JP5544588B2 - Peptide bond compatible polyurethane resin composition and molded product thereof - Google Patents

Description

  The present invention relates to a peptide bond-compatible polyurethane resin composition that can uniformly include a polymer compound having a peptide bond, and a molded product obtained therefrom.

  By-products such as skin, bone, animal hair, horns, hoofs, feathers, and scales that accompany livestock and fish production are natural protein resources that are rich in gelatin and keratin. For example, the leather is used as a leather product after being peeled, and the other by-products are used as feed, fertilizer, etc. after being hydrolyzed. However, since it is difficult to reflect the processing cost on the product unit price, it is often treated as industrial waste, and its usage is limited.

  On the other hand, especially gelatin is sol-formed when heated, and gelled when cooled. For food applications such as gummi, jelly, and heated food for microwave ovens, As an adhesive for wallpaper, it is also used as a medical material such as injection aids and capsules, and as a film coating agent for photography, and is a remarkable protein resource. When trying to utilize protein resources such as gelatin, there is a fear that sufficient mechanical strength, heat resistance, etc. cannot be secured. Various developments have been made in order to utilize the desired properties while overcoming the physical properties of protein resources, which are such weak points.

  For example, Patent Documents 1 and 2 disclose resin products that are given porosity by blending a resin such as polyurethane and a protein such as glue or gelatin in a specific quantitative ratio. Patent Document 3 discloses a resin product including a protein insolubilized in a synthetic resin. However, these are all aimed at modifying artificial leather, and do not contain proteins sufficiently uniformly and stably in the resin.

  On the other hand, Patent Document 4 discloses a composition comprising a protein material that can be made aqueous and a specific aqueous polyurethane resin. However, the film formed thereby has a high possibility of dissolving when immersed in water, and when a film or sheet is formed using such a resin, there is a problem in durability, and it is necessary from the viewpoint of more useful industrial utilization. There is still room for improvement.

Japanese Patent No. 2566799 Japanese Patent No. 3981242 Japanese Patent No. 3053879 JP 2003-238810 A

  The present invention relates to providing a highly durable resin composition and a molded product thereof while including protein resources such as gelatin that are inherently water-soluble.

  By using a polyether-based polyurethane resin containing a silanol group, the present inventors can effectively include a polymer compound having a peptide bond such as gelatin and can exhibit excellent durability. As a result, the present invention has been completed.

That is, the present invention includes a polymer compound having a peptide bond and a silanol group-containing polyether polyurethane resin,
The present invention relates to a peptide bond-compatible polyurethane resin composition characterized in that at least a part of silanol groups contained in the silanol group-containing polyether polyurethane resin forms a siloxane bond.

The present invention also relates to a molded article characterized by using the peptide bond-compatible polyurethane resin composition.
Furthermore, the present invention includes (A) a step of mixing a solution containing a polymer compound having a peptide bond and a solution containing a silanol group-containing polyether polyurethane resin to obtain a mixed solution,
(B) A step of obtaining a preformed product using the mixed solution, and (C) a step of obtaining a molded product by heating and drying the preformed product, to obtain a peptide bond-compatible polyurethane resin composition The manufacturing method of the molded article which consists of.

  According to the peptide bond-compatible polyurethane resin composition of the present invention, the —CO—NH— bond contained in the silanol group-containing polyether polyurethane resin ensures good affinity with a polymer compound having a peptide bond. The polymer compound can be uniformly dispersed in the resin composition. In addition, the silanol group of the polyurethane resin forms a siloxane bond, so that a polymer compound having a dispersed peptide bond can be tightly surrounded, while effectively suppressing elution of the polymer compound, A resin composition exhibiting excellent mechanical strength and heat resistance can be obtained.

  Therefore, if the above-mentioned peptide bond-compatible polyurethane resin composition is used, it is possible to easily obtain molded products such as films and sheets having excellent durability, and sufficiently exhibit the characteristics of polymer compounds having peptide bonds. Is possible.

It is a figure which shows the result of the film tension test in the wet state by this-article product. The vertical axis of (a) indicates load (N), and the vertical axis of (b) indicates elongation (mm). It is a figure which shows the result of having evaluated the thermal stability in this invention goods. The vertical axis represents heat flow and the horizontal axis represents temperature (° C.). It is a figure which shows the gelatin elution rate in this invention goods. The vertical axis represents gelatin elution rate (%). It is a figure which shows the result of having evaluated the water absorption rate in this invention goods. The vertical axis represents water absorption (%), and the horizontal axis represents time (min).

