JP4445424B2 - Molded body, molded body manufacturing method, adhesive, and wood board - Google Patents

Description

TECHNICAL FIELD The present invention relates to urethane resin recycling technology, and more specifically, a molded product produced using a urethane resin and a decomposed product obtained by chemically decomposing urethane resin, a method for producing the molded product, an adhesive, and this The present invention relates to a wood board manufactured using an adhesive.

  Examples of wastes containing urethane resin include refrigerators, building materials, and cushion materials. In recent years, the demand for this recycling has increased, and the reuse of these wastes has been studied in their respective fields. However, since urethane resin is a thermosetting resin having a three-dimensional network structure, it is difficult to recycle, and at present, disposal such as landfilling and incineration is performed.

As a method for recycling the urethane resin, a method is known in which a rigid urethane foam is pulverized to 1 mm or less, hot-press molded using a water-emulsified isocyanate and water as a binder, and recycled as a compression molded member (Patent Document 1). reference). However, this method has a drawback that the urethane resin is merely physically bonded to the binder resin, and the resulting molded article cannot have a very high strength.
JP 2000-313021 A

  The present invention has been made in view of the above problems, and in the production of a molded product obtained by hot-press molding a cured urethane pulverized product by adding a binder, it has higher strength than the conventional one. An object of the present invention is to provide a molded product having a simple method for recycling a urethane resin.

1st this invention, (1) Urethane resin, (2) Urethane decomposition thing obtained by making at least any one of a heat | fever or a decomposition agent act on 2nd urethane resin, and, (3) A molded product obtained by mixing and reacting with a compound having two or more epoxy groups .

The second aspect of the present invention is (1) a urethane resin, and (2) a urethane decomposition product obtained by chemically decomposing the second urethane resin by applying at least one of heat or a decomposition agent; (3) mixing a compound having two or more epoxy groups ;
It is a manufacturing method of the molded object which consists of the process of heat-pressing and molding this mixture.

  In the second aspect of the present invention, it is preferable that the hot press molding conditions are a temperature of 150 ° C. or higher and a pressure of 1 MPa or higher and a molding time of 3 minutes or longer.

According to a third aspect of the present invention, there is provided (1) a urethane resin, (2) a urethane decomposition product obtained by chemically decomposing the second urethane resin by applying at least one of heat or a decomposition agent; 3) An adhesive obtained by mixing a compound having two or more epoxy groups . This adhesive is suitable for use as a wood board adhesive.

  According to the present invention, by using a decomposition product obtained by chemically decomposing a urethane resin as an adhesive and hardening the cured urethane resin, it is possible to obtain a molded body having higher strength and better appearance than before.

As a result of studying a preferable resin in the production of a molded body or adhesive in which a cured urethane resin powder is bonded with a binder, the present inventors have studied (2) at least either a heat or a decomposition agent in the second urethane resin. By using either a urethane decomposition product obtained by chemically decomposing one of them and (3) a compound having two or more epoxy groups, it has been found that a molded body having higher strength than before can be obtained, The present invention has been completed. According to the present invention, used urethane resin can be reused as industrial materials such as refrigerators, building materials, cushion materials, etc., and it is very difficult to reduce waste and reduce environmental burden. Useful.

Hereinafter, embodiments of each component of the resin composition and the recycling method of the urethane resin according to the present invention will be described.
(1) Urethane resin The urethane resin used in this embodiment is a cured urethane resin, and is not particularly limited in its material, form, application, or the like. Specific examples include foamed rigid urethane (rigid foam), foamed semi-rigid urethane (semi-rigid foam), foamed flexible urethane (soft foam), urethane elastomer, RIM molded body, etc. , Structural materials, bedding, car seats, bumpers, etc. These urethane resins are pulverized in advance to 5 mm or less, preferably 1 mm or less. Moreover, it is preferable to remove in advance those containing freon.

