The dynamic fatigue and hysteresis performances of fiber reinforced rubber compounds are compared using different plasticizers. Fiber reinforced rubber compounds including a non-linear functionalized fatty acid ester, preferably a trimellitate, and more preferably Tris (2-Ethylhexyl) Trimellitate (TOTM) are shown to demonstrate greatly improved dynamic fatigue and hysteretic performance as compared to reference fiber reinforced rubber compounds including conventional reference plasticizers such as Di-isodecyl phthalate (DIDP).

The formulations and plasticizers described in this disclosure improve the dynamic fatigue properties of fiber reinforced rubbers, and thus are useful in many industrial and commercial applications where dynamic life is important. One such exemplary application is in fiber reinforced rubbers used in PDM stators, in which embodiments of the disclosed formulations and plasticizers improve dynamic fatigue in such reinforced rubbers. Although the reinforced rubber formulations and plasticizers described in this disclosure are not limited in their application or deployment PDM stators, such PDM stator embodiments are useful to demonstrate the advantages of the disclosed reinforce rubber formulations and plasticizers.
Persons of ordinary skill in this art will understand that, consistent with applicable standards such as ASTM D412, terms such as "Young's Modulus", "tensile modulus", or just "Modulus" (as used in this disclosure) are interchangeable to describe a parameter representing the general propensity of a material to deform (e.g. elongate) under a tensile stress load. The value of Modulus for a particular material is often measured in Pascals, and quantifies the material's propensity to deform under tensile load. The value of Modulus thus predicts a deformation in the material (or a "strain" in the material) for a given stress load. Conversely, the value of Modulus predicts the stress required to be applied to the material to achieve a certain deformation (or "strain"). Typically, although not exclusively, the measured deformation of the material (or "strain") will be an elongation under tensile stress load, or a rotation under a torque load. Thus, by way of example and again consistent with ASTM D412, the term "25% tensile Modulus" or "25% Modulus" refers to the tensile stress applied to a material (or seen in a material) at 25% elongation, "50% tensile Modulus" or "50% Modulus" refers to the tensile stress applied or seen at 50% elongation, "100% tensile Modulus" or "100% Modulus" at 100% elongation, and so on. Modulus is one important material performance property of rubber in PDM stators. Modulus is also a somewhat reliable indicator of other desirable material properties, in that higher Modulus will normally indicate higher tensile strength and crack resistance. Without some sort of reinforcement, the rubber anisotropy inevitably caused by injection molding in stator manufacturing causes the cured rubber to exhibit lower Modulus in the cylindrical transverse cross-section direction ("across the grain") versus in the cylindrical longitudinal direction ("with the grain"). Low Modulus in the transverse direction leads to premature breakdown and "chunking" of the rubber under cyclic operational loads in a PDM.
Elastic Modulus (also known as modulus of elasticity) is generally understood as a subset of Modulus, focusing on a material's characteristics in an elastic deformation region of its performance under load. Elastic Modulus describes a parameter representing the general propensity of a material to deform (e.g. elongate) elastically under a tensile stress load. Stated differently, Elastic Modulus measure's a material's resistance to being deformed elastically when a tensile stress is applied to it. The Elastic Modulus of a material may be expressed as the slope of its stress-strain curve in the elastic deformation region of its performance under load. A stiffer material will have a higher Elastic Modulus. Elastic Modulus has the formula:Elastic Modulus=Stress/Strainwhere stress is the force causing the elastic deformation divided by the area to which the force is applied, and strain is the ratio of the change in value of a selected parameter of the material caused by the stress to the original value of the parameter in an unstressed condition (such as, for example, (1) the ratio of the change in length of the material sample to the original length of the sample where the change in length is caused by tensile stress to the sample, or (2) the amount of rotation, normally measured in degrees, of the material sample about an axis where the rotation is caused by torque stress to the sample about the axis).
Dynamic Modulus (also sometimes called Complex Modulus) refers to the study of Elastic Modulus in vibration conditions when the material is subjected to multiple repeating cycles of stressing and relaxation. Dynamic Modulus (or Complex Modulus) is thus of interest in elastomer (rubber) applications such as in PDM stators. Dynamic Modulus or Complex Modulus is further relevant in analysis of materials under vibratory testing conditions such as in a rubber process analyzer or dynamic mechanical analyzer.
Storage Modulus is generally understood as a material parameter related to Elastic Modulus. The Storage Modulus reflects the elasticity of a material. If a material is 100% elastic, all of the work inputted to the material would hypothetically be returned. There would be no heat loss during stress and relaxation of the material, nor would the material ever deform inelastically after stress. In some examples, Storage Modulus reflects the amount of work returned elastically by a material when stress is applied over time. In other examples, Storage Modulus reflects the ability of a material to return to its original state after stress.
Loss Modulus is generally understood as a material parameter also related to Elastic Modulus. Loss Modulus reflects the viscous behavior of a material. Loss Modulus may also be referred to as Viscous Modulus. If a material is 100% viscous (as are most liquids), all work inputted is converted to heat and/or inelastic deformation, and the material does not return to its original state. It is desirable in elastomeric materials such as rubber to minimize the Loss Modulus in order to maximize elastic performance.
In a vibratory test, Storage Modulus measures the portion of the Complex Modulus where stress and strain occur simultaneously or in phase. In a similar vibratory test, Loss Modulus measures the portion of the Complex Modulus where strain lags stress by 90 degrees (π/2 radians).
Tan delta is a parameter of a material representing a ratio of the material's Loss Modulus to its Storage Modulus. The optimization and minimization of tan delta thus becomes important in designing elastomers (e.g. rubbers) for use in applications such as PDM stators. Low tan delta in a rubber predicts low heat loss and low permanent inelastic deformation of the elastomer under repetitive (and typically, cyclic) stress loading and relaxation during operational service.
The Payne effect is a particular feature of the Modulus-type (stress-strain) behavior of elastomers such as rubber, and is especially relevant in analysis of the performance of rubber compounds containing fillers such as carbon black and/or fiber reinforcement. Study of the Payne effect is thus advantageous in the design of fiber-reinforced elastomers (e.g. rubbers) for use in applications such as PDM stators. The Payne effect is observed in filled materials under cyclic loading conditions with small strain amplitudes. In such conditions of small strain amplitudes within each cycle, the Payne effect manifests itself as a variance of Storage Modulus depending on the amplitude of the strain responsive to the applied stress. Stated differently, the Payne effect manifests itself when Storage Modulus (the elasticity of the material) varies according to different values of strain amplitude in small strain cycle conditions.
Physically, the Payne effect can be attributed to deformation-induced changes in the material's microstructure, i.e. to breakage and recovery of weak physical bonds linking adjacent filler clusters. The specific Payne effect for a particular filled elastomer depends a lot on the filler—e.g. what the filler is, the filler's % content, etc. The Payne effect tends to vanish for unfilled elastomers.
Given the relevance of the Payne effect in the design of filled (e.g. fiber-reinforced) rubbers, constitutive models exist to represent and predict the Payne effect in exemplary situations. As a result, the Payne effect may be further illustrated very broadly and generally with reference to specific exemplary values. For some filled rubbers, The Payne effect manifests itself as Storage Modulus (i.e. the elasticity of the material) decreasing rapidly with increasing cyclic strain amplitudes between approximately 0.1% strain amplitude and approximately 20% strain amplitude. (Above approximately 20% strain amplitude, Storage Modulus stabilizes to a more constant value for different strain amplitudes.) Conversely, the Payne effect also manifests itself as Loss Modulus (i.e. the viscous behavior of the material) increasing to a corresponding maximum for the material in the same range of approximately 0.1% cyclic strain amplitude to approximately 20% cyclic strain amplitude.
As noted above, this disclosure describes optimized fiber-reinforced rubber formulations, and methods of making them, for exemplary use in PDM stator embodiments. During the rubber injection process to make PDM stators, the rubber is injected though a mold that requires the rubber to flow through a geometry with a very high length to cross section ratio. Typical stator tube geometries may have lengths of 120″ to 300″ for tube diameters of 4.75″ and larger. Stator tubes in the 2″ to 4″ diameter range have typical lengths of 60″ to 150″ and stator tubes in the 1.5″ to 2″ have typical lengths of 50″ to 100″.
Fibers introduced into a rubber are known to strengthen the rubber composite, and improve material properties such as Modulus and crack resistance. When added to rubber, small amounts of fiber can significantly improve the life of components by acting to distribute stress across the component more effectively. This is particularly effective as the component weakens during cyclic loading. Fibers distribute and dissipate energy at the crack tip of any flaw initiation site, thereby slowing the crack initiation and propagation stage of fatigue failures. Reinforcement fibers can be fibrillated, low-fibrillated, non-fibrillated, long, and/or short.
In some applications, however, fibers within a rubber composite, while providing improved material properties, can also be detrimental to dynamic fatigue properties. Applications such as PDM stators undergo rapid compression/relaxation cycles. Over the useful life of a PDM stator, the lobes can experience multi-millions of such cycles. The surface area of fibers added to rubber composites add internal friction to the rubber that is generally proportional to the surface area of the fiber. In service, the reinforced rubber exhibits hysteresis. Internal friction through multiple cycles generates internal heat that can be detrimental to the life of the rubber. The internal friction imparted by fiber reinforcement also prevents rubber from relaxing to its original shape through strain/relaxation cycles. The reinforced rubber shows an increased tan delta as compared to corresponding performance in unreinforced rubbers. The reinforced rubber also exhibits a Payne effect. Excessive hysteresis leads to shape deformation, internal heat buildup, and eventual loss of performance of the part. In some cases, hysteresis may lead to crack propagation and failure. Increased hysteresis imparted by fibers is therefore undesirable.
Plasticizers are conventionally used as admixtures in fiber-reinforced rubber formulations to address and remediate the hysteretic effects described above. Plasticizers and related processing aids are known in the art for decreasing overall viscosity of rubber compounds to make them easier to process. Plasticizers generally decrease the attraction between polymer chains in order to make the compounds more less viscous and more flexible. Plasticizers and such related processing aids are thus of interest in the design of rubbers for use in PDM stators. It will be understood that reduced viscosity and increased ability of a rubber to be processed is advantageous in an injection molding process such as is common in the manufacture of PDM stators. Choice of plasticizer has been traditionally made in part based on compatibility with a particular rubber, ease of mixing, objectives with respect to decreasing compound viscosity, and compatibility with the environment to which the rubber will be exposed. Chemical families of such processing aids and/or plasticizers may include but are not limited to, linear fatty acid esters, adipates, sebacates, maleates and phthalates, and the like. Low molecular weight naphthenic or paraffinic oils, low molecular weight waxes, and low molecular weight rubbers such as poly-butenes are also known to be used as plasticizers. In some cases, the addition of such plasticizers can require adding more reinforcing agent such as, for example, carbon black or fiber reinforcement to achieve the same properties in the rubber without plasticizer.
Choice of plasticizer also influences the ability of the selected plasticizer to mix properly with reinforcement agents such as carbon black, silica, or aramid fibers and the like. Lower molecular weight plasticizers, while providing a larger decrease in overall processing viscosity, often times make it more difficult to thoroughly mix the carbon black and/or other reinforcing agents. Lower molecular weight plasticizers with lower viscosities do not allow the mixing elements to impart as much shear into the mixture allowing carbon black and/or other reinforcement agents to stay more agglomerated. Reinforcement agents that are more agglomerated are less reinforcing in the final compound. Such an effect can be measured in a rubber process analyzer (RPA). As strain is increased in a rubber sample, the agglomerates tend to break, requiring less stress to achieve an equivalent shear. This difference in elastic stress (delta G′) at low strains and high strains indicates the degree of agglomeration of the reinforcing agent. A higher difference indicates more agglomeration. This measurement is manifested in the Payne Effect, described in more detail above.
Conversely, rubber chemists often compensate for lower shear in mixing by imparting more mechanical shear in the mixer. This in turn generates more heat which often "masticates" the elastomer decreasing its overall molecular weight. This can lead to degradation of mechanical properties. It is therefore desirable to use a plasticizing agent that minimizes the delta G′ while still achieving the objective viscosity of the final compound.
Rubber chemists have historically not given great consideration to the impact of plasticizers on their interaction with reinforcement agents during dynamic flexing over multiple cycles (such as seen in PDM stator service). With high surface area reinforcing agents such as fibrillated aramid fibers, there may be a higher degree of interfacial frictional slippage between rubber and reinforcement with dynamic flexing, leading to higher internal heat generation (hysteresis) in the rubber. This leads to compression set, loss of rebound, and thereby loss of rubber integrity through many cycles. It is therefore important for a plasticizer to be well mixed with the reinforcing agent and maintain lubricity between the rubber and reinforcing agent. The functionality and molecular weight of the plasticizer have a significant influence on this flex life and fatigue.
Di-isodecyl phthalate (DIDP) is a phthalate-based plasticizer, and is frequently used in plastics and polymer coatings to alter their viscosity and other physical properties. DIDP is a mixture of compounds derived from the esterification of phthalic acid and isomeric decyl alcohols and has a generally two-dimensional, V-like molecular shape. DIDP is a serviceable plasticizer in applications that are exposed to relatively high temperatures. DIDP is thus a commonly used plasticizer in rubbers deployed in downhole drilling applications, including in PDM stators in which fiber-reinforced rubber formulations are deployed.
While serviceable in many downhole drilling applications, the plasticizing performance currently provided by DIDP in PDM reinforced rubber applications could nonetheless be improved upon. It would be highly advantageous if an alternative plasticizer (or class of plasticizers) could be identified to improve upon DIDP's plasticizing performance in reinforced rubber applications. The improved plasticizing performance of such an alternative plasticizer would be characterized by demonstrably lowering hysteresis in the reinforced rubber while under cyclic load, thereby improving overall dynamic fatigue performance of the reinforced rubber during service. More specifically, the alternative plasticizer would lower tan delta in the reinforced rubber and lessen the prominence of a Payne effect.

