JPS5844070B2 - Manufacturing method of ink holding porous body - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel method for producing an ink-retaining porous body.

More specifically, the present invention relates to a method for producing an ink-retaining porous body, such as an ink roll or an ink pad, which is cross-cured at room temperature and contains ink in its continuous micropores.

Conventionally, methods for producing ink-retaining porous bodies such as ink rolls and ink pads have mainly involved sintering granular or powdered polymers, or molding polymers with water-soluble salts, and then eluting the salts. A method has been adopted in which a porous body having continuous fine pores is formed, and then ink is impregnated into the porous body.

However, in these methods, forming the porous body and impregnating the ink must be performed separately, which not only makes the process extremely complicated, but also makes it difficult to impregnate the porous body with the ink uniformly. This results in considerable variation in the ink content.

However, the inventors of the present invention have conducted intensive research to eliminate the drawbacks of Shino, and as a result, they have mixed a modifier into a type of liquid elastomer that cross-cures at room temperature or with slight heating, and have uniformly dispersed the modifier. A cured elastomer is produced by spraying and dispersing ink that is either incompatible with the liquid material or that becomes incompatible with each other upon curing, with stirring, and then hardening at room temperature. When dispersing the ink inside, eliminate the defects of the prince,
Discovering a new fact that a predetermined amount of ink is contained in the continuous micropores, and it is possible to provide an ink-retaining porous body that can be suitably used as an ink roll, an ink pad, etc.
This led to the completion of the present invention.

Examples of the room temperature curable liquid elastomer in the present invention include one-component or two-component liquid urethane elastomer, liquid nitrile rubber, room temperature curable liquid chloroprene rubber, and liquid oligoester acrylate. A curing agent, a reinforcing agent, and a stabilizer are mixed, and the ink is sprayed and dispersed under stirring into a liquid obtained by uniformly dispersing the ink. This is to form an ink retaining porous body that is uniformly contained within the micropores.

In the present invention, when using an ink that is incompatible with a liquid material, the liquid elastomer may be cross-cured with the ink being spray-dispersed dispersed in the liquid material in the form of particles. good.

When using inks that are compatible with the liquid material but become incompatible with each other due to curing of the liquid elastomer, the spray-dispersed ink will temporarily dissolve in the liquid material, but the ink will become highly soluble due to crosslinking and curing of the liquid elastomer. It becomes incompatible due to changes in solubility and viscosity associated with molecular weight, separates from the cured elastomer, and becomes dispersed in the form of particles in the cured elastomer, and the ink is dispersed in continuous fine particles in the same manner as when using incompatible inks. An ink retaining porous body is formed that is uniformly contained within the pores.

In the room temperature curing liquid urethane elastomer of the present invention, part A usually consists of an incyanate component, a polyester type and/or polyether type glycol component, a polyether type and/or polyester type glycol component, and a modifier. , and a part B consisting of a reinforcing agent and a hardening agent.

Examples of the isocyanate component include tolylene diisocyanate (hereinafter referred to as TDI), diphenylmethane diisocyanate, and bitolylene diisocyanate.

Further, the polyether type glycol component has a molecular weight of, for example, 2000 to 6000, more preferably 300.
0 to 4000 high molecular weight dipolyols or tripolyols (e.g. polypropylene glycol, polyoxypropylene glycol, trimethylolpropane, 1,
2,6-hexandriol, etc.).

Furthermore, the polyester type glycol component has a molecular weight of, for example, 2000 to 6000, more preferably 30
00 to 4000 saturated polyester type glycol (for example, ethylene adipate obtained by condensing an acid component such as adipic acid, maleic anhydride, or succinic acid with a glycol such as ethylene glycol, propylene gellicol, diethylene glycol, or glycerin, propylene succinate, etc.), and these can be used in combination with the polyether type glycol component as appropriate.

The ratio of the inocyanate component and the glycol component in these parts A and B is such that, for example, when parts A and B are mixed at a weight ratio of 1:1, the isocyanate component in part A is NGO in the urethane prepolymer. 7-13
It is preferable to mix so that the molar ratio is preferably 11 to 12, and the molar ratio of NC010H is 1 to 2:1.

Further, as a curing agent, for example, a combination of a tertiary amine and a metal salt can be used.