(2) Urethane resin degradation product The urethane resin degradation product in the present embodiment is a product obtained by chemically decomposing a urethane resin, that is, reducing the molecular weight. The urethane resin, which is a substance to be decomposed, is a polymer having a urethane bond or a urea bond in its structure. For example, hard urethane, soft urethane, semi-rigid urethane, urethane elastomer and the like can be mentioned. Isocyanurate materials having a nurate bond are also included. As the urethane resin which is a raw material for producing this urethane resin decomposition product, it is preferable to use the same one as the urethane resin of (1). However, when a decomposition product obtained by decomposing a hard urethane resin, which is a urethane resin having a hydroxyl value of 250 mgKOH / g or more, is used because the number of functional groups contained in the decomposition product increases, molding is performed. It is preferable because the strength of the body is improved. The upper limit of the hydroxyl value of the urethane raw material polyol is 1024 mgKOH / g. In order to obtain higher strength, it is desirable to use a urethane raw material polyol of 350 mgKOH / g or more.

When the urethane resin is chemically decomposed, a compound having a hydroxyl group in the structure (polyols) and a compound having an amino group in the structure (amines), mainly derived from the raw material, are generated in the decomposition product. This amino group is obtained by replacing the NCO group of the urethane raw material isocyanate component with the NH ₂ group. In order to obtain a molded product with higher strength, it is preferable that the decomposition product is decomposed so that the amine value of the decomposition product is 50 mgKOH / g or more and 250 mgKOH / g or less. In addition, it is desirable that the decomposition product is decomposed so that the hydroxyl value of the decomposition product is 300 mgKOH / g or more and 750 mgKOH / g or less, more preferably 400 mgKOH / g or more and 750 mgKOH / g or less.

  The method for chemically decomposing the urethane resin is not particularly limited as long as it generates a hydroxyl group and an amino group in the decomposition product. Specifically, a method in which at least one of heat and a decomposing agent is allowed to act to chemically decompose is mentioned.

  When carrying out decomposition by heat, it can be carried out, for example, at a temperature of 300 ° C. to 500 ° C. under normal pressure or under pressure. At this time, it is desirable to perform nitrogen substitution or an oxygen-free atmosphere. Moreover, it can carry out with screw feeders and furnaces, such as an extruder.

In addition, a method for decomposing using a decomposing agent will be described below.
Examples of the decomposing agent include amine decomposing agents, polyol decomposing agents, and hydrolysis catalysts. Among them, since the amine decomposing agent contains many amino groups in the decomposition product, the reaction with the epoxy group, isocyanate group, carboxy group and its anhydride is improved, and high strength is obtained. Particularly preferred.

  Examples of the amine decomposing agent include monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, propanediamine, 2-ethylhexylamine, isopropanolamine, 2- (2-aminoethylamino) ethanol, 2-amino-2-hydroxymethyl-1,3-propanediol, ethylaminoethanol, aminobutanol, n-propylamine, di-n-propylamine, n-amylamine, isobutylamine, methyldiethylamine, cyclohexylamine, piperazine, Piperidine, aniline, toluidine, benzylamine, phenylenediamine, xylylenediamine, chloroaniline, pyridine, picoline, N-methylmorpholine, ethylmol Orin, pyrazole, and the like. There is no problem even if a mixture of two or more of these compounds is used.

  Moreover, you may add an additive to amine decomposition agents as needed. Examples of additives that do not extremely inhibit the reaction of amine decomposing agents such as diluents such as water and alcohol polyols, reaction aids such as alkali metals and metal complexes, and fillers such as inorganic particles and organic particles Can be added.

  It is desirable to use 5 parts by weight or more, more preferably 10 parts by weight or more with respect to 100 parts by weight of the urethane resin as a decomposition target, for the amine decomposition agent. The upper limit is preferably 100 parts by weight or less, more preferably 40 parts by weight or less with respect to 100 parts by weight of the urethane resin.

  These amine decomposition agents and urethane resin are put into a decomposition apparatus to obtain a urethane decomposition product. Any known cracking device can be used as the cracking device, but it is particularly desirable to use an extruder capable of simultaneously heating, mixing and compressing because urethane can be continuously cracked. If the decomposition is carried out in a batch manner like a kettle, the thermal conductivity of urethane is poor, so there is a large difference in the start time of urethane decomposition. For this reason, since the part decomposed | disassembled earlier has a low molecular weight, and the thing decomposed | disassembled later becomes high molecular weight, it will become a decomposition product with a wide molecular weight. When decomposing, it is desirable that the temperature is 150 ° C. to 300 ° C., the decomposition time is several tens of minutes to several hours in a batch system, and about 1 to 10 minutes in a continuous system.

