JP2011226047A - Synthetic imitation leather made by using bio-polyurethane resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a synthetic imitation leather made by using bio-polyurethane resin, which allows product to show sufficient durability when especially used as a synthetic imitation leather material while the bio-polyurethane resin is an ecological material becoming countermeasures against the environmental problem that raw material derived from plants is used at a high ratio.SOLUTION: The synthetic imitation leather is composed a base fabric which constitutes a core part and a skin layer, and at least the skin layer is formed by using bio-polyurethane resin. The bio-polyurethane resin is made by making any one of a bio-polycarbonate polyol (A) or a bio-polyester polyol (B) synthesized from a short chain diol (a) derived from plants and a carbonate component(b) derived from petroleum or a carboxylic acid component (c) derived from plants, and a bio-polyether polyol (C) made from the short chain diol component (a) derived from plants react with an isocyanate component (d). Further, in the bio-polyurethane resin used to form the synthetic imitation leather, the content of the component derived from plants is 28-95 mass% in regard to 100 mass% of the bio-polyurethane resin.

Description

  The present invention relates to a synthetic artificial leather using an environmentally friendly biopolyurethane resin. More specifically, the present invention relates to a synthetic artificial leather using a bio-polyurethane resin having a high utilization rate (content) of plant-derived raw materials that greatly contributes to carbon neutral for the purpose of global warming countermeasures and environmental load reduction. In particular, it relates to synthetic artificial leather useful as a vehicle seat.

  In recent years, “biomass” has attracted attention as an industrial resource that is not a depletion resource, but the definition of “biomass” from this perspective is “renewable, organic organic resource excluding fossil resources”. Has been. Conventionally, natural systems such as cotton, wool, starch, and natural rubber and their derivatives have been used as classic biomass polymers. In addition, for the purpose of environmental conservation, biomass polymers have been actively developed since the 1980s, with an emphasis on biodegradability, such as polylactic acid, polybutylene succinate, and polyhydroxyalkanoic acid, using biomass as a raw material. . Since then, development has been carried out on the conversion of biomass-based polymers (bio-based polymers) by reacting petroleum monomers based on biomass, such as 1,3-propanediol, succinic acid, and chitin / chitosan. . These bio-based polymers are expected as raw materials for a wide variety of products as global warming prevention measures, and are expected to be applied to various industrial fields in a wide range of application fields. And some have been put to practical use. However, it is difficult to say that the biomass polymer has sufficient physical properties as a raw material depending on the use as compared with a conventional petroleum polymer, and development of a product using this is not easy.

  Here, polyurethane resin is excellent in various physical properties such as wear resistance, flexibility, flexibility, flexibility, processability, adhesiveness, chemical resistance, etc., and also excellent in suitability for various processing methods. Therefore, it is widely used as a material for synthetic artificial leather (generic name for artificial leather and synthetic leather), as a binder for various coating agents, inks, paints, etc., or as a material for films, sheets and various molded products. And the polyurethane-type resin suitable for these various uses is proposed. The “polyurethane resin” referred to in the present invention is a general term for polyurethane resin, polyurea resin, and polyurethane-polyurea resin. The polyurethane resin is basically obtained by reacting a high molecular weight polyol component, an organic polyisocyanate component, and further a chain extender component as required, and the type and combination of these components are changed. Thus, it is possible to provide polyurethane resins having various performances. In such a polyurethane-based resin having a wide range of uses, it is very useful if the aforementioned biomass polymer can be used.

  Among its wide range of uses, synthetic artificial leather using polyurethane resin, in particular, has a texture close to that of natural leather, so it is often used in fields that require a sense of quality, such as clothing, furniture, and vehicle interior materials. ing. In recent years, from the viewpoint of environmental protection, there is a strong demand for the development of synthetic artificial leather systems that take ecology into account. The reason is that, as described below, most of the raw materials for producing conventional synthetic artificial leather are composed of petroleum-derived raw materials and used as a polyurethane resin solution dissolved in an organic solvent.

  For example, synthetic artificial leather using a polyurethane-based resin is manufactured by a wet method or the like through the following main steps. First, a solution of an organic solvent mainly composed of a polyurethane resin N, N-dimethylformamide is applied on the fibrous base material layer and solidified in water to form a microporous layer. Next, a polyurethane resin solution dissolved in various organic solvents is directly coated on the microporous layer with a coating machine such as a gravure and dried to form a skin layer (silver surface layer), or a polyurethane-based layer. There is a method in which a resin solution is applied on a release paper and dried to form an adhesive layer on the surface of the skin layer film, and these layers are transferred to the substrate surface (see Non-Patent Document 1). On the other hand, from the viewpoint of environmental problems, safety and health, and fire fighting measures, there is an increasing need for polyurethane-based resin aqueous dispersions that do not use organic solvents and are effective for volatile organic compound (VOC) measures. There is a proposal for synthetic artificial leather using a polyurethane resin that can be dispersed or emulsified (see Patent Documents 1 and 2).

However, polyurethane-based resins mostly have a life cycle in which raw materials are procured, manufactured, used, and incinerated as trash. From this point of view, improvement in consideration of ecology is demanded. That is, global warming due to the generation of greenhouse gases such as carbon dioxide (CO ₂ ) and methane (CH ₄ ) generated by incineration of garbage disposal, and the depletion of petroleum resources are social problems. These greenhouse gases have the effect of preventing the heat from escaping from the surface to outer space, and the rise in the sea level caused by the increase in greenhouse gases and the increase in temperature and ecosystems and agriculture and forestry. Impact has been pointed out. Furthermore, in the life cycle from raw material procurement, raw material production, use, and disposal, at least the state of continuing to use conventional petroleum-derived raw materials is not environmentally friendly.

Meanwhile, raw materials of plant origin, in order to absorb the CO ₂ in the plants develop, CO ₂ occurs even if it is for example incineration can count zero, raw materials derived from plants, global warming There is an idea that can contribute to. However, for example, the conventionally known plant-derived polylactic acid has been promoted to expand its use from the standpoint that it can contribute to waste reduction by soil microbial degradation, but its durability is low, so it is limited There is a practical problem that it can be used only for the site that has been applied.

  As described above, polyurethane resin is excellent in various physical properties and excellent in suitability for various processing methods. Therefore, synthetic artificial leather materials are particularly adapted to the skin layer. In the case of substituting with a polyurethane-based resin using the above raw materials, it is necessary that the raw materials have a high utilization rate (content) of plant-derived raw materials and satisfy the following requirements. That is, synthetic artificial leather is used, for example, as a material used for automobiles, furniture, and the like. Therefore, the skin layer requires durability and, at the same time, a fibrous substrate layer (substrate or substrate). Adhesiveness, flexibility, and water resistance are required. Various studies have been made on polyurethane-based resins as synthetic artificial leather materials (see, for example, Patent Document 3). However, oil resistance, abrasion resistance, and durability (weather resistance, The required performance such as hydrolysis resistance and heat resistance is not completely satisfied, and further improvements are required. In addition, due to the circumstances described above, it is generally required to provide materials that are more environmentally friendly.

  One of the biopolymers that have been developed in recent years as a material that is friendly to the global environment, polyurethane foam manufactured with renewable components, in which at least part of the polyol derived from petroleum is replaced with plant-derived hydroxylate A body has been proposed (see, for example, Patent Document 4). In addition, a plant-derived polyol obtained by condensation reaction of a fossil fuel polyol and a plant-derived higher fatty acid, or a polyisocyanate prepolymer having an isocyanate group at the terminal by reacting the plant-derived polyol and isocyanate is used as a raw material. There is a proposal about the soft polyurethane foam used (see Patent Document 5). These documents propose that plant-derived raw materials can be used as part of the raw materials for producing urethane resins, but it is still not sufficient, and a polyurethane-based resin excellent in various physical properties is obtained. It shows that it is necessary to study in detail in order to make it a technology that can be put into practical use. In particular, synthetic artificial leather materials that require various performances such as durability and texture described above still have problems to be solved even when conventional polyurethane resins are used. In order to apply the biopolyurethane resin to the practical use, further detailed examination is required.

Edited by Keiji Iwata, Polyurethane resin handbook, pages 571-599, 15. Polyurethane leather (published by Nikkan Kogyo Shimbun, September 25, 1987)

Japanese Patent No. 3096230 Japanese Patent No. 4149882 JP-A-5-5280 JP 2006-291205 A JP 2009-167255 A

The polyurethane resin used in synthetic artificial leather is limited to the VOC countermeasures mentioned above for countermeasures against environmental problems, and it does not consider environmental problems with a view to CO ₂ problems. Currently. On the other hand, depending on the use of the product, generally, the following properties are required as physical properties required for synthetic artificial leather. That is, first, as durability properties, hydrolysis resistance, light resistance, heat resistance, gas discoloration resistance, wrinkle resistance, oleic acid resistance (human sweat component) and the like are required. Furthermore, various physical properties of synthetic artificial leather are required to have a natural leather-like appearance, soft texture, high strength, abrasion resistance, cold bending resistance, surface touch, blocking resistance, adhesion to a substrate, etc. The

  The present invention has been made in view of various problems in the prior art as described above. Its purpose is synthetic artificial leather made of ecological material that can be an effective countermeasure against environmental problems, using biopolyurethane resin in which a high percentage of plant-derived raw materials are used, and it is durable It is to provide a synthetic artificial leather that can sufficiently be used as a product in a field where a high-class feeling is required such as clothing use, furniture, and vehicle interior materials, which sufficiently satisfy various performances such as.

  The above object is achieved by the present invention described below. That is, the present invention provides a synthetic artificial leather composed of a base fabric and a skin layer constituting a core part, wherein at least the skin layer comprises a plant-derived short-chain diol component (a) and a petroleum-derived carbonate component (b) or Biopolycarbonate polyol (A) or biopolyester polyol (B) synthesized from plant-derived carboxylic acid component (c), biopolyether polyol (C) composed of plant-derived short-chain diol component (a) A biopolyurethane resin obtained by reacting any polyol with an isocyanate component (d), and the content of the plant-derived component is 28 to 95% by mass with respect to 100% by mass of the biopolyurethane resin. It is a synthetic artificial leather characterized by being formed using a polyurethane resin.

