Resin forming system and roll

Abstract

The primary objective of this technology is to provide a resin that incorporates biomass-derived materials to constitute components that come into contact with objects such as rolls, while simultaneously achieving improved mechanical strength and maintaining solvent resistance. [Solution] As a result of diligent research, the inventors have discovered that by incorporating needle-shaped particles composed of a polymer compound having a cellulose structure with hydroxyl groups or calcium carbonate, which are specific biomass-derived materials, into a resin obtained by reacting polyester polyol and isocyanate as a specific resin, the components that come into contact with the object being rolled can achieve both improved mechanical strength and maintained solvent resistance.

Description

Technical Field

[0001] The present technology relates to a roll to which a resin forming system and a resin obtained by curing this resin forming system are applied.

Background Art

[0002] A roll has various functions such as conveyance of an object, printing on an object, transfer of ink or the like, or formation of a pattern on an object to which ink or the like has been previously applied. In order to exhibit such functions, a roll has a member that can rotate while contacting the object and the like. Since the member rotates while contacting the object and the like, for example, characteristics such as wear due to friction with the object and the like and mechanical strength that can withstand the stress of rotation are required.

[0003] In a roll, the member may be formed of a resin. For example, Patent Document 1 discloses a roll for conveying paper sheets obtained by molding a kneaded polyurethane mainly composed of a polyester polyol of poly-ε-caprolactone diol and applying it to the member.

[0004] In a roll, in order to improve the mechanical strength of the member, it has also been proposed to blend a reinforcing material with the resin forming the member. From the viewpoint of reducing the load on the environment, biomass-derived materials have been attracting attention as such a reinforcing material.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] The components of a roll that come into contact with an object may become unintentionally contaminated with ink or other substances during its rotational operation. Furthermore, in rolls used for printing on objects, these components are exposed to ink. Similarly, in rolls used to form patterns on objects that have been pre-coated with ink, these components are also exposed to ink. Such components of a roll may be exposed to solvents to remove the ink.

[0007] Given the above background, it is desirable that the aforementioned components of the roll have not only mechanical strength but also properties that suppress degradation due to solvents, i.e., solvent resistance. On the other hand, when biomass-derived materials are blended as reinforcing materials into the resin constituting the aforementioned components, solvent resistance may decrease depending on the biomass-derived material blended. Furthermore, abrasion resistance may also decrease.

[0008] Therefore, the primary objective of this technology is to provide a resin that incorporates biomass-derived materials to constitute components that come into contact with objects such as rolls, while simultaneously achieving improved mechanical strength and maintaining solvent resistance. [Means for solving the problem]

[0009] As a result of diligent research, the inventors have discovered that by incorporating a specific biomass-derived material into a specific resin, the component that comes into contact with the object being rolled can achieve both improved mechanical strength and maintained solvent resistance. Here, the specific resin is a resin obtained by reacting a polyester polyol and an isocyanate, and the specific biomass-derived material is a needle-shaped particle composed of a polymer compound having a cellulose structure with hydroxyl groups or calcium carbonate.

[0010] In other words, this technology provides a resin forming system for a roll having a component that can be exposed to a solvent, wherein the resin is composed of a first liquid containing at least a polyester polyol and a second liquid containing at least an isocyanate, and the first liquid or the second liquid contains needle-shaped particles composed of a polymer compound having a cellulose structure with hydroxyl groups or calcium carbonate. Furthermore, the polyester polyol may be a reaction product of succinic acid and ethylene glycol, and the reaction product may be a compound represented by the following formula (1). [ka] In equation (1) above, n is an integer greater than or equal to 1. Furthermore, the needle-shaped particles composed of the above-mentioned calcium carbonate may be derived from seashells, and the seashells may be scallop shells. Furthermore, the amount of the second liquid may be 9.4 parts by mass or more and 12.5 parts by mass or less per 100 parts by mass of the first liquid. Also, the mass content of the polyester polyol relative to the first liquid may be 60% by mass or more. In addition, needle-shaped particles composed of the polymer compound having a cellulose structure with hydroxyl groups or the calcium carbonate may be included in the first liquid.

[0011] Next, the present technology provides a roll having a component that can be exposed to a solvent, wherein the component is made of a resin synthesized by mixing a first liquid containing at least a polyester polyol, a second liquid containing at least an isocyanate, and a biomass material having needle-shaped particles composed of a cellulose structure or calcium carbonate. Furthermore, in the rolls of this technology, the solvent resistance of the resin to methyl ethyl ketone, as measured in accordance with JIS K 6258, may be 40% or less. Also, the solvent resistance of the resin to toluene, as measured in accordance with JIS K 6258, may be 10% or less. Furthermore, in the roll of this technology, the Shore A hardness of the resin, measured according to JIS K 6253, may be 35 or higher and 45 or lower. Also, the tear strength of the resin, measured according to JIS K 6252, may be 15 N / mm or higher. Furthermore, the elongation at break of the resin, measured according to JIS K 6251, may be 500% or higher. Additionally, the wear volume of the resin per 1000 revolutions, measured by the Akron abrasion test in accordance with JIS K 6242-2:2005, may be 800 mm³. 3 The following is acceptable: [Modes for carrying out the invention]

[0012] The following describes preferred embodiments for carrying out the present invention. Note that the embodiments described below are merely examples of typical embodiments of the present invention, and this should not be interpreted as narrowing the scope of the present invention.