Hereinafter, the present invention will be described in detail.
The polymer compound having a peptide bond in the present invention means a naturally occurring polymer compound having a peptide bond in the molecule or a polymer compound obtained by chemical synthesis. For example, protein obtained from raw materials such as cattle, pig, sheep, goat, horse, chicken or fish dermis or bone or dermis, ligament, tendon, blood vessel wall, fish scales, feathers, wool, pig hair, cow hair, etc. Or a polymer compound obtained by chemical synthesis such as substitution of a desired functional group in a molecule with a peptide bond. More specifically, examples of the polymer compound having a peptide bond include gelatin, collagen, hydrolyzed collagen, and the like. These may be used alone or in combination of two or more. Of these, gelatin is preferable.

  The silanol group-containing polyether polyurethane resin in the present invention means a polyurethane resin having a polyether skeleton and having at least one silanol group in the molecule. Unlike the forced emulsification type polyurethane resin that requires the addition of an emulsifier such as a surfactant, the silanol group-containing polyether polyurethane resin is a self-emulsifying type that can be well emulsified and dispersed in water without the addition of an emulsifier. Polyurethane resin. In order to produce such a polyurethane resin, a urethane prepolymer obtained by chain extension reaction with a polyamine compound while reacting polyisocyanate and polyether polyol is usually dispersed in water to obtain a urethane prepolymer solution, and silanol is added to the solution. It is obtained by adding a group introducing agent and introducing silanol groups into part of the polymer chain.

The polyisocyanate is not particularly limited as long as it is a compound having a plurality of isocyanate groups in the molecule. Specifically, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate Aromatic polyisocyanates such as (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMH) DI), lysine diisocyanate, aliphatic polyisocyanate such as norbornane diisocyanate methyl (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), H ₁₂ MDI (water) Added MDI), diisocyanate compounds such as alicyclic polyisocyanates such as H ₆ TDI (hydrogenated TDI); polyisocyanate compounds such as polymethylene polyphenylene polyisocyanate; carbodiimide-modified polyisocyanates of these isocyanate compounds; Examples include isocyanurate-modified polyisocyanate. These may be used alone or in combination of two or more.

  The polyether polyol is not particularly limited as long as it is a compound containing a polyether skeleton having a plurality of hydroxyl groups in the molecule. Specifically, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3- Diols such as butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, bisphenol A; triols such as trimethylolethane, trimethylolpropane, glycerin; sorbitol, etc .; further ammonia, ethylenediamine, Ring-opening polymerization of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. in the presence of one or more amines such as urea, monomethyldiethanolamine and monoethyldiethanolamine Random or block copolymer obtained in this way; Polyolefin skeleton polyol having ethylene / α-olefin skeleton; Polyalkylene polyether polyol such as acrylic skeleton polyol, and polyether polyol such as epoxy polyol and butadiene polyol Can be mentioned. These may be used alone or in combination of two or more.

  The polyamine compound is not particularly limited as long as it has at least two amino groups or imino groups. Specifically, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, phenylenediamine, Examples include pentamethylenehexamine, hexamethyleneheptamine, hydrazine, phenylhydrazine, and polyethyleneimine.

  When performing the chain extension reaction, another chain extender other than the polyamine compound may be used. Examples of such chain extenders include 1,4-butanediol, 1,6-hexanediol, 1,4-bis (2-hydroxyethoxy) benzene, and the like. In addition, any additive may be used as long as the effects of the present invention are not impaired.

  In the preparation of the urethane prepolymer, a catalyst for urethanization reaction is preferably used. Examples of the catalyst for urethanization reaction include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, tin octenoate, monobutyltin oxide and the like; stannous chloride, etc. Inorganic lead compounds; organic lead compounds such as lead octenoate; cyclic amines such as triethylenediamine; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, fluorosulfuric acid; sulfuric acid, phosphoric acid, perchloric acid, etc. Inorganic acids; bases such as sodium alcoholate, lithium hydroxide, aluminum alcoholate, sodium hydroxide; titanium compounds such as tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate; bismuth tris (2-ethylhexyl) Bismuth compounds such as sanoates); quaternary ammonium salts and the like. These catalysts may be used alone or in combination of two or more.

