JP5474627B2 - Active hydrogen component for polyurethane resin production - Google Patents

Description

The present invention relates to an active hydrogen component for producing a polyurethane resin containing crystalline cellulose, a polyurethane resin using the active hydrogen component as a raw material, and a molded product thereof.

In recent years, plastics derived from plants and animals have been actively developed as an alternative to plastics derived from petroleum resources. One method is to use cellulose, which is the most abundant biomass resource on the earth. Cellulose can be produced from organisms other than plants such as plants, bacteria (acetic acid bacteria), and sea squirts, and is not an oil resource. Therefore, even if it is finally incinerated, its impact on the environment is small.

Many resins using cellulose have been reported so far. For example, a method of adding a cellulose powder of 40 to 500 mesh (0.425 to 0.025 mm) to a polyol stock solution to obtain a high-strength rigid urethane foam (Patent Document 1), molding and drying microfibrillated cellulose, It has been reported that a molded article having a relatively high strength can be obtained by impregnating the resin. (Patent Document 2) In addition, by mixing microfibrillated cellulose dispersed in water with resin powder and drying it, a composite resin of cellulose and resin can be created and molded to improve physical properties such as strength. It has been reported. (Patent Document 3)

Japanese Patent Laid-Open No. 7-82338 JP 2003-201695 A JP 2008-297364 A

However, in the method disclosed in Patent Document 1, since cellulose powder having a large amount of amorphous part in cellulose is used, the cellulose concentration is particularly introduced when introduced into a polyol for rigid polyurethane foam. When the viscosity is increased, the viscosity of the polyol component increases, and there is a problem that the mixing property is lowered when mixing with the isocyanate component, and the liquid flow property at the time of injection is lowered, so that the moldability is lowered. In the method disclosed in Patent Document 2, since the shape of a molded product depends on the shape of a cellulose sheet as a molded product precursor, it is difficult to create a molded product having a complicated shape. Further, the method disclosed in Patent Document 3 is a method for producing a thermoplastic resin powder for injection extrusion molding, such as a urethane resin generally used as a molding material resin such as a modeling material and a cushion sheet. This method cannot be applied to thermosetting resin raw materials. An object of the present invention is to obtain a polyurethane resin having a high strength and containing a high concentration of cellulose, which is a natural resource that has a low environmental burden and can be regenerated.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention comprises an active hydrogen component (A) for producing a polyurethane resin, comprising cellulose (b) having a crystallinity of 65% or more and an active hydrogen compound (a); A polyurethane resin (I) obtained by reacting (A) with a polyisocyanate component (C); a polyurethane resin molded article composed of the resin (I).

The active hydrogen component (A) for producing the polyurethane resin of the present invention and the polyurethane resin (I) using the component have the following effects.
(1) By containing cellulose, which is a renewable natural resource, the environmental burden is small.
(2) Since the raw material liquid has a low viscosity even when cellulose is contained in a high concentration, a high-strength polyurethane resin molded product with good moldability can be obtained.
(3) Cellulose acts as a high-strength organic filler, and a high-strength polyurethane resin can be obtained.

[Active hydrogen compound (a)]
The active hydrogen compound (a) in the present invention is a compound having active hydrogen capable of reacting with the polyisocyanate component (C), and is an active hydrogen-containing compound having 2 to 8 or more valences. It is preferably liquid at room temperature (25 ° C.). Examples of the active hydrogen include active hydrogen such as a hydroxyl group, an amino group, and a mercapto group.
The weight average molecular weight of the active hydrogen compound (a) is usually 150 to 20000, preferably 250 to 15000, more preferably 400 to 10,000.
Examples of the active hydrogen compound (a) include (1) polyoxyalkylene polyol active hydrogen-containing compounds (for example, polyhydric alcohols, amines, polyhydric phenols, polycarboxylic acids, and mixtures thereof. The contents thereof are described below. )) Is added a compound (2) polyester polyol to which an alkylene oxide (hereinafter abbreviated as AO) is added.