[0013] The present invention will be described in the following order. 1. Roles to which this technology is applied 2. Description of this technology 3. Resin forming system 4. Resin 5. Examples

[0014] 1. Roles to which this technology is applied

[0015] In this specification, "roll" means a tool having a rotatable member that is in contact with an object or the like. Here, the object that the rotatable member of the roll is in contact with is not limited to an object that is the object being manufactured or processed, but may be other rolls (for example, a blanket copper in the case of offset printing) rather than an object, such as a printing plate used as a part of an offset printing press.

[0016] The rolls to which this technology is applicable are not particularly limited as long as they can be used in manufacturing, processing, etc. For example, there are conveyance rolls used for conveying an object, printing rolls used for processing an object such as printing, and pattern forming rolls used for forming patterns on an object to which ink or the like has been previously applied. These rolls may be used as parts of equipment or as independent tools.

[0017] The "conveyance roll" can include, for example, a roll used to place an object on one surface and convey it, like a part such as a roller conveyor of equipment, or a roll used to press and convey an object from multiple directions, like a paper feed roll.

[0018] The "printing roll" can include, for example, a plate used as a part of an intaglio printing press, or a blanket cylinder and plate (transfer roll) used as parts of an offset printing press, and a pattern roll used as an independent tool.

[0019] The "pattern forming roll" can include, for example, those used as parts of equipment and pattern rolls used as independent tools.

[0020] In the above-mentioned rolls, members that can rotate while contacting an object or the like may be accidentally contaminated by ink or the like during the process of their rotational movement. In particular, in rolls used for printing an object or rolls used for forming a pattern on an object to which ink or the like has been previously applied, the member may be exposed to ink. Therefore, in such rolls, when ink adheres to the member, the ink or the like may be exposed to a solvent to be removed.

[0021] In the above case, the solvent used to remove the ink can be one that can remove the ink according to the composition of the ink used. Furthermore, when a rotatable component that comes into contact with the object being rolled is made of resin, solvent resistance is a concern for solvents that are generally organic solvents. Examples of such organic solvents include methyl ethyl ketone, toluene, anon, and mixed solvents such as paint thinner.

[0022] 2. Description of this technology

[0023] In this technology, a specific polyurethane resin containing a specific biomass-derived material is used as the resin constituting a rotatable component that can come into contact with an object or the like and may be exposed to the solvent of the roll. This allows the component to achieve both improved mechanical strength and maintained solvent resistance. Here, the specific polyurethane resin is a polyurethane resin obtained by reacting a polyester polyol and an isocyanate, and the specific biomass-derived material is a needle-shaped particle composed of a polymer compound having a cellulose structure with hydroxyl groups or calcium carbonate.

[0024] Here, "biomass" refers to renewable organic resources derived from plants and animals. For example, it includes organic matter of biological origin other than fossil fuels, such as forests, agricultural products, animal waste, marine products, and food waste and unused items. "Biomass-derived materials" refers to materials derived from the above-mentioned biomass.

[0025] <Polyester Polyol> Furthermore, "polyester polyol" is a type of polyol that has multiple ester bonds in its molecule and two or more hydroxyl groups. Note that "polyol" is a compound that has two or more hydroxyl groups in its molecule.

[0026] The polyester polyols used in this technology are reaction products synthesized, for example, by condensation or ring-opening polymerization of a carboxylic acid and a polyhydric alcohol. Such polyester polyols contain a skeleton within their molecule derived from the carboxylic acid and polyhydric alcohol that are the raw materials for the aforementioned reaction.

[0027] Polyester polyols synthesized by condensation polymerization can be obtained, for example, by condensing a dicarboxylic acid and a glycol according to a conventional method. The dicarboxylic acid may be an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, or sebacic acid, or an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, or terephthalic acid.

[0028] Polyester polyols synthesized by ring-opening polymerization can be obtained, for example, by reacting a cyclic ester compound with a glycol according to a conventional method, i.e., by ring-opening polymerization of the cyclic ester compound using the glycol as an initiator. The cyclic ester compound may be, for example, ε-caprolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, or δ-valerolactone.

[0029] The glycol reacted with the dicarboxylic acid or cyclic ester compound may be a dihydric alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, or neopentyl glycol, or a trihydric alcohol such as glycerin or trimethylolpropane.

[0030] Among these, the polyester polyol used in this technology is particularly preferably a reaction product of succinic acid and ethylene glycol, from the viewpoint of effectively interacting with the specific biomass-derived material described later.

[0031] Here, the "reaction product of succinic acid and ethylene glycol" refers to a polyester polyol obtained by the reaction of succinic acid and ethylene glycol. This polyester polyol contains a backbone derived from succinic acid and ethylene glycol within its molecule.

[0032] Such "reaction products of succinic acid and ethylene glycol" have a structure represented by the following formula (1), for example. [ka] In equation (1) above, n is an integer greater than or equal to 1.

[0033] In this technology, the polyester polyol used is particularly a reaction product of succinic acid and ethylene glycol, and the number-average molecular weight of the polyester polyol may be, for example, 500 or more, preferably 1000 or more, and more preferably 1500 or more. Alternatively, the number-average molecular weight of the polyester polyol may be, for example, 5000 or less, preferably 4000 or less, and more preferably 3000 or less.