  By reacting the urethane prepolymer prepared as described above with a silanol group-containing introduction agent, a silanol group is added to the polymer chain. The silanol group introducing agent means a compound having an active hydrogen group that reacts with an isocyanate group in the molecule and a hydrolyzable silicon group. Examples of the active hydrogen group that reacts with an isocyanate group include a mercapto group, a hydroxyl group, and an amino group. The hydrolyzable silicon group means a group in which a hydrolyzable group that can be hydrolyzed is bonded to one silicon atom in the range of 1 to 3, and specific examples of the hydrolyzable group include Examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group.

  Specific examples of the silanol group introducing agent include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ- (2 -Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, γ- (2-aminoethyl) aminopropyldiethoxysilane , Γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldimethoxysilane, γ-aminopropyldiethoxysilane, and the like. These may be used alone or in combination of two or more.

  The silanol group-containing polyether-based polyurethane resin obtained as described above is such that, in water, the polyether skeleton of the resin and the skeleton extended with a polyamine compound act, and some groups contained in the polymer chain It is considered that these groups form a —CO—NH— bond when the resin is stably dispersed to form ions and the resin is dried (dehydrated).

  The -CO-NH- bond has a structure similar to a peptide bond, and has a very high affinity with the peptide bond. Therefore, the polymer compound having a peptide bond is easily held firmly inside the resin, and can be effectively suppressed from being eluted to the outside. Similarly, a urethane bond formed by an isocyanate group and a hydroxyl group has a high affinity with a peptide bond, and the urethane bond of a silanol group-containing polyether polyurethane resin also holds a polymer compound having a peptide bond. It is thought that it contributes greatly.

  In obtaining the silanol group-containing polyether-based polyurethane resin, the silanol group introducing agent is usually 1 to 100 parts by mass with respect to 100 parts by mass (solid content) of the polyurethane prepolymer containing polyisocyanate, polyether polyol and polyamine compound. It is desirable to blend in an amount of preferably 20 to 60 parts by mass, more preferably 40 to 60 parts by mass. When the blending amount of the silanol group is within the above range, it is possible to prevent the resulting peptide bond-compatible polyurethane resin composition from becoming too hard while sufficiently suppressing elution of the polymer compound having a peptide bond. it can. In addition, it can be effectively avoided that the introduction of silanol groups into the polymer chain becomes saturated.

  The peptide bond-compatible polyurethane resin composition of the present invention comprises the polymer compound having the peptide bond and the silanol group-containing polyether polyurethane resin, and at least a part of the silanol groups contained in the polyurethane resin is A siloxane bond is formed. The polyurethane resin forms a complex three-dimensional structure by forming this siloxane bond, and can firmly include a polymer compound having a peptide bond in such a structure, and also has a high affinity with the peptide bond. Combined with the action of the —CO—NH— bond having the above, it is possible to effectively suppress the release of the polymer compound to the outside.

  Furthermore, it is considered that at least a part of the reactive group of the polymer compound having a peptide bond forms a bond with a part of the reactive group of the silanol group-containing polyether polyurethane resin. It is presumed that the polymer compound and the polyurethane resin are integrated by such a bond, and the elution of the polymer compound to the outside can be effectively prevented.

  The peptide bond-compatible polyurethane resin composition can be obtained by mixing a solution containing a polymer compound having a peptide bond and a solution containing a silanol group-containing polyether polyurethane resin. You may add saccharides to the obtained mixed solution further as needed. By adding a saccharide, in addition to the action of a polymer compound having a peptide bond, a product to which the action of a saccharide is added as desired can be obtained.

  Examples of the saccharide include monosaccharides such as glucose, fructose, galactose, and mannose; disaccharides and oligosaccharides such as maltose, lactose, and sucrose; and saccharides that are polysaccharides such as amylose, amylopectin, glycogen, cellulose, and alginic acid. In addition, glycoproteins and glycolipids can be mentioned.