Examples of the active hydrogen-containing compound polyhydric alcohol include dihydric alcohols having 2 to 20 carbon atoms (aliphatic diols such as ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, and 1,6-hexanediol. , Alkylene glycols such as neopentyl glycol; and alicyclic diols such as cycloalkylene glycols such as cyclohexanediol and cyclohexanedimethanol, trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols such as glycerin and trimethylol) Alkanetriols such as propane, trimethylolethane, hexanetriol); 4-8 or higher polyhydric alcohols having 5 to 20 carbon atoms (aliphatic polyols such as pentaerythritol, sorbitol, mannitol, Tail, diglycerol, intramolecular or intermolecular dehydration products of alkane polyols and their or alkane triol, such as dipentaerythritol; and sucrose, glucose, mannose, fructose, sugars and derivatives thereof), such as methyl glucoside.

Amines include alkanolamines, polyamines, and monoamines.
Examples of the alkanolamine include mono-, di- and tri-alkanolamines having 2 to 20 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine and isopropanolamine).
As polyamine (number of primary, secondary amino groups: 2 to 8 or more), aliphatic amine, alkylene diamine having 2 to 6 carbon atoms (for example, ethylene diamine, propylene diamine and hexamethylene diamine), carbon number 4-20 polyalkylene polyamines (dialkylene triamine having 2 to 6 carbon atoms in the alkylene group to hexaalkylene heptamine such as diethylenetriamine and triethylenetetramine) and the like.
Also, an aromatic polyamine having 6 to 20 carbon atoms (for example, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyletherdiamine); an alicyclic polyamine having 4 to 20 carbon atoms (for example, Isophoronediamine, cyclohexylenediamine and dicyclohexylmethanediamine); heterocyclic polyamines having 4 to 20 carbon atoms (for example, piperazine and aminoethylpiperazine) and the like.
As monoamine, ammonia; as aliphatic amine, alkylamine having 1 to 20 carbon atoms (for example, n-butylamine and octylamine); aromatic monoamine having 6 to 20 carbon atoms (for example, aniline and toluidine); -20 alicyclic monoamine (for example, cyclohexylamine); C4-C20 heterocyclic monoamine (for example, piperidine) and the like.

Polyhydric (2 to 8 or more) phenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A, bisphenol F, and bisphenol sulfone; condensates of phenol and formaldehyde (novolaks) For example, polyphenols described in US Pat. No. 3,265,641.

Examples of the polycarboxylic acid include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.), and aromatic polycarboxylic acids having 8 to 18 carbon atoms (phthalic acid, Terephthalic acid, isophthalic acid, trimellitic acid, etc.), and mixtures of two or more thereof.
Two or more of these active hydrogen-containing compounds may be used in combination. Of these, polyhydric alcohols are preferred.

(1) Polyoxyalkylene polyol As AO added to the above active hydrogen-containing compound, those having 2 to 8 carbon atoms are preferable, and propylene oxide (hereinafter abbreviated as PO), ethylene oxide (hereinafter abbreviated as EO). 2), 1,2-, 1,3-, 1,4-, or 2,3-butylene oxide, styrene oxide, and the like. AO is preferably a combination of PO and / or EO and, if necessary, other AO in the range of 10% by weight or less (especially 5% by weight or less) in AO. It may be an adduct. As an addition method when two or more kinds of AO are used, block addition, random addition, or a combination addition thereof may be used, but block addition is preferable.
As a catalyst used at the time of AO addition, in addition to a commonly used alkali catalyst (KOH, CsOH, etc.), a catalyst described in JP-A No. 2000-344881 [Tris (pentafluorophenyl) borane, etc.], JP-A No. 11-120300 You may use the catalyst (magnesium perchlorate etc.) described in the gazette.

