JP2006224664A - Ink-jet recording head, manufacturing method of the head and composition for ink-jet recording head - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink-jet recording head which has a high durability and ink resistance and enables a high-definition image recording and a method for precisely fabricating the ink-jet recording head. <P>SOLUTION: The internal-stress reduction in a passage formation member and a precise patterning are made possible by the way of using photo cationic polymerizing resin composition which includes condensation products of hydrolysis-nature organic silane compound as materials to form the passage formation member. Thereby, the ink-jet recording head which has the high durability and ink-jet resistance while enabling a high-definition printing for a long term and its manufacturing method can be provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an ink jet recording head using a cured product of a specific photopolymerizable composition as a flow path forming member, a manufacturing method thereof, and an ink jet recording head composition.

  2. Description of the Related Art Conventionally, technical development for various performance improvements has been continued in an ink jet recording system in which liquid is ejected as small droplets from an ejection port and adhered to a recording medium typified by paper to perform image recording. In particular, there is a strong demand for droplets to improve image quality, and a technique for manufacturing a minute structure that becomes an ink flow path or nozzle with high accuracy is required. As such a technique, photolithography is excellent both in terms of accuracy and process simplicity. In JP-A-6-286149, a method for producing an ink jet recording head by photolithography using cationic polymerization of an epoxy resin. Is disclosed.

  A material cured by cationic polymerization is generally excellent in ink resistance as compared with a material cured by radical polymerization, and is suitable as a material for an ink jet recording head.

  On the other hand, in order to improve the recording speed, it is very effective to increase the size of the recording head itself and to extend the printing width. However, in general, heat treatment is often performed during the manufacturing process, and when a nozzle member is made of a resin material, due to factors such as curing shrinkage and thermal history, the substrate and other adjacent inorganic materials It is known that residual stress is generated during this period. Furthermore, when the thickness or area of the nozzle member increases, the stress acting on the nozzle pattern increases, often causing problems such as delamination from the substrate and generation of cracks, and stress reduction is a major issue. It becomes.

  Typical methods for reducing the stress of resin coatings include adding inorganic materials such as fillers to reduce the thermal expansion of the resin, or adding highly flexible materials to increase the elastic modulus of the resin itself. The method of reducing etc. is mentioned. Actually, Japanese Patent Laid-Open No. 9-234874 discloses a method of molding using a resin containing a filler as a nozzle member and utilizing ablation by excimer laser. In addition, European Patent Application Publication No. 0431809 discloses a coating film forming material that imparts flexibility by adding an organosilane compound to an epoxy resin to improve the weakness of the resin itself. If the coating film becomes flexible, it is presumed that the internal stress itself has decreased. On the other hand, US Pat. No. 6,320,085 discloses a method for producing an ink jet head by performing patterning by photoradical polymerization and generating / curing siloxane bonds by heat treatment.

Regarding the formation of the nozzle member of the recording head that can cope with the expansion of the print width, Japanese Patent Laid-Open No. 9-234874 discloses a method in which a resin containing a filler is used as the nozzle member and molding is performed by using excimer laser ablation. It is disclosed. However, such materials sometimes have problems in terms of productivity, cost, and the like as compared with ordinary photolithography processes such as pattern exposure and development. In addition, the material disclosed in European Patent Application No. 0431809 is not intended for a fine structure such as an ink jet recording head. It contains problems such as pattern deformation and insufficient resolution. On the other hand, in the method disclosed in US Pat. No. 6,320,085, a crosslinked structure is formed by radical polymerization (methacryloxy group), so that the alkali resistance is not sufficient, and depending on the type of ink, the ink resistance is insufficient. was there.
JP-A-6-286149 JP 9-234874 A European Patent Application No. 0431809 US Pat. No. 6312085

  The present invention has been made in view of the above points, and by using a material having reduced internal stress and good patterning characteristics, it has high durability, ink resistance, and enables high-quality image recording. An inkjet recording head is provided. Furthermore, it is providing the manufacturing method which manufactures this inkjet recording head with high precision, and the composition for inkjet recording heads used for this inkjet recording head.

One aspect of the ink jet recording head of the present invention includes a substrate provided with an energy generating element for generating energy for discharging ink, an ejection port provided corresponding to the energy generating element, and the ejection port. In an ink jet recording head comprising: an ink flow path for supplying ink to an outlet; and a flow path forming member that forms the ink flow path together with the substrate.
The flow path forming member is:
(A) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional water having an aromatic ring (where bifunctional means that the number of condensable groups on the same Si atom is 2) An inkjet recording head comprising a cured product of a photocurable resin composition containing a condensate containing a decomposable organic silane compound and a trifunctional or higher functional hydrolyzable organic silane compound having no aromatic ring. is there.

Another aspect of the inkjet recording head of the present invention includes a substrate provided with an energy generating element for generating energy for discharging ink, an ejection port provided corresponding to the energy generating element, In an ink jet recording head comprising: an ink flow path for supplying ink to an ejection port; and a flow path forming member that forms the ink flow path together with the substrate.
The flow path forming member is:
(A) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (provided that trifunctional is a condensable group on the same Si atom) Means number)
It is an inkjet recording head characterized by including the hardened | cured material of the photocurable resin composition containing this.

One aspect of the method for producing an ink jet recording head of the present invention includes a substrate provided with an energy generating element for generating energy for discharging ink, and an ejection port provided corresponding to the energy generating element. In an ink jet recording head manufacturing method, comprising: an ink flow path for supplying ink to the ejection port; and a flow path forming member that forms the ink flow path together with the substrate.
Forming a layer of a photocurable resin composition on the substrate;
Performing pattern exposure on a layer of the photocurable resin composition on the substrate;
Developing the pattern-exposed photocurable resin composition layer to obtain an ink flow path pattern comprising a cured product of the photocurable resin composition; and
Laminating a member having the ejection port on the substrate on which the ink flow path is formed, and
The photopolymerizable resin composition is
(A) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional water having an aromatic ring (where bifunctional means that the number of condensable groups on the same Si atom is 2) A condensate comprising a decomposable organosilane compound and a trifunctional or higher functional hydrolyzable organosilane compound having no aromatic ring,
Is a method for producing an ink jet recording head.

Another aspect of the method for manufacturing an ink jet recording head of the present invention includes a substrate provided with an energy generating element for generating energy for discharging ink, and an ejection port provided corresponding to the energy generating element. And an ink flow path for supplying ink to the ejection port, and a flow path forming member that forms the ink flow path together with the substrate.
Forming a layer of a photocurable resin composition on the substrate;
Performing pattern exposure on a layer of the photocurable resin composition on the substrate;
Developing the pattern-exposed photocurable resin composition layer to obtain an ink flow path pattern comprising a cured product of the photocurable resin composition; and
Laminating a member having the discharge port on a substrate on which the ink flow path is formed;
Have
The photocurable resin composition is
(A) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (provided that trifunctional is a condensable group on the same Si atom) Means number)
Is a method for producing an ink jet recording head.

