JP2003277615A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition containing a lignin-based material which is a nonfossil resource as a main component, so as to be excellent in mechanical strengths and water resistance and environmental-friendly. <P>SOLUTION: This resin composition contains (A) the lignin-based material, (B) a waterproofing component, and (C) a crosslinking component as essential ingredients, wherein the waterproofing component (B) comprises at least one kind of a rosin derivative and a terpene phenol resin, and the crosslinking component (C) comprises a compound having a functional group crosslinkable with the waterproofing component (B). The resin composition is crosslinked by using a crosslinking catalyst to easily give the resin having the required characteristics. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing a lignin-based material obtained from wood as a main component, and particularly to a lignin-based resin composition excellent in mechanical strength and water resistance.

[0002]

2. Description of the Related Art In the twentieth century, petroleum resources have been mined and used as raw materials and energy for plastics. However, in recent years, serious environmental problems such as depletion of fossil resources such as petroleum, air pollution accompanying plastic combustion and global warming due to generation of large amount of carbon dioxide, environmental pollution due to industrial waste, etc. Has become.

Therefore, development of a plastic material using natural resources (so-called non-fossil resources) rather than fossil resources derived from petroleum or coal and less likely to cause environmental damage has been actively pursued. For example, plastics made from lignin, which is a main constituent of wood materials such as wood, have been studied (Japanese Patent Laid-Open No. 9-278904).
No. 11-29647).

[0004]

However, since the lignin-based plastics proposed in these are generally inferior in mechanical strength and water resistance, they have the drawback that they can be used only in a limited number of applications, which poses a practical problem. There were many.

The present invention has been made in view of the above-mentioned problems of plastics for molding materials, and without using fossil resources such as petroleum and coal, which have a risk of depletion and have a large environmental load, An object of the present invention is to provide a resin composition that is versatile and has excellent mechanical strength and water resistance, using a lignin-based material that is a non-fossil resource that is less likely to cause environmental problems.

[0006]

The resin composition of the present invention comprises:
A lignin-based material (A), at least one water-resistant component (B) selected from the group consisting of a rosin derivative and a terpene phenol resin, and a crosslink having a functional group capable of performing a crosslinking reaction with the water-resistant component (B). The gist is that the component (C) is an essential component.

The resin composition of the present invention is a crosslinked product containing a lignin-based material (A) and at least one water-resistant component (B) selected from the group consisting of rosin derivatives and terpene phenol resins. The summary is to contain.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention comprises a lignin-based material (A), a water-proofing component (B), and a crosslinkable cross-linking component (C) as essential components. ) Is at least one cross-linking crosslinking component (C) selected from the group consisting of rosin derivatives and terpene phenolic resins.
Is a compound having a functional group capable of undergoing a crosslinking reaction with the water-resistant component (B). Each constituent will be described in detail below.

[Lignin-based material (A)] Lignin is one of the three components (lignin, cellulose and hemicellulose, which are collectively referred to as lignocellulose) constituting the woody matter of plants and wood and has the following chemical formula ( 1),
It is a polymer compound obtained by condensing structural units having a basic skeleton of hydroxyphenylpropane containing a methoxy group as shown in (2).

[0010]

[Chemical 1] (Note that the elements that bond to hydrogen and carbon chains are -OH, -S.
It may be a substituent or element such as O ₃ H or ═O) The lignin-based material used in the present invention is a material obtained from a lignocellulosic material as a raw material and in the form of a residue after removing cellulose from the material. Indicates. In such a lignin-based material, the form of lignin changes depending on the method of removing cellulose, the method of recovering the residue, etc., so the components derived from lignin contained in the lignin-based material differ, but the lignin basic skeleton described above is present. is doing. Therefore, the lignin-based material is a material containing woody lignin or a component derived from lignin.

Examples of the (A) lignin-based material used in the present invention include lignin-based materials such as lignin derivatives, lignophenol derivatives, and lignocellulose decomposition products, but are not particularly limited thereto. .

Examples of the lignin derivative include "kraft lignin" and "lignin sulfonic acid" which are by-products of ordinary pulp production, as well as "acetic acid digested lignin", "boiled explosive lignin" and "organosolv lignin". To be

"Craft lignin" is obtained by cooking wood chips at a high temperature using a mixed aqueous solution of sodium hydroxide and sodium sulfate as a cooking liquor. "Lignin sulfonic acid" is obtained by digesting wood flour with a neutral or weakly alkaline sulfite solution at high temperature. "Acetic acid cooking lignin" is
It is obtained by high-temperature steaming wood chips with acetic acid and hydrochloric acid. "Steam-blasted lignin" is obtained by treating with high-pressure saturated steam and instantaneously releasing the pressure. In addition, "organosolv lignin" is obtained by digestion with an organic solvent such as alcohols, ethyl acetate, low molecular weight organic acid mainly containing acetic acid, phenols, ethanolamine and the like.

The lignophenol derivative is a phase composed of a phenol derivative phase (organic phase) and a concentrated acid phase (aqueous phase) obtained by adding a phenol derivative to a lignocellulosic material containing lignin and then adding concentrated acid. It is obtained from the phenol derivative phase of the separation system. By treating the lignocellulosic material with the phenol derivative, the lignin in the lignocellulosic material is extracted as the lignophenol derivative. A method for producing such a lignophenol derivative is described in JP-A-9-27.
It is disclosed in Japanese Patent No. 8904, Japanese Patent Laid-Open No. 2001-131201, and the like.

Examples of the lignocellulosic material containing lignin include wood powder, wood chips, sawdust, wood materials such as waste wood, mill ends, bark, and various plant materials such as straw, pagas, chaff, beet pulp and the like. Further, paper such as waste paper, pulp and the like can also be used. Further, as a phenol derivative which is a raw material for producing a lignophenol derivative, monovalent phenols such as phenol, cresol, alkylphenol, methoxyphenol and naphthol; divalent phenols such as catechol, resorcinol and hydroquinone; pyrogallol And trivalent phenols. As the concentrated acid used for extracting the water-soluble substance, for example, sulfuric acid having a concentration of 65% by weight or more, phosphoric acid of 85% by weight or more, hydrochloric acid of 38% by weight or more,
Examples thereof include p-toluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid, formic acid and the like.

The lignocellulosic decomposition product means a lignocellulosic material containing lignin in the presence of an acid catalyst or an alkali catalyst, a phenol compound, a polyhydric alcohol,
It is obtained by decomposing using a cyclic ester or the like. Alternatively, it is obtained by decomposing a lignocellulosic material with a compound such as hydroxycarboxylic acid, dicarboxylic acid or amino alcohol. Regarding the method for producing such a lignocellulose decomposition product, JP-A-4-106128 and JP-A-2000-325921 are mentioned.
And Japanese Patent Laid-Open No. 2001-354774.

