Polyurethane resins, paints, structures, and articles

Abstract

To provide a polyurethane resin capable of achieving both of excellent cold-resistant flexibility and chemical resistance.SOLUTION: A polyurethane resin contains a polyol component and an isocyanate component and satisfies following (1)-(3): (1) the polyurethane resin contains a polycarbonate diol component as the polyol component and contains 1,5-pentamethylene diisocyanate being a linear aliphatic isocyanate component as the isocyanate component; (2) the polycarbonate diol component has number average molecular weight of 500-3,000 and contains a C3-C10 diol-derived structure in its structure; and (3) 10 mol% or more of the isocyanate component is 1,5-pentamethylene diisocyanate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to polyurethane resins, coatings, structures, and articles. [Background technology]

[0002] Polyurethane resins are abrasion resistant, flexible, pliable, easy to process, adhesive, and chemical resistant. It has excellent physical properties such as durability and is also suitable for various processing methods, making it popular as synthetic imitation leather (combined with artificial leather). It is used as a material for synthetic leather (general term for leather), various coating agents, inks, paints, etc., or as a binder. It is widely used as a material for films, sheets and various moldings, and has a wide range of applications. Suitable polyurethane-based resins have been proposed.

[0003] For example, in the manufacturing process of synthetic imitation leather sheets, urea is added to improve the texture. This film is made of a tan resin. It is especially used for long-lasting consumer goods such as vehicle interior materials. When used, polycarbonate is used as the polyol in the synthesis of urethane resin. Polyols are generally used (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-108196 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when polycarbonate polyol is simply used, the resulting leather-like Although the sheet had excellent light resistance, the flexibility was sometimes deteriorated. In particular, materials that have flexibility in cold regions, i.e., cold-resistant flexibility, have not been found. There was no one there.

[0006] While flexibility in cold regions (cold resistance and flexibility) is required, for example, When trying to improve the cold resistance and flexibility of flexible materials such as synthetic imitation leather, chemical resistance is also a problem. This is because chemicals easily penetrate the resin skeleton, which affects the improvement of flexibility. There is a trade-off between cold resistance and chemical resistance. It was difficult to do so.

[0007] From the above, the present invention provides a polyurethane resin that can achieve both excellent cold bending resistance and chemical resistance. provide. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have discovered a polycarbonate having a specific number average molecular weight and structure. Diol is used, and the isocyanate component is a straight-chain aliphatic isocyanate having 4 to 10 carbon atoms. We have found that a polyurethane resin containing a specific amount of a hydroxy component can solve the above problems, and have completed the present invention. That is, the present invention is as follows.

[0009] [1] A polyurethane resin containing a polyol component and an isocyanate component, A polyurethane resin that satisfies 1) to (3). (1) The polyol component contains a polycarbonate diol component, and the isocyanate The isocyanate component contains a linear aliphatic isocyanate component. (2) The polycarbonate diol component has a number average molecular weight of 500 to 3000, The structure contains a diol-derived structure having 3 to 10 carbon atoms. (3) Of the isocyanate components, 10 mol% or more is a linear fatty acid having 4 to 10 carbon atoms. It is an aromatic isocyanate component. [2] A compound component having one or more active hydrogen groups and a hydrophilic group. The polyurethane resin according to [1], having an acid value of 5 to 40 mgKOH / g. [3] The proportion of the polycarbonate diol component in the polyol component is 50% by mass. The polyurethane resin according to [1] or [2] above. [4] Among the isocyanate components, the linear aliphatic isocyanate having 4 to 10 carbon atoms The polyurethane according to any one of [1] to [3], wherein the proportion of the carboxylate component is 15 mol % or more. Resin. [5] Further, the composition according to [1] to [4] containing a short-chain diol component and / or a short-chain diamine component. The polyurethane resin according to any one of the above. [6] The polyol component, the isocyanate component, the short-chain diol component, and the At least one selected from the group consisting of the short-chain diamine components is composed of plant-derived raw materials. The polyurethane resin according to any one of [1] to [5], [7] The ratio of the short-chain diol component to the polyol component is 0.1 to 1.0 in terms of molar ratio. [5] or [6], wherein the amount is three times the amount of the polyurethane resin. [8] The glass transition temperature of the polyurethane resin is -50 to -10°C [1] to [7] ] The polyurethane resin according to any one of the preceding items. [9] The maximum value of tan δ of the polyurethane resin is in the temperature range of -40 to -10°C. The polyurethane resin according to any one of [1] to [8].

[10] 100% modulus of the film at -10°C when made into a film The polyurethane resin according to any one of [1] to [9], which has a modulus of elasticity of 20 MPa or less.

[11] 10% of the film after immersion in oleic acid at 70°C for 24 hours [1] to

[10] , wherein the retention rate of the physical property value at 0% modulus is 20% or more. Polyurethane resin.

[12] A paint containing the polyurethane resin according to any one of [1] to

[11] .

[13] In addition, isocyanate-based crosslinkers, carbodiimide-based crosslinkers, and oxazoline-based crosslinkers and at least one selected from the group consisting of a crosslinking agent and an epoxy-based crosslinking agent.

[12] The paint according to claim 1.

[14] A structure comprising the polyurethane resin according to any one of [1] to

[11] .

