Title of invention: Polyurethane gel material, polyurethane gel, pseudo-biomaterial, and method for producing polyurethane gel.
Technical field
[0001]
　The present invention relates to polyurethane gel materials, polyurethane gels, pseudobiomaterials, and methods for producing polyurethane gels.
Background technology
[0002]
　Conventionally, low-hardness polyurethane gels have been used in the fields of vibration isolation / isolation members, shock absorbing members, cushioning members, surface protection members, and the like.
[0003]
　Since flexibility is required for such polyurethane gels, a plasticizer is usually added. However, the plasticizer may bleed, causing a problem that the surface of the polyurethane gel is contaminated.
[0004]
　Therefore, for example, as a polyurethane gel containing no plasticizer, a nurate-type polyisocyanate (A) having an average number of functional groups of 2.5 to 3.5 and a modified polytetramethylene glycol (B) having a number average molecular weight of 800 to 5000 are used. Proposed an ultra-low hardness thermosetting polyurethane elastomer forming composition having an Asker C hardness of 50 or less obtained by reacting the (A) and the (B) with an NCO / OH equivalent ratio of less than 1.0. (For example, see Patent Document 1 below).
[0005]
　However, in the ultra-low hardness thermosetting polyurethane elastomer forming composition of Patent Document 1 below, while the plasticizer does not bleed, the surface has high adhesiveness (tackiness), which causes inconvenience in handleability. Therefore, it is required to suppress the bleeding of the plasticizer and reduce the surface tackiness.
[0006]
　Therefore, it has been proposed to coat the polyurethane gel with a surface layer. Specifically, the gel layer is provided with a gel layer and a coat layer for coating the gel layer, and the gel layer has an average number of functional groups exceeding 2.0. It is obtained by reacting at least the aliphatic polyisocyanate to be treated with a polyol having an average number of functional groups of 3.0 or less, and the coat layer is composed of an aliphatic diisocyanate and / or an alicyclic diisocyanate and a bifunctional active hydrogen compound. A polyurethane gel obtained by at least reacting the above has been proposed (see, for example, Patent Document 2 below).
Prior art literature
Patent documents
[0007]
Patent Document 1: Japanese Patent Application Laid-Open No. 2011-79985
Patent Document 2: International Publication WO2017 / 01422
Outline of the invention
Problems to be solved by the invention
[0008]
　On the other hand, in order to improve the productivity of the polyurethane gel, it has been studied to remove the epidermis layer in the polyurethane gel described in Patent Document 2.
[0009]
　In other words, there is a demand for a polyurethane gel that can suppress bleeding of plasticizers and reduce surface tackiness even without a skin layer.
[0010]
　Further, the polyurethane gel is required to have curability, mechanical properties (elongation, etc.), appropriate hardness, etc., depending on the application.
[0011]
　INDUSTRIAL APPLICABILITY The present invention relates to a polyurethane gel material capable of suppressing bleeding of a plasticizer, reducing surface tackiness, and obtaining a polyurethane gel having excellent curability, mechanical properties and hardness, and a polyurethane gel obtained from the polyurethane gel material. It is a method for producing a pseudo-biomaterial and a polyurethane gel thereof.
Means to solve problems
[0012]
　The present invention [1] contains an aliphatic polyisocyanate (A) having an average functional group number of 2.3 or more and 3.2 or less, a polyol (B) having an average functional group number of 2.0 or more and 2.3 or less, and an ester group. A polyurethane gel material containing a plasticizing agent (C) to be used, wherein the aliphatic polyisocyanate (A) contains an isocyanurate derivative of an aliphatic diisocyanate and / or an alcohol-modified isocyanurate derivative of an aliphatic diisocyanate. The polyol (B) contains a polyoxyalkylene (2 to 3 carbon atoms) polyol having an ethylene oxide content of 30% by mass or less, and / or a polytetramethylene ether glycol, and is the same as the polyol (B). Polyurethane having an average hydroxyl value of 30 mgKOH / g or more and 70 mgKOH / g or less, and the ratio of the plasticizing agent (C) being 50 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the polyol component (B). Contains gel material.
[0013]
　The present invention [2] includes the polyurethane gel material according to the above [1], wherein the polyol (B) has an average number of functional groups of 2.0.
[0014]
　The present invention [3] includes the polyurethane gel material according to the above [1] or [2], wherein the average hydroxyl value of the polyol (B) is 37 mgKOH / g or more and 56 mgKOH / g or less.
[0015]
　The polyurethane gel material according to any one of the above [1] to [3], wherein the present invention [4] has an average number of functional groups of 2.3 or more and 3.0 or less of the aliphatic polyisocyanate (A). Includes.
[0016]
　The present invention [5] includes the polyurethane gel material according to any one of the above [1] to [4], wherein the aliphatic diisocyanate contains pentamethylene diisocyanate and / or hexamethylene diisocyanate.
[0017]
　In the present invention [6], the ratio of the plasticizer (C) is 100 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyol component (B), according to the above [1] to [5]. Contains the polyurethane gel material according to any one of the following items.
[0018]
　In the present invention [7], the polyurethane gel material according to any one of the above [1] to [6], wherein the plasticizer (C) is a cyclohexanedicarboxylic acid ester and / or an adipate ester. Includes.
[0019]
　The present invention [8] includes a polyurethane gel which is a reaction product of the polyurethane gel material according to any one of the above [1] to [7].
[0020]
　In the present invention [9], in the polyurethane gel material, the equivalent ratio (NCO / hydroxyl group) of the isocyanate group in the aliphatic polyisocyanate (A) to the hydroxyl group in the polyol (B) is 0.8 or more and 1.2 or less. The polyurethane gel according to the above [8] is contained.
[0021]
　The present invention [10] includes a pseudo-biomaterial comprising the polyurethane gel according to the above [8] or [9].
[0022]
　The present invention [11] comprises a preparatory step of preparing the polyurethane gel material according to any one of the above [1] to [7], and a reaction step of reacting and curing the polyurethane gel material to obtain a polyurethane gel. In the reaction step, the equivalent ratio (NCO / hydroxyl group) of the isocyanate group in the aliphatic polyisocyanate (A) to the hydroxyl group in the polyol (B) is 0.8 or more and 1.2 or less. Includes the manufacturing method of.
Effect of the invention
[0023]
　According to the polyurethane gel material of the present invention, bleeding of a plasticizer can be suppressed, surface tackiness can be reduced, and a polyurethane gel having excellent curability, mechanical properties and hardness can be obtained.
[0024]
　In addition, the polyurethane gel of the present invention can suppress bleeding of the plasticizer, reduce surface tackiness, and is excellent in curability, mechanical properties, and hardness.
[0025]
　Further, according to the method for producing a polyurethane gel of the present invention, it is possible to suppress bleeding of a plasticizer, reduce surface tackiness, and obtain a polyurethane gel having excellent curability, mechanical properties and hardness.
Mode for carrying out the invention
[0026]
　The polyurethane gel material of the present invention is a material that gels by a urethanization reaction described later to form a polyurethane gel (described later). That is, the polyurethane gel material is a raw material composition of a polyurethane gel (described later).
[0027]
　The polyurethane gel material is a plastic containing an aliphatic polyisocyanate (A) having an average functional group number of 2.3 or more and 3.2 or less, a polyol (B) having an average functional group number of 2.0 or more and 2.3 or less, and an ester group. It contains the agent (C), preferably an aliphatic polyisocyanate (A) having an average functional group number of 2.3 or more and 3.2 or less, and a polyol (B) having an average functional group number of 2.0 or more and 2.3 or less. , Contains only the plasticizer (C) containing an ester group.
[0028]
　The functional group of the aliphatic polyisocyanate (A) is an isocyanate group. Further, the functional group of the polyol (B) represents a hydroxyl group.
[0029]
　The aliphatic polyisocyanate (A) contains an isocyanurate derivative of an aliphatic diisocyanate and / or an alcohol-modified isocyanurate derivative, and preferably contains an alcohol-modified isocyanurate derivative.
[0030]
　Since such an aliphatic polyisocyanate (A) has both an aliphatic hydrocarbon group and an isocyanurate group, the aliphatic hydrocarbon group imparts appropriate flexibility to the polyurethane gel, and the isocyanurate group appropriately imparts the flexibility. The rigidity and polarity can be imparted, the affinity with the plastic agent (C) can be imparted, and the average number of functional groups can be adjusted within the range described later.
[0031]
　Examples of the aliphatic diisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate) and pentamethylene. Examples thereof include diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methylcaproate.
[0032]
　These aliphatic diisocyanates can be used alone or in combination of two or more.
[0033]
　As the aliphatic diisocyanate, pentamethylene diisocyanate (PDI) and hexamethylene diisocyanate (HDI) are preferably mentioned from the viewpoint of improving mechanical properties, and further, bleed resistance, low tack property, mechanical properties and hardness are improved. From the viewpoint of achieving the above, pentamethylene diisocyanate (PDI) is more preferable.
