JP4804774B2 - Adhesive composition, inkjet head, and method of manufacturing inkjet head - Google Patents

Description

  The present invention relates to an adhesive composition, an inkjet head manufactured using the adhesive composition, and a method for manufacturing the same.

  Currently, the screen printing method is used for the manufacture of liquid crystal color filters, the application of liquid crystal alignment films, and the manufacture of various precision electronic components such as organic EL. The outdoor signboard is printed on the PVC sheet by the screen printing method. As described above, business printing is generally performed by a screen printing method.

  Here, the screen printing method is a method in which a desired pattern is formed on a screen having a mesh, and ink that has passed this pattern is printed on a medium. The screen had to be designed and manufactured before printing, leading to an increase in manufacturing process and manufacturing cost. Another problem is that each time a pattern is changed, the screen must be recreated to match the pattern. Furthermore, since the screen is made of stainless steel mesh or the like, there is a problem that a fine pattern cannot be manufactured.

  Therefore, in recent years, with the advancement of the ink jet recording apparatus, it has become possible to print ultra-fine ink droplets at an arbitrary place, so that they are used instead of the conventional screen printing method. Unlike conventional screen printing methods, printing using an ink jet recording apparatus does not require a pattern, and can print finer than the screen printing method, and has an advantage that the apparatus is inexpensive.

  An ink jet head used in an ink jet recording apparatus includes a thermal method in which a heater is provided in an ink flow path to foam and discharge ink, and a piezo method in which a piezoelectric element is provided in the ink flow path to pressurize the ink with the piezoelectric element. There is. The thermal method is limited to water-based ink because organic solvent ink and oil-based ink do not foam. On the other hand, the piezo method is preferable because it can eject any of water-based, solvent-based and oil-based inks.

  In the piezoelectric method, the pressure chamber is deformed by expansion and contraction that occurs when an electric field is applied to the polarization direction of the piezoelectric element, and the pressure chamber is deformed by shear deformation that occurs when an electric field is applied in a direction perpendicular to the polarization direction. There is a method to make it. As a method using this shear deformation, there are a method in which two walls of the pressure chamber are made of piezoelectric elements and a method in which only one surface is made of piezoelectric elements.

  In such an ink jet head, an ink flow path is formed so as to be in contact with the piezoelectric element, and the internal volume of the ink flow path is also changed in accordance with the change of the piezoelectric element so that ink droplets are ejected. Each member such as a nozzle plate provided with a lid member and nozzle holes is bonded to the ink flow path.

  Here, in general, the ink used in the ink jet recording apparatus includes an aqueous ink and a solvent ink. A water-based ink is an ink composed of water, a dye, a water-soluble organic solvent, and an activator. The water-soluble organic solvent is a high-boiling glycol ether for preventing the evaporation of water from the ink discharge port during the discharge stop. On the other hand, the solvent ink uses a solvent having a strong resin dissolving power. By using such a solvent, the solvent ink penetrates into the recording medium after image recording and the durability thereof is improved. Therefore, it is used for commercial printing in which durability is important.

  Inkjet recording devices as an alternative to screen printing methods use various solvent inks such as solvent inks, oil-based inks, and UV curable inks, and the solvents used in these inks may swell or dissolve the ink jet head adhesive. There is. As such a solvent, for example, n-methylpyrrolidone, dimethylformamide, 2-pyrrolidinone, ethyl butyrate, diethylene glycol monoethyl ether acetate, cyclohexanone, butoxyethyl acetate and the like are used.

  However, an adhesive composition that can be used with high reliability even in an organic solvent having extremely strong dissolving power of resins has not been known so far.

  By the way, when bonding each member in the manufacturing process of the inkjet head, the temperature at which the inkjet head is heated is preferably low, and ideally room temperature is desirable. By bonding at a lower temperature, it is possible to prevent depolarization of the piezoelectric element and to reduce stress generated due to a difference in linear expansion coefficient between the members to be bonded. When members having greatly different linear expansion coefficients are bonded by heat curing, when the members are returned to room temperature, the stress is distorted, peeled off or cracked by the stress.

  Examples of the adhesive having solvent resistance in the solvent ink include the adhesives described in Patent Documents 1 to 3. The adhesive described in Patent Document 1 or Patent Document 2 is immersed in an oil-based ink containing a saturated hydrocarbon having 15 to 18 carbon atoms or a monohydric alcohol having 15 to 18 carbon atoms, and the mass increase is 5%. An amine-cured epoxy adhesive that is: Furthermore, Patent Document 3 discloses an adhesive made of an epoxy resin that is cured at 60 ° C. by using an amine curing agent.

Examples of the curing method of the adhesive that improves the solvent resistance include the methods described in Patent Document 4 and Patent Document 5. Patent Document 4 discloses a method of improving the solvent resistance by increasing the crosslinking density by slowing the rate of temperature rise from room temperature to 100 ° C. when curing an epoxy resin with a diandiamide curing agent. . Furthermore, Patent Document 5 discloses a method for assembling an electronic device by heating a polyfunctional epoxy resin with an imidazole-modified product at 150 ° C. for 1 minute to cure.
JP 2001-301160 A JP 2001-301178 A JP 2002-302591 A JP 2003-266708 A JP 2000-68294 A

  However, the adhesive composition described in Patent Document 1 or Patent Document 2 has insufficient resistance to solvent ink. Further, the adhesive composition described in Patent Document 3 is also excellent in alkali resistance, but has a problem that durability is low with respect to a solvent ink containing a resin dissolving agent. Furthermore, since Patent Document 4 requires a high curing temperature, there is a problem that warping, cracking, and emission performance are reduced due to stress generated when members having different thermal expansion coefficients are mounted. Furthermore, the method of curing an adhesive described in Patent Document 5 has a problem that it cannot be applied to an ink jet head using a piezoelectric element because the curing temperature is too high to cause depolarization of the piezoelectric element.

  Here, generally as an adhesive with high solvent resistance, an epoxy adhesive is mentioned as above-mentioned. It is known that epoxy adhesives have different properties depending on the curing agent used. Aliphatic polyamines, alicyclic polyamines and polyamides are known as curing agents that are cured at a relatively low temperature from room temperature to about 60 ° C. However, when the epoxy resin is cured at room temperature with these amine curing agents, there are disadvantages that a polar group is formed in the middle, and that the distance between the crosslinking points is long, so that it is vulnerable to water and solvents. Epoxy adhesives that cure at room temperature can be used from room temperature to medium temperature heating as long as water-based ink is used. However, the solvent ink having a strong resin dissolving power is insufficient in solvent resistance, so that ink leakage is likely to occur during use.

  The curing of the epoxy adhesive with the amine curing agent will be described. Since the primary amine in the amine curing agent has high activity, an epoxy group is opened at room temperature and added to form a secondary amine and a hydroxyl group. This is repeated and the chain grows linearly. When this secondary amine further reacts with an epoxy group, a tertiary amine and a hydroxyl group are formed, and this is repeated to form a three-dimensional structure. However, since this crosslinking structure incorporates an amine curing agent and contains a hydroxyl group, it is likely to swell by absorbing the solvent. The amine curing agent and hydroxyl group remaining in this three-dimensional structure may be reacted with the remaining epoxy group, but at this point, the glass transition temperature is high because the crosslinked structure has already been formed and the glass transition point is high. Unless heated above, these groups cannot contact and react. For this reason, heating at 150 to 200 ° C. or more is necessary, and the polarization of the piezoelectric element is deteriorated.

When an imidazole is used as a curing agent, a highly durable adhesive can be obtained, but the conventional technique requires heating at about 150 ° C. for curing. Since imidazole contains a secondary amine and a tertiary amine, the activity is slightly inferior to a curing agent containing a primary amine, the reaction is slow at room temperature, and it is necessary to heat to about 150 ° C. However, the curing reaction mechanism is different from the primary amine, and imidazole works as a catalyst for initiating the curing reaction, and when the curing reaction starts, the epoxy resins are cross-linked by an ether bond, so that no polar group is contained in the cured product. In addition, since the distance between the crosslinking points is short, the solvent resistance is excellent. In addition, primary amines are highly active, so they react when touching the skin, causing fog and itching, but imidazole does not.
The structure of a cured product cured with a primary amine typically contains a hydroxyl group and an amino bond, but when cured with imidazole, it only contains an ether bond. Carbon-carbon bonds constituting benzene rings and methyl groups have the highest chemical durability, followed by ether bonds. In contrast, hydroxyl groups and amino bonds have low chemical durability and are easily swollen or dissolved in organic solvents.

  From the above, when imidazoles are used as a curing agent, an adhesive layer with excellent solvent resistance is formed, but the conventional technique requires heating at about 150 ° C. due to the difference in thermal expansion. For this reason, it has been difficult to use it for manufacturing a piezo ink jet head.