Another aspect of the method for manufacturing an ink jet recording head of the present invention includes a substrate provided with an energy generating element for generating energy for discharging ink, and an ejection port provided corresponding to the energy generating element. And an ink flow path for supplying ink to the ejection port, and a flow path forming member that forms the ink flow path together with the substrate.
Forming an ink flow path pattern as an ink flow path forming mold material on a substrate provided with an energy generating element for generating energy for discharging ink;
Forming a photocurable resin composition layer on the substrate and covering the ink flow path pattern on the substrate;
Pattern exposure to a layer of the photocurable resin composition covering the ink flow path pattern, followed by development processing to obtain a flow path forming member having discharge ports;
Removing the ink flow path pattern covered with the flow path forming member from the substrate to form an ink flow path;
Have
The photopolymerizable resin composition is
(A) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional water having an aromatic ring (where bifunctional means that the number of condensable groups on the same Si atom is 2) A condensate comprising a decomposable organosilane compound and a trifunctional or higher functional hydrolyzable organosilane compound having no aromatic ring,
Is a method for producing an ink jet recording head.

Another aspect of the method for manufacturing an ink jet recording head of the present invention includes a substrate provided with an energy generating element for generating energy for discharging ink, and an ejection port provided corresponding to the energy generating element. And an ink flow path for supplying ink to the ejection port, and a flow path forming member that forms the ink flow path together with the substrate.
Forming an ink flow path pattern as an ink flow path forming mold material on a substrate provided with an energy generating element for generating energy for discharging ink;
Forming a photocurable resin composition layer on the substrate and covering the ink flow path pattern on the substrate;
Pattern exposure to a layer of the photocurable resin composition covering the ink flow path pattern, followed by development processing to obtain a flow path forming member having discharge ports;
Removing the ink flow path pattern covered with the flow path forming member from the substrate to form an ink flow path;
Have
The photocurable resin composition is
(A) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (provided that trifunctional is a condensable group on the same Si atom) Means number)
Is a method for producing an ink jet recording head.

Another aspect of the method for manufacturing an ink jet recording head of the present invention includes a substrate provided with an energy generating element for generating energy for discharging ink, and an ejection port provided corresponding to the energy generating element. And an ink flow path for supplying ink to the ejection port, and a flow path forming member that forms the ink flow path together with the substrate.
Forming a layer of the photocurable resin composition (1) on the substrate;
Performing pattern exposure on the layer of the photocurable resin composition (1) on the substrate;
Developing the pattern-exposed layer of the photocurable resin composition (1) to obtain a pattern of an ink flow path comprising a cured product of the photocurable resin composition;
A step of laminating a layer of the photocurable resin composition (2) on the substrate on which the ink flow path has been formed, and pattern exposure and development treatment on the layer of the photocurable resin composition (2). Forming an outlet;
And at least one of the photopolymerizable resin composition (1) and the photopolymerizable resin composition (2),
(A) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional water having an aromatic ring (where bifunctional means that the number of condensable groups on the same Si atom is 2) A condensate comprising a decomposable organosilane compound and a trifunctional or higher functional hydrolyzable organosilane compound having no aromatic ring,
Is a method for producing an ink jet recording head.

Another aspect of the method for manufacturing an ink jet recording head of the present invention includes a substrate provided with an energy generating element for generating energy for discharging ink, and an ejection port provided corresponding to the energy generating element. And an ink flow path for supplying ink to the ejection port, and a flow path forming member that forms the ink flow path together with the substrate.
Forming a layer of the photocurable resin composition (1) on the substrate;
Performing pattern exposure on the layer of the photocurable resin composition (1) on the substrate;
Developing the pattern-exposed layer of the photocurable resin composition (1) to obtain a pattern of an ink flow path comprising a cured product of the photocurable resin composition;
A step of laminating a layer of the photocurable resin composition (2) on the substrate on which the ink flow path has been formed, and pattern exposure and development treatment on the layer of the photocurable resin composition (2). Forming an outlet;
And at least one of the photopolymerizable resin composition (1) and the photopolymerizable resin composition (2),
(A) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (provided that trifunctional is a condensable group on the same Si atom) Means number)
Is a method for producing an ink jet recording head.

Another aspect of the method for manufacturing an ink jet recording head of the present invention includes a substrate provided with an energy generating element for generating energy for discharging ink, and an ejection port provided corresponding to the energy generating element. And an ink flow path for supplying ink to the ejection port, and a flow path forming member that forms the ink flow path together with the substrate.
Forming a layer of the photocurable resin composition (1) on the substrate;
Forming a latent image by performing pattern exposure on the layer of the photocurable resin composition (1) on the substrate;
A step of laminating a layer of the photocurable resin composition (2) on the layer of the photocurable resin composition (1) subjected to pattern exposure, and a layer of the photocurable resin composition (2). A step of forming a latent image by performing pattern exposure, and a step of forming an ink flow path pattern and a discharge port made of a cured product of the photo-curable resin composition (1), (2) by a development process,
And
At least one of the photopolymerizable composition (1) and the photopolymerizable composition (2) is (a) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional water having an aromatic ring (where bifunctional means that the number of condensable groups on the same Si atom is 2) A condensate comprising a decomposable organosilane compound and a trifunctional or higher functional hydrolyzable organosilane compound having no aromatic ring,
Is a method for producing an ink jet recording head.

Another aspect of the method for manufacturing an ink jet recording head of the present invention includes a substrate provided with an energy generating element for generating energy for discharging ink, and an ejection port provided corresponding to the energy generating element. And an ink flow path for supplying ink to the ejection port, and a flow path forming member that forms the ink flow path together with the substrate.
Forming a layer of the photocurable resin composition (1) on the substrate;
Forming a latent image by performing pattern exposure on the layer of the photocurable resin composition (1) on the substrate;
A step of laminating a layer of the photocurable resin composition (2) on the layer of the photocurable resin composition (1) subjected to pattern exposure, and a layer of the photocurable resin composition (2). A step of forming a latent image by performing pattern exposure, and a step of forming an ink flow path pattern and a discharge port made of a cured product of the photo-curable resin composition (1), (2) by a development process,
And
At least one of the photopolymerizable composition (1) and the photopolymerizable composition (2) is (a) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (provided that trifunctional is a condensable group on the same Si atom) Means number)
Is a method for producing an ink jet recording head.