Plasticizer improving dynamic fatigue performance in fiber reinforced elastomers


A separator for separating liquid components, in particular oil components, from a gas flow is disclosed including a cyclone and a tank. The liquid separator has a cyclone 1 with a separating chamber 2 including gas supply 3 and gas discharge 4 and a tank 5 which is connected to the cyclone 1 via a connection opening 6. The interior of the tank 5 is filled at least partially with a porous open-pore material 7 in order to interrupt the flow, dampen the flow, dampen the oscillations and/or discharge the liquid.

Devices and methods for separating liquid components from a gas flow by means of a cyclone and a collection tank are already known from the state of the art. Also corresponding devices or methods are known for separating solid, in particular pulverised particles. In the known devices or methods according to the state of the art, turbulences and/or oscillating air columns are produced due to the connection opening between cyclone and tank, in particular at very high flow rates, by means of which drainage of the liquid or discharge of the solid particles into the tank is prevented. In methods or devices for separating solid particles, cones or baffles are therefore fitted in part under the tank inlet opening. This in fact improves the situation, however particles are swirled upwardly for example by secondary turbulence from the opening towards the transition from the conical part to the cylindrical part of the cyclone.

Device for separating liquid components from a gas flow with a cyclone, a tank and a cyclone tank turbulence brake


A quadrature detector FM demodulates an intercarrier signal operating at an unknown frequency. An LC tank circuit develops a 90.degree. phase shift across inputs of a multiplier. The output signal of the multiplier is amplified and fedback to control a reactance stage and adjust the reactive load at an input of the multiplier so as to maintain a predetermined phase relationship independent of the frequency of the intercarrier signal. A phase compensation stage removes any real component at the inputs of the multiplier also in response to the feedback signal.

The present invention relates in general to FM demodulators, and more particularly, to an FM demodulator with a self-tuning quadrature detector.
FM demodulators are commonly used in television receivers where a transmitted signal must be demodulated to extract the audio and video signals from the RF (radio frequency) carrier. In a simplified view, the video information is AM modulated on a video carrier f.sub.c and the audio information is FM modulated on a sound carrier f.sub.s. The transmitted RF signal frequency is reduced through a tuner to an IF (intermediate frequency) signal and demodulated to baseband. After demodulation of the IF signal, the video information becomes a video baseband signal, while the audio information remains modulated on a sound intercarrier (f.sub.c -f.sub.s) at the difference between the video carrier f.sub.c and sound carrier f.sub.s. In the United States, the video carrier f.sub.c is set to 45.75 MHz, and the sound carrier f.sub.s is set to 41.25 MHz, leaving the f.sub.c -f.sub.s sound intercarrier at 4.5 MHz. The demodulated IF signal may be further processed through a trap (band-reject) filter to remove the f.sub.s sound carrier and retrieve the video information as luma (black and white) and chroma (color). An RGB signal may be generated from luma and chroma to drive the CRT screen. Likewise, the demodulated IF signal may be processed through a band-pass filter to isolate the sound intercarrier and then FM demodulated with a quadrature detector to retrieve the audio information.
One difficulty for FM demodulators in television receivers is the variety of carrier frequencies used worldwide for television signal transmission. There does not exist a single, worldwide television carrier frequency standard. In the audio processing path, the quadrature detector typically uses a fixed inductor-capacitor (LC) tank circuit tuned to produce a 90.degree. phase shift between the inputs of a multiplier at a predetermined sound intercarrier frequency. Unfortunately, the sound intercarrier frequency may vary between say 4.5 MHz and 6.5 MHz depending on the country of operation. Therefore, the quadrature detector manufacturer must be aware of the importing country's standard in order to properly pre-tune the LC tank circuit. This customization adds costs to the commercial manufacturing and complicates the distribution process.
With the multi-frequency standards, a need exists for a quadrature detector capable of self-tuning over a range of frequencies in a well determined manner while improving linearity.

FM demodulator with self-tuning quadrature detector


Concepts and technologies are disclosed herein for relative quality of service indicators. A processor obtains quality of service data for a sector that is serving a user device. In response to determining that a quality of service associated with the sector is degraded, an offer can be provided to the user device to upgrade the quality of service. In response to detecting acceptance of the offer, enhancement of the quality of service can be triggered. Quality of service data for the sector can be collected. The quality of service data can represent the quality of service for the user device and a further quality of service for another device located in the sector. Quality of service display data that presents the quality of service for the user device and the further quality of service for the other device can be generated and provided to the user device for display.