[15] The coating material according to

[12] or

[13] is contained on at least one of the surface and the interior. A structure that includes:

[16] Synthetic imitation leather containing the structure described in

[14] or

[15] . [Effects of the Invention]

[0010] According to the present invention, a polyurethane resin that can achieve both excellent cold-flexibility and chemical resistance is provided. It is possible. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. In the present invention, the polyurethane resin is A general term for polyurethane resins and polyurethane-urea resins.

[0012] [Polyurethane resin] The polyurethane resin of the present invention is a polyurethane containing a polyol component and an isocyanate component. The resin is a polyurethane resin that satisfies the following (1) to (3). (1) A polyol component containing a polycarbonate diol component and an isocyanate component It contains a linear aliphatic isocyanate component. (2) The polycarbonate diol component has a number average molecular weight of 500 to 3000, and its structure The structure contains a diol-derived structure with 3 to 10 carbon atoms. (3) Of the isocyanate components, 10 mol% or more is a linear aliphatic isocyanate having 4 to 10 carbon atoms. It is a socyanate component. Each component constituting the polyurethane resin will be described in more detail below.

[0013] [Polyol component] The polyol component in the present invention contains a polycarbonate diol component, The polycarbonate diol component includes at least: The number average molecular weight is 500 to 3000, and the structure contains a diol-derived structure having 3 to 10 carbon atoms. Use something that includes the structure. Here, "containing a structure derived from a diol having 3 to 10 carbon atoms in its structure" means a structure derived from a diol having 3 to 10 carbon atoms. It can also be called a polycarbonate diol, which gives a diol having 3 to 10 carbon atoms upon decomposition. For example, It is preferable to use a polycarbonate diol represented by the following formula (1) or formula (2): stomach.

[0014] [ka] JPEG0007738635000002.jpg27136

[0015] In the above formula (1), m is 3 to 10, and n is an integer of 1 to 500 such that the number average molecular weight is 500 to 3,000. For example, Ethanacol UH-200 (Ube Industries, Ltd.) used in the examples described later The polymer (manufactured by the company) has m=6, a number average molecular weight of about 2000, and a theoretical value of n of 13 or 14. In the above formula (2), m, n, and l are each 3 to 10, and o and p are each number-average molecular weights. It is a natural number whose amount is 500 to 3000. For example, All NL-2010DB (manufactured by Mitsubishi Chemical) has m=4, n=4, l=10, (o+1): With p=9:1, the number average molecular weight is about 2000, and the theoretical value of o is 13 or 14.

[0016] The number average molecular weight of the polycarbonate diol used in the present invention is 500 to 3000. The number average is preferably 700 to 2700, and more preferably 900 to 2500. If the molecular weight exceeds 3000, chemical resistance will decrease, and if it is less than 500, cold bending resistance will decrease. Sexuality will decrease. The number average molecular weight is a number average molecular weight converted into polystyrene equivalent, and is usually determined by gel permeation. It can be determined by measurement using gel permeation chromatography (GPC).

[0017] The proportion of polycarbonate diol in the polyol component must be 50% by mass or more. When the proportion of the polycarbonate diol component is 50% by mass or more, chemical resistance is improved. From this viewpoint, the proportion of the polycarbonate diol component in the polyol component is In this case, the content is more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0018] The polyol component in the present invention is a polyol other than a polycarbonate diol component. Examples of other polyol components include the following (1) to (5): Examples of polyols include polyols shown below (polyols having a number average molecular weight of 500 or more).

[0019] (1) Polyether polyol Polyether polyols include alkylene oxides (ethylene oxide, propane, pyrene oxide, butylene oxide, etc.) and heterocyclic ethers (tetrahydrofuran Specific examples include those obtained by polymerizing or copolymerizing any of polyethylene, Glycol, Polypropylene Glycol, Polyethylene Glycol-Polytetramethylene Glycol (block or random), polytetramethylene ether glycol and poly hexamethylene glycol, etc.

[0020] (2) Polyester polyol The polyester polyols include aliphatic dicarboxylic acids (e.g., succinic acid, azidopropyl alcohol, etc.). pinic acid, sebacic acid, glutaric acid and azelaic acid, etc.), and aromatic dicarboxylic acids (e.g. For example, at least one of isophthalic acid and terephthalic acid, and a low molecular weight glycol (e.g., ethylene glycol, 1,2-propylene glycol, 1,3-propylene Glycol, 1,3-butanediol, 1,4-butylene glycol, 1,6-hexamethasone Ethylene glycol, neopentyl glycol and 1,4-bishydroxymethylcyclohexane Examples include polycondensation products of olefins such as olefins (e.g., olefins obtained by polycondensation of olefins) and olefins (e.g., olefins obtained by polycondensation of olefins). Specifically, polyethylene adipate diol, polybutylene adipate diol, poly Hexamethylene adipate diol, polyneopentyl adipate diol, polyethylene Polyethylene / butylene adipate diol, polyneopentyl / hexyl adipate diol, poly Poly-3-methylpentane adipate diol and polybutylene isophthalate diol, etc. Examples include:

[0021] (3) Polylactone polyol Polylactone polyols include polycaprolactone diol and poly-3-methyl Valerolactone diol and the like. (4) Polyolefin polyol Polyolefin polyols include polybutadiene glycol and polyisoprene. Examples of suitable hydrides include ricor and its hydrides. (5) Polymethacrylate diol Polymethacrylate diols include α,ω-polymethyl methacrylate diol and and α,ω-polybutyl methacrylate diol.

