JP2008214367A - Oxygen-containing polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a blood cell storage bag for improving storage stability of blood cell (blood platelet, etc.) and to provide a method for improving storage stability of blood cell. <P>SOLUTION: The blood cell storage bag having a built-in oxygen-containing polyurethane foam is obtained by adding oxygen to a mixed liquid composed of a polyol component and an isocyanate component and foaming the mixed liquid and has an oxygen concentration in foam of 22-100 vol.%. The method for improving storage stability of blood cell comprises forming an oxygen-containing polyurethane foam having an oxygen concentration in foam of 22-100 vol.% built-in the blood cell storage bag and gradually releasing oxygen. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a blood cell (particularly platelet) storage bag containing a polyurethane foam having a high oxygen concentration in bubbles. More specifically, the present invention relates to a blood cell storage bag excellent in long-term storage stability of blood cells (particularly platelets).

  Conventionally, blood cells obtained by blood donation and blood donation, particularly platelets, are stored as concentrated platelet preparations, platelet-rich plasma, and the like, and various means for improving the storage stability have been studied. The preservation period of platelets is currently only 3 days in Japan, which is an obstacle to the effective use of platelet preparations.

Since platelet function is irreversibly lost when exposed to low temperatures, storage is performed at around 22 ° C. However, at a temperature around 22 ° C., platelet energy metabolism is very active. At this time, if oxygen supply to platelets is sufficiently performed, energy metabolism is maintained by “aerobic metabolism”, and water and carbon dioxide are produced as metabolites. However, if oxygen supply to platelets is insufficient, energy metabolism is maintained by “anaerobic metabolism” and lactic acid is produced as a metabolite. The lactic acid lowers the pH of the platelet suspension and causes a problem that the platelet function is significantly impaired. Therefore, platelet storage bags are required to have high oxygen permeability, and storage bags made of olefin resin have been developed (see, for example, Patent Document 1). In addition, the storage bag is required to reduce the permeability of carbon dioxide, which is said to cause a decrease in the pH of the platelet suspension, and various storage containers have been developed (see, for example, Patent Documents 2 and 3).
Special table hei 9-508052 JP 2003-47642 A JP 2002-136572 A

  However, the platelet storage containers described in Patent Documents 2 and 3 have sufficient oxygen permeability, but at the same time, the carbon dioxide permeability is higher than the oxygen permeability, so that the pH of the platelet suspension is lowered. is there. Therefore, in the prior art in which oxygen is supplied to platelets from the outside air of the storage bag by improving the oxygen permeability of the platelet storage bag and reducing the carbon dioxide permeability, the stable storage period of platelets is greatly improved. was difficult.

  As a result of intensive studies to solve the above problems, the present inventor has reached the present invention. That is, the present invention relates to an oxygen-containing polyurethane foam characterized in that oxygen is contained in a liquid mixture comprising a polyol component and an isocyanate component and foamed, and the oxygen concentration in the bubbles is 22 to 100% by volume. A blood cell storage bag containing the polyurethane foam; and a blood cell storage bag filled with blood cells containing an oxygen-containing polyurethane foam having an oxygen concentration in the bubbles of 22 to 100% by volume. Is a method for improving the storage stability of blood cells.

  Blood cells stored in a blood cell storage bag containing the oxygen-containing polyurethane foam of the present invention have an effect of excellent storage stability.

  The polyurethane foam of the present invention comprises a polyurethane resin formed from a polyol component and an isocyanate component.

[Polyol component]
The polyol (A) constituting the polyol component is a divalent to octavalent or higher polymer polyol [having an OH equivalent of 250 or more (based on OH value, molecular weight per OH)], a low molecular polyol ( Having an OH equivalent weight of less than 250), and mixtures of two or more thereof.
Low molecular polyols include polyhydric alcohols and low molecular OH-terminated polymers [polyether polyol (hereinafter abbreviated as PT polyol), polyester polyol (hereinafter abbreviated as PS polyol), etc.].

The polyhydric alcohol includes the following.
Dihydric alcohol [carbon number (hereinafter abbreviated as C) 2-20 or more), for example, C2-12
Aliphatic dihydric alcohols [(di) alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,
3-, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentanediol (hereinafter referred to as EG, DEG, PG, D, respectively)
PG, BD, HD, NPG and MPD), dodecanediol, etc.]; C6-10 alicyclic divalent alcohol [1,4-cyclohexanediol, cyclohexanedimethanol, etc.]; C8-20 aromatic ring-containing 2 Monohydric alcohol [xylylene glycol, bis (hydroxyethyl) benzene, etc.];
Trihydric to octahydric or higher polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol and dipentaerythritol (hereinafter referred to as GR, TM respectively)
P, PE, SO and DPE), 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins, etc.], sugars and their derivatives [eg sucrose, glucose , Fructose, mannose, lactose, and glycosides (such as methyl glucoside)];