Quality of service ("QoS") in communications networks can vary widely based on location, time, devices, applications, network conditions and capabilities, and policy rules. Latency, download speed, upload speed, call quality, and the like, may vary greatly among users across the network, within a particular geographic area, within a single cell cite, and even on a single cell sector. For example, within a cell site, if one sector antenna is aimed toward an interstate highway with heavy traffic and a second sector antenna is aimed at woods and hills behind the tower (relative to the interstate highway), the users in a sector associated with the first sector antenna may experience a lower quality of service than users in a sector associated with the second sector antenna. Similarly, within a cell sector, some users on calls during a particularly busy time, may not have any problems, while a user who is downloading a data-intensive video, for instance, may experience increased latency.
In a fourth generation ("4G") long term evolution ("LTE") network, some communications may be prioritized. Thus, for example, emergency communications may be given a high priority relative to reporting of call statistics. At times, however, even prioritized data communications may be slow due to heavy traffic, network conditions, or other factors. In such cases, users who would expect to have a high priority and thus a higher speed, lower latency, or the like, may not perceive that their traffic is being prioritized.

Generating and providing relative quality of service indicators


A network includes a plurality of redundant nodes and ordinary nodes. A first redundant node from among the redundant nodes sets a common address and setting information in a message packet and broadcasts the message packet over the network. The common address is commonly used by all the redundant nodes on the network. The setting information is indicative of the fact that the first redundant node is a redundant node. All the nodes have a topology table. The nodes that receive the message packet set in their topology table information indicating of presence of the first redundant node and the common address shared by the redundant nodes. When transmitting a packet to the first redundant node, a node sets the common address as a destination address of the packet.

1. Field of the Invention
The present invention relates to a node redundancy method, an interface card, an interface device, a node device, and a packet ring network system used in networks.
2. Description of the Related Art
Recently, there has been a remarkable increase in data traffics over the Internet mainly based on the Ethernet (Registered trade name) or IP (Internet Protocol) packets, rapid increase in ADSL (Asymmetric Digital Subscriber Line) users, and advent of VoIP (Voice over IP) technique. As a result, a network of packet rings (described as a packet ring network or simply, as a ring hereinafter), in which packets are directly processed on the ring network for band management for each packet or for statistic multieffect, has attracted attention as a potential alternative for a ring network based on the conventional SONET/SDH (Synchronous Optical Network/Synchronous Digital Hierarchy) devices.
Especially, the packet ring network is attracting high attentions as useful in networks in urban areas. In the IEEE, the work for standardizing the IEEE802.17 RPR, in which standard specifications for a packet ring are put into shape, are now in progress with November, 2003 as a target deadline.
The recent packet ring as described above is generally referred to as an RPR (Resilient Packet Ring) to differentiate it from the token ring or FDDI (Fiber Distributed Data Interface) ring.
The RPR is a network protocol technique mainly provided for an inter-city network (MAN/WAN (Metropolitan Area Network/Wide Area Network)).
The RPR is based on the SRP (Spatial Reuse Protocol) announced by Cisco Systems, Inc., and has the following features:
1. Support for an interactive dual ring network.
2. Support for an MAC (Media Access Control) layer (layer 2)
3. High utilization factor of a used band
4. Plug & Play
5. Capability of switching within 50 ms at occurrence of trouble.
FIG. 35 is a schematic of a conventional RPR network 10. The RPR network 10 includes node devices #a to #f connected to each other to form a duel ring of an inner loop communication path 11i and an outer loop communication path 11o. The inner loop communication path 11i and the outer loop communication path 11o allow bilateral communications in the RPR network 10. Because of the dual ring configuration, even when trouble occurs in one of the rings, communications can be continued via the other ring.
The nodes devices #a to #f are devices for transferring packet data and they function as nodes. The nodes devices #a to #f can be, for instance, a transfer device, a bridge node, a router, server, and any other device dedicated to the RPR.
A packet-based network such as Ethernet typically has the shoe-type or tree-type network. When node redundancy is to be built in the packet-based network as described above, generally the STP (Spanning Tree Protocol) is employed.
Patent document 1: U.S. Pat. No. 6,314,110
Non-patent document 1: IEEE802.17 Draft V2.1
In the conventional technology, when node redundancy is realized with a mesh-formed or a tree-type network, a number of optical fibers are disadvantageously required to be installed anew for connecting the node devices to the redundant node devices.
With the redundant node configuration using the STP, about one minute is required for switching to a bypass route when line trouble or node trouble occurs, and the requirement of telecommunications operators and the like for the high speed switching with the time of 50 milliseconds or below has not been satisfied at all.
Recently, the possibility of RSTP (Rapid Spanning Tree Protocol) developed by improving the STP has been examined, but sill the switching time of several seconds is required even when the RSTP is employed, and the requirement for the switching time of 50 milliseconds or below has not been realized.
The standard RPR (IEEE802.17 draft V2.1) for the conventional type of RPR network does not include any definition on a function for node redundancy. Moreover, the IETF RFC 2892 (The Cisco SRP MAC Layer Protocol) does not include any definition on node redundancy in a ring network.

Node redundancy method, interface card, interface device, node device, and packet ring network system


A robot system may include a robot controller; a target robot; and a host device. The target robot may include a first memory to store device specific data comprising information on the model of the target robot; individual identification data used to identify the target robot; and an individual difference parameter unique to the target robot. The robot controller may include a second memory to store information on the model of the target robot connected to the robot controller, the model configuration information, the individual identification data, and the individual difference parameter; and a controller to control the target robot on the basis of the model configuration information and the individual difference parameter stored in the second memory unit. The controller may read the model configuration information of the model and store the model configuration information in the second memory unit.

In general, a robot system is configured to include: a manipulator, that is, a robot body; and a robot controller that controls the manipulator. The manipulator includes: an arm and a hand that are coupled to each other; and a motor that drives a coupled portion of those arm and hand. In order to control rotation of each of the motors in the manipulator by the robot controller, an encoder is attached to each of the motors to detect a rotary position thereof, and rotary position information acquired by the encoder is transmitted to the robot controller as needed. In some cases, the robot system is provided with an auxiliary component such as an aligner that changes an attitude of a workpiece as a target of processing by the manipulator. The auxiliary component is also a control target of the robot controller.
In the manipulator as the robot body, numbers and dimensions of the arm and the hand, a connection relationship between those arm and hand, a specification of each of the motors mounted therein differ by robot models. In general, these types of robot configuration information are saved in advance in the robot controller. Thus, the robot controller is prepared for each of the robot models. The robot controller as is cannot control a robot of a model other than the model as the control target thereof. In order to set the robot controller for a certain model to have a specification enabling control of the robot of the different model, such work is required that a worker checks the robot model and replaces the robot configuration information in the robot controller with robot configuration information that is compatible with the checked robot model. Furthermore, even among the robots of the same model, individual differences of the manipulators are inevitable. Thus, when controlling such a manipulator, the robot controller has to control the manipulator in accordance with the individual difference thereof. An example of the individual difference is an offset value from a position of an origin. The position of the origin is set for each of the manipulators as a reference attitude for an operation thereof. However, due to attachment variations of the motors and the encoders, and the like, a value of rotary position data presented by the encoder of each of the motors at the position of the origin differs by units of the manipulators. The same applies to the auxiliary component having a motor. In view of the above, the individual difference is actually measured upon completion of assembly of each of the robots, or the like. The individual difference is then stored in a memory unit of the robot controller. For this reason, in the case where the manipulator is replaced with another manipulator of the same model, and the other manipulator of the same model is connected to the robot controller, the robot controller can no longer control the manipulator with a high degree of accuracy even when the manipulators of the same model are set as the control targets of the robot controller.
In Japanese Unexamined Patent Application Publication No. 2001-242922, as an attempt to allow replacement of the robot body that is connected to the robot controller, a robot system that can control the robot body by the robot controller even when a built-in board in the robot body is replaced is disclosed. In Japanese Unexamined Patent Application Publication No. 2004-148433, in order to automate work of updating data that is associated with a robot mechanism or a mechanism unit after replacement thereof, a technique of rewriting data in the robot controller by data read from the robot mechanism or the mechanism unit upon detection of the replacement is disclosed. Japanese Unexamined Patent Application Publication No. 2016-137526 relates to information on sensors provided in a robot and discloses a technique of reading the information into the robot controller from the robot body after replacement of the robot body. Japanese Unexamined Patent Application Publication No. 2013-56738 discloses a technique of using replacement memory to appropriately and easily migrate robot operation data from the robot controller that has been used so far to a new robot controller.
In addition to that the robot controller can be replaced and used for the robots of the same model, it has been desired that the robot controller can be replaced and used for the robots of the different models. Meanwhile, the techniques disclosed in Japanese Unexamined Patent Application Publication No. 2001-242922, 2004-148433, 2016-137526, and 2013-56738, each of which allows changing of the robot body connected to the robot controller, are not flexible enough in terms of reading of the robot configuration information into the robot controller. In addition, the techniques disclosed in Japanese Unexamined Patent Application Publication No. 2001-242922, 2004-148433, 2016-137526, and 2013-56738 are not necessarily optimized techniques in terms of changing of the robot controller to the robot controller for the robot of the same model. In the technique disclosed in Japanese Unexamined Patent Application Publication No. 2013-56738, when the robot controller is changed, a backup of a parameter relevant to the individual difference has to be created, which complicates a procedure.