The acid catalyst used in the decomposition treatment is sulfuric acid,
Examples thereof include hydrochloric acid, toluenesulfonic acid, phenolsulfonic acid, aluminum chloride, zinc chloride, boron trifluoride and the like. Examples of the alkali catalyst include metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide; metal carbonates such as calcium carbonate; amines such as ammonia and monoethanolamine. Further, various decomposition reagents include phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol and bisphenol A; ethylene glycol, propylene glycol, trimethylene glycol, polyethylene glycol, glycerin, 1,4-butanediol, 1, Polyhydric alcohols such as 6-hexanediol;
Cyclic esters such as propiolactone, β-butyrolactone, δ-valerolactone, ε-caprolactone, trimethyl carbonate; glycolic acid, lactic acid, 2-hydroxybutyric acid, 2-hydroxy-2-methylpropanoic acid, 3
-Hydroxycarboxylic acids such as hydroxypropionic acid, 10-hydroxystearic acid, hydroxybenzoic acid and salicylic acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid and fumaric acid; 2-
Aminoethanol, 2-amino-1-butanol, 2-
Examples thereof include amino alcohols such as amino-2-methyl-1-propanol, diethanolamine, and triethanolamine.

The lignin-based material as described above is a polymer compound having a functional group such as a phenolic and alcoholic OH group in the molecule and can be used as an adhesive between objects, so that it is used as a binder in a molding material. It can be used for the production of system molded bodies and the like. Further, since the OH group contained in the lignin-based material has reactivity with the epoxy compound or the isocyanate compound, it can be used as a raw material for an epoxy resin or urethane resin-based molded body.

[Water-Resistant Component (B)] The above-mentioned lignin-based material (A) has viscosity, but has no water resistance and strength. In the present invention, a rosin derivative and a terpene phenol resin, which are plant-based materials, are used as natural materials for supplementing water resistance.

[Rosin Derivative] The rosin derivative used in the present invention is not particularly limited as long as it is a rosin derivative having a reactive functional group. Examples thereof include carboxyl group-containing rosin, maleated rosin, epoxidized rosin, rosin amine, rosin amide, rosin skeleton-containing diol compound, and rosin-modified phenol resin.

Examples of carboxyl group-containing rosins include gum rosins, wood rosins, tall oil rosins and other natural rosins, disproportionated rosins, hydrogenated rosins, polymerized rosins, glycolic acid-modified rosins, and highly purified rosins. Commercial products of such rosin derivatives include products manufactured by Arakawa Chemical Co., Ltd. (No .: KR-85, KR-604,
KR-610, KR-612, AG-100) and the like.

Maleated rosin is a rosin-maleic anhydride adduct obtained by reacting rosin with maleic anhydride.

Epoxidized rosin is a rosing lysidyl ester obtained by reacting rosin with epichlorohydrin.

Rosin amine and rosin amide are, respectively,
It is a product obtained by modifying the carboxyl group of rosin to give an amino group or an amide group.

The rosin skeleton-containing diol compound is obtained by reacting one molecule of the diepoxy compound and two molecules of the rosin in the presence of a catalyst.
It is obtained by a ring-opening addition reaction at 0 to 200 ° C. until the acid value becomes 5 or less. Such diepoxy compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether. ether,
1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F
Examples thereof include diglycidyl ether. Such catalysts include trimethylamine, triethylamine, tributylamine, benzyldimethylamine, pyridine, amine catalysts such as 2-methylimidazole, quaternary ammonium salts such as benzyltrimethylammonium chloride, Lewis acids, borate esters, organometallic compounds, Organic metal salts and the like can be used. Commercially available products of the rosin skeleton-containing diol compound produced in this manner include Arakawa Chemical Co., Ltd.
Products (No .: KE-601, KE-615, KE-
624) and the like.

The rosin-modified phenolic resin is prepared by mixing rosin and phenol-formaldehyde initial condensate to obtain 200
It is produced by heating to a high temperature of ˜300 ° C. and then esterifying the carboxyl group in rosin with glycerin, pentaerythritol, ethylene glycol or the like. Examples of commercial products of the rosin-modified phenolic resin produced in this manner include products manufactured by Arakawa Chemical Co., Ltd. (product name: Tamanol 135, 145).

The addition amount of the rosin derivative in the present invention is not particularly limited, but is preferably 10 to 150 parts by weight with respect to 100 parts by weight of the lignin-based material (A). If it is less than 10 parts by weight, the effect of improving the water resistance of the resin composition is insufficient, and if it exceeds 150 parts by weight, the so-called biodegradability deteriorates.

The water-proofing component (B) is used as a crosslinked product which has reacted with the crosslinking component (C). When a rosin derivative is used as the water-resistant component (B), the water-resistant component (B), that is, the cross-linking component (C) having a functional group capable of undergoing a cross-linking reaction with the rosin derivative, depends on the type of the functional group of the rosin derivative. Then, a polyfunctional compound having a plurality of functional groups capable of reacting with the rosin derivative can be appropriately selected and used. Specific examples of the combination of the rosin derivative and the polyfunctional compound having such crosslinkability will be described in detail for each embodiment.

(First embodiment using rosin derivative) When the rosin derivative is at least one compound selected from carboxyl group-containing rosin, maleated rosin, epoxidized rosin, rosin amine and rosin amide, the crosslinking component (C ), An epoxy compound having two or more epoxy groups is preferably used.

The epoxy compound used in the present invention 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, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol type novolac type epoxy resin, bisphenol A.
Novolac type epoxy resin, naphthalene diol type epoxy resin, alicyclic epoxy resin, epoxy compound derived from tri- or tetra (hydroxyphenyl) alkane, bishydroxybiphenyl type epoxy resin,
Examples thereof include epoxy compounds of phenol aralkyl resin. These epoxy compounds may be used alone or in combination of two or more.

Here, the amount of the epoxy compound added is not particularly limited, but it is 1 per 100 parts by weight of the rosin derivative.
It is preferably in the range of 0 to 80 parts by weight, and preferably 20 to 7
It is more preferable to set the range of 0 parts by weight. If it is less than 10 parts by weight, the effect of improving the mechanical strength of the resin composition is not observed, and if it exceeds 80 parts by weight, the crosslink density becomes high and the recyclability is lowered when reused.

Further, in the present invention, a curing accelerator for promoting the reaction between the functional groups of the epoxy compound and the rosin derivative can be appropriately added. As the curing accelerator, for example, a basic catalyst can be used, and specific examples thereof include trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tri (p-methylphenyl) phosphine, methyldiphenylphosphine, tris (2 , 6-Dimethoxyphenyl) phosphine and other organic phosphine compounds; 2-ethylimidazole, 2,4-dimethylimidazole, 2-ethyl-
4-methylimidazole, 2-phenylimidazole,
Imidazole compounds such as 2-heptadecyl imidazole and derivatives thereof; DBU (1,8-diazabicycloundecene-7) or a phenol salt thereof, 6-dibutylamino-1,8-diazabicycloundecene-7 and the like Can be mentioned.