[0034]
　That is, if pentamethylene diisocyanate (PDI) is used as the aliphatic diisocyanate, a polyurethane gel having excellent bleed resistance, low tack property, mechanical properties and hardness can be obtained.
[0035]
　Then, the isocyanurate derivative of the aliphatic diisocyanate can be obtained by isocyanurate the above-mentioned aliphatic diisocyanate by a known method.
[0036]
　More specifically, the isocyanurate derivative of the aliphatic diisocyanate is, for example, an aliphatic diisocyanate of a known isocyanurate-forming catalyst (for example, N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2. -It can be obtained by reacting in the presence of (such as ethylhexanoate) and subjecting it to an isocyanurate-forming reaction.
[0037]
　The reaction conditions in the isocyanurate-forming reaction are not particularly limited and are appropriately set.
[0038]
　The alcohol-modified isocyanurate derivative of the aliphatic diisocyanate can be obtained by modifying the isocyanurate derivative of the aliphatic diisocyanate with alcohols.
[0039]
　The alcohols are not particularly limited, and examples thereof include aliphatic alcohols and aromatic alcohols, and preferred examples include aliphatic alcohols. Specifically, for example, methanol, ethanol, n-propanol, and isopropanol. , N-butanol, isobutanol (isobutyl alcohol), sec-butanol, tert-butanol, pentanol, hexanol, 2-ethylhexanol, octanol, decanol and other monohydric aliphatic alcohols such as ethylene glycol, 1,2- Dihydric fatty alcohols such as propanediol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, such as glycerin, tri. Examples thereof include trihydric aliphatic alcohols such as methylolpropane, and tetrahydric or higher aliphatic alcohols such as tetramethylolmethane.
[0040]
　These alcohols can be used alone or in combination of two or more. As the alcohols, a monohydric fatty alcohol is preferably mentioned, a monohydric fatty alcohol having 1 to 4 carbon atoms is more preferable, and isobutanol (also known as isobutyl alcohol) is more preferable. ..
[0041]
　Examples of the method of modifying the isocyanurate derivative of the aliphatic diisocyanate with alcohols include a method of first reacting the aliphatic diisocyanate with alcohols and then an isocyanurate-forming reaction in the presence of an isocyanurate-forming catalyst. For example, first, only the aliphatic diisocyanate is isocyanurate, and then the obtained polyisocyanurate is reacted with alcohols.
[0042]
　Preferably, the aliphatic diisocyanate is first reacted with alcohols, and then the isocyanurate-forming reaction is carried out in the presence of an isocyanurate-forming catalyst.
[0043]
　In such a reaction, the blending ratio of the aliphatic diisocyanate and the alcohols is appropriately set according to the purpose and use, but the alcohols are, for example, 0.1 with respect to 100 parts by mass of the aliphatic diisocyanate. By mass or more, preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, and for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 2 parts by mass. Parts or less, more preferably 1.5 parts by mass or less.
[0044]
　The reaction conditions between the aliphatic diisocyanate and the alcohols are appropriately set according to the purpose and use.
[0045]
　The reaction between the aliphatic diisocyanate and the alcohols is a urethanization reaction and an allophanation reaction, and an allophanate derivative of the aliphatic diisocyanate may be produced as a by-product. That is, the isocyanurate derivative of the aliphatic diisocyanate modified with alcohols may have both an isocyanurate group and an allophanate group.
[0046]
　In such a case, the molar ratio of allophanate groups in the alcohol-modified isocyanurate derivative of the aliphatic diisocyanate is less than the molar ratio of isocyanurate groups. For example, it is 0.05 mol or more, preferably 0.1 mol or more, more preferably 0.2 mol or more, and for example, less than 1.0 mol, preferably 0.5 mol or less.
[0047]
　When the molar ratio of allophanate groups is within the above range, mechanical properties and heat resistance can be improved.
[0048]
　The molar ratio of the allophanate group to the isocyanurate group can be determined according to the examples described later.
[0049]
　Further, in the above reaction, if necessary, further known additives such as storage stabilizers (o-toluenesulfonamide, p-toluenesulfonamide, etc.), reaction terminators (benzoyl chloride, etc.), antiblocking agents, etc. , Heat-resistant stabilizer, light-resistant stabilizer, ultraviolet absorber, antioxidant, antifoaming agent, mold release agent, pigment, dye, lubricant, filler, hydrolysis inhibitor and the like can be blended in an appropriate ratio.
[0050]
　Further, after completion of the above reaction, if necessary, the unreacted aliphatic diisocyanate can be removed by a known method such as distillation or extraction such as thin film distillation (Smith distillation).
[0051]
　The content ratio of the unreacted aliphatic diisocyanate (isocyanate monomer concentration) is, for example, 1% by mass or less, preferably 0.5% by mass or less, based on the total amount of the reaction solution obtained in the above reaction.
[0052]
　Further, the aliphatic polyisocyanate (A) may further contain other derivatives as long as it contains an isocyanurate derivative of an aliphatic diisocyanate and / or an alcohol-modified isocyanurate derivative.
[0053]
　Other derivatives are derivatives of the aliphatic diisocyanate, excluding the isocyanurate derivative of the aliphatic diisocyanate and the alcohol-modified isocyanurate derivative. For example, an allophanate derivative of the aliphatic diisocyanate, a uretdione derivative of the aliphatic diisocyanate, and a urea of ​​the aliphatic diisocyanate. Examples thereof include derivatives, carbodiimide derivatives of aliphatic diisocyanates, biuret derivatives of aliphatic diisocyanates, oxadiazine trione derivatives of aliphatic diisocyanates, uretonimine derivatives of aliphatic diisocyanates, and polyol modified products of aliphatic diisocyanates.
[0054]
　These other derivatives can be used alone or in combination of two or more.
[0055]
　As the other derivative, an allophanate derivative of an aliphatic diisocyanate is preferable.
[0056]
　The allophanate derivative of the aliphatic diisocyanate is obtained by subjecting the above-mentioned aliphatic diisocyanate to a urethanization reaction of the above-mentioned alcohols (preferably monohydric aliphatic alcohol), and then a known allophanization catalyst (for example, bismuth octylate, etc.). It can be obtained by performing an allophanation reaction in the presence of tris (2-ethylhexanoic acid) bismuth, etc.). The reaction conditions in the urethanization reaction and the allophanate reaction are not particularly limited and are appropriately set.
[0057]
　The content ratio of other derivatives (preferably allophanate derivatives) is appropriately set according to the purpose and application as long as the excellent effects of the present invention are not impaired. For example, with respect to 100 parts by mass of the total amount of the aliphatic polyisocyanate (A), the other derivatives are, for example, 0 parts by mass or more, for example, 50 parts by mass or less, preferably 40 parts by mass or less, more preferably 20 parts by mass. It is less than a part by mass.
[0058]
　Further, the aliphatic polyisocyanate (A) may contain an aliphatic polyisocyanate monomer, if necessary.
[0059]
　Examples of the aliphatic polyisocyanate monomer include the above-mentioned aliphatic diisocyanate (bifunctional aliphatic polyisocyanate monomer).
[0060]
　These aliphatic polyisocyanate monomers can be used alone or in combination of two or more.
[0061]
　The content ratio of the aliphatic polyisocyanate monomer is appropriately set according to the purpose and application as long as the excellent effects of the present invention are not impaired. For example, the amount of the aliphatic polyisocyanate monomer is, for example, 0 parts by mass or more, for example, 50 parts by mass or less, preferably 40 parts by mass or less, more preferably 40 parts by mass or less, based on 100 parts by mass of the total amount of the aliphatic polyisocyanate (A). , 20 parts by mass or less.
[0062]
　In the aliphatic polyisocyanate (A), the ratio of the isocyanurate derivative and / or the alcohol-modified isocyanurate derivative of the aliphatic diisocyanate, the other derivative, and the aliphatic polyisocyanate monomer is the aliphatic polyisocyanate (A). Is appropriately adjusted so that the average number of functional groups in the above is in the range of 2.3 to 3.2, as long as the excellent effect of the present invention is not impaired.
[0063]
　More specifically, the isocyanurate derivative and / or alcohol-modified isocyanurate derivative of the aliphatic diisocyanate is, for example, 50 parts by mass or more, preferably 60 parts by mass, based on 100 parts by mass of the total amount of the aliphatic polyisocyanate (A). More than parts by mass, more preferably 80 parts by mass or more, for example, 100 parts by mass or less, and other derivatives and / or aliphatic polyisocyanate monomers are, for example, 0 parts by mass or more, for example, 50 parts by mass or less, preferably 50 parts by mass or less. Is 40 parts by mass or less, more preferably 20 parts by mass or less.
[0064]
　From the viewpoint of bleed resistance and mechanical properties, the aliphatic polyisocyanate (A) is preferably composed of an isocyanurate derivative of an aliphatic diisocyanate and / or an alcohol-modified isocyanurate derivative, and more preferably of an aliphatic diisocyanate. It consists of an alcohol-modified isocyanurate derivative, more preferably an alcohol-modified isocyanurate derivative of pentamethylene diisocyanate (however, an allophanate derivative (alofanate derivative containing no isocyanurate group) and a uretdione derivative produced as a by-product during the production of the isocyanurate derivative). Is allowed to be contained.).