The urethane resin decomposition product contains the following components.
First, as amines contained in the urethane resin decomposition product, raw material 4-4 ′ diphenylmethane diisocyanate and its polymer-derived diaminodiphenylmethane (MDA) and its polymer, toluylenediamine (TDI) -derived toluylenediamine (TDI) ( TDA) and the like are listed as main amines. In addition, NDI (1,5-naphthalene diisocyanate), TODI (tolidine diisocyanate), HDI (hexamethylene diisocyanate), IPDI (isophorone diisocyanate), XDI (xylylene diisocyanate), H6XDA (hydrogenated MDI), LDI ( Lysine diisocyanate), triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, TMXDI (tetramethylxylene diisocyanate), lysine ester triisocyanate, etc. The thing which the terminal of the prepolymer converted into the amino group is also mentioned.

  Examples of the polyols in the decomposed urethane resin include polyols generally used as a urethane resin raw material, and are roughly classified into polyether polyols, polyester polyols, and polyether ester polyols. Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, pentaerythritol ethylenediamine, tolylenediamine, diphenylmethanediamine, tetramethylolcyclohexane, methylglucoside, sorbitol, mannitol, dulcitol, sucrose Specific examples include those obtained by addition reaction of propylene oxide, ethylene oxide or the like with saccharides.

  The above compounds include those in a liquid state at room temperature and those in a solid state at room temperature, either of which can be used. When using a solid compound at room temperature, it is pulverized to an appropriate size in advance. The pulverized diameter is not particularly limited, but it is preferable to use a pulverized diameter of 200 μm or less.

In the compounds present embodiment having (3) an epoxy group of two or more, and the compound of chromatic two or more epoxy groups, a compound that chromatic two or more epoxy groups in one compound. This compound may further contain other functional groups.
Hereinafter, this compound will be described.

(Compound containing two or more epoxy groups)
The epoxy resin used in the present embodiment is not particularly limited as long as it has two or more epoxy groups in one molecule. Specific examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, tris-hydroxyphenylmethane. Type epoxy resins, other polyfunctional epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins such as triglycidyl isocyanate and hydantoin epoxy, hydrogenated bisphenol A type epoxy resins, propylene glycol diglycidyl ether and penta Aliphatic epoxy resins such as erythritol-poly-glycidyl ether, epoxy resins obtained by reaction of aliphatic or aromatic carboxylic acids with epichlorohydrin, spiro -Containing epoxy resin, reaction product of ortho-allyl-phenol novolak compound and epichlorohydrin, glycidyl ether type epoxy resin, reaction product of diallyl bisphenol compound having an allyl group at each hydroxyl position of bisphenol A and epichlorohydrin And glycidyl ether type epoxy resin. In addition, for the purpose of imparting flexibility, there are oligomer-type modified bisphenol A type epoxy resins into which a low-polarity linking group is introduced, and it can also be used as a brominated epoxy resin for the purpose of imparting flame retardancy. . Among them, it is preferable to use an epoxy resin that is liquid at room temperature with a viscosity at room temperature of 500 poise or less, and further 300 poise or less, because it is easy to handle. Specific examples of the liquid epoxy resin include, for example, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 828EL, Epicoat 828XA, Epicoat 834, Epitoe 801, Epicoat 801P, Epicoat 802, Epicoat 802XA, Epicoat 815, Epicoat 815XA, Epicoat 816A, Epicoat 819, Epicoat 806, Epicoat 806L, Epicoat 807 (above Japan Epoxy Resin Co., Ltd.), EP-4100, EP-4100G, EP-4100E, EP-4100W, EP-4100TX, EP-4300E, EP-4340, EP- 4200, EP-4400, EP-4500A, EP-4510, EP-4520, EP-4520S, EP-4520TX, EP-4530 EP-4901, EP-4901E, EP-4950, EP-4000, EP-4005, EP-1307, EP-4004, Ep-4080E, EP-4012M, EP-4000S, EP-4000SS, EP-4003S, EP- 4010S, EP-4088S, EP-4085S (Asahi Denka Kogyo), EXA-4850-150, EXA-4850-1000, (Dainippon Ink and Chemicals, CEL-2021P (3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate, epoxy equivalent 128-140, viscosity 200-350 cP / 25 ° C., CEL-2021A (3,4-epoxycyclohexylmethyl 3′4′-epoxycyclohexanecarboxylate, epoxy equivalent 130-145, Viscosity 2 0-450 cP / 25 ° C.), CEL-2000 (1-vinyl-3,4-epoxycyclohexane, 1.5 cP / 25 ° C.), CEL-3000 (1,2,8,9-diepoxy limonene, epoxy equivalent 93) .5 or less, viscosity 5 to 20 cP / 25 ° C. (made by Daicel Chemical Industries), Denacol EX-421, 201 (resorcin diglycidyl ether), 211 (neopentyl glycol diglycidyl ether), 911 (propylene glycol diglycidyl) Ether), 701 (diglycidyl adipic acid ester) (manufactured by Nagase Kasei Kogyo Co., Ltd.), etc. These epoxy resins should be mixed and used from the viewpoint of viscosity, heat resistance, adhesiveness, and surface hardness. Can do.