One aspect of the composition for an inkjet recording head of the present invention is:
(A) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional water having an aromatic ring (where bifunctional means that the number of condensable groups on the same Si atom is 2) A condensate comprising a decomposable organosilane compound and a trifunctional or higher functional hydrolyzable organosilane compound having no aromatic ring,
A composition for an inkjet recording head, comprising a photocurable resin containing

Other aspects of the composition for inkjet recording head of the present invention include:
(A) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (provided that trifunctional is a condensable group on the same Si atom) Means number)
A composition for an inkjet recording head, comprising a photocurable resin containing

  According to the present invention, a photocationically polymerizable resin composition containing a condensate of a hydrolyzable organosilane compound is used as a material for forming a flow path forming member, thereby reducing internal stress in the flow path forming member. High-precision patterning is possible. Therefore, it is possible to provide an ink jet recording head having high durability and ink resistance and capable of high-quality printing over a long period of time and a method for manufacturing the same.

  Hereinafter, the present invention will be described in detail.

  As a result of intensive studies, the present inventors have used a photopolymerizable composition having the following composition as a material for producing a flow path forming member (also referred to as a nozzle material), thereby reducing internal stress and good patterning characteristics. It has been found that both of these can be realized. The inventors have found that an ink jet recording head having high ink resistance and durability can be produced with high accuracy.

Photopolymerizable composition A:
(A) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional water having an aromatic ring (where bifunctional means that the number of condensable groups on the same Si atom is 2) Condensate containing a decomposable organic silane compound and a trifunctional or higher functional hydrolyzable organic silane compound having no aromatic ring Photopolymerizable composition B:
(A) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (however, the number of functional groups here is condensable on the same Si atom) Means the number of groups.)
The cured product of the photopolymerizable composition includes a siloxane skeleton (inorganic skeleton) having a hydrolyzable organosilane compound condensate and an organic skeleton formed by curing using a group capable of cationic polymerization. It becomes an inorganic hybrid cured product. This is expected to improve physical properties such as low thermal expansion and low stress. In addition, when a typical epoxy group is used as a group capable of cationic polymerization, an ether bond is formed. Actually, the organic-inorganic hybrid cured product of the present invention exhibits greatly different physical properties as compared with the conventional epoxy resin, the residual stress of the coating film is reduced, the deformation of the substrate is prevented, and the substrate surface is protected. It was found that the effect of improving adhesion can be obtained.

  In the present invention, the hydrolyzable organic silane compound having an aromatic ring is bifunctional or more, and there is a trifunctional or more hydrolyzable organosilane compound (that is, (c-1) or (c-2). )) Is important. As a result, the compatibility between the cationic polymerizable resin and the siloxane skeleton and the film formability during coating can be improved, and good patterning characteristics can be obtained. Further, it is considered that the following reaction occurs through the patterning process and the curing process using light or heat. That is, the organic skeleton formed by the cationic polymerizable resin as the component (a) and the inorganic skeleton formed by the condensate containing the hydrolyzable organic silane compound of the component (c-1) or the component (c-2) It is considered that a bond is also generated between the two. This is because the unreacted cationically polymerizable site and the unreacted hydrolyzable / condensable site can react with an acid generated by (b) the photocationic polymerization initiator as a catalyst.

  In general, an organic skeleton obtained by cationic polymerization is excellent in alkali resistance, whereas a siloxane skeleton is often inferior in alkali resistance. However, in the cured product in which the organic skeleton by cationic polymerization and the inorganic skeleton by siloxane coexist as in the present invention, rehydration of the siloxane skeleton is surprisingly suppressed, and alkali resistance and ink resistance are improved. It was found.

  Next, each constituent material used in the present invention will be specifically described.

The cationic polymerizable resin as the component (a) means a resin containing a compound having a vinyl group, a cyclic ether group, or the like, which is a cationic polymerizable group. Of these, compounds having an epoxy group or an oxetane group are preferably used. Specific examples of the epoxy resin include bisphenol-A-diglycidyl ether, bisphenol-F-diglycidyl ether, and the like, bisphenol-type epoxy resins composed of monomers or oligomers having a bisphenol skeleton, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins. And resins having an alicyclic epoxy structure such as trisphenolmethane type epoxy resin and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate.
Furthermore, a resin having an epoxy group in the side chain of the alicyclic skeleton as in the following structure is also preferably used.

  In addition, a novolac resin having a bisphenol A skeleton as in the following structure is also preferably used. In the formula, n is preferably an integer of 1 to 3, particularly preferably n = 2.

  Examples of the resin containing an oxetane compound include resins made of a phenol novolac oxetane compound, a cresol novolac oxetane compound, a trisphenolmethane oxetane compound, a bisphenol oxetane compound, a biphenol oxetane compound, and the like. When a resin comprising these oxetane compounds is used in combination with an epoxy resin, the curing reaction may be accelerated, which may be preferable.

  In order to obtain good patterning characteristics, these cationic polymerizable resins are preferably solid at room temperature or have a melting point of 40 ° C. or higher at the stage before polymerization. Moreover, an epoxy equivalent (or oxetane equivalent) is 2000 or less, More preferably, a 1000 or less compound is used suitably. When the epoxy equivalent exceeds 2000, the crosslinking density during the curing reaction is lowered, and the Tg or heat distortion temperature of the cured product may be lowered, or there may be a problem in adhesion to the substrate and ink resistance.

  Examples of the photocationic polymerization initiator as the component (b) include those having a structure selected from an onium salt, a borate salt, a compound having an imide structure, a compound having a triazine structure, an azo compound, and a peroxide. In terms of sensitivity, stability, and reactivity, aromatic sulfonium salts and aromatic iodonium salts are preferred. It is also useful to use various photosensitizers for improving sensitivity and adjusting photosensitive wavelength.

  The condensate as component (c-1) is a condensation synthesized using a bifunctional hydrolyzable organosilane compound having an aromatic ring and a trifunctional or higher hydrolyzable organosilane compound having no aromatic ring as starting materials. It is a thing.

  In the formation of the condensate, at least one bifunctional hydrolyzable organosilane compound having an aromatic ring and at least one trifunctional or higher hydrolyzable organosilane compound having no aromatic ring are used. It can be a starting material.

  The blending ratio (on a molar basis) of the hydrolyzable organosilane compound having an aromatic ring and the hydrolyzable organosilane compound not having an aromatic ring is (with aromatic ring: no aromatic ring =) 1: 0.1 to 1: 4 It is preferable to do. In particular, (with aromatic ring: without aromatic ring) is preferably 1: 0.3 to 1: 2.

Examples of the hydrolyzable organosilane compound having an aromatic ring include compounds represented by the following general formula (1).
(R ³ ) _p -Si- (OR ² ) _q (R ¹ ) _r (1)
Here, p + q + r = 4 (p is 1, 2 or 3, q is 1, 2 or 3, r is 0, 1 or 2), and R ¹ and R ² are Each is independently a saturated or unsaturated hydrocarbon residue, and R ³ is a non-hydrolyzable substituent having an aromatic ring.