The following are mentioned as a preferable form of this invention.
The base fabric is either a woven fabric impregnated with a resin, a nonwoven fabric impregnated with a resin, or a fibrous base material on which a microporous layer of resin is formed, and these resins are Synthetic artificial leather that is a biopolyurethane resin.
The synthetic artificial leather, wherein the biopolyurethane resin further contains, as necessary, a plant-derived short-chain diol component (a), a petroleum-derived diol component and / or a diamine component (e) as a reaction component.
The biopolyurethane resin comprises the total active hydrogen-containing groups of the components (a), (A), (B), (C) and (e), and the isocyanate group of the component (d). The synthetic artificial leather obtained by reacting at an equivalent ratio of 0.9 to 1.5.
The synthetic artificial leather as described above, wherein the short-chain diol component (a) is at least one selected from plant-derived ethylene glycol, 1,3-propanediol, and 1,4-butanediol.
The synthetic artificial leather, wherein the carboxylic acid component (c) is sebacic acid and / or plant-derived succinic acid composed of a plant-derived castor oil derivative.
The synthetic artificial leather, wherein the carbonate component (b) is selected from dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, and diphenyl carbonate.
The isocyanate component (d) is at least one selected from the group consisting of diisocyanate components composed of derivatives of plant-derived components, dimer acid diisocyanate components derived from plants, polyisocyanate components derived from amino acids, and diisocyanate components derived from petroleum. A synthetic artificial leather as described above.
An organic solvent is used in the synthesis of the biopolyurethane resin or in forming a synthetic artificial leather using the biopolyurethane resin, and the organic solvent is derived from plants, ethanol, butanol, ethyl acetate, The synthetic artificial leather as described above, which is at least one selected from butyl acetate, ethyl lactate and butyl lactate.
The synthetic artificial leather according to any one of the above, which is for vehicle seats.

  According to the present invention, a bio-polyurethane resin (hereinafter also referred to as bio-urethane resin) in which plant-derived raw materials are used in a high ratio is used to form an ecological material that can be an effective countermeasure against environmental problems. Synthetic artificial leather that has been fully used and can be used as a product in fields that require a high-class feel, such as apparel, furniture, and vehicle interior materials, that sufficiently satisfy various performances such as durability and texture. Fake leather is provided.

Next, the present invention will be described in more detail with reference to preferred embodiments.
The synthetic artificial leather of the present invention is a synthetic artificial leather composed of a base fabric and a skin layer constituting a core part, and at least the skin layer and, if necessary, the base fabric, a specific biourethane characterizing the present invention. It is made of resin. The specific biourethane resin characterizing the present invention will be described later. The synthetic artificial leather material of the present invention can be manufactured by a conventionally known method using a general synthetic artificial leather forming paint except that a specific biourethane resin is used, and the manufacturing method itself is not particularly limited. . In addition, as the base fabric constituting the core portion used in the synthetic artificial leather of the present invention, any conventionally known base fabric used in the production of synthetic artificial leather can be used, and the optimal base fabric for the purpose of using the synthetic artificial leather. Is not particularly limited. Examples thereof include woven fabrics and nonwoven fabrics impregnated with a polyurethane resin, and those obtained by forming a microporous layer of a polyurethane resin on a fibrous base material by the above method. It is also a preferred embodiment of the present invention to use a specific biourethane resin to be described later for the polyurethane resin used in this case.

  When forming a synthetic artificial leather skin layer using a specific biourethane resin that characterizes the present invention, a skin layer-forming paint containing a biourethane resin may be applied to the base fabric by a conventionally known method. Yes, it is not particularly limited. For example, a surface forming method in which a coating material for forming a skin layer is directly applied onto a base fabric with a gravure coater, comma coater, knife coater, air knife coater, etc., and a film is formed from the coating material for forming a skin layer using a release paper. Examples thereof include a method in which a melt or a two-component biourethane resin is used and thermally transferred onto a base fabric. Moreover, in order to improve the surface designability, it is possible to apply a surface treatment agent or emboss the synthetic artificial leather of the present invention.

Specific methods for producing the synthetic artificial leather of the present invention include the following methods.
(1) A solution of a specific biourethane resin of a high molecular weight type synthesized as described later in an organic solvent mainly composed of N, N-dimethylformamide (hereinafter referred to as DMF) on the base material layer. (Paint) is applied, and the coating layer is solidified in water to form a microporous layer having a thickness of 200 to 2,000 μm. After drying this, on the formed microporous layer, the biourethane resin paint was directly coated with a coating machine such as a gravure and dried, and a skin layer having a thickness of 100 to 1,500 μm ( (Silver surface layer) is formed (system in which DMF is finally recovered).
(2) Applying an appropriate adhesive on the skin layer having a thickness of 20 to 100 μm formed by applying the bio-urethane resin paint on a release paper and drying it to form an adhesive layer having a thickness of 20 to 100 μm And transferring it to a desired substrate in accordance with the conditions of wet lamination or dry lamination.

  Any conventionally known synthetic artificial leather substrate can be used as the synthetic artificial leather substrate of the present invention. For example, brushed cloth, rayon cloth, nylon cloth, polyester cloth, kevlar cloth, non-woven fabric (naturally-derived polymers, biopolymers, polyesters, nylons, etc.) Latex) and various films and sheets.

  In addition, when the synthetic artificial leather of the present invention is produced by the method (2) described above, a specific biourethane resin characterizing the present invention can be used for the adhesive layer to further crosslink. . As a crosslinking method using a urethane group, for example, crosslinking with a polyisocyanate crosslinking agent can be mentioned. As the polyisocyanate crosslinking agent, conventionally known ones can be used, and are not particularly limited. For example, dimer of 2,4-toluylene diisocyanate, triphenylmethane triisocyanate, tris- (p-isocyanatephenyl) thiophosphite, polyfunctional aromatic isocyanate, polyfunctional aromatic aliphatic isocyanate, polyfunctional aliphatic Examples thereof include blocked polyisocyanates such as isocyanate, fatty acid-modified polyfunctional aliphatic isocyanate, and blocked polyfunctional aliphatic isocyanate, and polyisocyanate prepolymers. These polyisocyanate crosslinking agents are particularly effective in improving the adhesive strength if they are in an appropriate amount, but if the amount used is too large, the texture of the synthetic artificial leather produced is too hard or unreacted isocyanate remains, It is not preferable. The polyisocyanate crosslinking agent is used in an amount of 100 parts by mass or less, preferably 2 to 50 parts by mass with respect to 100 parts by mass of the specific biopolyurethane resin.

  The synthetic artificial leather of the present invention is characterized by using a biopolyurethane resin in which a plant-derived component is used in a high ratio. Hereinafter, the specific biopolyurethane resin will be described. That is, the biopolyurethane resin used in the present invention is obtained by using a plant-derived polycarbonate polyol, a plant-derived short-chain diol component, and a plant-derived component as a plant-derived component. A plant-derived polyester polyol obtained by using a carboxylic acid component of the above, or a plant-derived polyether polyol obtained by using a plant-derived short-chain diol component, and a plant-derived polyol component It is characterized by comprising as a main component a polyisocyanate component which can also use an isocyanate. Here, “polyurethane” is a general term for polyurethane and polyurethane-polyurea. Therefore, a diamine component is used as necessary. Further, the “active hydrogen-containing group” in the present invention means a functional group having an active hydrogen such as a hydroxyl group, a mercapto group, a carboxyl group, and an amino group that is reactive with an isocyanate group.

  The biourethane resin used in the present invention comprises an aliphatic diisocyanate, an aromatic diisocyanate, an alicyclic diisocyanate or a plant-derived isocyanate, a plant-derived short-chain diol as an active hydrogen-containing group, and a plant-derived polyol component. It consists of repeats with at least one block and / or polyurea block and is obtained by copolymerizing the polyurethane block and / or polyurea block.

  And the synthesis | combination based on the said multiblock condensate formed by reacting an aliphatic, aromatic, or alicyclic diisocyanate and the active hydrogen containing group containing a plant-derived component using the said biourethane resin. A pseudo leather composition may be used. For example, the molecular chain of the multi-block condensate is composed of a plant-derived short-chain diol component of 0 to 30% by mass, a plant-derived polyol component of 10 to 100% by mass, and a petroleum-derived diol component and / or Or a diamine component (e) and a polyurethane block and / or at least one polyurea block, and is composed of the biopolyurethane block and / or the biopolyurea block, and the plant-derived component is 28 to 95% by mass. In the range of. The weight average molecular weight is preferably about 2,000 to 500,000. The synthetic artificial leather obtained by the synthetic artificial leather composition having such a structure is excellent in hydrolysis resistance, light resistance, heat resistance, texture, adhesive strength, cold bending resistance, and abrasion resistance.

The form of the biourethane resin used in the present invention may be any of organic solvent-based, water-based, 100% solid, pellets, beads, etc., but since plant-derived components are used for forming the resin, it will be described below. Thus, in any case, the material is environmentally friendly. For example, an organic solvent-based biourethane resin contains a plant-derived short-chain diol component (for example, 1,3-propanediol component, 1,4-butanediol or ethylene glycol) and / or a plant-derived polyol component. because comprising, a resin that may contribute to the reduction of CO ₂ emissions. In addition, as described below, as an organic solvent used when biourethane resin is synthesized or synthetic artificial leather is produced using the resin, plant-derived ones (ethanol, butanol, ethyl acetate, If butyl acetate, ethyl lactate, butyl lactate, etc.) are used, not only the resin forming component but also the solvent component becomes a material or synthetic artificial leather product that takes into account the reduction of CO ₂ emissions. On the other hand, when the form of the biourethane resin is water-based, 100% solid, pellets and beads, from the viewpoint of measures against VOC (volatile organic compounds), it becomes a material or a synthetic artificial leather product that further considers the global environment.