Nitrogen-containing polyols (tertiary amino group-containing polyols and quaternary ammonium group-containing polyols): nitrogen-containing diols such as C1-12 aliphatic, alicyclic and aromatic ring-containing primary monoamines [methylamine, ethylamine, 1-and 2-propylamine, hexylamine,
1,3-dimethylbutylamine, 1-, 2- and 3-aminoheptane, dodecylamine, cyclopropylamine, cyclohexylamine, aniline, benzylamine and the like] bishydroxyalkyl (C2-4) chloride [bis (2-hydroxy Ethyl) compounds, bis (hydroxypropyl) compounds and the like, for example, tertiary nitrogen atom-containing polyols described in US Pat. No. 4,271,217], and quaternized products thereof [described in the above US patent specifications] Quaternizing agents or dialkyl carbonates (those with C1-4 alkyl groups such as dimethyl, diethyl and di-i-propyl carbonate) are included. ) Quaternized product], for example, quaternary nitrogen atom-containing polyols described in the above-mentioned U.S. Patent Specification; and trivalent to octavalent or higher nitrogen-containing polyols, such as trialkanol (C2-4) amine (triethanolamine) Etc.) and C2-12 aliphatic, cycloaliphatic, aromatic and heterocyclic polyamines [eg ethylenediamine, cyclohexanediamine, tolylenediamine, aminoethylpiperazine] polyhydroxyalkyl (C2-4) compounds [poly (2- Hydroxyethyl), bis (hydroxypropyl), etc. [eg tetrakis (2-hydroxypropyl)
Ethylenediamine, pentakis (2-hydroxypropyl) diethylenetriamine]],
And these quaternized compounds as described above.

Low molecular OH-terminated polymers include PT polyols, PS polyols and polyurethane (hereinafter abbreviated as PU) polyols having OH equivalents of less than 250, as described below. For example, a low-polymerization alkylene oxide (hereinafter abbreviated as AO) ring-opening polymer and a low-mol AO adduct of an active hydrogen atom-containing polyfunctional compound [for example, polyethylene glycol described below,
Polypropylene glycol and polytetramethylene glycol (hereinafter PEG and PP respectively)
G, PTMG), bis (hydroxyethoxy) benzene and bisphenol A
Ethylene oxide (hereinafter abbreviated as EO) 2-4 mol adduct], low-condensation condensation PS polyol and polyol low-mol lactone adduct [polycarboxylic acid and excess (1 mol per carboxyl group) polyhydric alcohol; Condensates of (eg dihydroxyethyl adipate)
And EG caprolactone 1-mol adduct], and a low polymerization degree PU polyol [reaction product of polyisocyanate (hereinafter referred to as PI) described later and excess (1 mol per isocyanate group) polyhydric alcohol. Product (for example, a reaction product of 1 mol of TDI and 2 mol of EG described later)].

AO includes C2-12 or more (preferably C2-4) AO such as ethylene oxide, 1,2-propylene oxide, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran and 3 -Methyl-tetrahydrofuran (hereinafter each EO
, PO, BO, THF and MTHF), 1,3-propylene oxide, isoBO
, C5-12 α-olefin oxides, substituted AOs such as styrene oxide and epihalohydrins (such as epichlorohydrin), and combinations of two or more thereof (random addition and / or block addition).

The polymeric polyol usually has an OH equivalent weight of 250 to 3,000 or more. The polyol is usually 500 to 5,000 or more, preferably 700 to 4,500.
The number average molecular weight (hereinafter abbreviated as Mn. Measurement is performed by gel permeation chromatography (G
PC) method. Preferably 500 to 6,000, particularly 700 to 4,000
The weight average molecular weight (hereinafter abbreviated as Mw. The measurement is based on the GPC method). Examples include OH-terminated polymers [PT, PS, polyamide (hereinafter abbreviated as PD), PU, vinyl polymer (hereinafter abbreviated as VP) and polymer polyol (hereinafter abbreviated as P / P)], and 2 A mixture of seeds or more is included.
The OH-terminated PT contains at least two AO ring-opening polymers (2 to 8 or more).
P having a structure in which one or two or more kinds of AO are added to an initiator having an active hydrogen atom of
T polyols (AO adducts) and PT polyols obtained by coupling two or more of them (same or different) with a coupling agent are included.

Initiators for AO addition include, for example, polyhydric alcohols (described above), hydroxylamines, aminocarboxylic acids and hydroxycarboxylic acids; polyhydric phenols; and polycarboxylic acids (described below).

Hydroxylamine includes C2-10 (di) alkanolamines, cycloalkanolamines and alkylalkanolamines such as 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-aminobutanol, 5- Aminopentanol, 6-aminohexanol, diethanolamine, di-n- and i-propanolamine, 3-aminomethyl-3,5,5-trimethylcyclohexanol, methylethanolamine and ethylethanolamine are included. Preference is given to 2-aminoethanol.

Aminocarboxylic acids include those having C2-12, such as amino acids [glycine, alanine, valine, (iso) leucine, phenylalanine, etc.], ω-aminoalkanoic acids (for example, ω-aminocapron, ω-aminoenanthate, ω-aminocapryl). , Ω-aminopergon, ω-aminocaprin, 11-aminoundecane and 12-aminododecanoic acid), and aromatic aminocarboxylic acids such as o-, m- and p-aminobenzoic acid.
Hydroxycarboxylic acid corresponds to the above aminocarboxylic acid (NH is replaced by O)
Such as ω-hydroxycaproic acid, salicylic acid, p- and m-hydroxybenzoic acid, and glycolic acid, glyceric acid, tartronic acid, malic acid, tartaric acid and benzylic acid. Preference is given to 12-aminododecanoic acid.