[0034] The hydroxyl value of the polyester polyol, which is the reaction product of succinic acid and ethylene glycol, may be, for example, 10 or more, preferably 20 or more, and more preferably 25 or more. Alternatively, the hydroxyl value of the polyester polyol may be, for example, 200 or less, preferably 150 or less, and more preferably 100 or less.

[0035] <Isocyanate> An "isocyanate" is a compound that has two or more isocyanate groups (-NCO) in its molecule.

[0036] Examples of isocyanates used in this technology include aliphatic polyisocyanates and their modified forms, as well as aromatic polyisocyanates and their modified forms. Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexamethane diisocyanate. Examples of aromatic polyisocyanates include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, and xylylene diisocyanate.

[0037] Furthermore, examples of the types of modification of the modified polyisocyanate include carbodiimide modification, polyol modification, and TMP modification. Among these, carbodiimide-modified MDI is preferred.

[0038] The NCO% (molar mass of isocyanate groups relative to the total isocyanate molecule) of the isocyanate used in this technology is, for example, 10% or more, 15% or more, 20% or more, etc. Furthermore, the upper limit of the NCO% within the isocyanate molecule is, for example, 50% or less, 45% or less, 40% or less, etc. The NCO% is measured according to Method A of JIS K1603-1.

[0039] The resin used in this technology is composed of a polyurethane resin obtained by reacting the above-mentioned polyester polyol with an isocyanate, and containing at least the aforementioned specific biomass-derived material.

[0040] <Biomass-derived materials> Among the materials derived from specific biomass, "polymer compounds having a cellulose structure" refers to polymer compounds having a skeleton in which glucose units derived from cellulose are repeatedly bonded, and which originate from forest and agricultural waste or unused materials. Among the resins used in this technology, polyurethane resins containing polymer compounds having a cellulose structure with hydroxyl groups are obtained by chemical bonding (crosslinking) between the urethane resin and the polymer compound having a cellulose structure when the polymer compound having a cellulose structure is present in the reaction system during the reaction of the polyester polyol and isocyanate. In particular, using a urethane resin derived from polyester polyol allows the chemical bonding with the polymer compound to proceed favorably. As a result, the resin can achieve both improved mechanical strength and maintenance of solvent resistance, making it suitable for use in components that may be exposed to solvents in rolls.

[0041] Polymeric compounds having a cellulose structure with hydroxyl groups are derived from forest and agricultural waste and unused materials, but are generally plant-derived. In particular, it is preferable that they be derived from cellulose powder obtained by processing plant-derived materials. Cellulose powder may be produced using paper, paper pulp, cotton, or cloth as materials, with reference to known manufacturing methods. Cellulose powder may contain cellulose fibers.

[0042] Furthermore, it is preferable that the hydroxyl groups of the cellulose structure of the polymer compound are not chemically modified. The hydroxyl groups of cellulose react with the isocyanate groups at the ends of the polyurethane polymer compound that is synthesized later, thereby forming urethane bonds at the ends of the polyurethane polymer compound. As a result, the mechanical properties of the polyurethane resin are improved, and solvent resistance can be maintained.

[0043] Furthermore, among the specific biomass-derived materials, "needle-shaped particles composed of calcium carbonate" refer to needle-shaped particles composed of calcium carbonate, derived, for example, from waste and unused products of marine products. Here, needle-shaped particles refer to particles whose crystalline form is an aragonite structure. In the polyurethane resin used in this technology, which contains needle-shaped particles composed of calcium carbonate, a portion of the polyurethane resin adheres to the needle-shaped particles. Therefore, when the resulting resin is used in a component that may be exposed to the solvent of a roll, it becomes relatively difficult for the solvent to penetrate. In particular, by using a polyurethane resin derived from polyester polyol, these needle-shaped particles can be suitably adhered. This makes it possible to achieve both improved mechanical strength and maintenance of solvent resistance.

[0044] Needle-shaped particles composed of calcium carbonate can be obtained, for example, from seashells by known manufacturing methods. Examples of seashells include scallops, oysters, surf clams (also known as surf clams), Manila clams, and freshwater clams. In particular, using particles derived from scallop shells, which produce a large amount of waste, can effectively reduce the burden on the environment. For this reason, the resin can achieve both improved mechanical strength and maintained solvent resistance, making it suitable for use in components that may be exposed to solvents in rolls.

[0045] In the polyurethane resin used in this technology, the aforementioned specific biomass-derived materials contained in the resin may be used individually or in combination. When both are used in combination, the aforementioned effects are obtained additively, making it more suitable for use in components of the roll that may be exposed to solvents.

[0046] <Other ingredients> The polyurethane resin used in this technology may contain unreacted substances, catalysts, crosslinking agents, etc., present in the reaction system of the polyurethane resin synthesis reaction. Furthermore, other components may be included depending on the intended use of the roll, as long as they do not significantly impair the desired physical properties. Examples of such other components include plasticizers, defoamers, colorants, conductive materials, etc.

[0047] 3. Resin forming system

[0048] The polyurethane resin used in this technology can be synthesized by reacting a resin-forming system consisting of a first liquid containing at least a polyester polyol and a second liquid containing at least an isocyanate. In this resin-forming system, needle-shaped particles composed of a polymer compound having a cellulose structure with hydroxyl groups or calcium carbonate, which are materials derived from specific biomass, may be contained in either the first liquid or the second liquid.