[0022] The number average molecular weight of the polyol is not particularly limited as long as it is 500 or more, but is preferably 500 to 4000. These polyols may be used alone or in combination of two or more. However, it is preferable to contain polycarbonate diol from the viewpoint of long-term durability.

[0023] [Isocyanate component] The isocyanate component in the present invention includes a linear aliphatic isocyanate component. At least 10 mol% of the cyanate component is a straight-chain aliphatic isomer having 4 to 10 carbon atoms. At least 10 mol% of the isocyanate component has carbon atoms. If the isocyanate is a linear aliphatic isocyanate having a molecular weight of 4 to 10, the cohesive force between the urethane groups is high, and the ring structure Since the polyurethane resin of the present invention has less steric hindrance than isocyanates having It can impart chemical resistance and cold-flexibility to paints and the like. Examples of linear aliphatic isocyanates having 4 to 10 carbon atoms include 1,4-tetramethyl Diisocyanate, 1,5-pentamethylene diisocyanate (1,5-pentamethylene diisocyanate), 1,6-hexamethylene diisocyanate, 1,7-heptame Examples include 1,8-octamethylene diisocyanate and 1,8-octamethylene diisocyanate. Among these, the polyurethane resin of the present invention is used to further improve the chemical resistance and cold bending resistance of paints and the like. From the viewpoint of increasing the polymerization efficiency, linear aliphatic isocyanates having 4 to 8 carbon atoms are preferred, and 1,5-phenyl isocyanates are preferred. 1,6-Hexamethylene diisocyanate is more preferred. stomach.

[0024] Of the isocyanate components, the amount of linear aliphatic isocyanate components with 4 to 10 carbon atoms is , preferably 15 mol % or more, more preferably 25 mol % or more, and even more preferably 35 % or more, and even more preferably 45 mol % or more.

[0025] The isocyanate component in the present invention is a linear aliphatic isocyanate having 4 to 10 carbon atoms. It may contain an isocyanate component other than toluene-2,4-diisocyanate, for example. 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), julienne Diisocyanate, Tolylene Diisocyanate, Xylylene Diisocyanate (XDI ), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate Aromatic diisocyanates such as benzidine diisocyanate and 4,4'-diisocyanate dibenzyl Cyanates; methylene diisocyanate, 1,10-decamethylene diisocyanate, etc. Aliphatic diisocyanates; 1,4-cyclohexylene diisocyanate, 4,4'-methyl Dicyclohexylisocyanate, 1,5-tetrahydronaphthalene diisocyanate Alicyclic diisocyanates such as anthracene, isophorone diisocyanate, hydrogenated MDI and hydrogenated XDI Diisocyanates; or these diisocyanate compounds and low molecular weight polyols or polyols Polyurethane prepolymer obtained by reacting amine with isocyanate at the end Marr et al.

[0026] [Chain extenders, etc.] The polyurethane resin of the present invention preferably contains a short-chain diol component and a short-chain diamine component. In the case of aqueous solution, the compound has one or more active hydrogen atoms and a hydrophilic group. It is preferred that the hydroxyl group contains hydroxyl groups.

[0027] (short chain diol) The short-chain diol component is a compound with a number average molecular weight of less than 500. ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butylene glycol Tandiol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol Aliphatic glycols such as glycols and their low-mole alkylene oxide adducts (number average (molecular weight less than 500), diethylene glycol, triethylene glycol, dipropylene glycol Alkylene ether glycols such as ethanol; 1,4-bishydroxymethylcyclohexyl Alicyclic glycols such as cyclohexane and 2-methyl-1,1-cyclohexanedimethanol, Its alkylene oxide low molar adduct (number average molecular weight less than 500), xylylene glycol Aromatic glycols such as glycols and their low-molecular-weight alkylene oxide adducts (number-average molecular weight less than 500), bisphenol A, thiobisphenol and sulfonbisphenol, etc. Bisphenols and their alkylene oxide low molar adducts (number average molecular weight less than 500) ), and alkyldialkanolamines such as C1 to C18 alkyldiethanolamines Among these, aliphatic glycols are preferred.

[0028] When the polyurethane resin of the present invention contains a short-chain diol, the proportion of the short-chain diol is m The amount is preferably 0.1 to 3 times the amount of the polyol component, and more preferably 0.1 to 2 times the amount of the polyol component. It is more preferable that the amount of the short-chain diol is 0.1 to 1 times the amount of the short-chain diol. When the ratio is within the above range, the chemical resistance and mechanical properties of the urethane resin of the present invention are improved.

[0029] (short chain diamine) The short-chain diamine components include ethylenediamine, trimethylenediamine, aliphatic diamine compounds such as methylamine, hexamethylenediamine, and octamethylenediamine; Phenylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4, 4'-methylenebis(phenylamine), 4,4'-diaminodiphenyl ether and 4 Aromatic diamine compounds such as 4'-diaminodiphenyl sulfone, cyclopentane diamine cyclohexyldiamine, 4,4-diaminodicyclohexylmethane, 1,4-diamino Alicyclic diamine compounds such as cyclohexane and isophoronediamine, hydrazine, carboxymethyl Rubidihydrazide, Adipic dihydrazide, Sebacic dihydrazide, Phthalic dihydrazide Among these, from the viewpoint of improving durability, ethyl hydrazines are preferred. Diamines are more preferred.