More specifically, examples of R ³ include a substituted or unsubstituted phenyl group, naphthyl group, and benzyl group. Examples of the substituent for the phenyl group, naphthyl group, and benzyl group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms; and further, a hydroxyl group, an epoxy group, A glycidyl group etc. can be mentioned.

Moreover, as R ² , an alkyl group having 20 or less carbon atoms is preferably used, and a methyl group, an ethyl group, a propyl group, and the like are particularly preferable from the viewpoint of reactivity. In addition to these, R ² may include a hydrogen atom. That is, when there are 2 or more-(OR ² ) groups (when q is 2 or more), R ² of at least one-(OR ² ) group in the 2 or more-(OR ² ) groups is other than hydrogen. A silane compound in which the remaining group is —OH can be used.

As R ¹ , a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms is preferably used. Moreover, as a substituent of this alkyl group, a C1-C20 alkyl group, a C1-C20 alkenyl group, a C1-C20 alkoxy group; Furthermore, a hydroxyl group, an epoxy group, a glycidyl group, etc. Can be mentioned.

  It has been found that patterning characteristics are remarkably improved by using a hydrolyzable organosilane compound having such an aromatic ring. It is considered that the steric and electronic action of the aromatic ring affects the reactivity of the condensation reaction and / or cationic polymerization reaction, and the structure of the generated resin skeleton is controlled.

Examples of the hydrolyzable organosilane compound having no aromatic ring include compounds represented by the following general formula (2).
(R ² O) _q -Si- (R ¹ ) _r (2)
here,
q + r = 4 (q is 1, 2, 3 or 4 and r is 0, 1, 2 or 3)
R ¹ and R ² are each independently a saturated or unsaturated hydrocarbon residue similar to the general formula (1).
As R ² , an alkyl group having 20 or less carbon atoms is preferably used, and a methyl group, an ethyl group, a propyl group, and the like are particularly preferable from the viewpoint of reactivity. In addition to these, R ² may include a hydrogen atom. That, - (OR ²⁾ if the group is 2 or more (when q is 2 or more), more than one - (OR ²⁾ in groups least the one - (OR ²⁾ R ² is other than hydrogen in group A silane compound in which the remaining group is —OH can be used.

As R ¹ , a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms is preferably used. Moreover, as a substituent of this alkyl group, a C1-C20 alkyl group, a C1-C20 alkenyl group, a C1-C20 alkoxy group; Furthermore, a hydroxyl group, an epoxy group, a glycidyl group, etc. Can be mentioned.

In these general formulas (1) and (2), R ² and R ¹ can each independently have a substituent as appropriate according to the target properties, and are long chains for solubility control. Introduction of alkyl groups and introduction of fluorine atoms for reducing hygroscopicity are also effective. For example, when a long-chain alkyl group is introduced, the compatibility with the resin to be mixed is improved, and further stress reduction is realized. When a flexible skeleton such as a long chain alkyl group is present as a side chain, it is presumed that the mobility of the molecular chain is improved and stress relaxation in the cooling process is promoted. However, if the number of carbon atoms is too large, uniform hydrolysis / condensation reaction becomes difficult due to its hydrophobicity. The alkyl group introduced as R ¹ is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 3 or more in terms of stress reduction, and 20 or less in terms of preventing excessive hydrophobic expression. Is preferably 12 or less.

In the general formulas (1) and (2), it is also very useful to introduce a cationically polymerizable group such as an epoxy group into the non-hydrolyzable group R ¹ . By introducing a cationically polymerizable group into the condensate itself, not only the compatibility with the cationically polymerizable resin of (a) is improved, but also the crosslinking density can be increased and the number of bonding sites between the resin and the condensate can be increased. Become. That is, by the cationic polymerization reaction, a crosslinked structure is further formed between the inorganic skeleton obtained from the organic silane compound and the organic skeleton formed of the epoxy resin, so that a good organic-inorganic hybrid material is obtained. Thereby, patterning characteristics such as sensitivity and pattern shape can be optimized, and mechanical strength, durability, and ink resistance can be improved, which is very useful. Specifically, a cationically polymerizable group, that is, a group having a vinyl group or a cyclic ether group can be suitably used as R ¹ . For example, examples of the compound represented by the general formula (2) in which a cationically polymerizable group is introduced into R ¹ include the following compounds. Of course, the present invention is not limited to the following compounds.
Glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidoxypropyldimethylmethoxysilane, glycidoxypropyldimethylethoxysilane, and 2- (epoxycyclohexyl) ethyltrimethoxysilane, 2- (epoxycyclohexyl) ethyltriethoxysilane.

  The hydrolyzable organosilane compound of the general formula (1) and the hydrolyzable organosilane compound of the general formula (2) have a group capable of forming a siloxane bond by hydrolysis and dehydration condensation reaction on the same Si atom. 1 to 4 are provided. In the present invention, the number of groups capable of forming a siloxane bond on the same Si atom is defined as the number of functional groups of the organosilane compound.

  In the structure of the present invention, an inorganic skeleton formed by the condensation reaction and having a siloxane bond is very important. A monofunctional silane compound can only be at the end of the siloxane skeleton, and cannot form a resin skeleton. Therefore, in this invention, it is preferable that a monofunctional silane compound is 30 mol% or less in raw material silane. On the other hand, since a bifunctional silane compound only forms a linear skeleton and cannot form a three-dimensionally crosslinked skeleton, it is more flexible than a three-dimensionally crosslinked skeleton and is effective in terms of stress reduction. However, in consideration of patterning characteristics, strength of the cured product as a flow path forming member, and durability, the bifunctional silane in the raw material silane is preferably 70 mol% or less. The tetrafunctional silane compound is preferably 40 mol% or less, preferably 20 mol% or less in the raw material silane from the viewpoint of control of the siloxane skeleton and patterning characteristics. For the reasons described above, the hydrolyzable organosilane compound having an aromatic ring is bifunctional and trifunctional in order to obtain the optimum composition by controlling the physical properties and patterning characteristics of the coating film (layer). It is important to have the above hydrolyzable organosilane compound. When the hydrolyzable organic silane compound having an aromatic ring is bifunctional, it is important to use a trifunctional silane compound as the hydrolyzable organic silane compound having no aromatic ring. In that case, mol% of Y based on the total number of moles of the hydrolyzable organosilane compound (X) having an aromatic ring and the trifunctional silane compound (Y) having no aromatic ring (number of moles of Y / (of X The number of moles + the number of moles of Y) is preferably in the range of 20 to 80 mol%, and the bifunctional hydrolyzable organosilane compound having an aromatic ring is preferably 20 mol% or more in the raw material silane. An organic silane compound having characteristics capable of achieving the object of the present invention may be selected.