[0049] Here, "resin-forming system" refers to a system for synthesizing resin, and consists of a first liquid and a second liquid in their pre-polyurethane resin states. The resin-forming system may be non-foaming. For example, if the resin-forming system is non-foaming, the polyurethane resin obtained by curing the resin-forming system will be non-foaming.

[0050] The first liquid in the resin-forming system of this technology contains at least a polyester polyol. The second liquid contains at least an isocyanate.

[0051] The mass content of polyester polyol relative to the mass of the first liquid may be, for example, 45% by mass or more, 50% by mass or more, or 55% by mass or more. Alternatively, the mass content of polyester polyol relative to the mass of the first liquid may be, for example, 80% by mass or less, 75% by mass or less, or 70% by mass or less.

[0052] The amount of isocyanate contained in the second solution may be selected based on the total number of moles of active hydrogen groups, such as polyester polyols, contained in the first solution, and the number of isocyanate groups in the isocyanate. The amount of isocyanate contained in the second solution may be adjusted so that the isocyanate index is, for example, 0.90 or higher, preferably 0.95 or higher, and 1.00 or higher. The amount of isocyanate contained in the second solution may be adjusted so that the isocyanate index is, for example, 1.20 or lower, preferably 1.15 or lower, and more preferably 1.10 or lower. The isocyanate index is the value obtained by dividing the number of moles of isocyanate groups in the isocyanate by the total number of moles of active hydrogen groups, such as hydroxyl groups in polyols, and is calculated as [NCO equivalent of isocyanate / active hydrogen equivalent]. The first and second solutions may be configured so that the isocyanate index falls within the above numerical range.

[0053] The first and second liquids constituting the resin-forming system of this technology may be adjusted such that, for example, the second liquid is 9.4 parts by mass or more, preferably 9.8 parts by mass or more, and more preferably 10.4 parts by mass or more, relative to 100 parts by mass of the first liquid. Furthermore, the upper limit of the ratio of the second liquid to 100 parts by mass of the first liquid may be adjusted to, for example, 12.5 parts by mass or less, preferably 12.0 parts by mass or less, and more preferably 11.5 parts by mass or less.

[0054] In the resin-forming system of this technology, polyester polyol or isocyanate can function as a solvent in the first and second liquids. However, other solvents may be included for purposes such as adjusting the viscosity or other physical properties of the first or second liquid.

[0055] In the resin-forming system of this technology, needle-shaped particles composed of a polymer compound having a cellulose structure with hydroxyl groups or calcium carbonate, which are specific biomass-derived materials, may be contained in either the first liquid or the second liquid. However, as described above, in the resin-forming system of this technology, the amount of the first liquid is greater than that of the second liquid. Therefore, from the viewpoint of increasing the content of these specific biomass-derived materials in the resin, it is preferable to include these specific biomass-derived materials in the first liquid.

[0056] In the resin-forming system of this technology, when a polymer compound having a cellulose structure with hydroxyl groups, which is a material derived from a specific biomass, is included in the first liquid, the mass content ratio of the polymer compound to the mass of the first liquid can be adjusted to, for example, 6% by mass or more, 7% by mass or more, or 8% by mass or more. Furthermore, the upper limit of the mass content ratio of the polymer compound to the mass of the first liquid can be adjusted to, for example, 18% by mass or less, 17% by mass or less, or 16% by mass or less.

[0057] In the resin-forming system of this technology, when needle-shaped particles composed of calcium carbonate, a material derived from specific biomass, are included in the first liquid, the mass content ratio of the needle-shaped particles to the mass of the first liquid can be adjusted to, for example, 8% by mass or more, 9% by mass or more, or 10% by mass or more. Furthermore, the upper limit of the mass content ratio of the needle-shaped particles to the mass of the first liquid can be adjusted to, for example, 20% by mass or less, 19% by mass or less, or 18% by mass or less.

[0058] In the resin-forming system of this technology, the components listed below may be appropriately included in either the first or second liquid, depending on the purpose. However, as stated above, in the resin-forming system of this technology, the first liquid is present in greater quantities than the second liquid. Therefore, from the viewpoint of efficiently dissolving the components, these components may be included in the first liquid.

[0059] <Plasticizer> In the resin forming system of this technology, either the first liquid or the second liquid may contain a plasticizer. Here, the "plasticizer" is included together with the polyurethane polymer compound that is synthesized later to improve the flexibility or elasticity of the polyurethane resin obtained later. By improving the flexibility or elasticity of the polyurethane resin, the processability (processability for processing the polyurethane resin as a roll body) and mechanical strength of the polyurethane resin can be improved. The plasticizer is not particularly limited, but may be, for example, a phthalate ester plasticizer or a benzoate ester plasticizer. Examples of phthalate ester plasticizers include DEP (diethyl phthalate), DOP (bis(2-ethylhexyl) phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate), BBP (benzyl butyl phthalate), and DUP (diundecyl phthalate). Examples of benzoate ester plasticizers include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and polyethylene glycol dibenzoate. The plasticizer may be one of these, or a combination of two or more.