  Moreover, since the density of the nozzle holes in the nozzle plate used in recent years is increased to 180 to 600 dpi (dpi represents the number of dots per inch, that is, 2.54 cm), The intervals between the ink flow paths are formed so as to be very narrow, 40 to 70 μm. In addition, the number of ink flow paths is very large, such as 100 to 1000 in the case of a serial head and 1000 to 8000 in the case of a line head. That is, there are thousands of fine bonding portions with a width of about 40 to 70 μm in one inkjet head, and bonding of the nozzle plate is the most difficult technique for manufacturing the head.

  For example, when an ink jet head is manufactured, if the adhesive composition flows into the ink flow path and hardens, the ink flow path may be blocked, so that the adhesive leaks even at one of thousands of bonding points. Ink droplets cannot be ejected from the nozzle holes. Moreover, solvent resistance is required for the adhesive used for the adhesive portion that always comes into contact with the ink. If the adhesive absorbs the ink and swells or dissolves, the ink may leak or fine particles such as filler added to the adhesive may flow into the ink flow path and clog the nozzle holes.

  Therefore, as the adhesive used for the ink jet head, one having a high viscosity is used so that it does not flow into the ink flow path at the time of adhesion (particularly heat curing). Further, an adhesive having a high solvent resistance that does not cause swelling or dissolution after being subjected to a long-time immersion test in an ink of normal temperature to 60 ° C. is used.

  By the way, when the adhesive is heated and cured at the time of manufacturing the ink jet head, the heating temperature is preferably as low as possible and ideally cured at room temperature. The reason for this is to prevent depolarization of the piezoelectric element and to prevent warping, cracking, and deterioration of the emission performance due to the difference in linear expansion coefficient.

  The depolarization of the piezoelectric element is a phenomenon in which the piezoelectric characteristics are lost when the piezoelectric element is heated to a high temperature. Due to such characteristics, there is a problem that the piezoelectric element cannot be heated to a temperature of 100 to 150 ° C. or higher.

  Here, in order to completely cure the conventional epoxy adhesive, it is necessary to heat to 150 ° C. or higher, and there is a problem that curing is insufficient at 150 ° C. or lower. Therefore, when water-based ink is used, problems such as dissolution of the adhesive do not occur even when cured at 100 ° C. or less, but when solvent ink is used, there is a problem that the adhesive dissolves.

  Damage due to difference in linear expansion coefficient means that when the linear expansion coefficients of the adherends are different, the contraction rate of the member when cooled after heat curing is different, such as peeling or cracking caused by distortion occurring in the bonded part It is a damage.

  As described above, even if members having different linear expansion coefficients are bonded to each other in the vicinity of room temperature, no problem occurs. However, the problem when members having different linear expansion coefficients are bonded by heating will be described in more detail.

The stress P due to thermal shrinkage generated between the adhesive and the member to be bonded when cooled to room temperature after heat curing is generally determined by the following equation.
P≈EΔα (t ₂ −t ₁ )
(Where E: elastic modulus of adhesive, α: difference in linear expansion coefficient, t ₂ : curing temperature, t ₁ : room temperature)

For example, when the linear expansion coefficient of the piezoelectric element PZT is 2 × 10 ⁻⁶ ppm / K, the linear expansion coefficient of the epoxy adhesive is 8 × 10 ⁻⁵ ppm / K, and the elastic modulus is E = 3430 MPa / ppm, the temperature is 100 ° C. When it is cured and returned to 25 ° C., the stress generated in the bonded portion is P = 20.07 MPa. For this reason, warpage occurs in the bonded portion, compressive stress is generated in the PZT, and PZT is partially depolarized, causing discharge fluctuation. When the curing temperature is lowered to 60 ° C., the internal stress becomes 9.3 MPa, and the warpage of the bonded portion is reduced, but warpage still remains at both ends of the PZT, and the ink flow path formed near the end of the PZT is deformed. Slight image unevenness occurs.

Generally, the linear expansion coefficient of PZT is 2 × 10 ⁻⁶ = 2 ppm / K, but the linear expansion coefficient of a resin member as a member to be bonded to which PZT is bonded is 8 × 10 ⁻⁵ to 2 × 10 ⁻⁴ (80 ˜200 ppm / K), for example, when 2 ppm / K PZT and 140 ppm / K resin member are cured at 100 ° C., the PZT stretches 15 μm per 100 mm length, the resin member stretches 1050 μm, and 1 mm in between Deviation occurs. In the case of a 180 dpi ink jet head, the gap between the ink flow paths is 70 μm, so this 1 mm deviation greatly affects.

  Here, when a fine filler is added to the epoxy adhesive, the linear expansion coefficient can be reduced in almost proportion to the amount added. For example, when 50% by mass or more of a filler is added to the epoxy adhesive, the linear expansion coefficient of PZT can be matched. However, in the inkjet head, since PZT and the resin member are bonded using an epoxy adhesive, even if the linear expansion coefficients of PZT and the epoxy adhesive are matched, the linear expansion coefficient of the resin member and the epoxy adhesive is If the difference is large, the bonded portion will be damaged. When the damaged part is large, ink leaks from the beginning, and thus such an ink jet head can be eliminated. However, when the damaged part is extremely small, the ink starts to leak during use, and the reliability of the ink jet head is lowered. For this reason, there is a problem that it is difficult to precisely and reliably bond members having different linear expansion coefficients.

  It is also possible to reduce the linear expansion coefficient by adding a filler to the resin member. Therefore, conventionally, the linear expansion coefficient of the resin member and the epoxy adhesive is reduced, and the influence due to the heat shrinkage is reduced. However, PZT is partially depolarized due to minute distortion, and the ejection amount from a part of the inkjet head, particularly from both ends, fluctuates, causing image unevenness. Also, it is preferable to reduce the curing temperature as much as possible from the point that it is difficult to accurately adjust the linear expansion coefficient of various members from different manufacturers with the amount of filler added. For example, when the curing temperature is lowered from 100 ° C. to 60 ° C., the influence of heat shrinkage can be halved.

  The filler is preferable because it not only reduces the linear expansion coefficient of the resin member but also improves the solvent resistance of the resin member. Examples of the filler include silica and alumina. The addition amount is preferably 30 to 50% by mass with respect to the resin.

  On the other hand, an epoxy adhesive is mentioned as another solvent-resistant adhesive which is another object of the present application. As described above, it is known that the epoxy adhesive has different properties depending on the curing agent. However, when the epoxy adhesive is cured using the curing agent, the reaction between the epoxy resin and the curing agent proceeds to form a polar group, which is disadvantageous in that it is easily dissolved. Epoxy adhesives that can be cured at low temperatures have these problems, so there is no problem as long as water-based inks are used, but when using solvent inks that have strong resin dissolving power, Is easily dissolved or the strength is lowered.

  The present invention has been made in view of such points, and has high chemical resistance and solvent resistance, and has excellent durability and discharge performance even when using an adhesive composition and solvent ink that can be cured at room temperature to medium temperature. An object of the present invention is to provide an inkjet head and a method for manufacturing the same.

  The above object of the present invention has been achieved by the following constitution.

The invention according to claim 1 is an adhesive composition,
It contains a compound having three or more epoxy groups with an epoxy equivalent of 120 or less as the main agent, and has a pyrrole type nitrogen atom and a pyridine type nitrogen atom as the curing agent , and the 2-position is unsubstituted and the 4-position is alkyl. imidazole substituted with a group or aralkyl group, characterized in that it contains 5 to 50 parts by weight relative to compound 100 parts by weight with the three or more epoxy groups.

  The invention according to claim 2 is the adhesive composition according to claim 1, further comprising bisphenol A type epoxy resin or bisphenol F type epoxy resin as a compound having two epoxy groups. To do.

The invention according to claim 3 is the adhesive composition according to claim 1 or 2 , wherein the compound having three or more epoxy groups is a compound of the following general formula (1): To do.

（式中、Ｒ₁、Ｒ₂は水素またはアルキル基を表す。）

(In the formula, R ₁ and R ₂ represent hydrogen or an alkyl group.)

The invention of claim 4 includes a channel substrate having a channel Lee ink, and the adhesive member is bonded to the channel substrate, and the second bonded component is further adhered to the adherend member, An inkjet head comprising:
The channel substrate and the adherend member, or the adherend member and the second adherend member contain, as a main agent, a compound having three or more epoxy groups having an epoxy equivalent of 120 or less, and cured. As an agent, imidazole having a pyrrole type nitrogen atom and a pyridine type nitrogen atom and substituted at the 4-position with an alkyl group or an aralkyl group is used in an amount of 5 to 50 weights with respect to 100 parts by weight of the compound having three or more epoxy groups. It is characterized by being bonded using a part-containing adhesive composition.