  Next, a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring as the component (c-2) will be described. For the reasons described above, this embodiment also satisfies the condition that the hydrolyzable organic silane compound having an aromatic ring is bifunctional or higher and the hydrolyzable organic silane compound is trifunctional or higher. . The condensate as the component (c-2) can be obtained by condensing at least one of trifunctional hydrolyzable organosilane compounds having an aromatic ring. Also in the component (c-2), the monofunctional silane compound is preferably 30 mol% or less in the raw material silane. On the other hand, the bifunctional silane compound is preferably 70 mol% or less in the raw material silane. Further, the tetrafunctional silane compound is preferably 40 mol% or less, preferably 20 mol% or less in the raw material silane. The trifunctional or higher functional hydrolyzable organosilane compound is desirably 20 mol% or more in the raw material silane. Further, a trifunctional hydrolyzable organosilane compound having an aromatic ring is also preferably used in an amount of 20 mol% or more in the raw material silane.

  In the present invention, the condensation reaction of the hydrolyzable organosilane compound is carried out by heating in the presence of water to advance the hydrolysis and condensation reaction. A desired degree of condensation can be obtained by appropriately controlling the hydrolysis / condensation reaction by temperature, time, pH and the like.

Here, the degree of progress of the condensation reaction (condensation degree) can be defined by the ratio of the number of condensed functional groups to the number of condensable functional groups. Actually, it can be estimated by Si-NMR measurement. For example, in the case of a trifunctional organosilane compound,
T0 body: Si atom T1 body not bonded to other silane molecules: Si atom T2 body bonded to one silane molecule through oxygen: Si bonded to two silane molecules through oxygen Atom T3 body: Calculated according to the following equation 1 from the ratio of Si atoms bonded to three silane molecules through oxygen.

In the case of a bifunctional silane,
D0 body: Si atom D1 body not bonded to other silane molecules: Si atom D2 body bonded to one silane molecule via oxygen: Si bonded to two silane molecules via oxygen It is calculated from the atomic ratio according to the following formula 2.

  The degree of condensation varies depending on the type of organosilane compound and the synthesis conditions, but if it is too low, it may be inferior in compatibility with the resin and coating properties. Therefore, the degree of condensation is preferably 20% or more. Further, it is more preferably 30% or more.

  Here, the resolution can be improved by controlling the degree of condensation. The condensate containing the trifunctional hydrolyzable organosilane compound preferably has a total ratio of the T0 and T1 isomers of 50% or less. More preferably, it is preferably 30% or less. Furthermore, the abundance ratio of the T3 body is preferably 15% or more. More preferably, it is preferably 20% or more.

  Here, the abundance ratio of the T0, T1, and T3 bodies is calculated according to the following equation 3.

  In the hydrolysis reaction, it is also possible to control the degree of condensation by using a metal alkoxide as a hydrolysis catalyst. Examples of the metal alkoxide include aluminum alkoxide, titanium alkoxide, zirconium alkoxide, and complexes thereof (acetylacetone complex and the like).

  The mixing weight ratio between the cationic polymerizable resin as component (a) and the condensate composed of the hydrolyzable organosilane compound (c-1) or (c-2) is preferably (a) / ( c) = 0.1 to 10, more preferably 0.3 to 3. When the mixing weight ratio is within these ranges, a better stress reduction effect can be obtained, and the mechanical characteristics and patterning characteristics can be further improved.

  Various additives may be used in combination with the above-mentioned nozzle material for the purpose of increasing the crosslink density, improving sensitivity, improving coating properties, preventing swelling by ink, imparting flexibility, and improving adhesion to the substrate. Is possible. For example, the crosslinking density can be increased by heating the photocationic polymerization initiator described above in combination with a reducing agent. As such a reducing agent, copper (II) trifluoromethanesulfonate, ascorbic acid and the like are suitable. It is also useful to add a low molecular fluorine compound described in JP-A-8-290572 in order to prevent swelling and dimensional deformation of the nozzle portion due to ink. A silane coupling agent, a sulfur-containing compound, or the like can be added to further improve the adhesion to the substrate and improve the coating property. Next, the manufacturing process of the ejection port and the ink flow path using the above-described nozzle material will be described. The present invention is suitable for a method of manufacturing an ink jet recording head in which at least an ink flow path is formed by performing pattern exposure and development processing. For example, the present invention can be applied to a method described in JP-A-6-286149, in which a photosensitive material is used for a nozzle portion and a precise nozzle structure is formed by a photolithography technique.

According to the method of manufacturing an ink jet recording head according to the present invention, for example,
On a substrate having an ink discharge energy generating element,
1) applying an ink flow path forming material according to the present invention on a substrate;
2) performing a pattern exposure on the ink flow path forming material;
3) forming a flow path forming member on a substrate having an ink discharge energy generating element by a method having a step of forming an ink flow path by development processing, and laminating a substrate provided with an ink discharge port thereon; Thus, an ink jet recording head can be manufactured.

  Hereinafter, the above manufacturing method will be described with reference to schematic conceptual diagrams. FIG. 1A shows an ink discharge port 4 in which an ink flow path forming member 3a is provided using a photopolymerizable composition of the present invention on a substrate 1 on which an ink discharge energy generating element 2 is formed. The member which has is shown. A stack of these is shown in FIG. 1 (2). When laminating, an adhesive layer may be used as necessary. Finally, if necessary, heat treatment is performed to completely cure the nozzle material and the photosensitive liquid repellent material, thereby completing the ink jet recording head.

Further, as another aspect of the ink jet recording head according to the present invention, on the substrate on which the ink ejection energy generating element is formed,
1) forming an ink flow path pattern as a mold material with a soluble resin;
2) A step of forming a coating resin layer serving as an ink flow path wall at a position covering the dissolvable resin layer using the photopolymerizable composition described above;
3) forming an ink discharge port in the coating resin layer above the ink discharge energy generating element;
4) eluting the soluble resin layer,
And a method for producing an inkjet recording head.

  Below, the manufacturing method using said mold material is demonstrated using a typical conceptual diagram. FIG. 2A is a perspective view of the substrate 1 on which the ink ejection energy generating element 2 is formed. FIG. 2 (2) is a cross-sectional view taken along the line BB ′ of FIG. 2 (1). FIG. 2 (3) is a diagram in which an ink flow path pattern 3b as a mold material is formed on the substrate 1 with a soluble resin. The ink flow path pattern 3b is preferably a positive resist, particularly a post-process. Thus, a photodegradable positive resist having a relatively high molecular weight is preferably used so that the mold does not lose its shape when the nozzle material is laminated. Next, FIG. 2 (4) is a diagram in which the photocurable resin layer 5 is disposed on the ink flow path pattern 3b. The photocurable resin layer 5 is polymerized by the application of light or thermal energy, and the photopolymerizable composition described above is used for forming this layer. The photocurable resin layer 5 can be appropriately formed by spin coating, direct coating, or the like using a photopolymerizable composition to which a solvent is added as necessary. Next, as shown in FIG. 2 (5), pattern exposure 6 is performed through a mask, development processing is performed, and the discharge port 4 is placed at a predetermined position of the photocurable resin layer 5 as shown in FIG. 2 (6). Form. Next, the ink supply port 7 is appropriately formed in the substrate 1 (FIG. 2 (7)), and the ink flow path pattern 3b is eluted (FIG. 2 (8)). Finally, if necessary, heat treatment is performed to completely cure the photocurable resin layer, thereby completing the ink jet recording head.