(2) Polyester polyol As the polyester polyol, the polyhydric alcohol [particularly, ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. A dihydric alcohol; the polyether polyol (particularly a diol); or a mixture thereof with a trihydric or higher polyhydric alcohol such as glycerin or trimethylolpropane] and the polycarboxylic acid or an ester-forming derivative thereof [acid Anhydride, lower alkyl (alkyl group having 1 to 4 carbon atoms) ester, etc.] (for example, adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate) polyester polyol, or carboxylic anhydride Thing and AO (EO, PO, etc.) adducts thereof; polylactone polyols, such as those obtained by ring-opening polymerization of lactones (e.g., ε-caprolactone) using the polyhydric alcohol as an initiator Polycarbonate polyol, for example, a reaction product of the polyhydric alcohol and alkylene carbonate;

  The average number of functional groups of the active hydrogen compound (a) used in the production method of the present invention is preferably 2 to 5, more preferably 2.5 to 4. When the active hydrogen compound (a) is a compound having a hydroxyl group, the average hydroxyl value thereof is preferably 20 to 1000, more preferably 24 to 800.

[Crystalline cellulose (b)]
The crystallinity of the crystalline cellulose (b) is 65% or more, preferably 70% or more.
When the degree of crystallinity is less than 65%, the viscosity of the active hydrogen component (A) in which the crystalline cellulose (b) is dispersed increases, so that a high-strength polyurethane resin molded product with good moldability cannot be obtained.
The crystallinity is usually measured by the X-ray diffraction method by pressing finely pulverized cellulose particles against an aluminum holder and operating the X-ray diffraction angle up to 5 to 30 °. At this time, two crystal scattering peaks occur in crystalline cellulose. On the other hand, an amorphous part becomes background scattering. The crystallinity is determined by the ratio of the crystal partial scattering peak area to the crystallinity total scattering peak area.

Crystalline cellulose (b) includes plants (for example, wood, bamboo, hemp, jute, kenaf, farmland waste, cloth, pulp, recycled pulp, waste paper), animals (for example, ascidians), algae, microorganisms (for example, acetic acid bacteria (for example, acetic acid bacteria ( Acetobacter)), a cellulose fiber originating from a microbial product or the like, any of which can be used in the present invention. The crystalline cellulose (b) is more preferably a plant-derived cellulose fiber.
Ordinary cellulose fibers have a crystalline part and an amorphous part, and in order to make it into crystalline cellulose (b), the amorphous part is generally hydrolyzed and removed.

As a method for producing crystalline cellulose (b), in general, cellulose fiber-containing materials such as pulp can be heated and hydrolyzed in an acidic atmosphere, and then filtered and dried. It can also be produced by a known method such as the method described in 2004-331925.
The average fiber length of the crystalline cellulose (b) is preferably 5 to 1000 μm, more preferably 10 to 500 μm, and more preferably 15 to 250 μm.
When the average fiber length of (b) is 5 to 1000 μm, the viscosity of the active hydrogen component (A) is preferably not increased.

[Active hydrogen component for polyurethane resin production (A)]
(A) contains an active hydrogen compound (a) and crystalline cellulose (b) as essential components.
The content% by weight of the crystalline cellulose (b) contained in (A) is preferably 1 to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight.
When the content (%) of (b) is 50% or less, the viscosity of (A) does not increase and the handling is easy, and the mixing property is good when mixed and reacted with the polyisocyanate component (C). When the content (%) of (b) is 1% or more, the polyurethane resin can have high strength.
In the present invention, the active hydrogen component (A) for producing the polyurethane resin contains the crystalline cellulose (b) in the active hydrogen compound (a), preferably using a general dispersion method such as mixing and stirring. And can be obtained by dispersing. In addition, when the raw material (b) contains moisture, the moisture (A) with less moisture can be obtained by removing the moisture by performing drying under heating or the like after being dispersed in (a) or while being dispersed. Can be obtained. The moisture is preferably 0.3% by weight or less.

Polyisocyanate component (C)
As the polyisocyanate component (C) used in the production method of the present invention, any compound having two or more isocyanate groups in the molecule may be used, and any of those conventionally used in the production of polyurethane foams can be used. Examples of such isocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (for example, urethane groups, carbodiimide groups, allophanate groups, urea groups, burettes). Group, an isocyanurate group, or an oxazolidone group-containing modified product) and a mixture of two or more thereof.