A fifth aspect of the present invention is the ink jet head according to the fourth aspect , wherein the channel substrate and the adherend member, or between the adherend member and the second adherend member. Thus, the difference in coefficient of linear expansion exceeds 12 ppm / K.

The invention according to claim 6 is the ink jet head according to claim 4 or 5 , wherein the ink to be ejected is a solvent ink.

The invention according to claim 7 is the ink jet head according to claim 6 , wherein the solvent ink has a SP value of 9.5 to 15.0 and a dipole efficiency of 2.0 to 5. It is characterized by containing 3% or more of 0 solvent with respect to the total solvent.
Here, specific examples of the solvent include N, N-dimethylformamide (SP = 12.1, dipole efficiency = 3.86), N-methyl-2-pyrrolidinone (SP = 11.3, dipole efficiency). = 4.09), ethyl lactate (SP = 10.0, dipole efficiency = 2.14), cyclohexanone (SP = 9.9, dipole efficiency = 3.01), 2-pyrrolidinone (SP = 14.7). , Dipole efficiency = 3.83) and the like. The SP (Solubility Parameter) value ((cal / cm) ^1/2 ) is calculated by the Bicerano method (see Prediction of Polymer Properties (Plastics Engineering, 65) Jozef Bicerano (Author)). The dipole efficiency is calculated by MOPAC AM1.

The invention according to claim 8 is a method of manufacturing an inkjet head,
It contains a compound having three or more epoxy groups having an epoxy equivalent of 120 or less as the main agent, and has a pyrrole nitrogen atom and a pyridine nitrogen atom as the curing agent, and is substituted with an alkyl group or an aralkyl group at the 4-position. imidazole, an adhesive composition containing 5 to 50 parts by weight relative to compound 100 parts by weight with the three or more epoxy groups, a member of linear expansion coefficient have a difference of more than 12 ppm / K at 60 ° C. or less It is characterized by bonding.

According to a ninth aspect of the invention, there is provided a channel substrate having an ink channel, an adherend member bonded to the channel substrate, and a second adherend member further bonded to the adherend member. An inkjet head manufacturing method comprising:
There is a difference in linear expansion coefficient exceeding 12 ppm / K between the channel substrate and the adherend member, or between the adherend member and the second adherend member,
The channel substrate and the adherend member, or the adherend member and the second adherend member contain, as a main agent, a compound having three or more epoxy groups having an epoxy equivalent of 120 or less, and cured. As an agent, imidazole having a pyrrole type nitrogen atom and a pyridine type nitrogen atom and substituted at the 4-position with an alkyl group or an aralkyl group is used in an amount of 5 to 50 weights with respect to 100 parts by weight of the compound having three or more epoxy groups. Part of an adhesive composition, wherein 0.2 to 10% of fine particles with an average particle size of 0.1 μm or less are added to increase the viscosity, and the adhesive composition is adhered. To do.

  According to the present invention, it is possible to provide an ink jet head that has high chemical resistance and solvent resistance, and has excellent durability and discharge performance even when an adhesive and solvent ink that can be cured at low temperature are used.

[First embodiment]

First, an embodiment of the adhesive composition according to the present invention will be described.
The adhesive composition according to the present invention contains imidazole having a pyrrole nitrogen atom and a pyridine nitrogen atom as a curing agent and substituted at the 4-position with an alkyl group or an aralkyl group, and has three or more epoxy groups as a main agent. It is an adhesive composition characterized by containing the compound which has this.

  The alkyl group represents a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a hexyl group, a dodecyl group, a pentadecyl group or the like, a straight chain alkyl group, and a cyclic alkyl group such as a cyclopentyl group or a cyclohexyl group. These can have substituents. Examples of the substituent include alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, halogen atoms, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, sulfonamido groups, sulfamoyl groups, ureido groups, and acyl groups. , Acyloxy group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, cyano group, nitro group, sulfo group, hydroxyl group and the like. The aralkyl group is an alkyl group substituted with an aryl group, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group, and these may be substituted with the substituents mentioned for the alkyl group.

  Further, in the imidazole having a pyrrole nitrogen atom and a pyridine nitrogen atom and substituted at the 4-position with an alkyl group or an aralkyl group, it may have a substituent at a position other than the 4-position. Are those exemplified as the substituent of the alkyl group. Specific examples include 2-ethyl-4-methylimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole and the like. Further, among imidazoles having a pyrrole type nitrogen atom and a pyridine type nitrogen atom and substituted at the 4-position with an alkyl group or an aralkyl group, 2-position unsubstituted imidazole is preferred.

  In addition to imidazole having a pyrrole type nitrogen atom and a pyridine type nitrogen atom and substituted at the 4-position with an alkyl group or an aralkyl group, hexahydrophthalic anhydride, diethylenetriamine, triethylenetetramine, polyamide, and JP-A-7-137265 A curing agent such as an aliphatic amine type or aromatic amine type described in (1) may be used in combination.

  The compounding amount of imidazole having a pyrrole type nitrogen atom and a pyridine type nitrogen atom as a curing agent and substituted at the 4-position with an alkyl group or an aralkyl group is 100 parts by mass of a compound having three or more epoxy groups as a main agent. On the other hand, it is 5 to 50 parts by weight, preferably 4 to 20 parts by weight, and more preferably 6 to 15 parts by weight.

Specific examples of the compound having three or more epoxy groups include triglycidyl-p-aminophenol (92.3), tetraglycidyldiaminodiphenylmethane (105.5), triglycidyl isocyanurate (99), and triglycidyl uranium. Zole (89.7), triglycidylaminocresol (97), tetraglycidyl-1,3-diaminomethylcyclohexane (91.5), and glycerol triglycidyl ether (86.7). In addition, the numerical value in a parenthesis represents each epoxy equivalent. Here, the epoxy equivalent is a value obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups, and the smaller the value, the shorter the distance between the crosslinking points.
Furthermore, a novolac epoxy resin may be used as the compound having three or more epoxy groups. As the novolac epoxy resin, a phenol novolac type epoxy resin and a cresol novolac type epoxy resin are applicable. Specific examples of the phenol novolac type epoxy resin include EPPN201 (manufactured by Nippon Kayaku Co., Ltd.), EPPN202 (manufactured by Nippon Kayaku Co., Ltd.), Epicoat 154 (manufactured by Japan Epoxy Resin Co., Ltd.), and DEN-438 (manufactured by Dow Chemical). Etc. Specific examples of the cresol novolak type epoxy resin include EOCN102 (manufactured by Nippon Kayaku Co., Ltd.), EOCN103S (manufactured by Nippon Kayaku Co., Ltd.), EOCN104S (manufactured by Nippon Kayaku Co., Ltd.), EOCN1020 (manufactured by Nippon Kayaku Co., Ltd.). EOCN1025 (manufactured by Nippon Kayaku Co., Ltd.), EOCN1027 (manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S (manufactured by Japan Epoxy Resin Co., Ltd.), and the like.
Moreover, as a compound which has 3 or more epoxy groups, the thing of Unexamined-Japanese-Patent No. 2002-210985 is mentioned. Here, the compound having three or more epoxy groups preferably has an epoxy equivalent of 120 or less, more preferably 100 or less.

The compound having three or more epoxy groups is more preferably the compound of the general formula (1). Examples of the alkyl group represented by R ₁ and R ₂ in the general formula (1) include a branched group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a hexyl group, a dodecyl group, a pentadecyl group, a linear alkyl group, and It represents a cyclic alkyl group such as a cyclopentyl group or a cyclohexyl group, and these may have a substituent. Examples of the substituent include alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, halogen atoms, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, sulfonamido groups, sulfamoyl groups, ureido groups, and acyl groups. , Acyloxy group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, cyano group, nitro group, sulfo group, hydroxyl group and the like.

  Specific examples of the compound having three or more epoxy groups include triglycidylaminophenol and triglycidylaminocresol.

You may mix and use the compound which has two epoxy groups with respect to the compound which has these 3 or more epoxy groups. The epoxy equivalent of the compound having two epoxy groups is preferably 150 or less. Examples of the compound having two epoxy groups include bisphenol A type epoxy resin (184 to 194) (Epicoat 828; manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol F type epoxy resin (160 to 170) (Epicoat 806; Japan Epoxy). Resin Co., Ltd.) and those described in JP-A No. 2002-210985. Moreover, the mixing | blending becomes like this. The compound which has 3 or more epoxy groups with respect to 100 mass parts of compounds which have two epoxy groups will be 10-100 mass parts, and 20-50 mass parts is more preferable.
As the main agent according to the present invention, not only one of these compounds having three or more epoxy groups and a compound having two epoxy groups are used in combination, but also several kinds of compounds having three or more epoxy groups are used. And a compound having two epoxy groups may be used in combination.