(Other additives)
Various additives can be added to the resin composition for producing the molded article of the present embodiment. Examples of such additives include inorganic fillers, organic fillers, adhesion-imparting agents, water repellents, oil repellents, insect repellents, ultraviolet absorbers, antibacterial agents, antistatic agents, paint fixing agents, anti-wrinkle agents, Examples thereof include an antioxidant, a surfactant, a coupling agent, and a colorant. Among these, the inorganic filler is added for the purpose of reducing the thermal expansion coefficient of the molded body and improving the elastic modulus of the molded body. Specific examples thereof include fused silica, crystalline silica, glass, talc, alumina, Calcium silicate, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, aluminum nitride, magnesium oxide, beryllium oxide, mica and the like can be used, and among these, fused silica and crystalline silica are particularly preferable. In addition, the shape of the inorganic filler can be crushed, spherical, subspherical, fibrous, or phosphorus pen-shaped, and is particularly spherical or subspherical with an average particle size of 10 μm or less in consideration of surface smoothness. The filler is particularly preferred. Moreover, a fibrous thing can also be used aiming at the crack-proof reinforcement effect. Fibrous fillers include titania, aluminum borate, silicon carbide, silicon nitride, potassium titanate, basic magnesium, zinc oxide, graphite, magnesia, calcium sulfate, magnesium borate, titanium diboride, α-alumina , Whiskers such as chrysotile and wollastonite, and E-glass fiber, silica-alumina fiber, silica glass fiber and other amorphous fibers, as well as Tyranno fiber, silicon carbide fiber, zirconia fiber, γ-alumina fiber, α-alumina fiber And crystalline fibers such as PAN-based carbon fibers and pitch-based carbon fibers. As the above fibrous filler, those having an average fiber diameter of 5 μm or less and a maximum fiber length of 10 μm or less are preferable in terms of uniformity of the coating film surface. The inorganic filler used in the present embodiment can be used in the range of 0.1% by weight to 50% by weight with respect to the total amount of the resin composition. When there are few inorganic fillers, the thermal expansion coefficient of hardened | cured material becomes large and thermal shock resistance becomes insufficient. On the other hand, if it exceeds 50% by weight, the fluidity of the resin composition becomes insufficient, the workability is lowered, and voids are generated, making it difficult to form a uniform molded product.

  To the resin composition of the present embodiment, an organic filler such as a thermoplastic resin, a rubber component, and various oligomers is added for the purpose of improving crack resistance or lowering the elastic modulus of the molded body. Also good. Specific examples of the thermoplastic resin can be modified with butyral resin, polyamide resin, aromatic polyester resin, phenoxy resin, MBS resin, ABS resin, silicone oil, silicone resin, silicone rubber, fluororubber, or the like. Various plastic powders, various engineering plastic powders, and the like can be added.