Examples of tertiary amines include triethylenediamine, bis(2-dimethylaminoethyl)ether, N-methylmorpholine, trialkylamine, N,N'-dimethylpiperidine, etc., and examples of metal salts include diptyltin dilaurate and starch. Nasu octanoate, etc., but preferably a combination of triethylenediamine, bis(2-dimethylaminoethyl) ether and diptyltin dilaurate, or N-methylmorpholine, N-methylmorpholine,
, N'-dimethylpiveridine and stannath octanoate.

The amount of these catalysts used is
For every 100 moles of O, the amount of tertiary amine is 0.3 to 3 moles, and the amount of metal salt is 0.01 to 0.07 mole.

Liquid urethane elastomers have a wide variety of molecular forms depending on the combination, and have remarkable specificity compared to other block copolymers.Also, unlike general vulcanized rubber, they exhibit mechanical strength properties due to intermolecular cohesive force, and are temperature-dependent. It is easy to process because of its high value.

In addition, as a raw material, this material easily liquefies at room temperature or low temperature and is easily compatible with the other materials, so it can be modified by blending.

Furthermore, among rubber-like elastic bodies, it has high mechanical properties, can have high dimensional stability, and is easy to cross-link at room temperature.

Examples of the liquid elastomer include liquid urethane elastomer, liquid Nitro rubber, room temperature curing liquid chloroprene rubber, and liquid oligoester acrylate.

Liquid nitrile rubber is a low molecular weight polymer whose main raw material is butadiene.The main chain is rubber-like butadiene, and acrylonitrile is introduced into this main chain to improve compatibility with polymers, oligomers, and monomers that are modifiers. , and reactive functional groups such as carboxyl groups, vinyl groups, amino groups, and epoxy groups at both ends of the main chain, it is possible to increase the molecular weight as is or by reacting with other reactive modifiers.

Diphenols, especially bisphenol A, as chain extenders
However, difunctional epoxides having reactive epoxy groups, such as aromatic or cycloaliphatic epoxy resins, are also used as modifiers, and tertiary amines, such as piperidine, dipiperidine, aminoethyl, are used as crosslinking hardening agents. Pyro 1J dine, aminopropyl piperidine, etc. are each used.

Room-temperature-curing liquid chloroprene rubber has an extremely slow crystallization rate, is liquid at room temperature, or liquefies when slightly heated, and is a reactive oligomer with terminal mercapto groups, carboxyl groups, hydroxyl groups, etc. Its solubility, compatibility, flame retardancy, etc. are similar to solid chloroprene rubber, but its storage stability is better.

Examples of hardening agents include aliphatic amines, alicyclic amines, modified amines (for example, a combination of tetraethylene pentamine and xylylene diamine, aminoethylpiperazine), and polyamide hardeners (for example, Daiichi General Mills Chemical Co., Ltd.). "Versamid 14D" etc.) can be used.

Furthermore, when zinc oxide is used in combination, curing is accelerated, and particularly when the chloroprene rubber has a mercapto group at the end, it exhibits remarkable low-temperature curing properties.

Other additives may be the same as those for solid chloroprene rubber.

Examples of the room temperature curable liquid chloroprene rubber include "Denka LCRXJ", "Denka LCRXAJ", "Denka LCRCJ", and "Denka LCRCEJ" (all manufactured by Denki Kagaku Kogyo ■).

Liquid oligoester acrylate is a liquid to oily oligomer obtained by co-condensing a monobasic acid, such as acrylic acid or methacrylic acid, as a third component during esterification of a polyhydric alcohol. It has one to several saturated groups (eg, acryloyl group, methacryloyl group) and does not contain volatile monomers or organic solvents.

As a modifier, various unsaturated monomer oligomer-1
Saturated polymers can be used.

Oliconister acrylate is mainly composed of ester bonds, so it is compatible with various organic additives, and the polymerization rate of methacryloyl and acryloyl groups is extremely fast.
It can be cured quickly by electron beam or ultraviolet irradiation, and because it is deep, it can be polycondensed on-site.
Moreover, since it does not contain volatile components, it does not generate unpleasant odors.