[0065]
　From the viewpoint of curability and mechanical properties, the average number of functional groups of the aliphatic polyisocyanate (A) is 2.3 or more, preferably 2.5 or more, more preferably 2.6 or more, still more preferably 2. It is 7 or more, 3.2 or less, preferably 3.1 or less, more preferably 3.0 or less, and further preferably 2.9 or less.
[0066]
　The average number of functional groups of the aliphatic polyisocyanate (A) is calculated according to Examples described later.
[0067]
　The isocyanate group concentration of the aliphatic polyisocyanate (A) is, for example, 20.0% by mass or more, preferably 22.0% by mass or more, and for example, 30.0% by mass or less, preferably 25. It is 0% by mass or less, more preferably 24.6% by mass or less.
[0068]
　The polyol (B) contains a polyoxyalkylene (2 to 3 carbon atoms) polyol having an ethylene oxide content of 30% by mass or less, and / or polytetramethylene ether glycol. If the polyol (B) contains these, a flexible polyurethane gel can be obtained.
[0069]
　The polyoxyalkylene (2 to 3 carbon atoms) polyol is an addition polymer of an alkylene oxide having 2 to 3 carbon atoms, for example, using a low molecular weight polyol or a known low molecular weight polyamine as an initiator.
[0070]
　The low molecular weight polyol is, for example, a compound having two or more hydroxyl groups in the molecule and having a molecular weight of 50 or more and 400 or less, and for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol. , 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2- Trimethylpentanediol, 3,3-dimethylolheptan, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and theirs. Divalents such as bisphenol A hydride, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, etc. Examples thereof include trivalent alcohols such as glycerin, trimethylolpropane and triisopropanolamine, and tetravalent alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin. These low molecular weight polyols can be used alone or in combination of two or more. The low molecular weight polyol preferably includes a dihydric alcohol and a trihydric alcohol, and more preferably a dihydric alcohol.
[0071]
　The polyoxyalkylene polyol (2 to 3 carbon atoms) can be obtained as a polyoxyalkylene polyol having an average number of functional groups according to the number of functional groups of the initiator. For example, when an initiator having 2 functional groups is used, a polyoxyalkylene diol having an average functional group of 2 is obtained, and when an initiator having 3 functional groups is used, a polyoxyalkylene triol having an average functional group of 3 is obtained. Is obtained.
[0072]
　Specific examples of the alkylene oxide having 2 to 3 carbon atoms include ethylene oxide and propylene oxide. The addition form of the alkylene oxide is not particularly limited and may be either block or random.
[0073]
　In the polyoxyalkylene (2 to 3 carbon atoms) polyol, the content of ethylene oxide is 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and further, from the viewpoint of bleed resistance. It is preferably 5% by mass or less, and particularly preferably 0% by mass.
[0074]
　That is, as the polyoxyalkylene (2 to 3 carbon atoms) polyol, an addition homopolymer of propylene oxide (polyoxypropylene polyol) and an addition copolymer of ethylene oxide and propylene oxide (random and / or block copolymer) ). Moreover, in the addition copolymer of ethylene oxide and propylene oxide, the content of ethylene oxide is in the above range.
[0075]
　The content of ethylene oxide can be calculated from the charging ratio in the production of polyoxyalkylene (2 to 3 carbon atoms) polyol.
[0076]
　These polyoxyalkylene (2 to 3 carbon atoms) polyols can be used alone or in combination of two or more.
[0077]
　As the polyoxyalkylene (2 to 3 carbon atoms) polyol, a polyoxypropylene polyol is preferably used from the viewpoint of bleed resistance.
[0078]
　Examples of the polytetramethylene ether glycol include a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran (crystalline polytetramethylene ether glycol) and an amorphous poly obtained by copolymerizing the above divalent alcohol with a polymerization unit such as tetrahydrofuran. Examples thereof include tetramethylene ether glycol. In addition, crystallinity means that it is solid at room temperature (25 ° C.), and amorphous means that it is liquid at room temperature (25 ° C.).
[0079]
　The amorphous polytetramethylene ether glycol is, for example, a copolymer of tetrahydrofuran and alkyl-substituted tetrahydrofuran (for example, 3-methyltetrahydrofuran) (tetrahydrofuran / alkyl-substituted tetrahydrofuran (molar ratio) = 15/85 to 85/15). ), For example, as a copolymer of tetrahydrofuran and branched glycol (for example, neopentyl glycol) (tetrahydrofuran / branched glycol (molar ratio) = 15/85 to 85/15). ..
[0080]
　Further, as the amorphous polytetramethylene ether glycol, a commercially available product can be used, and such commercially available products include, for example, "PTXG" series manufactured by Asahi Kasei Fibers Co., Ltd. and "PTG-L" manufactured by Hodogaya Chemical Co., Ltd. ”Series and so on.
[0081]
　In addition, plant-derived polytetramethylene ether glycol produced from a plant-based raw material such as furfural and using tetrahydrofuran as a starting material can also be used.
[0082]
　Examples of the polytetramethylene ether glycol include amorphous polytetramethylene ether glycol from the viewpoint of mechanical properties and hardness, and preferably crystalline polytetra from the viewpoint of bleed resistance and low tack property. Methylene ether glycol can be mentioned.
[0083]
　As the polyol (B), polyoxypropylene glycol and crystalline polytetramethylene ether glycol are preferable, and polyoxypropylene glycol is more preferable, from the viewpoint of bleed resistance, mechanical properties and hardness.
[0084]
　Further, the polyol (B) can contain the above polyoxyalkylene (2 to 3 carbon atoms) polyol and / or other polyol as long as it contains the above polytetramethylene ether glycol.
[0085]
　Examples of other polyols include the above-mentioned low molecular weight polyols, known high-molecular-weight polyols (excluding polyoxyalkylene (2 to 3 carbon atoms) polyols, and the above-mentioned polytetramethylene ether glycol). A high molecular weight polyol is a compound having a molecular weight (polystyrene-equivalent number average molecular weight measured by GPC) of more than 400 and having two or more hydroxyl groups, for example, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol. , Polyolefin polyol, acrylic polyol, vinyl monomer modified polyol and the like.
[0086]
　These other polyols can be used alone or in combination of two or more.
[0087]
　In the polyol (B), the content ratio of other polyols is appropriately adjusted as long as the excellent effects of the present invention are not impaired.
[0088]
　From the viewpoint of bleed resistance, low tack property, mechanical properties and hardness, the polyol (B) preferably contains no other polyol, is a polyoxyalkylene (2 to 3 carbon atoms) polyol, and / or poly. It consists of tetramethylene ether glycol, more preferably a polyoxyalkylene (2 to 3 carbon atoms) polyol.
[0089]
　Further, the polyol (B) is used alone or in combination of two or more so that the average number of functional groups and the average hydroxyl value (OH value) are in the range described later.
[0090]
　Specifically, the average number of functional groups of the polyol (B) is 2.0 or more from the viewpoint of curability, and 2.3 or less, preferably 2.2 or less, from the viewpoint of mechanical properties. Preferably, it is 2.1 or less. The average number of functional groups of the polyol (B) is 2.0, which is particularly preferable from the viewpoint of bleed resistance and low tack property.
[0091]
　The average hydroxyl value (OH value) of the polyol (B) is 30 mgKOH / g or more, preferably 35 mgKOH / g or more, more preferably 37 mgKOH / g or more, and further, from the viewpoint of bleed resistance and low tack property. It is preferably 40 mgKOH / g or more, 70 mgKOH / g or less, preferably 65 mgKOH / g or less, and more preferably 56 mgKOH / g or less.
[0092]
　The average number of functional groups of the polyol (B) is calculated from the formulation of the preparation, and the hydroxyl value of the polyol is measured according to the description of JIS K 1557-1 (2007).
[0093]
　The number average molecular weight of the polyol (B) (number average molecular weight calculated from the average number of functional groups and hydroxyl value) is preferably 1600 or more, for example, from the viewpoint of curability, mechanical properties, bleed resistance and low tackiness. Is 1800 or more, more preferably 2000 or more, for example, 4300 or less, preferably 3500 or less, more preferably 3000 or less, still more preferably 2500 or less.
[0094]
　When the hydroxyl value and the number average molecular weight are in the above ranges, hydrophobicity can be imparted to the obtained polyurethane gel, the affinity with the plasticizer (C) can be improved, and bleeding can be suppressed.
[0095]
　In the polyurethane gel material, the content ratio of the aliphatic polyisocyanate (A) and the polyol (B) is the equivalent ratio (NCO / hydroxyl group) of the isocyanate group in the aliphatic polyisocyanate (A) to the hydroxyl group in the polyol (B). , 0.8 to 1.2.
[0096]
　The plasticizer (C) contains an ester group. By using the plasticizer (C) containing an ester group, it is possible to improve the curability as compared with the case of using a plasticizer not containing an ester group (for example, chloroparaffin).