  Examples of a method for improving the crosslinking density of the adhesive composition for improving the resistance after curing include a method for increasing the functional number of the main agent. One method is to use a novolac epoxy resin having three or more epoxy groups as a main agent, but it has low fluidity at room temperature and it is difficult to obtain sufficient adhesive force at room temperature curing. There is a problem that sex cannot be obtained. However, the performance can be improved by using a compound having three or more epoxy groups and having an epoxy equivalent of 120 or less, and further 100 or less.

  From the cured adhesive composition, an imidazole ring-containing compound and a compound having three or more epoxy groups are detected in a form in which the epoxy group is eliminated by pyrolysis GC mass spectrum. Moreover, an imidazole ring containing compound is detected by solid state NMR.

  In addition, an inorganic filler is used in the adhesive composition of the present invention. Examples of the inorganic filler include carbonates such as calcium carbonate and magnesium carbonate; sulfates such as barium sulfate and magnesium sulfate; silicates such as aluminum silicate and zirconium silicate; iron oxide, titanium oxide, aluminum oxide and oxidation. Examples thereof include, but are not limited to, oxides such as zinc; kaolin, talc, asbestos powder, quartz powder, mica, and glass fiber. Among these, it is preferable to use one or more of titanium oxide and silica in combination from various points.

  When an inorganic filler is used, it is desirable to use a silane coupling agent, a titanium coupling agent, or the like as a coupling agent in order to couple the inorganic fine particles and the organic material contained in the adhesive composition.

  Specific examples of the silane coupling agent include, for example, γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, Aminosilane coupling agents such as N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane; γ-glycidoxypropyltrimethoxy Examples thereof include epoxy silane coupling agents such as silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane.

  Specific examples of the titanium coupling agent include, for example, isopropyl tri (N-aminoethyl-aminoethyl) titanate, dicumylphenyloxyacetate titanate, diisostearoyl ethylene titanate, and the like. It is not something. The addition amount of these coupling agents varies greatly depending on the type of the adhesive composition of the present invention, but when the total of the adhesive composition to which the inorganic filler is added is 100 parts by mass, it is 5 parts by mass or less. Preferably, when it exceeds 5 parts by mass, the cohesive strength of the organic material is lowered, and as a result, the adhesive strength and reliability of the adhesive composition are lowered.

  Moreover, it is preferable to add 0.2 to 10% of fine particles having an average particle size of 0.1 μm or less to the adhesive composition of the present invention to increase the viscosity, and fine particles having an average particle size of 0.1 μm or less. Specifically, Aerosil R202 manufactured by Nippon Aerosil Co., Ltd. may be mentioned.

  By using the adhesive composition in the present embodiment, curing at room temperature to 60 ° C. is possible, and the difference in linear expansion coefficient between the adherend members can be applied in the range of 12 ppm / K to 100 ppm / K. . In particular, curing at room temperature to 40 ° C. is preferable because solvent resistance is not lowered, and warping, cracking, and peeling due to a difference in linear expansion coefficient are reduced, and emission performance is improved.

  The present inventor has discovered that the imidazole curing agent according to the present invention can sufficiently withstand a strong resin solubilizing agent contained in a screen printing ink when used as an epoxy resin curing agent in the same manner as an amine. As a result, the vast ink jet technology that has been developed so far has been improved to enable inkjet application to screen printing, which has been impossible or problematic until now.

  Next, the structure of the inkjet head according to the present invention to which the above-described adhesive composition is applied will be described with reference to the drawings. FIG. 1 is a longitudinal sectional view of an ink jet head 1a according to the present embodiment. The inkjet head 1a is a piezo-type inkjet head, and is formed to extend in a direction substantially orthogonal to FIG. Here, as shown in FIG. 1, the direction substantially parallel to the recording medium and substantially orthogonal to the inkjet head 1a is defined as the front-rear direction, the width direction of the inkjet head 1a is defined as the left-right direction, and the direction substantially orthogonal to the recording medium is defined. The vertical direction.

  The inkjet head 1a is provided with a cover 10 that covers the entire inkjet head 1a. Inside the cover 10, an ink chamber 3 that discharges ink droplets D by deforming the internal volume is provided with one end protruding from the cover 10. The lower surface of the ink chamber 3 is an adhesive surface including an opening of the ink flow path 5 described later, and a flat nozzle plate 50 facing the recording medium is bonded. The nozzle plate 50 is bonded to the ink chamber 3 via the bonding portion b, and the bonding portion b is a portion where the adhesive composition according to the present invention is cured. The nozzle plate 50 is provided with a nozzle hole 51 for discharging the ink droplet D so as to face the ink chamber 3.

  FIG. 2 is an exploded perspective view of the ink chamber 3, the nozzle plate 50, and the lid member 2 described later. FIG. 3 is a cross-sectional view taken along the line II in FIGS. 1 and 2.

  The ink chamber 3 includes a piezoelectric ceramic substrate 11 serving as a substrate. The piezoelectric ceramic substrate 11 includes a piezoelectric element 11 </ b> A that serves as a substrate for the ink chamber 3. A piezoelectric element 11B polarized in the direction opposite to the piezoelectric element 11A is attached to the front surface of the piezoelectric element 11A. The piezoelectric element 11 </ b> A and the piezoelectric element 11 </ b> B are bonded via the bonding portion 80, and the bonding portion 80 is a portion where the adhesive composition according to the present invention is cured.

  On the front surface of the piezoelectric ceramic substrate 11, a plurality of concave portions 31 extending in the vertical direction are formed at predetermined intervals in the width direction (left-right direction) of the inkjet head. As shown in FIG. 2, the depth of the recess 31 is formed so as to be deeper than the bonding portion 80 of the piezoelectric ceramic substrate 11. Moreover, the upper end of the recessed part 31 is formed so that it may become a substantially circular arc shape in side view. Furthermore, an electrode film 3 a to which a voltage based on image information is transmitted is attached to the front surface of the recess 31.

  As shown in FIG. 1, an FPC 40 to which image information is input is electrically connected to the upper end of the electrode film 3a. An adhesion portion c made of the adhesive composition according to the present invention is formed at the adhesion site between the electrode film 3a and the FPC 40. Further, the FPC 40 is reinforced and bonded to the piezoelectric ceramic substrate 11 through the bonding portion i. A driving IC 45 that generates a voltage based on image information input to the FPC 40 is bonded to the front surface of the FPC 40. An adhesion portion d made of the adhesive composition according to the present invention is formed at the adhesion portion of the drive IC 45.

  An ink flow path 5 in which ink flows in the direction of the arrow shown in FIG. 1 is provided inside the electrode film 3a. As shown in FIG. 2, the ink flow path 5 is formed according to the shape of the recess 31, and the front surface of the ink chamber 3 is substantially uniform. A protective film 4 is provided on the outer surface of the ink flow path 5 as an outer film for preventing damage due to deformation of the electrode film 3a.

  On the front surface of the ink chamber 3, a flat lid member 2 formed so that the length in the vertical direction is shorter than the length of the recess 31 is bonded. The lid member 2 is formed of, for example, a flat plate made of glass, ceramics, metal, or plastic. Further, as shown in FIG. 3, an adhesive portion a made of the adhesive composition according to the present invention is interposed between the ink chamber 3 and the lid member 2.

  As shown in FIG. 1, a manifold member 20 described later is bonded to the front surface of the lid member 2 so as to cover the opening of the recess 31. These are bonded using the adhesive composition according to the present invention, and an adhesive portion f is provided between the lid member 2 and the manifold member 20, and between the piezoelectric ceramic substrate 11 and the manifold member 20. An adhesive portion e is formed.

  The manifold member 20 is provided with an ink tube 30 via an adhesive portion h. An ink storage (not shown) is connected to the ink tube 30 so as to supply ink to the manifold member 20. Further, a filter 35 that removes foreign matters in the supplied ink is provided inside the manifold member 20 via an adhesive portion g. The adhesive part g is also obtained by curing the adhesive composition according to the present invention, like the other adhesive parts.

  In the inkjet head 1a of the present embodiment, the bonding part a, the bonding part b, and the bonding part e to the bonding part h are parts that directly touch ink.

  Next, the ink used in this embodiment will be described.

  The ink used in the inkjet head of the present invention contains a solvent having an SP value of 9.5 to 15.0 and a dipole efficiency of 2.0 to 4.5 with respect to the total solvent of 3% or more. The effect of the present invention is remarkable.