[0030] In the present invention, from the viewpoint of eliminating concerns about the depletion of petroleum resources and from the viewpoint of environmental consideration, polyurethane is used. The polyol component, isocyanate component, short-chain diol component, and diamine component that make up the vinyl resin At least one selected from the group consisting of ingredients derived from plants is preferred.

[0031] (Compounds having one or more active hydrogen atoms and a hydrophilic group) The urethane resin of the present invention is a compound other than the above compounds, which has one or more active hydrogen atoms. The composition may contain a component derived from a compound having one or more active hydrogen atoms and a hydrophilic group. The compound having a hydrophilic group is a compound that imparts water dispersibility to the polyurethane resin. Any known compound used as a component can be used. In this compound, the active hydrogen is a hydrogen atom that reacts with the isocyanate group. Examples include hydrogen atoms of acid groups, mercapto groups, amino groups, etc., and among these, the hydrogen atoms of hydroxyl groups are The hydrophilic group is a functional group for imparting water dispersibility, and is preferably an anionic group. The anionic hydrophilicity is preferable. Examples of the functional group include a carboxyl group, a sulfo group, and a phosphate group. Xyl groups are preferred.

[0032] The compounds having anionic hydrophilic groups include sulfonic acid, carboxylic acid, and phosphoric acid. It is possible to use compounds having a hydrophilic group such as dimethylolpropanoic acid, dimethylolpropanoic acid, etc. Carboxylic acid compounds such as thyrolbutanoic acid, lactic acid, glycine, taurine, sulfoisophthalic acid Examples include sulfonic acid compounds such as acid-based polyester diols. Among these, carboxylic acid compounds of dihydric alcohols, especially dimethylolpropanoic acid, It is preferable to use a dimethylolalkanoic acid such as dimethylolbutanoic acid.

[0033] The hydrophilic group may be neutralized with a neutralizing agent to form a salt. Examples of the neutralizing agent include aqueous ammonia, organic amines such as ethylamine and trimethylamine, Alkylamines such as triethylamine, triisopropylamine, and tributylamine; Triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine , monoethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine alkanolamines such as ethanolamine and 2-amino-2-ethyl-1-propanol; Examples include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide. Among these, tertiary alkylamines such as triethylamine, hydroxide Sodium and tertiary alkanolamines such as dimethylaminoethanol are preferred. The alkanolamines exemplified above can also be used as chain terminators. .

[0034] The urethane resin of the present invention is a compound having one or more active hydrogen atoms and a hydrophilic group. When the polyurethane resin contains a component derived from When the acid value is within the above range, the polymer can be stably dispersed in water. From this viewpoint, the acid value is preferably 10 to 35 mgKOH / g, and more preferably 10 to 2 5 mg KOH / g is more preferred.

[0035] The biomass ratio (ratio of plant-derived raw materials) in polyurethane resin is increasing due to the risk of petroleum resource depletion. From the viewpoint of eliminating worries and being environmentally friendly, 10% by mass or more is preferable, and 20% by mass or more is more preferable. It is preferably 30% by mass or more, and more preferably 30% by mass or more.

[0036] The above are examples of preferred components, and the present invention is not limited to these. Therefore, in addition to the above-mentioned exemplary ingredients, other ingredients that are currently on the market and easily available on the market are also included. Any compound that can be used can be used.

[0037] [Polysiloxane Compound] Polysiloxane compounds are used when modifying polyurethane resins with polysiloxane. By modifying with polysiloxane, the abrasion resistance of paints and the like using the polyurethane resin of the present invention can be improved. The polysiloxane compound may have the following structures (1) to (4): Compounds of the formula:

[0038] (1) Amino-modified polysiloxane [ka] JPEG0007738635000004.jpg2778 JPEG0007738635000005.jpg2763 JPEG0007738635000006.jpg2074 JPEG0007738635000007.jpg3486 JPEG0007738635000008.jpg2672

[0039] (2) Epoxy-modified polysiloxane The following epoxy compounds are reacted with polyols, polyamides, polycarboxylic acids, etc. to form terminally activated It can be used with hydrogen. [ka] JPEG0007738635000010.jpg2671 JPEG0007738635000011.jpg25122 JPEG0007738635000012.jpg27111 JPEG0007738635000013.jpg3370 JPEG0007738635000014.jpg3386

[0040] (3) Alcohol-modified polysiloxane [ka] JPEG0007738635000016.jpg2572 JPEG0007738635000017.jpg26108 JPEG0007738635000018.jpg2568 JPEG0007738635000019.jpg2469 JPEG0007738635000020.jpg35134 JPEG0007738635000021.jpg27134

[0041] (4) Mercapto-modified polysiloxane [ka] JPEG0007738635000023.jpg2850 JPEG0007738635000024.jpg27113 JPEG0007738635000025.jpg2872

[0042] The polysiloxane compounds (1) to (4) above are examples of preferred compounds, and these The compounds are not limited to the exemplified compounds. Among the compounds listed above, alcohol-modified polysiloxane is The following compounds are preferred, and the following compounds are more preferred: [ka]

[0043] [Glass transition temperature of urethane resin] The glass transition temperature of the urethane resin of the present invention is preferably -50 to -10°C. When the glass transition temperature of the urethane resin is within the above range, the cold bending resistance is further improved. From this viewpoint, the glass transition temperature of the urethane resin of the present invention is preferably −50 to −20° C. The glass transition temperature is more preferably 50 to −30° C. The glass transition temperature can be measured by the method described in the examples. This can be done.