The biourethane resin constituting the synthetic artificial leather of the present invention also generates CO ₂ when incinerated. However, some of the raw materials for biourethane used in the present invention are plant-derived short-chain diols and polyols obtained from plants such as corn and castor (castor bean seeds). These materials plant in its growing process, given water, absorbs CO ₂ in the atmosphere by performing photosynthesis. In the present invention, bio-polyurethane resin is produced by reacting these plant-derived components with organic isocyanate. At that time, since plant-derived components are used at a high ratio, the carbon dioxide discharged by incineration is used. Even if carbon and carbon dioxide absorbed in the process of growing plants are not the same amount, it is in line with the idea of so-called carbon neutral.

From the concept of carbon neutral, it is preferable to use a plant-derived solvent as mentioned above for a part of the organic solvent when synthesizing a biourethane resin or using a synthetic artificial leather using the resin. . That is, when a synthetic artificial leather is produced by applying and drying a biourethane resin-containing paint, CO ₂ is generated when the evaporated organic solvent is recovered and incinerated. However, by adopting a form in which a plant-derived organic solvent is used, compared to the case of using a petroleum-derived organic solvent, it can contribute to the reduction of CO ₂ emissions.

  Next, each component which comprises the biourethane resin used for this invention is demonstrated in more detail. The biourethane resin used in the present invention is a biopolycarbonate polyol synthesized from a plant-derived short-chain diol component (a) and a petroleum-derived carbonate component (b) or a plant-derived carboxylic acid component (c) ( A) or a biopolyester polyol (B) or a biopolyether polyol (C) composed of a plant-derived short-chain diol component (a), obtained by reacting any of the polyols with the polyisocyanate component (d). . Furthermore, you may contain the diol component and / or diamine component (e) derived from petroleum as a reaction component as needed.

  The biourethane resin used in the present invention uses any of the polyols (A), (B) and (C) in the production thereof. As described above, these polyols are all plant-derived short-chain diols ( It uses a) as a raw material and contains plant-derived components. Examples of the plant-derived short-chain diol component (a) include 1,3-propanediol, 1,4-butanediol, ethylene glycol and the like obtained from plant raw materials by the following method. Can be used. These may be used alone or in combination.

1,3-propanediol (HOCH ₂ CH ₂ CH ₂ OH) is produced from glycerol via 3-hydroxypropyl aldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant resources (for example, corn). Is done. Compared with the 1,3-propanediol compound of the EO production method, 1,3-propanediol compound produced by a bio-method such as the above fermentation method yields a useful by-product such as lactic acid in terms of safety. In addition, the manufacturing cost can be kept low, which is also useful in this respect.

  As for 1,4-butanediol, biomass 1,4-butanediol can be produced by obtaining succinic acid obtained by producing glycol from plant resources and fermenting it, and hydrogenating this. Furthermore, the ethylene glycol is produced, for example, from bioethanol obtained by a conventional method via ethylene.

  Polyol (A), which is a biopolycarbonate polyol, is produced by synthesizing the aforementioned plant-derived short chain diol component (a) and petroleum-derived carbonate (b) component. Examples of the carbonate (b) include dimethyl carbonate, dipropyl carbonate, diethyl carbonate, diethylene carbonate, dibutyl carbonate, ethylene carbonate, diphenyl carbonate, and the like. These can be used alone or in combination of two or more.

  The polyol (B), which is a biopolyester polyol, can be obtained from the plant-derived carboxylic acid component (c) together with the short-chain diol (a). Examples of the carboxylic acid component (c) include sebacic acid, succinic acid, lactic acid, glutaric acid, and dimer acid. For example, sebacic acid is produced as a by-product of heptyl alcohol by alkaline pyrolysis of ricinoleic acid obtained from castor oil (extracted from castor bean seeds).

  The polyol B is produced as a 100% plant-derived biopolyester polyol by a condensation reaction between the plant-derived carboxylic acid component (c) and the plant-derived short-chain diol component (a). For this reason, it is suitable as a raw material for the biourethane resin of the present invention. For example, polytrimethylene sebacate polyol obtained by direct dehydration condensation of plant-derived sebacic acid and plant-derived 1,3-propanediol, plant-derived succinic acid and plant-derived 1,4-butanediol Examples thereof include polybutylene succinate polyols obtained by direct dehydration condensation and biopolyester polyols such as plant-derived polylactic acid polyols. These can be used alone or in combination of two or more. According to the study by the present inventors, all plant-derived biopolyester polyols obtained from the aforementioned sebacic acid and the aforementioned plant-derived short-chain diol are particularly useful as raw materials for urethane resins.

  In the biourethane resin used in the present invention, together with the polyols A and B, a plant-derived polyether polyol C can be used in combination as a polyol. By using a polyether polyol in combination, the proportion of plant-derived components in the biopolyurethane resin can be increased. As the polyether polyol, polyethylene glycol obtained by polymerizing plant-derived ethylene glycol, polytetramethylene glycol obtained by polymerizing 1,4-butanediol derived from plant (= polytetramethylene glycol ether polyol), or respectively Examples include ethylene glycol, 1,3-propanediol and 1,4-butanediol (block or random) copolymers derived from plants. For example, plant-derived 1,3-propanediol can be polycondensed by an acid catalyst. Alternatively, tetrahydrofuran can be synthesized from plant-derived 1,4-butanediol and then polycondensed by cationic polymerization. These polyether polyols can be used alone or in combination of two or more.

  The weight average molecular weights of the polyol A, polyol B and polyol C described above are not particularly limited, but the number average molecular weight is usually about 500 to 3,000. If it exceeds 3,000, the cohesive strength of urethane bonds will not be exhibited and the mechanical properties will deteriorate, and in the case of crystalline polyol, it may cause a whitening phenomenon when formed into a film, which is not preferable. Moreover, these polyols can be used individually or in combination of 2 or more types.

  In addition, for the synthesis of the biourethane resin used in the present invention, as a reaction component, any of the above-described polyol A, polyol B and polyol C, and if necessary, the plant-derived short chain diol described above Component (a) or petroleum-derived diol component and / or diamine component (e) can be used. As the petroleum-derived diol component, the following petroleum-derived short-chain polyol components and the like can be used. For example, aliphatic glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, and their alkylene oxides low molar addition (Number average molecular weight of less than 500); cycloaliphatic glycols such as 1,4-bishydroxymethylcyclohexane and 2-methyl-1,1-cyclohexanedimethanol and their alkylene oxide low-mole adducts (number average molecular weight of 500) Aromatic glycols such as xylylene glycol and their alkylene oxide low molar adducts (number average molecular weight less than 500); Bisphenols such as bisphenol A, thiobisphenol, sulfone bisphenol and their alkylene oxy De low molar adduct (number average molecular weight of less than 500); C1 - C18 compounds such as alkyl dialkanolamines, such as alkyl diethanolamine can be used. The petroleum-derived short-chain polyol component is not limited to the above, and polyhydric alcohol compounds such as those listed below can also be used. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tris- (2-hydroxyethyl) isocyanurate, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, and the like. These can be used alone or in combination of two or more.

  In addition, it is possible to use a biourethane resin obtained by using petroleum-derived polyester polyol together with polyol A, polyol B and polyol C, as long as they are within the scope of the effect of the present invention. Examples of petroleum-derived polyester polyols include petroleum-derived aliphatic dicarboxylic acids (for example, succinic acid, adipic acid, glutaric acid, azelaic acid, etc.) and / or aromatic dicarboxylic acids (for example, isophthalic acid, terephthalic acid). Etc.) and low molecular weight glycols derived from petroleum (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, 1 , 4-bishydroxymethylcyclohexane) and the like. More specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene / butylene adipate diol, polyneopentyl / hexyl adipate diol, poly-3-methylpentane adipate diol, Examples include polybutylene isophthalate diol, polylactone polyol, polycaprolactone diol or triol, and poly-3-methylvalerolactone diol. These can be used alone or in combination of two or more.

  In addition, petroleum-derived raw materials can be used as the low molecular weight glycols, and petroleum-derived polycarbonate polyols (for example, polytetramethylene carbonate, polypentamethylene carbonate, polyhexamethylene carbonate) can be used in combination.

  Furthermore, polyamines such as petroleum-derived diamine component (e) can be used for the synthesis of the biourethane resin used in the present invention within the scope of the effect of the present invention. Examples of petroleum-derived polyamines include short-chain diamines, aliphatic and aromatic diamines, and hydrazines. Examples of the short chain diamine include aliphatic diamine compounds such as methylene diamine, ethylene diamine, trimethylene diamine, hexamethylene diamine, and octamethylene diamine; phenylene diamine, 3,3′-dichloro-4,4′-diaminodiphenyl methane, Aromatic diamine compounds such as 4,4′-methylenebis (phenylamine), 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone; cyclopentadiamine, cyclohexyldiamine, 4,4-diaminodicyclohexylmethane, 1 And alicyclic diamine compounds such as 4-diaminocyclohexane and isophoronediamine. Further, hydrazines such as hydrazine, carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, and the like can be given. Other examples include amino-modified siloxane. These can be used alone or in combination of two or more. Of the polyols and polyamines listed above, diol compounds and diamine compounds are preferred.

  In addition, petroleum-derived polyolefin polyols can be used as necessary. For example, polybutadiene glycol, siloxane-modified polyol, polyisoprene glycol or a hydride thereof can be used. Examples of petroleum-derived polymethacrylate diols include α, ω-polymethyl methacrylate diol and α, ω-polybutyl methacrylate diol.

  As isocyanate (d) used for the biourethane resin used for this invention, all the polyisocyanate currently used for manufacture of a conventionally well-known polyurethane can be used, and it is not specifically limited. For example, preferred are toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy -1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4′-methylenebis (phenylene isocyanate) (MDI), durylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, Examples include aromatic diisocyanates such as benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4′-diisocyanate dibenzyl.

  In addition, aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) ), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, hydrogenated XDI, and other alicyclic diisocyanates, or these diisocyanate compounds and low molecular weight polyols and polyamines are reacted so that the end is isocyanate. Naturally, a polyurethane prepolymer or the like obtained by the above process can also be used. Moreover, the diisocyanate component which consists of a derivative of a plant-derived component, the dimer acid diisocyanate component derived from a plant, and the polyisocyanate component derived from an amino acid (lysine diisocyanate etc.) can also be used. If these plant-derived components are used, the ratio of the plant-derived components forming the biourethane resin used in the present invention can be further increased.