(Second embodiment using rosin derivative) When the rosin derivative is a rosin skeleton-containing diol compound or a rosin-modified phenol resin, the above-mentioned crosslinking component (C) is used.
As the above, a polyisocyanate compound (i) having two or more isocyanate groups, or a mixture (ii) composed of a polyvalent carboxylic acid and fats and oils is preferably used.

The polyisocyanate compound (i) used in the present invention is not particularly limited as long as it has two or more isocyanate groups in one molecule. Specific examples thereof include 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1 , 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,
4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane Diisocyanate compounds such as -4,4-diisocyanate and methylcyclohexanediisocyanate, polyfunctional isocyanate compounds such as dimethylenetriphenylmethanetetraisocyanate, triphenylmethanetriisocyanate and polymethylenepolyphenylpolyisocyanate, polyols such as glycerin and trimethylolpropane Reaction products of the above-mentioned diisocyanate compounds and the like These polyisocyanate compounds can be used alone or in admixture of two or more.

Here, the polyisocyanate compound (i)
The addition amount of is not particularly limited, but is preferably in the range of 10 to 80 parts by weight, and more preferably in the range of 20 to 70 parts by weight with respect to 100 parts by weight of the rosin derivative. If it is less than 10 parts by weight, the effect of improving the mechanical strength of the resin composition is not observed, and if it exceeds 80 parts by weight, the crosslink density becomes high and the recyclability is lowered when reused.

In the present invention, an active hydrogen atom compound can be appropriately blended as a urethane-forming reaction catalyst for promoting the reaction between the polyisocyanate compound (i) and the hydroxyl group of the rosin derivative. As the active hydrogen atom compound, for example, ethylenediamine, propylenediamine,
Hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane 4,4′-diamine and the like can be mentioned. Furthermore, triethylenediamine, triethylamine, tetraethylenediamine, N-methylmorpholine, tetramethylethylenediamine, 1,2-dimethylimidazole,
Amine-based catalysts such as DBU (1,8-diazabicycloundecene-7), tin-based catalysts such as dibutyltin dilaurate and dibutyltin dioctylate, organics such as iron acetylacetonate, zirconium acetylacetonate and aluminum acetylacetonate Metal compounds and the like can also be appropriately used as the urethanization reaction catalyst.

Further, known polyhydric alcohols may be added as appropriate within the range that does not impair the characteristics of the resin composition. As the polyhydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol,
1 such as polyethylene glycol, glycerin, butanediol, propanediol, trimethylolpropane
Examples thereof include alcohols having two or more hydroxyl groups in the molecule.

In the mixture (ii) consisting of a polyvalent carboxylic acid having two or more carboxyl groups in one molecule and an oil or fat used in the present invention, the polyvalent carboxylic acid is
For example, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, (anhydrous) trimellitic acid, adipic acid, (anhydrous) maleic acid, fumaric acid, benzoic acid, succinic acid, oxalic acid,
Examples thereof include malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid and speric acid. These polyvalent carboxylic acids can be used alone or in admixture of two or more.

The fats and oils are preferably natural fats and oils for the purpose of the present invention, and specific examples thereof include linseed oil, safflower oil, tung oil, castor oil, soybean oil, cottonseed oil, rice bran oil, sesame oil, corn oil, rapeseed oil, Vegetable oil such as olive oil, palm oil, sunflower oil, peanut oil, eno oil, camellia oil, whale oil,
Animal oils such as fish oil and liver oil and their fatty acids can be mentioned. These natural fats and oils can be used alone or in admixture of two or more.

In the present invention, the mixture (ii) consisting of polycarboxylic acid and fats and oils can be crosslinked by reacting with the hydroxyl group of the rosin derivative to form an ester bond. In addition, it is possible to form a stronger crosslinked structure by addition-polymerizing the unsaturated double bond contained in the polyvalent carboxylic acid or the oil and fat.

The addition amount of the mixture (ii) consisting of polycarboxylic acid and fats and oils is not particularly limited, but it is preferably in the range of 10 to 80 parts by weight with respect to 100 parts by weight of the rosin derivative. It is more preferable that the amount is in the range of to 70 parts by weight. If it is less than 10 parts by weight, the effect of improving the mechanical strength of the resin composition is not observed, and if it exceeds 80 parts by weight, the crosslink density becomes high and the recyclability is lowered when reused.

Further, the mixing ratio of the polycarboxylic acid and the fats and oils is preferably in the range of 80:20 to 20:80 by weight. If it is out of this range, the effect of improving the mechanical strength of the resin composition becomes insufficient.

In the present invention, an esterification catalyst for promoting the reaction of the mixture (ii) consisting of a polycarboxylic acid and fats and oils with the hydroxyl group of the rosin derivative can be appropriately added. As the esterification reaction catalyst, for example,
Tetrabutyl zirconate, zirconium naphthate,
Tetrabutyl titanate, tetraoctyl titanate,
Stannous oxalate, tetraphenyltin, dibutyltin dichloride, zinc acetate, zinc naphthenate, iron acetylacetonate, cobalt naphthenate, manganese naphthenate, triphenylbismuth, magnesium titanate,
Examples thereof include magnesium zirconate, zinc oxide, tin chloride, manganese acetate, cobalt acetate, nickel acetate, butyltin octylate, tetraphenyltin and tetrabutyltin.

Further, in the present invention, a polymerization catalyst for promoting the polymerization of unsaturated double bonds contained in the mixture (ii) composed of polyvalent carboxylic acid and fats and oils may be appropriately added. Examples of the polymerization catalyst include benzoyl peroxide (BPO), di-t-butyl peroxide,
Examples thereof include dicumyl peroxide, diacyl peroxide, dilauroyl peroxide, m-toluyl peroxide, azobisisobutyronitrile (AIBN), azobis-2,4-dimethylvaleronitrile and azobiscyclohexanecarbonitrile.

Further, known polyfunctional alcohols may be appropriately added as long as the characteristics of the resin composition are not impaired. Examples of the polyfunctional alcohol include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, butanediol and propanediol, or allyl alcohol, hydroxyethyl acrylate, hydroxyethyl methacrylate and 3-butene-2-. Examples thereof include alcohols having an unsaturated bond such as all, 2-hexen-1-ol, and 4-allylcatechol.

(Third Embodiment Using Rosin Derivative) When the rosin derivative is a carboxyl group-containing rosin, a mixture (iii) consisting of a polyhydric alcohol and fats and oils is preferably used as the crosslinking component (C).

The polyhydric alcohol used in this embodiment is not particularly limited as long as it has two or more hydroxyl groups in one molecule. Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, butanediol, propanediol, trimethylolethane, trimethylolpropane and pentaerythritol. These polyhydric alcohols are
They can be used alone or in combination of two or more.

As described above, the fats and oils are preferably natural fats and oils for the purpose of the present invention. Specific examples thereof include those described in the above mixture (ii), which may be used alone or in combination of two kinds. The above can be mixed and used.

In the present invention, the mixture (iii) consisting of such polyhydric alcohol and fats and oils can be crosslinked by reacting with the carboxyl group of the rosin derivative to form an ester bond. Further, by adding and polymerizing the unsaturated double bond contained in the polyhydric alcohol or the natural oil and fat, it becomes possible to form a stronger crosslinked structure.