Such liquid oligoester acrylates include, for example, "Aronix M5000J series (l-functionality)", "
Examples include Aronix M 6000J series (bifunctional) and Aronix M 8000J series (multifunctional) (both manufactured by Toagosei Kagaku Kogyo ■).

Furthermore, in the present invention, mechanical properties such as tensile strength and compressive modulus of the porous body obtained can be improved by adding a reinforcing agent in addition to these modifiers, curing agents, and the like.

Examples of such reinforcing agents include inorganic fine powders, inorganic single crystal fibers, and organic fibers coated with a coupling agent having a reactive functional group.

Examples of inorganic fine powders or inorganic single crystal fibers include fine powders of wollastonite, silica, etc. with a particle size of 0.1 μ or less, or single crystal fibers of potassium titanate, carbon fiber, talc, calcium sulfate, etc., and organic fibers. For example, polyamide, polyester, vinylon,
Examples include acrylic fibers.

Further, the coupling agent is used to adjust the viscosity of the liquid elastomer, as well as ionic bonding and curing between the prepolymer and these inorganic substances. Alternatively, a titanate coupling agent having a function capable of chemical bonding such as an ionic bond [for example, isopropyl tri(dioctyl pyrophosphate) titanate (trade name: KR-388) manufactured by Kenritsu Petrochemical Co., Ltd., titanium (dioctyl pyrophosphate) oxy Acetate (product name: 2KR-1388), Isoprobyl triisostearoyl titanate (product name: KR-TTS)
, and isoprobyl isostearoyl di-4-aminobenzoyl titanate (trade name: KR-37BS), etc.]
Furthermore, various silane coupling agents, zirconate coupling agents, aluminum coupling agents, calcium coupling agents, etc. can be suitably employed.

In addition to these modifiers, hardeners, stabilizers, and reinforcing agents if necessary, additional additives such as softeners and plasticizers, commercially available flame retardants, antistatic agents, and colorants are also required. It can be added as appropriate.

The modifier in the present invention is homogeneously dispersed and cured at room temperature while spraying and dispersing the ink into the liquid elastomer.
This is to adjust the viscosity to be suitable for open cell formation, cure at room temperature at an appropriate rate, and adjust the physical properties of the porous material obtained by curing at room temperature to be suitable for ink rolls and ink pads.

Modifiers for liquid elastomers in the present invention include, for example, thermoplastic elastomers, thermoplastics, room temperature crosslinking solid rubbers, room temperature curing resins, reactive liquid rubbers, reactive monomers, etc. A species or a combination of two or more species may be used.

The thermoplastic elastomer, thermoplastic plastic, room temperature crosslinking solid rubber, and room temperature curing resin function as polymer extenders, and the reactive liquid rubber and reactive monomer increase the viscosity of the liquid elastomer. figure,
In addition, when the liquid elastomer is cured, it reacts with the liquid elastomer to cause a crosslinking reaction, and has the function of adjusting the mechanical strength of the resulting porous body.

Examples of the thermoplastic elastomer include styrene-butadiene block copolymer, thermoplastic polyester elastomer, thermoplastic polyurethane elastomer,
Examples include polyethylene-butyl rubber graft polymer, ethylene-propylene-dietrimer, polyolefin blend polymer, and plasticized polyvinyl chloride, and more preferably thermoplastic polyurethane elastomer and styrene-butadiene block copolymer.

Examples of thermoplastics include polyethylene, polypropylene, polyvinyl chloride, and polyamide.

Examples of room temperature curing resins include phenolic resin,
Examples include coumaron-indene resin.

Further, examples of the room temperature crosslinkable solid rubber include crosslinked solid rubbers that can be used in an uncrosslinked state, such as polybutadiene rubber, butadiene acrylonitrile rubber, and chloroprene rubber.

These thermoplastic elastomers, thermoplastics, room temperature crosslinkable solid rubbers, and room temperature curing resins are in powder form.
It is added to the liquid elastomer in an amount of about 5 to 100 parts based on 100 parts (by weight, the same applies hereinafter) of the liquid elastomer.

By adding a coupling agent having the same reactive functional group as that used for the reinforcing agent to these solid polymer powders in advance, the viscosity of the liquid elastomer can be adjusted and the coupling agent between the liquid elastomer and the coupling agent can be adjusted. The liquid elastomer can be crosslinked and cured by molecular entanglement.