  Here, the SP value is a value of a solubility parameter used to determine the solubility of the resin member in the organic solvent. The solvent SP refers to the square root of the cohesive energy density of the solvent, and the resin SP is the solvent SP that best dissolves the resin. Since SP is a concept proposed for substances having no polarity, SPs match if they are nonpolar substances, or dissolve if the difference is within 1.35. However, this difference widens when it has polarity, and a wide range of resins dissolve in a wide range of solvents. Since many materials used for inkjet heads and inks have polarity, it is preferable to simultaneously consider the dipole efficiency representing the polarity of SP and the solvent in order to determine their solubility.

  Since N-methylpyrrolidone used as a solvent for vinyl chloride has SP = 11.3, a resin having SP = 10 to 13 is well dissolved. Furthermore, since N-methylpyrrolidone has a dipole efficiency of 4.09 and a high polarity, even if the resin has an SP value outside this range, those having polarity are dissolved. Thus, N-methylpyrrolidone has an extremely strong resin dissolving power, and most of the resin swells and dissolves except for fluororesins and completely cured thermosetting resins.

  The organic resin used in the ink jet head has an SP of about 9 to 11 including an epoxy resin, and almost all is soluble in N-methylpyrrolidone. N-methylpyrrolidone is a very strong solvent and dissolves many resins. The liquid crystal alignment film coating apparatus is made of stainless steel, and ink obtained by dissolving polyimide in N-methylpyrrolidone is used in a stainless steel container. If the ink jet head is made of stainless steel and the stainless steel members are joined with a eutectic alloy, the solvent resistance becomes perfect, but it is difficult to produce an ink jet head with a fine structure made of stainless steel with poor workability. Even if it can be manufactured, the price is high. In order to manufacture a high-performance inkjet head having a fine structure at an inexpensive price, it is preferable to manufacture by bonding a piezoelectric element and a resin member. Since resin can be injection molded, a manifold with a complex structure can be easily manufactured. However, there is no good solvent-resistant adhesive, and it cannot be manufactured, or a small head can be manufactured, but its life is short and its reliability is not sufficient.

Here, in the ink-jet head 1a, the adhesive part a and the adhesive part b are as thin as possible and need not protrude into unnecessary parts, and are the parts that require the highest bonding accuracy. It is preferable to use an adhesive having a small thermal shrinkage during curing so that the FPC 40 does not peel off. Since the bonding portion d is around the contact point with the driving IC, it is preferable to use an adhesive that is resistant to stress. It is preferable that the amount of the adhesive in the adhesive part g is small so as not to clog the filter.
In the bonding part a to the bonding part h and the bonding part 80, the bonding process is performed at a low temperature of 100 ° C. or less and in a short time at which the piezoelectricity of the piezoelectric ceramic substrate 11 is not lost, and the adhesive is in the middle of curing. It is preferable that does not flow out to other than the bonded portion.

  In the present embodiment, the above-described problems have been solved by using the adhesive composition according to the present invention for the adhesive part a to the adhesive part h and the adhesive part 80. Moreover, it is possible to adhere members having a difference in linear expansion coefficient exceeding 12 ppm / K. Further, solvent ink can be used, and the solvent contains a solvent having an SP value of 9.5 to 15.0 and a dipole efficiency of 2.0 to 4.5 with respect to the total solvent of 3% or more. Can be used.

  Next, the manufacturing method of the inkjet head 1a using the adhesive composition which concerns on this invention is demonstrated.

  First, a method for manufacturing the ink chamber 3 will be described. In the ink chamber 3 of this embodiment, the piezoelectric ceramic substrate 11 and the lid member 2 are bonded, and then cut in the front-rear direction of the ink chamber 3 to form two ink chambers 3.

  First, the piezoelectric ceramic substrate 11 is formed by bonding the piezoelectric element 11B to the front surface of the piezoelectric element 11A using the adhesive composition according to the present invention. At this time, the piezoelectric element 11A and the piezoelectric element 11B are bonded so that the polarization directions are reversed, and an adhesive portion 80 made of the adhesive composition according to the present invention is formed between the two.

  Subsequently, a recess 31 is formed on the front surface of the piezoelectric ceramic substrate 11 by dicing or the like. At this time, as shown in FIG. 4A, the side view of the recess 31 is formed such that both ends are arc-shaped and the center is substantially parallel to the front surface of the piezoelectric ceramic substrate 11.

  Then, the electrode film 3a is formed inside each recess 31 by a film forming method such as vapor deposition. Thereafter, similarly, the protective film 4 is formed inside the electrode film 3a. An FPC 40 is electrically connected to the upper end of the electrode film 3a, and an adhesive portion c is formed using the adhesive composition according to the present invention. Further, the FPC 40 is reinforced and bonded to the piezoelectric ceramic substrate 11 to form an adhesive portion i made of the adhesive composition according to the present invention.

  Next, the lid member 2 is bonded to the front surface of the piezoelectric ceramic substrate 11 by using the adhesive composition according to the present invention to form the bonded portion a. Since the length dimension in the vertical direction of the lid member 2 is formed to be shorter than the length dimension of the concave portion 31, a part of the front surface of the concave portion 31 is opened as shown in FIG. Will remain. Further, since the length dimension of the lid member 2 in the left-right direction is formed so as to be substantially the same as the length dimension of the ink chamber 3, as shown in FIG. All are covered. In this way, the lid member 2 is bonded to the piezoelectric ceramic substrate 11, whereby the inner side of the protective film 4 of the piezoelectric ceramic substrate 11 becomes the ink flow path 5. Here, FIG.4 (b) is sectional drawing in the II-II line | wire of Fig.4 (a). For simplification of illustration, the electrode film 3a and the protective film 4 are omitted in FIG.

  Then, in a state where the piezoelectric ceramic substrate 11 and the lid member 2 are bonded, they are cut into two so as to be symmetric along the left-right direction of the ink chamber 3. The state after cutting is shown in FIG.

  After the cutting, as shown in FIG. 6, the manifold member 20 is bonded using the adhesive composition according to the present invention so as to cover the open portion of the front surface of the recess 31. At this time, one end of the manifold member 20 is bonded to the front surface of the piezoelectric ceramic substrate 11 to form an adhesive portion e. Further, the other end of the manifold member 20 is bonded to the front surface of the lid member 2 to form an adhesive portion f. Since the manifold member 20 is connected to the ink storage unit via the ink tube 30, the ink from the manifold member 20 flows into the ink chamber 3 through the opening of the recess 31.

  Further, the nozzle plate 50 is bonded to the lower surface of the cut ink chamber 3 using the adhesive composition according to the present invention. At this time, adhesion is performed such that the nozzle hole 51 is opposed to a position facing the ink flow path 5 of the ink chamber 3, thereby forming an adhesion portion b.

  The ink chamber 3 manufactured in this way is attached to a cover 10 to form an ink jet head 1a.

  Next, the operation of the inkjet head 1a will be described with reference to FIGS. In FIGS. 7 and 8, the adhesive portions and the protective film 4 are omitted.

  FIG. 7 shows an example of a modification of the ink chamber 3. In the present embodiment, the ink chamber 3 varies in the left-right direction in FIG. 7 based on the input image signal, and the ink volume D is varied to eject the ink droplet D.

  First, when an image signal is input to the inkjet head 1a, the image signal is transmitted to the FPC 40. Since the driving IC 45 is bonded to the FPC 40, the driving IC 45 generates a voltage having a predetermined voltage value based on the transmitted image signal. The generated voltage is energized to the electrode film 3a of the ink chamber 3 through the bonding part i.

  Since the electrode film 3a is adhered to the piezoelectric ceramic substrate 11, when a voltage is applied to the electrode film 3a, a voltage is also applied to the piezoelectric ceramic substrate 11. Here, since the piezoelectric ceramic substrate 11 is composed of piezoelectric elements 11A and 11B polarized in opposite directions, when a voltage is applied to the polarization portion of the piezoelectric ceramic substrate 11, as shown in FIG. Shear deformation to be bent.

  In the present embodiment, the two wall surfaces of the ink flow path 5 that face the side surface of the recess 31 vary. As shown in FIG. 7, adjacent polarization sites are deformed so as to bend in the opposite direction in the left-right direction, and the internal volume of the ink flow path 5 varies. When the internal volume of the ink flow path 5 fluctuates, the ink droplet D is ejected from the ink flow path 5 whose internal volume is reduced accordingly.