The addition amount of the mixture (iii) consisting of polyhydric alcohol and fats and oils is not particularly limited, but it is preferably in the range of 10 to 80 parts by weight with respect to 100 parts by weight of the rosin derivative. It is more preferable to set it in the range of 70 parts by weight. If it is less than 10 parts by weight, the effect of improving the mechanical strength of the resin composition is not observed, and if it exceeds 80 parts by weight, the crosslink density becomes high and the recyclability is lowered when reused.

The mixing ratio of the polyhydric alcohol and the oil and fat is preferably in the range of 80:20 to 20:80 by weight. If it is out of this range, the effect of improving the mechanical strength of the resin composition becomes insufficient.

In the present invention, an esterification catalyst for accelerating the reaction between the mixture (iii) consisting of polyhydric alcohol and fats and oils and the carboxyl group of the rosin derivative can be appropriately added. As the esterification reaction catalyst, the same catalyst as described in the second aspect can be used.

Further, in the present invention, a polymerization catalyst for promoting the polymerization of unsaturated double bonds contained in the mixture (iii) consisting of polyhydric alcohol and fats and oils can be appropriately added. As the polymerization catalyst, the same polymerization catalyst as described in the second aspect can be used.

Further, a known polyvalent carboxylic acid may be appropriately added as long as the characteristics of the resin composition are not impaired. Examples of the polycarboxylic acid include (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, (anhydrous) trimellitic acid, adipic acid, (anhydrous) maleic acid, fumaric acid, benzoic acid, succinic acid, oxalic acid, and malon. Acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, speric acid and the like can be mentioned.

[Terpene Phenol Resin] The terpene phenol resin used in the present invention is a cyclic terpene phenol resin (a) obtained by copolymerizing a cyclic terpene compound and phenols, one molecule of the cyclic terpene compound and two molecules of the phenols. A cyclic terpene skeleton-containing phenol compound (b), which is added at a ratio of, a cyclic terpene skeleton-containing phenol resin (c) obtained by subjecting the cyclic terpene skeleton-containing phenol compound (b) and an aldehyde to a condensation reaction, and It is selected from the group consisting of a cyclic terpene skeleton-containing phenol resin (d) obtained by a condensation reaction of a cyclic terpene skeleton-containing phenol compound obtained by adding 1 molecule of a phenol to one molecule of a cyclic terpene compound and an aldehyde. At least one kind.

These terpene phenol resins can be used alone or in combination of two or more kinds.

The terpene compound as a raw material for producing the terpene phenol resin used in the present invention may be a monocyclic terpene compound or a bicyclic terpene compound, and is not particularly limited. . Specific examples thereof include α-pinene, β-pinene, dipentene, limonene, ferrandrene, α-terpinene, γ-terpinene, terpinolene, 1,8-cineole, 1,4-cineole, terpineol, paramentenes and paramenta. Examples thereof include dienes and currens.

The other raw materials for producing the terpene phenol resin used in the present invention include phenols, cresol, ethylphenol, butylphenol, xylenol, propylphenol, nonylphenol, phenylphenol, hydroquinone and resorcin. , Catechol, methoxyphenol, bisphenol A, bisphenol F, naphthol and the like, but are not limited thereto. These compounds can be used alone or in combination of two or more.

The cyclic terpene phenol resin (a) can be produced by copolymerizing a cyclic terpene compound and a phenol in the presence of a Friedel-Crafts type catalyst.

The copolymerization reaction of the cyclic terpene compound and the phenols for producing the cyclic terpene phenolic resin (a) is 0.1 to 12 moles of phenols, preferably 0.1 to 0.1 mole of the cyclic terpene compound. 2 to 6 moles are used in the presence of Friedel-Crafts type catalyst
The reaction is carried out at a temperature of ° C for 1 to 10 hours. Examples of the Friedel-Crafts catalyst include aluminum chloride, boron trifluoride, or a complex thereof. Commercial products of the cyclic terpene phenolic resin (a) produced in this manner include products manufactured by Yasuhara Chemical Co., Ltd. (product name:
YS Polystar, Mighty Ace) and the like.

The cyclic terpene skeleton-containing phenol compound (b) can be produced by subjecting a cyclic terpene compound and a phenol to an addition reaction in the presence of an acidic catalyst.

For the addition reaction of one molecule of the cyclic terpene compound and two molecules of the phenol, 1 to 12 mol, preferably 2 to 8 mol, of the phenol is used per 1 mol of the cyclic terpene compound in the presence of an acidic catalyst. It is carried out at a temperature of 20 to 150 ° C. for 1 to 10 hours. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boron trifluoride or its complex, cation exchange resin, activated clay and the like. Examples of commercially available products of the cyclic terpene skeleton-containing phenol compound (b) thus produced include a product (No .: YP-90) manufactured by Yasuhara Chemical Co., Ltd.

The cyclic terpene skeleton-containing phenol resin (c) can be produced by subjecting the cyclic terpene skeleton-containing phenol compound (b) and an aldehyde to a condensation reaction.

Aldehydes used as a condensing agent for producing the cyclic terpene skeleton-containing phenol resin (c) include, for example, formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde,
Examples thereof include benzaldehyde, hydroxybenzaldehyde and phenylacetaldehyde.

In the condensation reaction of the above-mentioned phenol compound (b) having a cyclic terpene skeleton with aldehydes, a usual novolak reaction is used. The reaction ratio between the phenol compound and the aldehyde in this condensation reaction is such that the aldehyde is 0.1 to 1 mol of the phenol compound.
The amount is 1.0 mol, preferably 0.2 to 0.7 mol, and the reaction is carried out in the presence of an acidic catalyst at a temperature of 40 to 200 ° C. for 1 to 12 hours. When the amount of aldehydes is too large, the phenol resin having a cyclic terpene skeleton has a high molecular weight. As the acidic catalyst for the condensation reaction, for example, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and the like, and organic acids such as formic acid, acetic acid, oxalic acid, toluene sulfonic acid and the like can be used. Commercially available products of the cyclic terpene skeleton-containing phenolic resin (c) thus produced include terpene-modified novolac resins manufactured by Yasuhara Chemical Co., Ltd. (resins of product number YP-90 are novolacized), Japan Epoxy Resins. Terpene modified phenol novolac resin (No .: MP4)
02FPY) and the like.

The cyclic terpene skeleton-containing phenol resin (d) is a cyclic terpene skeleton-containing phenol compound obtained by an addition reaction of one molecule of the cyclic terpene compound with one molecule of the phenol in the presence of an acidic catalyst, and an aldehyde. It can be produced by subjecting and to a condensation reaction.