  In addition to these, waste materials such as large sawdust, waste paper, resin waste, shells, sand, and building concrete can be mixed to obtain a molded body. By combining these waste materials, the amount of waste in the whole society can be reduced, and it can be effectively reused as a filler for molded products. Among these, it is better to use a material containing a large amount of lignin or hemicellulose in the raw material, such as a woody material. Lignin and hemicellulose can react appropriately with the amine in the decomposition product to obtain a stronger molded body. Examples of the woody material include plant-derived fibers such as sawdust, rice husk, straw, waste paper, and kenaf. These wood materials are generally used that have been pulverized to about 1 mm to 50 mm. In order to provide the orientation, it may be elongated and pulverized.

(Molded body manufacturing method)
Hereinafter, an embodiment of a method for producing a resin composition will be described.
In the molded body of the present embodiment, (1) urethane resin is pulverized to an appropriate size in advance, (2) urethane decomposition product and (3) compound having two or more epoxy groups are dispersed, It can be obtained by pressure heating molding. The size of the granular material obtained by pulverizing the urethane resin is 5 mm or less, preferably 1 mm or less. When the size of the granular material exceeds this range, the appearance of the resulting molded product is inferior. When using urethane foam, it is preferable to remove the foaming agent (for example, chlorofluorocarbon) by a method such as pulverization or preheating.

Hereinafter, the method for producing the molded body of the present embodiment will be described in more detail.
First, the above components are mixed. At this time, the mixing ratio of (1) urethane resin, (2) urethane decomposition product, and (3) compound having two or more epoxy groups is not particularly limited, but the compound (1) When the total of the compound (2) and the compound (3) is 100 parts by weight, the total of the compound (2) and the compound (3) is 5 parts by weight or more and 70 parts by weight or less, and the compound (1) is 30 parts by weight or more. It is desirable to be in the range of 95 parts by weight or less.

  More preferably, the total of the compound (2) and the compound (3) is 20 to 50 parts by weight, and more preferably 30 to 50 parts by weight. If the amount of the compound (2) and the compound (3) is too small, the urethane resin as the compound (1) will not be sufficiently bonded, so that the physical properties are deteriorated. On the other hand, the amount of the compound (2) and the compound (3) When there is much, the quantity of urethane powder will decrease too much and there will be no economical advantage.

The mixing method is not particularly limited, and examples thereof include a mixer, an extruder, a Henschel mixer, a concrete mixer, a roll, and a mill. The method and order of adding the resin are not particularly limited, but it is preferable to add the resin so that the dispersion state is improved by spraying or dropping the resin. Moreover, it is preferable to melt-knead with a roll, an extruder, etc. after adding in this way.
The mixture thus obtained is prepared into a predetermined shape including a board and press-molded. The molding method is not particularly limited, and examples thereof include a single stage press, a multistage press, and a continuous press. Molding conditions are not particularly limited, but molding with good appearance can be performed at a temperature of 150 ° C. to 230 ° C., a molding pressure of 10 kg / cm ^{2 to} 300 kg / cm ² and a molding time of 5 minutes to 25 minutes. You can get a body.

(How to use as an adhesive)
It can also be used as an adhesive by mixing (1) urethane resin, (2) decomposed urethane resin, and (3) a compound having an epoxy group, an isocyanate group, a carboxy group or an anhydrous carboxy group, followed by heat curing. As its use, it can be used as long as a general adhesive can be used. In particular, it is preferable to use it for materials containing cellulose, lignocellulose, lignin and the like, since the adhesive strength is increased. It can also be used as an adhesive when manufacturing chips by accumulating wood chips and the like.

  As a specific method of using the adhesive, the compound (1), the compound (2) and the compound (3) are separately applied to the surface of the adherend, or the compound (1), the compound (2), and The compound (3) is mixed and applied to the surface of the adherend and cured by heating. It is preferable to use the mixture in advance, and it is more preferable to knead with a roll or an extruder at this time. The temperature at the time of kneading may be room temperature, but it is preferable to apply a temperature of about 50 to 150 [deg.] C. because the mixture is uniformly mixed.