The aromatic polyisocyanate includes 6 to 16 aromatic diisocyanates, 6 to 20 aromatic triisocyanates, and crude products of these isocyanates (excluding carbon in the NCO group; the following isocyanates are also the same). Is mentioned. Specific examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4, 4'-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), and the like.
Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 6 to 10 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate and lysine diisocyanate.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 6 to 16 carbon atoms. Specific examples include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic polyisocyanate include araliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Specific examples of the modified polyisocyanate include urethane-modified MDI and carbodiimide-modified MDI.
The polyisocyanate (C) is preferably an aromatic polyisocyanate and a modified product thereof, more preferably 40 to 60% by weight of MDI, 1 to 10% by weight of carbodiimide-modified MDI, and 39 to 39% of urethane-modified MDI. It is an MDI-based isocyanate prepolymer containing 59% by weight.
The isocyanate group content of the entire polyisocyanate (C) used in the reaction is preferably 10 to 30% by weight.

The active hydrogen component (A) for producing the polyurethane resin of the present invention can be reacted with the polyisocyanate component (C) to produce the polyurethane resin (I). Reaction conditions are not particularly limited, and known conditions are applied. In the production method of the present invention, the isocyanate index [(NCO group / active hydrogen atom-containing group equivalent ratio × 100) (NCO index) in the production of the polyurethane resin is preferably 70 to 125, more preferably 75 to 120. Especially preferably, it is 85-115.

The polyurethane resin (I) of the present invention has the characteristics that it can reduce environmental burden by containing cellulose and that high mechanical strength can be expressed because the cellulose contained as a filler component is a crystalline polymer. In addition, since it is a two-component reaction type resin, the state before the resinification reaction is a low-viscosity liquid, has excellent fluidity in the mold for molding production, and can produce resin molding products with complicated shapes. Is possible.
The active hydrogen component (A) for producing the polyurethane resin of the present invention is excellent in dispersion stability and has a feature that there is little sediment of the dispersion (cellulose). Further, since the dispersion (cellulose) is an organic substance, there is little influence on the manufacturing apparatus such as wear of the apparatus.
The active hydrogen component (A) for producing the polyurethane resin of the present invention may contain a dispersion aid as necessary.
Examples of the dispersion aid include resin oligomers, surfactants, and the like, polyoxyalkylene polyols serving as base materials, and amphiphilic compounds with respect to cellulose. 0.1 to 5 parts, preferably 0.3 to 4 parts, more preferably 0.5 to 3 parts.

The active hydrogen component (A) for producing the polyurethane resin may contain a chain extender (D), a urethanization catalyst (E), a foam stabilizer (F), a foaming agent (G) and the like as necessary.

[Chain extender (D)]
As the chain extender (D) in the present invention, all substances usually used for the production of urethane resins can be used. Examples include ethylene glycol, 1,4 butanediol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol. Glycerin, trimethylolpropane, hexamethylenediamine, toluenediamine, dichlorodiaminodiphenylmethane (MOCA), diethanolamine, triethanolamine and the like. The amount of (D) added is usually 1 to 20 parts, preferably 5 to 10 parts per 100 parts of (A).

[Urethaneization catalyst (E)]
As the urethanization catalyst (E) in the present invention, all usual urethanization catalysts that promote the urethanation reaction can be used. Examples include triethylenediamine, bis (N, N-dimethylamino-2-ethyl) ether, N , N, N ′, N′-tetramethylhexamethylenediamine, tertiary amines such as PO adduct of N, N-dimethylaminopropylamine and carboxylates thereof, potassium acetate, potassium octylate, stannous octoate, etc. Organic metal compounds such as carboxylic acid metal salts and dibutyltin dilaurate. The amount of (E) added is usually 0.1 to 3 parts, preferably 0.3 to 2 parts, relative to 100 parts of (A).