  The production method of the biourethane resin obtained using the above raw materials is not particularly limited, and a conventionally known polyurethane production method can be used. For example, a plant-derived 1,3-propanediol compound and a plant-derived carboxylic acid component (c) as a short-chain diol component (a) in the presence or absence of an organic solvent containing no active hydrogen in the molecule ), A polyisocyanate (d), and, if necessary, a low molecular diamine as a chain extender, the equivalent ratio of the isocyanate group and the active hydrogen-containing functional group is usually 1.0. In the composition, the one-shot method or multistage method is usually used at 20 to 150 ° C., preferably 60 to 110 ° C., until the theoretical isocyanate percentage is reached, until the isocyanate group is almost eliminated, and biourethane A resin can be obtained.

  In the synthesis of the biourethane resin used in the present invention, a catalyst can be used as necessary. Examples of the catalyst include salts of metals and organic and inorganic acids such as dibutyltin laurate, dioctyltin laurate, stannous octoate, zinc octylate, and tetra n-butyl titanate, and organic metal derivatives such as triethylamine. Examples thereof include amines and diazabicycloundecene catalysts.

In addition, the biourethane resin used in the present invention may be synthesized without a solvent or may be synthesized using an organic solvent if necessary. Preferred organic solvents used in this case include those that are inert to isocyanate groups or less active than the reaction components. For example, ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), aromatic hydrocarbon solvents (toluene, xylene, swazol (aromatic hydrocarbon solvents manufactured by Cosmo Oil Co., Ltd.)), Solvesso (Exxon Chemical Co., Ltd.) Company-made aromatic hydrocarbon solvent)), aliphatic hydrocarbon solvent (n-hexane etc.), alcohol solvent (methanol, ethanol, isopropanol etc.), ether solvent (dioxane, tetrahydrofuran etc.), ester type Solvents (ethyl acetate, butyl acetate, isobutyl acetate, etc.), glycol ether ester solvents (ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3 Ethoxypropionate, etc.), amide solvents (dimethylformamide, dimethyl acetamide), lactam solvent (n- methyl-2-pyrrolidone, etc.). In particular, it is preferable to use plant-derived materials (ethanol, butanol, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, etc.) as part of the organic solvent used in the synthesis. As mentioned earlier, this way, in the process of producing synthetic artificial leather by applying and drying the paint containing the synthesized biourethane resin, even in the case where the evaporated organic solvent is recovered and incinerated This can contribute to the reduction of CO ₂ emissions.

  In addition, in the synthetic | combination process of the said biourethane resin, when an isocyanate group remains in a polymer terminal, you may add the termination reaction of an isocyanate terminal. For example, not only monofunctional compounds such as monoalcohols and monoamines, but also compounds having two functional groups having different reactivities with respect to isocyanate can be used. For example, monoalcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol; monoethylamine, n-propylamine, diethylamine, di-n-propylamine, Examples thereof include monoamines such as di-n-butylamine; alkanolamines such as monoethanolamine and diethanolamine, and among these, alkanolamines are preferable because of easy reaction control.

  In the production of the biourethane resin, additives may be added as necessary. For example, antioxidants (hindered phenols, phosphites, thioethers, etc.), light stabilizers (hindered amines, etc.), UV absorbers (benzophenones, benzotriazoles, etc.), gas discoloration stabilizers (hydrazines, etc.) ), Hydrolysis inhibitors (such as carbodiimide), metal deactivators (such as hydrazine), and combinations of two or more of these. Furthermore, designability imparting agents (organic fine particles, inorganic fine particles), organic pigments, inorganic pigments, antifungal agents, flame retardants and other additives can be used as appropriate. Examples of the organic fine particles and inorganic fine particles include silica, silicone resin fine particles, fluororesin fine particles, acrylic resin fine particles, silicone-modified urethane resin fine particles, polyethylene resin fine particles, and reactive siloxane.

  When manufacturing the biourethane resin used by this invention, it is preferable to mix | blend each component used for a synthesis | combination as follows. Plant-derived polyol component, biopolycarbonate polyol (A), biopolyester polyol (B) and biopolyether polyol (C) are used in an amount of 10 to 100% by mass and used as necessary. The short-chain diol component (a) and the petroleum-derived diol component and / or diamine component (e) to be used as necessary are 0 to 30% by mass (provided that the total amount of these reaction components is 100% by mass) %)), And used in these proportions. And when these reaction components and polyisocyanate compound (d) are reacted so that all active hydrogens in these reaction components and the isocyanate groups are approximately equimolar (0.9 to 1.5). Good.

  In this invention, it is necessary to use the biourethane resin comprised so that content of a plant-derived component may be 28 to 95 mass%, Preferably it is 39 to 95 mass%. This is because the higher the content of plant-derived components, the more carbon neutral that is a feature of the present invention can be realized. The molecular weight of the biourethane resin used in the synthetic artificial leather of the present invention is preferably in the range of 2,000 to 500,000 in terms of weight average molecular weight (measured by GPC, converted to standard polystyrene).

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples of intermediates, but the present invention is not limited to these. In the following text, “part” and “%” are based on mass unless otherwise specified.

<Synthesis of polyol>
[Polyester polyol synthesis example PES1]
After replacing the reaction vessel equipped with a stirrer, fractionator, thermometer, nitrogen blowing tube and manhole with nitrogen gas, 1,500 parts of sebacic acid (from castor oil) and 1,3-propanediol (from plant) 645 parts were charged and dissolved by heating to 130 ° C. in a nitrogen atmosphere. Thereafter, 0.21 part of tetrabutoxytitanium was added, the temperature was raised to 230 ° C., the reaction was carried out while distilling off the generated water, and the reaction was carried out until there was almost no distilling of water. While reducing the pressure and further distilling off the water, heating and depressurization were continued until the acid value became 0.5 mgKOH / g or less. Thus, 100% plant-derived polyester polyol PES1 [plant-derived component content (hereinafter referred to as BP) = 100%] having a hydroxyl value of 56.5 mgKOH / g and an acid value of 0.3 mgKOH / g is obtained. It was. Table 1 shows properties of the synthetic raw materials and the obtained polyol.

[Polyester polyol synthesis example PES2]
After replacing the reaction vessel equipped with a stirrer, a fractionating tube, a thermometer, a nitrogen blowing tube and a manhole with nitrogen gas, 1,333 parts of sebacic acid (derived from castor oil) and 1,3-propanediol (derived from plant) 547 parts were charged and dissolved by heating to 130 ° C. in a nitrogen atmosphere. Thereafter, 0.19 part of tetrabutoxytitanium was added, the temperature was raised to 230 ° C., and the reaction was carried out while distilling out the generated water, and the reaction was carried out until there was almost no distilling of water. While reducing the pressure and further distilling off the water, heating and depressurization were continued until the acid value became 0.5 mgKOH / g or less. In this way, 100% plant-derived polyester polyol PES2 (BP = 100%) having a hydroxyl value of 36.2 mgKOH / g and an acid value of 0.3 mgKOH / g was obtained. Table 1 shows properties of the synthetic raw materials and the obtained polyol.

[Polyester polyol synthesis example PES3]
After replacing the reaction vessel equipped with a stirrer, a fractionating tube, a thermometer, a nitrogen blowing tube and a manhole with nitrogen gas, 750 parts of sebacic acid (derived from castor oil), 750 parts of succinic acid (derived from plant), 1, 3-Propanediol (plant-derived) 855 parts was charged and dissolved by heating to 130 ° C. in a nitrogen atmosphere. Thereafter, 0.23 part of tetrabutoxytitanium was added, and the reaction was carried out while raising the temperature up to 230 ° C. while distilling out the generated water, and the reaction was carried out until almost no water was distilled out. While reducing the pressure and further distilling off the water, heating and depressurization were continued until the acid value became 0.5 mgKOH / g or less. Thus, 100% plant-derived polyester polyol PES3 (BP = 100%) having a hydroxyl value of 56.9 mgKOH / g and an acid value of 0.3 mgKOH / g was obtained. Table 1 shows properties of the synthetic raw materials and the obtained polyol.

[Polycarbonate polyol synthesis example PC1]
After replacing the reaction vessel equipped with a stirrer, a fractionating tube, a thermometer, a nitrogen blowing tube and a manhole with nitrogen gas, 450 parts of 1,3-propanediol (plant-derived) and 533 parts of dimethyl carbonate (1,3 -Equimolar with respect to propanediol) and 0.1 part of tetrabutoxytitanium, and in a nitrogen atmosphere, the temperature was raised to 180 ° C. and the reaction was carried out while distilling methanol, so that almost no methanol was distilled off. Reacted until. The generated methanol and excess dimethyl carbonate were removed under reduced pressure. In this way, polycarbonate polyol PC1 (BP = 73%) having a hydroxyl value of 59.5 mgKOH / g was obtained. Table 1 shows properties of the synthetic raw materials and the obtained polyol.

[Polycarbonate polyol synthesis example PC2]
After replacing the reaction vessel equipped with a stirrer, a distillation tube, a thermometer, a nitrogen blowing tube and a manhole with nitrogen gas, 390 parts of 1,3-propanediol (plant-derived) and 605 parts of diethyl carbonate (1,3 -Equimolar with respect to propanediol) and 0.1 part of tetrabutoxytitanium, and in a nitrogen atmosphere, the temperature was raised to 200 ° C. and the reaction was conducted while distilling ethanol, so that almost no ethanol was distilled. Reacted until. The generated ethanol and excess diethyl carbonate were removed under reduced pressure. In this way, polycarbonate polyol PC2 (BP = 73%) having a hydroxyl value of 56.1 mgKOH / g was obtained. Table 1 shows properties of the synthetic raw materials and the obtained polyol.