Hereinafter, it demonstrates in detail based on an Example.
<Creation of urethane resin decomposition product A>
Polyurethane resin A was synthesized by reacting polyol (manufactured by Mitsui Takeda Chemical Co., Ltd., ND450, hydroxy acid price 450 mgKOH / g) and isocyanate (Mitsui Takeda Chemical Co., Ltd., Cosmonate TP) in an equal ratio. The synthesized urethane resin A: diethanolamine = 15: 1 was introduced into a single screw extruder at 250 ° C. to obtain a urethane resin decomposition product A. When the hydroxyl value was measured based on JIS K 1557, it was about 350 mgKOH / g, and when the amine value was measured based on JIS K 7237, it was about 150 mgKOH / g. The softening point was 70 ° C., and it was a complete solid at room temperature.

<Creation of urethane resin decomposition product B>
Polyurethane (Mitsui Takeda Chemical Co., POP-34 / 45, Hydroxic Acid Price 42.5 mg KOH / g) and Isocyanate (Mitsui Takeda Chemical Co., Ltd. Cosmonate T-80) are reacted in an equal ratio to obtain a urethane resin. B was synthesized. Synthesized urethane resin B: diethanolamine = 10: 1 was mixed into a single screw extruder at 250 ° C. and decomposed to separate into a liquid upper layer and a solid lower layer. This was filtered to obtain a liquid urethane resin decomposition product B. When the hydroxyl value was measured based on JIS K 1557, it was about 200 mgKOH / g, and when the amine value was measured based on JIS K 7237, it was about 80 mgKOH / g.

<Creation of urethane resin decomposition product C>
Isocyanurate material (urethane resin C), which is a waste material of building materials, was put into a single screw extruder at 250 ° C. with a mixing ratio of diethanolamine = 7: 1 and decomposed to obtain a urethane resin decomposition product C. When the hydroxyl value was measured based on JIS K 1557, it was about 450 mgKOH / g, and when the amine value was measured based on JIS K 7237, it was about 130 mgKOH / g.

<Creation of urethane resin decomposition product D>
Urethane resin A: monoethanolamine = 4: 1 was introduced into a single screw extruder at 250 ° C. and decomposed to obtain a urethane resin decomposition product D. When the hydroxyl value was measured based on JIS K 1557, it was about 600 mgKOH / g, and when the amine value was measured based on JIS K 7237, it was about 190 mgKOH / g.

<Creation of urethane resin decomposition product E>
Urethane resin obtained as a waste material of the refrigerator: monoethanolamine = 4: 1 was introduced into a single screw extruder at 250 ° C. and decomposed to obtain a urethane resin decomposition product E. When the hydroxyl value was measured based on JIS K 1557, it was about 630 mg KOH / g, and when the amine value was measured based on JIS K 7237, it was about 220 mg KOH / g.

Example 1
15 parts by weight of urethane resin decomposition product A (pulverized to 180 μm or less), 15 parts by weight of epoxy resin EP4100E (manufactured by Japan Epoxy Resin Co., Ltd.), crushed cured urethane resin A (CFC recovered, 1 mm mesh) 70 parts by weight and 0.2 parts by weight of zinc stearate were previously mixed with a Henschel mixer and then melt-kneaded with two rolls. The melt-kneading temperature was 80 to 90 ° C. Thereafter, it was put into a mold and pressed at a molding temperature of 180 ° C. and a molding pressure of 20 kg / cm ² for 10 minutes to prepare a molded body. A brown transparent molded body was obtained, and the cured urethane resin was almost invisible. When the bending strength was measured based on JIS K 6911, it was 30.0 MPa.

(Examples 2 to 7)
In the same manner as in Example 1, a urethane resin decomposition product A, an epoxy resin EP4100E, and a pulverized cured urethane resin A with different mixing ratios were prepared.

(Comparative Example 1)
A molded body was prepared in the same manner as in Example 1 except that phenol (PR-217, manufactured by Sumitomo Bakelite Co., Ltd.) was used instead of the urethane resin decomposed product A and the epoxy resin EP4100E. However, since the melting point of PR-217 is high, the temperature of the roll was set to 95 to 100 ° C.

(Comparative Example 2)
A molded body was prepared in the same manner as in Example 1 except that isocyanate (M-200, manufactured by Mitsui Takeda Chemical Co., Ltd.) was used instead of the urethane resin decomposition product A and the epoxy resin EP4100E.