  In order to form a siloxane bond between silanol groups of the silanol group-containing polyether polyurethane resin, it is preferable to evaporate moisture by heating. Usually, it is dried at a temperature of 100 to 150 ° C., preferably 110 to 120 ° C., for 0.5 to 2 hours, preferably 0.5 to 1 hour. As described above, siloxane bonds can be formed by dehydration at a relatively low temperature for a short time.

  The peptide bond-compatible polyurethane resin composition can be formed into a molded product by various processes according to a conventional method. Such molded products include cosmetic films such as skin moisturizing sheets and face masks; household garden films, house cultivation film sheets, tunnel cultivation film sheets, compost sheets, agricultural storms and waterproof sheets, etc. Sheets: packaging materials for foods such as rice and cereals, packaging materials for stationery and miscellaneous goods, packaging materials for industrial materials, packaging materials for building materials, and the like. It is also possible to use it as a multilayer film or sheet by laminating with another base material such as nylon or polyester.

  When producing a film, it can be processed by forming a film according to a conventional method. Examples of such film molding include extrusion lamination molding, T-die film molding, inflation molding (air cooling, water cooling, multistage cooling, high-speed processing) and the like. The film thickness can vary depending on the application, but for example, in the case of a cosmetic sheet, it is usually 100 to 5000 μm.

Molded products such as the above film and sheet,
(A) A step of mixing a solution containing a polymer compound having a peptide bond with a solution containing the silanol group-containing polyether polyurethane resin to obtain a mixed solution;
(B) It can be manufactured by a method including a step of obtaining a preform using the mixed solution, and (C) a step of obtaining the molded product by heating and drying the preform.

About (A) process, as above-mentioned, the solution containing the high molecular compound which has a peptide bond, and the solution containing the said silanol group containing polyether polyurethane resin are prepared, these are mixed with a stirrer etc., and a mixed solution is prepared. obtain.
In the step (B), in obtaining a preformed product using the above mixed solution, the solution may be poured into a mold, applied onto a substrate, or preformed by a molding machine.

  In the step (C), drying is usually performed by heating for 0.5 to 2 hours, preferably 0.5 to 1 hour. In order to heat, it is good to dry using a drier etc., normally maintaining the temperature of 100-150 degreeC, Preferably 110-120 degreeC. By passing through this step (C), silanol groups of the polyether-based polyurethane resin form siloxane bonds.

  Thus, if a film or sheet is formed using the peptide bond-compatible polyurethane resin composition of the present invention, the shape as a film or sheet is effectively retained while ensuring appropriate flexibility by dipping in water. Therefore, elution of the polymer compound having a peptide bond can be effectively suppressed. Therefore, it becomes possible to bring about the action which the above-mentioned polymer compound has continuously to a pasting object only by sticking such a film or sheet. In addition, by appropriately selecting a polymer compound having a peptide bond, it is possible to realize a molded article adapted to various uses, for example, a film or sheet containing a wound healing agent, a cosmetic spreader or a moisturizing agent. it can. Furthermore, if a polymer compound exhibiting a fertilizer effect is selected, a film or sheet suitable for agricultural materials can be realized.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
In addition, the following polyurethane resin solution and the silanol group introduction | transduction agent were used as needed.

1) Polyurethane resin solution (solution b1)
Polyether-based polyurethane resin solution: Takelac WS-6061, manufactured by Mitsui Chemicals Polyurethanes, containing polyether-based polyurethane resin (excluding silanol groups), aqueous solvent 2) Polyurethane resin solution (solution b2)
Polyether-based polyurethane resin solution: Takelac WS-6021, manufactured by Mitsui Chemicals Polyurethanes, Silanol group-containing polyether-based polyurethane resin (blending amount of silanol group introducing agent with respect to 100 parts by mass of polyurethane prepolymer (solid content) = 20 mass Part) contained, aqueous solvent 3) Silanol group introducing agent: γ-mercaptopropyltrimethoxysilane (KBM-430, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Preparation of gelatin solution (solution a1)]
While stirring with a magnetic stirrer, 185 g of Milli Q water in a 300 ml beaker, 15 g of gelatin (Nippi 469-1-6 cowhide gelatin high molecular weight 30 mesh product) was added little by little, taking care not to cause lumps. It was. After dispersing 15 g, the beaker was wrapped and heated in an incubator at 80 ° C. for 30 minutes to dissolve the gelatin. After confirming that the transparency of the turbid solution before warming was increased, the solution was taken out from the incubator and stirred for 5 minutes with a magnetic stirrer to prepare a 5% gelatin aqueous solution (300 g) (solution a1).