Examples of the reactive liquid rubber include liquid materials having a reactive functional group at the end, such as 1,2-polybutadiene, 1,4-polybutadiene, butadiene-acrylonitrile rubber, polychloroprene rubber, and corrugated polyurethane rubber. However, it is more preferable to use a one-component polyurethane rubber.

Examples of the reactive monomer include liquid materials such as styrene and acrylic thread binders.

These reactive liquid rubbers and reactive monomers adjust the viscosity and crosslinking rate of the liquid elastomer when the liquid elastomer is cured, and provide an ink-retaining porous body having a desired compression modulus or porosity. be able to.

The amount of these modifiers to be added is such that the ratio of the resulting porous body to the ink contained in the micropores is 25, approximately 5 to 5.
0:50, and the mechanical properties of the liquid elastomer after room temperature curing, especially tensile modulus and bending modulus, are appropriately determined so that it is suitable for ink rolls and ink pads, but usually the ratio of liquid elastomer to modifier is The weight ratio is appropriately selected from the range of 80:20 to 95:5.

When the amount of the modifier added is more than the above range, the resulting porous body becomes hard, which is not preferable.

The ink used in the present invention uses a vehicle of oils and fats such as various vegetable oils, animal oils, mineral oils, synthetic oils, etc., and a colorant (dye, etc.) and a dispersant are added to this vehicle to form a liquid or paste at room temperature. An ink prepared in the following manner is preferably used.

As described above, such inks are either incompatible with the liquid material that is the porous body forming component such as the urethane prepolymer component or the modifier component, or even if they are compatible, they become incompatible with each other upon curing. Examples include components that become incompatible and result in a pressure-exudable ink that is uniformly contained within the micropores of the resulting porous body.

The oils and fats include, for example, vegetable oils such as rapeseed oil, castor oil, and soybean oil, animal oils such as whale oil and cow leg oil, mineral oils such as motor oil and spindle oil, and olefin polymerized oils (such as ethylene hydrocarbon oils). , butylene hydrocarbon oil, etc.), poly-, realkylene glycol oil (addition polymers of alkylene oxides such as ethylene oxide and propylene oxide and aliphatic monohydric alcohols, or copolymers thereof, such as union carbide,
Ucon manufactured by And Carbon Co., Ltd.
Diester oils [e.g. bis(2-ethylhexyl) sebacate, bis(1-ethylpropyl) sebacate, azelaic acid (2-ethylhexyl), bis(2-ethylhexyl) adipate]
2-ethylhexyl), synthetic oils such as silicone oil (for example, low-viscosity linear dimethylpolysiloxane), and fatty acids such as isostearic acid and oleic acid.

Examples of the colorant include dyes such as oil black, oil blue, oil red, methyl violet base, and nigrosine base.

Further, examples of the dispersant include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, hydrogenated castor oil derivative, polyoxyethylene castor oil etc.

These oils and fats, colorants and dispersants each have a weight of 75 to
95 parts, 5 to 20 parts and 5 parts or less, preferably 01 to
It is blended in a ratio of 2 parts.

The thus obtained ink of the present invention contains 70 parts based on the total amount of the liquid elastomer and modifier of 25 to 50 parts.
Spray-dispersed at a rate of ~50 parts.

Spray dispersion of the ink is preferably carried out using an airless spray gun so that air is not mixed into the liquid during spraying and voids are not generated in the resulting porous body.

In the present invention, by spraying and dispersing the ink in this way, the ink can be contained in a porous body that can be obtained with extremely small particle sizes, and unlike ordinary stirring, the particle size becomes large or non-uniform. Because it is possible to uniformly contain the desired amount of ink having the desired particle size in the porous material without causing any particles to become particles, it is extremely easy to manufacture ink rolls and ink pads, and continuous molding is possible. It has the excellent advantage of making it possible to reduce costs as well as to reduce costs.

In the present invention, even if a coupling agent having a directly reactive functional group is added to the liquid obtained by mixing the liquid elastomer, a modifier, a curing agent, and a reinforcing agent as described above, the viscosity of the liquid elastomer cannot be adjusted. The same effect can also be obtained by adding a coupling agent directly to the ink.