[0044] [Maximum value of tan δ] The maximum value (peak temperature) of tan δ of the urethane resin of the present invention is −40 to −10° C. When the maximum value of tan δ of the urethane resin is in the above temperature range, Energy during bending is more easily absorbed, cracks do not occur, and cold bending resistance is further improved. From this viewpoint, the maximum value of tan δ of the urethane resin of the present invention is preferably −40 to −15 The temperature range is preferably -40 to -25°C. The maximum value of tan δ is It can be measured by the method described in the Examples.

[0045] [100% modulus] When the urethane resin of the present invention is formed into a film, the film has a 100% The modulus value is preferably 20 MPa or less. If the modulus is 20 MPa or less, the cold bending resistance is improved. It is preferably 15 MPa or less, more preferably 10 MPa or less. 100% modulus The physical properties can be measured by the methods described in the examples. In addition, the film was immersed in oleic acid at 70°C for 24 hours. It is preferable that the retention rate of the physical property value of 100% modulus is 20% or more. If the property retention rate is 20% or more, chemical resistance will be improved. 100% modulus property retention The retention rate of the physical properties is preferably 30% or more, and more preferably 50% or more. It can be measured by the method described in the Examples.

[0046] (Method of manufacturing polyurethane resin) The method for producing the polyurethane resin according to the present invention is not particularly limited, and any known polyurethane resin may be used. The urethane manufacturing method can be used. and a chain extender such as a short-chain diol or a short-chain diamine, which may be added as needed; Siloxane compound, if water-based, further has one or more active hydrogen groups and a hydrophilic group Then, if necessary, a neutralizing agent, a chain extender, a terminator, etc. are added to produce the product. It can be made.

[0047] In the above production method, an organic solvent or water may be used if necessary. Examples of organic solvents include ketone solvents (acetone, methyl ethyl ketone, methyl isopropyl alcohol, etc.). isobutyl ketone, cyclohexanone, etc.), aromatic hydrocarbon solvents (toluene, xylene, Swazol (aromatic hydrocarbon solvent manufactured by Cosmo Oil Co., Ltd.), Solvesso (Exxon Aromatic hydrocarbon solvents (manufactured by NGK Corporation), aliphatic hydrocarbon solvents (n-hexane, etc.) Among these, N,N-dimethylformamide is preferred from the viewpoint of ease of handling. methyl ethyl ketone, acetone, tetrahydrofuran, and the like are preferred.

[0048] <Additives> The polyurethane resin of the present invention may contain additives as needed. For example, matting agents, antioxidants (hindered phenols, phosphites, thioesters) esters, etc.), light stabilizers (hindered amines, etc.), UV absorbers (benzophenones, Examples include gas discoloration stabilizers (hydrazine-based, etc.), and metal deactivators. can be.

[0049] Matting agents include resin particles, silica particles, talc, aluminum hydroxide, and calcium sulfate. Calcium, calcium silicate, calcium carbonate, magnesium carbonate, barium carbonate, alumina Examples of suitable silicates include silicates, molecular sieves, kaolin, mica, and the like. If the polyurethane resin contains a matte agent, the coating that will become the surface material will have a matte finish. can be done.

[0050] [paint] The coating material of the present invention contains a polyurethane resin, and the polyurethane resin is Because the isocyanate component is a straight-chain aliphatic isocyanate with 4 to 10 carbon atoms, This can improve the chemical resistance and cold bending resistance of the coating film.

[0051] In order to improve chemical resistance, the coating material of the present invention contains an isocyanate resin in addition to the polyurethane resin. Carbodiimide crosslinking agents, oxazoline crosslinking agents, and epoxy crosslinking agents It is preferable that the composition contains at least one selected from the group consisting of:

[0052] If the amount of cross-linking agent used is too large, problems such as film embrittlement and plasticization due to unreacted cross-linking agent may occur. For this reason, the amount of crosslinking agent used should be set to 100 parts by mass of polyurethane resin. The amount of the crosslinking agent is preferably 10 parts by mass or less in terms of solid content, and more preferably 1.0 to 7.5 parts by mass. It is more preferable to make it a part.

[0053] [Structure] The structure of the present invention is a structure containing the polyurethane resin of the present invention, or a structure showing the coating material of the present invention. The structure is contained in at least one of the surface and the interior. Examples include:

[0054] Specific synthetic imitation leather includes a base material and a surface layer, or a synthetic material consisting of a base material, an adhesive layer, and a surface layer. There are synthetic imitation leathers with a surface treatment layer on the outermost surface of imitation leathers or synthetic imitation leathers. Examples of the substrate for synthetic imitation leather include woven fabric, nonwoven fabric, sponge, etc. The synthetic imitation leather can be produced, for example, as follows: The polyurethane resin according to the present invention is used as a skin agent for forming a skin layer. The coating is applied by a known method such as a knife coat or a roll coat. A known polyurethane resin adhesive is applied to the surface of the skin layer in a comma-separated manner. It is applied by a known method such as coating, knife coating, roll coating, etc. After drying, It is pressed onto the base material for imitation leather. After aging, it is peeled off from the release paper to obtain synthetic imitation leather. do.