[0060] In the resin-forming system of this technology, if the first liquid contains a plasticizer, the mass content of the plasticizer relative to the mass of the first liquid may be 14% by mass or more, preferably 16% by mass or more, and more preferably 18% by mass or more. Alternatively, the mass content of the plasticizer relative to the mass of the first liquid may be 34% by mass or less, preferably 32% by mass or less, and more preferably 30% by mass or less.

[0061] <Crosslinking agent> In the resin-forming system of this technology, either the first liquid or the second liquid may contain a crosslinking agent. Here, the "crosslinking agent" is a compound used to improve the processability and mechanical strength of the polyurethane resin by linking (crosslinking) polyurethane polymer compounds that are synthesized later. The crosslinking agent is preferably a polyol-based crosslinking agent having multiple hydroxyl groups in its molecule. Examples of polyol-based crosslinking agents include TMP (trimethylolpropane), glycerin, pentaerythritol, sorbitol, and 1,2,6-hexanetriol. The crosslinking agent may be one of these, or a combination of two or more. Among these, TMP (trimethylolpropane) is preferred as the crosslinking agent.

[0062] In the resin-forming system of this technology, if the first liquid contains a crosslinking agent, the mass content ratio of the crosslinking agent to the mass of the first liquid may be 0.2% by mass or more, preferably 0.3% by mass or more, and more preferably 0.4% by mass or more. Alternatively, the mass content ratio of the crosslinking agent to the mass of the first liquid may be 1.0% by mass or less, preferably 0.9% by mass or less, and more preferably 0.8% by mass or less.

[0063] <Catalyst> In the resin-forming system of this technology, either the first liquid or the second liquid may contain a catalyst. Here, the "catalyst" is for promoting the reaction of the polyurethane polymer compound to be synthesized later. The catalyst may include, for example, an imidazole-based catalyst. Examples of imidazole-based catalysts include 1-methylimidazole and 1-isobutyl-2-methylimidazole. Alternatively, the catalyst may include a tin catalyst. Examples of tin catalysts include stanus octoate and dibutyltin dilaurate.

[0064] In the resin-forming system of this technology, if the first liquid contains a catalyst, the mass content ratio of the catalyst to the mass of the first liquid may be 0.001% by mass or more, preferably 0.002% by mass or more, and more preferably 0.003% by mass or more. Alternatively, the mass content ratio of the catalyst to the mass of the first liquid may be 0.1% by mass or less, preferably 0.05% by mass or less, and more preferably 0.01% by mass or less.

[0065] <Antifoaming agent> In the resin forming system of this technology, either the first liquid or the second liquid may contain an antifoaming agent. Here, the "antifoaming agent" is used to make the polyurethane resin obtained later non-foaming. The antifoaming agent is not particularly limited, but may be, for example, a silicone-based antifoaming agent, a surfactant, or an organic antifoaming agent such as a polyether or a higher alcohol.

[0066] In the resin-forming system of this technology, if the first liquid contains an antifoaming agent, the mass content ratio of the antifoaming agent to the mass of the first liquid may be 0.01% by mass or more, preferably 0.02% by mass or more, and more preferably 0.03% by mass or more. Alternatively, the mass content ratio of the antifoaming agent to the mass of the first liquid may be 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less.

[0067] <Other ingredients> The first or second liquid of the resin-forming system of this technology may contain other components shown above, depending on the intended use of the roll, as long as the desired physical properties are not significantly impaired.

[0068] <Method for producing the first or second liquid>

[0069] The resin-forming system of the present invention is manufactured by preparing a first liquid and a second liquid, respectively. Both the first liquid and the second liquid can be prepared by mixing them using methods known in the art.

[0070] <Method for producing the first liquid> The method for producing the first liquid may include, for example, a first step of mixing the components contained in the first liquid, and a second step of stirring the mixture obtained in the first step under reduced pressure. The mixture is degassed by stirring under reduced pressure. If degassing is not necessary, the second step may be omitted.

[0071] In the first step, the polyester polyol and other components different from the polyester polyol (e.g., biomass-derived materials, crosslinking agents, plasticizers, catalysts, and defoamers) are mixed to achieve the desired composition. The mixing may be carried out using a stirring device known in the art. The mixing may also be carried out at room temperature (20-30°C), for example.

[0072] In the second step, the mixture prepared in the first step is stirred under reduced pressure. In this specification, "reduced pressure" may mean, for example, an absolute pressure of 10 kPa or less, or 5 kPa or less, 3 kPa or less, or 2.5 kPa or less. The second step may also be carried out under absolute vacuum (0 kPa).

[0073] <Method for producing the second liquid> In one embodiment, the second liquid may consist of a single material. In this case, the second liquid may be used as is. In other embodiments, the second liquid may contain other components of isocyanate. In this case, the method for producing the second liquid may include a first step and a second step, similar to the method for producing the first liquid. In this case, the second step may be omitted if degassing is not required.

[0074] 4. Resin

[0075] The polyurethane resin used in this technology can be synthesized by reacting a resin-forming system composed of the first liquid and the second liquid described above. This reaction may be carried out at temperatures of, for example, 70°C or higher, 80°C or higher, or 90°C or higher. There is no particular upper limit to the reaction temperature, but it may be carried out at 130°C or lower, 120°C or lower, or 110°C or lower. By the above reaction, a polyurethane resin exhibiting the following physical properties can be obtained, for example.