[0097]
　Further, when the plasticizer (C) contains an ester group, it is possible to obtain an affinity for the urethane group obtained by the reaction of the aliphatic polyisocyanate (A) and the polyol (B).
[0098]
　More specifically, as the plasticizer (C) containing an ester group, for example, cyclohexanedicarboxylic acid esters, phthalates, isophthalates, tetrahydrophthalates, adipic acid esters, and azelaic acid esters. , Sebasic acid esters, fumaric acid esters, maleic acid esters, trimellitic acid esters, pyromellitic acid esters, citric acid esters, itaconic acid esters, oleic acid esters, ricinolic acid esters, stearers Examples thereof include acid esters, other fatty acid esters, and phosphoric acid esters.
[0099]
　Examples of cyclohexane dicarboxylic acid esters include dimethylcyclohexane-1,2-dicarboxylate, diethylcyclohexane-1,2-dicarboxylate, dibutylcyclohexane-1,2-dicarboxylate, and di (2-ethylhexyl) cyclohexane. -1,2-dicarboxylate, dioctylcyclohexane-1,2-dicarboxylate, diisodecylcyclohexane-1,2-dicarboxylate, diisononylcyclohexane-1,2-dicarboxylate, dimethylcyclohexane-1,3-dicarboxylate Carboxylate, diethylcyclohexane-1,3-dicarboxylate, dibutylcyclohexane-1,3-dicarboxylate, di (3-ethylhexyl) cyclohexane-1,3-dicarboxylate, dioctylcyclohexane-1,3-dicarboxylate Rate, diisodecylcyclohexane-1,3-dicarboxylate, diisononylcyclohexane-1,3-dicarboxylate, dimethylcyclohexane-1,4-dicarboxylate, diethylcyclohexane-1,4-dicarboxylate, dibutylcyclohexane-1 , 4-dicarboxylate, di (4-ethylhexyl) cyclohexane-1,4-dicarboxylate, dioctylcyclohexane-1,4-dicarboxylate, diisodecylcyclohexane-1,4-dicarboxylate, diisononylcyclohexane-1, 4-dicarboxylate, 3,4-epoxy-dimethylcyclohexane-1,2-dicarboxylate, 3,4-epoxy-diethylcyclohexane-1,2-dicarboxylate, 3,4-epoxy-dibutylcyclohexane-1 , 2-Dicarboxylate, 3,4-epoxy-di (2-ethylhexyl) cyclohexane-1,2-dicarboxylate, 4,5-epoxy-dimethylcyclohexane-1,2-dicarboxylate, 4,5- Epoxy-diethylcyclohexane-1,2-dicarboxylate, 4,5-epoxy-dibutylcyclohexane-1,2-dicarboxylateExamples thereof include xylate, 4,5-epoxy-di (2-ethylhexyl) cyclohexane-1,2-dicarboxylate and the like.
[0100]
　Examples of phthalates include dibutylphthalate, isobutylphthalate, diheptylphthalate, di- (2-ethylhexyl) phthalate, di-n-octylphthalate, dinonylphthalate, diisononylphthalate, diisodecylphthalate, diundecylphthalate, and ditri Examples thereof include decylphthalate, dicyclohexylphthalate and diphenylphthalate.
[0101]
　Examples of the isophthalate ester include di- (2-ethylhexyl) isophthalate and diisooctylisophthalate.
[0102]
　Examples of the tetrahydrophthalates include di- (2-ethylhexyl) tetrahydrophthalate and the like.
[0103]
　Examples of the adipate ester include di- (2-ethylhexyl) adipate, dibutoxyethyl adipate, diisononyl adipate and the like.
[0104]
　Examples of the azelaic acid ester include di-n-hexyl azelate and di- (2-ethylhexyl) azelate.
[0105]
　Examples of sebacic acid esters include di-n-butyl sebacate.
[0106]
　Examples of fumaric acid esters include di-n-butyl fumarate and di- (2-ethylhexyl) fumarate.
[0107]
　Examples of maleic acid esters include di-n-butyl maleate and di- (2-ethylhexyl) maleate.
[0108]
　Examples of the trimellitic acid esters include tri- (2-ethylhexyl) trimellitate, tri-n-octylrimerite, and triisooctylrimerite.
[0109]
　Examples of pyromellitic acid esters include tetra- (2-ethylhexyl) pyromeritate and tetra-n-octylpyromellitate.
[0110]
　Examples of citric acid esters include tri-n-butyl citrate and acetyl tributyl citrate.
[0111]
　Examples of itaconic acid esters include dimethylitaconate, diethylitaconate, dibutylitaconate, di- (2-ethylhexyl) itaconic acid and the like.
[0112]
　Examples of oleic acid esters include glyceryl monooleate and diethylene glycol monooleate.
[0113]
　Examples of ricinoleic acid esters include glyceryl monolithinolate and diethylene glycol monolithinolate.
[0114]
　Examples of stearic acid esters include glycerin monostearate and diethylene glycol distearate.
[0115]
　Examples of other fatty acid esters include diethylene glycol diperargonate and pentaerythritol fatty acid ester.
[0116]
　Examples of the phosphoric acid ester include tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyldecyl phosphate, diphenyloctyl phosphate and the like.
[0117]
　The plasticizer (C) containing these ester groups can be used alone or in combination of two or more.
[0118]
　Examples of the ester group-containing plasticizer (C) include cyclohexanedicarboxylic acid esters, phthalates, and adipates, and more preferably cyclohexanedicarboxylic acids, from the viewpoint of curability and bleed resistance. Examples thereof include acid esters, adipates and their combined use, and more preferably, cyclohexanedicarboxylic acid esters.
[0119]
　The boiling point of the plasticizer (C) is, for example, 180 ° C. or higher, preferably 200 ° C. or higher, and more preferably 220 ° C. or higher. The upper limit of the boiling point is about 400 ° C. from the viewpoint of industrial availability.
[0120]
　In the polyurethane gel material, the content ratio of the plastic agent (C) containing an ester group is 50 parts by mass or more with respect to 100 parts by mass of the polyol component (B) from the viewpoint of bleed resistance, low tack property and hardness. It is preferably 80 parts by mass or more, more preferably 100 parts by mass or more, further preferably 150 parts by mass or more, 400 parts by mass or less, preferably 300 parts by mass or less, and more preferably 250 parts by mass or less. More preferably, it is 200 parts by mass or less.
[0121]
　According to such a polyurethane gel material, bleeding of a plasticizer can be suppressed, surface tackiness can be reduced, and a polyurethane gel having excellent curability, mechanical properties and hardness can be obtained.
[0122]
　When the content ratio of the plasticizer (C) is relatively large, the polyol (B) having a relatively high average hydroxyl value is preferably used.
[0123]
　For example, when the content ratio of the plasticizer (C) is 300 parts by mass or more with respect to 100 parts by mass of the polyol component (B), the average hydroxyl value of the polyol (B) is preferably 40 mgKOH / g or more, more preferably. Is 50 mgKOH / g or more, more preferably 55 mgKOH / g or more, and 70 mgKOH / g or less.
[0124]
　Then, in order to obtain a polyurethane gel, first, the above polyurethane gel material is prepared (preparation step), and then the aliphatic polyisocyanate (A) and the polyol (B) are mixed with a plasticizer (C) containing an ester group. ), And preferably, in the absence of a solvent, a urethanization reaction (solvent-free reaction, bulk polymerization) is carried out (reaction step).
[0125]
　In the urethanization reaction, for example, a known method such as a one-shot method or a prepolymer method is adopted, and a one-shot method is preferably adopted.
[0126]
　In the one-shot method, for example, the aliphatic polyisocyanate (A) and the polyol (B) are equivalent to the hydroxyl group in the polyol (B) with the isocyanate group in the aliphatic polyisocyanate (A) (NCO / hydroxyl group). Is 0.8 or more, preferably 0.9 or more, and 1.2 or less, preferably 1.1 or less, more preferably 1.05 or less, and then, for example, The curing reaction is carried out at room temperature to 120 ° C., preferably room temperature to 100 ° C., for example, for 5 minutes to 72 hours, preferably 2 to 10 hours. The curing temperature may be a constant temperature, or may be raised or cooled stepwise.
[0127]
　When the equivalent ratio (NCO / hydroxyl group) of the isocyanate group in the aliphatic polyisocyanate (A) to the hydroxyl group in the polyol (B) is in the above range, the polyurethane gel can be used while suppressing the bleeding of the plasticizer (C). Both flexibility and shape retention (rigidity) can be achieved.
[0128]
　Further, in the above reaction, for example, a known urethanization catalyst such as amines or an organometallic compound can be added, if necessary.
[0129]
　Examples of amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether and N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, for example, imidazole. Examples thereof include imidazoles such as 2-ethyl-4-methylimidazole.