[0055] As an example of a structure, a method for producing the structure by applying the polyurethane resin of the present invention to a substrate is described below. I will explain. <Base material> Examples of the substrate include films and synthetic leather made of the following resins. The substrate may be a foam substrate. Resins include polyvinyl chloride resin, polyethylene resin, polypropylene resin, and heat Olefin resins such as plasticized polyolefin, ethylene propylene diene resins, styrene Acrylonitrile resin, polysulfone resin, polyphenylene ether resin, acrylic acrylate resin, silicone resin, fluorine resin, polyester resin, polyamide resin , polyimide resin, polystyrene resin, polyurethane resin, polycarbonate resin Fat, norbornene resin, cellulose resin, polyvinyl alcohol resin, polyvinyl Formal resin, polyvinyl butyral resin, polyvinyl pyrrolidone resin, polyvinyl Nylacetal resin, polyvinyl acetate resin, engineering plastic, biodegradable plastic Examples include sticks. In particular, for automobile interior materials, polyvinyl chloride resin, thermoplastic polyolefin, Examples of the material include polyurethane and polypropylene. In addition, when the substrate is a foam substrate, a substrate such as vinyl chloride resin can be used. do. The thickness of the substrate is preferably 0.2 to 0.8 mm, and the substrate is a foam substrate. When foaming, the thickness after foaming is preferably 0.3 to 4.5 mm.

[0056] <Manufacturing method> The polyurethane resin of the present invention is applied to a substrate, dried at 80 to 140°C, and optionally crosslinked. This causes a coating to be formed. When the substrate is a foam substrate, for example, a polyvinyl chloride resin substrate sheet, heating causes A step of foaming the foaming agent in the vinyl chloride foam layer composition to form a vinyl chloride foam layer (foaming For example, prior to this step, the polyurethane resin of the present invention may be applied to a substrate sheet. It is applied by spray coating, gravure coating, etc. to form a coating film. Then, it is dried at 80 to 140 °C for 1 to 3 minutes to form a film, and then foaming treatment is performed at 130 to 230 °C. Further, in order to impart design properties, an embossing roll with a pattern engraved on the surface treatment layer side is pressed against the surface while the surface is heated (100 to 190 °C), so that a synthetic resin skin material (for example, a car seat) with a pattern formed on the surface is obtained (pattern forming step ). When the polyurethane resin of the present invention is applied to a thermoplastic resin substrate with poor adhesion, a primer treatment may be performed to improve the adhesion to the paint. In addition, each of the foaming step and the pattern forming step may be performed prior to the step of forming the coating film, or may be performed after the surface treatment layer forming step. That is, there are methods of applying the polyurethane resin to the substrate before foaming and then heating and foaming it, and methods of applying the polyurethane resin to the substrate after foaming. However, due to the reasons of uniform coating property of the surface treatment layer and improvement of adhesion strength, the method of foaming [[ID=2f]] after applying the polyurethane resin is preferred.

Example

[0057] The present invention will be further specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto. In addition, "parts" below indicates parts by mass,

[0058] <Production of PU1 to 15> The polyurethane resins and siloxane-modified polyurethane resins PU 1 to 15 used in this example were produced as follows.

[0059] A reaction vessel equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen injection pipe, and a manhole was purged with nitrogen gas and then, using biomass PC diol (Beneviol NL-2010DB, manufactured by Mitsubishi Chemical , number average molecular weight 2000, biomass ratio 5.4%, corresponding to formula (2)) or non-biomass PC diol (Ethanacol UH-200, manufactured by Ube Industries, number average molecular weight 2000, corresponding to formula (1 )), 1,3-butanediol, and DMF (dimethylformamide), the solution concentration was adjusted to 80% and heated to 70 °C. For PU8 and PU15, polysiloxane diol (Compound a) with both ends was also added simultaneously. Here, isophorone diisocyanate and hexamethylene diisocyanate or 1, 5-pentamethylene diisocyanate (using the one with a biomass ratio of 70% by weight) was added in a predetermined amount (NCO / OH = 1.4), and the reaction was carried out until the NCO% reached 90-98% of the theoretical value . The solution concentration was diluted to 30%, cooled to 50 °C or lower, and then IPDA (isophorone diamine) was added in a molar amount of 90%-100% equivalent to the remaining NCO% for chain extension. The remaining NCO was terminated with isopropyl alcohol. Thereby, the polyurethane solution and the siloxane-modified polyurethane resin solution, PU1-15 used in this example were obtained.

[0060] <Production of PUD1-15> Next, the aqueous polyurethane resin and the aqueous siloxane-modified polyurethane resin PUD1-15 used in this example were produced as follows.

[0061] A reaction vessel equipped with a stirrer, a reflux cooling pipe, a thermometer, a nitrogen injection pipe, and a manhole was purged with nitrogen gas, and then biomass PC diol (Beneviol NL-2010DB, Mitsubishi Chemical (manufactured by Epson Corporation, number average molecular weight 2000, corresponds to formula (2)) or non-biomass PC diol (ethanol Coal UH-200, manufactured by Ube Industries, number average molecular weight 2000, corresponds to formula (1)) and 1,3 -Butanediol, dimethylolpropanoic acid and acetone were added in predetermined amounts and dissolved uniformly. The solution concentration was adjusted to 80%. Xanediol (compound a) was also added at the same time. Next, isophorone diisocyanate and hexamethylene diisocyanate or 1 ,5-Pentamethylene diisocyanate (biomass ratio 70% by weight) The reaction was carried out at 80°C in a predetermined equivalent ratio (NCO / OH = 1.4), and the NCO% was The reaction was continued until the solution reached 90-98% of the theoretical value, then the solution was diluted to 60% and cooled to 50°C. Add 20% ion-exchanged water to the solid content and a predetermined amount of neutralizer (triethylamine) Add ethylenediamine (an amount equivalent to the hydroxyl group -COOH) and emulsify the system uniformly. The chain was extended by adding acetone (100% molar amount of NCO%) and then terminated with water. The mixture is vacuum degassed to obtain an aqueous dispersion of polyurethane resin and siloxane-modified polyurethane resin. PUD1 to 15 were obtained.