This patent is subject to a terminal disclaimer.


The removable apparatus of a transparent filterable dust bag with a support container is designed as an attachment for a vacuum cleaner and like. A transparent filterable dust bag having an outer transparent wall and an inner filter cone coincides within a transparent support container which keeping the shape and position of the dust bag while separating dust from air. The transparent support container and the outer transparent wall of the dust bag allow to watch inside the filling level of the dust bag and to replace properly.

Collection equipments for separating dust, dirt and similar material from air, such as vacuum cleaners, require the use of filter, dust bags or containers for the material to be filtered and collected.
Theses conventional dust bags combine the functions of filtering and collecting. They can consist of paper, or any other filtration type material which on the one hand allows to collect dust and dust-like material and on the other hand has a porosity sufficient for the fluid carrying the dust or dust-like material with a minimum pressure drop. They are light and flexible.
Typically these dust bags are provided with an intake opening through which the dust or dust-like particles is to be transported and collected within the bags. The dust or dust-like material is packed into a bag and then the filled bag is disposed. A dust bag minimizes opportunities to contact collected dust by hand directly. A filter material is opaque normally to prevent people from watching the filling situation of dust bag directly. As long as the accumulation of dust, some methods are necessary to measure when it is time to replace the filled bag. In all of known filterable bag designs the replacing of filled bag is dependent on pressure differences measured.
The bag-less technology separates the functions of collecting and filtering. Normally a durable filter or a cyclone device is used to filter dust air and dirt, and trap dust and dirt in a surrounding transparent container. These containers can be made from strengthened plastic, or any other strengthened lighter and transparent type container material. Dirt and dust are seen and then a filled transparent container will be picked out of position from a vacuum cleaner. These filters can consist of paper, or any other filtration type material which form airflow path and trap dust. The cyclone separating technology has the advantage of collecting coarse particle and a disadvantage on filtering fine particles. A conventional filter can be combined into a cyclone type cleaner for increasing the capacity of collecting fine particles. Durable filters or washable filters are to be cleaned or replaced in a designed long period in most of bag-less vacuum cleaner. Sooner or later there still are some opportunities to touch dirty filters directly.
A need is identified for a way to retain the advantages of flexible filterable bags and transparent bag-less containers; and to reduce the disadvantages affection of no transparent filterable material and touching dirty durable filters.

Transparent filterable dust bag with support container for vacuum cleaner


An HVAC system includes a high-pressure subsystem and a low-pressure subsystem. After determining that refrigerant leak diagnostics should be performed, a controllable valve is closed between a condenser and compressor of the HVAC system. The compressor then operates until a predetermined input refrigerant pressure is reached. After the predetermined input refrigerant pressure is reached, operation of the compressor is stopped. After stopping operation of the compressor and waiting at least a predetermined wait time, the pressure in the low-pressure subsystem of the HVAC system is monitored. A rate of change of the pressure in the low-pressure subsystem is determined. If the rate of change is negative and a magnitude of the rate of change is greater than a threshold value, a leak location is determined to be in the low-pressure subsystem.

Heating, ventilation, and air conditioning (HVAC) systems are used to regulate environmental conditions within an enclosed space. Air is cooled via heat transfer with refrigerant flowing through the HVAC system and returned to the enclosed space as cooled conditioned air. Leakage of the refrigerant can result in decreased system performance.


Intercalates formed by contacting the layer material, e.g., a phyllosilicate, with an intercalant to sorb or intercalate the between adjacent platelets of the layered material. Sufficient intercalant polymer is sorbed between adjacent platelets to expand the adjacent platelets at least about 5 .ANG. (as measured after water removal to 5% by weight water), up to about 100 .ANG. and preferably in the range of about 10-45 .ANG., so that the intercalate easily can be exfoliated into individual platelets. A monovalent, divalent and/or trivalent cation is added to the intercalating composition, or after intercalation for surprising increases in viscosity. The intercalated complex is combined with an organic liquid into an unexpectedly viscous carrier material, for delivery of the carrier material, or for delivery of an active compound, e.g., a pharmaceutical, or cosmetic, or lubricant, e.g., food grade lubricants dissolved or dispersed in the carrier material. Alternatively, the intercalated complex can be exfoliated prior to combination with the organic liquid.