  Table 1 summarizes the results of Examples 1 to 7 and Comparative Examples 1 and 2. The bending strength was evaluated as ◎ for 50 MPa or more, ◯ for 30 MPa or more, Δ for 10 MPa or more, and x for less than 10 MPa. In addition, as for the appearance, a molded product with high transparency was marked with ◎, a slightly molded and uniform molded product with ◯, a slightly less transparent product with △, and a non-transparent or non-uniform product with ×. Looking at this result, when the urethane resin decomposition product was used, a part or all of the urethane resin was taken into the resin, and a highly transparent molded product could be obtained. However, when other adhesives were used, the urethane resin appeared on the surface and the appearance was poor. Moreover, it was confirmed that the strength of the molded body shows a large value when a urethane decomposition product is used. Adhesives other than the urethane resin decomposition products gave bad results.

(Examples 8 to 11)
A molded body was produced in the same manner as in Example 1 except that the type of urethane decomposition product was changed. The results of Examples 1 and 8-10 are summarized in Table 2. Looking at this result, the appearance improved with the decomposed product obtained by decomposing the urethane resin A (Examples 1 and 10), but the appearance deteriorated slightly when the urethane decomposed product obtained by decomposing a different urethane was used. It was. Moreover, when the thing (Examples 10 and 11) with a high hydroxyl value and amine value of the urethane decomposition product is used, the strength becomes high when a molded body is prepared under the same conditions, and when a low thing is used (Example) In 8), the strength decreased.

(Examples 12 to 15)
A molded body was produced under the same conditions as in Example 1 except that the molding temperature was changed. However, since the gel time of the resin becomes longer when the molding temperature is lowered, the molding time is 30 minutes at 120 ° C. and 20 minutes at 150 ° C. Examples 1 and 12-15 are summarized in Table 3. By changing the molding temperature, at 150 ° C. or higher, the molded body is transparent and the appearance is improved. However, it was found that when the temperature was raised to 240 ° C., the color was black but the appearance was deteriorated although there was transparency.

(Examples 16 to 21)
A molded body was produced under the same conditions as in Example 1 except that the molding pressure was changed. Examples 1 and 16-21 are summarized in Table 4. By changing the molding pressure, the strength increased at 10 kg / cm ² or more, and the strength and appearance tended to improve as the pressure increased. However, when the molding pressure was increased to 350 kg / cm ^2, white streaks that appeared to be deformed appeared inside the resin, and the appearance deteriorated.

(Examples 22 to 26)
A molded body was produced under the same conditions as in Example 1 except that the molding time was changed. Examples 1 and 22-26 are summarized in Table 5. When the molding time was short, the curing time of the resin was short and a molded body could not be obtained, but a molded body with a good appearance could be obtained after 5 minutes or more. Moreover, about what was shape | molded for 30 minutes, the molded object became a little blackish.

(Examples 27 to 32)
A molded body was produced under the same conditions except that Example 1 and the mixing method were changed. Examples 1 and 27-32 are summarized in Table 6. As a mixing method, it has been found that kneading with a device such as a roll or an extruder, which has high temperature, is preferable because the appearance is improved.

(Example 33)
15 parts by weight of urethane resin decomposition product A (pulverized to 180 μm or less), 15 parts by weight of epoxy resin EP4100E (manufactured by Japan Epoxy Resin Co., Ltd.), crushed cured urethane resin A (CFC recovered, 1 mm mesh) 70 parts by weight and 0.2 parts by weight of zinc stearate were previously mixed with a Henschel mixer and then melt-kneaded with two rolls. The melt-kneading temperature was 80 to 90 ° C. When cooled to room temperature, it was a solid. The solid was finely pulverized and then applied to the surface of wood (Akamatsu), pasted with other pieces of wood, and heated at 150 ° C. for 10 minutes. After cooling to room temperature, it was confirmed that the woods were well bonded.