[0062] The acid value is measured by titration in accordance with JIS K-1557, and the acid content per 1 g of resin is The content of functional groups in mg KOH equivalents is shown in Table 1. The unit is mg KOH / g is.

[0063] PU1, PU14, PUD1, and PUD14 are types that do not use biomass materials. PUD1-15 considers the environmental impact of volatile organic compounds and limits the organic solvent ratio to 5%. The stability of the obtained resin solution and resin dispersion was checked as follows: The results were evaluated on a 5-point scale according to the criteria, and are shown in Table 1.

[0064] <Evaluation criteria> (resin solution stability) 5: Fluid at room temperature. 4: Fluid at room temperature, but becomes cloudy. 3: Some fluidity is lost at room temperature. 2: Most of the fluidity is lost at room temperature. 1: Complete loss of fluidity at room temperature.

[0065] (Resin dispersion stability) 5: No settling or separation occurs at room temperature. 4: Some settling or separation occurs at room temperature. 3: Major settling or separation occurs at room temperature. 2: Partial gelation occurs at room temperature. 1: Significant sedimentation, separation, gelation, etc. occur at room temperature.

[0066] [Table 1]

[0067] The abbreviations in Table 1 are as follows: (1) PC diol: Polycarbonate diol (2) Si diol: Compound a represented by the following formula (n is an integer, number average molecular weight 1,900):

[0068] [ka]

[0069] (3) 1,3BD: 1,3-butanediol (4) IPDA: Isophoronediamine (5) IPDI: Isophorone diisocyanate (6) 1,5PDI: 1,5-pentamethylene diisocyanate (plant-derived) (7) HDI: Hexamethylene diisocyanate (8) EDA: Ethylenediamine (9) Polyols: PC diol and Si diol

[0070] (Examples 1 to 28, Comparative Examples 1 and 2) <Resin physical properties> Table 2 shows the test results obtained by the following method. (1) Film sample preparation First, polyurethane resin is applied to release paper and dried at 130°C for 2 minutes to form a coating. A test piece with a thickness of 50 μm, a length of 60 mm, and a width of 10 mm was prepared.

[0071] (2) Film property measurement (-10°C) The above film was measured using an Autograph (Shimadzu Corporation, model number: AGS-J), a thermostatic Using a tank (Shimadzu Corporation, model number: TCR1-200) DG0141014), The 100% modulus at 0°C was measured.

[0072] (3) Oleic acid resistance test The above film was immersed in oleic acid at 70°C for 24 hours, and then the same method as in (2) was used. The physical properties were measured at room temperature. The 100% modulus retention was calculated using the following formula: (100% modulus of film after immersion in oleic acid) ÷ (100% modulus of film before immersion in oleic acid) % modulus)

[0073] (4) Dynamic viscoelasticity Using a dynamic viscoelasticity device (01dB-Metravib, model number: DMA-50) The dynamic viscoelastic behavior of the film was measured and analyzed, and the glass transition temperature (Tg(E') was calculated. The tan δ peak temperature was obtained. The measurement conditions were as follows: Conditions: Frequency: 10Hz, Temperature rise: 5℃ / min, Temperature range: -110℃ to 250℃ (Until softened)

[0074] [Table 2]

[0075] (Examples 29 to 56, Comparative Examples 3 and 4) <Synthetic leather properties> Table 3 shows the test results obtained by the following method. (1) Synthetic imitation leather production [Contains epidermal layer] 1. Oil-based formulation ·PU1~PU15 100 copies 20 copies of Seika Seven BS-780(s) Black (manufactured by Dainichi Seika Color & Chemicals Co., Ltd.) DMF (amount to make the solid content 20%) 2.Aqueous formulation PUD1~15 100 copies 20 copies of Seika Seven DW-1780 Black (manufactured by Dainichi Seika Color & Chemicals Co., Ltd.)

[0076] [Adhesive layer formulation] 1. Oil-based formulation 100 units of Lezamin UD-8351 (polyurethane resin adhesive, manufactured by Dainichiseika Color & Chemicals Co., Ltd.) 10 parts C-50 crosslinking agent (isocyanate-based crosslinking agent, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) 2.Aqueous formulation 100 parts of Lezamin D-1060 (polyurethane resin adhesive, manufactured by Dainichiseika Color & Chemicals Co., Ltd.) 10 parts of Resamin D-65 (isocyanate crosslinking agent, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.)