It is well known that phyllosilicates, such as smectite clays, e.g., sodium montmorillonite and calcium montmorillonite, can be treated with organic molecules, such as organic ammonium ions, to intercalate the organic molecules between adjacent, planar silicate layers, thereby substantially increasing the interlayer (interlaminar) spacing between the adjacent silicate layers. The thustreated, intercalated phyllosilicates, then can be exfoliated, e.g., the silicate layers are separated, e.g., mechanically, by high shear mixing. The individual silicate layers, when admixed with a matrix polymer, before, after or during the polymerization of the matrix polymer, e.g., a polyamide--see 4,739,007; 4,810,734; and 5,385,776--have been found to substantially improve one or more properties of the polymer, such as mechanical strength and/or high temperature characteristics.
Exemplary of such prior art composites, also called "nanocomposites", are disclosed in published PCT disclosure of Allied Signal, Inc. WO 93/04118 and U.S. Pat. No. 5,385,776, disclosing the admixture of individual platelet particles derived from intercalated layered silicate materials, with a polymer to form a polymer matrix having one or more properties of the matrix polymer improved by the addition of the exfoliated intercalate. As disclosed in WO 93/04118, the intercalate is formed (the interlayer spacing between adjacent silicate platelets is increased) by adsorption of a silane coupling agent or an onium cation, such as a quaternary ammonium compound, having a reactive group which is compatible with the matrix polymer. Such quaternary ammonium cations are well known to convert a highly hydrophilic clay, such as sodium or calcium montmorillonite, into an organophilic clay capable of sorbing organic molecules. A publication that discloses direct intercalation (without solvent) of polystyrene and poly(ethylene oxide) in organically modified silicates is Synthesis and Properties of Two-Dimensional Nanostructures by Direct Intercalation of Polymer Melts in Layered Silicates, Richard A. Vaia, et al., Chem. Mater., 5:1694-1696(1993). Also as disclosed in Adv. Materials, 7, No. 2: (1985), pp, 154-156, New Polymer Electrolyte Nanocomposites: Melt Intercalation of Poly(Ethylene Oxide) in Mica-Type Silicates, Richard A. Vaia, et al., poly(ethylene oxide) can be intercalated directly into Na-montmorillonite and Li-montmorillonite by heating to 80.degree. C. for 2-6 hours to achieve a d-spacing of 17.7 .ANG.. The intercalation is accompanied by displacing water molecules, disposed between the clay platelets with polymer molecules. Apparently, however, the intercalated material could not be exfoliated and was tested in pellet form. It was quite surprising to one of the authors of these articles that exfoliated material could be manufactured in accordance with the present invention.
Previous attempts have been made to intercalate polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVOH) and poly(ethylene oxide) (PEO) between montmorillonite clay platelets with little success. As described in Levy, et al., Interlayer Adsorption of Polyvinylpyrrolidone on Montmorillonite, Journal of Colloid and Interface Science, Vol. 50, No. 3, March 1975, pages 442-450, attempts were made to sorb PVP (40,000 average M.W.) between monoionic montmorillonite clay platelets (Na, K, Ca and Mg) by successive washes with absolute ethanol, and then attempting to sorb the PVP by contact with 1% PVP/ethanol/water solutions, with varying amounts of water, via replacing the ethanol solvent molecules that were sorbed in washing (to expand the platelets to about 17.7 .ANG.). Only the sodium montmorillonite had expanded beyond a 20 .ANG. basal spacing (e.g., 26 .ANG. and 32 .ANG.), at 5.sup.+ % H.sub.2 O, after contact with the PVP/ethanol/H.sub.2 O solution. It was concluded that the ethanol was needed to initially increase the basal spacing for later sorption of PVP, and that water did not directly affect the sorption of PVP between the clay platelets (Table II, page 445), except for sodium montmorillonite. The sorption was time consuming and difficult and met with little success.
Further, as described in Greenland, Adsorption of Polyvinyl Alcohols by Montmorillonite, Journal of Colloid Sciences, Vol. 18, pages 647-664 (1963), polyvinyl alcohols containing 12% residual acetyl groups could increase the basal spacing by only about 10 .ANG. due to the sorbed polyvinyl alcohol (PVOH). As the concentration of polymer in the intercalant polymer-containing solution was increased from 0.25% to 4%, the amount of polymer sorbed was substantially reduced, indicating that sorption might only be effective at polymer concentrations in the intercalant polymer-containing composition on the order of 1% by weight polymer, or less. Such a dilute process for intercalation of polymer into layered materials would be exceptionally costly in drying the intercalated layered materials for separation of intercalate from the polymer carrier, e.g., water, and, therefore, apparently no further work was accomplished toward commercialization.
In accordance with an important feature of the present invention, intercalation is achieved using a water-soluble or water-insoluble (organic solvent-soluble) monomer, oligomer (herein defined as a pre-polymer having 2 to about 15 recurring monomeric units, which can be the same or different) or polymer (herein defined as having more than about 15 recurring monomeric units, which can be the same or different) composition for intercalation having at least about 2%, preferably at least about 5% by weight, more preferably at least about 10% by weight intercalant monomer, intercalant oligomer, or intercalant polymer concentration, most preferably about 30% to about 80% by weight monomer, oligomer and/or polymer, based on the weight of monomer, oligomer and/or polymer and carrier (e.g., water with or without another solvent for the intercalant monomer, intercalant oligomer, or intercalant polymer) to achieve better sorption of the intercalant between phyllosilicate platelets. Regardless of the concentration of intercalant in liquid solvent of the intercalating composition, the intercalating composition should have an intercalant layered material ratio of at least 1:20, preferably at least 1:10, more preferably at least 1:5, and most preferably about 1:4 to achieve efficient intercalation of the intercalant between adjacent platelets of the layered material. The intercalant (monomer, oligomer and/or polymer) sorbed between and permanently bonded to the silicate platelets causes separation or added spacing between adjacent silicate platelets and, for simplicity of description, the monomers, oligomers and polymers are hereinafter called the "intercalant" or "intercalant monomer", or "monomer intercalant", or "intercalant polymer" or "polymer intercalant". In this manner, the monomers, oligomers and/or polymers will be sorbed sufficiently to increase the interlayer spacing of the phyllosilicate in the range of about 5 .ANG. to about 100 .ANG., preferably at least about 10 .ANG., for easier and more complete exfoliation, in a commercially viable process, regardless of the particular phyllosilicate or intercalant polymer.
A phyllosilicate, such as a smectite clay, can be intercalated sufficiently for subsequent exfoliation by sorption of monomers, polymers or oligomers that have carbonyl, hydroxyl, carboxyl, amine, amide, ether, ester, sulfate, sulfonate, sulfinate, sulfamate, phosphate, phosphonate, phosphinate functionalities, or aromatic rings to provide metal cation complexing between two functional groups of one or two intercalant molecules and the metal cations complexing to the inner surfaces of the phyllosilicate platelets. Sorption and metal cation electrostatic attraction or bonding of a platelet metal cation between two oxygen or nitrogen atoms of the molecules; or the electrostatic bonding between the interlayer cations in hexagonal or pseudohexagonal rings of the smectite layers and an intercalant aromatic ring structure increases the interlayer spacing between adjacent silicate platelets or other layered material to least about 5 .ANG., preferably at least about 10 .ANG., and more preferably to at least about 20 .ANG., and most preferably to an interlayer spacing in the range of about 30 .ANG. to about 45 .ANG.. Such intercalated phyllosilicates can be exfoliated into individual phyllosilicate platelets before or during admixture with a liquid carrier or solvent, for example, one or more monohydric alcohols, such as methanol, ethanol, propanol, and/or butanol; polyhydric alcohols, such as glycerols and glycols, e.g., ethylene glycol, propylene glycol, butylene glycol, glycerine and mixtures thereof; aldehydes, ketones, carboxylic acids; amines; amides; and other solvents, for delivery of the solvent in a thixotropic composition, or for delivery of any active hydrophobic or hydrophilic organic compound, such as a topically active pharmaceutical, dissolved or dispersed in the carrier or solvent, in a thixotropic composition.
In accordance with an important feature of the present invention, it has been found that the addition of metal cations, preferably during intercalation and/or exfoliation, or the addition of metal cations to a nanocomposite composition of an organic liquid and an intercalate or exfoliate thereof, unexpectedly increases the viscosity of an organic liquid-containing nanocomposite composition. It is preferred that the metal cation has a valence of at least 2, more preferably at least 3, although monovalent salts (preferably not NaOH) also increase the viscosity to a lesser degree. The anion portion of the cation-containing compound, added to provide cations, may be inorganic or organic and the cation-containing compound is added in solution (with water and/or an organic solvent) to provide metal cations, as well as anions, in solution. The addition of the metal cations in solution to the intercalating composition results in sufficient intercalation for easy exfoliation using less intercalant. It is theorized that polar moieties from the intercalant molecules, which complex to the interlayer cations in the interlayer spaces between the platelets of the layered material, also complex with the added cations, and the complexed metal salt-derived cations carry their dissociated anions along with the cations, in the interlayer space, in order to maintain charge neutrality within the interlayer spaces of the layered material. It is theorized that such double intercalant complexing (intercalant with interlayer cations and with cations from the added metal salt compound) occurs on adjacent, opposed platelet surfaces, resulting in repulsion between closely spaced dissociated anions carried by the added cations, resulting in increased basal spacing and more complete exfoliation using less intercalant.
Addition of the dissolved salt compounds after exfoliation also increases the viscosity of the organic liquid/exfoliate nanocomposite composition since the added cations provide increased and essentially total exfoliation of tactoids so that more individual platelets are available for viscosity increase.
Depending upon the conditions that the composition is subjected to during intercalation and exfoliation, particularly temperature; pH; and amount of water and/or organic liquid contained in the intercalating composition, the intercalate and/or exfoliate/carrier composition can be formed to any desired viscosity, e.g., at least about 100 centipoises, preferably at least about 500-1000 centipoises, whether or not gelled, and particularly to extremely high viscosities of about 5,000 to about 5,000,000 centipoises. The compositions are thixotropic so that shearing will lower viscosity for easier delivery, and then by reducing shear or eliminating shear, the compositions will increase in viscosity. The intercalant intercalates between the spaces of adjacent platelets of the layered material for easy exfoliation, and complexes with the metal cations on the platelet surfaces where the intercalant remains after the intercalant, or exfoliate thereof, is combined with the carrier/solvent. It is theorized that the intercalant coating on the surfaces of the clay platelets is ionically complexed with interlayer cations, as well as with the added, metal salt-derived cations, and participates (aids) in the viscosification and thixotropy of the exfoliate/solvent composition. However, other forms of bonding such as electrostatic complexing, chelation, dipole/dipole, hydrogen bonding and/or Van Der Waals forces or molecular complexing also may be responsible for the adherence of the intercalant to the surfaces of the layered material, either entirely, or in part.

Viscous carrier compositions, including gels, formed with an organic liquid carrier, a layered material: polymer complex, and a di-, and/or tri-valent cation


The present disclosure describes various embodiments of systems, apparatuses, and methods for detecting a Trojan inserted integrated circuit design using delay-based side channel analysis. In one such embodiment, an automated test generation algorithm produces test patterns that are likely to activate trigger conditions and change critical paths of an integrated circuit design.

Side-channel analysis is widely used for hardware Trojan detection in integrated circuits by analyzing various side-channel signatures, such as timing, power, and path delay. Existing delay-based side-channel analysis techniques have two major bottlenecks: (i) they are not suitable in detecting Trojans since the delay difference between the golden design and a Trojan inserted design is negligible, and (ii) they are not effective in creating robust delay signatures due to a reliance on random and Automatic Test Pattern Generation (ATPG) based test patterns.

Delay-based side-channel analysis for trojan detection

University of Florida Research Foundation, Inc.


This invention relates to a photopolymerizable resin composition containing resin component (A) composed of a resin and/or a resin-forming ingredient and a photopolymerization initiator (B) wherein the component (A) comprises an addition-polymerizable compound (A1) having at least two ethylenically unsaturated groups and the photopolymerization initiator (B) comprises a diaminobenzophenone compound (B1), an N-phenylglycine compound (B2), and at least one kind of compound selected from a group of a 3,3xe2x80x2,4,4xe2x80x2-tetra(alkylperoxycarbonyl)benzophenone (B3), 2-methyl-1-[4-(thiomethyl)phenyl]- 2-morpholinopropan-1-one (B4), and a 1,3,5-triazine derivative (B5) containing at least one trihalomethyl group as substituent. A photopolymerizable resin composition of this invention excels in resolution, adhesion of patterns, development latitude, and curing on the surface and inside and can be used advantageously in insulating films, colored films, inks for color filters, resists for semiconductors, and insulating spacers for touch panels.