The polyhydric phenol includes C6-18 dihydric phenol such as monocyclic dihydric phenol (hydroquinone, catechol, resorcinol, urushiol, etc.), bisphenol (bisphenol A, F, C, B, AD and S, dihydroxybiphenyl, 4,4′-dihydroxydiphenyl-2,2-butane and the like), and condensed polycyclic dihydric phenol [dihydroxynaphthalene (eg, 1,5-dihydroxynaphthalene), binaphthol and the like];
Octavalent or higher polyhydric phenols such as monocyclic polyphenols (pyrogallol, phloroglucinol, and mono- or dihydric phenols (phenol, cresol, xylenol, resorcinol, etc.) aldehydes or ketones (formaldehyde, glutaraldehyde) , Glyoxal, acetone) low condensates (eg phenol or cresol novolac resin, intermediate of resole, polyphenol obtained by condensation reaction of phenol and glyoxal or glutaraldehyde, and polyphenol obtained by condensation reaction of resorcin and acetone) It is.

The addition of AO to the initiator can be carried out in the usual manner, and is carried out at atmospheric pressure in the absence of a catalyst or in the presence of a catalyst (alkali catalyst, amine catalyst, acidic catalyst, etc.) (particularly in the latter stage of AO addition). Alternatively, it is performed in one step or multiple steps under pressure. Two or more types of AO may be random addition, block addition, or a combination of both (for example, random addition followed by block addition).
AO adduct coupling agents include polyhalides such as C1-6 alkane polyhalides (eg C1-4 alkylene dihalides: methylene dichloride, 1,2-dibromoethane, etc.); epihalohydrins (eg epichlorohydrin, etc.); And polyepoxides.

Examples of OH-terminated PT include PT diols such as polyalkylene glycol (hereinafter PA).
Abbreviated as G) [eg, PEG, PPG and PTMG, poly-3-methyltetramethylene ether glycol], copolymerized polyoxyalkylene diol [EO / PO copolymer diol, THF / EO copolymer diol, THF / MTHF copolymer diol Etc. (weight ratio, eg 1
/ 9 to 9/1)], aromatic ring-containing polyoxyalkylene diol [polyoxyalkylene bisphenol A (EO and / or PO adduct of bisphenol A, etc.)]; and trifunctional or higher functional PT polyols such as polyoxypropylene triol (PO adducts of GR, etc.); and those obtained by coupling one or more of these with methylene dichloride.

The OH-terminated PS includes condensed PS polyol, polylactone (hereinafter abbreviated as PL) polyol, castor oil-based polyol [castor oil (ricinoleic acid triglyceride) and a modified polyol thereof), and polycarbonate polyol.
The condensed PS polyol is a polycondensation of a polyol and a polycarboxylic acid (refers to an acid or an ester-forming derivative thereof; the same shall apply hereinafter) (and a hydroxycarboxylic acid if necessary) or a reaction of the polyol with a polycarboxylic acid anhydride and AO. PL polyol is obtained by ring-opening addition of a lactone using a polyol as an initiator (or polycondensation of polyol and hydroxycarboxylic acid), a polyol modified product of castor oil is obtained by transesterification of castor oil and polyol, and polycarbonate. Polyol is a ring-opening addition / polycondensation of an alkylene carbonate using a polyol as an initiator, a polycondensation (transesterification) of a polyol and a diphenyl or dialkyl carbonate, or a polyol or a dihydric phenol (the above: bisphenol A, etc.) The Sugen reduction, can be produced.

The polyol used for the production of PS is usually 1,000 or less, preferably 30 to 500 O.
H equivalent (Mn per OH). Examples thereof include the above polyhydric alcohols [diols (eg, EG, 1,4-BD, NPG, HD and DEG) and trivalent or higher polyols (GR, TMP, PE, etc.)], the above PT polyols ( PEG, PPG, PTMG, etc.), and mixtures of two or more thereof. Preferred for the production of condensed PS polyols is
A combination of a diol and a small proportion (for example, 10 equivalent% or less) of a trivalent or higher polyol.

The polycarboxylic acid includes dicarboxylic acids and trivalent to tetravalent or higher polycarboxylic acids. Examples thereof include C2-30 or more (preferably C2-12) saturated and unsaturated aliphatic polycarboxylic acids, such as C2-15 dicarboxylic acids (eg, Shu, Aku, Maron, Adipine, Suberin, Azelain). , Sebatin, dodecanedicarboxylic,
Maleic, fumaric and itaconic acids), C6-20 tricarboxylic acids (eg tricarbaryl and hexanetricarboxylic acids)]; C8-15 aromatic polycarboxylic acids such as dicarboxylic acids (eg terephthalic, isophthalic and phthalic acids), tri- and Tetra-carboxylic acid (for example, trimellitic acid and pyromellitic acid); C6-40 alicyclic polycarboxylic acid (such as dimer acid); and sulfo group-containing polycarboxylic acid [in which a sulfo group is introduced into the above polycarboxylic acid] , E.g., sulfosuccinic, sulfomalon, sulfoglutar, sulfoadipine and sulfoisophthalic acid, and salts thereof (alkali metal, alkaline earth metal and group IIB metal salts, ammonium salts, amine salts, and quaternary ammonium salts, etc.)];
As well as carboxyl-terminated polymers.