[0077] The skin layer formulation was applied to a release paper and dried to form a skin layer having a thickness of 20 μm. The adhesive layer mixture liquid was applied onto the surface layer to form an adhesive layer having a thickness of 20 μm. After transferring onto a raised fabric under dry lamination conditions (150°C, clearance = 0) The mixture was aged at 50° C. for 48 hours to obtain synthetic imitation leathers of Examples 29 to 56 and Comparative Examples 3 and 4.

[0078] (2) Oleic acid resistance test 1 ml of oleic acid was dropped onto the synthetic imitation leather and left to stand at 80°C for 24 hours, after which the appearance was checked as follows: It was evaluated as follows. A: No visible change in appearance B: Slight swelling when visually observed C: Visually dissolved

[0079] (3) Cold resistance bending test The synthetic leather was used to test the Dematcha tester (manufactured by Yasuda Seiki Seisakusho, model number: NO. 119- Using a DEMATTIA FLEXING TESTER, a test piece measuring 50 mm in width and 15 mm in length was Using a test sheet with a diameter of 0.0 mm (evaluation range 100 mm), the test was carried out in a -10°C environment with a bending range of 72 to The bending test was carried out at 108% and a low temperature of -10°C. The evaluation criteria were as follows: A: No cracks after 30,000 cycles B: No cracks after 10,000 cycles, cracks after 30,000 cycles C: Cracks after 10,000 cycles

[0080] [Table 3]

[0081] (Examples 57 to 84, Comparative Examples 5 and 6) <Paint properties> Table 4 shows the test results obtained by the following method. (1) Preparation of surface treatment agent The matting agent and crosslinking agent for each of PU1 to PU15 and PUD1 to PUD15 are shown in Table 4 below. The surface treatment agents of Examples 57 to 84 and Comparative Examples 5 and 6 were obtained by blending them in the ratios shown in the table below. The details of the matting agent and the crosslinking agent are as follows. 1. Matting agent Polyurethane resin particles: Art Pearl C-400 transparent (manufactured by Negami Chemical Industries, Ltd., volume average Particle size 15μm, Tg=-13℃) Silica particles: ACEMATT TS-100 (manufactured by Evonik, volume average particle diameter 9. 5μm)

[0082] 2. Crosslinking agent Oil-based: C-50 crosslinking agent (Dainichiseika Color & Chemicals Mfg. Co., Ltd., isocyanate-based crosslinking agent) Water-based: Epocross WS-500 (manufactured by Nippon Shokubai Co., Ltd., oxazoline-based crosslinking agent, Tg = 1 6°C, oxazoline group equivalent weight = 220)

[0083] (2) Painting The surface treatment agent obtained in each example and comparative example was applied to a PVC sheet using a bar coater. The coating was dried in a dryer at 130°C for 2 minutes to prepare a test sheet with a coating thickness of 10 µm.

[0084] (3) Oleic acid resistance test 1 ml of oleic acid was dropped onto the test sheet, and the appearance after 24 hours at 80°C was evaluated as follows: It was worth it. A: No significant change in appearance when visually inspected B: Minor scratches and peeling of the paint film visible to the naked eye C: Significant paint peeling observed visually

[0085] (4) Cold resistance bending test Using the above test sheet, a bending test was carried out in the same manner as the cold bending test for synthetic imitation leather. The evaluation criteria were as follows: A: No whitening or cracking after 10,000 times B: Whitening after 10,000 times, no cracks C: Whitening and cracking after 10,000 cycles

[0086] [Table 4]

[0087] As is clear from the results of the Examples and Comparative Examples, the present invention provides excellent cold bending resistance and It is possible to provide a polyurethane resin that is both highly resistant to chemicals.

Claims

1. A polyurethane resin solution containing a polyol component, an isocyanate component, and an organic solvent, A polyurethane resin solution for synthetic imitation leather that satisfies the following (1) to (3): (1) The polyol component contains a polycarbonate diol component, and the isocyanate component is a combination of 1,5-pentamethylene diisocyanate and 4,4'-methylenebis(phenylene isocyanate). (2) The polycarbonate diol component has a number average molecular weight of 500 to 3,000, contains a structure derived from a diol having 3 to 10 carbon atoms in its structure, and a diol component having 10 carbon atoms is essential. (3) The isocyanate component contains 10 mol % or more and 80 mol % or less of the 1,5-pentamethylene diisocyanate.

2. 2. The polyurethane resin solution according to claim 1, wherein the proportion of the polycarbonate diol component in the polyol component is 50% by mass or more.

3. The polyurethane resin solution according to claim 1 or 2, further comprising a short-chain diol component and / or a short-chain diamine component.

4. The polyurethane resin solution according to claim 3 , wherein at least one selected from the group consisting of the polyol component, the isocyanate component, the short-chain diol component, and the short-chain diamine component is composed of a plant-derived raw material.

5. 4. The polyurethane resin solution according to claim 3, which contains the short-chain diol component, and the proportion of the short-chain diol component is 0.1 to 3 times the molar ratio of the polyol component.

6. 6. The polyurethane resin solution according to claim 1, wherein the polyurethane resin solution is formed into a film, and the resulting film has a glass transition temperature of −50 to −10° C.

7. 7. The polyurethane resin solution according to claim 1, wherein when the polyurethane resin solution is formed into a film, the film has a retention rate of 100% modulus of 20% or more after immersion in oleic acid at 70°C for 24 hours.

8. A structure comprising a dried product of the polyurethane resin solution according to any one of claims 1 to 7.

9. A synthetic imitation leather comprising the structure of claim 8.

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