The addition reaction between one molecule of the cyclic terpene compound and one molecule of the phenol for producing the cyclic terpene skeleton-containing phenol compound which is the precursor of the cyclic terpene skeleton-containing phenol resin (d) is carried out by the cyclic terpene compound 1
0.5 to 6 mol, preferably 1 to 4 mol, of phenol is used per mol, and 20 to 150 in the presence of an acidic catalyst.
It is carried out at a temperature of ° C for 1 to 10 hours. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boron trifluoride or its complex, cation exchange resin, activated clay and the like.

The condensation reaction between the above-mentioned cyclic terpene skeleton-containing phenol compound and the aldehyde for producing the cyclic terpene skeleton-containing phenol resin (d) is carried out in the same manner as in the production of the cyclic terpene skeleton-containing phenol resin (c). Commercially available products of the cyclic terpene skeleton-containing phenolic resin (d) produced in this manner include products manufactured by Yasuhara Chemical Co., Ltd. (Nos .: DLN-120, DLN).
-140) and the like.

The addition amount of the terpene phenol resin in the present invention is not particularly limited, but the lignin-based material (A) 1
10 to 150 parts by weight is preferable with respect to 00 parts by weight.
If it is less than 10 parts by weight, the effect of improving the water resistance of the resin composition is insufficient, and if it exceeds 150 parts by weight, the so-called biodegradability deteriorates.

The terpene phenol resin is used as a crosslinked product obtained by reacting with the crosslinking component (C). The compound having a functional group capable of undergoing a crosslinking reaction with the terpene phenol resin, which is the crosslinking component (C) component used in this embodiment, contains a functional group capable of reacting with the hydroxyl group of the terpene phenol resin, and has a known crosslinking property. Examples of the polyfunctional compounds include, among others, an epoxy compound (I) having two or more epoxy groups, a polyisocyanate compound (II) having two or more isocyanate groups, a polyvalent carboxylic acid and a fat and oil. A compound selected from the mixture (III) is preferably used.

The epoxy compound (I) used in this embodiment is not particularly limited as long as it has two or more epoxy groups in one molecule.
As a specific example thereof, the first rosin derivative is used.
Similar to the case of the embodiment of bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol type novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthalene Examples thereof include diol type epoxy resins, alicyclic epoxy resins, epoxy compounds derived from tri- or tetra (hydroxyphenyl) alkanes, bishydroxybiphenyl-based epoxy resins, and epoxidized phenol aralkyl resins. These epoxy compounds are
They can be used alone or in combination of two or more.

Here, the addition amount of the epoxy compound (I) is not particularly limited, but it is preferably in the range of 10 to 80 parts by weight, preferably 20 to 70 parts by weight, relative to 100 parts by weight of the terpene phenol resin. More preferably, If it is less than 10 parts by weight, the effect of improving the mechanical strength of the resin composition is not observed, and if it exceeds 80 parts by weight, the crosslink density becomes high and the recyclability is lowered when reused.

Further, in this embodiment, a curing accelerator for promoting the reaction between the epoxy compound (I) and the hydroxyl group of the terpene phenol resin can be appropriately added. As the curing accelerator, for example, a basic catalyst can be used, and specific examples thereof include trimethylphosphine,
Triethylphosphine, tributylphosphine, triphenylphosphine, tri (p-methylphenyl) phosphine, methyldiphenylphosphine, tris (2,6-
Organic phosphine compounds such as dimethoxyphenyl) phosphine; 2-ethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-
Imidazole compounds such as phenylimidazole and 2-heptadecylimidazole and derivatives thereof; DBU
(1,8-diazabicycloundecene-7) or a phenol salt thereof, 6-dibutylamino-1,8-diazabicycloundecene-7 and the like can be mentioned.

The polyisocyanate compound (II) used in the present invention is not particularly limited as long as it has two or more isocyanate groups in one molecule. Specific examples thereof include 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4, as in the second embodiment using the rosin derivative described above. 4'-dibenzyl isocyanate,
Dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-
Phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-
1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, Diisocyanate compounds such as dicyclohexylmethane-4,4-diisocyanate and methylcyclohexanediisocyanate, polyfunctional isocyanate compounds such as dimethylenetriphenylmethanetetraisocyanate, triphenylmethanetriisocyanate and polymethylenepolyphenylpolyisocyanate, glycerin and trimethylolpropane Examples of addition reaction products of the above polyols and the above diisocyanate compound include That. These polyisocyanate compounds can be used alone or in admixture of two or more.

Here, the polyisocyanate compound (II)
The amount added is not particularly limited, but is preferably in the range of 10 to 80 parts by weight, and more preferably in the range of 20 to 70 parts by weight, relative to 100 parts by weight of the terpene phenol resin. If it is less than 10 parts by weight, the effect of improving the mechanical strength of the resin composition is not observed, and if it exceeds 80 parts by weight, the crosslink density becomes high and the recyclability is lowered when reused.

In the present invention, an active hydrogen atom compound can be appropriately blended as a urethane-forming reaction catalyst for promoting the reaction between the polyisocyanate compound (II) and the hydroxyl group of the terpene phenol resin. Examples of the active hydrogen atom compound include ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane 4,4′-diamine and the like. Furthermore, amine catalysts such as triethylenediamine, triethylamine, tetraethylenediamine, N-methylmorpholine, tetramethylethylenediamine, 1,2-dimethylimidazole, DBU (1,8-diazabicycloundecene-7), dibutyltin dilaurate, Tin-based catalysts such as dibutyltin dioctylate, organometallic compounds such as iron acetylacetonate, zirconium acetylacetonate, and aluminum acetylacetonate can also be appropriately used as the urethanization reaction catalyst.

Further, known polyhydric alcohols may be appropriately added within a range that does not impair the characteristics of the resin composition. As the polyhydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol,
1 such as polyethylene glycol, glycerin, butanediol, propanediol, trimethylolpropane
Examples thereof include alcohols having two or more hydroxyl groups in the molecule.

2 in one molecule used in this embodiment
In the mixture (III) consisting of polycarboxylic acid having at least one carboxyl group and fat and oil, examples of the polycarboxylic acid include (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, (anhydrous) trimellitic acid, adipic acid. , (Anhydrous) maleic acid, fumaric acid, benzoic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, speric acid and the like. These polyvalent carboxylic acids can be used alone or in admixture of two or more.

Further, the fats and oils are preferably natural fats and oils for the purpose of the present invention, and specific examples thereof include linseed oil, safflower oil, tung oil, castor oil, soybean oil, cottonseed oil, as in the embodiment of the rosin derivative. Rice bran oil, sesame oil, corn oil, rapeseed oil, olive oil, coconut oil, sunflower oil, peanut oil,
Examples thereof include vegetable oils such as eno oil and camellia oil, animal oils such as whale oil, fish oil and liver oil, and fatty acids thereof. These natural fats and oils can be used alone or in admixture of two or more.

In the present invention, the mixture (III) consisting of polycarboxylic acid and fats and oils can be crosslinked by reacting with the hydroxyl group of the terpene phenol resin to form an ester bond. In addition, it is possible to form a stronger crosslinked structure by addition-polymerizing the unsaturated double bond contained in the polyvalent carboxylic acid or the oil and fat.