  Examples of the carboxyl group-terminated polymer include PT polycarboxylic acid, for example, carboxymethyl ether of polyol [the above-mentioned polyhydric alcohol, PT polyol, etc.] (obtained by reacting monochloroacetic acid in the presence of alkali); and PD, PS And / or PU polycarboxylic acid, for example, polylactam polycarboxylic acid and PL polycarboxylic acid obtained by ring-opening polymerization of lactam or lactone (described above) using the above polycarboxylic acid as an initiator, or two molecules of the above polycarboxylic acids or A condensed PS polycarboxylic acid and a condensed PD polycarboxylic acid obtained by coupling (esterification or amidation) with a polyol (described above) or a polyamine or polyisocyanate (PI, described later), and the polycarboxylic acids and polyols described above. React with PI Urethanization and esterification or amidation) is allowed include PU polycarboxylic acids comprising.

Lactams include those of C4-15 (preferably C6-12) such as caprolactam,
Enanthractams, laurolactams and undecanolactams; lactones include those corresponding to the above lactams (NH substituted with O) (for example, ε-caprolactone, γ-butyrolactone, γ-valerolactone).

Ester forming derivatives include acid anhydrides, lower alkyl (C1-4) esters and acid halides such as succinic, maleic, itacone and phthalic anhydride, dimethyl terephthalate, and malonyl dichloride.
Preferred for the production of the condensed PS polyol is a combination of a dicarboxylic acid and a small proportion (for example, 10 equivalent% or less) of a trivalent to tetravalent or higher polycarboxylic acid.
Lactones and hydroxycarboxylic acids include those listed above.
Alkylene carbonates include those having a C2-6 alkylene group, such as ethylene and propylene carbonate. Dialkyl carbonates include those having a C1-4 alkyl group, such as dimethyl, diethyl and di-i-propyl carbonate.

Specific examples of OH-terminated PS include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene / propylene adipate, polyethylene / butylene adipate, polybutylene / hexamethylene adipate, polydiethylene adipate, poly (poly Tetramethylene ether) adipate, polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol and polyhexamethylene carbonate diol.

The OH-terminated PD has a polycarboxylic acid (above) polycondensed with hydroxylamine (above) or polyol (above) and polyamine (PA) (below).
Ester) amide polyols are included.

The OH-terminated PU includes an OH-terminated urethane prepolymer obtained by modifying a polyol with PI. The polyol includes the above-mentioned polyhydric alcohol, polymer polyol (the above-mentioned OH-terminated PT and PS, and OH-terminated VP and P / P described later), and combinations of two or more thereof. Of the polyols, preferred are polymer polyols (especially OH
Terminal PS and especially PT) and low molecular polyols (especially polyhydric alcohols)
It is combined use with. The amount of the low molecular polyol to be used in combination can be appropriately changed according to the required performance, but is generally 0.01 to 0.5 equivalent, more preferably 0.02 to 0.00 with respect to 1 equivalent of the polymer polyol. 4 equivalents, particularly 0.1 to 0.2 equivalents are preferred.
In the production of OH-terminated urethane prepolymers, the equivalent ratio of polyol to PI (OH / NC
O ratio) is usually 1.1 / 1 to 10/1, preferably 1.4 / 1 to 4/1, especially 1.4 /.
1-2 / 1. The polyol and PI may be reacted in a single stage or in multiple stages (for example, after reacting a part of the polyol or PI, the remainder is reacted).

OH-terminated VPs include polybutadiene-based polyols such as OH-terminated butadiene homopolymers and copolymers (styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, etc.) [those having 1,2-vinyl structures, 1,4-trans structures. Those having 1,4-cis structure, and those having two or more of these (1,2
-Mole ratio of vinyl / 1,4-trans / 1,4-cis 100-0 / 100-0 / 100-
0, preferably 10-30 / 50 to 70 / 10-30], and hydrogenated products thereof (hydrogenation rate: for example, 20 to 100%); acrylic polyol, for example, acrylic copolymer [alkyl (C1-20) (Meth) acrylates, or these and other monomers (styrene,
A copolymer with acrylic acid, etc.]] [in which hydroxyl groups are introduced mainly by hydroxyethyl (meth) acrylate]; and partially saponified ethylene /
Vinyl acetate copolymers are included.

P / P is obtained by in situ polymerization of an ethylenically unsaturated monomer in a polyol (previously OH-terminated PT and / or PS, or a mixture thereof with the polyhydric alcohol). Ethylenically unsaturated monomers include acrylic monomers such as (meth)
Acrylonitrile and alkyl (C1-20 or higher) (meth) acrylate (
Methyl methacrylate, etc.); hydrocarbon (hereinafter abbreviated as HC) monomers, such as aromatic unsaturated HC (styrene, etc.) and aliphatic unsaturated HC (C2-20 or more alkenes,
Alkadienes and the like, for example, α-olefins and butadienes); and combinations of two or more of these [for example, acrylonitrile / styrene (weight ratio of 100/0 to 80/20)]. P / P has a polymer content of, for example, 5 to 80% or more, preferably 30 to 70%.
Among the above polymer polyols, PT polyol and PS polyol are preferable.