[0076] <Solvent resistance> The solvent resistance (also referred to as liquid resistance) of the polyurethane resin to MEK (methyl ethyl ketone) is, for example, 50% or less, preferably 45% or less, and more preferably 40% or less. The lower limit of the solvent resistance of the polyurethane resin to MEK (methyl ethyl ketone) is not particularly limited, and a value closer to 0% is preferable.

[0077] The solvent resistance of the resin to toluene is, for example, 10% or less, preferably 8% or less, and more preferably 6% or less. The lower limit of the solvent resistance of the polyurethane resin to toluene is not particularly limited, and it is preferable that it is as close to 0% as possible.

[0078] Solvent resistance is measured in accordance with JIS K 6258. Solvent resistance is determined by measuring the percentage change in weight (%) before and after immersing the polyurethane resin in MEK or toluene at 23°C for 24 hours.

[0079] <Wear amount> The wear amount of the polyurethane resin is, for example, 800 mm. 3 The following, preferably 600 mm 3 The following, more preferably 450 mm 3 The following is acceptable. The lower limit of the wear amount of the polyurethane resin is not particularly limited, but a smaller value is preferable.

[0080] The amount of wear is measured by the Akron wear test in accordance with JIS K 6264-2:2005. The amount of wear is measured under the following conditions: Type of test method: Method B Break-in operation: 500 times Main test run: 500 times Tilt angle: 15 degrees Added force: 27.0N Rotation speed: 75 ± 5 revolutions per minute Number of test specimens: 3 Measurement device: Akron abrasion tester manufactured by Ueshima Seisakusho Co., Ltd.

[0081] For measuring the amount of wear, a disc-shaped test specimen conforming to JIS K 6242-2:2005 is used.

[0082] <Shore A hardness> The Shore A hardness of the polyurethane resin may be adjusted to a range such as 20 or higher, 25 or higher, or 30 or higher, depending on the intended use of the roll. Furthermore, the upper limit of the Shore A hardness of the resin may also be adjusted to a range such as 55 or lower, 50 or lower, or 45 or lower, depending on the intended use of the roll.

[0083] Shore A hardness is measured in accordance with JIS K 6253. A Type A hardness tester (TECLOCK, spring-type rubber hardness tester, GS-719G) is used to measure Shore A hardness. The test specimen used to measure Shore A hardness is a cylindrical shape made of the polyurethane resin with a diameter of approximately 60 mm and a thickness of approximately 6-8 mm. Shore A hardness is the value obtained immediately after the hardness tester is brought into contact with the test specimen (also called the instantaneous value).

[0084] <Elongation at break> The elongation at break of the resin is, for example, 200% or more, preferably 400% or more, and more preferably 500% or more. The elongation at break is measured in accordance with JIS K 6251.

[0085] <Tensile strength at break> The tensile strength at break of the polyurethane resin is, for example, 1.0 MPa or more, preferably 2.0 MPa or more, and more preferably 3.0 MPa or more. There is no particular upper limit to the tensile strength at break, and a higher value is preferable. The tensile strength at break is measured in accordance with JIS K 6251.

[0086] <Tear strength> The tear strength of the polyurethane resin is, for example, 6 N / mm or more, preferably 10 N / mm or more, and more preferably 15 N / mm or more. There is no particular upper limit for the tear strength, but a higher value is preferable.

[0087] Tear strength is measured in accordance with JIS K 6252. A benchtop precision universal testing machine (Shimadzu Corporation, Autograph, AGS-5kNX) is used to measure tear strength. An angle-type test specimen conforming to JIS K 6252 is used as the test specimen for measuring tear strength. More specifically, this angle-type test specimen is a non-cut angle-type test specimen with a thickness of 2 mm.

[0088] Based on the above, this technology can provide a resin-forming system for forming a polyurethane resin obtained by the reaction of a polyester polyol and an isocyanate, and which includes a biomass-derived material. Here, the biomass-derived material is a polymer compound having a cellulose structure with hydroxyl groups or needle-shaped particles composed of calcium carbonate. Furthermore, this technology can provide a polyurethane resin obtained by curing the resin-forming system. Moreover, this technology can provide a roll in which the polyurethane resin is applied to the roll body.

[0089] Furthermore, this technology can be configured as follows: [1] A first liquid containing at least a polyester polyol, It consists of a second liquid containing at least an isocyanate, The first liquid or the second liquid contains needle-shaped particles composed of a polymer compound having a cellulose structure with hydroxyl groups or calcium carbonate. A resin forming system for forming a resin constituting a member of a roll that can be exposed to a solvent. [2] The resin-forming system described in [1], wherein the polyester polyol is a reaction product of succinic acid and ethylene glycol. [3] The resin-forming system according to [2], wherein the reaction product is a compound represented by the following formula (1). [ka] In equation (1) above, n is an integer greater than or equal to 1. [4] The resin forming system according to any one of [1] to [3], wherein the needle-shaped particles composed of calcium carbonate are derived from seashells. [5] The resin-forming system according to [4], wherein the shell is a scallop shell. [6] The resin forming system according to any one of [1] to [5], wherein the amount of the second liquid is 9.4 parts by mass or more and 12.5 parts by mass or less with respect to 100 parts by mass of the first liquid. [7] The resin forming system according to any one of [1] to [6], wherein the mass content of the polyester polyol in relation to the first liquid is 60% by mass or more. [8] Needle-shaped particles composed of a polymer compound having a cellulose structure having a hydroxyl group or calcium carbonate are included in the first liquid, according to any of [1] to [7]. [9] A roll having a component that can be exposed to a solvent, The roll is made of a resin synthesized by mixing a first liquid containing at least a polyester polyol, a second liquid containing at least an isocyanate, and a biomass material having needle-shaped particles composed of a cellulose structure or calcium carbonate.