The addition amount of the mixture (III) consisting of polycarboxylic acid and fats and oils is not particularly limited, but it is preferably in the range of 10 to 80 parts by weight with respect to 100 parts by weight of the terpene phenol resin, It is more preferable to set it in the range of 20 to 70 parts by weight. If it is less than 10 parts by weight, the effect of improving the mechanical strength of the resin composition is not observed, and if it exceeds 80 parts by weight, the crosslink density becomes high and the recyclability is lowered when reused.

The mixing ratio of the polycarboxylic acid and the fat or oil is preferably 80:20 to 20:80 by weight. If it is out of this range, the effect of improving the properties (mechanical strength, heat resistance) of the resin composition becomes insufficient.

In the present invention, an esterification catalyst for accelerating the reaction between the mixture (III) consisting of polycarboxylic acid and fats and oils and the hydroxyl group of the terpene phenol resin can be appropriately added. Examples of the esterification reaction catalyst include tetrabutyl zirconate, zirconium naphthate, tetrabutyl titanate, tetraoctyl titanate, stannous oxalate, tetraphenyl tin,
Dibutyltin dichloride, zinc acetate, zinc naphthenate, iron acetylacetonate, cobalt naphthenate, manganese naphthenate, triphenylbismuth, magnesium titanate, magnesium zirconate, zinc oxide,
Examples thereof include tin chloride, manganese acetate, cobalt acetate, nickel acetate, butyltin octylate, tetraphenyltin and tetrabutyltin.

In this embodiment, a polymerization catalyst for promoting the polymerization of unsaturated double bonds contained in the mixture (III) consisting of polycarboxylic acid and fats and oils can be appropriately added. Examples of the polymerization catalyst include benzoyl peroxide (BPO), di-t-butyl peroxide, dicumyl peroxide, diacyl peroxide, dilauroyl peroxide, m-toluyl peroxide, azobisisobutyronitrile ( AIB
N), azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile and the like.

Further, known polyfunctional alcohols may be appropriately added as long as the characteristics of the resin composition are not impaired. Examples of the polyfunctional alcohol include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, butanediol and propanediol, or allyl alcohol, hydroxyethyl acrylate, hydroxyethyl methacrylate and 3-butene-2-. Examples thereof include alcohols having an unsaturated bond such as all, 2-hexen-1-ol, and 4-allylcatechol.

[Additives] In the resin composition of the present invention, a resin composition having excellent mechanical properties and water resistance can be obtained by using only the essential components consisting of the above components (A) to (C). In order to effectively use wood resources and increase the strength of resin molded products, vegetable fiber powder can be further added. Examples of the vegetable fiber powder include wood powder, paper powder, and cellulose fiber powder.

Wood powder includes crushed chips, wood pulp,
Examples include finely crushed wood processing waste materials and sawdust.

Examples of the paper powder include virgin pulp and waste paper pulp powder, and finely crushed waste paper. As the used paper, high-quality paper such as OA paper, recycled used paper such as newspaper, weekly magazine, cardboard and the like can be used.

As the cellulose fibers, powders such as mechanical pulp, chemical pulp, semi-chemical pulp and recycled pulps thereof can be used. Examples of raw materials for such cellulose fibers include non-wood fibers such as wood fibers made from softwood and hardwood, kozo, kefuna, manila hemp, straw, pagas, bamboo, chaff and the like, and any of them can be used. . Further, as the cellulose fiber, those obtained by defibrating various paper products such as cardboard and newspaper can also be used.

In the present invention, the size of the vegetable fiber powder is not particularly limited, but crushed powder crushed to a range of 20 to 300 mesh is preferable. If the size is too coarse, the dispersion of the vegetable fiber powder will be poor, and the effect of addition will be insufficient. If it is too fine, the moldability of the resin composition will decrease.

The addition amount of the vegetable fiber powder is not particularly limited, but if the addition amount is too small, the effect of increasing the strength cannot be seen, and if it is too large, the moldability of the resin composition is significantly reduced.

In addition to the components described above, the resin composition of the present invention may further contain an inorganic filler, a plasticizer, a release agent, a pigment, a colorant, a solvent, a flame retardant, an antioxidant, if necessary. Various additives such as a heat stabilizer, a light stabilizer, a compatibilizer, a foaming agent, a fragrance, an antibacterial / antifungal agent, and an antiseptic agent may be appropriately mixed.

[Preparation Method of Composition] The resin composition of the present invention can be prepared by a conventionally known mixing method and is not particularly limited. For example, it can be easily prepared by melt-kneading the above-mentioned components using a heating roll, a super mixer, a Henschel mixer, a kneader, a universal mixing stirrer, a single-screw or twin-screw extruder, and the like. When a mixture of polyvalent carboxylic acids or polyhydric alcohols and fats and oils is used as the crosslinking component (C), the esterification reaction is performed by melt kneading as the first step, and then the polymerization catalyst is used as the second step. It is possible to use a method in which is added and mixed again. The temperature during the preparation generally depends on the crosslinking component (C).
When using an epoxy compound as about 60 ~ 120 ℃,
When using a polyisocyanate compound, about 40 to 10
At 0 ° C., when a mixture of polyhydric carboxylic acid or polyhydric alcohol and fat is used, it is about 120 because of esterification reaction.
It is preferably set to 180 ° C.

The molding method of the resin composition of the present invention includes:
Various molded articles can be produced by appropriately forming into desired shapes by conventionally known methods such as compression molding, film molding, extrusion molding, injection molding, inflation molding and blow molding.

The resin composition molded according to the present invention has a desired shape such as a film, a sheet, a molded body, a foamed body, a packaging container, a foamed body, a sheet, a building material, an automobile, a home electric appliance, an OA.
It can be effectively used as a member of equipment, an interior material, a housing, and the like.

The resin composition of the present invention has a three-dimensional crosslinked structure, but since it contains a lignin-based material having a lower crosslink density and biodegradability than conventional thermosetting resins, it is known to be decomposed. It can be easily decomposed by using an agent and can be reused or recycled.

[0097]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

[Examples 1 to 14 and Comparative Examples 1 to 4] The components shown below were used as raw materials in the proportions shown in Tables 1 and 2 (Examples 1 to 14 and Comparative Examples 1 to 4) below. Each component was mixed and prepared as shown below to obtain a desired resin composition. The blending amount in the table indicates parts by weight.