[Isocyanate component]
The polyisocyanate (B) constituting the isocyanate component in the present invention has the following polyisocyanate (hereinafter abbreviated as PI) having 2 to 6 or more (preferably 2 to 3, particularly 2) isocyanate groups. And mixtures of two or more of these.
(1) C (excluding carbon in the NCO group, the same shall apply hereinafter) 2 to 18 aliphatic PI:
Diisocyanates (hereinafter abbreviated as DI), such as ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, decamethylene DI, dodecamethylene DI, 2,2,4- and / or 2,4 , 4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) fumarate and bis (2-isocyanatoethyl) Carbonate;
Trifunctional or higher functional PI (such as triisocyanate), such as 1,6,1 1-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3
, 6-Hexamethylene triisocyanate and lysine ester triisocyanate (phosgenate of reaction product of lysine and alkanolamine, 2-isocyanatoethyl-2
, 6-Diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl-
2,6-diisocyanatohexanoate etc.);

(2) C4-15 alicyclic PI:
DI, for example isophorone DI (IPDI), dicyclohexylmethane-4,4′-DI
(Hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5
-And / or 2,6-norbornane DI;
Trifunctional or higher functional PI (such as triisocyanate), such as bicycloheptane triisocyanate;
(3) C8-15 araliphatic PI:
m- and / or p-xylylene DI (XDI), diethylbenzene DI and α,
α, α ′, α′-tetramethylxylylene DI (TMXDI);
(4) C6-20 aromatic PI:
DI, for example 1,3- and / or 1,4-phenylene DI, 2,4- and / or 2,6-tolylene DI (TDI), 4, 4′- and / or 2,4′-diphenylmethane DI ( MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4, 4'-diisocyanatodiphenylmethane and 1,5-naphthylene DI;
Trifunctional or higher functional PI (such as triisocyanate), for example, crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate);

(5) Modified form of PI:
Modified products of the above PI, such as modified products having carbodiimide, urethane, urea, isocyanurate, uretoimine, allophanate, biuret, oxazolidone and / or uretdione groups), such as urethane modified products such as MDI, TDI, HDI and IPDI (polyol and NCO-terminated urethane prepolymer obtained by reacting with excess PI), biuret modified product, isocyanurate modified product, trihydrocarbyl phosphate modified product, and mixtures thereof.
The polyol used for urethane modification includes the polyhydric alcohol, PT polyol and / or PS polyol. Preferred is 500 or less, particularly 30 to 200 O.
Polyols having H equivalents such as glycols (EG, PG, DEG, DPG, etc.), triols (TMP, GR, etc.), tetrafunctional or higher functional polyols (PE, SO, etc.) and their AOs (EO and / or PO) ) (1-40 mol) adducts, especially glycols and triols. The equivalent ratio (NCO / OH ratio) between PI and polyol in urethane modification is usually 1.1 / 1 to 10/1, preferably 1.4 / 1 to 4/1, particularly 1.4 / 1 to 2.
/ 1.
The free isocyanate group content (% by weight) of the modified PI is usually 8 to 33%, preferably 10 to 30%, particularly preferably 12 to 29%.

[Polyurethane resin]
When forming a polyurethane resin from the polyol (A) and the polyisocyanate (B), when the ratio of (A) and (B) is represented by an isocyanate index [(equivalent ratio of NCO group / OH group) × 100] The index can be variously changed, but is preferably 90 to 100, more preferably 95 to 100, and particularly preferably 98 to 100 from the viewpoint of polyurethane resin strength and reaction rate.
As a reaction method of (A) and (B), even if it is a one-shot method, after reacting a part of (A) with (B) in advance to form an NCO-terminated prepolymer, the remaining ( A prepolymer method may be used in which a reaction is performed with A), or a part of (A) and (B) are reacted in advance to form an OH-terminated prepolymer, and then the remaining (B) is reacted. . From the viewpoint of suppressing the residual amount of free isocyanate as much as possible, the prepolymer method is preferred.

[Polyurethane foam]
The polyurethane foam of the present invention is characterized in that the oxygen concentration in the bubbles is 22 to 100% by volume. If the oxygen concentration is less than 22%, the oxygen supply ability in the blood cell storage bag described later is deteriorated.
The method for producing the polyurethane foam includes (1) a mechanical floss foaming method, (2) an oxygen loading foaming method, and a method of combining (1) and (2).
The method (1) uses a mechanical froth foaming machine, and is a method in which a polyurethane resin-forming composition composed of the polyol component and the isocyanate component is mixed and reacted to blow oxygen into the mixture. is there. In general, the rotor of a mechanical floss foaming machine consisting of a cylindrical stator with a large number of teeth on the inner surface and a rotor with a large number of teeth inside the stator is inactive with the material to be foamed during rotation. A method of continuously discharging a foam material from a discharge port of the foaming machine by continuously injecting gas (generally air, nitrogen, and oxygen in the present invention) into the foaming machine simultaneously. (See selection FIG. 3 of Japanese Patent No. 3083751).

Since the mechanical floss foaming machine is provided with an arbitrary number of materials and inert gas inlets, it is possible to mix two or more kinds of materials and an inert gas. Even if the material is curable, it does not matter if it is cured after it leaves the foaming machine.
The mixture of material and inert gas discharged from the discharge port is cast on a mold (open mold or sealed mold) whose temperature is adjusted in advance to 25 to 120 ° C. or on a belt conveyor partitioned on both sides so as not to spill. Is done.
Metals (aluminum, stainless steel, etc.) and plastics (polypropylene, polycarbonate, etc.) are usually used as the material for the mold and belt conveyor.
The mechanical floss foaming method is preferable to a general foaming agent foaming method as a polyurethane foam production method in that the bubble diameter after foaming is small and the density distribution in the resulting cured product is uniform.
The polyurethane foam of the present invention can be produced by using oxygen as the inert gas.