In this case, the flow characteristics of the liquid are adjusted, and the elastomer cured at room temperature is molecularly entangled at the interface between the modifier and the elastomer, the modifier is bonded ionicly at the interface between the reinforcing agent and the elastomer. .

As a coupling agent having such a reactive functional group,
For example, the same coupling agent used to coat the reinforcing agent described above is used as is.

These coupling agents impart fluidity to the liquid material and improve the reinforcing effect of the modifier and/or reinforcing agent on the resulting porous body.

Accordingly, in the present invention, the amount of the coupling agent having a reactive functional group added to the liquid material is 0.1 to 1 (the same applies below) based on the rubber content in the compounding, preferably 0.1 to 1.
It is in the range of 2 to 0.4 articles.

As described above, in the method of the present invention, ink is sprayed and dispersed in a porous body-forming liquid material made of a liquid elastomer, a modifier, etc. The body is obtained in only one process,
In addition, the ink content can be changed arbitrarily, and since the porous body is hardened and molded at room temperature without heating, energy can be significantly reduced compared to normal heat molding. Extremely cost-effective;
In addition, there is no fear of fire, and there are no decomposition residues of organic compounds, such as those found in foams obtained by ordinary heat molding.

Furthermore, in the method of the present invention, since the liquid elastomer and ink that are the main components are liquid, paste, or gel, even if a solid substance is used as a modifier or the reinforcing agent is used, , have excellent miscibility, and because these modifiers or reinforcing agents are used by modifying the surface with a coupling agent that has a reactive functional group, they can be mixed and dispersed uniformly. ,
Therefore, the resulting porous body has uniform micropores and also has excellent flow characteristics, allowing even details of the mold to be filled uniformly and producing a remarkable effect that molded products can be changed to the exact shape.

However, the ink-retaining porous body obtained in the present invention has the same micropores (50 to 50) as ordinary ink rolls and ink pads.
110μ in size) or even smaller micropores (approximately 5 to 50μ in size) can be freely made, and as mentioned above, ink can be uniformly distributed within the micropores. This prevents the ink from scattering even when used.

Example 1 Room temperature cross-curing liquid urethane polymers having the following formulations were used as parts A and B.

Part A Part Tolylene diisocyanate (TDI) 208.8 Polypropylene glycol (molecular weight 3000) 335.0 Part A Part Polypropylene glycol (molecular weight 3000) 550 Triethylene diamine (curing agent) 30 Bis (2
-dimethylaminoethyl) ether (curing agent) 2 Dibutyltin dilaurate (curing agent) 0.5 KR-388 added to 10 parts of thermoplastic polyester elastomer in advance
A mixture of 0.2 parts of Part B and Part B were uniformly mixed and dissolved.

An ink having the following composition was also prepared.

Ingredients: Oil black 10 Nigrosine base 5 Methyl violet 1 Isostearic acid 40 Mineral oil 44 Part A and Part B containing a modifier are mixed, uniformly dispersed using a dispenser, and then dispensed in a certain amount. was placed in a container, and 200 parts of the ink was sprayed and dispersed into the liquid with a particle size of 15 μm using an airless sprayer while stirring.
Cross-curing was carried out at 25° C. for about 28 minutes to obtain an ink pad having a volume ratio (ratio of ink volume to total volume, hereinafter the same) of 0.4.

Example 2 Component A Hiker (Hycar) CTRN 1300
80 (Liquid nitrile rubber manufactured by BF Gutdrich Chemical Company) Triethanolamine (viscosity reducing agent) Bisphenol (chain extender) Epon 828 (Curing agent) (manufactured by Shell Chemical Company) BlenAct 55 0. 5 0 0 0.5 Component A Part Diphenylguanidine (curing catalyst) 5 For 100 parts of component A, No. 1 squid-C as component B.
20 parts of TBN 1300X8 and 10 parts of polyurethane elastomer were mixed.

Next, KR-TTS and KR-55 were added at 0.2% each.
Add them one by one and mix.

An ink having the following composition was also prepared.

Ingredients: Oil Red 10 Oil Orange 2 Isostearic Acid 42 Mineral Oil 46 parts Mix and stir 100 parts of a mixture of components and B with a dispenser, take a certain amount into a container, and add 200 parts of ink while stirring.
The sample was sprayed and dispersed with a particle size of 75μ by airless spraying, and cross-cured at 20°C for 20 hours to obtain a volume ratio of 0.
．． I got an ink roll of 38.