  Thus, by using the adhesive composition according to the present invention, a member having a difference in linear expansion coefficient exceeding 12 ppm / K can be bonded under a temperature condition of 60 ° C. or lower. An ink jet head 1a that can be easily manufactured and has high solvent resistance is manufactured. In addition, by using the adhesive composition according to the present invention, the bonded portion a to the bonded portion h and the bonded portion 80, the piezoelectric ceramic substrate 11 as a channel substrate, and the member to be bonded to the piezoelectric ceramic substrate 11. The stress acting between (the lid member 2, the nozzle plate 50, the manifold 20, etc.) or the second adherend member (manifold 20, ink tube 30, filter 35, etc.) bonded to the adherend member is alleviated. The

  In particular, when the manifold 20 is molded from a thermoplastic resin, the molding is easy. However, the manifold 20 has a large coefficient of linear expansion, and a linear expansion integer between the piezoelectric ceramic substrate 11 and the lid member 2. Is more than 12 ppm / K, and since the cross-sectional area is large, the stress received from the piezoelectric ceramic substrate 11 and the lid member 2 is large (conversely, the piezoelectric ceramic substrate 11 and the lid member 2 are also from the manifold 20. High stress is received). Therefore, in this case, the piezoelectric ceramic substrate 11, the cover plate 2, and the manifold 20 are likely to be cracked, distorted, peeled off, etc., but in this embodiment, these members are bonded with the above-mentioned adhesive. Cracking, distortion, peeling, etc. can be effectively prevented.

For example, taking the piezoelectric ceramic substrate 1 and the manifold 20 bonded through the bonding portion e as an example, the difference between the linear expansion coefficients of both exceeds 12 ppm / K.
Further, when the nozzle plate 50 made of polyimide is used, the difference between the linear expansion coefficient of the nozzle plate 50 and the linear expansion coefficient of the piezoelectric ceramic substrate 11 also exceeds 12 ppm / K. Conventionally, when such a nose plate and a channel substrate (in this embodiment, a piezoelectric ceramic substrate) are bonded, the nozzle plate may be bonded with the position shifted, or the adhesive composition in the nozzle hole. However, the above problem can be solved by adhering them using the adhesive composition according to the present invention.
Specifically, when bonding a nozzle plate having a difference in linear expansion coefficient exceeding 12 ppm / K to the end face of the ink chamber 3, fine particles having an average particle diameter of 0.1 μm or less are added to the adhesive composition according to the present invention. By adding 2 to 10% to increase the viscosity and adhering, it is possible to prevent the adhesive composition from flowing to a portion other than the adhesive portion when the adhesive composition is cured.

  In the present embodiment, the piezoelectric ceramic substrate 11 includes the piezoelectric elements 11A and 11B. However, as shown in FIG. 8, the piezoelectric ceramic substrate 11 includes a single piezoelectric element 11C. It is good. In this case, although the amount of fluctuation of the piezoelectric element 11C is limited, as shown in FIG. 8, when the electrode film 3a is provided on the upper half of the side surface of the recess 31 of the piezoelectric ceramic substrate 11, a voltage is applied to the electrode film 3a. When applied, the fluctuation of the ink flow path 5 becomes large, which is preferable.

  In addition, ink is supplied to all the ink flow paths 5 of the piezoelectric ceramic substrate 11 of the present embodiment, but the ink is not supplied to the recess 31 and the ink flow path 5 to which ink is supplied. The ink flow paths 5 may be alternately provided. In this case, as compared with the case where ink is ejected using all the ink flow paths 5, the influence of fluctuations of the piezoelectric element 11A and the piezoelectric element 11B can be absorbed by the ink flow path 5 to which the adjacent ink is not supplied. Therefore, the internal volume of each ink flow path 5 can be accurately changed.

[Second Embodiment]
FIG. 9 is a longitudinal sectional view of an ink jet head 1b of a type in which the internal volume of the ink flow path is changed by expansion and contraction of a piezoelectric element provided on the outer surface of the ink flow path.

  The inkjet head 1b is provided with a nozzle plate 50 in which nozzle holes 51 are formed so as to face the recording medium. A flow path plate 12a is bonded to the upper surface of the nozzle plate 50 through an adhesive portion j. In the flow path plate 12 a, a first ink flow path 5 a that extends in the vertical direction and has an inner diameter larger than the nozzle hole 51 by a predetermined dimension is formed so as to face the nozzle hole 51. A second ink channel 5b extending in the vertical direction is formed at a position not facing the nozzle hole 51 of the channel plate 12a.

  The supply plate 16 is bonded to the upper surface of the flow path plate 12a via the bonding portion k. The supply plate 16 is formed with a first hole 16b having substantially the same cross-sectional shape as the first ink channel 5a so as to face the first ink channel 5a. Further, an ink inlet 16a having a tapered cross section is formed at a position facing the second ink flow path 5b of the supply plate 16 so as to face a pressurizing chamber A which will be described later. A second hole 16c is formed at a position that does not oppose. An ink storage (not shown) is connected to the second hole 16c, and ink is supplied to the second ink flow path 5b through the second hole 16c.

On the upper surface of the supply plate 16, a connection plate 12 b formed so that the length dimension in the width direction is shorter than that of the supply plate 16 is bonded. The connection plate 12b and the supply plate are bonded via the bonding portion l. Here, the adhesive part j to the adhesive part 1 are obtained by curing the adhesive composition according to the present invention.
In the connection plate 12b, holes 12e and 12e are formed at positions facing the first hole 16b and the ink inlet 16a, respectively.

  A spacer plate 12c having an internal space covering the hole 12e is bonded to the upper surface of the connection plate 12b. A flat closing plate 12d is bonded to the upper surface of the spacer plate 12c. Here, the internal space of the spacer plate 12c is vertically surrounded by the closing plate 12d and the connection plate 12b to form the pressurizing chamber A. The closing plate 12d is made of a material that can be deformed in the vertical direction, and the pressurizing chamber A changes its internal volume in accordance with the deformation of the closing plate 12d.

  In this way, by stacking the plates, the ink reservoir, the second ink channel 5b, the pressure chamber A, the first ink channel 5a, and the nozzle hole 51 are connected in this order, and the arrows shown in FIG. Ink flows in the direction of and ink droplets D are ejected.

  A piezoelectric element 13 that varies based on an image signal is provided on the upper surface of the closing plate 12d. A conventionally known piezoelectric element 13 is used and includes an electrode 13a, a piezoelectric element film 13b, and an electrode 13a in this order.

  Each plate 15, 16, 12 a is preferably made of a metal such as plastic, nickel or stainless steel, or a ceramic such as silicon, in order to form the nozzle hole 15 a and the ink inlet 16 a with high dimensional accuracy. Further, as shown in the drawing, it is desirable that the ink inlet 16a is formed with a tapered shape that is reduced in diameter toward the ink circulation direction.

  The closing plate 12d, the spacer plate 12c, and the connection plate 12b are preferably made of ceramics. The material of this ceramic is preferably alumina, zirconia, etc. from the viewpoint of moldability. The plate thickness of the blocking plate 12d is preferably 50 μm or less, more preferably about 3 to 12 μm, the plate thickness of the connection plate 12b is preferably 10 μm or more, more preferably 50 μm or more, and the plate thickness of the spacer plate 12c is preferably 50 μm or more. More preferably, it is 100 μm or more.

  The pressurizing chamber A can be formed as an integrally fired product of ceramics, but it is preferable from the viewpoint of processing accuracy that each plate is bonded with an adhesive.

  The piezoelectric element 11B is formed by forming each component by a film forming method. In this case, it is preferable to use a ceramic substrate mainly composed of zirconium oxide as the closing plate 12d. PZT is preferably used as the material of the piezoelectric element film 13b constituting the piezoelectric operating portion.

[Third embodiment]
FIG. 10 is a cross-sectional view of an inkjet head 1c of the same type as the second embodiment in which the internal volume of the pressurizing chamber A is changed by expansion and contraction of a piezoelectric element provided outside the pressurizing chamber A, and having a different structure. is there.

  The ink jet 1c is provided with a nozzle plate 50 in which nozzle holes 51 are formed so as to face the recording medium. The spacer member 22 is bonded to the upper surface of the nozzle plate 50 via the bonding portion m. The spacer member 22 is provided with an ink flow path 5 made of an elastic material so that one end thereof is connected to the nozzle hole 51. The other end of the ink flow path 5 is provided with an ink supply part 27 connected to an ink storage part (not shown).

  A diaphragm 24 made of an elastic material is bonded to the upper surface of the spacer member 22, and an adhesive portion n is formed therebetween. Here, the adhesion parts m and n are formed of the adhesive composition according to the present invention.

  On the upper surface of the diaphragm 24, a base 21b having convex portions extending in the left-right direction on both side surfaces is provided. The piezoelectric element 23 is provided on the side surface of the base 21b and on the upper surface of the diaphragm 24 so as to expand and contract in the vertical direction when a voltage is applied to its electrode portion. The piezoelectric element 23 is configured to deform the ink flow path 5 via the vibration plate 24. When the piezoelectric element 23 expands below the ink jet head 1c, pressure is applied to reduce the internal volume of the ink flow path 5. It is like that.