The method (2) uses a general polyurethane foaming machine including a mechanical floss foaming machine. In the polyol component and / or isocyanate component, oxygen is dissolved and contained in advance under pressure, and then these components are added. It is produced by mixing, reacting and foaming.
The method for dissolving oxygen in the component under pressure may be the same as the usual general air loading method. That is, in a pressure vessel, in an oxygen atmosphere, the components are stirred for a predetermined time (usually 1 to 8 hours, preferably 2 to 6 hours) under pressure (usually 0.05 to 1.0 MPa, preferably 0.1 to 0.1 MPa). 0.9 MPa). Oxygen loading may be performed only on either the polyol component or the isocyanate component, but it is preferable to perform on both components from the viewpoint of the oxygen concentration in the bubbles of the polyurethane foam.

The method of (3) is a method in which the above (1) and (2) are combined, and the method is manufactured by blowing oxygen into a mixed solution of a polyol component and an isocyanate component previously loaded with oxygen under pressure to perform mechanical froth foaming. It is.
Among the production methods (1) to (3), the production method (1) or (3) is preferable from the viewpoint of the oxygen concentration in the bubbles of the polyurethane foam.

In the polyurethane resin-forming composition comprising a polyol component and an isocyanate component, an additive selected from the group consisting of a foam stabilizer (C1) and a dehydrating agent (C2) as necessary within a range not impairing the effects of the present invention ( C) can be included.
Examples of the foam stabilizer (C1) include dimethylpolysiloxane having a foam regulating effect, and non-reactive dimethyl whose main chain, side chain and / or terminal is modified with a polyoxyalkylene chain, phenyl, alkyl, aralkyl or arylalkyl group. Polysiloxane etc. are mentioned.
(C1) includes an excellent balance between the bubble regulating effect and the communicating effect [for example, trade name “SZ-1931”, manufactured by Nihon Unicar Co., Ltd.], which is particularly excellent in the foam regulating effect and increases the closed cell ratio. Those having excellent characteristics [for example, trade name “SZ-1932” manufactured by Nihon Unicar Co., Ltd.], those having a communication effect and relatively excellent characteristics for reducing the closed cell ratio [for example, trade name “SZ-1923” "Nippon Unicar Co., Ltd.]" and the like are included. By selecting these types and amounts used, the closed cell ratio can be widely adjusted.
Mn of (C1) is preferably 5,000 to 100,000, more preferably 10,000 to 50,000 from the viewpoint of the foam regulating effect.
The amount of (C1) used is usually 6% or less based on the total weight of (A) and (B), preferably from 0.05 to 5%, more preferably from the viewpoint of the foam stabilizing effect and the strength of the polyurethane resin. 0.3 to 3%, particularly preferably 0.5 to 2%.

The dehydrating agent (C2) prevents moisture and moisture from being mixed into the polyol (A) and becomes a foaming agent in the urethanization reaction to prevent carbon dioxide gas generation, thereby obtaining a polyurethane foam having denser bubbles. It is included for the purpose.
As (C2), a commonly used compound having a dehydrating effect can be used, but a neutral or alkaline dehydrating agent having a volume average particle size of 0.1 to 50 μm is preferred.
Specific examples of (C2) include calcium oxide, calcium sulfate (hemihydrate gypsum), calcium chloride, and molecular sieve. Of these, calcium sulfate (hemihydrate gypsum) is preferable from the viewpoint of small particle size, fine dispersion in the composition, and stability of dehydration effect.
And molecular sieves, more preferably molecular sieves.
The amount of (C2) used is usually 20% or less based on the total weight of (A) and (B), preferably from 0.3 to 15% from the viewpoint of dehydration effect and appropriate fluidity of the composition, Preferably it is 0.5 to 10%.

Examples of the catalyst (C3) include tertiary amines (such as triethylenediamine) and metal organic acid salts [dibutyltin dilaurate, di-2ethylhexyl lead, bismuth tris (2-ethylhexanoate), etc.]. When the tertiary amino group-containing polyol is used as the polyol (A), since the polyol has a catalytic effect, a so-called non-catalytic polyurethane foam can be obtained without adding a catalyst again.
The amount of (C3) used is usually 1% or less, preferably 0.001 to 0.5%, more preferably 0.005 to 0.3%, based on the total weight of (A) and (B). is there.
(C1) to (C3) are usually used in the polyol component.

The cell diameter of the polyurethane foam of the present invention is preferably from 0.5 to 300 μm, more preferably from 1 to 200 μm, from the viewpoint of oxygen supply ability and bubble stability in a blood cell storage bag to be described later.
In the production of the polyurethane foam, the amount (% by volume) of oxygen to be contained is determined based on the total volume of the polyol component and the isocyanate component described above, in terms of oxygen supply ability and bubble stability in the blood cell storage bag described later. From the viewpoint, it is preferably 10 to 95, more preferably 12 to 85, still more preferably 15 to 80, and particularly preferably 20 to 75.
The oxygen concentration (volume%) in the bubbles of the polyurethane foam is 22 to 100%, and preferably 50 to 100% from the viewpoint of oxygen supply. The oxygen concentration can be measured using a gas chromatograph GC-2010 (manufactured by Shimadzu Corporation) equipped with an RT-Msieve 5A column [manufactured by RESTEK Co., Ltd.].