[0130]
　Examples of the organic metal compound include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, and dibutyltin dilaurate (dilauric acid). Organic tin compounds such as dibutyltin (IV)), dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurylate, dibutyltin dichloride, eg organic lead compounds such as lead octanoate, lead naphthenate, eg Examples thereof include organic nickel compounds such as nickel naphthenate, for example, organic cobalt compounds such as cobalt naphthenate, for example, organic copper compounds such as copper octeneate, for example, organic bismuth compounds such as bismuth octylate and bismuth neodecanoate.
[0131]
　Further, examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate and potassium octylate.
[0132]
　These urethanization catalysts can be used alone or in combination of two or more.
[0133]
　The urethanization catalyst is preferably an organometallic compound, more preferably an organotin compound, and even more preferably dibutyltin dilaurate (dibutyltin dilaurate (IV)).
[0134]
　The timing of addition of the urethanization catalyst is not particularly limited, and may be added in advance to, for example, the aliphatic polyisocyanate (A) and / or the polyol (B), or they. It may be added at the same time as the compounding of, and further, it may be added separately after compounding them.
[0135]
　The addition ratio of the urethanization catalyst is not particularly limited, and is appropriately set according to the purpose and application.
[0136]
　Further, in the above reaction, if necessary, further known additives such as storage stabilizers (o-toluenesulfonamide, p-toluenesulfonamide, etc.), blocking inhibitors, heat-resistant stabilizers, light-resistant stabilizers, etc. An ultraviolet absorber, an antioxidant, an antifoaming agent, a mold release agent, a pigment, a dye, a lubricant, a filler, an antioxidant and the like can be blended in an appropriate ratio.
[0137]
　The timing of addition of the additive is not particularly limited, and may be added in advance to, for example, the aliphatic polyisocyanate (A) and / or the polyol (B), or any of them. It may be added at the same time as the compounding, and further, it may be added separately after the compounding. The addition ratio of the additive is not particularly limited, and is appropriately set according to the purpose and application.
[0138]
　Such a polyurethane gel contains polyurethane, which is a reaction product of aliphatic polyisocyanate (A) and polyol (B), and a plasticizer (C), and has a higher-order structure (three-dimensional network) of polyurethane. It has a high viscosity, loses its fluidity due to the plasticizer (C) being encapsulated in polyurethane, and is in a solid state as a whole system.
[0139]
　The shear modulus of the polyurethane gel at 25 ° C. is 1 × 10 3 to 1 × 10 7 Pa. The shear modulus is measured by a solid viscoelasticity measuring device.
[0140]
　Such a polyurethane gel has a higher-order structure (three-dimensional network) of polyurethane formed by the reaction of an aliphatic polyisocyanate (A) having a specific average functional group and a polyol (B) having a specific average functional group. ) Contains a plasticizer (C) having an ester group in a specific ratio. As a result, the plasticizer (C) is confined in the three-dimensional network. As a result, the polyurethane gel can achieve both suppression of bleed resistance and reduction of surface tackiness.
[0141]
　That is, since the polyurethane gel is obtained from the polyurethane gel material, it can suppress bleeding of the plasticizer, reduce surface tackiness, and is excellent in curability, mechanical properties, and hardness.
[0142]
　Further, according to the above-mentioned method for producing a polyurethane gel, it is possible to suppress bleeding of a plasticizer, reduce surface tackiness, and obtain a polyurethane gel having excellent curability, mechanical properties and hardness.
[0143]
　The size of the polyurethane gel is set according to the type of mold used and the like, and for example, the thickness is, for example, 0.03 mm or more, preferably 0.05 mm or more, for example, 500 mm or less, preferably 500 mm or less. , 400 mm or less.
[0144]
　In addition, the polyurethane gel can be coated on a base material such as leather, artificial or synthetic leather, non-woven fabric, felt, sheet, or film.
[0145]
　Specifically, the polyurethane gel is an ultra-low hardness polyurethane elastomer, and its Asker C hardness (JIS K 7312 (1996)) is, for example, 0 or more, for example, 40 or less, preferably 30 or less. , More preferably 20 or less, still more preferably 15 or less, still more preferably 12 or less, and particularly preferably 10 or less.
[0146]
　When the Asker C hardness is in the above range, particularly 40 or less, it can be particularly preferably used as a gel having a tactile sensation, elasticity and flexibility close to that of human skin.
[0147]
　Further, such a polyurethane gel can be further encapsulated in a cloth such as cotton, silk or synthetic fiber, natural leather, synthetic leather, paper, non-woven fabric, resin film, soft foam or the like.
[0148]
　Such polyurethane gels are used for vibration-proof / vibration-isolating members, shock-absorbing members, cushioning members, surface protection members, cushioning materials, elbow pads, arm pads, switches, robot members, robot skins, mannequins, and mobility members. , Pads, clothing materials, aircraft materials, cosmetics, medical equipment, diapers, floor slip prevention materials, etc. Nursing care / clothing products, wearable materials, eyewear such as frames, eyewear ear / nose pads, earphones, headphones, grips, etc. Suitable for use as protective equipment such as sports parts, toys, play equipment, helmets, furniture, flexible sensors, seats, flexible rods, non-woven fabrics, composite materials with felt, shoe soles, anti-scratch, actuators, pseudo-biomaterials, etc. In particular, it can be suitably used as a pseudo-biomaterial.
[0149]
　Since the polyurethane gel of the present invention has tactile sensation, elasticity and flexibility close to those of various organs and organs constituting the human body and the tissues constituting them, it can be used as a pseudo-biomaterial in the medical field, healthcare field, etc. It is preferably used.
[0150]
　More specifically, the pseudobiological material composed of the above polyurethane gel constitutes the skeletal system, the cartilage and joints, the muscular system, the muscles, the skeletal muscles, the smooth muscles and the myocardium, and the circulatory system. Heart and blood vessels, respiratory system, upper airway, lower airway and lung, sensory system, skin, ears and nose, digestive system, oral cavity, pharynx, esophagus, stomach, small intestine, pancreas , Anal duct, anus, digestive gland, liver, gallbladder and pancreas, urinary system, kidney, renal pelvis, ureter, bladder and urinary tract, reproductive system Pseudo-diaphragm, pituitary gall, thyroid, parathyroid, adrenal, pancreas, testis and ovaries, nervous system, brain, spinal cord, cerebrospinal nerve and autonomic nerve, which make up the ducts, uterus and vagina, endocrine system Formed as a biological model, for example, a pseudo-biological model for practicing various medical operations, a pseudo-biological model for practicing various tests (ultrasonography, CT scan, etc.), a pseudo-biological model in remote medicine and medical care, a healthcare field It is suitably used as wearable equipment and terminal equipment in the above, as well as exhibition samples, equipment for education, toys, and the like.
Example
[0151]
　Next, the present invention will be described with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples. In addition, "part" and "%" are based on mass unless otherwise specified. In addition, specific numerical values ​​such as the compounding ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned "Form for carrying out the invention", and the compounding ratios corresponding to them ( Substitute the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess") such as content ratio), physical property value, parameter, etc. be able to.
[0152]
　In addition, the measurement methods adopted in each production example, each example, and each comparative example are described below.
[0153]
　1. 1. Measuring method
　　 Using a
　potential differential titrator (manufactured by Kyoto Electronics Co., Ltd., model number: AT-510), JIS K-1603- The isocyanate group concentration (isocyanate group content) was measured by the toluene / dibutylamine / hydrochloric acid method based on 1 (2007), and the conversion rate of the isocyanate group of the measurement sample was calculated by the following formula.
[0154]
　　Isocyanate group conversion rate = 100- (isocyanate group concentration in the reaction mixture after the reaction / isocyanate group concentration in the reaction solution before the reaction x 100)
　　
　International Publication No. 2012/12291 Pentamethylene diisocyanate or commercially available hexamethylene diisocyanate produced in the same manner as in Example 1 in the specification of the No. pamphlet was used as a standard substance, labeled with dibenzylamine, and chromatograph obtained under the following HPLC measurement conditions. The concentration of unreacted isocyanate monomer (pentamethylene diisocyanate monomer or hexamethylene diisocyanate monomer) was calculated from the calibration line prepared from the area value of gram.
[0155]
　　Equipment; Prominence (manufactured by Shimadzu Corporation)
　　Pump LC-
　　20AT Degassa DGU-20A3
　　Auto Sampler SIL-20A
　　Column Constant Temperature Bath COT-20A
　　Detector SPD-20A
　　Column; SHISEIDO SILICA SG-120
　　Column Temperature; 40 ° C
　　Eluent; n- Hexane / methanol / 1,2-dichloroethane = 90/5/5 (volume ratio)
　　Flow rate; 0.2 mL / min
　　Detection method; UV 225 nm
　　
　E-type viscosity manufactured by Toki Sangyo Co., Ltd. Viscosity of sample measured at 25 ° C. using a total TV-30 (rotor angle: 1 ° 34', rotor radius: 24 cm) according to the cone plate viscometer method of JIS K5600-2-3 (2014). Was measured. The rotation speed of the cone plate at the time of measurement was sequentially changed from 100 rpm to 2.5 rpm as the viscosity increased.