(Raw material) Lignin-based material A: Lignin derivative (Lignin sulfonic acid manufactured by Nippon Paper Industries, product name: Vanillex RN) Lignin-based material B: Lignophenol derivative (wood powder as raw material, p-cresol and 72% sulfuric acid) Lignocresol derivative prepared by the phase separation process method using Lignin-based material C: Lignocellulosic decomposition product (derived from wood powder by adding polyethylene glycol, glycerin and concentrated sulfuric acid (catalyst) to the decomposition treatment) Decomposition products obtained: Rosin derivative A: carboxyl group-containing rosin (Arakawa Chemical Co., product number: KR-610, acid value 170) Rosin derivative B: maleated rosin (Arakawa Chemical Co., acid value = 366) rosin Derivative C: Epoxidized rosin (Arakawa Chemical Co., Ltd., epoxy equivalent = 350) Rosin derivative D: Logic Amine (manufactured by Arakawa Chemical Co., Ltd.) Rosin derivative E: rosin amide (manufactured by Arakawa Chemical Co., Ltd.) Rosin derivative F: diol compound containing rosin skeleton (manufactured by Arakawa Chemical Co., Ltd., product number: KE-601, hydroxyl value = 11)
0) Rosin derivative G: Rosin-modified phenol resin (Arakawa Chemical Co., Ltd., product name: Tamanol 135, acid value = 18) Rosin derivative H: Rosin ester (Arakawa Chemical Co., product number: KE-100, no functional group) Epoxy compound: Orthocresol novolac type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd., product number: ESCN-195X
L, epoxy equivalent = 197) Curing accelerator: 2-heptadecyl imidazole (manufactured by Shikoku Chemicals, product number: C17Z) Polyisocyanate compound: 4,4′-diphenylmethane diisocyanate urethane formation reaction catalyst: triethylenediamine polycarboxylic acid A : Maleic anhydride polycarboxylic acid B: Adipic acid polyhydric alcohol: Diethylene glycol oil / fat: Linseed oil esterification reaction catalyst: Tetrabutyl zirconate polymerization catalyst: Di-t-butyl peroxide Vegetable fiber powder A: Wood flour (Miki Sangyo Co., Ltd., product name: Lignocell) Plant fiber powder B: Finely pulverized powder of used paper (newspaper) Plant fiber powder C: Powder cellulose (Miki Sangyo Co., Ltd., product name: Arbocel) (Examples 1 to 5 and 11) Preparation of Comparative Examples 1 to 4) First, a lignin-based material, a rosin derivative, and an epoxy compound object,
The hardening accelerator or vegetable fiber powder was mixed with a Henschel mixer, and melt-kneaded with a heating roll heated to the temperature shown in the table. Next, the mixture is taken out in a sheet form,
After cooling, the desired resin composition was obtained by pulverizing.

(Preparation of Examples 6, 7 and 12) First,
A lignin-based material, a rosin derivative, a polyisocyanate compound, a urethane-forming reaction catalyst or a vegetable fiber powder was mixed with a Henschel mixer, and then melt-kneaded with a kneader heated to the temperature shown in the table. Next, this mixture was taken out in a sheet form or a bulk form to obtain a desired resin composition.

(Preparation of Examples 8 to 10 and 13, 14) First, a lignin-based material, a rosin derivative, a polyhydric carboxylic acid or polyhydric alcohol, an oil and fat and an esterification reaction catalyst were mixed by a universal mixing stirrer. The esterification reaction was carried out at room temperature under vacuum vacuum with melt mixing.
Next, a polymerization catalyst or vegetable fiber powder was added to this mixture and mixed by a kneader, and the mixture was taken out in a sheet form or a block form to obtain a desired resin composition.

[0102]

[Table 1]

[Table 2] (Evaluation of Resin Composition) Examples 1 to 14 and Comparative Examples 1 to 4
The following 18 evaluation tests were performed on the 18 resin compositions.

Each resin composition was compression molded by a compression molding machine at a molding temperature of 150 ° C. and a molding pressure of 100 kgf / cm ² for 10 minutes to obtain a plate-shaped molded product having a thickness of 4 mm. This molded product was used as a test piece for each evaluation test.

(1) Mechanical Strength Using an autograph, the tensile strength of the molded product of each resin composition was measured.

(2) Water resistance A plate-shaped molded product of each resin composition was immersed in water at 25 ° C. for 24 hours, and the weight change was measured to determine the water absorption.

The evaluation results obtained in the above test are shown in Table 3 below.
And shown in Table 4.

[0107]

[Table 3] −−−−−−−−−−−−−−−−−−−−−−−−−−−−−                             Example                     1 2 3 4 5 6 7 8 9 −−−−−−−−−−−−−−−−−−−−−−−−−−−−− Tensile strength (MPa) 62 77 70 63 72 60 58 54 54 Water absorption rate (%) 0.2 0.2 0.2 0.2 0.2 0.3 0.3 0.3 0.3 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−

[Table 4] ------------------------------- Actual Example Comparative Example 10 11 12 13 14 1 2 3 4 --- −−−−−−−−−−−−−−−−−−−−−−−−− Tensile strength (MPa) 58 96 93 90 92 15 42 20 36 Water absorption rate (%) 0.3 0.4 0.5 0.5 0.5 20 15 0.6 0.4 −−−−−−−−−−−−−−−−−−−−−−−−−−−− As shown in Tables 3 and 4 above, the resin composition of the present invention (implemented It was confirmed that Examples 1 to 14) were excellent in mechanical strength and water resistance.

On the other hand, as shown in Table 4, the resin composition (Comparative Example 1) containing only the lignin-based material
Mechanical strength and water resistance are extremely poor. The resin composition containing no water-resistant component (B) (Comparative Example 2) had insufficient water resistance, and the resin composition containing no crosslinking component (C) (Comparative Example 3) had poor mechanical strength. It is enough. Also,
Even if the crosslinking component (C) is blended, the water resistance component (B)
Is a rosin ester with no functional group (rosin derivative H)
In the case of (Comparative Example 4), the mechanical strength is lowered.

[Examples 15 to 25, Comparative Examples 5 to 8] The following components were used as raw materials and the following Tables 5 and 6 were used.
The components were mixed in the proportions shown in (Examples 15 to 25 and Comparative Examples 5 to 8) and prepared as follows to obtain the desired resin composition. The blending amount in the table indicates parts by weight.