  A fixing member 21 a that covers and fixes the upper surfaces of the piezoelectric element 23 and the base 21 b is provided on the upper end surface of the diaphragm 24.

  By forming the inkjet head 1c in this way, a voltage is applied to the piezoelectric element 23 based on image information, the ink flow path 5 is deformed, and the ink droplet D is ejected from the nozzle hole 51. Yes.

  In FIG. 10, the ink flow path 5 is assumed to have a uniform inner diameter. However, in order to efficiently transmit the pressure from the piezoelectric element 23 and eject the ink droplet D, the inner diameter of the ink flow path 5 is reduced. It may be smaller as the nozzle hole 51 is approached.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by this.

[Example 1]
In Example 1, adhesive compositions having various compositions (hereinafter referred to as “adhesives”) were prepared, and their solvent resistance was examined.

  After mixing the main agent and the curing agent described in Table 1, drop them onto a Teflon (registered trademark) sheet so that one drop is 0.1 to 0.2 g, and this is the longest at 35 ° C. as shown in Table 1. Cured for 36 hours to produce adhesive tablets.

Here, the compounds in Table 1 are as follows.
<Main agent>
E1: Bisphenol A type epoxy resin (epoxy equivalent 184 to 194) (Epicoat 828; manufactured by Japan Epoxy Resin Co., Ltd.)
E2: Bisphenol F type epoxy resin (epoxy equivalent 160-170) (Epicoat 806; manufactured by Japan Epoxy Resin Co., Ltd.)
E3: phenol novolac type epoxy resin (epoxy equivalents 172 to 178) (Epicoat 152; manufactured by Japan Epoxy Resin Co., Ltd.)
TGAP: triglycidyl-p-aminophenol novolak: phenol novolak type epoxy resin TGDADPM: tetraglycidyldiaminodiphenylmethane isocyanuric: triglycidyl isocyanurate glycerol: glycerol triglycidyl ether <imidazole-based curing agent>
4MZ: 4-methylimidazole 2MZ: 2-methylimidazole (added as a methanol solution)
2Ph4MZ: 2-Phenyl-4-methylimidazole <Hardener other than imidazole>
TETA: Triethylenetetramine

  Moreover, phr in Table 1 is a value determined by mass of curing agent / mass of main agent × 100.

After measuring the mass of the produced adhesive tablet, it was immersed in a solvent (N-methylpyrrolidone or ethyl lactate) shown in Table 1 and allowed to stand at 60 ° C. for 7 days. Then, the tablets were taken out from the solvent, washed with isopropyl alcohol in a washing bottle, and then the surface isopropyl alcohol was wiped off to measure the mass. In addition, the mass increase rate was calculated | required by the following formula.
Mass increase rate = 100 × (mass after immersion−mass before immersion) / mass before immersion

  From Table 1, the adhesive of the combination of the main agent and the curing agent according to the present invention (the present invention) cures quickly even at a low temperature, and the mass increase rate is smaller than that of the comparative example, and the solvent resistance is excellent. I understand.

[Example 2]
PZT (thickness 700 μm, Curie temperature 210 ° C., linear expansion coefficient 4 ppm / K) and PZT (thickness 150 μm, Curie temperature 210 ° C., linear expansion coefficient 4 ppm / K) are set as follows so that the polarization directions are opposite to each other. A piezoelectric ceramic substrate is obtained by bonding using the adhesive A according to the present invention as shown in FIG. Next, as shown in FIG. 3, a recess having a depth of 300 μm and a width of 70 μm is formed from the thinner PZT side, and aluminum is deposited on the side surface of the recess to form an electrode film. As shown in FIG. 4A, a lid member (AIN having a thickness of 700 μm, linear expansion coefficient 4 ppm / K) is bonded to the bonding member of the piezoelectric ceramic substrate and PZT using an adhesive A, and CVD is performed. Insulating film poly-p-xylylene is processed by the method. Then, it cut | disconnects along the direction orthogonal to the length direction of a recessed part, and forms a head chamber (refer FIG. 5). A nozzle plate (100 μm thick polyimide having a 30 μm diameter nozzle hole) is bonded to the head chamber using an adhesive A (see FIG. 6). Thereafter, as shown in FIG. 6, the electrode was taken out and the manifold (manufactured by PBT, linear expansion coefficient 100 ppm / K) was bonded using the adhesive A, and bonded and cured to form an ink jet head.

<Composition of adhesive A>
Epicoat 807 (bisphenol F; epoxy equivalent 165, manufactured by Japan Epoxy Resin Co., Ltd.) 70 parts by mass Triglycidyl-p-aminophenol (epoxy equivalent 95) 30 parts by mass 4-methylimidazole 10 parts by mass Gas phase method spherical silica (average particle diameter) 15 nm) 3 parts by mass

<Heating conditions for adhesive A during joining>
Heating temperature: 35 ° C
Heating time: 13 hours

<Outgoing test>
In the constructed ink-jet head, an emission test was performed using an emission evaluation dummy ink not including a coloring material. The composition of the dummy ink is as follows.
Butoxyethyl acetate 50 parts by weight Dimethylformamide (SP = 12.1, Dipole efficiency = 3.86) 50 parts by weight

  The difference between the maximum and minimum of the emission speed between the nozzles was 7%, and the uniformity was almost satisfactory. The ink jet head was filled with ink and left for one week at 60 ° C. to emit light, but there was no ink leakage.

  Next, as a comparative example, the adhesive A was replaced by the following adhesive B and cured under the same heating conditions, resulting in ink leakage. Therefore, when the temperature was set at 70 ° C., the difference between the maximum and minimum speeds in the emission test was 18%, and there was a problem in uniformity.

<Composition of adhesive B>
It was produced in the same manner as Adhesive A, except that 2-methylimidazole was used instead of 4-methylimidazole.

[Example 3]
PZT (thickness 700 μm, Curie temperature 210 ° C., linear expansion coefficient 4 ppm / K) and PZT (thickness 150 μm, Curie temperature 210 ° C., linear expansion coefficient 4 ppm / K) are as follows so that the polarization directions are opposite. Bonding is performed using the adhesive C according to the present invention as shown in the drawing to obtain a piezoelectric ceramic substrate. Next, as shown in FIG. 3, a recess having a depth of 300 μm and a width of 70 μm is formed from the 150 μm PZT side, and an electrode film is formed. As shown in FIG. 4A, a lid member (AIN having a thickness of 700 μm, linear expansion coefficient 4 ppm / K) is bonded to the bonding member of the piezoelectric ceramic substrate and PZT using an adhesive C. Parylene processing. Then, it cut | disconnects along the direction orthogonal to the length direction of a recessed part, and forms a head chamber (refer FIG. 5). A nozzle plate (100 μm thick polyimide having a 30 μm diameter nozzle hole) is bonded to the head chamber using an adhesive C (see FIG. 6). Thereafter, as shown in FIG. 6, the extraction of the electrode and the manifold (made of polyamide, linear expansion coefficient 50 ppm / K) were performed using the adhesive C, and bonded and cured to form an ink jet head.

<Composition of adhesive C (present invention)>
Epicoat 807 (bisphenol F; epoxy equivalent 165; manufactured by Japan Epoxy Resin Co., Ltd.) 35 parts by mass Epicoat 154 (produced by Japan Epoxy Resin Co., Ltd.) 35 parts by weight Triglycidyl-p-aminophenol 30 parts by mass 4-methylimidazole 10 parts by mass Aerosil 200 silica particles (manufactured by Nippon Aerosil; silica particles; primary particle size 14 nm)
2 parts by mass

<Heating conditions for adhesive C during bonding>
Heating temperature: 35 ° C
Heating time: 13 hours

<Outgoing test>
In the constructed ink-jet head, an emission test was performed using an emission evaluation dummy ink not including a coloring material. The composition of the dummy ink is as follows.
Butoxyethyl acetate 50 parts by weight Dimethylformamide (SP = 12.1, Dipole efficiency = 3.86) 50 parts by weight

  The difference between the maximum and minimum emission speeds between the nozzles was 7%, and the uniformity was almost satisfactory. The ink jet head was filled with ink and emitted after being left for 1 week at 60 ° C., 2 weeks at 60 ° C., 3 weeks at 60 ° C., and 1 month at 60 ° C., but there was no ink leakage. .

  Next, the adhesive C was replaced with the following adhesives D to H to form an ink jet head, and an emission test was performed.

<Composition of Adhesive D (Comparative Example)>
Epicoat 807 (bisphenol F; epoxy equivalent 165, manufactured by Japan Epoxy Resins Co., Ltd.) 100 parts by mass 2-ethyl-4-methylimidazole 10 parts by mass When cured under the same heating conditions as adhesive C, left at 60 ° C. for 1 week After that, when the emission test was performed, ink leakage occurred. Therefore, when the temperature was set at 100 ° C. and cured, the difference between the maximum and minimum speeds was 18% in the emission test, and uniformity was a problem.