The density of the polyurethane foam of the present invention is preferably 0.01 to 0.7 g / cm ³ , more preferably 0.03 to 0.5 g / cm ³ , and particularly preferably 0 from the viewpoint of mechanical strength and oxygen supply ability. 0.05 to 0.3 g / cm ³ .
Further, the closed cell ratio of the polyurethane foam is preferably 70 to 100%, more preferably 80 to 100% from the viewpoint of sustained release of oxygen and reduction of the brittleness of the polyurethane foam. The closed cell ratio can be measured by an air pycnometer method according to ASTM D-2856.
In addition to selecting the type and amount of foam stabilizer (C1), the closed cell ratio should be adjusted by selecting the types of polyol (A) and polyisocyanate (B) in the polyurethane resin-forming composition. Can do.
For example, as a polyol (A), a comparatively high functional (trivalent to hexavalent or higher) polyol or a low molecular polyol (having an OH equivalent of less than 250) is used, and compared as a polyisocyanate (B). The ratio of closed cells can be increased, for example, by increasing the proportion of the polyisocyanate having a high functionality (divalent to trivalent or higher). Conversely, as the polyol (A), a low-functional (divalent or lower) polyol The ratio of closed cells can be reduced by increasing the use ratio of the polymer polyol (having an OH equivalent of 250 or more) or increasing the use ratio of a low-functional (divalent) polyisocyanate as the polyisocyanate (B). .

[Blood cell storage bag with built-in polyurethane foam]
The blood cell storage bag is a bag-like container for storing blood cells (platelets and the like) for a certain period. It is usually made of a material such as vinyl chloride or polyolefin, and has a bag-like shape. Usually, the length is 14 to 22 cm, the width is 14 to 22 cm, and the maximum volume when filling is 250 to 700 cm ³ .
The polyurethane foam of the present invention is usually incorporated during the production of the bag-shaped storage bag.

[Blood cell preparation containing polyurethane foam]
Blood cells (platelets and the like) are filled into a blood cell storage bag containing the polyurethane foam to form a blood cell preparation. The proportion of polyurethane foam based on the volume of blood cells in the storage bag is preferably 30 to 100%, more preferably 40 to 80% from the viewpoint of oxygen supply and handling properties.
As described above, the storage stability of blood cells can be remarkably improved by incorporating the polyurethane foam of the present invention into a blood cell preparation in a storage bag. The storage stability can be evaluated by platelet count, plasma pH, aggregation ability, low osmotic shock recovery rate, swirling and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the following, parts represent parts by weight, and% represents volume%. The raw materials used in Examples and Comparative Examples are shown below.
Polyol (A1): PO addition product of glycerin [trade name “Sanix GP-400
"OH value 400, manufactured by Sanyo Chemical Industries Co., Ltd.]
Polyol (A2): Polymer polyol [trade name “SANNICS FP-202
"OH value 400, manufactured by Sanyo Chemical Industries Co., Ltd.]
Isocyanate (B1): Polymethylene polyphenylene polyisocyanate [trade name “Mi
Lionate MR-200 "manufactured by Nippon Polyurethane Industry Co., Ltd.]
Foam stabilizer (C1-1): trade name “SZ-1931”, Nippon Unicar Co., Ltd. foam stabilizer (C1-2): trade name “SZ-1932”, Nihon Unicar Co., Ltd. foam stabilizer ( C1-3): Trade name “SZ-1923”, Nippon Unicar Co., Ltd. dehydrating agent (C2-1): Synthetic zeolite [trade name “PURMOL 3ST”, CU
Made by Chemie Uetikon AG]
Catalyst (C3-1): Trade name “Neostan U-600”, Examples 1 to 4 manufactured by Nitto Kasei Co., Ltd.
With the composition shown in Table 1, each raw material was put into a planetary mixer, stirred at 130 rpm for 10 minutes, and then stirred and degassed at 30 mmHg or less for 5 minutes to obtain a polyol component. The isocyanate component was obtained in the same manner. The temperature of each component was adjusted to 25 ± 1 ° C.
Next, a polyol component and an isocyanate component were put in each of two tanks that can be pressurized and equipped with a stirrer, and stirred at 15 rpm at 0.2 Pa for 4 hours.
Mechanical floss foaming machine [trade name “MF-350 type mechanical floss foaming device” manufactured by Toho Machine Industry Co., Ltd. same as below. The polyol component and the isocyanate component are fed into the resin with a Mono pump, and the rotor of the mechanical froth foaming machine is rotated at 300 rpm, so that the total flow rate of the polyol component and the isocyanate component is 3 L / min, and the oxygen is the volume% shown in Table 1. The flow was continuously supplied to the mixing head inlet at a high flow rate. The mixed and discharged liquid is cast from a mixing head outlet through a vinyl hose with a length of 2 m and an inner diameter of 19 mm so that the inner dimension is a height of 500 mm and a width of 500 mm and a height of 150 mm. And cured to obtain a polyurethane foam molded article. The molded product was evaluated according to the following method. The results are shown in Table 1.