(Example 34)
15 parts by weight of urethane resin decomposition product A (pulverized to 180 μm or less), 15 parts by weight of epoxy resin EP4100E (manufactured by Japan Epoxy Resin Co., Ltd.), crushed cured urethane resin A (CFC recovered, 1 mm mesh) 70 parts by weight and 0.2 parts by weight of zinc stearate were previously mixed with a Henschel mixer and then melt-kneaded with two rolls. The melt-kneading temperature was 80 to 90 ° C. When cooled to room temperature, it was a solid. This solid material is finely pulverized, then mixed with large sawdust (Akamatsu) pulverized to a maximum diameter of 5 mm and solid / large sawdust = 20/80, put into a mold, pressed at 180 ° C., 10 minutes, 20 kg / cm ^2. As a result, a particle board with a good appearance was obtained.

(Example 35)
Urethane resin decomposition product A is 7.5 parts by weight (one pulverized to 180 μm or less), 7.5 parts by weight of epoxy resin EP4100E (manufactured by Japan Epoxy Resin Co., Ltd.), and pulverized cured urethane resin A (CFC recovered) 17 parts by weight passed through a 1 mm mesh), 0.2 parts by weight of zinc stearate, and 68 parts by weight of large sawdust (Akamatsu) ground to a maximum diameter of 5 mm were mixed with a Henschel mixer, then placed in a mold, 180 ° C., When press molding was performed at 20 kg / cm ² for 10 minutes, a particle board was obtained. The strength of this board was measured based on JIS K 6911 and found to be 33.5 MPa.

(Comparative Example 3)
A particle board was prepared in the same manner as in Example 35 except that large sawdust (Akamatsu) ground to a maximum diameter of 5 mm was used instead of the cured urethane resin A. The strength of the obtained board was 26.2 MPa, which was lower than that of Example 35.

(Example 36)
Urethane resin decomposition product A is 7.5 parts by weight (pulverized to 180 μm or less), 7.5 parts by weight of isocyanate M-200 (manufactured by Mitsui Takeda Chemical Co., Ltd.), and pulverized cured urethane resin A (recovered by CFC) 17 parts by weight passed through a 1 mm mesh), 0.2 parts by weight of zinc stearate, and 68 parts by weight of large sawdust (Akamatsu) ground to a maximum diameter of 5 mm were mixed with a Henschel mixer, and then placed in a mold at 180 ° C. When press molding was performed at 20 kg / cm ² for 10 minutes, a particle board was obtained.

(Example 37)
7.5 parts by weight of urethane resin decomposed product A (pulverized to 180 μm or less), 7.5 parts by weight of maleic anhydride, and pulverized cured urethane resin A (recovered by chlorofluorocarbon, passed through 1 mm mesh) 17 Part by weight, 0.2 parts by weight of zinc stearate and 68 parts by weight of large sawdust (Akamatsu) ground to a maximum diameter of 5 mm were mixed with a Henschel mixer, then placed in a mold and pressed at 180 ° C. for 10 minutes at 20 kg / cm ² When molded, a particle board was obtained.

Claims (6)

(1) a first urethane resin;
(2) a urethane decomposition product obtained by chemically decomposing by causing at least one of heat or a decomposition agent to act on the second urethane resin;
(3) A molded product obtained by mixing and reacting with a compound having two or more epoxy groups .   2. The molded product according to claim 1, wherein the urethane decomposed product has a hydroxyl value in the range of 300 to 750 mgKOH / g and an amine value of 50 to 250 mgKOH. (1) a first urethane resin;
(2) a urethane decomposition product obtained by chemically decomposing by causing at least one of heat or a decomposition agent to act on the second urethane resin;
(3) mixing a compound having two or more epoxy groups ;
The manufacturing method of the molded object which consists of the process of heat-pressing and forming this mixture.   The method for producing a molded body according to claim 3, wherein molding conditions in the step of molding by heating and pressing are a temperature of 150 ° C or higher and a pressure of 1MPa or higher. (1) a first urethane resin;
(2) a urethane decomposition product obtained by chemically decomposing by causing at least one of heat or a decomposition agent to act on the second urethane resin;
(3) An adhesive obtained by mixing a compound having two or more epoxy groups and heating and curing. (1) a first urethane resin;
(2) a urethane decomposition product obtained by chemically decomposing by causing at least one of heat or a decomposition agent to act on the second urethane resin;
(3) A wood board formed by accumulating and molding wood materials using an adhesive obtained by mixing a compound having two or more epoxy groups and heat-curing.