  In addition, when using the nozzle formation material by this invention as a photocurable resin layer, in order to obtain a desired coating film thickness, it is also possible to apply | coat several times. Moreover, the nozzle forming material according to the present invention includes a reactive group called a photosensitive group and a hydrolyzable group. These reactive groups remain even after patterning exposure and development, and the curing reaction can be further promoted by heat or light. In that case, adhesion to the substrate, durability against ink, wiping operation, and the like are further improved, which is preferable.

  As another aspect of the ink jet recording head according to the present invention, there is a manufacturing method shown in the schematic conceptual diagrams of FIGS. FIG. 3A shows a process of providing the photopolymerizable resin layer 1 of the present invention on the substrate 1 on which the ink ejection energy generating element 2 is formed. FIG. 3B shows a case where an ink flow path pattern is formed by subjecting these to pattern exposure and development processing. FIG. 3 (3) shows a laminate of the photopolymerizable resin layer 2 thereon. In laminating, if necessary, an adhesive layer may be provided, or a support film (a dry film used by being peeled from the support) may be used for the resin layer. FIG. 3 (4) shows an ink discharge port formed by subjecting the photopolymerizable resin layer 2 to discharge port pattern exposure and development processing. Finally, if necessary, heat treatment is performed to completely cure the nozzle material and the photosensitive liquid repellent material, thereby completing the ink jet recording head.

  FIG. 4 (1) shows a process of providing the photopolymerizable resin layer (1) of the present invention on the substrate 1 on which the ink ejection energy generating element 2 is formed. FIG. 4B shows a case where pattern exposure is performed to form a latent image of the ink flow path pattern. FIG. 4 (3) shows a laminate of the photopolymerizable resin layer 2 thereon. In laminating, if necessary, an adhesive layer may be provided, or a support film (a dry film used by being peeled from the support) may be used for the resin layer. FIG. 4 (4) shows a case where the photopolymerizable resin layer 2 is subjected to discharge port pattern exposure to form a latent image of the ink discharge port. FIG. 4 (5) shows an ink discharge port and an ink flow path pattern formed by development processing. Finally, if necessary, heat treatment is performed to completely cure the nozzle material and the photosensitive liquid repellent material, thereby completing the ink jet recording head.

  The photopolymerizable composition according to the present invention described above can be used for forming at least one of the photopolymerizable resin layers 1 and 2 in the method described with reference to FIGS.

  The ink jet recording head composition of the present invention can be publicly used in the above-described manufacturing method. By using the above manufacturing method, the composition has high durability and ink resistance, and has high quality. An ink jet recording head that enables image recording can be manufactured.

Examples of the present invention will be described below.
<Synthesis Example 1>
A hydrolyzable condensate was synthesized according to the following procedure. Using hydrochloric acid as a catalyst, 55.6 g (0.2 mol) of glycidoxypropyltriethoxysilane, 48.1 g (0.2 mol) of phenyltriethoxysilane, and 21.6 g of water were stirred at room temperature and then heated under reflux for 24 hours for hydrolysis. Sex condensate solution was obtained. ^When the degree of condensation of silane was measured by ²⁹ Si-NMR, it was about 69%.
<Example 1>
Using the compound of Synthesis Example 1, the composition shown in Table 1 was prepared to obtain a coating solution.

  Using the coating solution having the above composition, a coating layer was formed on a silicon substrate by spin coating, and prebaked at 90 ° C. for 4 minutes. The coating film thickness was 20 μm. Next, exposure was performed using a Canon mask aligner “MPA600 super”, and the film was heated at 90 ° C. for 4 minutes, then developed with methyl isobutyl ketone and rinsed with isopropyl alcohol to form an evaluation pattern. Then, it heated at 200 degreeC for 1 hour, and obtained hardened | cured material.

<Example 2-11 and Comparative Example 1-5>
In the same manner as in Synthesis Example 1, hydrolyzable condensates shown in Table 2 were synthesized. The composition shown in Table 1 was prepared in the same manner as in Example 1, and a cured product was obtained by coating, exposing, and heating.

here,
GPTES: Glycidoxypropyltriethoxysilane PhTES: Phenyltriethoxysilane DMDEOS: Dimethyldiethoxysilane HexylTES: Hexyltriethoxysilane ECETES: Epoxycyclohexylethyltriethoxysilane DPhDES: Diphenyldiethoxysilane
<Comparative Example 6>
A coating film was prepared in the same manner using the composition described in Table 1 except for the hydrolyzable condensate to obtain a cured product.

<Stress measurement>
When the stress of the coating film of Example 1-11 and Comparative Example 1-6 was measured using the thin film physical property measuring apparatus FLX-2320, the results shown in Table 3 were obtained. According to the composition of the present invention, It was confirmed that the stress of the coating film after curing was reduced.

<Resolution evaluation>
As an evaluation pattern, a line and space mask of 2 μm to 20 μm was used to evaluate the resolution of each composition. Moreover, the abundance ratio of T0 body, T1 body, and T3 body was measured by Si-NMR measurement. The results shown in Table 3 were obtained, and according to the composition of the present invention, it was confirmed that good resolution was obtained.

<Example 12>
In this example, an ink jet recording head was produced using the composition of Example 1 according to the procedure shown in FIGS. 2 (1) to 2 (8). First, polymethylisopropenyl ketone (ODUR-1010 manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied by spin coating as a resin layer that can be dissolved on a silicon substrate on which an electrothermal conversion element as an ink discharge energy generating element is formed. A film was formed. Next, after pre-baking at 120 ° C. for 6 minutes, the ink flow path was subjected to pattern exposure with a mask aligner UX3000 manufactured by USHIO. Exposure was for 3 minutes, development was methyl isobutyl ketone / xylene = 2/1, and rinse was xylene. The polymethyl isopropenyl ketone is a so-called positive resist that decomposes and becomes soluble in an organic solvent by UV irradiation. The pattern formed of the dissolvable resin is formed in an unexposed portion at the time of pattern exposure, and is for securing an ink flow path for supplying ink (FIG. 2 (3)). The film thickness of the soluble resin after development was 20 μm.