[Polycarbonate polyol synthesis example PC3]
After replacing the reaction vessel equipped with a stirrer, a fractionating tube, a thermometer, a nitrogen blowing tube and a manhole with nitrogen gas, 465 parts of 1,3-propanediol (plant-derived) and 538 parts of ethylene carbonate (1,3 -Equimolar to propanediol), and dissolved in a nitrogen atmosphere by raising the temperature to 70 ° C. Thereafter, 0.1 part of tetrabutoxytitanium was charged, the temperature was raised to 220 ° C. while distilling out the diol, and the reaction was continued until almost no distilling of the diol occurred. The generated diol and excess ethylene carbonate were removed under reduced pressure. In this way, polycarbonate polyol PC3 (BP = 73%) having a hydroxyl value of 60.2 mgKOH / g was obtained. Table 1 shows properties of the synthetic raw materials and the obtained polyol.

[Polycarbonate polyol synthesis example PC4]
After replacing the reaction vessel equipped with a stirrer, a fractionating tube, a thermometer, a nitrogen blowing tube and a manhole with nitrogen gas, 260 parts of 1,3-propanediol (plant-derived) and 733 parts of diphenyl carbonate (1,3 -Equimolar with respect to propanediol) and dissolved in a nitrogen atmosphere by raising the temperature to 150 ° C. Thereafter, 0.1 part of tetrabutoxytitanium was charged, the pressure was reduced while raising the temperature to 220 ° C., and the reaction was carried out while distilling out phenol. Furthermore, the temperature was raised to 250 ° C., and the reaction was carried out at an increased vacuum. The generated phenol and excess diphenyl carbonate were removed under reduced pressure at 270 ° C. In this way, polycarbonate polyol PC4 (BP = 73%) having a hydroxyl value of 55.8 mgKOH / g was obtained. Table 1 shows properties of the synthetic raw materials and the obtained polyol.

[Polycarbonate polyol synthesis example PC5]
After replacing the reaction vessel equipped with a stirrer, a fractionating tube, a thermometer, a nitrogen blowing tube and a manhole with nitrogen gas, 425 parts of 1,3-propanediol (plant-derived), 25 parts of 1,4-butanediol, In a nitrogen atmosphere, 25 parts of 1,5-pentanediol, 25 parts of 1,6-hexanediol, 569 parts of dimethyl carbonate (equimolar to all diols), and 0.1 part of tetrabutoxytitanium were charged. The temperature was raised to 180 ° C. and the reaction was carried out while distilling methanol, and the reaction was continued until almost no methanol was distilled off. The generated methanol and excess dimethyl carbonate were removed under reduced pressure. Thus, polycarbonate polyol PC5 (BP = 53%) having a hydroxyl value of 58.7 mgKOH / g was obtained.

[Polycarbonate polyol synthesis example PC6]
After replacing a reaction vessel equipped with a stirrer, a fractionating tube, a thermometer, a nitrogen blowing tube and a manhole with nitrogen gas, 500 parts of 1,4-butanediol (plant-derived) and 500 parts of dimethyl carbonate (1,4 -Equimolar with respect to butanediol) and 0.1 part of tetrabutoxytitanium, and in a nitrogen atmosphere, the temperature was raised to 180 ° C. and the reaction was carried out while distilling methanol, and almost no methanol was distilled off. Reacted until. The generated methanol and excess dimethyl carbonate were removed under reduced pressure. In this way, polycarbonate polyol PC6 (BP = 76%) having a hydroxyl value of 59.7 mgKOH / g was obtained.

<Synthesis of polyurethane>
Polyester polyurethane was synthesized using each of the polyols containing the plant-derived components synthesized above.
[Urethane Example 1: Polyester polyurethane synthesis example PES-PU1]
After replacing the reaction vessel equipped with a stirrer, a cooling tube, a thermometer, a nitrogen blowing tube and a manhole with nitrogen gas, 100 parts of polyester polyol PES1, 15 parts of ethylene glycol, and 282 parts of DMF (dimethylformamide) were charged. Warmed to 70 ° C. Here, 73 parts of MDI (methylenebis (4-phenylisocyanate)) (a hydroxyl group and an isocyanate group are equivalent) were added, and the mixture was heated and stirred until there was no isocyanate absorption in the IR spectrum. Thereafter, 157 parts of DMF was added to obtain a polyester polyurethane resin solution PES-PU1 (BP = 53%) having a solid content of 30%.

[Urethane Example 2: Synthesis Example of Polyester Polyurethane PES-PU2]
After replacing the reaction vessel equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, 100 parts of the polyester polyol PES1 synthesized earlier and 15 parts of 1,3-propanediol (plant-derived) were used. Part, 197.5 parts of DMF, and 82.5 parts of IPDI (isophorone diisocyanate) (the ratio of isocyanate group to hydroxyl group is 1.5) were heated and stirred at 90 ° C. When NCO% reached the theoretical value, it was cooled to 20 ° C., 21 parts of IPDA (isophoronediamine) and 312 parts of DMF were added to carry out a chain elongation reaction, and a polyester polyurethane resin solution PES-PU2 (BP having a solid content of 30%) = 53%).

[Urethane Example 3: Synthesis Example of Polyester Polyurethane PES-PU3]
After replacing the reaction vessel equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, 200 parts of polyester polyol PES2 and 90.5 parts of DMF were charged and heated to 70 ° C. To this, 11.2 parts of TDI (tolylene diisocyanate) (hydroxyl group and isocyanate group are equivalent) was added, and the mixture was heated and stirred until there was no absorption of isocyanate in the IR spectrum. -PU3 (BP = 95%) was obtained.

[Urethane Comparative Example 1: Synthesis Example of Polyester Polyurethane PES-PU4]
After replacing a reactor equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, a petroleum-derived polyester polyol (1,4-butanediol / adipic acid condensate, molecular weight 3,000) 200 parts and DMF 90.5 parts were charged and heated to 70 ° C. 11.2 parts of TDI (hydroxyl group and isocyanate group equivalent) was added thereto, and the mixture was heated and stirred until there was no isocyanate absorption in the IR spectrum. Polyester polyurethane resin solution PES-PU4 (BP = 0) with a solid content of 70% %).

[Urethane Example 4: Polyester polyurethane synthesis example PES-PU5]
After replacing the reactor equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, 100 parts of polyester polyol PES3, 4 parts of 1,3-propanediol (plant-derived), DMF 138.4 parts of IPDI and 34.4 parts of IPDI were added (the ratio of isocyanate groups to hydroxyl groups was 1.5), and the mixture was heated and stirred at 90 ° C. When NCO% reaches the theoretical value, it is cooled to 20 ° C., IPDA 8.8 parts and DMF 312 parts are added to carry out chain elongation reaction, and a 30% solid content polyester polyurethane resin solution PES-PU5 (BP = 52%) Got.

[Urethane Example 5: Polyester polyurethane synthesis example PES-PU6]
After replacing the reaction vessel equipped with a stirrer, cooling tube, thermometer, nitrogen blowing tube and manhole with nitrogen gas, 100 parts of polylactic acid polyol (molecular weight 2,000, derived from plant), 15 parts of ethylene glycol, DMF 282 parts of (dimethylformamide) was charged and heated to 70 ° C. Here, 73 parts of MDI (methylenebis (4-phenylisocyanate)) (a hydroxyl group and an isocyanate group are equivalent) were added, and the mixture was heated and stirred until there was no isocyanate absorption in the IR spectrum. Thereafter, 157 parts of DMF was added to obtain a polyester polyurethane resin solution PES-PU6 (BP = 53%) having a solid content of 30%.

Table 2-1 summarizes the properties of each component used in the synthesis and the resulting polyester polyurethane.

Polycarbonate polyurethane was synthesized using each of the polyols containing the plant-derived component synthesized above.
[Urethane Example 6: Polycarbonate polyurethane synthesis example PC-PU1]
After replacing the reaction vessel equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, 100 parts of polycarbonate polyol PC1, 15 parts of ethylene glycol and 284 parts of DMF were charged and heated to 70 ° C. Warm up. To this, 74 parts of MDI (hydroxyl group and isocyanate group are equivalent) was added, and the mixture was heated and stirred until there was no isocyanate absorption in the IR spectrum. Thereafter, 157 parts of DMF was added to obtain a polycarbonate polyurethane resin solution PC-PU1 (BP = 39%) having a solid content of 30%.

[Urethane Examples 7 to 11: Synthesis Examples of Polycarbonate Polyurethanes PC-PU2 to 6]
After replacing the reaction vessel equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, the polycarbonate polyol PC1 used in Synthesis Example PC-PU1 was replaced with PC2, PC3, PC4, PC5, In place of 100 parts of polycarbonate polyol of PC6, 15 parts of ethylene glycol and DMF having a solid content of 40% were charged and heated to 70 ° C. MDI was added thereto so that the hydroxyl group and the isocyanate group were equivalent, and the mixture was heated and stirred until there was no isocyanate absorption in the IR spectrum. Thereafter, DMF is added to obtain a polycarbonate polyurethane resin solution PC-PU2-4 (BP = 39%), PC-PU5 (BP = 28%) and PC-PU6 (BP = 40%) having a solid content of 30%. It was.

[Urethane Example 12: Synthesis Example of Polycarbonate Polyurethane PC-PU7]
After replacing a reactor equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, 100 parts of polycarbonate polyol PC1, 15 parts of 1,3-propanediol (plant-derived), and DMF 198 parts and 83 parts of IPDI (with a ratio of isocyanate group to hydroxyl group of 1.5) were charged, and the mixture was heated and stirred at 90 ° C. When NCO% reaches the theoretical value, it is cooled to 20 ° C., and 21 parts of IPDA and 313 parts of DMF are added to carry out chain elongation reaction to obtain a polycarbonate polyurethane resin solution PC-PU7 (BP = 40%) having a solid content of 30%. It was.

