, a second member, and a cured product of a two-component adhesive for bonding the first member and the second member. The aforementioned two-component adhesive is Solution A contains a main component which is an epoxy resin that does not contain bisphenol, Solution B comprises at least one of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, and an alkylphenol. A polymer of an aromatic amine contained in solution A or solution B, Includes, The alkylphenol mentioned above is (a) an alkylphenol having at least one ethyl group, (b) an alkylphenol having 1 to 3 carbon atoms in the alkyl group and having at least one methyl group and one isopropyl group, A liquid spray head characterized by the following features.

2. The alkylphenol comprises at least one of 4-ethylphenol and carvacrol. The liquid spray head according to feature 1.

3. The alkylphenol is the carvacrol. The liquid spray head according to feature 2.

4. The ratio of the phenol equivalent of carvacrol to the amine equivalent of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in solution B is 0.35 or more and 0.70 or less. The liquid spray head according to feature 3.

5. The aforementioned liquid B comprises at least one of the bisphenol-free epoxy resin and tyrosol. The liquid spray head according to feature 1.

6. The epoxy resin contained in the aforementioned solution B, which does not contain bisphenol, includes a tetrafunctional glycidylamine type epoxy resin. The liquid spray head according to feature 5.

7. The aforementioned tetrafunctional glycidylamine-type epoxy resin comprises at least one of N,N,N',N'-tetraglycidyl-m-xylenediamine and 4,4'-methylenebis(N,N-diglycidylaniline). The liquid spray head according to feature 6.

8. The ratio of the epoxy equivalent of the tetrafunctional glycidylamine-type epoxy resin contained in solution B to the amine equivalent of the 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and the 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in solution B is 0.14 or less. The liquid spray head according to feature 6.

9. The ratio of the epoxy equivalent of the tetrafunctional glycidylamine-type epoxy resin contained in solution B to the amine equivalent of the 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and the 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in solution B is 0.07 or higher. The liquid spray head according to feature 8.

10. The ratio of the amine equivalents of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in solution B to the amine equivalents of all amines contained in the two-component adhesive is 0.22 or less. The liquid spray head according to feature 1.

11. The ratio of the amine equivalents of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane contained in solution B to the amine equivalents of all amines contained in the two-component adhesive is 0.13 or greater. The liquid spray head according to claim 10.

12. The aforementioned solution A contains 3,4-dihydrocoumarin, The liquid spray head according to feature 1.

13. The polymer of the aromatic amine is contained in solution B. The liquid spray head according to feature 12.

14. The epoxy resin contained in the aforementioned solution A, which does not contain bisphenol, includes a tetrafunctional glycidylamine type epoxy resin. The liquid spray head according to feature 1.

15. The aforementioned tetrafunctional glycidylamine-type epoxy resin comprises at least one of N,N,N',N'-tetraglycidyl-m-xylenediamine and 4,4'-methylenebis(N,N-diglycidylaniline). The liquid spray head according to feature 14.

16. The polymer of the aromatic amine includes a 2-ethylaniline formaldehyde polymer. The liquid spray head according to feature 1.

17. Each of the first and second members communicates with the nozzle and defines a flow path through which liquid flows. The cured material connects the flow path of the first member and the flow path of the second member in a liquid-tight manner. The liquid spray head according to feature 1.

18. (a) is an alkylphenol represented by the following formula (1), and (b) is an alkylphenol represented by the following formula (2). The liquid spray head according to feature 1. 【Chemistry 1】 (However, R in equation (1) １ , R ２ , and R ３ R represents a hydrogen or ethyl group. １ , R ２ , and R ３ At least one of them represents an ethyl group. 【Chemistry 2】 (However, R in formula (2) １ , R ２ , R ３ , R ４ , and R ５ represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and at least one of R １ , R ２ , R ３ , R ４ , and R ５ represents a methyl group, and at least one of R １ , R ２ , R ３ , R ４ , and R ５ represents an isopropyl group.)

19. Solution A contains a main component which is an epoxy resin that does not contain bisphenol, Solution B comprises at least one of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, and an alkylphenol. A polymer of an aromatic amine contained in solution A or solution B, Equipped with, The alkylphenol mentioned above is (a) an alkylphenol having at least one ethyl group, (b) an alkylphenol having 1 to 3 carbon atoms in the alkyl group and having at least one methyl group and one isopropyl group, A two-component adhesive characterized by the following features.

20. (a) is an alkylphenol represented by the following formula (1), and (b) is an alkylphenol represented by the following formula (2). The two-component adhesive according to claim 19. 【Transformation 3】 (However, R in equation (1) １ , R ２ , and R ３ R represents a hydrogen or ethyl group. １ , R ２ , R ３ At least one of them represents an ethyl group. 【Chemistry 4】 (However, R in equation (2) １ , R ２ , R ３ , R ４ , and R ５ R represents hydrogen or an alkyl group having 1 to 3 carbon atoms. １ , R ２ , R ３ , R ４ , and R ５ At least one of them shows a methyl group, R １ , R ２ , R ３ , R ４ , and R ５ At least one of them shows an isopropyl group.

21. The aforementioned solution A contains 3,4-dihydrocoumarin, The two-component adhesive according to claim 19.

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