[10] The roll described in [9] has a solvent resistance of 40% or less to methyl ethyl ketone of the resin as measured in accordance with JIS K 6258.

[11] The roll according to [9] or

[10] , wherein the solvent resistance of the resin to toluene, as measured in accordance with JIS K 6258, is 10% or less.

[12] A roll according to any one of [9] to

[11] , wherein the Shore A hardness of the resin measured in accordance with JIS K 6253 is 35 or more and 45 or less.

[13] A roll according to any one of [9] to

[12] , wherein the tear strength of the resin measured in accordance with JIS K 6252 is 15 N / mm or more.

[14] A roll according to any one of [9] to

[13] , wherein the elongation at break of the resin measured in accordance with JIS K 6251 is 500% or more.

[15] The wear volume of the resin per 1000 revolutions, as measured by the Akron abrasion test in accordance with JIS K 6242-2:2005, was 800 mm 3 The roles listed in any of the following [9] through

[14] .

[0090] 5. Examples

[0091] The present invention will be described in more detail below based on examples. These examples are representative examples of the present invention, and the scope of the present invention is not limited to these examples.

[0092] <Example 1> 100 parts by weight of polyester polyol consisting of 80 parts by weight of material name [OD-X-2251] (manufactured by DIC Corporation) and 20 parts by weight of material name [Takelac U-6230] (manufactured by Mitsui Chemicals, Inc.), to which 20 parts by weight of material name [KC Floc W-400G] (manufactured by Nippon Paper Industries Co., Ltd.) is added as a polymer compound having a cellulose structure with hydroxyl groups derived from biomass, 1 part by weight of material name [TMP_Evyron T20 flakes] (manufactured by Perstorp Specialty Chemicals AB) is added as a crosslinking agent, 10 parts by weight of DEP (diethyl phthalate) (manufactured by Daihachi Chemical Industry Co., Ltd.) is added as a phthalate ester plasticizer, and material name [Monosizer] is added as a benzoic acid ester plasticizer. The first liquid was obtained by mixing 30 parts by mass of PB-3A (manufactured by DIC Corporation), 0.01 parts by mass of material name Kaorizer No. 120 (manufactured by Kao Corporation) as a catalyst, and 0.1 parts by mass of material name BYK-066N (manufactured by BYK Corporation) as an antifoaming agent at 90°C.

[0093] For the second liquid, we used a single material with the material name [Takenate LSI-990] (manufactured by Mitsui Chemicals, Inc.) as is.

[0094] The resin was obtained by mixing the first liquid, whose temperature was adjusted to 80°C, with the second liquid, which was at room temperature (15-30°C), under normal conditions, and then heating the mixture to 105°C to promote the polymerization reaction and allow it to harden. The mixing ratio was 11 parts by mass of the second liquid to 100 parts by mass of the first liquid.

[0095] <Example 2> In Example 2, the biomass-derived material is different from that used in Example 1. Specifically, instead of a polymer compound having a cellulose structure with hydroxyl groups, 20 parts by mass of scallop shell powder (manufactured by Nippon Rikagaku Kogyo Co., Ltd.) was used as needle-shaped particles composed of calcium carbonate, a biomass-derived material.

[0096] <Comparative Example 1> To 100 parts by weight of polyester polyol consisting of 80 parts by weight of material name [OD-X-2251] (manufactured by DIC Corporation) and 20 parts by weight of material name [Takelac U-6230] (manufactured by Mitsui Chemicals, Inc.), 1 part by weight of material name [TMP_Evyron T20 flakes] (manufactured by Perstorp Specialty Chemicals AB) as a crosslinking agent, 10 parts by weight of DEP (diethyl phthalate) as a phthalate ester plasticizer (manufactured by Daihachi Chemical Industry Co., Ltd.), 30 parts by weight of material name [Monosizer PB-3A] (manufactured by DIC Corporation) as a benzoate ester plasticizer, 0.01 parts by weight of material name [Kaorizer No. 120] (manufactured by Kao Corporation) as a catalyst, and 0.1 parts by weight of material name [BYK-066N] (manufactured by BYK Corporation) as an antifoaming agent were mixed at 90°C to obtain the first liquid.

[0097] For the second liquid, we used a single material with the material name [Takenate LSI-990] (manufactured by Mitsui Chemicals, Inc.) as is.

[0098] The resin was obtained by mixing the first liquid, whose temperature was adjusted to 80°C, with the second liquid, which was at room temperature (15-30°C), under normal conditions, and then heating the mixture to 105°C to promote the polymerization reaction and allow it to harden. The mixing ratio was 12 parts by mass of the second liquid to 100 parts by mass of the first liquid.