[Urethane Examples 13-17: Synthesis Examples of Polycarbonate Polyurethane PC-PU8-12]
After replacing the reaction vessel equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, the polycarbonate polyol PC1 used in Synthesis Example PC-PU5 was respectively PC2, PC3, PC4, PC5, In place of 100 parts of polycarbonate polyol of PC6, 15 parts of 1,3-propanediol (plant-derived), DMF having a solid content of 50%, and IPDI having a ratio of isocyanate groups to hydroxyl groups of 1.5 were charged at 90 ° C. And stirred with heating. When NCO% reaches the theoretical value, it is cooled to 20 ° C., IPDA and DMF equivalent to isocyanate are added to carry out chain elongation reaction, and a polycarbonate polyurethane resin solution PC-PU8-10 (BP = 10%) with a solid content of 30%. 40%) and PC-PU11 (BP = 31%) and PC-PU12 (BP = 41%) were obtained.

[Urethane Example 18: Polycarbonate polyurethane synthesis example PC-PU13]
After replacing a reactor equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, 100 parts of polycarbonate polyol PC1, 15 parts of 1,3-propanediol (plant-derived), and DMF 340 parts and 225 parts of DDI (dimer acid diisocyanate) having a ratio of isocyanate group to hydroxyl group of 1.5 were charged and stirred at 90 ° C. with heating. When NCO% reaches the theoretical value, it is cooled to 20 ° C., and 21 parts of IPDA and 502 parts of DMF are added to carry out a chain extension reaction to obtain a polycarbonate polyurethane resin solution PC-PU13 (BP = 77%) having a solid content of 30%. It was.

[Urethane Example 19: Synthesis Example of Polycarbonate Polyurethane PC-PU14]
After replacing a reactor equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, 100 parts of polycarbonate polyol PC1, 15 parts of 1,3-propanediol (plant-derived), and DMF 198 parts and 83 parts of IPDI (with a ratio of isocyanate group to hydroxyl group of 1.5) were charged, and the mixture was heated and stirred at 90 ° C. When NCO% reaches the theoretical value, it is cooled to 20 ° C., 21 parts of IPDA and 313 parts of ethyl lactate are added to carry out a chain elongation reaction, and a polycarbonate polyurethane resin solution PC-PU14 (BP = 40%) having a solid content of 30% Got. In addition, the content rate of the organic solvent (bio solvent) derived from a plant was 61%.

[Urethane Comparative Example 2: Polycarbonate Polyurethane Synthesis Example PC-PU15]
After replacing the reaction vessel equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, petroleum-derived CD-220 (manufactured by Daicel Chemical Industries, Ltd., 1,6-hexane carbonate diol, 100 parts of an average molecular weight (2,000), 15 parts of ethylene glycol, and 284 parts of DMF were charged and heated to 70 ° C. To this, 74 parts of MDI (hydroxyl group and isocyanate group are equivalent) was added, and the mixture was heated and stirred until there was no isocyanate absorption in the IR spectrum. Thereafter, 157 parts of DMF was added to obtain a polycarbonate polyurethane resin solution PC-PU15 (BP = 0%) having a solid content of 30%.

  Tables 2-2 and 2-3 collectively show the components used in the synthesis and the properties of the obtained polycarbonate polyurethane.

[Urethane Example 20: Synthesis Example WB-PU1 of Water-dispersed Polyurethane]
After replacing the reactor equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, 100 parts of polycarbonate polyol PC1, 7.1 parts of dimethylolpropanoic acid and 35.3 parts of IPDI (The ratio of isocyanate group to hydroxyl group was 1.5), and the mixture was heated and stirred at 90 ° C. When the NCO% reached the theoretical value, it was cooled to 40 ° C., and 5.3 parts of triethylamine was added. When uniform, 348 parts of deionized water was gradually added with vigorous stirring to disperse the prepolymer in water. A liquid was prepared. Subsequently, 9 parts of IPDA was added to carry out a chain elongation reaction to obtain a water-dispersed polycarbonate polyurethane resin WB-PU1 (BP = 48%) having a solid content of 30%. Table 2-4 shows the properties of each component used in the synthesis and the resulting polyurethane.

[Urethane Example 21: Synthesis Example of Thermoplastic Polycarbonate Polyurethane PC-TPU1]
100 parts of polycarbonate polyol PC1, 15 parts of 1,3-propanediol (plant-derived) and 63 parts of MDI (equal hydroxyl group and isocyanate group) are uniformly stirred and poured into a tray and reacted at 100 ° C. I let you. The obtained reaction product was pulverized and then pelletized at 200 to 230 ° C. using an extruder to obtain pellets of thermoplastic polycarbonate polyurethane PC-TPU1 (BP = 41%). Table 2-4 shows the properties of each component used in the synthesis and the resulting polyurethane.

[Urethane Example 22: Synthesis Example of Thermoplastic Polyester Polyurethane PES-TPU1]
100 parts of polyester polyol PES1, 15 parts of 1,3-propanediol (plant-derived) and 62 parts of MDI (hydroxyl group and isocyanate group are equivalent) are uniformly stirred, poured into a tray and reacted at 100 ° C. I let you. The obtained reaction product was pulverized and then pelletized at 200 to 230 ° C. using an extruder to obtain pellets of thermoplastic polyester polyurethane PES-TPU1 (BP = 65%). Table 2-4 shows the properties of each component used in the synthesis and the resulting polyurethane.

[Urethane Example 23: Synthesis example PE-TPU1 of thermoplastic polyether polyurethane]
Polytetramethylene glycol ether polyol (molecular weight 2,000, plant-derived) 100 parts, 1,3-propanediol (plant-derived) 15 parts, MDI 62 parts (hydroxyl group and isocyanate group equivalent) were stirred uniformly. The mixture was poured into a tray and reacted at 100 ° C. The obtained reaction product was pulverized and then pelletized at 200 to 230 ° C. using an extruder to obtain pellets of thermoplastic polyether polyurethane PE-TPU1 (BP = 65%). Table 2-4 shows the properties of each component used in the synthesis and the resulting polyurethane.

The chemical formula of the polytetramethylene glycol ether polyol used here is HO— (CH ₂ CH ₂ CH ₂ CH ₂ O) _n —H, and n is an integer having a molecular weight of 2,000.

[Urethane Example 24: Synthesis Example of Polyether Polyurethane PE-PU1]
After replacing the reaction vessel equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen blowing pipe and a manhole with nitrogen gas, 100 parts of poly (trimethylene / tetramethylene) glycol ether polyol (plant-derived, molecular weight 2,000), 1 , 3-propanediol (plant-derived) 15 parts and DMF 265 parts were charged and heated to 70 ° C. The poly (trimethylene / tetramethylene) glycol ether polyol used above is obtained by copolymerization of plant-derived 1,3-propanediol with plant-derived molecular weight of 1,000 methylene glycol. Here, 62 parts of MDI (hydroxyl group and isocyanate group are equivalent) were added, and the mixture was heated and stirred until there was no isocyanate absorption in the IR spectrum. Thereafter, 148 parts of DMF was added to obtain a polyether polyurethane resin solution PE-PU1 (BP = 65%) having a solid content of 30%. Table 2-4 shows the properties of each component used in the synthesis and the resulting polyurethane.

[Urethane Example 25: Synthesis Example of Polyester Polyurethane Beads PES-BZ1]
A polyol having a hydroxyl value of 119.5 mgKOH / g and a bifunctional oil-modified polyol (Uric Y-202, manufactured by Ito Oil Co., Ltd.) and 100 parts of n-octane were charged into a synthetic kettle equipped with a stirrer. Was dissolved. While stirring, the temperature was controlled at 50 ° C., 47.3 parts of IPDI prepared in advance so that NCO / OH = 2 was gradually added over 1 hour, and the reaction was continued for 3 hours under these conditions. The reaction was performed at 3 ° C. for 3 hours. Next, the concentration was adjusted to 50% with n-octane to obtain a prepolymer solution (PP-1) containing 3.0% of NCO groups. Its molecular weight is 1,383.

  40 parts of the prepolymer solution (PP-1) and 60 parts of n-octane were charged into a synthesis kettle equipped with a stirrer and dissolved. While controlling the temperature to 70 ° C. while stirring, 24.3 parts of a 10% solution of n-octane of isophoronediamine prepared in advance was gradually added over 5 hours to complete the reaction, and (polyamine (urea bond part) ) / Prepolymer chain) × 100 = 12.15% polyurea colloid solution (C-1: solid content 18.0%) was obtained. This solution was a blue opalescent stable solution.

  40 parts of the previously obtained polyester polyol PES1 was dissolved at 60 ° C., and further, isocyanurate polyisocyanate of hexamethylene diisocyanate represented by the following structural formula (manufactured by Asahi Kasei Kogyo Co., Ltd., Duranate TPA-100, NCO% = 7.3 parts of 23.1) was added and mixed uniformly. This was gradually added to a mixture of 5.0 parts of the previously obtained polyurea colloid solution (C-1) and 25 parts of n-octane prepared in a 1 liter stainless steel container, and homogenizer. And emulsified for 15 minutes. This emulsion was a stable emulsion having an average dispersoid particle size of 5 μm, no separation, and no separation.

  Next, this was charged in a reaction kettle equipped with a vertical stirrer, the temperature was raised to 80 ° C. while rotating at a speed of 400 rpm, the reaction for 6 hours was completed, and a solution of biopolyurethane beads was obtained. This solution was vacuum-dried at 100 Torr to separate n-octane to obtain biopolyurethane beads PES-BZ1 (BP = 85%). This was a spherical white powder having an average particle diameter of 5 μm and a circularity of 0.92. The compressive strength was 0.35 MPa and the recovery rate was 89%. Table 2-4 shows the properties of each component used in the synthesis and the resulting polyurethane.

<Making synthetic artificial leather>
[Wet processing method]
Example 1
(Base material creation)
An impregnating liquid composition liquid (impregnating liquid composition 1) was prepared with the following formulation, and after the liquid was sufficiently impregnated into the nonwoven fabric, it was dried and thermally cured at 130 ° C. to give flexibility, A nonwoven fabric was made.