[Foam stabilizer (F)]
As the foam stabilizer (F) in the present invention, all those used in the production of ordinary polyurethane resins can be used. For example, a dimethylsiloxane foam stabilizer [for example, “SRX manufactured by Toledo Corning Silicone Co., Ltd.” -253 "etc.], polyether-modified dimethylsiloxane foam stabilizers [for example," L-5309 "manufactured by Momentive Co., Ltd.," SF-2969 "manufactured by Toray Dow Corning Co., Ltd.," SRX-274C " , “SZ-1671”, “B-8462”, “B-8474” manufactured by Goldschmidt AG Co., Ltd., and the like. The amount of (F) added is usually 0.1 to 6% by weight, more preferably 0.5 to 3% by weight, based on (A).

The polyurethane resin (I) can contain various additives.
The polyurethane resin (I) in the present invention may further contain an additive (H) as necessary as long as the effects of the present invention are not impaired. (H) includes dehydrating agent (H1), lubricant (H2), plasticizer (H3), thixotropic agent (H4), filler (H6), ultraviolet absorber (H7), anti-aging agent (H8). Antioxidant (H9), Colorant (H10), Flame Retardant (H11), Antifungal Agent (H12), Antibacterial Agent (H13), Hollow Microsphere (H14), Inorganic Filler (H15), Dispersant (Sedimentation) 1 type or 2 or more types of additives chosen from the group which consists of (preventive material) (H16) are mentioned.

Examples of the dehydrating agent (H1) include calcium oxide, calcium sulfate (hemihydrate gypsum), calcium chloride, molecular sieve, etc .;
Examples of the lubricant (H2) include fatty acid alkanolamides (such as oleic acid monoethanolamide), fatty acid metal salts (such as calcium stearate), and ethylenediamine distearylamide;
Examples of the plasticizer (H3) include phthalic acid esters (dibutyl phthalate, dioctyl phthalate, etc.), adipic acid esters (dioctyl adipate, etc.), phosphoric acid triesters (triisopropylphenyl phosphate, etc.);
Examples of the thixotropic agent (H4) include fine-particle silica (volume average particle size of 100 nm or less), hydrogenated castor oil, organic bentonite, and the like;
Examples of the filler (H6) include inorganic fillers (calcium carbonate, talc, aluminum hydroxide, mica, milled fiber, etc.) and organic fillers (such as pulverized thermosetting resin).
Examples of the ultraviolet absorber (H7) include salicylate (such as phenyl salicylate), benzophenone (such as 2-hydroxy-4-methoxybenzophenone), and benzotriazole [2- (2-hydroxy-5-t-octylphenyl) benzotriazole. ]etc;
Examples of the anti-aging agent (H8) include amines (N-phenyl-α and -β-naphthylamine and the like), phenols [2,2′-methylenebis (4-methyl-6-t-butylphenol) and the like] and the like;
Examples of the antioxidant (H9) include phenol (hydroquinone, etc.), sulfur-containing compounds (dilauryl thiodipropionate, etc.), amine (octylated diphenylamine, etc.) and the like;
Examples of the colorant (H10) include pigments [inorganic pigments (titanium oxide, iron oxide, etc.), organic pigments (azo lake, monoazo, etc.)], dyes (azo, anthraquinone, etc.), etc .;
Flame retardants (H11) include halogen-containing flame retardants (hexachloropentadiene, hexabromodiphenyl, etc.), nitrogen-containing flame retardants (urea compounds, guanidine compounds, etc.), sulfur-containing flame retardants (sulfuric esters, sulfamic acids, etc.), phosphorus-containing Flame retardant (phosphoric acid, phosphate, etc.), etc .;
Examples of the antifungal agent (H12) include 4-chlorophenyl-3-iodopropargyl formal, 3-iodo-2-propenylbutyl carbamate and the like;
Antibacterial agents (H13) include antibacterial zeolite compounds, quaternary ammonium salts (didecyldimethylammonium chloride, etc.), organic iodine antibacterial agents (4-chlorophenyl-3-iodopropargyl formal, 3-iodo-2-propenyl) Butyl carbamate, etc.), organic nitrogen sulfur antibacterial agents (benzothiazole, 2,4-thiazolylbenzimidazole, etc.);
As hollow microspheres (H14), thermoplastic resins (polyvinylidene chloride, polymethyl methacrylate, polyacrylonitrile, etc.), thermosetting resins (phenol resins, epoxy resins, urea resins, etc.) and inorganic substances (glass, alumina, shirasu, Each hollow microsphere made of carbon etc .;
Examples of the inorganic filler (H15) include metal (aluminum etc.) powder, inorganic salt (calcium carbonate etc.), talc, glass fiber and the like.
Examples of the dispersion material (anti-settling material) (H16) include ionic surfactants, nonionic surfactants, ammonium salts of polycarboxylic acids, and the like. The amount of various (H) added is usually 40 parts or less, preferably 30 parts or less, more preferably 20 parts or less, relative to 100 parts of (I).