  Next, a photocurable resin layer of the composition of Example 1 was formed on the ink flow path pattern formed of the soluble resin layer by spin coating, and prebaked at 90 ° C. for 4 minutes. Coating and pre-baking were performed three times, and finally a photocurable resin layer was formed to a film thickness of 55 μm on the ink flow path pattern (FIG. 2 (4)). Next, using a mask aligner “MPA600 super” made by Canon, pattern exposure of the ink discharge ports was performed (FIG. 2 (5)). Next, it was heated at 90 ° C. for 4 minutes, developed with methyl isobutyl ketone (MIBK), and rinsed with isopropyl alcohol to form a discharge port pattern. In this way, a discharge port pattern having a sharp pattern edge shape was obtained (FIG. 2 (6)). Next, a mask for forming an ink supply port was appropriately disposed on the back surface of the substrate, and the ink supply port was formed by anisotropic etching of the silicon substrate (FIG. 2 (7)). During the anisotropic etching of silicon, the nozzle-formed substrate surface is protected with a rubber-based protective film.

After the anisotropic etching was completed, the rubber-based protective film was removed, and UV irradiation was performed again on the entire surface with the UX3000 to decompose the dissolvable resin layer forming the ink flow path pattern. Next, the substrate is immersed in methyl lactate for 1 hour while applying ultrasonic waves to elute the ink flow path pattern, and then heated at 200 ° C. for 1 hour to completely cure the photocurable resin layer. Processing was performed (FIG. 2 (8)). Finally, an ink supply member was bonded to the ink supply port to complete the ink jet recording head.
<Print quality evaluation>
When the ink jet recording head thus obtained was filled with the Canon black ink BCI-3Bk and printed, the resulting image was of high quality.
<Preservation evaluation>
Furthermore, when the inkjet recording head was filled with the ink, after storing at 60 ° C. for 2 months, printing was performed again, and a printed matter similar to that before the storage test could be obtained.

(1) And (2) is a figure which shows each process in an example of the manufacturing method of the inkjet recording head by this invention. (1)-(8) is a figure which shows each process in an example of the manufacturing method of the inkjet recording head by this invention. (1)-(4) is a figure which shows each process in another example of the manufacturing method of the inkjet recording head by this invention. (1)-(5) is a figure which shows each process in another example of the manufacturing method of the inkjet recording head by this invention.

Claims (25)