[0099] <Comparative Example 2> A resin according to Comparative Example 2 was obtained under the same conditions as in Comparative Example 1, except that the mixture consisted of 7 parts by mass of a phthalate ester plasticizer and 21 parts by mass of a benzoate ester plasticizer, and the mixing ratio was 13 parts by mass of the second liquid to 100 parts by mass of the first liquid. As the resin according to Comparative Example 2 has a lower plasticizer content than that of Comparative Example 1, the Shore A hardness is higher, as can be seen from Table 1 below.

[0100] <Measurement of physical properties> For each resin obtained in Examples 1 and 2, and Comparative Examples 1 and 2, the physical properties, namely solvent resistance, abrasion resistance, Shore A hardness, tensile strength at break, elongation at break, and tear strength, were measured. Each physical property was determined by the measurement method described in the above embodiments. For the test specimens used to measure the physical properties, a polyurethane resin obtained by pouring a mixture of the first and second liquids into a predetermined mold and curing it was used.

[0101] <Result> Table 1 shows the compositions of Examples 1 and 2, and Comparative Examples 1 and 2 described above. The units of the numerical values ​​listed in the compositions are parts by mass. In addition, Table 1 also shows the measurement results for solvent resistance, abrasion rate, Shore A hardness, tensile strength at break, elongation at break, and tear strength for the resins obtained in Examples 1 and 2, and Comparative Examples 1 and 2, along with their respective compositions.

[0102] [Table 1]

[0103] Table 1 shows that the solvent resistance of the resins in Examples 1 and 2 to MEK and to toluene was not lower than that of the resin in Comparative Example 1. On the other hand, the tensile strength at break, elongation at break, and tear strength of the resins in Examples 1 and 2 were found to be significantly improved compared to Comparative Example 1. Furthermore, compared to the resin in Comparative Example 2, which has a similar Shore A hardness, the resins in Examples 1 and 2 maintained their solvent resistance while showing improvements in tensile strength at break, elongation at break, and tear strength.

[0104] Previously, resins containing biomass-derived materials sometimes exhibited improved mechanical strength but reduced solvent resistance. However, the resin related to this technology surprisingly maintains solvent resistance while simultaneously improving mechanical strength. Furthermore, it has been confirmed that it can also improve abrasion resistance. Therefore, by applying this resin to the roll body, this technology can provide a roll that improves mechanical strength while ensuring solvent resistance. Moreover, it can provide a roll with improved abrasion resistance.

[0105] The embodiments and examples of this technology have been described in detail above, but this technology is not limited to the embodiments and examples described above, and various modifications are possible based on the technical concept of this technology. The configurations, methods, processes, shapes, materials, and numerical values ​​given in the embodiments and examples described above are merely examples, and different configurations, methods, processes, shapes, materials, and numerical values ​​may be used.

[0106] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step may be replaced with the upper or lower limit of a numerical range in another step. Unless otherwise specified, the materials exemplified in this specification may be used individually or in combination of two or more.

Claims

1. A first liquid containing at least a polyester polyol, It consists of a second liquid containing at least an isocyanate, The first liquid or the second liquid contains needle-shaped particles composed of a polymer compound having a cellulose structure with hydroxyl groups or calcium carbonate. A resin forming system for forming a resin constituting a member of a roll that can be exposed to a solvent.

2. The resin-forming system according to claim 1, wherein the polyester polyol is a reaction product of succinic acid and ethylene glycol.

3. The resin-forming system according to claim 2, wherein the reaction product is a compound represented by the following formula (1). 【Chemistry 1】 In equation (1) above, n is an integer greater than or equal to 1.

4. The resin-forming system according to any one of claims 1 to 3, wherein the needle-shaped particles composed of calcium carbonate are derived from seashells.

5. The resin forming system according to claim 4, wherein the seashell is a scallop shell.

6. The resin forming system according to any one of claims 1 to 3, wherein the amount of the second liquid is 9.4 parts by mass or more and 12.5 parts by mass or less with respect to 100 parts by mass of the first liquid.

7. The resin-forming system according to any one of claims 1 to 3, wherein the mass content of the polyester polyol in the first liquid is 60% by mass or more.

8. The resin-forming system according to any one of claims 1 to 3, wherein needle-shaped particles composed of the polymer compound having a cellulose structure having a hydroxyl group or the calcium carbonate are included in the first liquid.

9. A roll having a component that can be exposed to a solvent, The roll is made of a resin synthesized by mixing a first liquid containing at least a polyester polyol, a second liquid containing at least an isocyanate, and a biomass material having needle-shaped particles composed of a cellulose structure or calcium carbonate.

10. The roll according to claim 9, wherein the solvent resistance of the resin to methyl ethyl ketone, as measured in accordance with JIS K 6258, is 40% or less.

11. The roll according to claim 9, wherein the solvent resistance of the resin to toluene, as measured in accordance with JIS K 6258, is 10% or less.

12. The roll according to claim 9, wherein the Shore A hardness of the resin, as measured in accordance with JIS K 6253, is 35 or greater and 45 or less.

13. The roll according to claim 9, wherein the tear strength of the resin, as measured in accordance with JIS K 6252, is 15 N / mm or more.

14. The roll according to claim 9, wherein the elongation at break of the resin, as measured in accordance with JIS K 6251, is 500% or more.

15. The wear volume of the resin per 1000 revolutions, as measured by the Akron abrasion test in accordance with JIS K 6242-2:2005, was 800 mm³. ３ The roll according to claim 9, which is as follows:

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