(Raw material) Lignin-based material A: Lignin derivative (Lignin sulfonic acid manufactured by Nippon Paper Industries, product name: Pearlex NP) Lignin-based material B: Lignophenol derivative (wood flour as raw material, p-cresol and 72%) Lignocresol Derivative Prepared by Phase Separation Process Method Using Sulfuric Acid) Lignin-based Material C: Lignocellulosic decomposition product (from wood flour as a raw material, polyethylene glycol, glycerin and concentrated sulfuric acid (catalyst) were added for decomposition treatment Obtained decomposition product) Terpene phenol resin a: Cyclic terpene phenol resin (manufactured by Yasuhara Chemical Co., product name: YS Polystar N)
125, hydroxyl equivalent = 300) Terpene phenol resin b: Phenolic compound containing cyclic terpene skeleton (Yasuhara Chemical Co., product number: YP
-90, hydroxyl equivalent = 160) Terpene phenol resin c: Phenolic resin containing cyclic terpene skeleton (manufactured by Japan Epoxy Resins, product number:
MP402, hydroxyl equivalent = 174) Terpene phenolic resin d: Phenolic resin containing cyclic terpene skeleton (Yasuhara Chemical Co., product number: DLN
-120, hydroxyl equivalent = 190) Terpene resin: (Yasuhara Chemical Co., product name: YS
Resin PX1250, no hydroxyl group) Epoxy compound A: Orthocresol novolac type epoxy resin (Sumitomo Chemical Co., Ltd., product number: ESCN-195)
XL, epoxy equivalent = 197) Epoxy compound B: Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resins, product name: Epicoat 8)
28, epoxy equivalent = 190) Curing accelerator: 2-heptadecyl imidazole (manufactured by Shikoku Chemicals, product number: C17Z) Polyisocyanate compound A: 4,4'-diphenylmethane diisocyanate polyisocyanate compound B: isophorone diisocyanate urethane reaction catalyst : Triethylenediamine polycarboxylic acid A: maleic anhydride polycarboxylic acid B: adipic acid oil / fat: linseed oil esterification reaction catalyst: tetrabutyl zirconate polymerization catalyst: di-t-butyl peroxide vegetable fiber powder A: wood Powder (manufactured by Miki Sangyo Co., Ltd., product name: Lignocell) Vegetable fiber powder B: Finely pulverized powder of waste paper (newspaper) Vegetable fiber powder C: Powdered cellulose (manufactured by Miki Sangyo Co., Ltd., product name: Arbocel) (Example 15- 19 and 23, Preparation of Comparative Examples 5-8)
First, a lignin-based material, a terpene phenol resin, an epoxy compound, a curing accelerator or a vegetable fiber powder was mixed with a Henschel mixer, and melt-kneaded with a heating roll heated to the temperature shown in the table. Next, this mixture was taken out in a sheet form, cooled, and then pulverized to obtain a desired resin composition.

(Preparation of Examples 20, 21 and 24) First, a lignin-based material, a terpene phenol resin, a polyisocyanate compound, a urethanization reaction catalyst or vegetable fiber powder was mixed with a Henschel mixer, and the mixture was heated to the temperature shown in the table. It was melt-kneaded by a heated kneader. next,
The mixture was taken out in a sheet form or a bulk form to obtain a desired resin composition.

(Preparation of Examples 22 and 25) First, a lignin-based material, a terpene phenol resin, a polyvalent carboxylic acid, an oil and fat and an esterification reaction catalyst were melt-mixed at a temperature shown in the table under a vacuum and reduced pressure. While carrying out the esterification reaction. Next, a polymerization catalyst or vegetable fiber powder was added to this mixture and mixed by a kneader, and the mixture was taken out in a sheet shape or a block shape to obtain a desired resin composition.

[0113]

[Table 5]

[Table 6] (Evaluation of Resin Composition) Examples 15 to 25, Comparative Examples 5 to 8
The mechanical strength and water resistance were evaluated by the same evaluation tests as in Examples 1 to 14 and Comparative Examples 1 to 4 for the 15 kinds of resin compositions of No. 1.

Tables 7 and 8 show the obtained evaluation results.

[0115]

[Table 7] -----------------                       Example                     15 16 17 18 19 20 21 22 ----------------- Tensile strength (MPa) 60 75 72 61 62 60 58 54 Water absorption rate (%) 0.2 0.2 0.2 0.2 0.2 0.3 0.3 0.3 -----------------

[Table 8] As shown in Tables 7 and 8 above, it was confirmed that the resin compositions (Examples 15 to 25) of the present invention were excellent in mechanical strength and water resistance.

On the other hand, the resin composition (Comparative Example 5) consisting of the lignin-based material alone, as shown in Table 8,
Mechanical strength and water resistance are extremely poor. The resin composition containing no water-resistant component (B) (Comparative Example 6) had insufficient water resistance, and the resin composition containing no crosslinking component (C) (Comparative Example 7) had poor mechanical strength. It is enough. Also,
Even when the crosslinking component (C) is blended, the mechanical strength is lowered when the water-resistant component (B) is a terpene resin having no hydroxyl group (Comparative Example 8).

[0117]

According to the present invention, a resin composition having excellent mechanical strength and water resistance can be provided using a lignin-based material. Further, it is possible to provide a resin composition that can be easily decomposed and can be reused or recycled.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Yumiko Kaori, inventor             1st Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa             Inside the Toshiba Research and Development Center F term (reference) 4J002 AH001 BA002 CC072 CD002                       EC047 EC057 EF057 EF086                       ER007 FD01 FD14 GG00                       GG02 GL00 GN00 GQ00

Claims (9)

[Claims] 1. A lignin-based material (A), at least one water-resistant component (B) selected from the group consisting of rosin derivatives and terpene phenol resins, and a cross-linking reaction with the water-resistant component (B). Crosslinking component (C) having a functional group
A resin composition comprising: 2. The lignin-based material (A) contains a component having a lignin basic skeleton, and is at least one selected from a lignin derivative, a lignophenol derivative, and a lignocellulose decomposition product. Item 2. The resin composition according to item 1. 3. The water-resistant component (B) is a carboxyl group-containing rosin, maleated rosin, epoxidized rosin,
At least one selected from rosin amine and rosin amide
Cross-linking component (C)
Is an epoxy compound having two or more epoxy groups, and the resin composition according to claim 1 or 2. 4. The rosin derivative is a compound selected from the group consisting of a rosin skeleton-containing diol compound and a rosin-modified phenolic resin, and the crosslinking component (C).
Is selected from the group consisting of a polyisocyanate compound having two or more isocyanate groups, and a mixture consisting of a polycarboxylic acid and fats and oils.
Alternatively, the resin composition according to claim 2. 5. The rosin derivative is a carboxyl group-containing rosin, and the cross-linking component (C) is a mixture of a polyhydric alcohol and an oil or fat. The resin composition described. 6. The water-resistant component (B) is a cyclic terpene phenol resin (a) obtained by copolymerizing a cyclic terpene compound and a phenol, and 1 molecule of the cyclic terpene compound is added at a ratio of 2 molecules of the phenol compound. A cyclic terpene skeleton-containing phenol compound (b), a cyclic terpene skeleton-containing phenol resin (c) obtained by subjecting the cyclic terpene skeleton-containing phenol compound (b) and an aldehyde compound to a condensation reaction, and a phenol compound in one molecule of the cyclic terpene compound Cyclic terpene skeleton-containing phenolic resin (d) obtained by subjecting a phenolic compound having a cyclic terpene skeleton added at a ratio of 1 molecule to a condensation reaction with an aldehyde compound
The resin composition according to claim 1 or 2, wherein the resin composition is at least one terpene phenol resin selected from the group consisting of: 7. The group consisting of the crosslinking component (C), an epoxy compound having two or more epoxy groups, a polyisocyanate compound having two or more isocyanate groups, and a mixture of polyvalent carboxylic acid and fats and oils. The resin composition according to claim 6, which is at least one selected from the group consisting of: 8. The resin composition according to claim 1, further comprising a vegetable fiber powder. 9. A crosslinked product containing a lignin-based material (A) and at least one water-resistant component (B) selected from the group consisting of rosin derivatives and terpene phenol resins. Resin composition.