[Formulation of impregnation liquid composition 1]
・ Rezamin CUT-270W (manufactured by Dainichi Seika Kogyo) 100 parts ・ Rezamin CUT-275C (manufactured by Dainichi Seika Kogyo Co., Ltd.) 75 parts

  First, a wet composition liquid (wet compound liquid composition 2) was prepared according to the following formulation including the polycarbonate polyurethane resin solution PC-PU1 synthesized in Urethane Example 6. And after impregnating the nonwoven fabric obtained above and wet coagulating, it passed through washing | cleaning and a drying process, and also buffed the surface part of the skin in order to provide surface smoothness. As a result, an impregnated nonwoven fabric having a very soft texture was obtained. The urethane resin solution and the DMF in the coagulation tank were produced by a system that was recovered.

[Wet compounding liquid composition 2]
・ PC-PU1 (carbonate PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ Rezamin CUT-30 (wet additive, manufactured by Dainichi Seika Kogyo Co., Ltd.) 2 parts ・ Rezamin CUT-107 (wet additive, Dainichi Seika) 3 parts ・ Rezamin CUT-250 (wet additive, manufactured by Dainichi Seika Kogyo) 1 part ・ DMF 250 parts

  On the surface of the impregnated nonwoven fabric obtained above, the composition 3 prepared by the following formulation containing the water-dispersed polycarbonate polyurethane resin WB-PU1 obtained in Urethane Example 20 was directly applied by gravure printing. In that case, it apply | coated so that the thickness after drying might be set to 20 micrometers. After coating, the solvent (ion exchange water) was dried in a dryer to form a skin layer. Thereafter, a composition 4 for treating the surface is further prepared by the following formulation, and this is coated and dried with a gravure coater to form a surface treatment layer having a dry thickness of 5 μm, thereby obtaining a synthetic artificial leather 1. It was. Composition 4 contains WB-PU1 and biopolyurethane beads PES-BZ1 obtained in Urethane Example 25 during its formulation.

[Skin Formation Layer Composition Liquid Composition 3]
-100 parts of WB-PU1 (carbonate-based PUD, manufactured by Dainichi Seika Kogyo Co., Ltd.)-25 parts of Seika Seven DW-794 Black-Ion-exchanged water (in which the solid content is 20%) Predetermined quantity

[Surface treatment layer compound liquid composition 4]
· WB-PU1 (carbonate PUD, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts · PES-BZ1 (ester ester PU beads, manufactured by Dainichi Seika Kogyo Co., Ltd.) 30 parts · WB40-100
(Asahi Kasei Chemicals Co., Ltd., water-dispersed isocyanate) 15 parts ・ Ion-exchanged water (Solid content 15%)

(Example 2)
On the raised cloth obtained by mechanically raising a cotton fabric made of plain weave, the wet blended liquid composition 2-2 was prepared with the following blended formulation containing the polycarbonate polyurethane resin solution PC-PU1 synthesized in Urethane Example 6. The coated layer was solidified in water to form a microporous layer having a thickness of 1,000 μm, washed with water and dried. Thereafter, on the obtained microporous layer, the skin layer compounded liquid composition 5 was applied and dried with a knife coater with the following formulation including the polycarbonate polyurethane resin solution PC-PU7 obtained in Urethane Example 12, and dried thickness. A 20 μm skin layer was formed. Next, the surface treatment layer combination liquid composition 6 was similarly applied and dried by a gravure coater with the following formulation including PC-PU7 to form a surface treatment layer having a dry thickness of 5 μm. Furthermore, the synthetic artificial leather 2 was produced by processing hot water with hot water at 100 ° C.

[Wet blended liquid composition 2-2]
・ PC-PU1 (carbonate PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ Rezamin CUT-30 (wet additive, manufactured by Dainichi Seika Kogyo Co., Ltd.) 2 parts ・ Rezamin CUT-107 (wet additive, Dainichi Seika) 3 parts · Rezamin CUT-250 (wet additive, manufactured by Dainichi Seika Kogyo Co., Ltd.) 1 part · Seika Seven BS-780 (s) Black 5 parts · DMF 150 parts

[Skin forming layer composition liquid composition 5]
・ PC-PU7 (carbonate PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ Seika Seven BS-780 (s) Black 20 parts ・ MEK / DMF = 1/1 (amount that solid content becomes 20%) Predetermined amount

[Surface Treatment Layer Compound Liquid Composition 6]
・ PC-PU7 (carbonate-based PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ PES-BZ1 (ester-based PU beads, manufactured by Dainichi Seika Kogyo Co., Ltd.) 30 parts ・ MEK / DMF = 1/1 (solid content 10) %) Predetermined amount

(Example 3)
A wet blending solution having the following composition containing polycarbonate polyols PC-PU2, PC-PU3, and PC-PU4 obtained in Urethane Examples 7 to 9 on a raised cloth obtained by mechanically raising a cotton fabric made of plain weave. Composition 7 was applied. Then, the coating layer was solidified in water to form a 1,000 μm-thick microporous layer, washed with water and dried to prepare a moisture layer forming base fabric. Next, on the release paper (DE139 Dai Nippon Printing Co., Ltd.), the skin layer composition 8 containing polycarbonate polyol PC-PU8, PC-PU9, PC-PU10 obtained in Urethane Examples 13 to 15 was applied, A skin layer having a thickness of 20 μm was formed by drying, and heat release was performed on the microporous layer at 150 ° C. to release the release paper, thereby obtaining a synthetic artificial leather. Furthermore, the surface treatment layer compounded liquid composition 6 containing the polycarbonate polyol PC-PU7 obtained in Urethane Example 12 is applied and dried by a gravure coater to form a surface treatment layer having a dry thickness of 5 μm, thereby producing a synthetic artificial leather 3 did.

[Wet compounding liquid composition 7]
・ PC-PU2 (carbonate-based PU, manufactured by Dainichi Chemical Industries) 50 parts ・ PC-PU3 (carbonate-based PU, manufactured by Dainichi Chemical Industries) 25 parts ・ PC-PU4 (carbonate-based PU, Dainichi Chemical Industries) Made by) 25 parts · Rezamin CUT-30 (wet additive, manufactured by Dainichi Chemical Industries Co., Ltd.) 2 parts · Rezamin CUT-107 (wet additive, made by Dainichi Chemical Industries Co., Ltd.) 3 parts · Resamine CUT-250 modified (wet type) Additive, manufactured by Dainichi Seika Kogyo Co., Ltd.) 1 part Seika Seven BS-780 (s) Black 5 parts DMF 150 parts

[Skin Layer Compound Liquid Composition 8]
・ PC-PU8 (carbonate-based PU, manufactured by Dainichi Chemical Industries) 50 parts ・ PC-PU9 (carbonate-based PU, manufactured by Dainichi Chemical Industries) 25 parts ・ PC-PU10 (carbonate-based PU, Dainichi Chemical Industries) 25 parts / Seika Seven BS-780 (s) Black 20 parts / MEK / DMF = 1/1 (amount of solid content 20%) Predetermined amount

[Surface Treatment Layer Compound Liquid Composition 6]
・ PC-PU7 (carbonate-based PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ PES-BZ1 (ester-based PU beads, manufactured by Dainichi Seika Kogyo Co., Ltd.) 30 parts ・ MEK / DMF = 1/1 (solid content 10) %) Predetermined amount

[Dry processing method]
Example 4
On release paper (DE139 Dai Nippon Printing Co., Ltd.), the skin layer compounded liquid composition 5 containing polycarbonate polyol PC-PU7 obtained in Urethane Example 12 is applied and dried to form a skin layer having a thickness of 20 μm. did. On the formed skin layer, the adhesive layer compounded liquid composition 9 containing the polyester polyurethane resin solution PES-PU3 obtained in Urethane Example 3 was applied to form an adhesive layer having a thickness of 200 μm, and this was dried laminate ( It was transferred onto a raised cloth in accordance with the conditions of 150 ° C. and clearance = 0). The surface treatment layer compounded liquid composition 6 containing the polycarbonate polyol PC-PU7 obtained in Urethane Example 12 was applied and dried with a gravure coater to form a surface treatment layer having a dry thickness of 5 μm to produce a synthetic artificial leather 4 did.

[Skin Layer Compound Liquid Composition 5]
・ PC-PU7 (carbonate PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ Seika Seven BS-780 (s) Black 20 parts ・ MEK / DMF = 1/1 (amount that solid content becomes 20%) Predetermined amount

[Adhesive layer compound liquid composition 9]
・ PES-PU3 (ester PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ Rezamin UD-crosslinking agent (polyisocyanate cross-linking agent, manufactured by Dainichi Seika Kogyo Co., Ltd.) 10 parts ・ MEK / DMF = 1/1 (solid Amount that makes 40%) Predetermined amount

[Surface treatment layer blend composition 6]
・ PC-PU7 (carbonate-based PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ PES-BZ1 (ester-based PU beads, manufactured by Dainichi Seika Kogyo Co., Ltd.) 30 parts ・ MEK / DMF = 1/1 (solid content 10) %) Predetermined amount

[TPU leather method]
(Example 5)
A 300 μm thick sheet was prepared by calendering (150 ° C.) the TPU sheet blending composition 10 containing the thermoplastic polyester polyurethane PES-TPU1 obtained in Urethane Example 22. The surface treatment layer compound liquid composition 6 containing polycarbonate polyol PC-PU7 is applied to the sheet by gravure printing to a thickness of 10 μm, dried, and then subjected to a texture process (180 ° C). The synthetic | combination artificial leather 5 was produced by apply | coating the adhesive layer compound liquid composition 9 containing the polyester polyurethane resin solution PES-PU3 to this so that it might become thickness of 30 micrometers with a gravure coater, and bonding a base material.