This invention relates to photopolymerizable resin compositions which are useful for applications such as insulating films for semiconductors, resists for semiconductors, protective films for color filters, colored films, and insulating spacers for touch panels.
Photopolymerizable resin compositions are exposed to light, generally with the use of UV as light source, in their applications to letterpress, relief images, photoresists, and the like and the resin compositions of this type contain a resin component which constitutes the main body of an image to be formed and a photopolymerization initiator which, upon exposure to light such as UV, generates an active species for polymerization.
From the standpoint of environmental problems and ease of obtaining a large difference in solubility before and after exposure to light in recent years, there is a preference for an aqueous solution of alkali to an organic solvent in the development step in the application of photopolymerizable resin compositions. In such a case, a combination of an addition-polymerizable compound containing an ethylenically unsaturated group and a resin soluble in an aqueous solution of alkali is used preferentially for the resin component which constitutes the main body of an image. There is a demand for higher sensitivity for this type of photopolymerizable resin compositions and numerous studies are in progress on photopolymerization initiators in order to enhance the sensitivity.
Many substances are known already for photopolymerization initiators; for example, benzoin and its derivatives and substituted and unsubstituted quinones [Photopolymer Handbook, Chapter 6, edited by Photopolymer Konwakai (in Japanese)]. These compounds, however, are not sufficiently sensitive to the i-line (365 nm), h-line (405 nm) and g-line (437 nm) mainly emitted by a commonly used mercury vapor lamp.
A combination of benzophenone, a diaminobenzophenone compound, and an N-phenylglycine compound has been proposed for use as a photopolymerization initiator in order to obtain photopolymerizable resin compositions with enhanced sensitivity in the range 300-450 nm [Japan Tokkyo Koho Hei 4-27541 (1992)].
However, when a photopolymerizable resin composition containing this combination of benzophenone, a diaminobenzophenone compound, and an N-phenylglycine compound is exposed to light whose main component is the i-line, the composition lacks sufficient sensitivity to undergo curing on the surface when the film thickness is less than 10 xcexcm during exposure to light. On the other hand, when the film thickness exceeds 10 xcexcm during exposure to light, the addition of the diaminobenzophenone compound is diminished in order to advance the photocuring in the inside until the adherence of a pattern during development is secured; then the generation of radicals from the photopolymerization initiator diminishes, which leads to the hindrance of the surface curing and roughening of the surface of the film after development.
Methods for incorporating a halomethyltriazine as photopolymerization initiator into colored photopolymerizable compositions for use in color filters are known [Japan Tokkyo Koho Sho 59-28328 (1984), Japan Tokkyo Koho Hei 5-88243 (1993), Japan Kokai Tokkyo Koho Hei 6-167808 (1994), and Japan Kokai Tokkyo Koho Hei 6-27662 (1994)].
The aforementioned photopolymerizable compositions containing a halomethyltriazine are colored yellow, although highly sensitive, and posed a problem of reducing the transmission of blue filters in particular and the compound in question was a cause of extensive discoloration during heating.
There is a demand for displays with high color purity and brightness for color liquid crystal displays in recent years. In the case of color filters with high color purity, light in the ultraviolet region reaches the deep part of the film with difficulty and this poses problems such as poor adhesion of a pattern due to insufficient curing in the deep part of the film and peeling off of a pattern during development. Moreover, absorption of the photopolymerization initiator and yellowing after heat treatment sometimes diminished the brightness of color filters.
Accordingly, an object of this invention is to provide a photopolymerizable resin composition which excels in resolution, development latitude and surface curability and shows enhanced sensitivity particularly to the i-line and, furthermore, to provide a photopolymerizable resin composition which is curable even at a film thickness of, say, 10 xcexcm or more and, when used in a colored polymerizable composition, is highly transparent and does not significantly affect the color characteristics. Another object of this invention is to provide a photopolymerizable resin composition which is highly sensitive to UV, not only to the i-line but also to lines in the range to the g-line.
A further object of this invention is to provide a blue ink with excellent color characteristics. A still further object of this invention is to provide a film to be obtained by applying the aforementioned photopolymerizable resin composition or a blue ink followed by curing and to provide a color filter containing said film as blue filter or protective film.
Thus, this invention relates to a photopolymerizable resin composition comprising a resin and/or a resin-forming ingredient as component (A) and a photopolymerization initiator (B), wherein the component (A) comprises an addition-polymerizable compound (A1) which shows a boiling point of 100xc2x0 C. or higher at normal pressure and has at least 2 ethylenically unsaturated groups in the molecule and the component (B) comprises a diaminobenzophenone compound (B1) represented by the following general formula (1)
(in which R is a hydrogen atom or an alkyl group with 1-3 carbon atoms, either identical with or different from each other), an N-phenylglycine compound (B2) represented by the following general formula (2)
(in which R is an alkyl group with 1-8 carbon atoms, Rxe2x80x2 is a hydrogen atom or an alkyl group with 1-8 carbon atoms, n is an integer in the range 0-5, and R may be identical with or different from each other when n is 2 or more), and at least one kind of compound selected from a group of a 3,3xe2x80x2,4,4xe2x80x2-tetra(alkylperoxycarbonyl)benzophenone (B3) represented by the following general formula (3)
(in which R is an alkyl group with 1-8 carbon atoms, identical with or different from each other), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), and a 1,3,5-triazine derivative (B5) containing at least one trihalomethyl group as substituent.
This invention also relates to the aforementioned photopolymerizable resin composition wherein the component (A) composed of a resin and/or a resin-forming ingredient comprises the addition-polymerizable compound (A1) and an alkali-soluble resin (A2) and the ratio (A1)/(A2) by weight is 10/90-90/10.
This invention further relates to the aforementioned photopolymerizable resin composition which comprises 100 parts by weight of the component (A), 0.05-2.0 parts by weight of a diaminobenzophenone compound (B1), 0.2-2 parts by weight of an N-phenylglycine compound (B2), 0-2.5 parts by weight of a 3,3xe2x80x2,4,4xe2x80x2-tetra(alkylperoxycarbonyl)benzophenone (B3), 0-5 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), and 0-1 part by weight of a 1,3,5-triazine derivative (B5). Likewise, this invention relates to the aforementioned photopolymerizable resin composition which comprises 100 parts by weight of the component (A), 0.05-2.0 parts by weight of a diaminobenzophenone compound (B1), 0.2-2 parts by weight of an N-phenylglycine compound (B2), 0.1-2.5 parts by weight of a 3,3xe2x80x2,4,4xe2x80x2-tetra(alkylperoxycarbonyl)benzophenone (B3), 1-5 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), and 0-0.5 part by weight of a 1,3,5-triazine derivative (B5). Still more, this invention relates to the aforementioned photopolymerizable resin composition wherein the component (A) comprises the addition-polymerizable compound (A1) and the alkali-soluble resin (A2) at the ratio (A1)/(A2) by weight of 10/90-90/10 and the composition comprises 100 parts by weight of the sum of (A1) and (A2), 0.05-2.0 parts by weight of a diaminobenzophenone compound (B1), 0.2-2 parts by weight of an N-phenylglycine compound (B2), 0-2.5 parts by weight of a 3,3xe2x80x2,4,4xe2x80x2-tetra(alkylperoxycarbonyl)benzophenone (B3), 1-5 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), and 0-0.5 part by weight of a 1,3,5-triazine derivative (B5).
In addition, this invention relates to the aforementioned photopolymerizable resin composition into which a blue colorant is incorporated and to a blue ink. This invention relates to a film obtained by applying the photopolymerizable resin composition or blue ink followed by curing. This invention also relates to a color filter containing the aforementioned film.
A photopolymerizable resin composition of this invention contains the component (A) composed of a resin and/or a resin-forming ingredient and the photopolymerization initiator (B) as essential ingredients. As the component A comprises a resin and/or a resin-forming ingredient, that is, a resin and/or a compound polymerizable into resin, the component A as a whole is bound to exist as resin after polymerization. For this reason, the component A will be hereinafter referred to as resin component (A).
The addition-polymerizable compound (A1), an essential ingredient of the resin component (A), reacts with radicals generated by the photopolymerization initiator upon exposure to ultraviolet light, undergoes polymerization, crosslinking, and curing, and gives strength and hardness to the film after exposure. When coexisting with the alkali-soluble resin (A2), the compound (A1) becomes involved in alkali insolubilization of the exposed portion.
The addition-polymerizable compound (A1) may be any of those compounds which boil at 100xc2x0 C. or higher at normal pressure and contain at least 2 ethylenically unsaturated groups in the molecule and such compounds include esters resulting from the reaction of polyhydric alcohols with xcex1, xcex2-unsaturated carboxylic acids such as diethylene glycol di(meth)acrylate [(meth)acrylate means acrylate or methacrylate hereinafter], triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,3-propanediol (meth)acrylate, 1,3-butanediol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-methacryloyloxypentaethoxyphenyl)propane, and a mixture of 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propanes (BEP-500, tradename of Shin-Nakamura Chemical Co., Ltd.), compounds obtained by the addition of glycidyl group-containing compounds with xcex1, xcex2-unsaturated carboxylic acids such as trimethylolpropane triglycidyl ether tri(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, and fluorenebisphenol diglycidyl ether di(meth)acrylate (ASF400, tradename of Nippon Steel Chemical Co., Ltd.), unsaturated amides such as methylenebisacrylamide and 1,6-hexamethylenebisacrylamide, and vinyl esters such as divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, and divinyl benzene -1,3-disulfonate.