[Preparation of gelatin solution (solution a2)]
A 15% gelatin solution (solution a2) was prepared according to the preparation of the solution a1 except that the gelatin was 45 g.

[Preparation of polyurethane resin solution (solution b3)]
In a four-necked flask equipped with a stirrer, a Dimroth condenser, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 71.49 g of 1,3-bis (1-isocyanate-1-methylethyl) benzene, dimethylolpropion 13.41 g of acid and 90.00 g of acetone as a solvent were added, the temperature was raised to 50 ° C. in a nitrogen atmosphere, 0.05 g of dibutyltin dilaurate was further added, and the mixture was stirred for 4 hours. After completion of the stirring, it was confirmed that the reaction solution reached a predetermined amine equivalent, and 125.10 g of a polyester polyol having a molecular weight of 1000 generated by the reaction of adipic acid, neopentyl glycol, and 1,6-hexanediol was added, Stir for another 5 hours. After completion of the stirring, it was confirmed that the reaction liquid reached a predetermined amine equivalent, and after the temperature of the reaction liquid was lowered to 40 ° C., 9.62 g of triethylamine was added and a neutralization reaction was performed by stirring for 10 minutes. A polyurethane prepolymer solution was obtained.

  Next, a silanol group introducing agent is added to 100 parts by mass of the obtained polyurethane prepolymer solution (solid content) so as to have an amount of 50 parts by mass, and 2-[(2-aminoethyl) amino] ethanol 3 In an aqueous solution in which .34 g was dissolved in 537.16 g of water, 300.00 g of the polyurethane prepolymer solution obtained by the above reaction was added dropwise with stirring using a homodisper to carry out chain extension reaction and emulsification. . Next, 0.21 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) is added to the emulsion as a curing catalyst, and the mixture is further heated and stirred at 60 ° C. to obtain acetone used for the synthesis of the polyurethane prepolymer. Was distilled off to obtain a polyurethane resin solution (solution b3).

[Preparation of polyurethane resin solution (solution b4)]
A polyurethane resin solution (solution b4) was prepared in the same manner as the solution b3 except that the silanol group introducing agent was added to 100 parts by mass with respect to 100 parts by mass of the obtained polyurethane prepolymer solution (solid content). Obtained.

[Comparative Example 1: Production of Film (Sample a1-1)]
4 g (1.2 g in terms of solid content) of the gelatin solution (solution a1) was poured into a vat and air-dried to obtain sample a1-1.

[Comparative Example 2: Production of Film (Sample b1-1)]
Add the gelatin solution (solution a2) to the polyurethane resin solution (solution b1) (solid content mass ratio = urethane resin: gelatin = 2: 1), dilute with water, pour into an aluminum vat, air dry As a result, Sample b1-1 was obtained.

[Comparative Example 3: Production of Film (Sample b2-1)]
20 g of water was added to 8 g of the polyurethane resin solution (solution b2) (2.4 g in terms of solid content), mixed in a beaker, poured into an aluminum bat (200 mm × 170 mm), and air-dried to obtain sample b2-1. .

[Example 1: Production of film (sample b2-2)]
Add to the above polyurethane resin solution (solution b2) to be a gelatin solution (solution a2) (solid mass ratio = urethane resin: gelatin = 2: 1), dilute with water, pour into an aluminum vat, air dry And heated at 120 ° C. for 30 minutes to obtain Sample b2-2.

<< Formability evaluation >>
Using the films obtained in Comparative Examples 1 to 3 and Example 1, the moldability was evaluated by the tactile sensation and visual observation of the creator. In Comparative Examples 1 and 3, a transparent film was formed on the bat, but it became crisp and could not be peeled off. In particular, in Comparative Example 1, a soft film was obtained, but the adhesion to the bat was strong and could not be peeled off as one large film.
In Example 1 and Comparative Example 2, a transparent film was obtained, but when immersed in water, Comparative Example 2 collapsed, whereas in the film of Example 1, siloxane bonds were effectively formed. Retained a firm film shape.