A substrate provided with an energy generation element for generating energy for discharging ink, an ejection port provided corresponding to the energy generation element, and an ink flow path for supplying ink to the ejection port And an ink jet recording head comprising a flow path forming member that forms the ink flow path together with the substrate.
The flow path forming member is:
(A) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional water having an aromatic ring (where bifunctional means that the number of condensable groups on the same Si atom is 2) An ink jet recording head comprising a cured product of a photocurable resin composition containing a condensate containing a decomposable organic silane compound and a trifunctional or higher functional hydrolyzable organic silane compound having no aromatic ring.   2. The ink jet recording head according to claim 1, wherein the hydrolyzable organosilane compound having no aromatic ring has a group capable of cationic polymerization. A substrate provided with an energy generation element for generating energy for discharging ink, an ejection port provided corresponding to the energy generation element, and an ink flow path for supplying ink to the ejection port And an ink jet recording head comprising a flow path forming member that forms the ink flow path together with the substrate.
The flow path forming member is:
(A) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (provided that trifunctional is a condensable group on the same Si atom) Means number)
An ink jet recording head comprising a cured product of a photocurable resin composition containing   4. The ink jet recording head according to claim 3, wherein the condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring contains a hydrolyzable organosilane compound having no aromatic ring.   5. The ink jet recording head according to claim 3, wherein the hydrolyzable organosilane compound having no aromatic ring contains a bifunctional hydrolyzable organosilane compound.   6. The ink jet recording head according to claim 3, wherein the hydrolyzable organosilane compound having no aromatic ring includes a hydrolyzable organosilane compound having a dimethyl group.   The ink jet recording head according to claim 3, wherein the hydrolyzable organosilane compound having no aromatic ring has a group capable of cationic polymerization.   The ink jet recording head according to any one of claims 1 to 7, wherein the hydrolyzable organosilane compound has an alkyl group having 3 or more carbon atoms.   The inkjet recording head according to any one of claims 1 to 8, wherein the hydrolyzable organosilane compound having an aromatic ring has a phenyl group. The condensate containing the trifunctional hydrolyzable organosilane compound has a total ratio of T0 and T1 bodies of 50% or less and a ratio of T3 bodies of 15% or more. The ink jet recording head according to any one of Items 9 to 9.
However,
T0: Si atom not bonded to other silane molecules T1: Si atom bonded to one silane molecule via oxygen T2: Si atom T3 bonded to two silane molecules via oxygen T3: Si atoms bound to three silane molecules through oxygen,
Presence ratio of TX form (X = 0, 1, 2, 3) = TX / (T0 + T1 + T2 + T3) × 100%
It is.   The blending ratio of the condensate containing the hydrolyzable organosilane compound to 100 parts by weight of the cationic polymerization resin is in the range of 10 to 1000 parts by weight. The inkjet recording head of description. A substrate provided with an energy generation element for generating energy for discharging ink, an ejection port provided corresponding to the energy generation element, and an ink flow path for supplying ink to the ejection port And a flow path forming member that forms the ink flow path together with the substrate,
Forming a layer of a photocurable resin composition on the substrate;
Performing pattern exposure on a layer of the photocurable resin composition on the substrate;
Developing the pattern-exposed photocurable resin composition layer to obtain an ink flow path pattern comprising a cured product of the photocurable resin composition; and
Laminating a member having the ejection port on the substrate on which the ink flow path is formed, and
The photopolymerizable resin composition is
(A) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional water having an aromatic ring (where bifunctional means that the number of condensable groups on the same Si atom is 2) A condensate comprising a decomposable organosilane compound and a trifunctional or higher functional hydrolyzable organosilane compound having no aromatic ring,
A method for producing an ink jet recording head, comprising: A substrate provided with an energy generation element for generating energy for discharging ink, an ejection port provided corresponding to the energy generation element, and an ink flow path for supplying ink to the ejection port And a flow path forming member that forms the ink flow path together with the substrate,
Forming a layer of a photocurable resin composition on the substrate;
Performing pattern exposure on a layer of the photocurable resin composition on the substrate;
Developing the pattern-exposed photocurable resin composition layer to obtain an ink flow path pattern comprising a cured product of the photocurable resin composition; and
Laminating a member having the discharge port on a substrate on which the ink flow path is formed;
Have
The photocurable resin composition is
(A) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (provided that trifunctional is a condensable group on the same Si atom) Means number)
A method for producing an ink jet recording head, comprising: A substrate provided with an energy generation element for generating energy for discharging ink, an ejection port provided corresponding to the energy generation element, and an ink flow path for supplying ink to the ejection port And a flow path forming member that forms the ink flow path together with the substrate,
Forming an ink flow path pattern as an ink flow path forming mold material on a substrate provided with an energy generating element for generating energy for discharging ink;
Forming a photocurable resin composition layer on the substrate and covering the ink flow path pattern on the substrate;
Pattern exposure to a layer of the photocurable resin composition covering the ink flow path pattern, followed by development processing to obtain a flow path forming member having discharge ports;
Removing the ink flow path pattern covered with the flow path forming member from the substrate to form an ink flow path;
Have
The photopolymerizable resin composition is
(A) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional water having an aromatic ring (where bifunctional means that the number of condensable groups on the same Si atom is 2) A condensate comprising a decomposable organosilane compound and a trifunctional or higher functional hydrolyzable organosilane compound having no aromatic ring,
A method for producing an ink jet recording head, comprising: A substrate provided with an energy generation element for generating energy for discharging ink, an ejection port provided corresponding to the energy generation element, and an ink flow path for supplying ink to the ejection port And a flow path forming member that forms the ink flow path together with the substrate,
Forming an ink flow path pattern as an ink flow path forming mold material on a substrate provided with an energy generating element for generating energy for discharging ink;
Forming a photocurable resin composition layer on the substrate and covering the ink flow path pattern on the substrate;
Pattern exposure to a layer of the photocurable resin composition covering the ink flow path pattern, followed by development processing to obtain a flow path forming member having discharge ports;
Removing the ink flow path pattern covered with the flow path forming member from the substrate to form an ink flow path;
Have
The photocurable resin composition is
(A) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (provided that trifunctional is a condensable group on the same Si atom) Means number)
A method for producing an ink jet recording head, comprising: A substrate provided with an energy generation element for generating energy for discharging ink, an ejection port provided corresponding to the energy generation element, and an ink flow path for supplying ink to the ejection port And a flow path forming member that forms the ink flow path together with the substrate,
Forming a layer of the photocurable resin composition (1) on the substrate;
Performing pattern exposure on the layer of the photocurable resin composition (1) on the substrate;
Developing the pattern-exposed layer of the photocurable resin composition (1) to obtain an ink flow path pattern made of a cured product of the photocurable resin composition;
A step of laminating a layer of the photocurable resin composition (2) on the substrate on which the ink flow path has been formed, and pattern exposure and development treatment on the layer of the photocurable resin composition (2). Forming an outlet;
And at least one of the photopolymerizable resin composition (1) and the photopolymerizable resin composition (2),
(A) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional water having an aromatic ring (where bifunctional means that the number of condensable groups on the same Si atom is 2) A condensate comprising a decomposable organosilane compound and a trifunctional or higher functional hydrolyzable organosilane compound having no aromatic ring,
A method for producing an ink jet recording head, comprising: A substrate provided with an energy generation element for generating energy for discharging ink, an ejection port provided corresponding to the energy generation element, and an ink flow path for supplying ink to the ejection port And a flow path forming member that forms the ink flow path together with the substrate,
Forming a layer of the photocurable resin composition (1) on the substrate;
Performing pattern exposure on the layer of the photocurable resin composition (1) on the substrate;
Developing the pattern-exposed layer of the photocurable resin composition (1) to obtain a pattern of an ink flow path comprising a cured product of the photocurable resin composition;
A step of laminating a layer of the photocurable resin composition (2) on the substrate on which the ink flow path has been formed, and pattern exposure and development treatment on the layer of the photocurable resin composition (2). Forming an outlet;
And at least one of the photopolymerizable resin composition (1) and the photopolymerizable resin composition (2),
(A) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (provided that trifunctional is a condensable group on the same Si atom) Means number)
A method for producing an ink jet recording head, comprising: A substrate provided with an energy generation element for generating energy for discharging ink, an ejection port provided corresponding to the energy generation element, and an ink flow path for supplying ink to the ejection port And a flow path forming member that forms the ink flow path together with the substrate,
Forming a layer of the photocurable resin composition (1) on the substrate;
Forming a latent image by performing pattern exposure on the layer of the photocurable resin composition (1) on the substrate;
A step of laminating a layer of the photocurable resin composition (2) on the layer of the photocurable resin composition (1) subjected to pattern exposure, and a layer of the photocurable resin composition (2). A step of forming a latent image by performing pattern exposure, and a step of forming an ink flow path pattern and a discharge port made of a cured product of the photo-curable resin composition (1), (2) by a development process,
And
At least one of the photopolymerizable composition (1) and the photopolymerizable composition (2) is (a) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional hydration having an aromatic ring (however, difunctional means that the number of condensable groups on the same Si atom is 2) A condensate comprising a decomposable organosilane compound and a trifunctional or higher functional hydrolyzable organosilane compound having no aromatic ring,
A method for producing an ink jet recording head, comprising: A substrate provided with an energy generation element for generating energy for discharging ink, an ejection port provided corresponding to the energy generation element, and an ink flow path for supplying ink to the ejection port And a flow path forming member that forms the ink flow path together with the substrate,
Forming a layer of the photocurable resin composition (1) on the substrate;
Forming a latent image by performing pattern exposure on the layer of the photocurable resin composition (1) on the substrate;
A step of laminating a layer of the photocurable resin composition (2) on the layer of the photocurable resin composition (1) subjected to pattern exposure, and a layer of the photocurable resin composition (2). A step of forming a latent image by performing pattern exposure, and a step of forming an ink flow path pattern and a discharge port made of a cured product of the photo-curable resin composition (1), (2) by a development process,
And
At least one of the photopolymerizable composition (1) and the photopolymerizable composition (2) is (a) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (provided that trifunctional is a condensable group on the same Si atom) Means number)
A method for producing an ink jet recording head, comprising:   The method for manufacturing an ink jet recording head according to claim 10, wherein the hydrolyzable organosilane compound has an alkyl group having 3 or more carbon atoms.   21. The method of manufacturing an ink jet recording head according to claim 12, wherein the hydrolyzable organosilane compound having no aromatic ring has a group capable of cationic polymerization.   The method for manufacturing an ink jet recording head according to any one of claims 12 to 21, wherein the hydrolyzable organosilane compound having an aromatic ring has a phenyl group.   The mixing ratio of the condensate containing the hydrolyzable organosilane compound to 100 parts by weight of the cationic polymerization resin is in the range of 10 to 1000 parts by weight. Manufacturing method of the inkjet recording head. (A) a cationic polymerizable resin,
(B) photocationic polymerization initiator, and (c-1) difunctional water having an aromatic ring (where bifunctional means that the number of condensable groups on the same Si atom is 2) A condensate comprising a decomposable organosilane compound and a trifunctional or higher functional hydrolyzable organosilane compound having no aromatic ring,
A composition for an ink jet recording head, comprising a photocurable resin containing (A) a cationic polymerizable resin,
(B) a photocationic polymerization initiator, and (c-2) a condensate containing a trifunctional hydrolyzable organosilane compound having an aromatic ring (provided that trifunctional is a condensable group on the same Si atom) Means number)
A composition for an ink jet recording head, comprising a photocurable resin containing

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