[TPU sheet blending composition 10]
・ 100 parts of PES-TPU1 ・ 10 parts of Dymic SZ-7740 Black

[Surface Treatment Layer Compound Liquid Composition 6]
・ PC-PU7 (carbonate-based PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ PES-BZ1 (ester-based PU beads, manufactured by Dainichi Seika Kogyo Co., Ltd.) 30 parts ・ MEK / DMF = 1/1 (solid content 10) %) Predetermined amount

[Adhesive layer compound liquid composition 9]
・ PES-PU3 (ester PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ Rezamin UD-crosslinking agent (polyisocyanate cross-linking agent, manufactured by Dainichi Seika Kogyo Co., Ltd.) 10 parts ・ MEK / DMF = 1/1 (solid Amount that makes 40%) Predetermined amount

[TPU leather method]
(Example 6)
A 300 μm-thick sheet was prepared by calendering (150 ° C.) the TPU sheet blending composition 11 containing the thermoplastic polyether polyurethane PE-TPU1 obtained in Urethane Example 23. The surface treatment layer compound liquid composition 6 containing polycarbonate polyol PC-PU7 is applied to the sheet by gravure printing to a thickness of 10 μm, dried, and then subjected to a texture process (180 ° C). The synthetic | combination artificial leather 6 was produced by apply | coating the adhesive layer compound liquid composition 9 containing the polyester polyurethane resin solution PES-PU3 to this so that it might become thickness of 30 micrometers with a gravure coater, and bonding a base material.

[TPU sheet blending composition 11]
・ PE-TPU1 (ether PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ Dymic SZ-7740 black 10 parts

[Surface Treatment Layer Compound Liquid Composition 6]
・ PC-PU7 (carbonate-based PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ PES-BZ1 (ester-based PU beads, manufactured by Dainichi Seika Kogyo Co., Ltd.) 30 parts ・ MEK / DMF = 1/1 (solid content 10) %) Predetermined amount

[Adhesive layer compound liquid composition 9]
・ PES-PU3 (ester PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ Rezamin UD-crosslinking agent (polyisocyanate cross-linking agent, manufactured by Dainichi Seika Kogyo Co., Ltd.) 10 parts ・ MEK / DMF = 1/1 (solid Amount that makes 40%) Predetermined amount

(Comparative Example 1)
On the release layer (DE139 Dai Nippon Printing Co., Ltd.), the skin layer compound liquid composition 12 containing the polycarbonate polyurethane resin solution PC-PU15 obtained above is applied and dried to form a 20 μm thick skin layer. Then, an adhesive layer compound solution composition 13 containing the polyester polyurethane resin solution PES-PU4 was applied to form an adhesive layer having a thickness of 200 μm, and this was produced in accordance with the conditions of dry lamination (150 ° C., clearance = 0). Transferred onto a blanket. The surface treatment layer combination liquid composition 14 containing PC-PU15 was apply | coated and dried by this with the gravure coater, the surface treatment layer of dry thickness 5 micrometers was formed, and the synthetic artificial leather 7 was produced.

[Skin Layer Compound Liquid Composition 12]
-100 parts of PC-PU15 (carbonate-based PU, manufactured by Dainichi Seika Kogyo Co., Ltd.)-20 parts of Seika Seven BS-780 (s) black-MEK / DMF = 1/1 (amount that the solid content becomes 20%) Predetermined amount

[Adhesive layer compound liquid composition 13]
・ PES-PU4 (ester-based PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ Rezamin UD-crosslinking agent (polyisocyanate-based crosslinking agent, manufactured by Dainichi Seika Kogyo Co., Ltd.) 10 parts ・ MEK / DMF = 1/1 (solid Amount that makes 40%) Predetermined amount

[Surface treatment layer formulation 14]
・ PC-PU15 (carbonate PU, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ Dymic beads UCN-5070C (manufactured by Dainichi Seika Kogyo Co., Ltd.) 30 parts ・ MEK / DMF = 1/1 (with 10% solid content) Amount) Predetermined amount

  Each sample of synthetic artificial leather-like sheet obtained as described above was tested for bio-ratio, hydrolysis resistance, light resistance, heat resistance, texture, adhesive strength, cold bending resistance, abrasion resistance, etc. It was. The evaluation results are shown in Table 3 below.

<Evaluation>
The contents of each test item and the evaluation criteria at that time are shown below. The results are shown in Table 3.
[Bio ratio]
The ratio (bio ratio) of plant-derived components in the composition forming the synthetic artificial leather was calculated and evaluated.
(Evaluation criteria)
○: Bio ratio is 30% or more △: Bio ratio is 5% or more and less than 30% ×: Bio ratio is less than 5%

[Appearance and texture]
The produced synthetic artificial leather was visually evaluated according to the following criteria.
(Evaluation criteria)
1) Appearance ○: Good sensibility for viewing and close to natural leather tone ×: Not close to natural leather tone 2) Texture ○: There is volume and soft △: There is some volume, but middle Nothing ×: Hard thing without volume

[Cold-resistant bending]
Using a flexo testing machine, the change in performance was evaluated at 0 ° C. and 10,000 times of bending.
(Evaluation criteria)
○: No change △: Some cracks ×: Severe cracks

[Abrasion resistance test]
The produced synthetic artificial leather was tested with a wearer wheel H22, a load of 500 g, 100 times using a Taber wearer, and then visually evaluated for appearance.
(Evaluation criteria)
○: No change △: There is some wear ×: There is wear

[Adhesive strength]
In each synthetic artificial leather produced, the surfaces were affixed via an adhesive, and the adhesive strength was measured.
(Evaluation criteria)
○: 2 kg / cm or more Δ: 1 kg / cm or more and less than 2 kg / cm ×: less than 1 kg / cm

[Hydrolysis resistance]
About each produced synthetic | combination artificial leather, the jungle test (70 degreeC, relative humidity 95%, 3 weeks) in a hot and humid environment was done. The adhesive strength between the surface layer and the base material before and after the test was measured, and the strength retention compared with the initial strength was evaluated.
(Evaluation criteria)
○: Retention ratio is 60% or more Δ: Retention ratio is 30% or more and less than 60% ×: Retention ratio is less than 30%

[Light resistance]
Each synthetic artificial leather produced was subjected to a sunshine weatherometer test (63 ° C., no water, 120 hours) in a high-temperature dry environment. The adhesive strength between the surface layer and the base material before and after the test was measured, and the strength retention compared with the initial strength was evaluated.
(Evaluation criteria)
○: Retention ratio is 60% or more Δ: Retention ratio is 30% or more and less than 60% ×: Retention ratio is less than 30%

[Heat-resistant]
Each synthetic artificial leather produced was subjected to a test (120 ° C., 150 hours) in a gear oven. The adhesive strength between the surface layer and the base material before and after the test was measured, and the strength retention compared with the initial strength was evaluated.
(Evaluation criteria)
○: Retention ratio is 60% or more Δ: Retention ratio is 30% or more and less than 60% ×: Retention ratio is less than 30%

[VOC countermeasures]
The amount of the solvent released into the atmosphere in each synthetic artificial leather production process was calculated, and the ratio to the skin material was evaluated according to the following criteria.
(Evaluation criteria)
○: No organic solvent released into the atmosphere
Δ: Less than 5% of organic solvent released into the atmosphere ×: 5% or more of organic solvent released into the atmosphere

  However, the wet process (closed system) extracts DMF in water and does not release it into the atmosphere.

  Examples of the use of the synthetic artificial leather of the present invention include an ecological material that is a countermeasure against environmental problems using plant-derived raw materials in a high ratio, but artificial leather, synthetic leather, more specifically, shoes, bags Applicability to all products such as clothing, furniture, vehicle seats, miscellaneous goods can be expected. When the synthetic artificial leather of the present invention is used, the product is excellent in hydrolysis resistance, light resistance, heat resistance, texture, adhesive strength, cold bending resistance, wear resistance, and can be sufficiently put into practical use. Moreover, since the material is biomass and ecological material, it contributes to environmental problems.

Claims (10)

  In synthetic artificial leather comprising a base fabric and a skin layer constituting the core, at least the skin layer comprises a plant-derived short chain diol (a) and a petroleum-derived carbonate component (b) or a plant-derived carboxylic acid component ( c), a biopolycarbonate polyol (A) or a biopolyester polyol (B), a biopolyether polyol (C) comprising a plant-derived short-chain diol component (a), and an isocyanate A biopolyurethane resin obtained by reacting the component (d) and formed using a biopolyurethane resin in which the content of a plant-derived component is 28 to 95% by mass with respect to 100% by mass of the biopolyurethane resin. Synthetic artificial leather characterized by being.   The base fabric is either a woven fabric impregnated with a resin, a nonwoven fabric impregnated with a resin, or a fibrous base material on which a microporous layer of resin is formed, and these resins are The synthetic artificial leather according to claim 1, which is a biopolyurethane resin.   The bio-polyurethane resin further contains, as necessary, a plant-derived short-chain diol component (a) or a petroleum-derived diol component and / or a diamine component (e) as a reaction component. Synthetic artificial leather.   The biopolyurethane resin comprises the total active hydrogen-containing groups of the components (a), (A), (B), (C), and (e), and the isocyanate group of the component (d). The synthetic artificial leather according to any one of claims 1 to 3, which is obtained by reacting at an equivalent ratio of 0.9 to 1.5.   The short-chain diol component (a) is at least one selected from plant-derived ethylene glycol, 1,3-propanediol, and 1,4-butanediol. Synthetic artificial leather.   The synthetic artificial leather according to any one of claims 1 to 5, wherein the carboxylic acid component (c) is sebacic acid composed of a castor oil derivative derived from a plant and / or a succinic acid derived from a plant.   The synthetic artificial leather according to any one of claims 1 to 6, wherein the carbonate component (b) is at least one selected from dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, and diphenyl carbonate.   The isocyanate component (d) is at least one selected from the group consisting of diisocyanate components composed of derivatives of plant-derived components, dimer acid diisocyanate components derived from plants, polyisocyanate components derived from amino acids, and diisocyanate components derived from petroleum. The synthetic artificial leather according to any one of claims 1 to 7.   An organic solvent is used in the synthesis of the biopolyurethane resin or in forming a synthetic artificial leather using the biopolyurethane resin, and the organic solvent is derived from plants, ethanol, butanol, ethyl acetate, The synthetic artificial leather according to any one of claims 1 to 8, which is at least one selected from butyl acetate, ethyl lactate and butyl lactate.   The synthetic artificial leather according to any one of claims 1 to 9, which is used for a vehicle seat.