[Comparative Example 4: Production of Film (Sample a1-2)]
Weigh out the gelatin solution (solution a1) to a solid content of 2.4 g, pour it into a 150 mm x 100 mm x 40 mm polypropylene container, spread it thinly, and place it on a horizontal table in a room at 25 ° C and 50% humidity For 24 hours. The obtained film was preserve | saved in the desiccator and sample a1-2 was obtained.

[Comparative Example 5: Production of film (sample b1-2)]
The polyurethane resin solution (solution b1) is weighed to a solid content of 1.2 g, the gelatin solution: 24 g of solution a1 (1.2 g of the solid content) is added, and the gelatin solution and the urethane resin solution have a solid content ratio of 1 The total solid content of the film was 2.4 g. After stirring for 1 minute with a magnetic stirrer, the mixture was poured into a 150 mm × 100 mm × 40 mm polypropylene container, thinly spread over the whole, and left on a horizontal table in a room at 25 ° C. and 50% humidity for 24 hours. The obtained film was preserve | saved in the desiccator and sample b1-2 was obtained.

[Example 2: Production of film (sample b2-3)]
The polyurethane resin solution (solution b2) is weighed to a solid content of 1.2 g, the gelatin solution: 24 g of solution a1 (1.2 g of the solid content) is added, and the gelatin solution and the urethane resin solution have a solid content ratio of 1 The total solid content of the film was 2.4 g. After stirring for 1 minute with a magnetic stirrer, the mixture was poured into a 150 mm × 100 mm × 40 mm polypropylene container, thinly spread over the whole, and left on a horizontal table in a room at 25 ° C. and 50% humidity for 24 hours. The obtained film was stored in a desiccator and then crosslinked (siloxane bond formation) by drying in a dryer at 120 ° C. for 30 minutes to obtain sample b2-3.

[Example 3: Production of film (sample b3-1)]
The polyurethane resin solution (solution b3) is weighed to a solid content of 1.2 g, the gelatin solution: 24 g of solution a1 (1.2 g of the solid content) is added, and the gelatin solution and the urethane resin solution have a solid content ratio of 1 The total solid content of the film was 2.4 g. After stirring for 1 minute with a magnetic stirrer, the mixture was poured into a 150 mm × 100 mm × 40 mm polypropylene container, thinly spread over the whole, and left on a horizontal table in a room at 25 ° C. and 50% humidity for 24 hours. The obtained film was stored in a desiccator and then crosslinked (siloxane bond formation) by drying in a dryer at 120 ° C. for 30 minutes to obtain sample b3-1.
[Example 4: Production of film (sample b4-1)]
Sample b4-1 was obtained in the same manner as in Example 2 except that the solution b3 was replaced with the solution b4.

<< Evaluation of tensile test in wet condition >>
The samples obtained in Comparative Example 4 and Examples 2 to 4 were each cut with scissors to give a 10 mm × 100 mm test piece, and left in a temperature-controlled room at 20 ° C. and 65% humidity for 2 hours before the test. The length between the marked lines was 55 mm and fixed to a jig. For the tensile test, EZ-S, Trapezium manufactured by Shimadzu Corporation was used, and the test piece was immersed in distilled water at 20 ° C. for 1 hour before the test, and both surfaces were wiped with Kim Towel (registered trademark). The number of measurements was 15 and the average value was obtained.

  The result of the film tensile test in the wet state is shown in FIG. In Comparative Example 4, a siloxane bond was not formed, so the tensile test could not be performed. It can also be seen that the load was the largest in Example 3 and the elongation was the largest. Thus, in the wet state, Example 3 is considered to be optimal for the physical properties of the mixed film with gelatin.

<< Evaluation of thermal stability (DSC) >>
20 mg of the sample obtained in Comparative Example 4 and Examples 3 to 4 was measured in a silver cell (Seiko Instruments Inc .: AG70-CAPSULE P / N 560-003) and sealed with a sample sealer (Seiko Instruments Inc.). Measurements were made. Seiko Instruments Inc .: SSC / 5200 was used as a measuring apparatus. The measurement conditions were as follows, and the average value was obtained by setting the number of measurements to 5 times. The results are shown in FIG.
Temperature program: 15 ~ 250 ℃
Temperature increase rate: 5.0 ℃ / min
Reference: almina 30mg
Furnace atmosphere: He, 40ml / min
Data sampling rate: 0.5 sec / dot

  Comparative Example 4 showed endothermic peaks at 80 ° C and 180 ° C. The endothermic peak at 80 ° C. is attributed to gelatin dissolution, and the endothermic peak at 180 ° C. is believed to be due to thermal decomposition of gelatin. In the films of Examples 3 to 4, endothermic peaks were confirmed at 90 ° C and 170 ° C. This is probably because gelatin is effectively included in the urethane resin, and the gelatin and the urethane resin are more integrated by forming some bonds between them, and the respective endothermic peaks are smoothed.