The addition-polymerizable compound (A1) may be either a low-molecular-weight compound or a high-molecular-weight compound, but it is preferably a low-molecular-weight compound with a molecular weight of 1,000 or less from the standpoint of good solvent solubility and low viscosity.
Incorporation of the alkali-soluble resin (A2) as one of the resin components gives a resin composition of a good alkali development quality. Desirable as the alkali-soluble compound (A2) are those which contain acidic groups such as carboxylic and phenolic hydroxyl groups in the molecule and they may contain ethylenically unsaturated groups at terminal locations. Examples of the alkali-soluble resin (A2) are copolymers of (meth)acrylic acid and alkyl (meth)acrylate and copolymers of (meth)acrylic acid, alkyl (meth)acrylate and vinyl monomers copolymerizable with the foregoing two (meth)acrylic compounds. Alkyl (meth)acrylates here include butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate. Vinyl monomers copolymerizable with (meth)acrylic acid and alkyl (meth)acrylate include tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, acrylamide, diacetone acrylamide, styrene, and vinyltoluene.
Additional examples of the alkali-soluble resin (A2) are ester oligomers containing carboxyl groups such as partial esters of styrene-maleic anhydride copolymers, partial esters of the copolymers of a diol and an acid dianhydride, and partial esters of unsaturated polyesters.
Recommended for use as the alkali-soluble resin (A2) is a compound which contains alkali-developable acidic functional groups such as carboxyl and phenolic hydroxyl groups and, moreover, occurs either as a solid with a molecular weight of 600 or more or a polymer with a number average molecular weight of 1,000 or more in order to render the film free from cracking and tackiness after application and drying of the resin composition.
Furthermore, a compound containing both two or more ethylenically unsaturated groups and alkali-solubilizing carboxyl groups in the molecule may be used as alkali-soluble resin (A2) together with the addition-polymerizable compound (A1). Such simultaneous use desirably provides a photopolymerizable composition with good resolution. The case in point is an addition product of an acid anhydride with a compound containing a hydroxyl group and two or more ethylenically unsaturated groups. For example, addition products of an acid with bisphenol epoxy (meth)acrylate described in Japan Kokai Tokkyo Koho Hei 6-1938 (1994) are desirable as such. In the cases where the film shows no cracking after drying and the tackiness presents no problem, for example, when exposure is effected in proximity mode while avoiding exposure in contact mode, the alkali-soluble resin (A2) is not necessarily a resin and may be a compound capable of polymerizing into resin.
In case the addition-polymerizable compound (A1) and the alkali-soluble resin (A2) are used together, the ratio (A1)/(A2) by weight is 10/90-90/10, preferably 20/80-80/20. Where the proportion of the alkali-soluble resin (A2) is lower than what this ratio stipulates, the photocured product becomes brittle and the solubility in an alkaline developer decreases because of a low acid value of the unexposed portion of the resin composition. On the other hand, where the proportion of the alkali-soluble resin (A2) is higher, the addition-polymerizable compound (A1) does not function sufficiently to form a crosslinked structure and bring about alkali insolubilization in the exposed portion and, besides, the acid value increases to such an extent as to cause an increase in the solubility in an alkaline developer not only in the unexposed portion but also in the exposed portion.
In addition to the aforementioned (A1) and (A2), it is allowable to add, as other ingredients of the resin component (A), reactive diluents that are miscible with (A1) and (A2) and contain only one ethylenically unsaturated group in the molecule or resin ingredients that are neither photopolymerizable nor alkali-soluble, for example, epoxy resins, rosin resins, and alkyd resins, in proportions less than 50% by weight of the resin component (A) as a whole. When the addition is 50% by weight or more, the extra components cause such defects as decrease in solubility due to a drop of the acid value in the unexposed portion and loss of patterns during development due to a drop of crosslinking density in the exposed portion.
The photopolymerization initiator (B) to be used in photopolymerizable compositions of this invention generates radicals upon exposure to light, particularly to UV, and initiates the polymerization of the addition-polymerizable compound (A1). The photopolymerization initiator (B) to be used in photopolymerizable resin compositions of this invention comprises (B1) and (B2) as essential ingredients and additionally at least one kind of compound selected from (B3), (B4), and (B5).
The photopolymerization initiator (B1) is a diaminobenzophenone compound represented by the aforementioned general formula (1). In the general formula (1), R is a hydrogen atom or an alkyl group with 1-3 carbon atoms and, although R may be identical with or different from one another, it is preferably methyl or ethyl group. Typical examples of (B1) are 4,4xe2x80x2, -diethylaminobenzophenone and 4,4xe2x80x2-dimethylaminobenzophenone.
The photopolymerization initiator (B2) is an N-phenylglycine compound represented by the aforementioned general formula (2). In the general formula (2), R is an alkyl group with 1-8 carbon atoms, Rxe2x80x2 is a hydrogen atom or an alkyl group with 1-8 carbon atoms, n is an integer in the range 0-5, and R may be identical with or different from one another when n is 2 or more. Preferably, R is methyl or ethyl group, Rxe2x80x2 is a hydrogen atom or an alkyl group with 1-4 carbon atoms and n is 0 or 1. Examples of (B2) are N-phenylglycine, N-phenylglycine ethyl ester, N-phenylglycine methyl ester, N-phenylglycine butyl ester, and N-phenylglycine propyl ester.
The photopolymerization initiator (B3) is a 3,3xe2x80x2,4,4xe2x80x2-tetra(alkylperoxycarbonyl)benzophenone represented by the aforementioned general formula (3). In the general formula (3), R is an alkyl group with 1-8 carbon atoms and is either identical with or different from one another. Preferably, R is a branched alkyl group. A typical example of (B3) is 3,3xe2x80x2,4,4xe2x80x2-tetra(t-butylperoxycarbonyl)benzophenone.
The photopolymerization initiator (B4) is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one. This compound is available, for example, as Irgacure 907 (tradename of Ciba Speciality Chemical).
The photopolymerization initiator (B5) is a 1,3,5-triazine derivative containing at least one trihalomethyl group as substituent. The 1,3,5-triazine derivative (B5) needs to be 1,3,5-triazine substituted with at least one trihalomethyl group on a carbon atom in the ring. The other two carbon atoms in the ring may or may not contain a substituent; when a substituent is present, it may be a trihalomethyl group, an alkyl group with 1-18 carbon atoms, a substituted alkyl group, an alkylene group, a substituted alkylene group, an aryl group, or a substituted aryl group. The halogen in a trihalomethyl group may be chlorine or bromine. Examples of (B5) are 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine.
These photopolymerization initiators are incorporated into 100 parts by weight of the resin component (A) as follows: diaminobenzophenone compound-(B1), 0.05-2.0 parts by weight, preferably 0.08-1.0 part by weight; N-phenylglycine compound (B2), 0.2-2 parts by weight, preferably 0.3-1.5 parts by weight; 3,3xe2x80x2,4,4xe2x80x2-tetra(alkylperoxycarbonyl)benzophenone (B3), 0-2.5 parts by weight, preferably 0.1-2.5 parts by weight, more preferably 0.5-2.0 parts by weight; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), 0-5 parts by weight, preferably 1-5 parts by weight, more preferably 2-4 parts by weight; and 1,3,5-triazine derivative (B5), 0-1 part by weight, preferably 0 or 0.1-0.7 part by weight, more preferably 0 or 0.2-0.5 part by weight. The proportion of diaminobenzophenone compound (B1) is preferably controlled at 0.05-1 part by weight when the film thickness is 10 xcexcm or more and at 0.5-2 parts by weight when the film thickness is less than 10 xcexcm while that of 1,3,5-triazine derivative (B5) is controlled at 0-0.5 part by weight when the film thickness is 30 xcexcm or more or the composition is for blue ink.
A further advantage can be gained by incorporating the photopolymerization initiators into 100 parts by weight of the resin component (A) in the following proportions: diaminobenzophenone compound (B1), 0.05-2.0 parts by weight; N-phenylglycine compound (B2), 0.2-2 parts by weight; 3,3xe2x80x2,4,4xe2x80x2-tetra(alkylperoxycarbonyl)benzophenone (B3), 0.1-2.5 parts by weight; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), 1-5 parts by weight, and 1,3,5-triazine derivative (B5), 0-0.5 part by weight.
In the cases where the resin component (A) is mainly composed of the addition-polymerizable compound (A1) and the alkali-soluble resin (A2), that is, where (A1) and (A2) account for the greater part of (A), the expression xe2x80x9c100 parts by weight of the resin component (A)xe2x80x9d can be replaced by xe2x80x9c100 parts by weight of the sum of (A1) and (A2).xe2x80x9d
It is recommended to incorporate the photopolymerization initiators into 100 parts by weight of the sum of (A1) and (A2) in the following proportions: diaminobenzophenone compound (B1), 0.05-2.0 parts by weight, preferably 0.08-1.0 part by weight; N-phenylglycine compound (B2), 0.2-2 parts by weight, preferably 0.3-1.5 parts by weight; 3,3xe2x80x2,4,4xe2x80x2-tetra(alkylperoxycarbonyl)benzophenone (B3), 0-2.5 parts by weight, preferably 0.1-2.5 parts by weight, more preferably 0.5-2.0 parts by weight; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), 0-5 parts by weight, preferably 1-5 parts by weight, more preferably 2-4 parts by weight; and 1,3,5-triazine derivative (B5), 0-1 part by weight, preferably 0 or 0.1-0.7 part by weight, more preferably 0 or 0.2-0.5 part by weight.
When the proportion of diaminobenzophenone compound (B1) is short of the aforementioned range, the generation of radicals is insufficient and the surface curing becomes incomplete due to inhibition by oxygen and satisfactory properties are not obtained. Conversely, an excess proportion of (B1) causes the absorption of light to occur on the surface alone during exposure and photocuring of the inside becomes insufficient. As for the proportion of N-phenylglycine compound (B2), a shortage does not enhance the photosensitivity sufficiently while an excess lowers the storage stability of photopolymerizable resin compositions.