Example 3 A component part Denka LC1
l'? XA type 100 (Denki Kagaku Kogyo ■
Epicoat #828 100 (manufactured by Shell Chemical Co., Ltd.) ZnO (curing accelerator) 20 Persamide 14C (curing agent) 20 (Polyamide curing agent manufactured by Daiichi General Mills Chemical Co., Ltd.) Carbon black 60 parts of KR-TTSl was coated on the surface and added to component A.

Component B was prepared by mixing 100 parts of component A with 10 parts of solid rubber (Denka Chloroprene M-40J manufactured by Denki Kagaku Kogyo ■) and 2% KR-TTSl as a modifier. .

An ink having the following composition was also prepared.

Ingredients: Oil black 10 Nigrosine base 5 Methyl violet base 1 Isostearic acid 40 Mineral oil 44 parts A total of 100 parts of components and B are mixed and stirred in a dispenser, a certain amount of the mixture is placed in a container, and 200 parts of ink is added under stirring. Spray and disperse with an airless sprayer to a particle size of 50μ, and cure at 20°C for about 1 hour to obtain a volume ratio of 0.4.
I got an ink roll that was 2.

Example 4 Ingredient A: Aronix M-5700100 (liquid oligoester acrylate manufactured by Toagosei Kagaku Kogyo ■) Epoxy resin R-140 (modifier) 100 (manufactured by Mitsui Chemicals ■) Petrocyclic-containing aliphatic amine 80 parts Ingredients 100 parts of component A, 10 parts of thermoplastic elastomer "Hycar 1024J (manufactured by BF Gutdrich Chemical Co.) as a modifier, and KR9S0.
A product was prepared by mixing two parts.

An ink having the following composition was also prepared.

Ingredients Part Oil Blue 10 Nigrosine Base 5 Isostearic Acid 41 Mineral Oil 44 Parts A total of 100 parts of components and B are mixed and stirred in a dispenser, a certain amount of the mixture is placed in a container, and while stirring, 180 parts of the ink is sprayed using an airless sprayer. Spray-dispersed with a particle size of 25μ and cured at 25℃ for about 1 hour to obtain a volume ratio of 0.36.
I got an ink pad.

Claims (1)

[Claims] 1. A modifier is mixed into a liquid elastomer of the type that cross-cures at room temperature or slightly heated, and the modifier is uniformly dispersed therein. The elastomer is characterized by spraying and dispersing inks that are incompatible with each other or that become incompatible with each other upon curing, and then curing at room temperature to disperse the inks in the cured elastomer. A method for producing an ink-retaining porous body containing ink in continuous micropores. 2. The liquid elastomer is a one-component or two-component liquid urethane elastomer, liquid Nido IJ/L/rubber, liquid chloroprene rubber, or liquid oliconister acrylate, and the liquid elastomer is provided with a modifier, a curing agent, and a stabilizer. A method according to claim 1, characterized in that: 3. Claim 1, wherein the modifier is at least one member selected from the group consisting of thermoplastic elastomers, thermoplastic plastics, room temperature crosslinkable solid rubbers, room temperature curable resins, reactive liquid rubbers, and reactive monomers. The method described in section. 4. The method according to claim 1, wherein a coupling agent is added to the liquid elastomer or the modifier. 5. The ink according to claim 1, wherein the ink is prepared by using an oil or fat as a vehicle and adding a colorant, a dispersant, and a viscosity modifier to the ink to form a liquid, paste, or gel at room temperature. Method. 6. Claim 1, characterized in that the ink is sprayed and dispersed into a liquid material while being stirred by an airless sprayer.
The method described in section. γ The method according to claim 1, wherein a coupling agent is added after the ink is sprayed and dispersed in the liquid material. 8. The method according to claim 2, characterized in that a reinforcing agent is added to the liquid elastomer in addition to a modifier, a curing agent, and a stabilizer. 9. The method according to claim 8, wherein the reinforcing agent is at least one of inorganic fine powder, inorganic single crystal fiber, or organic fiber coated with a coupling agent.