[Foaming agent (G)]
Examples of the blowing agent (G) in the present invention include water that reacts with polyisocyanate to generate carbon dioxide, low-boiling hydrocarbons that vaporize and expand by reaction heat, and hydrogen atom-containing halogenated hydrocarbon-based blowing agents. . The low boiling point hydrocarbon is usually a hydrocarbon having a boiling point of −5 to 70 ° C., and specific examples thereof include butane, pentane, cyclopentane, and mixtures thereof. The amount used when using low-boiling hydrocarbons is preferably 30 parts or less, more preferably 20 parts or less, per 100 parts of (I).
Specific examples of hydrogen atom-containing halogenated hydrocarbon-based blowing agents include those of the HCFC (hydrochlorofluorocarbon) type (for example, HCFC-123, HCFC-141b, HCFC-22, and HCFC-142b); those of the HFC (hydrofluorocarbon) type (For example, HFC-134a, HFC-152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, and HFC-365mfc).
Among these, HCFC-141b, HFC-134a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, and HFC-365mfc and mixtures of two or more thereof are preferred.

Polyurethane resin (I) can be used in any application field where polyurethane resin is used, for example, resin molded products such as shoe soles, watch bands, casters, belts, wire covering materials, seat cushions, soundproof materials, filters, mattresses, sofas, heat insulating materials, It can be used in application fields such as urethane foam such as synthetic wood for modeling, sealing agents, paints and adhesives.
The polyurethane resin molded product obtained from the active hydrogen component (A) for producing the polyurethane resin of the present invention is a composite with foam, sheet, film, coating film, resin molded product, fiber, metal, etc. used in the above-mentioned fields. Materials and the like. Of these, foams and resin molded products are preferred.

A specific example of the method for producing the polyurethane resin molded product of the present invention is as follows. First, a predetermined amount of active hydrogen component (A), if necessary, chain extender (D), urethanization catalyst (E), foam stabilizer (F), foaming agent (G), and additive (H) are mixed. Subsequently, this mixture (polyol premix) and the polyisocyanate component (B) are rapidly mixed using a polyurethane foaming machine or a stirrer. The obtained mixed liquid is poured into a mold (for example, 55 to 75 ° C.) and demolded after a predetermined time to obtain a polyurethane resin molded article.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. Parts indicate parts by weight.