[0156]
　　< Moral ratio of allophanate group to isocyanurate group by 1 H-NMR> 1 H-NMR was measured under
　the following equipment and conditions, and the content ratio of allophanate group to 1 mol of isocyanurate group in aliphatic polyisocyanate (1) The molar ratio of allophanate group / isocyanurate group) was calculated by the following formula. Incidentally, as a reference for the chemical shift ppm, D 6 using tetramethylsilane -DMSO solvent (0 ppm). Device; JNM-AL400 (manufactured by JEOL) conditions; measurement frequency: 400 MHz, solvent: D 6 -DMSO, solute concentration: 5 wt% 　isocyanurate group (methylene group directly bonded to the isocyanurate group (CH 2 protons group)) Attribution peak (6H): 3.8ppm 　allophanate group (NH group in allophanate group) proton attribution peak (1H): 8.3-8.7ppm 　　allophanate group / isocyanurate group (molar ratio) = allophanate group Integrated value of the assigned peak of the proton / (Integrated value of the assigned peak of the proton of the isocyanurate group / 6) 　　

　The average number of isocyanate groups of the aliphatic polyisocyanate was calculated by the following formula from the isocyanate group concentration, the solid content concentration (NV), and the number average molecular weight of gel permeation chromatography measured under the following equipment and conditions.
[0157]
　Average number of isocyanate groups = A / B × C / 42.02
(In the formula, A indicates the isocyanate group concentration, B indicates the solid content concentration, and C indicates the number average molecular weight.)
Equipment: HLC-8220 GPC (Made by Tosoh)
Column: TSKgelG1000HXL, TSKgelG2000HXL, and TSKgelG3000HXL (manufactured by Tosoh) are connected in series
Detector: Differential refractive index meter
Measurement conditions
Injection amount: 100 μL
Eluent: tetrahydrofuran
Flow rate: 0.8 mL / min
Temperature: 40 ° C
Calibration line: Standard polyethylene oxide in the range of 106 to 22450 (manufactured by Toso, trade name: TSK standard polyethylene oxide)
　　 The
　hydroxyl value of potassium hydroxide corresponding to the hydroxyl group in 1 g of polyoxyalkylene polyol. It was defined as the number of mg. Then, the hydroxyl value of the polyol was measured according to JIS K1557 (2007) Section 6.4 “Hydroxylity value”.
[0158]
　2. 2. Raw Material
　(1) Aliphatic Polyisocyanate (A)
　Preparation Example 1 (Isocyanate (a-1) (alcohol-modified isocyanurate derivative of PDI))
　Four equipped with a thermometer, a stirrer, a reflux tube, and a nitrogen introduction tube. In the mouth flask, 500 parts by mass of pentamethylene diisocyanate (hereinafter referred to as PDI) produced in the same manner as in Example 1 in the specification of International Publication No. 2012/121291, and 6.9 parts by mass of isobutyl alcohol. , 2,6-Di (tert-butyl) -4-methylphenol was charged in an amount of 0.3 parts by mass, and tris (tridecyl) phosphite was charged in an amount of 0.3 parts by mass, respectively, and reacted at 80 ° C. for 2 hours. ..
[0159]
　Next, 0.05 parts by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was blended as an isocyanurate-forming catalyst. The isocyanate group concentration was measured and the reaction was continued until the concentration reached 48.3% by mass (ie, conversion rate 10% by mass). When the predetermined conversion rate (conversion rate 10% by mass) was reached after 20 minutes, 0.12 parts by mass of o-toluenesulfonamide was added. The obtained reaction mixture was passed through a thin film distillation apparatus (temperature: 150 ° C., vacuum degree: 0.093 kPa) to remove unreacted pentamethylene diisocyanate monomer, and further, with respect to 100 parts by mass of the obtained filtrate. , O-Toluene Sulfonamide (0.02 parts by mass) and Benzoyl Chloride (0.003 parts by mass) were added to obtain an alcohol-modified isocyanurate derivative of PDI. This was designated as isocyanate (a-1).
[0160]
　The average number of isocyanate groups of isocyanate (a-1) was 2.8, the isocyanate monomer concentration was 0.4% by mass, the isocyanate group concentration was 23.4% by mass, and the viscosity at 25 ° C. was 950 mPa · s.
[0161]
Also, 1 mol ratio of allophanate groups and isocyanurate groups by H-NMR measurement was allophanate groups / isocyanurate groups = 33.0 / 100.
[0162]
　Preparation Example 2 (Isocyanate (a-2) (alcohol-modified isocyanurate derivative of PDI))
　500 parts by mass of PDI, isobutyl in a four-necked flask equipped with a thermometer, a stirrer, a reflux tube, and a nitrogen introduction tube. 0.5 parts by mass of alcohol, 0.3 parts by mass of 2,6-di (tert-butyl) -4-methylphenol, 0.3 parts by mass of tris (tridecyl) phosphite were charged, respectively, and 80 parts were charged. The reaction was carried out at ° C. for 2 hours.
[0163]
　Next, 0.05 parts by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was blended as an isocyanurate-forming catalyst. The isocyanate group concentration was measured, and the reaction was continued until the concentration reached 48.9% by mass (that is, the conversion rate was 10% by mass). When the predetermined conversion rate (conversion rate 10% by mass) was reached after 50 minutes, 0.12 parts by mass of o-toluenesulfonamide was added. The obtained reaction mixture was passed through a thin film distillation apparatus (temperature: 150 ° C., vacuum degree: 0.093 kPa) to remove unreacted pentamethylene diisocyanate monomer, and further, with respect to 100 parts by mass of the obtained filtrate. , O-Toluene Sulfonamide (0.02 parts by mass) and Benzoyl Chloride (0.003 parts by mass) were added to obtain an alcohol-modified isocyanurate derivative of PDI. This was designated as isocyanate (a-2).
[0164]
　The average number of isocyanate groups of isocyanate (a-2) was 3.1, the isocyanate monomer concentration was 0.5% by mass, the isocyanate group concentration was 24.7% by mass, and the viscosity at 25 ° C. was 2000 mPa · s.
[0165]
Also, 1 mol ratio of allophanate groups and isocyanurate groups by H-NMR measurement was allophanate groups / isocyanurate groups = 7.4 / 100.
[0166]
　Preparation Example 3 (Isocyanate (a-3) (isocyanurate derivative of PDI))
　500 parts by mass of PDI, 2,6 in a four-necked flask equipped with a thermometer, a stirrer, a reflux tube, and a nitrogen introduction tube. -Di (tert-butyl) -4-methylphenol was charged in an amount of 0.3 parts by mass, and tris (tridecyl) phosphite was charged in an amount of 0.3 parts by mass, respectively, and heated to 80 ° C. Next, 0.05 parts by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was blended as an isocyanurate-forming catalyst.
The isocyanate group concentration was measured, and the reaction was continued until the concentration reached 49.0% by mass (that is, the conversion rate was 10% by mass). When the predetermined conversion rate (conversion rate 10% by mass) was reached after 50 minutes, 0.12 parts by mass of o-toluenesulfonamide was added. The obtained reaction mixture was passed through a thin film distillation apparatus (temperature: 150 ° C., vacuum degree: 0.093 kPa) to remove unreacted pentamethylene diisocyanate monomer, and further, with respect to 100 parts by mass of the obtained filtrate. , O-Toluene Sulfonamide was added in an amount of 0.02 parts by mass and benzoyl chloride was added in an amount of 0.003 parts by mass to obtain an isocyanurate derivative of PDI. This was designated as isocyanate (a-3).
[0167]
　The average number of isocyanate groups of isocyanate (a-3) was 3.2, the isocyanate monomer concentration was 0.5% by mass, the isocyanate group concentration was 24.9% by mass, and the viscosity at 25 ° C. was 2800 mPa · s.
[0168]
Also, 1 mol ratio of allophanate groups and isocyanurate groups by H-NMR measurement was allophanate groups / isocyanurate groups = 0/100.
[0169]
　Preparation Example 4 (Isocyanate (a-4) (alcohol-modified isocyanurate derivative of PDI))
　500 parts by mass of PDI, isobutyl in a four-necked flask equipped with a thermometer, a stirrer, a reflux tube, and a nitrogen introduction tube. 0.5 parts by mass of alcohol, 0.3 parts by mass of 2,6-di (tert-butyl) -4-methylphenol, 0.3 parts by mass of tris (tridecyl) phosphite were charged, respectively, and 80 parts were charged. The reaction was carried out at ° C. for 2 hours.
[0170]
　Next, 0.05 parts by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was blended as an isocyanurate-forming catalyst. The isocyanate group concentration was measured, and the reaction was continued until the concentration reached 40.3% by mass (that is, the conversion rate was 26% by mass). When the predetermined conversion rate (conversion rate 26% by mass) was reached after 130 minutes, 0.12 parts by mass of o-toluenesulfonamide was added. The obtained reaction mixture was passed through a thin film distillation apparatus (temperature: 150 ° C., vacuum degree: 0.093 kPa) to remove unreacted pentamethylene diisocyanate monomer, and further, with respect to 100 parts by mass of the obtained filtrate. , O-Toluene Sulfonamide (0.02 parts by mass) and Benzoyl Chloride (0.003 parts by mass) were added to obtain an alcohol-modified isocyanurate derivative of PDI. This was designated as isocyanate (a-4).