<Composition of adhesive E (present invention)>
Epicoat 807 (bisphenol F; epoxy equivalent 165; manufactured by Japan Epoxy Resin Co., Ltd.) 50 parts by mass tetraglycidyldiaminodiphenylmethane; epoxy equivalent 105.5
50 parts by mass 4-methylimidazole 10 parts by mass Aerosil 200 silica particles (manufactured by Nippon Aerosil Co., Ltd .; silica particles; primary particle diameter 14 nm)
2 parts by mass <heating conditions of adhesive E during bonding>
Heating temperature: 35 ° C
Heating time: 13 hours An emission test was conducted in the same manner as the adhesive C. The difference between the maximum and minimum emission speeds between the nozzles was 8%, and the uniformity was almost satisfactory. Further, when the ink was filled in the ink jet head and left at 60 ° C. for 3 weeks, leakage occurred.

<Composition of Adhesive F (Comparative Example)>
Epicoat 807 (bisphenol F; epoxy equivalent 165; manufactured by Japan Epoxy Resin Co., Ltd.) 70 parts by mass Triglycidyl-p-aminophenol 30 parts by mass 1-phenylimidazole 10 parts by mass Aerosil 200 silica particles (manufactured by Nippon Aerosil; silica particles; primary Particle size 14nm)
2 parts by mass <Conditions for heating adhesive F during bonding>
Heating temperature: 35 ° C
Heating time: 13 hours An emission test was conducted in the same manner as the adhesive C. When the ink jet head was filled with ink and ejected, leakage occurred. Further, although the same adhesive F was used to cure by changing the heating temperature to 70 ° C., leakage occurred during the emission test.

<Composition of adhesive G (comparative example)>
Epicoat 828 (bisphenol A type epoxy resin; epoxy equivalent 190; manufactured by Japan Epoxy Resin Co., Ltd.) 70 parts by mass Triglycidyl-p-aminophenol 30 parts by mass Triethylenetetramine 9 parts by mass Aerosil 200 silica particles (manufactured by Nippon Aerosil; silica particles; Primary particle diameter 14nm)
2 parts by mass <conditions for heating the adhesive G during bonding>
Heating temperature: 35 ° C
Heating time: 13 hours When the adhesive part was touched after heating, there was still stickiness and the curing was not completed. Next, when heating was performed at 70 ° C. for 13 hours, the difference between the maximum and minimum emission speeds between the nozzles was 15%, and uniformity was a problem. Further, the ink was filled in the ink jet head and left after being left at 60 ° C. for 2 weeks.

[Example 4]
The test was conducted in the same manner as in Example 3 except that an ink consisting only of N-methylpyrrolidinone (SP = 11.3, dipole efficiency = 4.09) was prepared and used. However, the heating conditions were a heating temperature of 45 ° C. and a heating time of 10 hours.

Adhesive C: The present invention The difference between the maximum and minimum ejection speed between the nozzles was 8%, and the uniformity was almost satisfactory. The ink jet head was filled with ink and left for one month at 60 ° C. and then emitted, but there was no ink leakage.

Adhesive D: Comparative Example Ink leakage occurred when the ink jet head was filled with ink and left for one week at 60 ° C. and then emitted.

Adhesive E: The present invention The ink was filled in the ink jet head, and the ink was not leaked until it was left at 60 ° C. for 2 weeks. However, the ink was leaked when left after being left for 3 weeks.

Adhesive F: Comparative Example When ink was filled in the ink jet head and ejected, ink leakage occurred.

Adhesive G: Comparative Example When the adhesive part was touched after heating, there was still stickiness and the film was not completely cured, but the ink was filled in the ink jet head as it was and left for one week at 60 ° C. More was produced.

It is a longitudinal cross-sectional view of the inkjet head in 1st embodiment. It is a disassembled perspective view of the ink chamber in 1st embodiment. It is sectional drawing in the II line | wire of FIG.1 and FIG.2. It is explanatory drawing of the manufacturing method of the inkjet head in 1st embodiment, (a) is sectional drawing which shows the state which adhere | attached two piezoelectric ceramic base | substrates, and a cover member, (b) is II of (a). It is sectional drawing in the -II line. It is explanatory drawing of the manufacturing method of an inkjet head. It is explanatory drawing of the manufacturing method of an inkjet head. It is explanatory drawing of a deformation | transformation of an ink flow path. It is explanatory drawing of a deformation | transformation of an ink flow path. It is a longitudinal cross-sectional view of the inkjet head concerning 2nd embodiment. It is a longitudinal cross-sectional view of the inkjet head concerning 3rd embodiment.

Explanation of symbols

1a, 1b, 1c Inkjet head 2 Lid member (bonded member)
3 Ink chamber 3a Electrode film 4 Protective film 5 Ink flow path 10 Cover 11 Piezoelectric ceramic substrate (channel substrate)
11A, 11B, 11C, 13, 23 Piezoelectric element 20 Manifold (bonded member, second bonded member)
30 Ink tube (second adherend)
31 Concave part 35 Filter (2nd to-be-adhered member)
40 FPC (Adhesive member)
45 Drive IC (second adherend)
50 Nozzle plate (adhered member)
A Pressure chamber D Ink droplet

Claims (9)

As a main agent, containing a compound having three or more epoxy groups having an epoxy equivalent of 120 or less,
Compound having 100 weights of three or more epoxy groups, imidazole having a pyrrole type nitrogen atom and a pyridine type nitrogen atom as the curing agent and having 2-position unsubstituted and 4-position substituted with alkyl group or aralkyl group 5-50 weight part is contained with respect to a part, The adhesive composition characterized by the above-mentioned.   Furthermore, bisphenol A type epoxy resin or bisphenol F type epoxy resin is contained as a compound which has two epoxy groups, The adhesive composition of Claim 1 characterized by the above-mentioned. The adhesive composition according to claim 1 or 2 , wherein the compound having three or more epoxy groups is a compound of the following general formula (1).

(In the formula, R ₁ and R ₂ represent hydrogen or an alkyl group.) An ink-jet head comprising: a channel substrate having an ink channel; a member to be bonded to the channel substrate; and a second member to be bonded to the member to be bonded.
The channel substrate and the adherend member, or the adherend member and the second adherend member contain, as a main agent, a compound having three or more epoxy groups having an epoxy equivalent of 120 or less, and cured. As an agent, imidazole having a pyrrole type nitrogen atom and a pyridine type nitrogen atom and substituted at the 4-position with an alkyl group or an aralkyl group is used in an amount of 5 to 50 weights with respect to 100 parts by weight of the compound having three or more epoxy groups. An ink jet head which is bonded using a part-containing adhesive composition. Said channel substrate and the between the bonded component, or the between the and the bonded component second bonded component, claim difference in linear expansion coefficient is equal to or more than 12 ppm / K 4 The inkjet head described in 1. 6. The ink jet head according to claim 4 , wherein the ink to be ejected is a solvent ink. As a solvent for the solvent ink, claim SP value is 9.5 to 15.0, which and dipole moment is characterized by containing 3% or more of the entire solvent of solvent 2.0-5.0 The inkjet head according to 6 . It contains a compound having three or more epoxy groups having an epoxy equivalent of 120 or less as the main agent, and has a pyrrole nitrogen atom and a pyridine nitrogen atom as the curing agent, and is substituted with an alkyl group or an aralkyl group at the 4-position. imidazole, an adhesive composition containing 5 to 50 parts by weight relative to compound 100 parts by weight with the three or more epoxy groups, a member of linear expansion coefficient have a difference of more than 12 ppm / K at 60 ° C. or less A method of manufacturing an ink jet head, comprising bonding. An inkjet head manufacturing method comprising: a channel substrate having an ink channel; a member to be bonded to the channel substrate; and a second member to be bonded further to the member to be bonded. ,
There is a difference in linear expansion coefficient exceeding 12 ppm / K between the channel substrate and the adherend member, or between the adherend member and the second adherend member,
The channel substrate and the adherend member, or the adherend member and the second adherend member contain, as a main agent, a compound having three or more epoxy groups having an epoxy equivalent of 120 or less, and cured. As an agent, imidazole having a pyrrole type nitrogen atom and a pyridine type nitrogen atom and substituted at the 4-position with an alkyl group or an aralkyl group is used in an amount of 5 to 50 weights with respect to 100 parts by weight of the compound having three or more epoxy groups. Part of an adhesive composition, wherein 0.2 to 10% of fine particles with an average particle size of 0.1 μm or less are added to increase the viscosity, and the adhesive composition is adhered. A method for manufacturing an inkjet head.

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