Comparative Examples 1-2
Molded articles were obtained in the same manner as in Examples 1 to 4 with the composition shown in Table 1. The molded product was evaluated according to the following method. The results are shown in Table 1.
<Method for evaluating molded products>
(1) Density (Unit: g / cm ³ )
A 200 × 200 × 10 mm test piece was cut out from the center of the polyurethane foam molded article, and the weight of the test piece measured after standing for 12 hours or more in a room temperature-controlled at 20 to 25 ° C. Divided by the volume calculated from the product of thickness, the density was obtained.
(2) Closed cell ratio (%)
The air pycnometer method was used in accordance with the method described in ASTM D-2856.
(3) Oxygen concentration in bubbles (%)
A test piece of 20 × 30 × 10 mm was cut out from the center of the polyurethane foam molded article and placed in a sealed bottle under an argon atmosphere. After leaving still at 150-250 degreeC for 5 minutes or more, gas chromatograph GC-2010 [made by Shimadzu Corporation] to which the gas in an airtight bottle was attached RT-Msieve 5A column [made by RESTEK Co., Ltd.] was used. It was measured. The calibration curve was prepared using a mixed gas composed of oxygen and nitrogen with at least three or more known oxygen concentrations.
(4) Oxygen content in foam (volume%)
The oxygen amount (volume%) in the polyurethane foam is represented by the following formula.

Form oxygen content _{(vol%) = V O × (D} J -D F) / D J

D _J : Density of polyurethane resin (g / cm ³ )
D _F : Polyurethane foam density (g / cm ³ )
V _O : Bubble oxygen concentration (% by volume)

(* 1) Volume%: Represented by the following formula. The amount of injected gas indicates the volume at 25 ° C. and 1 atmosphere.
Here, the injection gas is oxygen (Examples 1 to 3), oxygen / nitrogen mixed gas
(Volume ratio 50/50) (Example 4), oxygen / nitrogen mixed gas (volume ratio 10
/ 90) (Comparative Example 1) or air (Comparative Example 2).

Volume% = injected gas amount × 100 / (injected gas amount + total composition volume before gas injection)

Examples 5-8, Comparative Examples 3-5
A polyurethane foam (vertical x horizontal x thickness = 12 x 10 x 1 cm) cut out from each polyurethane foam molded product obtained in Examples 1 to 4 and Comparative Examples 1 to 2 was prepared, and a sheet for storage bags (vertical x Each of the storage bags in which the polyurethane foams were incorporated one by one was obtained when forming a horizontal shape (40 × 30 cm) into a bag shape. Each storage bag was dispensed and filled with 5 units of concentrated platelets (PC) (platelet number 1 × 10 ¹¹ ) to obtain platelet preparations (K1 to K4, ratio K1 to ratio K2). The platelet preparation was stored for 7 days while shaking horizontally at 22 ° C. and 60 rpm [shaker PR-12, manufactured by TAITEC Corporation]. The following items were measured for the platelets after storage to evaluate the storage stability of the platelets. A platelet storage bag without visceral polyurethane foam was prepared in the same manner as described above, and the storage bag filled with 5 units of concentrated platelets (PC) was designated ratio K3.

<Method for evaluating the storage stability of platelets>
(1) Platelet count An automatic blood cell counter [F-520, manufactured by Sysmex Corporation] was used.
(2) Plasma pH
Using a part of the platelets after storage, a pH meter [F8DP, Horiba, Ltd.] was used.
(3) Low osmotic shock recovery rate (% HSR)
1/3 volume of water was added to the platelets, and the absorbance at a wavelength of 610 nm was measured with a UV-visible spectrophotometer [UV-2550, manufactured by Shimadzu Corporation]. The value after 5 minutes of water addition and immediately after the water addition It was obtained from the ratio of the maximum values. The recovery rate of hypotonic shock indicates the vulnerability of the cells. The larger the value, the more the platelets are not denatured.
(4) Swirling Swirling is a phenomenon in which a spiral pattern occurs when a large surface of a bag containing platelets is held horizontally and moved slowly in a circle while holding it over a fluorescent lamp. It is. The easier this phenomenon occurs, the less the degree of platelet degeneration and the better the storage stability. Evaluation was made according to the following criteria.
(Evaluation criteria)
+ Swirling occurs easily ± Swirling occurs slightly-Swirling does not occur at all

  From the results shown in Table 2, the storage bag-containing platelet preparation (Examples 5 to 8) incorporating the polyurethane foam of the present invention has significantly better storage stability than the comparative platelet preparation (Comparative Examples 3 to 5). Recognize.

  The blood cell preparation containing a blood cell (particularly platelet) storage bag containing the polyurethane foam of the present invention is extremely excellent in storage stability. It is extremely useful as a general storage bag.

Claims (8)

An oxygen-containing polyurethane foam, characterized in that oxygen is contained in a mixed liquid composed of a polyol component and an isocyanate component and foamed, and the oxygen concentration in the bubbles is 22 to 100% by volume. The polyurethane foam according to claim 1, wherein the density of the polyurethane foam is 0.01 to 0.7 g / cm ³ . The polyurethane foam according to claim 1 or 2, wherein the closed cell ratio of the polyurethane foam is 70 to 100%. A blood cell storage bag containing the polyurethane foam according to any one of claims 1 to 3. A blood cell preparation comprising the storage bag according to claim 4 filled with blood cells. The blood cell preparation according to claim 5, wherein the ratio of the polyurethane foam based on the blood cell volume is 30 to 100% by volume. A method for producing an oxygen-containing polyurethane foam having an oxygen concentration in a bubble of 22 to 100% by volume, wherein oxygen is contained in a mixed liquid comprising a polyol component and an isocyanate component and foamed. Storage stability of blood cells, characterized in that a blood cell storage bag filled with blood cells incorporates an oxygen-containing polyurethane foam having an oxygen concentration in air bubbles of 22 to 100% by volume to release oxygen gradually. Improvement method.