The polyurethane resin raw materials in Examples and Comparative Examples are as follows.
(1) Crystalline cellulose (b-1): Cellulose powder having a degree of crystallinity of about 75%, an average fiber length of about 15 μm, and an average fiber diameter of about 0.1 μm [Seolas TG-F20 (plant-derived cellulose) manufactured by Asahi Kasei Chemicals)
(2) Cellulose powder (b ′): Cellulose powder having a crystallinity of about 55% and an average fiber length of about 20 μm [W300G manufactured by Nippon Paper Chemicals]
(3) Active hydrogen compound (a-1): PO adduct of glycerin having an average functional group number of 3.0, a number average molecular weight of 5000, and a hydroxyl value of 34.
(4) Active hydrogen compound (a-2): PO / EO adduct of glycerin having an average functional group number of 3.0, a number average molecular weight of 5000, and a hydroxyl value of 34.
(5) Chain extender: diethylene glycol (6) Urethane catalyst: 33 wt% dipropylene glycol solution of triethylenediamine [TEDA-L33 manufactured by Sankyo Airpro Co., Ltd.]
(7) Foam stabilizer: “B-8462” manufactured by Goldschmidt AG
(8) Polyisocyanate: MDI isocyanate prepolymer having an isocyanate group content of 17.1% by weight. [Sunform NC-703 manufactured by Sanyo Chemical Industries, Ltd.]

[Comparison of viscosity of cellulose-dispersed polyol with respect to cellulose concentration] Examples 1 to 4 and Comparative Examples 1 to 4
Table 1 shows the viscosities when added and dispersed at different concentrations of powdered cellulose and crystalline cellulose for each polyol. The viscosity was measured at 23 ° C. with a BL type viscometer.

Examples 5-8 and Comparative Examples 5-8
Using a high-speed stirrer, the polyol premix and weight part shown in Table 2 were mixed for 30 seconds and charged into a metal mold having a size of 300 mm × 300 mm × 10 mm whose temperature was adjusted to 70 ° C., 15 After curing for minutes, the mold was removed to obtain a polyurethane foam. The parts in Table 2 indicate parts by weight.
About the obtained polyurethane foam, the foam physical property was measured with the measuring method shown below. Table 3 shows the measurement results.

Foam physical property measuring method C hardness: The hardness after 5 minutes load was measured using an automatic hardness meter (PX-100 manufactured by Kobunshi Keiki Co., Ltd., weight 1 kg).
Elastic modulus: After slicing the created urethane foam into a sheet of 2mm thickness with a slicer (AN400D manufactured by FOTUNA, Germany), create a dumbbell-shaped test piece with a thickness of 2mm and a center width of 5mm with a No. 3 dumbbell. And an autograph (AGIS manufactured by Shimadzu Corporation, analysis software TRAPESIUM2, stretching speed 100 mm / min).
Density: A 2 cm × 2 cm square sheet was cut out from the 2 mm thick sheet from which the elastic modulus measurement sample was prepared, and an underwater substitution method was used.

As a result of comparison, the polyurethane foams of Examples 5 to 8 containing crystalline cellulose contained cellulose at a higher concentration than the powder cellulose-containing polyurethane foam of Comparative Example in which the polyol component had the same viscosity. (Example 7 and Comparative Example 6, Example 8 and Comparative Example 7) C hardness, strength at break, and elastic modulus were increased, and it was found that the resulting polyurethane resin had high strength.

   Urethane resin molded product containing crystalline cellulose of the present invention is generally used urethane resin, resin molded products such as shoe soles, watch bands, casters, belts, wire covering materials, seat cushions, soundproofing materials, It can be used in a wide range of applications such as filters, mattresses, sofas, heat insulating materials, synthetic wood for modeling, urethane foam such as abrasives, sealing agents, paints, and adhesives.

Claims (5)

Ri Na contain cellulose crystallinity of not less than 65% (b) and an active hydrogen compound comprising a polyoxyalkylene polyol (a), for the production polyurethane resin having a water content of 0.3 wt% or less Active hydrogen component (A). The active hydrogen component (A) according to claim 1, wherein the crystalline cellulose (b) is dispersed in the active hydrogen compound (a). The active hydrogen component (A) according to claim 1 or 2, wherein the average fiber length of the crystalline cellulose (b) is 5 to 1000 µm. A polyurethane resin (I) obtained by reacting the active hydrogen component (A) according to any one of claims 1 to 3 with a polyisocyanate component (C). A polyurethane resin molded article comprising the polyurethane resin (I) according to claim 4 .