<Evaluation of gelatin dissolution rate>
In a 15 ml Falcon tube, 0.07 g of the sample obtained in Comparative Example 4 and Examples 2 to 4 was placed, 14 g of Milli Q water was added, and the mixture was shaken in a temperature-controlled water tank for 12 hours. 1 ml of liquid was taken from the tube, 0.5 ml of microburette liquid was added, and the absorbance was measured at 310 nm. The blank was Milli-Q water. A calibration curve was prepared with a gelatin solution (solution a1). Dilute the stock solution to a concentration of 10 mg / ml, doubling from 2 to 4 times to 8 times, make up to a 128-fold dilution, add 0.5 ml of microburette to 1 ml, and absorb at 310 nm Was measured, and the ratio (%) to the blank was calculated as the gelatin elution rate. The results are shown in FIG.

  At 25 ° C. and 37 ° C., the elution of gelatin was clearly suppressed in Examples 2 to 4. This indicates that a siloxane bond is formed in the silanol group-containing polyether polyurethane resin, and the gelatin is held more firmly. In particular, Example 3 tended to suppress elution most.

<< Evaluation of water absorption speed >>
150 g of Milli-Q water was placed in a 150 mm × 100 mm × 40 mm polypropylene container, and the samples obtained in Comparative Example 5 and Examples 3 to 4 cut to about 0.20 g were immersed therein. Films were taken every 10 minutes up to 60 minutes and every 30 minutes thereafter, and water on both sides was sucked into Kim Towel (registered trademark) and the weight was measured. The end point was determined when the weight change of 4 times was within 0.01 g. Compared with the film weight before water absorption, the water absorption was calculated from the amount of water absorption according to the following formula. The number of measurements was 3 and the average value was determined. The water absorption curve of the obtained film is shown in FIG.
Water absorption rate = {(weight after water absorption−weight before water absorption) ÷ weight before water absorption × 100}

  From the results shown in FIG. 4, it can be seen that the water absorption decreases when a silanol-containing polyether polyurethane resin is used. In Comparative Example 5, the water absorption exceeded 400%, but in Examples 3 and 4, it decreased to 180%.

Claims (6)

It is obtained by mixing a polymer compound having a peptide bond and a silanol group-containing polyether polyurethane resin,
After mixing, at least a portion of the silanol groups contained in the silanol-group-containing polyether-based polyurethane resin, the peptide bond compatible polyurethane resin composition characterized by comprising forming a siloxane bond.   The peptide bond-compatible polyurethane resin composition according to claim 1, wherein the polymer compound having a peptide bond is at least one selected from the group consisting of gelatin, collagen and hydrolyzed collagen.   The silanol group-containing polyether-based polyurethane resin is blended in an amount of 1 to 100 parts by mass of a silanol group introduction agent with respect to 100 parts by mass (solid content) of a polyurethane prepolymer containing polyisocyanate, polyether polyol and polyamine compound. The peptide bond-compatible polyurethane resin composition according to claim 1, wherein the composition is a peptide bond-compatible polyurethane resin composition.   A molded article comprising the peptide bond-compatible polyurethane resin composition according to claim 1.   The molded product according to claim 4, wherein the molded product is a film or a sheet. (A) a step of mixing a solution containing a polymer compound having a peptide bond and a solution containing a silanol group-containing polyether polyurethane resin to obtain a mixed solution;
(B) the mixed solution obtaining a preform with, and (C) wherein the Rukoto the preform is heated and dried, the silanol group-containing polyether least some of the silanol groups contained in the polyurethane resin A method for producing a molded product comprising a peptide bond-compatible polyurethane resin composition, comprising the step of forming a siloxane bond in the product to obtain a molded product.