[0171]
　The average number of isocyanate groups of isocyanate (a-4) was 3.8, the isocyanate monomer concentration was 0.5% by mass, the isocyanate group concentration was 23.1% by mass, and the viscosity at 25 ° C. was 9000 mPa · s.
[0172]
Also, 1 mol ratio of allophanate groups and isocyanurate groups by H-NMR measurement was = 5.0 / 100 allophanate / isocyanurate groups.
[0173]
　Preparation Example 5 (Isocyanate (a-5) (alophanate derivative of PDI)) In
　a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube and a cooling tube, 1500 parts by mass of PDI and isobutanol were added under a nitrogen atmosphere. 24 parts by mass, 0.3 parts by mass of 2,6-di (t-butyl) -4-methylphenol and 0.3 parts by mass of tris (tridecyl) phosphite were charged, and the urethanization reaction was carried out at 85 ° C. for 3 hours. I let you.
[0174]
　Next, 0.02 parts by mass of tris (2-ethylhexanoic acid) bismuth was added as an allophanation catalyst, and the reaction was carried out until the isocyanate group concentration reached the calculated value (46.7% by mass, that is, the conversion rate was 10% by mass). After that, 0.02 parts by mass of o-toluenesulfonamide was added.
[0175]
　Then, the obtained reaction solution was passed through a thin film distillation apparatus (vacuum degree 0.093 KPa, temperature 150 ° C.) to remove unreacted pentamethylene diisulfate, and further, o was applied to 100 parts by mass of the obtained filter medium. -Toluene sulfonamide was added in an amount of 0.02 parts by mass to obtain an allophanate derivative of PDI. This was designated as isocyanate (a-5).
[0176]
　The average number of isocyanate groups of isocyanate (a-5) is 2.0, the isocyanate group concentration is 20.4% by mass, the viscosity at 25 ° C. is 24 mPa · s, and the isocyanate monomer concentration is 0.2 mass. %Met.
[0177]
Also, 1 mol ratio of allophanate groups and isocyanurate groups by H-NMR measurement was = 100/0 allophanate / isocyanurate groups.
[0178]
　Preparation Example 6 (Isocyanate (a-6) (alcohol-modified isocyanurate derivative of HDI)
　PDI was changed to hexamethylene diisocyanate (manufactured by Mitsui Chemicals, Inc., trade name: Takenate 700 (hereinafter referred to as HDI)), except that it was changed. An alcohol-modified isocyanurate derivative of HDI was obtained by the same method as in Preparation Example 1. This was designated as isocyanate (a-6).
[0179]
　The average number of isocyanate groups of isocyanate (a-6) was 2.9, the isocyanate monomer concentration was 0.5% by mass, the isocyanate group concentration was 22.1% by mass, and the viscosity at 25 ° C. was 840 mPa · s.
[0180]
Also, 1 mol ratio of allophanate groups and isocyanurate groups by H-NMR measurement was allophanate groups / isocyanurate groups = 34.3 / 100.
[0181]
　Preparation Example 7 (Isocyanate (a-7) (polypoly derivative of PDI (TMP modified product))
　200 parts by mass of PDI is placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube. The temperature was raised to 95 ° C. with stirring under a nitrogen atmosphere. Then, 21.1 parts by mass of trimethylol propane (hereinafter referred to as TMP) was charged into the dropping funnel and heated by a ribbon heater.
[0182]
　The molten TMP was added dropwise over about 60 minutes. Then, the urethanization reaction was continued for about 3 hours until the isocyanate group concentration reached the calculated value. The obtained reaction solution was passed through a thin film distillation apparatus (vacuum degree 50 Pa, temperature 130 ° C.) to remove unreacted PDI to obtain a polyol derivative (TMP modified product) of PDI. This was designated as isocyanate (a-7).
[0183]
　The average number of isocyanate groups of isocyanate (a-7) was 3.7, the isocyanate group concentration was 13.8% by mass, and the viscosity at 3.7 and 25 ° C. was 450 mPa · s.
[0184]
　(2) polyol (B)
　Preparation Example 1 (polyol (b-1))
　Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to propylene glycol, number average molecular weight (Mn) = 2000, average number of functional groups 2, A hydroxyl value of 56 mgKOH / g and an ethylene oxide concentration in the total oxyalkylene (0% by mass) were used as the polyol (b-1).
[0185]
　The polyol (b-1) is polyoxypropylene glycol (PPG).
[0186]
　Preparation Example 2 (Polyxe (b-2))
　Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to propylene glycol, number average molecular weight (Mn) = 1000, average number of functional groups 2, hydroxyl value 112 mgKOH / g, total The ethylene oxide concentration in the oxyalkylene (0% by mass) was used as the polyol (b-2).
[0187]
　The polyol (b-2) is polyoxypropylene glycol (PPG).
[0188]
　Preparation Example 2-1 (polyol (b-2-1))
　A polyol (b-1 ) having a number average molecular weight of 2000 and a polyol (b-2) having a number average molecular weight of 1000 are mixed at 1: 1 (b-1 :). It was mixed so as to have b-2 (mass ratio)), and a polyol (b-2-1) was obtained as a mixture. The number average molecular weight of the polyol (b-2-1) was about 1300 (1335), the average number of functional groups was 2, the hydroxyl value was 84 mgKOH / g, and the ethylene oxide concentration in the total oxyalkylene was 0% by mass.
[0189]
　The polyol (b-2-1) is polyoxypropylene glycol (PPG).
[0190]
　Preparation Example 2-2 (polyol (b-2-2))
　A polyol (b-1 ) having a number average molecular weight of 2000 and a polyol (b-2) having a number average molecular weight of 1000 are mixed at 4: 1 (b-1 :). It was mixed so as to have b-2 (mass ratio)), and a polyol (b-2-2) was obtained as a mixture. The number average molecular weight of the polyol (b-2-2) was about 1700 (1674), the average number of functional groups was 2, the hydroxyl value was 67 mgKOH / g, and the ethylene oxide concentration in the total oxyalkylene was 0% by mass.
[0191]
　The polyol (b-2-2) is polyoxypropylene glycol (PPG).
[0192]
　Preparation Example 3 (Polyxe (b-3))
　Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to propylene glycol, number average molecular weight (Mn) = 3000, average number of functional groups 2, hydroxyl value 37 mgKOH / g, total The ethylene oxide concentration in the oxyalkylene (0% by mass) was used as the polyol (b-3).
[0193]
　The polyol (b-3) is polyoxypropylene glycol (PPG).
[0194]
　Preparation Example 4 (
　Polycarbonate (b-4)) Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to propylene glycol, number average molecular weight (Mn) = 4000, average number of functional groups 2, hydroxyl value 28 mgKOH / g, total Ethylene oxide concentration in oxyalkylene = 0% by mass) was designated as a polyol (b-4).
[0195]
　The polyol (b-4) is polyoxypropylene glycol (PPG).
[0196]
　Preparation Example 5 (Polyxe (b-5))
　Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to glycerin, number average molecular weight (Mn) = 3000, average number of functional groups 3, hydroxyl value 56 mgKOH / g, total oxy Ethylene oxide concentration in alkylene = 0% by mass) was designated as a polyol (b-5).
[0197]
　The polyol (b-5) is polypropylene triol (PPT).
[0198]
　Preparation Example 6 (
　Polycarbonate (b-6)) Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to glycerin and then addition polymerization of ethylene oxide, number average molecular weight (Mn) = 2000, average number of functional groups 2, A hydroxyl value of 56 mgKOH / g and an ethylene oxide concentration in the total oxyalkylene (20% by mass) were used as a polyol (b-6).
[0199]
　The polyol (b-6) is an ethylene oxide (EO) / propylene oxide (PO) copolymer.
[0200]
　Preparation Example 7 (
　Polycarbonate (b-7)) Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to glycerin and then addition polymerization of ethylene oxide, number average molecular weight (Mn) = 2000, average number of functional groups 2, A hydroxyl value of 56 mgKOH / g and an ethylene oxide concentration in the total oxyalkylene (40% by mass) were used as a polyol (b-7).
[0201]
　The polyol (b-7) is an ethylene oxide (EO) / propylene oxide (PO) copolymer.
[0202]
　Preparation Example 8 (polypoly (b-8))
　number of polytetramethylene ether glycols having an average molecular weight of 2000 (PTMEG, manufactured by Hodogaya Chemical Co., Ltd., trade name: PTG-2000SN, hydroxyl value 56 mgKOH / g, average number of functional groups 2). It was designated as a polyol (b-8).
[0203]
　Preparation Example 9 (polypoly (b-9))
　number of polytetramethylene ether glycols having an average molecular weight of 1000 (PTMEG, manufactured by Hodogaya Chemical Co., Ltd., trade name: PTG-1000, hydroxyl value 112 mgKOH / g, average number of functional groups 2). It was designated as a polyol (b-9).