In the co-presence of (B1) and (B2), 3,3xe2x80x2,4,4xe2x80x2-tetra(alkylperoxycarbonyl)benzophenone (B3), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), and 1,3,5-triazine derivative (B5) enhance the sensitivity and, in particular, promote the surface curing. In addition to enhancement of the sensitivity and promotion of the surface curing, (B3) is effective for enhancing the sensitivity, particularly not only to the i-line but also to the g-line and the h-line. The proportion of (B3), when in use, must be 0.1 part by weight or more per 100 parts by weight of the resin component (A) to enhance the sensitivity sufficiently. An excess of (B3), however, lowers the storage stability. When used in combination with the aforementioned (B1) and (B2), (B4) markedly enhances the photosensitivity. Sufficient enhancement is not obtained unless (B4) is used in a proportion of 1 part by weight or more per 100 parts by weight of the resin component (A). Although 1,3,5-triazine derivative (B5) is effective for enhancing the sensitivity and promoting the surface curing, an excess of it causes insufficient curing inside the film or loss of patters and also hinders the transmission of blue light. Therefore, it is recommended to control the proportion of (B5) at 1 part by weight or less, preferably 0.5 part by weight or less, per 100 parts by weight of the resin component (A).
These photopolymerization initiators are used desirably in the following combinations:
{circle around (1)} (B1)-(B2)-(B3)-(B4)-(B5)
{circle around (2)} (B1)-(B2)-(B3)-(B4)
{circle around (3)} (B1)-(B2)-(B3)
{circle around (4)} (B1)-(B2)-(B4)
In particular, in the case of the preparation of blue inks where the transmission of the i-line needed for curing diminishes, it is advantageous to use the combination of {circle around (1)}, {circle around (2)} or {circle around (3)} containing (B1), (B2), and (B3) which are capable of enhancing sensitivity even to the g-line to effect sufficient curing of the inside. The combination {circle around (1)}, {circle around (2)} or {circle around (3)} which contains (B4) or (B5) is advantageous for raising the surface hardness. However, (B5) absorbs a part of blue light as mentioned above, and it needs to be used in a restricted amount. Therefore, an alternative is to use (B3) or (B4) as a whole or partial substitute for (B5).
In formulating photopolymerizable resin compositions of this invention, it is necessary to exercise special care in determining the amount of the photopolymerization initiator (B) to be incorporated into the resin component (A) because a shortage of (B) causes insufficient photocuring with the resultant thinning of the lines and roughening of the surface during development while an excess of (B) causes the majority of light to be absorbed in the upper portion of the film leaving the lower portion of the film uncured.
In the cases where a photopolymerizable resin composition of this invention is applied in a relatively thick layer and cured, special care must be given to the amount of photopolymerization initiator to be added. With addition of an excessive amount, the absorption of light occurs mostly in the upper portion with little light reaching the lower portion and the lower portion remains uncured. On the other hand, with addition of a too small amount, the curing occurs insufficiently and thinning of the lines and overdevelopment occur. One of the methods to determine the optimal composition of additives is to apply a photopolymerizable resin composition, expose the film of the applied composition to light, and choose such an amount of additives as to give a transmission of 5-80% at the main wavelength of the light in use. For example, in case the curing is effected by the i-line, it is desirable to add the photopolymerization initiators so that the transmission at 365 nm becomes 50-80% at a film thickness of 10 xcexcm or exceeds 5% at a film thickness of 40 xcexcm.
In formulating photopolymerizable resin compositions of this invention, it is allowable to use other known photopolymerization initiators whose maximum absorption wavelngth lies in the region shorter than the i-line (365 nm) in addition to the aforementioned photopolymerization initiators (B1) to (B5). An example of photopolymerization initiators to be used for this purpose is benzophenone. However, if such a polymerization initiator is added in excess of the amount which reduces the transmission of the light for exposure at its main wavelenght to 5% or less, it would undesirably cause insufficient curing in the inside. Therefore, the polymerization initiator in question is never used in excess of 3 parts by weight per 100 parts by weight of the resin component (A).
In addition to the resin components and photopolymerization initiators, colorants such as dyes and pigments may be incorporated into photopolymerizable resin compositions of this invention. A variety of colorants are useful for colorants, for example, titania, carbon black, iron oxide, quinacridone pigments, phthalocyanine pigments, azo pigments, and acid dyes. Preferable among them are blue dyes or pigments such as phthalocyanine blue.
Where the application involves the color filters for liquid crystal displays and liquid crystal projectors, organic pigments are used on account of their transparency and color purity. The following are desirable examples of such organic pigments: for blue, phthalocyanine pigments and indanthrene pigments, particularly xcex5-phthalocyanine blue (C.I. Pigment Blue 15:6); for red, anthraquinone pigments, quinacridone pigments, diketopyrrolopyrrole pigments, perylene pigments, and particularly diketopyrrolopyrrole red (C.I. Pigment Red 254) and dianthraquinonyl red (C.I. Pigment Red 177); for green, chlorinated phthalocyanine green (C.I. Pigment Green 7) and brominated phthalocyanine green (C.I. Pigment Green 36); for violet, Dioxazine Violet (C.I. Pigment Violet 23); for yellow, isoindoline yellow (C.I. Pigment Yellow 83) and Diarylide Yellow (C.I. Pigment Yellow 83). These pigments are micro-dispersed in an organic solvent to an average particle diameter of 0.2 xcexcm or less in a sand mill together with those pigment derivatives and graft polymers which contribute to stabilize the microdispersion and then mixed with photopolymerizable resin compositions to give colored photopolymerizable resin compositions or inks of this invention.
Additives such as the following may also be incorporated into photopolymerizable resin compositions of this invention: surfactants for improving levelling during application and reducing uneven evaporation during drying, coupling agents for improving adhesion to the base plate, fillers for improving the crack resistance during the heat cycle test, and adhesion promoters for facilitating adhesion to fillers.
Moreover, in order to prepare photopolymerizable resin compositions of this invention as homogeneous solutions, solvents which are capable of dissolving the aforementioned components may be incorporated into the compositions. Such solvents include, for example, a variety of glycol ethers such as ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monophenyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, pentoquinone, N-methylpyrrolidone, and xcex3-butyrolactone, ethers such as butyl ether, dioxane, and tetrahydrofuran, alcohols such as methoxybutanol, diacetone alcohol, butanol, and isopropanol, hydrocarbons such as toluene, xylene, and hexane, and esters such as ethyl acetate, butyl acetate, and ethyl benzoate.
Colorant-containing photopolymerizable resin compositions of this invention can be used as inks. In particular, those containing blue colorants give excellent blue inks. In applications of the conventional blue inks composed of photopolymerizable resin composition containing blue colorants, the blue colorants often hinder the photocuring of the inks. With blue inks of this invention, the photocuring proceeds into the depth because of high sensitivity to a relatively wide wavelength range of UV.
Photopolymerizable resin compositions of this invention are available in two kinds, one composed of the resin component (A) and the photopolymerization initiator (B) only and the other composed of (A), (B) and other additives and solvents, and they are used differentially depending upon the end use. For example, compositions in solution and inks are used in insulating films for semiconductors, resist materials for semiconductors, liquid crystal displays, color filter materials for CCD cameras, colored films, touch panels, and insulating spacers for displays and they are also used as pattern-forming materials and image-forming materials.
Regarding the method of use, the one in general practice is to apply a photopolymerizable resin composition prepared as solution to the base to a given thickness, dry, and expose to active light (UV) of a given wavelength range to effect photocuring, although not restricted to this particular one. The thickness of the applied composition is 0.2-100 xcexcm, preferably 1-3 xcexcm, under a dry condition. The source of active light is preferably the one which emits mainly the i-, g-, and h-lines. As for development, it is preferable to dissolve and remove the unexposed portion by alkali development with the use of an aqueous solution of alkali. There may be a case, as needed, where the whole surface is exposed and the development is omitted.
The application of a photopolymerizable resin composition of this invention as color filter is described as an example. A photopolymerizable resin composition of this invention, preferably containing a suitable solvent and additives, is made into a homogeneous solution or an ink. The solution or ink is applied to the base plate of a color filter to a given thickness by such means as spin coating, bar coating, spray coating, or printing coating and dried to form a film with a thickness of 0.2-100 xcexcm. The film is exposed through a photomask to a light source such as super high-pressure mercury lamp, high-pressure mercury lamp, metal halide lamp, far ultraviolet lamp, and visible light laser and cured. The exposed film is then developed by dissolving the uncured portion in a stream or shower of an aqueous solution of alkali or an organic solvent, typical alkali being an alkali metal carbonate such as lithium carbonate, an alkali metal hydroxide such as sodium hydroxide, and an organic base such as tetramethylammonium hydroxide, and washing with water. In the case of an ink, the procedure is repeated for each color. A photopolymerizable resin composition containing no colorant is used as a protective film for color filter and it is applied to the base plate for color filter on which the ink has been developed, and then similarly dried, exposed, and developed.

Photopolymerizable resin compositions and use thereof