[0204]
　Preparation Example 10 (Polyol (b-10))
　Amorphous polytetramethylene ether glycol with a number average molecular weight of 1800 (manufactured by Asahi Kasei Fibers Co., Ltd., trade name: PTXG, hydroxyl value 60 mgKOH / g, average number of functional groups 2, tetrahydrofuran and neopentyl The copolymer with glycol) was designated as polyol (b-10).
[0205]
　(3) Plasticizer (c)
　Preparation Example 11 (Plasticizer (c-1))
　Diisononylcyclohexane-1,2-dicarboxylate (manufactured by BASF, trade name: Hexamol DINCH, boiling point 394 ° C.) was added to the plasticizer ( It was designated as c-1).
[0206]
　Preparation Example 12 (Plasticizer (c-2))
　Diisononyl adipate (manufactured by Mitsubishi Chemical Corporation, trade name: DINA, boiling point 250 ° C.) was used as a plasticizer (c-2).
[0207]
　Preparation Example 13 (plasticizer (c-3))
　di- (2-ethylhexyl) phthalate (manufactured by Mitsubishi Chemical Corporation, trade name: DOP, boiling point 386 ° C.) was used as the plasticizer (c-3).
[0208]
　Preparation Example 14 (Plasticizer (c-4))
　Chlorinated paraffin (manufactured by SIGMA-ALDRICH, trade name: Chloroparaffin) was used as a plasticizer (c-4).
(4) Catalyst (d)
　Tokyo Chemical Industry Co., Ltd., reagent dibutyltin dilaurate
(5) antifoaming agent (e)
　manufactured by Big Chemie Japan Co., Ltd., trade name: BYK-088
　3. Production
　Example 1 of Polyurethane Gel In the
　mass ratio shown in Table 1, isocyanate (a-1), polyol (b-1) and plasticizer (c-1) were prepared to obtain a polyurethane gel material (polyurethane gel material). Preparation process).
[0209]
　Next, 100 parts by weight of the polyol (b-1) adjusted to 25 ° C. and 17.93 parts by weight of the polyisocyanate (a-1) (equivalent ratio of isocyanate groups to hydroxyl group (NCO / hydroxyl group = 1.0)). 200 parts by weight of the plasticizer (c-1), 0.03 parts by weight of the catalytic dibutyltin dilaurate (d), and 0.2 parts by weight of the defoaming agent (e) are placed in a plastic container, and three-one motor (new). Using Togakusha Co., Ltd .: trade name: HEIDOM FBL3000), the mixture was stirred and mixed for 1 minute under stirring at 7000 rpm.
[0210]
　Immediately after that, defoaming under reduced pressure was performed to remove bubbles from the mixed solution, and then the mixed solution was poured into the following mold, which was pre-coated with Teflon (registered trademark) and adjusted to 80 ° C. It was poured and reacted at 80 ° C. for 2 hours to obtain a urethane gel.
[0211]

　-Sheet 　mold with a thickness of 2 mm-Square block mold with a thickness of 5 cm x 5 cm x 15
　mm-Cylindrical mold with a diameter of 29 mm x a height of 13 mm
　This polyurethane gel is allowed to stand in a room at 23 ° C and 55% relative humidity for 7 days. After placing, it was subjected to various physical property measurements.
[0212]

　Polyurethane gels were obtained in the same manner as in Example 1 except that the formulations shown in 　Examples 2 to 17 and Comparative Examples 1 to 12 Tables 1 to 4 were changed.
[0213]
　4. Evaluation
　　
　A mixed solution of polyurethane gel materials was poured into a block mold and reacted at 80 ° C. for 2 hours. After that, the fluidity of the polyurethane gel material was confirmed, and the curability of the polyurethane gel was evaluated. The evaluation criteria are as follows.
[0214]
　X: The polyurethane gel material has fluidity and cannot retain its shape after demolding.
[0215]
　◯: The polyurethane gel material has fluidity and can maintain its shape after demolding.
[0216]
　　
　A polyurethane gel prepared with a 2 mm sheet die was punched into a No. 3 test piece shape to prepare a measurement sample. The measurement sample was subjected to a tensile test according to JIS K-6400 (2012) using a tensile compression tester (Model 205N manufactured by Intesco), and the elongation at break was calculated.
[0217]
　　 The
　polyurethane gel obtained from the columnar die was punched into a columnar test piece to prepare a measurement sample, and the weight was measured (W1).
[0218]
　The upper and lower surfaces of the sample are sandwiched between filter papers (FILTER PAPER No. 5C manufactured by ADVANTEC), treated in an oven at 80 ° C. for 5 days, allowed to stand in a room at 23 ° C. and 55% relative humidity for 1 day, and then the surface is further filtered. After wiping well with, the weight was measured again (W2).
[0219]
　The bleed resistance was evaluated by the weight change (W: W = (W1-W2) / W1 × 100 (unit:%)) before and after the treatment.
[0220]
　　
　A stainless steel plate with a thickness of 1 mm x 4 cm x 4 cm (material: JIS G 4305 SUS304, surface finish BA, surface roughness: JIS
　B0601, tolerance Ra =) is added to the polyurethane gel obtained by the block mold. 50 ± 25 nm) was placed, and the mixture was allowed to stand in a room at 23 ° C. and a relative humidity of 55% for 1 day, and then the stress (kgf / 16 cm 2 ) required for peeling the stainless steel plate was measured with a push-pull gauge .
[0221]
　　 The Asker C hardness of
　the polyurethane gel obtained by the block mold was measured by the type C hardness test of JIS K 7312 (1996).
[0222]
[table 1]

[0223]
[Table 2]

[0224]
[Table 3]

[0225]
[Table 4]

[0226]
　Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an example and should not be construed in a limited manner. Modifications of the present invention that will be apparent to those skilled in the art are included in the claims below.
Industrial applicability
[0227]
　The polyurethane gel material, polyurethane gel, pseudo-biomaterial, and method for producing a polyurethane gel of the present invention are preferably used in the field of pseudo-biomaterial such as the medical field and the healthcare field.
The scope of the claims
[Claim 1]
　An aliphatic polyisocyanate (A) having an
　average functional group number of 2.3 or more and 3.2 or less, a polyol (B) having an average functional group number of 2.0 or more and 2.3 or less, and
　a plasticizer (C) containing an ester group
The
　aliphatic polyisocyanate (A) contains an isocyanurate derivative of an aliphatic diisocyanate and / or an alcohol-modified isocyanurate derivative of an aliphatic diisocyanate, and the
　polyol (B) is a polyurethane gel material containing , Polyoxyalkylene (2 to 3 carbon atoms) polyol having an ethylene oxide content of 30% by mass or less, and / or polytetramethylene ether glycol, and
　the average hydroxyl value of the polyol (B) is 30 mgKOH / g. The polyurethane gel material is 70 mgKOH / g or less, and
　the ratio of the plasticizer (C) is 50 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the polyol component (B).
..
[Claim 2]

The polyurethane gel material according to claim 1, 　wherein the polyol (B) has an average number of functional groups of 2.0 .
[Claim 3]

The polyurethane gel material according to claim 1, 　wherein the average hydroxyl value of the polyol (B) is 37 mgKOH / g or more and 56 mgKOH / g or less .
[Claim 4]

The polyurethane gel material according to claim 1, 　wherein the aliphatic polyisocyanate (A) has an average number of functional groups of 2.3 or more and 3.0 or less .
[Claim 5]

The polyurethane gel material according to claim 1, 　wherein the aliphatic diisocyanate contains pentamethylene diisocyanate and / or hexamethylene diisocyanate .
[Claim 6]

The polyurethane gel material according to claim 1 　, wherein the ratio of the plasticizer (C) is 100 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyol component (B) .
[Claim 7]

The polyurethane gel material according to claim 1, 　wherein the plasticizer (C) is a cyclohexanedicarboxylic acid ester and / or an adipate ester .
[Claim 8]
　A polyurethane gel, which is a reaction product of the polyurethane gel material according to claim 1
.
[Claim 9]
　In the polyurethane gel material,
　the equivalent ratio of the isocyanate groups in the aliphatic polyisocyanate (A) to the hydroxyl group in the polyol (B) (NCO / hydroxyl group) is 0.8 to 1.2
, characterized in that , The polyurethane gel according to claim 8.
[Claim 10]
　A pseudo-biomaterial comprising the polyurethane gel according to claim 8.
[Claim 11]
　A preparatory step for preparing the polyurethane gel material according to claim 1 and a
　reaction step for reacting and curing the polyurethane gel material to obtain a polyurethane gel are provided. In the
　reaction step, the
　fat with respect to the hydroxyl group in the polyol (B) is provided. A
method for producing a polyurethane gel, wherein the equivalent ratio (NCO / hydroxyl group) of the isocyanate groups in the group polyisocyanate (A) is 0.8 or more and 1.2 or less .